молекулярные ph-контролируемые устройства. данные ямр

Раздел 2
623
ɍȾɄ 543.429.23:547.022:539.2;
ɆɈɅȿɄɍɅəɊɇɕȿ PH-ɄɈɇɌɊɈɅɂɊɍȿɆɕȿ ɍɋɌɊɈɃɋɌȼȺ.
ȾȺɇɇɕȿ əɆɊ ɋɉȿɄɌɊɈɋɄɈɉɂɂ ȼɕɋɈɄɈȽɈ ɊȺɁɊȿɒȿɇɂə
ɏɚɪɥɚɦɨɜ ɋ. ȼ., Ɂɢɝɚɧɲɢɧɚ Ⱥ.ɘ., Ʉɚɡɚɤɨɜɚ ɗ.ɏ.,
Ⱥɝɚɧɨɜ Ⱥ.ȼ.*, Ʌɚɬɵɩɨɜ ɒ.Ʉ., Ʉɨɧɨɜɚɥɨɜ Ⱥ.ɂ.
ɂɈɎɏ ɢɦ. Ⱥ.ȿ. Ⱥɪɛɭɡɨɜɚ Ʉɚɡɇɐ ɊȺɇ
Ʉɚɡɚɧɫɤɢɣ ɝɨɫɭɞɚɪɫɬɜɟɧɧɵɣ ɭɧɢɜɟɪɫɢɬɟɬ
*
1. ȼɜɟɞɟɧɢɟ
Ⱦɢɡɚɣɧ ɢ ɢɫɫɥɟɞɨɜɚɧɢɟ ɦɨɥɟɤɭɥɹɪɧɵɯ ɤɨɦɩɥɟɤɫɨɜ, ɫɩɨɫɨɛɧɵɯ
ɜɵɩɨɥɧɹɬɶ ɦɟɯɚɧɢɱɟɫɤɨɟ ɞɜɢɠɟɧɢɟ, ɨɩɢɫɵɜɚɟɦɨɟ ɤɥɚɫɫɢɱɟɫɤɨɣ ɬɟɨɪɢɟɣ
– ɦɨɥɟɤɭɥɹɪɧɵɯ ɦɚɲɢɧ – ɨɱɟɧɶ ɜɚɠɧɚɹ ɢ ɚɤɬɭɚɥɶɧɚɹ ɩɪɨɛɥɟɦɚ
ɫɨɜɪɟɦɟɧɧɨɣ ɧɚɭɤɢ, ɢ ɜ ɬɨɦ ɱɢɫɥɟ – ɫɭɩɪɚɦɨɥɟɤɭɥɹɪɧɨɣ ɯɢɦɢɢ ɢ
ɦɨɥɟɤɭɥɹɪɧɨɣ ɦɟɞɢɰɢɧɵ [1ɚ]. ȼ ɩɟɪɜɭɸ ɨɱɟɪɟɞɶ ɷɬɨ ɫɜɹɡɚɧɨ ɫ ɬɟɦ, ɱɬɨ
ɨɞɧɢɦ ɢɡ ɨɫɧɨɜɧɵɯ ɬɪɟɛɨɜɚɧɢɣ ɪɚɡɜɢɬɢɹ ɷɥɟɤɬɪɨɧɢɤɢ ɢ ɬɟɯɧɨɥɨɝɢɢ
ɹɜɥɹɟɬɫɹ ɦɢɧɢɚɬɸɪɢɡɚɰɢɹ ɤɨɦɩɨɧɟɧɬ, ɢɫɩɨɥɶɡɭɟɦɵɯ ɞɥɹ ɫɨɡɞɚɧɢɹ
ɫɨɜɪɟɦɟɧɧɵɯ ɭɫɬɪɨɣɫɬɜ [1ɛ]. ɋ ɞɪɭɝɨɣ ɫɬɨɪɨɧɵ, ɦɨɥɟɤɭɥɹɪɧɵɟ
ɭɫɬɪɨɣɫɬɜɚ ɹɜɥɹɸɬɫɹ ɱɚɫɬɶɸ ɥɸɛɨɝɨ ɠɢɜɨɝɨ ɨɪɝɚɧɢɡɦɚ, ɪɟɝɭɥɢɪɭɹ ɧɚ
ɦɨɥɟɤɭɥɹɪɧɨɦ
ɭɪɨɜɧɟ
ɩɪɨɰɟɫɫɵ
ɪɚɫɩɨɡɧɚɜɚɧɢɹ,
ɫɜɹɡɵɜɚɧɢɹ,
ɪɟɩɥɢɤɚɰɢɢ, ɬɪɚɧɫɩɨɪɬɚ ɢ ɬ.ɞ. ɉɨɷɬɨɦɭ ɢɫɫɥɟɞɨɜɚɧɢɟ ɞɚɧɧɵɯ ɫɢɫɬɟɦ ɢ
ɢɯ ɦɨɞɟɥɟɣ ɹɜɥɹɟɬɫɹ ɨɞɧɢɦ ɢɡ ɤɥɸɱɟɜɵɯ ɲɚɝɨɜ ɜ ɩɨɡɧɚɧɢɢ ɬɨɧɤɢɯ
ɮɚɤɬɨɪɨɜ, ɪɟɝɭɥɢɪɭɸɳɢɯ ɩɪɨɰɟɫɫɵ ɠɢɡɧɟɞɟɹɬɟɥɶɧɨɫɬɢ.
ȼɨɨɛɳɟ, ɦɨɥɟɤɭɥɹɪɧɚɹ ɦɚɲɢɧɚ ɦɨɠɟɬ ɛɵɬɶ ɨɩɪɟɞɟɥɟɧɚ ɤɚɤ ɚɧɫɚɦɛɥɶ
ɦɨɥɟɤɭɥɹɪɧɵɯ ɤɨɦɩɨɧɟɧɬ, ɫɤɨɧɫɬɪɭɢɪɨɜɚɧɧɵɣ ɬɚɤɢɦ ɨɛɪɚɡɨɦ, ɱɬɨɛɵ ɜ
ɨɬɜɟɬ ɧɚ ɜɧɟɲɧɢɣ ɫɬɢɦɭɥ ɜɵɩɨɥɧɹɬɶ ɨɩɪɟɞɟɥɟɧɧɭɸ ɦɟɯɚɧɢɱɟɫɤɭɸ
ɮɭɧɤɰɢɸ [1ɛ]. Ⱦɚɧɧɵɣ ɚɧɫɚɦɛɥɶ ɞɨɥɠɟɧ ɫɨɫɬɨɹɬɶ, ɤɚɤ ɦɢɧɢɦɭɦ, ɢɡ
ɞɜɭɯ ɤɨɦɩɨɧɟɧɬ – ɦɨɛɢɥɶɧɨɣ ɢ ɫɬɚɰɢɨɧɚɪɧɨɣ [1ɜ]. ȼɧɟɲɧɟɟ ɜɨɡɞɟɣɫɬɜɢɟ
ɩɪɢ ɷɬɨɦ ɩɪɢɜɨɞɢɬ ɤ ɫɦɟɳɟɧɢɸ ɩɟɪɜɨɣ ɤɨɦɩɨɧɟɧɬɵ ɨɬɧɨɫɢɬɟɥɶɧɨ
ɜɬɨɪɨɣ. ɇɚɢɛɨɥɟɟ ɷɮɮɟɤɬɢɜɧɵɦɢ ɫɬɢɦɭɥɚɦɢ ɹɜɥɹɸɬɫɹ ɮɨɬɨ- ɢɥɢ
ɷɥɟɤɬɪɨɯɢɦɢɱɟɫɤɨɟ ɜɨɡɞɟɣɫɬɜɢɹ. ȼ ɩɨɫɥɟɞɧɟɦ ɫɥɭɱɚɟ ɭɫɩɟɲɧɨ ɦɨɠɟɬ
ɛɵɬɶ ɢɫɩɨɥɶɡɨɜɚɧɚ ɜɚɪɢɚɰɢɹ pH ɫɪɟɞɵ [1, 2]. ȼɚɠɧɨ ɨɬɦɟɬɢɬɶ, ɱɬɨ
ɤɢɫɥɨɬɧɨɫɬɶ ɫɪɟɞɵ ɜ ɠɢɜɨɣ ɩɪɢɪɨɞɟ ɹɜɥɹɟɬɫɹ ɨɞɧɢɦ ɢɡ ɜɚɠɧɟɣɲɢɯ
ɪɟɝɭɥɢɪɭɸɳɢɯ ɮɚɤɬɨɪɨɜ.
ȼ ɞɚɧɧɨɣ ɪɚɛɨɬɟ ɪɚɫɫɦɨɬɪɟɧɚ ɜɨɡɦɨɠɧɨɫɬɶ ɫɨɡɞɚɧɢɹ pHɤɨɧɬɪɨɥɢɪɭɟɦɨɝɨ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɩɟɪɟɤɥɸɱɚɬɟɥɹ ɧɚ ɨɫɧɨɜɟ ɤɚɥɢɤɫɚɪɟɧɚ
(ɪɢɫɭɧɨɤ 1), ɮɭɧɤɰɢɨɧɚɥɢɡɢɪɨɜɚɧɧɨɝɨ ɜɢɨɥɨɝɟɧɨɜɵɦɢ ɡɚɦɟɫɬɢɬɟɥɹɦɢ
ɩɨ ɜɟɪɯɧɟɦɭ ɨɛɨɞɭ. Ɉɧ ɢɦɟɟɬ ɜ ɫɨɫɬɚɜɟ ɩɨɥɨɠɢɬɟɥɶɧɨ ɡɚɪɹɠɟɧɧɵɟ
ɮɪɚɝɦɟɧɬɵ ɢ, ɩɨɷɬɨɦɭ, ɦɨɠɟɬ ɫɟɥɟɤɬɢɜɧɨ ɫɜɹɡɵɜɚɬɶ ɬɨɥɶɤɨ
ɧɟɡɚɪɹɠɟɧɧɵɟ ɢɥɢ ɨɬɪɢɰɚɬɟɥɶɧɨ ɡɚɪɹɠɟɧɧɵɟ ɦɨɥɟɤɭɥɵ «ɝɨɫɬɟɣ». Ɍɚɤɢɦ
624
Структура и динамика молекулярных систем, 2007 г., Выпуск №1
ɨɛɪɚɡɨɦ, ɢɡɦɟɧɟɧɢɟ ɡɚɪɹɞɚ «ɝɨɫɬɹ» (ɧɚɩɪɢɦɟɪ, ɩɭɬɟɦ ɢɡɦɟɧɟɧɢɹ pH
ɫɪɟɞɵ) ɦɨɠɟɬ ɫɬɢɦɭɥɢɪɨɜɚɬɶ ɫɦɟɳɟɧɢɟ ɷɬɨɣ ɦɨɥɟɤɭɥɵ (ɦɨɛɢɥɶɧɨɣ
ɤɨɦɩɨɧɟɧɬɵ) ɨɬɧɨɫɢɬɟɥɶɧɨ «ɯɨɡɹɢɧɚ» (ɫɬɚɰɢɨɧɚɪɧɨɣ ɤɨɦɩɨɧɟɧɬɵ), ɢɥɢ,
ɢɧɵɦɢ ɫɥɨɜɚɦɢ, ɩɟɪɟɤɥɸɱɟɧɢɟ ɭɫɬɪɨɣɫɬɜɚ ɢɡ ɨɞɧɨɝɨ ɫɨɫɬɨɹɧɢɹ ɜ ɞɪɭɝɨɟ
(ɫɯɟɦɚ 1).
ȼ ɧɚɫɬɨɹɳɟɣ ɪɚɛɨɬɟ ɦɵ ɩɪɢɜɨɞɢɦ ɩɪɟɞɜɚɪɢɬɟɥɶɧɵɟ ɪɟɡɭɥɶɬɚɬɵ
ɩɪɨɜɟɞɟɧɧɵɯ ɢɫɫɥɟɞɨɜɚɧɢɣ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɭɸɳɢɯ ɫɜɨɣɫɬɜ ɧɨɜɨɝɨ
ɜɨɞɨɪɚɫɬɜɨɪɢɦɨɝɨ ɤɚɥɢɤɫ[4]ɪɟɡɨɪɰɢɧɚɪɟɧɚ (1) ɫ ɞɜɭɦɹ ɚɪɨɦɚɬɢɱɟɫɤɢɦɢ
«ɝɨɫɬɹɦɢ» (ɪɢɫɭɧɨɤ 1) ɤɚɤ ɦɨɞɟɥɢ pH-ɩɟɪɟɤɥɸɱɚɬɟɥɹ.
CH3
N+
OH
2
+
N
CH2
O
NH2
O
C
H2
CH
R
R= H2C
H2
C
C
H2
H2
C
NH2
4
3
CH3
1
Ɋɢɫɭɧɨɤ 1. ɋɬɪɭɤɬɭɪɧɵɟ ɱɚɫɬɢ ɢɫɫɥɟɞɭɟɦɨɣ ɦɨɞɟɥɢ ɦɨɥɟɤɭɥɹɪɧɨɣ ɦɚɲɢɧɵ (1 –
ɤɚɥɢɤɫ[4]ɪɟɡɨɪɰɢɧɚɪɟɧ, 2 – 2-ɧɚɮɬɨɥ, 3 – 1,5-ɧɚɮɬɚɥɟɧɞɢɚɦɢɧ)
ɋɯɟɦɚ 1. pH-ɤɨɧɬɪɨɥɶ ɫɬɪɭɤɬɭɪɵ ɤɨɦɩɥɟɤɫɚ «ɝɨɫɬɶ-ɯɨɡɹɢɧ» ɧɚ ɨɫɧɨɜɟ
ɮɭɧɤɰɢɨɧɚɥɢɡɢɪɨɜɚɧɧɨɝɨ ɤɚɥɢɤɫɚɪɟɧɚ (ɫɟɪɵɟ ɨɜɚɥɵ – ɦɨɥɟɤɭɥɵ «ɝɨɫɬɹ»)
2. Ɋɟɡɭɥɶɬɚɬɵ ɢ ɢɯ ɨɛɫɭɠɞɟɧɢɟ
ɉɪɟɠɞɟ,
ɱɟɦ
ɧɚɱɚɬɶ
ɢɫɫɥɟɞɨɜɚɧɢɟ
ɜɨɡɦɨɠɧɨɫɬɢ
ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɹ ɜ ɫɢɫɬɟɦɚɯ 1-3 ɢ ɢɡɭɱɚɬɶ ɜɥɢɹɧɢɟ pH ɫɪɟɞɵ ɧɚ
ɫɬɚɛɢɥɶɧɨɫɬɶ ɷɬɢɯ ɤɨɦɩɥɟɤɫɨɜ, ɦɵ ɩɪɨɚɧɚɥɢɡɢɪɨɜɚɥɢ ɡɚɜɢɫɢɦɨɫɬɶ ɨɬ
ɤɨɧɰɟɧɬɪɚɰɢɢ ɢ pH ɫɪɟɞɵ ɫɜɨɣɫɬɜ ɪɚɫɬɜɨɪɨɜ ɢɧɞɢɜɢɞɭɚɥɶɧɵɯ
ɤɨɦɩɨɧɟɧɬ. Ȼɵɥɨ ɨɛɧɚɪɭɠɟɧɨ, ɱɬɨ 1H əɆɊ ɯɢɦɢɱɟɫɤɢɟ ɫɞɜɢɝɢ (ɏɋ) 1 ɢ
2 ɫɥɚɛɨ ɡɚɜɢɫɹɬ ɨɬ ɤɢɫɥɨɬɧɨɫɬɢ ɫɪɟɞɵ, ɜ ɬɨ ɜɪɟɦɹ ɤɚɤ ɏɋ 3 ɡɚɦɟɬɧɨ
Раздел 2
625
ɢɡɦɟɧɹɸɬɫɹ ɩɪɢ ɜɚɪɢɚɰɢɢ pH ɢɡ-ɡɚ ɩɪɨɬɨɧɢɪɨɜɚɧɢɹ ɚɦɢɧɨɝɪɭɩɩ
ɦɨɥɟɤɭɥ 3.
Ⱥɧɚɥɢɡ ɡɚɜɢɫɢɦɨɫɬɢ ɏɋ ɫɨɟɞɢɧɟɧɢɣ 1-3 ɨɬ ɤɨɧɰɟɧɬɪɚɰɢɢ ɩɨɡɜɨɥɢɥ
ɩɪɟɞɩɨɥɨɠɢɬɶ, ɱɬɨ 2 ɧɟ ɫɤɥɨɧɧɵ ɤ ɫɚɦɨɚɫɫɨɰɢɚɰɢɢ ɩɪɢ ɥɸɛɵɯ pH; 1 ɢ
3, ɩɨ ɜɫɟɣ ɜɢɞɢɦɨɫɬɢ, ɚɫɫɨɰɢɢɪɭɸɬ ɜ ɧɟɣɬɪɚɥɶɧɨɣ ɫɪɟɞɟ, ɜ ɬɨ ɜɪɟɦɹ ɤɚɤ
ɜ ɤɢɫɥɨɣ ɫɪɟɞɟ ɚɫɫɨɰɢɚɰɢɹ ɨɬɫɭɬɫɬɜɭɟɬ.
Ⱦɚɥɟɟ ɛɵɥ ɩɪɨɜɟɞɟɧ ɚɧɚɥɢɡ ɏɋ ɜ ɫɢɫɬɟɦɚɯ ɫ ɪɚɡɥɢɱɧɵɦɢ
ɷɤɜɢɦɨɥɹɪɧɵɦɢ ɤɨɦɛɢɧɚɰɢɹɦɢ ɫɨɟɞɢɧɟɧɢɣ 1, 2 ɢ 3. ɏɚɪɚɤɬɟɪɢɫɬɢɱɧɵɟ
ɜɵɫɨɤɨɩɨɥɶɧɵɟ ɫɞɜɢɝɢ ɏɋ 1H əɆɊ ɫɢɝɧɚɥɨɜ ɦɨɥɟɤɭɥ «ɝɨɫɬɟɣ» (ɞɨ 1.19
ɦ.ɞ.) ɫɜɢɞɟɬɟɥɶɫɬɜɭɸɬ ɨɛ ɨɛɪɚɡɨɜɚɧɢɢ ɜ ɫɢɫɬɟɦɚɯ 1+2 ɢ 1+3 ɫɬɚɛɢɥɶɧɵɯ
ɤɨɦɩɥɟɤɫɨɜ ɬɢɩɚ «ɝɨɫɬɶ-ɯɨɡɹɢɧ». ɉɪɢ ɷɬɨɦ ɦɵ ɨɛɧɚɪɭɠɢɥɢ, ɱɬɨ
ɜɚɪɢɚɰɢɹ pH ɫɪɟɞɵ ɧɟ ɜɥɢɹɟɬ ɧɚ ɫɬɚɛɢɥɶɧɨɫɬɶ ɤɨɦɩɥɟɤɫɚ 1+2. ȼ ɬɨ ɠɟ
ɜɪɟɦɹ, ɩɪɢ ɭɦɟɧɶɲɟɧɢɢ pH ɤɨɦɩɥɟɤɫ 1+3 ɪɚɡɪɭɲɚɟɬɫɹ. ɗɬɨ ɫɜɹɡɚɧɨ ɫ
ɩɪɨɬɨɧɢɪɨɜɚɧɢɟɦ ɦɨɥɟɤɭɥ 3 ɢ ɩɨɫɥɟɞɭɸɳɢɦ ɢɯ ɜɵɯɨɞɨɦ ɢɡ ɩɨɥɨɫɬɢ
ɤɚɥɢɤɫɚɪɟɧɚ 1 ɢɡ-ɡɚ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɨɝɨ ɨɬɬɚɥɤɢɜɚɧɢɹ ɦɟɠɞɭ
ɦɨɥɟɤɭɥɚɦɢ «ɯɨɡɹɢɧɚ» ɢ «ɝɨɫɬɹ».
Ɉɞɧɚɤɨ
ɨɬɤɪɵɬɵɦɢ
ɨɫɬɚɜɚɥɢɫɶ
ɜɨɩɪɨɫɵ,
ɫɜɹɡɚɧɧɵɟ
ɫɨ
ɫɬɟɯɢɨɦɟɬɪɢɟɣ, ɪɚɡɦɟɪɨɦ ɢ ɫɬɚɛɢɥɶɧɨɫɬɶɸ ɤɨɦɩɥɟɤɫɨɜ. ɉɨɷɬɨɦɭ ɞɥɹ
ɬɨɝɨ, ɱɬɨɛɵ ɩɨɥɭɱɢɬɶ ɧɚɝɥɹɞɧɵɟ ɫɜɢɞɟɬɟɥɶɫɬɜɚ ɨɛɪɚɡɨɜɚɧɢɹ ɤɨɦɩɥɟɤɫɨɜ
«ɝɨɫɬɶ-ɯɨɡɹɢɧ» ɜ ɪɚɫɫɦɚɬɪɢɜɚɟɦɵɯ ɫɢɫɬɟɦɚɯ, ɚ ɬɚɤɠɟ ɩɨɥɭɱɢɬɶ
ɢɧɮɨɪɦɚɰɢɸ ɨɛ ɢɯ ɪɚɡɦɟɪɚɯ, ɦɵ ɢɡɦɟɪɢɥɢ ɤɨɷɮɮɢɰɢɟɧɬɵ
ɫɚɦɨɞɢɮɮɭɡɢɢ (ɄɋȾ) ɢɫɫɥɟɞɭɟɦɵɯ ɨɛɴɟɤɬɨɜ ɜ ɪɚɡɥɢɱɧɵɯ ɫɢɫɬɟɦɚɯ ɫ
ɩɨɦɨɳɶɸ ɦɟɬɨɞɚ 2D DOSY, ɫɨɱɟɬɚɸɳɟɝɨ ɜ ɫɟɛɟ ɞɨɫɬɨɢɧɫɬɜɚ ɜɵɫɨɤɨɝɨ
ɪɚɡɪɟɲɟɧɢɹ əɆɊ ɢ ɜɨɡɦɨɠɧɨɫɬɶ ɨɩɪɟɞɟɥɟɧɢɹ ɤɨɷɮɮɢɰɢɟɧɬɨɜ
ɫɚɦɨɞɢɮɮɭɡɢɢ [3].
Ȼɵɥɨ ɧɚɣɞɟɧɨ, ɱɬɨ ɄɋȾ «ɯɨɡɹɢɧɚ» 1 ɢ «ɝɨɫɬɟɣ» 2, 3 ɫɭɳɟɫɬɜɟɧɧɨ
ɪɚɡɥɢɱɧɵ ɢ ɤɨɪɪɟɥɢɪɭɸɬ ɫ ɪɚɡɦɟɪɚɦɢ ɦɨɥɟɤɭɥ (0.21, 0.77 ɢ 0.72u10-10
ɦ2/ɫ, ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ; ɤɨɧɰɟɧɬɪɚɰɢɹ ɋ=1ɦɆ).
Ⱦɚɥɟɟ, ɦɵ ɨɛɧɚɪɭɠɢɥɢ, ɱɬɨ ɄɋȾ 1 ɭɦɟɧɶɲɚɟɬɫɹ ɩɪɢ ɭɜɟɥɢɱɟɧɢɢ
ɤɨɧɰɟɧɬɪɚɰɢɢ, ɱɬɨ ɫɜɹɡɚɧɨ ɫ ɫɚɦɨɚɫɫɨɰɢɚɰɢɟɣ ɦɨɥɟɤɭɥ «ɯɨɡɹɢɧɚ»,
ɩɪɢɱɟɦ ɚɧɚɥɢɡ ɄɋȾ ɩɨɤɚɡɵɜɚɟɬ, ɱɬɨ ɩɪɢ ɋ=5ɦɆ ɦɨɥɟɤɭɥɵ 1
ɫɭɳɟɫɬɜɭɸɬ ɜ ɪɚɫɬɜɨɪɟ ɜ ɜɢɞɟ ɞɢɦɟɪɚ.
ɉɪɢ ɩɟɪɟɯɨɞɟ ɨɬ ɢɧɞɢɜɢɞɭɚɥɶɧɵɯ ɪɚɫɬɜɨɪɨɜ ɤ ɫɢɫɬɟɦɚɦ 1+2 ɢ 1+3
ɄɋȾ ɦɨɥɟɤɭɥ 1, 2 ɢ 3 ɫɬɚɧɨɜɹɬɫɹ ɪɚɜɧɵɦɢ, ɱɬɨ ɞɨɤɚɡɵɜɚɟɬ ɨɛɪɚɡɨɜɚɧɢɟ
ɜ ɷɬɢɯ ɫɢɫɬɟɦɚɯ ɤɨɦɩɥɟɤɫɨɜ ɬɢɩɚ «ɝɨɫɬɶ-ɯɨɡɹɢɧ». ɉɪɢɱɟɦ ɬɳɚɬɟɥɶɧɵɣ
ɚɧɚɥɢɡ ɄɋȾ ɩɨɡɜɨɥɹɟɬ ɡɚɤɥɸɱɢɬɶ, ɱɬɨ ɫɬɟɯɢɨɦɟɬɪɢɹ ɤɨɦɩɥɟɤɫɨɜ ɜ
ɩɟɪɜɨɣ ɫɢɫɬɟɦɟ ɜɵɲɟ, ɱɟɦ 1:1, ɚ ɜɨ ɜɬɨɪɨɣ – ɜɵɲɟ, ɱɟɦ 2:2.
ȼɚɪɢɚɰɢɹ pH ɧɟ ɩɪɢɜɨɞɢɬ ɤ ɤɚɤɢɦ-ɥɢɛɨ ɡɚɦɟɬɧɵɦ ɢɡɦɟɧɟɧɢɹɦ ɜ
ɡɧɚɱɟɧɢɢ ɄɋȾ 2 ɜ ɫɢɫɬɟɦɟ 1+2, ɱɬɨ ɩɨɞɬɜɟɪɠɞɚɟɬ ɩɪɟɞɩɨɥɨɠɟɧɢɹ,
ɫɞɟɥɚɧɧɵɟ ɧɚ ɨɫɧɨɜɟ ɚɧɚɥɢɡɚ ɏɋ. ȼ ɫɢɫɬɟɦɟ 1+3, ɨɞɧɚɤɨ, ɜɚɪɢɚɰɢɹ pH
626
Структура и динамика молекулярных систем, 2007 г., Выпуск №1
ɩɪɢɜɨɞɢɬ ɤ ɞɪɚɦɚɬɢɱɟɫɤɢɦ ɢɡɦɟɧɟɧɢɹɦ ɄɋȾ 3 – ɟɝɨ ɡɧɚɱɟɧɢɟ ɪɟɡɤɨ
ɜɨɡɪɚɫɬɚɟɬ ɩɪɢ ɩɟɪɟɯɨɞɟ ɨɬ pH=5 ɤ pH=2. ɗɬɨ ɹɜɥɹɟɬɫɹ ɫɜɢɞɟɬɟɥɶɫɬɜɨɦ
ɪɚɡɪɭɲɟɧɢɹ ɤɨɦɩɥɟɤɫɚ ɜ ɞɚɧɧɨɣ ɫɢɫɬɟɦɟ.
2D DOSY ɷɤɫɩɟɪɢɦɟɧɬɵ ɜ ɫɢɫɬɟɦɟ 1+2+3 ɩɨɤɚɡɚɥɢ, ɱɬɨ ɜ ɧɟɣ ɬɚɤɠɟ
ɨɛɪɚɡɭɸɬɫɹ ɤɨɦɩɥɟɤɫ ɬɢɩɚ «ɝɨɫɬɶ-ɯɨɡɹɢɧ», ɩɪɢɱɟɦ 1 ɨɞɧɨɜɪɟɦɟɧɧɨ
ɫɜɹɡɵɜɚɟɬ ɨɛɟ ɦɨɥɟɤɭɥɵ «ɝɨɫɬɟɣ». ɉɪɢ ɷɬɨɦ ɜɥɢɹɧɢɟ pH ɫɪɟɞɵ ɧɚ
ɫɬɚɛɢɥɶɧɨɫɬɶ ɷɬɨɝɨ ɤɨɦɩɥɟɤɫɚ ɜɟɫɶɦɚ ɫɩɟɰɢɮɢɱɧɨ: ɩɪɢ ɭɦɟɧɶɲɟɧɢɢ pH
ɨɬ 5 ɞɨ 2 ɩɪɨɢɫɯɨɞɢɬ ɱɚɫɬɢɱɧɨɟ ɪɚɡɪɭɲɟɧɢɟ ɤɨɦɩɥɟɤɫɚ – ɦɨɥɟɤɭɥɚ 3
ɩɪɨɬɨɧɢɪɭɟɬɫɹ ɢ ɜɵɯɨɞɢɬ ɢɡ ɤɨɦɩɥɟɤɫɚ, ɜ ɬɨ ɜɪɟɦɹ ɤɚɤ ɦɨɥɟɤɭɥɚ 2
ɨɫɬɚɟɬɫɹ ɜ ɩɨɥɨɫɬɢ ɤɚɥɢɤɫɚɪɟɧɚ.
3. Ɂɚɤɥɸɱɟɧɢɟ
Ⱥɧɚɥɢɡ 1H əɆɊ ɏɋ ɢ ɄɋȾ ɜ ɫɢɫɬɟɦɚɯ 1+2, 1+3, 1+2+3 ɩɨɤɚɡɚɥ, ɱɬɨ ɜ
ɞɚɧɧɵɯ ɫɢɫɬɟɦɚɯ ɨɛɪɚɡɭɸɬɫɹ ɤɨɦɩɥɟɤɫɵ ɬɢɩɚ «ɝɨɫɬɶ-ɯɨɡɹɢɧ». ɉɪɢ ɷɬɨɦ
ɡɚɜɢɫɢɦɨɫɬɶ ɫɬɚɛɢɥɶɧɨɫɬɢ ɷɬɢɯ ɤɨɦɩɥɟɤɫɨɜ ɨɬ pH ɫɪɟɞɵ ɦɨɠɟɬ ɛɵɬɶ
ɢɧɬɟɪɩɪɟɬɢɪɨɜɚɧɚ ɫɥɟɞɭɸɳɢɦ ɨɛɪɚɡɨɦ:
1) ɫɨɫɬɨɹɧɢɟ ɫɢɫɬɟɦ 1+2 ɢ 1+2+3 ɦɨɠɟɬ ɤɨɧɬɪɨɥɢɪɨɜɚɬɶɫɹ ɩɭɬɟɦ
ɜɚɪɢɚɰɢɢ pH ɫɪɟɞɵ ɨɛɪɚɬɢɦɵɦ ɨɛɪɚɡɨɦ; ɬɚɤɨɟ ɩɨɜɟɞɟɧɢɟ
ɩɨɡɜɨɥɹɟɬ ɪɚɫɫɦɚɬɪɢɜɚɬɶ ɞɚɧɧɵɟ ɫɢɫɬɟɦɵ ɤɚɤ ɦɨɞɟɥɢ pHɭɩɪɚɜɥɹɟɦɵɯ ɦɨɥɟɤɭɥɹɪɧɵɯ ɩɟɪɟɤɥɸɱɚɬɟɥɟɣ;
2) ɫɢɫɬɟɦɚ 1+2+3 ɦɨɠɟɬ ɪɚɫɫɦɚɬɪɢɜɚɬɶɫɹ ɤɚɤ ɦɨɞɟɥɶ
ɦɨɥɟɤɭɥɹɪɧɨɣ «ɥɨɜɭɲɤɢ», ɩɨɡɜɨɥɹɸɳɟɣ ɷɮɮɟɤɬɢɜɧɨ ɨɬɞɟɥɹɬɶ
ɦɨɥɟɤɭɥɵ ɪɚɡɧɵɯ ɫɨɪɬɨɜ ɞɪɭɝ ɨɬ ɞɪɭɝɚ.
Ʌɢɬɟɪɚɬɭɪɚ
[1] (ɚ) Balzani, V., Credi, A., Venturi, M.: Molecular Devices and Machines
– A Journey into the Nano World. Wiley-VCH, 369 Weinheim (2003);
(ɛ) Balzani, V., Credi, A., Raymo, F.M., Stoddart, J.F.: Angew. Chem.
Int. Ed. 39, 3348 (2000); (ɜ) Lehn, J.-M.: Supramolecular Chemistry,
Concepts and 373 Perspectives. Wiley-VCH, Weinheim (1995).
[2] Balzani, V., Credi, A., Matersteig, G., Matthews, O.A., Raymo, F.M.,
Stoddart, J.F., Venturi, M., White, A.J.P., Williams, D.J.: J. Org. Chem.
65, 1924 (2000).
[3] (ɚ) Johnson, C.S. Jr.: Prog. NMR Spectrosc. 34, 203 (1999); (ɛ) Cameron,
K.S., Fielding, L.: Magn. Reson. Chem. 40, 106 (2002)