ȱɧɫɬɢɬɭɬ ɪɚɞɿɨɮɿɡɢɤɢ ɬɚ ɟɥɟɤɬɪɨɧɿɤɢ ɿɦ. Ɉ. ə. ɍɫɢɤɨɜɚ ɇɚɰɿɨɧɚɥɶɧɚ ɚɤɚɞɟɦɿɹ ɧɚɭɤ ɍɤɪɚʀɧɢ ɏɚɪɤɿɜɫɶɤɢɣ ɧɚɰɿɨɧɚɥɶɧɢɣ ɭɧɿɜɟɪɫɢɬɟɬ ɿɦɟɧɿ ȼ.ɇ. Ʉɚɪɚɡɿɧɚ Ɇɿɧɿɫɬɟɪɫɬɜɨ ɨɫɜɿɬɢ ɿ ɧɚɭɤɢ ɍɤɪɚʀɧɢ Ʉɜɚɥɿɮɿɤɚɰɿɣɧɚ ɧɚɭɤɨɜɚ ɩɪɚɰɹ ɧɚ ɩɪɚɜɚɯ ɪɭɤɨɩɢɫɭ ȻɅɂɁɇɘɄ ɘɅȱə ɆɂɄɈɅȺȲȼɇȺ ɍȾɄ 577.323 ȾɂɋȿɊɌȺɐȱə ɆȿɏȺɇȱɁɆɂ ȺɋɈɐȱȺɐȱȲ ȻȱɈɅɈȽȱɑɇɈ ȺɄɌɂȼɇɂɏ ɊȿɑɈȼɂɇ ɌȺ Ȳɏ ɄɈɆɉɅȿɄɋɈɍɌȼɈɊȿɇɇə Ɂ ȾɇɄ ɋɩɟɰɿɚɥɶɧɿɫɬɶ 03.00.02 – «Ȼɿɨɮɿɡɢɤɚ» (Ɏɿɡɢɤɨ-ɦɚɬɟɦɚɬɢɱɧɿ ɧɚɭɤɢ) ɉɨɞɚɽɬɶɫɹ ɧɚ ɡɞɨɛɭɬɬɹ ɧɚɭɤɨɜɨɝɨ ɫɬɭɩɟɧɹ ɤɚɧɞɢɞɚɬɚ ɮɿɡɢɤɨ-ɦɚɬɟɦɚɬɢɱɧɢɯ ɧɚɭɤ Ⱦɢɫɟɪɬɚɰɿɹ ɦɿɫɬɢɬɶ ɪɟɡɭɥɶɬɚɬɢ ɜɥɚɫɧɢɯ ɞɨɫɥɿɞɠɟɧɶ. ȼɢɤɨɪɢɫɬɚɧɧɹ ɿɞɟɣ, ɪɟɡɭɥɶɬɚɬɿɜ ɿ ɬɟɤɫɬɿɜ ɿɧɲɢɯ ɚɜɬɨɪɿɜ ɦɚɸɬɶ ɩɨɫɢɥɚɧɧɹ ɧɚ ɜɿɞɩɨɜɿɞɧɟ ɞɠɟɪɟɥɨ ɘ.Ɇ. Ȼɥɢɡɧɸɤ ɇɚɭɤɨɜɢɣ ɤɟɪɿɜɧɢɤ ɒɟɫɬɨɩɚɥɨɜɚ Ƚɚɧɧɚ ȼɿɤɬɨɪɿɜɧɚ, ɞɨɤɬɨɪ ɮɿɡɢɤɨ- ɦɚɬɟɦɚɬɢɱɧɢɯ ɧɚɭɤ, ɫɬɚɪɲɢɣ ɧɚɭɤɨɜɢɣ ɫɩɿɜɪɨɛɿɬɧɢɤ ɏɚɪɤɿɜ 2017 2 ȺɇɈɌȺɐȱə Ȼɥɢɡɧɸɤ ɘ. Ɇ. Ɇɟɯɚɧɿɡɦɢ ɚɫɨɰɿɚɰɿʀ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ ɡ ȾɇɄ. – Ʉɜɚɥɿɮɿɤɚɰɿɣɧɚ ɧɚɭɤɨɜɚ ɩɪɚɰɹ ɧɚ ɩɪɚɜɚɯ ɪɭɤɨɩɢɫɭ. Ⱦɢɫɟɪɬɚɰɿɹ ɧɚ ɡɞɨɛɭɬɬɹ ɧɚɭɤɨɜɨɝɨ ɫɬɭɩɟɧɹ ɤɚɧɞɢɞɚɬɚ ɮɿɡɢɤɨɦɚɬɟɦɚɬɢɱɧɢɯ ɧɚɭɤ ɡɚ ɫɩɟɰɿɚɥɶɧɿɫɬɸ 03.00.02 – ɛɿɨɮɿɡɢɤɚ (Ɏɿɡɢɤɨɦɚɬɟɦɚɬɢɱɧɿ ɧɚɭɤɢ). – ȱɧɫɬɢɬɭɬ ɪɚɞɿɨɮɿɡɢɤɢ ɬɚ ɟɥɟɤɬɪɨɧɿɤɢ ɿɦ. Ɉ. ə. ɍɫɢɤɨɜɚ ɇɚɰɿɨɧɚɥɶɧɨʀ ɚɤɚɞɟɦɿʀ ɧɚɭɤ ɍɤɪɚʀɧɢ; ɏɚɪɤɿɜɫɶɤɢɣ ɧɚɰɿɨɧɚɥɶɧɢɣ ɭɧɿɜɟɪɫɢɬɟɬ ɿɦɟɧɿ ȼ. ɇ. Ʉɚɪɚɡɿɧɚ Ɇɿɧɿɫɬɟɪɫɬɜɚ ɨɫɜɿɬɢ ɿ ɧɚɭɤɢ ɍɤɪɚʀɧɢ, ɏɚɪɤɿɜ, 2017. Ⱦɢɫɟɪɬɚɰɿɣɧɭ ɪɨɛɨɬɭ ɩɪɢɫɜɹɱɟɧɨ ɜɢɪɿɲɟɧɧɸ ɨɞɧɿɽʀ ɡ ɚɤɬɭɚɥɶɧɢɯ ɩɪɨɛɥɟɦ ɫɭɱɚɫɧɨʀ ɦɨɥɟɤɭɥɹɪɧɨʀ ɛɿɨɮɿɡɢɤɢ – ɡ'ɹɫɭɜɚɧɧɹ ɪɨɥɿ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ (ɇ-ɡɜ'ɹɡɤɿɜ) ɿ ɦɨɥɟɤɭɥ ɜɨɞɢ ɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɫɚɦɨɚɫɨɰɿɚɬɿɜ ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɪɹɞɭ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ (ȻȺɊ) ɿ ɩɪɢ ʀɯ ɡɜ'ɹɡɭɜɚɧɧɿ ɡ ȾɇɄ. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɦɟɬɨɞɭ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɩɨɝɥɢɧɚɧɧɹ ɛɭɥɨ ɩɥɿɜɨɤ ɨɬɪɢɦɚɧɨ ɬɚ ɩɪɨɚɧɚɥɿɡɨɜɚɧɨ ɫɩɟɤɬɪɢ ɫɚɦɨɚɫɨɰɿɚɬɭ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ (FMN), ɜɢɪɨɳɟɧɢɯ ɡ ɧɟɣɬɪɚɥɶɧɢɯ ɿ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ. Ⱥɧɚɥɿɡ ȱɑ-ɫɩɟɤɬɪɿɜ ɩɥɿɜɤɢ FMN, ɨɬɪɢɦɚɧɨʀ ɡɿ ɫɥɚɛɨɤɢɫɥɨɝɨ ɪɨɡɱɢɧɭ (ɪɇ ~ 6,0), ɞɨɡɜɨɥɢɜ ɜɢɹɜɢɬɢ ɜɢɫɨɤɨɱɚɫɬɨɬɧɟ ɡɦɿɳɟɧɧɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɨɥɢɜɚɧɶ ɋ4=Ɉ ɿ ɋ2=Ɉ ɝɪɭɩ ɚɬɨɦɿɜ. Ⱦɥɹ ɩɨɹɫɧɟɧɧɹ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɯ ɡɦɿɳɟɧɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɋ4=Ɉ ɿ ɋ2=Ɉ ɤɨɥɢɜɚɧɶ ɛɭɥɨ ɪɨɡɝɥɹɧɭɬɨ ɞɢɧɚɦɿɱɧɭ (ɪɟɡɨɧɚɧɫɧɭ) ɜɡɚɽɦɨɞɿɸ ɞɢɩɨɥɶɧɢɯ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɿɜ ɰɢɯ ɝɪɭɩ ɚɬɨɦɿɜ ɭ ɞɢɩɨɥɶɞɢɩɨɥɶɧɨɦɭ ɧɚɛɥɢɠɟɧɧɿ. ȼɿɞɩɨɜɿɞɧɿɫɬɶ ɪɨɡɪɚɯɭɧɤɨɜɢɯ ɡɫɭɜɿɜ ɱɚɫɬɨɬ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɞɨ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɡɧɚɱɟɧɶ ɫɩɨɫɬɟɪɿɝɚɥɨɫɹ ɞɥɹ nɦɨɥɟɤɭɥɹɪɧɨʀ ɫɬɪɭɤɬɭɪɢ ɫɚɦɨɚɫɨɰɿɚɬɭ FMN (n t 3). ɋɬɚɛɿɥɶɧɿɫɬɶ ɬɚɤɢɯ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN ɜɢɡɧɚɱɚɽɬɶɫɹ ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɦɿɠ ɤɿɥɶɰɹɦɢ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɯɪɨɦɨɮɨɪɭ, ɹɤɿ ɩɟɪɟɤɪɢɜɚɸɬɶɫɹ. Ⱦɨɫɥɿɞɠɟɧɧɹ ɫɨɪɛɰɿʀ ɜɨɞɢ ɧɚ ɩɥɿɜɤɚɯ, ɜɢɪɨɳɟɧɢɯ ɡɿ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ FMN (ɪɇ ~ 6,0), ɩɨɤɚɡɚɥɢ, ɳɨ ɬɿɥɶɤɢ ɧɚ ɩɟɪɲɨɦɭ ɟɬɚɩɿ ɡɜɨɥɨɠɟɧɧɹ ɜɨɞɚ ɩɪɚɤɬɢɱɧɨ ɧɟ ɡɜ'ɹɡɭɽɬɶɫɹ ɡ 3 ɝɿɞɪɚɬɧɨ-ɚɤɬɢɜɧɢɦɢ ɝɪɭɩɚɦɢ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ, ɚ ɩɪɢ ɡɛɿɥɶɲɟɧɧɿ ʀʀ ɚɤɬɢɜɧɨɫɬɿ (ɩɪɢ ɡɜ'ɹɡɭɜɚɧɧɿ ɛɿɥɶɲɟ 6 ɦɨɥɟɤɭɥ ɜɨɞɢ ɧɚ ɦɨɥɟɤɭɥɭ FMN, N > 6) ɝɿɞɪɚɬɚɰɿɹ ɿɫɬɨɬɧɨ ɡɪɨɫɬɚɽ. ȼɨɱɟɜɢɞɶ, ɦɨɥɟɤɭɥɢ ɜɨɞɢ ɬɚɤɨɠ ɦɨɠɭɬɶ ɜɩɥɢɜɚɬɢ ɧɚ ɫɬɚɛɿɥɶɧɿɫɬɶ n-ɦɨɥɟɤɭɥɹɪɧɢɯ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN, ɳɨ ɮɨɪɦɭɸɬɶɫɹ ɜ ɩɥɿɜɤɚɯ, ɜɢɪɨɳɟɧɢɯ ɡɿ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ. Ɍɚɤɨɠ ɛɭɥɨ ɞɨɫɥɿɞɠɟɧɨ ȱɑɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɣ ɩɪɨɹɜ ɩɪɨɬɨɧɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN. Ⱦɟɬɚɥɶɧɢɣ ɚɧɚɥɿɡ ȱɑ-ɫɩɟɤɬɪɿɜ ɜ ɨɛɥɚɫɬɿ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɋ–ɋ ɿ ɋ–N ɤɨɥɢɜɚɧɶ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN ɭ ɜɢɫɭɲɟɧɿɣ ɩɥɿɜɰɿ (0% Ɉȼ), ɜɢɪɨɳɟɧɿɣ ɡɿ ɫɥɚɛɨɤɢɫɥɨɝɨ ɪɨɡɱɢɧɭ, ɩɨɤɚɡɚɜ, ɳɨ ɩɪɨɬɨɧɭɜɚɧɧɹ ɤɿɥɶɰɹ ɜɿɞɛɭɜɚɽɬɶɫɹ ɩɨ ɚɬɨɦɚɯ ɚɡɨɬɭ N1 ɿ N5. Ʉɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɿ ɪɨɡɪɚɯɭɧɤɢ ɡɚɪɹɞɿɜ ɧɚ ɚɬɨɦɚɯ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɩɿɞɬɜɟɪɞɢɥɢ ɰɟɣ ɜɢɫɧɨɜɨɤ, ɨɫɤɿɥɶɤɢ ɧɚ ɰɢɯ ɚɬɨɦɚɯ ɡɧɚɯɨɞɹɬɶɫɹ ɡɧɚɱɧɿ ɧɟɝɚɬɢɜɧɿ ɡɚɪɹɞɢ. Ɇɟɬɨɞɚɦɢ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɬɚ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ (ɄɊ) ɫɜɿɬɥɚ ɛɭɥɨ ɩɪɨɜɟɞɟɧɨ ɞɨɫɥɿɞɠɟɧɧɹ ɧɟɣɬɪɚɥɶɧɢɯ ɪɨɡɱɢɧɿɜ ȻȺɊ: ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ (FMN), ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ (EB), ɩɪɨɮɥɚɜɿɧɭ (PRF), ɬɟɨɮɿɥɿɧɭ (TPH), ɤɨɮɟʀɧɭ (CAF) ɬɚ ʀɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ. Ɍɚɤɨɠ ɜɢɤɨɧɚɧɨ ʀɯ ɞɟɬɚɥɶɧɢɣ ɚɧɚɥɿɡ ɡɚ ɞɨɩɨɦɨɝɨɸ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ. Ȼɭɥɨ ɩɪɨɜɟɞɟɧɨ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɟ ɞɨɫɥɿɞɠɟɧɧɹ ɧɟɣɬɪɚɥɶɧɢɯ ɪɨɡɱɢɧɿɜ FMN, TPH ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɭ ɜ ɨɛɥɚɫɬɿ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ (1600-1750 ɫɦ-1). ɑɚɫɬɨɬɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ FMN ɬɚ TPH ɡɚɡɧɚɥɢ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɯ ɡɦɿɳɟɧɶ, ɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɫɩɟɤɬɪɭ ɩɨɝɥɢɧɚɧɧɹ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ ɡɧɚɱɧɨ ɡɦɟɧɲɢɥɚɫɹ (ɿɧɮɪɚɱɟɪɜɨɧɢɣ ɝɿɩɨɯɪɨɦɿɡɦ). Ɍɚɤɿ ɡɦɿɧɢ ɫɩɟɤɬɪɚɥɶɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-TPH ɫɜɿɞɱɚɬɶ ɩɪɨ ɬɟ, ɳɨ ɭɬɜɨɪɟɧɧɹ ɫɬɚɛɿɥɶɧɨɝɨ ɚɫɨɰɿɚɬɭ ɦɨɠɟ ɫɭɩɪɨɜɨɞɠɭɜɚɬɢɫɹ ɪɟɡɨɧɚɧɫɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɿɜ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ FMN ɿ TPH. Ⱦɥɹ ɩɿɞɬɜɟɪɞɠɟɧɧɹ ɰɶɨɝɨ ɩɪɢɩɭɳɟɧɧɹ ɿ ɡ'ɹɫɭɜɚɧɧɹ ɦɟɯɚɧɿɡɦɭ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ FMN-TPH ɛɭɥɨ ɩɪɨɜɟɞɟɧɨ ɨɛɱɢɫɥɟɧɧɹ ɪɟɡɨɧɚɧɫɧɢɯ ɜɡɚɽɦɨɞɿɣ ɤɨɥɢɜɚɧɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ FMN ɿ TPH. ɐɟɣ ɪɨɡɪɚɯɭɧɨɤ ɞɨɡɜɨɥɢɜ ɡɪɨɛɢɬɢ ɜɢɫɧɨɜɨɤ, ɳɨ FMN ɿ TPH ɭɬɜɨɪɸɸɬɶ n-ɦɨɥɟɤɭɥɹɪɧɢɣ ɚɝɪɟɝɚɬ (n t 3). 4 Ȼɭɥɨ ɞɨɫɥɿɞɠɟɧɨ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɸ ɬɟɨɮɿɥɿɧɭ ɬɚ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ. Ⱥɧɚɥɿɡ ɤɨɥɢɜɚɥɶɧɢɯ ɫɩɟɤɬɪɿɜ ɧɟɣɬɪɚɥɶɧɢɯ ɪɨɡɱɢɧɿɜ TPH, EB ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɭ ɩɨɤɚɡɚɜ ɧɢɡɶɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ TPH ɜ ȱɑ-ɫɩɟɤɬɪɿ ɬɚ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ NH2-ɝɪɭɩ ȿȼ ɭ ɄɊ-ɫɩɟɤɬɪɿ. ɐɟ ɫɜɿɞɱɢɬɶ ɩɪɨ ɮɨɪɦɭɜɚɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɦɿɠ ɥɿɝɚɧɞɚɦɢ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ. Ɉɞɧɚɤ, ɡɚ ɥɿɬɟɪɚɬɭɪɧɢɦɢ ɞɚɧɢɦɢ ɜɿɞɫɬɚɧɶ ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ EB ɿ TPH ɡɚɧɚɞɬɨ ɜɟɥɢɤɚ ɞɥɹ ɬɨɝɨ, ɳɨɛ ɭɬɜɨɪɢɜɫɹ ɇ-ɡɜ'ɹɡɨɤ. ɐɿɥɤɨɦ ɿɦɨɜɿɪɧɨ, ɳɨ ɰɸ ɜɿɞɫɬɚɧɶ ɦɿɝ ɩɟɪɟɤɪɢɬɢ ɥɚɧɰɸɠɨɤ ɡ ɦɨɥɟɤɭɥ ɜɨɞɢ ɡ ɇ-ɡɜ'ɹɡɤɚɦɢ ɬɢɩɭ C O  ( H  O ) n  ( H  N  H ) . ɐɟ ɩɪɢɩɭɳɟɧɧɹ ɦɨɠɟ ɛɭɬɢ ɩɿɞɬɜɟɪɞɠɟɧɨ | | ɚɛɨ ɫɩɪɨɫɬɨɜɚɧɨ ɡɚ ɞɨɩɨɦɨɝɨɸ ɪɟɡɭɥɶɬɚɬɿɜ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɫɢɫɬɟɦɢ «TPH-EB – ɜɨɞɚ». Ⱦɨɫɥɿɞɠɟɧɧɹ ɫɩɟɤɬɪɿɜ ɩɨɝɥɢɧɚɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ TPH-PRF ɿ CAF-EB ɩɨɤɚɡɚɥɢ ɜɿɞɫɭɬɧɿɫɬɶ ɡɦɿɧ ɫɩɟɤɬɪɚɥɶɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɫɭɦɿɲɚɯ. ɐɟ ɦɨɠɟ ɛɭɬɢ ɨɡɧɚɤɨɸ ɬɨɝɨ, ɳɨ ɜ ɰɢɯ ɭɦɨɜɚɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɢ ɧɟ ɫɮɨɪɦɭɜɚɥɢɫɹ. Ɉɞɧɚɤ, ɡɝɿɞɧɨ ɡ ɥɿɬɟɪɚɬɭɪɧɢɦɢ ɞɚɧɢɦɢ, TPH ɿ PRF, CAF ɿ EB ɭɬɜɨɪɸɸɬɶ ɝɟɬɟɪɨɚɫɨɰɿɚɬɢ. Ⱦɥɹ ɡ'ɹɫɭɜɚɧɧɹ ɦɨɠɥɢɜɨɫɬɿ ɭɬɜɨɪɟɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ TPH-PRF ɿ CAF-EB ɿ ɦɟɯɚɧɿɡɦɿɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɛɭɥɨ ɩɪɨɜɟɞɟɧɨ ɤɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ ɰɢɯ ɫɢɫɬɟɦ ɭ ɜɨɞɧɨɦɭ ɨɬɨɱɟɧɧɿ. Ɂɝɿɞɧɨ ɡ ɞɚɧɢɦɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ (Ɇɋ) ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɧɟ ɜɢɹɜɥɟɧɨ ɧɿ ɜ ɨɞɧɿɣ ɡɿ ɫɬɪɭɤɬɭɪ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-TPH. Ⱥɧɚɥɿɡ ɦɢɬɬɽɜɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (800 ɦɨɥɟɤɭɥ ɜɨɞɢ), ɚ ɬɚɤɨɠ ɦɢɬɬɽɜɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ F-ɫɬɪɭɤɬɭɪ, ɞɨɡɜɨɥɢɜ ɜɫɬɚɧɨɜɢɬɢ ɞɜɚ ɜɨɞɧɢɯ ɦɿɫɬɤɚ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ FMN-TPH. Ɉɞɧɚɤ, ɡɝɿɞɧɨ ɡ ɞɚɧɢɦɢ ɤɨɥɢɜɚɥɶɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ, ɛɿɥɶɲ ɜɿɪɨɝɿɞɧɨɸ ɮɨɪɦɨɸ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ ɽ nɦɨɥɟɤɭɥɹɪɧɢɣ ɚɝɪɟɝɚɬ FMN-TPH. Ɍɨɦɭ ɧɟɨɛɯɿɞɧɨ ɜ ɩɨɞɚɥɶɲɨɦɭ ɜɢɤɨɧɚɬɢ ɤɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ n-ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɚɝɪɟɝɚɬɭ FMN-TPH ɦɟɬɨɞɨɦ ɦɨɥɟɤɭɥɹɪɧɨʀ ɞɢɧɚɦɿɤɢ. 5 Ɂɝɿɞɧɨ ɡ ɞɚɧɢɦɢ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ TPHEB ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɦɿɠ ɥɿɝɚɧɞɚɦɢ ɧɟɦɨɠɥɢɜɟ. ȼɢɤɨɧɚɧɢɣ ɞɥɹ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ TPH-EB ɚɧɚɥɿɡ ɦɢɬɬɽɜɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (800 ɦɨɥɟɤɭɥ ɜɨɞɢ) ɬɚ F-ɫɬɪɭɤɬɭɪ ɞɨɡɜɨɥɢɜ ɜɢɡɧɚɱɢɬɢ ɿɫɧɭɜɚɧɧɹ ɬɪɶɨɯ ɜɨɞɧɢɯ ɦɿɫɬɤɿɜ, ɳɨ ɫɮɨɪɦɭɜɚɥɢɫɹ ɦɿɠ ɞɨɧɨɪɧɨɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɥɿɝɚɧɞɿɜ. Ɇɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɧɟ ɮɨɪɦɭɸɬɶɫɹ ɧɿ ɜ ɨɞɧɿɣ ɡɿ ɫɬɪɭɤɬɭɪ ɝɟɬɟɪɨɞɢɦɟɪɿɜ TPH-PRF ɿ CAF-EB. Ⱥɧɚɥɿɡ ɦɢɬɬɽɜɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ ɬɚ F-ɫɬɪɭɤɬɭɪ ɞɨɡɜɨɥɢɜ ɜɢɡɧɚɱɢɬɢ ɞɜɚ ɜɨɞɧɢɯ ɦɿɫɬɤɢ ɦɿɠ ɦɨɧɨɦɟɪɚɦɢ ɜ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿ TPH-PRF ɿ ɬɪɢ ɜɨɞɧɢɯ ɦɿɫɬɤɢ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɞɢɦɟɪɭ CAF-EB. Ⱦɥɹ ɡ'ɹɫɭɜɚɧɧɹ ɿɫɧɭɜɚɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-EB ɛɭɥɨ ɨɬɪɢɦɚɧɨ ɿ ɩɪɨɚɧɚɥɿɡɨɜɚɧɨ ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɢ ɧɟɣɬɪɚɥɶɧɢɯ ɪɨɡɱɢɧɿɜ FMN, EB ɬɚ ʀɯ ɫɭɦɿɲɿ. ɇɢɡɶɤɨɱɚɫɬɨɬɧɟ ɡɦɿɳɟɧɧɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɋ=Ɉ ɝɪɭɩ FMN ɿ ɜɢɫɨɤɨɱɚɫɬɨɬɧɟ ɡɦɿɳɟɧɧɹ ɄɊ-ɫɦɭɝ NH2-ɝɪɭɩ EB ɨɞɧɨɡɧɚɱɧɨ ɫɜɿɞɱɢɬɶ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɜ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿ FMN-EB. ɉɨɞɿɛɧɟ ɞɨɫɥɿɞɠɟɧɧɹ ɛɭɥɨ ɜɢɤɨɧɚɧɨ ɞɥɹ FMN, PRF ɬɚ ʀɯ ɫɭɦɿɲɿ. əɤ ɿ ɭ ɜɢɩɚɞɤɭ ɫɢɫɬɟɦɢ FMN-EB, ɞɥɹ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-PRF ɫɩɨɫɬɟɪɿɝɚɜɫɹ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɣ ɡɫɭɜ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɋ=Ɉ ɝɪɭɩ FMN ɿ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɣ ɡɫɭɜ ɄɊ-ɫɦɭɝ NH2-ɝɪɭɩ PRF. Ɍɚɤɿ ɫɩɟɤɬɪɚɥɶɧɿ ɡɦɿɧɢ ɫɜɿɞɱɚɬɶ ɩɪɨ ɮɨɪɦɭɜɚɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-PRF. Ⱦɥɹ ɿɧɬɟɪɩɪɟɬɚɰɿʀ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɪɟɡɭɥɶɬɚɬɿɜ ɤɨɥɢɜɚɥɶɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɬɚ ɩɨɹɫɧɟɧɧɹ ɦɟɯɚɧɿɡɦɿɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ FMN-EB ɿ FMN-PRF, ɚ ɬɚɤɨɠ ɩɨɛɭɞɨɜɢ ʀɯ ɦɨɥɟɤɭɥɹɪɧɢɯ ɦɨɞɟɥɟɣ, ɛɭɥɨ ɜɢɤɨɧɚɧɨ ɤɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ ɫɢɫɬɟɦ, ɳɨ ɦɿɫɬɹɬɶ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɢ FMN-EB, FMN-PRF ɿ ɜɨɞɧɿ ɤɥɚɫɬɟɪɢ. Ɂɝɿɞɧɨ ɡ ɪɟɡɭɥɶɬɚɬɚɦɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɝɟɬɟɪɨɞɢɦɟɪɿ FMN-EB ɭɬɜɨɪɸɸɬɶɫɹ ɬɪɢ 6 ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ, ɬɨɞɿ ɹɤ ɭ ɝɟɬɟɪɨɞɢɦɟɪɿ FMN-PRF ɭɬɜɨɪɸɽɬɶɫɹ ɨɞɢɧ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɣ ɇ-ɡɜ'ɹɡɨɤ. ɇɚ ɩɿɞɫɬɚɜɿ ɞɚɧɢɯ ɤɨɥɢɜɚɥɶɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɛɭɥɨ ɨɰɿɧɟɧɨ ɜɧɟɫɨɤ ɟɧɟɪɝɿʀ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɫɬɚɛɿɥɿɡɚɰɿɸ ɫɬɨɩɤɨɜɢɯ ɚɫɨɰɿɚɬɿɜ. Ɍɚɤ ɛɭɥɨ ɡɧɚɣɞɟɧɨ, ɳɨ ɟɧɟɪɝɿɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-EB ɫɬɚɧɨɜɢɬɶ |ǻɇ| = 8,4 ɤȾɠ/ɦɨɥɶ. Ɍɚɤɿ ɠ ɪɨɡɪɚɯɭɧɤɢ ɞɥɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ FMN-PRF ɞɨɡɜɨɥɢɥɢ ɨɬɪɢɦɚɬɢ ɟɧɬɚɥɶɩɿɸ ɇ-ɡɜ'ɹɡɤɭ ɬɢɩɭ C4=O(FMN)··· H  N  Ǿ (PRF), ɪɿɜɧɭ |ǻɇ| = 7,3 ɤȾɠ/ɦɨɥɶ, ɚ ɞɥɹ ɇ-ɡɜ'ɹɡɤɭ ɬɢɩɭ C2=O(FMN)··· H  N  Ǿ (PRF) – |ǻɇ| = 2,5 ɤȾɠ/ɦɨɥɶ. Ɇɿɠɦɨɥɟɤɭɥɹɪɧɿ ɜɨɞɧɟɜɿ ɡɜ'ɹɡɤɢ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɚɯ FMNEB ɿ FMN-PRF ɞɚɸɬɶ ~ 25-30% -ɢɣ ɜɧɟɫɨɤ ɭ ɡɚɝɚɥɶɧɭ ɟɧɬɚɥɶɩɿɸ ɫɬɚɛɿɥɿɡɚɰɿʀ ɰɢɯ ɤɨɦɩɥɟɤɫɿɜ, ɚ ɿɧɲɚ ɟɧɬɚɥɶɩɿɹ ɡɞɟɛɿɥɶɲɨɝɨ ɽ ɜɧɟɫɤɨɦ ɦɿɠɩɥɨɳɢɧɧɢɯ ɜɡɚɽɦɨɞɿɣ ɦɿɠ ɯɪɨɦɨɮɨɪɚɦɢ ɦɨɥɟɤɭɥ ɿ ɝɿɞɪɚɬɧɨɸ ɜɨɞɨɸ ɧɚɜɤɨɥɨ ɤɨɦɩɥɟɤɫɿɜ. Ⱦɚɥɿ ɧɚ ɩɪɢɤɥɚɞɿ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɨʀ ɪɟɱɨɜɢɧɢ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɛɭɥɨ ɩɨɤɚɡɚɧɨ ɪɨɥɶ ɇ-ɡɜ'ɹɡɤɭ ɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɤɨɦɩɥɟɤɫɭ EB-ȾɇɄ. Ȼɭɥɨ ɩɪɨɜɟɞɟɧɨ ɄɊ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɟ ɞɨɫɥɿɞɠɟɧɧɹ EB ɬɚ ɣɨɝɨ ɫɭɦɿɲɟɣ ɡ ȾɇɄ. Ⱥɧɚɥɿɡ ɄɊɫɩɟɤɬɪɿɜ ɞɨɡɜɨɥɢɜ ɜɫɬɚɧɨɜɢɬɢ, ɳɨ ɩɪɢ ɜɢɫɨɤɢɯ ɡɧɚɱɟɧɧɹɯ P/D, ɤɨɥɢ ɤɨɧɰɟɧɬɪɚɰɿɹ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɜ ɪɨɡɱɢɧɿ ɦɚɥɚ, ɫɬɚɛɿɥɿɡɚɰɿɹ ɤɨɦɩɥɟɤɫɭ EBȾɇɄ ɡɞɿɣɫɧɸɽɬɶɫɹ ɧɟ ɬɿɥɶɤɢ ɡɚ ɪɚɯɭɧɨɤ ɦɿɠɩɥɨɳɢɧɧɢɯ ɜɡɚɽɦɨɞɿɣ ɿɧɬɟɪɤɚɥɶɨɜɚɧɨɝɨ ɯɪɨɦɨɮɨɪɭ, ɚɥɟ ɣ ɲɥɹɯɨɦ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇɡɜ'ɹɡɤɿɜ ɦɿɠ ɚɦɿɧɨɝɪɭɩɚɦɢ EB ɬɚ ɚɬɨɦɚɦɢ Ɉ4' ɬɚ Ɉ5' ɞɟɡɨɤɫɢɪɢɛɨɡɢ. ɍ ɰɶɨɦɭ ɜɢɩɚɞɤɭ ȾɇɄ ɡɛɟɪɿɝɚɽɬɶɫɹ ɜ ȼ-ɮɨɪɦɿ. ɉɪɢ ɧɢɡɶɤɢɯ ɡɧɚɱɟɧɧɹɯ P/D ɮɨɪɦɭɜɚɧɧɹ ɤɨɦɩɥɟɤɫɭ EB-ȾɇɄ ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɫɬɪɭɤɬɭɪɧɢɦ ɩɟɪɟɯɨɞɨɦ ȾɇɄ ɡ ȼ- ɞɨ Ⱥ-ɩɨɞɿɛɧɨʀ ɤɨɧɮɨɪɦɚɰɿʀ, ɚ ɚɦɿɧɨɝɪɭɩɢ EB ɜɡɚɽɦɨɞɿɸɬɶ ɡ ɰɭɤɪɨɮɨɫɮɚɬɧɢɦ ɨɫɬɨɜɨɦ ɩɨɥɿɧɭɤɥɟɨɬɢɞɧɨʀ ɦɚɬɪɢɰɿ, ɫɬɚɛɿɥɿɡɭɸɱɢ ɡɨɜɧɿɲɧɸ «ɩɨɫɚɞɤɭ» ɯɪɨɦɨɮɨɪɭ ɧɚ ɩɨɜɟɪɯɧɿ ɦɨɥɟɤɭɥɢ ȾɇɄ. Ʉɥɸɱɨɜɿ ɫɥɨɜɚ: ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɚ ɪɟɱɨɜɢɧɚ, ɜɨɞɧɟɜɢɣ ɡɜ'ɹɡɨɤ, ȱɑ| | ɫɩɟɤɬɪɨɫɤɨɩɿɹ, ɄɊ-ɫɩɟɤɬɪɨɫɤɨɩɿɹ, ɫɚɦɨɚɫɨɰɿɚɬ, ɝɟɬɟɪɨɚɫɨɰɿɚɬ, ɦɿɠɩɥɨɳɢɧɧɿ ɜɡɚɽɦɨɞɿʀ, ɫɬɚɛɿɥɶɧɿɫɬɶ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ, ɤɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ. 7 ABSTRACT Blyzniuk Iu. M. Mechanisms of the association of biologically active compounds and their complexation with DNA. – Qualification scientific paper, manuscript. Dissertation for a Candidate of Science Degree in Physics and Mathematics (PhD) by speciality – biophysics (Physics and mathematics). – O. Ya. Usikov Institute for Radiophysics and Electronics, National Academy of Sciences of Ukraine; V. N. Karazin Kharkiv National University, Ministry of Education and Science of Ukraine, Kharkiv, 2017. The dissertation is devoted to the solution of one of the main problems in modern molecular biophysics – clarifying the role of hydrogen bonds (H-bonds) and water molecules in the stabilization of self-associates and hetero-associates of a number of biologically active compounds (BAC) and their binding to DNA. Using the IR spectroscopy method the absorption spectra of flavinmononucleotide (FMN) self-associate films grown from neutral and weakly acidic solutions were obtained and analyzed. Analysis of the IR spectra of the FMN film obtained from a weakly acid solution (pH ~ 6.0) has allowed to determine a highfrequency shift of the absorption bands of the C4=O and C2=O atom groups. To explain the high-frequency shifts of C4=O and C2=O carbonyl vibrations the dynamic (resonant) interaction of the dipole moments of these atomic groups transitions in the dipole-dipole approximation was considered. The correspondence of the calculated shifts of the frequencies of carbonyl vibrations to the experimental values was observed for the n-molecular structure of the selfassociate FMN (n t 3). The stability of such FMN self-associates is determined by interplanar interactions between overlapping isoalloxazine chromophore rings. The studies of water sorption by films grown from weakly acidic solutions (pH ~ 6.0) showed that only at the first stage of wetting the water practically does not bind to the hydrated-active groups of the isoalloxazine ring, but with an increase of its 8 activity (when more than 6 water molecules are bound to the FMN molecule, N > 6), hydration significantly increases. Obviously, water molecules can also affect the stability of FMN n-molecular self-associates, which are formed in films grown from weakly acidic solutions. IR spectroscopic manifestation of the FMN isoalloxazine ring protonation was also studied. IR spectra were also analyzed in the absorption region of intraring C–C and C–N vibrations of the FMN isoalloxazine ring of a dry film (0% RH) grown from a weakly acidic solution. This analysis showed that the protonation of the ring occurs by the nitrogen atoms N1 and N5. Quantum-chemical calculations of isoalloxazine ring atom charges confirmed this conclusion since there are significant negative charges on N1 and N5 atoms. Neutral solutions of BAC: flavin mononucleotide (FMN), ethidium bromide (EB), proflavine (PRF), theophylline (TPH), caffeine (CAF) and their heterocomplexes were studied by IR spectroscopy and Raman spectroscopy. Also, their detailed analysis was performed using computer simulation. IR spectroscopic study of neutral solutions of FMN, TPH and their complex in the region of carbonyl vibrations 1600-1750 cm-1 was carried out. The frequencies of the absorption bands of the FMN and TPH carbonyl groups underwent high-frequency shifts, and the intensity of the absorption spectrum of the hetero-complex significantly decreased (infrared hypochromism). Such changes of the spectral parameters of the FMN-TPH hetero-complex indicate that the formation of a stable associate may be accompanied by resonant interactions of the transition moments of the FMN and TPH carbonyl groups. To confirm this hypothesis and determine the stabilization mechanism of the hetero-associate FMN-TPH, the resonance interactions of the vibrations of the FMN and TPH carbonyl groups were calculated. This calculation allowed us to conclude that FMN and TPH form an n-molecular aggregate (n t 3). The hetero-association of theophylline and ethidium bromide was investigated. Analysis of the vibrational spectra of neutral solutions of TPH, EB 9 and their complex showed the low-frequency shifts of the TPH carbonyl vibrations in the IR spectrum and the high-frequency shifts of NH2 deformation vibrations of the EB in the Raman spectrum. It indicates the formation of H-bonds between the ligands in the hetero-complex. However, the distance between the donor-acceptor groups of EB and TPH is too large to form an H-bond according to the literature data. It is quite likely that a chain of water molecules with H-bonds of the type C O  ( H  O) n  ( H  N  H ) could cover this distance. This hypothesis can | | be confirmed or refuted by means of computer simulation results of the “TPH-EB – water” system. Studies of the absorption spectra of the hetero-associates TPH-PRF and CAF-EB showed no changes in the spectral parameters of the carbonyl vibrations in the mixtures. It may indicate that hetero-complexes did not form under these conditions. However, TPH and PRF, CAF and EB form hetero-associates according to the literature data. Computer simulation of hetero-associates TPHPRF and CAF-EB was carried out to determine the possibility of hetero-complex formation and mechanisms of stabilization of these systems in the water environment. According to Monte Carlo simulation (MC), intermolecular H-bonds are not detected in any structure of the FMN-TPH hetero-complex. The analysis of instantaneous configurations in water cluster (800 water molecules) and instantaneous configurations of F-structures allows us to determine two water bridges around TPH-FMN hetero-dimer. However, according to vibrational spectroscopy, the most probable form of the hetero-complex is the n-molecular aggregate FMN-TPH. It is necessary to perform computer simulation of the FMNTPH n-molecular aggregate by the molecular dynamics method in the future. According to computer simulation data in the TPH-EB hetero-complex, the formation of intermolecular H-bonds between ligands is impossible. The performed analysis of instant configurations for the TPH-EB hetero-complex in 10 water cluster (800 water molecules) and of F-structures allowsed us to determine the existence of three water bridges formed between donor-acceptor groups of ligands. Intermolecular H-bonds are not formed in any of the structures of the heterodimers TPH-PRF and CAF-EB. The analysis of instant configurations in water cluster and of F-structures allowed us to determine two water bridges between the monomers in the TPH-PRF hetero-associate and three water bridges around the CAF-EB hetero-dimer. IR and Raman spectra of neutral FMN, EB solutions, and their mixtures were obtained and analyzed to determine the existence of an intermolecular Hbond in the FMN-EB hetero-complex. The low-frequency shift of the absorption bands of the C=O FMN groups and the high-frequency shift of the Raman bands of the NH2-groups EB unambiguously indicate the formation of an intermolecular Hbond in the FMN-EB hetero-associate. A similar study was performed for FMN, PRF and their mixtures. Similar to the case of the FMN-EB system for FMN-PRF hetero-complex a low-frequency shift of the absorption bands of the FMN C=O groups and a high-frequency shift of the Raman bands of PRF NH2-groups of were observed. Such spectral changes indicate the formation of an intermolecular H-bond in the FMN-PRF heterocomplex. Computer modeling using the Monte Carlo method of systems containing hetero-complexes FMN-EB, FMN-PRF and water clusters was performed to interpret the experimental results of vibrational spectroscopy and explain mechanisms of stabilization of hetero-associates FMN-EB and FMN-PRF, as well as to construct their molecular models. According to the results of the MC simulation, three intermolecular H-bonds are formed in FMN-EB hetero-dimer, whereas one intermolecular H-bond is formed in the FMN-PRF hetero-associate. 11 The contribution of the H-bond energy to the stabilization of the stack associates was estimated based on the data of vibrational spectroscopy. It was found that the energy of the intermolecular H-bond in the FMN-EB heterocomplex is |ǻɇ| = 8.4 kJ/mol. The same calculations for the hetero-associate FMNPRF allowed us to obtain the enthalpy of the H-bond of the type C4=O(FMN)··· H  N  Ǿ (PRF) equal to |ǻɇ| = 7.3 kJ/mol, and for the H-bond of the type C2=O(FMN)··· H  N  Ǿ (PRF) – equal to |ǻɇ| = 2.5 kJ/mol. Intermolecular hydrogen bonds in the heterocomplexes FMN-EB and FMN-PRF give a 25-30% contribution to the overall enthalpy of stabilization of these complexes, and the remaining enthalpy is mainly a contribution of interplanar interactions between the chromophores of molecules and hydrated water around the complexes. Using the example of the biologically active compound of ethidium bromide was demonstrated the role of the H-bond in the stabilization of the EB-DNA complex. Raman spectroscopic study of EB and its mixtures with DNA was carried out. The analysis of Raman spectra allowed to determine that at high P/D values, when the concentration of ethidium bromide in the solution is low, stabilization of the EB-DNA complex occurs not only due to interplanar interactions of the intercalated chromophore, but also by formation of intermolecular H-bonds between the amino groups of EB and O4' and O5' deoxyribose. In this case the DNA stays in the B-form. At low P/D values, the formation of the EB-DNA complex is accompanied by a structural transition of DNA from B- to the A-like conformation, and the amino groups of EB interact with the sugar-phosphate backbone of the polynucleotide matrix, stabilizing the external "landing" of the chromophore on the surface of the DNA molecule. Keywords: biologically active compound, hydrogen bond, IR spectroscopy, | | Raman spectroscopy, self-associate, hetero-associate, interplanar interactions, stability of self- and hetero-associates, computer modeling. 12 ɋɉɂɋɈɄ ɉɍȻɅȱɄȺɐȱɃ ɁȾɈȻɍȼȺɑȺ ɁȺ ɌȿɆɈɘ ȾɂɋȿɊɌȺɐȱȲ Ȼɥɢɡɧɸɤ ɘ. ɇ., 1. Ȼɨɥɶɛɭɯ Ɍ. ȼ., Ʉɪɭɝɥɨɜɚ ȿ. Ȼ., ɋɟɦɟɧɨɜ Ɇ. Ⱥ., Ɇɚɥɟɟɜ ȼ. ə. ɂɫɫɥɟɞɨɜɚɧɢɟ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ɛɪɨɦɢɫɬɨɝɨ ɷɬɢɞɢɹ ɫ ȾɇɄ ɦɟɬɨɞɨɦ ɫɩɟɤɬɪɨɫɤɨɩɢɢ ɤɨɦɛɢɧɚɰɢɨɧɧɨɝɨ ɪɚɫɫɟɹɧɢɹ ɫɜɟɬɚ // Ȼɢɨɩɨɥɢɦɟɪɵ ɢ ɤɥɟɬɤɚ. 2009. ʋ 25(2). ɋ. 126–132. 2. Ȼɥɢɡɧɸɤ ɘ. ɇ., ɋɟɦɺɧɨɜ Ɇ. 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VI ɏɚɪɶɤɨɜɫɤɚɹ ɤɨɧɮɟɪɟɧɰɢɹ ɦɨɥɨɞɵɯ ɭɱɟɧɵɯ, 13–14 ɞɟɤɚɛ. 2006 ɝ. ɏɚɪɶɤɨɜ, 2006. ɋ. 33–34. 9. Ȼɥɢɡɧɸɤ ɘ. ɇ., Ȼɨɥɶɛɭɯ Ɍ. ȼ. ɋɬɪɭɤɬɭɪɧɵɟ ɢɡɦɟɧɟɧɢɹ ȾɇɄ ɩɪɢ ɜɡɚɢɦɨɞɟɣɫɬɜɢɢ ɫ ɗȻ ɩɨ ɞɚɧɧɵɦ Ɋɚɦɚɧ ɫɩɟɤɬɪɨɫɤɨɩɢɢ // ɍȻɎɌ-2006 : ɬɟɡɢ ɞɨɩ. IV Ɂ'ʀɡɞ ɍɤɪɚʀɧɫɶɤɨɝɨ ɛɿɨɮɿɡɢɱɧɨɝɨ ɬɨɜɚɪɢɫɬɜɚ, 19–21 ɝɪɭɞ. 2006 ɪ. Ⱦɨɧɟɰɶɤ, 2006. ɋ. 274-275. 10. Ȼɥɢɡɧɸɤ ɘ. ɇ., ɝɟɬɟɪɨɚɫɫɨɰɢɚɰɢɢ ɋɟɦɟɧɨɜ Ɇ. Ⱥ., ɮɥɚɜɢɧ ɒɟɫɬɨɩɚɥɨɜɚ Ⱥ. ȼ. ɂɫɫɥɟɞɨɜɚɧɢɟ ɷɬɢɞɢɹ ɢ ɦɨɧɨɧɭɤɥɟɨɬɢɞɚ, ɛɪɨɦɢɫɬɨɝɨ ɬɟɨɮɢɥɥɢɧɚ ɜ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɚɯ ɦɟɬɨɞɚɦɢ ɂɄ ɢ Ɋɚɦɚɧ ɫɩɟɤɬɪɨɫɤɨɩɢɢ // ɍȻɎɌ-2011 : ɬɟɡɢ ɞɨɩ. V Ɂ'ʀɡɞ ɍɤɪɚʀɧɫɶɤɨɝɨ ɛɿɨɮɿɡɢɱɧɨɝɨ ɬɨɜɚɪɢɫɬɜɚ, 22– 25 ɱɟɪɜ. 2011 ɪ. Ʌɭɰɶɤ, 2011. ɋ. 24–25. 11. Blyzniuk Iu. N. Study of heteroassociation of biologically active compounds by IR and Raman spectroscopy [ɗɥɟɤɬɪɨɧɧɵɣ ɪɟɫɭɪɫ] // Radiophysics, Electronics, Photonics and Biophysics : abstr. 11th Kharkiv Young Scientists Conf., 29 Nov.–1 Dec. 2011. Kharkiv, 2011. 12. Blyzniuk Iu. N. Formation of intermolecular hydrogen bonds in hetero-complexes of biologically active compounds probed by vibrational spectroscopy // Modern Problems of Theoretical Physics : abstr. III Young Scientist Conference, 21–23 Dec. 2011. Kyiv, 2011. P. 93. 13. Ȼɥɢɡɧɸɤ ɘ. ɇ. Ɉɛɪɚɡɨɜɚɧɢɟ ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɯ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ ɜ ɝɟɬɟɪɨɚɫɫɨɰɢɚɬɚɯ ɛɢɨɥɨɝɢɱɟɫɤɢ ɚɤɬɢɜɧɵɯ ɜɟɳɟɫɬɜ ɩɨ ɞɚɧɧɵɦ ɤɨɥɟɛɚɬɟɥɶɧɨɣ ɫɩɟɤɬɪɨɫɤɨɩɢɢ // Ⱥɤɬɭɚɥɶɧɵɟ ɜɨɩɪɨɫɵ ɛɢɨɥɨɝɢɱɟɫɤɨɣ ɮɢɡɢɤɢ ɢ ɯɢɦɢɢ. ȻɎɎɏ – 2012 : ɬɟɡɢɫɵ ɞɨɤɥ. VIII Ɇɟɠɞɭɧɚɪɨɞɧɚɹ 14 ɧɚɭɱɧɨ-ɬɟɯɧɢɱɟɫɤɚɹ ɤɨɧɮɟɪɟɧɰɢɹ, 23–27 ɚɩɪ. 2012 ɝ. ɋɟɜɚɫɬɨɩɨɥɶ, 2012. ɋ. 128–129. 14. Blyzniuk Iu. N., Semenov M. A., Shestopalova A. V. Intermolecular hydrogen bonds in hetero-complexes of biologically active aromatic ligands: Monte Carlo simulations // Methods and Applications of Computational Chemistry : abstr. 5th International Symposium, 1–5 July 2013. Kharkiv, 2013. P. 107. 15. Blyzniuk Iu. N. pH-dependent self-association of flavin-mononucleotide. [ɗɥɟɤɬɪɨɧɧɵɣ ɪɟɫɭɪɫ] // Radiophysics, Electronics, Photonics and Biophysics : abstr. 13th Kharkiv Young Scientists Conference, 2–6 Dec. 2013. Kharkiv, 2013. 16. Blyzniuk Iu. N., Glibitskiy D. M. Self-association and hydration of flavinmononucleotide in films // Problems of Theoretical Physics : abstr. V Young scientists conference, 24–27 December 2013. Kyiv, 2013. P. 72. 17. Ȼɥɢɡɧɸɤ ɘ. Ɇ., ɒɟɫɬɨɩɚɥɨɜɚ Ƚ. ȼ. ɉɟɫɿɧɚ Ⱦ. Ɉ., ɋɚɦɨɚɫɨɰɿɚɰɿɹ Ƚɥɢɛɢɰɶɤɢɣ Ⱦ. Ɇ., ɿɡɨɚɥɥɨɤɫɚɡɢɧɨɜɢɯ ɋɟɦɟɧɨɜ Ɇ. Ɉ., ɤɿɥɟɰɶ ɮɥɚɜɿɧ- ɦɨɧɨɧɭɤɥɟɨɬɢɞɚ ɭ ɜɨɥɨɝɢɯ ɩɥɿɜɤɚɯ, ɜɢɪɨɳɟɧɢɯ ɡ ɧɟɣɬɪɚɥɶɧɢɯ ɿ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ // ɍȻɎɌ-2015 : ɬɟɡɢ ɞɨɩ. VI Ɂ'ʀɡɞ ɍɤɪɚʀɧɫɶɤɨɝɨ ɛɿɨɮɿɡɢɱɧɨɝɨ ɬɨɜɚɪɢɫɬɜɚ, 28–30 ɬɪɚɜ. 2015 ɪ. Ʌɭɰɶɤ-ɋɜɿɬɹɡɶ, 2015. ɋ. 40. Ɉɫɨɛɢɫɬɢɣ ɜɧɟɫɨɤ ɡɞɨɛɭɜɚɱɚ ɭ ɪɨɛɨɬɚɯ ʋ 1, 2, 3, 4, 5 – ɩɨɲɭɤ ɿ ɤɪɢɬɢɱɧɢɣ ɚɧɚɥɿɡ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɚɧɢɯ, ɨɬɪɢɦɚɧɧɹ ɤɨɥɢɜɚɥɶɧɢɯ ɫɩɟɤɬɪɿɜ, ɚɧɚɥɿɡ ɬɚ ɿɧɬɟɪɩɪɟɬɚɰɿɹ ɨɬɪɢɦɚɧɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɚɧɢɯ, ɧɚɩɢɫɚɧɧɹ ɫɬɚɬɟɣ; ɭ ɪɨɛɨɬɚɯ ʋ 7, 8, 9, 10, 11, 12, 13, 15, 16, 17 – ɚɧɚɥɿɡ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɚɧɢɯ, ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɟ ɨɬɪɢɦɚɧɧɹ ɤɨɥɢɜɚɥɶɧɢɯ ɫɩɟɤɬɪɿɜ, ɚɧɚɥɿɡ ɬɚ ɿɧɬɟɪɩɪɟɬɚɰɿɹ ɨɬɪɢɦɚɧɢɯ ɞɚɧɢɯ, ɧɚɩɢɫɚɧɧɹ ɬɟɡ; ɭ ɪɨɛɨɬɚɯ ʋ 6, 14 – ɚɧɚɥɿɡ ɿ ɨɛɝɨɜɨɪɟɧɧɹ ɨɬɪɢɦɚɧɢɯ ɪɟɡɭɥɶɬɚɬɿɜ, ɧɚɩɢɫɚɧɧɹ ɫɬɚɬɬɿ ɿ ɬɟɡ. 15 ɁɆȱɋɌ ɉȿɊȿɅȱɄ ɍɆɈȼɇɂɏ ɉɈɁɇȺɑȿɇɖ..................................................................... 18 ȼɋɌɍɉ ...................................................................................................................... 20 ɊɈɁȾȱɅ 1 ȺɋɈɐȱȺɐȱə ȺɊɈɆȺɌɂɑɇɂɏ ȻȱɈɅɈȽȱɑɇɈ ȺɄɌɂȼɇɂɏ ɊȿɑɈȼɂɇ ɍ ȼɈȾɇɂɏ ɊɈɁɑɂɇȺɏ ..................................................................... 27 1.1 Ⱥɪɨɦɚɬɢɱɧɿ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɿ ɪɟɱɨɜɢɧɢ ............................................. 28 1.1.1 Ɂɚɝɚɥɶɧɿ ɜɿɞɨɦɨɫɬɿ ɩɪɨ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɿ ɪɟɱɨɜɢɧɢ .................. 28 1.1.2 Ɇɭɬɚɝɟɧɢ ɩɪɨɮɥɚɜɿɧ ɿ ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ ..................................... 30 1.1.3 Ɇɟɬɢɥɤɫɚɧɬɢɧɢ ɤɨɮɟʀɧ ɿ ɬɟɨɮɿɥɿɧ ................................................. 32 1.1.4 Ɏɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ .................................................................... 33 1.2 ɋɚɦɨɚɫɨɰɿɚɰɿɹ ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ .......... 35 1.2.1 ɋɚɦɨɚɫɨɰɿɚɰɿɹ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ ............................................ 36 1.2.2 Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ ......................................... 40 1.3 Ɇɟɬɨɞɢ ɞɨɫɥɿɞɠɟɧɧɹ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ȻȺɊ. Ɋɨɥɶ ɜɨɞɢ ɬɚ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɫɬɚɛɿɥɿɡɚɰɿʀ ɚɫɨɰɿɚɬɿɜ ȻȺɊ ɿ ɩɪɢ ɤɨɦɩɥɟɤɨɫɭɬɜɨɪɟɧɧɿ ɡ ȾɇɄ ............................................................................................................... 42 1.3.1 ɋɩɟɤɬɪɨɫɤɨɩɿɱɧɿ ɦɟɬɨɞɢ ɞɨɫɥɿɞɠɟɧɧɹ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ .......................................................... 42 1.3.2 ȼɢɡɧɚɱɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɚɫɨɰɿɚɬɚɯ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ..................................................................................... 45 1.4 ȱɧɬɟɪɰɟɩɬɨɪɧɿ ɜɥɚɫɬɢɜɨɫɬɿ ɬɚ ɛɿɨɥɨɝɿɱɧɨ ɜɚɠɥɢɜɿ ɤɨɦɛɿɧɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ........................................................................................... 48 1.5 Ɉɫɨɛɥɢɜɨɫɬɿ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ.............. 51 ȼɢɫɧɨɜɤɢ ɞɨ ɪɨɡɞɿɥɭ 1 ................................................................................... 55 ɊɈɁȾȱɅ 2 ȿɄɋɉȿɊɂɆȿɇɌȺɅɖɇȱ ɌȺ ɊɈɁɊȺɏɍɇɄɈȼȱ ɆȿɌɈȾɂ ȾɈɋɅȱȾɀȿɇɖ. ɉɊɂȽɈɌɍȼȺɇɇə ɁɊȺɁɄȱȼ ...................................................... 56 2.1 Ʉɨɥɢɜɚɥɶɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ: ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɢ. ɉɪɨɹɜ ɇ-ɡɜ'ɹɡɤɿɜ ......... 56 2.1.1 ɋɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ ȱɑ-ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ............................... 56 2.1.2 Ɍɟɯɧɿɤɚ ɨɬɪɢɦɚɧɧɹ ȱɑ-ɫɩɟɤɬɪɿɜ ..................................................... 62 16 2.1.3 ɋɩɟɤɬɪɨɫɤɨɩɿɹ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ............................... 64 2.1.4 Ɍɟɯɧɿɤɚ ɨɬɪɢɦɚɧɧɹ ɫɩɟɤɬɪɿɜ ɄɊ ..................................................... 67 2.2 Ɇɟɬɨɞ ɩ'ɽɡɨɝɪɚɜɿɦɟɬɪɿʀ ɞɥɹ ɨɬɪɢɦɚɧɧɹ ɿɡɨɬɟɪɦ ɝɿɞɪɚɬɚɰɿʀ ................... 68 2.3 Ɇɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ ɬɚ ɨɩɬɢɦɿɡɚɰɿɹ ɝɟɨɦɟɬɪɿʀ ɿ ɪɨɡɪɚɯɭɧɨɤ ɚɬɨɦɧɢɯ ɡɚɪɹɞɿɜ ȻȺɊ ............................................................... 69 2.4 ɉɪɢɝɨɬɭɜɚɧɧɹ ɡɪɚɡɤɿɜ ɞɥɹ ɞɨɫɥɿɞɠɟɧɧɹ ................................................. 73 ȼɢɫɧɨɜɤɢ ɞɨ ɪɨɡɞɿɥɭ 2 ................................................................................... 75 ɊɈɁȾȱɅ 3 ɋȺɆɈȺɋɈɐȱȺɐȱə ɎɅȺȼȱɇɆɈɇɈɇɍɄɅȿɈɌɂȾɍ ȼ ɊɈɁɑɂɇȺɏ ȱ ɉɅȱȼɄȺɏ ......................................................................................... 76 3.1 ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɣ ɩɪɨɹɜ ɫɚɦɨɚɫɨɰɿɚɰɿʀ FMN ɭ ɩɥɿɜɤɚɯ .................. 77 3.2 Ɋɟɡɨɧɚɧɫɧɿ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɫɬɨɩɤɚɯ FMN. ɉɨɛɭɞɨɜɚ n-ɦɨɥɟɤɭɥɹɪɧɨʀ ɫɬɪɭɤɬɭɪɢ ɫɚɦɨɚɫɨɰɿɚɬɭ FMN.......................... 81 3.3 ɉɪɨɬɨɧɭɜɚɧɧɹ FMN ɡɚ ɞɚɧɢɦɢ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɬɚ ɤɜɚɧɬɨɜɨɯɿɦɿɱɧɢɯ ɪɨɡɪɚɯɭɧɤɿɜ ɡɚɪɹɞɿɜ ɧɚ ɚɬɨɦɚɯ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɿ ɩɨɪɹɞɤɭ ʀɯ ɡɜ'ɹɡɤɿɜ ........................................................................................ 86 3.3.1 ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɣ ɩɪɨɹɜ ɩɪɨɬɨɧɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN............................................................... 86 3.3.2 Ʉɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɢɣ ɪɨɡɪɚɯɭɧɨɤ ɡɚɪɹɞɿɜ ɧɚ ɚɬɨɦɚɯ ɿ ɩɨɪɹɞɤɭ ɡɜ'ɹɡɤɿɜ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN .................................. 89 3.4 Ɋɨɥɶ ɜɨɞɢ ɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN ......................................... 92 ȼɢɫɧɨɜɤɢ ɞɨ ɪɨɡɞɿɥɭ 3 ................................................................................... 96 ɊɈɁȾȱɅ 4 ɆȱɀɉɅɈɓɂɇɇȱ ȼɁȺȯɆɈȾȱȲ ɉɊɂ ɎɈɊɆɍȼȺɇɇȱ ȽȿɌȿɊɈɄɈɆɉɅȿɄɋȱȼ FMN-TPH, TPH-EB, TPH-PRF ɌȺ EB-CAF ................ 98 4.1 ȱɧɮɪɚɱɟɪɜɨɧɿ ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ FMN, TPH ɬɚ ʀɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ ............................................................................................. 98 4.2 Ɋɟɡɨɧɚɧɫɧɿ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-TPH......................................................................... 101 4.2.1 ɋɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ FMN ɿ TPH ɭ ɪɨɡɱɢɧɚɯ D2O .............................................................................. 101 17 4.2.2 Ɋɨɡɪɚɯɭɧɨɤ ɪɟɡɨɧɚɧɫɧɢɯ ɜɡɚɽɦɨɞɿɣ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɤɨɦɩɥɟɤɫɿ FMN-TPH ɿ ɩɨɛɭɞɨɜɚ ɦɨɞɟɥɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ ................. 103 4.3 Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ TPH-EB ....................................................................... 107 4.4 Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ TPH-PRF ɿ CAF-EB.................................................... 109 4.5 Ʉɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ........................................ 111 4.5.1 Ƚɟɬɟɪɨɞɢɦɟɪ FMN-TPH................................................................ 115 4.5.2 Ƚɟɬɟɪɨɞɢɦɟɪ TPH-EB ................................................................... 118 4.5.3 Ƚɟɬɟɪɨɞɢɦɟɪ TPH-PRF ................................................................. 120 4.5.4 Ƚɟɬɟɪɨɞɢɦɟɪ CAF-EB ................................................................... 122 ȼɢɫɧɨɜɤɢ ɞɨ ɪɨɡɞɿɥɭ 4 ................................................................................. 125 ɊɈɁȾȱɅ 5 ɉɊɈəȼ ȼɈȾɇȿȼɈȽɈ Ɂȼ'əɁɄɍ ȼ ɄɈɅɂȼȺɅɖɇɂɏ ɋɉȿɄɌɊȺɏ ȽȿɌȿɊɈȺɋɈɐȱȺɌȱȼ ȱ ɉɊɂ Ɂȼ'əɁɍȼȺɇɇȱ ȻȺɊ Ɂ ȾɇɄ ............ 126 5.1 Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɿ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ......... 126 5.2 Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɿ ɩɪɨɮɥɚɜɿɧɭ ...................... 129 5.3 Ʉɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ-Ʉɚɪɥɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ FMN-EB ɿ FMN-PRF ɭ ɜɨɞɧɢɯ ɤɥɚɫɬɟɪɚɯ ....................... 133 5.3.1 Ƚɟɬɟɪɨɞɢɦɟɪ FMN-EB .................................................................. 133 5.3.2 Ƚɟɬɟɪɨɞɢɦɟɪ FMN-PRF ................................................................ 135 5.4 ȼɧɟɫɨɤ ɟɧɟɪɝɿʀ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɡɚɝɚɥɶɧɭ ɟɧɟɪɝɿɸ ɫɬɚɛɿɥɿɡɚɰɿʀ ɤɨɦɩɥɟɤɫɿɜ FMN ɡ EB ɿ PRF ........................................................................ 137 5.5 ȼɩɥɢɜ ɜɨɞɧɟɜɨɝɨ ɡɜ'ɹɡɤɭ ɧɚ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ EB ɡ ȾɇɄ ............ 139 ȼɢɫɧɨɜɤɢ ɞɨ ɪɨɡɞɿɥɭ 5 ................................................................................. 146 ɁȺȽȺɅɖɇȱ ȼɂɋɇɈȼɄɂ ....................................................................................... 148 ɋɉɂɋɈɄ ȼɂɄɈɊɂɋɌȺɇɂɏ ȾɀȿɊȿɅ .............................................................. 150 ȾɈȾȺɌɈɄ Ⱥ ɋɩɢɫɨɤ ɩɭɛɥɿɤɚɰɿɣ ɡɞɨɛɭɜɚɱɚ ɡɚ ɬɟɦɨɸ ɞɢɫɟɪɬɚɰɿʀ .................... 174 ȾɈȾȺɌɈɄ ȼ ɇɭɦɟɪɚɰɿɹ ɚɬɨɦɿɜ ɿ ɡɚɪɹɞɢ ɧɚ ɚɬɨɦɚɯ ɜɿɞɩɨɜɿɞɧɢɯ ɥɿɝɚɧɞɿɜ, ɳɨ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɢɫɶ ɜ ɦɨɞɟɥɸɜɚɧɧɿ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ ......................... 177 18 ɉȿɊȿɅȱɄ ɍɆɈȼɇɂɏ ɉɈɁɇȺɑȿɇɖ ȻȺɊ ȾɇɄ əɆɊ-ɫɩɟɤɬɪɨɫɤɨɩɿɹ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɄɊ-ɫɩɟɤɬɪɨɫɤɨɩɿɹ Ʌɉ ɍɎ-ɫɩɟɤɬɪɨɫɤɨɩɿɹ ȼȼ AO PRF EB PI DAU DOX NOG NOV NOR RBF NMD FMN CAF TPH THB FAD ɇ-ɡɜ'ɹɡɨɤ ǻH ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɚ ɪɟɱɨɜɢɧɚ ɞɟɡɨɤɫɢɪɢɛɨɧɭɤɥɟʀɧɨɜɚ ɤɢɫɥɨɬɚ ɹɞɟɪɧɚ ɦɚɝɧɿɬɧɨ-ɪɟɡɨɧɚɧɫɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɿɧɮɪɚɱɟɪɜɨɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ɥɿɤɚɪɫɶɤɢɣ ɩɪɟɩɚɪɚɬ ɭɥɶɬɪɚɮɿɨɥɟɬɨɜɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɜɿɞɧɨɫɧɚ ɜɨɥɨɝɿɫɬɶ ɚɤɪɢɞɢɧɨɜɢɣ ɩɨɦɚɪɚɧɱɟɜɢɣ (acridine orange) ɩɪɨɮɥɚɜɿɧ (proflavine) ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ (ethidium bromide) ɩɪɨɩɿɞɿɸ ɣɨɞɢɞ (propidium iodide) ɞɚɭɧɨɦɿɰɢɧ (daunomycin) ɞɨɤɫɨɪɭɛɿɰɢɧ (doxorubicin) ɧɨɝɚɥɚɦɿɰɢɧ (nogalamycin) ɧɨɜɚɧɬɪɨɧ (novatron) ɧɨɪɮɥɨɤɫɚɰɢɧ (norfloxacin) ɪɢɛɨɮɥɚɜɿɧ (riboflavin) ɧɿɤɨɬɢɧɚɦɿɞ (nicotinamide) ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ (flavin mononucleotide) ɤɨɮɟʀɧ (caffeine) ɬɟɨɮɿɥɿɧ (theophylline) ɬɟɨɛɪɨɦɿɧ (theobromine) ɮɥɚɜɿɧɚɞɟɧɿɧɞɢɧɭɤɥɟɨɬɢɞ (flavin adenine dinucleotide) ɜɨɞɧɟɜɢɣ ɡɜ'ɹɡɨɤ (hydrogen bond) ɟɧɬɚɥɶɩɿɹ ɚɫɨɰɿɚɰɿʀ 19 ǻG ǻS KC DFT Ȟ į ɦɟɬɨɞ Ɇɋ F-ɫɬɪɭɤɬɭɪɚ D2Ɉ ɪɨɡɱɢɧ ɋ=Ɉ P/D Etotal EMEAN EWW-MEAN EW-BAC-MEAN EL1-L2 Eel-st Evdw SASA ɜɿɥɶɧɚ ɟɧɟɪɝɿɹ ɚɫɨɰɿɚɰɿʀ ɟɧɬɪɨɩɿɹ ɚɫɨɰɿɚɰɿʀ ɤɨɧɫɬɚɧɬɚ ɚɫɨɰɿɚɰɿʀ ɬɟɨɪɿɹ ɮɭɧɤɰɿɨɧɚɥɭ ɝɭɫɬɢɧɢ ɜɚɥɟɧɬɧɟ ɤɨɥɢɜɚɧɧɹ ɞɟɮɨɪɦɚɰɿɣɧɟ ɤɨɥɢɜɚɧɧɹ ɦɟɬɨɞ Ɇɨɧɬɟ Ʉɚɪɥɨ (Monte Carlo) «ɡɚɦɨɪɨɠɟɧɚ – frozen» ɫɬɪɭɤɬɭɪɚ ɪɨɡɱɢɧ ɜɚɠɤɨʀ ɜɨɞɢ ɤɚɪɛɨɧɿɥɶɧɟ ɤɨɥɢɜɚɧɧɹ ɫɩɿɜɜɿɞɧɨɲɟɧɧɹ ɦɨɥɶɧɢɯ ɤɨɧɰɟɧɬɪɚɰɿɣ ȾɇɄ ɬɚ ɥɿɝɚɧɞɭ ɩɨɜɧɚ ɩɨɬɟɧɰɿɣɧɚ ɟɧɟɪɝɿɹ ɫɢɫɬɟɦ ɫɟɪɟɞɧɽ ɡɧɚɱɟɧɧɹ ɡɚɝɚɥɶɧɨʀ ɩɨɬɟɧɰɿɣɧɨʀ ɟɧɟɪɝɿʀ ɫɢɫɬɟɦ ɫɟɪɟɞɧɽ ɡɧɚɱɟɧɧɹ ɩɨɬɟɧɰɿɣɧɨʀ ɟɧɟɪɝɿʀ ɜɨɞɚ-ɜɨɞɚ (ɧɚ ɨɞɧɭ ɦɨɥɟɤɭɥɭ ɜɨɞɢ) ɫɟɪɟɞɧɽ ɡɧɚɱɟɧɧɹ ɩɨɬɟɧɰɿɣɧɨʀ ɟɧɟɪɝɿʀ ɜɨɞɚ-Ʌɿɝɚɧɞ ɫɟɪɟɞɧɽ ɡɧɚɱɟɧɧɹ ɩɨɬɟɧɰɿɣɧɨʀ ɟɧɟɪɝɿʀ Ʌɿɝɚɧɞ1Ʌɿɝɚɧɞ2 ɭ ɝɟɬɟɪɨɚɫɨɰɿɚɬɢ ɟɥɟɤɬɪɨɫɬɚɬɢɱɧɿ ɜɡɚɽɦɨɞɿʀ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɿ ɜɡɚɽɦɨɞɿʀ ɩɥɨɳɚɿ ɩɨɜɟɪɯɧɿ, ɹɤɚ ɞɨɫɬɭɩɧɚ ɪɨɡɱɢɧɧɢɤɭ (Solvent Ⱥccessible Surface Ⱥrea) 20 ȼɋɌɍɉ Ɉɛʉɪɭɧɬɭɜɚɧɧɹ ɜɢɛɨɪɭ ɬɟɦɢ ɞɨɫɥɿɞɠɟɧɧɹ. Ɇɿɠɦɨɥɟɤɭɥɹɪɧɿ ɜɡɚɽɦɨɞɿʀ ɛɿɨɥɨɝɿɱɧɨ ɜɚɠɥɢɜɢɯ ɦɨɥɟɤɭɥ ɽ ɤɥɸɱɨɜɢɦ ɦɨɦɟɧɬɨɦ ɩɪɨɬɿɤɚɧɧɹ ɛɿɥɶɲɨɫɬɿ ɤɥɿɬɢɧɧɢɯ ɩɪɨɰɟɫɿɜ ɿ ɫɤɥɚɞɚɸɬɶ ɨɞɢɧ ɡ ɧɚɣɜɚɠɥɢɜɿɲɢɯ ɨɛ'ɽɤɬɿɜ ɞɨɫɥɿɞɠɟɧɧɹ ɦɨɥɟɤɭɥɹɪɧɨʀ ɛɿɨɮɿɡɢɤɢ. ɇɟ ɦɟɧɲ ɜɚɠɥɢɜɢɦɢ ɡ ɬɨɱɤɢ ɡɨɪɭ ɮɭɧɤɰɿɨɧɭɜɚɧɧɹ ɠɢɜɨʀ ɤɥɿɬɢɧɢ ɽ ɧɟɤɨɜɚɥɟɧɬɧɿ ɜɡɚɽɦɨɞɿʀ ɛɿɨɩɨɥɿɦɟɪɿɜ (ɛɿɥɤɿɜ ɬɚ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ) ɡ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɦɢ ɪɟɱɨɜɢɧɚɦɢ (ȻȺɊ, ɥɿɝɚɧɞɚɦɢ). Ɂɨɤɪɟɦɚ, ɦɨɥɟɤɭɥɚɦɢ-ɦɿɲɟɧɹɦɢ ɞɥɹ ɞɿʀ ɛɚɝɚɬɶɨɯ ȻȺɊ ɽ ɦɨɥɟɤɭɥɢ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ (ɇɄ). Ɋɚɡɨɦ ɡ ɬɢɦ ɧɟɤɨɜɚɥɟɧɬɧɿ ɜɡɚɽɦɨɞɿʀ – ɰɟ ɨɫɧɨɜɧɢɣ ɬɢɩ ɜɡɚɽɦɨɞɿɣ, ɹɤɿ ɜɢɡɧɚɱɚɸɬɶ ɦɟɯɚɧɿɡɦɢ ɭɬɜɨɪɟɧɧɹ ɫɬɚɛɿɥɶɧɢɯ ɤɨɦɩɥɟɤɫɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ, ɦɨɥɟɤɭɥɢ ɹɤɢɯ ɡɞɚɬɧɿ ɮɨɪɦɭɜɚɬɢ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɜɟɪɬɢɤɚɥɶɧɿ ɫɬɟɤɿɧɝɚɝɪɟɝɚɬɢ. Ɋɟɡɭɥɶɬɚɬɢ ɞɨɫɥɿɞɠɟɧɶ ɦɟɯɚɧɿɡɦɿɜ ɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɩɪɟɞɫɬɚɜɥɹɸɬɶ ɡɧɚɱɧɢɣ ɿɧɬɟɪɟɫ ɡ ɨɝɥɹɞɭ ɧɚ ɪɨɥɶ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɜɡɚɽɦɨɞɿɣ ɭ ɮɨɪɦɭɜɚɧɧɿ ɫɭɩɪɚɦɨɥɟɤɭɥɹɪɧɢɯ ɫɬɪɭɤɬɭɪ, ɹɤɿ ɡɧɚɯɨɞɹɬɶ ɡɚɫɬɨɫɭɜɚɧɧɹ ɜ ɫɭɱɚɫɧɢɯ ɧɚɧɨɬɟɯɧɨɥɨɝɿɹɯ. ɍɬɜɨɪɟɧɧɹ ɚɫɨɰɿɚɬɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ɜɚɠɥɢɜɟ ɡ ɨɝɥɹɞɭ ɦɨɥɟɤɭɥɹɪɧɨʀ ɮɚɪɦɚɤɨɥɨɝɿʀ, ɬɨɦɭ ɳɨ ɜɟɥɢɱɟɡɧɢɣ ɤɥɚɫ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ ɽ ɨɫɧɨɜɨɸ ɞɥɹ ɦɟɞɢɱɧɢɯ ɩɪɟɩɚɪɚɬɿɜ, ɧɚɫɚɦɩɟɪɟɞ, ɩɪɨɬɢɩɭɯɥɢɧɧɢɯ ɚɧɬɢɛɿɨɬɢɤɿɜ. Ɉɫɤɿɥɶɤɢ ʀɯ ɤɥɿɧɿɱɧɟ ɡɚɫɬɨɫɭɜɚɧɧɹ ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɧɟɛɚɠɚɧɢɦɢ ɩɨɛɿɱɧɢɦɢ ɟɮɟɤɬɚɦɢ, ɡɨɤɪɟɦɚ, ɜɢɫɨɤɨɸ ɬɨɤɫɢɱɧɿɫɬɸ, ɨɞɧɢɦ ɡ ɩɨɲɢɪɟɧɢɯ ɫɩɨɫɨɛɿɜ ɡɧɢɠɟɧɧɹ ɧɟɝɚɬɢɜɧɨʀ ɞɿʀ ɬɚ ɩɨɫɢɥɟɧɧɹ ɦɟɞɢɤɨ-ɛɿɨɥɨɝɿɱɧɨɝɨ ɟɮɟɤɬɭ ɽ ɫɩɿɥɶɧɟ ɜɢɤɨɪɢɫɬɚɧɧɹ ȻȺɊ, ɹɤɟ ɫɬɚɧɨɜɢɬɶ ɨɫɧɨɜɭ ɫɭɱɚɫɧɨʀ ɫɬɪɚɬɟɝɿʀ ɤɨɦɛɿɧɨɜɚɧɨʀ ɯɿɦɿɨɬɟɪɚɩɿʀ. Ɉɞɧɿɽɸ ɡ ɩɪɢɱɢɧ ɡɦɿɧɢ ɛɿɨɥɨɝɿɱɧɨʀ ɚɤɬɢɜɧɨɫɬɿ ɜɢɡɧɚɱɟɧɢɯ ȻȺɊ ɜ ɩɪɢɫɭɬɧɨɫɬɿ ɿɧɲɢɯ ɽ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɚɛɨ ɿɧɬɟɪɰɟɩɬɨɪɧɢɣ ɦɟɯɚɧɿɡɦ. Ɍɨɦɭ ɤɨɪɟɤɬɧɢɣ ɚɧɚɥɿɡ ɜɩɥɢɜɭ ɨɞɧɨɝɨ ɥɿɝɚɧɞɭ ɧɚ ɡɜ'ɹɡɭɜɚɧɧɹ ɿɧɲɨɝɨ ɡ ɛɿɨɦɨɥɟɤɭɥɹɪɧɨɸ ɦɚɬɪɢɰɟɸ-ɦɿɲɟɧɧɸ ɬɪɟɛɚ ɜɢɤɨɧɭɜɚɬɢ ɡ ɭɪɚɯɭɜɚɧɧɹɦ ɬɚɤɢɯ ɮɚɤɬɨɪɿɜ ɹɤ ɫɚɦɨɚɫɨɰɿɚɰɿɹ ɿ/ɚɛɨ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɦɨɥɟɤɭɥ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ ɜ ɪɨɡɱɢɧɿ. Ɍɨɛɬɨ ɞɥɹ ɪɨɡɭɦɿɧɧɹ ɦɨɥɟɤɭɥɹɪɧɢɯ ɦɟɯɚɧɿɡɦɿɜ ɤɥɿɧɿɱɧɨʀ ɟɮɟɤɬɢɜɧɨɫɬɿ 21 ɤɨɦɛɿɧɨɜɚɧɨʀ ɯɿɦɿɨɬɟɪɚɩɿʀ ɧɟɨɛɯɿɞɧɨ ɜɫɟɛɿɱɧɟ ɜɢɜɱɟɧɧɹ ɹɤ ɤɨɦɩɥɟɤɫɿɜ ɛɿɨɦɨɥɟɤɭɥɚ-ɥɿɝɚɧɞ, ɡɨɤɪɟɦɚ, ȾɇɄ-ɥɿɝɚɧɞ, ɬɚɤ ɿ ɜɿɞɧɨɫɧɨ ɩɪɨɫɬɢɯ ɫɢɫɬɟɦ, ɳɨ ɦɿɫɬɹɬɶ ɚɫɨɰɿɚɬɢ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ. Ɉɫɬɚɧɧɿɦ ɱɚɫɨɦ ɛɭɥɨ ɞɨɫɹɝɧɭɬɨ ɡɧɚɱɧɨɝɨ ɩɪɨɝɪɟɫɭ ɜ ɪɨɡɭɦɿɧɧɿ ɫɬɪɭɤɬɭɪɧɢɯ ɬɚ ɞɢɧɚɦɿɱɧɢɯ ɜɥɚɫɬɢɜɨɫɬɟɣ ɤɨɦɩɥɟɤɫɿɜ ɥɿɝɚɧɞ-ȾɇɄ. ɐɹ ɿɧɮɨɪɦɚɰɿɹ ɡɚɛɟɡɩɟɱɢɥɚ ɜɚɝɨɦɢɣ ɜɧɟɫɨɤ ɜ ɫɬɜɨɪɟɧɧɹ ɛɿɥɶɲ ɟɮɟɤɬɢɜɧɢɯ ɯɿɦɿɨɬɟɪɚɩɟɜɬɢɱɧɢɯ ɩɪɟɩɚɪɚɬɿɜ ɞɪɭɝɨɝɨ ɿ ɬɪɟɬɶɨɝɨ ɩɨɤɨɥɿɧɧɹ ɞɥɹ ɭɫɩɿɲɧɨɝɨ ɥɿɤɭɜɚɧɧɹ ɛɚɝɚɬɶɨɯ ɜɢɞɿɜ ɨɧɤɨɥɨɝɿɱɧɢɯ ɡɚɯɜɨɪɸɜɚɧɶ. Ɉɞɧɚɤ, ɩɢɬɚɧɧɹ ɩɪɨ ɡɜ'ɹɡɨɤ ɮɿɡɢɤɨ-ɯɿɦɿɱɧɢɯ ɜɥɚɫɬɢɜɨɫɬɟɣ ɤɨɦɩɥɟɤɫɿɜ ɥɿɝɚɧɞ-ȾɇɄ ɡ ʀɯ ɦɟɞɢɤɨɛɿɨɥɨɝɿɱɧɨɸ ɟɮɟɤɬɢɜɧɿɫɬɸ ɡɚɥɢɲɚɽɬɶɫɹ ɩɪɚɤɬɢɱɧɨ ɧɟɡ'ɹɫɨɜɚɧɢɦ. Ⱦɨɬɟɩɟɪ ɜɿɞɫɭɬɧɹ ɞɟɬɚɥɶɧɚ ɿɧɮɨɪɦɚɰɿɹ ɩɪɨ ɦɨɠɥɢɜɿɫɬɶ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ ɿ ɜɩɥɢɜɭ ɪɨɡɱɢɧɧɢɤɚ, ɚ ɬɚɤɨɠ ɩɪɨ ɨɰɿɧɤɭ ɜɤɥɚɞɭ ɪɿɡɧɢɯ ɜɢɞɿɜ ɜɡɚɽɦɨɞɿɣ ɜ ɭɬɜɨɪɟɧɧɹ ɫɬɿɣɤɢɯ ɚɝɪɟɝɚɬɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ. ȼɿɞɨɦɨ, ɳɨ ɫɚɦɟ ɜɨɞɧɟɜɿ ɡɜ'ɹɡɤɢ ɜɿɞɿɝɪɚɸɬɶ ɫɭɬɬɽɜɭ ɪɨɥɶ ɭ ɮɨɪɦɭɜɚɧɧɿ ɫɬɚɛɿɥɶɧɢɯ ɩɪɨɫɬɨɪɨɜɢɯ ɫɬɪɭɤɬɭɪ ɛɿɨɩɨɥɿɦɟɪɿɜ ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɿɜ ɡ ɥɿɝɚɧɞɚɦɢ, ɚ ɬɚɤɨɠ ɭ ɞɨɞɚɬɤɨɜɿɣ ɫɬɚɛɿɥɿɡɚɰɿʀ ɜɟɪɬɢɤɚɥɶɧɢɯ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ. Ȼɿɥɶɲɿɫɬɶ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɦɟɬɨɞɿɜ ɧɚɞɚɸɬɶ ɥɢɲɟ ɧɟɩɪɹɦɭ ɿɧɮɨɪɦɚɰɿɸ ɳɨɞɨ ɦɨɠɥɢɜɨɫɬɿ ɮɨɪɦɭɜɚɧɧɹ ɬɚ ɟɧɟɪɝɿʀ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ. ɉɨɽɞɧɚɧɧɹ ɪɟɡɭɥɶɬɚɬɿɜ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɦɟɬɨɞɿɜ ɡ ɞɚɧɢɦɢ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɽ ɩɟɪɫɩɟɤɬɢɜɧɢɦɢ ɞɥɹ ɜɫɬɚɧɨɜɥɟɧɧɹ ɿ ɞɟɬɚɥɶɧɨɝɨ ɚɧɚɥɿɡɭ ɪɿɡɧɢɯ ɬɢɩɿɜ ɜɡɚɽɦɨɞɿɣ ɭ ɡ ɩɪɨɰɟɫɚɯ ȾɇɄ. ɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɡɚɜɞɹɤɢ ɬɚɤɢɦ ȻȺɊ ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɿ Ɉɬɪɢɦɚɧɚ ɞɨɫɥɿɞɠɟɧɧɹɦ ɿɧɮɨɪɦɚɰɿɹ ɞɨɡɜɨɥɢɬɶ ɛɭɞɭɜɚɬɢ ɦɨɥɟɤɭɥɹɪɧɿ ɦɨɞɟɥɿ ɿ ɩɪɨɝɧɨɡɭɜɚɬɢ ɫɬɚɧ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɿɜ ɡ ɦɨɥɟɤɭɥɚɦɢ-ɦɿɲɟɧɹɦɢ ɜ ɭɦɨɜɚɯ, ɛɥɢɡɶɤɢɯ ɞɨ ɮɿɡɿɨɥɨɝɿɱɧɢɯ. ɐɟɣ ɟɬɚɩ ɽ ɜɚɠɥɢɜɢɦ ɞɥɹ ɭɫɩɿɲɧɨɝɨ ɫɢɧɬɟɡɭ ɧɨɜɢɯ ȻȺɊ ɡ ɜɢɡɧɚɱɟɧɨɸ ɧɚɩɪɚɜɥɟɧɿɫɬɸ ʀɯ ɜɩɥɢɜɭ ɧɚ ɫɬɚɧ ɬɚ ɮɭɧɤɰɿɨɧɭɜɚɧɧɹ ɛɿɨɥɨɝɿɱɧɢɯ ɦɨɥɟɤɭɥ. Ɇɟɬɚ ɿ ɡɚɞɚɱɿ ɞɨɫɥɿɞɠɟɧɧɹ. ȼɫɬɚɧɨɜɢɬɢ ɫɬɪɭɤɬɭɪɧɿ ɨɫɨɛɥɢɜɨɫɬɿ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɿɜ ɡ ȾɇɄ, ɚ ɬɚɤɨɠ 22 ɡ'ɹɫɭɜɚɬɢ ɪɨɥɶ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ ɿ ɦɨɥɟɤɭɥ ɜɨɞɢ ɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɤɨɦɩɥɟɤɫɿɜ, ɹɤɿ ɧɟɨɛɯɿɞɧɿ ɞɥɹ ɜɢɡɧɚɱɟɧɧɹ ɿɧɬɟɪɰɟɩɬɨɪɧɨɝɨ ɦɟɯɚɧɿɡɦɭ ɞɿʀ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɧɚ ȾɇɄ. Ⱦɥɹ ɞɨɫɹɝɧɟɧɧɹ ɩɨɫɬɚɜɥɟɧɨʀ ɦɟɬɢ ɧɟɨɛɯɿɞɧɨ ɛɭɥɨ ɜɢɪɿɲɢɬɢ ɬɚɤɿ ɡɚɞɚɱɿ: 1. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɦɟɬɨɞɚ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɜ ɩɪɨɜɟɫɬɢ ɩɥɿɜɤɚɯ, ɞɨɫɥɿɞɠɟɧɧɹ ɜɢɪɨɳɟɧɢɯ ɡ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɧɟɣɬɪɚɥɶɧɢɯ ɿ ɫɥɚɛɨ ɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ, ɪɇ ɹɤɢɯ ɜɩɥɢɜɚɽ ɧɚ ɡɚɪɹɞɢ ɚɬɨɦɿɜ ɯɪɨɦɨɮɨɪɭ (ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ) ɿ ɮɨɫɮɚɬɧɢɯ ɝɪɭɩ. 2. Ⱦɥɹ ɜɫɬɚɧɨɜɥɟɧɧɹ ɰɟɧɬɪɿɜ ɡɜ'ɹɡɭɜɚɧɧɹ ɩɪɨɬɨɧɿɜ ɩɪɨɜɟɫɬɢ ɩɨɪɿɜɧɹɥɶɧɢɣ ɚɧɚɥɿɡ ɭ ɧɟɣɬɪɚɥɶɧɿɣ ɿ ɩɪɨɬɨɧɨɜɚɧɿɣ ɮɨɪɦɚɯ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɩɨɥɨɫ ɩɨɝɥɢɧɚɧɧɹ, ɩɨɜ'ɹɡɚɧɢɯ ɡ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɦɢ ɤɨɥɢɜɚɧɧɹɦɢ ɚɬɨɦɿɜ ɋ– ɋ, ɋ–N1 ɿ ɋ–N5 ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ. 3. Ⱦɥɹ ɜɢɹɜɥɟɧɧɹ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ (ɇ-ɡɜ'ɹɡɤɿɜ) ɬɚ ʀɯ ɜɤɥɚɞɭ ɞɨ ɡɚɝɚɥɶɧɨʀ ɟɧɟɪɝɿʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɫɩɟɤɬɪɢ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɮɭɧɤɰɿɨɧɚɥɶɧɢɯ ɨɬɪɢɦɚɬɢ ɿ ɩɪɨɚɧɚɥɿɡɭɜɚɬɢ (C=O ɿ NH2) ɤɨɥɢɜɚɥɶɧɿ ɝɪɭɩ ɚɬɨɦɿɜ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ȻȺɊ: ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ (FMN), ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ (EB), ɩɪɨɮɥɚɜɿɧɭ (PRF) , ɤɨɮɟʀɧɭ (CAF) ɿ ɬɟɨɮɿɥɿɧɭ (TPH) ɬɚ ʀɯ ɫɭɦɿɲɟɣ ɜ ɭɦɨɜɚɯ, ɧɚɛɥɢɠɟɧɢɯ ɞɨ ɮɿɡɿɨɥɨɝɿɱɧɢɯ. 4. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ ɜɢɡɧɚɱɢɬɢ ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɜ ɫɢɫɬɟɦɚɯ, ɹɤɿ ɦɿɫɬɹɬɶ ɝɟɬɟɪɨɞɢɦɟɪɢ ɚɪɨɦɚɬɢɱɧɢɯ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɥɿɝɚɧɞɿɜ FMN-EB, FMN-PRF, TPH-EB, EB-CAF, FMN-TPH, PRF-TPH ɡ ɹɜɧɢɦ ɭɪɚɯɭɜɚɧɧɹɦ ɦɨɥɟɤɭɥ ɜɨɞɢ. 5. Ɇɟɬɨɞɨɦ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ (ɄɊ) ɞɨɫɥɿɞɢɬɢ ɡɜ'ɹɡɭɜɚɧɧɹ EB ɡ ɬɢɦɭɫɧɨɸ ȾɇɄ ɩɪɢ ɧɢɡɶɤɢɯ ɿ ɜɢɫɨɤɢɯ ɡɧɚɱɟɧɧɹɯ ɫɩɿɜɜɿɞɧɨɲɟɧɶ ɤɨɧɰɟɧɬɪɚɰɿɣ ɥɿɝɚɧɞ/ȾɇɄ; ɜɢɡɧɚɱɢɬɢ ɜɩɥɢɜ ɇ-ɡɜ'ɹɡɤɿɜ ɧɚ ɦɨɥɟɤɭɥɹɪɧɿ ɦɟɯɚɧɿɡɦɢ ɡɜ'ɹɡɭɜɚɧɧɹ EB ɡ ȾɇɄ ɩɪɢ ɭɬɜɨɪɟɧɧɿ ɤɨɦɩɥɟɤɫɿɜ ɡɚ ɬɢɩɨɦ ɿɧɬɟɪɤɚɥɹɰɿʀ ɬɚ ɡɨɜɧɿɲɧɶɨɝɨ ɡɜ'ɹɡɭɜɚɧɧɹ, ɚ ɬɚɤɨɠ ɜɢɹɜɢɬɢ ɫɬɪɭɤɬɭɪɧɢɣ ɫɬɚɧ ȾɇɄ ɩɪɢ ɳɿɥɶɧɨɦɭ ʀʀ ɡɚɩɨɜɧɟɧɧɿ ɥɢɝɚɧɞɨɦ. 23 Ɉɛ'ɽɤɬ ɞɨɫɥɿɞɠɟɧɧɹ. ɉɪɨɰɟɫɢ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ ɡ ȾɇɄ. ɉɪɟɞɦɟɬ ɞɨɫɥɿɞɠɟɧɧɹ. ɋɬɪɭɤɬɭɪɧɿ ɨɫɨɛɥɢɜɨɫɬɿ ɚɫɨɰɿɚɬɿɜ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɿ ɤɨɦɩɥɟɤɫɿɜ ȾɇɄ-ȻȺɊ ɬɚ ɜɧɟɫɨɤ ɪɿɡɧɢɯ ɜɢɞɿɜ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɜɡɚɽɦɨɞɿɣ ɿ ɦɨɥɟɤɭɥ ɜɨɞɢ ɜ ʀɯ ɫɬɚɛɿɥɿɡɚɰɿɸ. Ɇɟɬɨɞɢ ɞɨɫɥɿɞɠɟɧɧɹ. ȱɧɮɪɚɱɟɪɜɨɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɬɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ɫɜɿɬɥɚ, ɹɤɿ ɞɨɡɜɨɥɢɥɢ ɜɫɬɚɧɨɜɢɬɢ ɚɬɨɦɧɿ ɝɪɭɩɢ, ɳɨ ɛɟɪɭɬɶ ɭɱɚɫɬɶ ɭ ɜɡɚɽɦɨɞɿʀ, ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ, ɪɟɡɨɧɚɧɫɧɿ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ. Ɇɟɬɨɞ ɩ'ɽɡɨɝɪɚɜɿɦɟɬɪɿʀ ɞɥɹ ɨɬɪɢɦɚɧɧɹ ɿɡɨɬɟɪɦ ɝɿɞɪɚɬɚɰɿʀ. Ʉɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɢɣ ɪɨɡɪɚɯɭɧɨɤ ɬɚ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ, ɡɚ ɞɨɩɨɦɨɝɨɸ ɹɤɢɯ ɛɭɥɨ ɩɨɛɭɞɨɜɚɧɨ ɦɨɞɟɥɿ ɚɫɨɰɿɚɬɿɜ, ɜɫɬɚɧɨɜɥɟɧɨ ɜɤɥɚɞɢ ɪɿɡɧɢɯ ɜɢɞɿɜ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɜɡɚɽɦɨɞɿɣ ɬɚ ɦɨɥɟɤɭɥ ɜɨɞɢ ɜ ɫɬɚɛɿɥɿɡɚɰɿɸ ɚɫɨɰɿɚɬɿɜ ɬɚ ɨɛɱɢɫɥɟɧɨ ɟɧɟɪɝɟɬɢɱɧɿ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɤɨɦɩɥɟɤɫɿɜ, ɳɨ ɭɬɜɨɪɸɸɬɶɫɹ. ɇɚɭɤɨɜɚ ɧɨɜɢɡɧɚ ɨɞɟɪɠɚɧɢɯ ɪɟɡɭɥɶɬɚɬɿɜ. 1. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɦɟɬɨɞɿɜ ɤɨɥɢɜɚɥɶɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɜɩɟɪɲɟ ɛɭɥɨ ɨɬɪɢɦɚɧɨ ɩɪɹɦɢɣ ɞɨɤɚɡ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɦɿɠ ɞɨɧɨɪɧɢɦɢ (NH2) ɿ ɚɤɰɟɩɬɨɪɧɢɦɢ (ɋ=Ɉ) ɨɰɿɧɤɭ ɝɪɭɩɚɦɢ ɟɧɬɚɥɶɩɿʀ ɩɪɢ ɮɨɪɦɭɜɚɧɧɿ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ (FMN-EB, FMN-PRF, TPH-EB). ɉɪɨɜɟɞɟɧɨ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɝɟɬɟɪɨɚɫɨɰɿɚɬɚɯ FMN-EB ɿ FMN-PRF. 2. ȼɩɟɪɲɟ ɧɚ ɩɿɞɫɬɚɜɿ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɯ ɞɚɧɢɯ ɜɢɹɜɥɟɧɨ ɜɢɫɨɤɨɱɚɫɬɨɬɧɟ ɡɦɿɳɟɧɧɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɨɥɢɜɚɧɶ ɋ4=Ɉ ɿ ɋ2=Ɉ ɝɪɭɩ ɚɬɨɦɿɜ ɞɥɹ ɩɥɿɜɤɢ FMN, ɨɬɪɢɦɚɧɨʀ ɡɿ ɫɥɚɛɨɤɢɫɥɨɝɨ ɪɨɡɱɢɧɭ (ɪɇ ~ 6,0). Ɂɚ ɞɨɩɨɦɨɝɨɸ ɪɨɡɪɚɯɭɧɤɿɜ ɪɟɡɨɧɚɧɫɧɨʀ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɋ4=Ɉ ɿ ɋ2=Ɉ ɝɪɭɩ ɭ ɞɢɩɨɥɶ-ɞɢɩɨɥɶɧɨɦɭ ɧɚɛɥɢɠɟɧɧɿ ɛɭɥɚ ɩɨɛɭɞɨɜɚɧɚ ɦɨɞɟɥɶ nɦɨɥɟɤɭɥɹɪɧɨʀ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ. Ⱥɧɚɥɿɡ ȱɑ-ɫɩɟɤɬɪɿɜ ɫɭɯɢɯ ɩɥɿɜɨɤ FMN, ɜɢɪɨɳɟɧɢɯ ɡ ɪɨɡɱɢɧɿɜ ɡ ɪɇ ~ 6,0, ɩɨɤɚɡɚɜ, ɳɨ ɩɪɨɬɨɧɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɜɿɞɛɭɜɚɽɬɶɫɹ ɩɨ ɚɬɨɦɚɯ ɚɡɨɬɭ N1 ɿ N5. Ʉɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɿ ɪɨɡɪɚɯɭɧɤɢ ɡɚɪɹɞɿɜ ɧɚ ɚɬɨɦɚɯ 3. 24 ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɩɿɞɬɜɟɪɞɢɥɢ ɰɟɣ ɜɢɫɧɨɜɨɤ, ɨɫɤɿɥɶɤɢ ɧɚ ɚɬɨɦɚɯ N1 ɿ N5 ɡɧɚɯɨɞɹɬɶɫɹ ɡɧɚɱɧɿ ɧɟɝɚɬɢɜɧɿ ɡɚɪɹɞɢ. 4. ɇɚ ɩɿɞɫɬɚɜɿ ɞɚɧɢɯ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɜɩɟɪɲɟ ɜɫɬɚɧɨɜɥɟɧɨ, ɳɨ ɭ ɝɟɬɟɪɨɚɫɨɰɿɚɬɚɯ FMN-TPH, TPH-PRF ɿ CAF-EB ɜɨɞɧɟɜɿ ɡɜ'ɹɡɤɢ ɧɟ ɭɬɜɨɪɸɸɬɶɫɹ, ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɚ ɫɬɚɛɿɥɿɡɚɰɿɹ ɜɡɚɽɦɨɞɿɹɦɢ. ɰɢɯ ɤɨɦɩɥɟɤɫɿɜ ɜɢɡɧɚɱɚɽɬɶɫɹ ɡɫɭɜɢ ȼɢɹɜɥɟɧɿ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-TPH ɛɭɥɨ ɩɨɹɫɧɟɧɨ ɪɟɡɨɧɚɧɫɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ, ɳɨ ɞɨɡɜɨɥɢɥɨ ɩɨɛɭɞɭɜɚɬɢ n-ɦɨɥɟɤɭɥɹɪɧɭ ɫɬɪɭɤɬɭɪɭ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ. 5. Ɂ ɚɧɚɥɿɡɭ ɞɚɧɢɯ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ ɜɫɬɚɧɨɜɥɟɧɨ, ɳɨ ɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɚɯ FMN-EB ɿ FMN-PRF ɭɬɜɨɪɸɸɬɶɫɹ ɇ-ɡɜ'ɹɡɤɢ, ɹɤɿ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɸɬɶ ʀɯ ɫɬɪɭɤɬɭɪɢ. Ⱦɥɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ FMN-TPH, TPH-EB, TPH-PRF ɿ CAF-EB ɜɫɬɚɧɨɜɥɟɧɢɣ ɮɚɤɬ ɞɨɞɚɬɤɨɜɨʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɰɢɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɭ ɪɟɡɭɥɶɬɚɬɿ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɢɯ ɦɿɫɬɤɿɜ ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɥɿɝɚɧɞɿɜ. Ɍɚɤɢɦ ɱɢɧɨɦ, ɧɚ ɩɿɞɫɬɚɜɿ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɚɧɢɯ ɬɚ ɪɟɡɭɥɶɬɚɬɿɜ ɤɨɦɩ’ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɞɨɜɟɞɟɧɨ, ɳɨ FMN, CAF ɿ TPH ɽ ɿɧɬɟɪɰɟɩɬɨɪɚɦɢ, ɹɤɿ ɡɞɚɬɧɿ ɡɦɟɧɲɭɜɚɬɢ ɤɨɧɰɟɧɬɪɚɰɿɸ ɦɭɬɚɝɟɧɿɜ EB ɬɚ PRF. ȼɩɟɪɲɟ ɦɟɬɨɞɨɦ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɄɊ ɩɨɤɚɡɚɧɨ, ɳɨ ɤɨɦɩɥɟɤɫɢ EB-ȾɇɄ (ɡɚ ɬɢɩɨɦ ɿɧɬɟɪɤɚɥɹɰɿʀ ɬɚ ɡɨɜɧɿɲɧɶɨɝɨ ɡɜ'ɹɡɭɜɚɧɧɹ) ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɸɬɶɫɹ ɜɨɞɧɟɜɢɦɢ ɡɜ'ɹɡɤɚɦɢ, ɹɤɿ ɭɬɜɨɪɸɸɬɶɫɹ ɦɿɠ NH2-ɝɪɭɩɚɦɢ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɬɚ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɩɨɥɿɧɭɤɥɟɨɬɢɞɧɨʀ ɦɚɬɪɢɰɿ. Ɉɫɨɛɢɫɬɢɣ ɜɧɟɫɨɤ ɡɞɨɛɭɜɚɱɚ. 6. Ⱥɜɬɨɪɨɦ ɞɢɫɟɪɬɚɰɿɣɧɨʀ ɪɨɛɨɬɢ ɫɚɦɨɫɬɿɣɧɨ ɩɪɨɜɟɞɟɧɨ ɚɧɚɥɿɡ ɧɚɭɤɨɜɨʀ ɥɿɬɟɪɚɬɭɪɢ, ɨɬɪɢɦɚɧɨ ɪɟɡɭɥɶɬɚɬɢ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɨɫɥɿɞɠɟɧɶ ɿ ɩɪɨɜɟɞɟɧɨ ʀɯ ɨɛɪɨɛɤɭ. Ⱥɜɬɨɪɨɦ ɨɫɨɛɢɫɬɨ ɜɢɤɨɧɚɧɢɣ ɩɟɪɜɢɧɧɢɣ ɚɧɚɥɿɡ ɪɟɡɭɥɶɬɚɬɿɜ ɿ ɫɮɨɪɦɭɥɶɨɜɚɧɿ ɩɨɩɟɪɟɞɧɿ ɜɢɫɧɨɜɤɢ. Ɋɚɡɨɦ ɡ ɧɚɭɤɨɜɢɦ ɤɟɪɿɜɧɢɤɨɦ, ɞ.ɮ.-ɦ.ɧ. ɒɟɫɬɨɩɚɥɨɜɨɣ Ƚ.ȼ., ɛɭɥɢ ɜɢɡɧɚɱɟɧɿ ɦɟɬɚ, ɡɚɞɚɱɿ ɪɨɛɨɬɢ ɿ ɫɩɨɫɨɛɢ ʀɯ ɜɢɪɿɲɟɧɧɹ, ɡɞɿɣɫɧɟɧɨ ɿɧɬɟɪɩɪɟɬɚɰɿɸ ɨɬɪɢɦɚɧɢɯ ɪɟɡɭɥɶɬɚɬɿɜ ɿ ɡɪɨɛɥɟɧɿ ɨɫɬɚɬɨɱɧɿ ɜɢɫɧɨɜɤɢ. ȼ 25 ɨɩɭɛɥɿɤɨɜɚɧɢɯ ɫɩɿɥɶɧɨ ɡɿ ɫɩɿɜɚɜɬɨɪɚɦɢ ɩɪɚɰɹɯ ɨɫɨɛɢɫɬɢɣ ɜɧɟɫɨɤ ɡɞɨɛɭɜɚɱɚ ɩɨɥɹɝɚɽ: [1,2,3,4,5] – ɩɨɲɭɤ ɿ ɤɪɢɬɢɱɧɢɣ ɚɧɚɥɿɡ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɚɧɢɯ, ɨɬɪɢɦɚɧɧɹ ɤɨɥɢɜɚɥɶɧɢɯ ɫɩɟɤɬɪɿɜ, ɚɧɚɥɿɡ ɬɚ ɿɧɬɟɪɩɪɟɬɚɰɿɹ ɨɬɪɢɦɚɧɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɚɧɢɯ, ɧɚɩɢɫɚɧɧɹ ɫɬɚɬɟɣ; [7,8,9,10,11,12,13,15,16,17] – ɚɧɚɥɿɡ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɚɧɢɯ, ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɟ ɨɬɪɢɦɚɧɧɹ ɤɨɥɢɜɚɥɶɧɢɯ ɫɩɟɤɬɪɿɜ, ɚɧɚɥɿɡ ɬɚ ɿɧɬɟɪɩɪɟɬɚɰɿɹ ɨɬɪɢɦɚɧɢɯ ɞɚɧɢɯ, ɧɚɩɢɫɚɧɧɹ ɬɟɡ; ɭ ɪɨɛɨɬɚɯ [6,14] – ɚɧɚɥɿɡ ɿ ɨɛɝɨɜɨɪɟɧɧɹ ɨɬɪɢɦɚɧɢɯ ɪɟɡɭɥɶɬɚɬɿɜ, ɧɚɩɢɫɚɧɧɹ ɫɬɚɬɬɿ ɿ ɬɟɡ. Ⱥɩɪɨɛɚɰɿɹ ɪɟɡɭɥɶɬɚɬɿɜ ɞɢɫɟɪɬɚɰɿʀ. Ɇɚɬɟɪɿɚɥɢ ɞɢɫɟɪɬɚɰɿɣɧɨʀ ɪɨɛɨɬɢ ɞɨɩɨɜɿɞɚɥɢɫɹ ɬɚ ɨɛɝɨɜɨɪɸɜɚɥɢɫɹ ɧɚ ɦɿɠɧɚɪɨɞɧɢɯ ɬɚ ɜɿɬɱɢɡɧɹɧɢɯ ɤɨɧɮɟɪɟɧɰɿɹɯ: V ɏɚɪɶɤɨɜɫɤɚɹ ɤɨɧɮɟɪɟɧɰɢɹ ɦɨɥɨɞɵɯ ɭɱɟɧɵɯ «Ɋɚɞɢɨɮɢɡɢɤɚ ɢ ɋȼɑ ɷɥɟɤɬɪɨɧɢɤɚ». – ɏɚɪɶɤɨɜ (ɍɤɪɚɢɧɚ), 2005; VI ɏɚɪɶɤɨɜɫɤɚɹ ɤɨɧɮɟɪɟɧɰɿɹ ɦɨɥɨɞɵɯ ɭɱɟɧɵɯ «Ɋɚɞɢɨɮɢɡɢɤɚ ɢ ɗɥɟɤɬɪɨɧɢɤɚ». –ɏɚɪɶɤɨɜ (ɍɤɪɚɢɧɚ), 2006; IV Ɂ'ʀɡɞ ɍɤɪɚʀɧɫɶɤɨɝɨ ɛɿɨɮɿɡɢɱɧɨɝɨ ɬɨɜɚɪɢɫɬɜɚ. – Ⱦɨɧɟɰɶɤ (ɍɤɪɚʀɧɚ), 2006; V ɿ VI Ɂ'ʀɡɞ ɍɤɪɚʀɧɫɶɤɨɝɨ ɛɿɨɮɿɡɢɱɧɨɝɨ ɬɨɜɚɪɢɫɬɜɚ. – Ʌɭɰɶɤ (ɍɤɪɚʀɧɚ), 2011, 2015.; 11th ɿ 13th Kharkiv Young Scientists Conference on Radiophysics, Electronics, Photonics and Biophysics. – Kharkiv (Ukraine), 2011, 2013; III ɿ V Young Scientist Conference «Modern Problems of Theoretical Physics». – Kyiv (Ukraine), 2011, 2013; VIII Ɇɟɠɞɭɧɚɪɨɞɧɚɹ ɧɚɭɱɧɨ-ɬɟɯɧɢɱɟɫɤɚɹ ɤɨɧɮɟɪɟɧɰɢɹ «Ⱥɤɬɭɚɥɶɧɵɟ ɜɨɩɪɨɫɵ ɛɢɨɥɨɝɢɱɟɫɤɨɣ ɮɢɡɢɤɢ ɢ ɯɢɦɢɢ. ȻɎɎɏ – 2012». – ɋɟɜɚɫɬɨɩɨɥɶ (ɍɤɪɚɢɧɚ), 2012; 5th International Symposium «Methods and Applications of Computational Chemistry». – Kharkiv (Ukraine), 2013. Ɂɜ'ɹɡɨɤ ɪɨɛɨɬɢ ɡ ɧɚɭɤɨɜɢɦɢ ɩɪɨɝɪɚɦɚɦɢ, ɩɥɚɧɚɦɢ, ɬɟɦɚɦɢ. Ⱦɨɫɥɿɞɠɟɧɧɹ ɡɚ ɬɟɦɨɸ ɞɢɫɟɪɬɚɰɿʀ ɩɪɨɜɨɞɢɥɢɫɶ ɡɝɿɞɧɨ ɡ ɩɥɚɧɨɦ ɧɚɭɤɨɜɨɞɨɫɥɿɞɧɢɯ ɪɨɛɿɬ ɜɿɞɞɿɥɭ ɛɿɨɮɿɡɢɤɢ ȱɧɫɬɢɬɭɬɭ ɪɚɞɿɨɮɿɡɢɤɢ ɬɚ ɟɥɟɤɬɪɨɧɿɤɢ ɿɦ. Ɉ. ə. ɍɫɢɤɨɜɚ ɇȺɇ ɍɤɪɚʀɧɢ ɜ ɪɚɦɤɚɯ ɮɭɧɞɚɦɟɧɬɚɥɶɧɢɯ ɞɟɪɠɛɸɞɠɟɬɧɢɯ ɇȾɊ: «Ɇɨɥɟɤɭɥɹɪɧɿ ɦɨɞɟɥɿ ɤɨɦɩɥɟɤɫɿɜ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɡ ɧɭɤɥɟʀɧɨɜɢɦɢ ɤɢɫɥɨɬɚɦɢ ɡɚ ɭɦɨɜɚɦɢ ɦɭɥɶɬɢɦɨɞɚɥɶɧɨɝɨ ɬɚ ɤɨɧɤɭɪɟɧɬɧɨɝɨ ɡɜ'ɹɡɭɜɚɧɧɹ» (ɲɢɮɪ «Ɇɨɞɟɥɶ», ɧɨɦɟɪ ɞɟɪɠɪɟɽɫɬɪɚɰɿʀ 0107U001079); «Ɇɟɯɚɧɿɡɦɢ ɜɩɥɢɜɭ ɛɿɨɥɨɝɿɱɧɨ-ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɿ ɟɥɟɤɬɪɨɦɚɝɧɿɬɧɢɯ ɩɨɥɿɜ 26 ɝɿɝɚ- ɬɚ ɬɟɪɚɝɟɪɰɟɜɨɝɨ ɞɿɚɩɚɡɨɧɿɜ ɧɚ ɛɿɨɨɛ'ɽɤɬɢ ɪɿɡɧɨɝɨ ɪɿɜɧɸ ɨɪɝɚɧɿɡɚɰɿʀ (ɛɿɨɩɨɥɿɦɟɪɢ, ɛɿɨɦɟɦɛɪɚɧɢ, ɤɥɿɬɢɧɢ)» (ɲɢɮɪ «Ɇɨɞɟɥɶ-2», ɧɨɦɟɪ ɞɟɪɠɪɟɽɫɬɪɚɰɿʀ 0111U010475). ɉɪɚɤɬɢɱɧɟ ɡɧɚɱɟɧɧɹ ɨɞɟɪɠɚɧɢɯ ɪɟɡɭɥɶɬɚɬɿɜ. Ɉɞɟɪɠɚɧɿ ɪɟɡɭɥɶɬɚɬɢ ɬɚ ɜɢɫɧɨɜɤɢ ɪɨɛɨɬɢ ɞɚɸɬɶ ɜɧɟɫɨɤ ɭ ɪɨɡɭɦɿɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɦɟɯɚɧɿɡɦɿɜ ɜɡɚɽɦɨɞɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ. Ɂɚɩɪɨɩɨɧɨɜɚɧɿ ɦɟɬɨɞɢɤɢ ɜɢɡɧɚɱɟɧɧɹ ɜɤɥɚɞɭ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ ɿ ɦɿɠɩɥɨɳɢɧɧɢɯ ɜɡɚɽɦɨɞɿɣ ɭ ɫɬɚɛɿɥɶɧɿɫɬɶ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɭ ɩɨɞɚɥɶɲɨɦɭ ɦɨɠɭɬɶ ɛɭɬɢ ɜɢɤɨɪɢɫɬɚɧɿ ɩɪɢ ɩɪɨɝɧɨɡɭɜɚɧɧɿ ɬɟɪɚɩɟɜɬɢɱɧɨʀ ɟɮɟɤɬɢɜɧɨɫɬɿ ɤɨɦɛɿɧɨɜɚɧɨʀ ɯɿɦɿɨɬɟɪɚɩɿʀ. ȼ ɰɿɥɨɦɭ ɪɟɡɭɥɶɬɚɬɢ ɞɨɫɥɿɞɠɟɧɶ ɦɨɠɭɬɶ ɡɚɫɬɨɫɨɜɭɜɚɬɢɫɹ ɜ ɝɚɥɭɡɿ ɦɨɥɟɤɭɥɹɪɧɨʀ ɛɿɨɮɿɡɢɤɢ (ɞɨɫɥɿɞɠɟɧɧɹ ɩɪɨɰɟɫɿɜ ɭɬɜɨɪɟɧɧɹ ɤɨɦɩɥɟɤɫɿɜ), ɦɨɥɟɤɭɥɹɪɧɨʀ ɛɿɨɥɨɝɿʀ (ɦɨɞɭɥɹɰɿɹ ɛɿɨɥɨɝɿɱɧɨɝɨ ɟɮɟɤɬɭ ɪɿɡɧɨɦɚɧɿɬɧɢɦɢ ɤɨɦɛɿɧɚɰɿɹɦɢ ɡɚɯɜɨɪɸɜɚɧɶ). ɉɭɛɥɿɤɚɰɿʀ. Ɉɫɧɨɜɧɿ ɪɟɡɭɥɶɬɚɬɢ ɞɢɫɟɪɬɚɰɿʀ ɨɩɭɛɥɿɤɨɜɚɧɨ ɜ 17 ɧɚɭɤɨɜɢɯ ȻȺɊ), ɛɿɨɬɟɯɧɨɥɨɝɿʀ ɬɚ ɮɚɪɦɚɤɨɥɨɝɿʀ (ɪɨɡɪɨɛɤɚ ɧɨɜɢɯ ɟɮɟɤɬɢɜɧɢɯ ɩɪɟɩɚɪɚɬɿɜ ɞɥɹ ɥɿɤɭɜɚɧɧɹ ɬɚ ɩɪɨɮɿɥɚɤɬɢɤɢ ɨɧɤɨɥɨɝɿɱɧɢɯ ɩɪɚɰɹɯ; ɡ ɧɢɯ: 6 ɫɬɚɬɟɣ ɭ ɦɿɠɧɚɪɨɞɧɢɯ ɬɚ ɜɿɬɱɢɡɧɹɧɢɯ ɮɚɯɨɜɢɯ ɧɚɭɤɨɜɢɯ ɠɭɪɧɚɥɚɯ ɬɚ 11 ɬɟɡ ɞɨɩɨɜɿɞɟɣ ɧɚ ɦɿɠɧɚɪɨɞɧɢɯ ɬɚ ɜɿɬɱɢɡɧɹɧɢɯ ɤɨɧɮɟɪɟɧɰɿɹɯ. ɋɬɪɭɤɬɭɪɚ ɬɚ ɨɛɫɹɝ ɞɢɫɟɪɬɚɰɿʀ. Ⱦɢɫɟɪɬɚɰɿɣɧɚ ɪɨɛɨɬɚ ɫɤɥɚɞɚɽɬɶɫɹ ɡɿ ɜɫɬɭɩɭ, 5 ɪɨɡɞɿɥɿɜ, ɡɚɝɚɥɶɧɢɯ ɜɢɫɧɨɜɤɿɜ, ɫɩɢɫɤɭ ɜɢɤɨɪɢɫɬɚɧɢɯ ɞɠɟɪɟɥ ɬɚ 2 ɞɨɞɚɬɤɿɜ. Ɉɛɫɹɝ ɡɚɝɚɥɶɧɨɝɨ ɬɟɤɫɬɭ ɞɢɫɟɪɬɚɰɿʀ ɫɤɥɚɞɚɽ 8,3 ɚ.ɚ. (182 ɫɬɨɪ.), ɡ ɧɢɯ ɨɫɧɨɜɧɨɝɨ ɬɟɤɫɬɭ 6,1 ɚ.ɚ. (137 ɫɬɨɪ.). Ɋɨɛɨɬɚ ɿɥɸɫɬɪɨɜɚɧɚ 14 ɬɚɛɥɢɰɹɦɢ ɬɚ 45 ɪɢɫɭɧɤɚɦɢ. ɋɩɢɫɨɤ ɜɢɤɨɪɢɫɬɚɧɢɯ ɞɠɟɪɟɥ ɦɿɫɬɢɬɶ 255 ɧɚɣɦɟɧɭɜɚɧɶ ɬɚ ɫɤɥɚɞɚɽ 24 ɫɬɨɪɿɧɤɢ. 27 ɊɈɁȾȱɅ 1 ȺɋɈɐȱȺɐȱə ȺɊɈɆȺɌɂɑɇɂɏ ȻȱɈɅɈȽȱɑɇɈ ȺɄɌɂȼɇɂɏ ɊȿɑɈȼɂɇ ɍ ȼɈȾɇɂɏ ɊɈɁɑɂɇȺɏ Ȼɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɿ ɪɟɱɨɜɢɧɢ (ȻȺɊ) ɜɤɥɸɱɚɸɬɶ ɭ ɫɟɛɟ ɜɟɥɢɱɟɡɧɢɣ ɤɥɚɫ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ (ɥɿɝɚɧɞɿɜ), ɹɤɿ ɽ ɨɫɧɨɜɨɸ ɞɥɹ ɦɟɞɢɱɧɢɯ ɩɪɟɩɚɪɚɬɿɜ. Ɇɟɞɢɤɨ-ɛɿɨɥɨɝɿɱɧɚ ɞɿɹ ɞɟɹɤɢɯ ɡ ɧɢɯ ɨɛɭɦɨɜɥɟɧɚ ɡɞɚɬɧɿɫɬɸ ɭɬɜɨɪɸɜɚɬɢ ɧɟɤɨɜɚɥɟɧɬɧɿ ɤɨɦɩɥɟɤɫɢ ɡ ɦɨɥɟɤɭɥɚɦɢ-ɦɿɲɟɧɹɦɢ, ɡɨɤɪɟɦɚ, ɡ ȾɇɄ [1]. ɇɚ ɞɚɧɢɣ ɱɚɫ ɨɞɧɢɦ ɡ ɩɟɪɫɩɟɤɬɢɜɧɢɯ ɧɚɩɪɹɦɤɿɜ ɪɨɡɜɢɬɤɭ ɦɟɞɢɤɚɦɟɧɬɨɡɧɨɝɨ ɥɿɤɭɜɚɧɧɹ ɪɿɡɧɢɯ ɡɚɯɜɨɪɸɜɚɧɶ ɽ ɤɨɦɛɿɧɨɜɚɧɟ ɜɢɤɨɪɢɫɬɚɧɧɹ ɪɿɡɧɢɯ ɥɿɤɚɪɫɶɤɢɯ ɩɪɟɩɚɪɚɬɿɜ, ɳɨ ɩɨɫɥɚɛɥɸɸɬɶ ɚɛɨ ɩɿɞɫɢɥɸɸɬɶ ɟɮɟɤɬ ɨɞɢɧ ɨɞɧɨɝɨ. Ⱦɥɹ ɪɨɡɭɦɿɧɧɹ ɦɨɥɟɤɭɥɹɪɧɢɯ ɦɟɯɚɧɿɡɦɿɜ ɬɟɪɚɩɟɜɬɢɱɧɨʀ ɟɮɟɤɬɢɜɧɨɫɬɿ ɤɨɦɛɿɧɨɜɚɧɨʀ ɯɿɦɿɨɬɟɪɚɩɿʀ ɧɟɨɛɯɿɞɧɨ ɜɫɟɛɿɱɧɟ ɜɢɜɱɟɧɧɹ ɹɤ ɤɨɦɩɥɟɤɫɿɜ ȾɇɄɥɿɝɚɧɞ, ɬɚɤ ɿ ɜɿɞɧɨɫɧɨ ɩɪɨɫɬɢɯ ɫɢɫɬɟɦ, ɳɨ ɦɿɫɬɹɬɶ ɚɫɨɰɿɚɬɢ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ. ɍɬɜɨɪɟɧɧɹ ɬɚɤɢɯ ɚɫɨɰɿɚɬɿɜ ɦɨɠɟ ɿɫɬɨɬɧɨ ɡɦɿɧɸɜɚɬɢ ɦɟɞɢɤɨɛɿɨɥɨɝɿɱɧɭ ɟɮɟɤɬɢɜɧɿɫɬɶ ɥɿɝɚɧɞɿɜ, ɳɨ ɡɜ'ɹɡɭɸɬɶɫɹ ɡ ȾɇɄ. ɉɪɢ ɪɨɡɝɥɹɞɿ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ (ɚɫɨɰɿɚɰɿʀ) ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɥɿɝɚɧɞɿɜ, ɳɨ ɡɜ'ɹɡɭɸɬɶɫɹ ɡ ȾɇɄ, ɪɨɡɪɿɡɧɹɸɬɶ ɩɪɨɰɟɫɢ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ. ȼɡɚɽɦɨɞɿɸ ɨɞɧɚɤɨɜɢɯ ɦɨɥɟɤɭɥ Ʌɿɝɚɧɞ1-Ʌɿɝɚɧɞ1 ɧɚɡɢɜɚɸɬɶ ɫɚɦɨɚɫɨɰɿɚɰɿɽɸ, ɚ ɭɬɜɨɪɟɧɧɹ ɤɨɦɩɥɟɤɫɿɜ ɪɿɡɧɢɯ ɦɨɥɟɤɭɥ Ʌɿɝɚɧɞ1-Ʌɿɝɚɧɞ2, ɜɿɞɩɨɜɿɞɧɨ, ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɽɸ (ɪɢɫ. 1.1) [2, 3]. Ʌɿɝɚɧɞ1-Ʌɿɝɚɧɞ1 Ʌɿɝɚɧɞ1-Ʌɿɝɚɧɞ2 (ɚ) ( ɛ) Ɋɢɫɭɧɨɤ 1.1 ɋɚɦɨɚɫɨɰɿɚɰɿɹ (ɚ) ɬɚ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɹ (ɛ) ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ 28 Ʉɪɿɦ ɡɚɫɬɨɫɭɜɚɧɧɹ ɜ ɹɤɨɫɬɿ ɮɚɪɦɚɰɟɜɬɢɱɧɢɯ ɩɪɟɩɚɪɚɬɿɜ, ɚɪɨɦɚɬɢɱɧɿ ɫɩɨɥɭɤɢ ɩɪɨɬɹɝɨɦ ɛɿɥɶɲ ɧɿɠ ɩɿɜɫɬɨɥɿɬɬɹ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶɫɹ ɹɤ ɦɨɞɟɥɶɧɿ ɫɢɫɬɟɦɢ ɞɥɹ ɞɨɫɥɿɞɠɟɧɧɹ ɦɟɯɚɧɿɡɦɿɜ ɮɿɡɢɱɧɢɯ ɜɡɚɽɦɨɞɿɣ, ɹɤɿ ɜɿɞɿɝɪɚɸɬɶ ɿɫɬɨɬɧɭ ɪɨɥɶ ɭ ɫɬɚɛɿɥɿɡɚɰɿʀ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ, ɛɿɥɤɿɜ ɬɚ ɿɧɲɢɯ ɦɨɥɟɤɭɥɹɪɧɨɛɿɨɥɨɝɿɱɧɢɯ ɫɢɫɬɟɦ [4, 5]. Ʉɪɿɦ ɬɨɝɨ, ɧɚ ɞɚɧɢɣ ɱɚɫ ɪɟɡɭɥɶɬɚɬɢ ɞɨɫɥɿɞɠɟɧɶ ɦɟɯɚɧɿɡɦɿɜ ɚɝɪɟɝɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɫɬɚɧɨɜɥɹɬɶ ɜɟɥɢɤɢɣ ɿɧɬɟɪɟɫ ɡɚɜɞɹɤɢ ɪɨɥɿ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɜɡɚɽɦɨɞɿɣ ɭ ɮɨɪɦɭɜɚɧɧɿ ɫɭɩɪɚɦɨɥɟɤɭɥɹɪɧɢɯ ɫɬɪɭɤɬɭɪ, ɹɤɿ ɡɧɚɯɨɞɹɬɶ ɡɚɫɬɨɫɭɜɚɧɧɹ ɜ ɫɭɱɚɫɧɢɯ ɧɚɧɨɬɟɯɧɨɥɨɝɿɹɯ [6, 7]. Ɉɫɬɚɧɧɿɦ ɱɚɫɨɦ ɛɭɥɨ ɞɨɫɹɝɧɭɬɨ ɡɧɚɱɧɨɝɨ ɩɪɨɝɪɟɫɭ ɜ ɪɨɡɭɦɿɧɧɿ ɫɬɪɭɤɬɭɪɧɢɯ ɿ ɞɢɧɚɦɿɱɧɢɯ ɜɥɚɫɬɢɜɨɫɬɟɣ ɛɚɝɚɬɶɨɯ ɤɨɦɩɥɟɤɫɿɜ ɥɿɝɚɧɞ-ȾɇɄ [812]. ɐɹ ɿɧɮɨɪɦɚɰɿɹ ɡɚɛɟɡɩɟɱɢɥɚ ɨɫɧɨɜɧɟ ɭɹɜɥɟɧɧɹ ɩɪɨ ɩɪɨɟɤɬɭɜɚɧɧɹ ɬɚ ɪɨɡɪɨɛɤɭ ɛɿɥɶɲ ɟɮɟɤɬɢɜɧɢɯ ɯɿɦɿɨɬɟɪɚɩɟɜɬɢɱɧɢɯ ɩɪɟɩɚɪɚɬɿɜ ɞɪɭɝɨɝɨ ɿ ɬɪɟɬɶɨɝɨ ɩɨɤɨɥɿɧɧɹ ɞɥɹ ɭɫɩɿɲɧɨɝɨ ɥɿɤɭɜɚɧɧɹ ɛɚɝɚɬɶɨɯ ɜɢɞɿɜ ɪɚɤɭ [13]. ɉɪɨɬɟ, ɩɢɬɚɧɧɹ ɩɪɨ ɡɜ'ɹɡɨɤ ɮɿɡɢɤɨ-ɯɿɦɿɱɧɢɯ ɜɥɚɫɬɢɜɨɫɬɟɣ ɰɢɯ ɤɨɦɩɥɟɤɫɿɜ ɡ ʀɯ ɦɟɞɢɤɨ-ɛɿɨɥɨɝɿɱɧɨɸ ɟɮɟɤɬɢɜɧɿɫɬɸ ɡɚɥɢɲɚɽɬɶɫɹ ɧɟɡ'ɹɫɨɜɚɧɢɦ. 1.1 Ⱥɪɨɦɚɬɢɱɧɿ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɿ ɪɟɱɨɜɢɧɢ 1.1.1 Ɂɚɝɚɥɶɧɿ ɜɿɞɨɦɨɫɬɿ ɩɪɨ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɿ ɪɟɱɨɜɢɧɢ ɋɩɟɰɢɮɿɱɧɨɸ ɨɫɨɛɥɢɜɿɫɬɸ ɝɪɭɩɢ ɚɪɨɦɚɬɢɱɧɢɯ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɽ ɧɚɹɜɧɿɫɬɶ ɜ ʀɯ ɫɬɪɭɤɬɭɪɿ ɩɥɨɫɤɨɝɨ ɯɪɨɦɨɮɨɪɭ, ɭɬɜɨɪɟɧɨɝɨ ɫɩɨɥɭɱɟɧɧɹɦ ɞɟɤɿɥɶɤɨɯ ɚɪɨɦɚɬɢɱɧɢɯ ɝɟɬɟɪɨɰɢɤɥɿɜ. Ɍɚɤɚ ɛɭɞɨɜɚ ɦɨɥɟɤɭɥɢ ɜɢɹɜɥɹɽɬɶɫɹ ɝɟɨɦɟɬɪɢɱɧɨ ɩɨɞɿɛɧɨɸ ɩɚɪɚɦ ɨɫɧɨɜ, ɳɨ ɭɬɜɨɪɸɸɬɶ ɩɟɪɜɢɧɧɭ ɫɬɪɭɤɬɭɪɭ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ. ɐɟ ɞɨɡɜɨɥɹɽ ɚɪɨɦɚɬɢɱɧɢɦ ȻȺɊ ɟɮɟɤɬɢɜɧɨ ɜɡɚɽɦɨɞɿɹɬɢ ɡ ȾɇɄ, ɭɬɜɨɪɸɸɱɢ ɧɟɤɨɜɚɥɟɧɬɧɨ ɡɜ'ɹɡɚɧɿ ɤɨɦɩɥɟɤɫɢ ȾɇɄ-ɥɿɝɚɧɞ. ɇɚ ɨɫɧɨɜɿ ɜɡɚɽɦɨɞɿʀ ȾɇɄ ɡ ɚɪɨɦɚɬɢɱɧɢɦɢ ȻȺɊ ɡɞɿɣɫɧɸɽɬɶɫɹ ɛɚɝɚɬɨ ɛɿɨɥɨɝɿɱɧɢɯ ɩɪɨɰɟɫɿɜ: ɜɿɞ ɭɫɿɯ ɟɬɚɩɿɜ ɛɿɨɫɢɧɬɟɡɭ ɬɚ ɣɨɝɨ ɪɟɝɭɥɹɰɿʀ ɜ ɤɥɿɬɢɧɿ ɞɨ ɦɨɥɟɤɭɥɹɪɧɢɯ ɟɮɟɤɬɿɜ ɪɿɡɧɢɯ ɮɚɪɦɚɤɨɥɨɝɿɱɧɢɯ ɩɪɟɩɚɪɚɬɿɜ [1, 14]. Ʉɪɿɦ ɬɨɝɨ 29 ɡɜ'ɹɡɭɜɚɧɧɹ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ ɡ ȾɇɄ ɩɨɪɭɲɭɽ ʀʀ ɛɿɨɥɨɝɿɱɧɿ ɮɭɧɤɰɿʀ, ɝɨɥɨɜɧɢɦ ɱɢɧɨɦ, ɭ ɪɟɡɭɥɶɬɚɬɿ ɡɦɿɧɢ ɤɨɧɮɨɪɦɚɰɿʀ ȾɇɄ ɚɛɨ ɫɬɟɪɢɱɧɨɝɨ ɟɤɪɚɧɭɜɚɧɧɹ ɰɢɯ ɦɚɤɪɨɦɨɥɟɤɭɥ ɩɪɢ ɜɚɠɥɢɜɢɯ ɦɟɬɚɛɨɥɿɱɧɢɯ ɩɪɨɰɟɫɚɯ [15-19]. Ⱦɨ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ɜɿɞɧɨɫɹɬɶɫɹ ɦɭɬɚɝɟɧɧɿ ɬɚ ɤɚɧɰɟɪɨɝɟɧɧɿ ɪɟɱɨɜɢɧɢ, ɞɟɹɤɿ ɩɪɨɬɢɩɭɯɥɢɧɧɿ ɚɧɬɢɛɿɨɬɢɤɢ, ɜɿɬɚɦɿɧɢ, ɤɨɦɩɨɧɟɧɬɢ ɩɪɨɞɭɤɬɿɜ ɯɚɪɱɭɜɚɧɧɹ. ɍɫɿ ɜɨɧɢ ɲɢɪɨɤɨ ɡɚɫɬɨɫɨɜɭɸɬɶɫɹ ɜ ɦɨɥɟɤɭɥɹɪɧɨ-ɛɿɨɥɨɝɿɱɧɢɯ ɿ ɮɚɪɦɚɤɨɥɨɝɿɱɧɢɯ ɞɨɫɥɿɞɠɟɧɧɹɯ ɬɚ ɭ ɤɥɿɧɿɱɧɿɣ ɩɪɚɤɬɢɰɿ [20]. Ⱥɤɪɢɞɢɧɨɜɿ – ɚɤɪɢɞɢɧɨɜɢɣ ɩɨɦɚɪɚɧɱɟɜɢɣ (AO) ɿ ɩɪɨɮɥɚɜɿɧ (PRF) – ɿ ɮɟɧɚɧɬɪɢɞɢɧɨɜɿ – ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ (EB) ɿ ɩɪɨɩɿɞɿɸ ɣɨɞɢɞ (PI) – ɛɚɪɜɧɢɤɢ ɜɿɞɧɨɫɹɬɶɫɹ ɞɨ ɬɢɩɨɜɢɯ ɦɭɬɚɝɟɧɧɢɯ ɚɝɟɧɬɿɜ (ɤɚɧɰɟɪɨɝɟɧɿɜ), ɞɿɹ ɹɤɢɯ ɡɚɫɧɨɜɚɧɚ ɧɚ ʀɯ ɡɞɚɬɧɨɫɬɿ ɜɡɚɽɦɨɞɿɹɬɢ ɡ ȾɇɄ ɭ ɪɟɡɭɥɶɬɚɬɿ ɜɛɭɞɨɜɭɜɚɧɧɹ (ɿɧɬɟɪɤɚɥɹɰɿʀ) ɯɪɨɦɨɮɨɪɿɜ ɦɿɠ ɩɥɨɳɢɧɚɦɢ ɨɫɧɨɜ ȾɇɄ (ɿɧɬɟɪɤɚɥɹɰɿɣɧɢɣ ɬɢɩ ɡɜ'ɹɡɭɜɚɧɧɹ). Ⱥɧɬɪɚɰɢɤɥɿɧɨɜɿ ɚɧɬɢɛɿɨɬɢɤɢ ɞɚɭɧɨɦɿɰɢɧ (DAU), ɞɨɤɫɨɪɭɛɿɰɢɧ (DOX), ɧɨɝɚɥɚɦɿɰɢɧ (NOG), ɧɨɜɚɧɬɪɨɧ (NOV) ɿ ɬɨɩɨɬɟɤɚɧ ɽ ɟɮɟɤɬɢɜɧɢɦɢ ɩɪɨɬɢ ɩɭɯɥɢɧ ɿ ɥɟɣɤɨɡɿɜ. ɏɿɧɨɥɨɧɨɜɿ ɚɧɬɢɛɿɨɬɢɤɢ – ɧɨɪɮɥɨɤɫɚɰɢɧ (NOR) ɬɚ ɨɮɥɨɤɫɚɰɢɧ, ɩɪɨɹɜɥɹɸɬɶ ɲɢɪɨɤɢɣ ɫɩɟɤɬɪ ɚɧɬɢɛɚɤɬɟɪɿɚɥɶɧɨʀ ɚɤɬɢɜɧɨɫɬɿ. ȼɜɚɠɚɸɬɶ, ɳɨ ɜɡɚɽɦɨɞɿɹ ɡ ȾɇɄ ɽ ɨɫɧɨɜɧɨɸ ɩɪɢɱɢɧɨɸ ɩɪɨɬɢɩɭɯɥɢɧɧɨʀ ɚɤɬɢɜɧɨɫɬɿ, ɹɤɭ ɩɪɨɹɜɥɹɸɬɶ ɰɿ ɚɧɬɢɛɿɨɬɢɤɢ, ɳɨ ɡɭɦɨɜɢɥɨ ɲɢɪɨɤɟ ɜɢɤɨɪɢɫɬɚɧɧɹ ʀɯ ɞɥɹ ɯɿɦɿɨɬɟɪɚɩɿʀ ɛɚɝɚɬɶɨɯ ɜɢɞɿɜ ɪɚɤɨɜɢɯ ɡɚɯɜɨɪɸɜɚɧɶ [18, 21, 22]. ɉɪɨɬɢɩɭɯɥɢɧɧɿ ɚɧɬɢɛɿɨɬɢɤɢ ɜ ɤɥɿɬɢɧɿ ɜɛɭɞɨɜɭɸɬɶɫɹ ɞɨ ɹɞɟɪɧɨʀ ȾɇɄ ɿ ɜɢɤɥɢɤɚɸɬɶ ɯɪɨɦɨɫɨɦɧɿ ɚɛɟɪɚɰɿʀ [23, 24]. Ⱥɪɨɦɚɬɢɱɧɿ ɜɿɬɚɦɿɧɢ ɪɢɛɨɮɥɚɜɿɧ (RBF), ɧɿɤɨɬɢɧɚɦɿɞ (NMD) ɿ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ (FMN) ɜɢɤɨɪɢɫɬɨɜɭɸɬɶɫɹ ɜ ɹɤɨɫɬɿ ɚɧɬɢɨɤɫɢɞɚɧɬɿɜ ɭ ɯɿɦɿɨɬɟɪɚɩɿʀ. Ɇɟɬɢɥɤɫɚɧɬɢɧɢ ɤɨɮɟʀɧ (CAF), ɬɟɨɮɿɥɿɧ (TPH) ɿ ɬɟɨɛɪɨɦɿɧ (THB), ɹɤɿ ɩɪɢɫɭɬɧɿ ɭ ɜɢɫɨɤɢɯ ɤɨɧɰɟɧɬɪɚɰɿɹɯ ɭ ɩɪɨɞɭɤɬɚɯ ɯɚɪɱɭɜɚɧɧɹ, ɬɚɤɨɠ ɽ ɩɪɟɞɫɬɚɜɧɢɤɚɦɢ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ɿ ɦɚɸɬɶ ɩɟɜɧɿ ɦɟɞɢɤɨ-ɛɿɨɥɨɝɿɱɧɿ ɜɥɚɫɬɢɜɨɫɬɿ [18, 24]. 30 1.1.2 Ɇɭɬɚɝɟɧɢ ɩɪɨɮɥɚɜɿɧ ɿ ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ Ⱥɤɪɢɞɢɧɨɜɿ ɛɚɪɜɧɢɤɢ ɦɚɸɬɶ ɛɚɤɬɟɪɿɨɫɬɚɬɢɱɧɿ ɿ ɦɭɬɚɝɟɧɧɿ ɜɥɚɫɬɢɜɨɫɬɿ ɜɧɚɫɥɿɞɨɤ ʀɯ ɡɞɚɬɧɨɫɬɿ ɡɜ'ɹɡɭɜɚɬɢɫɹ ɡ ɧɭɤɥɟʀɧɨɜɢɦɢ ɤɢɫɥɨɬɚɦɢ. Ʉɨɦɩɥɟɤɫɢ ɚɤɪɢɞɢɧɨɜɢɯ ɛɚɪɜɧɢɤɿɜ ɦɨɠɭɬɶ ɛɭɬɢ ɜɢɤɨɪɢɫɬɚɧɿ ɹɤ ɦɨɞɟɥɶɧɿ ɫɢɫɬɟɦɢ ɞɥɹ ɞɨɫɥɿɞɠɟɧɧɹ ɪɨɥɿ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɢɯ ɿ ɝɿɞɪɨɮɨɛɧɢɯ ɜɡɚɽɦɨɞɿɣ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ (ɫɬɟɤɿɧɝ-ɜɡɚɽɦɨɞɿʀ), ɚ ɬɚɤɨɠ ɟɥɟɤɬɪɨɫɬɚɬɢɱɧɢɯ ɜɡɚɽɦɨɞɿɣ ʀɯ ɡɚɪɹɞɠɟɧɢɯ ɛɿɱɧɢɯ ɝɪɭɩ ɭ ɮɨɪɦɭɜɚɧɧɿ ɫɬɚɛɿɥɶɧɢɯ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɤɨɦɩɥɟɤɫɿɜ ɡ ɛɿɨɥɨɝɿɱɧɢɦɢ ɦɚɤɪɨɦɨɥɟɤɭɥɚɦɢ ɜ ɪɨɡɱɢɧɿ. ɉɪɨɮɥɚɜɿɧ (PRF, 3,6-ɞɿɚɦɿɧɨɚɤɪɢɞɢɧ, ɪɢɫ. 1.2 ɚ) ɜɢɤɨɪɢɫɬɨɜɭɽɬɶɫɹ ɜ ɮɨɪɦɿ ɫɨɥɟɣ ɞɢɝɿɞɪɨɯɥɨɪɢɞɭ ɿ ɝɟɦɿɫɭɥɶɮɚɬɚ ɹɤ ɞɟɡɢɧɮɿɤɭɸɱɢɣ ɛɚɤɬɟɪɢɨɫɬɚɬɢɱɧɢɣ ɩɪɟɩɚɪɚɬ [25], ɦɚɽ ɚɧɬɢɛɚɤɬɟɪɿɚɥɶɧɿ ɜɥɚɫɬɢɜɨɫɬɿ ɜɿɞɧɨɫɧɨ ɪɿɡɧɢɯ ɲɬɚɦɿɜ ɝɪɚɦɩɨɡɢɬɢɜɧɢɯ ɛɚɤɬɟɪɿɣ, ɚ ɬɚɤɨɠ ɩɪɨɹɜɥɹɽ ɩɪɨɬɢɦɚɥɹɪɿɣɧɭ ɬɚ ɚɧɬɢɜɿɪɭɫɧɭ ɚɤɬɢɜɧɿɫɬɶ [26, 27]. Ⱦɥɹ ɩɨɹɫɧɟɧɧɹ ɩɟɪɟɥɿɱɟɧɢɯ ɜɥɚɫɬɢɜɨɫɬɟɣ ɩɪɨɮɥɚɜɿɧɭ ɛɭɥɨ ɜɢɫɥɨɜɥɟɧɨ ɩɪɢɩɭɳɟɧɧɹ ɩɪɨ ɣɨɝɨ ɛɟɡɩɨɫɟɪɟɞɧɽ ɡɜ'ɹɡɭɜɚɧɧɹ ɡ ɧɭɤɥɟʀɧɨɜɢɦɢ ɤɢɫɥɨɬɚɦɢ, ɹɤɟ ɜɢɤɥɢɤɚɽ ɩɨɪɭɲɟɧɧɹ ɫɢɧɬɟɡɭ ȾɇɄ ɿ ɩɨɹɜɭ ɜɟɥɢɤɨʀ ɤɿɥɶɤɨɫɬɿ ɞɟɥɟɰɿɣɧɢɯ ɦɭɬɚɰɿɣ [28]. NH2 BrH2N N + CH2CH3 H2N + N H NH2 (ɚ) ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ (ɛ) (ɛ) Ɋɢɫɭɧɨɤ 1.2 ɋɬɪɭɤɬɭɪɧɿ ɮɨɪɦɭɥɢ ɦɨɥɟɤɭɥ ɩɪɨɮɥɚɜɿɧɭ (ɚ) ɬɚ ɍ ɪɨɛɨɬɿ [29] ɩɪɢ ɞɨɫɥɿɞɠɟɧɧɿ ɫɢɫɬɟɦ, ɹɤɿ ɦɿɫɬɹɬɶ ȾɇɄ ɬɚ ɪɿɡɧɿ ɤɨɧɰɟɧɬɪɚɰɿʀ PRF ɛɭɥɨ ɡɪɨɛɥɟɧɨ ɧɚɫɬɭɩɧɿ ɜɢɫɧɨɜɤɢ. Ɂɚɥɟɠɧɨ ɜɿɞ 31 ɫɩɿɜɜɿɞɧɨɲɟɧɧɹ ɤɨɧɰɟɧɬɪɚɰɿɣ PRF/ȾɇɄ ɿɫɧɭɸɬɶ ɞɜɚ ɬɢɩɢ ɡɜ'ɹɡɭɜɚɧɧɹ: «ɫɢɥɶɧɟ ɡɜ'ɹɡɭɜɚɧɧɹ» ɥɿɝɚɧɞɭ (ɪɿɜɧɨɜɚɠɧɚ ɤɨɧɫɬɚɧɬɚ ɡɜ'ɹɡɭɜɚɧɧɹ ~ 106 M-1) ɩɪɢ ɧɢɡɶɤɢɯ ɤɨɧɰɟɧɬɪɚɰɿɹɯ PRF ɿ «ɫɥɚɛɤɟ ɡɜ'ɹɡɭɜɚɧɧɹ» ɚɫɨɰɿɚɬɿɜ PRF ɩɪɢ ɜɢɫɨɤɢɯ ɤɨɧɰɟɧɬɪɚɰɿɹɯ ɥɿɝɚɧɞɭ. Ⱦɥɹ ɨɩɢɫɭ «ɫɢɥɶɧɨɝɨ ɡɜ'ɹɡɭɜɚɧɧɹ» PRF ɡ ȾɇɄ ɜɩɟɪɲɟ Ʌɟɪɦɚɧɨɦ ɛɭɥɚ ɡɚɩɪɨɩɨɧɨɜɚɧɚ ɿɧɬɟɪɤɚɥɹɰɿɣɧɚ ɦɨɞɟɥɶ [30]. ȼɿɞɩɨɜɿɞɧɨ ɞɨ ɰɿɽʀ ɦɨɞɟɥɿ ɦɨɥɟɤɭɥɚ PRF ɜɛɭɞɨɜɭɽɬɶɫɹ ɦɿɠ ɩɥɨɳɢɧɚɦɢ ɩɚɪ ɨɫɧɨɜ ɞɨ ɩɨɞɜɿɣɧɨʀ ɫɩɿɪɚɥɿ ȾɇɄ ɡ ɛɨɤɭ ɜɟɥɢɤɨɝɨ ɠɨɥɨɛɤɚ [31-33], ɳɨ ɩɪɢɡɜɨɞɢɬɶ ɞɨ ɩɨɞɨɜɠɟɧɧɹ ɿ ɪɨɡɤɪɭɱɭɜɚɧɧɹ ȾɇɄ. ɉɪɢ ɰɶɨɦɭ ɩɥɨɳɢɧɚ ɿɧɬɟɪɤɚɥɶɨɜɚɧɨɝɨ ɯɪɨɦɨɮɨɪɭ PRF ɨɪɿɽɧɬɨɜɚɧɚ ɩɟɪɩɟɧɞɢɤɭɥɹɪɧɨ ɞɨ ɨɫɿ ɩɨɞɜɿɣɧɨʀ ɫɩɿɪɚɥɿ ȾɇɄ, ɚ ɣɨɝɨ ɩɨɡɞɨɜɠɧɹ ɜɿɫɶ ɩɚɪɚɥɟɥɶɧɚ ɞɨɜɝɿɣ ɨɫɿ ɩɚɪɢ ɨɫɧɨɜ. Ɏɟɧɚɧɬɪɢɞɢɧɨɜɢɣ ɩɪɟɩɚɪɚɬ ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ (EB, 3,8-ɞɿɚɦɿɧɨ-5-ɟɬɢɥ6-ɮɟɧɿɥɮɟɧɚɧɬɪɢɞɿɧɭɦ ɛɪɨɦɢɞ, ɪɢɫ. 1.2 ɛ) ɬɚɤɨɠ ɡɜ'ɹɡɭɽɬɶɫɹ ɡ ȾɇɄ ɡɚ ɞɨɩɨɦɨɝɨɸ ɿɧɬɟɪɤɚɥɹɰɿʀ [8, 34]. Ɇɨɥɟɤɭɥɚ ȿȼ ɜɛɭɞɨɜɭɽɬɶɫɹ ɫɜɨʀɦ ɯɪɨɦɨɮɨɪɨɦ ɞɨ ɩɨɞɜɿɣɧɨʀ ɫɩɿɪɚɥɿ ɡ ɛɨɤɭ ɦɚɥɨɝɨ ɠɨɥɨɛɤɚ, ɜ ɹɤɨɦɭ ɪɨɡɦɿɳɭɽɬɶɫɹ ʀʀ ɮɟɧɨɥɶɧɟ ɤɿɥɶɰɟ [35]. Ɂɚɜɞɹɤɢ ɰɢɦ ɜɥɚɫɬɢɜɨɫɬɹɦ, ȿȼ ɡɧɚɣɲɨɜ ɲɢɪɨɤɟ ɡɚɫɬɨɫɭɜɚɧɧɹ ɜ ɛɿɨɯɿɦɿɱɧɢɯ ɬɚ ɮɿɡɢɱɧɢɯ ɞɨɫɥɿɞɠɟɧɧɹɯ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ. ȼɿɧ ɬɚɤɨɠ ɲɢɪɨɤɨ ɜɢɤɨɪɢɫɬɨɜɭɽɬɶɫɹ ɜ ɥɚɛɨɪɚɬɨɪɧɿɣ ɩɪɚɤɬɢɰɿ ɜ ɹɤɨɫɬɿ ɮɥɭɨɪɟɫɰɟɧɬɧɨɝɨ ɦɚɪɤɟɪɚ ɞɜɨɫɩɿɪɚɥɶɧɨʀ ȾɇɄ ɬɚ ɹɤ ɦɨɞɟɥɶɧɚ ɫɢɫɬɟɦɚ ɞɥɹ ɞɨɫɥɿɞɠɟɧɧɹ ɩɨɜɟɞɿɧɤɢ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ [36]. ɇɟɳɨɞɚɜɧɿ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɿ ɞɨɫɥɿɞɠɟɧɧɹ [37, 38] ɜɡɚɽɦɨɞɿʀ EB ɡ ȾɇɄ ɩɨɤɚɡɚɥɢ, ɳɨ ɰɟɣ ɥɿɝɚɧɞ ɦɨɠɟ ɡɜ'ɹɡɭɜɚɬɢɫɹ ɡ ɩɨɥɿɧɭɤɥɟɨɬɢɞɚɦɢ ɞɟɤɿɥɶɤɨɦɚ ɫɩɨɫɨɛɚɦɢ. Ɍɟɨɪɟɬɢɱɧɿ ɞɨɫɥɿɞɠɟɧɧɹ ɤɪɢɜɢɯ ɩɥɚɜɥɟɧɧɹ ɤɨɦɩɥɟɤɫɿɜ ȾɇɄ-EB [37] ɞɨɡɜɨɥɢɥɢ ɜɫɬɚɧɨɜɢɬɢ, ɳɨ, ɤɪɿɦ ɭɬɜɨɪɟɧɧɹ ɿɧɬɟɪɤɚɥɹɰɿɣɧɢɯ ɤɨɦɩɥɟɤɫɿɜ ȾɇɄ ɡ EB, ɡɚ ɩɟɜɧɢɯ ɭɦɨɜ ɦɨɠɥɢɜɟ ɮɨɪɦɭɜɚɧɧɹ ɤɨɦɩɥɟɤɫɿɜ ɡɚ ɬɢɩɨɦ ɡɨɜɧɿɲɧɶɨɝɨ ɡɜ'ɹɡɭɜɚɧɧɹ. Ʉɪɿɦ ɬɨɝɨ ɡɚ ɞɨɩɨɦɨɝɨɸ ɞɢɮɟɪɟɧɰɿɚɥɶɧɨʀ ɿɦɩɭɥɶɫɧɨʀ ɜɨɥɶɬɚɦɩɟɪɨɦɟɬɪɿʀ [38] ɚɜɬɨɪɚɦɢ ɡɪɨɛɥɟɧɨ ɜɢɫɧɨɜɨɤ, ɳɨ ɩɪɨɹɜɥɹɸɬɶɫɹ ɹɤ ɦɿɧɿɦɭɦ ɞɜɚ ɫɩɨɫɨɛɢ ɜɡɚɽɦɨɞɿʀ EB ɡ ȾɇɄ: 1) ɿɧɬɟɪɤɚɥɹɰɿɹ ɬɚ 32 ɟɥɟɤɬɪɨɫɬɚɬɢɱɧɚ ɜɡɚɽɦɨɞɿɹ ɩɪɢ ɧɢɡɶɤɿɣ ɿɨɧɧɿɣ ɫɢɥɿ, ɬɚ 2) ɧɚɩɿɜɿɧɬɟɪɤɚɥɹɰɿɹ ɬɚ ɟɥɟɤɬɪɨɫɬɚɬɢɱɧɚ ɜɡɚɽɦɨɞɿɹ ɩɪɢ ɛɿɥɶɲ ɜɢɫɨɤɿɣ ɿɨɧɧɿɣ ɫɢɥɿ ɪɨɡɱɢɧɭ. 1.1.3 Ɇɟɬɢɥɤɫɚɧɬɢɧɢ ɤɨɮɟʀɧ ɿ ɬɟɨɮɿɥɿɧ Ɇɟɬɢɥɤɫɚɧɬɢɧɢ ɽ ɜɚɠɥɢɜɢɦɢ ɩɪɟɞɫɬɚɜɧɢɤɚɦɢ ɤɥɚɫɭ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɪɟɱɨɜɢɧ, ɹɤɿ ɩɪɢɫɭɬɧɿ ɭ ɜɟɥɢɤɿɣ ɤɿɥɶɤɨɫɬɿ ɜ ɪɨɫɥɢɧɧɢɯ ɞɠɟɪɟɥɚɯ ɿ ɜɿɞɪɿɡɧɹɸɬɶɫɹ ɡɚ ɯɿɦɿɱɧɨɸ ɫɬɪɭɤɬɭɪɨɸ ɬɿɥɶɤɢ ɤɿɥɶɤɿɫɬɸ ɿ ɩɨɥɨɠɟɧɧɹɦ ɦɟɬɢɥɶɧɢɯ ɝɪɭɩ ɭ ɤɫɚɧɬɢɧɨɜɨɦɭ ɯɪɨɦɨɮɨɪɿ. Ʉɨɮɟʀɧ (CAF, 1,3,7-ɬɪɢɦɟɬɢɥɤɫɚɧɬɢɧ, ɪɢɫ. 1.3 ɚ) – ɰɟ ɚɥɤɚɥɨʀɞ, ɳɨ ɦɿɫɬɢɬɶɫɹ ɜ ɥɢɫɬɿ ɱɚɸ (ɛɥɢɡɶɤɨ 2%), ɧɚɫɿɧɧɿ ɤɚɜɢ (1-2%), ɝɨɪɿɯɚɯ ɤɨɥɚ, ɚ ɬɚɤɨɠ ɰɟ ɨɞɢɧ ɡ ɧɚɣɛɿɥɶɲ ɩɨɲɢɪɟɧɢɯ ɥɿɤɚɪɫɶɤɢɯ ɩɪɟɩɚɪɚɬɿɜ. Ɂɚ ɛɭɞɨɜɨɸ ɬɚ ɮɚɪɦɚɤɨɥɨɝɿɱɧɢɦɢ ɜɥɚɫɬɢɜɨɫɬɹɦɢ ɤɨɮɟʀɧ ɛɥɢɡɶɤɢɣ ɞɨ ɬɟɨɛɪɨɦɿɧɭ ɬɚ ɬɟɨɮɿɥɿɧɭ. ɍɫɿ ɬɪɢ ɚɥɤɚɥɨʀɞɢ ɽ ɩɨɯɿɞɧɢɦɢ ɩɭɪɢɧɭ ɿ ɜɿɞɧɨɫɹɬɶɫɹ ɞɨ ɝɪɭɩɢ ɦɟɬɢɥɤɫɚɧɬɢɧɿɜ. Ɂ ɰɢɯ ɚɥɤɚɥɨʀɞɿɜ ɧɚɣɫɢɥɶɧɿɲɢɣ ɡɛɭɞɠɭɸɱɢɣ ɜɩɥɢɜ ɧɚ ɰɟɧɬɪɚɥɶɧɭ ɧɟɪɜɨɜɭ ɫɢɫɬɟɦɭ (ɐɇɋ) ɧɚɞɚɽ CAF [39]. O CH3 O N1 6 5 7 9 CH3 N 8 O CH3 H H 5 7 N1 2 6 N 8 2 3 4 N CH3 N 3 4 9 H O N CH3 N (ɚ) ( ɛ) Ɋɢɫɭɧɨɤ 1.3 ɋɬɪɭɤɬɭɪɧɿ ɮɨɪɦɭɥɢ ɦɨɥɟɤɭɥ ɤɨɮɟʀɧɭ (ɚ) ɿ ɬɟɨɮɿɥɿɧɭ (ɛ) Ʉɨɮɟʀɧ ɜɩɥɢɜɚɽ ɧɚ ɛɚɝɚɬɨ ɩɪɨɰɟɫɿɜ, ɳɨ ɩɪɨɯɨɞɹɬɶ ɧɚ ɪɿɜɧɿ ɤɥɿɬɢɧ ɿ ɨɪɝɚɧɿɡɦɭ. Ⱦɨ ɬɚɤɢɯ ɩɪɨɰɟɫɿɜ ɜɿɞɧɨɫɹɬɶɫɹ: ɲɜɢɞɤɿɫɬɶ ɩɪɨɜɟɞɟɧɧɹ ɧɟɪɜɨɜɨɝɨ ɿɦɩɭɥɶɫɭ [40-42], ɮɨɫɮɨɪɢɥɸɜɚɧɧɹ ɿ ɞɟɮɨɫɮɨɪɢɥɸɜɚɧɧɹ ɪɟɰɟɩɬɨɪɿɜ [43], ɩɪɨɯɨɞɠɟɧɧɹ ɤɥɿɬɢɧɚɦɢ ɩɨɜɧɨɝɨ ɤɥɿɬɢɧɧɨɝɨ ɰɢɤɥɭ ɿ ɩɪɨɰɟɫɢ ɪɟɩɚɪɚɰɿʀ ȾɇɄ [44, 45], ɚ ɬɚɤɨɠ ɚɩɨɩɬɨɡ [46, 47]. Ɍɚɤɢɣ ɲɢɪɨɤɢɣ ɫɩɟɤɬɪ ɜɩɥɢɜɭ ɤɨɮɟʀɧɭ ɧɚ ɧɚɣɜɚɠɥɢɜɿɲɿ ɛɿɨɥɨɝɿɱɧɿ ɩɪɨɰɟɫɢ ɜɢɤɥɢɤɚɽ ɩɨɫɬɿɣɧɢɣ ɿɧɬɟɪɟɫ ɞɨ ɜɢɜɱɟɧɧɹ 33 ɦɨɥɟɤɭɥɹɪɧɢɯ ɦɟɯɚɧɿɡɦɿɜ ɣɨɝɨ ɞɿʀ. ȼɢɫɥɨɜɥɸɜɚɥɢɫɹ ɩɪɢɩɭɳɟɧɧɹ ɩɪɨ ɩɪɹɦɭ ɜɡɚɽɦɨɞɿɸ ɤɨɮɟʀɧɭ ɡ ɛɿɨɩɨɥɿɦɟɪɚɦɢ – ɩɪɨɬɟʀɧɚɦɢ ɿ ȾɇɄ, ɱɢɦ ɦɨɠɧɚ ɛɭɥɨ ɩɨɹɫɧɢɬɢ ɣɨɝɨ ɜɩɥɢɜ ɧɚ ɪɟɩɚɪɚɰɿɣɧɿ ɩɪɨɰɟɫɢ ɜ ɤɥɿɬɢɧɿ [48-50]. Ɍɟɨɮɿɥɿɧ (TPH, 1,3-ɞɿɦɟɬɢɥɤɫɚɧɬɢɧ, ɪɢɫ. 1.3 ɛ) ɜɩɥɢɜɚɽ ɧɚ ɪɿɡɧɿ ɮɭɧɤɰɿʀ ɨɪɝɚɧɿɡɦɭ, ɧɚɣɛɿɥɶɲ ɜɚɠɥɢɜɨɸ ɡ ɹɤɢɯ ɽ ɣɨɝɨ ɡɞɚɬɧɿɫɬɶ ɜɢɤɥɢɤɚɬɢ ɛɪɨɧɯɨɪɨɡɲɢɪɸɸɱɢɣ ɟɮɟɤɬ. ȼɿɧ ɦɚɽ ɫɬɢɦɭɥɸɸɱɭ ɞɿɸ ɧɚ ɰɟɧɬɪɚɥɶɧɭ ɧɟɪɜɨɜɭ ɫɢɫɬɟɦɭ, ɯɨɱɚ ɿ ɦɟɧɲ ɜɢɪɚɠɟɧɭ, ɧɿɠ ɭ ɤɨɮɟʀɧɭ; ɩɿɞɫɢɥɸɽ ɫɤɨɪɨɱɭɜɚɥɶɧɭ ɞɿɹɥɶɧɿɫɬɶ ɦɿɨɤɚɪɞɭ; ɞɟɳɨ ɪɨɡɲɢɪɸɽ ɩɟɪɢɮɟɪɢɱɧɿ, ɤɨɪɨɧɚɪɧɿ, ɥɟɝɟɧɟɜɿ ɬɚ ɧɢɪɤɨɜɿ ɫɭɞɢɧɢ; ɜɢɹɜɥɹɽ ɩɨɦɿɪɧɭ ɞɿɭɪɟɬɢɱɧɭ ɞɿɸ; ɩɪɢɝɧɿɱɭɽ ɚɝɪɟɝɚɰɿɸ ɬɪɨɦɛɨɰɢɬɿɜ; ɩɿɞɜɢɳɭɽ ɟɥɚɫɬɢɱɧɿɫɬɶ ɟɪɢɬɪɨɰɢɬɿɜ; ɝɚɥɶɦɭɽ ɜɢɜɿɥɶɧɟɧɧɹ ɨɩɚɫɢɫɬɢɦɢ ɤɥɿɬɢɧɚɦɢ ɦɟɞɿɚɬɨɪɿɜ ɚɥɟɪɝɿʀ (ɩɪɨɹɜɥɹɽ ɚɧɬɢɚɥɟɪɝɿɱɧɭ ɞɿɸ) [39]. ɍ ɦɟɯɚɧɿɡɦɿ ɞɿʀ ɬɟɨɮɿɥɿɧɭ, ɹɤ ɿ ɿɧɲɢɯ ɦɟɬɢɥɤɫɚɧɬɢɧɿɜ, ɩɟɜɧɭ ɪɨɥɶ ɜɿɞɿɝɪɚɸɬɶ ɿɧɝɿɛɭɜɚɧɧɹ ɮɨɫɮɨɞɿɟɫɬɟɪɚɡɢ ɿ ɧɚɤɨɩɢɱɟɧɧɹ ɜ ɬɤɚɧɢɧɚɯ ɰɢɤɥɿɱɧɨɝɨ 3',5'-ɚɞɟɧɨɡɢɧɦɨɧɨɮɨɫɮɚɬɭ. ɋɟɪɟɞ ɦɟɬɢɥɤɫɚɧɬɢɧɿɜ ɬɟɨɮɿɥɿɧ ɽ ɨɞɧɢɦ ɡ ɧɚɣɛɿɥɶɲ ɫɢɥɶɧɢɯ ɿɧɝɿɛɿɬɨɪɿɜ ɮɨɫɮɨɞɿɟɫɬɟɪɚɡɢ. ȼɢɹɜɥɟɧɚ ɨɫɬɚɧɧɿɦ ɱɚɫɨɦ ɡɞɚɬɧɿɫɬɶ ɬɟɨɮɿɥɿɧɭ ɛɥɨɤɭɜɚɬɢ ɚɞɟɧɨɡɢɧɨɜɿ (ɩɭɪɢɧɟɪɝɿɱɧɿ) ɪɟɰɟɩɬɨɪɢ ɦɚɽ ɨɫɨɛɥɢɜɟ ɡɧɚɱɟɧɧɹ ɜ ɣɨɝɨ ɦɨɥɟɤɭɥɹɪɧɨɦɭ ɦɟɯɚɧɿɡɦɿ ɞɿʀ. ɍ ɬɟɪɚɩɿʀ ɬɟɨɮɿɥɿɧ ɡɚɫɬɨɫɨɜɭɸɬɶ ɹɤ ɛɪɨɧɯɨɥɿɬɢɱɧɢɣ ɡɚɫɿɛ ɩɪɢ ɨɛɨɪɨɬɧɢɯ ɛɪɨɧɯɨɨɛɫɬɪɭɤɬɢɜɧɢɯ ɡɚɯɜɨɪɸɜɚɧɧɹɯ [39]. ɍɫɿ ɩɟɪɟɪɚɯɨɜɚɧɿ ɦɟɬɢɥɤɫɚɧɬɢɧɢ ɽ ɭɧɿɤɚɥɶɧɢɦ ɤɥɚɫɨɦ ɥɿɤɚɪɫɶɤɢɯ ɡɚɫɨɛɿɜ, ɳɨ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶɫɹ ɩɪɢ ɥɿɤɭɜɚɧɧɿ ɚɫɬɦɢ [51]. 1.1.4 Ɏɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ Ɏɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ (FMN, ɪɢɛɨɮɥɚɜɿɧ-5'-ɮɨɫɮɚɬ, ɪɢɫ. 1.4) – ɚɧɚɥɨɝ ɜɿɬɚɦɿɧɭ B2 (ɪɢɛɨɮɥɚɜɿɧɭ, RBF), ɹɤɢɣ ɜɢɤɨɧɭɽ ɤɚɬɚɥɿɬɢɱɧɭ ɮɭɧɤɰɿɸ ɜ ɤɥɿɬɢɧɚɯ ɭ ɫɤɥɚɞɿ ɛɚɝɚɬɶɨɯ ɨɤɢɫɧɨ-ɜɿɞɧɨɜɧɢɯ ɮɟɪɦɟɧɬɿɜ, ɬɚɤɢɯ ɹɤ ɨɤɫɢɞɨɪɟɞɭɤɬɚɡɢ, ɿ ɡɨɤɪɟɦɚ, ɚɟɪɨɛɧɿ ɞɟɝɿɞɪɨɝɟɧɚɡɢ. Ɏɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ ɜɯɨɞɢɬɶ ɞɨ ɩɪɨɫɬɟɬɢɱɧɨʀ ɝɪɭɩɢ ɮɥɚɜɨɩɪɨɬɟʀɧɿɜ, ɛɟɪɟ ɭɱɚɫɬɶ ɭ ɪɟɝɭɥɸɜɚɧɧɿ ɨɤɢɫɥɸɜɚɥɶɧɨ-ɜɿɞɧɨɜɧɢɯ ɩɪɨɰɟɫɿɜ ɿ ɜ ɩɟɪɟɧɟɫɟɧɧɿ ɜɨɞɧɸ. 34 OO P OO H C H HO C H H C OH HO C H H H3C 8 7 9 Ɋɢɫɭɧɨɤ 1.4. ɋɬɪɭɤɬɭɪɧɚ ɮɨɪɦɭɥɚ ɨɤɢɫɥɟɧɨʀ ɮɨɪɦɢ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ N 1 2 3 H C H 10 5 N O NH H 3C 6 4 N H O Ɋɢɛɨɮɥɚɜɿɧ ɲɢɪɨɤɨ ɪɨɫɩɨɜɫɸɞɠɟɧɢɣ ɭ ɩɪɢɪɨɞɿ ɜ ɦɿɤɪɨɨɪɝɚɧɿɡɦɚɯ ɬɚ ɜ ɪɨɫɥɢɧɧɢɯ ɿ ɬɜɚɪɢɧɧɢɯ ɤɥɿɬɢɧɚɯ. ɀɢɜɿ ɨɪɝɚɧɿɡɦɢ ɨɬɪɢɦɭɸɬɶ ɪɢɛɨɮɥɚɜɿɧ ɡ ʀɠɟɸ ɚɛɨ ɜ ɪɟɡɭɥɶɬɚɬɿ ɞɿɹɥɶɧɨɫɬɿ ɦɿɤɪɨɮɥɨɪɢ ɲɥɭɧɤɨɜɨ-ɤɢɲɤɨɜɨɝɨ ɬɪɚɤɬɭ. ɍ ɬɜɚɪɢɧɧɢɯ ɬɤɚɧɢɧɚɯ ɪɢɛɨɮɥɚɜɿɧ ɡɧɚɯɨɞɢɬɶɫɹ ɩɟɪɟɜɚɠɧɨ ɭ ɜɢɝɥɹɞɿ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ, ɮɥɚɜɿɧɚɞɟɧɿɧɞɢɧɭɤɥɟɨɬɢɞɭ (FAD) ɿ 8-Į-ɩɨɯɿɞɧɢɯ FAD, ɬɚ ɦɿɫɬɢɬɶɫɹ ɜ ɪɿɡɧɢɯ ɨɪɝɚɧɚɯ ɿ ɬɤɚɧɢɧɚɯ, ɦɚɣɠɟ ɜ ɭɫɿɯ ɚɟɪɨɛɧɢɯ ɤɥɿɬɢɧɚɯ [52]. ɇɚ ɜɿɞɦɿɧɭ ɜɿɞ RBF, ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ ɤɪɚɳɟ ɪɨɡɱɢɧɧɢɣ ɭ ɜɨɞɿ, ɬɨɦɭ FMN ɱɚɫɬɨ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶ ɹɤ ɦɨɞɟɥɶ ɜɿɬɚɦɿɧɭ B2 ɜ ɛɿɨɮɿɡɢɱɧɢɯ ɞɨɫɥɿɞɠɟɧɧɹɯ [53-56]. Ɏɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ ɡɚɛɟɡɩɟɱɭɽ ɩɟɪɟɧɟɫɟɧɧɹ ɞɜɨɯ ɚɬɨɦɿɜ ɜɨɞɧɸ ɜ ɨɤɢɫɧɨ-ɜɿɞɧɨɜɧɢɯ ɪɟɚɤɰɿɹɯ. Ɉɤɢɫɥɸɜɚɥɶɧɨ-ɜɿɞɧɨɜɧɿ ɩɪɨɰɟɫɢ, ɩɨɜ'ɹɡɚɧɿ ɡ ɩɟɪɟɧɨɫɨɦ ɩɪɨɬɨɧɿɜ ɬɚ ɟɥɟɤɬɪɨɧɿɜ ɜɿɞ ɫɭɛɫɬɪɚɬɭ, ɽ pH-ɡɚɥɟɠɧɢɦɢ. Ɍɨɦɭ ɜɢɜɱɟɧɧɹ ɫɬɪɭɤɬɭɪɧɨɝɨ ɫɬɚɧɭ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɩɪɢ ɮɿɡɿɨɥɨɝɿɱɧɢɯ ɡɧɚɱɟɧɧɹɯ ɤɢɫɥɨɬɧɨɫɬɿ ɫɟɪɟɞɨɜɢɳɚ (ɧɟɣɬɪɚɥɶɧɿ ɬɚ ɫɥɚɛɨɤɢɫɥɿ ɪɇ ~ 6,0-7,0) ɦɚɸɬɶ ɜɚɠɥɢɜɟ ɡɧɚɱɟɧɧɹ ɜ ɛɿɨɮɿɡɢɱɧɢɯ ɞɨɫɥɿɞɠɟɧɧɹɯ. ɍ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɠɟɪɟɥɚɯ ɽ ɿɧɮɨɪɦɚɰɿɹ, ɳɨ ɩɪɢɽɞɧɚɧɧɹ ɚɬɨɦɿɜ ɜɨɞɧɸ ɡɞɿɣɫɧɸɽɬɶɫɹ ɩɨ ɚɬɨɦɚɯ ɚɡɨɬɭ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ [57, 58], ɚɥɟ ɡɚ ɞɚɧɢɦɢ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɨɫɥɿɞɠɟɧɶ ɧɟ ɫɮɨɪɦɭɥɶɨɜɚɧɨ ɨɞɧɨɡɧɚɱɧɨɝɨ ɜɢɫɧɨɜɤɭ ɳɨɞɨ ɦɿɫɰɶ ɩɪɨɬɨɧɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN. 35 ɇɟɨɛɯɿɞɧɨ ɬɚɤɨɠ ɜɿɞɡɧɚɱɢɬɢ, ɳɨ ɜɚɠɥɢɜɢɦɢ ɞɥɹ ɦɨɥɟɤɭɥɹɪɧɨʀ ɛɿɨɮɿɡɢɤɢ ɽ ɞɨɫɥɿɞɠɟɧɧɹ, ɪɟɡɭɥɶɬɚɬɢ ɹɤɢɯ ɞɨɡɜɨɥɹɬɶ ɜɢɡɧɚɱɢɬɢ ɫɬɪɭɤɬɭɪɧɢɣ ɫɬɚɧ FMN, ɯɚɪɚɤɬɟɪɧɢɣ ɞɥɹ ɠɢɜɢɯ ɫɢɫɬɟɦ: ɦɨɧɨɦɟɪɧɚ ɚɛɨ ɚɫɨɰɿɣɨɜɚɧɚ ɮɨɪɦɚ. ɍ ɪɨɛɨɬɚɯ [55, 59] ɩɨɤɚɡɚɧɨ, ɳɨ ɜ ɧɟɣɬɪɚɥɶɧɨɦɭ ɫɟɪɟɞɨɜɢɳɿ FMN ɡɧɚɯɨɞɢɬɶɫɹ ɜ ɞɢɦɟɪɧɿɣ ɮɨɪɦɿ. Ɉɞɧɚɤ ɭ ɤɨɧɰɟɧɬɪɨɜɚɧɨɦɭ ɫɬɚɧɿ ɬɚ ɜ ɫɥɚɛɨɤɢɫɥɢɯ ɫɟɪɟɞɨɜɢɳɚɯ, ɳɨ ɽ ɛɿɥɶɲ ɯɚɪɚɤɬɟɪɧɢɦ ɞɥɹ ɠɢɜɢɯ ɨɪɝɚɧɿɡɦɿɜ, ɚɝɪɟɝɚɬɧɢɣ ɫɬɚɧ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɧɟ ɞɨɫɥɿɞɠɭɜɚɜɫɹ. 1.2 ɋɚɦɨɚɫɨɰɿɚɰɿɹ ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ȼɢɜɱɟɧɧɹ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɬɚ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ ɬɚ ʀɯ ɤɨɧɤɭɪɟɧɬɧɟ ɡɜ'ɹɡɭɜɚɧɧɹ ɡ ɦɿɲɟɧɹɦɢ – ɦɨɥɟɤɭɥɚɦɢ ȾɇɄ, ɽ ɜɚɠɥɢɜɢɦ ɚɫɩɟɤɬɨɦ ɩɪɨɛɥɟɦɢ ɦɨɥɟɤɭɥɹɪɧɢɯ ɜɡɚɽɦɨɞɿɣ [8]. ɐɿ ɞɨɫɥɿɞɠɟɧɧɹ ɫɬɚɧɨɜɥɹɬɶ ɿɧɬɟɪɟɫ ɧɟ ɬɿɥɶɤɢ ɡ ɬɨɱɤɢ ɡɨɪɭ ɜɢɜɱɟɧɧɹ ɮɿɡɢɤɨ-ɯɿɦɿɱɧɢɯ ɜɥɚɫɬɢɜɨɫɬɟɣ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ ɿ ɜɩɥɢɜɭ ɫɬɪɭɤɬɭɪɢ ɯɪɨɦɨɮɨɪɨɜ ɬɚ ʀɯ ɛɿɱɧɢɯ ɪɚɞɢɤɚɥɿɜ ɧɚ ɜɢɛɿɪɤɨɜɿɫɬɶ ɜɡɚɽɦɨɞɿʀ ɥɿɝɚɧɞɿɜ ɿ ȾɇɄ [3], ɚɥɟ ɿ ɡ ɬɨɱɤɢ ɡɨɪɭ ɮɚɪɦɚɤɨɥɨɝɿɱɧɨʀ ɚɤɬɢɜɧɨɫɬɿ, ɹɤɚ ɦɨɠɟ ɡɦɿɧɸɜɚɬɢɫɹ ɜ ɪɟɡɭɥɶɬɚɬɿ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ. Ⱦɜɚ ɧɚɣɛɿɥɶɲ ɩɨɲɢɪɟɧɢɯ ɩɪɢɤɥɚɞɢ ɬɚɤɨʀ ɩɪɨɛɥɟɦɢ – ɜɡɚɽɦɨɞɿʀ ɥɿɤɚɪɫɶɤɢɯ ɩɪɟɩɚɪɚɬɿɜ ɡ ɚɪɨɦɚɬɢɱɧɢɦɢ ɦɨɥɟɤɭɥɚɦɢ, ɳɨ ɜɯɨɞɹɬɶ ɞɨ ɫɤɥɚɞɭ ɩɪɨɞɭɤɬɿɜ ɯɚɪɱɭɜɚɧɧɹ (ɧɚɩɪɢɤɥɚɞ, ɤɨɮɟʀɧ, ɩɨɥɿɮɟɧɨɥɢ ɬɚ ɿɧ.) [60], ɿ ɜɢɤɨɪɢɫɬɚɧɧɹ ɥɿɤɚɪɫɶɤɢɯ ɩɪɟɩɚɪɚɬɿɜ ɭ ɤɨɦɛɿɧɨɜɚɧɿɣ ɯɿɦɿɨɬɟɪɚɩɿʀ [61]. Ɍɨɦɭ ɜɚɠɥɢɜɨ ɡɧɚɬɢ ɤɿɥɶɤɿɫɧɿ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ȻȺɊ ɿ ɜɤɥɚɞɢ ɪɿɡɧɢɯ ɜɡɚɽɦɨɞɿɣ ɜ ʀɯ ɫɬɚɛɿɥɿɡɚɰɿɸ ɞɥɹ ɬɨɝɨ, ɳɨɛ ɨɰɿɧɢɬɢ ɜɩɥɢɜ ɤɨɧɤɭɪɟɧɬɧɨɝɨ ɡɜ'ɹɡɭɜɚɧɧɹ ɪɿɡɧɢɯ ɩɪɟɩɚɪɚɬɿɜ ɧɚ ʀɯ ɜɡɚɽɦɨɞɿɸ ɡ ɦɨɥɟɤɭɥɚɦɢ ȾɇɄ [9, 14] ɚɛɨ ɩɪɨɬɟʀɧɚɦɢ [62]. Ⱥɪɨɦɚɬɢɱɧɿ ɦɨɥɟɤɭɥɢ ɦɚɸɬɶ ɩɥɨɫɤɿ ɝɟɬɟɪɨɰɢɤɥɿɱɧɿ ɫɬɪɭɤɬɭɪɢ, ɯɪɨɦɨɮɨɪ ɹɤɢɯ ɦɿɫɬɢɬɶ ɫɢɫɬɟɦɢ ɡɜ'ɹɡɚɧɢɯ ɩɨɞɜɿɣɧɢɯ C=C ɡɜ'ɹɡɤɿɜ ɡ ɞɟɥɨɤɚɥɿɡɨɜɚɧɢɦɢ ɧɚ ɧɢɯ S-ɟɥɟɤɬɪɨɧɚɦɢ. ɑɢɫɥɟɧɧɿ ɞɨɫɥɿɞɠɟɧɧɹ ɩɨɜɟɞɿɧɤɢ 36 ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ ɜɤɚɡɭɸɬɶ ɧɚ ɬɟ, ɳɨ ɞɥɹ ɬɚɤɢɯ ɫɩɨɥɭɤ ɩɟɪɟɜɚɠɧɢɦɢ ɽ ɧɟɤɨɜɚɥɟɧɬɧɿ ɜɡɚɽɦɨɞɿʀ ɬɢɩɭ ɜɟɪɬɢɤɚɥɶɧɢɯ ɫɬɟɤɿɧɝ-ɜɡɚɽɦɨɞɿɣ ɯɪɨɦɨɮɨɪɿɜ, ɹɤɿ ɩɪɢɡɜɨɞɹɬɶ ɞɨ ɮɨɪɦɭɜɚɧɧɹ ɫɬɨɩɨɤ ɚɛɨ ɚɝɪɟɝɚɬɿɜ ɡ ɱɢɫɥɨɦ ɦɨɧɨɦɟɪɿɜ ɭ ɚɝɪɟɝɚɬɿ ɞɜɚ ɬɚ ɛɿɥɶɲɟ [2]. ȿɧɟɪɝɟɬɢɱɧɢɣ ɟɮɟɤɬ ɧɟɤɨɜɚɥɟɧɬɧɢɯ ɜɡɚɽɦɨɞɿɣ, ɹɤɿ ɜɢɡɧɚɱɚɸɬɶ ɭɬɜɨɪɟɧɧɹ ɫɬɨɩɤɨɜɢɯ ɚɫɨɰɿɚɬɿɜ, ɦɨɠɧɚ ɩɨɪɿɜɧɹɬɢ ɡ ɟɧɟɪɝɟɬɢɤɨɸ ɬɟɩɥɨɜɨɝɨ ɪɭɯɭ, ɬɨɦɭ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɭ ɪɨɡɱɢɧɿ ɧɨɫɢɬɶ ɞɢɧɚɦɿɱɧɢɣ ɯɚɪɚɤɬɟɪ, ɹɤɢɣ ɩɪɨɹɜɥɹɽɬɶɫɹ ɜ ɲɜɢɞɤɨɦɭ ɭɬɜɨɪɟɧɧɿ ɬɚ ɪɭɣɧɭɜɚɧɧɿ ɤɨɦɩɥɟɤɫɿɜ ɦɨɥɟɤɭɥ. 1.2.1 ɋɚɦɨɚɫɨɰɿɚɰɿɹ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ Ⱦɨɫɥɿɞɠɟɧɧɹ ɩɪɨɰɟɫɿɜ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɩɪɨɜɨɞɢɥɢɫɹ ɞɥɹ ɩɨɹɫɧɟɧɧɹ ɜɟɪɬɢɤɚɥɶɧɨʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ (ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɩɨɯɿɞɧɢɯ ɧɭɤɥɟʀɧɨɜɢɯ ɨɫɧɨɜ) ɿ ɞɥɹ ɭɬɨɱɧɟɧɧɹ ɩɚɪɚɦɟɬɪɿɜ, ɨɬɪɢɦɚɧɢɯ ɭ ɪɟɡɭɥɶɬɚɬɿ ɪɿɡɧɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɨɫɥɿɞɠɟɧɶ ɡɚ ɭɱɚɫɬɸ ɰɢɯ ɫɩɨɥɭɤ [11]. Ɂɨɤɪɟɦɚ, ɛɭɥɨ ɩɨɤɚɡɚɧɨ, ɳɨ ɤɨɪɟɤɬɧɢɣ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɣ ɚɧɚɥɿɡ ɜɡɚɽɦɨɞɿʀ ɚɧɬɪɚɰɢɤɥɿɧɨɜɢɯ ɚɧɬɢɛɿɨɬɢɤɿɜ ɡ ȾɇɄ ɩɨɬɪɟɛɭɽ ɜɪɚɯɭɜɚɧɧɹ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɥɿɝɚɧɞɭ, ɹɤɳɨ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɿ ɤɨɧɰɟɧɬɪɚɰɿʀ, ɹɤɿ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶɫɹ, ɩɨɬɪɚɩɥɹɸɬɶ ɭ ɞɿɚɩɚɡɨɧ ɞɟɫɹɬɤɿɜ PM ɿ ɜɢɳɟ [63, 64]. Ɋɚɡɨɦ ɡ ɬɢɦ ɫɚɦɨɚɫɨɰɿɚɰɿɹ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɦɨɠɟ ɦɚɬɢ ɫɚɦɨɫɬɿɣɧɟ ɛɿɨɥɨɝɿɱɧɟ ɡɧɚɱɟɧɧɹ (ɞɢɜ. ɨɝɥɹɞɢ [11, 65]). Ɋɟɡɭɥɶɬɚɬɢ ɞɨɫɥɿɞɠɟɧɧɹ ɚɝɪɟɝɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ, ɩɪɨɜɟɞɟɧɿ ɪɿɡɧɢɦɢ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɦɢ ɦɟɬɨɞɚɦɢ [64, 66-68] ɩɨɤɚɡɚɥɢ, ɳɨ ɩɚɪɚɦɟɬɪɢ ʀɯ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɜ ɡɧɚɱɧɿɣ ɦɿɪɿ ɜɢɡɧɚɱɚɸɬɶɫɹ ɛɭɞɨɜɨɸ ɯɪɨɦɨɮɨɪɭ ɿ ɯɚɪɚɤɬɟɪɨɦ ɛɿɱɧɢɯ ɝɪɭɩ ɿ ɥɚɧɰɸɝɿɜ ɯɪɨɦɨɮɨɪɿɜ. Ɍɚɤ, ɪɿɜɧɨɜɚɠɧɚ ɤɨɧɫɬɚɧɬɚ ɚɫɨɰɿɚɰɿʀ KC ɨɞɧɨɡɧɚɱɧɨ ɩɨɜ'ɹɡɚɧɚ ɡ ɱɢɫɥɨɦ ɚɪɨɦɚɬɢɱɧɢɯ ɤɿɥɟɰɶ ɭ ɯɪɨɦɨɮɨɪɿ ɥɿɝɚɧɞɭ. ɇɚɣɦɟɧɲɨɸ ɫɩɨɪɿɞɧɟɧɿɫɬɸ ɞɨ ɚɝɪɟɝɚɰɿʀ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ ɦɚɸɬɶ ɥɿɝɚɧɞɢ, ɳɨ ɦɿɫɬɹɬɶ ɨɞɧɟ ɚɪɨɦɚɬɢɱɧɟ ɤɿɥɶɰɟ ɭ ɯɪɨɦɨɮɨɪɿ, ɧɚɩɪɢɤɥɚɞ, ɩɿɪɢɦɿɞɢɧ ɿ ɣɨɝɨ ɩɨɯɿɞɧɿ. Ⱦɚɧɿ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɨɫɥɿɞɠɟɧɶ ɫɜɿɞɱɚɬɶ ɩɪɨ ɬɟ, ɳɨ ɪɿɜɧɨɜɚɠɧɚ 37 ɤɨɧɫɬɚɧɬɚ ɚɫɨɰɿɚɰɿʀ ɩɿɪɢɦɿɞɢɧɿɜ ɧɟ ɩɟɪɟɜɢɳɭɽ 1 Ɇ-1 ɩɪɢ Ɍ = 298 Ʉ [69]. Ɇɨɥɟɤɭɥɢ, ɯɪɨɦɨɮɨɪɢ ɹɤɢɯ ɦɿɫɬɹɬɶ ɞɜɚ ɚɪɨɦɚɬɢɱɧɢɯ ɤɿɥɶɰɹ, ɧɚɩɪɢɤɥɚɞ, ɩɭɪɢɧɢ ɬɚ ʀɯ ɩɨɯɿɞɧɿ, ɯɚɪɚɤɬɟɪɢɡɭɸɬɶɫɹ ɧɚ ɩɨɪɹɞɨɤ ɛɿɥɶɲɢɦɢ ɤɨɧɫɬɚɧɬɚɦɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ, ɧɿɠ ɩɿɪɢɦɿɞɢɧɢ, ɿ ɜɨɧɢ ɦɨɠɭɬɶ ɭɬɜɨɪɢɬɢ ɧɟ ɬɿɥɶɤɢ ɞɢɦɟɪɢ, ɚɥɟ ɣ ɚɫɨɰɿɚɬɢ ɛɿɥɶɲ ɜɢɫɨɤɨɝɨ ɩɨɪɹɞɤɭ [68, 69]. Ɇɨɥɟɤɭɥɢ, ɳɨ ɦɿɫɬɹɬɶ ɬɪɢ ɚɪɨɦɚɬɢɱɧɢɯ ɤɿɥɶɰɹ ɭ ɯɪɨɦɨɮɨɪɿ, ɦɚɸɬɶ ɡɧɚɱɟɧɧɹ ɤɨɧɫɬɚɧɬ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɧɚ ɞɜɚ-ɬɪɢ ɩɨɪɹɞɤɢ ɜɢɳɟ, ɧɿɠ ɭ ɩɭɪɢɧɿɜ. Ɂɚɫɬɨɫɭɜɚɧɧɹ ɞɥɹ ɚɧɚɥɿɡɭ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɚɧɢɯ, ɨɬɪɢɦɚɧɢɯ ɩɿɞ ɱɚɫ ɜɢɜɱɟɧɧɹ ɩɪɨɰɟɫɭ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɚɞɢɬɢɜɧɨʀ ɧɟɫɤɿɧɱɟɧɧɨɜɢɦɿɪɧɨʀ ɦɨɞɟɥɿ ɚɫɨɰɿɚɰɿʀ [70], ɞɨɡɜɨɥɹɽ ɜɪɚɯɨɜɭɜɚɬɢ ɭɬɜɨɪɟɧɧɹ n-ɦɨɥɟɤɭɥɹɪɧɢɯ ɚɝɪɟɝɚɬɿɜ ɿ ɬɢɦ ɫɚɦɢɦ ɜɢɤɨɧɭɜɚɬɢ ɛɿɥɶɲ ɤɨɪɟɤɬɧɢɣ ɪɨɡɪɚɯɭɧɨɤ ɫɬɪɭɤɬɭɪɧɢɯ ɿ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɪɟɚɤɰɿʀ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ. Ɋɟɡɭɥɶɬɚɬɢ ɨɞɧɨɜɢɦɿɪɧɨʀ ɬɚ ɞɜɨɜɢɦɿɪɧɨʀ əɆɊ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ [71, 72] ɩɨɤɚɡɚɥɢ ɬɚɤɨɠ, ɳɨ ɩɚɪɚɦɟɬɪɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɬɚ ɯɚɪɚɤɬɟɪ ɫɬɟɤɿɧɝ-ɜɡɚɽɦɨɞɿɣ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɿɫɬɨɬɧɨ ɡɚɥɟɠɚɬɶ ɜɿɞ ɫɬɪɭɤɬɭɪɢ ɯɪɨɦɨɮɨɪɭ: ɧɚɣɛɿɥɶɲɟ ɡɧɚɱɟɧɧɹ ɪɿɜɧɨɜɚɠɧɨʀ ɤɨɧɫɬɚɧɬɢ ɚɫɨɰɿɚɰɿʀ ɦɚɸɬɶ ɚɤɪɢɞɢɧɨɜɿ ɛɚɪɜɧɢɤɢ ɡ ɥɿɧɿɣɧɢɦ ɪɨɡɬɚɲɭɜɚɧɧɹɦ ɤɿɥɟɰɶ ɯɪɨɦɨɮɨɪɚ, ɬɨɞɿ ɹɤ ɦɟɧɲɟ ɡɧɚɱɟɧɧɹ ɤɨɧɫɬɚɧɬɢ ɞɥɹ EB ɦɨɠɟ ɛɭɬɢ ɨɛɭɦɨɜɥɟɧɨ ɦɟɧɲɢɦ ɩɟɪɟɤɪɢɬɬɹɦ ɤɿɥɟɰɶ ɮɟɧɚɧɬɪɢɞɢɧɨɜɨɝɨ ɯɪɨɦɨɮɨɪɭ ɩɪɢ ɭɬɜɨɪɟɧɧɿ ɚɝɪɟɝɚɬɿɜ ɭ ɜɢɝɥɹɞɿ ɫɬɨɩɨɤ. ɍ ɬɚɛɥ. 1.1 ɧɚɜɟɞɟɧɨ ɪɿɜɧɨɜɚɠɧɿ ɤɨɧɫɬɚɧɬɢ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɞɥɹ ɞɟɹɤɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ, ɨɬɪɢɦɚɧɿ ɡ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ əɆɊ ɞɚɧɢɯ. Ɇɟɬɢɥɸɜɚɧɧɹ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɡɛɿɥɶɲɭɽ ɫɩɨɪɿɞɧɟɧɿɫɬɶ ɦɨɥɟɤɭɥ ɞɨ ɚɝɪɟɝɚɰɿʀ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ. Ɋɿɜɧɨɜɚɠɧɚ ɤɨɧɫɬɚɧɬɚ ɫɚɦɨɚɫɨɰɿɚɰɿʀ CAF, ɳɨ ɦɿɫɬɢɬɶ ɬɪɢ ɦɟɬɢɥɶɧɿ ɝɪɭɩɢ ɭ ɩɭɪɢɧɨɜɨɦɭ ɝɟɬɟɪɨɰɢɤɥɿ, ɫɬɚɧɨɜɢɬɶ 11 Ɇ-1 [9], ɬɨɞɿ ɹɤ ɞɥɹ TPH, ɜ ɹɤɨɝɨ ɥɢɲɟ ɞɜɿ ɦɟɬɢɥɶɧɿ ɝɪɭɩɢ, ɤɨɧɫɬɚɧɬɚ ɞɨɪɿɜɧɸɽ 7 Ɇ-1 [88]. Ʉɨɧɫɬɚɧɬɚ ɪɿɜɧɨɜɚɝɢ ȺɈ (| 6100 Ɇ-1), ɳɨ ɦɚɽ ɱɨɬɢɪɢ ɦɟɬɢɥɶɧɿ ɝɪɭɩɢ ɩɪɢɛɥɢɡɧɨ ɧɚ ɩɨɪɹɞɨɤ ɜɢɳɚ, ɧɿɠ ɞɥɹ PRF (| 700 Ɇ-1) [71] (ɬɚɛɥ. 1.1). ɐɟ ɦɨɠɟ ɩɨɹɫɧɸɜɚɬɢɫɹ ɞɨɞɚɬɤɨɜɢɦ ɫɬɚɛɿɥɿɡɭɸɱɢɦ ɜɧɟɫɤɨɦ ɝɿɞɪɨɮɨɛɧɢɯ ɜɡɚɽɦɨɞɿɣ ɦɟɬɢɥɶɧɢɯ ɝɪɭɩ ɩɪɢ ɚɝɪɟɝɚɰɿʀ ɦɨɥɟɤɭɥ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ. 38 Ɍɚɛɥɢɰɹ 1.1 Ɋɿɜɧɨɜɚɠɧɿ ɤɨɧɫɬɚɧɬɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɬɚ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ (Ɇ-1) ɞɥɹ ɪɿɡɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ CAF DAU CAF 11,8 [9] 72±4 [9] TPH FMN ȺɈ PRF EB NOV NOG 161±26 264±21 160±17 [9] 62±4 [9] [81] [9] 256±30 180±40 [87] [76, 77] 210 [85] 324 [85] 720 190±30 453±28 2470±4 [73] [88, 89] [82,83] 40 [33] 7,4±0,4 180±4 [88] [88] 265 [55] 6100 ±700 [71] 157 [79] 1650±120 2700±440 3333±350 2700±1200 [11] [80] [10, 78] [33] 2080 [90] 3850 [90] 15000 [85] 3400 [85] 180±20 102±6 [88, [88, 89] 89] 920±80 [86] 640±75 [86] 100±10 [88, 89] 33700±100 790±50 [11] [84] 965 [85] 49000 [85] ȺɈ FMN TPH DAU 700 [71] 690±60 [74,75] 305 [71] 5200±2500 [11] 12000 [85] 7400 [73] NOV EB PRF 28600 [76] NOG ɇɚɹɜɧɿɫɬɶ ɡɚɪɹɞɠɟɧɢɯ ɚɬɨɦɿɜ ɿ ɝɪɭɩ ɭ ɛɨɤɨɜɢɯ ɥɚɧɰɸɝɚɯ ɚɪɨɦɚɬɢɱɧɢɯ ɡ'ɽɞɧɚɧɶ ɬɚɤɨɠ ɿɫɬɨɬɧɨ ɜɩɥɢɜɚɽ ɧɚ ɩɚɪɚɦɟɬɪɢ ɚɝɪɟɝɚɰɿʀ ɦɨɥɟɤɭɥ ɿ ɯɚɪɚɤɬɟɪ ʀɯ ɫɬɟɤɿɧɝ-ɜɡɚɽɦɨɞɿɣ. ɇɚɩɪɢɤɥɚɞ, ɨɬɪɢɦɚɧɿ ɩɪɢ ɨɞɧɚɤɨɜɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɭɦɨɜɚɯ ɤɨɧɫɬɚɧɬɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɮɟɧɚɧɬɪɢɞɢɧɨɜɨɝɨ ɛɚɪɜɧɢɤɚ PI (63 r 6 Ɇ-1), 39 ɭ ɛɿɱɧɨɦɭ ɥɚɧɰɸɡɿ ɹɤɨɝɨ ɦɿɫɬɢɬɶɫɹ ɡɚɪɹɞɠɟɧɢɣ ɚɬɨɦ ɚɡɨɬɭ, ɬɚ EB (305 r 14 Ɇ-1) ɜɿɞɪɿɡɧɹɸɬɶɫɹ ɦɚɣɠɟ ɜ ɩ'ɹɬɶ ɪɚɡɿɜ [72, 91]. ɇɚ ɩɿɞɫɬɚɜɿ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɚɧɢɯ (əɆɊ ɫɩɟɤɬɪɨɫɤɨɩɿʀ, ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɜ ɍɎ- ɿ ɜɢɞɢɦɿɣ ɨɛɥɚɫɬɹɯ) ɛɭɥɨ ɩɨɛɭɞɨɜɚɧɨ ɦɨɞɟɥɿ ɫɚɦɨɚɫɨɰɿɚɬɿɜ ɿ ɩɨɤɚɡɚɧɨ, ɳɨ ɩɪɢ ɭɬɜɨɪɟɧɧɿ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿɜ ɦɚɽ ɦɿɫɰɟ ɚɧɬɢɩɚɪɚɥɟɥɶɧɚ ɨɪɿɽɧɬɚɰɿɹ ɯɪɨɦɨɮɨɪɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ – ɞɢɦɟɪɿɜ ɩɪɨɮɥɚɜɿɧɭ, ɚɤɬɢɧɨɦɿɰɢɧɭ D ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɬɚ ɚɤɪɢɞɢɧɨɜɨɝɨ ɩɨɦɚɪɚɧɱɟɜɨɝɨ, Ɂɚ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ, ɞɨɩɨɦɨɝɨɸ ɩɟɪɟɥɿɱɟɧɢɯ ɫɬɟɤɿɧɝ [70, 71, 92, 93]. ɜɢɞ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɦɟɬɨɞɿɜ ɛɭɥɨ ɜɢɡɧɚɱɟɧɨ ɬɟɪɦɨɞɢɧɚɦɿɱɧɿ ɩɚɪɚɦɟɬɪɢ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ – ɜɟɪɬɢɤɚɥɶɧɢɣ ɯɪɨɦɨɮɨɪɿɜ. Ɍɚɤɨɠ ɛɭɥɨ ɡɚɩɪɨɩɨɧɨɜɚɧɨ ɧɚɣɛɿɥɶɲ ɿɦɨɜɿɪɧɿ ɩɪɨɫɬɨɪɨɜɿ ɫɬɪɭɤɬɭɪɢ ɞɢɦɟɪɿɜ ɬɚ ɜɫɬɚɧɨɜɥɟɧɨ ɹɤɿɫɧɢɣ ɜɡɚɽɦɨɡɜ'ɹɡɨɤ ɩɚɪɚɦɟɬɪɿɜ ɪɟɚɤɰɿɣ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɦɨɥɟɤɭɥ ɡ ɪɨɡɦɿɪɨɦ ɿ ɯɚɪɚɤɬɟɪɨɦ ɛɿɱɧɢɯ ɝɪɭɩ ɿ ɥɚɧɰɸɝɿɜ [65]. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɨɬɪɢɦɚɧɨ ɫɬɪɭɤɬɭɪɢ ɹɤ ɞɢɦɟɪɿɜ ɫɚɦɨɚɫɨɰɿɚɬɿɜ, ɬɚɤ ɿ ɚɝɪɟɝɚɬɿɜ ɛɿɥɶɲ ɜɢɫɨɤɨɝɨ ɩɨɪɹɞɤɭ [94]. Ɇɨɥɟɤɭɥɹɪɧɨ-ɞɢɧɚɦɿɱɧɟ ɦɨɞɟɥɸɜɚɧɧɹ ɩɨɤɚɡɚɥɨ, ɳɨ ɤɨɥɢ ɫɢɫɬɟɦɚ ɦɿɫɬɢɬɶ ɜɿɫɿɦ ɦɨɥɟɤɭɥ ɤɨɮɟʀɧɭ ɜ ɨɫɟɪɟɞɤɭ ɡ 4067 ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ ɩɪɢ 300 Ʉ ɿ ɜɿɞɩɨɜɿɞɚɽ ɦɟɠɿ ɪɨɡɱɢɧɧɨɫɬɿ ɤɨɮɟʀɧɭ ɩɪɢ ɤɿɦɧɚɬɧɿɣ ɬɟɦɩɟɪɚɬɭɪɿ, ɬɨ ɦɨɠɥɢɜɟ ɭɬɜɨɪɟɧɧɹ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿɜ ɡ 2, 3, 5 ɿ 6 ɦɨɥɟɤɭɥ ɤɨɮɟʀɧɭ. ɇɚɣɛɿɥɶɲ ɫɬɿɣɤɢɦ ɜɢɹɜɢɜɫɹ ɨɤɬɚɦɟɪ, ɹɤɢɣ ɡɛɟɪɿɝɚɜɫɹ ɩɪɨɬɹɝɨɦ 1 ɧɫ. ɋɬɚɛɿɥɿɡɚɰɿɹ ɚɫɨɰɿɚɬɿɜ ɡɞɿɣɫɧɸɜɚɥɚɫɶ ɡɚ ɪɚɯɭɧɨɤ ɦɿɠɩɥɨɳɢɧɧɢɯ ɿ ɝɿɞɪɨɮɨɛɧɢɯ ɜɡɚɽɦɨɞɿɣ. ɍ ɰɿɥɨɦɭ ɚɧɚɥɿɡ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɚɧɢɯ ɫɜɿɞɱɢɬɶ ɩɪɨ ɬɟ, ɳɨ ɞɥɹ ɜɫɿɯ ɜɢɜɱɟɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɫɢɫɬɟɦ, ɛɟɡ ɜɢɧɹɬɤɭ ɿ ɧɟɡɚɥɟɠɧɨ ɜɿɞ ɬɢɩɭ ɛɿɱɧɢɯ ɝɪɭɩ, ɞɥɹ ɪɟɚɤɰɿʀ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɽ ɯɚɪɚɤɬɟɪɧɢɦ ɧɟɝɚɬɢɜɧɚ ɡɦɿɧɚ ɟɧɬɚɥɶɩɿʀ ɬɚ ɟɧɬɪɨɩɿʀ ɫɚɦɨɚɫɨɰɿɚɰɿʀ; ɜɟɥɢɱɢɧɚ ɪɿɜɧɨɜɚɠɧɨʀ ɤɨɧɫɬɚɧɬɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɡɦɿɧɸɽɬɶɫɹ ɜ ɞɿɚɩɚɡɨɧɿ ɜɿɞ ɱɚɫɬɨɤ M-1 (ɧɿɤɨɬɢɧɚɦɿɞ ɿ ɩɿɪɢɦɿɞɢɧɢ) ɞɨ ɞɟɫɹɬɤɿɜ ɬɢɫɹɱ M-1 (ɧɨɜɚɬɪɨɧ) ɿ ɤɨɪɟɥɸɸɬɶ ɡ ɬɢɩɨɦ ɛɿɱɧɢɯ ɝɪɭɩ ɯɪɨɦɨɮɨɪɭ ɬɚ ɤɿɥɶɤɿɫɬɸ ɚɪɨɦɚɬɢɱɧɢɯ ɤɿɥɟɰɶ ɞɨɫɥɿɞɠɭɜɚɧɨʀ ɫɩɨɥɭɤɢ. Ɂɪɨɛɥɟɧɨ ɜɢɫɧɨɜɨɤ ɩɪɨ ɫɬɨɩɤɨɜɭ ɨɪɿɽɧɬɚɰɿɸ ɯɪɨɦɨɮɨɪɿɜ, ɳɨ ɭɬɜɨɪɸɸɬɶ ɚɝɪɟɝɚɬɢ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɭ 40 ɜɨɞɧɨ-ɫɨɥɶɨɜɨɦɭ ɪɨɡɱɢɧɿ (ɜɟɪɬɢɤɚɥɶɧɢɣ ɫɬɟɤɿɧɝ), ɿ ɡɧɚɱɧɢɣ ɜɧɟɫɨɤ ɜ ʀɯ ɫɬɚɛɿɥɿɡɚɰɿɸ ɝɿɞɪɨɮɨɛɧɢɯ ɜɡɚɽɦɨɞɿɣ ɿ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ (ɇ-ɡɜ'ɹɡɤɿɜ), ɳɨ ɡɚɥɟɠɚɬɶ ɜɿɞ ɬɢɩɭ ɛɿɱɧɢɯ ɝɪɭɩ ɿ ɫɬɪɭɤɬɭɪɢ ɚɪɨɦɚɬɢɱɧɨɝɨ ɯɪɨɦɨɮɨɪɭ, ɹɤɚ ɜɢɡɧɚɱɚɽ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɞɢɫɩɟɪɫɿɣɧɢɯ ɜɡɚɽɦɨɞɿɣ. Ɍɨɛɬɨ, ɡɞɚɬɧɿɫɬɶ ɞɨ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ ɩɪɨɹɜɥɹɽɬɶɫɹ ɫɩɟɰɢɮɿɱɧɨ ɿ ɞɥɹ ɤɨɠɧɨʀ ɤɨɧɤɪɟɬɧɨʀ ɫɩɨɥɭɤɢ. ɇɚɣɛɿɥɶɲ ɞɢɫɤɭɬɨɜɚɧɢɦ ɧɚ ɞɚɧɢɣ ɱɚɫ ɩɢɬɚɧɧɹɦ ɽ ɩɨɪɹɞɨɤ ɚɫɨɰɿɚɬɚɬɿɜ, ɹɤɿ ɦɨɠɭɬɶ ɭɬɜɨɪɢɬɢ ɜ ɪɨɡɱɢɧɿ ɚɪɨɦɚɬɢɱɧɿ ɦɨɥɟɤɭɥɢ: ɞɢɦɟɪɢ ɚɛɨ ɚɝɪɟɝɚɬɢ ɛɿɥɶɲ ɜɢɫɨɤɨɝɨ ɩɨɪɹɞɤɭ, ɬɚ ɹɤɿ ɱɢɧɧɢɤɢ ɜɩɥɢɜɚɸɬɶ ɧɚ ɩɨɪɹɞɨɤ ɫɚɦɨɚɫɨɰɿɚɰɿʀ. 1.2.2 Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ ɉɟɪɫɩɟɤɬɢɜɚ ɪɟɝɭɥɸɜɚɧɧɹ ɮɚɪɦɚɤɨɥɨɝɿɱɧɨʀ ɚɤɬɢɜɧɨɫɬɿ ɬɚ ɡɧɢɠɟɧɧɹ ɬɨɤɫɢɱɧɨɫɬɿ ɩɪɨɬɢɩɭɯɥɢɧɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɿɧɬɟɪɤɚɥɹɬɨɪɿɜ ɭ ɩɪɢɫɭɬɧɨɫɬɿ CAF, ɜɿɬɚɦɿɧɿɜ FMN/RBF, ɚ ɬɚɤɨɠ ɜ ʀɯ ɩɨɽɞɧɚɧɧɿ ɫɬɢɦɭɥɸɜɚɥɢ ɱɢɫɥɟɧɧɿ ɞɨɫɥɿɞɠɟɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɹɤ ɩɨɬɟɧɰɿɣɧɨɝɨ ɮɿɡɢɱɧɨɝɨ ɦɟɯɚɧɿɡɦɭ, ɳɨ ɥɟɠɢɬɶ ɜ ɨɫɧɨɜɿ ɫɩɨɫɬɟɪɟɠɭɜɚɧɢɯ ɹɜɢɳ. Ⱦɨɫɥɿɞɠɟɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ, ɜɢɤɨɧɚɧɿ ɡɚ ɞɨɩɨɦɨɝɨɸ əɆɊ, ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɜ ɍɎ- ɬɚ ɜɢɞɢɦɿɣ ɨɛɥɚɫɬɿ ɬɚ ɮɥɸɨɪɟɫɰɟɧɰɿʀ (ɞɢɜ. ɨɝɥɹɞ [2, 11]), ɩɨɤɚɡɚɥɢ, ɳɨ ɜ ɪɨɡɱɢɧɚɯ ɜ ɭɦɨɜɚɯ, ɛɥɢɡɶɤɢɯ ɞɨ ɮɿɡɿɨɥɨɝɿɱɧɢɯ, ɦɨɥɟɤɭɥɢ ȻȺɊ ɭɬɜɨɪɸɸɬɶ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɢ ɜ ɮɨɪɦɿ ɫɬɨɩɨɤ ɡ ɩɚɪɚɥɟɥɶɧɢɦ ɪɨɡɬɚɲɭɜɚɧɧɹɦ ɯɪɨɦɨɮɨɪɿɜ (ʌ-ɫɬɟɤɿɧɝ). Ⱥɧɚɥɿɡ ɪɟɡɭɥɶɬɚɬɿɜ ɞɨɫɥɿɞɠɟɧɶ ɩɨɤɚɡɚɜ, ɳɨ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ, ɹɤɿ ɦɿɫɬɹɬɶ ɦɨɥɟɤɭɥɢ ɞɜɨɯ ɪɿɡɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ Ʌɿɝɚɧɞ1-Ʌɿɝɚɧɞ2, ɩɨɞɿɛɧɨ ɞɨ ɫɢɫɬɟɦ, ɳɨ ɦɿɫɬɹɬɶ ɦɨɥɟɤɭɥɢ ɨɞɧɨɝɨ ɬɢɩɭ Ʌɿɝɚɧɞ1-Ʌɿɝɚɧɞ1, ɜɿɞɛɭɜɚɸɬɶɫɹ ɪɟɚɤɰɿʀ ɚɫɨɰɿɚɰɿʀ ɡ ɭɬɜɨɪɟɧɧɹɦ ɚɝɪɟɝɚɬɿɜ ɭ ɮɨɪɦɿ ɫɬɨɩɨɤ. Ɉɫɧɨɜɧɿ ɡɚɤɨɧɨɦɿɪɧɨɫɬɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɡɜɨɞɹɬɶɫɹ ɞɨ ɧɚɫɬɭɩɧɨɝɨ: 41 1. Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɭ ɜɨɞɧɨ-ɫɨɥɶɨɜɨɦɭ ɪɨɡɱɢɧɿ ɧɨɫɢɬɶ ɯɚɪɚɤɬɟɪ ɜɟɪɬɢɤɚɥɶɧɨɝɨ ɫɬɟɤɿɧɝɭ ɯɪɨɦɨɮɨɪɿɜ, ɫɬɚɛɿɥɿɡɨɜɚɧɨɝɨ ɩɟɪɟɜɚɠɧɨ ɞɢɫɩɟɪɫɿɣɧɢɦɢ ɬɚ ɝɿɞɪɨɮɨɛɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ, ɚ ɬɚɤɨɠ ɜ ɨɤɪɟɦɢɯ ɜɢɩɚɞɤɚɯ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɦɢ ɜɨɞɧɟɜɢɦɢ ɡɜ'ɹɡɤɚɦɢ [65]. Ⱦɥɹ ɜɫɿɯ ɜɢɜɱɟɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɫɢɫɬɟɦ ɛɟɡ ɜɢɧɹɬɤɭ ɿ ɧɟɡɚɥɟɠɧɨ ɜɿɞ ɬɢɩɭ ɛɿɱɧɢɯ ɝɪɭɩ ɽ ɯɚɪɚɤɬɟɪɧɢɦ ɧɟɝɚɬɢɜɧɚ ɡɦɿɧɚ ɟɧɬɚɥɶɩɿʀ (ǻH < 0) ɿ ɧɟɝɚɬɢɜɧɚ ɡɦɿɧɚ ɟɧɬɪɨɩɿʀ (ǻS < 0) (ɡɚ ɜɢɧɹɬɤɨɦ ɫɢɫɬɟɦɢ ɦɿɬɨɤɫɚɧɬɪɨɧɤɨɮɟʀɧ ɡ ɜɟɥɢɤɢɦ ɝɿɞɪɨɮɨɛɧɢɦ ɜɧɟɫɤɨɦ [95]). Ɋɿɜɧɨɜɚɠɧɚ ɤɨɧɫɬɚɧɬɚ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɬɚ ɚɛɫɨɥɸɬɧɿ ɡɧɚɱɟɧɧɹ ɟɧɬɚɥɶɩɿʀ ɬɚ ɟɧɬɪɨɩɿʀ ɦɚɸɬɶ ɩɪɨɦɿɠɧɿ ɡɧɚɱɟɧɧɹ ɦɿɠ ɚɧɚɥɨɝɿɱɧɢɦɢ ɩɚɪɚɦɟɬɪɚɦɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɜɡɚɽɦɨɞɿɸɱɢɯ ɪɟɱɨɜɢɧ. ɉɟɪɟɜɢɳɟɧɧɹ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ (ɜɿɥɶɧɨʀ ɟɧɟɪɝɿʀ ǻG, ɟɧɬɚɥɶɩɿʀ ǻH, ɟɧɬɪɨɩɿʀ ǻS) ɧɚɞ ɩɚɪɚɦɟɬɪɚɦɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɫɩɨɫɬɟɪɿɝɚɽɬɶɫɹ ɬɿɥɶɤɢ ɞɥɹ ɫɢɫɬɟɦ, ɹɤɿ ɦɨɠɭɬɶ ɛɭɬɢ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɨɜɚɧɿ ɜ ɪɨɡɱɢɧɿ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɦɢ ɇɡɜ'ɹɡɤɚɦɢ [2]. ȼɫɬɚɧɨɜɥɟɧɨ ɤɨɪɟɥɹɰɿɸ ɩɚɪɚɦɟɬɪɿɜ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɬɚ ɬɢɩɭ ɛɿɱɧɢɯ ɥɚɧɰɸɝɿɜ ɥɿɝɚɧɞɭ. Ɂɨɤɪɟɦɚ, ɧɚɹɜɧɿɫɬɶ ɦɚɫɢɜɧɢɯ ɛɿɱɧɢɯ ɪɚɞɢɤɚɥɿɜ ɩɪɨɹɜɥɹɽɬɶɫɹ ɜ ɩɨɦɿɬɧɨɦɭ ɩɨɡɢɬɢɜɧɨɦɭ ɝɿɞɪɨɮɨɛɧɨɦɭ ɜɤɥɚɞɿ ɜ ɟɧɬɪɨɩɿɸ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ [65]. Ɉɱɟɜɢɞɧɨ, ɳɨ ɜɪɚɯɭɜɚɧɧɹ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɡɚɥɢɲɚɽɬɶɫɹ 2. 3. 4. ɧɟɨɛɯɿɞɧɢɦ ɩɪɢ ɩɪɨɜɟɞɟɧɧɿ ɛɿɨɮɿɡɢɱɧɢɯ ɞɨɫɥɿɞɠɟɧɶ ɡɚ ɭɱɚɫɬɸ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɩɪɟɩɚɪɚɬɿɜ. Ⱥɥɟ ɡ ɟɤɫɩɟɪɢɦɟɧɬɿɜ ɛɟɡɩɨɫɟɪɟɞɧɶɨ ɜɢɡɧɚɱɚɸɬɶ, ɹɤ ɩɪɚɜɢɥɨ, ɬɿɥɶɤɢ ɪɿɜɧɨɜɚɠɧɿ ɤɨɧɫɬɚɧɬɢ ɚɫɨɰɿɚɰɿʀ ɬɚ ɬɟɪɦɨɞɢɧɚɦɿɱɧɿ ɩɚɪɚɦɟɬɪɢ, ɬɨɞɿ ɹɤ ɜɤɥɚɞɢ ɪɿɡɧɢɯ ɜɡɚɽɦɨɞɿɣ ɿ ɪɨɥɶ ɜɨɞɧɨɝɨ ɨɬɨɱɟɧɧɹ ɜ ɫɬɚɛɿɥɿɡɚɰɿɸ ɚɫɨɰɿɚɬɿɜ ɨɰɿɧɸɸɬɶɫɹ ɨɩɨɫɟɪɟɞɤɨɜɚɧɨ ɿ ɧɚ ɹɤɿɫɧɨɦɭ ɪɿɜɧɿ. Ɍɨɦɭ ɹɤ ɿ ɪɚɧɿɲɟ ɚɤɬɭɚɥɶɧɿ ɹɤ ɨɬɪɢɦɚɧɧɹ ɧɨɜɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɚɧɢɯ ɩɪɨ ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɜɡɚɽɦɨɞɿʀ ɩɿɞ ɱɚɫ ɚɝɪɟɝɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ, ɬɚɤ ɿ ɪɨɡɪɨɛɤɚ ɦɟɬɨɞɿɜ ʀɯ ɤɨɪɟɤɬɧɨʀ ɿɧɬɟɪɩɪɟɬɚɰɿʀ. 42 1.3 Ɇɟɬɨɞɢ ɞɨɫɥɿɞɠɟɧɧɹ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ȻȺɊ. Ɋɨɥɶ ɜɨɞɢ ɬɚ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɫɬɚɛɿɥɿɡɚɰɿʀ ɚɫɨɰɿɚɬɿɜ ȻȺɊ ɿ ɩɪɢ ɤɨɦɩɥɟɤɨɫɭɬɜɨɪɟɧɧɿ ɡ ȾɇɄ 1.3.1 ɋɩɟɤɬɪɨɫɤɨɩɿɱɧɿ ɦɟɬɨɞɢ ɞɨɫɥɿɞɠɟɧɧɹ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ɋɩɟɤɬɪɨɫɤɨɩɿɱɧɿ ɦɟɬɨɞɢ – ɫɩɟɤɬɪɨɮɨɬɨɦɟɬɪɿɹ ɜ ɍɎ- ɿ ɜɢɞɢɦɿɣ ɨɛɥɚɫɬɿ, əɆɊ ɫɩɟɤɬɪɨɫɤɨɩɿɹ, ɤɨɥɢɜɚɥɶɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ (ɿɧɮɪɚɱɟɪɜɨɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɿ ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ɫɜɿɬɥɚ) – ɨɱɟɜɢɞɧɨ, ɽ ɧɚɣɛɿɥɶɲ ɟɮɟɤɬɢɜɧɢɦɢ ɦɟɬɨɞɚɦɢ ɞɥɹ ɨɬɪɢɦɚɧɧɹ ɿɧɮɨɪɦɚɰɿʀ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɦɨɥɟɤɭɥɹɪɧɢɯ ɤɨɦɩɥɟɤɫɿɜ ɜ ɭɦɨɜɚɯ, ɧɚɛɥɢɠɟɧɢɯ ɞɨ ɮɿɡɿɨɥɨɝɿɱɧɢɯ. ɍ ɛɿɥɶɲɨɫɬɿ ɜɢɩɚɞɤɿɜ ɩɟɪɟɯɿɞ ɜɿɞ ɦɨɧɨɦɟɪɧɨʀ ɮɨɪɦɢ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ ɞɨ ɚɝɪɟɝɨɜɚɧɨʀ ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɫɩɟɤɬɪɚɥɶɧɢɦɢ ɡɦɿɧɚɦɢ – ɝɿɩɨɯɪɨɦɿɡɦɨɦ ɿ ɤɨɪɨɬɤɨɯɜɢɥɶɨɜɢɦ ɡɦɿɳɟɧɧɹɦ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɜ ɍɎ- ɿ ɜɢɞɢɦɿɣ ɨɛɥɚɫɬɿ ɫɩɟɤɬɪɭ [70]. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɱɢɫɟɥɶɧɨɝɨ ɚɧɚɥɿɡɭ ɨɬɪɢɦɚɧɢɯ ɫɩɟɤɬɪɚɥɶɧɢɯ ɡɚɥɟɠɧɨɫɬɟɣ ɭ ɲɢɪɨɤɿɣ ɨɛɥɚɫɬɿ ɞɨɜɠɢɧ ɯɜɢɥɶ, ɤɨɧɰɟɧɬɪɚɰɿɣ ɪɟɚɝɭɸɱɢɯ ɤɨɦɩɨɧɟɧɬɿɜ ɿ ɬɟɦɩɟɪɚɬɭɪ ɦɨɠɧɚ ɜɢɡɧɚɱɢɬɢ ɿɧɞɢɜɿɞɭɚɥɶɧɿ ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ, ɤɨɧɫɬɚɧɬɢ ɚɫɨɰɿɚɰɿʀ (KC) ɿ ɬɟɪɦɨɞɢɧɚɦɿɱɧɿ ɩɚɪɚɦɟɬɪɢ ('H, 'G ɿ 'S) ɞɥɹ ɦɨɧɨɦɟɪ-ɞɢɦɟɪɧɨʀ ɪɿɜɧɨɜɚɝɢ, ɜɢɤɨɪɢɫɬɨɜɭɸɱɢ ɪɿɜɧɹɧɧɹ ʈɿɛɛɡɚȽɟɥɶɦɝɨɥɶɰɚ ɿ ȼɚɧɬ-Ƚɨɮɮɚ [96, 97]. ɍɬɜɨɪɟɧɧɹ ɜɟɪɬɢɤɚɥɶɧɢɯ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿɜ (ɫɬɨɩɨɤ) ɡ ɝɟɬɟɪɨɰɢɤɥɿɜ ɚɡɨɬɢɫɬɢɯ ɨɫɧɨɜ ɪɚɧɿɲɟ ɛɭɥɨ ɜɢɹɜɥɟɧɨ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɿ ɩɥɿɜɤɚɯ ɧɭɤɥɟɨɬɢɞɿɜ, ɚ ɬɚɤɨɠ ɩɪɢ ɡɜ'ɹɡɭɜɚɧɧɿ ɦɨɥɟɤɭɥ ɜɨɞɢ ɜ ɩɥɿɜɤɚɯ ɩɨɥɿɧɭɤɥɟɨɬɢɞɿɜ [98-101]. Ɇɿɠɩɥɨɳɢɧɧɿ ɜɡɚɽɦɨɞɿʀ ɝɟɬɟɪɨɰɢɤɥɿɜ ɚɡɨɬɢɫɬɢɯ ɨɫɧɨɜ ɫɭɩɪɨɜɨɞɠɭɸɬɶɫɹ ɜ ɍɎ-ɫɩɟɤɬɪɿ ɝɿɩɨɯɪɨɦɿɡɦɨɦ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɩɪɢ Ȝ = 260 ɧɦ [102], ɚ ɜ ɿɧɮɪɚɱɟɪɜɨɧɨɦɭ ɫɩɟɤɬɪɿ – ɝɿɩɨɯɪɨɦɿɡɦɨɦ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ C=N ɤɨɥɢɜɚɧɶ ɿ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɦɢ ɡɫɭɜɚɦɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɨɥɢɜɚɧɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɋ=Ɉ [103, 104]. Ɏɨɪɦɭɜɚɧɧɹ ɫɬɨɩɨɤ ɦɨɥɟɤɭɥ ɤɨɮɟʀɧɭ, ɳɨ ɮɿɤɫɭɽɬɶɫɹ ɦɟɬɨɞɨɦ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ, ɬɚɤɨɠ 43 ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɦ ɡɫɭɜɨɦ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɨɥɢɜɚɧɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ [105]. Ɂɚɮɿɤɫɨɜɚɧɿ ɦɟɬɨɞɨɦ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɫɩɟɤɬɪɚɥɶɧɿ ɟɮɟɤɬɢ, ɳɨ ɜɢɧɢɤɚɸɬɶ ɭ ɪɟɡɭɥɶɬɚɬɿ ɜɡɚɽɦɨɞɿɣ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɿɜ ɤɚɪɛɨɧɿɥɶɧɢɯ ɿ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɤɨɥɢɜɚɧɶ ɭ ɫɬɨɩɤɚɯ ɪɿɡɧɢɯ ɝɟɬɟɪɨɰɢɤɥɿɜ, ɡɧɚɣɲɥɢ ɩɨɹɫɧɟɧɧɹ ɜ ɪɚɦɤɚɯ ɬɟɨɪɿʀ ɦɨɥɟɤɭɥɹɪɧɢɯ ɟɤɫɢɬɨɧɿɜ ɭ ɞɢɩɨɥɶɞɢɩɨɥɶɧɨɦɭ ɧɚɛɥɢɠɟɧɧɿ [106, 107]. Ɍɟɪɦɨɞɢɧɚɦɿɱɧɿ ɩɚɪɚɦɟɬɪɢ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ ɦɨɠɭɬɶ ɛɭɬɢ ɜɢɡɧɚɱɟɧɿ ɡɚ ɞɨɩɨɦɨɝɨɸ ɦɿɤɪɨɤɚɥɨɪɢɦɟɬɪɢɱɧɨɝɨ ɬɢɬɪɭɜɚɧɧɹ ɿ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ, ɧɚɩɪɢɤɥɚɞ, ɤɨɧɫɬɚɧɬɢ ɬɚ ɟɧɬɚɥɶɩɿʀ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɤɨɮɟʀɧɭ ɿ ɦɿɬɨɤɫɚɧɬɪɨɧɭ [108]. ɍ ɰɶɨɦɭ ɞɨɫɥɿɞɠɟɧɧɿ ɩɟɪɟɞɛɚɱɚɽɬɶɫɹ, ɳɨ ɡɧɚɱɧɭ ɪɨɥɶ ɭ ɮɨɪɦɭɜɚɧɧɿ ɫɬɚɛɿɥɶɧɢɯ ɫɬɪɭɤɬɭɪ ɫɬɟɤɿɧɝɚɫɨɰɿɚɬɿɜ ɜɿɞɿɝɪɚɸɬɶ ɝɿɞɪɨɮɨɛɧɿ ɜɡɚɽɦɨɞɿʀ, ɹɤɿ ɩɨɜ'ɹɡɚɧɿ ɡɿ ɡɦɿɧɨɸ ɜɨɞɧɨɝɨ ɨɬɨɱɟɧɧɹ ɜ ɩɪɨɰɟɫɿ ɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ. ɐɟɣ ɜɢɫɧɨɜɨɤ ɭɡɝɨɞɠɭɽɬɶɫɹ ɡ ɪɟɡɭɥɶɬɚɬɚɦɢ ɞɨɫɥɿɞɠɟɧɧɹ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɧɭɤɥɟʀɧɨɜɢɯ ɨɫɧɨɜ ɬɚ ʀɯ ɩɨɯɿɞɧɢɯ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ, ɡɝɿɞɧɨ ɡ ɹɤɢɦɢ ɨɫɧɨɜɢ ɭ ɜɢɝɥɹɞɿ ɫɬɨɩɨɤ ɫɬɚɛɿɥɿɡɭɸɬɶɫɹ ɪɿɜɧɨɜɚɠɧɿ ɝɿɞɪɨɮɨɛɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɜ ɪɟɡɭɥɶɬɚɬɿ ɡɦɿɧɢ ɜɩɨɪɹɞɤɨɜɚɧɨɫɬɿ ɫɬɪɭɤɬɭɪɢ ɦɨɥɟɤɭɥ ɜɨɞɢ [109-112]. ɍ ɛɿɥɶɲɨɫɬɿ ɜɢɩɚɞɤɿɜ ɤɨɧɫɬɚɧɬɢ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɯɚɪɚɤɬɟɪɢɡɭɸɬɶɫɹ ɩɪɨɦɿɠɧɢɦɢ ɡɧɚɱɟɧɧɹɦɢ ɦɿɠ ɤɨɧɫɬɚɧɬɚɦɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɜɡɚɽɦɨɞɿɸɱɢɯ ɪɟɱɨɜɢɧ. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɦɟɬɨɞɭ əɆɊ ɜɢɡɧɚɱɚɽɬɶɫɹ ɯɿɦɿɱɧɢɣ ɡɫɭɜ, ɹɤɢɣ ɜɢɤɨɪɢɫɬɨɜɭɽɬɶɫɹ ɞɥɹ ɡɧɚɯɨɞɠɟɧɧɹ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɪɟɚɤɰɿɣ ɚɫɨɰɿɚɰɿʀ ɬɚ ɩɪɨɫɬɨɪɨɜɨʀ ɫɬɪɭɤɬɭɪɢ ɚɫɨɰɿɚɬɿɜ ɭ ɪɨɡɱɢɧɿ [71, 80, 113]. Ɂɚɡɜɢɱɚɣ, ɦɨɧɨɦɟɪɢ ɜ ɬɚɤɢɯ ɤɨɦɩɥɟɤɫɚɯ ɦɚɸɬɶ ɚɧɬɢɩɚɪɚɥɟɥɶɧɭ ɨɪɿɽɧɬɚɰɿɸ ɯɪɨɦɨɮɨɪɿɜ ɭ ɫɬɨɩɰɿ ɡ ɜɿɞɫɬɚɧɧɸ ɦɿɠ ɩɥɨɳɢɧɚɦɢ 3,2 - 3,7 Å, ɡɚɥɟɠɧɨ ɜɿɞ ɬɢɩɭ ȻȺɊ, ɿ ɞɨɞɚɬɤɨɜɨ ɩɨɜɟɪɧɟɧɿ ɧɚɜɤɨɥɨ ɩɨɩɟɪɟɱɧɨʀ ɨɫɿ ɯɪɨɦɨɮɨɪɚ ɧɚ |180ɨ [76, 114]. Ɇɟɬɨɞɨɦ əɆɊ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɛɭɥɨ ɩɪɨɜɟɞɟɧɨ ɜɟɥɢɤɭ ɤɿɥɶɤɿɫɬɶ ɞɨɫɥɿɞɠɟɧɶ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɪɿɡɧɢɯ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ. Ⱦɥɹ ɮɟɧɚɧɬɪɢɞɢɧɨɜɢɯ ɩɪɟɩɚɪɚɬɿɜ (EB ɿ PI) ɛɭɥɨ ɨɬɪɢɦɚɧɨ, ɳɨ ɜɟɥɢɱɢɧɢ ɤɨɧɫɬɚɧɬɢ ɪɿɜɧɨɜɚɠɧɨʀ ɪɟɚɤɰɿʀ ɿ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɯ ɩɚɪɚɦɟɬɪɿɜ 44 ɡɚɣɦɚɸɬɶ ɩɪɨɦɿɠɧɟ ɡɧɚɱɟɧɧɹ ɦɿɠ ɬɢɦɢ ɩɚɪɚɦɟɬɪɚɦɢ, ɳɨ ɫɩɨɫɬɟɪɿɝɚɸɬɶɫɹ ɞɥɹ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɰɢɯ ɦɨɥɟɤɭɥ [92]. Ɍɚɤɢɣ ɠɟ ɟɮɟɤɬ ɫɩɨɫɬɟɪɿɝɚɜɫɹ ɞɥɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɚɤɪɢɞɢɧɨɜɨɝɨ ɩɨɦɚɪɚɧɱɟɜɨɝɨ ɡ ɞɚɭɧɨɦɿɰɢɧɨɦ. Ɋɟɡɭɥɶɬɚɬɢ əɆɊ ɩɨɤɚɡɭɸɬɶ, ɳɨ ɝɿɞɪɨɮɨɛɧɿ ɜɡɚɽɦɨɞɿʀ ɜɿɞɿɝɪɚɸɬɶ ɿɫɬɨɬɧɭ ɪɨɥɶ ɭ ɫɬɚɛɿɥɿɡɚɰɿʀ ɤɨɦɩɥɟɤɫɭ ȺɈ-DAU, ɹɤɢɣ ɯɚɪɚɤɬɟɪɢɡɭɽɬɶɫɹ ɜɿɞɧɨɫɧɨ ɧɟɜɟɥɢɤɨɸ ɡɦɿɧɨɸ ɟɧɬɪɨɩɿʀ ɩɪɢ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɿ, ɜ ɩɨɪɿɜɧɹɧɧɿ ɡ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɨɦ PF-DAU, ɹɤɢɣ ɡɞɟɛɿɥɶɲɨɝɨ ɫɬɚɛɿɥɿɡɭɽɬɶɫɹ ɞɢɫɩɟɪɫɿɣɧɢɦɢ ɜɚɧ-ɞɟɪɜɚɚɥɶɫɨɜɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɿ, ɦɨɠɥɢɜɨ, ɜɨɞɧɟɜɢɦ ɡɜ'ɹɡɤɨɦ [33]. Ⱦɥɹ ɬɨɝɨ ɳɨɛ ɨɰɿɧɢɬɢ ɜɩɥɢɜ ɛɿɱɧɢɯ ɥɚɧɰɸɝɿɜ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɿ ɩɪɨɩɿɞɿɹ ɣɨɞɢɞɭ ɧɚ ɤɨɧɤɭɪɟɧɬɧɟ ɡɜ'ɹɡɭɜɚɧɧɹ ɦɿɠ ɞɚɭɧɨɦɿɰɢɧɨɦ ɿ ɦɭɬɚɝɟɧɚɦɢ ɡ ȾɇɄ, ɛɭɥɨ ɩɪɨɜɟɞɟɧɨ əɆɊ ɞɨɫɥɿɞɠɟɧɧɹ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɮɟɧɚɧɬɪɢɞɢɧɿɜ ɿ DAU, ʀɯ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ ɡ ɮɪɚɝɦɟɧɬɨɦ ȾɇɄ, ɬɟɬɪɚɧɭɤɥɟɨɬɢɞɨɦ ɜɢɤɨɪɢɫɬɚɧɧɹ 5'-d(TpGpCpA)2. Ȼɭɥɨ ɜɢɹɜɥɟɧɨ, ɩɪɢɡɜɨɞɢɬɶ ɳɨ ɞɨ ɤɨɦɛɿɧɨɜɚɧɟ ɡɦɟɧɲɟɧɧɹ ɿɧɬɟɪɤɚɥɸɸɱɢɯ ɩɪɟɩɚɪɚɬɿɜ ɡɜ'ɹɡɭɜɚɧɧɹ ɥɿɤɚɪɫɶɤɨɝɨ ɩɪɟɩɚɪɚɬɭ (Ʌɉ) ɚɛɨ ɦɭɬɚɝɟɧɿɜ ɡ ȾɇɄ, ɳɨ ɩɨɜ'ɹɡɚɧɨ ɹɤ ɡ ɭɬɜɨɪɟɧɧɹɦ ɭ ɫɭɦɿɲɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɤɨɦɩɥɟɤɫɿɜ Ʌɉ-ɦɭɬɚɝɟɧ, ɬɚɤ ɿ ɡ ɤɨɧɤɭɪɟɧɰɿɽɸ ɡɚ ɫɚɣɬɢ ɡɜ'ɹɡɭɜɚɧɧɹ ɡ ɚɪɨɦɚɬɢɱɧɢɦɢ ɦɨɥɟɤɭɥɚɦɢ [10]. ɍ ɞɟɹɤɢɯ ɜɢɩɚɞɤɚɯ, ɹɤ ɛɭɥɨ ɩɨɤɚɡɚɧɨ [33, 86], ɤɨɧɫɬɚɧɬɢ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɩɪɢɣɦɚɸɬɶ ɛɿɥɶɲ ɜɢɫɨɤɿ ɡɧɚɱɟɧɧɹ, ɧɿɠ ɤɨɧɫɬɚɧɬɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ. ɇɚɩɪɢɤɥɚɞ, ɞɥɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ PRF-DAU ɜɟɥɢɱɢɧɚ ɤɨɧɫɬɚɧɬɢ ɪɿɜɧɨɜɚɝɢ ɜɢɹɜɥɹɽɬɶɫɹ ɿɫɬɨɬɧɨ ɜɢɳɨɸ, ɧɿɠ ɤɨɧɫɬɚɧɬɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɰɢɯ ɦɨɥɟɤɭɥ, ɳɨ ɦɨɠɟ ɛɭɬɢ ɧɚɫɥɿɞɤɨɦ ɞɨɞɚɬɤɨɜɨʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ȻȺɊ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɦɢ ɜɨɞɧɟɜɢɦɢ ɡɜ'ɹɡɤɚɦɢ. Ɉɩɨɫɟɪɟɞɤɨɜɚɧɨ ɰɟɣ ɜɢɫɧɨɜɨɤ ɛɭɥɨ ɧɟɞɚɜɧɨ ɩɿɞɬɜɟɪɞɠɟɧɨ ɧɚ ɩɿɞɫɬɚɜɿ ɚɧɚɥɿɡɭ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɜɢɦɿɪɹɧɨʀ ɟɧɬɚɥɶɩɿʀ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɜɟɥɢɤɨʀ ɤɿɥɶɤɨɫɬɿ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ [115], ɚ ɬɚɤɨɠ ɭ ɪɟɡɭɥɶɬɚɬɿ ɪɨɡɝɥɹɞɭ ɦɨɠɥɢɜɨɫɬɿ ɚɥɶɬɟɪɧɚɬɢɜɧɨʀ ɿɧɬɟɪɩɪɟɬɚɰɿʀ ɞɨɞɚɬɤɨɜɨʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɧɟ H-ɡɜ'ɹɡɤɚɦɢ, ɚ ɜɡɚɽɦɨɞɿɹɦɢ ɡɚ ɬɢɩɨɦ «ɩɟɪɟɧɟɫɟɧɧɹ ɡɚɪɹɞɭ» [116]. 45 1.3.2 ȼɢɡɧɚɱɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɚɫɨɰɿɚɬɚɯ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ȼɢɫɧɨɜɤɢ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ H-ɡɜ'ɹɡɤɿɜ ɭ ɪɨɛɨɬɚɯ [33, 82, 84, 86, 115, 116] ɡɪɨɛɥɟɧɿ ɨɩɨɫɟɪɟɞɤɨɜɚɧɨ ɧɚ ɩɿɞɫɬɚɜɿ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɜɢɦɿɪɹɧɿɣ ɡɦɿɧɿ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɯ ɩɚɪɚɦɟɬɪɿɜ: ɱɟɪɟɡ ɜɟɥɢɤɭ ɜɟɥɢɱɢɧɭ ɦɨɞɭɥɹ ɟɧɬɚɥɶɩɿʀ ɚɫɨɰɿɚɰɿʀ ǻH ɿ ɤɨɧɫɬɚɧɬɢ ɚɫɨɰɿɚɰɿʀ Ʉɋ, ɭ ɩɨɽɞɧɚɧɧɿ ɡɿ ɫɬɪɭɤɬɭɪɧɢɦɢ ɞɚɧɢɦɢ (ɪɟɡɭɥɶɬɚɬɢ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɚɧɚɥɿɡɭ ɿ ɦɟɬɨɞɿɜ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ, ɞɢɜ. ɨɝɥɹɞɢ [2, 117-119]). Ɍɚɤɨɠ ɜɿɞɨɦɨ, ɳɨ ɜɨɞɧɟ ɨɬɨɱɟɧɧɹ ɜɿɞɿɝɪɚɽ ɿɫɬɨɬɧɭ ɪɨɥɶ ɭ ɩɪɨɰɟɫɚɯ ɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ [97, 120, 121], ɩɪɢ ɮɨɪɦɭɜɚɧɧɿ ɧɚɬɢɜɧɨʀ ɫɬɪɭɤɬɭɪɢ ɦɨɥɟɤɭɥ ȾɇɄ, ɳɨ ɽ ɦɿɲɟɧɧɸ ɞɥɹ ɩɪɨɬɢɩɭɯɥɢɧɧɢɯ ɚɧɬɢɛɿɨɬɢɤɿɜ [122], ɿ ɩɪɢ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɿ ȻȺɊ ɡ ȾɇɄ [123, 124]. ɉɪɨɬɟ, ɜɿɞɫɭɬɧɹ ɛɿɥɶɲ ɞɟɬɚɥɶɧɚ ɿɧɮɨɪɦɚɰɿɹ ɩɪɨ ɜɩɥɢɜ ɪɨɡɱɢɧɧɢɤɚ ɿ ɩɪɨ ɦɨɠɥɢɜɿɫɬɶ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ, ɩɪɨ ɨɰɿɧɤɭ ɜɧɟɫɤɭ ɪɿɡɧɢɯ ɜɢɞɿɜ ɜɡɚɽɦɨɞɿɣ ɜ ɭɬɜɨɪɟɧɧɹ ɫɬɿɣɤɢɯ ɚɝɪɟɝɚɬɿɜ ɭ ɿɨɧ-ɝɿɞɪɚɬɧɨɦɭ ɨɬɨɱɟɧɧɿ. Ɍɢɩɨɜɢɦɢ ɩɪɢɤɥɚɞɚɦɢ ɽ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɢ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɡ ɦɭɬɚɝɟɧɚɦɢ, ɬɚɤɢɦɢ ɹɤ ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ ɿ ɩɪɨɮɥɚɜɿɧ, ɹɤɿ ɪɚɧɿɲɟ ɛɭɥɢ ɨɯɚɪɚɤɬɟɪɢɡɨɜɚɧɿ ɹɤ ɬɟɪɦɨɞɢɧɚɦɿɱɧɨ ɛɿɥɶɲ ɫɬɚɛɿɥɶɧɿ, ɧɿɠ ʀɯ ɫɚɦɨɚɫɨɰɿɚɬɢ ɜɧɚɫɥɿɞɨɤ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɦɿɠ NH2 ɿ ɋ=Ɉ ɝɪɭɩɚɦɢ ɜɡɚɽɦɨɞɿɸɱɢɯ ɫɶɨɝɨɞɧɿ ɦɨɥɟɤɭɥ ɜ [86]. ɉɨɲɭɤ ɦɟɬɨɞɭ ɩɪɹɦɨɝɨ əɆɊ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɝɨ ɩɨ ɡɦɿɧɿ ɩɿɞɬɜɟɪɞɠɟɧɧɹ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ, ɳɨ ɩɪɨɜɨɞɢɜɫɹ ɞɨ ɬɿɥɶɤɢ ɪɚɦɤɚɯ (ɧɚɩɪɢɤɥɚɞ, ɿɧɬɟɧɫɢɜɧɨɫɬɿ/ɩɨɥɨɠɟɧɧɹ ɫɢɝɧɚɥɿɜ ɩɪɨɬɨɧɿɜ, ɹɤɿ ɣɦɨɜɿɪɧɨ ɛɟɪɭɬɶ ɭɱɚɫɬɶ ɭ ɮɨɪɦɭɜɚɧɧɿ ɇ-ɡɜ'ɹɡɤɭ), ɧɟ ɡɚɜɟɪɲɢɜɫɹ ɭɫɩɿɯɨɦ [33, 86]. Ⱥɥɶɬɟɪɧɚɬɢɜɨɸ ɦɟɬɨɞɭ əɆɊ ɬɢɩɨɦ ɦɨɥɟɤɭɥɹɪɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ, ɳɨ ɞɨɡɜɨɥɹɽ ɨɬɪɢɦɚɬɢ ɿɧɮɨɪɦɚɰɿɸ ɩɪɨ ɭɬɜɨɪɟɧɧɹ H-ɡɜ'ɹɡɤɿɜ, ɽ ɤɨɥɢɜɚɥɶɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ: ɿɧɮɪɚɱɟɪɜɨɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ (ȱɑ) ɿ ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ɫɜɿɬɥɚ (ɄɊ). ȼɿɞɨɦɨ, ɳɨ ɜ ȱɑ-ɞɿɚɩɚɡɨɧɿ 46 ɮɨɪɦɭɜɚɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɦɿɠ ɞɨɧɨɪɚɦɢ ɩɪɨɬɨɧɿɜ (ɝɪɭɩɢ ɚɬɨɦɿɜ Ɉɇ, NH, NH2, CH) ɿ ɚɤɰɟɩɬɨɪɚɦɢ (C=Ɉ, ɋ–Ɉ, C–N, C=N) ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɦ ɡɫɭɜɨɦ ɜɚɥɟɧɬɧɢɯ ɤɨɥɢɜɚɧɶ, ɚ ɬɚɤɨɠ ɡɧɚɱɧɢɦ ɡɪɨɫɬɚɧɧɹɦ ɿɧɬɟɧɫɢɜɧɨɫɬɿ ɿ ɡɛɿɥɶɲɟɧɧɹɦ ɧɚɩɿɜɲɢɪɢɧɢ ʀɯ ɫɦɭɝ [125, 126]. ɍ ɬɨɣ ɠɟ ɱɚɫ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ (ɧɚɩɪɢɤɥɚɞ, NH2 ɿ OH-ɝɪɭɩ ɚɬɨɦɿɜ) ɡɚɡɧɚɸɬɶ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɪɭɲɟɧɧɹ [127]. ɐɿ ɫɩɟɤɬɪɚɥɶɧɿ ɨɫɨɛɥɢɜɨɫɬɿ ɽ ɩɪɹɦɢɦ ɞɨɤɚɡɨɦ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɦɿɠ ɜɡɚɽɦɨɞɿɸɱɢɦɢ ɦɨɥɟɤɭɥɚɦɢ ɜ ɪɨɡɱɢɧɿ. ȱɑɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɣ ɩɪɨɹɜ «ɞɨɧɨɪɧɨʀ» ɱɚɫɬɢɧɢ ɇ-ɡɜ'ɹɡɤɭ ɜ ɞɚɧɢɣ ɱɚɫ ɞɨɛɪɟ ɜɢɜɱɟɧɢɣ ɹɤ ɬɟɨɪɟɬɢɱɧɨ, ɬɚɤ ɿ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ [128]. ɇɚ ɠɚɥɶ, ɱɟɪɟɡ ɫɢɥɶɧɟ ɩɨɝɥɢɧɚɧɧɹ Ɉɇ-ɝɪɭɩ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɜɢɜɱɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɬɢɩɭ N-H···O ɚɛɨ N-H···N ɦɚɽ ɬɪɭɞɧɨɳɿ. ɍ ɰɶɨɦɭ ɜɢɩɚɞɤɭ ɞɨɫɥɿɞɠɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɩɪɨɜɨɞɹɬɶɫɹ ɭ ɪɨɡɱɢɧɚɯ ɜɚɠɤɨʀ ɜɨɞɢ, ɜ ɹɤɢɯ ɜɿɞɛɭɜɚɽɬɶɫɹ ɫɭɬɬɽɜɢɣ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɣ ɿɡɨɬɨɩɧɢɣ ɡɫɭɜ ɜɚɥɟɧɬɧɢɯ ɿ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ ɝɪɭɩɢ OD, ɳɨ ɞɨɡɜɨɥɹɽ ɩɪɨɜɟɫɬɢ ɚɧɚɥɿɡ ɩɨɜɟɞɿɧɤɢ ɜɚɥɟɧɬɧɢɯ ɤɨɥɢɜɚɧɶ ɚɤɰɟɩɬɨɪɭ (ɧɚɩɪɢɤɥɚɞ, ɤɚɪɛɨɧɿɥɶɧɨʀ ɝɪɭɩɢ ɋ=Ɉ). ɍ ɪɨɛɨɬɿ [129] ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɪɨɡɝɥɹɞɚɽɬɶɫɹ ɧɚ ɨɫɧɨɜɿ ɡɧɚɱɟɧɶ ɱɚɫɬɨɬɢ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ ɿ ɜɫɬɚɧɨɜɥɟɧɨʀ ɟɦɩɿɪɢɱɧɨʀ ɡɚɥɟɠɧɨɫɬɿ ɡɦɿɧɢ ɱɚɫɬɨɬɢ ɤɨɥɢɜɚɧɧɹ ɋ=Ɉ-ɝɪɭɩ ɚɬɨɦɿɜ ɜɿɞ ɟɧɬɚɥɶɩɿʀ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ. Ɉɞɧɚɤ ɚɧɚɥɿɡ ɇ-ɡɜ'ɹɡɤɭ ɡɚ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɦ ɩɪɨɹɜɨɦ «ɞɨɧɨɪɧɨʀ» ɱɚɫɬɢɧɢ (ɧɚɩɪɢɤɥɚɞ, ɚɬɨɦɿɜ ɤɢɫɧɸ) ɩɨɜ'ɹɡɚɧɢɣ ɡ ɩɟɜɧɢɦɢ ɭɫɤɥɚɞɧɟɧɧɹɦɢ. əɤ ɛɭɥɨ ɩɨɤɚɡɚɧɨ ɪɚɧɿɲɟ [107], ɩɪɢ ɮɨɪɦɭɜɚɧɧɿ ɫɬɨɩɤɨɜɢɯ ɫɬɪɭɤɬɭɪ ɳɨ ɝɟɬɟɪɨɰɢɤɥɿɱɧɢɯ ɪɟɱɨɜɢɧ ɜɢɧɢɤɚɸɬɶ ɭɦɨɜɢ, ɩɪɢ ɹɤɢɯ ɫɬɚɸɬɶ ɦɨɠɥɢɜɢɦɢ ɪɟɡɨɧɚɧɫɧɿ (ɞɢɧɚɦɿɱɧɿ) ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ, ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ʀɯ ɱɚɫɬɨɬɧɢɦ ɡɫɭɜɨɦ. Ɍɨɦɭ ɩɪɢ ɚɧɚɥɿɡɿ ɇ-ɡɜ'ɹɡɤɿɜ ɡɚ ɱɚɫɬɨɬɨɸ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ ɰɟɣ ɟɮɟɤɬ ɧɟɨɛɯɿɞɧɨ ɜɪɚɯɨɜɭɜɚɬɢ. Ⱦɨɞɚɬɤɨɜɭ ɿɧɮɨɪɦɚɰɿɸ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ – ɜɧɭɬɪɿɲɧɶɨ- ɿ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ – ɦɨɠɧɚ ɨɬɪɢɦɚɬɢ ɧɚ ɩɿɞɫɬɚɜɿ ɚɧɚɥɿɡɭ ɪɟɡɭɥɶɬɚɬɿɜ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ: ɤɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɢɯ ɪɨɡɪɚɯɭɧɤɿɜ ɿ ɦɟɬɨɞɿɜ Ɇɨɧɬɟ-Ʉɚɪɥɨ ɬɚ ɦɨɥɟɤɭɥɹɪɧɨʀ ɞɢɧɚɦɿɤɢ. 47 Ɇɿɠɦɨɥɟɤɭɥɹɪɧɿ ɜɨɞɧɟɜɿ ɡɜ'ɹɡɤɢ ɛɭɥɢ ɜɢɹɜɥɟɧɿ ɭ ɧɭɤɥɟɨɡɢɞɿɜ [130, 131], ɧɭɤɥɟɨɬɢɞɿɜ [132] ɬɚ ɤɨɦɩɥɟɤɫɿɜ ɧɭɤɥɟʀɧɨɜɢɯ ɨɫɧɨɜ ɡ ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ [133], ɨɩɬɢɦɿɡɨɜɚɧɿ ɫɬɪɭɤɬɭɪɢ ɹɤɢɯ ɨɬɪɢɦɚɧɿ ɦɟɬɨɞɚɦɢ ɤɜɚɧɬɨɜɨʀ ɯɿɦɿʀ ɡɚ ɞɨɩɨɦɨɝɨɸ ɬɟɨɪɿʀ ɮɭɧɤɰɿɨɧɚɥɭ ɝɭɫɬɢɧɢ. ɍɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɜɢɡɧɚɱɚɥɨɫɹ ɡɚ ɤɪɢɬɟɪɿɹɦɢ, ɡɚɩɪɨɩɨɧɨɜɚɧɢɦɢ ɉɨɩɟɥ'ɽ ɬɚ Ʉɨɯɨɦ [134, 135], ɡɚ ɞɨɩɨɦɨɝɨɸ ɟɧɟɪɝɟɬɢɱɧɢɯ ɿ ɫɬɪɭɤɬɭɪɧɢɯ ɤɪɢɬɟɪɿʀɜ ɇ-ɡɜ'ɹɡɤɿɜ [136, 137] ɬɚ ɧɚ ɩɿɞɫɬɚɜɿ ɚɧɚɥɿɡɭ ɬɨɩɨɥɨɝɿʀ ɪɨɡɩɨɞɿɥɭ ɟɥɟɤɬɪɨɧɧɨʀ ɝɭɫɬɢɧɢ ɜ ɧɚɛɥɢɠɟɧɧɿ AIM (Atoms in Molecules) [138]. Ⱦɥɹ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɤɨɮɟʀɧɭ, ɩɨɯɿɞɧɢɯ ɚɤɬɢɧɨɰɢɧɭ (ɚɧɚɥɨɝɿɜ ɩɪɨɬɢɩɭɯɥɢɧɧɨɝɨ ɚɧɬɢɛɿɨɬɢɤɚ ɝɟɨɦɟɬɪɢɱɧɢɯ ɤɪɢɬɟɪɿʀɜ. ɇ-ɡɜ'ɹɡɤɭ ɚɤɬɢɧɨɦɿɰɢɧɭ Ȼɭɥɨ HB 'Gim D) [139] ɜɧɭɬɪɿɲɧɶɨɡɧɚɱɟɧɧɹ ɨɬɪɢɦɚɧɟ ɿ ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɜɢɡɧɚɱɚɥɢɫɹ ɬɚɤɨɠ ɧɚ ɩɿɞɫɬɚɜɿ ɟɧɟɪɝɟɬɢɱɧɢɯ ɿ ɜɢɤɨɪɢɫɬɚɧɨ = -9 ɤɤɚɥ/ɦɨɥɶ, ɟɧɟɪɝɿʀ ɲɥɹɯɨɦ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɭɫɟɪɟɞɧɟɧɧɹ ɪɟɡɭɥɶɬɚɬɿɜ ɤɚɥɨɪɢɦɟɬɪɢɱɧɢɯ ɜɢɦɿɪɿɜ ɪɨɡɝɨɪɬɚɧɧɹ ɛɿɥɤɿɜ, ɹɤɟ ɭɡɝɨɞɠɭɽɬɶɫɹ ɡ ɬɟɨɪɟɬɢɱɧɢɦɢ ɡɧɚɱɟɧɧɹɦɢ ɞɥɹ HB ɜɧɭɬɪɿɲɧɶɨɦɨɥɟɤɭɥɹɪɧɢɯ ɇ- ɡɜ'ɹɡɤɿɜ ɭ ɛɿɥɤɚɯ 'Gim = (-6...-18) ɤɤɚɥ/ ɦɨɥɶ [140] ( ɫɟɪɟɞɧɽ ɡɧɚɱɟɧɧɹ § -9 ɤɤɚɥ/ɦɨɥɶ [141]). Ɍɚɤɨɠ ɞɥɹ ɜɫɬɚɧɨɜɥɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶɫɹ ɝɟɨɦɟɬɪɢɱɧɿ ɤɪɢɬɟɪɿʀ ȼ. ȱ. ɉɨɥɬɽɜɚ: ɧɚɹɜɧɿɫɬɶ ɇ-ɡɜ'ɹɡɤɭ ɮɿɤɫɭɽɬɶɫɹ, ɹɤɳɨ ɜɿɞɫɬɚɧɶ ɦɿɠ ɚɬɨɦɚɦɢ ɞɨɧɨɪɭ ɬɚ ɚɤɰɟɩɬɨɪɭ ɧɟ ɩɟɪɟɜɢɳɭɽ 3,2 Å, ɚ ɦɿɠ ɚɬɨɦɚɦɢ ɜɨɞɧɸ ɬɚ ɚɤɰɟɩɬɨɪɭ – 2,4 Å [142, 143]. ɉɢɬɚɧɧɹ ɩɪɨ ɞɨɞɚɬɤɨɜɭ ɫɬɚɛɿɥɿɡɚɰɿɸ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ɪɨɡɝɥɹɞɚɽɬɶɫɹ ɜ ɞɚɧɢɣ ɱɚɫ ɜ ɹɤɨɫɬɿ ɨɞɧɿɽʀ ɡɿ ɫɬɪɚɬɟɝɿɣ ɫɬɜɨɪɟɧɧɹ ɟɮɟɤɬɢɜɧɢɯ ɦɨɥɟɤɭɥ-ɿɧɬɟɪɰɟɩɬɨɪɿɜ, ɹɤɿ ɡɚ ɪɚɯɭɧɨɤ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɩɟɪɟɯɨɩɥɸɸɬɶ ɜɢɫɨɤɨɬɨɤɫɢɱɧɿ ɚɪɨɦɚɬɢɱɧɿ ɦɭɬɚɝɟɧɢ ɿ ɤɚɧɰɟɪɨɝɟɧɢ [11]. Ɍɨɦɭ ɡ'ɹɫɭɜɚɧɧɹ ɪɨɥɿ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ H-ɡɜ'ɹɡɤɿɜ ɭ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ȻȺɊ ɽ ɚɤɬɭɚɥɶɧɨɸ ɡɚɞɚɱɟɸ. 48 1.4 ȱɧɬɟɪɰɟɩɬɨɪɧɿ ɜɥɚɫɬɢɜɨɫɬɿ ɬɚ ɛɿɨɥɨɝɿɱɧɨ ɜɚɠɥɢɜɿ ɤɨɦɛɿɧɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ Ʌɿɤɚɪɫɶɤɿ ɩɪɟɩɚɪɚɬɢ, ɨɫɧɨɜɨɸ ɹɤɢɯ ɽ ɚɪɨɦɚɬɢɱɧɿ ɫɩɨɥɭɤɢ, ɞɨɫɢɬɶ ɲɢɪɨɤɨ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶɫɹ ɜ ɤɨɦɛɿɧɨɜɚɧɿɣ ɬɟɪɚɩɿʀ ɪɚɤɨɜɢɯ ɡɚɯɜɨɪɸɜɚɧɶ. ȼɢɫɨɤɚ ɩɨɛɿɱɧɚ ɬɨɤɫɢɱɧɿɫɬɶ ɩɪɨɬɢɩɭɯɥɢɧɧɢɯ ɚɧɬɢɛɿɨɬɢɤɿɜ ɞɭɠɟ ɫɢɥɶɧɨ ɨɛɦɟɠɭɽ ɦɨɠɥɢɜɿɫɬɶ ʀɯ ɡɚɫɬɨɫɭɜɚɧɧɹ. Ɉɞɧɢɦ ɿɡ ɦɨɠɥɢɜɢɯ ɦɟɯɚɧɿɡɦɿɜ ɫɩɿɥɶɧɨʀ ɞɿʀ ɬɚɤɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ, ɳɨ ɪɟɝɭɥɸɸɬɶ ɦɟɞɢɤɨ-ɛɿɨɥɨɝɿɱɧɭ ɚɤɬɢɜɧɿɫɬɶ ɩɪɟɩɚɪɚɬɿɜ, ɦɨɠɟ ɜɢɫɬɭɩɚɬɢ ɿɧɬɟɪɰɟɩɬɨɪɧɢɣ ɦɟɯɚɧɿɡɦ, ɹɤɢɦ ɽ ɭɬɜɨɪɟɧɧɹ ɤɨɦɩɥɟɤɫɿɜ Ʌɿɝɚɧɞ-Ʌɿɝɚɧɞ [11, 144]. ȼɿɞɨɦɨ, ɳɨ ɦɨɥɟɤɭɥɢ ɤɫɚɧɬɢɧɨɜɨɝɨ ɬɢɩɭ, ɡɨɤɪɟɦɚ, ɤɨɮɟʀɧ ɬɚ ɣɨɝɨ ɩɨɯɿɞɧɿ, ɩɟɪɟɲɤɨɞɠɚɸɬɶ ɛɿɨɥɨɝɿɱɧɿɣ ɞɿʀ ɩɪɟɩɚɪɚɬɿɜ, ɦɿɲɟɧɧɸ ɞɥɹ ɹɤɢɯ ɽ ȾɇɄ. CAF ɦɨɠɟ ɡɦɿɧɸɜɚɬɢ ɬɟɪɚɩɟɜɬɢɱɧɭ ɟɮɟɤɬɢɜɧɿɫɬɶ ɞɟɹɤɢɯ ɥɿɤɚɪɫɶɤɢɯ ɩɪɟɩɚɪɚɬɿɜ, ɡɨɤɪɟɦɚ, ɩɪɨɬɢɩɭɯɥɢɧɧɢɯ ɚɧɬɢɛɿɨɬɢɤɿɜ – ɚɤɬɢɧɨɦɿɰɢɧɭ D, ɞɚɭɧɨɦɿɰɢɧɭ, ɦɿɬɚɤɫɚɧɬɪɨɧɭ ɿ ɤɚɧɰɟɪɨɝɟɧɧɢɯ ɫɩɨɥɭɤ – ɟɬɢɞɿɹ ɛɪɨɦɿɞɭ, ɩɪɨɮɥɚɜɿɧɭ, ɚɤɪɢɞɢɧɨɜɨɝɨ ɩɨɦɚɪɚɧɱɟɜɨɝɨ [145-147]. ɉɪɟɩɚɪɚɬɢ, ɛɿɨɥɨɝɿɱɧɭ ɞɿɸ ɹɤɢɯ ɡɦɿɧɸɽ ɤɨɮɟʀɧ, – ɰɟ ɚɪɨɦɚɬɢɱɧɿ ɫɩɨɥɭɤɢ, ɞɨ ɫɤɥɚɞɭ ɹɤɢɯ ɜɯɨɞɹɬɶ ɩɨɥɿɰɢɤɥɿɱɧɿ ɩɥɨɫɤɿ ɯɪɨɦɨɮɨɪɢ. Ɉɤɪɿɦ ɬɨɝɨ, ɳɨ ɜɨɧɢ ɽ ɤɥɚɫɢɱɧɢɦɢ ɿɧɬɟɪɤɚɥɹɬɨɪɚɦɢ, ɜɨɧɢ ɦɚɸɬɶ ɜɢɫɨɤɿ ɤɨɧɫɬɚɧɬɢ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ [9, 33, 148, 149]. Ʉɨɮɟʀɧ, ɛɭɞɭɱɢ ɝɟɬɟɪɨɰɢɤɥɿɱɧɨɸ ɫɩɨɥɭɤɨɸ, ɬɚɤɨɠ ɡɞɚɬɧɢɣ ɭɬɜɨɪɸɜɚɬɢ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɚɫɨɰɿɚɬɢ ɭ ɮɨɪɦɿ ɫɬɨɩɨɤ [150, 151], ɚɥɟ ɦɚɽ ɛɿɥɶɲ ɧɢɡɶɤɭ ɤɨɧɫɬɚɧɬɭ ɫɚɦɨɚɫɨɰɿɚɰɿʀ [9]. Ɍɚɤɨɠ ɩɨɤɚɡɚɧɨ, ɳɨ CAF ɭɬɜɨɪɸɽ ɝɟɬɟɪɨɚɫɨɰɿɚɬɢ ɡ ɩɟɪɟɥɿɱɟɧɢɦɢ ɜɢɳɟ ȻȺɊ [9, 152]. Ɂɚ ɞɚɧɢɦɢ ɜɢɜɱɟɧɧɹ ɪɨɡɱɢɧɿɜ ɩɪɨɬɢɩɭɯɥɢɧɧɢɯ ɚɧɬɢɛɿɨɬɢɤɿɜ, ɩɨɯɿɞɧɢɯ ɚɤɬɢɧɨɰɢɧɭ ɬɚ ʀɯ ɡɦɿɲɚɧɢɯ ɪɨɡɱɢɧɿɜ ɡ ɤɨɮɟʀɧɨɦ ɦɟɬɨɞɨɦ əɆɊ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɨɬɪɢɦɚɧɨ ɦɨɠɥɢɜɿ ɫɬɪɭɤɬɭɪɢ ɞɢɦɟɪɿɜ, ɳɨ ɭɬɜɨɪɸɸɬɶɫɹ, ɭ ɮɨɪɦɿ ɫɬɨɩɨɤ [9, 76, 108, 146, 153] ɬɚ ɜɢɡɧɚɱɟɧɨ ɬɟɪɦɨɞɢɧɚɦɿɱɧɿ ɩɚɪɚɦɟɬɪɢ ɩɪɨɰɟɫɿɜ ɚɫɨɰɿɚɰɿʀ [9, 96, 154]. ɇɚ ɩɿɞɫɬɚɜɿ ɚɧɚɥɿɡɭ ɰɢɯ ɪɟɡɭɥɶɬɚɬɿɜ ɛɭɥɨ ɜɢɫɥɨɜɥɟɧɨ ɩɪɢɩɭɳɟɧɧɹ ɩɪɨ ɡɞɚɬɧɿɫɬɶ CAF ɡɦɟɧɲɭɜɚɬɢ ɤɨɧɰɟɧɬɪɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ɜ ɪɨɡɱɢɧɚɯ ɬɚ, ɹɤ 49 ɧɚɫɥɿɞɨɤ, ɡɧɢɠɭɜɚɬɢ ʀɯ ɛɿɨɥɨɝɿɱɧɭ ɚɤɬɢɜɧɿɫɬɶ. Ɍɨɛɬɨ ɦɨɥɟɤɭɥɢ ɤɨɮɟʀɧɭ ɽ ɿɧɬɟɪɰɟɩɬɨɪɚɦɢ – «ɩɟɪɟɯɨɩɥɸɜɚɱɚɦɢ» – ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ [146, 151]. Ɂɚ ɬɚɤɢɦ ɠɟ ɦɟɯɚɧɿɡɦɨɦ ɦɨɠɧɚ ɡɧɢɠɭɜɚɬɢ ɬɨɤɫɢɱɧɿɫɬɶ ɩɪɨɬɢɩɭɯɥɢɧɧɢɯ ɩɪɟɩɚɪɚɬɿɜ ɿ ɦɭɬɚɝɟɧɿɜ. ɍ ɪɨɛɨɬɿ [155] ɛɭɥɨ ɩɨɤɚɡɚɧɨ, ɳɨ ɰɢɬɨɬɨɤɫɢɱɧɿɫɬɶ ɚɞɪɿɚɦɿɰɿɧɭ ɡɦɟɧɲɢɥɚɫɹ ɜ ɩɪɢɫɭɬɧɨɫɬɿ CAF, ɬɨɞɿ ɹɤ ɰɢɬɨɬɨɤɫɢɱɧɨɫɬɶ ɟɥɥɿɩɬɿɰɿɧɭ, ɚɤɬɢɧɨɦɿɰɢɧɭ D ɿ ɯɿɤɚɧɬɨɧɭ ɡɧɚɱɧɨ ɡɛɿɥɶɲɢɥɚɫɹ. ɇɚ ɩɿɞɫɬɚɜɿ ɰɢɯ ɮɚɤɬɨɪɿɜ ɛɭɥɨ ɡɪɨɛɥɟɧɨ ɩɪɢɩɭɳɟɧɧɹ, ɳɨ ɿɧɬɟɪɤɚɥɸɸɱɿ ɚɝɟɧɬɢ ɜɢɤɥɢɤɚɸɬɶ ɭɬɜɨɪɟɧɧɹ ɪɨɡɪɢɜɿɜ ɭ ȾɇɄ. Ⱥɜɬɨɪɚɦɢ ɪɨɛɨɬɢ [156] ɬɚɤɨɠ ɡɪɨɛɥɟɧɨ ɜɢɫɧɨɜɨɤ ɩɪɨ ɬɟ, ɳɨ CAF ɩɨɦɿɬɧɨ ɡɧɢɠɭɽ ɰɢɬɨɬɨɤɫɢɱɧɿɫɬɶ ɚɞɪɿɚɦɿɰɢɧɭ ɬɚ ɣɨɝɨ ɚɧɚɥɨɝɭ AD32 (N-ɬɪɢɮɬɨɪɨ-ɚɰɟɬɿɥɚɞɪɿɚɦɿɰɢɧ-14-ɜɚɥɟɪɚɬɭ). ɐɟɣ ɟɮɟɤɬ ɩɨɬɟɧɰɿɣɧɨ ɦɨɠɟ ɦɚɬɢ ɞɭɠɟ ɜɚɠɥɢɜɟ ɡɧɚɱɟɧɧɹ ɜ ɤɥɿɧɿɱɧɿɣ ɩɪɚɤɬɢɰɿ, ɧɚɩɪɢɤɥɚɞ, ɞɥɹ ɲɜɢɞɤɨɝɨ ɪɟɝɭɥɸɜɚɧɧɹ ɪɿɜɧɹ ɬɨɤɫɢɱɧɨɫɬɿ ɩɪɢ ɩɟɪɟɞɨɡɭɜɚɧɧɿ. Ɇɟɯɚɧɿɡɦ ɬɚɤɨʀ ɞɿʀ ɤɨɮɟʀɧɭ ɜ ɫɢɫɬɟɦɚɯ Ʌɉ-CAF ɦɨɠɧɚ ɩɨɹɫɧɢɬɢ ɡ ɬɨɱɤɢ ɡɨɪɭ ɞɜɨɯ ɨɫɧɨɜɧɢɯ ɦɨɥɟɤɭɥɹɪɧɢɯ ɩɪɨɰɟɫɿɜ, ɳɨ ɞɿɸɬɶ ɨɞɧɨɱɚɫɧɨ, ɚ ɫɚɦɟ: ɿɧɬɟɪɰɟɩɬɨɪɧɚ ɞɿɹ (ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɹ CAF ɿ ɥɿɤɚɪɫɶɤɨɝɨ ɩɪɟɩɚɪɚɬɭ) [145, 146] ɿ ɩɪɨɬɟɤɬɨɪɧɚ ɞɿɹ (ɜɢɬɿɫɧɟɧɧɹ ɥɿɤɚɪɫɶɤɨɝɨ ɩɪɟɩɚɪɚɬɭ ɡ ȾɇɄ ɜɧɚɫɥɿɞɨɤ ɡɜ'ɹɡɭɜɚɧɧɹ CAF ɡ ȾɇɄ) [9, 153, 157] (ɪɢɫ. 1.5). ɩɪɨɬɟɤɬɨɪɧɢɣ ɦɟɯɚɧɿɡɦ Ɋɢɫɭɧɨɤ 1.5 ȱɧɬɟɪɰɟɩɬɨɪɧɢɣ ɿ ɩɪɨɬɟɤɬɨɪɧɢɣ ɦɟɯɚɧɿɡɦɢ ɡɦɿɧɢ ɧɚ ɦɨɥɟɤɭɥɹɪɧɨɦɭ ɪɿɜɧɿ ɛɿɨɥɨɝɿɱɧɨʀ ɚɤɬɢɜɧɨɫɬɿ ɚɪɨɦɚɬɢɱɧɢɯ ɥɿɝɚɧɞɿɜ ɿɧɬɟɪɰɟɩɬɨɪɧɢɣ ɦɟɯɚɧɿɡɦ 50 ȼ ɨɛɨɯ ɜɢɩɚɞɤɚɯ ɩɪɢ ɞɨɞɚɜɚɧɧɿ ɦɨɥɟɤɭɥ ɤɨɮɟʀɧɭ ɜ ɛɿɨɥɨɝɿɱɧɭ ɫɢɫɬɟɦɭ, ɹɤɚ ɦɿɫɬɢɬɶ ɥɿɤɚɪɫɶɤɢɣ ɩɪɟɩɚɪɚɬ, ɤɨɧɰɟɧɬɪɚɰɿɹ ɤɨɦɩɥɟɤɫɿɜ Ʌɉ-ȾɇɄ ɡɦɟɧɲɭɽɬɶɫɹ, ɳɨ ɩɪɢɡɜɨɞɢɬɶ ɞɨ ɡɦɿɧɢ ɛɿɨɥɨɝɿɱɧɨʀ ɞɿʀ ɩɪɟɩɚɪɚɬɭ. Ȼɭɥɨ ɩɨɤɚɡɚɧɨ, ɳɨ ɞɨɞɚɜɚɧɧɹ CAF ɜ ɪɨɡɱɢɧ ɩɪɢɡɜɨɞɢɬɶ ɞɨ ɡɧɢɠɟɧɧɹ ɡɜ'ɹɡɭɜɚɧɧɹ ɥɿɤɚɪɫɶɤɨɝɨ ɩɪɟɩɚɪɚɬɭ ɚɛɨ ɦɭɬɚɝɟɧɚ ɡ ȾɇɄ, ɳɨ ɜɢɡɧɚɱɚɽɬɶɫɹ ɤɨɧɤɭɪɟɧɰɿɽɸ ɡɚ ɦɿɫɰɹ ɡɜ'ɹɡɭɜɚɧɧɹ ɦɿɠ CAF ɿ ɚɪɨɦɚɬɢɱɧɢɦɢ ɦɨɥɟɤɭɥɚɦɢ ɚɛɨ ɮɨɪɦɭɜɚɧɧɹɦ ɤɨɦɩɥɟɤɫɿɜ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ CAF-ɥɿɝɚɧɞ ɜ ɡɦɿɲɚɧɢɯ ɪɨɡɱɢɧɚɯ [9]. ɍ ɪɨɛɨɬɿ [158] ɜɢɹɜɥɟɧɨ ɤɨɧɰɟɧɬɪɚɰɿɣɧɨ-ɡɚɥɟɠɧɢɣ ɩɪɨɬɟɤɬɨɪɧɢɣ ɟɮɟɤɬ ɞɿʀ ɤɨɮɟʀɧɭ ɧɚ ɛɿɨɥɸɦɿɧɟɫɰɟɧɰɿɸ ɤɭɥɶɬɭɪɢ ɛɚɤɬɟɪɿɣ P. leiognathi Sh1, ɳɨ ɫɜɿɬɹɬɶɫɹ, ɹɤɚ ɦɿɫɬɢɬɶ ɬɢɩɨɜɿ ɦɭɬɚɝɟɧɧɿ ɩɪɟɩɚɪɚɬɢ ɩɪɨɮɥɚɜɿɧ ɿ ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ. ɐɹ ɞɿɹ ɩɨɥɹɝɚɽ ɭ ɜɿɞɧɨɜɥɟɧɧɿ ɛɿɨɥɸɦɿɧɟɫɰɟɧɬɧɨɝɨ ɫɢɝɧɚɥɭ ɩɿɞ ɱɚɫ ɜɜɟɞɟɧɧɹ CAF. Ɉɬɪɢɦɚɧɿ ɞɚɧɿ ɨɩɨɫɟɪɟɞɤɨɜɚɧɨ ɜɤɚɡɭɸɬɶ ɧɚ ɬɟ, ɳɨ ɜ ɨɫɧɨɜɿ ɫɩɨɫɬɟɪɟɠɭɜɚɧɨɝɨ ɟɮɟɤɬɭ ɥɟɠɢɬɶ ɿɧɬɟɪɰɟɩɬɨɪɧɢɣ ɦɟɯɚɧɿɡɦ, ɨɛɭɦɨɜɥɟɧɢɣ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɽɸ ɩɪɟɩɚɪɚɬɿɜ ɡ CAF, ɝɚɪɧɨ ɜɿɞɨɦɢɣ ɡ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɚɧɢɯ ɞɥɹ ɿɧɲɢɯ ɤɥɿɬɢɧɧɢɯ ɫɢɫɬɟɦ. ȼɿɬɚɦɿɧɢ ɝɪɭɩɢ B2 ɲɢɪɨɤɨ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶɫɹ ɜ ɹɤɨɫɬɿ ɟɥɟɦɟɧɬɿɜ ɜɿɬɚɦɿɧɨɬɟɪɚɩɿʀ, ɹɤɚ ɡɧɢɠɭɽ ɩɨɛɿɱɧɿ ɟɮɟɤɬɢ ɜɿɞ ɜɜɟɞɟɧɧɹ ɜ ɨɪɝɚɧɿɡɦ ɜɢɫɨɤɨɬɨɤɫɢɱɧɨɝɨ ɩɪɟɩɚɪɚɬɭ. Ɏɥɚɜɿɧɨɜɿ ɧɭɤɥɟɨɬɢɞɢ ɜɿɞɿɝɪɚɸɬɶ ɜɚɠɥɢɜɭ ɪɨɥɶ ɭ ɡɚɯɢɫɬɿ ɬɜɚɪɢɧ ɚɛɨ ɥɸɞɢɧɢ ɜɿɞ ɧɟɫɩɪɢɹɬɥɢɜɢɯ ɛɿɨɥɨɝɿɱɧɢɯ ɧɚɫɥɿɞɤɿɜ ɜɩɥɢɜɭ ɩɨɥɿɰɢɤɥɿɱɧɢɯ ɜɭɝɥɟɜɨɞɧɿɜ [159]. Ⱦɨɫɥɿɞɠɟɧɧɹ ɜɡɚɽɦɨɞɿʀ ɮɥɚɜɿɧɨɜɢɯ ɫɩɨɥɭɤ ɡ ɞɟɹɤɢɦɢ ɩɨɯɿɞɧɢɦɢ ȕ-ɤɚɪɛɨɥɿɧɭ (ɩɪɟɩɚɪɚɬɢ-ɚɧɬɢɞɟɩɪɟɫɚɧɬɢ, ɹɤɿ ɦɚɸɬɶ ɹɫɤɪɚɜɨ ɜɢɪɚɠɟɧɟ ɿɧɝɿɛɭɜɚɧɧɹ ɦɨɧɨɚɦɿɧɨɤɫɢɞɚɡɢ, MAO) ɩɨɤɚɡɚɥɨ, ɳɨ ȕ-ɤɚɪɛɨɥɿɧɢ ɦɨɠɭɬɶ ɤɨɧɤɭɪɭɜɚɬɢ ɡ ɚɦɿɧɨɦ ɡɚ ɞɨɩɨɦɨɝɨɸ ɮɥɚɜɿɧɨɜɨɝɨ ɡɚɥɢɲɤɭ ɆȺɈ ɬɚ ɿɦɿɬɭɜɚɬɢ ɩɪɨɰɟɫ ɩɟɪɟɧɟɫɟɧɧɹ ɟɥɟɤɬɪɨɧɿɜ, ɛɥɨɤɭɸɱɢ ɚɤɬɢɜɧɢɣ ɰɟɧɬɪ [160, 161]. Ɍɚɤɨɠ ɪɢɛɨɮɥɚɜɿɧ ɧɚɞɚɽ ɤɚɪɞɿɨɩɪɨɬɟɤɬɨɪɧɢɣ ɟɮɟɤɬ ɩɪɢ ɪɟɨɤɫɢɝɟɧɚɰɿʀ ɫɟɪɰɹ [162]. ȼɜɟɞɟɧɧɹ RBF ɡɧɢɠɭɽ ɤɿɥɶɤɿɫɬɶ ɨɞɢɧɨɱɧɢɯ ɪɨɡɪɢɜɿɜ ɭ ɹɞɟɪɧɿɣ ȾɇɄ, ɿɧɞɭɤɨɜɚɧɢɯ ɚɮɥɚɬɨɤɫɢɧɨɦ ȼ1 ɬɚ N-ɧɿɬɪɨɡɨɞɢɦɟɬɢɥɚɦɿɧɨɦ [163]. Ɉɫɤɿɥɶɤɢ ɩɨɲɤɨɞɠɟɧɧɹ ȾɇɄ ɬɚ ʀʀ ɪɟɩɚɪɚɰɿɹ ɦɨɠɭɬɶ ɛɭɬɢ ɩɨɜ'ɹɡɚɧɿ ɡ ɤɚɧɰɟɪɨɝɟɧɟɡɨɦ, ɡɦɿɧɚ ɰɢɯ ɩɚɪɚɦɟɬɪɿɜ ɡɚ ɞɨɩɨɦɨɝɨɸ ɪɢɛɨɮɥɚɜɿɧɭ ɩɟɪɟɞɛɚɱɚɽ 51 ɩɨɬɟɧɰɿɣɧɭ ɯɿɦɿɨɩɪɨɮɿɥɚɤɬɢɱɧɭ ɪɨɥɶ ɰɶɨɝɨ ɜɿɬɚɦɿɧɭ. Ɋɚɧɿɲɟ ɛɭɥɨ ɜɢɹɜɥɟɧɨ ɩɪɨɬɟɤɬɨɪɧɭ ɞɿɸ ɪɢɛɨɮɥɚɜɿɧɭ ɩɨ ɜɿɞɧɨɲɟɧɧɸ ɞɨ ȾɇɄ, ɹɤɚ ɩɨɥɹɝɚɽ ɜ ɡɧɚɱɧɨɦɭ ɡɦɟɧɲɟɧɧɿ ɡɜ'ɹɡɭɜɚɧɧɹ ɚɪɨɦɚɬɢɱɧɢɯ ɦɭɬɚɝɟɧɿɜ ɡ ȾɇɄ ɭ ɩɪɢɫɭɬɧɨɫɬɿ ɜɿɬɚɦɿɧɭ. Ʉɪɿɦ ɬɨɝɨ ɧɟɞɨɥɿɤ ɪɢɛɨɮɥɚɜɿɧɭ ɜ ɨɪɝɚɧɿɡɦɿ ɦɨɠɟ ɡɛɿɥɶɲɢɬɢ ɪɢɡɢɤ ɤɚɪɰɟɧɨɝɟɧɟɡɭ [164]. Ɇɟɬɨɞɨɦ ɨɞɧɨɜɢɦɿɪɧɨʀ ɬɚ ɞɜɨɜɢɦɿɪɧɨʀ 1 ɇ-əɆɊ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ (500 ɆȽɰ) ɛɭɥɨ ɞɨɫɥɿɞɠɟɧɨ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɸ ɩɪɨɬɢɩɭɯɥɢɧɧɨɝɨ ɚɧɬɢɛɿɨɬɢɤɚ ɧɨɜɚɬɪɨɧɭ ɡ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɨɦ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ ɞɥɹ ɜɢɡɧɚɱɟɧɧɹ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɦɟɯɚɧɿɡɦɭ ɦɨɠɥɢɜɨʀ ɤɨɦɛɿɧɨɜɚɧɨʀ ɞɿʀ ɚɧɬɢɛɿɨɬɢɤɭ ɿ FMN. Ⱥɧɚɥɿɡ ɨɬɪɢɦɚɧɢɯ ɪɟɡɭɥɶɬɚɬɿɜ ɫɜɿɞɱɢɬɶ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ ɡɚ ɪɚɯɭɧɨɤ ɫɬɟɤɿɧɝ-ɜɡɚɽɦɨɞɿɣ ɦɿɠ ɚɪɨɦɚɬɢɱɧɢɦɢ ɯɪɨɦɨɮɨɪɚɦɢ ɡ ɦɨɠɥɢɜɨɸ ɞɨɞɚɬɤɨɜɨɸ ɫɬɚɛɿɥɿɡɚɰɿɽɸ ɡɚ ɞɨɩɨɦɨɝɨɸ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ. Ⱥɜɬɨɪɚɦɢ ɡɪɨɛɥɟɧɢɣ ɜɢɫɧɨɜɨɤ [84], ɳɨ ɚɪɨɦɚɬɢɱɧɿ ɦɨɥɟɤɭɥɢ ɜɿɬɚɦɿɧɿɜ, ɡɨɤɪɟɦɚ ɪɢɛɨɮɥɚɜɿɧ, ɦɨɠɭɬɶ ɭɬɜɨɪɸɜɚɬɢ ɟɧɟɪɝɟɬɢɱɧɨ ɫɬɚɛɿɥɶɧɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɢ ɡ ɩɪɨɬɢɩɭɯɥɢɧɧɢɦɢ ɚɧɬɢɛɿɨɬɢɤɚɦɢ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ ɿ, ɬɢɦ ɫɚɦɢɦ, ɜɩɥɢɜɚɬɢ ɧɚ ɟɮɟɤɬɢɜɧɿɫɬɶ ʀɯ ɦɟɞɢɤɨ-ɛɿɨɥɨɝɿɱɧɨʀ ɞɿʀ. 1.5 Ɉɫɨɛɥɢɜɨɫɬɿ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ȼɢɜɱɟɧɧɹ ɫɬɪɭɤɬɭɪɧɨɝɨ ɫɬɚɧɭ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɜ ɡɜɨɥɨɠɟɧɢɯ ɩɥɿɜɤɚɯ ɽ ɧɟɨɛɯɿɞɧɿɫɬɸ, ɨɫɤɿɥɶɤɢ ɫɚɦɟ ɬɚɤɢɣ ɤɨɧɞɟɧɫɨɜɚɧɢɣ ɫɬɚɧ ɦɚɤɫɢɦɚɥɶɧɨ ɧɚɛɥɢɠɟɧɢɣ ɞɨ ɩɪɢɪɨɞɧɢɯ ɭɦɨɜ ɮɭɧɤɰɿɨɧɭɜɚɧɧɹ FMN ɭ ɠɢɜɢɯ ɫɢɫɬɟɦɚɯ. Ⱦɨɫɥɿɞɠɟɧɧɹ ɫɬɪɭɤɬɭɪɢ FMN ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɦɟɬɨɞɨɦ əɆɊɫɩɟɤɬɪɨɫɤɨɩɿʀ ɩɨɤɚɡɚɥɨ, ɳɨ ɜ ɧɟɣɬɪɚɥɶɧɢɯ ɫɟɪɟɞɨɜɢɳɚɯ (pH = 7) ɣɨɝɨ ɦɨɥɟɤɭɥɢ ɚɝɪɟɝɭɸɬɶ ɡ ɤɨɧɫɬɚɧɬɨɸ ɫɚɦɨɚɫɨɰɿɚɰɿʀ 265 Ɇ-1 [54, 55]. ɐɟ ɞɨɡɜɨɥɢɥɨ ɜɢɡɧɚɱɢɬɢ ɬɟɪɦɨɞɢɧɚɦɿɱɧɿ ɩɚɪɚɦɟɬɪɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɬɚ ɪɨɡɪɚɯɭɜɚɬɢ ɩɪɨɫɬɨɪɨɜɭ ɫɬɪɭɤɬɭɪɭ ɞɢɦɟɪɭ FMN [55, 56], ɹɤɢɣ ɭɬɜɨɪɸɽɬɶɫɹ ɜ ɪɟɡɭɥɶɬɚɬɿ ɫɬɟɤɿɧɝ-ɜɡɚɽɦɨɞɿɣ ɦɿɠ ɯɪɨɦɨɮɨɪɚɦɢ FMN – ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɦɢ ɤɿɥɶɰɹɦɢ. ɍ ɪɨɛɨɬɿ [55] ɧɚ ɨɫɧɨɜɿ ɚɧɚɥɿɡɭ ɫɩɟɤɬɪɿɜ əɆɊ ɡɚɩɪɨɩɨɧɨɜɚɧɨ ɩɚɪɚɥɟɥɶɧɟ 52 ɪɨɡɬɚɲɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ ɭ ɫɬɨɩɤɨɨɛɪɚɡɧɢɯ ɫɚɦɨɚɫɨɰɿɚɬɚɯ FMN. Ɇɟɬɨɞɨɦ ɦɨɥɟɤɭɥɹɪɧɨʀ ɞɢɧɚɦɿɤɢ ɨɬɪɢɦɚɧɨ ɿɧɲɟ, ɚɧɬɢɩɚɪɚɥɟɥɶɧɟ ɪɨɡɬɚɲɭɜɚɧɧɹ ɤɿɥɟɰɶ ɭ ɫɬɟɤɿɧɝ-ɞɢɦɟɪɿ FMN [165] (ɪɢɫ. 1.6). Ɋɢɫɭɧɨɤ 1.6 ɫɬɪɭɤɬɭɪɢ ɜɚɤɭɭɦɿ [165] ɞɢɦɟɪɭ ɉɪɨɟɤɰɿɹ FMN ɭ Ⱦɨɫɥɿɞɠɟɧɧɹ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɧɭɤɥɟɨɡɢɞɿɜ, ɧɭɤɥɟɨɬɢɞɿɜ ɬɚ ɚɪɨɦɚɬɢɱɧɢɯ ɩɪɨɬɢɩɭɯɥɢɧɧɢɯ ɚɧɬɢɛɿɨɬɢɤɿɜ, ɜɢɤɨɧɚɧɿ ɪɿɡɧɢɦɢ ɮɿɡɢɱɧɢɦɢ ɦɟɬɨɞɚɦɢ (əɆɊ, ȱɑ-, ɍɎ-ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɬɚ ɿɧ.), ɩɨɤɚɡɚɥɢ, ɳɨ ɫɬɚɛɿɥɶɧɿɫɬɶ ʀɯ ɫɬɨɩɤɨɜɢɯ ɫɬɪɭɤɬɭɪ ɡɚɥɟɠɢɬɶ ɜɿɞ ɛɚɝɚɬɶɨɯ ɮɚɤɬɨɪɿɜ, ɭ ɬɨɦɭ ɱɢɫɥɿ ɜɿɞ ɪɿɜɧɹ ɝɿɞɪɚɬɚɰɿʀ [103, 104] ɬɚ ɟɥɟɤɬɪɨɫɬɚɬɢɱɧɢɯ ɜɡɚɽɦɨɞɿɣ, ɳɨ ɡɦɿɧɸɸɬɶɫɹ ɩɪɢ ɩɪɨɬɨɧɭɜɚɧɧɿ ɝɟɬɟɪɨɰɢɤɥɿɜ ɿ ɮɨɫɮɚɬɧɢɯ ɝɪɭɩ ɧɭɤɥɟɨɬɢɞɿɜ [65, 103, 166, 167]. Ɉɫɤɿɥɶɤɢ ɜ ɦɨɥɟɤɭɥɿ FMN ɽ ɮɨɫɮɚɬɧɚ ɝɪɭɩɚ ɿ ɦɨɠɥɢɜɟ ɩɪɨɬɨɧɭɜɚɧɧɹ ɩɨ ɚɬɨɦɚɯ ɚɡɨɬɭ N1 ɿ N5 ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ (ɞɢɜ. ɪɢɫ. 1.4), ɬɨ ɩɟɪɟɥɿɱɟɧɿ ɜɢɳɟ ɮɚɤɬɨɪɢ ɬɚɤɨɠ ɦɨɠɭɬɶ ɿɫɬɨɬɧɨ ɜɩɥɢɧɭɬɢ ɧɚ ɮɨɪɦɭɜɚɧɧɹ ɿ ɫɬɚɛɿɥɶɧɿɫɬɶ ɫɬɟɤɿɧɝɚɫɨɰɿɚɬɿɜ FMN ɭ ɧɟɣɬɪɚɥɶɧɢɯ ɿ ɫɥɚɛɨɤɢɫɥɢɯ ɜɨɞɧɢɯ ɫɟɪɟɞɨɜɢɳɚɯ. ɉɪɢ ɞɨɫɥɿɞɠɟɧɧɿ ɫɩɟɤɬɪɿɜ FMN ɜ ɍɎɿ ɜɢɞɢɦɿɣ ɨɛɥɚɫɬɿ ɩɨɝɥɢɧɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ (230-500 ɧɦ) ɛɭɥɨ ɨɬɪɢɦɚɧɨ ɞɚɧɿ ɩɪɨ ɩɪɨɬɨɧɭɜɚɧɧɹ FMN ɩɨ ɚɬɨɦɚɯ N1 ɿ N5 ɭ ɤɢɫɥɢɯ ɪɨɡɱɢɧɚɯ [168]. ɉɪɹɦɿ ɜɿɞɨɦɨɫɬɿ ɩɪɨ ɩɪɢɽɞɧɚɧɧɹ ɩɪɨɬɨɧɿɜ ɞɨ ɚɬɨɦɿɜ N1 ɿ N5 ɦɨɠɟ ɧɚɞɚɬɢ ɿɧɮɪɚɱɟɪɜɨɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ, ɨɫɤɿɥɶɤɢ ɧɚ ɞɚɧɢɣ ɱɚɫ ɜɢɤɨɧɚɧɨ ɞɨɫɢɬɶ ɧɚɞɿɣɧɚ ɿɧɬɟɪɩɪɟɬɚɰɿɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɤɨɥɢɜɚɧɶ ɡɚ ɭɱɚɫɬɸ ɚɬɨɦɿɜ 53 ɚɡɨɬɭ N1 ɿ N5 ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ȱɑ-ɫɩɟɤɬɪɿɜ FMN [169, 170]. Ⱦɨɞɚɬɤɨɜɿ ɜɿɞɨɦɨɫɬɿ ɩɪɨ ɜɩɥɢɜ ɩɪɨɬɨɧɭɜɚɧɧɹ ɧɚ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɿ ɤɨɥɢɜɚɧɧɹ ɦɨɠɧɚ ɨɬɪɢɦɚɬɢ ɡɚ ɞɨɩɨɦɨɝɨɸ ɤɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɢɯ ɪɨɡɪɚɯɭɧɤɿɜ [57, 58]. ɍ ɪɨɛɨɬɿ [57] ɞɨɫɥɿɞɠɟɧɧɹ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ, ɩɪɨɜɟɞɟɧɟ ɡɚ ɞɨɩɨɦɨɝɨɸ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɛɚɝɚɬɨɮɨɬɨɧɧɨʀ ɞɢɫɨɰɿɚɰɿʀ (IRMPD) ɿ ɤɜɚɧɬɨɜɨɯɿɦɿɱɧɢɯ ɪɨɡɪɚɯɭɧɤɿɜ ɭ ɧɚɛɥɢɠɟɧɧɿ ɬɟɨɪɿʀ ɮɭɧɤɰɿɨɧɚɥɭ ɝɭɫɬɢɧɢ (DFT), ɩɨɤɚɡɚɥɨ, ɳɨ FMN ɧɚɣɛɿɥɶɲ ɫɬɚɛɿɥɶɧɢɣ ɭ ɜɢɝɥɹɞɿ O2- ɿ N1-ɩɪɨɬɨɧɨɜɚɧɨɝɨ ɬɚɭɬɨɦɟɪɭ. Ⱦɨɫɥɿɞɠɟɧɧɹ ɮɿɡɢɤɨ-ɯɿɦɿɱɧɢɯ ɜɥɚɫɬɢɜɨɫɬɟɣ ɥɸɦɿɮɥɚɜɿɧɭ (ɦɨɞɟɥɶɧɨʀ ɫɩɨɥɭɤɢ ɪɢɛɨɮɥɚɜɿɧɭ) ɜ ɪɨɡɱɢɧɚɯ ɦɟɬɨɞɨɦ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɡ ɪɨɡɞɿɥɟɧɧɹɦ ɭ ɱɚɫɿ (TRIR) ɿ ɤɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɢɦɢ ɪɨɡɪɚɯɭɧɤɚɦɢ ɜ ɧɚɛɥɢɠɟɧɧɿ DFT ɩɨɤɚɡɚɥɢ, ɳɨ ɬɟɪɦɨɞɢɧɚɦɿɱɧɨ ɜɢɝɿɞɧɟ ɩɨɥɨɠɟɧɧɹ ɞɥɹ ɩɪɢɽɞɧɚɧɧɹ ɩɪɨɬɨɧɭ – ɰɟ ɚɬɨɦ ɚɡɨɬɭ N5 ɤɿɥɶɰɟɜɨʀ ɫɢɫɬɟɦɢ ɮɥɚɜɿɧɭ [57]. ɇɚɣɛɿɥɶɲ ɞɟɬɚɥɶɧɿ ɞɨɫɥɿɞɠɟɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɫɢɫɬɟɦ RBF/FMN-Ʌɉ ɛɭɥɢ ɜɢɤɨɧɚɧɿ ɡɚ ɞɨɩɨɦɨɝɨɸ əɆɊ ɫɩɟɤɬɪɨɫɤɨɩɿʀ. ɉɿɞ ɱɚɫ ɜɢɜɱɟɧɧɹ ɜɡɚɽɦɨɞɿʀ FMN ɡ ɚɧɬɢɛɿɨɬɢɤɚɦɢ (DAU, NOG, ɚɤɬɢɧɨɦɿɰɢɧɨɦ D ɬɚ NOV [82, 84]) ɬɚ ɦɭɬɚɝɟɧɚɦɢ (EB ɬɚ PF [86]) ɫɬɪɭɤɬɭɪɧɿ ɬɚ ɬɟɪɦɨɞɢɧɚɦɿɱɧɿ ɩɚɪɚɦɟɬɪɢ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɜɢɡɧɚɱɚɥɢ ɡ ɤɨɧɰɟɧɬɪɚɰɿɣɧɨʀ ɬɚ ɬɟɦɩɟɪɚɬɭɪɧɨʀ ɡɚɥɟɠɧɨɫɬɿ ɯɿɦɿɱɧɢɯ ɡɫɭɜɿɜ ɩɪɨɬɨɧɿɜ ɨɛɨɯ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ ɭ ɡɦɿɲɚɧɢɯ ɪɨɡɱɢɧɚɯ. Ⱥɜɬɨɪɚɦɢ ɛɭɥɨ ɡɪɨɛɥɟɧɨ ɜɢɫɧɨɜɨɤ [82, 84, 86], ɳɨ ɜ ɪɨɡɱɢɧɿ ɚɪɨɦɚɬɢɱɧɿ ɦɨɥɟɤɭɥɢ ɭɬɜɨɪɸɜɚɥɢ ɤɨɦɩɥɟɤɫɢ ɬɢɩɭ «ɫɟɧɞɜɿɱ», ɹɤɿ ɫɬɚɛɿɥɿɡɭɜɚɥɢɫɹ ɫɬɟɤɿɧɝɜɡɚɽɦɨɞɿɹɦɢ ɯɪɨɦɨɮɨɪɿɜ. ȼɟɥɢɱɢɧɢ ɪɿɜɧɨɜɚɠɧɢɯ ɤɨɧɫɬɚɧɬ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɞɥɹ ɜɡɚɽɦɨɞɿʀ FMN ɡ NOG, DAU, NOR ɬɚ ɚɤɬɢɧɨɦɿɰɢɧɨɦ D ɩɪɢɣɦɚɥɢ ɩɪɨɦɿɠɧɿ ɡɚ ɜɟɥɢɱɢɧɨɸ ɡɧɚɱɟɧɧɹ ɦɿɠ ɤɨɧɫɬɚɧɬɚɦɢ ɪɿɜɧɨɜɚɝɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɨɤɪɟɦɢɯ ɦɨɥɟɤɭɥ. ɍ ɬɨɣ ɠɟ ɱɚɫ ɡɧɚɱɟɧɧɹ ɤɨɧɫɬɚɧɬ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɞɥɹ ɜɡɚɽɦɨɞɿʀ FMN ɡ NOV, EB, PF ɛɭɥɢ ɛɿɥɶɲɟ, ɧɿɠ ɜɿɞɩɨɜɿɞɧɿ ɤɨɧɫɬɚɧɬɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ, ɹɤɿ ɩɨɤɚɡɚɥɢ, ɳɨ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɰɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ɟɧɟɪɝɟɬɢɱɧɨ ɛɿɥɶɲ ɜɢɝɿɞɧɚ. Ʉɿɥɶɤɿɫɧɢɣ ɚɧɚɥɿɡ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɜɡɚɽɦɨɞɿʀ FMN ɡ ɰɢɦɢ ȻȺɊ, ɞɨɩɨɜɧɟɧɢɣ ɩɪɹɦɨɸ ɫɬɪɭɤɬɭɪɧɨɸ ɿɧɮɨɪɦɚɰɿɽɸ, 54 ɨɬɪɢɦɚɧɨɸ ɡ ɞɜɨɜɢɦɿɪɧɢɯ əɆɊ-ɫɩɟɤɬɪɿɜ, ɩɿɞɬɜɟɪɞɢɜ ɝɿɩɨɬɟɡɭ ɩɪɨ ɞɨɞɚɬɤɨɜɭ ɫɬɚɛɿɥɿɡɚɰɿɸ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɦ ɜɨɞɧɟɜɢɦ ɡɜ'ɹɡɤɨɦ. ɇɟ ɡɜɚɠɚɸɱɢ ɧɚ ɬɟ, ɳɨ ɜ ɥɿɬɟɪɚɬɭɪɿ ɡ'ɹɜɥɹɸɬɶɫɹ ɧɨɜɿ ɮɚɤɬɢ ɩɪɨ ɩɪɨɰɟɫɢ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ, ɩɪɨɛɥɟɦɚ ɩɪɨɹɜɭ ɛɿɨɥɨɝɿɱɧɨʀ ɚɤɬɢɜɧɨɫɬɿ ɛɭɞɶ-ɹɤɨʀ ɚɪɨɦɚɬɢɱɧɨʀ ɫɩɨɥɭɤɢ ɜ ɩɪɢɫɭɬɧɨɫɬɿ ɞɪɭɝɨɝɨ ɚɪɨɦɚɬɢɱɧɨɝɨ ɥɿɝɚɧɞɭ ɞɨ ɫɢɯ ɩɿɪ ɧɟ ɜɢɪɿɲɟɧɚ. Ɂɨɤɪɟɦɚ, ɧɟɞɨɫɬɚɬɧɶɨ ɜɢɜɱɟɧɿ ɦɟɯɚɧɿɡɦɢ ɡɜ'ɹɡɭɜɚɧɧɹ ȻȺɊ ɡ ȾɇɄ (ɩɪɢ ɩɪɨɬɟɤɬɨɪɧɿɣ ɞɿʀ), ɫɬɚɛɿɥɶɧɿɫɬɶ ɚɫɨɰɿɚɬɿɜ (ɩɪɢ ɿɧɬɟɪɰɟɩɬɨɪɧɿɣ ɞɿʀ), ɪɨɥɶ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ ɿ ɜɩɥɢɜ ɦɨɥɟɤɭɥ ɜɨɞɢ ɧɚ ɫɬɚɛɿɥɶɧɿɫɬɶ ɚɝɪɟɝɚɬɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ. Ɍɚɤɢɦ ɱɢɧɨɦ, ɞɥɹ ɜɫɬɚɧɨɜɥɟɧɧɹ ɫɬɪɭɤɬɭɪɧɢɯ ɨɫɨɛɥɢɜɨɫɬɟɣ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɪɟɱɨɜɢɧ ɜ ɩɪɟɞɫɬɚɜɥɟɧɿɣ ɞɢɫɟɪɬɚɰɿɣɧɿɣ ɪɨɛɨɬɿ ɛɭɥɢ ɩɨɫɬɚɜɥɟɧɿ ɿ ɜɢɪɿɲɟɧɿ ɧɚɫɬɭɩɧɿ ɡɚɜɞɚɧɧɹ. 1. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɦɟɬɨɞɭ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɿ ɩɪɨɜɟɫɬɢ ɩɨɪɿɜɧɹɥɶɧɟ ɜɢɜɱɟɧɧɹ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɬɚ ɝɿɞɪɚɬɚɰɿʀ FMN ɭ ɩɥɿɜɤɚɯ, ɜɢɪɨɳɟɧɢɯ ɡ ɧɟɣɬɪɚɥɶɧɢɯ ɿ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ, pH ɹɤɢɯ ɜɩɥɢɜɚɽ ɧɚ ɡɚɪɹɞɢ ɚɬɨɦɿɜ ɯɪɨɦɨɮɨɪɭ (ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ) ɿ ɮɨɫɮɚɬɧɢɯ ɝɪɭɩ. 2. Ⱦɥɹ ɜɫɬɚɧɨɜɥɟɧɧɹ ɰɟɧɬɪɿɜ ɡɜ'ɹɡɭɜɚɧɧɹ ɩɪɨɬɨɧɿɜ ɩɪɨɜɟɫɬɢ ɩɨɪɿɜɧɹɥɶɧɢɣ ɚɧɚɥɿɡ ɭ ɧɟɣɬɪɚɥɶɧɿɣ ɿ ɩɪɨɬɨɧɨɜɚɧɿɣ ɮɨɪɦɿ FMN ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɜ ɨɛɥɚɫɬɿ 1450-1600 ɫɦ-1, ɩɨɜ'ɹɡɚɧɢɯ ɡ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɦɢ ɤɨɥɢɜɚɧɧɹɦɢ ɚɬɨɦɿɜ ɋ–ɋ, ɋ–N1 ɿ ɋ–N5 ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ. 3. Ⱦɥɹ ɜɢɹɜɥɟɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɬɚ ʀɯ ɜɤɥɚɞɭ ɜ ɡɚɝɚɥɶɧɭ ɟɧɟɪɝɿɸ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɨɬɪɢɦɚɬɢ ɿ ɩɪɨɚɧɚɥɿɡɭɜɚɬɢ ɤɨɥɢɜɚɥɶɧɿ ɫɩɟɤɬɪɢ (ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɢ) ɮɭɧɤɰɿɨɧɚɥɶɧɢɯ ɝɪɭɩ ɚɬɨɦɿɜ (C=O ɿ NH2) ɪɿɡɧɢɯ ȻȺɊ ɬɚ ʀɯ ɫɭɦɿɲɟɣ ɜ ɭɦɨɜɚɯ, ɧɚɛɥɢɠɟɧɢɯ ɞɨ ɮɿɡɿɨɥɨɝɿɱɧɢɯ. 4. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ ɜɢɡɧɚɱɢɬɢ ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɜ ɫɢɫɬɟɦɚɯ, ɹɤɿ ɦɿɫɬɹɬɶ ɝɟɬɟɪɨɞɢɦɟɪɢ ɚɪɨɦɚɬɢɱɧɢɯ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɥɿɝɚɧɞɿɜ FMN-EB, FMN-PRF, TPH-EB, EB-CAF, FMN-TPH, PRF-TPH ɡ ɹɜɧɢɦ ɭɪɚɯɭɜɚɧɧɹɦ ɦɨɥɟɤɭɥ ɜɨɞɢ. 55 5. Ɇɟɬɨɞɚɦɢ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɄɊ ɫɜɿɬɥɚ ɞɨɫɥɿɞɢɬɢ ɡɜ'ɹɡɭɜɚɧɧɹ EB ɡ ɬɢɦɭɫɧɨɸ ȾɇɄ ɩɪɢ ɧɢɡɶɤɢɯ ɿ ɜɢɫɨɤɢɯ ɡɧɚɱɟɧɧɹɯ ɫɩɿɜɜɿɞɧɨɲɟɧɶ ɤɨɧɰɟɧɬɪɚɰɿɣ ɥɿɝɚɧɞ/ȾɇɄ; ɜɢɡɧɚɱɢɬɢ ɜɩɥɢɜ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ ɧɚ ɦɨɥɟɤɭɥɹɪɧɿ ɦɟɯɚɧɿɡɦɢ ɡɜ'ɹɡɭɜɚɧɧɹ EB ɡ ȾɇɄ ɩɪɢ ɭɬɜɨɪɟɧɧɿ ɤɨɦɩɥɟɤɫɿɜ ɡɚ ɬɢɩɨɦ ɿɧɬɟɪɤɚɥɹɰɿʀ ɬɚ ɡɨɜɧɿɲɧɶɨɝɨ ɡɜ'ɹɡɭɜɚɧɧɹ, ɚ ɬɚɤɨɠ ɜɢɹɜɢɬɢ ɫɬɪɭɤɬɭɪɧɢɣ ɫɬɚɧ ȾɇɄ ɩɪɢ ɳɿɥɶɧɨɦɭ ʀʀ ɡɚɩɨɜɧɟɧɧɿ ɥɢɝɚɧɞɨɦ. ȼɢɫɧɨɜɤɢ ɞɨ ɪɨɡɞɿɥɭ 1 1. ɇɚɜɟɞɟɧɨ ɡɚɝɚɥɶɧɭ ɯɚɪɚɤɬɟɪɢɫɬɢɤɭ ɚɪɨɦɚɬɢɱɧɢɯ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ, ɡɨɤɪɟɦɚ ɦɭɬɚɝɟɧɿɜ ɬɚ ɩɪɨɮɥɚɜɿɧɭ ɬɟɨɮɿɥɿɧɭ ɬɚ ɬɚ ɛɪɨɦɢɫɬɨɝɨ ɚɧɚɥɨɝɭ ɟɬɢɞɿɸ, ȼ2 ɦɟɬɢɥɤɫɚɧɬɢɧɿɜ ɤɨɮɟʀɧɭ ɜɿɬɚɦɿɧɭ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ. 2. Ⱦɚɧɨ ɡɚɝɚɥɶɧɭ ɯɚɪɚɤɬɟɪɢɫɬɢɤɭ ɿɧɬɟɪɰɟɩɬɨɪɧɢɦ ɜɥɚɫɬɢɜɨɫɬɹɦ ɿ ɛɿɨɥɨɝɿɱɧɨ ɜɚɠɥɢɜɢɦ ɤɨɦɛɿɧɚɰɿɹɦ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ. 3. Ⱦɟɬɚɥɶɧɨ ɪɨɡɝɥɹɧɭɬɨ ɫɚɦɨɚɫɨɰɿɚɰɿɸ ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɸ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ. ɇɚɜɟɞɟɧɨ ɡɚɝɚɥɶɧɿ ɭɹɜɥɟɧɧɹ ɩɪɨ ɨɫɨɛɥɢɜɨɫɬɿ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ. 4. ɉɪɨɚɧɚɥɿɡɨɜɚɧɨ ɿɫɧɭɸɱɿ ɦɟɬɨɞɢ ɞɨɫɥɿɞɠɟɧɧɹ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ȻȺɊ ɿ ɜɢɡɧɚɱɟɧɨ ɪɨɥɶ ɜɨɞɢ ɿ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɫɬɚɛɿɥɿɡɚɰɿʀ ɚɫɨɰɿɚɬɿɜ ȻȺɊ ɿ ɤɨɦɩɥɟɤɫɿɜ ȻȺɊ ɡ ȾɇɄ. Ɂɨɤɪɟɦɚ, ɪɨɡɝɥɹɧɭɬɨ ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɿ ɦɟɬɨɞɢ ɞɨɫɥɿɞɠɟɧɧɹ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ. 5. ɉɪɨɜɟɞɟɧɨ ɚɧɚɥɿɡ ɪɨɛɿɬ, ɩɪɢɫɜɹɱɟɧɢɯ ɩɪɨɛɥɟɦɚɦ ɜɢɡɧɚɱɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɜ ɚɫɨɰɿɚɬɚɯ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ. 6. Ɉɤɪɟɫɥɟɧɨ ɤɨɥɨ ɧɟɜɢɪɿɲɟɧɢɯ ɩɢɬɚɧɶ, ɹɤɿ ɫɬɨɫɭɸɬɶɫɹ ɩɪɨɛɥɟɦɢ ɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɿ ɫɬɚɛɿɥɿɡɚɰɿʀ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ. 56 ɊɈɁȾȱɅ 2 ȿɄɋɉȿɊɂɆȿɇɌȺɅɖɇȱ ɌȺ ɊɈɁɊȺɏɍɇɄɈȼȱ ɆȿɌɈȾɂ ȾɈɋɅȱȾɀȿɇɖ. ɉɊɂȽɈɌɍȼȺɇɇə ɁɊȺɁɄȱȼ 2.1 Ʉɨɥɢɜɚɥɶɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ: ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɢ. ɉɪɨɹɜ ɇ-ɡɜ'ɹɡɤɿɜ Ʉɨɥɢɜɚɥɶɧɚ ɫɩɟɤɬɪɨɫɤɨɩɿɹ ɽ ɨɞɧɢɦ ɡ ɧɚɣɛɿɥɶɲ ɿɧɮɨɪɦɚɬɢɜɧɢɯ ɦɟɬɨɞɿɜ ɞɥɹ ɜɢɜɱɟɧɧɹ ɫɬɪɭɤɬɭɪɢ ɜɧɭɬɪɿɲɧɶɨ- ɿ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɜɡɚɽɦɨɞɿɣ ɭ ɩɨɥɿɦɟɪɚɯ ɿ ɛɿɨɩɨɥɿɦɟɪɚɯ [34, 171-173]. ɍ ɛɚɝɚɬɶɨɯ ɜɢɩɚɞɤɚɯ ɤɨɥɢɜɚɥɶɧɢɣ ɫɩɟɤɬɪ ɽ ɫɩɟɰɢɮɿɱɧɢɦ, ɳɨ ɞɨɡɜɨɥɹɽ ɞɨɫɥɿɞɠɭɜɚɬɢ ɛɭɞɨɜɭ ɛɚɝɚɬɨɚɬɨɦɧɢɯ ɦɨɥɟɤɭɥ ɬɚ ʀɯ ɜɥɚɫɬɢɜɨɫɬɿ. Ʉɨɥɢɜɚɥɶɧɿ ɫɩɟɤɬɪɢ ɦɨɥɟɤɭɥ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɜɢɜɱɚɸɬɶɫɹ ɦɟɬɨɞɚɦɢ ɿɧɮɪɚɱɟɪɜɨɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɬɚ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ɫɜɿɬɥɚ. ɐɿ ɫɩɟɤɬɪɢ ɩɨɜ'ɹɡɚɧɿ ɡ ɩɟɪɟɯɨɞɚɦɢ ɦɿɠ ɤɨɥɢɜɚɥɶɧɢɦɢ ɟɧɟɪɝɟɬɢɱɧɢɦɢ ɫɬɚɧɚɦɢ ɚɛɨ, ɜ ɤɥɚɫɢɱɧɿɣ ɿɧɬɟɪɩɪɟɬɚɰɿʀ, ɡ ɤɨɥɢɜɚɧɧɹɦɢ ɚɬɨɦɿɜ ɭ ɦɨɥɟɤɭɥɿ. Ⱦɥɹ ɜɢɦɿɪɸɜɚɧɧɹ ɜɫɿɯ ɤɨɥɢɜɚɥɶɧɢɯ ɱɚɫɬɨɬ ɦɨɥɟɤɭɥɢ ɡɚɡɜɢɱɚɣ ɡɚɫɬɨɫɨɜɭɸɬɶ ɫɩɿɥɶɧɟ ɜɢɤɨɪɢɫɬɚɧɧɹ ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɿɜ, ɹɤɿ ɞɨɩɨɜɧɸɸɬɶ ɨɞɢɧ ɨɞɧɨɝɨ. Ɇɟɬɨɞɢ ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ʉɪɭɧɬɭɸɬɶɫɹ ɧɚ ɪɿɡɧɢɯ ɮɿɡɢɱɧɢɯ ɩɪɨɰɟɫɚɯ ɿ ɩɿɞɤɨɪɹɸɬɶɫɹ ɫɜɨʀɦ ɫɩɟɰɢɮɿɱɧɢɦ ɩɪɚɜɢɥɚɦ ɜɿɞɛɨɪɭ. Ɉɞɧɚɤ ɞɟɹɤɿ ɱɚɫɬɨɬɢ ɦɨɠɭɬɶ ɩɪɨɹɜɥɹɬɢɫɹ ɹɤ ɜ ȱɑ-ɫɩɟɤɬɪɚɯ, ɬɚɤ ɿ ɜ ɄɊ-ɫɩɟɤɬɪɚɯ, ɬɨɦɭ ɳɨ ɿɧɮɨɪɦɚɰɿɹ, ɹɤɭ ɞɚɸɬɶ ɰɿ ɞɜɚ ɦɟɬɨɞɢ, ɡɚɥɟɠɢɬɶ ɜɿɞ ɫɢɦɟɬɪɿʀ ɬɚ ɩɨɥɹɪɧɨɫɬɿ ɦɨɥɟɤɭɥ. ɋɢɦɟɬɪɢɱɧɿ ɤɨɥɢɜɚɧɧɹ ɿ ɧɟɩɨɥɹɪɧɿ ɝɪɭɩɢ ɜɢɜɱɚɸɬɶ ɡɚ ɞɨɩɨɦɨɝɨɸ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɄɊ, ɚ ɚɧɬɢɫɢɦɟɬɪɢɱɧɿ ɤɨɥɢɜɚɧɧɹ ɿ ɩɨɥɹɪɧɿ ɝɪɭɩɢ – ɡɚ ɞɨɩɨɦɨɝɨɸ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ. 2.1.1 ɋɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ ȱɑ-ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ Ɇɟɬɨɞ ɿɧɮɪɚɱɟɪɜɨɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɡɚɫɧɨɜɚɧɢɣ ɧɚ ɬɨɦɭ, ɳɨ ɩɪɢ ɩɪɨɯɨɞɠɟɧɧɿ ȱɑ ɜɢɩɪɨɦɿɧɸɜɚɧɧɹ ɱɟɪɟɡ ɪɟɱɨɜɢɧɭ ɜɿɞɛɭɜɚɽɬɶɫɹ ɣɨɝɨ 57 ɩɨɝɥɢɧɚɧɧɹ ɧɚ ɱɚɫɬɨɬɚɯ, ɳɨ ɡɛɿɝɚɸɬɶɫɹ ɡ ɞɟɹɤɢɦɢ ɜɥɚɫɧɢɦɢ ɤɨɥɢɜɚɥɶɧɢɦɢ ɬɚ ɨɛɟɪɬɚɥɶɧɢɦɢ ɱɚɫɬɨɬɚɦɢ ɦɨɥɟɤɭɥ. ɐɟ ɩɨɝɥɢɧɚɧɧɹ ɜɿɞɛɭɜɚɽɬɶɫɹ ɬɿɥɶɤɢ ɩɪɢ ɡɦɿɧɿ ɞɢɩɨɥɶɧɨɝɨ ɦɨɦɟɧɬɭ ɦɨɥɟɤɭɥɢ, ɳɨ ɤɨɥɢɜɚɽɬɶɫɹ. Ɉɫɧɨɜɧɢɦɢ ɩɚɪɚɦɟɬɪɚɦɢ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɽ ɱɚɫɬɨɬɚ ɜ ɦɚɤɫɢɦɭɦɿ ɩɨɝɥɢɧɚɧɧɹ, ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɿ ɧɚɩɿɜɲɢɪɢɧɚ. ȼ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɡɚɡɜɢɱɚɣ ɤɨɪɢɫɬɭɸɬɶɫɹ ɱɚɫɬɨɬɨɸ, ɜɢɪɚɠɟɧɨɸ ɜ ɡɜɨɪɨɬɧɿɯ ɫɚɧɬɢɦɟɬɪɚɯ (ɫɦ-1). Ʉɨɥɢɜɚɥɶɧɿ ɫɩɟɤɬɪɢ ɜɿɞɩɨɜɿɞɚɸɬɶ ɤɨɥɢɜɚɥɶɧɨɦɭ ɪɭɯɭ ɹɞɟɪ ɨɞɧɟ ɳɨɞɨ ɨɞɧɨɝɨ ɡ ɩɟɜɧɨɸ ɱɚɫɬɨɬɨɸ. ɍ ɪɚɡɿ ɞɜɨɚɬɨɦɧɨʀ ɦɨɥɟɤɭɥɢ, ɳɨ ɦɚɽ ɨɞɧɟ ɧɨɪɦɚɥɶɧɟ ɤɨɥɢɜɚɧɧɹ n, ɭ ɧɚɛɥɢɠɟɧɧɿ ɝɚɪɦɨɧɿɱɧɨɝɨ ɨɫɰɢɥɹɬɨɪɚ ɱɚɫɬɨɬɭ ɦɨɠɧɚ ɜɢɡɧɚɱɢɬɢ ɡɚ ɮɨɪɦɭɥɨɸ [174]: Q 1 2S k P , (2.1) ɞɟ k – ɫɢɥɨɜɚ ɩɨɫɬɿɣɧɚ; ȝ – ɩɪɢɜɟɞɟɧɚ ɦɚɫɚ: P ɞɟ m1 ˜ m2 , m1  m2 (2.2) m1 ɿ m2 – ɦɚɫɢ ɚɬɨɦɿɜ, ɳɨ ɤɨɥɢɜɚɸɬɶɫɹ. ɍ ɪɚɡɿ ɛɚɝɚɬɨɚɬɨɦɧɨʀ ɦɨɥɟɤɭɥɢ ɱɚɫɬɨɬɚ ɤɨɠɧɨɝɨ ɧɨɪɦɚɥɶɧɨɝɨ k ɤɨɥɢɜɚɧɧɹ ɬɚɤɨɠ ɜɢɡɧɚɱɚɽɬɶɫɹ ɰɢɦ ɜɢɪɚɡɨɦ, ɚɥɟ ɜɿɞɧɨɲɟɧɧɹ P ɜ ɪɿɜɧɹɧɧɿ (2.1) ɽ ɫɤɥɚɞɧɨɸ ɮɭɧɤɰɿɽɸ ɦɚɫ, ɤɨɨɪɞɢɧɚɬ ɚɬɨɦɿɜ ɿ ɫɢɥɨɜɢɯ ɩɨɫɬɿɣɧɢɯ ɞɥɹ ɜɫɿɯ ɯɿɦɿɱɧɢɯ ɡɜ'ɹɡɤɿɜ. ȼ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɦɭ ɫɩɟɤɬɪɿ ɤɿɥɶɤɿɫɬɶ ɫɦɭɝ ɡɛɿɥɶɲɭɽɬɶɫɹ ɡɚ ɪɚɯɭɧɨɤ ɮɚɤɬɨɪ-ɝɪɭɩɨɜɨɝɨ ɪɨɡɳɟɩɥɟɧɧɹ ɬɚ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨʀ ɜɡɚɽɦɨɞɿʀ ɦɨɥɟɤɭɥɢ ɡ ɨɬɨɱɟɧɧɹɦ [175]. Ⱦɥɹ ɧɟɥɿɧɿɣɧɨʀ ɛɚɝɚɬɨɚɬɨɦɧɨʀ ɦɨɥɟɤɭɥɢ ɤɿɥɶɤɿɫɬɶ ɧɨɪɦɚɥɶɧɢɯ ɤɨɥɢɜɚɧɶ n ɡɚɥɟɠɢɬɶ ɜɿɞ ɱɢɫɥɚ ɚɬɨɦɿɜ N ɿ ɜɢɡɧɚɱɚɽɬɶɫɹ ɹɤ n 3 N  6 . 58 ɇɨɪɦɚɥɶɧɿ ɤɨɥɢɜɚɧɧɹ ɩɨɞɿɥɹɸɬɶɫɹ ɧɚ ɜɚɥɟɧɬɧɿ Ȟ ɿ ɞɟɮɨɪɦɚɰɿɣɧɿ į. ɍ ɪɚɡɿ ɜɚɥɟɧɬɧɢɯ ɤɨɥɢɜɚɧɶ ɜɿɞɛɭɜɚɽɬɶɫɹ ɡɦɿɧɚ ɞɨɜɠɢɧɢ ɡɜ'ɹɡɤɭ ɭɡɞɨɜɠ ʀʀ ɨɫɿ, ɩɪɢ ɰɶɨɦɭ ɪɨɡɪɿɡɧɹɸɬɶ ɜɚɥɟɧɬɧɿ ɫɢɦɟɬɪɢɱɧɿ ɬɚ ɚɫɢɦɟɬɪɢɱɧɿ ɤɨɥɢɜɚɧɧɹ. Ⱦɟɮɨɪɦɚɰɿɣɧɿ ɤɨɥɢɜɚɧɧɹ ɫɭɩɪɨɜɨɞɠɭɸɬɶɫɹ ɡɦɿɧɨɸ ɤɭɬɚ ɦɿɠ ɡɜ'ɹɡɤɚɦɢ (ɪɢɫ. 2.1). Qɫɢɦ ɜɚɥɟɧɬɧɟ ɫɢɦɟɬɪɢɱɧɟ ɤɨɥɢɜɚɧɧɹ Qɚɫɢɦ ɜɚɥɟɧɬɧɟ ɚɫɢɦɟɬɪɢɱɧɟ ɤɨɥɢɜɚɧɧɹ G ɞɟɮɨɪɦɚɰɿɣɧɿ ɤɨɥɢɜɚɧɧɹ Ɋɢɫɭɧɨɤ 2.1 Ɍɢɩɢ ɧɨɪɦɚɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ȼɚɠɥɢɜɨɸ ɯɚɪɚɤɬɟɪɢɫɬɢɤɨɸ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɽ ɿɧɬɟɧɫɢɜɧɿɫɬɶ, ɜɿɞɩɨɜɿɞɚɥɶɧɚ ɡɚ ɟɥɟɤɬɪɨɧɧɨ-ɨɩɬɢɱɧɢɣ ɫɬɚɧ ɡɜ'ɹɡɤɭ. ȼɢɡɧɚɱɢɜɲɢ ʀʀ ɡɧɚɱɟɧɧɹ, ɦɨɠɧɚ ɨɛɱɢɫɥɢɬɢ ɜɟɥɢɱɢɧɭ ɞɢɩɨɥɶɧɨɝɨ ɦɨɦɟɧɬɭ ɡɜ'ɹɡɤɭ ɬɚ ɣɨɝɨ ɩɨɯɿɞɧɭ ɩɨ ɤɨɥɢɜɚɥɶɧɢɯ ɤɨɨɪɞɢɧɚɬɚɯ. ɐɿ ɞɚɧɿ ɞɨɡɜɨɥɹɸɬɶ ɡɪɨɛɢɬɢ ɜɢɫɧɨɜɤɢ ɩɪɨ ɩɪɢɪɨɞɭ ɯɿɦɿɱɧɨɝɨ ɡɜ'ɹɡɤɭ ɜ ɦɨɥɟɤɭɥɿ, ɪɨɡɩɨɞɿɥ ɡɚɪɹɞɿɜ ɧɚ ɚɬɨɦɚɯ, ɫɬɪɭɤɬɭɪɧɿ ɡɦɿɧɢ ɿ ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɜɡɚɽɦɨɞɿʀ. ȼ ɨɫɧɨɜɿ ɜɢɦɿɪɸɜɚɧɧɹ ɿɧɬɟɧɫɢɜɧɨɫɬɿ ɥɟɠɢɬɶ ɡɚɤɨɧ Ȼɭɝɟɪɚ-Ʌɚɦɛɟɪɬɚ-Ȼɟɪɚ [175]: D Q lg I I0 H Q ˜ c ˜ l , (2.3) ɞɟ D(Q) – ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɩɪɢ ɩɨɬɨɱɧɿɣ ɱɚɫɬɨɬɿ; I0 ɬɚ I – ɿɧɬɟɧɫɢɜɧɨɫɬɿ ɩɚɞɚɸɱɨɝɨ ɫɜɿɬɥɨɜɨɝɨ ɩɨɬɨɤɭ ɬɚ ɫɜɿɬɥɨɜɨɝɨ ɩɨɬɨɤɭ, ɳɨ ɩɪɨɣɲɨɜ; İ(Q) – ɦɨɥɹɪɧɢɣ ɤɨɟɮɿɰɿɽɧɬ ɟɤɫɬɢɧɤɰɿʀ; c – ɤɨɧɰɟɧɬɪɚɰɿɹ ɪɟɱɨɜɢɧɢ; 59 l – ɬɨɜɳɢɧɚ ɩɨɝɥɢɧɚɸɱɨɝɨ ɲɚɪɭ. ȱɧɬɟɝɪɚɥɶɧɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ȼ ɜɢɡɧɚɱɚɽɬɶɫɹ ɹɤ ɩɥɨɳɚ ɩɿɞ ɤɪɢɜɨɸ ɩɨɝɥɢɧɚɧɧɹ: B 2,3³ H Q dQ . ɿ ɧɚɩɿɜɲɢɪɢɧɚ ɫɦɭɝɢ (2.4) ɉɪɢ ɞɨɫɥɿɞɠɟɧɧɿ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨʀ ɜɡɚɽɦɨɞɿʀ ɜɚɠɥɢɜɢɦɢ ɩɚɪɚɦɟɬɪɚɦɢ ɽ ɱɚɫɬɨɬɚ ɤɨɥɢɜɚɧɧɹ, ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɩɨɝɥɢɧɚɧɧɹ, ɜɢɤɥɢɤɚɧɚ ɤɨɥɢɜɚɧɧɹɦɢ ɚɬɨɦɿɜ, ɳɨ ɭɬɜɨɪɸɸɬɶ ɜɨɞɧɟɜɢɣ ɡɜ'ɹɡɨɤ. ȼɿɞɨɦɨ, ɳɨ ɜ ȱɑ-ɞɿɚɩɚɡɨɧɿ ɮɨɪɦɭɜɚɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɦɿɠ ɞɨɧɨɪɚɦɢ ɩɪɨɬɨɧɿɜ (ɝɪɭɩɢ ɚɬɨɦɿɜ Ɉɇ, NH, NH2 , CH) ɬɚ ɚɤɰɟɩɬɨɪɚɦɢ (ɝɪɭɩɢ ɚɬɨɦɿɜ C=Ɉ, ɋ–Ɉ, C–N, C=N) ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɦ ɡɫɭɜɨɦ, ɚ ɬɚɤɨɠ ɡɪɨɫɬɚɧɧɹɦ ɿɧɬɟɧɫɢɜɧɨɫɬɿ ɬɚ ɡɛɿɥɶɲɟɧɧɹɦ ɧɚɩɿɜɲɢɪɢɧɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɜɚɥɟɧɬɧɢɯ ɤɨɥɢɜɚɧɶ. ɍ ɬɨɣ ɠɟ ɱɚɫ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ (ɧɚɩɪɢɤɥɚɞ, NH2 ɿ OH-ɝɪɭɩ ɚɬɨɦɿɜ) ɡɚɡɧɚɸɬɶ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɪɭɲɟɧɧɹ [125, 176]. ȱɧɬɟɧɫɢɜɧɿɫɬɶ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɨʀ ɝɪɭɩɢ ɡɚɜɠɞɢ ɞɨɫɢɬɶ ɜɟɥɢɤɚ. ɑɢɦ ɛɿɥɶɲɭ ɟɥɟɤɬɪɨɧɟɝɚɬɢɜɧɿɫɬɶ ɦɚɽ ɝɪɭɩɚ ɏ ɜ ɫɢɫɬɟɦɿ R–CO–X, ɬɢɦ ɜɢɳɟ ɛɭɞɟ ɱɚɫɬɨɬɚ ɤɨɥɢɜɚɧɧɹ. ɑɢɦ ɫɢɥɶɧɿɲɟ ɫɩɨɥɭɱɟɧɧɹ ɡɜ'ɹɡɤɭ ɋ=Ɉ, ɬɢɦ ɛɿɥɶɲɨɸ ɦɿɪɨɸ ɜɨɧɚ ɨɫɥɚɛɥɟɧɚ, ɚ ɜɚɥɟɧɬɧɟ ɤɨɥɢɜɚɧɧɹ ɡɫɭɧɭɬɨ ɜ ɛɿɤ ɦɟɧɲɢɯ ɯɜɢɥɶɨɜɢɯ ɱɢɫɟɥ. ɍɬɜɨɪɟɧɧɹ ɜɨɞɧɟɜɨɝɨ ɡɜ'ɹɡɤɭ ɩɪɢɡɜɨɞɢɬɶ ɞɨ ɡɦɿɳɟɧɧɹ ɜɿɞɩɨɜɿɞɧɨʀ ɫɦɭɝɢ ɜɚɥɟɧɬɧɢɯ ɤɨɥɢɜɚɧɶ ɋ=Ɉ ɝɪɭɩɢ ɞɨ ɛɿɥɶɲ ɧɢɡɶɤɢɯ ɱɚɫɬɨɬ [177]. Ɇɟɬɨɞ ȱɑɫɩɟɤɬɪɨɫɤɨɩɿʀ ɽ ɝɨɥɨɜɧɢɦ ɦɟɬɨɞɨɦ ɜɢɜɱɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ. ȿɤɫɩɟɪɢɦɟɧɬɚɥɶɧɿ ɞɨɫɥɿɞɠɟɧɧɹ ɜɟɥɢɤɨʀ ɤɿɥɶɤɨɫɬɿ ɦɨɥɟɤɭɥ, ɳɨ ɦɚɸɬɶ ɨɞɧɚɤɨɜɿ ɯɿɦɿɱɧɿ ɝɪɭɩɢ, ɩɨɤɚɡɚɥɢ, ɳɨ, ɧɟɡɚɥɟɠɧɨ ɜɿɞ ɡɦɿɧ ɜ ɿɧɲɿɣ ɱɚɫɬɢɧɿ ɦɨɥɟɤɭɥɢ, ɰɿ ɨɞɧɚɤɨɜɿ ɝɪɭɩɢ ɩɨɝɥɢɧɚɸɬɶ ɭ ɜɭɡɶɤɨɦɭ ɿɧɬɟɪɜɚɥɿ ɱɚɫɬɨɬ. Ɍɚɤɿ ɱɚɫɬɨɬɢ ɧɚɡɢɜɚɸɬɶ ɯɚɪɚɤɬɟɪɢɫɬɢɱɧɢɦɢ. Ⱦɨ ɧɢɯ ɜɿɞɧɨɫɹɬɶɫɹ, ɧɚɩɪɢɤɥɚɞ, ɤɨɥɢɜɚɧɧɹ ɝɪɭɩ CH, CH2 , CH3 , O–H, N–H, NH2 , C=C, C=O, NO2 ɬɚ ɿɧ. ɇɚɹɜɧɿɫɬɶ ɝɪɭɩɨɜɢɯ ɱɚɫɬɨɬ ɜɢɤɥɢɤɚɧɨ ɬɢɦ, ɳɨ ɜ ɬɚɤɨɦɭ ɤɨɥɢɜɚɧɧɿ ɧɚɣɛɿɥɶɲɭ ɭɱɚɫɬɶ ɩɪɢɣɦɚɽ ɞɟɹɤɚ ɝɪɭɩɚ ɚɬɨɦɿɜ, ɜɧɟɫɨɤ ɪɟɲɬɢ ɦɨɥɟɤɭɥɢ ɦɚɥɢɣ, ɯɨɱɚ ɜ 60 ɤɨɠɧɨɦɭ ɤɨɥɢɜɚɧɧɿ ɡɦɿɧɸɸɬɶɫɹ ɞɨɜɠɢɧɢ ɜɫɿɯ ɡɜ'ɹɡɤɿɜ ɿ ɜɟɥɢɱɢɧɢ ɤɭɬɿɜ ɦɿɠ ɡɜ'ɹɡɤɚɦɢ. ɍ ɬɚɛɥ. 2.1 ɧɚɜɟɞɟɧɨ ɞɟɹɤɿ ɯɚɪɚɤɬɟɪɢɫɬɢɱɧɿ ɱɚɫɬɨɬɢ ɪɿɡɧɢɯ ɝɪɭɩ. Ɍɚɛɥɢɰɹ 2.1 Ⱦɟɹɤɿ ɯɚɪɚɤɬɟɪɢɫɬɢɱɧɿ ɤɨɥɢɜɚɧɧɹ ɪɿɡɧɢɯ ɝɪɭɩ ɚɬɨɦɿɜ [178] Ʉɨɥɢɜɚɧɧɹ* Ȟ(O–H) Ȟ(N–H) Ȟ(=C–H) Ȟ(–C–H) Ȟ(C=O) Ȟ(C=C) Ȟ(C=N) Ȟ(N–N), ɚɥɿɮɚɬɢɱɧɢɣ ɡɚɦɿɧɧɢɤ Ȟ(N–N), ɚɪɨɦɚɬɢɱɧɢɣ ɡɚɦɿɧɧɢɤ į(ɋɇ2), įɚ(ɋɇ3) įɫ(ɋɇ3) Ȟ(ɋɋ), ɚɪɨɦɚɬɢɱɧɿ ɫɩɨɥɭɤɢ Ɉɛɥɚɫɬɶ (ɫɦ-1) 3650-3000 3500-3300 3100-3000 3000-2800 1820-1650 1900-1500 1680-1610 1580-1550 1440-1410 1470-1400 1380 1600, 1580, 1500, 1450, 1000 * Ȟ – ɜɚɥɟɧɬɧɟ ɤɨɥɢɜɚɧɧɹ, į – ɞɟɮɨɪɦɚɰɿɣɧɟ ɤɨɥɢɜɚɧɧɹ, įɚ – ɚɫɢɦɟɬɪɢɱɧɟ ɤɨɥɢɜɚɧɧɹ, įɫ – ɫɢɦɟɬɪɢɱɧɟ ɤɨɥɢɜɚɧɧɹ ɑɢɫɥɟɧɧɿ ɞɨɫɥɿɞɠɟɧɧɹ ȱɑ-ɫɩɟɤɬɪɿɜ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ [107, 179, 180] ɩɨɤɚɡɚɥɢ, ɳɨ ɮɨɪɦɭɜɚɧɧɹ ɫɬɪɭɤɬɭɪ ɫɬɨɩɨɤ ɚɡɨɬɢɫɬɢɯ ɨɫɧɨɜ ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɡɦɟɧɲɟɧɧɹɦ ɿɧɬɟɧɫɢɜɧɨɫɬɿ ɜɧɭɬɪɿɲɧɶɨ- ɬɚ ɡɨɜɧɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɤɨɥɢɜɚɧɶ C=N ɿ C=O-ɝɪɭɩ ɚɬɨɦɿɜ (ɿɧɮɪɚɱɟɪɜɨɧɢɣ ɝɿɩɨɯɪɨɦɿɡɦ). ɉɨɞɿɛɧɿ ɟɮɟɤɬɢ ɦɨɠɧɚ ɩɨɹɫɧɢɬɢ, ɜɢɤɨɪɢɫɬɨɜɭɸɱɢ ɬɟɨɪɿɸ ɦɨɥɟɤɭɥɹɪɧɢɯ ɟɤɫɢɬɨɧɿɜ [181]. ȿɧɟɪɝɿɹ ɤɨɥɢɜɚɥɶɧɨɝɨ ɟɤɫɢɬɨɧɧɨɝɨ ɡɛɭɞɠɟɧɧɹ ɞɨɪɿɜɧɸɽ: 'E 0f ɞɟ f 'E 0  A  H ɪɟɡ , (2.5) 61 ǻE0 – ɟɧɟɪɝɿɹ ɡɛɭɞɠɟɧɧɹ ɤɨɥɢɜɚɥɶɧɨʀ ɝɪɭɩɢ ɜ ɿɡɨɥɶɨɜɚɧɿɣ ɦɨɥɟɤɭɥɿ; Ⱥ – ɪɿɡɧɢɰɹ ɤɨɥɢɜɚɥɶɧɨʀ ɟɧɟɪɝɿʀ ɜɡɚɽɦɨɞɿʀ ɡɛɭɞɠɟɧɨʀ ɬɚ ɧɨɪɦɚɥɶɧɨʀ ɤɨɥɢɜɚɥɶɧɢɯ ɝɪɭɩ ɡ ɭɫɿɦɚ ɿɧɲɢɦɢ ɝɪɭɩɚɦɢ ɜ ɦɨɥɟɤɭɥɿ; f H ɪɟɡ – ɟɧɟɪɝɿɹ ɪɟɡɨɧɚɧɫɧɨʀ ɜɡɚɽɦɨɞɿʀ ɞɥɹ ɤɨɥɢɜɚɧɧɹ ɡ ɬɢɩɨɦ ɫɢɦɟɬɪɿʀ f. əɤɳɨ ɩɪɢɩɭɫɬɢɬɢ, ɳɨ ɱɚɫɬɨɬɚ ɧɟɡɛɭɪɟɧɨɝɨ ɤɨɥɢɜɚɧɧɹ: Q0 1 ('E 0  A) , h (2.6) ɬɨ, ɜɿɞɩɨɜɿɞɧɨ ɞɨ ɪɿɜɧɹɧɧɹ (2.5), ɱɚɫɬɨɬɚ ɩɟɪɟɯɨɞɭ ɞɨɪɿɜɧɸɽ: Q ɞɟ f f Q 0  H ɪɟɡ , 1 h (2.7) h – ɩɨɫɬɿɣɧɚ ɉɥɚɧɤɚ, ɹɤɚ ɞɨɪɿɜɧɸɽ 6,62·10-34 Ⱦɠ·ɫ. ɍ ɪɟɚɥɶɧɢɯ ɭɦɨɜɚɯ (ɧɚɩɪɢɤɥɚɞ, ɜ ɪɨɡɱɢɧɚɯ ɜɨɞɢ) ɧɚ ɱɚɫɬɨɬɭ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ, ɤɪɿɦ ɪɟɡɨɧɚɧɫɧɨʀ ɜɡɚɽɦɨɞɿʀ, ɜɩɥɢɜɚɽ ɜɨɞɧɟɜɢɣ ɡɜ'ɹɡɨɤ, ɹɤɢɣ ɭɬɜɨɪɸɽɬɶɫɹ ɦɿɠ ɚɬɨɦɨɦ ɤɢɫɧɸ C=O ɝɪɭɩ ɿ ɚɬɨɦɨɦ ɜɨɞɧɸ (ɜ ɫɤɥɚɞɿ ɦɨɥɟɤɭɥ ɜɨɞɢ ɚɛɨ ɿɧɲɢɯ ɦɨɥɟɤɭɥ). ɍ ɪɚɦɤɚɯ ɦɨɞɟɥɿ ɫɥɚɛɨɡɜ'ɹɡɚɧɢɯ ɨɫɰɢɥɹɬɨɪɿɜ [182], ɡ ɭɪɚɯɭɜɚɧɧɹɦ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɟɜɨɝɨ ɡɜ'ɹɡɤɭ ɬɚ ɪɟɡɨɧɚɧɫɧɨʀ ɜɡɚɽɦɨɞɿʀ, ɱɚɫɬɨɬɭ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ C=O ɝɪɭɩɢ ɚɬɨɦɿɜ ɭ ȱɑ-ɫɩɟɤɬɪɚɯ ɩɨɝɥɢɧɚɧɧɹ ɦɨɠɧɚ ɡɚɩɢɫɚɬɢ ɹɤ: Q Q 0  'Q H  ɡɜ r 'Q ɪɟɡ , ɞɟ Ȟ0 – ɱɚɫɬɨɬɚ ɧɟɡɛɭɪɟɧɨɝɨ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ; ǻȞɇ–ɡɜ – ɡɦɿɳɟɧɧɹ ɱɚɫɬɨɬɢ ɡɚ ɪɚɯɭɧɨɤ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ; ǻȞɪɟɡ – ɪɟɡɨɧɚɧɫɧɢɣ ɡɫɭɜ. Ɋɟɡɨɧɚɧɫɧɢɣ ɡɫɭɜ ɜɢɡɧɚɱɚɽɬɶɫɹ ɬɚɤ [183]: 'Q ɪɟɡ 2 ( 'Q 11,12 cos M  'Q 11,13 cos 2M  ...  'Q 11,1k cos kM ) , (2.8) (2.9) ɞɟ k – ɤɿɥɶɤɿɫɬɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɜ ɚɝɪɟɝɚɬɿ; 62 ǻȞ11,12 – ɡɦɿɳɟɧɧɹ ɱɚɫɬɨɬɢ C=O ɤɨɥɢɜɚɧɧɹ ɡɚ ɪɚɯɭɧɨɤ ɪɟɡɨɧɚɧɫɧɨʀ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɭ ɩɨɥɨɠɟɧɧɿ 11, 12 ɿ ɬ.ɞ.; ij – ɤɭɬ ɩɨɜɨɪɨɬɭ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ ɫɭɫɿɞɧɿɯ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ. Ɂɚɡɜɢɱɚɣ ɩɪɢ ɪɨɡɪɚɯɭɧɤɭ ɪɟɡɨɧɚɧɫɧɨʀ (ɞɢɧɚɦɿɱɧɨʀ) ɜɡɚɽɦɨɞɿʀ ɤɨɥɢɜɚɥɶɧɢɯ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶ ɞɢɩɨɥɶ-ɞɢɩɨɥɶɧɟ ɧɚɛɥɢɠɟɧɧɹ [107, 183, 184]. ɍ ɡɝɨɪɧɭɬɨɦɭ ɜɢɝɥɹɞɿ ɪɟɡɨɧɚɧɫɧɢɣ ɱɚɫɬɨɬɧɢɣ ɡɫɭɜ ɭ ɩɪɨɫɬɨɦɭ ɜɢɩɚɞɤɭ ɞɜɨɯ ɜɡɚɽɦɨɞɿɸɱɢɯ ɤɨɥɢɜɚɥɶɧɢɯ ɝɪɭɩ (ɪɢɫ. 2.2) ɡɚɩɢɲɟɬɶɫɹ ɬɚɤ [183]: 'Q ɪɟɡ M cos M  3 cos E cos J ˜ hH R3 M ˜G , hH (2.10) ɞɟ G – ɝɟɨɦɟɬɪɢɱɧɢɣ ɮɚɤɬɨɪ, ɳɨ ɡɚɥɟɠɢɬɶ ɜɿɞ ɪɨɡɬɚɲɭɜɚɧɧɹ ɞɢɩɨɥɿɜ ɭ ɚɝɪɟɝɚɬɿ; M & & wP1 wP 2 ˜ wS1 wS 2 – ɞɨɛɭɬɨɤ ɞɢɩɨɥɶɧɢɯ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ, ɹɤɿ ɜɢɡɧɚɱɚɸɬɶɫɹ ɡ ɚɛɫɨɥɸɬɧɢɯ ɿɧɬɟɧɫɢɜɧɨɫɬɟɣ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɜ ɿɧɮɪɚɱɟɪɜɨɧɨɦɭ ɫɩɟɤɬɪɿ; S1 ɿ S2 – ɜɚɥɟɧɬɧɿ ɤɨɨɪɞɢɧɚɬɢ; R – ɜɿɞɫɬɚɧɶ ɦɿɠ ɞɢɩɨɥɹɦɢ; İ – ɞɿɟɥɟɤɬɪɢɱɧɚ ɩɨɫɬɿɣɧɚ. & wP 2 ij wS 2 Ȗ & R & wP 1 wS1 ȕ Ɋɢɫɭɧɨɤ 2.2 ɋɯɟɦɚ ɞɢɩɨɥɶɧɢɯ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ ɜɡɚɽɦɨɞɿʀ 2.1.2 Ɍɟɯɧɿɤɚ ɨɬɪɢɦɚɧɧɹ ȱɑ-ɫɩɟɤɬɪɿɜ ȱɑ-ɫɩɟɤɬɪɢ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ɪɟɱɨɜɢɧ ɪɟɽɫɬɪɭɜɚɥɢɫɹ ɡɚ ɞɨɩɨɦɨɝɨɸ ɞɜɨɩɪɨɦɟɧɟɜɨɝɨ ɫɩɟɤɬɪɨɦɟɬɪɚ UR-20 (Karl Zeiss, Jena, ɇɿɦɟɱɱɢɧɚ) ɡ ɜɢɤɨɪɢɫɬɚɧɧɹɦ ɩɪɢɡɦɢ NaCl. Ɉɩɬɢɦɚɥɶɧɚ ɲɢɪɢɧɚ ɳɿɥɢɧɢ ɜɿɞɩɨɜɿɞɚɥɚ ɳɿɥɢɧɧɿɣ ɩɪɨɝɪɚɦɿ 6,0, ɲɜɢɞɤɿɫɬɶ ɫɤɚɧɭɜɚɧɧɹ – 50 ɫɦ-1/ɫ. Ⱦɥɹ ɡɚɩɨɛɿɝɚɧɧɹ 63 ɪɨɡɿɝɪɿɜɭ ɡɪɚɡɤɚ ɜɢɤɨɪɢɫɬɨɜɭɜɚɜɫɹ ɝɟɪɦɚɧɿɽɜɢɣ ɮɿɥɶɬɪ, ɩɨɦɿɳɟɧɢɣ ɞɨ ɤɚɦɟɪɢ ɝɥɨɛɚɪɭ. Ⱦɥɹ ɡɚɩɢɫɭ ɫɩɟɤɬɪɿɜ ɩɨɝɥɢɧɚɧɧɹ ɪɨɡɱɢɧɿɜ ɛɭɥɨ ɜɢɤɨɪɢɫɬɚɧɨ ɤɸɜɟɬɢ ɡ ɮɥɸɨɪɢɬɨɜɢɦɢ ɜɿɤɨɧɰɹɦɢ ɡ ɬɨɜɳɢɧɨɸ ɪɨɛɨɱɨɝɨ ɲɚɪɭ 50 ɦɤɦ, ɡɪɨɛɥɟɧɿ ɡɚ ɦɨɞɟɥɥɸ, ɡɚɩɪɨɩɨɧɨɜɚɧɨɸ Ɏɿɲɦɚɧɨɦ [185]. ȱɑ-ɫɩɟɤɬɪɢ ɩɥɿɜɨɤ ɛɭɥɢ ɨɬɪɢɦɚɧɿ ɡɚ ɞɨɩɨɦɨɝɨɸ ɪɨɡɪɨɛɥɟɧɨʀ ɪɚɧɿɲɟ ɝɟɪɦɟɬɢɱɧɨʀ ɤɸɜɟɬɢ [186]. ɉɥɿɜɤɢ ɜɢɪɨɳɭɜɚɥɢɫɹ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɿ 4qɋ ɲɥɹɯɨɦ ɩɨɜɿɥɶɧɨɝɨ ɜɢɩɚɪɨɜɭɜɚɧɧɹ ɜɨɞɢ ɡ ɪɨɡɱɢɧɿɜ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ɪɟɱɨɜɢɧ, ɪɨɡɦɿɳɟɧɢɯ ɧɚ ɝɨɪɢɡɨɧɬɚɥɶɧɨ ɪɨɡɬɚɲɨɜɚɧɿɣ ɩɿɞɥɨɠɰɿ. ȼ ɹɤɨɫɬɿ ɩɿɞɥɨɠɤɢ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɢɫɹ ɜɿɤɨɧɰɹ ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɨʀ ɤɸɜɟɬɢ, ɜɢɝɨɬɨɜɥɟɧɿ ɡ ɮɥɸɨɪɢɬɭ (CaF2). ȼɢɤɨɪɢɫɬɚɧɧɹ ɮɥɸɨɪɢɬɭ ɨɛɭɦɨɜɥɟɧɨ ɬɢɦ, ɳɨ ɰɟɣ ɦɚɬɟɪɿɚɥ ɩɪɚɤɬɢɱɧɨ ɧɟ ɩɨɝɥɢɧɚɽ ɭ ɲɢɪɨɤɿɣ ɫɩɟɤɬɪɚɥɶɧɿɣ ɨɛɥɚɫɬɿ (1200-5000 ɫɦ-1) ɿ ɧɟ ɪɨɡɱɢɧɹɽɬɶɫɹ ɭ ɜɨɞɿ. Ɏɥɸɨɪɢɬɨɜɟ ɜɿɤɨɧɰɟ ɡ ɩɥɿɜɤɨɸ ɩɨɦɿɳɚɥɢ ɞɨ ɝɟɪɦɟɬɢɱɧɨʀ ɤɸɜɟɬɢ. Ⱦɟɣɬɟɪɭɜɚɧɧɹ ɿ ɡɜɨɥɨɠɟɧɧɹ ɩɥɿɜɤɨɜɢɯ ɡɪɚɡɤɿɜ ɞɨ 92% ɜɿɞɧɨɫɧɨʀ ɜɨɥɨɝɨɫɬɿ (ȼȼ) ɡɞɿɣɫɧɸɜɚɥɢ ɡɚ ɞɨɩɨɦɨɝɨɸ ɧɚɫɢɱɟɧɢɯ ɭ D2O ɪɨɡɱɢɧɿɜ ɧɚɛɨɪɨɦ ɫɨɥɟɣ, ɹɤ ɨɩɢɫɚɧɨ ɜ ɪɨɛɨɬɿ [100]. Ɋɿɜɧɨɜɚɠɧɢɣ ɫɬɚɧ ɩɨ ɜɨɥɨɝɨɫɬɿ ɬɚ ɞɟɣɬɟɪɭɜɚɧɧɹ ɞɨɫɹɝɚɥɢɫɹ ɩɪɨɬɹɝɨɦ 1-2 ɞɿɛ. Ɂɧɚɱɟɧɧɹ ɱɚɫɬɨɬɢ Ȟ ɬɚ ɨɩɬɢɱɧɨʀ ɳɿɥɶɧɨɫɬɿ D ɨɬɪɢɦɭɜɚɥɢɫɶ ɭɫɟɪɟɞɧɸɜɚɧɧɹɦ ɪɟɡɭɥɶɬɚɬɿɜ ɧɟ ɦɟɧɲɟ ɞɟɫɹɬɢ ɧɟɡɚɥɟɠɧɢɯ ɟɤɫɩɟɪɢɦɟɧɬɿɜ ɡ ɞɟɤɿɥɶɤɨɦɚ ɜɢɦɿɪɚɦɢ ɜ ɤɨɠɧɿɣ ɬɨɱɰɿ. Ⱦɨɫɬɨɜɿɪɧɿɫɬɶ ɜɢɡɧɚɱɟɧɧɹ ɱɚɫɬɨɬ ɩɟɪɟɜɿɪɹɥɚɫɹ ɡɚ ɞɨɩɨɦɨɝɨɸ ɫɩɟɤɬɪɚ ɟɬɚɥɨɧɧɨʀ ɩɥɿɜɤɢ ɩɨɥɿɫɬɢɪɨɥɭ. ɉɨɦɢɥɤɚ ɜɢɡɧɚɱɟɧɧɹ ɨɩɬɢɱɧɨʀ ɳɿɥɶɧɨɫɬɿ ɫɬɚɧɨɜɢɥɚ ɧɟ ɛɿɥɶɲɟ 2%, ɚ ɱɚɫɬɨɬ – ±1 ɫɦ-1. Ⱦɟɬɚɥɶɧɢɣ ɚɧɚɥɿɡ ȱɑ-ɫɩɟɤɬɪɿɜ ɭ ɨɛɥɚɫɬɿ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɋ=Ɉ (1600-1800 ɫɦ-1) ɿ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɋ=N ɤɨɥɢɜɚɧɶ (1450-1600 ɫɦ-1) ɩɪɨɜɨɞɢɥɢ ɲɥɹɯɨɦ ɩɨɛɭɞɨɜɢ ɡɚɥɟɠɧɨɫɬɟɣ ɱɚɫɬɨɬ Ȟ ɬɚ ɿɧɬɟɧɫɢɜɧɨɫɬɟɣ R (ɭ ɜɿɞɧɨɫɧɢɯ ɨɞɢɧɢɰɹɯ) ɜɿɞ ɱɢɫɥɚ ɫɨɪɛɨɜɚɧɢɯ ɦɨɥɟɤɭɥ ɜɨɞɢ N ɧɚ ɦɨɥɶ ɞɨɫɥɿɞɠɭɜɚɧɨʀ ɪɟɱɨɜɢɧɢ, ɜɢɤɨɪɢɫɬɨɜɭɸɱɢ ɪɚɧɿɲɟ ɪɨɡɪɨɛɥɟɧɭ ɦɟɬɨɞɢɤɭ ɞɥɹ ɩɥɿɜɨɤ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ [98]. ȼɿɞɧɨɫɧɭ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɜɢɡɧɚɱɚɥɢ ɹɤ: 64 R ɞɟ Di , D0 (2.11) Di ɿ D0 – ɨɩɬɢɱɧɿ ɳɿɥɶɧɨɫɬɿ ɜ ɦɚɤɫɢɦɭɦɿ ɩɨɝɥɢɧɚɧɧɹ ɩɪɢ i-ɬɿɣ ɬɚ ɧɭɥɶɨɜɿɣ ɜɨɝɤɨɫɬɿ, ɜɿɞɩɨɜɿɞɧɨ. ɑɢɫɥɨ ɫɨɪɛɨɜɚɧɢɯ ɦɨɥɟɤɭɥ N ɜɡɹɬɨ ɡ ɿɡɨɬɟɪɦ ɝɿɞɪɚɬɚɰɿʀ. Ɉɩɬɢɱɧɚ ɳɿɥɶɧɿɫɬɶ D ɜɢɡɧɚɱɚɥɚɫɹ ɦɟɬɨɞɨɦ ɛɚɡɨɜɨʀ ɥɿɧɿʀ [187], ɡɚ ɹɤɭ ɛɪɚɥɢ ɡɧɚɱɟɧɧɹ D ɩɪɢ ɱɚɫɬɨɬɿ Ȟ = 1800 ɫɦ-1. 2.1.3 ɋɩɟɤɬɪɨɫɤɨɩɿɹ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ɋɩɟɤɬɪɨɫɤɨɩɿɹ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ɫɜɿɬɥɚ ɽ ɳɟ ɨɞɧɢɦ ɦɟɬɨɞɨɦ, ɳɨ ɞɨɡɜɨɥɹɽ ɨɬɪɢɦɚɬɢ ɿɧɮɨɪɦɚɰɿɸ ɩɪɨ ɤɨɥɢɜɚɥɶɧɿ ɫɬɚɧɢ ɦɨɥɟɤɭɥ. Ⱦɥɹ ɩɨɹɜɢ ɄɊ-ɫɦɭɝ ɧɟɨɛɯɿɞɧɨ, ɳɨɛ ɪɭɯɢ ɹɞɟɪ ɩɪɢɡɜɨɞɢɥɢ ɞɨ ɡɦɿɧɢ ɩɨɥɹɪɢɡɨɜɚɧɨɫɬɿ, ɚ ɧɟ ɩɨɫɬɿɣɧɨɝɨ ɞɢɩɨɥɶɧɨɝɨ ɦɨɦɟɧɬɭ, ɹɤ ɭ ɜɢɩɚɞɤɭ ȱɑ-ɫɩɟɤɬɪɿɜ. Ɉɫɧɨɜɧɨɸ ɩɟɪɟɜɚɝɨɸ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɄɊ ɽ ɬɟ, ɳɨ ɜɨɞɚ ɬɭɬ ɩɨɝɥɢɧɚɽ ɞɨɫɢɬɶ ɫɥɚɛɨ. Ɉɬɠɟ, ɦɟɬɨɞ ɡɪɭɱɧɢɣ ɩɪɢ ɜɢɜɱɟɧɧɿ ɛɿɨɥɨɝɿɱɧɢɯ ɫɢɫɬɟɦ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ. ɋɩɟɤɬɪɨɫɤɨɩɿɹ ɩɨɫɬɿɣɧɚ ɉɥɚɧɤɚ, ɄɊ Ȟ0 ɡɚɫɧɨɜɚɧɚ ɱɚɫɬɨɬɚ ɧɚ ɧɟɩɪɭɠɧɨɦɭ ɪɨɡɫɿɹɧɧɿ ȼɟɥɢɤɚ ɮɨɬɨɧɿɜ. ɱɚɫɬɢɧɚ ɉɪɢɩɭɫɬɢɦɨ, ɳɨ ɧɚ ɦɨɥɟɤɭɥɭ ɩɚɞɚɽ ɜɢɩɪɨɦɿɧɸɜɚɧɧɹ ɡ ɟɧɟɪɝɿɽɸ hȞ0 (h – – ɩɚɞɚɸɱɨɝɨ ɤɜɚɧɬɚ). ɜɢɩɪɨɦɿɧɸɜɚɧɧɹ ɭ ɪɚɡɿ ɧɟɩɨɝɥɢɧɚɸɱɨʀ ɪɟɱɨɜɢɧɢ ɛɭɞɟ ɩɪɨɯɨɞɢɬɢ ɤɪɿɡɶ ɧɟʀ. ɇɟɜɟɥɢɤɚ ɱɚɫɬɢɧɚ ɜɢɩɪɨɦɿɧɸɜɚɧɧɹ ɛɭɞɟ ɩɪɭɠɧɨ ɪɨɡɫɿɸɜɚɬɢɫɹ. ɐɟɣ ɩɪɨɰɟɫ ɦɨɠɧɚ ɩɪɟɞɫɬɚɜɢɬɢ ɹɤ ɡɛɭɞɠɟɧɧɹ ɦɨɥɟɤɭɥɢ ɞɨ ɜɿɪɬɭɚɥɶɧɨɝɨ ɫɬɚɧɭ ɡ ɟɧɟɪɝɿɽɸ hȞ0 ɿ ɩɨɜɟɪɧɟɧɧɹ ʀʀ ɜ ɨɫɧɨɜɧɢɣ ɫɬɚɧ (ɪɟɥɟʀɜɫɶɤɟ ɪɨɡɫɿɸɜɚɧɧɹ). Ɇɨɥɟɤɭɥɚ, ɳɨ ɡɧɚɯɨɞɢɬɶɫɹ ɭ ɡɛɭɞɠɟɧɨɦɭ ɫɬɚɧɿ ɡ ɟɧɟɪɝɿɽɸ ȿ0 , ɩɿɞ ɞɿɽɸ ɤɜɚɧɬɚ ɡ ɟɧɟɪɝɿɽɸ hȞ0 ɡɛɭɞɠɭɽɬɶɫɹ ɞɨ ɩɪɨɦɿɠɧɨɝɨ (ɜɿɪɬɭɚɥɶɧɨɝɨ) ɫɬɚɧɭ ɡ ɟɧɟɪɝɿɽɸ Eɜɿpɬ , ɡɜɿɞɤɢ ɦɨɠɟ ɚɛɨ ɩɨɜɟɪɧɭɬɢɫɹ ɞɨ ɩɨɱɚɬɤɨɜɨɝɨ ɫɬɚɧɭ, ɜɢɩɭɫɬɢɜɲɢ ɤɜɚɧɬ hȞ0 (ɪɟɥɟʀɜɫɶɤɟ ɪɨɡɫɿɸɜɚɧɧɹ), ɚɛɨ ɩɟɪɟɣɬɢ ɞɨ ɫɬɚɧɭ ȿi , ɜɢɩɭɫɬɢɜɲɢ ɤɜɚɧɬ h(Ȟ0-Ȟi), ɳɨ 65 ɩɪɢɡɜɨɞɢɬɶ ɞɨ ɩɨɹɜɢ ɭ ɫɩɟɤɬɪɿ ɪɨɡɫɿɹɧɨɝɨ ɜɢɩɪɨɦɿɧɸɜɚɧɧɹ ɥɿɧɿɣ ɡ ɱɚɫɬɨɬɚɦɢ Ȟ0-Ȟi (ɫɬɨɤɫɨɜɿ ɥɿɧɿʀ) (ɪɢɫ. 2.3). ȼɿɪɬɭɚɥɶɧɢɣ ɫɬɚɧ Ʉɨɥɢɜɚɥɶɧɿ ɩɿɞɪɿɜɧɿ Ɋɟɥɟʀɜɫɶɤɟ ɪɨɡɫɿɸɜɚɧɧɹ Ɋɢɫɭɧɨɤ 2.3 ɋɯɟɦɚ ɩɟɪɟɯɨɞɿɜ ɦɨɥɟɤɭɥɢ ɧɚ ɪɿɡɧɿ ɟɧɟɪɝɟɬɢɱɧɿ ɪɿɜɧɿ ɋɬɨɤɫɨɜɨ ɪɨɡɫɿɸɜɚɧɧɹ Ⱥɧɬɢɫɬɨɤɫɨɜɨ ɪɨɡɫɿɸɜɚɧɧɹ əɤɳɨ ɞɨ ɩɨɝɥɢɧɚɧɧɹ ɮɨɬɨɧɚ ɦɨɥɟɤɭɥɚ ɩɟɪɟɛɭɜɚɥɚ ɭ ɡɛɭɞɠɟɧɨɦɭ ɫɬɚɧɿ ɡ ɟɧɟɪɝɿɽɸ Ei , ɬɨ ɩɿɫɥɹ ɪɨɡɫɿɸɜɚɧɧɹ ɫɜɿɬɥɚ ɜɨɧɚ ɦɨɠɟ ɩɟɪɟɣɬɢ ɹɤ ɞɨ ɩɨɱɚɬɤɨɜɨɝɨ, ɬɚɤ ɿ ɞɨ ɨɫɧɨɜɧɨɝɨ ɫɬɚɧɭ E0 , ɬɨɞɿ ɟɧɟɪɝɿɹ ɪɨɡɫɿɹɧɨɝɨ ɫɜɿɬɥɚ ɡɪɨɫɬɚɽ, ɫɤɥɚɞɚɸɱɢ h(Ȟ0+Ȟi), ɳɨ ɩɪɢɡɜɨɞɢɬɶ ɞɨ ɩɨɹɜɢ ɭ ɫɩɟɤɬɪɿ ɥɿɧɿɣ ɡ ɱɚɫɬɨɬɚɦɢ Ȟ0+Ȟi (ɚɧɬɢɫɬɨɤɫɨɜɿ ɥɿɧɿʀ). ȿɧɟɪɝɟɬɢɱɧɢɣ ɫɬɚɧ ɪɟɱɨɜɢɧɢ ɯɚɪɚɤɬɟɪɢɡɭɽ ɪɿɡɧɢɰɹ ɟɧɟɪɝɿɣ ɡɛɭɞɠɭɸɱɨɝɨ ɿ ɪɨɡɫɿɹɧɨɝɨ ɫɜɿɬɥɚ Ei+hȞi , ɬɨɛɬɨ, ɧɚɣɜɚɠɥɢɜɿɲɨɸ ɯɚɪɚɤɬɟɪɢɫɬɢɤɨɸ ɫɩɟɤɬɪɿɜ ɄɊ ɽ ɧɟ ɫɚɦɿ ɱɚɫɬɨɬɢ, ɚ ʀɯ ɡɫɭɜ ɜɿɞɧɨɫɧɨ ɱɚɫɬɨɬɢ ɪɟɥɟʀɜɫɶɤɨʀ ɥɿɧɿʀ (ɪɢɫ. 2.3). ɋɭɬɧɿɫɬɶ ɹɜɢɳɚ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ɦɨɠɧɚ ɩɨɹɫɧɢɬɢ ɭ ɪɚɦɤɚɯ ɤɜɚɧɬɨɜɨʀ ɬɟɨɪɿʀ ɜɢɩɪɨɦɿɧɸɜɚɧɧɹ [174]. əɤɳɨ ɩɨɦɿɫɬɢɬɢ ɦɨɥɟɤɭɥɭ ɜ ɩɨɫɬɿɣɧɟ ɟɥɟɤɬɪɢɱɧɟ ɩɨɥɟ, ɬɨ ɩɨɡɢɬɢɜɧɨ ɡɚɪɹɞɠɟɧɿ ɹɞɪɚ ɩɪɢɬɹɝɭɜɚɬɢɦɭɬɶɫɹ ɞɨ ɧɟɝɚɬɢɜɧɨɝɨ ɩɨɥɸɫɚ, ɚ ɟɥɟɤɬɪɨɧɢ – ɞɨ ɩɨɡɢɬɢɜɧɨɝɨ, ɳɨ ɩɪɢɡɜɟɞɟ ɞɨ ɞɟɮɨɪɦɭɜɚɧɧɹ ɦɨɥɟɤɭɥɢ. Ɍɚɤɟ ɪɨɡɞɿɥɟɧɧɹ ɰɟɧɬɪɿɜ ɡɚɪɹɞɿɜ ɩɪɢɡɜɟɞɟ ɞɨ ɮɨɪɦɭɜɚɧɧɹ ɧɚɜɟɞɟɧɨɝɨ ɟɥɟɤɬɪɢɱɧɨɝɨ ɞɢɩɨɥɶɧɨɝɨ ɦɨɦɟɧɬɭ, ɬɨɛɬɨ ɦɨɥɟɤɭɥɚ ɩɨɥɹɪɢɡɭɽɬɶɫɹ. ȼɟɥɢɱɢɧɭ ɧɚɜɟɞɟɧɨɝɨ ɞɢɩɨɥɹ ȝ ɦɨɠɧɚ ɡɚɩɢɫɚɬɢ ɹɤ: 66 P DE , (2.12) ɞɟ Į – ɩɨɥɹɪɢɡɨɜɚɧɿɫɬɶ ɦɨɥɟɤɭɥɢ; ȿ – ɧɚɩɪɭɠɟɧɿɫɬɶ ɩɪɢɤɥɚɞɟɧɨɝɨ ɩɨɥɹ. Ʉɨɥɢ ɦɨɥɟɤɭɥɢ ɩɨɬɪɚɩɥɹɸɬɶ ɜ ɩɨɥɟ ɜɢɩɪɨɦɿɧɸɜɚɧɧɹ ɱɚɫɬɨɬɢ Ȟ, ɤɨɠɧɚ ɡ ɧɢɯ ɨɩɢɧɹɽɬɶɫɹ ɜ ɟɥɟɤɬɪɢɱɧɨɦɭ ɩɨɥɿ, ɳɨ ɡɦɿɧɸɽɬɶɫɹ ɡɚ ɡɚɤɨɧɨɦ: E E 0 sin 2SQ t , (2.13) ɨɬɠɟ, ɧɚɜɟɞɟɧɢɣ ɞɢɩɨɥɶɧɢɣ ɦɨɦɟɧɬ ɬɚɤɨɠ ɨɫɰɢɥɸɽ ɡ ɱɚɫɬɨɬɨɸ Ȟ: P DE DE0 sin 2SQ t . (2.14) Ɉɫɰɢɥɸɸɱɢɣ ɞɢɩɨɥɶ ɜɢɩɪɨɦɿɧɸɽ ɡ ɱɚɫɬɨɬɨɸ ɩɚɞɚɸɱɨɝɨ ɧɚ ɧɶɨɝɨ ɜɢɩɪɨɦɿɧɸɜɚɧɧɹ. Ɍɚɤɢɦ ɱɢɧɨɦ, ɭ ɮɨɪɦɭɥɿ (2.14) ɦɿɫɬɢɬɶɫɹ ɤɥɚɫɢɱɧɟ ɩɨɹɫɧɟɧɧɹ ɪɟɥɟʀɜɫɶɤɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ. əɤɳɨ ɠ ɭ ɦɨɥɟɤɭɥɿ ɜɿɞɛɭɜɚɸɬɶɫɹ ɞɟɹɤɿ ɜɧɭɬɪɿɲɧɿ ɪɭɯɢ (ɧɚɩɪɢɤɥɚɞ, ɤɨɥɢɜɚɧɧɹ ɚɛɨ ɨɛɟɪɬɚɧɧɹ), ɹɤɿ ɩɟɪɿɨɞɢɱɧɨ ɜɩɥɢɜɚɸɬɶ ɧɚ ɩɨɥɹɪɢɡɨɜɚɧɿɫɬɶ, ɬɨ ɨɫɰɢɥɸɸɱɢɣ ɞɢɩɨɥɶ ɛɭɞɟ ɞɨɞɚɬɤɨɜɨ ɜɿɞɱɭɜɚɬɢ ɤɨɥɢɜɚɥɶɧɿ ɚɛɨ ɨɛɟɪɬɚɥɶɧɿ ɨɫɰɢɥɹɰɿʀ. ȼɩɥɢɜ ɤɨɥɢɜɚɧɧɹ ɱɚɫɬɨɬɢ Ȟɤɨɥ ɧɚ ɩɨɥɹɪɢɡɨɜɚɧɿɫɬɶ ɦɨɠɧɚ ɡɚɩɢɫɚɬɢ ɬɚɤ: D D 0  E sin 2SQ ɤɨɥ t , (2.15) ɞɟ Į0 – ɪɿɜɧɨɜɚɠɧɚ ɩɨɥɹɪɢɡɨɜɚɧɿɫɬɶ; ȕ – ɯɚɪɚɤɬɟɪɢɡɭɽ ɲɜɢɞɤɿɫɬɶ ɡɦɿɧɢ ɩɨɥɹɪɢɡɨɜɚɧɨɫɬɿ ɩɪɢ ɤɨɥɢɜɚɧɧɿ. Ɍɨɞɿ ɦɚɽɦɨ: P DE (D 0  E sin 2SQ ɤɨɥ t ) E0 sin 2SQ t , (2.16) ɫɩɿɜɜɿɞɧɨɲɟɧɧɹ ɿ ɡ ɭɪɚɯɭɜɚɧɧɹɦ ɬɪɢɝɨɧɨɦɟɬɪɢɱɧɨɝɨ sin A sin B 1 >cos( A  B)  cos( A  B)@ ɜ ɨɫɬɚɬɨɱɧɨɦɭ ɜɢɝɥɹɞɿ ɦɨɠɧɚ ɡɚɩɢɫɚɬɢ: 2 67 P D 0 E0 sin 2SQ t  E E0 >cos 2S (Q  Q ɤɨɥ )t  cos 2S (Q  Q ɤɨɥ )t @ . (2.17) 1 2 Ɂ ɮɨɪɦɭɥɢ (2.17) ɜɢɞɧɨ, ɳɨ ɭ ɞɢɩɨɥɹ, ɹɤɢɣ ɨɫɰɢɥɸɽ, ɩɨɪɹɞ ɡɿ ɡɛɭɞɠɭɸɱɨɸ ɱɚɫɬɨɬɨɸ Ȟ ɡ'ɹɜɥɹɸɬɶɫɹ ɤɨɦɩɨɧɟɧɬɢ ɡ ɱɚɫɬɨɬɨɸ Ȟ±Ȟɤɨɥ (ɜɿɞɩɨɜɿɞɧɨ ɫɬɨɤɫɨɜɿ ɬɚ ɚɧɬɢɫɬɨɤɫɨɜɿ ɥɿɧɿʀ). Ɉɬɠɟ, ɞɥɹ ɩɪɨɹɜɭ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ɦɨɥɟɤɭɥɹɪɧɟ ɨɛɟɪɬɚɧɧɹ ɚɛɨ ɤɨɥɢɜɚɧɧɹ ɩɨɜɢɧɧɨ ɜɢɤɥɢɤɚɬɢ ɡɦɿɧɭ ɛɭɞɶ-ɹɤɨʀ ɫɤɥɚɞɨɜɨʀ ɩɨɥɹɪɢɡɨɜɚɧɨɫɬɿ ɦɨɥɟɤɭɥɢ. ɍ ɪɚɡɿ, ɤɨɥɢ ɱɚɫɬɨɬɚ ɡɛɭɞɠɭɸɱɨɝɨ ɫɜɿɬɥɚ ɛɥɢɡɶɤɚ ɞɨ ɱɚɫɬɨɬɢ ɩɨɝɥɢɧɚɧɧɹ ɡɪɚɡɤɚ, ɫɩɨɫɬɟɪɿɝɚɽɬɶɫɹ ɟɮɟɤɬ ɩɪɢɪɟɡɨɧɚɧɫɧɨɝɨ ɄɊ [188]. ɍ ɰɶɨɦɭ ɜɢɩɚɞɤɭ ɩɨɥɹɪɢɡɨɜɚɧɿɫɬɶ ɧɚ ɰɿɣ ɱɚɫɬɨɬɿ ɛɭɞɟ ɜɢɡɧɚɱɚɬɢɫɹ ɜ ɨɫɧɨɜɧɨɦɭ ɩɨɥɹɪɢɡɨɜɚɧɿɫɬɸ ɩɨɝɥɢɧɚɸɱɨʀ ɪɟɱɨɜɢɧɢ. ȼɧɚɫɥɿɞɨɤ ɰɶɨɝɨ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɫɦɭɝ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ, ɳɨ ɜɿɞɧɨɫɹɬɶɫɹ ɞɨ ɤɨɥɢɜɚɧɶ ɰɿɽʀ ɪɟɱɨɜɢɧɢ, ɪɿɡɤɨ ɡɪɨɫɬɟ. ɐɟɣ ɟɮɟɤɬ ɞɨɡɜɨɥɹɽ ɜɢɜɱɚɬɢ ɤɨɥɢɜɚɥɶɧɿ ɫɩɟɤɬɪɢ ɨɤɪɟɦɢɯ ɯɪɨɦɨɮɨɪɿɜ ɧɚɜɿɬɶ ɩɪɢ ɧɚɹɜɧɨɫɬɿ ɜɟɥɢɱɟɡɧɨɝɨ ɱɢɫɥɚ ɿɧɲɢɯ ɤɨɥɢɜɚɧɶ. 2.1.4 Ɍɟɯɧɿɤɚ ɨɬɪɢɦɚɧɧɹ ɫɩɟɤɬɪɿɜ ɄɊ ɋɩɟɤɬɪɢ ɄɊ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ɪɟɱɨɜɢɧ ɛɭɥɢ ɡɚɩɢɫɚɧɿ ɡɚ ɞɨɩɨɦɨɝɨɸ ɫɩɟɤɬɪɨɦɟɬɪɚ DILOR Z-16 (Ɏɪɚɧɰɿɹ) ɡ ɩɨɞɜɿɣɧɢɦ ɦɨɧɨɯɪɨɦɚɬɨɪɨɦ. Ƚɪɚɞɭɸɜɚɧɧɹ ɫɩɟɤɬɪɨɦɟɬɪɚ ɡɞɿɣɫɧɸɜɚɥɨɫɹ ɩɨ ɱɚɫɬɨɬɚɯ ɫɩɟɤɬɪɭ CCl4 [178]. ɍ ɪɨɛɨɬɿ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɢ ɚɪɝɨɧɨɜɢɣ ɥɚɡɟɪ ɡ ɥɿɧɿɽɸ ɡɛɭɞɠɟɧɧɹ Ȝ = 488 ɬɚ 514,5 ɧɦ. Ⱦɨɫɥɿɞɠɭɜɚɧɿ ɪɨɡɱɢɧɢ ɩɨɦɿɳɚɥɢ ɞɨ ɤɜɚɞɪɚɬɧɢɯ ɤɜɚɪɰɨɜɢɯ ɤɸɜɟɬ ɡ ɞɨɜɠɢɧɨɸ ɨɩɬɢɱɧɨɝɨ ɲɥɹɯɭ ɫɜɿɬɥɚ 10 ɦɦ ɬɚ ɝɟɪɦɟɬɢɡɭɜɚɥɢ. ɉɨɬɭɠɧɿɫɬɶ ɥɚɡɟɪɧɨɝɨ ɜɢɩɪɨɦɿɧɸɜɚɧɧɹ ɧɟ ɩɟɪɟɜɢɳɭɜɚɥɚ 20-25 ɦȼɬ, ɳɨ ɧɟ ɜɢɤɥɢɤɚɥɨ ɮɨɬɨ- ɬɚ ɬɟɩɥɨɪɭɣɧɭɜɚɧɧɹ ɡɪɚɡɤɿɜ. ɋɩɟɤɬɪɚɥɶɧɚ ɲɢɪɢɧɚ ɳɿɥɢɧɢ ɫɬɚɧɨɜɢɥɚ 4,5 ɫɦ-1, ɲɜɢɞɤɿɫɬɶ ɫɤɚɧɭɜɚɧɧɹ 30 ɫɦ-1/ɯɜ. Ɍɨɱɧɿɫɬɶ ɜɿɞɬɜɨɪɟɧɧɹ ɫɦɭɝ ɫɩɟɤɬɪɿɜ ɄɊ ɛɭɥɚ ɭ ɦɟɠɚɯ ±2 ɫɦ-1. ɋɩɟɤɬɪɢ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ɪɟɱɨɜɢɧ ɡɚɩɢɫɭɜɚɥɢ ɩɪɢ ɤɿɦɧɚɬɧɿɣ ɬɟɦɩɟɪɚɬɭɪɿ (t = 20-22°ɋ). ɍɫɿ ɫɩɟɤɬɪɢ ɛɭɥɨ ɨɬɪɢɦɚɧɨ ɭɫɟɪɟɞɧɟɧɧɹɦ ɧɟ ɦɟɧɲ ɞɟɫɹɬɢ ɜɢɦɿɪɸɜɚɧɶ ɜ ɨɞɧɚɤɨɜɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɭɦɨɜɚɯ. 68 2.2 Ɇɟɬɨɞ ɩ'ɽɡɨɝɪɚɜɿɦɟɬɪɿʀ ɞɥɹ ɨɬɪɢɦɚɧɧɹ ɿɡɨɬɟɪɦ ɝɿɞɪɚɬɚɰɿʀ Ⱦɥɹ ɜɢɡɧɚɱɟɧɧɹ ɱɢɫɥɚ ɦɨɥɟɤɭɥ ɜɨɞɢ N, ɫɨɪɛɨɜɚɧɢɯ ɡɪɚɡɤɚɦɢ ɩɪɢ ɡɚɞɚɧɿɣ ɜɿɞɧɨɫɧɿɣ ɜɨɥɨɝɨɫɬɿ (ȼȼ), ɡɚɫɬɨɫɨɜɭɜɚɜɫɹ ɦɟɬɨɞ ɩ'ɽɡɨɝɪɚɜɿɦɟɬɪɢɱɧɨɝɨ ɦɿɤɪɨɡɜɚɠɭɜɚɧɧɹ ɡ ɜɢɤɨɪɢɫɬɚɧɧɹɦ ɪɨɡɪɨɛɥɟɧɨʀ ɪɚɧɿɲɟ ɭɫɬɚɧɨɜɤɢ [189, 190]. Ƚɨɥɨɜɧɢɦɢ ɩɟɪɟɜɚɝɚɦɢ ɰɶɨɝɨ ɦɟɬɨɞɭ ɽ ɜɿɞɫɭɬɧɿɫɬɶ ɜɩɥɢɜɭ ɧɚɜɤɨɥɢɲɧɶɨɝɨ ɫɟɪɟɞɨɜɢɳɚ, ɜɢɫɨɤɚ (ɛɥɢɡɶɤɨ ɧɚɧɨɝɪɚɦɿɜ) ɱɭɬɥɢɜɿɫɬɶ ɿ ɦɚɥɚ ɜɢɬɪɚɬɚ ɞɨɫɥɿɞɠɭɜɚɧɨʀ ɪɟɱɨɜɢɧɢ ~10-5 ɝ. ɉ'ɽɡɨɝɪɚɜɿɦɟɬɪɢɱɧɢɣ ɦɟɬɨɞ ɨɬɪɢɦɚɧɧɹ ɿɡɨɬɟɪɦ ɝɿɞɪɚɬɚɰɿʀ ɪɟɱɨɜɢɧ ɡɚɫɧɨɜɚɧɢɣ ɧɚ ɜɢɡɧɚɱɟɧɧɿ ɡɚɥɟɠɧɨɫɬɿ ɡɦɿɧɢ ɪɟɡɨɧɚɧɫɧɨʀ ɱɚɫɬɨɬɢ ǻf ɤɜɚɪɰɨɜɨɝɨ ɪɟɡɨɧɚɬɨɪɚ ɜɿɞ ɦɚɫɢ ɪɟɱɨɜɢɧɢ m, ɧɚɧɟɫɟɧɨɝɨ ɧɚ ɩɨɜɟɪɯɧɸ ɤɜɚɪɰɨɜɨʀ ɩɥɚɫɬɢɧɢ [191]: 'f  f 02 Km , nUA (2.18) ɞɟ f 0 – ɪɟɡɨɧɚɧɫɧɚ ɱɚɫɬɨɬɚ; U – ɳɿɥɶɧɿɫɬɶ ɤɜɚɪɰɨɜɨʀ ɩɥɚɫɬɢɧɢ; Ⱥ – ɩɥɨɳɚ ɤɜɚɪɰɨɜɨʀ ɩɥɚɫɬɢɧɢ; n ɿ K – ɩɨɫɬɿɣɧɿ ɤɜɚɪɰɭ. Ɂɧɚɱɟɧɧɹ K ɡɚɥɟɠɢɬɶ ɜɿɞ ɪɨɡɩɨɞɿɥɭ ɦɚɫɢ ɩɨ ɩɨɜɟɪɯɧɿ ɤɜɚɪɰɭ ɿ ɡɚɡɜɢɱɚɣ ɞɨɪɿɜɧɸɽ § 1, ɹɤɳɨ ɪɟɱɨɜɢɧɚ ɪɿɜɧɨɦɿɪɧɨ ɪɨɡɩɨɞɿɥɟɧɚ ɩɨ ɤɨɧɬɚɤɬɭ ɩɥɚɫɬɢɧɢ. Ɂɝɿɞɧɨ ɡ ɜɢɪɚɡɨɦ (2.18) ɧɚɜɿɬɶ ɧɟɡɧɚɱɧɟ ɡɛɿɥɶɲɟɧɧɹ ɦɚɫɢ įm ɡɚ ɪɚɯɭɧɨɤ ɚɞɫɨɪɛɰɿʀ ɜɨɞɢ ɧɚ ɩɥɿɜɰɿ ɜɢɤɥɢɤɚɽ ɜɿɞɩɨɜɿɞɧɭ ɡɦɿɧɭ ɱɚɫɬɨɬɢ įf ɭ ɤɪɢɫɬɚɥɿ, ɬɨɞɿ: Gf 'f Gm 'm . (2.19) ȼɢɤɨɪɢɫɬɨɜɭɸɱɢ ɰɟ ɫɩɿɜɜɿɞɧɨɲɟɧɧɹ, ɜɢɡɧɚɱɚɽɦɨ ɫɟɪɟɞɧɽ ɱɢɫɥɨ ɦɨɥɟɣ ɜɨɞɢ ɧɚ ɦɨɥɶ ɞɨɫɥɿɞɠɭɜɚɧɨʀ ɪɟɱɨɜɢɧɢ ɡɚ ɮɨɪɦɭɥɨɸ: 69 N M ɪɟɱ ˜ G f M H 2O ˜ ' f m , (2.20) ɞɟ įf = ¨fi – ¨fm; ¨fi – ɩɨɬɨɱɧɟ ɡɧɚɱɟɧɧɹ ɪɿɡɧɢɰɟɜɨʀ ɱɚɫɬɨɬɢ ɦɿɠ ɨɩɨɪɧɢɦ ɿ ɜɢɦɿɪɸɜɚɥɶɧɢɦ ɤɜɚɪɰɨɜɢɦɢ ɪɟɡɨɧɚɬɨɪɚɦɢ ɩɪɢ i-ɬɿɣ ɜɨɥɨɝɨɫɬɿ; ¨fm – ɡɦɿɧɚ ɪɿɡɧɢɰɟɜɨʀ ɱɚɫɬɨɬɢ, ɜɢɤɥɢɤɚɧɚ ɫɭɯɢɦ ɡɪɚɡɤɨɦ; Mɪɟɱ – ɦɨɥɟɤɭɥɹɪɧɚ ɦɚɫɚ ɞɨɫɥɿɞɠɭɜɚɧɨʀ ɪɟɱɨɜɢɧɢ; M H 2O – ɦɨɥɟɤɭɥɹɪɧɚ ɦɚɫɚ ɜɨɞɢ. Ⱦɥɹ ɩ'ɽɡɨɝɪɚɜɿɦɟɬɪɢɱɧɨɝɨ ɞɨɫɥɿɞɠɟɧɧɹ ɩɥɿɜɤɢ ɪɟɱɨɜɢɧ, ɳɨ ɜɢɜɱɚɸɬɶɫɹ, ɨɬɪɢɦɭɜɚɥɢ ɡ ɤɨɧɰɟɧɬɪɨɜɚɧɨɝɨ ɪɨɡɱɢɧɭ, ɹɤɢɣ ɧɚɧɨɫɢɥɢ ɭ ɜɢɝɥɹɞɿ ɦɿɤɪɨɤɪɚɩɥɿ ɧɚ ɤɨɧɬɚɤɬɢ ɤɜɚɪɰɨɜɨɝɨ ɪɟɡɨɧɚɬɨɪɚ ɿ ɫɭɲɢɥɢ ɭ ɜɚɤɭɭɦɧɿɣ ɤɚɦɟɪɿ ɩɿɞ ɬɢɫɤɨɦ 10-3 Ɍɨɪɪ. Ɂɜɨɥɨɠɟɧɧɹ ɩɥɿɜɨɤ ɡɞɿɣɫɧɸɜɚɥɨɫɹ ɲɥɹɯɨɦ ɞɨɡɨɜɚɧɨʀ ɩɨɞɚɱɿ ɩɚɪɿɜ ɞɜɿɱɿ ɞɢɫɬɢɥɶɨɜɚɧɨʀ ɬɚ ɞɟɝɚɡɨɜɚɧɨʀ ɜɨɞɢ ɞɨ ɤɚɦɟɪɢ. ɉɨɦɢɥɤɚ ɜɢɡɧɚɱɟɧɧɹ ɤɿɥɶɤɨɫɬɿ ɫɨɪɛɨɜɚɧɨʀ ɜɨɞɢ ɜ ɿɧɬɟɪɜɚɥɿ ȼȼ ɞɨ 70% ɫɬɚɧɨɜɢɥɚ 0,05 ɦɨɥɟɤɭɥ ɜɨɞɢ ɧɚ ɦɨɥɟɤɭɥɭ ɞɨɫɥɿɞɠɭɜɚɧɨʀ ɪɟɱɨɜɢɧɢ, ɜɢɳɟ 70% – 0,5 ɦɨɥɟɤɭɥ ɜɨɞɢ. ȼɢɦɿɪɢ ɩɪɨɜɨɞɢɥɢɫɹ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɿ 20qɋ. ȱɡɨɬɟɪɦɢ ɝɿɞɪɚɬɚɰɿʀ ɡɚɩɢɫɭɜɚɥɢɫɹ ɭ ɜɢɝɥɹɞɿ ɡɚɥɟɠɧɨɫɬɿ ɤɿɥɶɤɨɫɬɿ ɫɨɪɛɭɽɦɨʀ ɡɪɚɡɤɨɦ ɜɨɞɢ N (ɭ Ƚɇ2Ɉ/Ƚɪɟɱ ɚɛɨ ɜ MH2O/Mɪɟɱ) ɜɿɞ ɜɿɞɧɨɫɧɨʀ ɜɨɥɨɝɨɫɬɿ (%). 2.3 Ɇɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ ɬɚ ɨɩɬɢɦɿɡɚɰɿɹ ɝɟɨɦɟɬɪɿʀ ɿ ɪɨɡɪɚɯɭɧɨɤ ɚɬɨɦɧɢɯ ɡɚɪɹɞɿɜ ȻȺɊ Ɉɞɧɢɦ ɿɡ ɫɭɱɚɫɧɢɯ ɦɟɬɨɞɿɜ ɜɢɡɧɚɱɟɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɧɚ ɦɨɥɟɤɭɥɹɪɧɨɦɭ ɪɿɜɧɿ ɽ ɞɚɧɿ ɤɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɢɯ ɪɨɡɪɚɯɭɧɤɿɜ ɡ ɜɢɤɨɪɢɫɬɚɧɧɹɦ Ɍɟɨɪɿʀ ɮɭɧɤɰɿɨɧɚɥɭ ɝɭɫɬɢɧɢ (DFT) ɬɚ Ȼɟɣɞɟɪɿɜɫɶɤɨɝɨ ɚɧɚɥɿɡɭ (AIM ɚɧɚɥɿɡ [138, 192]). ȼɿɞɩɨɜɿɞɧɨ ɞɨ ɬɟɨɪɿʀ AIM, ɇ-ɡɜ'ɹɡɨɤ ɩɨɜɢɧɟɧ ɜɿɞɩɨɜɿɞɚɬɢ ɩɟɜɧɢɦ ɡɧɚɱɟɧɧɹɦ ɟɥɟɤɬɪɨɧɧɨʀ ɝɭɫɬɢɧɢ ɦɿɠ ɚɬɨɦɨɦ ɜɨɞɧɸ ɬɚ ɚɬɨɦɨɦ-ɚɤɰɟɩɬɨɪɨɦ ɧɚ 70 ɬɨɩɨɥɨɝɿɱɧɿɣ ɤɚɪɬɿ ɟɥɟɤɬɪɨɧɧɨʀ ɝɭɫɬɢɧɢ (0,002 y 0,035 au) ɿ ɥɚɩɥɚɫɿɚɧɚ ɟɥɟɤɬɪɨɧɧɨʀ ɝɭɫɬɢɧɢ (0,024 y 0,139 au) [134, 135]. ȱɧɲɿ ɤɪɢɬɟɪɿʀ ɡɚɫɧɨɜɚɧɿ ɧɚ ɡɦɿɧɚɯ ɜɥɚɫɬɢɜɨɫɬɟɣ ɜɡɚɽɦɨɞɿɸɱɢɯ ɚɬɨɦɿɜ (ɡɚɪɹɞɿɜ, ɩɨɥɹɪɢɡɚɰɿɣɧɢɯ ɦɨɦɟɧɬɿɜ, ɪɚɞɿɭɫɿɜ) ɿ ɩɨɪɿɜɧɹɧɧɿ ɡ ɚɧɚɥɨɝɿɱɧɢɦɢ ɜɥɚɫɬɢɜɨɫɬɹɦɢ ɧɟɜɡɚɽɦɨɞɿɸɱɢɯ ɚɬɨɦɿɜ. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɬɚɤɨɝɨ ɩɿɞɯɨɞɭ ɜɢɡɧɚɱɟɧɨ, ɡɨɤɪɟɦɚ, ɭɬɜɨɪɟɧɧɹ ɧɟɤɥɚɫɢɱɧɢɯ C– H···O ɡɜ'ɹɡɤɿɜ ɭ ɧɭɤɥɟɨɬɢɞɚɯ ɬɚ ʀɯ ɩɪɨɬɨɧɨɜɚɧɢɯ ɮɨɪɦɚɯ [132, 135, 193]. ɇɟɞɨɥɿɤɨɦ ɰɢɯ ɦɟɬɨɞɿɜ ɨɰɿɧɤɢ ɦɨɠɥɢɜɨɫɬɿ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɽ ɦɨɞɟɥɸɜɚɧɧɹ ɜɿɞɧɨɫɧɨ ɧɟɜɟɥɢɤɢɯ ɫɢɫɬɟɦ (ɧɟ ɛɿɥɶɲɟ 100-150 ɚɬɨɦɿɜ) ɭ ɝɚɡɨɜɿɣ ɮɚɡɿ, ɳɨ ɧɟ ɜɿɞɩɨɜɿɞɚɽ ɭɦɨɜɚɦ ɟɤɫɩɟɪɢɦɟɧɬɿɜ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ. Ȼɿɥɶɲ ɚɞɟɤɜɚɬɧɢɦ ɦɨɠɟ ɛɭɬɢ ɜɢɤɨɪɢɫɬɚɧɧɹ ɦɟɬɨɞɿɜ ɦɨɥɟɤɭɥɹɪɧɨʀ ɞɢɧɚɦɿɤɢ ɬɚ ɦɟɬɨɞɭ Ɇɨɧɬɟ Ʉɚɪɥɨ (Ɇɋ), ɹɤɿ ɞɨɡɜɨɥɹɸɬɶ ɜ ɹɜɧɨɦɭ ɜɢɝɥɹɞɿ ɜɪɚɯɭɜɚɬɢ ɪɨɥɶ ɪɨɡɱɢɧɧɢɤɚ ɭ ɮɨɪɦɭɜɚɧɧɿ ɫɬɚɛɿɥɶɧɢɯ ɚɫɨɰɿɚɬɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ ɿ ɧɚ ɚɬɨɦɧɨɦɭ ɪɿɜɧɿ ɜɢɡɧɚɱɢɬɢ ɫɬɪɭɤɬɭɪɭ ɬɚ ɨɛɱɢɫɥɢɬɢ ɟɧɟɪɝɟɬɢɱɧɿ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɫɚɦɨ- ɿ/ɚɛɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ, ɳɨ ɭɬɜɨɪɸɸɬɶɫɹ [120, 121, 139, 144, 194-197]. Ȼɭɥɢ ɞɨɫɥɿɞɠɟɧɿ ɫɢɫɬɟɦɢ, ɳɨ ɦɿɫɬɹɬɶ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɢ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ (ɝɟɬɟɪɨɞɢɦɟɪɢ) ɿ ɜɨɞɧɿ ɤɥɚɫɬɟɪɢ ɪɿɡɧɨɝɨ ɪɨɡɦɿɪɭ. ɍ Ɇɋ ɤɨɦɩ'ɸɬɟɪɧɨɦɭ ɟɤɫɩɟɪɢɦɟɧɬɿ ɪɨɡɪɚɯɭɧɤɢ ɛɭɥɢ ɜɢɤɨɧɚɧɿ ɭ ɤɚɧɨɧɿɱɧɨɦɭ (N, V, Ɍ) ɚɧɫɚɦɛɥɿ ɭ ɪɚɦɤɚɯ ɚɥɝɨɪɢɬɦɭ Ɇɟɬɪɨɩɨɥɿɫɚ ɩɪɢ 298 Ʉ [198]. Ʉɨɠɧɚ ɫɢɫɬɟɦɚ «ɝɟɬɟɪɨɞɢɦɟɪ + ɜɨɞɚ» ɦɿɫɬɢɥɚ 800 ɦɨɥɟɤɭɥ ɜɨɞɢ. ɉɨɱɚɬɤɨɜɿ ɫɬɪɭɤɬɭɪɢ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɞɥɹ Ɇɋ ɦɨɞɟɥɸɜɚɧɧɹ ɛɭɥɢ ɨɬɪɢɦɚɧɿ ɡ əɆɊ ɞɚɧɢɯ (Evstigneev M.P., personal communication). Ⱦɨ ɜɢɜɱɟɧɧɹ ɝɿɞɪɚɬɚɰɿʀ ɫɬɟɤɿɧɝ-ɝɟɬɟɪɨɞɢɦɟɪɿɜ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ ɛɭɥɨ ɡɧɚɣɞɟɧɨ ɤɨɧɮɿɝɭɪɚɰɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɭ ɜɚɤɭɭɦɿ ɡɚ ɞɨɩɨɦɨɝɨɸ ɩɪɨɰɟɞɭɪɢ Ɇɋ ɨɩɬɢɦɿɡɚɰɿʀ. ȼ ɹɤɨɫɬɿ ɫɬɚɪɬɨɜɢɯ ɫɬɪɭɤɬɭɪ ɜɡɹɬɨ ɧɚɣɛɿɥɶɲ ɟɧɟɪɝɟɬɢɱɧɨ ɜɢɝɿɞɧɿ ɤɨɧɮɿɝɭɪɚɰɿʀ. ɍ ɩɪɨɰɟɫɿ ɦɨɞɟɥɸɜɚɧɧɹ ɨɞɧɚ ɡ ɦɨɥɟɤɭɥ ɭ ɫɬɟɤɿɧɝ-ɝɟɬɟɪɨɞɢɦɟɪɿ ɡɦɿɳɭɜɚɥɚɫɹ ɡɝɿɞɧɨ ɡ ɚɥɝɨɪɢɬɦɨɦ Ɇɟɬɪɨɩɨɥɿɫɚ. ȿɧɟɪɝɿʀ ɜɡɚɽɦɨɞɿʀ ɝɟɬɟɪɨɞɢɦɟɪ-ɜɨɞɚ ɿ ɥɿɝɚɧɞ-ɥɿɝɚɧɞ ɚɩɪɨɤɫɢɦɭɜɚɥɢɫɶ ɡɚ ɞɨɩɨɦɨɝɨɸ ɚɬɨɦ-ɚɬɨɦɧɢɯ ɩɨɬɟɧɰɿɣɧɢɯ ɮɭɧɤɰɿɣ 1-6-12 (ɚɬɨɦ-ɚɬɨɦɧɿ ɩɨɬɟɧɰɿɣɧɿ ɮɭɧɤɰɿʀ Ɇɚɥɟɧɤɨɜɚ-ɉɨɥɬɽɜɚ) [97, 143, 199]: 71 U ij ¦« i, j ª qi q j « rij ¬ º  Bij rij12  Aij rij6 » , » ¼ (2.21) ɞɟ qi , qj – ɩɚɪɰɿɚɥɶɧɿ ɡɚɪɹɞɢ ɧɚ ɚɬɨɦɚɯ; rij – ɜɿɞɫɬɚɧɿ ɦɿɠ i ɬɚ j ɚɬɨɦɚɦɢ. ɉɚɪɚɦɟɬɪɢ ɰɿɽʀ ɮɭɧɤɰɿʀ Aij , Bij ɜɿɞɬɜɨɪɸɸɬɶ ɞɨɜɠɢɧɢ ɇ-ɡɜ'ɹɡɤɿɜ ɦɿɠ ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ ɬɚ ɧɭɤɥɟɨɬɢɞɚɦɢ ɚɛɨ ɥɿɝɚɧɞɚɦɢ (ɧɚɩɪɢɤɥɚɞ, CAF), ɚ ɬɚɤɨɠ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɿ ɩɨɥɨɠɟɧɧɹ ɦɨɥɟɤɭɥ ɜɨɞɢ ɜ ɤɪɢɫɬɚɥɨɝɿɞɪɚɬɚɯ ɰɢɯ ɦɨɥɟɤɭɥ. ȿɧɟɪɝɿɹ ɜɡɚɽɦɨɞɿʀ ɜɨɞɚ-ɜɨɞɚ ɛɭɥɚ ɚɩɪɨɤɫɢɦɨɜɚɧɚ ɡɚ ɞɨɩɨɦɨɝɨɸ ɩɨɬɟɧɰɿɣɧɨʀ ɮɭɧɤɰɿʀ 1-6-exp [199, 200]: U ij ¦« i, j ª qi q j « ¬ rij º  Bij exp(C ij rij )  Aij rij6 » , » ¼ (2.22) ɞɟ qi , qj – ɩɚɪɰɿɚɥɶɧɿ ɡɚɪɹɞɢ ɧɚ ɚɬɨɦɚɯ; rij – ɜɿɞɫɬɚɧɿ ɦɿɠ i ɬɚ j ɚɬɨɦɚɦɢ. ɉɚɪɚɦɟɬɪɢ ɰɿɽʀ ɮɭɧɤɰɿʀ Aij , Bij ɿ Cij ɨɛɪɚɧɿ ɬɚɤ, ɳɨɛ ɜɿɞɬɜɨɪɸɜɚɥɢɫɹ ɟɧɟɪɝɿʀ ɝɟɤɫɚɝɨɧɚɥɶɧɨʀ ɤɪɢɫɬɚɥɿɱɧɨʀ ɪɟɲɿɬɤɢ ɥɶɨɞɭ ɿ ɫɢɥɨɜɚ ɩɨɫɬɿɣɧɚ ɞɟɮɨɪɦɚɰɿʀ ɇ-ɡɜ'ɹɡɤɿɜ. ɋɭɦɭɜɚɧɧɹ ɜɢɤɨɧɭɽɬɶɫɹ ɩɨ ɜɫɿɦ ɩɚɪɚɦ ɚɬɨɦɿɜ i ɬɚ j. Ɇɨɞɟɥɶ ɦɨɥɟɤɭɥɢ ɜɨɞɢ Ɇɚɥɟɧɤɨɜɚ [200, 201], ɳɨ ɜɢɤɨɪɢɫɬɨɜɭɽɬɶɫɹ ɭ ɪɨɡɪɚɯɭɧɤɚɯ, ɜɿɞɬɜɨɪɸɽ ɬɟɪɦɨɞɢɧɚɦɿɱɧɿ ɬɚ ɫɬɪɭɤɬɭɪɧɿ ɨɫɨɛɥɢɜɨɫɬɿ ɪɿɞɤɨʀ ɜɨɞɢ, ɨɬɪɢɦɚɧɿ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ. ɉɨɜɧɚ ɟɧɟɪɝɿɹ ɜɡɚɽɦɨɞɿʀ ɨɛɱɢɫɥɸɜɚɥɚɫɹ ɹɤ ɫɭɦɚ ɟɧɟɪɝɿɣ ɜɡɚɽɦɨɞɿɣ ɜɨɞɚɜɨɞɚ, ɥɿɝɚɧɞ-ɜɨɞɚ ɬɚ ɥɿɝɚɧɞ-ɥɿɝɚɧɞ. ȼ ɹɤɨɫɬɿ ɝɪɚɧɢɱɧɢɯ ɭɦɨɜ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɨɫɹ ɤɥɚɫɬɟɪɧɟ ɧɚɛɥɢɠɟɧɧɹ [202, 203]. ɉɪɢ ɬɚɤɨɦɭ ɩɿɞɯɨɞɿ ɫɢɫɬɟɦɚ ɦɿɫɬɢɥɚɫɹ ɜ ɫɮɟɪɭ ɡ ɧɟɩɪɨɧɢɤɧɢɦɢ ɫɬɿɧɤɚɦɢ ɬɚɤɢɦ ɱɢɧɨɦ, ɳɨɛ ɰɟɧɬɪ ɦɚɫ ɪɨɡɱɢɧɟɧɨʀ ɪɟɱɨɜɢɧɢ ɡɛɿɝɚɜɫɹ ɡ ɰɟɧɬɪɨɦ ɫɮɟɪɢ. ɋɩɨɱɚɬɤɭ ɜ ɫɮɟɪɭ ɩɨɦɿɳɚɥɚɫɹ ɬɿɥɶɤɢ ɤɨɧɮɿɝɭɪɚɰɿɹ ɡ N ɦɨɥɟɤɭɥ ɜɨɞɢ. ɐɹ ɤɨɧɮɿɝɭɪɚɰɿɹ ɝɟɧɟɪɭɽɬɶɫɹ ɡɚ ɞɨɩɨɦɨɝɨɸ ɫɩɟɰɿɚɥɶɧɨʀ 72 ɩɪɨɝɪɚɦɢ ɞɥɹ ɫɬɜɨɪɟɧɧɹ ɟɧɟɪɝɟɬɢɱɧɨ ɜɢɝɿɞɧɨʀ ɫɬɪɭɤɬɭɪɢ ɜɨɞɧɨɝɨ ɤɥɚɫɬɟɪɭ ɩɟɜɧɨɝɨ ɪɨɡɦɿɪɭ. Ɋɚɞɿɭɫ ɫɮɟɪɢ ɞɨɪɿɜɧɸɽ ɪɚɞɿɭɫɭ, ɨɬɪɢɦɚɧɨɦɭ ɞɥɹ ɜɨɞɧɨɝɨ ɤɥɚɫɬɟɪɚ ɜɿɞɩɨɜɿɞɧɨɝɨ ɪɨɡɦɿɪɭ ɬɚ ɦɚɽ ɝɭɫɬɢɧɭ, ɜɿɞɩɨɜɿɞɧɭ ɝɭɫɬɢɧɿ ɜɨɞɢ ɩɪɢ ɧɨɪɦɚɥɶɧɢɯ ɭɦɨɜɚɯ (ɬɟɦɩɟɪɚɬɭɪɿ 298 Ʉ ɬɚ ɬɢɫɤɭ 1 ɚɬɦ). ɉɨɬɿɦ ɭ ɜɨɞɧɿɣ «ɤɪɚɩɥɿ» ɮɨɪɦɭɜɚɥɚɫɹ ɩɨɪɨɠɧɢɧɚ, ɧɟɨɛɯɿɞɧɚ ɞɥɹ ɪɨɡɬɚɲɭɜɚɧɧɹ ɞɢɦɟɪɚ ɜ ɰɟɧɬɪɿ ɫɮɟɪɢ, ɚ ɪɚɞɿɭɫ ɫɮɟɪɢ ɡɛɿɥɶɲɭɜɚɜɫɹ ɧɚ ɜɟɥɢɱɢɧɭ, ɧɟɨɛɯɿɞɧɭ ɞɥɹ ɪɨɡɦɿɳɟɧɧɹ ɦɨɥɟɤɭɥ ɜɨɞɢ, «ɜɢɬɢɫɧɭɬɢɯ» ɞɢɦɟɪɨɦ. Ⱦɨɜɠɢɧɚ ɥɚɧɰɸɝɚ Ɇɚɪɤɨɜɚ, ɳɨ ɝɟɧɟɪɭɽɬɶɫɹ, ɧɚɥɿɱɭɜɚɥɚ ɞɨ 5-7u106 ɟɥɟɦɟɧɬɚɪɧɢɯ ɤɪɨɤɿɜ ɞɨ ɞɨɫɹɝɧɟɧɧɹ ɫɬɚɰɿɨɧɚɪɧɨʀ ɨɛɥɚɫɬɿ. ȼ ɨɛɥɚɫɬɿ ɭɫɟɪɟɞɧɟɧɧɹ ɛɭɥɨ ɨɬɪɢɦɚɧɨ 4-6u106 ɟɥɟɦɟɧɬɚɪɧɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ ɞɥɹ ɪɨɡɪɚɯɭɧɤɭ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɯ ɯɚɪɚɤɬɟɪɢɫɬɢɤ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ɫɢɫɬɟɦ ɭ ɪɿɜɧɨɜɚɠɧɨɦɭ ɫɬɚɧɿ. ɋɬɚɬɢɫɬɢɱɧɚ ɩɨɦɢɥɤɚ, ɜɢɤɥɢɤɚɧɚ ɤɿɧɰɟɜɢɦ ɱɢɫɥɨɦ ɪɨɡɝɥɹɧɭɬɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ, ɪɨɡɪɚɯɨɜɚɧɚ ɡ ɜɢɤɨɪɢɫɬɚɧɧɹɦ ɦɟɬɨɞɭ ɤɨɧɬɪɨɥɶɧɢɯ ɮɭɧɤɰɿɣ. Ɂɧɚɱɟɧɧɹ ɫɬɚɬɢɫɬɢɱɧɨʀ ɩɨɦɢɥɤɢ ɧɟ ɩɟɪɟɜɢɳɭɜɚɥɨ r 0,005. Ⱦɥɹ ɨɬɪɢɦɚɧɧɹ ɿɧɮɨɪɦɚɰɿʀ ɩɪɨ ɇ-ɡɜ'ɹɡɤɢ, ɳɨ ɮɨɪɦɭɸɬɶɫɹ ɭ ɝɟɬɟɪɨɞɢɦɟɪɚɯ ɿ/ɚɛɨ ɦɿɠ ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ ɿ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɚɦɢ, ɩɪɨɜɨɞɢɥɨɫɹ Ɇɋ ɦɨɞɟɥɸɜɚɧɧɹ (1-2u103 ɟɥɟɦɟɧɬɚɪɧɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ) ɩɪɢ 5 Ʉ («ɡɚɦɨɪɨɠɟɧɿ – frozen» ɚɛɨ F-ɫɬɪɭɤɬɭɪɢ). ɇ-ɡɜ'ɹɡɤɢ ɜ F-ɫɬɪɭɤɬɭɪɚɯ ɜɢɡɧɚɱɚɥɢɫɹ ɜɿɞɩɨɜɿɞɧɨ ɞɨ ɝɟɨɦɟɬɪɢɱɧɢɯ ɬɚ ɟɧɟɪɝɟɬɢɱɧɢɯ ɤɪɢɬɟɪɿʀɜ [204]. Ɉɩɬɢɦɿɡɚɰɿɹ ɝɟɨɦɟɬɪɿʀ ɬɚ ɪɨɡɪɚɯɭɧɨɤ ɚɬɨɦɧɢɯ ɡɚɪɹɞɿɜ ɜɿɥɶɧɢɯ ɥɿɝɚɧɞɿɜ ɜɢɤɨɧɭɜɚɥɢɫɶ ɡɚ ɞɨɩɨɦɨɝɨɸ DFT/B3LYP/6-31G(d) ɡ ɜɢɤɨɪɢɫɬɚɧɧɹɦ ɩɪɨɝɪɚɦ GAMESS [205] ɞɥɹ CAF (ɡɚɝɚɥɶɧɢɣ ɡɚɪɹɞ 0), THP (ɡɚɝɚɥɶɧɢɣ ɡɚɪɹɞ 0), PRF (ɡɚɝɚɥɶɧɢɣ ɡɚɪɹɞ +1), EB (ɡɚɝɚɥɶɧɢɣ ɡɚɪɹɞ +1) ɬɚ Orca [206] ɞɥɹ FMN (ɡɚɝɚɥɶɧɢɣ ɡɚɪɹɞ -2). Ɂɚɪɹɞɢ ɧɚ ɚɬɨɦɚɯ ɨɬɪɢɦɚɧɿ ɡɚ ɞɨɩɨɦɨɝɨɸ ɫɯɟɦɢ MerzKollman-Singh ɪɨɡɩɨɞɿɥɭ ɡɚɪɹɞɿɜ. ɋɬɪɭɤɬɭɪɧɿ ɮɨɪɦɭɥɢ CAF, THP, PRF, ȿȼ ɿ FMN, ɧɭɦɟɪɚɰɿɹ ɚɬɨɦɿɜ ɿ ɡɚɪɹɞɢ, ɹɤɿ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɢɫɹ ɜ ɦɨɞɟɥɸɜɚɧɧɿ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ, ɧɚɜɟɞɟɧɿ ɭ ɞɨɞɚɬɤɭ ȼ, ɪɢɫ. ȼ.1-ȼ.5, ɬɚɛɥ. ȼ.1-ȼ.5. 73 2.4 ɉɪɢɝɨɬɭɜɚɧɧɹ ɡɪɚɡɤɿɜ ɞɥɹ ɞɨɫɥɿɞɠɟɧɧɹ ɍ ɪɨɛɨɬɿ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɢ ɥɿɝɚɧɞɢ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ ɿ ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ ɮɿɪɦɢ "Fluka", ɥɿɝɚɧɞɢ ɩɪɨɮɥɚɜɿɧ, ɤɨɮɟʀɧ ɿ ɬɟɨɮɿɥɿɧ ɮɿɪɦɢ "Sigma", ɫɬɪɭɤɬɭɪɧɿ ɮɨɪɦɭɥɢ ɹɤɢɯ ɧɚɜɟɞɟɧɿ ɧɚ ɪɢɫ. 1.2, 1.3 ɿ 1.4, ɿ ȾɇɄ ɡ ɬɢɦɭɫɚ ɬɟɥɹɬɢ ("Serva", ɎɊɇ). ɍɫɿ ɩɪɟɩɚɪɚɬɢ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɢɫɹ ɛɟɡ ɞɨɞɚɬɤɨɜɨɝɨ ɨɱɢɳɟɧɧɹ. Ʉɨɧɰɟɧɬɪɚɰɿʀ ɪɨɡɱɢɧɿɜ ȻȺɊ ɜɢɡɧɚɱɚɥɢ ɡ ɜɢɤɨɪɢɫɬɚɧɧɹɦ ɦɨɥɹɪɧɢɯ ɤɨɟɮɿɰɿɽɧɬɿɜ ɟɤɫɬɢɧɤɰɿʀ: ɞɥɹ FMN İ445 = 12500 Ɇ-1ɫɦ-1 [207], ɞɥɹ PRF İ444 = 41000 Ɇ-1ɫɦ-1 [208], ɞɥɹ EB İ480 = 5860 Ɇ-1ɫɦ-1 ɿ ɞɥɹ ȾɇɄ İ260 = 6400 Ɇ-1ɫɦ-1 [209], ɚ ɬɚɤɨɠ ɞɥɹ CAF İ270 = 10000 Ɇ-1ɫɦ-1 [210]. Ʉɨɧɰɟɧɬɪɚɰɿɸ TPH ɜɢɡɧɚɱɚɥɢ ɡɚ ɜɚɝɨɸ (Ɇ = 180,16 ɝ/ɦɨɥɶ). ɑɟɪɟɡ ɫɢɥɶɧɟ ɩɨɝɥɢɧɚɧɧɹ Ɉɇ-ɝɪɭɩ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɥɟɝɤɨʀ ɜɨɞɢ (ɇ2Ɉ) ɜɢɜɱɟɧɧɹ ɇ-ɡɜ`ɹɡɤɭ ɬɢɩɭ N–H···O ɚɛɨ N–H···N ɡɚɡɜɢɱɚɣ ɭɫɤɥɚɞɧɟɧɨ. ɍ ɰɶɨɦɭ ɜɢɩɚɞɤɭ ɞɨɫɥɿɞɠɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɩɪɨɜɨɞɹɬɶɫɹ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɜɚɠɤɨʀ ɜɨɞɢ (D2O), ɜ ɹɤɢɯ ɜɿɞɛɭɜɚɽɬɶɫɹ ɫɭɬɬɽɜɢɣ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɣ ɿɡɨɬɨɩɧɢɣ ɡɫɭɜ ɜɚɥɟɧɬɧɢɯ ɿ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ ɝɪɭɩɢ OD, ɳɨ ɞɨɡɜɨɥɹɽ ɩɪɨɜɟɫɬɢ ɚɧɚɥɿɡ ɩɨɜɟɞɿɧɤɢ ɜɚɥɟɧɬɧɢɯ ɤɨɥɢɜɚɧɶ ɜɢɤɥɸɱɧɨ ɚɤɰɟɩɬɨɪɚ (ɧɚɩɪɢɤɥɚɞ, ɤɚɪɛɨɧɿɥɶɧɨʀ ɝɪɭɩɢ ɋ=Ɉ). Ɋɨɡɱɢɧɢ ɞɥɹ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɯ ɞɨɫɥɿɞɠɟɧɶ ɝɨɬɭɜɚɥɢ ɜ D2O (99,8% ɱɢɫɬɨɬɢ), ɧɟɣɬɪɚɥɶɧɟ ɡɧɚɱɟɧɧɹ pɇ (pɇ = 6,9÷7,1) ɞɨɫɹɝɚɥɢ ɞɨɞɚɜɚɧɧɹɦ ɦɚɥɨʀ ɤɿɥɶɤɨɫɬɿ NaOD. Ʉɨɧɰɟɧɬɪɚɰɿɹ ɥɿɝɚɧɞɿɜ FMN, EB, CAF ɿ TPH ɭ ɜɿɥɶɧɨɦɭ ɫɬɚɧɿ ɬɚ ɜ ɫɭɦɿɲɚɯ ɫɬɚɧɨɜɢɥɚ ɋ = 1,3u10-2 M, ɬɨɞɿ ɹɤ ɤɨɧɰɟɧɬɪɚɰɿɹ PRF ɱɟɪɟɡ ɧɢɡɶɤɭ ɪɨɡɱɢɧɧɿɫɬɶ ɫɬɚɧɨɜɢɥɚ ɋ = 7,7u10-3 Ɇ. Ⱦɥɹ ɬɨɝɨ ɳɨɛ ɞɨɫɹɝɬɢ ɪɿɜɧɨɦɨɥɹɪɧɨʀ ɤɨɧɰɟɧɬɪɚɰɿʀ ɤɨɦɩɨɧɟɧɬɿɜ ɭ ɫɭɦɿɲɿ FMN-PRF, ɤɨɧɰɟɧɬɪɚɰɿɸ FMN ɬɚɤɨɠ ɛɭɥɨ ɞɨɜɟɞɟɧɨ ɞɨ ɋ = 7,7u10-3 Ɇ. ȼɫɿ ɪɨɡɱɢɧɢ ɛɭɥɨ ɩɨɦɿɳɟɧɨ ɞɨ ɝɟɪɦɟɬɢɱɧɢɯ ɪɿɞɢɧɧɢɯ ɤɸɜɟɬ. Ɉɫɤɿɥɶɤɢ ɫɦɭɝɚ ɩɨɝɥɢɧɚɧɧɹ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ OD-ɝɪɭɩɢ ɡɧɚɯɨɞɢɬɶɫɹ ɜ ɨɛɥɚɫɬɿ ɡ ɦɚɤɫɢɦɭɦɨɦ ɩɨɝɥɢɧɚɧɧɹ 1200 ɫɦ-1, ɰɟ ɞɨɡɜɨɥɢɥɨ ɡɚɩɢɫɚɬɢ ȱɑ-ɫɩɟɤɬɪɢ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ȻȺɊ ɬɚ ʀɯ ɫɭɦɿɲɟɣ ɭ 74 ɫɩɟɤɬɪɚɥɶɧɿɣ ɨɛɥɚɫɬɿ 1600-1750 ɫɦ-1 ɛɟɡ ɭɪɚɯɭɜɚɧɧɹ ɩɨɝɥɢɧɚɧɧɹ ɜɨɞɢ. ɜɧɟɫɤɭ ɫɢɥɶɧɨɝɨ Ⱦɥɹ ɨɬɪɢɦɚɧɧɹ ȱɑ-ɫɩɟɤɬɪɿɜ ɩɨɝɥɢɧɚɧɧɹ ɩɥɿɜɨɤ FMN ɝɨɬɭɜɚɥɢ ɪɨɡɱɢɧɢ ɡ ɤɨɧɰɟɧɬɪɚɰɿɽɸ ɋ§0,01 Ɇ. Ɂɧɚɱɟɧɧɹ pH = 6,0÷6,4 ɨɬɪɢɦɭɜɚɥɢ ɩɪɢ ɞɨɞɚɜɚɧɧɿ ɩɚɪɿɜ ɪɨɡɱɢɧɭ HCl, ɬɨɞɿ ɹɤ ɧɟɣɬɪɚɥɶɧɟ ɡɧɚɱɟɧɧɹ (pH = 6,8÷7,1) ɞɨɫɹɝɚɥɨɫɹ ɞɨɞɚɜɚɧɧɹɦ ɦɚɥɨʀ ɤɿɥɶɤɨɫɬɿ NaOɇ (ɞɥɹ ɪɨɡɱɢɧɿɜ FMN ɭ D2O ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɢ DCl ɿ NaOD, ɜɿɞɩɨɜɿɞɧɨ). Ɂɧɚɱɟɧɧɹ ɪɇ ɜɢɦɿɪɸɜɚɥɢ ɡɚ ɞɨɩɨɦɨɝɨɸ ɿɨɧɨɦɿɪɚ ȱ-115 (Antex, ɌɈȼ, Ɋɨɫɿɹ) ɡ ɬɨɱɧɿɫɬɸ ±0,05. ɋɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɋ2=Ɉ ɿ ɋ4=Ɉ ɛɭɥɢ ɨɬɪɢɦɚɧɿ ɪɨɡɤɥɚɞɚɧɧɹɦ ɫɩɟɤɬɪɭ ɡɚ ɫɬɚɧɞɚɪɬɧɨɸ ɦɟɬɨɞɢɤɨɸ [211]. Ɋɨɡɪɚɯɭɧɨɤ ɪɟɡɨɧɚɧɫɧɢɯ ɱɚɫɬɨɬ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɜɢɤɨɧɭɜɚɜɫɹ ɬɚɤ ɫɚɦɨ, ɹɤ ɭ ɪɨɛɨɬɿ [107]. Ⱦɥɹ ɨɬɪɢɦɚɧɧɹ ɄɊ-ɫɩɟɤɬɪɿɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɭɫɿ ɪɨɡɱɢɧɢ ɝɨɬɭɜɚɥɢɫɹ ɜ ɫɬɚɧɞɚɪɬɧɨɦɭ ɮɨɫɮɚɬɧɨɦɭ ɛɭɮɟɪɧɨɦɭ ɪɨɡɱɢɧɿ (2,5u10-2 Ɇ KH2PO4, 2,5u10-2 Ɇ Na2HPO4) ɩɪɢ pH = 6,86. Ʉɨɧɰɟɧɬɪɚɰɿɹ ɜɫɿɯ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ɪɟɱɨɜɢɧ ɫɬɚɧɨɜɢɥɚ ɋ = 1,5u10-5 M. ɋɭɦɿɲɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɝɨɬɭɜɚɥɢ ɜ ɫɩɿɜɜɿɞɧɨɲɟɧɧɿ 1:1. Ɋɨɡɱɢɧɢ ȻȺɊ ɬɚ ʀɯ ɫɭɦɿɲɟɣ ɩɨɦɿɳɚɥɢ ɞɨ ɤɜɚɪɰɨɜɢɯ ɤɸɜɟɬ ɤɜɚɞɪɚɬɧɨɝɨ ɩɟɪɟɬɢɧɭ ɬɨɜɳɢɧɨɸ 10 ɦɦ ɿ ɝɟɪɦɟɬɢɡɭɜɚɥɢ. Ʉɨɦɩɥɟɤɫɢ EB-ȾɇɄ ɞɥɹ ɜɢɦɿɪɸɜɚɧɶ ɦɟɬɨɞɨɦ ɄɊ ɝɨɬɭɜɚɥɢ ɩɪɢ ɪɿɡɧɢɯ ɡɧɚɱɟɧɧɹɯ P/D (ɫɩɿɜɜɿɞɧɨɲɟɧɧɹ ɦɨɥɶɧɢɯ ɤɨɧɰɟɧɬɪɚɰɿɣ ȾɇɄ ɿ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ), ɩɪɢ ɰɶɨɦɭ ɤɨɧɰɟɧɬɪɚɰɿɹ ɥɿɝɚɧɞɭ ɡɚɥɢɲɚɥɚɫɹ ɧɟɡɦɿɧɧɨɸ (ɋEB = 1,1u10-4 Ɇ). ɍɫɿ ɪɨɡɱɢɧɢ ɝɨɬɭɜɚɥɢɫɹ ɜ ɫɬɚɧɞɚɪɬɧɨɦɭ ɮɨɫɮɚɬɧɨɦɭ ɛɭɮɟɪɧɨɦɭ ɪɨɡɱɢɧɿ (2,5u10-2 Ɇ KH2PO4, 2,5u10-2 Ɇ Na2HPO4) ɩɪɢ pH = 6,86. ɉɥɿɜɤɢ ȾɇɄ ɨɬɪɢɦɭɜɚɥɢ ɜɢɩɚɪɨɜɭɜɚɧɧɹɦ ɜɨɞɢ ɩɪɢ t = 4°ɋ ɡ ɪɨɡɱɢɧɭ ɩɨɥɿɧɭɤɥɟɨɬɢɞɭ ɡ ɋȾɇɄ = 10-3 Ɇ. Ⱦɥɹ ɨɬɪɢɦɚɧɧɹ Ⱥ- ɬɚ ȼ-ɮɨɪɦ ȾɇɄ ɜ ɝɟɪɦɟɬɢɱɧɨ ɡɚɤɪɢɬɭ ɤɸɜɟɬɭ ɡ ɩɥɿɜɤɨɸ ȾɇɄ ɩɨɦɿɳɚɥɢ ɜɿɞɩɨɜɿɞɧɿ ɪɨɡɱɢɧɢ ɧɚɫɢɱɟɧɢɯ ɫɨɥɟɣ ɞɥɹ ɞɨɫɹɝɧɟɧɧɹ ɧɟɨɛɯɿɞɧɨɝɨ ɡɧɚɱɟɧɧɹ ɜɿɞɧɨɫɧɨʀ ɜɨɥɨɝɨɫɬɿ: NaCl – 76% ȼȼ ɿ K2SO4 – 96% ȼȼ ɞɥɹ Ⱥ- ɬɚ ȼ-ɮɨɪɦ ȾɇɄ, ɜɿɞɩɨɜɿɞɧɨ [212- 75 214]. Ɋɨɡɱɢɧɢ EB ɬɚ ɣɨɝɨ ɫɭɦɿɲɟɣ ɡ ȾɇɄ, ɚ ɬɚɤɨɠ ɩɥɿɜɤɢ ȾɇɄ ɩɨɦɿɳɚɥɢ ɞɨ ɤɜɚɞɪɚɬɧɢɯ ɤɜɚɪɰɨɜɢɯ ɤɸɜɟɬ (10 ɦɦ) ɿ ɝɟɪɦɟɬɢɡɭɜɚɥɢ. ȼɢɫɧɨɜɤɢ ɞɨ ɪɨɡɞɿɥɭ 2 1. Ⱦɨɤɥɚɞɧɨ ɨɩɢɫɚɧɨ ɮɿɡɢɱɧɿ ɩɪɢɧɰɢɩɢ ɿɧɮɪɚɱɟɪɜɨɧɨʀ (ȱɑ) ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɿ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ (ɄɊ) ɬɚ ɩɪɨɜɟɞɟɧɨ ʀɯ ɩɨɪɿɜɧɹɥɶɧɢɣ ɚɧɚɥɿɡ. Ɋɨɡɝɥɹɧɭɬɨ ɫɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɿ ɨɩɢɫɚɧɨ ɬɟɯɧɿɤɭ ɨɬɪɢɦɚɧɧɹ ȱɑ-ɫɩɟɤɬɪɿɜ. ɇɚɜɟɞɟɧɨ ɛɚɡɨɜɿ ɩɪɢɧɰɢɩɢ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɄɊ ɬɚ ɨɩɢɫɚɧɨ ɦɟɬɨɞɢɤɭ ɨɬɪɢɦɚɧɧɹ ɫɩɟɤɬɪɿɜ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ. Ⱦɟɬɚɥɶɧɨ ɨɩɢɫɚɧɨ ɦɟɬɨɞ ɩ'ɟɡɨɝɪɚɜɿɦɟɬɪɿɿ ɞɥɹ ɨɬɪɢɦɚɧɧɹ ɿɡɨɬɟɪɦ ɝɿɞɪɚɬɚɰɿʀ. Ɋɨɡɝɥɹɧɭɬɨ ɬɟɨɪɟɬɢɱɧɿ ɦɟɬɨɞɢ ɞɨɫɥɿɞɠɟɧɧɹ, ɹɤɿ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɢɫɹ ɞɥɹ ɜɢɜɱɟɧɧɹ ɟɧɟɪɝɟɬɢɱɧɢɯ ɯɚɪɚɤɬɟɪɢɫɬɢɤ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɿɜ. Ⱦɟɬɚɥɶɧɨ ɨɩɢɫɚɧɨ ɦɟɬɨɞɢɤɭ ɩɪɢɝɨɬɭɜɚɧɧɹ ɡɪɚɡɤɿɜ ɞɥɹ ɞɨɫɥɿɞɠɟɧɶ. 2. 3. 4. 5. 6. 76 ɊɈɁȾȱɅ 3 ɋȺɆɈȺɋɈɐȱȺɐȱə ɎɅȺȼȱɇɆɈɇɈɇɍɄɅȿɈɌɂȾɍ ȼ ɊɈɁɑɂɇȺɏ ȱ ɉɅȱȼɄȺɏ ȼɢɜɱɟɧɧɹ ɩɪɢɪɨɞɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ (ɬɨɛɬɨ ɫɬɪɭɤɬɭɪɢ ɿ ɬɟɪɦɨɞɢɧɚɦɿɤɢ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ) ɽ ɜɚɠɥɢɜɢɦ ɟɬɚɩɨɦ ɞɥɹ ɪɨɡɭɦɿɧɧɹ ɦɟɯɚɧɿɡɦɿɜ ɜɡɚɽɦɨɞɿʀ ɬɚɤɢɯ ɦɨɥɟɤɭɥ ɡ ɧɭɤɥɟʀɧɨɜɢɦɢ ɤɢɫɥɨɬɚɦɢ ɬɚ ʀɯ ɤɨɦɩɨɧɟɧɬɚɦɢ. Ⱥɧɚɥɨɝ ɜɿɬɚɦɿɧɭ ȼ2 (ɪɢɛɨɮɥɚɜɿɧɭ), ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ, ɽ ɩɪɨɬɟɬɢɱɧɨɸ ɝɪɭɩɨɸ ɮɥɚɜɨɩɪɨɬɟʀɧɿɜ, ɹɤɿ ɛɟɪɭɬɶ ɭɱɚɫɬɶ ɭ ɩɟɪɟɧɟɫɟɧɿ ɜɨɞɧɸ ɬɚ ɪɟɝɭɥɹɰɿʀ ɨɤɢɫɥɸɜɚɥɶɧɨ-ɜɿɞɧɨɜɧɢɯ ɩɪɨɰɟɫɿɜ. ɇɚ ɜɿɞɦɿɧɭ ɜɿɞ ɪɢɛɨɮɥɚɜɿɧɭ, ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ ɞɨɛɪɟ ɪɨɡɱɢɧɹɽɬɶɫɹ ɭ ɜɨɞɧɨɦɭ ɫɟɪɟɞɨɜɢɳɿ, ɳɨ ɞɨɡɜɨɥɹɽ ɜɢɤɨɪɢɫɬɨɜɭɜɚɬɢ ɣɨɝɨ ɜ ɪɿɡɧɢɯ ɮɿɡɢɤɨ-ɯɿɦɿɱɧɢɯ ɿ ɛɿɨɮɿɡɢɱɧɢɯ ɞɨɫɥɿɞɠɟɧɧɹɯ ɜɡɚɽɦɨɞɿʀ ɜɿɬɚɦɿɧɭ ȼ2 ɡ ɪɿɡɧɢɦɢ ɫɩɨɥɭɤɚɦɢ. ȿɤɫɩɟɪɢɦɟɧɬɚɥɶɧɿ ɞɨɫɥɿɞɠɟɧɧɹ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɨɝɨ ɜɿɬɚɦɿɧɭ B2 ɬɚ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɜɢɤɨɧɭɜɚɥɢɫɹ ɪɚɧɿɲɟ ɬɿɥɶɤɢ ɜ ɪɨɡɱɢɧɿ ɬɚɤɢɦɢ ɦɟɬɨɞɚɦɢ ɹɤ əɆɊ-ɫɩɟɤɬɪɨɫɤɨɩɿɹ, ɫɩɟɤɬɪɨɮɨɬɨɦɟɬɪɿɹ ɜ ɍɎ ɿ ɜɢɞɢɦɿɣ ɨɛɥɚɫɬɿ ɬɚ ɮɥɸɨɪɟɫɰɟɧɰɿɹ [54, 55, 59, 84], ɳɨ ɞɨɡɜɨɥɢɥɨ ɜɢɡɧɚɱɢɬɢ ɬɟɪɦɨɞɢɧɚɦɿɱɧɿ ɩɚɪɚɦɟɬɪɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɬɚ ɡɚɩɪɨɩɨɧɭɜɚɬɢ ɩɪɨɫɬɨɪɨɜɭ ɫɬɪɭɤɬɭɪɭ ɞɢɦɟɪɧɨɝɨ ɤɨɦɩɥɟɤɫɭ [55, 56, 84]. Ɏɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ ɮɭɧɤɰɿɨɧɭɽ ɜ ɤɥɿɬɢɧɚɯ ɭ ɤɨɧɞɟɧɫɨɜɚɧɨɦɭ ɫɬɚɧɿ ɜ ɹɤɨɫɬɿ ɤɨɮɟɪɦɟɧɬɭ ɞɟɹɤɢɯ ɮɥɚɜɿɧɨɡɚɥɟɠɧɢɯ ɞɟɝɿɞɪɨɝɟɧɚɡ. Ɍɨɦɭ ɞɨɫɥɿɞɠɟɧɧɹ ɨɫɨɛɥɢɜɨɫɬɟɣ ɮɿɡɢɤɨ-ɯɿɦɿɱɧɢɯ ɯɚɪɚɤɬɟɪɢɫɬɢɤ FMN ɭ ɜɨɥɨɝɢɯ ɩɥɿɜɤɚɯ ɫɬɚɧɨɜɢɬɶ ɿɧɬɟɪɟɫ ɞɥɹ ɪɨɡɭɦɿɧɧɹ ɜɩɥɢɜɭ ɣɨɝɨ ɤɨɧɞɟɧɫɨɜɚɧɨɝɨ ɫɬɚɧɭ ɧɚ ɨɤɢɫɥɸɜɚɥɶɧɿ ɮɭɧɤɰɿʀ, ɨɫɤɿɥɶɤɢ ɫɚɦɟ ɬɚɤɢɣ ɫɬɚɧ ɦɚɤɫɢɦɚɥɶɧɨ ɧɚɛɥɢɠɟɧɢɣ ɞɨ ɩɪɢɪɨɞɧɢɯ ɭɦɨɜ ɮɭɧɤɰɿɨɧɭɜɚɧɧɹ FMN ɭ ɠɢɜɢɯ ɫɢɫɬɟɦɚɯ. 77 3.1 ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɣ ɩɪɨɹɜ ɫɚɦɨɚɫɨɰɿɚɰɿʀ FMN ɭ ɩɥɿɜɤɚɯ ȱɑ-ɫɩɟɤɬɪɢ FMN ɭ ɪɨɡɱɢɧɚɯ ɬɚ ɭ ɜɨɥɨɝɢɯ ɩɥɿɜɤɚɯ ɡɚɩɢɫɚɧɨ ɜ ɨɛɥɚɫɬɿ 1600-1800 ɫɦ-1. Ɋɨɡɱɢɧɢ ɞɥɹ ɨɬɪɢɦɚɧɧɹ ɩɥɿɜɨɤ ɝɨɬɭɜɚɥɢɫɹ ɩɪɢ ɧɟɣɬɪɚɥɶɧɢɯ (pH = 7) ɿ ɫɥɚɛɨɤɢɫɥɢɯ (pH = 6,2) ɫɟɪɟɞɨɜɢɳɚɯ. ɇɚ ɪɢɫ. 3.1 ɩɪɢɜɟɞɟɧɨ ȱɑ-ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ FMN ɭ ɧɟɣɬɪɚɥɶɧɨɦɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ ɜ D2O (ɪɢɫ. 3.1 ɚ) ɬɚ ɭ ɜɨɥɨɝɢɯ ɩɥɿɜɤɚɯ (ɪɢɫ. 3.1 ɛ). ɍɫɿ ɫɩɟɤɬɪɢ ɛɭɥɨ ɨɬɪɢɦɚɧɨ ɭɫɟɪɟɞɧɟɧɧɹɦ 10 ɫɤɚɧɿɜ, ɡɚɩɢɫɚɧɢɯ ɩɪɢ ɨɞɧɚɤɨɜɢɯ ɭɦɨɜɚɯ. ȼɢɞɧɨ, ɳɨ ɜ ɨɛɥɚɫɬɿ ɩɨɝɥɢɧɚɧɧɹ 1600-1800 ɫɦ-1 ɧɚɹɜɧɿ ɞɜɿ ɤɨɦɩɨɧɟɧɬɢ. ȼɢɤɨɪɢɫɬɨɜɭɸɱɢ ɜɿɞɧɟɫɟɧɧɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ, ɧɚɜɟɞɟɧɿ ɭ ɪɨɛɨɬɚɯ [215-217], ɜɢɫɨɤɨɱɚɫɬɨɬɧɭ ɫɦɭɝɭ ɩɨɝɥɢɧɚɧɧɹ ɡ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ Ȟ1 = 1704 ɫɦ-1 (±1 ɫɦ-1) ɦɨɠɧɚ ɜɿɞɧɟɫɬɢ ɞɨ ɤɨɥɢɜɚɧɶ C4=O ɝɪɭɩɢ ɚɬɨɦɿɜ, ɚ ɧɢɡɶɤɨɱɚɫɬɨɬɧɭ ɫɦɭɝɭ ɩɪɢ Ȟ2 = 1653-1655 ɫɦ-1 (±1 ɫɦ-1) – ɞɨ ɤɨɥɢɜɚɧɶ ɤɚɪɛɨɧɿɥɶɧɨʀ ɝɪɭɩɢ C2=O FMN (ɞɢɜ. ɪɢɫ. 1.4). Ɂɿ ɫɩɟɤɬɪɿɜ ɜɢɞɧɨ, ɳɨ ɞɥɹ ɡɪɚɡɤɿɜ FMN ɭ ɪɨɡɱɢɧɚɯ ɿ ɜɨɥɨɝɢɯ ɩɥɿɜɤɚɯ ɱɚɫɬɨɬɢ ɤɨɥɢɜɚɧɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɋ2=Ɉ ɿ ɋ4=Ɉ ɜ ɦɟɠɚɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨʀ ɩɨɦɢɥɤɢ (±1 ɫɦ-1) ɩɪɚɤɬɢɱɧɨ ɡɛɿɝɚɸɬɶɫɹ. ɍ ɧɟɩɨɥɹɪɧɿɣ ɪɿɞɢɧɿ (ɯɥɨɪɨɮɨɪɦɿ) ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɜɿɥɶɧɢɯ ɜɿɞ ɛɭɞɶɹɤɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɝɪɭɩ C4=O ɿ C2=O ɦɚɸɬɶ ɛɿɥɶɲ ɜɢɫɨɤɿ ɡɧɚɱɟɧɧɹ ɱɚɫɬɨɬ 1710 ɫɦ-1 ɿ 1685 ɫɦ-1, ɜɿɞɩɨɜɿɞɧɨ [218]. ɍ ɧɟɣɬɪɚɥɶɧɢɯ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɿ ɜ ɩɥɿɜɤɚɯ FMN (ɪɢɫ. 3.1) ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɰɢɯ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɦɚɸɬɶ ɛɿɥɶɲ ɧɢɡɶɤɿ ɱɚɫɬɨɬɢ, ɳɨ ɩɨɜ'ɹɡɚɧɨ ɡ ɜɩɥɢɜɨɦ ɜɨɞɧɨɝɨ ɨɬɨɱɟɧɧɹ ɿ ɧɚɹɜɧɿɫɬɸ ɫɭɫɿɞɧɿɯ ɦɨɥɟɤɭɥ FMN. ɇɚɦɢ ɧɟ ɜɢɹɜɥɟɧɨ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɯ ɡɪɭɲɟɧɶ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɜ ɫɚɦɨɚɫɨɰɿɚɬɿ FMN [219], ɹɤ ɩɪɢ ɭɬɜɨɪɟɧɧɿ ɫɬɨɩɨɤ ɚɡɨɬɢɫɬɢɯ ɨɫɧɨɜ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ [98, 103, 104] ɿ ɤɨɮɟʀɧɭ [105]. Ɉɱɟɜɢɞɧɨ, ɫɚɦɨɚɫɨɰɿɚɰɿɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɩɪɨɣɲɥɚ ɬɚɤɢɦ ɱɢɧɨɦ, ɳɨ ɞɢɧɚɦɿɱɧɚ ɜɡɚɽɦɨɞɿɹ ɞɢɩɨɥɶɧɢɯ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ C2=O ɿ C4=O ɜɢɹɜɢɥɚɫɹ ɧɟɦɨɠɥɢɜɨɸ. ɐɟɣ ɜɢɫɧɨɜɨɤ ɩɿɞɬɜɟɪɞɠɭɽɬɶɫɹ ɪɟɡɭɥɶɬɚɬɚɦɢ ɜɢɤɨɧɚɧɨɝɨ ɪɨɡɪɚɯɭɧɤɭ ɞɢɧɚɦɿɱɧɨʀ 78 ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɞɢɦɟɪɧɿɣ ɦɨɞɟɥɿ [56], ɹɤɿ ɞɚɥɢ ɧɭɥɶɨɜɢɣ ɡɫɭɜ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ C2=O ɿ C4=O ɝɪɭɩ ɚɬɨɦɿɜ (ɞɢɜ. ɧɢɠɱɟ). D C2=O 1655 C4=O 0,2 1704 0,1 0,0 1600 1650 1700 1750 Q, ɫɦ -1 (ɚ) D 0,15 C2=O 2 1 1653 0,10 C4=O 1704 0,05 0,00 1600 1650 1700 1750 Q, ɫɦ -1 (ɛ) Ɋɢɫɭɧɨɤ 3.1 ȱɑ-ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ FMN ɭ D2O ɪɨɡɱɢɧɿ ɩɪɢ ɪɇ = 7,0 (±0,05) (ɚ) ɿ ɩɥɿɜɤɚɯ (ɛ), ɜɢɪɨɳɟɧɢɯ ɡ ɪɨɡɱɢɧɿɜ ɡ ɪɇ = 6,9 (±0,05), ɩɪɢ ɡɧɚɱɟɧɧɹɯ ȼȼ 32 % (1) ɿ 86 % (2) Ɍɚɤɨɠ ɜɚɪɬɨ ɜɿɞɡɧɚɱɢɬɢ, ɳɨ ɜ ɧɟɣɬɪɚɥɶɧɨɦɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ, ɩɨ ɚɧɚɥɨɝɿʀ ɡ ɧɭɤɥɟɨɬɢɞɚɦɢ, ɧɚɬɪɿɣ-ɮɨɫɮɚɬɧɚ ɝɪɭɩɚ ɦɨɥɟɤɭɥɢ FMN ɞɢɫɨɰɿɸɽ, ɿ ɧɟɝɚɬɢɜɧɢɣ ɡɚɪɹɞ ɧɚ ɚɬɨɦɚɯ ɤɢɫɧɸ ɮɨɫɮɚɬɧɢɯ ɝɪɭɩ, ɦɚɛɭɬɶ, ɜɩɥɢɜɚɽ ɧɚ 79 ɫɬɪɭɤɬɭɪɭ ɫɚɦɨɚɫɨɰɿɚɬɿɜ. ɍ ɪɨɛɨɬɿ [56] ɪɨɡɝɥɹɞɚɽɬɶɫɹ ɞɢɦɟɪɧɚ ɦɨɞɟɥɶ ɡ ɚɧɬɢɩɚɪɚɥɟɥɶɧɢɦ ɭɤɥɚɞɚɧɧɹɦ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ FMN, ɩɪɢ ɹɤɨɦɭ ɮɨɫɮɚɬɧɿ ɝɪɭɩɢ ɪɨɡɬɚɲɨɜɭɸɬɶɫɹ ɞɚɥɟɤɨ ɨɞɧɚ ɜɿɞ ɨɞɧɨʀ. Ɍɚɤɟ ɪɨɡɬɚɲɭɜɚɧɧɹ ɮɨɫɮɚɬɧɢɯ ɝɪɭɩ ɩɪɚɤɬɢɱɧɨ ɜɢɤɥɸɱɚɽ ɜɩɥɢɜ ʀɯ ɤɭɥɨɧɿɜɫɶɤɨʀ ɜɡɚɽɦɨɞɿʀ (ɟɥɟɤɬɪɨɫɬɚɬɢɱɧɨɝɨ ɜɿɞɲɬɨɜɯɭɜɚɧɧɹ) ɧɚ ɫɬɚɛɿɥɶɧɿɫɬɶ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN. Ɍɨɦɭ ɦɨɠɧɚ ɩɪɢɩɭɫɬɢɬɢ, ɳɨ ɧɚɜɟɞɟɧɚ ɭ ɪɨɛɨɬɿ [56] ɫɬɪɭɤɬɭɪɚ ɫɚɦɨɚɫɨɰɿɚɬɚ FMN, ɜ ɹɤɿɣ ɧɟ ɪɟɚɥɿɡɭɸɬɶɫɹ ɞɢɧɚɦɿɱɧɿ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɿ ɜɪɚɯɨɜɚɧɨ ɡɦɟɧɲɟɧɧɹ ɟɥɟɤɬɪɨɫɬɚɬɢɱɧɨɝɨ ɜɿɞɲɬɨɜɯɭɜɚɧɧɹ ɮɨɫɮɚɬɧɢɯ ɝɪɭɩ, ɭɡɝɨɞɠɭɽɬɶɫɹ ɡ ɨɬɪɢɦɚɧɢɦɢ ɧɚɦɢ ɪɟɡɭɥɶɬɚɬɚɦɢ [219]. ȼ ɭɦɨɜɚɯ ɫɥɚɛɨɤɢɫɥɨɝɨ ɫɟɪɟɞɨɜɢɳɚ, ɹɤ ɜɿɞɨɦɨ, ɜɿɞɛɭɜɚɽɬɶɫɹ ɩɪɨɬɨɧɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɩɨ ɚɬɨɦɭ N5 ɡ pK = 5,2 [169] ɿ ɧɟɣɬɪɚɥɿɡɚɰɿɹ ɮɨɫɮɚɬɧɨʀ ɝɪɭɩɢ. Ɍɨɦɭ, ɜ ɩɨɪɿɜɧɹɧɧɿ ɡ ɫɚɦɨɚɫɨɰɿɚɬɚɦɢ, ɹɤɿ ɭɬɜɨɪɸɸɬɶɫɹ ɜ ɧɟɣɬɪɚɥɶɧɢɯ ɫɟɪɟɞɨɜɢɳɚɯ [55, 56], ɭ ɫɥɚɛɨɤɢɫɥɨɦɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ ɿ ɜ ɩɥɿɜɰɿ, ɜɢɪɨɳɟɧɿɣ ɡɿ ɫɥɚɛɨɤɢɫɥɨɝɨ ɪɨɡɱɢɧɭ, ɡ ɜɟɥɢɤɨɸ ɣɦɨɜɿɪɧɿɫɬɸ ɦɨɠɧɚ ɨɱɿɤɭɜɚɬɢ ɭɬɜɨɪɟɧɧɹ ɿɧɲɨʀ ɫɬɪɭɤɬɭɪɢ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿɜ FMN. ɇɚ ɫɶɨɝɨɞɧɿɲɧɿɣ ɞɟɧɶ ɧɟɦɚɽ ɞɨɫɬɨɜɿɪɧɢɯ ɞɨɫɥɿɞɠɟɧɶ ɫɚɦɨɚɫɨɰɿɚɰɿʀ FMN ɜ ɭɦɨɜɚɯ ɫɥɚɛɨɤɢɫɥɨɝɨ ɫɟɪɟɞɨɜɢɳɚ. Ɍɚɤɨɠ ɧɟ ɞɨɫɥɿɞɠɭɜɚɜɫɹ ɿ ɜɩɥɢɜ ɜɨɞɢ ɧɚ ɫɬɚɛɿɥɿɡɚɰɿɸ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿɜ FMN. Ɍɨɦɭ ɧɚɦɢ ɛɭɥɨ ɩɪɨɜɟɞɟɧɨ ɞɨɫɥɿɞɠɟɧɧɹ ȱɑ-ɫɩɟɤɬɪɿɜ, ɨɬɪɢɦɚɧɢɯ ɞɥɹ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ FMN ɿ ɩɥɿɜɨɤ, ɜɢɪɨɳɟɧɢɯ ɡ ɧɢɯ, ɭ ɫɩɟɤɬɪɚɥɶɧɿɣ ɨɛɥɚɫɬɿ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ 1600-1800 ɫɦ-1 [219]. ɇɚ ɪɢɫ. 3.2 ɩɪɟɞɫɬɚɜɥɟɧɨ ɫɩɟɤɬɪɢ FMN ɭ D2Ɉ ɪɨɡɱɢɧɿ ɩɪɢ pH = 6,4 ɿ ɩɥɿɜɨɤ, ɜɢɪɨɳɟɧɢɯ ɡ ɪɨɡɱɢɧɭ ɡ pH = 6,2. ɉɪɟɞɫɬɚɜɥɟɧɿ ɫɩɟɤɬɪɢ ɛɭɥɨ ɨɬɪɢɦɚɧɨ ɲɥɹɯɨɦ ɭɫɟɪɟɞɧɟɧɧɹ ɧɟ ɦɟɧɲɟ 10 ɫɤɚɧɿɜ, ɡɚɩɢɫɚɧɢɯ ɩɪɢ ɨɞɧɚɤɨɜɢɯ ɭɦɨɜɚɯ. ɍ ɩɥɿɜɤɚɯ FMN, ɜɢɪɨɳɟɧɢɯ ɡɿ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ (ɪɢɫ. 3.2 ɛ), ɡɚɮɿɤɫɨɜɚɧɨ ɡɧɚɱɧɭ ɡɦɿɧɭ ɫɩɟɤɬɪɿɜ ɜ ɨɛɥɚɫɬɿ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɭ ɩɨɪɿɜɧɹɧɧɿ ɡɿ ɫɩɟɤɬɪɚɦɢ FMN ɭ ɧɟɣɬɪɚɥɶɧɨɦɭ ɫɟɪɟɞɨɜɢɳɿ (ɞɢɜ. ɪɢɫ. 3.1) ɬɚ ɡɿ ɫɩɟɤɬɪɨɦ ɪɨɡɱɢɧɭ ɩɪɢ ɪɇ = 6,4 (ɪɢɫ. 3.2 ɚ). əɤɳɨ ɱɚɫɬɨɬɚ ɤɨɥɢɜɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɨʀ ɝɪɭɩɢ C2=O (Ȟ2 = 1656 ɫɦ-1 (±1 ɫɦ-1)) ɡɦɿɧɢɥɚɫɹ ɧɟɿɫɬɨɬɧɨ, ɬɨ ɫɦɭɝɚ ɩɨɝɥɢɧɚɧɧɹ C4=O (Ȟ1 = 1704 ɫɦ-1 (±1 ɫɦ-1)) ɡɦɿɫɬɢɥɚɫɹ ɭ ɜɢɫɨɤɨɱɚɫɬɨɬɧɭ 80 ɨɛɥɚɫɬɶ ɞɨ 1729 ɫɦ-1 (±1 ɫɦ-1), ɚ ʀʀ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɡɦɟɧɲɢɥɚɫɹ, ɬɨɛɬɨ ɞɥɹ ɰɿɽʀ ɫɦɭɝɢ ɜɢɹɜɥɟɧɨ ɝɿɩɨɯɪɨɦɿɡɦ. D 0,3 C2=O 1651 C4=O 0,2 1702 0,1 0,0 1600 1650 1700 1750 Q, ɫɦ -1 (ɚ) D 0,3 C2=O 2 1 1656 0,2 C4=O 1729 0,1 0,0 1600 1650 1700 1750 Q, ɫɦ -1 (ɛ) Ɋɢɫɭɧɨɤ 3.2 ȱɑ-ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ FMN ɭ D2O ɪɨɡɱɢɧɿ ɩɪɢ ɪɇ = 6,4 (±0,05) (ɚ) ɬɚ ɩɥɿɜɤɚɯ (ɛ), ɜɢɪɨɳɟɧɢɯ ɡ ɪɨɡɱɢɧɿɜ ɡ ɪɇ = 6,2 (±0,05), ɩɪɢ ɡɧɚɱɟɧɧɹɯ ȼȼ 32% (1) ɿ 80% (2) Ɍɚɤɢɣ ɯɚɪɚɤɬɟɪ ɡɦɿɧɢ ɫɩɟɤɬɪɚɥɶɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɤɨɥɢɜɚɧɧɹ C4=O, ɹɤ ɿ ɜ ɪɚɡɿ ɩɨɜɟɞɿɧɤɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɨɫɧɨɜ ɭ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ [103, ɭ ɫɬɨɩɤɚɯ ɦɨɠɟ ɝɟɬɟɪɨɰɢɤɥɿɜ ɚɡɨɬɢɫɬɢɯ ɩɨɥɿɧɭɤɥɟɨɬɢɞɚɯ 104], 81 ɩɨɹɫɧɸɜɚɬɢɫɹ ɞɢɧɚɦɿɱɧɨɸ ɜɡɚɽɦɨɞɿɽɸ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ C4=O, ɹɤɚ ɜɢɧɢɤɥɚ ɜ ɪɟɡɭɥɶɬɚɬɿ ɫɬɟɤɿɧɝɭ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ ɩɪɢ ɭɬɜɨɪɟɧɧɿ ɫɚɦɨɚɫɨɰɿɚɬɿɜ. ɐɿɤɚɜɨ ɜɿɞɡɧɚɱɢɬɢ, ɳɨ ɜ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɚɯ ɧɟ ɜɢɹɜɥɟɧɨ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɯ ɡɫɭɜɿɜ ɤɨɥɢɜɚɧɶ C2=O ɿ C4=O ɝɪɭɩ ɚɬɨɦɿɜ (ɪɢɫ. 3.2 ɚ). ɐɟ ɫɜɿɞɱɢɬɶ ɩɪɨ ɬɟ, ɳɨ ɜ ɫɥɚɛɨɤɢɫɥɨɦɭ ɪɨɡɱɢɧɿ ɹɤɳɨ ɿ ɜɿɞɛɭɥɚɫɹ ɫɚɦɨɚɫɨɰɿɚɰɿɹ FMN, ɬɨ ɫɬɪɭɤɬɭɪɚ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɭ ɿ ɪɨɡɬɚɲɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ ɿɧɲɨɝɨ ɬɢɩɭ, ɧɿɠ ɭ ɩɥɿɜɤɚɯ. Ⱦɥɹ ɩɨɹɫɧɟɧɧɹ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɯ ɡɦɿɳɟɧɶ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɋ4=Ɉ ('Ȟ1 = 25 ɫɦ-1 (± 1 ɫɦ-1)) ɿ ɋ2=Ɉ ('Ȟ2 | 3-4 ɫɦ-1 (± 1 ɫɦ-1)), ɳɨ ɩɪɨɹɜɥɹɸɬɶɫɹ ɜ ɭɦɨɜɚɯ ɡɜɨɥɨɠɟɧɢɯ ɩɥɿɜɨɤ, ɜɢɪɨɳɟɧɢɯ ɡɿ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ, ɭ ɩɨɪɿɜɧɹɧɧɿ ɡ ɩɨɜɟɞɿɧɤɨɸ ɰɢɯ ɫɦɭɝ ɭ ɫɩɟɤɬɪɚɯ ɩɥɿɜɨɤ, ɨɬɪɢɦɚɧɢɯ ɡ ɧɟɣɬɪɚɥɶɧɢɯ ɪɨɡɱɢɧɿɜ, ɪɨɡɝɥɹɧɭɬɨ ɞɢɧɚɦɿɱɧɭ (ɪɟɡɨɧɚɧɫɧɭ) ɜɡɚɽɦɨɞɿɸ ɞɢɩɨɥɶɧɢɯ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɿɜ ɰɢɯ ɝɪɭɩ ɚɬɨɦɿɜ. 3.2 Ɋɟɡɨɧɚɧɫɧɿ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɫɬɨɩɤɚɯ FMN. ɉɨɛɭɞɨɜɚ n-ɦɨɥɟɤɭɥɹɪɧɨʀ ɫɬɪɭɤɬɭɪɢ ɫɚɦɨɚɫɨɰɿɚɬɭ FMN Ɍɟɨɪɟɬɢɱɧɨɸ ɨɫɧɨɜɨɸ ɞɢɧɚɦɿɱɧɨʀ (ɪɟɡɨɧɚɧɫɧɨʀ) ɜɡɚɽɦɨɞɿʀ ɽ ɬɟɨɪɿɹ ɦɨɥɟɤɭɥɹɪɧɢɯ ɟɤɫɢɬɨɧɿɜ [181]. Ɉɫɧɨɜɧɿ ɩɨɥɨɠɟɧɧɹ ɰɿɽʀ ɬɟɨɪɿʀ ɪɨɡɝɥɹɧɭɬɨ ɜ ɩɿɞɪɨɡɞɿɥɿ 2.1.1. Ⱥɛɫɨɥɸɬɧɿ ɿɧɬɟɧɫɢɜɧɨɫɬɿ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ FMN ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ (D2O) ɜɢɡɧɚɱɟɧɨ ɡɿ ɫɩɟɤɬɪɭ (ɞɢɜ. ɪɢɫ. 3.1 ɚ), ɭ ɹɤɨɦɭ ɜɢɞɧɨ ɹɤɿɫɧɟ ɪɨɡɞɿɥɟɧɧɹ ɤɨɦɩɨɧɟɧɬɿɜ. Ɂɧɚɱɟɧɧɹ ɱɚɫɬɨɬ ɿ ɧɚɩɿɜɲɢɪɢɧɭ ɫɦɭɝ, ɹɤɿ ɫɥɚɛɨ ɩɟɪɟɤɪɢɜɚɸɬɶɫɹ, ɍ ɬɚɛɥ. 3.1 ɜɢɡɧɚɱɚɥɢ ɧɚɜɟɞɟɧɨ ɡ ɬɨɱɧɿɫɬɸ ±1 ɫɦ-1, ɩɨɦɢɥɤɚ ɫɦɭɝ ɪɨɡɪɚɯɭɧɤɭ ɩɨɝɥɢɧɚɧɧɹ ɚɛɫɨɥɸɬɧɢɯ ɿɧɬɟɧɫɢɜɧɨɫɬɟɣ ɫɬɚɧɨɜɢɥɚ 10%. ɫɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ (C2=O ɿ C4=O) FMN, ɹɤɿ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɢɫɹ ɩɪɢ ɪɨɡɪɚɯɭɧɤɭ ɪɟɡɨɧɚɧɫɧɢɯ ɡɫɭɜɿɜ ɭ ɫɚɦɨɚɫɨɰɿɚɬɿ FMN ɭ ɩɥɿɜɰɿ. 82 Ɍɚɛɥɢɰɹ 3.1 ɋɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ FMN: ɱɚɫɬɨɬɚ Ȟ0 ɿ ɧɚɩɿɜɲɢɪɢɧɚ ǻȞ1/2 ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ, ɦɚɤɫɢɦɭɦ ɩɨɝɥɢɧɚɧɧɹ İ0, ɿɧɬɟɝɪɚɥɶɧɿ ɿɧɬɟɧɫɢɜɧɨɫɬɿ B ɿ ɦɨɦɟɧɬɢ ɩɟɪɟɯɨɞɿɜ ȝ (ɭ Ⱦɟɛɚɹɯ) ȼɿɞɧɟɫɟɧɧɹ C2=O C4=O Ȟ0, ɫɦ -1 ǻȞ1/2, ɫɦ 58,7 45,4 -1 1655 1704 İ0·10-3, B·10-4, ɥ·ɦɨɥɶ-1·ɫɦ-1 ɥ·ɦɨɥɶ-1·ɫɦ-2 9,3 12,8 5,9 6,4 ȝ, Ⱦ 0,56 0,39 Ɂ ɬɚɛɥɢɰɿ ɜɢɞɧɨ, ɳɨ ɞɢɩɨɥɶɧɿ ɦɨɦɟɧɬɢ ɩɟɪɟɯɨɞɿɜ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɦɚɸɬɶ ɡɧɚɱɧɭ ɜɟɥɢɱɢɧɭ (~ 0,4-0,6 Ⱦ), ɬɨɦɭ ɦɨɠɧɚ ɨɱɿɤɭɜɚɬɢ, ɳɨ ɩɪɢ ɩɟɜɧɿɣ ɫɬɪɭɤɬɭɪɿ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN ɦɨɠɥɢɜɟ ɜɢɧɢɤɧɟɧɧɹ ɜɡɚɽɦɨɞɿɣ ɦɿɠ ɤɨɥɢɜɚɧɧɹɦɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ. ɉɪɨɜɟɞɟɧɢɣ ɧɚɦɢ [219] ɪɨɡɪɚɯɭɧɨɤ ɪɟɡɨɧɚɧɫɧɢɯ ɜɡɚɽɦɨɞɿɣ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɿɜ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɋ2=Ɉ ɿ ɋ4=Ɉ ɞɥɹ ɦɨɞɟɥɟɣ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN, ɩɪɟɞɫɬɚɜɥɟɧɢɯ ɭ ɪɨɛɨɬɚɯ [55, 56], ɡ ɜɢɤɨɪɢɫɬɚɧɧɹɦ ɞɚɧɢɯ ɬɚɛɥ. 3.1, ɩɨɤɚɡɚɜ ɜɿɞɫɭɬɧɿɫɬɶ ɡɫɭɜɭ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ('Ȟ = 0 ɫɦ-1). ɐɟɣ ɪɟɡɭɥɶɬɚɬ ɧɟ ɭɡɝɨɞɠɭɽɬɶɫɹ ɡ ɩɨɜɟɞɿɧɤɨɸ ɰɢɯ ɫɦɭɝ ɜ ɨɬɪɢɦɚɧɢɯ ȱɑ-ɫɩɟɤɬɪɚɯ (ɞɢɜ. ɪɢɫ. 3.1 ɿ 3.2). Ɇɢ ɩɪɢɩɭɫɤɚɽɦɨ, ɳɨ ɫɬɪɭɤɬɭɪɚ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN ɭ ɰɢɯ ɦɨɞɟɥɹɯ ɬɚɤɚ, ɳɨ ɜɿɞɫɬɚɧɶ ɦɿɠ ɤɚɪɛɨɧɿɥɶɧɢɦɢ ɝɪɭɩɚɦɢ, ɜɿɞɩɨɜɿɞɧɨ ɞɨ ɮɨɪɦɭɥɢ (2.10), ɜɢɹɜɢɥɚɫɹ ɡɧɚɱɧɨɸ – ɩɨɧɚɞ 4,5 Å, ɬɨɦɭ ɜɡɚɽɦɨɞɿɹ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɿɜ ɰɢɯ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɭ ɬɚɤɢɯ ɫɬɪɭɤɬɭɪɚɯ ɫɚɦɨɚɫɨɰɿɚɬɿɜ ɧɟɦɨɠɥɢɜɚ. Ⱦɥɹ ɩɨɹɫɧɟɧɧɹ ɫɩɨɫɬɟɪɟɠɭɜɚɧɢɯ ɜ ȱɑ-ɫɩɟɤɬɪɚɯ ɡɦɿɧ ɦɢ ɜɢɤɨɧɚɥɢ ɩɨɲɭɤ ɿɧɲɢɯ ɫɬɪɭɤɬɭɪ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿɜ FMN. Ɉɫɤɿɥɶɤɢ ɜ ɮɨɪɦɭɥɿ (2.10) M/hİ – ɩɨɫɬɿɣɧɚ ɜɟɥɢɱɢɧɚ (ɜ ɩɪɢɩɭɳɟɧɧɿ, ɳɨ İ = 1), ɬɨ ɩɨɲɭɤ ɦɨɠɥɢɜɨʀ ɤɨɧɮɿɝɭɪɚɰɿʀ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿɜ FMN ɩɪɨɜɨɞɢɥɢ, ɜɚɪɿɸɸɱɢ ɧɚɫɬɭɩɧɿ ɫɬɪɭɤɬɭɪɧɿ ɩɚɪɚɦɟɬɪɢ: ɡɦɿɳɟɧɧɹ ɦɨɥɟɤɭɥɢ ɭɡɞɨɜɠ ɜɟɥɢɤɨʀ ɨɫɿ (C2–C8) ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ (x), ɦɚɥɨʀ ɨɫɿ (N10–N5) ɤɿɥɶɰɹ (y) ɬɚ ɩɟɪɩɟɧɞɢɤɭɥɹɪɚ ɞɨ ɩɥɨɳɢɧɢ ɤɿɥɶɰɹ (z), ɜɿɞɩɨɜɿɞɧɨ; ș – ɤɭɬ ɩɨɜɨɪɨɬɭ ɧɚɜɤɨɥɨ ɨɫɿ Z, ɳɨ ɩɪɨɯɨɞɢɬɶ ɱɟɪɟɡ ɰɟɧɬɪ ɤɿɥɶɰɹ; ij1, ij2 – ɤɭɬɢ ɜɿɞɯɢɥɟɧɶ (ɜ ɩɥɨɳɢɧɿ ɤɿɥɶɰɹ) ɤɨɥɢɜɚɥɶɧɢɯ ɦɨɦɟɧɬɿɜ ɋ2=Ɉ ɿ ɋ4=Ɉ ɜɿɞ ɧɚɩɪɹɦɤɿɜ ɜɿɞɩɨɜɿɞɧɢɯ 83 ɡɜ'ɹɡɤɿɜ. ɇɚ ɩɿɞɫɬɚɜɿ ɰɢɯ ɫɬɪɭɤɬɭɪɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɨɛɱɢɫɥɸɜɚɥɢɫɹ ɜɿɞɫɬɚɧɿ R ɦɿɠ ɫɟɪɟɞɧɿɦɢ ɬɨɱɤɚɦɢ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ ɿ ɤɭɬɢ ij, ȕ, Ȗ – ɤɭɬɢ ɦɿɠ ɧɚɩɪɹɦɚɦɢ ɞɢɩɨɥɿɜ ɬɚ ɥɿɧɿɽɸ, ɳɨ ɡ'ɽɞɧɭɽ ʀɯ ɰɟɧɬɪɢ ɡɜ'ɹɡɤɿɜ. ɇɚ ɩɨɱɚɬɤɭ ɪɨɡɪɚɯɭɧɤɭ ɦɢ ɩɪɢɣɧɹɥɢ, ɳɨ ɦɨɦɟɧɬɢ ɩɟɪɟɯɨɞɿɜ ɫɩɪɹɦɨɜɚɧɨ ɩɨ ɡɜ'ɹɡɤɚɦ ɚɬɨɦɿɜ ɜɭɝɥɟɰɸ ɿ ɤɢɫɧɸ, ɚ ɩɨɬɿɦ – ɞɥɹ ɨɬɪɢɦɚɧɧɹ ɤɪɚɳɨʀ ɭɡɝɨɞɠɭɜɚɧɨɫɬɿ ɪɨɡɪɚɯɨɜɚɧɢɯ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɯ ɡɫɭɜɿɜ ɡ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɡɚɮɿɤɫɨɜɚɧɢɦɢ – ɡɦɿɧɸɜɚɥɢ ɧɚɩɪɹɦɨɤ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɿɜ (ɞɢɜ. ɪɨɛɨɬɢ [103, 104]). Ʉɪɢɬɟɪɿɹɦɢ (1) ɜɿɞɩɨɜɿɞɧɿɫɬɶ ɜɿɞɛɨɪɭ ɝɟɨɦɟɬɪɿʀ «ɩɪɚɜɢɥɶɧɢɯ» ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿɜ ɫɬɪɭɤɬɭɪ ɭɦɨɜɚɦ ɫɥɭɝɭɜɚɥɢ: ɡɛɟɪɟɠɟɧɧɹ ɦɿɠɩɥɨɳɢɧɧɢɯ ɜɡɚɽɦɨɞɿɣ ɦɿɠ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɦɢ ɤɿɥɶɰɹɦɢ (ɩɥɨɳɢɧɢ ɤɿɥɟɰɶ ɩɨɜɢɧɧɿ ɩɟɪɟɤɪɢɜɚɬɢɫɹ); (2) ɧɟɡɧɚɱɧɿ ɜɿɞɯɢɥɟɧɧɹ ɜɟɤɬɨɪɿɜ ɤɨɥɢɜɚɥɶɧɢɯ ɦɨɦɟɧɬɿɜ ɜɿɞ ɧɚɩɪɹɦɤɭ ɡɜ'ɹɡɤɿɜ; (3) ɜɿɞɫɭɬɧɿɫɬɶ ɫɬɟɪɢɱɧɢɯ ɩɟɪɟɲɤɨɞ. ɉɚɪɚɦɟɬɪɢ ɜɚɪɿɸɜɚɥɢɫɹ ɜ ɬɚɤɢɯ ɦɟɠɚɯ: x – ɞɨ 2,45 Å (ɩɪɢ ɬɚɤɨɦɭ ɡɦɿɳɟɧɧɿ ɩɟɪɟɤɪɢɜɚɸɬɶɫɹ ɞɜɚ ɡ ɬɪɶɨɯ ɰɢɤɥɿɜ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ), y – ɞɨ 0,6 Å (ɡɦɿɳɟɧɧɹ, ɨɬɪɢɦɚɧɟ ɞɥɹ ɫɬɪɭɤɬɭɪɢ ɫɬɟɤɿɧɝ-ɞɢɦɟɪɭ FMN ɩɪɢ ɦɨɥɟɤɭɥɹɪɧɨɦɭ ɦɨɞɟɥɸɜɚɧɧɿ ɬɚ ɜ əɆɊ ɞɨɫɥɿɞɠɟɧɧɹɯ [55, 56]), z – ɜɿɞ 3,4 ɞɨ 3,7 Å (ɞɿɚɩɚɡɨɧ ɦɿɠɩɥɨɳɢɧɧɢɯ ɜɿɞɫɬɚɧɟɣ, ɯɚɪɚɤɬɟɪɧɢɯ ɞɥɹ ɫɬɟɤɿɧɝɭ ɚɫɨɰɿɚɬɿɜ ɛɿɥɶɲɨɫɬɿ ɝɟɬɟɪɨɰɢɤɥɿɱɧɢɯ ɬɚ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ [65, 103]), ș – ɞɨ 30º, ij1 ɿ ij2 – ɞɨ 10º. ȼɿɞɩɨɜɿɞɧɿɫɬɶ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɫɩɨɫɬɟɪɟɠɭɜɚɧɨɝɨ ɡɫɭɜɭ ɱɚɫɬɨɬ ɞɥɹ C2=O ɿ C4=O ɞɨɫɹɝɚɽɬɶɫɹ ɩɪɢ x = 2,45 Å, y = 0,6 Å, z = 3,44 Å, ș = 4º, ij1 = 0,6º, ij2 = 9,9º. ȼɿɞɩɨɜɿɞɧɿ ɰɿɣ ɤɨɧɮɿɝɭɪɚɰɿʀ ɡɧɚɱɟɧɧɹ R, ij, ȕ, Ȗ ɧɚɜɟɞɟɧɨ ɭ ɬɚɛɥ. 3.2. ɇɚ ɪɢɫ. 3.3 ɩɪɢɜɟɞɟɧɨ ɪɨɡɪɚɯɨɜɚɧɿ ɡɚɥɟɠɧɨɫɬɿ ɡɫɭɜɿɜ ɱɚɫɬɨɬ ǻȞ ɞɥɹ ɨɞɧɿɽʀ ɦɨɥɟɤɭɥɢ FMN ɜɿɞ ɤɿɥɶɤɨɫɬɿ ʀʀ ɫɭɫɿɞɿɜ ɜɡɞɨɜɠ n-ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɫɚɦɨɚɫɨɰɿɚɬɭ. Ɍɚɛɥɢɰɹ 3.2 Ɂɧɚɱɟɧɧɹ ɩɚɪɚɦɟɬɪɿɜ ɝɟɨɦɟɬɪɢɱɧɨɝɨ ɮɚɤɬɨɪɚ ɞɥɹ ɋ2=Ɉ ɿ ɋ4=Ɉ ȼɿɞɧɟɫɟɧɧɹ C2=O C4=O R, Å 4,27 4,16 ij, ° 4,0 4,0 ȕ, ° 123,3 91,5 Ȗ, ° 124,3 89,1 84 3,1 3 ˜Ȟ, ɫɦع 2,9 2,8 2,7 0 20 40 60 80 100 Ʉɿɥɶɤɿɫɬɶ ɫɭɫɿɞɧɿɯ ɦɨɥɟɤɭɥ (ɚ) 26 25 24 ˜Ȟ, ɫɦع 23 22 21 20 0 20 40 60 80 100 Ʉɿɥɶɤɿɫɬɶ ɫɭɫɿɞɧɿɯ ɦɨɥɟɤɭɥ (ɛ) Ɋɢɫɭɧɨɤ 3.3 Ɂɚɥɟɠɧɿɫɬɶ ɱɚɫɬɨɬɧɢɯ ɡɫɭɜɿɜ ɨɞɧɿɽʀ ɦɨɥɟɤɭɥɢ FMN ɜɿɞ ɤɿɥɶɤɨɫɬɿ ʀʀ ɫɭɫɿɞɿɜ (2, 4, 6, ... n) ɩɪɢ ɜɡɚɽɦɨɞɿʀ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɿɜ ɞɥɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ C2=O (ɚ) ɿ C4=O (ɛ) ȼɢɞɧɨ, ɳɨ ɧɚɣɛɿɥɶɲɢɣ ɡɫɭɜ ɡɚ ɱɚɫɬɨɬɨɸ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɞɨɫɹɝɚɽɬɶɫɹ ɜ ɪɚɡɿ, ɤɨɥɢ ɫɬɨɩɤɚ FMN ɦɿɫɬɢɬɶ ɛɿɥɶɲɟ ɞɜɨɯ ɦɨɥɟɤɭɥ. Ɍɪɟɛɚ ɬɚɤɨɠ ɡɚɡɧɚɱɢɬɢ, ɳɨ ɜɿɞɩɨɜɿɞɧɿɫɬɶ ɪɨɡɪɚɯɭɧɤɨɜɢɯ ɡɫɭɜɿɜ ɱɚɫɬɨɬ ɤɚɪɛɨɧɿɥɶɧɢɯ 85 ɤɨɥɢɜɚɧɶ ɞɨ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɡɧɚɱɟɧɶ ('Ȟ1 = 25 ɫɦ-1 (± 1 ɫɦ-1)) ɩɪɢ n = 2 (ɞɢɦɟɪ FMN) ɨɬɪɢɦɚɧɨ ɞɥɹ ɫɚɦɨɚɫɨɰɿɚɬɭ FMN, ɜ ɹɤɨɝɨ ɧɟ ɫɩɨɫɬɟɪɿɝɚɽɬɶɫɹ ɩɟɪɟɤɪɢɜɚɧɧɹ ɩɥɨɳɢɧ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ, ɬɨɛɬɨ, ɩɪɢ ɦɿɧɿɦɚɥɶɧɨɦɭ ɫɬɟɤɿɧɝɭ ɿ, ɨɬɠɟ, ɧɟɫɬɚɛɿɥɶɧɿɣ ɫɬɪɭɤɬɭɪɿ ɫɚɦɨɚɫɨɰɿɚɬɭ. ɐɟ ɨɡɧɚɱɚɽ, ɳɨ ɤɨɧɮɿɝɭɪɚɰɿɹ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN ɦɿɫɬɢɬɶ ɹɤ ɦɿɧɿɦɭɦ ɬɪɢ ɦɨɥɟɤɭɥɢ. ȼɿɞɩɨɜɿɞɧɨ ɞɨ ɮɨɪɦɭɥɢ (2.9) ɛɭɥɢ ɨɬɪɢɦɚɧɿ ɪɨɡɪɚɯɭɧɤɨɜɿ ɡɫɭɜɢ ɱɚɫɬɨɬ, ɳɨ ɭɡɝɨɞɠɭɸɬɶɫɹ ɡ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɦɢ ('Ȟ2 § 3 ɫɦ-1 (± 1 ɫɦ-1) ɿ 'Ȟ1 § 25 ɫɦ-1 (± 1 ɫɦ-1)), ɫɚɦɟ ɞɥɹ n-ɦɨɥɟɤɭɥɹɪɧɨʀ ɫɬɪɭɤɬɭɪɢ ɫɚɦɨɚɫɨɰɿɚɬɭ (n t 3). ɇɚ ɪɢɫ. 3.4 ɩɪɟɞɫɬɚɜɥɟɧɨ ɩɪɨɫɬɨɪɨɜɭ ɫɬɪɭɤɬɭɪɭ ɫɚɦɨɚɫɨɰɿɚɬɭ FMN. ɉɭɧɤɬɢɪɨɦ ɜɤɚɡɚɧɨ ɜɡɚɽɦɨɞɿɸɱɿ ɤɚɪɛɨɧɿɥɶɧɿ ɝɪɭɩɢ. Ɋɢɫɭɧɨɤ 3.4 ɩɪɨɫɬɨɪɨɜɨʀ C2=O C4=O n-ɦɨɥɟɤɭɥɹɪɧɨɝɨ Ɏɪɚɝɦɟɧɬ ɫɬɪɭɤɬɭɪɢ ɫɚɦɨɚɫɨɰɿɚɬɭ ɜɤɚɡɚɧɨ FMN. ɉɭɧɤɬɢɪɨɦ ɜɡɚɽɦɨɞɿɸɱɿ ɤɚɪɛɨɧɿɥɶɧɿ ɝɪɭɩɢ ɋ2=Ɉ ɿ ɋ4=Ɉ əɤɿ ɨɫɧɨɜɧɿ ɮɚɤɬɨɪɢ, ɳɨ ɜɢɡɧɚɱɚɸɬɶ ɫɬɚɛɿɥɶɧɿɫɬɶ n-ɦɨɥɟɤɭɥɹɪɧɢɯ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN, ɳɨ ɭɬɜɨɪɸɸɬɶɫɹ ɜ ɭɦɨɜɚɯ ɫɥɚɛɨɤɢɫɥɨɝɨ ɫɟɪɟɞɨɜɢɳɚ? ɉɪɨɜɟɞɟɧɿ ɧɚɦɢ [219] ɞɨɫɥɿɞɠɟɧɧɹ ɜɩɥɢɜɭ ɜɨɞɢ ɧɚ ɫɬɚɛɿɥɶɧɿɫɬɶ ɫɚɦɨɚɫɨɰɿɚɬɿɜ ɞɨɡɜɨɥɢɥɢ ɜɢɹɜɢɬɢ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ (ɞɢɜ. ɪɢɫ. 3.2 ɛ) ɜ ɩɥɿɜɰɿ FMN. Ɇɨɠɧɚ ɩɪɢɩɭɫɬɢɬɢ, ɳɨ ɭɬɜɨɪɟɧɧɹ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿɜ FMN ɿ ɪɨɡɬɚɲɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ ɜ ɧɢɯ ɧɟ ɜɢɡɧɚɱɚɽɬɶɫɹ 86 ɜɡɚɽɦɨɞɿɽɸ ɡ ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ. Ɉɫɤɿɥɶɤɢ ɜ n-ɦɨɥɟɤɭɥɹɪɧɿɣ ɫɬɪɭɤɬɭɪɿ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN ɩɥɨɳɢɧɢ I-II ɬɚ II-III ɤɿɥɟɰɶ (ɪɢɫ. 3.4) ɩɟɪɟɤɪɢɜɚɸɬɶɫɹ, ɬɨ ɦɢ ɜɜɚɠɚɽɦɨ, ɳɨ ɫɬɚɛɿɥɿɡɚɰɿɹ ɬɚɤɨʀ ɫɬɪɭɤɬɭɪɢ ɜ ɩɥɿɜɰɿ ɞɨɫɹɝɚɽɬɶɫɹ ɜ ɪɟɡɭɥɶɬɚɬɿ ɫɬɟɤɿɧɝ-ɜɡɚɽɦɨɞɿɣ ɦɿɠ ɰɢɦɢ ɤɿɥɶɰɹɦɢ. ɉɪɨ ɰɟ ɫɜɿɞɱɚɬɶ ɱɢɫɥɟɧɧɿ ɪɨɡɪɚɯɭɧɤɢ ɳɨɞɨ ɨɰɿɧɤɢ ɜɤɥɚɞɭ ɦɿɠɩɥɨɳɢɧɧɢɯ ɜɡɚɽɦɨɞɿɣ ɜ ɫɬɚɛɿɥɶɧɿɫɬɶ ɚɫɨɰɿɚɬɿɜ ɪɿɡɧɢɯ ɝɟɬɟɪɨɰɢɤɥɿɱɧɢɯ ɫɩɨɥɭɤ, ɹɤɿ ɭɬɜɨɪɸɸɬɶ ɫɬɨɩɤɢ (ɞɢɜ., ɧɚɩɪɢɤɥɚɞ, [65]). əɤ ɩɨɤɚɡɚɥɢ ɧɚɲɿ ɞɨɫɥɿɞɠɟɧɧɹ ɫɨɪɛɰɿʀ ɜɨɞɢ ɧɚ ɩɥɿɜɤɚɯ, ɜɢɪɨɳɟɧɢɯ ɡɿ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ FMN [219], ɬɿɥɶɤɢ ɧɚ ɩɟɪɲɨɦɭ ɟɬɚɩɿ ɡɜɨɥɨɠɟɧɧɹ ɜɨɞɚ ɩɪɚɤɬɢɱɧɨ ɧɟ ɡɜ'ɹɡɭɽɬɶɫɹ ɡ ɝɿɞɪɚɬɧɨ-ɚɤɬɢɜɧɢɦɢ ɝɪɭɩɚɦɢ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ (ɞɢɜ. ɩɿɞɪɨɡɞɿɥ 3.4, ɪɢɫ. 3.9), ɚ ɩɪɢ ɡɛɿɥɶɲɟɧɧɿ ʀʀ ɚɤɬɢɜɧɨɫɬɿ (ɩɪɢ ɡɜ'ɹɡɭɜɚɧɧɿ ɛɿɥɶɲɟ 6 ɦɨɥɟɤɭɥ ɜɨɞɢ ɧɚ ɦɨɥɟɤɭɥɭ FMN, N > 6) ɝɿɞɪɚɬɚɰɿɹ ɿɫɬɨɬɧɨ ɡɪɨɫɬɚɽ. ȼɨɱɟɜɢɞɶ, ɦɨɥɟɤɭɥɢ ɜɨɞɢ ɬɚɤɨɠ ɦɨɠɭɬɶ ɜɩɥɢɜɚɬɢ ɧɚ ɫɬɚɛɿɥɶɧɿɫɬɶ n-ɦɨɥɟɤɭɥɹɪɧɢɯ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN, ɳɨ ɮɨɪɦɭɸɬɶɫɹ ɜ ɩɥɿɜɤɚɯ, ɜɢɪɨɳɟɧɢɯ ɡɿ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ. 3.3 ɉɪɨɬɨɧɭɜɚɧɧɹ FMN ɡɚ ɞɚɧɢɦɢ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɬɚ ɤɜɚɧɬɨɜɨɯɿɦɿɱɧɢɯ ɪɨɡɪɚɯɭɧɤɿɜ ɡɚɪɹɞɿɜ ɧɚ ɚɬɨɦɚɯ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɿ ɩɨɪɹɞɤɭ ʀɯ ɡɜ'ɹɡɤɿɜ 3.3.1 ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɣ ɩɪɨɹɜ ɩɪɨɬɨɧɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN ɇɚ ɪɢɫ. 3.5 ɩɪɟɞɫɬɚɜɥɟɧɨ ȱɑ-ɫɩɟɤɬɪ ɜ ɨɛɥɚɫɬɿ ɩɨɝɥɢɧɚɧɧɹ 1450-1600 ɫɦ-1 ɫɭɯɨʀ ɩɥɿɜɤɢ FMN (0% ȼȼ), ɜɢɪɨɳɟɧɨʀ ɡ ɧɟɣɬɪɚɥɶɧɨɝɨ ɪɨɡɱɢɧɭ (ɪɇ = 7,0). ɋɩɟɤɬɪ ɛɭɜ ɨɬɪɢɦɚɧɢɣ ɭɫɟɪɟɞɧɟɧɧɹɦ ɧɟ ɦɟɧɲɟ 10 ɫɤɚɧɿɜ, ɡɪɨɛɥɟɧɢɯ ɩɪɢ ɨɞɧɚɤɨɜɢɯ ɭɦɨɜɚɯ ɡɚɩɢɫɭ. ȼɢɞɧɨ, ɳɨ ɰɹ ɫɩɟɤɬɪɚɥɶɧɚ ɨɛɥɚɫɬɶ ɫɤɥɚɞɚɽɬɶɫɹ ɡ ɬɪɶɨɯ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɡ ɜɢɪɚɠɟɧɢɦɢ ɦɚɤɫɢɦɭɦɚɦɢ, ɳɨ ɩɟɪɟɤɪɢɜɚɸɬɶɫɹ. ɒɥɹɯɨɦ ɪɨɡɤɥɚɞɚɧɧɹ ɫɩɟɤɬɪɚ ɡɚ ɫɬɚɧɞɚɪɬɧɨɸ ɦɟɬɨɞɢɤɨɸ [220] ɬɚ ɡɝɿɞɧɨ ɡ ɪɨɛɨɬɨɸ [170] ɛɭɥɨ ɜɢɞɿɥɟɧɨ ɧɚɣɫɢɥɶɧɿɲɭ ɫɦɭɝɭ ɩɪɢ Ȟ1 = 1541 ɫɦ-1 (± 1 ɫɦ-1), 87 ɧɢɡɶɤɨɱɚɫɬɨɬɧɭ ɤɨɦɩɨɧɟɧɬɭ ɡ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ Ȟ2 = 1501 ɫɦ-1 (± 1 ɫɦ-1) ɿ ɜɢɫɨɤɨɱɚɫɬɨɬɧɭ ɫɦɭɝɭ ɡ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ Ȟ3 = 1575 ɫɦ-1 (± 1 ɫɦ-1). 1541 D 0,6 Ɋɢɫɭɧɨɤ 3.5 ɋ–ɋ ɿ ɋ–N ȱɑ-ɫɩɟɤɬɪ ɤɨɥɢɜɚɧɶ ɨɬɪɢɦɚɧɢɣ ɣɨɝɨ ɫɩɟɤɬɪ, ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN: ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɫɩɟɤɬɪ (—) ɬɚ 0,4 1501 1575 0,2 ɨɬɪɢɦɚɧɢɣ ɦɟɬɨɞɨɦ ɪɨɡɤɥɚɞɚɧɧɹ (---). ɉɥɿɜɤɭ FMN ɜɢɪɨɳɟɧɨ ɡ ɪɨɡɱɢɧɭ ɡ ɪɇ = 7,0 (±0,05) 1500 1550 Q , ɫɦ -1 0,0 1450 Ɂɝɿɞɧɨ ɡ ɞɚɧɢɦɢ ɪɨɛɨɬɢ [170] ɰɿ ɫɦɭɝɢ ɩɨɜ'ɹɡɚɧɿ ɡ ɤɨɥɢɜɚɧɧɹɦɢ ɚɬɨɦɿɜ ɋ– ɋ ɿ ɋ–N ɜ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɦɭ ɤɿɥɶɰɿ FMN (ɞɢɜ. ɪɢɫ. 1.4). ɍ ɬɚɛɥ. 3.3 ɧɚɜɟɞɟɧɨ ɜɢɞɿɥɟɧɿ ɫɦɭɝɢ ɬɚ ʀɯ ɜɿɞɧɟɫɟɧɧɹ. Ɍɚɛɥɢɰɹ 3.3 ȱɑ-ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɤɨɥɢɜɚɧɶ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN ɬɚ ʀɯ ɜɿɞɧɟɫɟɧɧɹ [170] ɑɚɫɬɨɬɚ (Ȟ), ɫɦ-1 1501 (Ȟ2) 1541 (Ȟ1) 1575 (Ȟ3) ȼɿɞɧɟɫɟɧɧɹ ɉɨɥɨɫɚ IV, Ȟ(C6=C7); Ȟ(C9–C9a); Ȟ(C10a=N1) ɉɨɥɨɫɚ III, Ȟ(C5a=C6); Ȟ(C8–C9); Ȟ(C5a=N5) ɉɨɥɨɫɚ II, Ȟ(C4a=N5); Ȟ(C4–C4a); Ȟ(C10a=N1) əɤ ɜɢɞɧɨ ɡ ɬɚɛɥ. 3.3, ɱɚɫɬɨɬɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ Ȟ1 ɿ Ȟ2 ɦɨɠɭɬɶ ɛɭɬɢ ɱɭɬɥɢɜɿ «ɜ ɱɢɫɬɨɦɭ ɜɢɝɥɹɞɿ» ɞɨ ɩɪɨɬɨɧɭɜɚɧɧɹ ɩɨ ɚɬɨɦɚɦ ɚɡɨɬɭ N1 ɿ N5. ɍ ɫɦɭɝɭ Ȟ3 ɞɚɸɬɶ ɜɧɟɫɨɤ ɨɛɢɞɜɚ ɚɬɨɦɢ ɚɡɨɬɭ N1 ɿ N5. 88 Ⱦɥɹ ɡ'ɹɫɭɜɚɧɧɹ ɜɩɥɢɜɭ ɩɪɨɬɨɧɭɜɚɧɧɹ ɧɚ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ Ȟ1, Ȟ2 ɿ Ȟ3 ɛɭɜ ɨɬɪɢɦɚɧɢɣ ɫɩɟɤɬɪ ɫɭɯɨʀ ɩɥɿɜɤɢ FMN, ɜɢɪɨɳɟɧɨʀ ɡɿ ɫɥɚɛɨɤɢɫɥɨɝɨ (ɪɇ = 6,0) ɜɨɞɧɨɝɨ ɪɨɡɱɢɧɭ. ɉɟɪɟɞɛɚɱɚɽɬɶɫɹ, ɳɨ ɜ ɰɢɯ ɭɦɨɜɚɯ ɜɿɞɛɭɜɚɽɬɶɫɹ ɩɪɨɬɨɧɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɩɨ ɚɬɨɦɚɯ N1 ɿ N5 [168]. ɇɚ ɪɢɫ. 3.6 ɩɪɟɞɫɬɚɜɥɟɧɨ ȱɑ-ɫɩɟɤɬɪ ɩɥɿɜɤɢ FMN (ɪɇ = 6,0) ɜ ɨɛɥɚɫɬɿ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɤɨɥɢɜɚɧɶ ɬɚ ɣɨɝɨ ɤɨɦɩɨɧɟɧɬɢ, ɨɬɪɢɦɚɧɿ ɪɨɡɤɥɚɞɚɧɧɹɦ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɝɨ ɫɩɟɤɬɪɚ. D 1554 1583 Ɋɢɫɭɧɨɤ 3.6 0,3 ȱɑ-ɫɩɟɤɬɪ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɋ–ɋ ɬɚ ɋ–N ɤɨɥɢɜɚɧɶ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ 1517 0,2 FMN: ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɨɬɪɢɦɚɧɢɣ ɫɩɟɤɬɪ (—) ɬɚ ɣɨɝɨ ɫɩɟɤɬɪ, ɨɬɪɢɦɚɧɢɣ ɦɟɬɨɞɨɦ ɪɨɡɤɥɚɞɚɧɧɹ (---). ɉɥɿɜɤɭ FMN ɛɭɥɨ ɜɢɪɨɳɟɧɨ ɡ ɪɨɡɱɢɧɭ ɡ ɪɇ = 6,0 (±0,05) 0,1 0,0 1450 1500 1550 Q , ɫɦ -1 Ɍɚɛɥɢɰɹ 3.4 ɑɚɫɬɨɬɢ ɿ ɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɞɥɹ ɩɥɿɜɨɤ FMN, ɜɢɪɨɳɟɧɢɯ ɡ ɧɟɣɬɪɚɥɶɧɨɝɨ ɿ ɫɥɚɛɨɤɢɫɥɨɝɨ ɪɨɡɱɢɧɿɜ ɋɦɭɝɚ Ɇɚɤɫɢɦɭɦ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɩɥɿɜɤɢ FMN (pH = 7,0), ɫɦ-1 Ȟ1 1541 (±1) Ȟ2 1501 (±1) Ȟ3 1575 (±1) Ɇɚɤɫɢɦɭɦ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɩɥɿɜɤɢ FMN (pH = 6,0), ɫɦ-1 1555 (±1) 1517 (±1) 1583 (±1) ɑɚɫɬɨɬɧɢɣ ǻȞ, ɫɦ-1 +14 (±1) +16 (±1) +8 (±1) ɡɫɭɜ 89 Ɇɨɠɧɚ ɛɚɱɢɬɢ ɿɫɬɨɬɧɿ ɡɫɭɜɢ ɪɨɡɝɥɹɧɭɬɢɯ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ, ɩɨɪɿɜɧɹɧɨ ɡ ɬɚɤɢɦ ɠɟ ɫɩɟɤɬɪɨɦ ɞɥɹ ɩɥɿɜɤɢ, ɜɢɪɨɳɟɧɨʀ ɡ ɧɟɣɬɪɚɥɶɧɨɝɨ ɪɨɡɱɢɧɭ (ɞɢɜ. ɪɢɫ. 3.5 ɿ ɞɚɧɿ ɬɚɛɥ. 3.4). Ɂ ɪɟɡɭɥɶɬɚɬɿɜ, ɩɪɟɞɫɬɚɜɥɟɧɢɯ ɭ ɬɚɛɥ. 3.4, ɜɢɞɧɨ, ɳɨ ɧɚɹɜɧɿɫɬɶ ɩɪɨɬɨɧɭ ɇ+ ɭ ɫɥɚɛɨɤɢɫɥɨɦɭ ɫɟɪɟɞɨɜɢɳɿ ɜɢɤɥɢɤɚɽ ɡɧɚɱɧɟ ɡɛɿɥɶɲɟɧɧɹ ɱɚɫɬɨɬ ɤɨɥɢɜɚɧɶ Ȟ1 ɬɚ Ȟ2 ɿ ɜ ɦɟɧɲɿɣ ɦɿɪɿ – ɞɥɹ ɫɦɭɝɢ Ȟ3. Ɂ ɬɟɨɪɿʀ ɤɨɥɢɜɚɧɧɹ ɦɨɥɟɤɭɥ [175] ɜɿɞɨɦɨ, ɳɨ ɡɛɿɥɶɲɟɧɧɹ ɡɚɪɹɞɿɜ ɿ ɩɨɪɹɞɤɿɜ ɡɜ'ɹɡɤɿɜ ɩɪɢɡɜɨɞɢɬɶ ɞɨ ɡɛɿɥɶɲɟɧɧɹ ɫɢɥɨɜɢɯ ɩɨɫɬɿɣɧɢɯ ɚɬɨɦɿɜ, ɳɨ ɤɨɥɢɜɚɸɬɶɫɹ, ɿ, ɨɬɠɟ, ɞɨ ɡɪɨɫɬɚɧɧɹ ɱɚɫɬɨɬɢ ɤɨɥɢɜɚɧɧɹ. ȼɢɹɜɥɟɧɟ ɜɢɫɨɤɨɱɚɫɬɨɬɧɟ ɡɦɿɳɟɧɧɹ ɫɦɭɝ ɦɨɠɟ ɛɭɬɢ ɩɨɹɫɧɟɧɟ ɩɪɨɬɨɧɭɜɚɧɧɹɦ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɩɨ ɚɬɨɦɚɯ N1 ɿ N5. Ʉɜɚɧɬɨɜɨɯɿɦɿɱɧɢɣ ɪɨɡɪɚɯɭɧɨɤ ɟɥɟɤɬɪɨɧɧɨʀ ɝɭɫɬɢɧɢ (ɡɚɪɹɞɿɜ) ɧɚ ɚɬɨɦɚɯ ɿ ɩɨɪɹɞɤɭ ɡɜ'ɹɡɤɿɜ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɞɨɡɜɨɥɢɬɶ ɞɚɬɢ ɜɿɞɩɨɜɿɞɶ ɧɚ ɩɢɬɚɧɧɹ: ɱɢ ɩɪɨɬɨɧɭɸɬɫɹ ɚɬɨɦɢ N1 ɿ N5. 3.3.2 Ʉɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɢɣ ɪɨɡɪɚɯɭɧɨɤ ɡɚɪɹɞɿɜ ɧɚ ɚɬɨɦɚɯ ɿ ɩɨɪɹɞɤɭ ɡɜ'ɹɡɤɿɜ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN Ʉɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɿ ɪɨɡɪɚɯɭɧɤɢ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɛɭɥɨ ɜɢɤɨɧɚɧɨ ɡ ɜɢɤɨɪɢɫɬɚɧɧɹɦ ɩɪɨɝɪɚɦɢ Orca 2.9 [221]. Ȼɿɥɶɲ ɞɨɤɥɚɞɧɨ ɦɟɬɨɞ ɨɩɢɫɚɧɨ ɜ ɧɚɲɿɣ ɪɨɛɨɬɿ [222]. ɍ ɬɚɛɥ. 3.5 ɩɪɟɞɫɬɚɜɥɟɧɨ ɡɚɪɹɞɢ ɧɚ ɚɬɨɦɚɯ ɞɥɹ ɩɪɨɬɨɧɨɜɚɧɨɝɨ ɩɨ ɚɬɨɦɚɯ N1 ɿ N5 (FMN N1H+N5H+) ɿ ɧɟɣɬɪɚɥɶɧɨɝɨ FMN ɬɚ ɪɿɡɧɢɰɹ ɡɚɪɹɞɿɜ FMN N1H+N5H+ - FMN N1N5. Ɂ ɰɢɯ ɞɚɧɢɯ ɜɢɞɧɨ, ɳɨ ɧɚ ɚɬɨɦɚɯ ɚɡɨɬɭ N1 ɿ N5 ɡɧɚɯɨɞɹɬɶɫɹ ɡɧɚɱɧɿ ɧɟɝɚɬɢɜɧɿ ɡɚɪɹɞɢ -0,612 ɿ -0,545, ɜɿɞɩɨɜɿɞɧɨ. Ɍɨɦɭ ɡɜ'ɹɡɭɜɚɧɧɹ ɩɨɡɢɬɢɜɧɨ ɡɚɪɹɞɠɟɧɨɝɨ ɚɬɨɦɚ ɜɨɞɧɸ (ɩɪɨɬɨɧɭ), ɣɦɨɜɿɪɧɨ, ɛɭɞɟ ɣɬɢ ɩɨ ɰɢɯ ɚɬɨɦɚɯ. 90 Ɍɚɛɥɢɰɹ 3.5 Ɂɚɪɹɞɢ ɧɚ ɚɬɨɦɚɯ ɩɪɨɬɨɧɨɜɚɧɨɝɨ ɿ ɧɟɩɪɨɬɨɧɨɜɚɧɨɝɨ ɿɡɨɚɥɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN ɬɚ ʀɯ ɪɿɡɧɢɰɹ (ɭɫɿ ɡɚɪɹɞɢ ɩɪɢɜɟɞɟɧɨ ɜ ɚɬɨɦɧɢɯ ɨɞɢɧɢɰɹɯ, ɚ.u.) ɇɭɦɟɪɚɰɿɹ ɚɬɨɦɿɜ N1 C2 O N3 C4 O C4a N5 C5a C6 C7 C C8 C C9 C9a N10 C10a C(R) FMN N1H N5H -0,447 0,725 -0,405 -0,575 0,643 -0,420 -0,054 -0,122 0,258 -0,379 0,259 -0,421 0,237 -0,434 -0,272 0,035 0,153 0,307 -0,416 + + FMN N1N5 -0,612 0,927 -0,623 -0,756 0,742 -0,581 0,236 -0,545 0,570 -0,473 0,203 -0,416 0,185 -0,468 -0,289 -0,283 0,349 0,179 -0,528 FMN N1H+N5H+ – FMN N1N5 0,165 -0,202 0,218 0,181 -0,099 0,161 -0,290 0,423 -0,311 0,094 0,056 -0,005 0,053 0,034 0,017 0,318 -0,196 0,128 0,112 Ɂ ɬɚɛɥ. 3.5 ɬɚɤɨɠ ɦɨɠɧɚ ɛɚɱɢɬɢ, ɳɨ ɩɪɨɬɨɧɭɜɚɧɧɹ ɚɬɨɦɿɜ N1 ɿ N5 ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɩɟɪɟɪɨɡɩɨɞɿɥɨɦ ɟɥɟɤɬɪɨɧɧɨʀ ɝɭɫɬɢɧɢ (ɡɚɪɹɞɿɜ): (i) ɩɨ ɚɬɨɦɚɯ ɋ5ɚ , ɋ6 , ɋ8 ɿ ɋ9 ɫɩɿɥɶɧɨ ɡ ɚɬɨɦɨɦ N5 (ɞɢɜ. ɬɚɛɥ. 3.3), ɳɨ ɜɢɡɧɚɱɚɸɬɶ ɱɚɫɬɨɬɭ ɫɦɭɝɢ III (Ȟ1); (ii) ɩɨ ɚɬɨɦɚɯ ɋ6 , ɋ7 , ɋ9 , ɋ9ɚ ɿ ɋ10ɚ ɿ N1, ɳɨ ɜɢɡɧɚɱɚɸɬɶ ɱɚɫɬɨɬɭ ɫɦɭɝɢ IV (Ȟ2); (iii) ɩɨ ɚɬɨɦɚɯ ɋ4ɚ , N5 , ɋ4 , ɋ10ɚ ɿ N1 , ɳɨ ɜɢɡɧɚɱɚɸɬɶ ɱɚɫɬɨɬɭ ɫɦɭɝɢ II (Ȟ3). 91 Ⱦɥɹ ɩɨɪɿɜɧɹɥɶɧɨɝɨ ɚɧɚɥɿɡɭ ɜ ɪɨɛɨɬɿ ɛɭɥɨ ɪɨɡɪɚɯɨɜɚɧɨ ɩɨɪɹɞɤɢ ɡɜ'ɹɡɤɿɜ ɚɬɨɦɿɜ ɭ ɩɪɨɬɨɧɨɜɚɧɨɦɭ ɿ ɧɟɩɪɨɬɨɧɨɜɚɧɨɦɭ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɶɰɹɯ FMN ɬɚ ʀɯ ɪɿɡɧɢɰɹ (ɬɚɛɥ. 3.6). Ɍɚɛɥɢɰɹ 3.6 ɉɨɪɹɞɤɢ ɡɜ'ɹɡɤɿɜ ɩɪɨɬɨɧɨɜɚɧɨɝɨ ɿ ɧɟɩɪɨɬɨɧɨɜɚɧɨɝɨ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ FMN ɬɚ ʀɯ ɪɿɡɧɢɰɹ Ɂɜ'ɹɡɤɢ N1–C2 N1–ɋ10a N1–H C2–O C2–N3 N3–C4 N3–H C4–O C4–C4a C4a–N5 C4a–C10a N5–C5a N5–H C5a–C6 C5a–C9a C6–C7 C6–H C7–C8 C8–C9 C9–C9a C9a–N10 N10–C10a N10–C FMN N1H+N5H+ 0,9762 1,3301 0,7721 2,2159 1,0538 1,1522 0,8759 2,1831 0,8850 1,4361 1,1588 1,2734 0,8422 1,2325 1,1772 1,4499 0,9953 1,1800 1,3610 1,3307 1,1259 1,2681 0,8998 FMN N1N5 1,1138 1,5857 – 2,1143 1,0307 1,1293 0,8921 2,2582 0,8828 1,7284 1,0737 1,3684 – 1,2560 1,2714 1,4007 1,0022 1,2868 1,3827 1,2826 1,1170 1,1968 0,9436 FMN N1H+N5H+ FMN N1N5 -0,1376 -0,2556 – 0,1016 0,0231 0,0229 -0,162 -0,0751 0,0022 -0,2653 0,0851 -0,095 – -0,0235 -0,0942 0,0492 -0,0069 -0,1068 -0,0217 0,0481 0,0089 0,0713 -0,0438 92 Ɂ ɪɟɡɭɥɶɬɚɬɿɜ, ɩɪɟɞɫɬɚɜɥɟɧɢɯ ɭ ɬɚɛɥ. 3.6, ɜɢɩɥɢɜɚɽ, ɳɨ ɞɥɹ ɫɦɭɝɢ Ȟ1 (ɞɢɜ. ɬɚɛɥ. 3.3) ɩɨɪɹɞɨɤ ɡɜ'ɹɡɤɿɜ ɋ5ɚ–ɋ6, ɋ8–ɋ9 ɿ ɋ5ɚ–N5 ɧɟɡɧɚɱɧɨ ɡɦɟɧɲɢɜɫɹ (ɜɿɞ 0,022 ɞɨ 0,095); ɞɥɹ ɫɦɭɝɢ Ȟ2 ɩɨɪɹɞɨɤ ɡɜ'ɹɡɤɿɜ ɋ6–ɋ7, ɋ9–ɋ9ɚ ɧɟɡɧɚɱɧɨ ɡɛɿɥɶɲɭɽɬɶɫɹ (ɧɚ 0,049), ɚ ɞɥɹ ɋ10ɚ–N1 ɜ ɬɨɣ ɠɟ ɱɚɫ ɡɦɟɧɲɭɽɬɶɫɹ (ɧɚ 0,256); ɞɥɹ ɫɦɭɝɢ Ȟ3 ɩɨɪɹɞɨɤ ɡɜ'ɹɡɤɭ ɋ4–ɋ4ɚ ɩɪɚɤɬɢɱɧɨ ɧɟ ɡɦɿɧɢɜɫɹ, ɬɨɞɿ ɹɤ ɩɨɪɹɞɨɤ ɡɜ'ɹɡɤɿɜ ɋ4ɚ–N5 ɿ ɋ10ɚ–N1 ɡɦɟɧɲɭɽɬɶɫɹ ɧɚ 0,265 ɿ 0,256, ɜɿɞɩɨɜɿɞɧɨ. Ɉɬɪɢɦɚɧɿ ɞɚɧɿ ɩɪɨ ɩɨɪɹɞɤɢ ɡɜ'ɹɡɤɿɜ ɤɨɪɟɥɸɸɬɶ ɡ ɱɚɫɬɨɬɧɢɦɢ ɡɦɿɳɟɧɧɹɦɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ Ȟ1 , Ȟ2 ɿ Ȟ3 (ɞɢɜ. ɬɚɛɥ. 3.5), ɨɫɤɿɥɶɤɢ ɧɚɣɛɿɥɶɲɿ ɡɦɿɧɢ ɩɨɪɹɞɤɿɜ ɡɜ'ɹɡɤɿɜ ɫɩɨɫɬɟɪɿɝɚɸɬɶɫɹ ɩɟɪɟɜɚɠɧɨ ɞɥɹ ɬɢɯ ɩɚɪ ɚɬɨɦɿɜ, ɞɨ ɹɤɢɯ ɜɯɨɞɹɬɶ ɚɬɨɦɢ ɚɡɨɬɭ N1 ɿ N5. ȼɢɹɜɥɟɧɿ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɤɨɥɢɜɚɧɶ ɩɨɜ'ɹɡɚɧɿ ɡɿ ɡɛɿɥɶɲɟɧɧɹɦ ɫɢɥɨɜɨʀ ɩɨɫɬɿɣɧɨʀ (k): ɱɚɫɬɨɬɚ ɤɨɥɢɜɚɧɶ ɩɪɨɩɨɪɰɿɣɧɚ k. ɍ ɜɟɥɢɱɢɧɭ k, ɜɿɞɩɨɜɿɞɧɨ ɞɨ ɬɟɨɪɿʀ ɤɨɥɢɜɚɧɶ ɛɚɝɚɬɨɚɬɨɦɧɢɯ ɦɨɥɟɤɭɥ, ɭ ɬɨɦɭ ɱɢɫɥɿ ɝɟɬɟɪɨɰɢɤɥɿɱɧɢɯ [175], ɜɧɨɫɹɬɶ ɜɤɥɚɞ ɡɦɿɧɢ ɡɚɪɹɞɿɜ ɿ ɩɨɪɹɞɤɿɜ ɡɜ'ɹɡɤɿɜ, ɳɨ ɿ ɛɭɥɨ ɜɢɡɧɚɱɟɧɨ ɩɪɢ ɩɪɨɜɟɞɟɧɧɿ ɤɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɢɯ ɪɨɡɪɚɯɭɧɤɿɜ ɩɪɨɬɨɧɨɜɚɧɨʀ ɮɨɪɦɢ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN. Ⱥɥɟ ɡɜ'ɹɡɨɤ ɦɿɠ ɫɢɥɨɜɢɦɢ ɩɨɫɬɿɣɧɢɦɢ k ɚɬɨɦɿɜ, ɳɨ ɤɨɥɢɜɚɸɬɶɫɹ, ɿ ɡɦɿɧɨɸ ɡɚɪɹɞɿɜ ɿ ɩɨɪɹɞɤɿɜ ɡɜ'ɹɡɤɿɜ ɜɢɦɚɝɚɽ ɫɩɟɰɿɚɥɶɧɨɝɨ ɬɟɨɪɟɬɢɱɧɨɝɨ ɪɨɡɝɥɹɞɭ. 3.4 Ɋɨɥɶ ɜɨɞɢ ɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN ȼɿɞɨɦɨ, ɳɨ ɪɨɡɬɚɲɭɜɚɧɧɹ ɭ ɜɢɝɥɹɞɿ ɫɬɨɩɨɤ ɚɡɨɬɢɫɬɢɯ ɨɫɧɨɜ ɭ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬɚɯ ɿɫɬɨɬɧɨ ɫɬɚɛɿɥɿɡɭɽɬɶɫɹ ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ [101], ɹɤɿ ɡɚɣɦɚɸɬɶ ɦɿɫɬɤɨɜɿ ɩɨɥɨɠɟɧɧɹ ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɨɫɧɨɜ ɿ ɰɭɤɪɨɮɨɫɮɚɬɧɨɝɨ ɨɫɬɨɜɭ. ɓɨɛ ɜɫɬɚɧɨɜɢɬɢ, ɱɢ ɦɨɠɥɢɜɚ ɫɬɚɛɿɥɿɡɚɰɿɹ ɫɬɟɤɿɧɝɚɫɨɰɿɚɬɿɜ FMN ɡɚ ɪɚɯɭɧɨɤ ɚɧɚɥɨɝɿɱɧɢɯ ɜɨɞɧɢɯ ɦɿɫɬɤɿɜ, ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɚɫɹ ɪɚɧɿɲɟ ɪɨɡɪɨɛɥɟɧɚ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɚ ɦɟɬɨɞɢɤɚ ɜɢɡɧɚɱɟɧɧɹ ɰɟɧɬɪɿɜ ɝɿɞɪɚɬɚɰɿʀ ɞɥɹ ɩɥɿɜɨɤ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ [98, 103, 104]. Ȼɭɥɨ ɩɪɨɜɟɞɟɧɨ ɞɨɫɥɿɞɠɟɧɧɹ ɡɚɥɟɠɧɨɫɬɿ ɫɩɟɤɬɪɚɥɶɧɢɯ ɩɚɪɚɦɟɬɪɿɜ (ɱɚɫɬɨɬ Ȟ ɬɚ ɿɧɬɟɧɫɢɜɧɨɫɬɟɣ R, ɞɢɜ. 93 ɮɨɪɦɭɥɭ (2.11)) ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɨɥɢɜɚɧɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɋ2=Ɉ, ɋ4=Ɉ ɿ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɋ=N ɿ ɋ=ɋ ɤɨɥɢɜɚɧɶ ɜɿɞ ɤɿɥɶɤɨɫɬɿ ɫɨɪɛɨɜɚɧɢɯ ɦɨɥɟɤɭɥ ɜɨɞɢ N ɧɚ ɦɨɥɶ FMN. Ɂɧɚɱɟɧɧɹ N ɜɡɹɬɨ ɡ ɨɬɪɢɦɚɧɢɯ ɧɚɦɢ ɿɡɨɬɟɪɦ ɝɿɞɪɚɬɚɰɿʀ (ɪɢɫ. 3.7). 15 12 1 Ɋɢɫɭɧɨɤ 3.7 ȱɡɨɬɟɪɦɢ ɝɿɞɪɚɬɚɰɿʀ ɩɥɿɜɨɤ FMN, ɿ 2 N, MH2O/MFMN 9 6 3 0 0 20 40 60 80 ɜɢɪɨɳɟɧɢɯ ɡ ɧɟɣɬɪɚɥɶɧɨɝɨ ɪɇ = 7,0 (±0,05) (1) ɫɥɚɛɨɤɢɫɥɨɝɨ (±0,05) (2) ɪɨɡɱɢɧɿɜ ɪɇ = 6,2 ȼȼ, % Ɂ ɪɢɫ. 3.7 ɜɢɞɧɨ, ɳɨ ɿɡɨɬɟɪɦɚ ɝɿɞɪɚɬɚɰɿʀ ɞɥɹ ɩɥɿɜɤɢ FMN, ɜɢɪɨɳɟɧɨʀ ɡ ɪɨɡɱɢɧɭ ɩɪɢ ɪɇ = 6,2, ɩɪɨɯɨɞɢɬɶ ɧɢɠɱɟ ɿɡɨɬɟɪɦɢ, ɨɬɪɢɦɚɧɨʀ ɞɥɹ ɧɟɣɬɪɚɥɶɧɨʀ (ɪɇ = 7,0) ɮɨɪɦɢ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ. Ɂɧɢɠɟɧɧɹ ɪɿɜɧɹ ɚɞɫɨɪɛɰɿʀ ɜɨɞɢ ɩɪɢ ɪɇ = 6,2 ɫɜɿɞɱɢɬɶ ɩɪɨ ɬɟ, ɳɨ ɪɨɡɬɚɲɭɜɚɧɧɹ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ FMN ɭ ɰɢɯ ɭɦɨɜɚɯ ɩɪɢɡɜɨɞɢɬɶ ɞɨ ɡɦɟɧɲɟɧɧɹ ɤɿɥɶɤɨɫɬɿ ɚɬɨɦɧɢɯ ɝɪɭɩ, ɞɨɫɬɭɩɧɢɯ ɦɨɥɟɤɭɥɚɦ ɜɨɞɢ. ɐɟɣ ɮɚɤɬ ɬɚɤɨɠ ɩɿɞɬɜɟɪɞɠɭɽ ɡɪɨɛɥɟɧɢɣ ɪɚɧɿɲɟ ɜɢɫɧɨɜɨɤ (ɞɢɜ. ɩɿɞɪɨɡɞɿɥ 3.1) ɩɪɨ ɬɟ, ɳɨ ɫɚɦɨɚɫɨɰɿɚɰɿɹ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɜ ɧɟɣɬɪɚɥɶɧɢɯ ɿ ɫɥɚɛɨɤɢɫɥɢɯ ɭɦɨɜɚɯ ɪɨɡɪɿɡɧɹɽɬɶɫɹ ɹɤ ɡɚ ɫɬɪɭɤɬɭɪɨɸ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN, ɬɚɤ ɿ ɡɚ ʀɯ ɜɡɚɽɦɨɞɿɽɸ ɡ ɜɨɞɧɢɦ ɨɬɨɱɟɧɧɹɦ. ɇɚ ɪɢɫ. 3.8 ɩɪɟɞɫɬɚɜɥɟɧɨ ɡɚɥɟɠɧɨɫɬɿ Ȟ ɿ R ɜɿɞ N ɞɥɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɨɥɢɜɚɧɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɋ2=Ɉ, ɋ4=Ɉ ɬɚ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɋ=N ɿ ɋ=ɋ ɤɨɥɢɜɚɧɶ ɭ ɧɟɣɬɪɚɥɶɧɨɦɭ ɫɟɪɟɞɨɜɢɳɿ (ɪɇ = 7,0). ȼɢɞɧɨ, ɳɨ ɱɚɫɬɨɬɢ ɪɨɡɝɥɹɧɭɬɢɯ ɫɦɭɝ Ȟ(N) ɡɦɟɧɲɭɸɬɶɫɹ, ɚ ʀɯ ɿɧɬɟɧɫɢɜɧɿɫɬɶ R(N) ɡɛɿɥɶɲɭɽɬɶɫɹ. Ɍɚɤɢɣ ɯɚɪɚɤɬɟɪ ɡɦɿɧɢ ɡɚɥɟɠɧɨɫɬɟɣ R(N) ɿ Ȟ(N) ɜ ɿɧɬɟɪɜɚɥɿ ɫɨɪɛɰɿʀ ɜɨɞɢ 0 ” N ” 12 ɞɥɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ FMN ɫɜɿɞɱɢɬɶ ɩɪɨ ɩɨɥɹɪɢɡɚɰɿɸ ɡɜ'ɹɡɤɿɜ ɚɬɨɦɿɜ ɩɪɢ ɮɨɪɦɭɜɚɧɧɿ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ ɡ ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ. Ɉɞɧɨɱɚɫɧɟ ɡɪɨɫɬɚɧɧɹ 94 ɿɧɬɟɧɫɢɜɧɨɫɬɟɣ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɨɥɢɜɚɧɶ C2=O, C4=O ɿ ɤɨɥɢɜɚɧɶ ɡɚ ɭɱɚɫɬɸ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɨɝɨ ɚɬɨɦɚ ɚɡɨɬɭ N5 ɞɨɡɜɨɥɹɽ ɩɪɢɩɭɫɬɢɬɢ ɦɨɠɥɢɜɿɫɬɶ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɢɯ «ɦɿɫɬɤɿɜ» ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ FMN ɿ ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ, ɹɤɿ, ɪɚɡɨɦ ɡɿ ɫɬɟɤɿɧɝ-ɜɡɚɽɦɨɞɿɹɦɢ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɸɬɶ ɫɚɦɨɚɫɨɰɿɚɬɢ FMN. R 1,6 Q, ɫɦ -1 R 1,6 Q, ɫɦ -1 1548 1544 1540 1536 0 2 4 6 8 10 12 1656 1,4 1,4 1652 1,2 1,2 1648 1,0 1,0 0 2 4 6 8 10 12 1644 N, MH2O/MFMN N, MH2O/MFMN (ɚ) R 1,4 Q, ɫɦ -1 (ɛ) 1708 1704 1,2 1700 1,0 0 2 4 6 8 10 12 1696 N, MH2O/MFMN (ɜ) Ɋɢɫɭɧɨɤ 3.8 Ɂɚɥɟɠɧɿɫɬɶ ɱɚɫɬɨɬɢ (Ȟ) ɬɚ ɜɿɞɧɨɫɧɨʀ ɿɧɬɟɧɫɢɜɧɨɫɬɿ (R) ɜɿɞ ɤɿɥɶɤɨɫɬɿ ɫɨɪɛɨɜɚɧɢɯ ɦɨɥɟɤɭɥ ɜɨɞɢ (N) ɞɥɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ C=N5 , C=C (ɚ) ɿ ɤɚɪɛɨɧɿɥɶɧɢɯ ɋ2=Ɉ (ɛ) ɬɚ ɋ4=Ɉ (ɜ) ɝɪɭɩ ɚɬɨɦɿɜ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN (ɪɇ = 7,0 (±0,05)) Ɇɢ ɬɚɤɨɠ ɞɨɫɥɿɞɢɥɢ ɜɩɥɢɜ ɜɨɞɢ ɧɚ ɫɬɚɛɿɥɶɧɿɫɬɶ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN ɜ ɩɥɿɜɤɚɯ, ɜɢɪɨɳɟɧɢɯ ɡɿ ɫɥɚɛɨɤɢɫɥɨɝɨ ɪɨɡɱɢɧɭ [219]. ɇɚ ɪɢɫ. 3.9 ɩɪɟɞɫɬɚɜɥɟɧɨ ɡɚɥɟɠɧɨɫɬɿ Ȟ ɿ R ɜɿɞ N ɞɥɹ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɡ ɱɚɫɬɨɬɚɦɢ 95 Ȟ1 = 1729 ɫɦ-1 ɿ Ȟ2 = 1656 ɫɦ-1 (ɤɨɥɢɜɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɋ4=Ɉ ɿ ɋ2=Ɉ), ɚ ɬɚɤɨɠ Ȟ3 = 1552 ɫɦ-1 (ɤɨɥɢɜɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɝɪɭɩ C=N, C=C). R 1,4 1656 1,2 Q, ɫɦ -1 R 1,4 Q, ɫɦ -1 1732 1,2 1652 1728 1648 1,0 0 2 4 6 8 1,0 0 2 4 6 8 1724 n, MH2O/MFMN N, MH2O/MFMN (ɚ) R 1,4 1556 1,2 1552 1548 1,0 0 2 4 6 8 Q, ɫɦ (ɛ) -1 N, MH2O/MFMN (ɜ) Ɋɢɫɭɧɨɤ 3.9 Ɂɚɥɟɠɧɿɫɬɶ ɱɚɫɬɨɬɢ (Ȟ) ɿ ɜɿɞɧɨɫɧɨʀ ɿɧɬɟɧɫɢɜɧɨɫɬɿ (R) ɜɿɞ ɤɿɥɶɤɨɫɬɿ ɫɨɪɛɨɜɚɧɢɯ ɦɨɥɟɤɭɥ ɜɨɞɢ (N) ɞɥɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɋ2=Ɉ (ɚ), ɋ4=Ɉ (ɛ) ɿ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ C=N5 , C=C (ɜ) ɝɪɭɩ ɚɬɨɦɿɜ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN (ɪɇ = 6,2 (±0,05)) ȼɢɞɧɨ, ɳɨ ɱɚɫɬɨɬɚ ɤɚɪɛɨɧɢɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ ɋ2=Ɉ (ɪɢɫ. 3.9 ɚ) ɿɡ ɡɪɨɫɬɚɧɧɹɦ ɫɨɪɛɰɿʀ ɜɨɞɢ ɜ ɿɧɬɟɪɜɚɥɿ 0 ” N ” 6 ɡɦɟɧɲɭɽɬɶɫɹ ɧɚ ǻȞ = 4 ɫɦ-1 (±1 ɫɦ-1). Ɂɧɢɠɟɧɧɹ ɱɚɫɬɨɬɢ ɫɜɿɞɱɢɬɶ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɦɨɥɟɤɭɥ ɜɨɞɢ ɡ ɤɚɪɛɨɧɿɥɶɧɨɸ ɝɪɭɩɨɸ ɋ2=Ɉ. Ɉɞɧɚɤ, ɱɚɫɬɨɬɚ ɤɨɥɢɜɚɧɧɹ ɋ4=Ɉ ɝɪɭɩɢ ɚɬɨɦɿɜ ɭ ɰɶɨɦɭ ɿɧɬɟɪɜɚɥɿ N ɩɪɚɤɬɢɱɧɨ ɧɟ ɡɦɿɧɢɥɚɫɹ (ɪɢɫ. 3.9 ɛ), ɳɨ ɩɨɜ'ɹɡɚɧɨ ɡ ɨɛɦɟɠɟɧɨɸ ɞɨɫɬɭɩɧɿɫɬɸ ɦɨɥɟɤɭɥ ɜɨɞɢ ɱɟɪɟɡ ɛɿɥɶɲ ɳɿɥɶɧɟ ɭɩɚɤɭɜɚɧɧɹ 96 ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ ɫɚɦɨɚɫɨɰɿɚɬɭ ɩɪɨɬɨɧɨɜɚɧɨʀ ɮɨɪɦɢ FMN ɩɨɪɿɜɧɹɧɨ ɡ ɧɟɣɬɪɚɥɶɧɨɸ. ɇɚ ɜɿɞɦɿɧɭ ɜɿɞ ɧɟɣɬɪɚɥɶɧɨʀ ɮɨɪɦɢ FMN (ɞɢɜ. ɪɢɫ. 3.8 ɚ) ɱɚɫɬɨɬɚ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɤɨɥɢɜɚɧɶ Ȟ3 (ɡɚ ɭɱɚɫɬɸ ɝɪɭɩ ɚɬɨɦɿɜ C=N5 ɿ ɋ=ɋ) ɜ ɰɶɨɦɭ ɿɧɬɟɪɜɚɥɿ ɫɨɪɛɰɿʀ ɬɚɤɨɠ ɩɪɚɤɬɢɱɧɨ ɧɟ ɡɦɿɧɢɥɚɫɹ (ɪɢɫ. 3.9 ɜ). Ɉɞɧɚɤ ɡ ɩɿɞɜɢɳɟɧɧɹɦ ɚɤɬɢɜɧɨɫɬɿ ɜɨɞɢ ɜ ɿɧɬɟɪɜɚɥɿ 6 ” N ” 8 ɿɧɬɟɧɫɢɜɧɨɫɬɿ ɫɦɭɝ ɋ2=Ɉ, ɋ4=Ɉ ɿ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɤɨɥɢɜɚɧɶ (ɪɢɫ. 3.9) ɨɞɧɨɱɚɫɧɨ ɪɿɡɤɨ ɡɪɨɫɬɚɸɬɶ, ɹɤ ɿ ɭ ɜɢɩɚɞɤɭ ɧɟɣɬɪɚɥɶɧɨʀ ɮɨɪɦɢ FMN. ɇɚɣɛɿɥɶɲ ɣɦɨɜɿɪɧɨ, ɰɟ ɩɨɜ'ɹɡɚɧɨ ɡ ɮɨɪɦɭɜɚɧɧɹɦ ɜɨɞɧɢɯ «ɦɿɫɬɤɿɜ» ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɚɬɨɦɿɜ ɜ ɭɬɜɨɪɟɧɨɦɭ ɫɚɦɨɚɫɨɰɿɚɬɿ ɩɪɨɬɨɧɨɜɚɧɨʀ ɮɨɪɦɢ FMN. ɐɿ ɜɨɞɧɿ «ɦɿɫɬɤɢ» ɪɚɡɨɦ ɡ ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɸɬɶ n-ɦɨɥɟɤɭɥɹɪɧɭ ɫɬɪɭɤɬɭɪɭ ɩɪɨɬɨɧɨɜɚɧɨʀ ɮɨɪɦɢ FMN. ȼɢɫɧɨɜɤɢ ɞɨ ɪɨɡɞɿɥɭ 3 1. Ⱥɧɚɥɿɡ ȱɑ-ɫɩɟɤɬɪɿɜ ɜ ɨɛɥɚɫɬɿ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɋ–ɋ, ɋ–N ɬɚ ɤɚɪɛɨɧɿɥɶɧɢɯ ɋ2=Ɉ, ɋ4=Ɉ ɤɨɥɢɜɚɧɶ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN ɩɨɤɚɡɚɜ, ɳɨ ɭɬɜɨɪɟɧɧɹ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN ɭ ɧɟɣɬɪɚɥɶɧɢɯ ɫɟɪɟɞɨɜɢɳɚɯ (ɪɇ ~ 7,0) ɜɿɞɛɭɜɚɽɬɶɫɹ ɛɟɡ ɜɢɧɢɤɧɟɧɧɹ ɞɢɧɚɦɿɱɧɨʀ ɜɡɚɽɦɨɞɿʀ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ ɤɨɥɢɜɚɧɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ. ɋɩɟɤɬɪɢ ɧɟɣɬɪɚɥɶɧɢɯ ɪɨɡɱɢɧɿɜ FMN ɿ ɩɥɿɜɨɤ, ɜɢɪɨɳɟɧɢɯ ɡ ɧɢɯ, ɩɪɚɤɬɢɱɧɨ ɧɟ ɜɿɞɪɿɡɧɹɸɬɶɫɹ, ɳɨ ɫɜɿɞɱɢɬɶ ɩɪɨ ɨɞɧɚɤɨɜɢɣ ɬɢɩ ɫɚɦɨɚɫɨɰɿɚɰɿʀ FMN ɭ ɧɟɣɬɪɚɥɶɧɢɯ ɫɟɪɟɞɨɜɢɳɚɯ. Ɋɨɡɪɚɯɭɧɤɢ ɫɩɟɤɬɪɚɥɶɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɞɥɹ ɜɿɞɨɦɢɯ ɫɬɪɭɤɬɭɪ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN, ɹɤɿ ɭɡɝɨɞɠɭɸɬɶɫɹ ɡ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɦɢ ɞɚɧɢɦɢ, ɩɿɞɬɜɟɪɞɢɥɢ ɰɟɣ ɜɢɫɧɨɜɨɤ. 2. ȼɩɟɪɲɟ ɜɢɹɜɥɟɧɨ ɜɢɫɨɤɨɱɚɫɬɨɬɧɟ ɡɦɿɳɟɧɧɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɨɥɢɜɚɧɶ ɋ4=Ɉ ɿ ɋ2=Ɉ ɝɪɭɩ ɚɬɨɦɿɜ ɞɥɹ ɩɥɿɜɤɢ FMN, ɨɬɪɢɦɚɧɨʀ ɡɿ ɫɥɚɛɨɤɢɫɥɨɝɨ ɪɨɡɱɢɧɭ (ɪɇ ~ 6,0). Ɂɚ ɞɨɩɨɦɨɝɨɸ ɪɨɡɪɚɯɭɧɤɿɜ ɪɟɡɨɧɚɧɫɧɨʀ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɋ4=Ɉ ɿ ɋ2=Ɉ ɝɪɭɩ ɭ ɞɢɩɨɥɶ-ɞɢɩɨɥɶɧɨɦɭ 97 ɧɚɛɥɢɠɟɧɧɿ ɛɭɥɨ ɩɨɛɭɞɨɜɚɧɨ ɦɨɞɟɥɶ n-ɦɨɥɟɤɭɥɹɪɧɨʀ ɫɚɦɨɚɫɨɰɿɚɰɿʀ FMN. ɋɬɚɛɿɥɶɧɿɫɬɶ ɬɚɤɢɯ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN ɜɢɡɧɚɱɚɽɬɶɫɹ ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ Ⱥɧɚɥɿɡ ɦɿɠ ɤɿɥɶɰɹɦɢ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɜ ɯɪɨɦɨɮɨɪɚ, ɹɤɿ ɩɟɪɟɤɪɢɜɚɸɬɶɫɹ. 3. ɨɬɪɢɦɚɧɢɯ ȱɑ-ɫɩɟɤɬɪɿɜ ɨɛɥɚɫɬɿ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɋ–ɋ ɿ ɋ–N ɤɨɥɢɜɚɧɶ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ FMN ɭ ɜɢɫɭɲɟɧɿɣ ɩɥɿɜɰɿ (0% ȼȼ), ɜɢɪɨɳɟɧɿɣ ɡɿ ɫɥɚɛɨɤɢɫɥɨɝɨ ɪɨɡɱɢɧɭ, ɩɨɤɚɡɚɜ, ɳɨ ɩɪɨɬɨɧɭɜɚɧɧɹ ɤɿɥɶɰɹ ɜɿɞɛɭɜɚɽɬɶɫɹ ɩɨ ɚɬɨɦɚɯ ɚɡɨɬɭ N1 ɿ N5. Ʉɜɚɧɬɨɜɨ-ɯɿɦɿɱɧɿ ɪɨɡɪɚɯɭɧɤɢ ɡɚɪɹɞɿɜ ɧɚ ɚɬɨɦɚɯ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɩɿɞɬɜɟɪɞɢɥɢ ɰɟɣ ɜɢɫɧɨɜɨɤ, ɨɫɤɿɥɶɤɢ ɧɚ ɚɬɨɦɚɯ N1 ɿ N5 ɡɧɚɯɨɞɹɬɶɫɹ ɡɧɚɱɧɿ ɧɟɝɚɬɢɜɧɿ ɡɚɪɹɞɢ. 4. Ⱦɨɫɥɿɞɠɟɧɧɹ ɝɿɞɪɚɬɚɰɿʀ FMN ɩɨɤɚɡɚɥɨ, ɳɨ ɞɨɞɚɬɤɨɜɚ ɫɬɚɛɿɥɿɡɚɰɿɹ ɧɟɣɬɪɚɥɶɧɨʀ ɬɚ ɩɪɨɬɨɧɨɜɚɧɨʀ ɮɨɪɦ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɞɨɫɹɝɚɽɬɶɫɹ ɲɥɹɯɨɦ ɮɨɪɦɭɜɚɧɧɹ ɜɨɞɧɢɯ «ɦɿɫɬɤɿɜ» ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɚɬɨɦɿɜ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɢɯ ɤɿɥɟɰɶ. ɉɨɤɚɡɚɧɨ, ɳɨ ɜ ɧɟɣɬɪɚɥɶɧɿɣ ɮɨɪɦɿ FMN ɜɨɞɧɿ «ɦɿɫɬɤɢ» ɮɨɪɦɭɸɬɶɫɹ ɜ ɭɫɶɨɦɭ ɿɧɬɟɪɜɚɥɿ ɫɨɪɛɰɿʀ ɜɨɞɢ (0 ” N ” 12), ɬɨɞɿ ɹɤ ɜ ɫɮɨɪɦɨɜɚɧɨɦɭ n-ɦɨɥɟɤɭɥɹɪɧɨɦɭ ɚɫɨɰɿɚɬɢ FMN ɭ ɫɥɚɛɨɤɢɫɥɨɦɭ ɫɟɪɟɞɨɜɢɳɿ (ɪɇ~6,0) ɬɚɤɿ «ɦɿɫɬɤɢ» ɭɬɜɨɪɸɸɬɶɫɹ ɩɿɞ ɱɚɫ ɜɢɫɨɤɨʀ ɚɤɬɢɜɧɨɫɬɿ ɜɨɞɢ (6 ” N ” 8). Ɋɟɡɭɥɶɬɚɬɢ ɞɨɫɥɿɞɠɟɧɶ ɞɚɧɨɝɨ ɪɨɡɞɿɥɭ ɧɚɜɟɞɟɧɨ ɜ ɩɭɛɥɿɤɚɰɿɹɯ ɡɞɨɛɭɜɚɱɚ: [219], [222]. 98 ɊɈɁȾȱɅ 4 ɆȱɀɉɅɈɓɂɇɇȱ ȼɁȺȯɆɈȾȱȲ ɉɊɂ ɎɈɊɆɍȼȺɇɇȱ ȽȿɌȿɊɈɄɈɆɉɅȿɄɋȱȼ FMN-TPH, TPH-EB, TPH-PRF ɌȺ EB-CAF ȼɢɜɱɟɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ɩɪɟɞɫɬɚɜɥɹɽ ɿɧɬɟɪɟɫ ɡ ɮɿɡɢɤɨ-ɯɿɦɿɱɧɨʀ ɬɨɱɤɢ ɡɨɪɭ, ɨɫɤɿɥɶɤɢ ɞɨɡɜɨɥɹɽ ɜɢɡɧɚɱɢɬɢ ɜɩɥɢɜ ɫɬɪɭɤɬɭɪɢ ɯɪɨɦɨɮɨɪɿɜ ɬɚ ɛɿɱɧɢɯ ɥɚɧɰɸɝɿɜ ɧɚ ɭɬɜɨɪɟɧɧɹ ɚɫɨɰɿɚɬɿɜ ɿ ɨɰɿɧɢɬɢ ɜɧɟɫɨɤ ɪɿɡɧɢɯ ɜɡɚɽɦɨɞɿɣ ɜ ʀɯ ɫɬɚɛɿɥɶɧɿɫɬɶ. Ɍɚɤɿ ɞɨɫɥɿɞɠɟɧɧɹ ɧɟɨɛɯɿɞɧɿ ɞɥɹ ɪɨɡɭɦɿɧɧɹ ɦɟɯɚɧɿɡɦɿɜ ɦɟɞɢɤɨ-ɛɿɨɥɨɝɿɱɧɢɯ ɟɮɟɤɬɿɜ, ɹɤɿ ɫɩɨɫɬɟɪɿɝɚɸɬɶɫɹ ɩɿɞ ɱɚɫ ɫɩɿɥɶɧɨɝɨ ɜɢɤɨɪɢɫɬɚɧɧɹ ɪɿɡɧɢɯ ɬɟɪɚɩɟɜɬɢɱɧɢɯ ȻȺɊ. Ʉɪɿɦ ɬɨɝɨ, ɝɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɪɨɡɝɥɹɞɚɽɬɶɫɹ ɹɤ ɨɫɧɨɜɧɢɣ ɦɟɯɚɧɿɡɦ ɡɛɿɥɶɲɟɧɧɹ ɪɨɡɱɢɧɧɨɫɬɿ ɜɚɠɤɨ ɪɨɡɱɢɧɧɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ɭ ɩɪɢɫɭɬɧɨɫɬɿ ɿɧɲɢɯ ɚɪɨɦɚɬɢɱɧɢɯ ɦɨɥɟɤɭɥ. ɍɬɜɨɪɟɧɧɹ ɫɬɚɛɿɥɶɧɢɯ ɫɚɦɨ- ɬɚ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ɫɩɨɥɭɤ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɜɢɡɧɚɱɚɽɬɶɫɹ ɩɟɪɲ ɡɚ ɜɫɟ ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɯɪɨɦɨɮɨɪɿɜ, ɩɨɜ'ɹɡɚɧɢɯ ɹɤ ɡɿ ɜɡɚɽɦɨɞɿɹɦɢ ʀɯ S-ɫɢɫɬɟɦ, ɬɚɤ ɿ ɜɩɥɢɜɨɦ ɩɨɥɹɪɧɨɝɨ ɜɨɞɧɨɝɨ ɨɬɨɱɟɧɧɹ ɧɚ ɝɿɞɪɨɮɨɛɧɿ ɦɨɥɟɤɭɥɢ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ. Ⱦɨɞɚɬɤɨɜɢɣ ɜɤɥɚɞ ɭ ɫɬɚɛɿɥɶɧɿɫɬɶ ɬɚɤɢɯ ɚɫɨɰɿɚɬɿɜ ɦɨɠɭɬɶ ɜɧɨɫɢɬɢ ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɜɨɞɧɟɜɿ ɡɜ'ɹɡɤɢ. ɍ ɰɶɨɦɭ ɪɨɡɞɿɥɿ ɞɢɫɟɪɬɚɰɿʀ ɛɭɞɟ ɪɨɡɝɥɹɧɭɬɨ ɪɟɡɭɥɶɬɚɬɢ ȱɑ- ɿ ɄɊɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɯ ɞɨɫɥɿɞɠɟɧɶ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ, ɹɤɿ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ, ɡɝɿɞɧɨ ɡ ɞɚɧɢɦɢ əɆɊ, ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɜ ɍɎ- ɿ ɜɢɞɢɦɿɣ ɨɛɥɚɫɬɿ ɬɚ ɥɸɦɿɧɟɫɰɟɧɰɿʀ, ɮɨɪɦɭɸɬɶ ɝɟɬɟɪɨɚɫɨɰɿɚɬɢ ɛɟɡ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇɡɜ'ɹɡɤɿɜ, ɿ ɜɢɤɨɧɚɧɨ ʀɯ ɞɟɬɚɥɶɧɢɣ ɚɧɚɥɿɡ ɡɚ ɞɨɩɨɦɨɝɨɸ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ [223, 224]. ȱɧɮɪɚɱɟɪɜɨɧɿ ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ ɬɚ ʀɯ 4.1 FMN, TPH ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ ɉɪɨɜɟɞɟɧɿ ɪɚɧɿɲɟ ɞɨɫɥɿɞɠɟɧɧɹ ɦɟɬɨɞɨɦ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɹɞɟɪɧɨɝɨ ɦɚɝɧɿɬɧɨɝɨ ɪɟɡɨɧɚɧɫɭ ɩɨɤɚɡɚɥɢ, ɳɨ ɡɚ ɭɦɨɜ, ɛɥɢɡɶɤɢɯ ɞɨ ɮɿɡɿɨɥɨɝɿɱɧɢɯ, 99 ɦɨɥɟɤɭɥɢ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ – ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɿɞɭ ɿ ɬɟɨɮɿɥɿɧɭ – ɮɨɪɦɭɸɬɶ ɫɚɦɨ- ɿ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɢ ɭ ɜɢɝɥɹɞɿ ɫɬɨɩɨɤ. Ɋɿɜɧɨɜɚɠɧɚ ɤɨɧɫɬɚɧɬɚ ʀɯ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɡɚ ɜɟɥɢɱɢɧɨɸ ɡɚɣɦɚɽ ɩɪɨɦɿɠɧɟ ɡɧɚɱɟɧɧɹ (Kɋ = 180 M-1) ɦɿɠ ɤɨɧɫɬɚɧɬɚɦɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɰɢɯ ɦɨɥɟɤɭɥ (KFMN = 265 M-1 ɬɚ KTPH = 7,4 M-1) [11]. ȼ ɹɤɨɫɬɿ ɧɟɩɪɹɦɨɝɨ ɤɪɢɬɟɪɿɸ ɞɨɞɚɬɤɨɜɨʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɪɨɤɨɦɩɥɟɤɫɿɜ ɩɪɢ ɭɬɜɨɪɟɧɧɿ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɛɭɥɨ ɡɚɩɪɨɩɨɧɨɜɚɧɨ ɮɚɤɬɨɪ fC K FMN KC [91, 116]. Ɂɚ ɭɦɨɜɢ fC • 35% ɽ ɜɢɫɨɤɚ ɣɦɨɜɿɪɧɿɫɬɶ ɫɚɦɟ  K TPH  K C ɬɚɤɨɝɨ ɬɢɩɭ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ. Ⱦɥɹ ɤɨɦɩɥɟɤɫɭ FMN ɿ TPH ɡɧɚɱɟɧɧɹ fC = 39,7, ɳɨ ɜɤɚɡɭɽ ɧɚ ɦɨɠɥɢɜɿɫɬɶ ɞɨɞɚɬɤɨɜɨʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ ɇ-ɡɜ'ɹɡɤɨɦ. ɉɪɨɫɬɨɪɨɜɚ ɦɨɞɟɥɶ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-TPH, ɩɨɛɭɞɨɜɚɧɚ ɡɚ ɞɨɩɨɦɨɝɨɸ ɦɟɬɨɞɭ ɦɨɥɟɤɭɥɹɪɧɨʀ ɦɟɯɚɧɿɤɢ ɡɚ ɨɬɪɢɦɚɧɢɦɢ ɡɧɚɱɟɧɧɹɦɢ ɯɿɦɿɱɧɢɯ ɡɦɿɳɟɧɶ [88], ɜɤɚɡɭɽ ɧɚ ɬɟ, ɳɨ ɬɟɨɮɿɥɿɧ ɭɬɜɨɪɸɽ ɤɨɦɩɥɟɤɫɢ ɡ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɨɦ, ɹɤɿ ɫɬɚɛɿɥɿɡɭɸɬɶɫɹ ɩɟɪɟɜɚɠɧɨ ɫɬɟɤɿɧɝɜɡɚɽɦɨɞɿɹɦɢ. Ʉɪɿɦ ɬɨɝɨ, ɪɨɡɪɚɯɭɧɤɨɜɚ ɫɬɪɭɤɬɭɪɚ ɤɨɦɩɥɟɤɫɭ ɫɜɿɞɱɢɬɶ ɩɪɨ ɦɨɠɥɢɜɿɫɬɶ ɭɬɜɨɪɟɧɧɹ ɦɿɠ ɦɨɥɟɤɭɥɚɦɢ ɇ-ɡɜ'ɹɡɤɭ. Ɉɞɧɚɤ ɰɟɣ ɜɢɫɧɨɜɨɤ ɛɭɥɨ ɡɪɨɛɥɟɧɨ ɨɩɨɫɟɪɟɞɤɨɜɚɧɨ ɧɚ ɩɿɞɫɬɚɜɿ ɡɦɿɧɢ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɯ ɩɚɪɚɦɟɬɪɿɜ. Ⱦɥɹ ɨɬɪɢɦɚɧɧɹ ɩɪɹɦɨɝɨ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɝɨ ɩɿɞɬɜɟɪɞɠɟɧɧɹ ɚɛɨ ɫɩɪɨɫɬɭɜɚɧɧɹ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɟɜɨɝɨ ɡɜ'ɹɡɤɭ ɧɚɦɢ ɛɭɥɨ ɩɪɨɜɟɞɟɧɨ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɟ ɞɨɫɥɿɞɠɟɧɧɹ ɧɟɣɬɪɚɥɶɧɢɯ D2O ɪɨɡɱɢɧɿɜ FMN, TPH ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɭ ɜ ɨɛɥɚɫɬɿ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ (1600-1750 ɫɦ-1) [223]. ɇɚ ɪɢɫ. 4.1 ɩɪɟɞɫɬɚɜɥɟɧɨ ȱɑ-ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ ɧɟɣɬɪɚɥɶɧɢɯ ɜɨɞɧɢɯ (D2O) ɪɨɡɱɢɧɿɜ FMN ɿ TPH ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɭ. ɋɩɟɤɬɪɢ ɨɬɪɢɦɚɧɨ ɲɥɹɯɨɦ ɭɫɟɪɟɞɧɟɧɧɹ ɧɟ ɦɟɧɲɟ 10 ɜɢɦɿɪɸɜɚɧɶ, ɜɢɤɨɧɚɧɢɯ ɜ ɨɞɧɚɤɨɜɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɭɦɨɜɚɯ. ȼɢɞɧɨ, ɳɨ ɰɿ ɫɩɟɤɬɪɢ ɫɤɥɚɞɚɸɬɶɫɹ ɡ ɞɜɨɯ ɤɨɦɩɨɧɟɧɬ. əɤ ɡɚɡɧɚɱɚɥɨɫɹ ɜɢɳɟ (ɞɢɜ. ɩɿɞɪɨɡɞɿɥ 3.1) ɜɢɫɨɤɨɱɚɫɬɨɬɧɚ ɫɦɭɝɚ ɩɨɝɥɢɧɚɧɧɹ FMN ɡ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ 1704 ɫɦ-1 (±1 ɦ-1) (ɪɢɫ. 4.1, ɫɩɟɤɬɪ 1) ɜɿɞɧɨɫɢɬɶɫɹ ɩɟɪɟɜɚɠɧɨ ɞɨ ɤɨɥɢɜɚɧɶ 100 ɤɚɪɛɨɧɿɥɶɧɨʀ ɝɪɭɩɢ ɋ4=Ɉ, ɚ ɛɿɥɶɲ ɧɢɡɶɤɨɱɚɫɬɨɬɧɚ ɫɦɭɝɚ ɩɪɢ 1653 ɫɦ-1 (±1 ɫɦ-1) ɩɨɜ'ɹɡɚɧɚ ɡ ɤɨɥɢɜɚɧɧɹɦɢ ɤɚɪɛɨɧɿɥɶɧɨʀ ɝɪɭɩɢ ɋ2=Ɉ (ɞɢɜ. ɪɢɫ. 1.4). C6=O(TPH) D 0,20 1654 C2=O(TPH) 1702 1658 2 1704 3 Ɋɢɫɭɧɨɤ 4.1 ȱɑ-ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ (1), ɪɨɡɱɢɧɿɜ (2) ɜɫɿɯ FMN ɿ 0,15 TPH Ⱦɥɹ 0,10 1653 C2=O(FMN) 1 1704 C4=O(FMN) ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ (3). ɪɇ = 6,9÷7,0 (±0,05) Q, ɫɦ -1 FMN-TPH ɪɨɡɱɢɧɿɜ 0,05 0,00 1600 1650 1700 Ɍɟɨɮɿɥɿɧ ɧɚɥɟɠɢɬɶ ɞɨ ɤɫɚɧɬɢɧɨɜɢɯ ɩɨɯɿɞɧɢɯ ɬɚ ɣɨɝɨ ɫɬɪɭɤɬɭɪɚ ɛɥɢɡɶɤɚ ɞɨ ɤɨɮɟʀɧɭ, ɞɥɹ ɹɤɨɝɨ ɧɚɞɿɣɧɨ ɜɢɤɨɧɚɧɨ ɜɿɞɧɟɫɟɧɧɹ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɜ ȱɑɫɩɟɤɬɪɿ ɧɚ ɩɿɞɫɬɚɜɿ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɿ ɪɨɡɪɚɯɭɧɤɨɜɢɯ ɞɨɫɥɿɞɠɟɧɶ [151, 225]. Ɍɚɤ, ɜɢɫɨɤɨɱɚɫɬɨɬɧɚ ɫɦɭɝɚ ɩɨɝɥɢɧɚɧɧɹ TPH ɩɪɢ 1702 ɫɦ-1 (±1 ɫɦ-1) (ɪɢɫ. 4.1, ɫɩɟɤɬɪ 2) ɩɨɜ'ɹɡɚɧɚ ɡ ɤɨɥɢɜɚɧɧɹɦ ɤɿɥɶɰɹ ɜ ɮɚɡɿ ɡ ɨɫɧɨɜɧɢɦ ɜɧɟɫɤɨɦ ɤɚɪɛɨɧɿɥɶɧɨʀ ɝɪɭɩɢ ɋ2=Ɉ, ɬɨɞɿ ɹɤ ɧɢɡɶɤɨɱɚɫɬɨɬɧɚ ɫɦɭɝɚ ɩɨɝɥɢɧɚɧɧɹ ɩɪɢ 1654 ɫɦ-1 (±1 ɫɦ-1) ɜɿɞɧɨɫɢɬɶɫɹ ɞɨ ɤɿɥɶɰɟɜɨɝɨ ɤɨɥɢɜɚɧɧɹ ɜ ɩɪɨɬɢɮɚɡɿ ɡ ɩɟɪɟɜɚɠɧɢɦ ɜɧɟɫɤɨɦ ɋ6=Ɉ-ɝɪɭɩ ɚɬɨɦɿɜ (ɞɢɜ. ɪɢɫ. 1.3 ɛ). D 0,20 1654 1702 1658 2 1704 1 Ɋɢɫɭɧɨɤ 4.2 ȱɑ-ɫɩɟɤɬɪ ɩɨɝɥɢɧɚɧɧɹ ɿ ɫɭɦɚɪɧɢɣ ɪɨɡɱɢɧɭ ɫɩɟɤɬɪ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-TPH (1) FMN+TPH (2). Ⱦɥɹ ɜɫɿɯ ɪɨɡɱɢɧɿɜ (±0,05) ɪɇ = 6,9÷7,0 0,15 0,10 0,05 0,00 1600 1650 1700 Q, ɫɦ -1 101 ɇɚ ɪɢɫ. 4.2 ɧɚɜɟɞɟɧɨ ȱɑ-ɫɩɟɤɬɪ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-TPH ɿ ɫɭɦɚɪɧɢɣ ɫɩɟɤɬɪ ɥɿɝɚɧɞɿɜ FMN ɿ TPH. ȼɢɞɧɨ, ɳɨ ɱɚɫɬɨɬɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɋ2=Ɉ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɿɞɭ ɬɚ ɋ6=Ɉ ɬɟɨɮɿɥɿɧɭ ɡɚɡɧɚɥɢ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɦɿɳɟɧɧɹ ɧɚ ǻȞ = 4-5 ɫɦ-1 (±1 ɫɦ-1), ɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɫɩɟɤɬɪɭ ɩɨɝɥɢɧɚɧɧɹ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ ɿɫɬɨɬɧɨ ɡɦɟɧɲɢɥɚɫɹ (ɿɧɮɪɚɱɟɪɜɨɧɢɣ ɝɿɩɨɯɪɨɦɿɡɦ). Ɇɨɠɧɚ ɬɚɤɨɠ ɜɿɞɡɧɚɱɢɬɢ, ɳɨ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɫɦɭɝɢ ɋ4=Ɉ (FMN) ɿ ɋ2=Ɉ (TPH) ɫɜɨɝɨ ɩɨɥɨɠɟɧɧɹ ɭ ɤɨɦɩɥɟɤɫɿ ɩɪɚɤɬɢɱɧɨ ɧɟ ɡɦɿɧɢɥɢ. Ɍɚɤɢɦ ɱɢɧɨɦ, ɜ ȱɑ-ɫɩɟɤɬɪɚɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-TPH ɱɚɫɬɨɬɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɡɚɡɧɚɸɬɶ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɦɿɳɟɧɧɹ ɿ ɡɦɟɧɲɟɧɧɹ ɿɧɬɟɧɫɢɜɧɨɫɬɿ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɿ FMN, ɿ TPH. Ⱥɧɚɥɨɝɿɱɧɿ ɡɦɿɧɢ ȱɑ-ɫɩɟɤɬɪɿɜ ɫɩɨɫɬɟɪɿɝɚɥɢɫɹ ɜ ɫɬɨɩɤɚɯ ɝɟɬɟɪɨɰɢɤɥɿɜ ɚɡɨɬɢɫɬɢɯ ɨɫɧɨɜ ɭ ɩɨɥɿɧɭɤɥɟɨɬɢɞɚɯ [103, 104], ɞɥɹ ɹɤɢɯ ɬɚɤɚ ɩɨɜɟɞɿɧɤɚ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɩɨɹɫɧɸɜɚɥɚɫɹ ɪɟɡɨɧɚɧɫɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ. Ɉɱɟɜɢɞɧɨ, ɫɩɨɫɬɟɪɟɠɭɜɚɧɿ ɧɚɦɢ ɡɦɿɧɢ ɫɩɟɤɬɪɚɥɶɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMNTPH ɫɜɿɞɱɚɬɶ ɩɪɨ ɬɟ, ɳɨ ɭɬɜɨɪɟɧɧɹ ɫɬɚɛɿɥɶɧɨɝɨ ɚɫɨɰɿɚɬɭ ɦɨɠɟ ɫɭɩɪɨɜɨɞɠɭɜɚɬɢɫɹ ɪɟɡɨɧɚɧɫɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɿɜ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ FMN ɿ TPH. Ⱦɥɹ ɩɿɞɬɜɟɪɞɠɟɧɧɹ ɰɶɨɝɨ ɩɪɢɩɭɳɟɧɧɹ ɿ ɡ'ɹɫɭɜɚɧɧɹ ɦɟɯɚɧɿɡɦɭ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ FMN-TPH ɦɢ ɩɪɨɜɟɥɢ ɨɛɱɢɫɥɟɧɧɹ ɪɟɡɨɧɚɧɫɧɢɯ ɜɡɚɽɦɨɞɿɣ ɤɨɥɢɜɚɧɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ FMN ɿ TPH. 4.2 Ɋɟɡɨɧɚɧɫɧɿ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-TPH 4.2.1 ɋɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ FMN ɿ TPH ɭ ɪɨɡɱɢɧɚɯ D2O Ⱦɥɹ ɪɨɡɪɚɯɭɧɤɭ ɪɟɡɨɧɚɧɫɧɢɯ ɜɡɚɽɦɨɞɿɣ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɧɟɨɛɯɿɞɧɨ ɜɢɡɧɚɱɢɬɢ ʀɯ ɦɨɦɟɧɬɢ ɩɟɪɟɯɨɞɿɜ, ɹɤɿ ɪɨɡɪɚɯɨɜɭɸɬɶɫɹ ɡ ɚɛɫɨɥɸɬɧɢɯ ɿɧɬɟɧɫɢɜɧɨɫɬɟɣ. 102 Ⱥɛɫɨɥɸɬɧɿ ɿɧɬɟɧɫɢɜɧɨɫɬɿ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɿ ɬɟɨɮɿɥɿɧɭ ɜɢɡɧɚɱɟɧɿ ɡɿ ɫɩɟɤɬɪɭ (ɪɢɫ. 4.1), ɜ ɹɤɢɯ, ɹɤ ɦɨɠɧɚ ɛɚɱɢɬɢ, ɤɨɦɩɨɧɟɧɬɢ ɞɨɛɪɟ ɪɨɡɞɿɥɟɧɿ. ɉɪɢ ɰɶɨɦɭ ɮɨɪɦɭ ɫɦɭɝ ɨɩɢɫɭɜɚɥɢ ɥɿɧɿɣɧɨɸ ɤɨɦɛɿɧɚɰɿɽɸ ɮɭɧɤɰɿɣ Ƚɚɭɫɫɚ ɿ Ʌɨɪɟɧɰɚ, ɹɤ ɭ ɪɨɛɨɬɿ [211]. ɉɨɲɭɤ ɩɨɬɪɿɛɧɢɯ ɡɧɚɱɟɧɶ ɩɚɪɚɦɟɬɪɿɜ ɡɞɿɣɫɧɸɜɚɥɢ ɦɟɬɨɞɨɦ ɞɟɮɨɪɦɨɜɚɧɨɝɨ ɛɚɝɚɬɨɝɪɚɧɧɢɤɚ [220] ɞɨ ɞɨɫɹɝɧɟɧɧɹ ɦɿɧɿɦɚɥɶɧɨɝɨ ɡɧɚɱɟɧɧɹ ¦ >D(Q ) n i 1 i ɟɤɫɩ  D (Q i ) ɪɨɡɪɚɯ , ɞɟ D(Qi)ɟɤɫɩ ɿ D(Qi)ɪɨɡɪɚɯ – ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɿ ɬɚ @ 2 ɪɨɡɪɚɯɭɧɤɨɜɿ ɡɧɚɱɟɧɧɹ ɩɨɝɥɢɧɚɧɧɹ ɩɪɢ i-ɬɿɣ ɱɚɫɬɨɬɿ. ȱɧɬɟɝɪɚɥɶɧɭ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɜɢɪɚɯɨɜɭɜɚɥɢ ɡɚ ɮɨɪɦɭɥɨɸ [226]: B 2,3³ H (Q )dQ H (Q 0 )'Q 1 / 2 2 ( fG S ln 2  (1  f G )S ) , (4.1) ɞɟ ǻȞ1/2 – ɧɚɩɿɜɲɢɪɢɧɚ ɫɦɭɝɢ; fG – ɮɚɤɬɨɪ Ƚɚɭɫɚ, ɳɨ ɩɨɤɚɡɭɽ ɜɧɟɫɨɤ ɪɨɡɩɨɞɿɥɭ Ƚɚɭɫɚ ɭ ɤɨɧɬɭɪ, ɹɤɢɣ ɨɩɢɫɭɽ ɮɭɧɤɰɿɸ; İ(Ȟ0) – ɦɨɥɹɪɧɢɣ ɤɨɟɮɿɰɿɽɧɬ ɩɨɝɥɢɧɚɧɧɹ, ɩɨɜ'ɹɡɚɧɢɣ ɡ D(Ȟ) ɫɩɿɜɜɿɞɧɨɲɟɧɧɹɦ Ȼɭɝɟɪɚ-Ʌɚɦɛɟɪɬɚ-Ȼɟɪɚ: D(Q ) H (Q ) ˜ k ˜ l , (4.2) ɞɟ k – ɤɨɧɰɟɧɬɪɚɰɿɹ ɪɟɱɨɜɢɧɢ; l – ɬɨɜɳɢɧɚ ɩɨɝɥɢɧɚɸɱɨɝɨ ɲɚɪɭ. Ɇɚɬɪɢɱɧɢɣ ɦɨɦɟɧɬ ɩɟɪɟɯɨɞɭ P ɜɢɡɧɚɱɚɜɫɹ ɡɿ ɫɩɿɜɜɿɞɧɨɲɟɧɧɹ: A 0,5 ˜10 10 B 8S 3Q P 3ch 2 , (4.3) ɞɟ Ⱥ – ɚɛɫɨɥɸɬɧɚ ɿɢɧɬɟɧɫɢɜɧɿɫɬɶ ɜ ɨɞɢɧɢɰɹɯ (ɫɦ2·ɫ-1·ɦɨɥɟɤɭɥɚ-1); 103 ɫ – ɲɜɢɞɤɿɫɬɶ ɫɜɿɬɥɚ; h – ɩɨɫɬɿɣɧɚ ɉɥɚɧɤɚ. Ɂɧɚɱɟɧɧɹ ɱɚɫɬɨɬ ɿ ɧɚɩɿɜɲɢɪɢɧɭ ɫɦɭɝ, ɹɤɿ ɱɚɫɬɤɨɜɨ ɩɟɪɟɤɪɢɜɚɸɬɶɫɹ, ɜɢɡɧɚɱɚɥɢɫɹ ɡ ɬɨɱɧɿɫɬɸ ±1 ɫɦ-1, ɩɨɦɢɥɤɚ ɪɨɡɪɚɯɭɧɤɭ ɚɛɫɨɥɸɬɧɢɯ ɿɧɬɟɧɫɢɜɧɨɫɬɟɣ ɫɬɚɧɨɜɢɥɚ 10%. Ⱦɥɹ ɜɢɡɧɚɱɟɧɧɹ ɪɟɡɨɧɚɧɫɧɨʀ (ɞɢɧɚɦɿɱɧɨʀ) ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɛɭɥɢ ɪɨɡɪɚɯɨɜɚɧɿ ɫɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ (ɱɚɫɬɨɬɢ ɬɚ ɿɧɬɟɧɫɢɜɧɨɫɬɿ) ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɬɟɨɮɿɥɿɧɭ (ɋ2=Ɉ, ɋ6=Ɉ) ɿ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ (ɋ2=Ɉ, ɋ4=Ɉ). ɐɿ ɞɚɧɿ ɧɚɜɟɞɟɧɨ ɭ ɬɚɛɥ. 4.1. Ɍɚɛɥɢɰɹ 4.1 ɋɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ FMN ɿ TPH Ʌɿɝɚɧɞ ȼɿɞɧɟɫɟɧɧɹ FMN TPH C2=O C4=O C2=O C6=O Ȟ0, ɫɦ-1 1653 1704 1702 1654 İ, ɥ·ɦɨɥɶ-1·ɫɦ-1 1,09·105 3,85·104 4,98·104 6,45·104 ǻȞ1/2, ɫɦ-1 50 32 46 34 fG 0,1 0,69 0 0,57 B·10-4, ɥ·ɦɨɥɶ-1·ɫɦ-2 10,9 3,9 5,0 6,4 ȝ, D 0,514 0,301 0,342 0,395 Ɂ ɪɟɡɭɥɶɬɚɬɿɜ, ɩɪɟɞɫɬɚɜɥɟɧɢɯ ɭ ɬɚɛɥ. 4.1 ɜɢɞɧɨ, ɳɨ ɞɢɩɨɥɶɧɿ ɦɨɦɟɧɬɢ ɩɟɪɟɯɨɞɿɜ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɦɚɸɬɶ ɡɧɚɱɧɭ ɜɟɥɢɱɢɧɭ, ɬɨɦɭ ɦɨɠɧɚ ɨɱɿɤɭɜɚɬɢ, ɳɨ ɩɪɢ ɩɟɜɧɿɣ ɫɬɪɭɤɬɭɪɿ ɤɨɦɩɥɟɤɫɭ ɦɨɠɭɬɶ ɜɡɚɽɦɨɞɿɹɬɢ ɝɪɭɩɢ: (1) ɋ2=Ɉ (FMN) ɿ ɋ6=Ɉ (TPH) ɿ (2) ɋ4=Ɉ (FMN) ɿ ɋ2=Ɉ (TPH). 4.2.2 Ɋɨɡɪɚɯɭɧɨɤ ɪɟɡɨɧɚɧɫɧɢɯ ɜɡɚɽɦɨɞɿɣ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɤɨɦɩɥɟɤɫɿ FMN-TPH ɿ ɩɨɛɭɞɨɜɚ ɦɨɞɟɥɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ ȼɢɹɜɥɟɧɿ ɪɚɧɿɲɟ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɝɭɚɧɿɧɭ, ɬɢɦɿɞɢɧɭ ɿ ɭɪɚɰɢɥɭ ɩɪɢ ɜɢɜɱɟɧɧɿ ɮɨɪɦɭɜɚɧɧɹ ɫɬɨɩɨɤ ɚɡɨɬɢɫɬɢɯ ɨɫɧɨɜ ɭ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬɚɯ [107] ɛɭɥɢ ɩɨɹɫɧɟɧɿ ɞɢɧɚɦɿɱɧɨɸ ɜɡɚɽɦɨɞɿɽɸ ɦɨɦɟɧɬɿɜ 104 ɩɟɪɟɯɨɞɭ ɋ=Ɉ-ɝɪɭɩ ɚɬɨɦɿɜ. ɇɟ ɜɢɤɥɸɱɟɧɚ ɦɨɠɥɢɜɿɫɬɶ, ɳɨ ɬɚɤɢɣ ɬɢɩ ɜɡɚɽɦɨɞɿɣ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɜɢɧɢɤɚɽ ɜ ɚɝɪɟɝɚɬɚɯ ɞɢɦɟɪɧɢɯ ɮɨɪɦ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ FMN-TPH, ɹɤɿ ɮɨɪɦɭɸɬɶɫɹ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ. əɤ ɿ ɭ ɜɢɩɚɞɤɭ ɫɬɨɩɨɤ ɫɚɦɨɚɫɨɰɿɚɬɿɜ FMN (ɞɢɜ. ɩɿɞɪɨɡɞɿɥ 3.3), ɪɨɡɪɚɯɭɧɨɤ ɪɟɡɨɧɚɧɫɧɢɯ ɜɡɚɽɦɨɞɿɣ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɤɨɦɩɥɟɤɫɿ FMNTPH ɦɨɠɧɚ ɜɢɤɨɧɚɬɢ ɡ ɜɢɤɨɪɢɫɬɚɧɧɹɦ ɬɟɨɪɿʀ ɦɨɥɟɤɭɥɹɪɧɢɯ ɟɤɫɢɬɨɧɿɜ [181]. Ɉɫɧɨɜɧɿ ɩɨɥɨɠɟɧɧɹ ɰɿɽʀ ɬɟɨɪɿʀ ɫɬɢɫɥɨ ɜɢɤɥɚɞɟɧɨ ɜ ɩɿɞɪɨɡɞɿɥɿ 2.1.1. əɤɳɨ ɩɪɢɩɭɫɬɢɬɢ, ɳɨ ɜ ɪɨɡɱɢɧɿ FMN ɿ TPH ɭɬɜɨɪɢɜɫɹ n-ɦɨɥɟɤɭɥɹɪɧɢɣ ɚɝɪɟɝɚɬ (ɧɟɨɛɦɟɠɟɧɢɣ ɨɞɧɨɜɢɦɿɪɧɢɣ ɤɪɢɫɬɚɥ), ɜ ɹɤɨɦɭ ɩɨɫɥɿɞɨɜɧɨ ɱɟɪɝɭɸɬɶɫɹ ɝɟɬɟɪɨɰɢɤɥɢ ɡ ɰɢɯ ɦɨɥɟɤɭɥ, ɬɨ ɡɝɿɞɧɨ ɡ ɪɨɛɨɬɨɸ [227] ɚɤɬɢɜɧɢɦɢ ɛɭɞɭɬɶ ɩɨɜɧɨɫɢɦɟɬɪɢɱɧɿ ɤɨɥɢɜɚɧɧɹ ɬɢɩɭ Ⱥ (ɩɨɥɹɪɢɡɨɜɚɧɿ ɜɡɞɨɜɠ ɨɫɿ ɩɨɥɿɦɟɪɧɨʀ ɦɨɥɟɤɭɥɢ ɚɛɨ ɚɝɪɟɝɚɬɭ) ɬɚ ɞɜɿɱɿ ɜɢɪɨɞɠɟɧɿ ɬɢɩɭ ȿ (ɩɨɥɹɪɢɡɨɜɚɧɿ ɩɟɪɩɟɧɞɢɤɭɥɹɪɧɨ ɞɨ ɨɫɿ ɚɝɪɟɝɚɬɭ). ɍ ɪɟɚɥɶɧɢɯ ɭɦɨɜɚɯ (ɭ ɜɨɞɧɨɦɭ ɫɟɪɟɞɨɜɢɳɿ) ɧɚ ɱɚɫɬɨɬɭ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ ɤɪɿɦ ɪɟɡɨɧɚɧɫɧɨʀ ɜɡɚɽɦɨɞɿʀ ɜɩɥɢɜɚɽ ɜɨɞɧɟɜɢɣ ɡɜ'ɹɡɨɤ, ɹɤɢɣ ɭɬɜɨɪɸɽɬɶɫɹ ɦɿɠ ɤɢɫɧɟɦ ɋ=Ɉ-ɝɪɭɩ ɚɬɨɦɿɜ ɬɚ ɜɨɞɧɟɦ ɦɨɥɟɤɭɥɢ ɜɨɞɢ. ɍ ɪɚɦɤɚɯ ɦɨɞɟɥɿ ɫɥɚɛɨɡɜ'ɹɡɚɧɢɯ ɨɫɰɢɥɹɬɨɪɿɜ [182], ɡ ɭɪɚɯɭɜɚɧɧɹɦ ɇ-ɡɜ'ɹɡɤɭ ɚɛɨ «ɟɮɟɤɬɭ» ɫɟɪɟɞɨɜɢɳɚ ɿ ɪɟɡɨɧɚɧɫɧɢɯ ɜɡɚɽɦɨɞɿɣ, ɱɚɫɬɨɬɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɋ=Ɉ-ɝɪɭɩ, ɩɨɥɹɪɢɡɨɜɚɧɢɯ ɩɚɪɚɥɟɥɶɧɨ ɿ ɩɟɪɩɟɧɞɢɤɭɥɹɪɧɨ, ɡɚɩɢɲɭɬɶɫɹ ɬɚɤ: Ⱥ Q A Q 0  'Q H  ɡɜ r 'Q ɪɟɡ , ȿ Q ȿ Q 0  'Q H  ɡɜ r 'Q ɪɟɡ , (4.4) (4.5) ɞɟ Ȟ0 – ɱɚɫɬɨɬɚ ɧɟɡɛɭɪɟɧɨɝɨ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ; Ⱥ ȿ 'Q ɪɟɡ ɿ 'Q ɪɟɡ – ɪɟɡɨɧɚɧɫɧɿ ɡɫɭɜɢ ɞɥɹ ɬɢɩɿɜ ɤɨɥɢɜɚɧɶ Ⱥ ɬɚ ȿ; ǻȞɇ-ɡɜ – ɡɫɭɜ ɡɚ ɪɚɯɭɧɨɤ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ. Ɋɟɡɨɧɚɧɫɧɿ ɡɫɭɜɢ ɞɥɹ ɰɢɯ ɬɢɩɿɜ ɤɨɥɢɜɚɧɶ ɡɚɩɢɲɭɬɶɫɹ ɬɚɤ [183]: 105 Ⱥ 'Q ɪɟɡ ȿ 'Q ɪɟɡ 2('Q 11,12  'Q 11,13    'Q 11,1k ) , (4.6) (4.7) 2('Q 11,12 ˜ cos M  'Q 11,13 ˜ cos 2M    'Q 11,1k ˜ cos kM ) , ɞɟ k – ɱɢɫɥɨ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɜ ɚɝɪɟɝɚɬɿ ɚɛɨ ɩɨɥɿɦɟɪɧɿɣ ɦɨɥɟɤɭɥɿ ; ǻȞ11,12 – ɡɦɿɳɟɧɧɹ ɱɚɫɬɨɬɢ ɤɨɥɢɜɚɧɧɹ ɋ=Ɉ ɡɚ ɪɚɯɭɧɨɤ ɪɟɡɨɧɚɧɫɧɨʀ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ ɭ ɩɨɥɨɠɟɧɧɿ 11 ɬɚ 12 ɿ ɬ.ɞ .; ij – ɤɭɬ ɩɨɜɨɪɨɬɭ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ ɫɭɫɿɞɧɿɯ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ. Ɂɚɡɜɢɱɚɣ ɩɿɞ ɱɚɫ ɪɨɡɪɚɯɭɧɤɭ ɪɟɡɨɧɚɧɫɧɨʀ (ɞɢɧɚɦɿɱɧɨʀ) ɜɡɚɽɦɨɞɿʀ ɤɨɥɢɜɚɥɶɧɢɯ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ ɜ ɛɿɨɩɨɥɿɦɟɪɚɯ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶ ɞɢɩɨɥɶɞɢɩɨɥɶɧɟ ɧɚɛɥɢɠɟɧɧɹ [107, 184, 228]. ɉɪɢ ɰɶɨɦɭ ɪɟɡɨɧɚɧɫɧɟ ɡɪɭɲɟɧɧɹ ɜɢɪɚɠɚɽɬɶɫɹ ɮɨɪɦɭɥɨɸ: 'Q ɪɟɡ ɞɟ Q ɋ Q 0  1 f f La L pQ nD ,mE , h (4.8) h – ɩɨɫɬɿɣɧɚ ɉɥɚɧɤɚ; f La ɿ L fp – ɤɨɟɮɿɰɿɽɧɬɢ ɫɢɦɟɬɪɿʀ ɞɥɹ ɤɨɥɢɜɚɧɶ ɬɢɩɭ f; Ȟ0 – ɧɟɡɛɭɪɟɧɚ ɱɚɫɬɨɬɚ; m ɿ n – ɱɢɫɥɚ, ɹɤɿ ɧɭɦɟɪɭɸɬɶ ɤɨɥɢɜɚɥɶɧɿ ɝɪɭɩɢ ɜ ɟɥɟɦɟɧɬɚɪɧɨɦɭ ɨɫɟɪɟɞɤɭ (ɩɨɥɿɦɟɪɧɨʀ ɦɨɥɟɤɭɥɢ ɚɛɨ ɚɝɪɟɝɚɬɭ); Q nD ,mE – ɦɚɬɪɢɱɧɢɣ ɟɥɟɦɟɧɬ ɨɩɟɪɚɬɨɪɚ ɞɢɩɨɥɶ-ɞɢɩɨɥɶɧɨʀ ɜɡɚɽɦɨɞɿʀ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ, ɥɨɤɚɥɿɡɨɜɚɧɢɯ ɭ ɞɜɨɯ ɨɞɧɚɤɨɜɢɯ ɤɨɥɢɜɚɥɶɧɢɯ ɝɪɭɩɚɯ. ɍ ɫɩɪɨɳɟɧɨɦɭ ɜɢɝɥɹɞɿ ɟɧɟɪɝɿɹ ɜɡɚɽɦɨɞɿʀ ɦɿɠ ɞɜɨɦɚ ɨɪɿɽɧɬɨɜɚɧɢɦɢ ɞɢɩɨɥɶɧɢɦɢ ɦɨɦɟɧɬɚɦɢ ɩɟɪɟɯɨɞɭ (ɞɢɜ. ɪɢɫ. 2.2) ɦɨɠɟ ɛɭɬɢ ɡɚɩɢɫɚɧɚ ɹɤ [229]: wP V 1 wS1 ˜ wP 3 wS 2 H (cos M  3 cos E ˜ cos J ) ˜ S1 ˜ S 2 , (4.9) R ɞɟ 106 İ – ɞɿɟɥɟɤɬɪɢɱɧɚ ɩɨɫɬɿɣɧɚ; wP wS1 – ɞɢɩɨɥɶɧɢɣ ɦɨɦɟɧɬ ɩɟɪɟɯɨɞɭ (D1Å); S1 ɿ S2 – ɜɚɥɟɧɬɧɿ ɤɨɨɪɞɢɧɚɬɢ; R – ɜɿɞɫɬɚɧɶ ɦɿɠ ɰɟɧɬɪɚɦɢ ɜɡɚɽɦɨɞɿɸɱɢɯ ɞɢɩɨɥɿɜ (Å). ɍ ɡɝɨɪɧɭɬɨɦɭ ɜɢɝɥɹɞɿ ɪɟɡɨɧɚɧɫɧɢɣ ɱɚɫɬɨɬɧɢɣ ɡɫɭɜ ɭ ɜɢɩɚɞɤɭ ɞɜɨɯ ɜɡɚɽɦɨɞɿɸɱɢɯ ɤɨɥɢɜɚɥɶɧɢɯ ɝɪɭɩ ɜɿɞɩɨɜɿɞɧɨ ɞɨ ɮɨɪɦɭɥ (4.8) ɿ (4.9) ɡɚɩɢɫɭɽɬɶɫɹ ɬɚɤ: 'Q ɪɟɡ M cos D  3 cos E ˜ cos J ˜ hH R3 M ˜G , hH (4.10) ɞɟ ɩɟɪɲɢɣ ɱɥɟɧ ɽ ɩɨɫɬɿɣɧɨɸ ɜɟɥɢɱɢɧɨɸ ɿ ɦɿɫɬɢɬɶ ɞɨɛɭɬɨɤ ɞɢɩɨɥɶɧɢɯ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ M w P1 w P 2 , ɹɤɿ ɜɢɡɧɚɱɚɸɬɶɫɹ ɡ ɚɛɫɨɥɸɬɧɢɯ ɿɧɬɟɧɫɢɜɧɨɫɬɟɣ ɫɦɭɝ ˜ wS 1 wS 2 ɩɨɝɥɢɧɚɧɧɹ ɜ ɿɧɮɪɚɱɟɪɜɨɧɢɯ ɫɩɟɤɬɪɚɯ ɡɚ ɮɨɪɦɭɥɨɸ: P ɞɟ 2 2 Ach , 8S 3Q (4.11) Ⱥ – ɚɛɫɨɥɸɬɧɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ; ɫ – ɲɜɢɞɤɿɫɬɶ ɫɜɿɬɥɚ ɭ ɜɚɤɭɭɦɿ; Ȟ – ɱɚɫɬɨɬɚ ɦɚɤɫɢɦɭɦɭ ɫɦɭɝɢ; h – ɩɨɫɬɿɣɧɚ ɉɥɚɧɤɚ. ɍ ɪɨɛɨɬɿ [88] ɦɟɬɨɞɨɦ əɆɊ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ ɜɢɡɧɚɱɟɧɨ ɤɨɨɪɞɢɧɚɬɢ ɚɬɨɦɿɜ ɞɢɦɟɪɧɨɝɨ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-TPH. ȼɢɤɨɪɢɫɬɨɜɭɸɱɢ ɰɿ ɞɚɧɿ ɦɨɠɧɚ ɜɢɡɧɚɱɢɬɢ ɝɟɨɦɟɬɪɢɱɧɢɣ ɮɚɤɬɨɪ G ɭ ɮɨɪɦɭɥɿ (4.10), ɜɜɚɠɚɸɱɢ, ɜ ɩɟɪɲɨɦɭ ɧɚɛɥɢɠɟɧɧɿ, ɳɨ ɞɢɩɨɥɶɧɢɣ ɦɨɦɟɧɬ ɩɟɪɟɯɨɞɭ ɫɩɪɹɦɨɜɚɧɢɣ ɩɨ ɡɜ'ɹɡɤɭ ɋ=Ɉ. Ɋɨɡɪɚɯɭɧɨɤ ɩɨɤɚɡɭɽ, ɳɨ ɜɟɥɢɱɢɧɚ R ɭ ɮɨɪɦɭɥɿ (4.10) ɦɿɠ ɡɜ'ɹɡɤɚɦɢ ɋ2=Ɉ TPH ɿ ɋ4=Ɉ FMN ɛɿɥɶɲɟ 7 Å, ɬɨɦɭ ɦɨɦɟɧɬɢ ɩɟɪɟɯɨɞɿɜ ɰɢɯ ɝɪɭɩ ɚɬɨɦɿɜ ɭ ɞɢɦɟɪɿ ɩɪɚɤɬɢɱɧɨ ɧɟ ɜɡɚɽɦɨɞɿɸɬɶ. Ɉɞɧɚɤ ɡɜ'ɹɡɤɢ ɋ2=Ɉ FMN ɿ ɋ6=Ɉ TPH 107 ɪɨɡɬɚɲɨɜɭɸɬɶɫɹ ɭ ɞɢɦɟɪɿ ɧɚ ɞɨɫɢɬɶ ɛɥɢɡɶɤɿɣ ɜɿɞɫɬɚɧɿ (R § 5 Å) ɿ ɰɶɨɝɨ ɜɢɹɜɢɥɨɫɹ ɰɿɥɤɨɦ ɞɨɫɬɚɬɧɶɨ, ɳɨɛ ɜɢɧɢɤɥɚ ɜɡɚɽɦɨɞɿɹ ʀɯ ɦɨɦɟɧɬɿɜ ɩɟɪɟɯɨɞɭ. ȼɢɤɨɪɢɫɬɨɜɭɸɱɢ ɫɩɟɤɬɪɚɥɶɧɿ ɩɚɪɚɦɟɬɪɢ ɡ ɬɚɛɥ. 4.1 ɞɥɹ ɨɛɱɢɫɥɟɧɧɹ ɝɟɨɦɟɬɪɢɱɧɨɝɨ ɮɚɤɬɨɪɚ G ɿ ɜɜɚɠɚɸɱɢ, ɳɨ ɦɨɦɟɧɬɢ ɩɟɪɟɯɨɞɿɜ ɪɨɡɬɚɲɨɜɭɸɬɶɫɹ ɩɨ ɡɜ'ɹɡɤɚɯ ɋ2=Ɉ FMN ɿ ɋ6=Ɉ TPH, ɦɨɠɧɚ ɨɬɪɢɦɚɬɢ, ɳɨ ǻȞɪɟɡ = 3,5 ɫɦ-1. ȼɿɞɨɦɨ, ɳɨ ɞɥɹ ɦɨɥɟɤɭɥ ɛɿɥɤɿɜ ɬɚ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ ɦɨɦɟɧɬɢ ɩɟɪɟɯɨɞɿɜ ɋ=Ɉ-ɝɪɭɩ ɚɬɨɦɿɜ ɜɿɞɯɢɥɟɧɿ ɜɿɞ ɧɚɩɪɹɦɭ ɡɜ'ɹɡɤɭ ɧɚ ɤɭɬ ij § 20° [107, 184]. ȼɪɚɯɨɜɭɸɱɢ ɰɟ ɿ ɜɜɚɠɚɸɱɢ, ɳɨ ɚɝɪɟɝɚɬ FMN-TPH ɽ n-ɦɨɥɟɤɭɥɹɪɧɢɦ (n t 3), ɚ ɬɚɤɨɠ ɜɪɚɯɨɜɭɸɱɢ ɜ ɪɨɡɪɚɯɭɧɤɚɯ ɬɿɥɶɤɢ ɜɡɚɽɦɨɞɿɸ ɧɚɣɛɥɢɠɱɢɯ ɫɭɫɿɞɿɜ, ɨɬɪɢɦɭɽɦɨ ɱɚɫɬɨɬɧɢɣ ɡɫɭɜ ɞɥɹ ɩɟɪɩɟɧɞɢɤɭɥɹɪɧɨʀ ɩɨɥɹɪɢɡɚɰɿʀ ȿ 'Q ɪɟɡ § 5,5 ɫɦ-1 (±1 ɫɦ-1), ɳɨ ɭɡɝɨɞɠɭɽɬɶɫɹ ɡ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ Ⱥ ɫɩɨɫɬɟɪɟɠɭɜɚɧɨɸ ɜɟɥɢɱɢɧɨɸ. Ⱦɥɹ ɩɚɪɚɥɟɥɶɧɨʀ ɩɨɥɹɪɢɡɚɰɿʀ – 'Q ɪɟɡ § 7 ɫɦ-1 (±1 ɫɦ-1). ȼɿɞɫɭɬɧɿɫɬɶ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɝɨ ɡɧɚɱɟɧɧɹ ɩɨɤɢ ɧɟ ɞɨɡɜɨɥɹɽ ɩɪɨɜɟɫɬɢ ɩɨɪɿɜɧɹɧɧɹ ɡ ɬɟɨɪɟɬɢɱɧɨ ɪɨɡɪɚɯɨɜɚɧɢɦ ɡɧɚɱɟɧɧɹɦ. Ɍɚɤɢɦ ɱɢɧɨɦ, ɦɨɠɧɚ ɡɪɨɛɢɬɢ ɜɢɫɧɨɜɨɤ, ɳɨ FMN ɿ TPH ɭɬɜɨɪɸɸɬɶ nɦɨɥɟɤɭɥɹɪɧɢɣ ɚɝɪɟɝɚɬ (n t 3). 4.3 Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ TPH-EB Ⱦɨɫɥɿɞɠɟɧɧɹ ɦɟɬɨɞɨɦ əɆɊ ɩɨɤɚɡɚɥɢ, ɳɨ ɜ ɧɟɣɬɪɚɥɶɧɨɦɭ ɪɨɡɱɢɧɿ ɜ ɫɭɦɿɲɿ ɬɟɨɮɿɥɿɧɭ ɿ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɹ ɮɨɪɦɭɽɬɶɫɹ ɫɬɨɩɤɨɜɢɣ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫ ɡ ɤɨɧɫɬɚɧɬɨɸ ɪɿɜɧɨɜɚɝɢ 102 Ɇ-1, ɹɤɚ ɡɚɣɦɚɽ ɩɪɨɦɿɠɧɟ ɡɧɚɱɟɧɧɹ ɦɿɠ ɤɨɧɫɬɚɧɬɚɦɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɜɢɯɿɞɧɢɯ ɪɟɱɨɜɢɧ (KEB = 305 M-1, ɄTPH = 7,4 Ɇ-1) [88]. Ⱦɥɹ ɡ'ɹɫɭɜɚɧɧɹ ɦɨɠɥɢɜɨɫɬɿ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɜ ɫɬɨɩɤɨɜɿɣ ɫɬɪɭɤɬɭɪɿ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ TPH ɿ EB ɧɚɦɢ ɛɭɥɨ ɨɬɪɢɦɚɧɨ ȱɑ- ɬɚ ɄɊ-ɫɩɟɤɬɪɢ ɜ ɿɧɬɟɪɜɚɥɿ ɱɚɫɬɨɬ ɮɭɧɤɰɿɨɧɚɥɶɧɢɯ ɝɪɭɩ TPH ɿ EB [223]. ɇɚ ɪɢɫ. 4.3 ɚ ɧɚɜɟɞɟɧɨ ȱɑ-ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ ɧɟɣɬɪɚɥɶɧɢɯ ɜɨɞɧɢɯ (D2O) ɪɨɡɱɢɧɿɜ TPH, EB ɬɚ ʀɯ ɤɨɦɩɥɟɤɫɭ, ɚ ɬɚɤɨɠ ɫɭɦɚɪɧɢɣ ȱɑ-ɫɩɟɤɬɪ 108 TPH+EB. ɍɫɿ ɩɪɟɞɫɬɚɜɥɟɧɿ ɫɩɟɤɬɪɢ ɽ ɪɟɡɭɥɶɬɚɬɨɦ ɭɫɟɪɟɞɧɟɧɧɹ 10 ɜɢɦɿɪɸɜɚɧɶ, ɜɢɤɨɧɚɧɢɯ ɜ ɨɞɧɚɤɨɜɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɭɦɨɜɚɯ. 1600 1620 1640 1660 1613 1628 1702 1 1654 0,1 1644 C6=O(TPH) D 0,2 1654 ȼɿɞɧɨɫɧɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ C2=O(TPH) 1 1620 1650 4 3 1702 1602 1639 1652 2 1698 1637 0,0 1600 1650 2 1700 Q, ɫɦ -1 1600 1620 1640 Q , ɫɦ -1 (ɛ) Ɋɢɫɭɧɨɤ 4.3 (ɚ) ȱɑ-ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ ɪɨɡɱɢɧɿɜ ɬɟɨɮɿɥɿɧɭ (1), ɛɪɨɦɢɫɬɨɝɨ ɷɬɢɞɿɸ (2), ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ TPH-EB (3) ɿ ɫɭɦɚɪɧɢɣ ɫɩɟɤɬɪ TPH+EB (4); (ɛ) ɫɩɟɤɬɪɢ ɄɊ ɪɨɡɱɢɧɿɜ ɛɪɨɦɢɫɬɨɝɨ ɷɬɢɞɿɸ (1) ɿ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ TPH-EB (2). Ⱦɥɹ ɜɫɿɯ ɪɨɡɱɢɧɿɜ ɪɇ = 6,9÷7,0 (±0,05) Ɂɜɟɪɬɚɽ ɧɚ ɫɟɛɟ ɭɜɚɝɭ ɧɟɜɟɥɢɤɢɣ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɣ ɡɫɭɜ (ǻȞ = 4 ɫɦ-1 (±1 cɦ-1)) ɤɚɪɛɨɧɿɥɶɧɢɯ ɚɬɨɦɧɢɯ ɝɪɭɩ TPH ɋ2=Ɉ ɿ ɋ6=Ɉ (ɪɢɫ. 4.3 ɚ, ɫɩɟɤɬɪ 3), ɳɨ ɫɜɿɞɱɢɬɶ ɩɪɨ ɦɨɠɥɢɜɟ ɭɬɜɨɪɟɧɧɹ ɫɥɚɛɤɢɯ ɇ-ɡɜ'ɹɡɤɿɜ. ɇɚ ɪɢɫ. 4.3 ɛ ɧɚɜɟɞɟɧɨ ɄɊ-ɫɩɟɤɬɪɢ EB ɿ ɫɭɦɿɲɿ TPH-EB, ɹɤɿ ɨɬɪɢɦɚɧɿ ɡɚ ɪɟɡɭɥɶɬɚɬɚɦɢ ɭɫɟɪɟɞɧɟɧɧɹ 10 ɜɢɦɿɪɸɜɚɧɶ, ɜɢɤɨɧɚɧɢɯ ɜ ɨɞɧɚɤɨɜɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɭɦɨɜɚɯ. ȼɿɞɩɨɜɿɞɧɨ ɞɨ ɪɨɛɿɬ [230, 231] ɧɚ ɄɊ-ɫɩɟɤɬɪɿ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɫɦɭɝɢ ɩɪɢ Ȟ = 1628 ɿ 1644 ɫɦ-1 (±2 ɫɦ-1) ɜɿɞɧɨɫɹɬɶɫɹ ɞɨ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ NH2-ɝɪɭɩ ɚɬɨɦɿɜ ȿȼ (ɞɢɜ. ɪɢɫ. 1.2 ɛ). ȼɢɞɧɨ, ɳɨ ɰɿ (ɚ) 109 ɫɦɭɝɢ EB ɡɚɡɧɚɥɢ ɜ ɫɭɦɿɲɿ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɯ ɡɦɿɳɟɧɶ ɞɨ 1639 ɿ 1652 ɫɦ-1 (±2 cɦ-1), ɜɿɞɩɨɜɿɞɧɨ. ɇɢɡɶɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ TPH ɜ ȱɑ-ɫɩɟɤɬɪɿ ɬɚ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ NH2-ɝɪɭɩ ȿȼ ɭ ɄɊ-ɫɩɟɤɬɪɿ ɜɤɚɡɭɸɬɶ ɧɚ ɮɨɪɦɭɜɚɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ. Ɉɞɧɚɤ ɰɟ ɧɟ ɭɡɝɨɞɠɭɽɬɶɫɹ ɡ ɞɚɧɢɦɢ ɪɨɛɨɬɢ [88]. Ɂɝɿɞɧɨ ɡ ɦɨɞɟɥɥɸ ɫɬɪɭɤɬɭɪɢ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ TPH-EB, ɡɚɩɪɨɩɨɧɨɜɚɧɿɣ ɭ ɰɿɣ ɪɨɛɨɬɿ, ɜɿɞɫɬɚɧɶ ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ EB ɿ TPH ɡɚɧɚɞɬɨ ɜɟɥɢɤɚ ɞɥɹ ɬɨɝɨ, ɳɨɛ ɭɬɜɨɪɢɜɫɹ ɇ-ɡɜ'ɹɡɨɤ. Ɇɢ ɩɪɢɩɭɫɤɚɽɦɨ, ɳɨ ɰɸ ɜɿɞɫɬɚɧɶ ɦɿɝ ɩɟɪɟɤɪɢɬɢ ɥɚɧɰɸɠɨɤ ɡ ɦɨɥɟɤɭɥ ɜɨɞɢ ɡ ɇ-ɡɜ'ɹɡɤɚɦɢ ɬɢɩɭ C O  ( H  O ) n  ( H  N  H ) . ɐɟ ɩɪɢɩɭɳɟɧɧɹ ɦɨɠɟ ɛɭɬɢ ɩɿɞɬɜɟɪɞɠɟɧɨ | | ɚɛɨ ɫɩɪɨɫɬɨɜɚɧɨ ɡɚ ɞɨɩɨɦɨɝɨɸ ɪɟɡɭɥɶɬɚɬɿɜ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɫɢɫɬɟɦɢ «TPH-EB – ɜɨɞɚ» (ɞɢɜ. ɩɿɞɪɨɡɞɿɥ 4.5.2). 4.4 Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ TPH-PRF ɿ CAF-EB Ɂɚ ɞɚɧɢɦɢ ɫɩɟɤɬɪɨɫɤɨɩɿʀ əɆɊ ɬɟɨɮɿɥɿɧ ɬɚ ɩɪɨɮɥɚɜɿɧ, ɤɨɮɟʀɧ ɬɚ ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɮɨɪɦɭɸɬɶ ɫɬɨɩɤɨɜɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɢ [9, 88]. ȼɟɥɢɱɢɧɢ ɪɿɜɧɨɜɚɠɧɢɯ ɤɨɧɫɬɚɧɬ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɩɪɢɣɦɚɸɬɶ ɩɪɨɦɿɠɧɿ ɡɧɚɱɟɧɧɹ ɦɿɠ ɤɨɧɫɬɚɧɬɚɦɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɰɢɯ ɪɟɱɨɜɢɧ (KTPH = 7,4 M-1, ɄPRF = 698 M-1, KTPH-PRF = 180 M-1 [88] ɿ ɄCAF = 11,8 M-1, KEB = 305 M-1, KCAF-EB =62 M-1 [9]), ɚɥɟ ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɜ ɰɢɯ ɫɢɫɬɟɦɚɯ ɧɟ ɜɢɹɜɥɟɧɿ. Ɋɚɡɨɦ ɡ ɬɢɦ ɡɚɡɧɚɱɟɧɿ ɦɨɥɟɤɭɥɢ ɜ ɫɜɨʀɯ ɫɬɪɭɤɬɭɪɚɯ ɦɿɫɬɹɬɶ ɞɨɧɨɪɧɿ ɬɚ ɚɤɰɟɩɬɨɪɧɿ ɝɪɭɩɢ, ɹɤɿ ɡɞɚɬɧɿ ɭɬɜɨɪɸɜɚɬɢ ɇ-ɡɜ'ɹɡɤɢ. Ɍɨɦɭ ɦɢ ɫɤɨɪɢɫɬɚɥɢɫɹ ɦɟɬɨɞɨɦ ɤɨɥɢɜɚɥɶɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɞɥɹ ɨɰɿɧɤɢ ɦɨɠɥɢɜɨɫɬɿ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɰɢɯ ɝɟɬɟɪɨɚɫɨɰɿɚɬɚɯ [223]. ɇɚ ɪɢɫ. 4.4 ɿ 4.5 ɩɪɢɜɟɞɟɧɨ ȱɑ-ɫɩɟɤɬɪɢ ɫɭɦɿɲɟɣ TPH-PRF ɿ CAF-EB, ɹɤɿ ɽ ɪɟɡɭɥɶɬɚɬɨɦ ɭɫɟɪɟɞɧɟɧɧɹ 10 ɜɢɦɿɪɸɜɚɧɶ, ɜɢɤɨɧɚɧɢɯ ɜ ɨɞɧɚɤɨɜɢɯ 110 ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɭɦɨɜɚɯ, ɿ ɫɭɦɚɪɧɿ ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ ɦɨɥɟɤɭɥ ʀɯ ɫɤɥɚɞɨɜɢɯ. D 0,20 1654 1 2 1702 Ɋɢɫɭɧɨɤ 4.4 ɫɩɟɤɬɪɢ ȱɑ- ɩɨɝɥɢɧɚɧɧɹ 0,15 ɪɨɡɱɢɧɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ 1702 1654 0,10 TPH-PRF (1) ɿ ɫɭɦɚɪɧɢɣ ɫɩɟɤɬɪ TPH+PRF (2). Ⱦɥɹ ɜɫɿɯ ɪɨɡɱɢɧɿɜ ɪɇ = 6,9÷7,0 (±0,05) 0,05 0,00 1600 1650 1700 Q, ɫɦ -1 D 0,20 1651 1 1700 Ɋɢɫɭɧɨɤ 4.5 ɫɩɟɤɬɪɢ ȱɑ- ɩɨɝɥɢɧɚɧɧɹ 0,15 ɪɨɡɱɢɧɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ 1652 1702 2 0,10 CAF-EB (1) ɿ ɫɭɦɚɪɧɢɣ ɫɩɟɤɬɪ CAF+EB (2). Ⱦɥɹ ɜɫɿɯ ɪɨɡɱɢɧɿɜ ɪɇ = 6,9÷7,0 (±0,05) 0,05 0,00 1600 1650 1700 Q, ɫɦ -1 ȼɢɞɧɨ, ɳɨ ɱɚɫɬɨɬɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ TPH (ɪɢɫ. 4.4) ɿ CAF (ɪɢɫ. 4.5) ɭ ɫɭɦɿɲɚɯ ɩɪɚɤɬɢɱɧɨ ɧɟ ɡɦɿɧɢɥɢɫɹ ɜ ɩɨɪɿɜɧɹɧɧɿ ɡɿ ɫɭɦɚɪɧɢɦɢ ɫɩɟɤɬɪɚɦɢ. Ɍɚɤɢɣ ɠɟ ɱɚɫɬɨɬɧɢɣ ɟɮɟɤɬ (ɜɿɞɫɭɬɧɿɫɬɶ ɡɫɭɜɿɜ ɩɨ ɱɚɫɬɨɬɿ) ɫɦɭɝ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ NH2-ɝɪɭɩ PRF ɿ EB ɫɩɨɫɬɟɪɿɝɚɜɫɹ ɜ ɫɩɟɤɬɪɚɯ ɄɊ (ɞɚɧɿ ɧɟ ɧɚɜɟɞɟɧɨ). Ɍɨɦɭ ɫɥɿɞ ɜɢɤɥɸɱɢɬɢ ɿɫɧɭɜɚɧɧɹ ɜ ɰɢɯ ɝɟɬɟɪɨɚɫɨɰɿɚɬɚɯ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ. ɐɟɣ ɜɢɫɧɨɜɨɤ ɭɡɝɨɞɠɭɽɬɶɫɹ ɡ ɪɟɡɭɥɶɬɚɬɚɦɢ ɚɧɚɥɿɡɭ ɞɚɧɢɯ əɆɊ [9, 88]. 111 ȼɿɞɫɭɬɧɿɫɬɶ ɡɦɿɧ ɫɩɟɤɬɪɚɥɶɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɫɭɦɿɲɚɯ TPH-PRF ɿ CAF-EB ɦɨɠɟ ɛɭɬɢ ɨɡɧɚɤɨɸ ɬɨɝɨ, ɳɨ ɜ ɰɢɯ ɭɦɨɜɚɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɢ ɧɟ ɫɮɨɪɦɭɜɚɥɢɫɹ. Ɉɞɧɚɤ, ɡɚ ɞɚɧɢɦɢ ɪɨɛɿɬ [9, 88, 232], TPH ɿ PRF, CAF ɿ EB ɭɬɜɨɪɸɸɬɶ ɝɟɬɟɪɨɚɫɨɰɿɚɬɢ. Ⱦɥɹ ɡ'ɹɫɭɜɚɧɧɹ ɦɨɠɥɢɜɨɫɬɿ ɭɬɜɨɪɟɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ TPH-PRF ɿ CAF-EB ɿ ɦɟɯɚɧɿɡɦɿɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɧɚɦɢ ɛɭɥɨ ɩɪɨɜɟɞɟɧɨ ɤɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ ɰɢɯ ɫɢɫɬɟɦ ɭ ɜɨɞɧɨɦɭ ɨɬɨɱɟɧɧɿ [224]. 4.5 Ʉɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ȼɩɥɢɜ ɦɿɠɩɥɨɳɢɧɧɢɯ ɜɡɚɽɦɨɞɿɣ, ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɬɚ ɦɨɥɟɤɭɥ ɜɨɞɢ ɧɚ ɫɬɚɛɿɥɿɡɚɰɿɸ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ȻȺɊ ɛɭɥɨ ɞɨɫɥɿɞɠɟɧɨ ɡɚ ɞɨɩɨɦɨɝɨɸ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ (Ɇɋ) ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (800 ɦɨɥɟɤɭɥ ɜɨɞɢ), ɞɨɤɥɚɞɧɢɣ ɨɩɢɫ ɹɤɨɝɨ ɧɚɞɚɧɨ ɜ ɩɿɞɪɨɡɞɿɥɿ 2.3. Ɋɟɡɭɥɶɬɚɬɢ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɜɫɿɯ ɞɨɫɥɿɞɠɟɧɢɯ ɧɚɦɢ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɧɚɜɟɞɟɧɨ ɭ ɬɚɛɥ. 4.2 [224]. Ɍɚɤɿ ɜɿɞɨɦɨɫɬɿ ɧɟɨɛɯɿɞɧɿ ɧɚɦ ɞɥɹ ɨɛʉɪɭɧɬɭɜɚɧɧɹ ɚɞɟɤɜɚɬɧɨɫɬɿ ɞɚɧɢɯ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ, ɹɤɿ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶɫɹ ɩɪɢ ɩɨɛɭɞɨɜɿ ɦɨɥɟɤɭɥɹɪɧɢɯ ɦɨɞɟɥɟɣ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɬɚ ɨɩɢɫɿ ɦɟɯɚɧɿɡɦɿɜ ʀɯ ɫɬɚɛɿɥɿɡɚɰɿʀ. Ɋɟɡɭɥɶɬɚɬɢ ɦɟɬɨɞɭ Ɇɋ ɜɤɥɸɱɚɸɬɶ ɭ ɫɟɛɟ ɟɧɟɪɝɟɬɢɱɧɿ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ (ɧɚɜɟɞɟɧɿ ɜ ɤɤɚɥ/ɦɨɥɶ): Etotal – ɩɨɜɧɚ ɩɨɬɟɧɰɿɣɧɚ ɟɧɟɪɝɿɹ ɫɢɫɬɟɦ; EMEAN – ɫɟɪɟɞɧɽ ɡɧɚɱɟɧɧɹ ɡɚɝɚɥɶɧɨʀ ɩɨɬɟɧɰɿɣɧɨʀ ɟɧɟɪɝɿʀ ɫɢɫɬɟɦ; EWW-MEAN – ɫɟɪɟɞɧɽ ɡɧɚɱɟɧɧɹ ɩɨɬɟɧɰɿɣɧɨʀ ɟɧɟɪɝɿʀ ɜɨɞɚ-ɜɨɞɚ (ɧɚ ɨɞɧɭ ɦɨɥɟɤɭɥɭ ɜɨɞɢ); EW-BAC-MEAN – ɫɟɪɟɞɧɽ ɡɧɚɱɟɧɧɹ ɩɨɬɟɧɰɿɣɧɨʀ ɟɧɟɪɝɿʀ ɜɨɞɚ-Ʌɿɝɚɧɞ; EL1-L2 – ɫɟɪɟɞɧɽ ɡɧɚɱɟɧɧɹ ɩɨɬɟɧɰɿɣɧɨʀ ɟɧɟɪɝɿʀ Ʌɿɝɚɧɞ1-Ʌɿɝɚɧɞ2 ɭ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿ; N, H2O – ɤɿɥɶɤɿɫɬɶ ɇɩɨɜ'ɹɡɚɧɢɯ ɦɨɥɟɤɭɥ ɜɨɞɢ ɜ ɤɥɚɫɬɟɪɚɯ, ɨɛɪɚɧɢɯ ɞɥɹ ɦɨɞɟɥɸɜɚɧɧɹ F-ɫɬɪɭɤɬɭɪ (1-2u103 ɟɥɟɦɟɧɬɚɪɧɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ ɩɪɢ 5 Ʉ). 112 Ɍɚɛɥɢɰɹ 4.2 Ɋɟɡɭɥɶɬɚɬɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɫɢɫɬɟɦ «ɝɟɬɟɪɨɞɢɦɟɪ + 800 ɇ2Ɉ» ɬɚ ʀɯ F-ɫɬɪɭɤɬɭɪ; ɭɫɿ ɡɧɚɱɟɧɧɹ ɟɧɟɪɝɿɣ ɧɚɜɨɞɹɬɶɫɹ ɭ ɤɤɚɥ/ɦɨɥɶ 800 ɦɨɥɟɤɭɥ ɜɨɞɢ ɝɟɬɟɪɨɞɢɦɟɪ EMEAN -9,2821 r0,0043 Etotal EWWMEAN F-ɫɬɪɭɤɬɭɪɚ EWBAC-MEAN N, H2O 113 EW-BAC, EL1-L2 EW-FMN = -811,48 EW-TɊɇ = -72,27 EFMN-TɊɇ = -10,08 EW-EB = -38,52 EW-TPH = -57,00 EEB-TPH = -2,78 EW-EB = -174,30 EW-TPH = -113,18 EEB-TPH = -2,74 EW-TPH = -53,76 EW-PRF = -59,81 ETPH-PRF = -7,73 EW-TPH = -92,62 EW-PRF = -113,34 ETPH-PRF = -7,73 EW-CAF = -46,11 ȿW-EB = -40,73 ECAF-EB = -10,41 ȿW-CAF = -91,45 ȿW-EB = -138,38 ECAF-EB = -10,43 EW-FMN = -903,72 EW-EB = -97,83 EFMN-EB = -85,75 EW-FMN = -553,48 EW-PRF = -96,53 EFMN-PRF = -73,09 FMN-TPH -7383,85 -8,06 EW-TɇɊ = -69,24 EW-FMN = -894,22 EFMN-TɊɇ = -11,13 TPH-EB -8,6897 r0,0049 -6951,76 -8,36 EW-TPH = -107,52 EW-EB = -160,26 ETPH-EB = -4,24 14 98 TPH-PRF -8,6968 r0,005 -7046,94 -8,36 EW-TPH = -108,51 EW-PRF = -137,17 ETPH-PRF = -8,56 13 46 EB-CAF -8,7007 r0,0059 -6979,32 -8,39 ȿW-CAF = -91,23 ȿW-EB = -144,88 ECAF-EB = -10,95 13 79 FMN-EB -9,4182 r0,0048 -9,1704 r0,0036 -7534,56 -7,97 EW-FMN = -988,92 EW-EB = -113,72 EFMN-EB = -91,59 EW-FMN = -604,77 EW-PRF = -108,42 E FMN-PRF = -75,78 106 FMN-PRF -7336,32 -8,24 84 əɤ ɜɢɞɧɨ ɡ ɬɚɛɥ. 4.2, ɜɫɿ ɫɢɫɬɟɦɢ «ɝɟɬɟɪɨɞɢɦɟɪ + 800 ɇ2Ɉ» ɽ ɟɧɟɪɝɟɬɢɱɧɨ ɜɢɝɿɞɧɢɦɢ ɬɚ ɫɬɚɛɿɥɶɧɢɦɢ (ɡɧɚɱɟɧɧɹ EMEAN ɿ Etotal , ɬɚɛɥ. 4.2). ɋɬɪɭɤɬɭɪɚ ɜɨɞɧɨɝɨ ɤɥɚɫɬɟɪɭ ɡɛɟɪɿɝɚɽɬɶɫɹ (ɡɧɚɱɟɧɧɹ EWW-MEAN , ɬɚɛɥ. 4.2), 113 ɨɫɤɿɥɶɤɢ ɭ «ɱɢɫɬɨɦɭ» ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ ɞɥɹ ɦɨɞɟɥɿ ɦɨɥɟɤɭɥɢ ɜɨɞɢ Ɇɚɥɟɧɤɨɜɚ ɬɚ ɚɬɨɦ-ɚɬɨɦɧɢɯ ɩɨɬɟɧɰɿɣɧɢɯ ɮɭɧɤɰɿɣ Ɇɚɥɟɧɤɨɜɚ-ɉɨɥɬɽɜɚ, ɹɤɿ ɜɢɤɨɪɢɫɬɨɜɭɸɬɶɫɹ ɜ ɪɨɡɪɚɯɭɧɤɚɯ, ɡɧɚɱɟɧɧɹ ɟɧɟɪɝɿʀ ɜɡɚɽɦɨɞɿʀ ɩɨɪɹɞɤɭ -8,50 y -8,60 ɤɤɚɥ/ɦɨɥɶ. ȿɤɫɩɟɪɢɦɟɧɬɚɥɶɧɟ ɡɧɚɱɟɧɧɹ ɟɧɟɪɝɿʀ ɜɡɚɽɦɨɞɿʀ ɜɨɞɚɜɨɞɚ ɩɨɪɹɞɤɭ -9,90 ɤɤɚɥ/ɦɨɥɶ [233]. Ɍɚɤɨɠ ɦɨɠɧɚ ɩɨɪɿɜɧɹɬɢ ɟɧɟɪɝɿɸ ɜɡɚɽɦɨɞɿʀ Ʌɿɝɚɧɞ-Ʌɿɝɚɧɞ, ɨɬɪɢɦɚɧɭ ɞɥɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ (EL1-L2 , ɬɚɛɥ. 4.2) ɡ ɞɚɧɢɦɢ ɩɪɨ ɜɤɥɚɞɢ ɟɥɟɤɬɪɨɫɬɚɬɢɱɧɢɯ Eel-st ɿ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɢɯ Evdw ɜɡɚɽɦɨɞɿɣ, ɨɬɪɢɦɚɧɢɯ ɡ ɪɟɡɭɥɶɬɚɬɿɜ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ ɦɨɥɟɤɭɥɹɪɧɨʀ ɞɢɧɚɦɿɤɢ [234-236]. Ɂɧɚɱɟɧɧɹ ɟɧɟɪɝɿɣ ɬɚɤɢɯ ɜɡɚɽɦɨɞɿɣ Eel-st + Evdw ɞɥɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ FMN-EB ɿ FMN-PRF ɫɬɚɧɨɜɢɥɢ -39,8 ɤɤɚɥ/ɦɨɥɶ ɿ -28,9 ɤɤɚɥ/ɦɨɥɶ, ɜɿɞɩɨɜɿɞɧɨ. Ɇɿɠ ɰɢɦɢ ɡɧɚɱɟɧɧɹɦɢ Eel-st + Evdw ɿ ɞɚɧɢɦɢ ɬɚɛɥ. 4.2 (EL1-L2) ɧɟɦɚɽ ɩɪɹɦɨʀ ɜɿɞɩɨɜɿɞɧɨɫɬɿ, ɚɥɟ ɫɩɨɫɬɟɪɿɝɚɽɬɶɫɹ ɡɚɝɚɥɶɧɚ ɬɟɧɞɟɧɰɿɹ ɡɦɿɧɢ ɰɢɯ ɜɟɥɢɱɢɧ, ɨɬɪɢɦɚɧɢɯ ɞɜɨɦɚ ɪɿɡɧɢɦɢ ɦɟɬɨɞɚɦɢ. Ɉɛɢɞɜɿ ɫɟɪɿʀ ɞɚɧɢɯ ɞɨɡɜɨɥɹɸɬɶ ɩɪɢɩɭɫɬɢɬɢ ɧɚɫɬɭɩɧɭ ɩɨɫɥɿɞɨɜɧɿɫɬɶ ɡɦɟɧɲɟɧɧɹ ɟɧɟɪɝɿʀ ɜ ɝɟɬɟɪɨɞɢɦɟɪɚɯ: FMN-EB > FMN-PRF. Ⱦɥɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ TPH-EB, FMN-TPH, TPH-PRF ɞɚɧɿ ɞɥɹ ɟɧɟɪɝɿɣ ɟɥɟɤɬɪɨɫɬɚɬɢɱɧɢɯ, ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɢɯ ɿ ɝɿɞɪɨɮɨɛɧɢɯ ɜɡɚɽɦɨɞɿɣ ɭ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɠɟɪɟɥɚɯ ɜɿɞɫɭɬɧɿ. Ɉɬɪɢɦɚɧɿ ɪɟɡɭɥɶɬɚɬɢ ɞɥɹ ɟɧɟɪɝɿɣ ɜɡɚɽɦɨɞɿʀ EL1-L2 ɦɨɠɧɚ ɩɨɪɿɜɧɹɬɢ ɬɿɥɶɤɢ ɡ ɤɨɧɫɬɚɧɬɚɦɢ ɬɚ ɟɧɬɚɥɶɩɿɹɦɢ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ, ɨɞɟɪɠɚɧɢɦɢ ɡ əɆɊ ɟɤɫɩɟɪɢɦɟɧɬɿɜ [11, 88]. Ʉɨɧɫɬɚɧɬɢ ɚɫɨɰɿɚɰɿʀ ɞɨɪɿɜɧɸɸɬɶ 102 M-1, 180 M-1 ɿ 180 M-1, ɚ ɟɧɬɚɥɶɩɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ -5,98 ɤɚɥ/ɦɨɥɶ, -8,01 ɤɚɥ/ɦɨɥɶ ɿ -8,21 ɤɚɥ/ɦɨɥɶ ɞɥɹ TPH-EB, FMN-TPH ɿ TPH-PRF, ɜɿɞɩɨɜɿɞɧɨ. ɍ ɰɶɨɦɭ ɜɢɩɚɞɤɭ ɦɨɠɧɚ ɝɨɜɨɪɢɬɢ ɬɿɥɶɤɢ ɩɪɨ ɡɚɝɚɥɶɧɭ ɬɟɧɞɟɧɰɿɸ: ɫɩɨɪɿɞɧɟɧɿɫɬɶ TPH ɞɨ FMN ɿ ɞɨ PRF ɽ ɫɚɦɟ ɬɚɤɨɸ ɚɛɨ ɛɿɥɶɲɨɸ, ɧɿɠ ʀɯ ɫɩɨɪɿɞɧɟɧɿɫɬɶ ɞɨ EB, ɳɨ ɭɡɝɨɞɠɭɽɬɶɫɹ ɡ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɦɢ ɞɚɧɢɦɢ ɪɨɛɨɬɢ [88] ɿ ɧɚɲɢɦɢ ɪɟɡɭɥɶɬɚɬɚɦɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ [224]. 114 Ɍɚɛɥɢɰɹ 4.3 Ƚɿɞɪɨɮɨɛɧɿ ɜɡɚɽɦɨɞɿʀ ɜ ɫɢɫɬɟɦɿ ɝɟɬɟɪɨɞɢɦɟɪ + ɇ2Ɉ ɡɚ ɞɚɧɢɦɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ; ɩɨɱɚɬɤɨɜɿ ɫɬɪɭɤɬɭɪɢ ɝɟɬɟɪɨɞɢɦɟɪɿɜ ɜɡɹɬɿ ɡ əɆɊ ɞɚɧɢɯ (əɆɊ); «MC, ɜɨɞɚ» ɜɿɞɩɨɜɿɞɚɽ ɫɬɪɭɤɬɭɪɚɦ ɝɟɬɟɪɨɞɢɦɟɪɿɜ, ɨɬɪɢɦɚɧɢɯ ɦɨɞɟɥɸɜɚɧɧɹɦ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ ɡ 800 H2O; «MC, F-ɫɬɪ» ɜɿɞɩɨɜɿɞɚɽ ɫɬɪɭɤɬɭɪɚɦ ɝɟɬɟɪɨɞɢɦɟɪɿɜ, ɨɬɪɢɦɚɧɢɯ ɦɨɞɟɥɸɜɚɧɧɹɦ ɦɟɬɨɞɨɦ Ɇɋ F-ɫɬɪɭɤɬɭɪ; ɭ ɞɭɠɤɚɯ ɧɚɜɟɞɟɧɿ 'SȺSA ɿ Ehyd, ɨɬɪɢɦɚɧɿ ɦɟɬɨɞɨɦ ɦɨɥɟɤɭɥɹɪɧɨʀ ɞɢɧɚɦɿɤɢ [240] ɝɟɬɟɪɨɞɢɦɟɪ FMN-TPH (əɆɊ) FMN-TPH (MC, ɜɨɞɚ) FMN-TPH (MC, F-ɫɬɪ) TPH-EB (MC, ɜɚɤ)* TPH-EB (MC, ɜɨɞɚ) TPH-EB (MC, F-ɫɬɪ) TPH-PRF (əɆɊ) TPH-PRF (MC, ɜɨɞɚ) TPH-PRF (F-ɫɬɪ) EB-CAF (əɆɊ) EB-CAF (MC, ɜɨɞɚ) EB-CAF (MC, F-ɫɬɪ) FMN-EB (əɆɊ) FMN-EB (MC, ɜɨɞɚ) FMN-EB (MC, F-ɫɬɪ) FMN-PRF (əɆɊ) FMN- PRF (MC, ɜɨɞɚ) FMN- PRF (MC, F-ɫɬɪ) 'SȺSA, Å2 224,92 205,79 190,14 217,16 161,77 132,23 199,39 182,18 183,27 237,06 245,39 246,4 (258) 353,44 282,45 313,5 (308) 244,88 230,52 251,94 (252) Ehyd, ɤɤɚɥ/ɦɨɥɶ -11,3 -10,3 -9,5 -10,9 -8,1 -6,6 -9,9 -9,1 -9,2 -11,9 -12,3 -12,3 (-12,9) -17,7 -14,1 -15,7 (-15,4) -12,2 -11,5 -12,6 (-12,6) * – ɩɨɱɚɬɤɨɜɭ ɫɬɪɭɤɬɭɪɭ ɨɬɪɢɦɚɧɨ ɩɪɢ ɨɩɬɢɦɿɡɚɰɿʀ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɚɤɭɭɦɿ Ɍɚɤɨɠ ɛɭɥɨ ɪɨɡɪɚɯɨɜɚɧɨ ɟɧɟɪɝɿɸ ɝɿɞɪɨɮɨɛɧɢɯ ɜɡɚɽɦɨɞɿɣ ɚɫɨɰɿɚɬɿɜ, ɳɨ ɭɬɜɨɪɸɸɬɶɫɹ, ɡɚ ɞɨɩɨɦɨɝɨɸ ɦɟɬɨɞɭ, ɡɚɫɧɨɜɚɧɨɝɨ ɧɚ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɜɫɬɚɧɨɜɥɟɧɿɣ ɥɿɧɿɣɧɿɣ ɡɚɥɟɠɧɨɫɬɿ ɦɿɠ ɟɧɟɪɝɿɽɸ ɪɨɡɱɢɧɟɧɧɹ ɝɿɞɪɨɮɨɛɧɢɯ ɚɦɿɧɨɤɢɫɥɨɬ ɿ ɩɪɨɫɬɢɯ ɜɭɝɥɟɜɨɞɧɿɜ ɬɚ ɡɦɿɧɢ ɩɥɨɳɿ ɩɨɜɟɪɯɧɿ, ɹɤɚ ɞɨɫɬɭɩɧɚ ɪɨɡɱɢɧɧɢɤɭ (Solvent Ⱥccessible Surface Ⱥrea, SASA): ¨ȿhyd = Ȗ¨SASA [237, 115 238]. Ɂɦɟɧɲɟɧɧɹ SASA ɧɚ 1 Å2 ɡɦɿɧɸɽ ɝɿɞɪɨɮɨɛɧɿ ɜɡɚɽɦɨɞɿʀ ɧɚ Ȗ ~ 50 ɤɚɥ/ɦɨɥɶ [239]. SASA ɜɢɡɧɚɱɚɽɬɶɫɹ ɡɚ ɞɨɩɨɦɨɝɨɸ «ɨɛɤɚɬɭɜɚɧɧɹ» ɩɨɜɟɪɯɧɿ ɦɨɥɟɤɭɥɢ ɩɪɨɛɧɨɸ ɤɭɥɟɸ ɡ ɪɚɞɿɭɫɨɦ 1,4 Å. Ɋɨɡɪɚɯɭɧɨɤ ɡɦɿɧɢ SASA ɩɿɫɥɹ ɚɫɨɰɿɚɰɿʀ ɜɢɡɧɚɱɚɥɢ ɹɤ ¨SASA = (SASAL1 + SASAL2) – SASAh, ɞɟ SASAL1 ɿ SASAL2 – ɰɟ SASA ɦɨɧɨɦɟɪɿɜ, SASAh – ɰɟ SASA ɝɟɬɟɪɨɞɢɦɟɪɿɜ, ɜɿɞɩɨɜɿɞɧɨ. Ɂɧɚɱɟɧɧɹ 'SASA (Å2) ɿ Ehyd (ɤɤɚɥ/ɦɨɥɶ) ɧɚɜɟɞɟɧɿ ɭ ɬɚɛɥ. 4.3. ɐɿ ɪɟɡɭɥɶɬɚɬɢ ɞɨɡɜɨɥɹɸɬɶ ɡɪɨɛɢɬɢ ɜɢɫɧɨɜɨɤ ɩɪɨ ɡɧɚɱɧɭ ɪɨɥɶ ɝɿɞɪɨɮɨɛɧɢɯ ɜɡɚɽɦɨɞɿɣ ɭ ɫɬɚɛɿɥɿɡɚɰɿʀ ɜɫɿɯ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ɝɟɬɟɪɨɞɢɦɟɪɿɜ. Ɉɬɪɢɦɚɧɿ ɞɚɧɿ ɭɡɝɨɞɠɭɸɬɶɫɹ ɡ ɪɟɡɭɥɶɬɚɬɚɦɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ ɦɨɥɟɤɭɥɹɪɧɨʀ ɞɢɧɚɦɿɤɢ ɝɟɬɟɪɨɞɢɦɟɪɿɜ FMN-EB, FMN-PRF ɿ CAF-EB [240]. Ɍɚɤɢɦ ɱɢɧɨɦ, ɚɧɚɥɿɡ ɟɧɟɪɝɟɬɢɱɧɢɯ ɯɚɪɚɤɬɟɪɢɫɬɢɤ ɜɫɿɯ ɜɢɜɱɟɧɢɯ ɫɢɫɬɟɦ ɝɟɬɟɪɨɞɢɦɟɪ-ɜɨɞɚ ɞɨɡɜɨɥɹɽ ɡɪɨɛɢɬɢ ɜɢɫɧɨɜɨɤ, ɳɨ ɪɟɡɭɥɶɬɚɬɢ, ɨɬɪɢɦɚɧɿ ɡɚ ɞɨɩɨɦɨɝɨɸ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ, ɽ ɤɨɪɟɤɬɧɢɦɢ, ɿ ɰɟɣ ɦɟɬɨɞ ɦɨɠɟ ɜɢɤɨɪɢɫɬɨɜɭɜɚɬɢɫɹ ɩɪɢ ɚɧɚɥɿɡɿ ɫɬɪɭɤɬɭɪ ɝɟɬɟɪɨɞɢɦɟɪɿɜ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ ɬɚ ɞɥɹ ɩɨɛɭɞɨɜɢ ʀɯ ɦɨɥɟɤɭɥɹɪɧɢɯ ɦɨɞɟɥɟɣ. Ⱦɚɥɿ ɪɨɡɝɥɹɧɭɬɨ ɛɿɥɶɲ ɞɨɤɥɚɞɧɨ ɪɟɡɭɥɶɬɚɬɢ Ɇɋ ɦɨɞɟɥɸɜɚɧɧɹ ɝɟɬɟɪɨɞɢɦɟɪɿɜ FMN-TPH, TPH-EB, TPH-PRF ɿ CAF-EB. Ɋɟɡɭɥɶɬɚɬɢ ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɨɝɨ ɞɨɫɥɿɞɠɟɧɧɹ ɿ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɫɢɫɬɟɦ FMN-EB ɿ FMN-PRF ɛɭɞɭɬɶ ɜɢɤɥɚɞɟɧɿ ɜ Ɋɨɡɞɿɥɿ 5. 4.5.1 Ƚɟɬɟɪɨɞɢɦɟɪ FMN-TPH Ɂɝɿɞɧɨ ɡ ɞɚɧɢɦɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɫɬɪɭɤɬɭɪɚ FMN-TPH ɜɿɞɪɿɡɧɹɽɬɶɫɹ ɜɿɞ ɫɬɪɭɤɬɭɪɢ, ɳɨ ɫɩɨɫɬɟɪɿɝɚɥɚɫɹ ɡɚ ɞɨɩɨɦɨɝɨɸ əɆɊ ɚɛɨ ɛɭɥɚ ɨɬɪɢɦɚɧɚ ɡɚ ɞɨɩɨɦɨɝɨɸ ɨɩɬɢɦɿɡɚɰɿʀ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɚɤɭɭɦɿ (ɪɢɫ. 4.6): ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɧɟ ɜɢɹɜɥɟɧɨ ɧɿ ɜ ɨɞɧɿɣ ɡɿ ɫɬɪɭɤɬɭɪ FMN-TPH. 116 (a) (ɛ) (ɜ) Ɋɢɫɭɧɨɤ 4.6 Ʉɨɧɮɿɝɭɪɚɰɿɹ ɝɟɬɟɪɨɞɢɦɟɪɭ FMN-TPH: (a) ɩɨɱɚɬɤɨɜɚ ɫɬɪɭɤɬɭɪɚ (əɆɊ ɞɚɧɿ), EFMN-TPH = -17,1 ɤɤɚɥ/ɦɨɥɶ; (ɛ) ɨɩɬɢɦɿɡɚɰɿɹ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɚɤɭɭɦɿ, EFMN-TPH = -12,8 ɤɤɚɥ/ɦɨɥɶ; (ɜ) ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɨɞɿ (800 H2O): EFMN-TPH = -10,2 ɤɤɚɥ/ɦɨɥɶ Ɂɚ ɪɟɡɭɥɶɬɚɬɚɦɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɜɢɡɧɚɱɟɧɨ ɤɨɨɪɞɢɧɚɬɢ ɚɬɨɦɿɜ ɞɢɦɟɪɧɨɝɨ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-TPH. əɤ ɿ ɜ ɪɚɡɿ ɜɢɡɧɚɱɟɧɧɹ ɤɨɨɪɞɢɧɚɬ ɡ ɞɚɧɢɯ əɆɊ (ɞɢɜ. ɩɿɞɪɨɡɞɿɥ 4.2.2), ɜɢɡɧɚɱɚɥɢ ɝɟɨɦɟɬɪɢɱɧɢɣ ɮɚɤɬɨɪ G ɿ ɜɿɞɫɬɚɧɶ R ɡɚ ɮɨɪɦɭɥɨɸ (4.10) ɦɿɠ ɦɨɦɟɧɬɚɦɢ ɩɟɪɟɯɨɞɿɜ ɧɚ ɡɜ'ɹɡɤɚɯ ɋ2=Ɉ (FMN) ɿ ɋ6=Ɉ (TPH) ɿ ɦɿɠ ɦɨɦɟɧɬɚɦɢ ɩɟɪɟɯɨɞɿɜ ɧɚ ɡɜ'ɹɡɤɚɯ ɋ4=Ɉ (FMN) ɿ ɋ2=Ɉ (TPH). ȼɿɞɫɬɚɧɿ R ɞɥɹ ɝɟɬɟɪɨɞɢɦɟɪɚ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (ɹɤ ɿ ɞɥɹ ɨɩɬɢɦɿɡɨɜɚɧɨʀ ɭ ɜɚɤɭɭɦɿ ɣɨɝɨ ɫɬɪɭɤɬɭɪɢ) ɜɢɹɜɢɥɢɫɹ ɛɥɢɡɶɤɨ 9 Å. Ɍɨɦɭ ɦɨɠɧɚ ɡɪɨɛɢɬɢ ɜɢɫɧɨɜɨɤ, ɳɨ ɞɥɹ ɞɢɦɟɪɧɨʀ ɮɨɪɦɢ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-TPH, ɨɬɪɢɦɚɧɨɝɨ ɡ ɪɟɡɭɥɶɬɚɬɿɜ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ, ɦɨɦɟɧɬɢ ɩɟɪɟɯɨɞɿɜ ɰɢɯ ɝɪɭɩ ɚɬɨɦɿɜ ɭ ɞɢɦɟɪɿ ɩɪɚɤɬɢɱɧɨ ɧɟ ɜɡɚɽɦɨɞɿɸɬɶ. ȼɢɤɨɪɢɫɬɨɜɭɸɱɢ ɞɚɧɿ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ, ɛɭɥɨ ɜɢɡɧɚɱɟɧɨ ɤɿɥɶɤɿɫɬɶ ɦɨɥɟɤɭɥ ɜɨɞɢ, ɹɤɿ ɭɬɜɨɪɸɸɬɶ ɇ-ɡɜ'ɹɡɤɢ ɡ FMN ɿ/ɚɛɨ TPH ɡɝɿɞɧɨ ɡ ɟɧɟɪɝɟɬɢɱɧɢɦɢ ɿ ɝɟɨɦɟɬɪɢɱɧɢɦɢ ɤɪɢɬɟɪɿɹɦɢ (113 ɦɨɥɟɤɭɥ ɜɨɞɢ). 117 ɉɨɬɿɦ ɛɭɥɨ ɫɮɨɪɦɨɜɚɧɨ ɫɢɫɬɟɦɭ FMN-TPH + 113 ɇ2Ɉ ɿ ɜɢɤɨɧɚɧɨ ʀʀ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɞɥɹ ɨɬɪɢɦɚɧɧɹ F-ɫɬɪɭɤɬɭɪɢ. Ɇɢɬɬɽɜɿ ɤɨɧɮɿɝɭɪɚɰɿʀ ɝɟɬɟɪɨɞɢɦɟɪɭ FMN-TPH ɩɪɢɜɟɞɟɧɨ ɧɚ ɪɢɫ. 4.7 ɿ 4.8. Ɋɢɫɭɧɨɤ 4.7 Ɇɢɬɬɽɜɚ ɤɨɧɮɿɝɭɪɚɰɿɹ ɝɟɬɟɪɨɞɢɦɟɪɭ FMNTPH ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (Fɫɬɪɭɤɬɭɪɚ): FMN-TPH + 113 H2O, EFMN-TɊɇ = -10,08 ɤɤɚɥ/ɦɨɥɶ; ɇɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ (a) (ɛ ) Ɋɢɫɭɧɨɤ 4.8 Ɇɢɬɬɽɜɿ ɤɨɧɮɿɝɭɪɚɰɿʀ F-ɫɬɪɭɤɬɭɪɢ ɝɟɬɟɪɨɞɢɦɟɪɭ FMNTPH; ɫɩɨɫɬɟɪɿɝɚɸɬɶɫɹ ɞɜɚ ɜɨɞɧɢɯ ɦɿɫɬɤɢ ɦɿɠ: (a) PO ɝɪɭɩɨɸ FMN ɿ C9=O12 ɝɪɭɩɨɸ TPH; (ɛ) C24=O25 ɝɪɭɩɨɸ «ɯɜɨɫɬɚ» FMN ɿ N1H21 ɝɪɭɩɨɸ TPH. ɇ-ɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ Ⱥɧɚɥɿɡ ɦɢɬɬɽɜɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ ɡ 800 ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ, ɚ ɬɚɤɨɠ ɦɢɬɬɽɜɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ F-ɫɬɪɭɤɬɭɪ, ɞɨɡɜɨɥɢɜ ɜɫɬɚɧɨɜɢɬɢ ɞɜɚ ɜɨɞɧɢɯ ɦɿɫɬɤɢ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɞɢɦɟɪɭ FMN-TPH. ɉɟɪɲɢɣ ɪɨɡɬɚɲɨɜɭɽɬɶɫɹ ɦɿɠ PO ɚɤɰɟɩɬɨɪɧɨɸ ɝɪɭɩɨɸ FMN ɿ ɋ9=Ɉ12 (ɝɪɭɩɚ ɋ6=Ɉ ɜ ɟɤɫɩɟɪɢɦɟɧɬɿ) ɚɤɰɟɩɬɨɪɧɨɸ ɝɪɭɩɨɸ TPH (6 ɦɨɥɟɤɭɥ ɜɨɞɢ, ɪɢɫ. 4.8 ɚ), ɚ ɞɪɭɝɢɣ – ɦɿɠ ɋ24=O25 ɚɤɰɟɩɬɨɪɧɨɸ ɝɪɭɩɨɸ «ɯɜɨɫɬɚ» FMN ɿ N1H21 (ɝɪɭɩɚ N7–H ɜ ɟɤɫɩɟɪɢɦɟɧɬɿ) ɞɨɧɨɪɧɨɸ ɝɪɭɩɨɸ TPH (3 ɦɨɥɟɤɭɥɢ 118 ɜɨɞɢ, ɪɢɫ. 4.8 ɛ). Ⱦɥɹ ɪɟɡɭɥɶɬɚɬɿɜ Ɇɋ ɦɨɞɟɥɸɜɚɧɧɹ ɧɭɦɟɪɚɰɿɹ ɚɬɨɦɿɜ ɬɚ ɡɚɪɹɞɢ ɧɚ ɚɬɨɦɚɯ ɜɿɞɩɨɜɿɞɧɢɯ ɥɿɝɚɧɞɿɜ ɰɶɨɝɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ ɩɪɢɜɟɞɟɧɨ ɭ ɞɨɞɚɬɤɭ ȼ, ɪɢɫ. ȼ.1 ɿ ȼ.2, ɬɚɛɥ. ȼ.1 ɿ ȼ.2. Ɉɞɧɚɤ, ɧɟɨɛɯɿɞɧɨ ɜɿɞɡɧɚɱɢɬɢ, ɳɨ ɡɝɿɞɧɨ ɡ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɦɢ ɞɚɧɢɦɢ, ɛɿɥɶɲ ɜɿɪɨɝɿɞɧɨɸ ɮɨɪɦɨɸ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-TPH ɽ n-ɦɨɥɟɤɭɥɹɪɧɢɣ ɚɝɪɟɝɚɬ FMN-TPH ɡɚ ɬɢɩɨɦ ʌ-ɫɬɟɤɿɧɝɭ. Ɉɬɪɢɦɚɧɿ ɧɚɦɢ ɞɚɧɿ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɜɤɚɡɭɸɬɶ ɧɚ ɬɟ, ɳɨ ɫɬɪɭɤɬɭɪɢ ɝɟɬɟɪɨɞɢɦɟɪɿɜ ɫɬɚɛɿɥɿɡɭɸɬɶɫɹ ɹɤ ɜɡɚɽɦɨɞɿɹɦɢ ɦɿɠ ɦɨɥɟɤɭɥɚɦɢ FMN ɿ TPH ɭ ɫɬɨɩɰɿ (ɟɧɟɪɝɿʀ ɜɡɚɽɦɨɞɿʀ ɭ ɜɚɤɭɭɦɿ EFMN-TPH = -12,8 ɤɤɚɥ/ɦɨɥɶ ɬɚ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ EFMN-TPH = -10,20 ɤɤɚɥ/ɦɨɥɶ), ɬɚɤ ɿ ɜɨɞɧɢɦɢ ɦɿɫɬɤɚɦɢ [224]. Ɉɞɧɚɤ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɢɯ ɦɿɫɬɤɿɜ ɦɿɠ ɦɨɥɟɤɭɥɚɦɢ ɜ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿ ɧɟ ɩɿɞɬɜɟɪɞɠɭɽɬɶɫɹ ɧɚɲɢɦɢ ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɢɦɢ ɞɚɧɢɦɢ [223], ɨɫɤɿɥɶɤɢ ɜ ȱɑɫɩɟɤɬɪɚɯ ɧɟ ɡɚɮɿɤɫɨɜɚɧɨ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɯ ɡɫɭɜɿɜ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɞɨɧɨɪɧɨɚɤɰɟɩɬɨɪɧɢɯ ɝɪɭɩ, ɹɤɿ ɡɚɡɜɢɱɚɣ ɩɨɜ'ɹɡɭɸɬɶ ɡ ɝɿɞɪɚɬɚɰɿɽɸ ɜɿɞɩɨɜɿɞɧɢɯ ɝɿɞɪɚɬɧɨ-ɚɤɬɢɜɧɢɯ ɰɟɧɬɪɿɜ. ɇɟɨɛɯɿɞɧɨ ɜ ɩɨɞɚɥɶɲɨɦɭ ɜɢɤɨɧɚɬɢ ɤɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ n-ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɚɝɪɟɝɚɬɭ FMN-TPH ɦɟɬɨɞɨɦ ɦɨɥɟɤɭɥɹɪɧɨʀ ɞɢɧɚɦɿɤɢ. 4.5.2 Ƚɟɬɟɪɨɞɢɦɟɪ TPH-EB ɉɪɢ ɩɟɪɟɯɨɞɿ ɡ ɜɚɤɭɭɦɭ ɞɨ ɜɨɞɧɨɝɨ ɤɥɚɫɬɟɪɭ ɝɟɬɟɪɨɚɫɨɰɿɚɬ TPH-EB ɩɪɚɤɬɢɱɧɨ «ɪɨɡɜɚɥɢɜɫɹ» (ɪɢɫ. 4.9 ɚ): ɟɧɟɪɝɿɹ ɜɡɚɽɦɨɞɿʀ ɝɟɬɪɨɚɫɫɨɰɿɚɬɭ TPH-EB ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ ɡɦɟɧɲɢɥɚɫɹ ɩɪɢɛɥɢɡɧɨ ɜ ɱɨɬɢɪɢ ɪɚɡɢ ɜ ɩɨɪɿɜɧɹɧɧɿ ɡ ʀʀ ɡɧɚɱɟɧɧɹɦ ɭ ɜɚɤɭɭɦɿ, ɚ ɯɪɨɦɨɮɨɪɢ ɞɜɨɯ ɥɿɝɚɧɞɿɜ ɜɢɹɜɢɥɢɫɹ ɪɨɡɬɚɲɨɜɚɧɢɦɢ ɩɿɞ ɡɧɚɱɧɢɦ ɤɭɬɨɦ (ɪɢɫ. 4.9 ɛ). Ɉɪɿɽɧɬɚɰɿɹ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɯ ɝɪɭɩ (C=O ɿ NH2) ɨɛɨɯ ɥɿɝɚɧɞɿɜ ɜɢɹɜɢɥɚɫɹ ɬɚɤɨɸ, ɳɨ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇɡɜ'ɹɡɤɿɜ ɦɿɠ ɧɢɦɢ ɧɟɦɨɠɥɢɜɟ. 119 (a) ( ɛ) Ɋɢɫɭɧɨɤ 4.9 Ʉɨɧɮɿɝɭɪɚɰɿɹ ɝɟɬɟɪɨɞɢɦɟɪɭ TPH-EB: (ɚ) ɭ ɜɚɤɭɭɦɿ, ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ, ETPH-EB = -11,62 ɤɤɚɥ/ɦɨɥɶ; (ɛ) ɝɟɬɟɪɨɞɢɦɟɪ TPHEB ɿ ɧɚɣɛɥɢɠɱɿ 98 H2O, ETPH-EB = -2,74 ɤɤɚɥ/ɦɨɥɶ. ɇ-ɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ ɋɥɿɞ ɡɚɡɧɚɱɢɬɢ, ɳɨ ɡɝɿɞɧɨ ɡ əɆɊ ɞɚɧɢɦɢ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɣ ɇ-ɡɜ'ɹɡɨɤ ɭ ɝɟɬɟɪɨɞɢɦɟɪɿ TPH-EB ɧɟ ɭɬɜɨɪɸɽɬɶɫɹ. Ɂɧɚɱɟɧɧɹ ɤɨɧɫɬɚɧɬɢ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ TPH-EB (102 Ɇ-1) ɡɚɣɦɚɽ ɩɪɨɦɿɠɧɟ ɡɧɚɱɟɧɧɹ ɦɿɠ ɤɨɧɫɬɚɧɬɚɦɢ ɫɚɦɨɚɫɨɰɿɚɰɿʀ EB ɿ TPH (Ʉȿȼ-ȿȼ = 305 M-1, ɄɌɊɇ-ɌɊɇ = 7,4 M-1) [11, 88]. Ⱥɥɟ ɩɨɤɚɡɚɧɿ ɧɚɦɢ [223] ɧɢɡɶɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ TPH ɜ ȱɑ-ɫɩɟɤɬɪɿ ɬɚ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ NH2-ɝɪɭɩ EB ɭ ɄɊ-ɫɩɟɤɬɪɿ ɜɤɚɡɭɸɬɶ ɧɚ ɮɨɪɦɭɜɚɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ. Ƀɦɨɜɿɪɧɨ, ɬɚɤɭ ɡɦɿɧɭ ɫɩɟɤɬɪɿɜ ɫɬɟɤɿɧɝɞɢɦɟɪɭ TPH-EB ɦɨɠɧɚ ɩɨɹɫɧɢɬɢ ɜɡɚɽɦɨɞɿɽɸ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɯ ɝɪɭɩ ɥɿɝɚɧɞɿɜ ɡ ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ. Ⱦɿɣɫɧɨ, ɚɧɚɥɿɡ ɦɢɬɬɽɜɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (800 ɦɨɥɟɤɭɥ ɜɨɞɢ) ɿ ɜ F-ɫɬɪɭɤɬɭɪɚɯ ɞɨɡɜɨɥɢɜ ɜɢɡɧɚɱɢɬɢ ɿɫɧɭɜɚɧɧɹ ɬɪɶɨɯ ɜɨɞɧɢɯ ɦɿɫɬɤɿɜ, ɳɨ ɫɮɨɪɦɭɜɚɥɢɫɹ ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɥɿɝɚɧɞɿɜ (ɪɢɫ. 4.10). 120 (a) ( ɛ) ( ɜ) Ɋɢɫɭɧɨɤ 4.10 Ɇɢɬɬɽɜɿ ɤɨɧɮɿɝɭɪɚɰɿʀ F-ɫɬɪɭɤɬɭɪɢ TPH-EB ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ, ɬɪɢ ɜɨɞɧɢɯ ɦɿɫɬɤɢ: (ɚ) TPH N4···H2N24 EB (5 H2O); (ɛ) TPH N4···H2N23 EB (4 H2O); (ɜ) TPH C9=O12···H2N23 EB (3 H2O). ɇ-ɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ ɉɟɪɲɢɣ ɭɬɜɨɪɸɽɬɶɫɹ ɦɿɠ ɚɬɨɦɨɦ-ɚɤɰɟɩɬɨɪɨɦ N4 TPH (ɝɪɭɩɚ N9 ɜ ɟɤɫɩɟɪɢɦɟɧɬɿ) ɿ ɞɨɧɨɪɧɨɸ ɝɪɭɩɨɸ N24ɇ2 EB ɿ ɫɤɥɚɞɚɽɬɶɫɹ ɡ 5 ɦɨɥɟɤɭɥ ɜɨɞɢ (ɪɢɫ. 4.10 ɚ, ɞɥɹ ɪɟɡɭɥɶɬɚɬɿɜ Ɇɋ ɦɨɞɟɥɸɜɚɧɧɹ ɰɶɨɝɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ ɧɭɦɟɪɚɰɿɹ ɚɬɨɦɿɜ ɬɚ ɡɚɪɹɞɢ ɧɚ ɚɬɨɦɚɯ ɜɿɞɩɨɜɿɞɧɢɯ ɥɿɝɚɧɞɿɜ ɩɪɢɜɟɞɟɧɨ ɭ ɞɨɞɚɬɤɭ ȼ, ɪɢɫ. ȼ.2 ɿ ȼ.3, ɬɚɛɥ. ȼ.2 ɿ ȼ.3). Ⱦɪɭɝɢɣ ɫɤɥɚɞɚɽɬɶɫɹ ɡ 4 ɦɨɥɟɤɭɥ ɜɨɞɢ, ɪɨɡɬɚɲɨɜɚɧɢɯ ɦɿɠ ɬɢɦ ɠɟ ɚɤɰɟɩɬɨɪɨɦ TPH ɿ ɞɨɧɨɪɧɨɸ ɚɦɿɧɨɝɪɭɩɨɸ N23H2 EB (ɪɢɫ. 4.10 ɛ). Ɍɪɟɬɿɣ ɜɨɞɧɢɣ ɦɿɫɬɨɤ ɪɨɡɬɚɲɨɜɚɧɢɣ ɦɿɠ ɚɤɰɟɩɬɨɪɧɨɸ ɤɚɪɛɨɧɿɥɶɧɨɸ ɝɪɭɩɨɸ C9=O12 TPH (C6=O-ɝɪɭɩɚ ɜ ɟɤɫɩɟɪɢɦɟɧɬɿ) ɿ ɞɨɧɨɪɧɨɸ ɚɦɿɧɨɝɪɭɩɨɸ N23H2 EB (ɪɢɫ. 4.10 ɜ). Ɍɚɤɚ «ɭɩɨɪɹɞɤɨɜɚɧɚ» ɜɨɞɧɚ ɫɬɪɭɤɬɭɪɚ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ TPH-EB ɦɨɠɟ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɜɚɬɢ ɝɟɬɟɪɨɞɢɦɟɪ, ɨɛɦɟɠɭɸɱɢ ɪɭɯɥɢɜɿɫɬɶ ɦɨɥɟɤɭɥ ɭ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿ. 4.5.3 Ƚɟɬɟɪɨɞɢɦɟɪ TPH-PRF Ɇɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɧɟ ɮɨɪɦɭɸɬɶɫɹ ɧɿ ɜ ɨɞɧɿɣ ɡɿ ɫɬɪɭɤɬɭɪ ɝɟɬɟɪɨɞɢɦɟɪɭ TPH-PRF. ȼɢɤɨɪɢɫɬɨɜɭɸɱɢ ɞɚɧɿ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ, ɧɚɦɢ ɛɭɥɨ ɜɢɡɧɚɱɟɧɨ ɤɿɥɶɤɿɫɬɶ ɦɨɥɟɤɭɥ ɜɨɞɢ, ɳɨ 121 ɭɬɜɨɪɸɸɬɶ ɇ-ɡɜ'ɹɡɤɢ ɡ PRF ɿ/ɚɛɨ TPH ɡɝɿɞɧɨ ɡ ɟɧɟɪɝɟɬɢɱɧɢɦɢ ɬɚ ɝɟɨɦɟɬɪɢɱɧɢɦɢ ɤɪɢɬɟɪɿɹɦɢ (56 ɦɨɥɟɤɭɥ ɜɨɞɢ). ɉɨɬɿɦ ɛɭɥɨ ɫɮɨɪɦɨɜɚɧɨ ɫɢɫɬɟɦɭ TPH-PRF + 56 ɇ2Ɉ ɿ ɜɢɤɨɧɚɧɨ ʀʀ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɞɥɹ ɨɬɪɢɦɚɧɧɹ F-ɫɬɪɭɤɬɭɪɢ [224]. Ɇɢɬɬɽɜɿ ɤɨɧɮɿɝɭɪɚɰɿʀ ɝɟɬɟɪɨɞɢɦɟɪɭ TPH-PRF ɩɪɢɜɟɞɟɧɨ ɧɚ ɪɢɫ. 4.11. ( ɛ) Ɋɢɫɭɧɨɤ 4.11 Ɇɢɬɬɽɜɿ ɤɨɧɮɿɝɭɪɚɰɿʀ ɝɟɬɟɪɨɞɢɦɟɪɭ TPH-PRF: (ɚ) ɨɩɬɢɦɿɡɚɰɿɹ ɭ ɜɚɤɭɭɦɿ, ETPH-PRF = -9,92 ɤɤɚɥ/ɦɨɥɶ; (ɛ) ɦɢɬɬɽɜɚ ɤɨɧɮɿɝɭɪɚɰɿɹ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ: TPH-PRF + 56 H2O, ETPH-PRF = -7,73 ɤɤɚɥ/ɦɨɥɶ. ɇ-ɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ Ⱥɧɚɥɿɡ ɦɢɬɬɽɜɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ ɬɚ F-ɫɬɪɭɤɬɭɪ ɞɨɡɜɨɥɢɜ ɜɢɡɧɚɱɢɬɢ 11 ɦɨɥɟɤɭɥ ɜɨɞɢ, ɳɨ ɭɬɜɨɪɸɸɬɶ ɇ-ɡɜ'ɹɡɤɢ ɡ PRF ɿ/ɚɛɨ TPH ɿ ɞɜɚ ɜɨɞɧɢɯ ɦɿɫɬɤɢ ɦɿɠ ɦɨɧɨɦɟɪɚɦɢ ɜ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿ TPH-PRF (ɞɥɹ ɪɟɡɭɥɶɬɚɬɿɜ Ɇɋ ɦɨɞɟɥɸɜɚɧɧɹ ɧɭɦɟɪɚɰɿɹ ɚɬɨɦɿɜ ɬɚ ɡɚɪɹɞɢ ɧɚ ɚɬɨɦɚɯ ɜɿɞɩɨɜɿɞɧɢɯ ɥɿɝɚɧɞɿɜ ɰɶɨɝɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ ɩɪɢɜɟɞɟɧɨ ɭ ɞɨɞɚɬɤɭ ȼ, ɪɢɫ. ȼ.2 ɿ ȼ.4, ɬɚɛɥ. ȼ.2 ɿ ȼ.4). ɉɟɪɲɢɣ ɦɿɫɬɨɤ (6 ɦɨɥɟɤɭɥ ɜɨɞɢ, ɪɢɫ. 4.12 ɚ) ɜɢɹɜɥɟɧɨ ɦɿɠ N15H2 ɞɨɧɨɪɧɨɸ ɝɪɭɩɨɸ PRF ɿ N1H21 ɞɨɧɨɪɧɨɸ ɝɪɭɩɨɸ TPH (ɝɪɭɩɚ N7– H ɜ ɟɤɫɩɟɪɢɦɟɧɬɿ). Ⱦɪɭɝɢɣ (1 ɦɨɥɟɤɭɥɚ ɜɨɞɢ, ɪɢɫ. 4.12 ɛ) ɜɢɹɜɥɟɧɨ ɦɿɠ N16H2 (a) 122 ɞɨɧɨɪɧɨɸ ɝɪɭɩɨɸ PRF ɿ ɋ7=Ɉ10 ɚɤɰɟɩɬɨɪɧɨɸ ɝɪɭɩɨɸ TPH (ɋ2=Ɉ-ɝɪɭɩɚ ɜ ɟɤɫɩɟɪɢɦɟɧɬɿ). (a) (ɛ) Ɋɢɫɭɧɨɤ 4.12 Ɇɢɬɬɽɜɿ ɤɨɧɮɿɝɭɪɚɰɿʀ F-ɫɬɪɭɤɬɭɪɢ ɝɟɬɟɪɨɞɢɦɟɪɭ TPH-PRF; ɜɨɞɧɿ ɦɿɫɬɤɢ ɦɿɠ N15H2 ɝɪɭɩɨɸ PRF ɿ N1-H21 ɝɪɭɩɨɸ TPH (a); ɬɚ ɦɿɠ N16H2 ɝɪɭɩɨɸ PRF ɿ C7=O10 ɝɪɭɩɨɸ TPH (ɛ). ɇ-ɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ Ɍɚɤɿ ɜɨɞɧɿ ɦɿɫɬɤɢ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ TPH-PRF ɦɨɠɭɬɶ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɜɚɬɢ ɝɟɬɟɪɨɞɢɦɟɪ, ɨɛɦɟɠɭɸɱɢ ɪɭɯɥɢɜɿɫɬɶ ɦɨɥɟɤɭɥ ɭ ɫɬɟɤɿɧɝɚɫɨɰɿɚɬɿ. 4.5.4 Ƚɟɬɟɪɨɞɢɦɟɪ CAF-EB Ɂɝɿɞɧɨ ɡ ɞɚɧɢɦɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɫɬɪɭɤɬɭɪɚ CAF-EB ɞɟɳɨ ɜɿɞɪɿɡɧɹɽɬɶɫɹ ɜɿɞ ɫɬɪɭɤɬɭɪɢ, ɨɬɪɢɦɚɧɨʀ ɡɚ ɞɨɩɨɦɨɝɨɸ əɆɊ ɚɛɨ ɩɿɫɥɹ ɨɩɬɢɦɿɡɚɰɿʀ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɚɤɭɭɦɿ: ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɧɟ ɮɨɪɦɭɸɬɶɫɹ ɧɿ ɜ ɨɞɧɿɣ ɡɿ ɫɬɪɭɤɬɭɪ CAF-EB. ȼɢɤɨɪɢɫɬɨɜɭɸɱɢ ɞɚɧɿ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ, ɛɭɥɨ ɜɢɡɧɚɱɟɧɨ ɤɿɥɶɤɿɫɬɶ ɦɨɥɟɤɭɥ ɜɨɞɢ, ɹɤɿ ɭɬɜɨɪɸɸɬɶ ɇ-ɡɜ'ɹɡɤɢ ɡ EB ɿ/ɚɛɨ CAF ɡɝɿɞɧɨ ɡ ɟɧɟɪɝɟɬɢɱɧɢɦɢ ɬɚ ɝɟɨɦɟɬɪɢɱɧɢɦɢ ɤɪɢɬɟɪɿɹɦɢ (79 ɦɨɥɟɤɭɥ ɜɨɞɢ). ɉɨɬɿɦ ɞɥɹ ɨɬɪɢɦɚɧɧɹ F-ɫɬɪɭɤɬɭɪɢ ɧɚɦɢ ɛɭɥɨ ɫɮɨɪɦɨɜɚɧɨ ɫɢɫɬɟɦɭ CAF-EB + 79 H2O ɿ ɩɪɨɜɟɞɟɧɨ ʀʀ Ɇɋ ɦɨɞɟɥɸɜɚɧɧɹ [224]. Ⱥɧɚɥɿɡ ɦɢɬɬɽɜɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ ɡ 800 ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɢ ɿ ɦɢɬɬɽɜɢɯ ɤɨɧɮɿɝɭɪɚɰɿɣ F-ɫɬɪɭɤɬɭɪ ɞɨɡɜɨɥɢɜ ɜɫɬɚɧɨɜɢɬɢ ɬɪɢ ɜɨɞɧɢɯ ɦɿɫɬɤɢ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɞɢɦɟɪɭ CAF-EB. ɉɟɪɲɢɣ ɦɿɫɬɨɤ ɭɬɜɨɪɸɽɬɶɫɹ ɦɿɠ ɚɤɰɟɩɬɨɪɧɨɸ 123 N9 ɝɪɭɩɨɸ CAF ɿ ɞɨɧɨɪɧɨɸ N23H2 ɝɪɭɩɨɸ EB (9 ɦɨɥɟɤɭɥ ɜɨɞɢ, ɪɢɫ. 4.13 ɚ), ɞɪɭɝɢɣ – ɦɿɠ C2=O11 ɚɤɰɟɩɬɨɪɧɨɸ ɝɪɭɩɨɸ CAF ɿ N24H2 ɞɨɧɨɪɧɨɸ ɝɪɭɩɨɸ EB (2 ɦɨɥɟɤɭɥɢ ɜɨɞɢ, ɪɢɫ. 4.13 ɛ), ɬɪɟɬɿɣ – ɦɿɠ ɋ6=Ɉ13 ɚɤɰɟɩɬɨɪɧɨɸ ɝɪɭɩɨɸ CAF ɿ N23H2 ɞɨɧɨɪɧɨɸ ɝɪɭɩɨɸ EB (5 ɦɨɥɟɤɭɥ ɜɨɞɢ, ɪɢɫ. 4.13 ɜ). (a) ( ɛ) (ɜ) Ɋɢɫɭɧɨɤ 4.13 ɫɩɨɫɬɟɪɿɝɚɸɬɶɫɹ (a) 3 Ɇɢɬɬɽɜɿ ɜɨɞɧɢɯ ɤɨɧɮɿɝɭɪɚɰɿʀ ɦɿɫɬɤɢ ɧɚɜɤɨɥɨ (ɛ) ɝɟɬɟɪɨɞɢɦɟɪɭ ɝɟɬɟɪɨɞɢɦɟɪɭ CAF-EB; CAF-EB: CAF N9...H2N23 EB; CAF C2=O11···H2N24 EB; (ɜ) CAF C6=O13···H2N23 EB. ɇ-ɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ Ⱦɥɹ ɤɨɮɟʀɧɭ ɧɭɦɟɪɚɰɿɹ ɨɫɧɨɜɧɢɯ ɚɬɨɦɿɜ ɤɿɥɶɰɹ ɞɥɹ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨʀ ɱɚɫɬɢɧɢ ɡɛɿɝɚɽɬɶɫɹ ɡ ɧɭɦɟɪɚɰɿɽɸ ɚɬɨɦɿɜ, ɳɨ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɚɫɹ ɜ ɦɨɞɟɥɸɜɚɧɧɿ Ɇɋ. Ⱦɥɹ ɪɟɡɭɥɶɬɚɬɿɜ Ɇɋ ɦɨɞɟɥɸɜɚɧɧɹ ɧɭɦɟɪɚɰɿɹ ɚɬɨɦɿɜ ɬɚ ɡɚɪɹɞɢ ɜɿɞɩɨɜɿɞɧɢɯ ɥɿɝɚɧɞɿɜ ɰɶɨɝɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ ɩɪɢɜɟɞɟɧɨ ɭ ɞɨɞɚɬɤɭ ȼ, ɪɢɫ. ȼ.3 ɿ ȼ.5, ɬɚɛɥ. ȼ.3 ɿ ȼ.5. ɇɚ ɪɢɫ. 4.14 ɿ 4.15 ɩɪɢɜɟɞɟɧɨ ɦɢɬɬɽɜɿ ɤɨɧɮɿɝɭɪɚɰɿʀ ɝɟɬɟɪɨɞɢɦɟɪɭ CAF-EB. 124 (ɚ) (ɛ) (ɜ) Ɋɢɫɭɧɨɤ 4.14 Ʉɨɧɮɿɝɭɪɚɰɿʀ ɝɟɬɟɪɨɞɢɦɟɪɭ CAF-EB: (ɚ) ɩɨɱɚɬɤɨɜɚ ɫɬɪɭɤɬɭɪɚ (əɆɊ ɞɚɧɿ), ECAF-EB = -9,53 ɤɤɚɥ/ɦɨɥɶ; (ɛ) Ɇɋ ɨɩɬɢɦɿɡɚɰɿɹ ɝɟɨɦɟɬɪɿʀ ɭ ɜɚɤɭɭɦɿ, ECAF-EB = -12,66 ɤɤɚɥ/ɦɨɥɶ; (ɜ) ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɨɞɿ (800 H2O), ECAF-EB = -10,95 ɤɤɚɥ/ɦɨɥɶ. ɇ-ɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ Ɋɢɫɭɧɨɤ 4.15 ɭ ɜɨɞɧɨɦɭ Ɇɢɬɬɽɜɚ ɤɥɚɫɬɟɪɿ ɤɨɧɮɿɝɭɪɚɰɿɹ ɝɟɬɟɪɨɞɢɦɟɪɭ CAFEB (Fɇɫɬɪɭɤɬɭɪɚ): ɡɜ'ɹɡɤɢ ɥɿɧɿɹɦɢ CAF-EB + 79 H2O, ɩɭɧɤɬɢɪɧɢɦɢ ECAF-EB = -10,43 ɤɤɚɥ/ɦɨɥɶ. ɩɨɤɚɡɚɧɨ ɇɚ ɩɿɞɫɬɚɜɿ ɪɟɡɭɥɶɬɚɬɿɜ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɦɨɠɧɚ ɫɬɜɟɪɞɠɭɜɚɬɢ, ɳɨ ɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɚɯ TPH-EB, TPH-PRF ɿ CAF-EB 125 ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɧɟ ɭɬɜɨɪɸɸɬɶɫɹ. ɐɿ ɪɟɡɭɥɶɬɚɬɢ ɭɡɝɨɞɠɭɸɬɶɫɹ ɡ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɦɢ ɞɨɫɥɿɞɠɟɧɧɹɦɢ ɚɫɨɰɿɚɰɿʀ ɥɿɝɚɧɞɿɜ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ [11, 86, 88, 223], ɤɪɿɦ TPH-EB [223]. ɍ ɪɚɡɿ ɝɟɬɟɪɨɞɢɦɟɪɿɜ TPH-EB, TPH-PRF ɿ CAF-EB ɞɨɤɥɚɞɧɢɣ ɨɩɢɫ ʀɯ ɜɡɚɽɦɨɞɿʀ ɡ ɜɨɞɧɢɦ ɨɬɨɱɟɧɧɹɦ, ɨɬɪɢɦɚɧɢɣ ɡɚ ɪɟɡɭɥɶɬɚɬɚɦɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ, ɞɨɡɜɨɥɹɽ ɲɥɹɯɨɦ ɩɨɹɫɧɢɬɢ ɭɬɜɨɪɟɧɧɹ ɞɨɞɚɬɤɨɜɭ ɜɨɞɧɢɯ ɫɬɚɛɿɥɿɡɚɰɿɸ ɦɿɠ ɰɢɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɦɿɫɬɤɿɜ ɞɨɧɨɪɧɨ- ɚɤɰɟɩɬɨɪɧɢɦɢ ɚɬɨɦɧɢɦɢ ɝɪɭɩɚɦɢ ɥɿɝɚɧɞɿɜ. ɍɬɜɨɪɟɧɧɹ «ɜɩɨɪɹɞɤɨɜɚɧɨʀ» ɜɨɞɧɨʀ ɫɬɪɭɤɬɭɪɢ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɦɨɠɟ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɜɚɬɢ ɝɟɬɟɪɨɞɢɦɟɪɢ, ɨɛɦɟɠɭɸɱɢ ɪɭɯɥɢɜɿɫɬɶ ɦɨɥɟɤɭɥ ɭ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿ, ɚ ɬɚɤɨɠ ɪɭɯɥɢɜɿɫɬɶ ʀɯ ɛɿɱɧɢɯ ɥɚɧɰɸɠɤɿɜ. ȼɢɫɧɨɜɤɢ ɞɨ ɪɨɡɞɿɥɭ 4 1. ȱɑ-ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɿ ɞɨɫɥɿɞɠɟɧɧɹ ɜ ɧɟɣɬɪɚɥɶɧɢɯ ɪɨɡɱɢɧɚɯ ɩɨɤɚɡɚɥɢ ɜɿɞɫɭɬɧɿɫɬɶ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɝɟɬɟɪɨɚɫɨɰɿɚɬɚɯ FMN-TPH, TPH-PRF ɿ CAF-EB, ɧɚ ɜɿɞɦɿɧɭ ɜɿɞ ɤɨɦɩɥɟɤɫɭ TPH-EB, ɜ ɹɤɨɦɭ ɮɨɪɦɭɽɬɶɫɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɣ ɇ-ɡɜ'ɹɡɨɤ. Ɂɪɨɛɥɟɧɨ ɜɢɫɧɨɜɨɤ ɩɪɨ ɬɟ, ɳɨ FMN ɿ TPH ɮɨɪɦɭɸɬɶ n-ɦɨɥɟɤɭɥɹɪɧɢɣ ɚɝɪɟɝɚɬ. Ɇɟɬɨɞɨɦ Ɇɋ ɦɨɞɟɥɸɜɚɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ FMN-TPH, TPH-EB, TPHPRF ɿ CAF-EB ɜɫɬɚɧɨɜɥɟɧɨ ɮɚɤɬ ɞɨɞɚɬɤɨɜɨʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɰɢɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɲɥɹɯɨɦ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɢɯ ɦɿɫɬɤɿɜ ɦɿɠ ɞɨɧɨɪɧɨɚɤɰɟɩɬɨɪɧɢɦɢ ɚɬɨɦɧɢɦɢ ɝɪɭɩɚɦɢ ɥɿɝɚɧɞɿɜ. ɍɬɜɨɪɟɧɧɹ «ɜɩɨɪɹɞɤɨɜɚɧɨʀ» ɜɨɞɧɨʀ ɫɬɪɭɤɬɭɪɢ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɦɨɠɟ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɜɚɬɢ ɝɟɬɟɪɨɞɢɦɟɪɢ, ɨɛɦɟɠɭɸɱɢ ɪɭɯɥɢɜɿɫɬɶ ɦɨɥɟɤɭɥ ɭ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɚɯ, ɚ ɬɚɤɨɠ ɪɭɯɥɢɜɿɫɬɶ ʀɯ ɛɿɱɧɢɯ ɥɚɧɰɸɠɤɿɜ. Ɋɟɡɭɥɶɬɚɬɢ ɞɨɫɥɿɞɠɟɧɶ ɞɚɧɨɝɨ ɪɨɡɞɿɥɭ ɧɚɜɟɞɟɧɨ ɜ ɩɭɛɥɿɤɚɰɿɹɯ 2. ɡɞɨɛɭɜɚɱɚ: [223], [224]. 126 ɊɈɁȾȱɅ 5 ɉɊɈəȼ ȼɈȾɇȿȼɈȽɈ Ɂȼ'əɁɄɍ ȼ ɄɈɅɂȼȺɅɖɇɂɏ ɋɉȿɄɌɊȺɏ ȽȿɌȿɊɈȺɋɈɐȱȺɌȱȼ ȱ ɉɊɂ Ɂȼ'əɁɍȼȺɇɇȱ ȻȺɊ Ɂ ȾɇɄ ɍ ɰɶɨɦɭ ɪɨɡɞɿɥɿ ɞɢɫɟɪɬɚɰɿʀ ɩɪɟɞɫɬɚɜɥɟɧɿ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɿ ɪɟɡɭɥɶɬɚɬɢ ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɬɚ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ FMNEB ɿ FMN-PRF [223, 241], ɹɤɿ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ, ɡɝɿɞɧɨ ɡ ɞɚɧɢɦɢ əɆɊ ɿ ɍɎɫɩɟɤɬɪɨɫɤɨɩɿʀ, ɮɨɪɦɭɸɬɶ ɝɟɬɟɪɨɚɫɨɰɿɚɬɢ ɡ ɭɬɜɨɪɟɧɧɹɦ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇɡɜ'ɹɡɤɿɜ, ɿ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɡ ȾɇɄ [242]. 5.1 Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɿ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɍ ɪɨɛɨɬɿ [86] ɩɨɤɚɡɚɧɨ, ɳɨ ɩɪɢ ɮɿɡɿɨɥɨɝɿɱɧɢɯ ɭɦɨɜɚɯ (ɪɇ = 7,1 ɿ 0,1 Ɇ Na-ɮɨɫɮɚɬɧɢɣ ɛɭɮɟɪ) ɦɭɬɚɝɟɧ ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ ɮɨɪɦɭɽ ʌ-ɫɬɨɩɤɨɜɢɣ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫ ɡ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɨɦ ɡ ɤɨɧɫɬɚɧɬɨɸ ɪɿɜɧɨɜɚɝɢ ɄC = 640 Ɇ-1 ɿ ɟɧɟɪɝɿɽɸ (ɟɧɬɚɥɶɩɿɽɸ) ¨HC = -7,9 ɤɤɚɥ/ɦɨɥɶ, ɳɨ ɜ 2,0-2,5 ɪɚɡɢ ɜɢɳɟ, ɧɿɠ ɤɨɧɫɬɚɧɬɚ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɞɥɹ ɤɨɠɧɨʀ ɡ ɪɟɱɨɜɢɧ (ɄFMN = 265 M-1, KEB = 305 M-1). | ɉɟɪɟɞɛɚɱɚɥɨɫɹ, ɳɨ ɡɛɿɥɶɲɟɧɧɹ ɫɬɚɛɿɥɶɧɨɫɬɿ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ ɩɨɜ'ɹɡɚɧɨ ɡ ɭɬɜɨɪɟɧɧɹɦ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ H-ɡɜ'ɹɡɤɭ, C2=O(FMN) ·· H  N  Ǿ (EB), ɩɪɨ ɳɨ ɬɚɤɨɠ ɫɜɿɞɱɢɥɚ ɫɬɪɭɤɬɭɪɚ, ɪɨɡɪɚɯɨɜɚɧɚ ɞɥɹ ɫɭɦɿɲɿ 1:1 ɜɢɯɿɞɧɢɯ ɪɟɱɨɜɢɧ [86]. ɐɹ ɪɨɡɪɚɯɨɜɚɧɚ ɫɬɪɭɤɬɭɪɚ ɞɟɦɨɧɫɬɪɭɽ ɜɢɫɨɤɭ ɫɬɭɩɿɧɶ ɩɟɪɟɤɪɢɜɚɧɧɹ ɚɪɨɦɚɬɢɱɧɢɯ ɯɪɨɦɨɮɨɪɿɜ ɥɿɝɚɧɞɿɜ, ɞɨ ɟɧɟɪɝɿʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɹɤɢɯ ɧɚɣɛɿɥɶɲɢɣ ɜɧɟɫɨɤ ɞɚɸɬɶ ɞɢɫɩɟɪɫɿɣɧɿ ɜɡɚɽɦɨɞɿʀ. Ⱦɥɹ ɡ'ɹɫɭɜɚɧɧɹ ɿɫɧɭɜɚɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-EB ɧɚɦɢ ɛɭɥɨ ɡɚɩɢɫɚɧɨ ȱɑ-ɫɩɟɤɬɪɢ ɜɨɞɧɢɯ (D2O) ɪɨɡɱɢɧɿɜ FMN, EB ɬɚ ʀɯ ɫɭɦɿɲɿ ɜ ɨɛɥɚɫɬɿ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ (ɪɢɫ. 5.1 ɚ). Ɍɚɤɨɠ ɛɭɥɨ ɡɚɩɢɫɚɧɨ ɄɊ-ɫɩɟɤɬɪɢ ɪɨɡɱɢɧɿɜ EB ɿ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ ɜ ɨɛɥɚɫɬɿ NH2 ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ (ɪɢɫ. 5.1 ɛ) [223, 241]. ɍɫɿ ɫɩɟɤɬɪɢ 127 ɨɬɪɢɦɚɧɨ ɭɫɟɪɟɞɧɟɧɧɹɦ ɧɟ ɦɟɧɲɟ 10 ɜɢɦɿɪɸɜɚɧɶ, ɜɢɤɨɧɚɧɢɯ ɜ ɨɞɧɚɤɨɜɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɭɦɨɜɚɯ. 1600 1620 1640 1660 1613 1644 1628 D 1644 1623 3 1704 ȼɿɞɧɨɫɧɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ 1 1608 0,15 0,10 1651 1653 C2=O(FMN) 1 1704 C4=O(FMN) 0,05 1637 2 1631 2 0,00 1600 1650 1700 Q , ɫɦ -1 ( ɛ) Ɋɢɫɭɧɨɤ 5.1 (ɚ) ȱɑ-ɫɩɟɤɬɪɢ ɩɨɝɥɢɧɚɧɧɹ ɪɨɡɱɢɧɿɜ FMN (1), EB (2) ɿ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-EB (3); (ɛ) ɄɊ-ɫɩɟɤɬɪɢ ɪɨɡɱɢɧɿɜ EB (1), ɿ ɫɭɦɿɲɿ FMN-EB (2). Ⱦɥɹ ɜɫɿɯ ɪɨɡɱɢɧɿɜ ɪɇ = 6,9÷7,0 (±0,05) əɤ ɡɝɚɞɭɜɚɥɨɫɹ ɜ ɩɿɞɪɨɡɞɿɥɿ 3.1, ɜɢɫɨɤɨɱɚɫɬɨɬɧɚ ɫɦɭɝɚ ɩɨɝɥɢɧɚɧɧɹ ɡ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ Ȟ = 1704 ɫɦ-1 (±1 cɦ-1) ɩɨɜ'ɹɡɚɧɚ ɡ ɤɨɥɢɜɚɧɧɹɦɢ ɤɚɪɛɨɧɿɥɶɧɨʀ ɋ4=Ɉ-ɝɪɭɩɢ FMN, ɚ ɛɿɥɶɲ ɧɢɡɶɤɨɱɚɫɬɨɬɧɚ ɫɦɭɝɚ ɩɨɜ'ɹɡɚɧɚ ɡ ɤɨɥɢɜɚɧɧɹɦɢ ɤɚɪɛɨɧɿɥɶɧɨʀ ɝɪɭɩɢ ɋ2=Ɉ (ɞɢɜ. ɪɢɫ. 1.4) [215-217]. Ɍɚɤɨɠ ɭ ɩɿɞɪɨɡɞɿɥɿ 4.3 ɛɭɥɨ ɧɚɜɟɞɟɧɨ ɞɚɧɿ ɩɪɨ ɬɟ, ɳɨ ɧɚ ɫɩɟɤɬɪɿ ɄɊ ɫɦɭɝɢ ɩɪɢ Ȟ = 1628 ɿ 1644 ɫɦ-1 (±2 ɫɦ-1) ɜɿɞɧɨɫɹɬɶɫɹ ɞɨ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ NH2-ɝɪɭɩ ɚɬɨɦɿɜ ȿȼ (ɞɢɜ. ɪɢɫ. 1.2 ɛ) [230, 231]. ɇɚ ɪɢɫ. 5.2 ɩɪɢɜɟɞɟɧɨ ȱɑ-ɫɩɟɤɬɪ ɩɨɝɥɢɧɚɧɧɹ ɫɭɦɿɲɿ FMN-EB ɿ ɫɩɟɤɬɪ ɫɭɦɢ ɨɞɧɨɤɨɦɩɨɧɟɧɬɧɢɯ ɫɩɟɤɬɪɿɜ FMN ɿ EB. ȼɢɞɧɨ, ɳɨ ɿɧɬɟɧɫɢɜɧɿɫɬɶ (ɚ) 1600 1620 1640 Q , ɫɦ -1 128 ɫɩɟɤɬɪɭ ɫɭɦɿɲɿ ɿɫɬɨɬɧɨ ɡɪɨɫɥɚ, ɚ ɱɚɫɬɨɬɚ ɤɨɥɢɜɚɧɧɹ ɝɪɭɩɢ ɋ2=Ɉ ɜ ɤɨɦɩɥɟɤɫɿ ɡɚɡɧɚɥɚ ɧɢɡɶɤɨɱɚɫɬɨɬɧɨɝɨ ɡɫɭɜɭ ɧɚ ǻȞ = 9 ɫɦ-1 (±1 cɦ-1) (ɪɢɫ. 5.1 ɚ). ɍ ɬɨɣ ɠɟ ɱɚɫ ɫɦɭɝɚ ɩɨɝɥɢɧɚɧɧɹ ɝɪɭɩɢ ɋ4=Ɉ ɡ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ 1704 ɫɦ-1 (±1 cɦ-1) ɧɟ ɡɚɡɧɚɥɚ ɛɭɞɶ-ɹɤɢɯ ɱɚɫɬɨɬɧɢɯ ɡɦɿɳɟɧɶ ɭ ɩɨɪɿɜɧɹɧɧɿ ɡɿ ɫɩɟɤɬɪɨɦ FMN ɛɟɡ EB. ɍ ɫɩɟɤɬɪɿ ɄɊ (ɪɢɫ. 5.1 ɛ) ɩɪɢ ɭɬɜɨɪɟɧɧɿ ɤɨɦɩɥɟɤɫɭ FMN-EB ɫɦɭɝɚ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɩɪɢ 1644 ɫɦ-1 (±2 ɫɦ-1) ɡɦɿɫɬɢɥɚɫɹ ɭ ɜɢɫɨɤɨɱɚɫɬɨɬɧɭ ɨɛɥɚɫɬɶ ɧɚ ǻȞ = 7 ɫɦ-1 (±2 ɫɦ-1). D 0,15 1644 1623 1 1704 Ɋɢɫɭɧɨɤ 5.2 ȱɑ-ɫɩɟɤɬɪ ɩɨɝɥɢɧɚɧɧɹ ɪɨɡɱɢɧɭ ɫɭɦɿɲɿ FMN-EB (1) ɿ ɫɩɟɤɬɪ ɫɭɦɢ ɨɞɧɨɤɨɦɩɨɧɟɧɬɧɢɯ ɫɩɟɤɬɪɿɜ 2 1704 0,10 1652 0,05 FMN ɿ EB (2). Ⱦɥɹ ɜɫɿɯ ɪɨɡɱɢɧɿɜ ɪɇ = 6,9÷7,0 0,00 1600 1650 1700 Q , ɫɦ -1 (±0,05) Ɍɚɤɢɣ ɯɚɪɚɤɬɟɪ ɡɦɿɧɢ ɱɚɫɬɨɬ ɬɚ ɿɧɬɟɧɫɢɜɧɨɫɬɟɣ ɜ ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɚɯ ɨɞɧɨɡɧɚɱɧɨ ɫɜɿɞɱɢɬɶ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɬɢɩɭ C2=O(FMN) ·· H  N  Ǿ (EB) ɦɿɠ ɦɨɥɟɤɭɥɚɦɢ FMN ɿ EB ɜ 1:1 ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿ. ɐɟɣ ɜɢɫɧɨɜɨɤ ɭɡɝɨɞɠɭɽɬɶɫɹ ɡ ɩɪɢɩɭɳɟɧɧɹɦ ɩɪɨ ɮɨɪɦɭɜɚɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-EB, ɡɚɡɧɚɱɟɧɨɦɭ ɜ ɩɨɫɢɥɚɧɧɿ [86] ɿ ɨɬɪɢɦɚɧɢɦ ɨɩɨɫɟɪɟɞɤɨɜɚɧɨ ɡ əɆɊ ɞɚɧɢɯ, ɧɚ ɩɿɞɫɬɚɜɿ ɚɧɚɥɿɡɭ ɟɧɬɚɥɶɩɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ [115] ɿ ɣɦɨɜɿɪɧɨɫɬɿ ɩɟɪɟɧɟɫɟɧɧɹ ɡɚɪɹɞɭ [116]. əɤ ɜɠɟ ɡɝɚɞɭɜɚɥɨɫɹ ɪɚɧɿɲɟ (ɞɢɜ. ɩɿɞɪɨɡɞɿɥ 4.1), ɚɜɬɨɪɚɦɢ ɪɨɛɿɬ [91, 116] ɜ ɹɤɨɫɬɿ ɧɟɩɪɹɦɨɝɨ ɤɪɢɬɟɪɿɸ ɞɨɞɚɬɤɨɜɨʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɛɭɥɨ ɡɚɩɪɨɩɨɧɨɜɚɧɨ ɮɚɤɬɨɪ fC , ɳɨ ɜɿɞɨɛɪɚɠɚɽ ɜɿɞɧɨɫɧɢɣ ɜɧɟɫɨɤ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɜ | 129 ɫɭɦɚɪɧɭ ɞɢɧɚɦɿɱɧɭ ɪɿɜɧɨɜɚɝɭ ɜ ɪɨɡɱɢɧɿ. Ɂɝɿɞɧɨ ɡ [91, 116], ɡɚ ɭɦɨɜɢ fC • 35% ɽ ɜɢɫɨɤɚ ɣɦɨɜɿɪɧɿɫɬɶ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ H-ɡɜ'ɹɡɤɨɦ. ȼɟɥɢɱɢɧɚ ɮɚɤɬɨɪɚ fC ɞɥɹ ɫɢɫɬɟɦɢ FMN-EB (KFMN = 265 M-1, KEB = 305 M-1, KC = 640 M-1 [86]) ɞɨɪɿɜɧɸɽ fC = 52,9%, ɳɨ ɩɨɦɿɬɧɨ ɩɟɪɟɜɢɳɭɽ ɩɨɪɿɝ 35% ɿ ɬɚɤɨɠ ɩɿɞɬɜɟɪɞɠɭɽ ɩɪɢɩɭɳɟɧɧɹ ɩɪɨ ɮɨɪɦɭɜɚɧɧɹ H-ɡɜ'ɹɡɤɭ. 5.2 Ƚɟɬɟɪɨɚɫɨɰɿɚɰɿɹ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɿ ɩɪɨɮɥɚɜɿɧɭ əɆɊ ɞɨɫɥɿɞɠɟɧɧɹ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ ɡ ɦɭɬɚɝɟɧɨɦ ɩɪɨɮɥɚɜɿɧɨɦ ɬɚɤ ɫɚɦɨ, ɹɤ ɿ ɭ ɜɢɩɚɞɤɭ ɡ ɛɪɨɦɢɫɬɢɦ ɟɬɢɞɿɽɦ, ɩɨɤɚɡɚɥɢ, ɳɨ ɪɿɜɧɨɜɚɠɧɚ ɤɨɧɫɬɚɧɬɚ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ (KC = 920 M-1) ɿ ɟɧɬɚɥɶɩɿɹ (¨ɇ = -9,8 ɤɤɚɥ/ɦɨɥɶ) ɡɧɚɱɧɨ ɜɢɳɟ ɡɚ ɚɛɫɨɥɸɬɧɨɸ ɜɟɥɢɱɢɧɨɸ, ɧɿɠ ɡɧɚɱɟɧɧɹ ɬɢɯ ɠɟ ɩɚɪɚɦɟɬɪɿɜ ɞɥɹ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɜɢɯɿɞɧɢɯ ɪɟɱɨɜɢɧ (KFMN = 265 M-1, KPRF = 700 M-1) [86]. ɍ ɰɿɣ ɠɟ ɪɨɛɨɬɿ ɚɜɬɨɪɢ ɩɪɢɩɭɫɬɢɥɢ, ɳɨ ɡɛɿɥɶɲɟɧɧɹ ɡɧɚɱɟɧɶ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɬɚɤɨɠ ɦɨɠɧɚ ɩɨɹɫɧɢɬɢ ɭɬɜɨɪɟɧɧɹɦ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɦɿɠ ɜɿɞɩɨɜɿɞɧɢɦɢ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɦɨɥɟɤɭɥ FMN ɿ PRF. Ⱥɧɚɥɿɡ ȱɑ-ɫɩɟɤɬɪɿɜ ɿ ɫɩɟɤɬɪɿɜ ɤɨɦɛɿɧɚɰɿɣɧɨɝɨ ɪɨɡɫɿɸɜɚɧɧɹ ɫɜɿɬɥɚ FMN, PRF ɬɚ ʀɯ ɫɭɦɿɲɿ ɦɢ ɩɪɨɜɨɞɢɥɢ, ɹɤ ɿ ɭ ɜɢɩɚɞɤɭ ɫɢɫɬɟɦɢ FMN-EB [223, 241]. ɇɚ ɪɢɫ. 5.3 ɚ ɩɪɢɜɟɞɟɧɨ ȱɑ-ɫɩɟɤɬɪɢ ɫɭɦɿɲɿ FMN-PRF ɿ ɫɩɟɤɬɪ ɫɭɦɢ FMN ɿ PRF ɨɞɧɨɤɨɦɩɨɧɟɧɬɧɢɯ ɫɩɟɤɬɪɿɜ, ɹɤɿ ɨɬɪɢɦɚɧɿ ɧɚ ɨɫɧɨɜɿ ɭɫɟɪɟɞɧɟɧɧɹ 10 ɜɢɦɿɪɸɜɚɧɶ, ɜɢɤɨɧɚɧɢɯ ɜ ɨɞɧɚɤɨɜɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɭɦɨɜɚɯ. Ɂ ɪɢɫ. 5.3 ɚ ɦɨɠɧɚ ɛɚɱɢɬɢ, ɳɨ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɫɩɟɤɬɪɭ ɫɭɦɿɲɿ ɡɧɚɱɧɨ ɡɛɿɥɶɲɭɽɬɶɫɹ, ɚ ɦɚɤɫɢɦɭɦ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɩɪɢ 1650 ɫɦ-1 (±1 cɦ-1) (ɤɨɥɢɜɚɧɧɹ ɋ2=Ɉ-ɝɪɭɩɢ FMN) ɡɦɿɫɬɢɜɫɹ ɜ ɦɟɠɚɯ ɩɨɦɢɥɤɢ (ǻȞ = 2 ɫɦ-1 (±1 cɦ-1)). Ɋɚɡɨɦ ɡ ɰɢɦ ɦɚɤɫɢɦɭɦ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɋ4=Ɉ-ɝɪɭɩɢ FMN ɡɦɿɳɭɽɬɶɫɹ ɜ ɧɢɡɶɤɨɱɚɫɬɨɬɧɭ ɨɛɥɚɫɬɶ ɧɚ ǻȞ = 6 ɫɦ-1 (±1 cɦ-1) ɩɪɢ ɮɨɪɦɭɜɚɧɧɿ ɤɨɦɩɥɟɤɫɭ. ȼ ɬɨɣ ɠɟ ɱɚɫ ɭ ɄɊ-ɫɩɟɤɬɪɚɯ (ɪɢɫ. 5.3 ɛ) ɫɦɭɝɢ ɡ 130 1600 1625 1650 1628 D 1650 ȼɿɞɧɨɫɧɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ 1607 1650 0,2 1 1619 1622 1 1698 0,1 1652 2 1704 Q, cɦ -1 1635 1663 2 1600 1625 1650 Q, ɫɦ -1 0,0 1600 1650 1700 ( ɛ) Ɋɢɫɭɧɨɤ 5.3 (ɚ) ȱɑ-ɫɩɟɤɬɪ ɩɨɝɥɢɧɚɧɧɹ ɪɨɡɱɢɧɭ ɫɭɦɿɲɿ FMN-PRF (1) ɿ ɫɩɟɤɬɪ ɫɭɦɢ ɨɞɧɨɤɨɦɩɨɧɟɧɬɧɢɯ ɫɩɟɤɬɪɿɜ FMN ɿ PRF (2); (ɛ) ɄɊ-ɫɩɟɤɬɪɢ ɪɨɡɱɢɧɿɜ PRF (1) ɿ ɫɭɦɿɲɿ FMN-PRF (2). Ⱦɥɹ ɜɫɿɯ ɪɨɡɱɢɧɿɜ ɪɇ = 6,9÷7,0 (±0,05) ɦɚɤɫɢɦɭɦɚɦɢ Ȟ = 1628 ɿ 1650 ɫɦ-1 (±2 cɦ-1), ɩɨɜ'ɹɡɚɧɿ ɡ ɞɟɮɨɪɦɚɰɿɣɧɢɦɢ ɤɨɥɢɜɚɧɧɹɦɢ NH2-ɝɪɭɩ ɩɪɨɮɥɚɜɿɧɭ (ɞɢɜ. ɪɢɫ. 1.2 ɚ) [230], ɡɚɡɧɚɥɢ ɜɿɞɩɨɜɿɞɧɨ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɣ ɡɫɭɜ ɞɨ Ȟ = 1635 ɿ 1663 ɫɦ-1 (±2 cɦ-1), ɬɨɛɬɨ ɧɚ ǻȞ=7 ɿ 13 ɫɦ-1. Ɍɚɤɢɣ ɱɚɫɬɨɬɧɢɣ ɡɫɭɜ ɯɚɪɚɤɬɟɪɢɫɬɢɱɧɢɯ ɫɦɭɝ ɿ ɡɪɨɫɬɚɧɧɹ ɿɧɬɟɧɫɢɜɧɨɫɬɿ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɫɩɟɤɬɪɿ ɩɨɝɥɢɧɚɧɧɹ ɫɜɿɞɱɢɬɶ ɩɪɨ ɮɨɪɦɭɜɚɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɬɢɩɭ C4=O(FMN)··· H  N  Ǿ (PRF) ɿ ɛɿɥɶɲ ɫɥɚɛɤɨɝɨ ɇ-ɡɜ'ɹɡɤɭ C2=O(FMN)··· H  N  Ǿ (PRF) ɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-PRF. ɐɟɣ ɜɢɫɧɨɜɨɤ ɡɧɚɯɨɞɢɬɶɫɹ ɜ ɡɝɨɞɿ ɡ ɩɪɢɩɭɳɟɧɧɹɦ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-PRF, ɨɬɪɢɦɚɧɨɦɭ ɡɚ ɧɟɩɪɹɦɢɦɢ ɨɡɧɚɤɚɦɢ ɡ ɞɚɧɢɯ əɆɊ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ, ɧɚ ɩɿɞɫɬɚɜɿ ɚɧɚɥɿɡɭ ɟɧɬɚɥɶɩɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ [115] ɿ ɣɦɨɜɿɪɧɨɫɬɿ ɩɟɪɟɧɟɫɟɧɧɹ ɡɚɪɹɞɭ [116]. ȼɟɥɢɱɢɧɚ ɮɚɤɬɨɪɭ fC ɞɥɹ ɫɢɫɬɟɦɢ FMN-PRF (KFMN = 265 M-1, KPRF = 700 M-1, KC = 920 M-1 [11]) ɞɨɪɿɜɧɸɽ | | (ɚ) 131 fC = 48,8%, ɳɨ ɩɨɦɿɬɧɨ ɩɟɪɟɜɢɳɭɽ ɩɨɪɿɝ 35%. ȼɫɟ ɰɟ, ɹɤ ɿ ɭ ɜɢɩɚɞɤɭ ɪɨɡɝɥɹɧɭɬɨʀ ɜɢɳɟ ɫɢɫɬɟɦɢ FMN-EB, ɬɚɤɨɠ ɩɿɞɬɜɟɪɞɠɭɽ ɮɨɪɦɭɜɚɧɧɹ Hɡɜ'ɹɡɤɭ. Ɉɞɧɚɤ ɫɥɿɞ ɡɚɡɧɚɱɢɬɢ, ɳɨ ɡɚ ɞɚɧɢɦɢ əɆɊ [86] ɫɚɦɟ ɤɚɪɛɨɧɿɥɶɧɚ ɝɪɭɩɚ C2=O (FMN) ɩɨɜɢɧɧɚ ɛɭɬɢ ɡɚɥɭɱɟɧɚ ɜ ɭɬɜɨɪɟɧɧɹ H-ɡɜ'ɹɡɤɭ. Ⱦɥɹ ɬɨɝɨ ɳɨɛ ɡ'ɹɫɭɜɚɬɢ ɱɢ ɫɭɩɟɪɟɱɢɬɶ ɰɟɣ ɪɟɡɭɥɶɬɚɬ ɞɚɧɢɦ ɤɨɥɢɜɚɥɶɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ, ɧɚɜɟɞɟɧɢɦɢ ɜ ɰɶɨɦɭ ɪɨɡɞɿɥɿ, ɧɚɦɢ ɩɪɨɚɧɚɥɿɡɨɜɚɧɨ ɞɚɧɿ əɆɊ, ɩɪɟɞɫɬɚɜɥɟɧɿ ɜ ɪɨɛɨɬɿ [86], ɜ ɤɨɧɬɟɤɫɬɿ ɦɨɠɥɢɜɨɝɨ ɮɨɪɦɭɜɚɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɋ4=Ɉ-ɝɪɭɩɨɸ FMN, ɹɤ ɜɫɬɚɧɨɜɥɟɧɨ ɜɢɳɟ. ɍ ɪɨɛɨɬɿ [86] ɧɚɛɿɪ ɧɚɜɟɞɟɧɢɯ ɤɪɨɫ-ɩɿɤɿɜ ɛɭɥɨ ɪɨɡɞɿɥɟɧɨ ɧɚ ɞɜɿ ɱɚɫɬɢɧɢ, ɤɨɠɧɚ ɡ ɹɤɢɯ ɜɿɞɩɨɜɿɞɚɽ ɞɜɨɦ ɪɿɡɧɢɦ ɫɬɪɭɤɬɭɪɚɦ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ FMN-PRF: ɫɬɪɭɤɬɭɪɚ 1 ɡ ɜ 3,6-NH2-ɝɪɭɩɚɦɢ ɩɪɨɬɢɥɟɠɧɭ ɜɿɞ PRF, ɨɪɿɽɧɬɨɜɚɧɢɦɢ ɜ ɧɚɩɪɹɦɤɭ ɫɬɨɪɨɧɭ. ɪɢɛɿɬɢɥɶɧɨɝɨ ɥɚɧɰɸɠɤɚ FMN, ɿ ɫɬɪɭɤɬɭɪɚ 2 ɡ 3,6-NH2-ɝɪɭɩɚɦɢ PRF, ɨɪɿɽɧɬɨɜɚɧɢɦɢ ɪɢɛɿɬɢɥɶɧɨɝɨ ɥɚɧɰɸɠɤɚ ɋɬɪɭɤɬɭɪɚ 1 ɩɨɜɧɿɫɬɸ ɜɿɞɩɨɜɿɞɚɽ ɭɱɚɫɬɿ ɜ ɭɬɜɨɪɟɧɧɿ ɇ-ɡɜ'ɹɡɤɭ ɝɪɭɩɢ ɋ2=Ɉ (FMN) ɿ ɧɟ ɞɨɩɭɫɤɚɽ ɭɱɚɫɬɿ ɜ ɭɬɜɨɪɟɧɧɿ ɇ-ɡɜ'ɹɡɤɭ ɝɪɭɩɢ ɋ4=Ɉ, ɧɟ ɪɭɣɧɭɸɱɢ ʌ-ɫɬɟɤɿɧɝɭ ɯɪɨɦɨɮɨɪɿɜ. ȱ ɧɚɜɩɚɤɢ, ɫɬɪɭɤɬɭɪɚ 2 ɯɚɪɚɤɬɟɪɢɡɭɽɬɶɫɹ ɛɥɢɡɶɤɢɦ ɪɨɡɬɚɲɭɜɚɧɧɹɦ ɨɞɧɿɽʀ ɡ NH2-ɝɪɭɩ PRF ɚɛɨ ɞɨ ɋ2=Ɉ, ɚɛɨ ɞɨ ɋ4=Ɉ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ FMN. ȼɿɞɦɿɧɧɨɸ ɨɫɨɛɥɢɜɿɫɬɸ ɧɚɛɨɪɭ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ NOE ɤɪɨɫ-ɩɿɤɿɜ ɭ ɪɨɛɨɬɿ [86] ɽ ɬɟ, ɳɨ ɜɨɧɢ ɫɩɨɫɬɟɪɿɝɚɥɢɫɹ ɜɢɤɥɸɱɧɨ ɞɥɹ ɛɟɧɡɨɥɶɧɨɝɨ ɤɿɥɶɰɹ ɦɨɥɟɤɭɥɢ FMN (ɞɢɜ. ɪɢɫ. 1.4), ɡɛɚɝɚɱɟɧɨɝɨ ɧɟɡɞɚɬɧɢɦɢ ɞɨ ɨɛɦɿɧɭ ɩɪɨɬɨɧɚɦɢ. ɐɟ ɡɛɿɥɶɲɭɽ ɦɨɠɥɢɜɿɫɬɶ ɞɥɹ ɨɛɟɪɬɚɧɧɹ ɯɪɨɦɨɮɨɪɿɜ FMN ɿ PRF ɨɞɢɧ ɳɨɞɨ ɨɞɧɨɝɨ ɛɟɡ ɫɩɨɬɜɨɪɟɧɧɹ ʌ-ɫɬɟɤɿɧɝɭ ɿ ɜɬɪɚɬɢ NOE ɤɨɧɬɚɤɬɿɜ, ɯɚɪɚɤɬɟɪɧɢɯ ɞɥɹ ɫɬɪɭɤɬɭɪɢ 2. Ɇɨɠɥɢɜɿɫɬɶ ɭɬɜɨɪɟɧɧɹ ɬɚɤɨʀ ɫɬɪɭɤɬɭɪɢ ɛɭɥɨ ɩɿɞɬɜɟɪɞɠɟɧɨ ɩɨɜɬɨɪɧɢɦ ɦɨɞɟɥɸɜɚɧɧɹɦ ɦɟɬɨɞɨɦ ɦɨɥɟɤɭɥɹɪɧɨʀ ɦɟɯɚɧɿɤɢ ɡ ɭɪɚɯɭɜɚɧɧɹɦ ɜɿɞɩɨɜɿɞɧɢɯ ɨɛɦɟɠɟɧɶ (ɩɪɨɬɨɤɨɥ ɦɨɞɟɥɸɜɚɧɧɹ ɿɞɟɧɬɢɱɧɢɣ ɜɢɤɨɪɢɫɬɚɧɨɦɭ ɜ ɪɨɛɨɬɿ [86]). Ɉɬɪɢɦɚɧɭ ɫɬɪɭɤɬɭɪɭ ɩɪɟɞɫɬɚɜɥɟɧɨ ɧɚ ɪɢɫ. 5.4. 132 Ɋɢɫɭɧɨɤ 5.4 ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɭ ɡ ɭɪɚɯɭɜɚɧɧɹɦ ɩɨɤɚɡɚɧɨ ɋɬɪɭɤɬɭɪɚ FMN-PRF, ɜɿɞɩɨɜɿɞɧɢɯ NOE ɫɬɪɿɥɤɚɦɢ. ɇ-ɡɜ'ɹɡɨɤ ɨɬɪɢɦɚɧɚ ɩɨɜɬɨɪɧɢɦ ɦɨɞɟɥɸɜɚɧɧɹɦ ɨɛɦɟɠɟɧɶ. ɤɨɧɬɚɤɬɢ Ɇɿɠɦɨɥɟɤɭɥɹɪɧɿ Ɇɿɠɦɨɥɟɤɭɥɹɪɧɢɣ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɨɦ ȿɧɟɪɝɟɬɢɱɧɨ ɰɹ ɫɬɪɭɤɬɭɪɚ ɩɪɚɤɬɢɱɧɨ ɟɤɜɿɜɚɥɟɧɬɧɚ ɫɬɪɭɤɬɭɪɿ 2, ɹɤɚ ɩɪɟɞɫɬɚɜɥɟɧɚ ɜ ɪɨɛɨɬɿ [86], ɚɥɟ ɪɨɡɬɚɲɭɜɚɧɧɹ ɦɨɥɟɤɭɥ ɭ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿ ɪɿɡɧɢɬɶɫɹ. ɏɪɨɦɨɮɨɪɢ FMN ɿ PRF ɩɨɜɟɪɧɟɧɿ ɜɿɞɧɨɫɧɨ ɨɞɢɧ ɨɞɧɨɝɨ ɧɚ 15º, ɿ, ɳɨ ɞɭɠɟ ɜɚɠɥɢɜɨ, ʀɯ ɪɨɡɬɚɲɭɜɚɧɧɹ ɫɬɟɪɢɱɧɨ ɫɩɪɢɹɽ ɭɬɜɨɪɟɧɧɸ ɇ-ɡɜ'ɹɡɤɭ ɦɿɠ ɋ4=O (FMN) ɿ NH2-ɝɪɭɩɨɸ PRF. Ɍɚɤɚ ɫɬɪɭɤɬɭɪɚ (ɪɢɫ. 5.4) ɭɡɝɨɞɠɭɽɬɶɫɹ ɹɤ ɡ ɞɚɧɢɦɢ əɆɊ, ɬɚɤ ɿ ɡ ɞɚɧɢɦɢ ɤɨɥɢɜɚɥɶɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ. ɇɟɨɛɯɿɞɧɨ ɜɿɞɡɧɚɱɢɬɢ ɳɟ ɨɞɢɧ ɦɨɦɟɧɬ, ɳɨ ɫɬɨɫɭɽɬɶɫɹ ɦɨɠɥɢɜɨɫɬɿ ɿɫɧɭɜɚɧɧɹ ɞɜɨɯ ɪɿɡɧɢɯ ɫɬɪɭɤɬɭɪ ɤɨɦɩɥɟɤɫɭ FMN-PRF. ȼ ɭɦɨɜɚɯ ɜɿɞɧɨɫɧɨ ɜɢɫɨɤɢɯ ɤɨɧɰɟɧɬɪɚɰɿɣ ɜɡɚɽɦɨɞɿɸɱɢɯ ɦɨɥɟɤɭɥ ɭ ɪɨɡɱɢɧɿ (ɦɆ) ɰɿɥɤɨɦ ɦɨɠɥɢɜɟ ɮɨɪɦɭɜɚɧɧɹ ɚɝɪɟɝɚɬɿɜ ɛɿɥɶɲ ɜɢɫɨɤɨɝɨ ɩɨɪɹɞɤɭ, ɬɚɤɢɯ ɹɤ 1:2 ɿ ɜɢɳɟ. ɐɟ ɡɚɡɜɢɱɚɣ ɜɪɚɯɨɜɭɽɬɶɫɹ ɩɪɢ ɪɨɡɪɚɯɭɧɤɭ ɪɿɜɧɨɜɚɠɧɨʀ ɤɨɧɫɬɚɧɬɢ ɡɜ'ɹɡɭɜɚɧɧɹ KC, ɿ ɬɟɪɦɨɞɢɧɚɦɿɱɧɢɯ ɩɚɪɚɦɟɬɪɿɜ ɡ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɤɪɢɜɢɯ ɬɢɬɪɭɜɚɧɧɹ ɜ əɆɊ [33, 86] ɿ ɚɧɚɥɿɡɿ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ ɡɚ ɞɚɧɢɦɢ ɫɩɟɤɬɪɨɮɨɬɨɦɟɬɪɿʀ ɜ ɍɎ- ɿ ɜɢɞɢɦɿɣ ɨɛɥɚɫɬɿ [108]. Ⱦɨɤɚɡ ɿɫɧɭɜɚɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɡ ɞɜɨɦɚ ɤɚɪɛɨɧɿɥɶɧɢɦɢ ɝɪɭɩɚɦɢ ɦɨɥɟɤɭɥɢ FMN (ɋ4=Ɉ ɿ ɋ2=Ɉ) ɦɨɠɟ ɛɭɬɢ ɩɨɹɫɧɟɧɨ, ɹɤ ɧɚɫɥɿɞɨɤ ɮɨɪɦɭɜɚɧɧɹ ɤɨɦɩɥɟɤɫɭ 1:2 PRF:FMN:PRF, ɜ ɹɤɨɦɭ ɞɜɿ ɝɟɬɟɪɨ-ɫɬɨɩɤɢ PRF:FMN ɫɬɚɛɿɥɿɡɭɸɬɶɫɹ ɇ-ɡɜ'ɹɡɤɚɦɢ ɡ ɞɜɨɦɚ ɪɿɡɧɢɦɢ ɤɚɪɛɨɧɿɥɶɧɢɦɢ ɝɪɭɩɚɦɢ ɦɨɥɟɤɭɥɢ FMN. ɇɚ ɠɚɥɶ, ɩɨɞɿɥ ɜɤɥɚɞɭ 1:1 ɿ 1:2 ɭ ɫɩɨɫɬɟɪɟɠɭɜɚɧɢɯ 133 ɧɚɦɢ ɱɚɫɬɨɬɧɢɯ ɡɫɭɜɚɯ [223, 241] ɜɢɤɨɧɚɬɢ ɧɟɦɨɠɥɢɜɨ, ɩɪɨɬɟ, ɫɢɫɬɟɦɚ PRFFMN ɦɨɠɟ ɫɥɭɠɢɬɢ ɦɨɞɟɥɥɸ ɞɥɹ ɩɨɞɚɥɶɲɨɝɨ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɝɨ ɬɟɫɬɭɜɚɧɧɹ ɚɝɪɟɝɚɰɿʀ ɛɿɥɶɲ ɜɢɫɨɤɨɝɨ ɩɨɪɹɞɤɭ. Ʉɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ-Ʉɚɪɥɨ 5.3 ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ FMN-EB ɿ FMN-PRF ɭ ɜɨɞɧɢɯ ɤɥɚɫɬɟɪɚɯ Ⱦɥɹ ɿɧɬɟɪɩɪɟɬɚɰɿʀ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɪɟɡɭɥɶɬɚɬɿɜ ɤɨɥɢɜɚɥɶɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɿ ɩɨɹɫɧɟɧɧɹ ɦɟɯɚɧɿɡɦɿɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ FMN-EB ɿ FMN-PRF, ɚ ɬɚɤɨɠ ɩɨɛɭɞɨɜɢ ʀɯ ɦɨɥɟɤɭɥɹɪɧɢɯ ɦɨɞɟɥɟɣ, ɧɚɦɢ ɜɢɤɨɧɚɧɨ ɤɨɦɩ'ɸɬɟɪɧɟ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ ɫɢɫɬɟɦ, ɳɨ ɦɿɫɬɹɬɶ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɢ FMN-EB, FMN-PRF ɿ ɜɨɞɧɿ ɤɥɚɫɬɟɪɢ [224]. ɉɪɨɰɟɞɭɪɭ ɜɢɤɨɧɚɧɧɹ ɦɨɞɟɥɸɜɚɧɧɹ ɞɨɤɥɚɞɧɨ ɨɩɢɫɚɧɨ ɜ ɩɿɞɪɨɡɞɿɥɿ 2.3. 5.3.1 Ƚɟɬɟɪɨɞɢɦɟɪ FMN-EB Ɂɝɿɞɧɨ ɡ ɪɟɡɭɥɶɬɚɬɚɦɢ əɆɊ ɞɚɧɢɯ ɿ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɜ ɝɟɬɟɪɨɞɢɦɟɪɿ FMN-EB ɭɬɜɨɪɸɸɬɶɫɹ ɬɪɢ ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ (ɪɢɫ. 5.5 ɚ) ɦɿɠ C2=O3 ɝɪɭɩɨɸ FMN ɿ N24H2 ɝɪɭɩɨɸ EB (R = 3,17 Å; ɤɭɬ N24H EB···C2O3 FMN = 138°), C5=O6 ɝɪɭɩɨɸ FMN ɿ C16H ɝɪɭɩɨɸ EB (R = 3,21 Å; ɤɭɬ C16H EB···C5O6 FMN = 127°), C20=O21 ɝɪɭɩɨɸ FMN ɿ C20H ɝɪɭɩɨɸ EB (R = 3,20 Å; ɤɭɬ C20H EB···C20O21 FMN = 111°). ɇɭɦɟɪɚɰɿɹ ɚɬɨɦɿɜ ɿ ɡɚɪɹɞɢ ɜɿɞɩɨɜɿɞɧɢɯ ɥɿɝɚɧɞɿɜ ɩɪɢɜɟɞɟɧɨ ɜ ɞɨɞɚɬɤɭ ȼ (ɪɢɫ. ȼ.1 ɿ ȼ.3, ɬɚɛɥ. ȼ.1 ɿ ȼ.3). ȼɿɞɫɭɬɧɿɫɬɶ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɯ ɡɫɭɜɿɜ ɫɦɭɝɢ ɩɨɝɥɢɧɚɧɧɹ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ ɋ4=Ɉ FMN ɧɚ ȱɑ-ɫɩɟɤɬɪɚɯ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ FMN-EB, ɹɤɿɣ ɜɿɞɩɨɜɿɞɚɽ ɤɚɪɛɨɧɿɥɶɧɚ ɝɪɭɩɚ C5=O6 ɭ Ɇɋ ɦɨɞɟɥɸɜɚɧɧɿ, ɦɨɠɧɚ ɩɨɹɫɧɢɬɢ ɜɿɞɧɨɫɧɨ ɫɥɚɛɤɢɦɢ ɡɜ'ɹɡɤɚɦɢ ɬɢɩɭ ɋ=Ɉ···ɇ–ɋ, ɹɤɿ ɧɟ ɡɚɜɠɞɢ ɩɪɢɡɜɨɞɹɬɶ ɞɨ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɯ ɡɦɿɳɟɧɶ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ [128]. 134 ( ɛ) Ɋɢɫɭɧɨɤ 5.5 Ɇɢɬɬɽɜɿ ɤɨɧɮɿɝɭɪɚɰɿʀ FMN-EB ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ: (ɚ) ɤɨɧɮɿɝɭɪɚɰɿɹ ɝɟɬɟɪɨɞɢɦɟɪɭ FMN-ȿȼ, EFMN-EB = -91,59 ɤɤɚɥ/ɦɨɥɶ; (b) F-ɫɬɪɭɤɬɭɪɚ: ɞɜɚ ɜɨɞɧɢɯ ɦɿɫɬɤɢ: C5=O6 FMN ɿ N24H2 EB (3 H2O, ɜɧɢɡɭ); C2=O3 FMN ɿ N24H2 EB (1 H2O, ɜɢɞɿɥɟɧɨ ɱɨɪɧɢɦ ɨɜɚɥɨɦ); ɧɟɜɟɥɢɤɢɣ ɜɨɞɧɢɣ ɤɥɚɫɬɟɪ ɧɚɜɤɨɥɨ FMN (11 H2O, ɡɥɿɜɚ, ɡɜɟɪɯɭ). ɇ-ɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ Ⱦɥɹ ɦɨɞɟɥɸɜɚɧɧɹ F-ɫɬɪɭɤɬɭɪɢ ɛɭɥɨ ɫɮɨɪɦɨɜɚɧɨ ɫɢɫɬɟɦɭ, ɹɤɚ ɦɿɫɬɢɬɶ ɝɟɬɟɪɨɞɢɦɟɪ FMN-EB ɿ 106 ɦɨɥɟɤɭɥ ɜɨɞɢ. ȼɿɞɛɿɪ ɬɚɤɨɝɨ ɱɢɫɥɚ ɦɨɥɟɤɭɥ ɜɨɞɢ ɜɢɡɧɚɱɚɽɬɶɫɹ ɟɧɟɪɝɟɬɢɱɧɢɦɢ ɿ ɝɟɨɦɟɬɪɢɱɧɢɦɢ ɤɪɢɬɟɪɿɹɦɢ ɇ-ɡɜ'ɹɡɤɭ: ɡɧɚɱɟɧɧɹɦɢ ɟɧɟɪɝɿɣ ɜɡɚɽɦɨɞɿɣ ɜɨɞɚ-ɝɟɬɟɪɨɞɢɦɟɪ ɿ ɨɪɿɽɧɬɚɰɿɽɸ ɦɨɥɟɤɭɥ ɜɨɞɢ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɞɢɦɟɪɭ. ɑɚɫɬɢɧɚ ɜɿɞɿɛɪɚɧɢɯ ɡɚ ɰɢɦɢ ɤɪɢɬɟɪɿɹɦɢ ɦɨɥɟɤɭɥ ɜɨɞɢ ɭɬɜɨɪɸɸɬɶ ɇ-ɡɜ'ɹɡɤɢ ɡ FMN ɿ/ɚɛɨ EB. Ɋɟɲɬɚ ɦɨɥɟɤɭɥɢ ɜɨɞɢ ɨɛ'ɽɞɧɭɽɬɶɫɹ ɜɨɞɧɟɜɢɦɢ ɡɜ'ɹɡɤɚɦɢ, ɭɬɜɨɪɸɸɱɢ ɡ ɦɨɥɟɤɭɥ ɜɨɞɢ ɨɞɧɭ «ɧɚɧɨɤɪɚɩɥɸ». Ɇɢɬɬɽɜɭ ɤɨɧɮɿɝɭɪɚɰɿɸ ɝɟɬɟɪɨɞɢɦɟɪɭ FMN-EB ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (Fɫɬɪɭɤɬɭɪɚ) ɩɪɢɜɟɞɟɧɨ ɧɚ ɪɢɫ. 5.6. Ȼɭɥɨ ɜɫɬɚɧɨɜɥɟɧɨ ɭɬɜɨɪɟɧɧɹ ɞɜɨɯ ɜɨɞɧɢɯ ɦɿɫɬɤɿɜ ɧɚɜɤɨɥɨ FMN-EB ɹɤ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (800 ɇ2Ɉ), ɬɚɤ ɿ ɞɥɹ F-ɫɬɪɭɤɬɭɪɢ ɰɿɽʀ ɫɢɫɬɟɦɢ. ɉɟɪɲɢɣ ɦɿɫɬɨɤ ɫɤɥɚɞɚɽɬɶɫɹ ɡ ɬɪɶɨɯ ɦɨɥɟɤɭɥ ɜɨɞɢ, ɪɨɡɬɚɲɨɜɚɧɢɯ ɦɿɠ C5=O6 ɝɪɭɩɨɸ FMN (ɝɪɭɩɚ ɋ4=Ɉ ɜ ɟɤɫɩɟɪɢɦɟɧɬɿ) ɿ N24H2 ɝɪɭɩɨɸ EB. Ⱦɪɭɝɢɣ ɫɤɥɚɞɚɽɬɶɫɹ ɡ ɨɞɧɿɽʀ ɦɨɥɟɤɭɥɢ ɜɨɞɢ, ɪɨɡɬɚɲɨɜɚɧɨʀ ɦɿɠ C2=O3 ɝɪɭɩɨɸ FMN (ɝɪɭɩɚ ɋ2=Ɉ ɜ ɟɤɫɩɟɪɢɦɟɧɬɿ) ɿ N24H2 ɝɪɭɩɨɸ EB (ɪɢɫ. 5.5 ɛ). (a) 135 Ɋɢɫɭɧɨɤ 5.6 ɤɨɧɮɿɝɭɪɚɰɿɹ ɫɬɪɭɤɬɭɪɚ): ɇ-ɡɜ'ɹɡɤɢ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ Ɇɢɬɬɽɜɚ ɝɟɬɟɪɨɞɢɦɟɪɭ FMN-EB ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (FFMN-ȿȼ+106 H2O, ɩɨɤɚɡɚɧɨ EFMN-EB = -85,75 ɤɤɚɥ/ɦɨɥɶ. ȱɧɲɿ 11 ɦɨɥɟɤɭɥ ɜɨɞɢ ɭɬɜɨɪɸɸɬɶ ɧɟɜɟɥɢɤɿ ɜɨɞɧɿ ɤɥɚɫɬɟɪɢ. Ɍɚɤɿ «ɜɩɨɪɹɞɤɨɜɚɧɿ» ɫɬɪɭɤɬɭɪɢ ɜɨɞɢ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ FMN-EB ɦɨɠɭɬɶ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɜɚɬɢ ɝɟɬɟɪɨɞɢɦɟɪ, ɨɛɦɟɠɭɸɱɢ ɪɭɯɥɢɜɿɫɬɶ ɦɨɥɟɤɭɥ ɜ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿ, ɚ ɬɚɤɨɠ ɪɭɯɥɢɜɿɫɬɶ ɛɿɱɧɨɝɨ ɥɚɧɰɸɠɤɚ FMN. 5.3.2 Ƚɟɬɟɪɨɞɢɦɟɪ FMN-PRF ɍ ɝɟɬɟɪɨɞɢɦɟɪɿ FMN-PRF ɭɬɜɨɪɸɽɬɶɫɹ ɨɞɢɧ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɣ ɇɡɜ'ɹɡɨɤ ɦɿɠ ɋ2=Ɉ3 ɝɪɭɩɨɸ FMN ɿ N16H2 ɝɪɭɩɨɸ PRF (R = 3,12 Å; ɤɭɬ N16H2 PRF···C2O3 FMN = 143°), ɹɤ ɨɬɪɢɦɚɧɨ ɡɚ ɞɨɩɨɦɨɝɨɸ əɆɊ, ɚ ɬɚɤɨɠ ɩɪɢ Ɇɋ ɨɩɬɢɦɿɡɚɰɿʀ ɫɬɪɭɤɬɭɪɢ FMN-PRF ɭ ɜɚɤɭɭɦɿ ɬɚ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (ɪɢɫ. 5.7). ɍ ɞɨɞɚɬɤɭ ȼ ɩɪɢɜɟɞɟɧɨ ɜɿɞɩɨɜɿɞɧɭ ɧɭɦɟɪɚɰɿɸ ɚɬɨɦɿɜ ɿ ɡɚɪɹɞɢ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ɥɿɝɚɧɞɿɜ (ɪɢɫ. ȼ.1 ɿ ȼ.4, ɬɚɛɥ. ȼ.1 ɿ ȼ.4). ȼɢɤɨɪɢɫɬɨɜɭɸɱɢ ɞɚɧɿ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (800 H2O), ɧɚɦɢ ɛɭɥɨ ɜɢɡɧɚɱɟɧɨ ɤɿɥɶɤɿɫɬɶ ɦɨɥɟɤɭɥ ɜɨɞɢ, ɹɤɿ ɭɬɜɨɪɸɸɬɶ ɇɡɜ'ɹɡɤɢ ɡ FMN ɿ/ɚɛɨ PRF ɡɝɿɞɧɨ ɡ ɟɧɟɪɝɟɬɢɱɧɢɦɢ ɬɚ ɝɟɨɦɟɬɪɢɱɧɢɦɢ ɤɪɢɬɟɪɿɹɦɢ (84 ɦɨɥɟɤɭɥ ɜɨɞɢ) [224]. ɉɨɬɿɦ ɛɭɥɨ ɫɮɨɪɦɨɜɚɧɨ ɫɢɫɬɟɦɭ FMNPRF + 84 H2O ɿ ɩɪɨɜɟɞɟɧɨ ʀʀ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ (ɪɢɫ. 5.8). 136 (a) (ɛ ) ( ɜ) Ɋɢɫɭɧɨɤ 5.7 Ʉɨɧɮɿɝɭɪɚɰɿʀ ɝɟɬɟɪɨɞɢɦɟɪɭ FMN-PRF: (a) əɆɊ ɞɚɧɿ; (ɛ) Ɇɋ ɨɩɬɢɦɿɡɚɰɿɹ ɭ ɜɚɤɭɭɦɿ, EFMN-PRF = -78,75 ɤɤɚɥ/ɦɨɥɶ; (ɜ) ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ, EFMN-PRF = -74,94 ɤɤɚɥ/ɦɨɥɶ. ɇ-ɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ Ɋɢɫɭɧɨɤ 5.8 (F-ɫɬɪɭɤɬɭɪɚ): Ɇɢɬɬɽɜɚ ɤɨɧɮɿɝɭɪɚɰɿɹ ɝɟɬɟɪɨɞɢɦɟɪɭ FMN-PRF ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ FMN-PRF + 84 H2O, ɇ-ɡɜ'ɹɡɤɢ EFMN-PRF = -73,09 ɤɤɚɥ/ɦɨɥɶ. ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ əɤ ɭ ɜɨɞɧɨɦɭ ɤɥɚɫɬɟɪɿ (800 ɦɨɥɟɤɭɥ ɜɨɞɢ), ɬɚɤ ɿ ɞɥɹ F-ɫɬɪɭɤɬɭɪɢ, ɜɢɹɜɥɟɧɨ ɨɞɢɧ ɜɨɞɧɢɣ ɦɿɫɬɨɤ, ɪɨɡɬɚɲɨɜɚɧɢɣ ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɨɛɨɯ ɥɿɝɚɧɞɿɜ: C5=O6 ɝɪɭɩɚ FMN ɿ N16H2 ɝɪɭɩɚ PRF (ɪɢɫ. 5.9), ɹɤɢɣ ɫɤɥɚɞɚɽɬɶɫɹ ɡ ɫɟɦɢ ɦɨɥɟɤɭɥ ɜɨɞɢ. Ɍɚɤɨɠ ɛɭɥɨ ɜɢɹɜɥɟɧɨ ɞɜɚ ɥɚɧɰɸɠɤɢ ɦɨɥɟɤɭɥ ɜɨɞɢ, ɳɨ ɫɮɨɪɦɭɜɚɥɢɫɹ ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɚɪɨɦɚɬɢɱɧɨɝɨ ɤɿɥɶɰɹ ɿ ɛɿɱɧɢɦ ɥɚɧɰɸɝɨɦ FMN (ɪɢɫ. 5.9). 137 Ɋɢɫɭɧɨɤ 5.9 ɜɨɞɧɢɣ ɦɿɫɬɨɤ ɛɿɥɹ Ɇɢɬɬɽɜɚ ɝɟɬɟɪɨɞɢɦɟɪɭ ɤɨɧɮɿɝɭɪɚɰɿɹ F-ɫɬɪɭɤɬɭɪɢ FMN-PRF, FMN-PRF: 7 H2O ɦɿɠ C5=O6 FMN ɿ N16H2 PRF (ɡɟɥɟɧɢɣ, ɫɩɪɚɜɚ); ɞɜɿ ɜɨɞɧɿ ɫɿɬɤɢ ɧɚɜɤɨɥɨ FMN: 6 H2O ɢ 6 H2O (ɮɿɨɥɟɬɨɜɿ, ɡɥɿɜɚ). H-ɡɜ'ɹɡɤɢ ɩɨɤɚɡɚɧɨ ɩɭɧɤɬɢɪɧɢɦɢ ɥɿɧɿɹɦɢ Ɍɚɤɚ «ɭɩɨɪɹɞɤɨɜɚɧɚ» ɜɨɞɧɚ ɫɬɪɭɤɬɭɪɚ ɧɚɜɤɨɥɨ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ FMNPRF, ɹɤ ɿ ɭ ɜɢɩɚɞɤɭ FMN-EB, ɦɨɠɟ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɜɚɬɢ ɝɟɬɟɪɨɞɢɦɟɪ, ɨɛɦɟɠɭɸɱɢ ɪɭɯɥɢɜɿɫɬɶ ɦɨɥɟɤɭɥ ɭ ɫɬɟɤɿɧɝ-ɚɫɨɰɿɚɬɿ, ɚ ɬɚɤɨɠ ɪɭɯɥɢɜɿɫɬɶ ɛɿɱɧɨɝɨ ɥɚɧɰɸɠɤɚ FMN. 5.4 ȼɧɟɫɨɤ ɟɧɟɪɝɿʀ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɡɚɝɚɥɶɧɭ ɟɧɟɪɝɿɸ ɫɬɚɛɿɥɿɡɚɰɿʀ ɤɨɦɩɥɟɤɫɿɜ FMN ɡ EB ɿ PRF ɇɚ ɨɫɧɨɜɿ ɞɚɧɢɯ ɤɨɥɢɜɚɥɶɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɦɨɠɧɚ ɨɰɿɧɢɬɢ ɜɧɟɫɨɤ ɟɧɟɪɝɿʀ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɫɬɚɛɿɥɿɡɚɰɿɸ ɫɬɨɩɤɨɜɢɯ ɚɫɨɰɿɚɬɿɜ. ɇɚɣɛɿɥɶɲ ɛɥɢɡɶɤɢɦ ɚɧɚɥɨɝɨɦ ɞɨ ɫɬɨɩɤɨɜɨʀ ɚɝɪɟɝɚɰɿʀ ɚɪɨɦɚɬɢɱɧɢɯ ȻȺɊ ɽ ɜɟɪɬɢɤɚɥɶɧɟ ɿ ɝɨɪɢɡɨɧɬɚɥɶɧɟ ɭɤɥɚɞɚɧɧɹ ɚɡɨɬɢɫɬɢɯ ɩɚɪ ɨɫɧɨɜ ɭ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬɚɯ, ɭ ɞɚɧɢɣ ɱɚɫ ɞɨɫɢɬɶ ɞɨɛɪɟ ɜɢɜɱɟɧɟ ɦɟɬɨɞɚɦɢ ɤɨɥɢɜɚɥɶɧɨʀ ɫɩɟɤɬɪɨɫɤɨɩɿʀ. ȼ ɚɡɨɬɢɫɬɢɯ ɝɟɬɟɪɨɰɢɤɥɚɯ ɨɫɧɨɜ ɧɭɤɥɟʀɧɨɜɢɯ ɤɢɫɥɨɬ ɩɪɢ ɭɬɜɨɪɟɧɧɿ ɦɿɠɩɚɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɜɚɥɟɧɬɧɿ ɤɨɥɢɜɚɧɧɹ ɧɚ ɤɚɪɛɨɧɿɥɶɧɢɯ [126]. ɝɪɭɩ Ɍɚɤɢɦ ɡɦɿɳɭɸɬɶɫɹ ɱɢɧɨɦ, ɜ ɧɢɡɶɤɨɱɚɫɬɨɬɧɭ ɨɛɥɚɫɬɶ 10-30 ɫɦ-1 ɱɚɫɬɨɬɚ ɫɩɨɫɬɟɪɟɠɭɜɚɧɨɝɨ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ (Ȟɫɩɨɫɬ) ɡɚɩɢɫɭɽɬɶɫɹ ɹɤ: Ȟɫɩɨɫɬ= Ȟ0  ǻȞɇ  ɡɜ , ɞɟ Ȟ0 – ɧɟɡɛɭɪɟɧɚ ɱɚɫɬɨɬɚ ɋ=Ɉ-ɝɪɭɩ (ɜɢɡɧɚɱɚɽɬɶɫɹ ɜ ɧɟɩɨɥɹɪɧɢɯ ɪɿɞɢɧɚɯ); (5.1) 138 ǻȞɇ-ɡɜ – ɡɫɭɜ ɡɚ ɪɚɯɭɧɨɤ ɇ-ɡɜ'ɹɡɤɭ. ɉɪɨɜɟɞɟɧɢɣ ɭ ɩɿɞɪɨɡɞɿɥɚɯ 5.1 ɿ 5.2 ɚɧɚɥɿɡ ɫɜɿɞɱɢɬɶ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɚɯ FMN-EB/PRF ɩɨ ɯɚɪɚɤɬɟɪɢɫɬɢɱɧɨɦɭ ɡɫɭɜɭ ɱɚɫɬɨɬɢ ɤɨɥɢɜɚɧɶ ɚɬɨɦɿɜ, ɹɤɿ ɧɚɥɟɠɚɬɶ ɜɿɞɩɨɜɿɞɧɢɦ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦ ɝɪɭɩɚɦ. ɍ ɫɜɨɸ ɱɟɪɝɭ ɰɟɣ ɯɚɪɚɤɬɟɪɢɫɬɢɱɧɢɣ ɡɫɭɜ ɞɚɽ ɦɨɠɥɢɜɿɫɬɶ ɨɰɿɧɢɬɢ ɟɧɟɪɝɟɬɢɤɭ H-ɡɜ'ɹɡɭɜɚɧɧɹ. Ɇɨɠɧɚ ɜɢɤɨɧɚɬɢ ɨɰɿɧɤɭ ɟɧɬɚɥɶɩɿʀ H-ɡɜ'ɹɡɤɭ ɞɥɹ ɞɚɧɢɯ ɞɜɨɯ ɫɢɫɬɟɦ. ȿɧɬɚɥɶɩɿɹ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɦɨɠɟ ɛɭɬɢ ɨɰɿɧɟɧɚ, ɹɤɳɨ ɜɿɞɨɦɚ ɧɟɡɛɭɪɟɧɚ Ȟ0 ɱɚɫɬɨɬɚ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ (ɞɢɜ. ɮɨɪɦɭɥɭ (5.1)). ɑɚɫɬɨɬɚ Ȟ0 ɦɨɠɟ ɛɭɬɢ ɜɢɡɧɚɱɟɧɚ ɡ ɤɨɥɢɜɚɥɶɧɨɝɨ ɫɩɟɤɬɪɭ ɞɨɫɥɿɞɠɭɜɚɧɨʀ ɪɟɱɨɜɢɧɢ ɜ ɪɨɡɱɢɧɿ ɧɟɩɨɥɹɪɧɨʀ ɪɿɞɢɧɢ, ɨɫɤɿɥɶɤɢ ɦɨɥɟɤɭɥɢ ɬɚɤɨʀ ɪɿɞɢɧɢ ɧɟ ɡɛɭɪɸɸɬɶ ɤɚɪɛɨɧɿɥɶɧɿ ɤɨɥɢɜɚɧɧɹ. ɍ ɪɨɛɨɬɿ [218] ɩɨɤɚɡɚɧɨ, ɳɨ ɜ ɪɨɡɱɢɧɿ ɯɥɨɪɨɮɨɪɦɭ ɤɚɪɛɨɧɿɥɶɧɟ ɤɨɥɢɜɚɧɧɹ ɋ2=Ɉ-ɝɪɭɩɢ ɪɢɛɨɮɥɚɜɿɧ ɬɟɬɪɚɚɰɟɬɚɬɭ ɦɚɽ ɧɟɡɛɭɪɟɧɭ ɱɚɫɬɨɬɭ Ȟ0=1685 ɫɦ-1, ɚ ɤɨɥɢɜɚɧɧɹ ɝɪɭɩɢ ɋ4=Ɉ – Ȟ0=1710 ɫɦ-1. əɤ ɩɨɤɚɡɚɧɨ ɜ ɩɿɞɪɨɡɞɿɥɿ 5.1 ɡɛɭɪɟɧɚ ɱɚɫɬɨɬɚ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ ɋ2=Ɉ ɜ C2=O ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-EB ɫɬɚɧɨɜɢɬɶ Ȟɫɩɨɫɬ = 1644 ɫɦ-1, ɨɬɠɟ, ɭɬɜɨɪɟɧɧɹ ɇ- ɡɜ'ɹɡɤɭ ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɦ ɡɫɭɜɨɦ ǻȞɇ-ɡɜ = 41 ± 10 ɫɦ-1. ȼɢɤɨɪɢɫɬɨɜɭɸɱɢ ɟɦɩɿɪɢɱɧɭ ɡɚɥɟɠɧɿɫɬɶ ɟɧɬɚɥɶɩɿʀ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɭ ɜɿɞɧɨɫɧɨ ɟɧɟɪɝɿʀ ɜɡɚɽɦɨɞɿʀ ɜɨɞɚ-ɜɨɞɚ (ǻɇ) ɜɿɞ ɱɚɫɬɨɬɧɨɝɨ ɡɫɭɜɭ ɤɚɪɛɨɧɿɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ [129, 243]: ǻǾ = 0 ,205 ˜ ǻȞ ɇ  ɡɜ ɤȾɠ , ɦɨɥɶ (5.2) ɦɢ ɡɧɚɣɲɥɢ, ɳɨ ɟɧɟɪɝɿɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɇ-ɡɜ'ɹɡɤɭ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-EB ɛɭɞɟ |ǻɇ| = 8,4 ɤȾɠ/ɦɨɥɶ [223, 241], ɳɨ ɫɬɚɧɨɜɢɬɶ ɩɪɢɛɥɢɡɧɨ 25% ɜɿɞ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɜɢɦɿɪɹɧɨʀ ɡɚɝɚɥɶɧɨʀ ɟɧɬɚɥɶɩɿʀ ɮɨɪɦɭɜɚɧɧɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ [86]. ɉɪɨɜɿɜɲɢ ɬɚɤɿ ɠ ɪɨɡɪɚɯɭɧɤɢ ɞɥɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ FMN-PRF (ɩɿɞɪɨɡɞɿɥ 5.2), ɦɢ ɨɬɪɢɦɭɽɦɨ ɟɧɬɚɥɶɩɿɸ ɇ-ɡɜ'ɹɡɤɭ ɬɢɩɭ C4=O(FMN)··· H  N  Ǿ (PRF), ɪɿɜɧɭ |ǻɇ| = 7,3 ɤȾɠ/ɦɨɥɶ, ɚ ɞɥɹ ɇ-ɡɜ'ɹɡɤɭ ɬɢɩɭ C2=O(FMN)··· H  N  Ǿ (PRF) | | 139 – |ǻɇ| = 2,5 ɤȾɠ/ɦɨɥɶ [223, 241]. Ɂɜɿɞɫɢ ɜɢɩɥɢɜɚɽ, ɳɨ ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɜɨɞɧɟɜɿ ɡɜ'ɹɡɤɢ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɚɯ FMN-EB ɿ FMN-PRF ɞɚɸɬɶ ~ 25-30% -ɢɣ ɜɧɟɫɨɤ ɭ ɡɚɝɚɥɶɧɭ ɟɧɬɚɥɶɩɿɸ ɫɬɚɛɿɥɿɡɚɰɿʀ ɰɢɯ ɤɨɦɩɥɟɤɫɿɜ, ɚ ɿɧɲɚ ɟɧɬɚɥɶɩɿɹ ɡɞɟɛɿɥɶɲɨɝɨ ɽ ɜɧɟɫɤɨɦ ɦɿɠɩɥɨɳɢɧɧɢɯ ɜɡɚɽɦɨɞɿɣ ɦɿɠ ɯɪɨɦɨɮɨɪɚɦɢ ɦɨɥɟɤɭɥ [234] ɿ ɝɿɞɪɚɬɧɨʀ ɜɨɞɨɸ ɧɚɜɤɨɥɨ ɤɨɦɩɥɟɤɫɿɜ [101]. Ɉɞɧɚɤ ɧɟɨɛɯɿɞɧɨ ɜɿɞɡɧɚɱɢɬɢ, ɳɨ ɰɟ ɧɟ ɡɚɜɠɞɢ ɜɿɪɧɨ ɞɥɹ ɡɦɿɧɢ «ɱɢɫɬɨʀ» ɜɿɥɶɧɨʀ ɟɧɟɪɝɿʀ ʈɿɛɛɡɚ ɪɟɚɤɰɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ. Ɋɟɡɭɥɶɬɚɬɢ ɧɟɳɨɞɚɜɧɶɨɝɨ ɬɟɨɪɟɬɢɱɧɨɝɨ ɨɰɿɧɸɜɚɧɧɹ ɜɤɥɚɞɭ ɪɿɡɧɢɯ ɮɿɡɢɱɧɢɯ ɮɚɤɬɨɪɿɜ ɭ ɡɚɝɚɥɶɧɭ ɟɧɟɪɝɿɸ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ (ǻGɋ) [234] ɩɨɤɚɡɚɥɢ, ɳɨ ɜɧɟɫɨɤ ɇ-ɡɜ'ɹɡɤɭ ɜ ǻGɋ ɦɨɠɟ ɛɭɬɢ ɩɨɪɿɜɧɹɧɢɣ ɡ ɫɚɦɢɦ ǻGɋ , ɹɤ ɧɚɫɥɿɞɨɤ ɤɨɦɩɟɧɫɚɰɿʀ ɮɚɤɬɨɪɿɜ, ɳɨ ɮɨɪɦɭɸɬɶ ǻGɋ ɭ ɜɨɞɧɨɦɭ ɪɨɡɱɢɧɿ. ɏɨɱɚ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɡɚɡɜɢɱɚɣ ɜɢɜɨɞɢɬɶɫɹ ɡ ɪɿɜɧɨɜɚɝɢ ɟɧɟɪɝɟɬɢɱɧɨ ɧɟɫɩɪɢɹɬɥɢɜɨɸ ɜɬɪɚɬɨɸ ɇ-ɡɜ'ɹɡɤɿɜ ɡ ɜɨɞɧɢɦ ɨɬɨɱɟɧɧɹɦ, ɞɨɤɥɚɞɧɢɣ ɪɨɡɝɥɹɞ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɹɤ ɧɚ ɪɿɜɧɿ ɟɧɬɚɥɶɩɿʀ, ɬɚɤ ɿ ɜɿɥɶɧɨʀ ɟɧɟɪɝɿʀ ʈɿɛɛɡɚ ɦɚɽ ɜɚɠɥɢɜɟ ɡɧɚɱɟɧɧɹ ɞɥɹ ɩɪɚɜɢɥɶɧɨɝɨ ɪɨɡɭɦɿɧɧɹ ɟɧɟɪɝɟɬɢɤɢ ɪɟɚɤɰɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ. 5.5 ȼɩɥɢɜ ɜɨɞɧɟɜɨɝɨ ɡɜ'ɹɡɤɭ ɧɚ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ EB ɡ ȾɇɄ ɍ ɩɨɩɟɪɟɞɧɿɯ ɪɨɡɞɿɥɚɯ ɜɫɬɚɧɨɜɥɟɧɨ, ɳɨ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɿ ɪɟɱɨɜɢɧɢ ɦɚɸɬɶ ɭ ɫɜɨʀɯ ɫɬɪɭɤɬɭɪɚɯ ɚɬɨɦɧɿ ɝɪɭɩɢ, ɡɞɚɬɧɿ ɮɨɪɦɭɜɚɬɢ ɜɨɞɧɟɜɿ ɡɜ'ɹɡɤɢ ɜ ɤɨɦɩɥɟɤɫɚɯ. ɍ ɰɶɨɦɭ ɩɿɞɪɨɡɞɿɥɿ ɧɚ ɩɪɢɤɥɚɞɿ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɨʀ ɪɟɱɨɜɢɧɢ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɧɚɦɢ ɛɭɥɨ ɩɨɤɚɡɚɧɨ ɪɨɥɶ ɇ-ɡɜ'ɹɡɤɭ ɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɤɨɦɩɥɟɤɫɭ EB-ȾɇɄ [242]. ȼɿɞɨɦɨ, ɳɨ ɛɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ ɭ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɜ ɡɚɥɟɠɧɨɫɬɿ ɜɿɞ ɤɨɧɰɟɧɬɪɚɰɿʀ ɦɨɠɟ ɩɟɪɟɛɭɜɚɬɢ ɜ ɦɨɧɨɦɟɪɧɿɣ ɿ ɞɢɦɟɪɧɿɣ ɮɨɪɦɚɯ [244]. Ɍɨɦɭ ɞɥɹ ɜɢɡɧɚɱɟɧɧɹ ɫɩɟɤɬɪɚɥɶɧɢɯ ɜɿɞɦɿɧɧɨɫɬɟɣ ɦɨɧɨɦɟɪɧɨʀ ɬɚ ɞɢɦɟɪɧɨʀ ɮɨɪɦ EB ɛɭɥɨ ɡɚɩɢɫɚɧɨ ɫɩɟɤɬɪɢ ɄɊ ɩɪɢ ɪɿɡɧɢɯ ɤɨɧɰɟɧɬɪɚɰɿɹɯ. ɍ ɬɚɛɥ. 5.1 ɧɚɜɟɞɟɧɨ ɱɚɫɬɨɬɢ ɫɦɭɝ ɭ ɫɩɟɤɬɪɚɯ ɄɊ ɞɥɹ ɩɨɥɿɤɪɢɫɬɚɥɿɱɧɨɝɨ ɡɪɚɡɤɭ EB ɬɚ EB ɭ ɛɭɮɟɪɧɨɦɭ ɪɨɡɱɢɧɿ ɡ ɤɨɧɰɟɧɬɪɚɰɿɹɦɢ 140 ɋEB § 10-2 Ɇ ɿ CEB § 10-4÷10-5 Ɇ. ȼɿɞɧɟɫɟɧɧɹ ɱɚɫɬɨɬ ɚɬɨɦɧɢɯ ɝɪɭɩ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɞɥɹ ɫɩɟɤɬɪɿɜ ɄɊ ɡɪɨɛɥɟɧɿ ɧɚ ɩɿɞɫɬɚɜɿ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɚɧɢɯ [230, 231, 245, 246]. ɋɦɭɝɭ ɩɪɢ Ȟ = 1372-1377 ɫɦ-1 (±2 cɦ-1) ɜɿɞɧɟɫɟɧɨ ɞɨ ɜɚɥɟɧɬɧɢɯ ɫɢɦɟɬɪɢɱɧɢɯ ɤɨɥɢɜɚɧɶ ɫɩɨɥɭɱɟɧɢɯ ɡɜ'ɹɡɤɿɜ C–C ɿ C–N ɮɟɧɚɧɬɪɢɞɢɧɨɜɨɝɨ ɤɿɥɶɰɹ [246], ɫɦɭɝɭ ɩɪɢ Ȟ = 1411-1417 ɫɦ-1 (±2 cɦ-1) – ɞɨ ɞɢɯɚɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ ɮɟɧɚɧɬɪɢɞɢɧɨɜɨɝɨ ɤɿɥɶɰɹ (ɞɢɜ. ɪɢɫ. 1.2 ɛ) [245]. Ɍɚɛɥɢɰɹ 5.1 ɑɚɫɬɨɬɢ ɫɦɭɝ ɭ ɫɩɟɤɬɪɿ ɄɊ ɬɚ ʀɯ ɜɿɞɧɟɫɟɧɧɹ ɞɥɹ ɤɪɢɫɬɚɥɿɱɧɨɝɨ ɡɪɚɡɤɭ ɿ ɛɭɮɟɪɧɢɯ ɪɨɡɱɢɧɿɜ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ (EB) ɩɪɢ ɞɜɨɯ ɤɨɧɰɟɧɬɪɚɰɿɹɯ (ɋ) ȼɿɞɧɟɫɟɧɧɹ Ɏɟɧɚɧɬɪ. ɤɿɥɶɰɟ Q(C–C, C–N) į(CH3) Ⱦɢɯɚɥɶɧɟ ɤɨɥ. ɮɟɧɚɧɬɪ. ɤɿɥɶɰɹ į(CH2) į(CH3) Ɏɟɧɿɥɶɧɟ ɤɿɥɶɰɟ į(NH2) ɉɨɥɿɤɪɢɫɬ. EB, ɫɦ-1 1354±2 1375±2 1389±2 1412±2 — 1454±2 1605±2 1626±2 EB (C§10-2 M), EB (C§10-4 M), ɫɦ-1 ɫɦ-1 1350±2 1351±2 1372±2 1394±2 1417±2 1442±2 1462±2 1605±2 1627±2 1377±2 1389±2 1411±2 1434±2 1452±2 1602±2 1626±2 Ɂ ɞɚɧɢɯ ɬɚɛɥ. 5.1 ɜɢɩɥɢɜɚɽ, ɳɨ ɩɪɢ ɜɟɥɢɤɿɣ ɤɨɧɰɟɧɬɪɚɰɿʀ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ (§10-2 Ɇ), ɩɪɢ ɹɤɿɣ ɭ ɪɨɡɱɢɧɿ ɭɬɜɨɪɸɽɬɶɫɹ ɩɪɢɛɥɢɡɧɨ ɨɞɧɚɤɨɜɚ ɤɿɥɶɤɿɫɬɶ ɦɨɧɨɦɟɪɧɨʀ ɬɚ ɞɢɦɟɪɧɨʀ ɮɨɪɦ ɥɿɝɚɧɞɭ [113], ɫɩɨɫɬɟɪɿɝɚɽɬɶɫɹ ɫɦɭɝɚ ɤɨɥɢɜɚɧɶ C–C-, C–N-ɝɪɭɩ ɮɟɧɚɧɬɪɢɞɢɧɨɜɨɝɨ ɯɪɨɦɨɮɨɪɭ ɡ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ Ȟ = 1372 ɫɦ-1 (±2 cɦ-1). Ⱦɥɹ ɪɨɡɱɢɧɿɜ ɥɿɝɚɧɞɭ ɡ ɦɟɧɲɢɦɢ ɤɨɧɰɟɧɬɪɚɰɿɹɦɢ (§10-4 ÷ 10-5 Ɇ, ɤɨɥɢ ɩɟɪɟɜɚɠɚɽ ɤɨɧɰɟɧɬɪɚɰɿɹ ɦɨɧɨɦɟɪɧɨʀ ɮɨɪɦɢ EB [113]) ɰɟɣ ɦɚɤɫɢɦɭɦ ɡɫɭɜɚɽɬɶɫɹ ɭ ɜɢɫɨɤɨɱɚɫɬɨɬɧɭ ɨɛɥɚɫɬɶ ɞɨ Ȟ=1377 ɫɦ-1 (±2 cɦ-1). ɇɢɡɶɤɨɱɚɫɬɨɬɧɢɣ ɡɫɭɜ ɫɦɭɝɢ ɞɨ Ȟ = 1372 ɫɦ-1 (±2 cɦ-1) ɫɥɿɞ ɩɨɜ'ɹɡɚɬɢ ɡɿ ɜɡɚɽɦɨɞɿɽɸ ɚɪɨɦɚɬɢɱɧɢɯ ɤɿɥɟɰɶ ɥɿɝɚɧɞɭ ɜ ɞɢɦɟɪɿ. 141 ɇɚ ɪɢɫ. 5.10 ɧɚɜɟɞɟɧɨ ɫɩɟɤɬɪɢ ɄɊ ɞɥɹ ɜɿɥɶɧɨɝɨ EB ɬɚ ɣɨɝɨ ɫɭɦɿɲɟɣ ɡ ȾɇɄ, ɚ ɜ ɬɚɛɥ. 5.2 – ɜɿɞɩɨɜɿɞɧɿ ɱɚɫɬɨɬɢ ɫɦɭɝ ɄɊ ɬɚ ʀɯ ɜɿɞɧɟɫɟɧɧɹ ɞɥɹ EB ɜ ɤɨɦɩɥɟɤɫɿ ɡ ȾɇɄ. ɍɫɿ ɫɩɟɤɬɪɢ ɨɬɪɢɦɚɧɨ ɭɫɟɪɟɞɧɟɧɧɹɦ ɧɟ ɦɟɧɲɟ 10 ɜɢɦɿɪɸɜɚɧɶ, ɜɢɤɨɧɚɧɢɯ ɭ ɨɞɧɚɤɨɜɢɯ ɭɦɨɜɚɯ. Ɉɫɤɿɥɶɤɢ ɩɪɢ ɪɨɡɝɥɹɧɭɬɢɯ ɤɨɧɰɟɧɬɪɚɰɿɹɯ ȾɇɄ ɜ ɰɢɯ ɫɭɦɿɲɚɯ ɜɠɟ ɩɪɚɤɬɢɱɧɨ ɜɿɞɫɭɬɧɿɣ ɜɿɥɶɧɢɣ ɥɿɝɚɧɞ, ɫɩɨɫɬɟɪɟɠɭɜɚɧɿ ɪɨɡɛɿɠɧɨɫɬɿ ɜ ɫɩɟɤɬɪɚɯ ɄɊ ɞɥɹ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɦɨɠɧɚ ɜɿɞɧɟɫɬɢ ɞɨ ɞɜɨɯ ɪɿɡɧɢɯ ɬɢɩɿɜ ɣɨɝɨ ɡɜ'ɹɡɭɜɚɧɧɹ ɡ ȾɇɄ. əɤ ɜɢɞɧɨ ɡ ɄɊ-ɫɩɟɤɬɪɭ ɤɨɦɩɥɟɤɫɭ EB-ȾɇɄ ɩɪɢ P/D = 20 (ɪɢɫ. 5.10), ɤɨɥɢɜɚɧɧɹ ɮɟɧɚɧɬɪɢɞɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɡ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ Ȟ = 1377 ɫɦ-1 ɡɫɭɜɚɽɬɶɫɹ ɧɚ 5 ɫɦ-1 (±2 ɫɦ-1) ɭ ɧɢɡɶɤɨɱɚɫɬɨɬɧɭ ɨɛɥɚɫɬɶ ɩɨɪɿɜɧɹɧɨ ɡ ɜɿɥɶɧɢɦ ɥɿɝɚɧɞɨɦ. ɉɨɞɿɛɧɢɣ ɧɢɡɶɤɨɱɚɫɬɨɬɧɢɣ ɡɫɭɜ ɫɩɨɫɬɟɪɿɝɚɜɫɹ ɬɚɤɨɠ ɞɥɹ ɞɢɦɟɪɿɜ EB, ɳɨ ɫɜɿɞɱɢɬɶ ɩɪɨ ɜɡɚɽɦɨɞɿɸ ɚɪɨɦɚɬɢɱɧɢɯ ɤɿɥɟɰɶ EB ɡ ɚɡɨɬɢɫɬɢɦɢ ɨɫɧɨɜɚɦɢ ȾɇɄ. Ɍɨɦɭ ɬɚɤɢɣ ɡɫɭɜ ɫɦɭɝɢ ɮɟɧɚɧɬɪɢɞɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɦɨɠɟ ɛɭɬɢ 1350 1380 1410 1440 1470 1377 1411 1389 1351 ȼɿɞɧɨɫɧɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ 1434 1452 1428 1415 1360 1403 1446 1462 1 Ɋɢɫɭɧɨɤ 5.10 ɋɩɟɤɬɪɢ ɄɊ ɪɨɡɱɢɧɿɜ ɛɪɨɦɢɫɬɨɝɨ ɷɬɢɞɿɸ (1) ɿ ɤɨɦɩɥɟɤɫɿɜ P/D = 3 (2) ɿ EB-ȾɇɄ P/D = 20 (3) ɩɪɢ ɜ 2 ɿɧɬɟɪɜɚɥɚɯ ɱɚɫɬɨɬ 1340-1470 ɫɦ-1; ɋEB = 1,1×10-4 Ɇ, ɪɇ = 6,86 1356 1372 1395 1412 1424 3 1350 1380 1410 1440 -1 Q, ɫɦ 1470 142 Ɍɚɛɥɢɰɹ 5.2 ɑɚɫɬɨɬɢ ɫɦɭɝ ɭ ɫɩɟɤɬɪɿ ɄɊ ɬɚ ʀɯ ɜɿɞɧɟɫɟɧɧɹ ɞɥɹ ɛɪɨɦɢɫɬɨɝɨ ɷɬɢɞɿɸ (EB) ɿ ɜ ɤɨɦɩɥɟɤɫɿ ɡ ȾɇɄ ɜ ɱɚɫɬɨɬɧɨɦɭ ɞɿɚɩɚɡɨɧɿ 1350-1465 ɫɦ-1 EB (C§1,1×10-4 M), ȼɿɞɧɟɫɟɧɧɹ ɫɦ-1 1351±2 Ɏɟɧɚɧɬɪ. ɤɿɥɶɰɟ (C-C, C-N) 1377±2 į(CH3) 1389±2 Ⱦɢɯɚɥɶɧɟ ɤɨɥ. 1411±2 ɮɟɧɚɧɬɪ. ɤɿɥɶɰɹ į(CH2) 1434±2 į(CH3) 1452±2 EB-ȾɇɄ P/D = 20, ɫɦ-1 P/D = 3, ɫɦ-1 1360±2 1356±2 1377±2 1372±2 1388±2 1395±2 1415±2 1446±2 1462±2 1412±2 1447±2 1462±2 ɤɪɢɬɟɪɿɽɦ ɿɧɬɟɪɤɚɥɹɰɿʀ ɯɪɨɦɨɮɨɪɭ EB ɦɿɠ ɩɚɪɚɦɢ ɨɫɧɨɜ ȾɇɄ. ɋɯɨɠɢɣ ɟɮɟɤɬ ɫɩɨɫɬɟɪɿɝɚɜɫɹ ɜ ɫɩɟɤɬɪɚɯ ɄɊ ɞɨɤɫɨɪɭɛɿɰɢɧɭ ɩɪɢ ɣɨɝɨ ɿɧɬɟɪɤɚɥɹɰɿʀ ɞɨ ȾɇɄ [247]. Ɂɿ ɫɩɟɤɬɪɚ ɄɊ ɤɨɦɩɥɟɤɫɭ ɩɪɢ P/D = 3 (ɪɢɫ. 5.10) ɜɢɞɧɨ, ɳɨ ɫɦɭɝɚ ɩɪɢ Ȟ = 1377 ɫɦ-1 (±2 cɦ-1) ɧɟ ɡɚɡɧɚɽ ɧɢɡɶɤɨɱɚɫɬɨɬɧɨɝɨ ɡɦɿɳɟɧɧɹ ɩɨɪɿɜɧɹɧɨ ɡɿ ɫɩɟɤɬɪɨɦ ɜɿɥɶɧɨɝɨ EB. ɐɟ ɩɨɜ'ɹɡɚɧɨ ɡ ɬɢɦ, ɳɨ ɩɪɢ ɧɢɡɶɤɢɯ ɡɧɚɱɟɧɧɹɯ P/D ɭ ɫɭɦɿɲɚɯ EB-ȾɇɄ ɭɬɜɨɪɸɸɬɶɫɹ ɡɞɟɛɿɥɶɲɨɝɨ ɤɨɦɩɥɟɤɫɢ ɡɚ ɡɨɜɧɿɲɧɿɦ ɬɢɩɨɦ ɡɜ'ɹɡɭɜɚɧɧɹ, ɚ ɤɨɧɰɟɧɬɪɚɰɿɹ ɤɨɦɩɥɟɤɫɿɜ ɡɚ ɬɢɩɨɦ ɿɧɬɟɪɤɚɥɹɰɿʀ ɧɟɡɧɚɱɧɚ ɿ ɩɪɚɤɬɢɱɧɨ ɧɟ ɜɧɨɫɢɬɶ ɡɦɿɧ ɭ ɄɊ-ɫɦɭɝɢ. Ⱦɥɹ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ ɋɇ2- ɿ ɋɇ3-ɝɪɭɩ EB ɫɩɨɫɬɟɪɿɝɚɸɬɶɫɹ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɩɪɢ ɭɬɜɨɪɟɧɧɿ ɨɛɨɯ ɬɢɩɿɜ ɤɨɦɩɥɟɤɫɿɜ ɡ ȾɇɄ (ɪɢɫ. 5.10, Ɍɚɛɥ. 5.2). Ɂ Ɍɚɛɥ. 5.1 ɬɚɤɨɠ ɜɢɞɧɨ, ɳɨ ɰɿ ɤɨɥɢɜɚɧɧɹ ɱɭɬɥɢɜɿ ɞɨ ɦɨɧɨɦɟɪɧɨɞɢɦɟɪɧɨɝɨ ɩɟɪɟɯɨɞɭ. Ɉɞɧɚɤ ɩɨɹɫɧɟɧɧɹ ɬɚɤɨʀ ɡɚɥɟɠɧɨɫɬɿ ɜɢɦɚɝɚɽ ɞɨɞɚɬɤɨɜɢɯ ɞɨɫɥɿɞɠɟɧɶ. ȱɧɲɚ ɫɦɭɝɚ ɮɟɧɚɧɬɪɢɞɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɩɪɢ 1411 ɫɦ-1 (±2 cɦ-1) (ɪɢɫ. 5.10), ɳɨ ɜɿɞɧɨɫɢɬɶɫɹ ɞɨ ɞɢɯɚɥɶɧɨɝɨ ɤɨɥɢɜɚɧɧɹ ɤɿɥɶɰɹ, ɜ ɪɨɡɱɢɧɿ ɡ P/D = 3 ɡɫɭɜɚɽɬɶɫɹ ɞɨ ɛɿɥɶɲ ɜɢɫɨɤɨɱɚɫɬɨɬɧɨɝɨ ɡɧɚɱɟɧɧɹ ɩɪɢ 1415 ɫɦ-1 (±2 cɦ-1). ɉɨɞɿɛɧɢɣ ɟɮɟɤɬ ɜɿɞɦɿɱɟɧɨ ɭ ɪɨɛɨɬɿ [245] ɩɪɢ ɡɚɦɿɳɟɧɧɿ ɚɬɨɦɚ ɜɨɞɧɸ N2H2-ɝɪɭɩɢ EB ɧɚ ɤɿɥɶɰɟ 2-ɚɦɿɧɨ-4-ɯɥɨɪ-6-ɦɟɬɢɥɩɿɪɢɦɿɞɢɧɭ. ɉɪɢ P/D = 20 ɰɹ 143 ɫɦɭɝɚ ɧɟ ɡɦɿɧɸɽ ɫɜɨɝɨ ɩɨɥɨɠɟɧɧɹ. Ɍɚɤɿ ɜɿɞɦɿɧɧɨɫɬɿ ɬɚɤɨɠ ɦɨɠɭɬɶ ɫɜɿɞɱɢɬɢ ɩɪɨ ɪɿɡɧɿ ɬɢɩɢ ɤɨɦɩɥɟɤɫɿɜ ɥɢɝɚɧɞɭ ɡ ɩɨɥɿɧɭɤɥɟɨɬɢɞɧɨɸ ɦɚɬɪɢɰɟɸ, ɳɨ ɭɬɜɨɪɸɸɬɶɫɹ ɩɪɢ ɜɢɫɨɤɢɯ ɿ ɧɢɡɶɤɢɯ ɡɧɚɱɟɧɧɹɯ P/D. Ⱥɥɟ ɞɥɹ ɨɞɧɨɡɧɚɱɧɨɝɨ ɜɢɫɧɨɜɤɭ ɩɨɬɪɿɛɟɧ ɛɿɥɶɲ ɞɟɬɚɥɶɧɢɣ ɚɧɚɥɿɡ, ɹɤ ɿ ɭ ɜɢɩɚɞɤɭ ɋɇ2- ɿ ɋɇ3-ɝɪɭɩ. ɇɚ ɪɢɫ. 5.11 ɧɚɜɟɞɟɧɨ ɫɩɟɤɬɪɢ ɄɊ ɫɭɦɿɲɟɣ EB-ȾɇɄ ɩɪɢ ɪɿɡɧɢɯ ɡɧɚɱɟɧɧɹɯ P/D, ɚ ɬɚɤɨɠ ɫɩɟɤɬɪ ɜɿɥɶɧɨɝɨ EB. ɉɪɟɞɫɬɚɜɥɟɧɿ ɫɩɟɤɬɪɢ ɛɭɥɨ ɨɬɪɢɦɚɧɨ ɲɥɹɯɨɦ ɭɫɟɪɟɞɧɟɧɧɹ ɧɟ ɦɟɧɲɟ 10 ɫɤɚɧɿɜ, ɡɚɩɢɫɚɧɢɯ ɩɪɢ ɨɞɧɚɤɨɜɢɯ ɭɦɨɜɚɯ. ȼ ɰɸ ɫɩɟɤɬɪɚɥɶɧɭ ɨɛɥɚɫɬɶ ɨɫɧɨɜɧɢɣ ɜɧɟɫɨɤ ɞɚɸɬɶ ɞɟɮɨɪɦɚɰɿɣɧɿ ɤɨɥɢɜɚɧɧɹ NH2-ɝɪɭɩ [230, 231] ɿ ɤɨɥɢɜɚɧɧɹ ɮɟɧɢɥɶɧɨɝɨ ɤɿɥɶɰɹ EB [231, 245]. ȼɿɞɩɨɜɿɞɧɿ ɫɦɭɝɢ ɄɊ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɬɚ ʀɯ ɜɿɞɧɟɫɟɧɧɹ ɧɚɜɟɞɟɧɨ ɜ ɬɚɛɥ. 5.3. əɤ ɜɢɞɧɨ ɡɿ ɫɩɟɤɬɪɿɜ 2 ɿ 3 (ɪɢɫ. 5.11), ɚ ɬɚɤɨɠ ɡ ɞɚɧɢɯ, ɧɚɜɟɞɟɧɢɯ ɭ Ɍɚɛɥ. 5.3, ɭɬɜɨɪɟɧɧɹ ɞɜɨɯ ɬɢɩɿɜ ɤɨɦɩɥɟɤɫɿɜ EB-ȾɇɄ (P/D = 3 ɿ P/D = 20) ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɜɢɫɨɤɨɱɚɫɬɨɬɧɢɦ ɡɫɭɜɨɦ ɧɚ ǻȞ = 5 ɫɦ-1 (±2 cɦ-1) ɫɦɭɝɢ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ NH2-ɝɪɭɩ ɮɟɧɚɧɬɪɢɞɢɧɨɜɨɝɨ ɯɪɨɦɨɮɨɪɚ ɥɿɝɚɧɞɭ [245]. 1605 1620 1635 1650 1602 1626 1642 ȼɿɞɧɨɫɧɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ 1615 1 1648 Ɋɢɫɭɧɨɤ 5.11 ɋɩɟɤɬɪɢ ɄɊ ɪɨɡɱɢɧɿɜ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ (1) ɿ 1613 1631 ɤɨɦɩɥɟɤɫɿɜ EB-ȾɇɄ ɩɪɢ P/D = 3 (2) ɿ P/D = 20 (3) ɜ ɿɧɬɟɪɜɚɥɚɯ ɱɚɫɬɨɬ 2 1617 1600-1660 ɫɦ-1; ɪɇ = 6,86 ɋEB = 1,1×10-4 Ɇ, 3 1605 1620 1635 Q , ɫɦ -1 1650 144 Ɍɚɛɥɢɰɹ 5.3 ɑɚɫɬɨɬɢ ɫɦɭɝ ɭ ɫɩɟɤɬɪɿ ɄɊ ɬɚ ʀɯ ɜɿɞɧɟɫɟɧɧɹ ɞɥɹ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɜ ɤɨɦɩɥɟɤɫɿ ɡ ȾɇɄ ɜ ɱɚɫɬɨɬɧɨɦɭ ɞɿɚɩɚɡɨɧɿ 1600-1660 ɫɦ-1 ȼɿɞɧɟɫɟɧɧɹ Ɏɟɧɢɥɶɧɟ ɤɿɥɶɰɟ Ɏɟɧɢɥɶɧɟ ɤɿɥɶɰɟ (C=C) į(NH2) EB (C§1,1×10-4 M), ɫɦ-1 1602±2 1615±2 1626±2 EB-ȾɇɄ P/D = 3, P/D = 20, -1 ɫɦ ɫɦ-1 1603±2 1602±2 1617±2 1631±2 1613±2 1631±2 ɐɟɣ ɮɚɤɬ ɫɜɿɞɱɢɬɶ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ ɦɿɠ NH2-ɝɪɭɩɚɦɢ EB ɿ ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ȾɇɄ. Ɂɝɿɞɧɨ ɿɡ ɡɚɩɪɨɩɨɧɨɜɚɧɨɸ ɜ ɪɨɛɨɬɿ [246] ɦɨɞɟɥɥɸ ɿɧɬɟɪɤɚɥɹɰɿʀ ɮɟɧɚɧɬɪɢɞɢɧɨɜɨɝɨ ɯɪɨɦɨɮɨɪɭ EB, ɬɚɤɢɦɢ ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɦɨɠɭɬɶ ɛɭɬɢ ɚɬɨɦɢ N1 ɰɢɬɨɡɢɧɭ ɿ N9 ɝɭɚɧɿɧɭ ɜ ɩɪɨɬɢɥɟɠɧɢɯ ɥɚɧɰɸɝɚɯ ȾɇɄ. Ɉɞɧɚɤ ɭ ɪɨɛɨɬɿ [248] ɦɟɬɨɞɨɦ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɞɨɤɿɧɝɭ ɩɨɤɚɡɚɧɨ ɦɨɠɥɢɜɿɫɬɶ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɦɿɠ NH2-ɝɪɭɩɚɦɢ EB, ɿɧɬɟɪɤɚɥɶɨɜɚɧɨɝɨ ɜ GC-ɫɚɣɬ ȾɇɄ, ɡ ɚɬɨɦɚɦɢ Ɉ4' ɿ O5' ɞɟɡɨɤɫɢɪɢɛɨɡɢ ɝɭɚɧɿɧɭ ɩɪɨɬɢɥɟɠɧɢɯ ɥɚɧɰɸɝɿɜ. Ɍɚɤɚ ɦɨɞɟɥɶ ɩɿɞɬɜɟɪɞɠɭɽɬɶɫɹ ɞɚɧɢɦɢ ɪɟɧɬɝɟɧɨ-ɫɬɪɭɤɬɭɪɧɨɝɨ ɚɧɚɥɿɡɚ ɤɨɦɩɥɟɤɫɭ EB ɡ ɞɢɧɭɤɥɟɨɬɢɞɨɦ d(CpG), ɜ ɹɤɨɦɭ ɜɢɹɜɥɟɧɨ ɇ-ɡɜ'ɹɡɨɤ ɦɿɠ NH2 ɝɪɭɩɨɸ EB ɿ ɚɬɨɦɨɦ Ɉ5' ɞɟɡɨɤɫɢɪɢɛɨɡɢ [249]. Ɍɚɤɢɦ ɱɢɧɨɦ, ɩɪɢ ɜɢɫɨɤɢɯ ɬɚ ɧɢɡɶɤɢɯ ɡɧɚɱɟɧɧɹɯ P/D ɧɚ ɫɩɟɤɬɪɚɯ ɄɊ ɫɩɨɫɬɟɪɿɝɚɸɬɶɫɹ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɫɦɭɝ ɞɟɮɨɪɦɚɰɿɣɧɢɯ ɤɨɥɢɜɚɧɶ NH2ɝɪɭɩ ɥɿɝɚɧɞɭ, ɳɨ ɫɜɿɞɱɢɬɶ ɩɪɨ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ ɰɢɯ ɝɪɭɩ ɡ ȾɇɄ ɹɤ ɭ ɜɢɩɚɞɤɭ ɿɧɬɟɪɤɚɥɶɨɜɚɧɨɝɨ ɯɪɨɦɨɮɨɪɭ EB, ɬɚɤ ɿ ɭ ɜɢɩɚɞɤɭ ɡɨɜɧɿɲɧɶɨɝɨ ɡɜ'ɹɡɭɜɚɧɧɹ ɧɚ ɩɨɜɟɪɯɧɿ ɦɨɥɟɤɭɥɢ ȾɇɄ. ɐɿ ɜɨɞɧɟɜɿ ɡɜ'ɹɡɤɢ ɪɚɡɨɦ ɡ ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɚɪɨɦɚɬɢɱɧɢɯ ɤɿɥɟɰɶ ɯɪɨɦɨɮɨɪɭ EB ɿ ɚɡɨɬɢɫɬɢɯ ɨɫɧɨɜ (ɰɢɬɨɡɢɧɭ ɿ ɝɭɚɧɿɧɭ) ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɸɬɶ ɤɨɦɩɥɟɤɫ EB-ȾɇɄ, ɳɨ ɩɪɢɡɜɨɞɢɬɶ ɞɨ ɡɛɿɥɶɲɟɧɧɹ ɣɨɝɨ ɬɟɪɦɨɫɬɚɛɿɥɶɧɨɫɬɿ [250]. 145 Ⱦɥɹ ɬɨɝɨ ɳɨɛ ɜɫɬɚɧɨɜɢɬɢ, ɜ ɹɤɨɦɭ ɫɬɪɭɤɬɭɪɧɨɦɭ ɫɬɚɧɿ ɡɧɚɯɨɞɢɬɶɫɹ ȾɇɄ ɭ ɤɨɦɩɥɟɤɫɿ ɡ EB ɩɪɢ ɧɢɡɶɤɢɯ ɿ ɜɢɫɨɤɢɯ ɡɧɚɱɟɧɧɹɯ P/D, ɛɭɥɨ ɨɬɪɢɦɚɧɨ ɄɊ-ɫɩɟɤɬɪɢ ɤɨɦɩɥɟɤɫɿɜ ɭ ɨɛɥɚɫɬɿ ɦɚɪɤɟɪɧɢɯ ɫɦɭɝ ȾɇɄ [212, 251-253]. ɇɚ ɪɢɫ. 5.12 ɧɚɜɟɞɟɧɨ ɱɚɫɬɨɬɧɢɣ ɞɿɚɩɚɡɨɧ Ȟ = 750-850 ɫɦ-1 ɞɥɹ ɫɩɟɤɬɪɭ ɱɢɫɬɨɝɨ EB, ɫɩɟɤɬɪɿɜ ɫɭɦɿɲɟɣ EB-ȾɇɄ ɩɪɢ ɞɜɨɯ ɡɧɚɱɟɧɧɹɯ P/D ɿ ɫɩɟɤɬɪɿɜ ȾɇɄ ɜ ȼ- ɬɚ Ⱥ-ɮɨɪɦɚɯ. ɍɫɿ ɫɩɟɤɬɪɢ ɛɭɥɨ ɨɬɪɢɦɚɧɨ ɲɥɹɯɨɦ ɭɫɟɪɟɞɧɟɧɧɹ ɧɟ ɦɟɧɲɟ 10 ɫɤɚɧɿɜ, ɡɚɩɢɫɚɧɢɯ ɩɪɢ ɨɞɧɚɤɨɜɢɯ ɭɦɨɜɚɯ. Ⱦɭɠɟ ɫɥɚɛɤɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ ɄɊ-ɫɦɭɝ EB ɭ ɰɶɨɦɭ ɫɩɟɤɬɪɚɥɶɧɨɦɭ ɞɿɚɩɚɡɨɧɿ ɩɨɪɿɜɧɹɧɨ ɡɿ ɫɩɟɤɬɪɚɦɢ ȾɇɄ ɞɨɡɜɨɥɹɽ ɡɧɟɯɬɭɜɚɬɢ ɜɧɟɫɤɨɦ ɤɨɥɢɜɚɧɶ ɥɿɝɚɧɞɭ ɜ ɫɩɟɤɬɪ ɤɨɦɩɥɟɤɫɿɜ EB-ȾɇɄ ɿ ɫɬɟɠɢɬɢ ɡɚ ɩɨɜɟɞɿɧɤɨɸ ɦɨɥɟɤɭɥɢ ȾɇɄ. 750 775 800 825 810 766 780 807 825 1 2 ȼɿɞɧɨɫɧɚ ɿɧɬɟɧɫɢɜɧɿɫɬɶ 796 816 781 788 798 816 782 803 832 4 5 834 Ɋɢɫɭɧɨɤ 5.12 ɋɩɟɤɬɪɢ ɄɊ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ (1), ɤɨɦɩɥɟɤɫɿɜ EB-ȾɇɄ ɩɪɢ P/D = 3 (2) ɿ P/D = 20 (3) 3 ɿ ɫɩɟɤɬɪɢ ɩɥɿɜɨɤ ȾɇɄ ɩɪɢ ɪɿɡɧɢɯ ɜɿɞɧɨɫɧɢɯ ɜɨɥɨɝɨɫɬɹɯ: 96% ȼȼ – ȼȾɇɄ (4) ɿ 76% ȼȼ – Ⱥ-ȾɇɄ (5); ɋEB = 1,1×10-4 Ɇ, ɪɇ = 6,86 750 775 800 Q , ɫɦ -1 825 əɤ ɜɢɞɧɨ ɡ ɪɢɫ. 5.12, ɩɪɢ ɛɿɥɶɲ ɳɿɥɶɧɨɦɭ ɡɚɩɨɜɧɟɧɧɿ ɦɚɬɪɢɰɿ ȾɇɄ ɥɿɝɚɧɞɨɦ (P/D = 3) ɭɬɜɨɪɟɧɧɹ ɤɨɦɩɥɟɤɫɭ ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɩɨɹɜɨɸ ɫɦɭɝ ɩɪɢ Ȟ = 780 ɿ 807 ɫɦ-1 (±2 cɦ-1). əɤ ɜɿɞɨɦɨ [212, 251-253], ɰɿ ɫɦɭɝɢ ɽ ɯɚɪɚɤɬɟɪɧɢɦɢ 146 ɦɚɪɤɟɪɚɦɢ Ⱥ-ɮɨɪɦɢ ȾɇɄ. Ɍɨɦɭ ɩɪɨɜɟɞɟɧɟ ɞɨɫɥɿɞɠɟɧɧɹ ɩɿɞɬɜɟɪɞɠɭɽ ɡɪɨɛɥɟɧɿ ɪɚɧɿɲɟ ɜɢɫɧɨɜɤɢ ɩɪɨ ɬɟ, ɳɨ ɳɿɥɶɧɟ ɡɚɩɨɜɧɟɧɧɹ ɦɚɬɪɢɰɿ ȾɇɄ ɛɪɨɦɢɫɬɢɦ ɟɬɢɞɿɽɦ ɩɟɪɟɜɨɞɢɬɶ ʀʀ ɡ ȼ-ɮɨɪɦɢ ɞɨ Ⱥ-ɩɨɞɿɛɧɨʀ ɤɨɧɮɨɪɦɚɰɿʀ [231, 254, 255]. ɉɪɢ P/D = 20 ɭ ɫɩɟɤɬɪɿ ɄɊ ɫɩɨɫɬɟɪɿɝɚɸɬɶɫɹ ɫɦɭɝɢ ɩɪɢ Ȟ = 834, 796 ɿ 781 ɫɦ-1 (ɪɢɫ. 5.12), ɹɤɿ ɯɚɪɚɤɬɟɪɧɿ ɞɥɹ ȼ-ɮɨɪɦɢ ȾɇɄ [212, 251-253]. Ɉɬɠɟ, ɩɪɢ ɜɟɥɢɤɢɯ ɡɧɚɱɟɧɧɹɯ P/D (• 20) ȾɇɄ ɜ ɤɨɦɩɥɟɤɫɚɯ ɡ EB ɡɧɚɯɨɞɢɬɶɫɹ ɭ ȼɤɨɧɮɨɪɦɚɰɿʀ. Ɏɨɪɦɭɜɚɧɧɹ ɤɨɦɩɥɟɤɫɭ ɩɪɢ ɦɚɥɢɯ ɡɧɚɱɟɧɧɹɯ P/D (” 3) ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɜɢɬɿɫɧɟɧɧɹɦ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɹ ɡ ɿɧɬɟɪɤɚɥɹɰɿɣɧɨɝɨ ɫɚɣɬɭ ɩɿɞ ɱɚɫ ɫɬɪɭɤɬɭɪɧɨɝɨ ɩɟɪɟɯɨɞɭ ȾɇɄ ɞɨ Ⱥ-ɩɨɞɿɛɧɨʀ ɮɨɪɦɢ, ɭ ɹɤɿɣ ɦɿɧɨɪɧɢɣ ɠɨɥɨɛɨɤ ɲɢɪɲɚɽ ɿ ɫɬɚɽ ɞɪɿɛɧɿɲɢɦ, ɿ ɩɪɢɡɜɨɞɢɬɶ ɞɨ ɡɨɜɧɿɲɧɶɨɝɨ ɬɢɩɭ ɡɜ'ɹɡɭɜɚɧɧɹ ɥɿɝɚɧɞɭ. ȼɢɫɧɨɜɤɢ ɞɨ ɪɨɡɞɿɥɭ 5 1. ɇɚ ɩɿɞɫɬɚɜɿ ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɜɩɟɪɲɟ ɨɬɪɢɦɚɧɨ ɩɪɹɦɢɣ ɞɨɤɚɡ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɚɯ ɚɪɨɦɚɬɢɱɧɢɯ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ (FMN-EB, FMN-PRF). ɍ ɧɟɣɬɪɚɥɶɧɢɯ ɪɨɡɱɢɧɚɯ ɭ ɫɬɨɩɤɨɜɢɯ ɫɬɪɭɤɬɭɪɚɯ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ FMN-EB ɿ FMN-PRF ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɸɬɶ ɰɿ ɤɨɦɩɥɟɤɫɢ ɪɚɡɨɦ ɡ ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɦɿɠ ɯɪɨɦɨɮɨɪɚɦɢ ɦɨɥɟɤɭɥ ɭ ɤɨɦɩɥɟɤɫɚɯ ɬɚ ʀɯ ɜɡɚɽɦɨɞɿɽɸ ɡ ɜɨɞɧɢɦ ɨɬɨɱɟɧɧɹɦ. ȼɢɤɨɧɚɧɢɣ ɦɟɬɨɞɨɦ Ɇɋ ɞɟɬɚɥɶɧɢɣ ɚɧɚɥɿɡ ɟɧɟɪɝɟɬɢɱɧɢɯ ɿ ɫɬɪɭɤɬɭɪɧɢɯ ɯɚɪɚɤɬɟɪɢɫɬɢɤ ɫɢɫɬɟɦ, ɳɨ ɦɿɫɬɹɬɶ ɝɟɬɟɪɨɚɫɨɰɿɚɬɢ ɚɪɨɦɚɬɢɱɧɢɯ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɥɿɝɚɧɞɿɜ FMN, EB, PRF ɿ ɜɨɞɧɿ ɤɥɚɬɟɪɢ, ɩɿɞɬɜɟɪɞɢɜ, ɳɨ ɜ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɚɯ FMN-EB, FMN-PRF ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɮɨɪɦɭɸɬɶɫɹ ɦɿɠ ɮɭɧɤɰɿɨɧɚɥɶɧɢɦɢ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ (C=O ɿ NH2), ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɸɱɢ ɫɬɪɭɤɬɭɪɢ ɝɟɬɟɪɨɞɢɦɟɪɿɜ. Ɋɟɡɭɥɶɬɚɬɢ ɦɨɞɟɥɸɜɚɧɧɹ ɦɟɬɨɞɨɦ Ɇɋ ɩɪɨɞɟɦɨɧɫɬɪɭɜɚɥɢ ɦɨɠɥɢɜɿɫɬɶ 2. 147 ɮɨɪɦɭɜɚɧɧɹ ɜɨɞɧɢɯ «ɦɿɫɬɤɿɜ» ɬɚ ʀɯ ɪɨɥɶ ɭ ɞɨɞɚɬɤɨɜɿɣ ɫɬɚɛɿɥɿɡɚɰɿʀ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɞɨɫɥɿɞɠɭɜɚɧɢɯ ȻȺɊ. 3. ȼɢɤɨɧɚɧɨ ɨɰɿɧɤɭ ɟɧɬɚɥɶɩɿʀ ɇ-ɡɜ'ɹɡɤɭ ɞɥɹ ɫɢɫɬɟɦ FMN-EB ɿ FMN-PRF. ȼɧɟɫɨɤ ɇ-ɡɜ'ɹɡɤɿɜ ɫɬɚɧɨɜɢɬɶ ~25-30% ɜɿɞ ɡɚɝɚɥɶɧɨʀ ɟɧɬɚɥɶɩɿʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɰɢɯ ɤɨɦɩɥɟɤɫɿɜ. Ɉɞɧɚɤ, ɞɟɬɚɥɶɧɢɣ ɪɨɡɝɥɹɞ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɦɚɽ ɜɟɥɢɤɟ ɡɧɚɱɟɧɧɹ ɞɥɹ ɩɪɚɜɢɥɶɧɨɝɨ ɪɨɡɭɦɿɧɧɹ ɟɧɟɪɝɟɬɢɤɢ ɪɟɚɤɰɿɣ ɝɟɬɟɪɨɚɫɨɰɿɚɰɿʀ. 4. ɉɪɨɜɟɞɟɧɟ ɞɨɫɥɿɞɠɟɧɧɹ ɤɨɦɩɥɟɤɫɨɭɬɜɨɪɟɧɧɹ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɡ ȾɇɄ ɦɟɬɨɞɨɦ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɄɊ ɞɨɡɜɨɥɢɥɨ ɜɫɬɚɧɨɜɢɬɢ, ɳɨ ɩɪɢ ɜɢɫɨɤɢɯ ɡɧɚɱɟɧɧɹɯ P/D, ɤɨɥɢ ɤɨɧɰɟɧɬɪɚɰɿɹ ɥɿɝɚɧɞɭ ɜ ɪɨɡɱɢɧɿ ɦɚɥɚ, ɫɬɚɛɿɥɿɡɚɰɿɹ ɤɨɦɩɥɟɤɫɭ ɡɞɿɣɫɧɸɽɬɶɫɹ ɧɟ ɬɿɥɶɤɢ ɡɚ ɪɚɯɭɧɨɤ ɦɿɠɩɥɨɳɢɧɧɢɯ ɜɡɚɽɦɨɞɿɣ ɿɧɬɟɪɤɚɥɶɨɜɚɧɨɝɨ ɯɪɨɦɨɮɨɪɭ, ɚɥɟ ɣ ɲɥɹɯɨɦ ɭɬɜɨɪɟɧɧɹ ɦɿɠɦɨɥɟɤɭɥɹɪɧɢɯ ɇ-ɡɜ'ɹɡɤɿɜ ɦɿɠ ɚɦɿɧɨɝɪɭɩɚɦɢ EB ɿ ɚɬɨɦɚɦɢ Ɉ4' ɿ Ɉ5' ɞɟɡɨɤɫɢɪɢɛɨɡɢ. ɍ ɰɶɨɦɭ ɜɢɩɚɞɤɭ ȾɇɄ ɡɛɟɪɿɝɚɽɬɶɫɹ ɭ ȼ-ɮɨɪɦɿ. ɉɪɢ ɧɢɡɶɤɢɯ ɡɧɚɱɟɧɧɹɯ P/D ɮɨɪɦɭɜɚɧɧɹ ɤɨɦɩɥɟɤɫɭ EB-ȾɇɄ ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɫɬɪɭɤɬɭɪɧɢɦ ɩɟɪɟɯɨɞɨɦ ȾɇɄ ɡ ȼ- ɞɨ Ⱥ-ɩɨɞɿɛɧɨʀ ɤɨɧɮɨɪɦɚɰɿʀ, ɚ ɚɦɿɧɨɝɪɭɩɢ EB ɜɡɚɽɦɨɞɿɸɬɶ ɡ ɰɭɤɪɨɮɨɫɮɚɬɧɢɦ ɨɫɬɨɜɨɦ ɩɨɥɿɧɭɤɥɟɨɬɢɞɧɨʀ ɦɚɬɪɢɰɿ, ɫɬɚɛɿɥɿɡɭɸɱɢ ɡɨɜɧɿɲɧɸ «ɩɨɫɚɞɤɭ» ɯɪɨɦɨɮɨɪɭ ɧɚ ɩɨɜɟɪɯɧɿ ɦɨɥɟɤɭɥɢ ȾɇɄ. Ɋɟɡɭɥɶɬɚɬɢ ɞɨɫɥɿɞɠɟɧɶ ɞɚɧɨɝɨ ɪɨɡɞɿɥɭ ɧɚɜɟɞɟɧɨ ɜ ɩɭɛɥɿɤɚɰɿɹɯ ɡɞɨɛɭɜɚɱɚ: [223], [241], [242] 148 ɁȺȽȺɅɖɇȱ ȼɂɋɇɈȼɄɂ ɍ ɞɢɫɟɪɬɚɰɿɣɧɿɣ ɪɨɛɨɬɿ ɜɢɪɿɲɟɧɨ ɨɞɧɭ ɡ ɚɤɬɭɚɥɶɧɢɯ ɩɪɨɛɥɟɦ ɫɭɱɚɫɧɨʀ ɦɨɥɟɤɭɥɹɪɧɨʀ ɛɿɨɮɿɡɢɤɢ – ɡ'ɹɫɭɜɚɧɧɹ ɪɨɥɿ ɜɨɞɧɟɜɢɯ ɡɜ'ɹɡɤɿɜ ɿ ɦɨɥɟɤɭɥ ɜɨɞɢ ɜ ɫɬɚɛɿɥɿɡɚɰɿʀ ɫɚɦɨɚɫɨɰɿɚɬɿɜ ɿ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɪɹɞɭ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ ɿ ɩɪɢ ʀɯ ɡɜ'ɹɡɭɜɚɧɧɿ ɡ ȾɇɄ. Ɂ ɜɢɤɨɪɢɫɬɚɧɧɹɦ ɦɟɬɨɞɿɜ ɤɨɥɢɜɚɥɶɧɨʀ (ȱɑ ɿ ɄɊ) ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɬɚ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɩɨɛɭɞɨɜɚɧɨ ɤɨɦɩɥɟɤɫɢ ȻȺɊ ɿ ɜɢɤɨɧɚɧɨ ɨɰɿɧɤɭ ɜɤɥɚɞɭ ɇ-ɡɜ'ɹɡɤɿɜ ɭ ɡɚɝɚɥɶɧɭ ɟɧɟɪɝɿɸ ʀɯ ɫɬɚɛɿɥɿɡɚɰɿʀ. Ɉɬɪɢɦɚɧɿ ɪɟɡɭɥɶɬɚɬɢ ɡɚɤɥɚɞɚɸɬɶ ɨɫɧɨɜɭ ɞɥɹ ɛɿɥɶɲ ɩɨɜɧɨɝɨ ɪɨɡɭɦɿɧɧɹ ɦɨɥɟɤɭɥɹɪɧɢɯ ɦɟɯɚɧɿɡɦɿɜ ɿɧɬɟɪɰɟɩɬɨɪɧɨʀ ɞɿʀ ȻȺɊ ɧɚ ȾɇɄ. Ɉɫɧɨɜɧɿ ɪɟɡɭɥɶɬɚɬɢ, ɨɬɪɢɦɚɧɿ ɜ ɪɨɛɨɬɿ, ɦɨɠɧɚ ɫɮɨɪɦɭɥɸɜɚɬɢ ɧɚɫɬɭɩɧɢɦ ɱɢɧɨɦ: 1. ȼɩɟɪɲɟ ɧɚ ɩɿɞɫɬɚɜɿ ȱɑ- ɿ ɄɊ-ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɨɬɪɢɦɚɧɨ ɩɪɹɦɢɣ ɞɨɤɚɡ ɭɬɜɨɪɟɧɧɹ ɇ-ɡɜ'ɹɡɤɿɜ ɦɿɠ ɞɨɧɨɪɧɢɦɢ (NH2) ɬɚ ɚɤɰɟɩɬɨɪɧɢɦɢ (ɋ=Ɉ) ɝɪɭɩɚɦɢ ɩɪɢ ɮɨɪɦɭɜɚɧɧɿ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɚɪɨɦɚɬɢɱɧɢɯ ɛɿɨɥɨɝɿɱɧɨ ɚɤɬɢɜɧɢɯ ɪɟɱɨɜɢɧ (FMN-EB, FMN-PRF, TPH-EB). ɉɨɤɚɡɚɧɨ, ɳɨ ɜ ɧɟɣɬɪɚɥɶɧɢɯ ɜɨɞɧɢɯ ɪɨɡɱɢɧɚɯ ɭ ɫɬɨɩɤɨɜɢɯ ɫɬɪɭɤɬɭɪɚɯ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɸɬɶ ɤɨɦɩɥɟɤɫɢ ɪɚɡɨɦ ɡ ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɬɚ ɜɡɚɽɦɨɞɿɽɸ ɡ ɜɨɞɧɢɦ ɨɬɨɱɟɧɧɹɦ. ɍ ɝɟɬɟɪɨɚɫɫɨɰɿɚɬɿɜ FMN-EB ɿ FMN-PRF ɦɿɠɦɨɥɟɤɭɥɹɪɧɿ ɇ-ɡɜ'ɹɡɤɢ ɜɧɨɫɹɬɶ ɜɤɥɚɞ ɞɨ 30% ɭ ɡɚɝɚɥɶɧɭ ɟɧɟɪɝɿɸ ɫɬɚɛɿɥɿɡɚɰɿʀ ɤɨɦɩɥɟɤɫɿɜ. 2. ɉɨɤɚɡɚɧɨ, ɳɨ ɜɢɹɜɥɟɧɿ ɜ ɫɭɯɢɯ ɩɥɿɜɤɚɯ, ɨɬɪɢɦɚɧɢɯ ɡɿ ɫɥɚɛɨɤɢɫɥɢɯ (ɪɇ ~ 6,0) ɪɨɡɱɢɧɿɜ FMN, ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɫɦɭɝ ɩɨɝɥɢɧɚɧɧɹ ɜɧɭɬɪɿɲɧɶɨɤɿɥɶɰɟɜɢɯ ɤɨɥɢɜɚɧɶ ɚɬɨɦɿɜ ɿɡɨɚɥɨɤɫɚɡɢɧɨɜɨɝɨ ɤɿɥɶɰɹ ɩɨɜ'ɹɡɚɧɿ ɡ ɩɪɨɬɨɧɭɜɚɧɧɹɦ ɚɬɨɦɿɜ ɚɡɨɬɭ N1 ɿ N5, ɳɨ ɩɿɞɬɜɟɪɞɠɭɽɬɶɫɹ ɤɜɚɧɬɨɜɨɯɿɦɿɱɧɢɦɢ ɪɨɡɪɚɯɭɧɤɚɦɢ ɡɚɪɹɞɿɜ ɧɚ ɚɬɨɦɚɯ ɤɿɥɶɰɹ. 3. ȼɢɤɨɪɢɫɬɨɜɭɸɱɢ ɨɬɪɢɦɚɧɿ ɫɩɟɤɬɪɨɫɤɨɩɿɱɧɿ ɩɚɪɚɦɟɬɪɢ ɤɨɥɢɜɚɧɶ ɋ4=Ɉ ɿ ɋ2=Ɉ ɝɪɭɩ ɚɬɨɦɿɜ FMN ɿ ɪɨɡɪɚɯɭɧɤɢ ɪɟɡɨɧɚɧɫɧɨʀ ɜɡɚɽɦɨɞɿʀ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɞɢɩɨɥɶ-ɞɢɩɨɥɶɧɨɦɭ ɧɚɛɥɢɠɟɧɧɿ, ɜɩɟɪɲɟ ɩɨɛɭɞɨɜɚɧɨ ɦɨɞɟɥɶ n-ɦɨɥɟɤɭɥɹɪɧɨʀ ɫɚɦɨɚɫɨɰɿɚɰɿʀ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ. 149 4. ȼɩɟɪɲɟ ɜɫɬɚɧɨɜɥɟɧɨ, ɳɨ ɜ ɝɟɬɟɪɨɚɫɨɰɿɚɬɚɯ FMN-TPH, TPH-PRF ɿ CAF-EB ɜɨɞɧɟɜɿ ɡɜ'ɹɡɤɢ ɧɟ ɭɬɜɨɪɸɸɬɶɫɹ, ɚ ɫɬɚɛɿɥɿɡɚɰɿɹ ɰɢɯ ɤɨɦɩɥɟɤɫɿɜ ɜɢɡɧɚɱɚɽɬɶɫɹ ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ. ȼɢɹɜɥɟɧɿ ɜɢɫɨɤɨɱɚɫɬɨɬɧɿ ɡɫɭɜɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɤɨɥɢɜɚɧɶ ɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿ FMN-TPH ɩɨɹɫɧɟɧɨ ɪɟɡɨɧɚɧɫɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɤɚɪɛɨɧɿɥɶɧɢɯ ɝɪɭɩ, ɳɨ ɞɨɡɜɨɥɢɥɨ ɩɨɛɭɞɭɜɚɬɢ n-ɦɨɥɟɤɭɥɹɪɧɭ ɫɬɪɭɤɬɭɪɭ ɝɟɬɟɪɨɚɫɨɰɿɚɬɭ, ɫɬɚɛɿɥɿɡɨɜɚɧɭ ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ. 5. Ɂɚ ɞɨɩɨɦɨɝɨɸ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɩɨɤɚɡɚɧɨ, ɳɨ ɭɬɜɨɪɟɧɧɹ ɇɡɜ'ɹɡɤɿɜ ɭ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɚɯ FMN-EB ɿ FMN-PRF ɞɨɞɚɬɤɨɜɨ ɫɬɚɛɿɥɿɡɭɽ ʀɯ ɫɬɪɭɤɬɭɪɢ. Ⱦɥɹ ɝɟɬɟɪɨɚɫɨɰɿɚɬɿɜ FMN-TPH, TPH-EB, TPH-PRF ɿ CAF-EB ɛɭɥɨ ɜɫɬɚɧɨɜɥɟɧɨ ɮɚɤɬ ɞɨɞɚɬɤɨɜɨʀ ɫɬɚɛɿɥɿɡɚɰɿʀ ɰɢɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɿɜ ɭ ɪɟɡɭɥɶɬɚɬɿ ɭɬɜɨɪɟɧɧɹ ɜɨɞɧɢɯ ɦɿɫɬɤɿɜ ɦɿɠ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɥɿɝɚɧɞɿɜ. Ɍɚɤɢɦ ɱɢɧɨɦ, ɧɚ ɩɿɞɫɬɚɜɿ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɚɧɢɯ ɬɚ ɪɟɡɭɥɶɬɚɬɿɜ ɤɨɦɩ'ɸɬɟɪɧɨɝɨ ɦɨɞɟɥɸɜɚɧɧɹ ɞɨɜɟɞɟɧɨ, ɳɨ FMN, CAF ɿ TPH ɽ ɿɧɬɟɪɰɟɩɬɨɪɚɦɢ, ɹɤɿ ɡɞɚɬɧɿ ɡɦɟɧɲɭɜɚɬɢ ɤɨɧɰɟɧɬɪɚɰɿɸ ɦɭɬɚɝɟɧɿɜ EB ɬɚ PRF. 6. Ɇɟɬɨɞɨɦ ɫɩɟɤɬɪɨɫɤɨɩɿʀ ɄɊ ɩɨɤɚɡɚɧɨ, ɳɨ ɩɪɢ P/D • 20 ɫɬɚɛɿɥɿɡɚɰɿɹ ɤɨɦɩɥɟɤɫɭ EB-ȾɇɄ (ɡɿ ɡɛɟɪɟɠɟɧɧɹɦ ȼ-ɮɨɪɦɢ ȾɇɄ) ɞɨɫɹɝɚɽɬɶɫɹ ɧɟ ɬɿɥɶɤɢ ɦɿɠɩɥɨɳɢɧɧɢɦɢ ɜɡɚɽɦɨɞɿɹɦɢ ɿɧɬɟɪɤɚɥɶɨɜɚɧɨɝɨ ɯɪɨɦɨɮɨɪɭ, ɚɥɟ ɣ ɇɡɜ'ɹɡɤɚɦɢ ɦɿɠ NH2-ɝɪɭɩɚɦɢ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ ɬɚ ɞɨɧɨɪɧɨ-ɚɤɰɟɩɬɨɪɧɢɦɢ ɝɪɭɩɚɦɢ ɞɟɡɨɤɫɢɪɢɛɨɡɢ. ɉɪɢ P/D ” 3 ɮɨɪɦɭɜɚɧɧɹ ɤɨɦɩɥɟɤɫɭ EB-ȾɇɄ ɫɭɩɪɨɜɨɞɠɭɽɬɶɫɹ ɫɬɪɭɤɬɭɪɧɢɦ ɩɟɪɟɯɨɞɨɦ ȾɇɄ ɡ ȼ- ɞɨ Ⱥ-ɩɨɞɿɛɧɨʀ ɤɨɧɮɨɪɦɚɰɿʀ, ɚ ɚɦɿɧɨɝɪɭɩɢ EB ɭɬɜɨɪɸɸɬɶ ɇ-ɡɜ'ɹɡɤɢ ɡ ɩɨɥɿɧɭɤɥɟɨɬɢɞɧɨɸ ɦɚɬɪɢɰɟɸ, ɫɬɚɛɿɥɿɡɭɸɱɢ ɡɨɜɧɿɲɧɸ «ɩɨɫɚɞɤɭ» ɯɪɨɦɨɮɨɪɭ ɧɚ ɩɨɜɟɪɯɧɿ ɦɨɥɟɤɭɥɢ ȾɇɄ. 150 ɋɉɂɋɈɄ ȼɂɄɈɊɂɋɌȺɇɂɏ ȾɀȿɊȿɅ Palchaudhuri R. Hergenrother P. J. DNA as a target for anticancer compounds: methods to determine the mode of binding and the mechanism of action // Current Opinion in Biotechnology. 2007. Vol. 18. P. 497–503. DOI: 10.1016/j.copbio.2007.09.006 2. Evstigneev M. P. Hetero-association of aromatic molecules in aqueous solution // International Reviews in Physical Chemistry. 2014. Vol. 33. P. 229–273. DOI: 10.1080/0144235X.2014.926151 3. 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Vol. 27(1). P. 77–89. DOI 10.1007/s11224-015-0696-3 175 7. Ȼɭɞɶɤɨ Ʌ. ȼ., Ȼɥɢɡɧɸɤ ɘ. ɇ. ɉɪɢɦɟɧɟɧɢɟ Ɋɚɦɚɧ ɫɩɟɤɬɪɨɫɤɨɩɢɢ ɞɥɹ ɢɫɫɥɟɞɨɜɚɧɢɹ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ɷɬɢɞɢɭɦɚ ɛɪɨɦɢɞɚ ɫ ȾɇɄ // Ɋɚɞɢɨɮɢɡɢɤɚ ɢ ɋȼɑ ɷɥɟɤɬɪɨɧɢɤɚ : ɬɟɡɢɫɵ ɞɨɤɥ. V ɏɚɪɶɤɨɜɫɤɚɹ ɤɨɧɮɟɪɟɧɰɢɹ ɦɨɥɨɞɵɯ ɭɱɟɧɵɯ, 14–16 ɞɟɤɚɛ. 2005 ɝ. ɏɚɪɶɤɨɜ, 2005. ɋ. 47. 8. Ȼɥɢɡɧɸɤ ɘ. ɇ., Ʉɪɭɝɥɨɜɚ ȿ. Ȼ. Ɋɚɦɚɧ ɢɫɫɥɟɞɨɜɚɧɢɟ ȼĺȺ ɫɬɪɭɤɬɭɪɧɨɝɨ ɩɟɪɟɯɨɞɚ ȾɇɄ ɜ ɩɪɢɫɭɬɫɬɜɢɢ ɷɬɢɞɢɹ ɛɪɨɦɢɞɚ // Ɋɚɞɢɨɮɢɡɢɤɚ ɢ ɗɥɟɤɬɪɨɧɢɤɚ : ɬɟɡɢɫɵ ɞɨɤɥ. VI ɏɚɪɶɤɨɜɫɤɚɹ ɤɨɧɮɟɪɟɧɰɢɹ ɦɨɥɨɞɵɯ ɭɱɟɧɵɯ, 13–14 ɞɟɤɚɛ. 2006 ɝ. ɏɚɪɶɤɨɜ, 2006. ɋ. 33–34. 9. Ȼɥɢɡɧɸɤ ɘ. ɇ., Ȼɨɥɶɛɭɯ Ɍ. ȼ. ɋɬɪɭɤɬɭɪɧɵɟ ɢɡɦɟɧɟɧɢɹ ȾɇɄ ɩɪɢ ɜɡɚɢɦɨɞɟɣɫɬɜɢɢ ɫ ɗȻ ɩɨ ɞɚɧɧɵɦ Ɋɚɦɚɧ ɫɩɟɤɬɪɨɫɤɨɩɢɢ // ɍȻɎɌ-2006 : ɬɟɡɢ ɞɨɩ. IV Ɂ'ʀɡɞ ɍɤɪɚʀɧɫɶɤɨɝɨ ɛɿɨɮɿɡɢɱɧɨɝɨ ɬɨɜɚɪɢɫɬɜɚ, 19–21 ɝɪɭɞ. 2006 ɪ. Ⱦɨɧɟɰɶɤ, 2006. ɋ. 274–275. 10. Ȼɥɢɡɧɸɤ ɘ. ɇ., ɝɟɬɟɪɨɚɫɫɨɰɢɚɰɢɢ ɋɟɦɟɧɨɜ Ɇ. Ⱥ., ɮɥɚɜɢɧ ɒɟɫɬɨɩɚɥɨɜɚ Ⱥ. ȼ. ɂɫɫɥɟɞɨɜɚɧɢɟ ɷɬɢɞɢɹ ɢ ɦɨɧɨɧɭɤɥɟɨɬɢɞɚ, ɛɪɨɦɢɫɬɨɝɨ ɬɟɨɮɢɥɥɢɧɚ ɜ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɚɯ ɦɟɬɨɞɚɦɢ ɂɄ ɢ Ɋɚɦɚɧ ɫɩɟɤɬɪɨɫɤɨɩɢɢ // ɍȻɎɌ-2011 : ɬɟɡɢ ɞɨɩ. V Ɂ'ʀɡɞ ɍɤɪɚʀɧɫɶɤɨɝɨ ɛɿɨɮɿɡɢɱɧɨɝɨ ɬɨɜɚɪɢɫɬɜɚ, 22– 25 ɱɟɪɜ. 2011 ɪ. Ʌɭɰɶɤ, 2011. ɋ. 24–25. 11. Blyzniuk Iu. N. Study of heteroassociation of biologically active compounds by IR and Raman spectroscopy [ɗɥɟɤɬɪɨɧɧɵɣ ɪɟɫɭɪɫ] // Radiophysics, Electronics, Photonics and Biophysics : abstr. 11th Kharkiv Young Scientists Conf., 29 Nov.–1 Dec. 2011. Kharkiv, 2011. 12. Blyzniuk Iu. N. Formation of intermolecular hydrogen bonds in hetero-complexes of biologically active compounds probed by vibrational spectroscopy // Modern Problems of Theoretical Physics : abstr. III Young Scientist Conference, 21–23 Dec. 2011. Kyiv, 2011. P. 93. 13. Ȼɥɢɡɧɸɤ ɘ. ɇ. Ɉɛɪɚɡɨɜɚɧɢɟ ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɯ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ ɜ ɝɟɬɟɪɨɚɫɫɨɰɢɚɬɚɯ ɛɢɨɥɨɝɢɱɟɫɤɢ ɚɤɬɢɜɧɵɯ ɜɟɳɟɫɬɜ ɩɨ ɞɚɧɧɵɦ ɤɨɥɟɛɚɬɟɥɶɧɨɣ ɫɩɟɤɬɪɨɫɤɨɩɢɢ // Ⱥɤɬɭɚɥɶɧɵɟ ɜɨɩɪɨɫɵ ɛɢɨɥɨɝɢɱɟɫɤɨɣ ɮɢɡɢɤɢ ɢ ɯɢɦɢɢ. ȻɎɎɏ – 2012 : ɬɟɡɢɫɵ ɞɨɤɥ. VIII Ɇɟɠɞɭɧɚɪɨɞɧɚɹ 176 ɧɚɭɱɧɨ-ɬɟɯɧɢɱɟɫɤɚɹ ɤɨɧɮɟɪɟɧɰɢɹ, 23–27 ɚɩɪ. 2012 ɝ. ɋɟɜɚɫɬɨɩɨɥɶ, 2012. ɋ. 128–129. 14. Blyzniuk Iu. N., Semenov M. A., Shestopalova A. V. Intermolecular hydrogen bonds in hetero-complexes of biologically active aromatic ligands: Monte Carlo simulations // Methods and Applications of Computational Chemistry : abstr. 5th International Symposium, 1–5 July 2013. Kharkiv, 2013. P. 107. 15. Blyzniuk Iu. N. pH-dependent self-association of flavin-mononucleotide. [ɗɥɟɤɬɪɨɧɧɵɣ ɪɟɫɭɪɫ] // Radiophysics, Electronics, Photonics and Biophysics : abstr. 13th Kharkiv Young Scientists Conference, 2–6 Dec. 2013. Kharkiv, 2013. 16. Blyzniuk Iu. N., Glibitskiy D. M. Self-association and hydration of flavinmononucleotide in films // Problems of Theoretical Physics : abstr. V Young scientists conference, 24–27 December 2013. Kyiv, 2013. P. 72. 17. Ȼɥɢɡɧɸɤ ɘ. Ɇ., ɒɟɫɬɨɩɚɥɨɜɚ Ƚ. ȼ. ɉɟɫɿɧɚ Ⱦ. Ɉ., ɋɚɦɨɚɫɨɰɿɚɰɿɹ Ƚɥɢɛɢɰɶɤɢɣ Ⱦ. Ɇ., ɿɡɨɚɥɥɨɤɫɚɡɢɧɨɜɢɯ ɋɟɦɟɧɨɜ Ɇ. Ɉ., ɤɿɥɟɰɶ ɮɥɚɜɿɧ- ɦɨɧɨɧɭɤɥɟɨɬɢɞɚ ɭ ɜɨɥɨɝɢɯ ɩɥɿɜɤɚɯ, ɜɢɪɨɳɟɧɢɯ ɡ ɧɟɣɬɪɚɥɶɧɢɯ ɿ ɫɥɚɛɨɤɢɫɥɢɯ ɪɨɡɱɢɧɿɜ // ɍȻɎɌ-2015 : ɬɟɡɢ ɞɨɩ. VI Ɂ'ʀɡɞ ɍɤɪɚʀɧɫɶɤɨɝɨ ɛɿɨɮɿɡɢɱɧɨɝɨ ɬɨɜɚɪɢɫɬɜɚ, 28–30 ɬɪɚɜ. 2015 ɪ. Ʌɭɰɶɤ-ɋɜɿɬɹɡɶ, 2015. ɋ. 40. Ɉɫɨɛɢɫɬɢɣ ɜɧɟɫɨɤ ɡɞɨɛɭɜɚɱɚ ɭ ɪɨɛɨɬɚɯ ʋ 1, 2, 3, 4, 5 – ɩɨɲɭɤ ɿ ɤɪɢɬɢɱɧɢɣ ɚɧɚɥɿɡ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɚɧɢɯ, ɨɬɪɢɦɚɧɧɹ ɤɨɥɢɜɚɥɶɧɢɯ ɫɩɟɤɬɪɿɜ, ɚɧɚɥɿɡ ɬɚ ɿɧɬɟɪɩɪɟɬɚɰɿɹ ɨɬɪɢɦɚɧɢɯ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɞɚɧɢɯ, ɧɚɩɢɫɚɧɧɹ ɫɬɚɬɟɣ; ɭ ɪɨɛɨɬɚɯ ʋ 7, 8, 9, 10, 11, 12, 13, 15, 16, 17 – ɚɧɚɥɿɡ ɥɿɬɟɪɚɬɭɪɧɢɯ ɞɚɧɢɯ, ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɟ ɨɬɪɢɦɚɧɧɹ ɤɨɥɢɜɚɥɶɧɢɯ ɫɩɟɤɬɪɿɜ, ɚɧɚɥɿɡ ɬɚ ɿɧɬɟɪɩɪɟɬɚɰɿɹ ɨɬɪɢɦɚɧɢɯ ɞɚɧɢɯ, ɧɚɩɢɫɚɧɧɹ ɬɟɡ; ɭ ɪɨɛɨɬɚɯ ʋ 6, 14 – ɚɧɚɥɿɡ ɿ ɨɛɝɨɜɨɪɟɧɧɹ ɨɬɪɢɦɚɧɢɯ ɪɟɡɭɥɶɬɚɬɿɜ, ɧɚɩɢɫɚɧɧɹ ɫɬɚɬɬɿ ɿ ɬɟɡ. 177 ȾɈȾȺɌɈɄ ȼ ɇɭɦɟɪɚɰɿɹ ɚɬɨɦɿɜ ɿ ɡɚɪɹɞɢ ɧɚ ɚɬɨɦɚɯ ɜɿɞɩɨɜɿɞɧɢɯ ɥɿɝɚɧɞɿɜ, ɳɨ ɜɢɤɨɪɢɫɬɨɜɭɜɚɥɢɫɶ ɜ ɦɨɞɟɥɸɜɚɧɧɿ ɦɟɬɨɞɨɦ Ɇɨɧɬɟ Ʉɚɪɥɨ Ɋɢɫɭɧɨɤ ȼ.1 ɋɬɪɭɤɬɭɪɧɚ ɮɨɪɦɭɥɚ ɮɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞɭ Ɋɢɫɭɧɨɤ ȼ.2 ɋɬɪɭɤɬɭɪɧɚ ɮɨɪɦɭɥɚ ɬɟɨɮɿɥɿɧɭ 178 Ɋɢɫɭɧɨɤ ȼ.3 ɋɬɪɭɤɬɭɪɧɚ ɮɨɪɦɭɥɚ ɛɪɨɦɢɫɬɨɝɨ ɟɬɢɞɿɸ Ɋɢɫɭɧɨɤ ȼ.4 ɋɬɪɭɤɬɭɪɧɚ ɮɨɪɦɭɥɚ ɩɪɨɮɥɚɜɿɧɭ Ɋɢɫɭɧɨɤ ȼ.5 ɋɬɪɭɤɬɭɪɧɚ ɮɨɪɦɭɥɚ ɤɨɮɟʀɧɭ 179 Ɍɚɛɥɢɰɹ ȼ.1 Ɏɥɚɜɿɧɦɨɧɨɧɭɤɥɟɨɬɢɞ; ɡɚɪɹɞɢ ESP1 (ɚɬɨɦɧɿ ɡɚɪɹɞɢ ɨɛɱɢɫɥɸɸɬɶɫɹ ɧɚ ɨɫɧɨɜɿ ɪɨɡɩɨɞɿɥɭ ɟɥɟɤɬɪɨɫɬɚɬɢɱɧɨɝɨ ɩɨɬɟɧɰɿɚɥɭ – ESP, ɡɚ ɫɯɟɦɨɸ ɆɟɪɰɚɄɨɥɥɦɚɧɚ); ɨɩɬɢɦɿɡɚɰɿɹ ɝɟɨɦɟɬɪɿʀ – DFT/B3LYP/6-31G(d, p) N 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 ɚɬɨɦɢ N C O N C O C N C C C C C C C C N ɡɚɪɹɞɢ -0,2433 1,0571 -0,4071 -0,8240 0,6737 -0,4697 0,2990 -0,5852 0,8448 -0,5577 0,5833 -0,3898 0,1411 -0,4001 -0,2258 0,0504 0,1745 N 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 ɚɬɨɦɢ C C C O C O C O C O P O O O HN4 HC10 HC12 ɡɚɪɹɞɢ 0,4271 0,1976 0,1592 -0,5366 -0,0326 -0,5880 0,2320 -0,6110 -0,1177 -0,3547 1,0708 -0,6089 -0,6012 -0,6256 0,3871 0,2156 0,1247 N 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 ɚɬɨɦɢ HC12 HC12 HC14 HC14 HC14 HC15 HC19 HC19 HC20 HO21 HC22 HO23 HC24 HO25 HC26 HC26 ɡɚɪɹɞɢ 0,1220 0,1250 0,1192 0,1262 0,1375 0,2076 0,0428 0,0251 0,0426 0,3876 0,1388 0,4085 0,0681 0,4110 0,1356 0,1370 Ɍɚɛɥɢɰɹ ȼ.2 Ɍɟɨɮɿɥɿɧ; ESP ɡɚɪɹɞɢ, DFT/B3LYP/6-31G(d,p) N 1 2 3 4 5 6 7 8 9 10 11 ɚɬɨɦɢ N C ɋ N C N C N C O C ɡɚɪɹɞɢ -0,2613 0,5509 -0,3892 -0,1882 0,2605 -0,1241 0,1186 -0,1484 -0,2383 -0,3594 -0,2571 N 12 13 14 15 16 17 18 19 20 21 ɚɬɨɦɢ O C HC11 HC11 HC11 HC13 HC13 HC13 HC5 HN1 ɡɚɪɹɞɢ -0,3865 -0,3265 0,1988 0,2015 0,1991 0,2046 0,1811 0,1997 0,2273 0,3366 180 Ɍɚɛɥɢɰɹ ȼ.3 Ȼɪɨɦɢɫɬɢɣ ɟɬɢɞɿɣ; ɡɚɪɹɞɢ ESP1, DFT/B3LYP/6-31G(d,p) N 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 ɚɬɨɦɢ C C C C N C C C C C C C C C C C C C C C C C ɡɚɪɹɞɢ -0,4631 0,7864 -0,3911 -0,1059 0,1183 -0,1535 -0,0483 -0,5074 0,1516 0,0165 0,1161 0,2426 -0,2542 -0,1705 0,3924 -0,4332 -0,4404 0,4363 -0,2253 -0,1950 0,2026 -0,3194 N 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 ɚɬɨɦɢ N N HC4 HC2 HC1 HC10 HC9 HC7 HC16 HC17 HC18 HC19 HC20 HC21 HC21 HC22 HC22 HC22 HN23 HN23 HN24 HN24 ɡɚɪɹɞɢ -0,8538 -0,8070 0,2322 0,1865 0,1745 0,1793 0,1845 0,2036 0,1989 0,1604 0,1556 0,1490 0,1994 0,0216 0,0032 0,1068 0,0877 0,1089 0,4007 0,3953 0,3718 0,3855 181 Ɍɚɛɥɢɰɹ ȼ.4 ɉɪɨɮɥɚɜɿɧ; ɡɚɪɹɞɢ ESP1, DFT/B3LYP/6-31G(d,p) N 1 2 3 4 5 6 7 8 9 10 11 12 13 14 ɚɬɨɦɢ C C C C C C C C C N C C C C ɡɚɪɹɞɢ -0,5402 0,3144 0,0250 -0,1440 -0,3342 0,6357 -0,1349 0,0468 0,3007 -0,3857 -0,1578 -0,3299 0,6344 -0,5348 N 15 16 17 18 19 20 21 22 23 24 25 26 27 28 ɚɬɨɦɢ N N Hɋ5 Hɋ7 Hɋ4 Hɋ11 Hɋ12 Hɋ1 Hɋ14 HN16 HN16 HN15 HN15 HN10 ɡɚɪɹɞɢ -0,9596 -0,9588 0,2048 0,1666 0,1835 0,1854 0,2030 0,2215 0,2202 0,4487 0,4404 0,4501 0,4413 0,3574 Ɍɚɛɥɢɰɹ ȼ.5 Ʉɨɮɟʀɧ; ESP ɡɚɪɹɞɢ, DFT/B3LYP/6-31G(d,p) N 1 2 3 4 5 6 7 8 9 10 11 12 ɚɬɨɦɢ N C N C C C N C N C O C ɡɚɪɹɞɢ -0,388 0,671 -0,343 0,555 -0,498 0,723 0,193 0,065 -0,531 -0,113 -0,519 -0,076 N 13 14 15 16 17 18 19 20 21 22 23 24 ɚɬɨɦɢ O C HC8 HC10 HC10 HC10 HC12 HC12 HC12 HC14 HC14 HC14 ɡɚɪɹɞɢ -0,532 -0,294 0,155 0,089 0,094 0,101 0,077 0,083 0,095 0,127 0,160 0,103 182 ɉɈȾəɄȺ ɇɚ ɡɚɜɟɪɲɟɧɧɹ ɹ ɯɨɱɭ ɜɢɫɥɨɜɢɬɢ ɳɢɪɭ ɜɞɹɱɧɿɫɬɶ ɦɨɽɦɭ ɧɚɭɤɨɜɨɦɭ ɤɟɪɿɜɧɢɤɭ ɞɨɤɬɨɪɭ ɮɿɡ.-ɦɚɬ. ɧɚɭɤ ɒɟɫɬɨɩɚɥɨɜɨɣ Ƚɚɧɧɿ ȼɿɤɬɨɪɿɜɧɿ ɡɚ ɱɭɣɧɟ ɧɚɭɤɨɜɟ ɤɟɪɿɜɧɢɰɬɜɨ, ɩɨɫɬɿɣɧɭ ɭɜɚɝɭ ɿ ɩɿɞɬɪɢɦɤɭ ɧɚ ɜɫɿɯ ɟɬɚɩɚɯ ɜɢɤɨɧɚɧɧɹ ɪɨɛɨɬɢ. ɉɪɢɧɨɲɭ ɨɫɨɛɥɢɜɭ ɩɨɞɹɤɭ ɩɪɨɮ. ɋɟɦɟɧɨɜɭ Ɇɢɯɚɣɥɭ Ɉɥɟɤɫɿɣɨɜɢɱɭ ɡɚ ɚɤɬɢɜɧɭ ɭɱɚɫɬɶ, ɞɨɩɨɦɨɝɭ ɿ ɩɪɚɤɬɢɱɧɿ ɩɨɪɚɞɢ ɩɿɞ ɱɚɫ ɜɢɤɨɧɚɧɧɹ ɟɤɫɩɟɪɢɦɟɧɬɚɥɶɧɢɯ ɪɨɛɿɬ ɿ ɩɪɢ ɨɮɨɪɦɥɟɧɧɿ ɞɢɫɟɪɬɚɰɿɣɧɨʀ ɪɨɛɨɬɢ. ə ɜɞɹɱɧɚ ɫ.ɧ.ɫ. Ȼɟɪɟɡɧɹɤ Ʉɚɬɟɪɢɧɿ Ƚɟɪɦɚɧɿɜɧɿ ɿ ɫ.ɧ.ɫ Ⱦɭɯɨɩɟɥɶɧɢɤɨɜɭ ȯɜɝɟɧɭ ȼɨɥɨɞɢɦɢɪɨɜɢɱɭ ɡɚ ɭɜɚɠɧɟ ɨɡɧɚɣɨɦɥɟɧɧɹ ɡ ɞɢɫɟɪɬɚɰɿɽɸ, ɤɨɪɢɫɧɿ ɡɚɭɜɚɠɟɧɧɹ ɿ ɪɟɤɨɦɟɧɞɚɰɿʀ. Ⱦɹɤɭɸ ɜɫɿɦ ɫɩɿɜɪɨɛɿɬɧɢɤɚɦ ɜɿɞɞɿɥɭ ɛɿɨɥɨɝɿɱɧɨʀ ɮɿɡɢɤɢ ȱɧɫɬɢɬɭɬɭ ɪɚɞɿɨɮɿɡɢɤɢ ɬɚ ɟɥɟɤɬɪɨɧɿɤɢ ɿɦ. Ɉ.ə. ɍɫɢɤɨɜɚ ɇȺɇ ɍɤɪɚʀɧɢ ɡɚ ɿɧɬɟɪɟɫ, ɩɪɨɹɜɥɟɧɢɣ ɞɨ ɪɨɛɨɬɢ, ɜɫɟɛɿɱɧɭ ɩɿɞɬɪɢɦɤɭ, ɨɛɝɨɜɨɪɟɧɧɹ ɪɟɡɭɥɶɬɚɬɿɜ ɬɚ ɤɪɢɬɢɱɧɿ ɡɚɭɜɚɠɟɧɧɹ. ɏɨɱɭ ɬɚɤɨɠ ɩɨɞɹɤɭɜɚɬɢ ɦɨʀɦ ɪɿɞɧɢɦ ɿ ɛɥɢɡɶɤɢɦ ɡɚ ɞɨɩɨɦɨɝɭ ɿ ɩɿɞɬɪɢɦɤɭ.