A synthetic host-guest system achieves avidin-biotin affinity by overcoming enthalpy-entropy compensation

被引：483

作者：

Rekharsky, Mikhail V. ^{[1
]}

Mori, Tadashi ^{[2
]}

Yang, Cheng ^{[2
]}

Ko, Young Ho ^{[3
]}

Selvapalam, N. ^{[7
]}

Kim, Hyunuk ^{[3
,7
]}

Sobransingh, David

Kaifer, Angel E. ^{[4
]}

Liu, Simin ^{[5
,6
]}

Isaacs, Lyle ^{[5
,6
]}

Chen, Wei ^{[5
,6
,7
]}

Moghaddam, Sarvin ^{[5
,6
]}

Gilson, Michael K. ^{[5
,6
,7
]}

Kim, Kimoon ^{[3
,7
]}

Inoue, Yoshihisa ^{[1
,2
]}

机构：

[1] Osaka Univ, ICORP Entropy Control Project, JST, Suita, Osaka 5650871, Japan

[2] Osaka Univ, Dept Appl Chem, Suita, Osaka 5650871, Japan

[3] Pohang Univ Sci & Technol, Natl Creat Res Initiat Ctr Smart Supramol, Dept Chem, Pohang 790784, South Korea

[4] Univ Miami, Ctr Supramol Sci, Dept Chem, Coral Gables, FL 33124 USA

[5] Univ Maryland, Dept Chem & Biochem, College Pk, MD 20742 USA

[6] Univ Maryland, Inst Biotechnol, Ctr Adv Res Biotechnol, Rockville, MD 20850 USA

[7] VeraChem LLC, Germantown, MD 20874 USA

来源：

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | 2007年 / 104卷 / 52期

关键词：

cucurbituril entropy control; ferrocene derivatives; host-guest complexation; thermodynamics;

D O I：

10.1073/pnas.0706407105

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The molecular host cucurbit[7]uril forms an extremely stable inclusion complex with the dicationic ferrocene derivative bis(trimethylammoniomethyl)ferrocene in aqueous solution. The equilibrium association constant for this host-guest pair is 3 x 1015 M-1 (K-d = 3 x 10(-16) M), equivalent to that exhibited by the avidin-biotin pair. Although purely synthetic systems with larger association constants have been reported, the present one is unique because it does not rely on polyvalency. Instead, it achieves its extreme affinity by overcoming the compensatory enthalpy-entropy relationship usually observed in supramolecular complexes. Its disproportionately low entropic cost is traced to extensive host desolvation and to the rigidity of both the host and the guest.

引用

页码：20737 / 20742

页数：6

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