ɀ ɍ Ɋ ɇ Ⱥ Ʌ ɋ Ɍ Ɋ ɍ... Ɍɨɦ 47, ʋ 1 əɧɜɚɪɶ – ɮɟɜɪɚɥɶ ɋ. 178 – 184
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ɀɍɊɇȺɅ ɋɌɊɍɄɌɍɊɇɈɃ ɏɂɆɂɂ 2006. Ɍɨɦ 47, ʋ 1 əɧɜɚɪɶ – ɮɟɜɪɚɥɶ ɋ. 178 – 184 ɍȾɄ 541.64 ɋɉȿɐɂɎɂɄȺ ȼɁȺɂɆɈȾȿɃɋɌȼɂə ɋ ɆɈɅȿɄɍɅɈɃ ȾɇɄ ɊȺɁɅɂɑɇɕɏ ɂɁɈɆȿɊɈȼ ɂ ɆɈȾɂɎɂɄȺɐɂɃ ȾȼɍəȾȿɊɇɕɏ ɄɈɈɊȾɂɇȺɐɂɈɇɇɕɏ ɋɈȿȾɂɇȿɇɂɃ ɉɅȺɌɂɇɕ(II) 2006 Ⱥ.Ⱥ. Ȼɨɝɞɚɧɨɜ1*, ɘ.ȼ. Ʉɨɫɦɨɬɵɧɫɤɚɹ1, Ʉ.ɂ. əɤɨɜɥɟɜ2, ɇ.Ⱥ. Ʉɚɫɶɹɧɟɧɤɨ1 1 ɋɚɧɤɬ-ɉɟɬɟɪɛɭɪɝɫɤɢɣ ɝɨɫɭɞɚɪɫɬɜɟɧɧɵɣ ɭɧɢɜɟɪɫɢɬɟɬ ɋɚɧɤɬ-ɉɟɬɟɪɛɭɪɝɫɤɚɹ ɯɢɦɢɤɨ-ɮɚɪɦɚɰɟɜɬɢɱɟɫɤɚɹ ɚɤɚɞɟɦɢɹ 2 ɋɬɚɬɶɹ ɩɨɫɬɭɩɢɥɚ 7 ɚɩɪɟɥɹ 2005 ɝ. ɉɪɨɜɟɞɟɧɨ ɫɪɚɜɧɟɧɢɟ ɤɨɧɮɨɪɦɚɰɢɨɧɧɵɯ ɢɡɦɟɧɟɧɢɣ ɦɨɥɟɤɭɥɵ ȾɇɄ ɩɪɢ ɟɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɢ ɜ ɪɚɫɬɜɨɪɟ ɫ ɪɚɡɥɢɱɧɵɦɢ ɞɜɭɹɞɟɪɧɵɦɢ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɦɢ ɫɨɟɞɢɧɟɧɢɹɦɢ ɩɥɚɬɢɧɵ [Pt(NH3)2Cl—R—Pt(NH3)2Cl]Cl ɜ ɰɢɫ- ɢ ɬɪɚɧɫ-ɤɨɧɮɨɪɦɚɰɢɹɯ, ɫɨɞɟɪɠɚɳɢɦɢ ɜ ɤɚɱɟɫɬɜɟ ɨɛɳɟɝɨ ɥɢɝɚɧɞɚ (R) ɰɢɬɨɡɢɧ, ɩɢɪɚɡɢɧ ɢ ɤɚɪɛɨɤɫɢɩɢɪɚɡɢɧ. ɂɡɭɱɟɧɨ ɜɥɢɹɧɢɟ ɤɨɧɰɟɧɬɪɚɰɢɢ ɤɨɦɩɨɧɟɧɬɨɜ, ɜ ɱɚɫɬɧɨɫɬɢ, ɢɨɧɧɨɣ ɫɢɥɵ ɪɚɫɬɜɨɪɚ, ɧɚ ɩɪɨɰɟɫɫ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ. Ɋɚɫɫɦɨɬɪɟɧɨ ɜɥɢɹɧɢɟ ɩɪɢɪɨɞɵ ɨɛɳɟɝɨ ɥɢɝɚɧɞɚ, ɰɢɫ- ɢ ɬɪɚɧɫ-ɤɨɧɮɨɪɦɚɰɢɢ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɧɚ ɯɚɪɚɤɬɟɪ ɢɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɫ ȾɇɄ. ɉɪɨɜɟɞɟɧɨ ɫɪɚɜɧɟɧɢɟ ɫɬɪɨɟɧɢɹ ɤɨɦɩɥɟɤɫɨɜ ȾɇɄ ɫ ɫɨɟɞɢɧɟɧɢɹɦɢ ɦɨɧɨ- ɢ ɛɢɹɞɟɪɧɨɝɨ ɬɢɩɚ ɫ ɨɞɢɧɚɤɨɜɵɦ ɧɚɛɨɪɨɦ ɥɢɝɚɧɞɨɜ ɜ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɣ ɫɮɟɪɟ ɩɥɚɬɢɧɵ. Ʉ ɥ ɸ ɱ ɟ ɜ ɵ ɟ ɫ ɥ ɨ ɜ ɚ : ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɟ ɫɨɟɞɢɧɟɧɢɹ ɩɥɚɬɢɧɵ, ȾɇɄ-ɩɥɚɬɢɧɨɜɵɟ ɤɨɦɩɥɟɤɫɵ, ɞɜɭɹɞɟɪɧɵɟ ɫɨɟɞɢɧɟɧɢɹ Pt(II). ȼȼȿȾȿɇɂȿ ȼ ɩɨɫɥɟɞɧɟɟ ɜɪɟɦɹ ɜɨɡɪɨɫ ɢɧɬɟɪɟɫ ɤ ɢɡɭɱɟɧɢɸ ɤɨɦɩɥɟɤɫɨɜ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɩɥɚɬɢɧɵ ɫ ɛɢɨɥɨɝɢɱɟɫɤɢɦɢ ɦɚɤɪɨɦɨɥɟɤɭɥɚɦɢ. ɗɬɨ ɨɛɭɫɥɨɜɥɟɧɨ ɬɟɦ, ɱɬɨ ɩɪɟɩɚɪɚɬɵ ɧɚ ɨɫɧɨɜɟ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɩɥɚɬɢɧɵ ɚɤɬɢɜɧɨ ɢɫɩɨɥɶɡɭɸɬɫɹ ɜ ɫɨɜɪɟɦɟɧɧɨɣ ɦɟɞɢɰɢɧɟ ɞɥɹ ɥɟɱɟɧɢɹ ɡɥɨɤɚɱɟɫɬɜɟɧɧɵɯ ɧɨɜɨɨɛɪɚɡɨɜɚɧɢɣ. ɇɚɢɛɨɥɟɟ ɲɢɪɨɤɨɟ ɩɪɢɦɟɧɟɧɢɟ ɜ ɯɢɦɢɨɬɟɪɚɩɢɢ ɨɩɭɯɨɥɟɣ ɢɦɟɟɬ ɰɢɫ-ɞɢɚɦɦɢɧɞɢɯɥɨɪɩɥɚɬɢɧɚ(II) (ɰɢɫ-ȾȾɉ). ɏɨɬɹ ɛɢɨɥɨɝɢɱɟɫɤɚɹ ɚɤɬɢɜɧɨɫɬɶ ɰɢɫ-ȾȾɉ ɛɵɥɚ ɭɫɬɚɧɨɜɥɟɧɚ ɨɤɨɥɨ 40 ɥɟɬ ɧɚɡɚɞ, ɞɨ ɧɚɫɬɨɹɳɟɝɨ ɜɪɟɦɟɧɢ ɩɪɨɞɨɥɠɚɸɬɫɹ ɢɫɫɥɟɞɨɜɚɧɢɹ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɦɟɯɚɧɢɡɦɚ ɞɟɣɫɬɜɢɹ ɷɬɨɝɨ ɫɨɟɞɢɧɟɧɢɹ [ 1 — 4 ]. ɰɢɫ-ȾȾɉ ɨɛɥɚɞɚɟɬ ɜɵɫɨɤɨɣ ɷɮɮɟɤɬɢɜɧɨɫɬɶɸ, ɧɨ ɩɥɨɯɚɹ ɪɚɫɬɜɨɪɢɦɨɫɬɶ, ɬɨɤɫɢɱɧɨɫɬɶ ɢ ɧɟɢɡɛɢɪɚɬɟɥɶɧɨɫɬɶ ɞɟɣɫɬɜɢɹ ɡɚɫɬɚɜɥɹɸɬ ɢɫɫɥɟɞɨɜɚɬɟɥɟɣ ɨɫɭɳɟɫɬɜɥɹɬɶ ɩɨɞɛɨɪ ɢ ɫɢɧɬɟɡ ɧɨɜɵɯ ɫɨɟɞɢɧɟɧɢɣ ɢɡ ɱɢɫɥɚ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɩɥɚɬɢɧɵ, ɫɩɨɫɨɛɧɵɯ ɡɚɦɟɧɢɬɶ ɢɥɢ ɞɨɩɨɥɧɢɬɶ ɰɢɫ-ȾȾɉ ɜ ɩɪɨɰɟɫɫɟ ɥɟɱɟɧɢɹ [ 5 — 8 ]. Ɉɞɧɢɦ ɢɡ ɩɟɪɫɩɟɤɬɢɜɧɵɯ ɧɚɩɪɚɜɥɟɧɢɣ ɹɜɥɹɟɬɫɹ ɫɢɧɬɟɡ ɛɢɹɞɟɪɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɩɥɚɬɢɧɵ ɬɪɢɚɦɢɧɨɜɨɝɨ ɬɢɩɚ [ 9 — 11 ]. Ȼɢɹɞɟɪɧɵɟ ɰɢɫ-ɤɨɦɩɥɟɤɫɵ ɩɥɚɬɢɧɵ ɬɪɢɚɦɢɧɨɜɨɝɨ ɬɢɩɚ ɩɪɨɹɜɥɹɸɬ ɛɨɥɶɲɭɸ ɰɢɬɨɬɨɤɫɢɱɟɫɤɭɸ ɚɤɬɢɜɧɨɫɬɶ ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɢɦɟɸɳɢɦɢ ɬɚɤɨɣ ɠɟ ɥɢɝɚɧɞ ɦɨɧɨɹɞɟɪɧɵɦɢ ɤɨɦɩɥɟɤɫɚɦɢ [ 12 ]. ɋɭɳɟɫɬɜɭɟɬ ɦɧɟɧɢɟ, ɱɬɨ ɧɟɤɨɬɨɪɵɟ ɬɪɚɧɫ-ɢɡɨɦɟɪɵ ɛɢɹɞɟɪɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɞɜɭɯɜɚɥɟɧɬɧɨɣ ɩɥɚɬɢɧɵ ɚɤɬɢɜɧɵ ɩɨ ɨɬɧɨɲɟɧɢɸ ɤ ɨɩɭɯɨɥɹɦ, ɤɨɬɨɪɵɟ ɨɛɥɚɞɚɸɬ ɩɪɢɨɛɪɟɬɟɧɧɨɣ ɥɟɤɚɪɫɬɜɟɧɧɨɣ ɭɫɬɨɣɱɢɜɨɫɬɶɸ ɤ ɰɢɫ-ȾȾɉ [ 11 ], ɬɨɝɞɚ ɤɚɤ ɬɪɚɧɫ-ȾȾɉ ɩɪɨɬɢɜɨɨɩɭɯɨɥɟɜɨɣ ɚɤɬɢɜɧɨɫɬɶɸ ɧɟ ɨɛɥɚɞɚɟɬ. ɂɡɭɱɟɧɢɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɦɨɥɟɤɭɥɵ ȾɇɄ ɫ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɦɢ ɫɨɟɞɢɧɟɧɢɹɦɢ ɩɥɚɬɢɧɵ ɧɚ ɭɪɨɜɧɟ ɦɨɞɟɥɶɧɵɯ ɫɢɫɬɟɦ (ɪɚɡɛɚɜɥɟɧɧɵɯ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɨɜ) ɦɨɠɟɬ ɞɚɬɶ ɢɧɮɨɪɦɚɰɢɸ ɨ ɦɨɥɟɤɭɥɹɪɧɨɦ ɦɟɯɚɧɢɡɦɟ ɞɟɣɫɬɜɢɹ ɩɪɟɩɚɪɚɬɨɜ ɩɥɚɬɢɧɵ, ɨ ɜɥɢɹɧɢɢ ɫɬɪɭɤɬɭɪɧɵɯ ɨɫɨɛɟɧɧɨɫɬɟɣ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɧɚ ɯɚɪɚɤɬɟɪ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ. ɏɨɬɹ ɜ ɪɟɚɥɶɧɵɯ ɛɢɨɥɨɝɢɱɟ* E-mail: [email protected] ȼɁȺɂɆɈȾȿɃɋɌȼɂȿ ɋ ɆɈɅȿɄɍɅɈɃ ȾɇɄ ɊȺɁɅɂɑɇɕɏ ɂɁɈɆȿɊɈȼ ɂ ɆɈȾɂɎɂɄȺɐɂɃ ɋɈȿȾɂɇȿɇɂɃ ɉɅȺɌɂɇɕ(II) 179 ɫɤɢɯ ɫɬɪɭɤɬɭɪɚɯ ɜ ɩɪɨɰɟɫɫɟ ɮɨɪɦɢɪɨɜɚɧɢɹ ɤɨɦɩɥɟɤɫɚ ɦɨɝɭɬ ɩɪɢɧɢɦɚɬɶ ɭɱɚɫɬɢɟ ɪɚɡɥɢɱɧɵɟ ɚɝɟɧɬɵ, ɤ ɧɚɫɬɨɹɳɟɦɭ ɜɪɟɦɟɧɢ ɭɫɬɚɧɨɜɥɟɧɨ, ɱɬɨ ɞɟɣɫɬɜɢɟ ɩɪɟɩɚɪɚɬɨɜ ɩɥɚɬɢɧɵ ɨɫɧɨɜɚɧɨ ɧɚ ɨɛɪɚɡɨɜɚɧɢɢ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɣ ɫɜɹɡɢ ɩɥɚɬɢɧɵ ɫ ɦɨɥɟɤɭɥɨɣ ȾɇɄ, ɩɪɟɩɹɬɫɬɜɭɸɳɟɣ ɪɟɩɥɢɤɚɰɢɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɢ ɞɟɥɟɧɢɸ ɤɥɟɬɤɢ. ɍɱɢɬɵɜɚɹ, ɱɬɨ ɜ ɹɞɪɟ ɤɥɟɬɤɢ ȾɇɄ ɧɚɯɨɞɹɬɫɹ ɜ ɝɢɞɪɚɬɢɪɨɜɚɧɧɨɦ ɫɨɫɬɨɹɧɢɢ, ɢɡɭɱɟɧɢɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ȾɇɄ ɫ ɫɨɟɞɢɧɟɧɢɹɦɢ ɩɥɚɬɢɧɵ ɜ ɜɨɞɧɨɦ ɪɚɫɬɜɨɪɟ ɦɨɠɟɬ ɫɩɨɫɨɛɫɬɜɨɜɚɬɶ ɩɨɧɢɦɚɧɢɸ ɦɨɥɟɤɭɥɹɪɧɵɯ ɨɫɧɨɜ ɛɢɨɥɨɝɢɱɟɫɤɨɣ ɚɤɬɢɜɧɨɫɬɢ ɫɨɟɞɢɧɟɧɢɣ ɷɬɨɝɨ ɤɥɚɫɫɚ, ɚ ɬɚɤɠɟ ɩɟɪɜɨɧɚɱɚɥɶɧɨɦɭ ɨɬɛɨɪɭ ɧɚɢɛɨɥɟɟ ɩɟɪɫɩɟɤɬɢɜɧɵɯ ɧɨɜɵɯ ɫɨɟɞɢɧɟɧɢɣ ɞɥɹ ɞɚɥɶɧɟɣɲɢɯ ɢɫɩɵɬɚɧɢɣ ɢɯ ɩɪɨɬɢɜɨɨɩɭɯɨɥɟɜɨɝɨ ɞɟɣɫɬɜɢɹ. ɆȺɌȿɊɂȺɅɕ ɂ ɆȿɌɈȾɕ ɍɫɥɨɜɢɹ ɷɤɫɩɟɪɢɦɟɧɬɚ. ȼ ɪɚɛɨɬɟ ɢɫɩɨɥɶɡɨɜɚɥɢ ɬɢɦɭɫɧɭɸ ȾɇɄ ɮɢɪɦɵ Sigma (ɋɒȺ) ɫ ɦɨɥɟɤɭɥɹɪɧɨɣ ɦɚɫɫɨɣ 9u106 ɝ/ɦɨɥɶ, ɨɩɪɟɞɟɥɟɧɧɨɣ ɩɨ ɡɧɚɱɟɧɢɸ ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɣ ɜɹɡɤɨɫɬɢ ɜ 0,15 M NaCl. Ʉɨɨɪɞɢɧɚɰɢɨɧɧɵɟ ɫɨɟɞɢɧɟɧɢɹ ɩɥɚɬɢɧɵ ɛɵɥɢ ɫɢɧɬɟɡɢɪɨɜɚɧɵ ɜ ɋɚɧɤɬɉɟɬɟɪɛɭɪɝɫɤɨɣ ɯɢɦɢɤɨ-ɮɚɪɦɚɰɟɜɬɢɱɟɫɤɨɣ ɚɤɚɞɟɦɢɢ. ɇɚ ɪɢɫ. 1 ɩɪɟɞɫɬɚɜɥɟɧɵ ɫɬɪɭɤɬɭɪɧɵɟ ɮɨɪɦɭɥɵ ɫɨɟɞɢɧɟɧɢɣ ɢ ɢɯ ɭɫɥɨɜɧɵɟ ɨɛɨɡɧɚɱɟɧɢɹ, ɢɫɩɨɥɶɡɭɟɦɵɟ ɜ ɪɚɛɨɬɟ. Ȼɢɹɞɟɪɧɵɟ ɩɪɟɩɚɪɚɬɵ Pt1 ɢ Pt10 ɫɨɞɟɪɠɚɬ ɜ ɤɚɱɟɫɬɜɟ ɨɛɳɟɝɨ ɥɢɝɚɧɞɚ ɩɢɪɚɡɢɧ ɢ ɤɚɪɛɨɤɫɢɩɢɪɚɡɢɧ, ɚ Pt11 ɢ Pt12 — ɰɢɬɨɡɢɧ, ɩɪɢɱɟɦ ɞɥɹ Pt11 ɰɢɬɨɡɢɧ ɧɚɯɨɞɢɬɫɹ ɜ ɰɢɫ-ɩɨɥɨɠɟɧɢɢ ɨɬɧɨɫɢɬɟɥɶɧɨ ɚɬɨɦɚ ɯɥɨɪɚ, ɚ ɞɥɹ Pt12 — ɜ ɬɪɚɧɫ-. ɋɨɟɞɢɧɟɧɢɟ Pt13 ɹɜɥɹɟɬɫɹ ɦɨɧɨɹɞɟɪɧɵɦ ɚɧɚɥɨɝɨɦ ɛɢɹɞɟɪɧɨɝɨ ɩɪɟɩɚɪɚɬɚ Pt11. Ⱦɥɹ ɢɫɫɥɟɞɨɜɚɧɢɹ ɢɫɩɨɥɶɡɨɜɚɥɢ ɦɟɬɨɞɵ, ɩɨɡɜɨɥɹɸɳɢɟ ɫɥɟɞɢɬɶ ɡɚ ɫɨɫɬɨɹɧɢɟɦ ɜɬɨɪɢɱɧɨɣ ɢ ɬɪɟɬɢɱɧɨɣ ɫɬɪɭɤɬɭɪɵ ɦɨɥɟɤɭɥɵ ȾɇɄ. ȼɫɟ ɢɡɦɟɪɟɧɢɹ ɜɵɩɨɥɧɹɥɢ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ 21 qɋ. Ɇɟɬɨɞ ɞɢɧɚɦɢɱɟɫɤɨɝɨ ɞɜɨɣɧɨɝɨ ɥɭɱɟɩɪɟɥɨɦɥɟɧɢɹ ɩɨɡɜɨɥɹɟɬ ɨɩɪɟɞɟɥɢɬɶ ɨɩɬɢɱɟɫɤɭɸ ɚɧɢɡɨɬɪɨɩɢɸ ɦɚɤɪɨɦɨɥɟɤɭɥ ȾɇɄ. ɉɪɢ ɢɫɩɨɥɶɡɨɜɚɧɢɢ ɜɵɫɨɤɨɦɨɥɟɤɭɥɹɪɧɨɣ ȾɇɄ, ɤɨɬɨɪɚɹ ɜ ɜɨɞɧɨɦ ɪɚɫɬɜɨɪɟ ɩɪɢɧɢɦɚɟɬ ɤɨɧɮɨɪɦɚɰɢɸ ɧɚɛɭɯɲɟɝɨ ɤɥɭɛɤɚ, ɦɵ ɦɨɠɟɦ ɨɰɟɧɢɬɶ ɨɩɬɢɱɟɫɤɭɸ ɚɧɢɡɨɬɪɨɩɢɸ ɫɬɚɬɢɫɬɢɱɟɫɤɨɝɨ ɫɟɝɦɟɧɬɚ, ɤɨɬɨɪɚɹ ɡɚɜɢɫɢɬ ɨɬ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɨɣ ɠɟɫɬɤɨɫɬɢ (ɩɟɪɫɢɫɬɟɧɬɧɨɣ ɞɥɢɧɵ) ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɢ ɫɪɟɞɧɟɣ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ɩɚɪɵ ɨɫɧɨɜɚɧɢɣ (ɪɚɡɧɨɫɬɢ ɩɨɥɹɪɢɡɚɰɢɢ ɜɞɨɥɶ ɨɫɢ ɫɩɢɪɚɥɢ ɢ ɩɟɪɩɟɧɞɢɤɭɥɹɪɧɨ ɤ ɧɟɣ). ȼɟɥɢɱɢɧɭ ɞɜɨɣɧɨɝɨ ɥɭɱɟɩɪɟɥɨɦɥɟɧɢɹ 'n ɪɚɫɬɜɨɪɨɜ ȾɇɄ ɪɚɡɧɵɯ ɤɨɧɰɟɧɬɪɚɰɢɣ ɨɩɪɟɞɟɥɹɥɢ ɩɪɢ ɪɚɡɧɵɯ ɝɪɚɞɢɟɧɬɚɯ ɫɤɨɪɨɫɬɢ ɩɨɬɨɤɚ g ɧɚ ɭɫɬɚɧɨɜɤɟ ɫ ɩɨɥɭɬɟɧɟɜɵɦ ɷɥɥɢɩɬɢɱɟɫɤɢɦ ɤɨɦɩɟɧɫɚɬɨɪɨɦ, ɩɪɢɧɰɢɩɢɚɥɶɧɚɹ ɫɯɟɦɚ ɤɨɬɨɪɨɣ ɨɩɢɫɚɧɚ ɜ [ 13 ]. Ⱦɥɹ ɪɚɡɛɚɜɥɟɧɧɵɯ ɪɚɫɬɜɨɪɨɜ ɜɵɫɨɤɨɦɨɥɟɤɭɥɹɪɧɨɣ ȾɇɄ ɫɩɪɚɜɟɞɥɢɜɨ [ 14 ]: Ɋɢɫ. 1. ɋɬɪɭɤɬɭɪɧɵɟ ɮɨɪɦɭɥɵ ɢ ɭɫɥɨɜɧɵɟ ɨɛɨɡɧɚɱɟɧɢɹ ɢɫɩɨɥɶɡɨɜɚɧɧɵɯ ɜ ɪɚɛɨɬɟ ɫɨɟɞɢɧɟɧɢɣ 180 Ⱥ.Ⱥ. ȻɈȽȾȺɇɈȼ, ɘ.ȼ. ɄɈɋɆɈɌɕɇɋɄȺə, Ʉ.ɂ. əɄɈȼɅȿȼ, ɇ.Ⱥ. ɄȺɋɖəɇȿɇɄɈ ('n / g ) g o0 ~ (Ȗ1 Ȗ 2 ) . (Șr 1)Ș0 Ɂɞɟɫɶ K0 — ɜɹɡɤɨɫɬɶ ɪɚɫɬɜɨɪɢɬɟɥɹ; Kr — ɨɬɧɨɫɢɬɟɥɶɧɚɹ ɜɹɡɤɨɫɬɶ ɪɚɫɬɜɨɪɚ; g — ɝɪɚɞɢɟɧɬ ɫɤɨɪɨɫɬɢ; (J1 – J2) — ɨɩɬɢɱɟɫɤɚɹ ɚɧɢɡɨɬɪɨɩɢɹ ɦɨɥɟɤɭɥɵ, ɝɞɟ J1 ɢ J2 — ɟɟ ɩɨɥɹɪɢɡɭɟɦɨɫɬɢ ɜɞɨɥɶ ɝɥɚɜɧɵɯ ɨɫɟɣ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɷɥɥɢɩɫɨɢɞɚ. ɇɢɡɤɨɝɪɚɞɢɟɧɬɧɚɹ ɜɢɫɤɨɡɢɦɟɬɪɢɹ. Ɉɬɧɨɫɢɬɟɥɶɧɵɟ ɜɹɡɤɨɫɬɢ Kr ɪɚɫɬɜɨɪɨɜ ȾɇɄ ɨɩɪɟɞɟɥɹɥɢ ɫ ɩɨɦɨɳɶɸ ɧɢɡɤɨɝɪɚɞɢɟɧɬɧɨɝɨ ɪɨɬɚɰɢɨɧɧɨɝɨ ɜɢɫɤɨɡɢɦɟɬɪɚ ɬɢɩɚ Ɂɢɦɦɚ—Ʉɪɨɡɟɪɫɚ [ 15 ]. ȼɟɥɢɱɢɧɚ ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɣ ɜɹɡɤɨɫɬɢ ȾɇɄ, ɩɨɥɭɱɚɟɦɚɹ ɩɭɬɟɦ ɷɤɫɬɪɚɩɨɥɹɰɢɢ ɩɪɢɜɟɞɟɧɧɨɣ ɜɹɡɤɨɫɬɢ (Kr – 1)/C ɤ ɋȾɇɄ = 0, ɫɜɹɡɚɧɚ ɫ ɤɨɧɮɨɪɦɚɰɢɨɧɧɵɦɢ ɩɚɪɚɦɟɬɪɚɦɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɫɨ3/ 2 (h 2 ) ɨɬɧɨɲɟɧɢɟɦ > Ș@ Ɏ(İ) 0 D3 , ɝɞɟ Ɇ — ɦɨɥɟɤɭɥɹɪɧɚɹ ɦɚɫɫɚ ȾɇɄ; Ɏ(H) — ɩɚɪɚɦɟɬɪ Ɏɥɨɪɢ, M ɡɚɜɢɫɹɳɢɣ ɨɬ ɤɚɱɟɫɬɜɚ ɪɚɫɬɜɨɪɢɬɟɥɹ ɢ ɠɟɫɬɤɨɫɬɢ ɦɚɤɪɨɦɨɥɟɤɭɥ [ 16, 17 ]; D — ɤɨɷɮɮɢɰɢɟɧɬ ɥɢɧɟɣɧɨɝɨ ɧɚɛɭɯɚɧɢɹ ɦɚɤɪɨɦɨɥɟɤɭɥɵ, ɪɚɜɧɵɣ ɨɬɧɨɲɟɧɢɸ ɫɪɟɞɧɟɤɜɚɞɪɚɬɢɱɧɵɯ ɪɚɫɫɬɨɹɧɢɣ ɦɟɠɞɭ ɤɨɧɰɚɦɢ ɪɟɚɥɶɧɨɣ ɢ ɢɞɟɚɥɶɧɨɣ ɦɨɥɟɤɭɥɵ: D = (h 2 / h02 )1/ 2 . Ⱦɢɚɩɚɡɨɧ ɢɫɩɨɥɶɡɭɟɦɵɯ ɝɪɚɞɢɟɧɬɨɜ ɫɤɨɪɨɫɬɢ ɫɨɫɬɚɜɥɹɥ g # (0,5y2) ɫ–1. ɋɩɟɤɬɪɚɥɶɧɵɟ ɢɫɫɥɟɞɨɜɚɧɢɹ. Ʉɨɧɰɟɧɬɪɚɰɢɸ ȾɇɄ ɜ ɪɚɫɬɜɨɪɟ ɨɩɪɟɞɟɥɹɥɢ ɩɨ ɪɚɡɧɢɰɟ ɨɩɬɢɱɟɫɤɨɝɨ ɩɨɝɥɨɳɟɧɢɹ ɟɟ ɝɢɞɪɨɥɢɡɨɜɚɧɧɵɯ ɜ ɩɪɢɫɭɬɫɬɜɢɢ 6%-ɯ ɪɚɫɬɜɨɪɨɜ HClO4 ɩɪɢ O = 270 ɢ 290 ɧɦ [ 18 ]. ɇɚɬɢɜɧɨɫɬɶ ȾɇɄ ɤɨɧɬɪɨɥɢɪɨɜɚɥɢ ɩɨ ɜɟɥɢɱɢɧɟ ɝɢɩɟɪɯɪɨɦɧɨɝɨ ɷɮɮɟɤɬɚ ɩɪɢ ɞɟɧɚɬɭɪɚɰɢɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ. ɋɩɟɤɬɪɵ ɤɪɭɝɨɜɨɝɨ ɞɢɯɪɨɢɡɦɚ (ɄȾ) ȾɇɄ ɪɟɝɢɫɬɪɢɪɨɜɚɥɢ ɫ ɩɨɦɨɳɶɸ ɞɢɯɪɨɝɪɚɮɚ Jobin-Yvon Mark 4 (Ɏɪɚɧɰɢɹ). ɊȿɁɍɅɖɌȺɌɕ ɂ ɂɏ ɈȻɋɍɀȾȿɇɂȿ Ɋɚɧɟɟ ɜ ɪɚɛɨɬɟ [ 19 ] ɦɵ ɢɡɭɱɚɥɢ ɤɨɦɩɥɟɤɫɵ ȾɇɄ ɫ ɫɨɟɞɢɧɟɧɢɟɦ Pt1, ɫɨɞɟɪɠɚɳɢɦ ɜ ɤɚɱɟɫɬɜɟ ɫɜɹɡɭɸɳɟɝɨ ɥɢɝɚɧɞɚ ɩɢɪɚɡɢɧ (ɫɦ. ɪɢɫ. 1). ɗɬɨɬ ɞɜɭɹɞɟɪɧɵɣ ɤɨɦɩɥɟɤɫ ɩɥɚɬɢɧɵ ɜ ɰɢɫɤɨɧɮɨɪɦɚɰɢɢ ɛɨɥɟɟ ɚɤɬɢɜɧɨ ɜɡɚɢɦɨɞɟɣɫɬɜɭɟɬ ɫ ȾɇɄ ɜ ɪɚɫɬɜɨɪɟ ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɢɡɜɟɫɬɧɵɦ ɩɪɨɬɢɜɨɨɩɭɯɨɥɟɜɵɦ ɩɪɟɩɚɪɚɬɨɦ ɰɢɫ-ȾȾɉ. ɇɚɩɪɢɦɟɪ, ɜ ɭɫɥɨɜɢɹɯ ɛɨɥɶɲɨɣ ɢɨɧɧɨɣ ɫɢɥɵ (1Ɇ NaCl), ɤɨɝɞɚ ɰɢɫ-ȾȾɉ ɧɟ ɫɜɹɡɵɜɚɟɬɫɹ ɫ ȾɇɄ, ɦɵ ɮɢɤɫɢɪɨɜɚɥɢ ɨɛɪɚɡɨɜɚɧɢɟ ɤɨɦɩɥɟɤɫɨɜ Pt1 ɫ ɦɚɤɪɨɦɨɥɟɤɭɥɨɣ. ȼ ɭɫɥɨɜɢɹɯ ɦɚɥɨɣ ɢɨɧɧɨɣ ɫɢɥɵ (0,005 Ɇ NaCl) ɜ ɩɪɨɰɟɫɫɟ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ɧɚɛɥɸɞɚɥɢ ɛɨɥɟɟ ɫɭɳɟɫɬɜɟɧɧɵɟ ɤɨɧɮɨɪɦɚɰɢɨɧɧɵɟ ɢɡɦɟɧɟɧɢɹ ɦɚɤɪɨɦɨɥɟɤɭɥɵ, ɩɪɢɱɟɦ ɩɪɢ ɤɨɧɰɟɧɬɪɚɰɢɹɯ Pt1 ɜ ɪɚɫɬɜɨɪɟ ɧɚ ɩɨɪɹɞɨɤ ɦɟɧɶɲɢɯ, ɱɟɦ ɞɥɹ ɰɢɫ-ȾȾɉ. Ɉɩɵɬ ɩɨɤɚɡɚɥ, ɱɬɨ ɜ ɩɪɨɰɟɫɫɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɜɨɡɧɢɤɚɟɬ ɤɨɨɪɞɢɧɚɰɢɨɧɧɚɹ ɫɜɹɡɶ Pt1 ɫ ȾɇɄ. ɉɪɢ ɫɜɹɡɵɜɚɧɢɢ Pt1 ɛɥɨɤɢɪɭɟɬ ɨɫɧɨɜɧɨɣ ɩɪɨɬɨɧ-ɚɤɰɟɩɬɨɪɧɵɣ ɰɟɧɬɪ ȾɇɄ (N7 ɝɭɚɧɢɧɚ) ɢ ɩɪɟɩɹɬɫɬɜɭɟɬ ɩɪɨɬɨɧɢɪɨɜɚɧɢɸ ɦɚɤɪɨɦɨɥɟɤɭɥɵ [ 19 ]. ȼ ɩɪɨɰɟɫɫɟ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ɫɨɟɞɢɧɟɧɢɹ Pt1 ɫ ȾɇɄ ɧɚɛɥɸɞɚɥɚɫɶ ɫɭɳɟɫɬɜɟɧɧɚɹ ɡɚɜɢɫɢɦɨɫɬɶ ɤɨɧɮɨɪɦɚɰɢɨɧɧɵɯ ɩɚɪɚɦɟɬɪɨɜ ȾɇɄ, ɤɨɬɨɪɚɹ ɢɦɟɥɚ ɧɟɦɨɧɨɬɨɧɧɵɣ ɯɚɪɚɤɬɟɪ. Ȼɵɥɨ ɜɵɫɤɚɡɚɧɨ ɩɪɟɞɩɨɥɨɠɟɧɢɟ, ɱɬɨ ɨɛɪɚɡɨɜɚɧɢɟ ɤɨɦɩɥɟɤɫɚ ɫɨɩɪɨɜɨɠɞɚɟɬɫɹ ɩɨɹɜɥɟɧɢɟɦ sɢɡɥɨɦɨɜs ɞɜɨɣɧɨɣ ɫɩɢɪɚɥɢ ȾɇɄ, ɤɨɬɨɪɵɟ ɜɨɡɧɢɤɚɸɬ ɢɡ-ɡɚ ɫɜɹɡɵɜɚɧɢɹ ɞɜɭɯ ɚɬɨɦɨɜ ɩɥɚɬɢɧɵ ɜ ɫɨɫɬɚɜɟ ɫɨɟɞɢɧɟɧɢɹ ɫ ɚɡɨɬɢɫɬɵɦɢ ɨɫɧɨɜɚɧɢɹɦɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɫ ɩɨɦɨɳɶɸ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɫɜɹɡɟɣ [ 19 ]. Ɉɫɧɨɜɧɨɣ ɰɟɥɶɸ ɞɚɧɧɨɣ ɪɚɛɨɬɵ ɛɵɥɨ ɢɡɭɱɟɧɢɟ ɜɥɢɹɧɢɹ ɩɪɢɪɨɞɵ ɫɜɹɡɵɜɚɸɳɟɝɨ ɥɢɝɚɧɞɚ ɜ ɫɨɫɬɚɜɟ ɞɜɭɹɞɟɪɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ ɧɚ ɩɪɨɰɟɫɫ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ɫ ȾɇɄ. Ʉɪɨɦɟ ɬɨɝɨ, ɦɵ ɩɪɨɜɨɞɢɥɢ ɫɪɚɜɧɟɧɢɟ ɫɜɹɡɵɜɚɧɢɹ ɫ ȾɇɄ ɞɜɭɹɞɟɪɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɩɥɚɬɢɧɵ ɨɞɢɧɚɤɨɜɨɝɨ ɫɨɫɬɚɜɚ ɜ ɰɢɫ- ɢ ɬɪɚɧɫ-ɤɨɧɮɨɪɦɚɰɢɹɯ, ɚ ɬɚɤɠɟ ɞɜɭɹɞɟɪɧɨɝɨ ɢ ɚɧɚɥɨɝɢɱɧɨɝɨ ɦɨɧɨɹɞɟɪɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ ɩɥɚɬɢɧɵ ɜ ɰɢɫ-ɤɨɧɮɨɪɦɚɰɢɢ ɫ ɨɞɢɧɚɤɨɜɵɦɢ ɥɢɝɚɧɞɚɦɢ ɜ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɣ ɫɮɟɪɟ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɭɸɳɟɝɨ ɢɨɧɚ. Ɉɫɬɚɧɨɜɢɦɫɹ ɧɚ ɪɚɫɫɦɨɬɪɟɧɢɢ ɤɨɦɩɥɟɤɫɨɜ ȾɇɄ ɫ ɫɨɟɞɢɧɟɧɢɟɦ Pt10, ɤɨɬɨɪɨɟ ɨɬɥɢɱɚɟɬɫɹ ɨɬ ɢɡɭɱɟɧɧɨɝɨ ɪɚɧɟɟ Pt1 ɡɚɦɟɧɨɣ ɩɢɪɚɡɢɧɚ ɧɚ ɤɚɪɛɨɤɫɢɩɢɪɚɡɢɧ (ɫɦ. ɪɢɫ. 1). Ɍɚɤɚɹ ɦɨɞɢɮɢɤɚɰɢɹ ɫɨɟɞɢɧɟɧɢɹ ɤɚɪɞɢɧɚɥɶɧɨ ɦɟɧɹɟɬ ɫɬɪɭɤɬɭɪɭ ɤɨɦɩɥɟɤɫɚ ɫ ɦɨɥɟɤɭɥɨɣ ȾɇɄ. Ȼɵɥɨ ɨɛɧɚɪɭɠɟɧɨ, ɱɬɨ ɨɛɚ ɫɨɟɞɢɧɟɧɢɹ (Pt1 ɢ Pt10) ɫɜɹɡɵɜɚɸɬɫɹ ɫ ȾɇɄ ɩɭɬɟɦ ɨɛɪɚɡɨɜɚɧɢɹ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɣ ɫɜɹɡɢ, ɨ ɱɟɦ ɫɜɢɞɟɬɟɥɶɫɬɜɭɸɬ ɷɤɫɩɟɪɢɦɟɧɬɵ ɩɨ ɪɚɡɛɚɜɥɟɧɢɸ ɪɚɫɬɜɨɪɨɜ ɤɨɦɩɥɟɤɫɨɜ ɪɚɡɧɵɦɢ ɫɩɨɫɨɛɚɦɢ, ɜɵɩɨɥɧɟɧɧɵɟ ɫɨɝɥɚɫɧɨ ɦɟɬɨɞɢɤɟ, ɨɩɢɫɚɧɧɨɣ ɜ ɪɚɛɨɬɟ [ 20 ]. ɂɫɫɥɟɞɨɜɚɧɢɟ ɩɪɨɬɨɧɢɪɨɜɚɧɢɹ ȾɇɄ ɩɨɫɥɟ ɨɛɪɚɡɨɜɚɧɢɹ ɤɨɦɩɥɟɤɫɨɜ ɫ Pt10 ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɨ ɬɨɦ, ȼɁȺɂɆɈȾȿɃɋɌȼɂȿ ɋ ɆɈɅȿɄɍɅɈɃ ȾɇɄ ɊȺɁɅɂɑɇɕɏ ɂɁɈɆȿɊɈȼ ɂ ɆɈȾɂɎɂɄȺɐɂɃ ɋɈȿȾɂɇȿɇɂɃ ɉɅȺɌɂɇɕ(II) 181 Ɋɢɫ. 2. ɋɩɟɤɬɪɵ ɤɪɭɝɨɜɨɝɨ ɞɢɯɪɨɢɡɦɚ ȾɇɄ ɜ ɤɨɦɩɥɟɤɫɟ ɫ Pt10 ɩɪɢ ɪɚɡɧɵɯ ɡɧɚɱɟɧɢɹɯ pH ɜ 0,005 M NaCl. CPt10 = 1u10–5 Ɇ, ɡɧɚɱɟɧɢɹ pH ɩɪɢɜɟɞɟɧɵ ɧɚ ɪɢɫɭɧɤɟ. ɇɚ ɜɫɬɚɜɤɟ — ɪɟɡɭɥɶɬɚɬ ɩɪɨɬɨɧɢɪɨɜɚɧɢɹ ɫɜɨɛɨɞɧɨɣ ɞɜɭɫɩɢɪɚɥɶɧɨɣ ȾɇɄ ɜ 0,005 M NaCl ɱɬɨ ɜ ɤɨɦɩɥɟɤɫɟ ɛɥɨɤɢɪɨɜɚɧ ɨɫɧɨɜɧɨɣ ɩɪɨɬɨɧ-ɚɤɰɟɩɬɨɪɧɵɣ ɰɟɧɬɪ ɞɜɭɫɩɢɪɚɥɶɧɨɣ ȾɇɄ (N7 ɝɭɚɧɢɧɚ), ɤɚɤ ɷɬɨ ɧɚɛɥɸɞɚɥɨɫɶ ɢ ɩɪɢ ɢɫɩɨɥɶɡɨɜɚɧɢɢ ɫɨɟɞɢɧɟɧɢɹ Pt1. Ɉɛ ɷɬɨɦ ɫɜɢɞɟɬɟɥɶɫɬɜɭɸɬ, ɧɚɩɪɢɦɟɪ, ɫɩɟɤɬɪɚɥɶɧɵɟ ɢɫɫɥɟɞɨɜɚɧɢɹ, ɪɟɡɭɥɶɬɚɬɵ ɤɨɬɨɪɵɯ ɩɪɟɞɫɬɚɜɥɟɧɵ ɧɚ ɪɢɫ. 2. Ʉɚɤ ɜɢɞɧɨ ɢɡ ɪɢɫɭɧɤɚ, ɩɨɫɥɟ ɨɛɪɚɡɨɜɚɧɢɹ ɤɨɦɩɥɟɤɫɚ ɞɚɠɟ ɩɪɢ ɛɨɥɟɟ ɧɢɡɤɢɯ ɪɇ ɧɟ ɧɚɛɥɸɞɚɟɬɫɹ ɯɚɪɚɤɬɟɪɧɵɯ ɢɡɦɟɧɟɧɢɣ ɫɩɟɤɬɪɚ ɄȾ ȾɇɄ, ɮɢɤɫɢɪɭɟɦɵɯ ɩɪɢ ɩɪɨɬɨɧɢɪɨɜɚɧɢɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ (ɫɦ. ɜɫɬɚɜɤɭ ɧɚ ɪɢɫ. 2). Ɂɚɦɟɬɢɦ, ɱɬɨ ɞɥɹ ɜɫɟɯ ɫɢɫɬɟɦ, ɩɪɟɞɫɬɚɜɥɟɧɧɵɯ ɧɚ ɪɢɫɭɧɤɟ, ȾɇɄ ɫɨɯɪɚɧɹɥɚ ɞɜɭɫɩɢɪɚɥɶɧɭɸ ɮɨɪɦɭ (ɜ ɩɪɨɰɟɫɫɟ ɷɤɫɩɟɪɢɦɟɧɬɚ ɤɨɧɬɪɨɥɢɪɨɜɚɥɢ ɫɨɫɬɨɹɧɢɟ ɟɟ ɜɬɨɪɢɱɧɨɣ ɫɬɪɭɤɬɭɪɵ ɩɭɬɟɦ ɨɩɪɟɞɟɥɟɧɢɹ ɍɎ ɩɨɝɥɨɳɟɧɢɹ ɪɚɫɬɜɨɪɨɜ ɩɪɢ O = 260 ɧɦ). ɋɥɟɞɭɟɬ ɨɬɦɟɬɢɬɶ, ɱɬɨ ɯɚɪɚɤɬɟɪ ɢɡɦɟɧɟɧɢɹ ɫɩɟɤɬɪɨɜ ɄȾ ȾɇɄ ɜ ɪɟɡɭɥɶɬɚɬɟ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ɫ Pt10 ɢɧɨɣ, ɱɟɦ ɜ ɫɥɭɱɚɟ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ɫ Pt1. ɋɜɹɡɵɜɚɧɢɟ Pt10 ɫ ɦɚɤɪɨɦɨɥɟɤɭɥɨɣ ɜɵɡɵɜɚɟɬ ɭɦɟɧɶɲɟɧɢɟ ɚɦɩɥɢɬɭɞɵ ɢ ɫɦɟɳɟɧɢɟ ɩɨɥɨɠɢɬɟɥɶɧɨɝɨ ɦɚɤɫɢɦɭɦɚ ɫɩɟɤɬɪɚ ɄȾ ȾɇɄ ɜ ɨɛɥɚɫɬɶ ɛɨɥɶɲɢɯ ɞɥɢɧ ɜɨɥɧ, ɬɨɝɞɚ ɤɚɤ ɫɨɟɞɢɧɟɧɢɟ Pt1 ɩɪɢ ɬɟɯ ɠɟ ɤɨɧɰɟɧɬɪɚɰɢɹɯ ɜ ɪɚɫɬɜɨɪɟ ɩɨɧɢɠɚɟɬ ɚɦɩɥɢɬɭɞɭ ɩɨɥɨɠɢɬɟɥɶɧɨɝɨ ɦɚɤɫɢɦɭɦɚ ɛɟɡ ɟɝɨ ɫɦɟɳɟɧɢɹ. Ɂɚɦɟɬɢɦ, ɱɬɨ ɚɧɚɥɨɝɢɱɧɨɟ ɫɦɟɳɟɧɢɟ ɩɨɥɨɠɢɬɟɥɶɧɨɝɨ ɦɚɤɫɢɦɭɦɚ ɯɚɪɚɤɬɟɪɧɨ ɞɥɹ ɤɨɦɩɥɟɤɫɨɜ ȾɇɄ ɫ ɩɪɨɬɢɜɨɨɩɭɯɨɥɟɜɵɦ ɩɪɟɩɚɪɚɬɨɦ ɰɢɫ-ȾȾɉ [ 20 ], ɨɞɧɚɤɨ ɩɪɢ ɦɚɥɵɯ ɤɨɧɰɟɧɬɪɚɰɢɹɯ ɷɬɨɝɨ ɫɨɟɞɢɧɟɧɢɹ ɜ ɪɚɫɬɜɨɪɟ ɧɚɛɥɸɞɚɟɬɫɹ ɭɜɟɥɢɱɟɧɢɟ ɟɝɨ ɚɦɩɥɢɬɭɞɵ, ɚ ɫ ɪɨɫɬɨɦ ɋPt ɜ ɪɚɫɬɜɨɪɟ — ɩɚɞɟɧɢɟ. ɇɚɢɛɨɥɟɟ ɭɞɢɜɢɬɟɥɶɧɵɦ ɪɟɡɭɥɶɬɚɬɨɦ ɫɜɹɡɵɜɚɧɢɹ Pt1 c ɦɨɥɟɤɭɥɨɣ ȾɇɄ ɹɜɥɹɟɬɫɹ ɞɜɭɤɪɚɬɧɨɟ ɭɦɟɧɶɲɟɧɢɟ ɨɛɴɟɦɚ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɩɪɢ ɜɟɫɶɦɚ ɦɚɥɵɯ ɤɨɧɰɟɧɬɪɚɰɢɹɯ ɫɨɟɞɢɧɟɧɢɹ ɜ ɪɚɫɬɜɨɪɟ ɦɚɥɨɣ ɢɨɧɧɨɣ ɫɢɥɵ ɫ ɞɚɥɶɧɟɣɲɢɦ ɜɨɡɪɚɫɬɚɧɢɟɦ ɷɬɨɝɨ ɩɚɪɚɦɟɬɪɚ ɩɪɢ ɭɜɟɥɢɱɟɧɢɢ ɋ(Pt). ɉɪɢ ɢɫɩɨɥɶɡɨɜɚɧɢɢ ɠɟ Pt10 ɜ ɚɧɚɥɨɝɢɱɧɵɯ ɭɫɥɨɜɢɹɯ ɧɚɛɥɸɞɚɟɬɫɹ ɥɢɲɶ ɧɟɛɨɥɶɲɨɟ ɭɦɟɧɶɲɟɧɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɣ ɜɹɡɤɨɫɬɢ ȾɇɄ [ K ] (ɪɢɫ. 3). Ɍɚɤ ɤɚɤ [ K ] — ɩɪɨɩɨɪɰɢɨɧɚɥɶɧɚ ɭɞɟɥɶɧɨɦɭ ɨɛɴɟɦɭ ɦɚɤɪɨɦɨɥɟɤɭɥɵ, ɦɨɠɧɨ ɫɞɟɥɚɬɶ ɜɵɜɨɞ ɨ ɬɨɦ, ɱɬɨ ɩɪɢ CPt10 < 0,8u10–5 Ɇ ɨɛɴɟɦ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɧɟ ɩɪɟɬɟɪɩɟɜɚɟɬ ɫɭɳɟɫɬɜɟɧɧɵɯ ɢɡɦɟɧɟɧɢɣ, ɬɨɝɞɚ ɤɚɤ ɢɦɟɧɧɨ ɜ ɷɬɨɦ ɞɢɚɩɚɡɨɧɟ ɤɨɧɰɟɧɬɪɚɰɢɣ Pt1 ɧɚɛɥɸɞɚɟɬɫɹ ɟɝɨ ɧɚɢɛɨɥɟɟ ɫɭɳɟɫɬɜɟɧɧɨɟ ɩɚɞɟɧɢɟ [ 19 ]. ɏɚɪɚɤɬɟɪ ɢɡɦɟɧɟɧɢɹ [ K ] ɫ ɪɨɫɬɨɦ ɤɨɧɰɟɧɬɪɚɰɢɢ Pt10 ɜ ɪɚɫɬɜɨɪɟ ɤɨɪɪɟɥɢɪɭɟɬ ɫ ɩɨɜɟɞɟɧɢɟɦ ȾɇɄ ɜ ɤɨɦɩɥɟɤɫɟ ɫ ɰɢɫȾȾɉ [ 20 ]. Ɉ ɫɯɨɞɫɬɜɟ ɜ ɩɨɜɟɞɟɧɢɢ Pt10 ɢ ɰɢɫ-ȾȾɉ ɩɪɢ ɜɡɚɢɦɨɞɟɣɫɬɜɢɢ ɫ ɦɨɥɟɤɭɥɨɣ ȾɇɄ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɢ ɨɬɫɭɬɫɬɜɢɟ ɡɚɦɟɬɧɨɝɨ ɢɡɦɟɧɟɧɢɹ ɩɚɪɚɦɟɬɪɨɜ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɜ ɞɨɫɬɚɬɨɱɧɨ ɲɢ- 182 Ⱥ.Ⱥ. ȻɈȽȾȺɇɈȼ, ɘ.ȼ. ɄɈɋɆɈɌɕɇɋɄȺə, Ʉ.ɂ. əɄɈȼɅȿȼ, ɇ.Ⱥ. ɄȺɋɖəɇȿɇɄɈ Ɋɢɫ. 3. Ɉɬɧɨɫɢɬɟɥɶɧɨɟ ɢɡɦɟɧɟɧɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɣ ɜɹɡɤɨɫɬɢ (1), ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ (2ɚ, 2ɛ) ɢ ɚɦɩɥɢɬɭɞɵ ɦɚɤɫɢɦɭɦɚ ɫɩɟɤɬɪɨɜ ɤɪɭɝɨɜɨɝɨ ɞɢɯɪɨɢɡɦɚ ȾɇɄ (3) ɩɪɢ ɪɚɡɧɵɯ ɤɨɧɰɟɧɬɪɚɰɢɹɯ Pt10 ɜ ɪɚɫɬɜɨɪɟ. ɂɡɦɟɪɟɧɢɹ 1, 2ɚ ɢ 3 ɜɵɩɨɥɧɟɧɵ ɞɥɹ ɪɚɫɬɜɨɪɨɜ ɫ ɤɨɧɰɟɧɬɪɚɰɢɟɣ 0,005 M NaCl, 2ɛ — 1 Ɇ NaCl ɪɨɤɨɦ ɞɢɚɩɚɡɨɧɟ ɤɨɧɰɟɧɬɪɚɰɢɣ Pt10 ɜ ɪɚɫɬɜɨɪɚɯ ɛɨɥɶɲɨɣ ɢɨɧɧɨɣ ɫɢɥɵ (ɫɦ. ɪɢɫ. 3, 2ɛ), ɤɨɝɞɚ ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ ɰɢɫ-ȾȾɉ ɫ ȾɇɄ ɨɬɫɭɬɫɬɜɭɟɬ [ 20 ]. ȼ ɫɩɟɤɬɪɟ ɄȾ ȾɇɄ ɩɪɢ ɞɨɛɚɜɥɟɧɢɢ Pt10 ɧɚɛɥɸɞɚɟɬɫɹ ɩɚɞɟɧɢɟ ɚɦɩɥɢɬɭɞɵ ɩɨɥɨɠɢɬɟɥɶɧɨɝɨ ɦɚɤɫɢɦɭɦɚ (ɫɦ. ɪɢɫ. 3). Ʉɪɨɦɟ ɬɨɝɨ, ɩɪɨɢɫɯɨɞɢɬ ɫɞɜɢɝ ɩɨɥɨɠɟɧɢɹ ɦɚɤɫɢɦɭɦɚ ɜ ɞɥɢɧɧɨɜɨɥɧɨɜɭɸ ɨɛɥɚɫɬɶ ɫɩɟɤɬɪɚ, ɱɬɨ ɹɜɥɹɟɬɫɹ ɯɚɪɚɤɬɟɪɧɨɣ ɱɟɪɬɨɣ ɫɩɟɤɬɪɚɥɶɧɵɯ ɢɡɦɟɧɟɧɢɣ, ɮɢɤɫɢɪɭɟɦɵɯ ɩɪɢ ɫɜɹɡɵɜɚɧɢɢ ȾɇɄ ɫ ɰɢɫ-ȾȾɉ. ɏɚɪɚɤɬɟɪ ɢɡɦɟɧɟɧɢɹ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ȾɇɄ (J1 – J2) ɩɪɢ ɫɜɹɡɵɜɚɧɢɢ ɫ Pt10 ɜ ɪɚɫɬɜɨɪɟ ɦɚɥɨɣ ɢɨɧɧɨɣ ɫɢɥɵ ɬɚɤɠɟ ɢɦɟɟɬ ɫɯɨɞɫɬɜɨ ɫ ɧɚɛɥɸɞɚɟɦɵɦ ɩɪɢ ɢɫɩɨɥɶɡɨɜɚɧɢɢ ɰɢɫ-ȾȾɉ ɢ ɨɬɥɢɱɚɟɬɫɹ ɨɬ ɧɚɛɥɸɞɚɟɦɨɝɨ ɞɥɹ Pt1: ɭɦɟɧɶɲɟɧɢɟ (J1 – J2) ɦɟɧɟɟ ɫɭɳɟɫɬɜɟɧɧɨ ɢ ɨɧɨ ɧɚɱɢɧɚɟɬɫɹ ɩɪɢ ɛɨɥɶɲɢɯ ɤɨɧɰɟɧɬɪɚɰɢɹɯ Pt10. ɉɪɢ ɞɨɫɬɢɠɟɧɢɢ ɬɚɤɨɣ ɤɨɧɰɟɧɬɪɚɰɢɢ ɫɨɟɞɢɧɟɧɢɹ, ɫɨɞɟɪɠɚɳɟɝɨ ɩɥɚɬɢɧɭ, ɤɨɝɞɚ ɧɚ 10 ɩɚɪ ɨɫɧɨɜɚɧɢɣ ȾɇɄ ɩɪɢɯɨɞɢɬɫɹ ɨɞɧɚ-ɞɜɟ ɟɝɨ ɦɨɥɟɤɭɥɵ, ɧɚɛɥɸɞɚɟɬɫɹ ɧɚɫɵɳɟɧɢɟ ɫɜɹɡɵɜɚɧɢɹ. ɗɬɚ ɨɰɟɧɤɚ ɯɨɪɨɲɨ ɫɨɜɩɚɞɚɟɬ ɫ ɨɰɟɧɤɨɣ ɤɨɧɰɟɧɬɪɚɰɢɨɧɧɨɝɨ ɩɪɟɞɟɥɚ ɫɜɹɡɵɜɚɧɢɹ ɰɢɫ-ȾȾɉ ɫ ȾɇɄ [ 20 ]. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɡɚɦɟɧɚ ɩɢɪɚɡɢɧɚ ɧɚ ɤɚɪɛɨɤɫɢɩɢɪɚɡɢɧ ɜ ɞɜɭɹɞɟɪɧɨɦ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɦ ɫɨɟɞɢɧɟɧɢɢ ɞɜɭɯɜɚɥɟɧɬɧɨɣ ɩɥɚɬɢɧɵ ɜ ɰɢɫ-ɤɨɧɮɨɪɦɚɰɢɢ ɩɪɢɜɨɞɢɬ ɤ ɫɭɳɟɫɬɜɟɧɧɨɦɭ ɢɡɦɟɧɟɧɢɸ ɫɬɪɭɤɬɭɪɵ ɨɛɪɚɡɭɸɳɟɝɨɫɹ ɤɨɦɩɥɟɤɫɚ. Ⱥɧɚɥɢɡ ɞɚɧɧɵɯ ɩɨɡɜɨɥɹɟɬ ɩɪɟɞɩɨɥɨɠɢɬɶ, ɱɬɨ, ɯɨɬɹ ɨɛɚ ɫɨɟɞɢɧɟɧɢɹ ɨɛɪɚɡɭɸɬ ɤɨɨɪɞɢɧɚɰɢɨɧɧɭɸ ɫɜɹɡɶ ɫ ɦɚɤɪɨɦɨɥɟɤɭɥɨɣ ɩɨ ɩɨɡɢɰɢɢ N7 ɝɭɚɧɢɧɚ, ɜ ɫɥɭɱɚɟ Pt10 ɜ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɢ ɭɱɚɫɬɜɭɟɬ ɨɞɢɧ ɚɬɨɦ ɩɥɚɬɢɧɵ, ɚ ɜ ɫɥɭɱɚɟ Pt1 — ɞɜɚ. ɉɨɫɥɟɞɧɟɟ ɜɵɡɵɜɚɟɬ ɛɨɥɟɟ ɫɟɪɶɟɡɧɵɟ ɫɬɪɭɤɬɭɪɧɵɟ ɢɡɦɟɧɟɧɢɹ ȾɇɄ (ɧɚɩɪɢɦɟɪ, ɪɟɡɤɢɣ ɢɡɝɢɛ ɰɟɩɢ). ɋɯɨɞɫɬɜɨ ɩɪɨɰɟɫɫɨɜ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ȾɇɄ ɫ Pt10 ɢ ɫ ɰɢɫ-ȾȾɉ ɦɨɠɟɬ ɭɤɚɡɵɜɚɬɶ ɧɚ ɫɯɨɞɧɭɸ ɫɬɪɭɤɬɭɪɭ ɤɨɦɩɥɟɤɫɨɜ. ɉɨ-ɜɢɞɢɦɨɦɭ, ɚɬɨɦ ɯɥɨɪɚ ɢɡ ɩɟɪɜɨɣ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɣ ɫɮɟɪɵ ɨɞɧɨɝɨ ɢɡ ɚɬɨɦɨɜ ɩɥɚɬɢɧɵ ɡɚɦɟɳɚɟɬɫɹ ɧɚ ɜɯɨɞɹɳɭɸ ɝɪɭɩɩɭ ɦɚɤɪɨɦɨɥɟɤɭɥɵ, ɩɪɢ ɷɬɨɦ ɨɫɬɚɥɶɧɚɹ ɱɚɫɬɶ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ ɪɚɫɩɨɥɚɝɚɟɬɫɹ ɜ ɛɨɥɶɲɨɣ ɛɨɪɨɡɞɤɟ ȾɇɄ. Ɇɵ ɧɟ ɜɢɞɢɦ ɭɜɟɥɢɱɟɧɢɹ ɚɦɩɥɢɬɭɞɵ ɩɨɥɨɠɢɬɟɥɶɧɨɝɨ ɦɚɤɫɢɦɭɦɚ ɜ ɫɩɟɤɬɪɟ ɄȾ ȾɇɄ, ɤɨɬɨɪɨɟ ɨɛɵɱɧɨ ɫɜɹɡɵɜɚɸɬ ɫ ɨɛɪɚɡɨɜɚɧɢɟɦ ɛɢɞɟɧɬɚɬɧɨɝɨ ɤɨɦɩɥɟɤɫɚ ɰɢɫ-ȾȾɉ ɫ ɦɚɤɪɨɦɨɥɟɤɭɥɨɣ [ 20 ]. ɗɬɨ ɨɛɫɬɨɹɬɟɥɶɫɬɜɨ, ɜ ɱɚɫɬɧɨɫɬɢ, ɭɤɚɡɵɜɚɟɬ ɧɚ ɬɨ, ɱɬɨ ɜ ɩɪɨɰɟɫɫɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ Pt10 ɫ ȾɇɄ ɤɚɪɛɨɤɫɢɩɢɪɚɡɢɧ ɨɫɬɚɟɬɫɹ ɜ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɣ ɫɮɟɪɟ ɩɥɚɬɢɧɵ, ɬɚɤ ɤɚɤ ɜ ɩɪɨɬɢɜɧɨɦ ɫɥɭɱɚɟ ɢɡɦɟɧɟɧɢɟ ɤɨɧɮɨɪɦɚɰɢɨɧɧɵɯ ɩɚɪɚɦɟɬɪɨɜ ȾɇɄ ɛɵɥɨ ɛɵ ɢɞɟɧɬɢɱɧɨ ɩɨɥɭɱɟɧɧɵɦ ɪɚɧɟɟ ɞɥɹ ɤɨɦɩɥɟɤɫɨɜ ȾɇɄ ɫ ɰɢɫ-ȾȾɉ. ɋɥɟɞɭɟɬ ɨɬɦɟɬɢɬɶ, ɞɢɫɫɨɰɢɚɰɢɹ Pt1 ɢ Pt10 ɜ ɪɚɫɬɜɨɪɟ ɩɪɢɜɨɞɢɬ ɤ ɨɛɪɚɡɨɜɚɧɢɸ ɤɨɦɩɥɟɤɫɧɵɯ ɢɨɧɨɜ, ɨɛɥɚɞɚɸɳɢɯ ɪɚɡɧɵɦɢ ɡɚɪɹɞɚɦɢ (Pt12+ ɢ Pt10+). ɗɬɚ ɪɚɡɧɢɰɚ ɬɚɤɠɟ ɦɨɠɟɬ ɨɩɪɟɞɟɥɹɬɶ ȼɁȺɂɆɈȾȿɃɋɌȼɂȿ ɋ ɆɈɅȿɄɍɅɈɃ ȾɇɄ ɊȺɁɅɂɑɇɕɏ ɂɁɈɆȿɊɈȼ ɂ ɆɈȾɂɎɂɄȺɐɂɃ ɋɈȿȾɂɇȿɇɂɃ ɉɅȺɌɂɇɕ(II) 183 Ɋɢɫ. 4. Ɂɚɜɢɫɢɦɨɫɬɶ ɩɨɥɨɠɟɧɢɹ ɦɚɤɫɢɦɭɦɚ ɫɩɟɤɬɪɨɜ ɤɪɭɝɨɜɨɝɨ ɞɢɯɪɨɢɡɦɚ ȾɇɄ ɨɬ ɤɨɧɰɟɧɬɪɚɰɢɢ Pt11 (1), Pt12 (2), Pt13 (3) ɜ ɪɚɫɬɜɨɪɟ 0,005 M NaCl ɨɬɥɢɱɢɟ ɜ ɯɚɪɚɤɬɟɪɟ ɢɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɫ ɦɨɥɟɤɭɥɨɣ ȾɇɄ ɜ ɪɚɫɬɜɨɪɟ. ɉɪɢ ɢɫɩɨɥɶɡɨɜɚɧɢɢ Pt11, ɫɨɞɟɪɠɚɳɟɝɨ ɜ ɤɚɱɟɫɬɜɟ ɫɜɹɡɭɸɳɟɝɨ ɥɢɝɚɧɞɚ ɰɢɬɨɡɢɧ, ɡɚɦɟɬɧɨ ɛɨɥɶɲɨɟ ɫɯɨɞɫɬɜɨ ɯɚɪɚɤɬɟɪɚ ɤɨɧɮɨɪɦɚɰɢɨɧɧɵɯ ɢɡɦɟɧɟɧɢɣ ȾɇɄ ɩɪɢ ɫɜɹɡɵɜɚɧɢɢ ɫ ɧɚɛɥɸɞɚɟɦɵɦɢ ɩɪɢ ɟɟ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɢ ɫ Pt10. ɂɫɫɥɟɞɨɜɚɧɢɟ ɩɪɨɬɨɧɢɪɨɜɚɧɢɹ ȾɇɄ ɩɨɫɥɟ ɨɛɪɚɡɨɜɚɧɢɹ ɤɨɦɩɥɟɤɫɨɜ ɫ Pt11 ɩɨɤɚɡɚɥɨ, ɱɬɨ ɫɜɹɡɵɜɚɧɢɟ ɩɪɨɢɫɯɨɞɢɬ ɩɨ ɩɨɡɢɰɢɢ N7 ɝɭɚɧɢɧɚ ɫ ɨɛɪɚɡɨɜɚɧɢɟɦ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɣ ɫɜɹɡɢ. ɉɪɢ ɷɬɨɦ ɜ ɫɩɟɤɬɪɟ ɤɪɭɝɨɜɨɝɨ ɞɢɯɪɨɢɡɦɚ ȾɇɄ ɧɚɛɥɸɞɚɸɬɫɹ ɢɡɦɟɧɟɧɢɹ, ɫɯɨɞɧɵɟ ɫ ɪɚɫɫɦɨɬɪɟɧɧɵɦɢ ɪɚɧɟɟ ɞɥɹ ɤɨɦɩɥɟɤɫɨɜ ɫ Pt10. ɉɨɜɟɞɟɧɢɟ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ȾɇɄ ɩɪɢ ɫɜɹɡɵɜɚɧɢɢ ɫ Pt10 ɢ Pt11 ɚɧɚɥɨɝɢɱɧɨ (ɪɢɫ. 3 ɢ 4). Ɇɨɠɧɨ ɩɪɟɞɩɨɥɨɠɢɬɶ, ɱɬɨ ɢ ɜ ɫɥɭɱɚɟ Pt11 ɜ ɫɜɹɡɵɜɚɧɢɢ ɫ ȾɇɄ ɭɱɚɫɬɜɭɟɬ ɨɞɢɧ ɚɬɨɦ ɩɥɚɬɢɧɵ, ɚ ɨɛɪɚɡɭɸɳɢɣɫɹ ɤɨɦɩɥɟɤɫ ɩɪɚɤɬɢɱɟɫɤɢ ɧɟ ɨɬɥɢɱɚɟɬɫɹ ɨɬ ɤɨɦɩɥɟɤɫɚ ȾɇɄ ɫ Pt10. ɋɥɟɞɨɜɚɬɟɥɶɧɨ, ɩɪɢɪɨɞɚ ɫɜɹɡɵɜɚɸɳɟɝɨ ɥɢɝɚɧɞɚ ɨɤɚɡɵɜɚɟɬ ɦɟɧɶɲɟɟ ɜɥɢɹɧɢɟ ɧɚ ɯɚɪɚɤɬɟɪ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ, ɱɟɦ ɡɚɪɹɞ ɤɨɦɩɥɟɤɫɧɨɝɨ ɢɨɧɚ. ɉɨ-ɜɢɞɢɦɨɦɭ, ɜ ɫɥɭɱɚɟ Pt1 ɢɦɟɧɧɨ ɛɨɥɶɲɢɣ ɫɭɦɦɚɪɧɵɣ ɡɚɪɹɞ ɢɨɧɚ ɨɩɪɟɞɟɥɹɟɬ ɫɭɳɟɫɬɜɟɧɧɵɟ ɤɨɧɮɨɪɦɚɰɢɨɧɧɵɟ ɢɡɦɟɧɟɧɢɹ ȾɇɄ ɩɪɢ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɢ. ȼɨɡɦɨɠɧɨ, ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɢɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɫɩɨɫɨɛɫɬɜɭɸɬ ɧɟɨɛɯɨɞɢɦɨɣ ɨɪɢɟɧɬɚɰɢɢ ɞɥɹ ɜɨɜɥɟɱɟɧɢɹ ɨɛɨɢɯ ɚɬɨɦɨɜ ɩɥɚɬɢɧɵ ɜ ɩɪɨɰɟɫɫ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ. ɋɪɚɜɧɢɦ ɪɚɫɫɦɨɬɪɟɧɧɵɟ ɞɚɧɧɵɟ ɫ ɪɟɡɭɥɶɬɚɬɚɦɢ, ɩɨɥɭɱɟɧɧɵɦɢ ɩɪɢ ɢɡɭɱɟɧɢɢ ɫɜɹɡɵɜɚɧɢɹ ɦɨɥɟɤɭɥɵ ȾɇɄ ɫ Pt12, ɩɪɟɞɫɬɚɜɥɹɸɳɢɦ ɫɨɛɨɣ ɬɪɚɧɫ-ɢɡɨɦɟɪ Pt11. ɋ ɪɨɫɬɨɦ CPt12 ɩɪɨɢɫɯɨɞɢɬ ɭɦɟɧɶɲɟɧɢɟ ɚɦɩɥɢɬɭɞɵ ɩɨɥɨɠɢɬɟɥɶɧɨɝɨ ɦɚɤɫɢɦɭɦɚ, ɧɨ ɩɨɥɨɠɟɧɢɟ ɷɬɨɝɨ ɦɚɤɫɢɦɭɦɚ ɫɦɟɳɚɟɬɫɹ ɜ ɨɛɥɚɫɬɶ ɛɨɥɟɟ ɤɨɪɨɬɤɢɯ ɞɥɢɧ ɜɨɥɧ (ɫɦ. ɪɢɫ. 4), ɬɨɝɞɚ ɤɚɤ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɟ ȾɇɄ ɫ ɦɨɧɨɹɞɟɪɧɵɦ ɫɨɟɞɢɧɟɧɢɟɦ ɜ ɰɢɫ-ɤɨɧɮɨɪɦɚɰɢɢ, ɫɨɞɟɪɠɚɳɢɦ ɰɢɬɨɡɢɧ (Pt13), ɧɟ ɜɵɡɵɜɚɟɬ ɫɦɟɳɟɧɢɹ ɦɚɤɫɢɦɭɦɚ ɜɨɨɛɳɟ, ɯɨɬɹ ɩɪɢ ɷɬɨɦ ɬɚɤɠɟ ɮɢɤɫɢɪɭɟɬɫɹ ɭɦɟɧɶɲɟɧɢɟ ɟɝɨ ɚɦɩɥɢɬɭɞɵ. ɂɡɦɟɧɟɧɢɟ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ɦɨɥɟɤɭɥɵ ȾɇɄ ɩɪɢ ɨɛɪɚɡɨɜɚɧɢɢ ɤɨɦɩɥɟɤɫɨɜ ɫ ɞɜɭɹɞɟɪɧɵɦɢ ɫɨɟɞɢɧɟɧɢɹɦɢ ɜ ɰɢɫ- ɢ ɬɪɚɧɫ-ɤɨɧɮɨɪɦɚɰɢɹɯ ɫɯɨɞɧɨ, ɯɨɬɹ ɜ ɩɨɫɥɟɞɧɟɦ ɫɥɭɱɚɟ ɩɚɞɟɧɢɟ ɜɟɥɢɱɢɧɵ (J1–J2) ɧɚɱɢɧɚɟɬɫɹ ɩɪɢ ɦɟɧɶɲɢɯ ɋPt. ɗɬɢ ɞɚɧɧɵɟ ɩɨɡɜɨɥɹɸɬ ɩɪɟɞɩɨɥɨɠɢɬɶ, ɱɬɨ ɢ Pt12 ɨɛɪɚɡɭɟɬ ɤɨɦɩɥɟɤɫ ɫ ɦɨɥɟɤɭɥɨɣ ȾɇɄ ɫ ɭɱɚɫɬɢɟɦ ɬɨɥɶɤɨ ɨɞɧɨɝɨ ɚɬɨɦɚ ɩɥɚɬɢɧɵ, ɯɨɬɹ ɞɟɬɚɥɢ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɰɢɫ- ɢ ɬɪɚɧɫ-ɢɡɨɦɟɪɨɜ ɫ ɦɚɤɪɨɦɨɥɟɤɭɥɨɣ ɧɟɫɤɨɥɶɤɨ ɨɬɥɢɱɚɸɬɫɹ. ɇɚ ɨɫɧɨɜɚɧɢɢ ɜɫɟɣ ɫɨɜɨɤɭɩɧɨɫɬɢ ɪɚɫɫɦɨɬɪɟɧɧɵɯ ɞɚɧɧɵɯ ɦɨɠɧɨ ɡɚɤɥɸɱɢɬɶ, ɱɬɨ ɰɢɫ- ɢ ɬɪɚɧɫ-ɢɡɨɦɟɪɵ ɜɡɚɢɦɨɞɟɣɫɬɜɭɸɬ ɫ ɦɚɤɪɨɦɨɥɟɤɭɥɨɣ ɩɨ ɨɞɧɨɣ ɢ ɬɨɣ ɠɟ ɩɨɡɢɰɢɢ (ɬɚɤ ɠɟ ɤɚɤ ɢ ɦɨɧɨɹɞɟɪɧɨɟ ɫɨɟɞɢɧɟɧɢɟ Pt13), ɜɫɟ ɢɡɭɱɟɧɧɵɟ ɜ ɪɚɛɨɬɟ ɫɨɟɞɢɧɟɧɢɹ ɨɛɪɚɡɭɸɬ ɤɨɨɪɞɢɧɚɰɢɨɧɧɭɸ ɫɜɹɡɶ ɫ ɦɨɥɟɤɭɥɨɣ ȾɇɄ, ɩɪɨɰɟɫɫ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ɫɨɩɪɨɜɨɠɞɚɟɬɫɹ ɢɡɦɟɧɟɧɢɟɦ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ȾɇɄ ɢ ɫɩɟɤɬɪɚɥɶɧɵɯ ɫɜɨɣɫɬɜ ɦɚɤɪɨɦɨɥɟɤɭɥɵ. Ʉɨɧɮɨɪɦɚɰɢɹ ɫɨɟɞɢɧɟɧɢɹ (ɰɢɫ- ɢɥɢ ɬɪɚɧɫ-), ɛɟɡɭɫɥɨɜɧɨ, ɜɥɢɹɟɬ ɧɚ ɯɚɪɚɤɬɟɪ ɫɜɹɡɵɜɚɧɢɹ, ɧɨ ɢɡɦɟɧɟɧɢɟ ɩɚɪɚɦɟɬɪɨɜ ȾɇɄ ɜ ɩɪɨɰɟɫɫɟ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ɜ ɰɟɥɨɦ ɫɯɨɞɧɨ. ɉɪɢɪɨɞɚ ɫɜɹɡɭɸɳɟɝɨ ɥɢɝɚɧɞɚ ɜ ɫɨɫɬɚɜɟ ɞɜɭɹɞɟɪɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ, ɫɨɞɟɪɠɚɳɟɝɨ ɩɥɚɬɢɧɭ, ɩɪɚɤɬɢɱɟɫɤɢ ɧɟ ɨɤɚɡɵɜɚɟɬ ɜɥɢɹɧɢɹ ɧɚ ɫɬɪɭɤɬɭɪɭ ɨɛɪɚɡɭɸɳɟɝɨ ɤɨɦɩɥɟɤɫɚ, ɬɨɝɞɚ ɤɚɤ ɨɛɳɢɣ ɡɚɪɹɞ ɤɨɦɩɥɟɤɫɧɨɝɨ ɢɨɧɚ ɢɦɟɟɬ ɪɟɲɚɸɳɟɟ ɡɧɚɱɟɧɢɟ. ȼɨɡɦɨɠɧɨ, ɱɬɨ ɭ ɢɨɧɨɜ ɫ ɡɚɪɹɞɨɦ 1+ ɜ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɢ ɫ ȾɇɄ ɭɱɚɫɬɜɭɟɬ ɬɨɥɶɤɨ ɨɞɢɧ ɢɡ ɞɜɭɯ ɚɬɨɦɨɜ ɩɥɚɬɢɧɵ, ɜɯɨɞɹɳɢɯ ɜ ɢɯ ɫɨɫɬɚɜ. Ɉɛɧɚɪɭɠɟɧɚ ɫɭɳɟɫɬɜɟɧɧɚɹ ɪɚɡɧɢɰɚ ɜ ɢɡɦɟɧɟɧɢɢ ɢɫɫɥɟɞɨɜɚɧɧɵɯ ɩɚɪɚɦɟɬɪɨɜ ɩɪɢ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɢ ȾɇɄ ɫ ɞɜɭɹɞɟɪɧɵɦ ɢ ɚɧɚɥɨɝɢɱɧɵɦ ɦɨɧɨɹɞɟɪɧɵɦ ɫɨɟɞɢɧɟɧɢɟɦ. ɉɨɦɢɦɨ ɨɩɢɫɚɧɧɵɯ ɜɵɲɟ ɫɩɟɤɬɪɚɥɶɧɵɯ ɞɚɧɧɵɯ, ɨɛ ɷɬɨɦ ɫɜɢɞɟɬɟɥɶɫɬɜɭɸɬ ɢ ɪɟɡɭɥɶɬɚɬɵ ɢɡɭɱɟɧɢɹ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ȾɇɄ: ɞɥɹ ɦɨɧɨɹɞɟɪɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ, ɜ ɨɬɥɢɱɢɟ ɨɬ ɜɫɟɯ ɪɚɫɫɦɨɬɪɟɧɧɵɯ ɜɵɲɟ ɞɜɭɹɞɟɪɧɵɯ, ɧɚɛɥɸɞɚɟɬɫɹ ɟɟ ɭɜɟɥɢɱɟɧɢɟ ɩɪɢ ɧɟɛɨɥɶɲɢɯ ɤɨɧɰɟɧɬɪɚɰɢɹɯ CPt (ɪɢɫ. 5, 3). Ⱥɧɚɥɨɝɢɱɧɵɣ ɪɟɡɭɥɶɬɚɬ ɛɵɥ ɩɨɥɭɱɟɧ ɪɚɧɟɟ ɜ ɧɚɲɟɣ ɥɚɛɨɪɚɬɨɪɢɢ ɩɪɢ ɢɫɫɥɟɞɨɜɚɧɢɢ ɫɯɨɞɧɵɯ ɦɨɧɨɹɞɟɪ- 184 Ⱥ.Ⱥ. ȻɈȽȾȺɇɈȼ, ɘ.ȼ. ɄɈɋɆɈɌɕɇɋɄȺə, Ʉ.ɂ. əɄɈȼɅȿȼ, ɇ.Ⱥ. ɄȺɋɖəɇȿɇɄɈ Ɋɢɫ. 5. Ɉɬɧɨɫɢɬɟɥɶɧɨɟ ɢɡɦɟɧɟɧɢɟ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ȾɇɄ ɜ ɤɨɦɩɥɟɤɫɟ ɫ Pt11 (1), Pt12 (2), Pt13 (3), Pt10 (4) ɜ 0,005 Ɇ NaCl ɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɜ ɰɢɫ-ɤɨɧɮɨɪɦɚɰɢɢ, ɫɨɞɟɪɠɚɳɢɯ ɭɪɚɰɢɥ [ 21 ]. ȼ ɤɚɱɟɫɬɜɟ ɜɨɡɦɨɠɧɨɣ ɦɨɞɟɥɢ ɫɜɹɡɵɜɚɧɢɹ ɪɚɫɫɦɚɬɪɢɜɚɥɚɫɶ ɱɚɫɬɢɱɧɚɹ ɢɧɬɟɪɤɚɥɹɰɢɹ ɭɪɚɰɢɥɚ ɦɟɠɞɭ ɨɫɧɨɜɚɧɢɹɦɢ ȾɇɄ ɩɨɫɥɟ ɨɛɪɚɡɨɜɚɧɢɹ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɣ ɫɜɹɡɢ ɩɥɚɬɢɧɵ ɫ ɚɡɨɬɢɫɬɵɦɢ ɨɫɧɨɜɚɧɢɹɦɢ ɜ ɪɟɡɭɥɶɬɚɬɟ ɡɚɦɟɳɟɧɢɹ ɚɬɨɦɚ ɯɥɨɪɚ (ɱɟɪɟɡ ɨɛɪɚɡɨɜɚɧɢɟ ɚɤɜɚɤɨɦɩɥɟɤɫɨɜ). Ɍɚɤɚɹ ɦɨɞɟɥɶ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɧɟ ɩɪɨɬɢɜɨɪɟɱɢɬ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɦ ɞɚɧɧɵɦ, ɩɨɥɭɱɟɧɧɵɦ ɜ ɞɚɧɧɨɣ ɪɚɛɨɬɟ ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ ɪɚɡɧɵɯ ɦɟɬɨɞɨɜ. ɉɨ-ɜɢɞɢɦɨɦɭ, ɞɥɹ ɜɫɟɯ ɢɫɩɨɥɶɡɨɜɚɧɧɵɯ ɞɜɭɹɞɟɪɧɵɯ ɫɨɟɞɢɧɟɧɢɣ (ɤɪɨɦɟ Pt1) ɪɟɚɥɢɡɭɟɬɫɹ ɦɨɧɨɞɟɧɬɚɬɧɨɟ ɫɜɹɡɵɜɚɧɢɟ ɫ ɦɚɤɪɨɦɨɥɟɤɭɥɨɣ. Ⱦɥɹ Pt13 ɜɨɡɦɨɠɧɨ ɞɨɩɨɥɧɢɬɟɥɶɧɨɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ ɫ ȾɇɄ ɩɭɬɟɦ ɜɨɜɥɟɱɟɧɢɹ ɰɢɬɨɡɢɧɨɜɨɝɨ ɥɢɝɚɧɞɚ ɜɨ ɜɧɭɬɪɟɧɧɟɟ ɩɪɨɫɬɪɚɧɫɬɜɨ ɞɜɨɣɧɨɣ ɫɩɢɪɚɥɢ ɢ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɫ ɚɡɨɬɢɫɬɵɦɢ ɨɫɧɨɜɚɧɢɹɦɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ, ɱɬɨ ɨɛɟɫɩɟɱɢɜɚɟɬɫɹ ɭɞɨɛɧɵɦ ɪɚɫɩɨɥɨɠɟɧɢɟɦ ɚɪɨɦɚɬɢɱɟɫɤɨɝɨ ɥɢɝɚɧɞɚ ɜ ɫɨɫɬɚɜɟ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɣ ɫɮɟɪɵ ɩɥɚɬɢɧɵ ɩɨ ɨɬɧɨɲɟɧɢɸ ɤ ɚɬɨɦɭ ɯɥɨɪɚ, ɡɚɦɟɳɚɸɳɟɝɨɫɹ ɜɯɨɞɹɳɟɣ ɝɪɭɩɩɨɣ ɦɚɤɪɨɦɨɥɟɤɭɥɵ. ɋɉɂɋɈɄ ɅɂɌȿɊȺɌɍɊɕ 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. Rosenberg B., Van Camp L., Krigas T. // Nature. – 1965. – 205. – P. 698 – 699. Stehlikova K., Kostrhunova H., Kasparkova J., Brabec V. // Nucl. Acids Res. – 2002. – 30. – P. 2894 – 2899. Giaccone G. // Drugs. – 2000. – 59. – P. 9 – 17. OcDwyer P.J., Stevenson J.P., Johnson S.W. Chemistry and Biochemistry of a Leading Anticancer Drug / Ed. B. Lippert. – VHCA: Wiley, 1999. – P. 31 – 72. Wong E., Giandomenico C.M. // Chem. Rev. – 1999. – 99. – P. 2451 – 2466. 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