Strong Short-Range Cooperativity in Hydrogen-Bond Chains

被引：47

作者：

Dominelli-Whiteley, Nicholas ^{[1
]}

Brown, James J. ^{[1
]}

Muchowska, Kamila B. ^{[1
]}

Mati, Ioulia K. ^{[1
]}

Adam, Catherine ^{[1
]}

Hubbard, Thomas A. ^{[1
]}

Elmi, Alex ^{[1
]}

Brown, Alisdair J. ^{[2
]}

Bell, Ian A. W. ^{[2
]}

Cockroft, Scott L. ^{[1
]}

机构：

[1] Univ Edinburgh, EaStCHEM Sch Chem, Joseph Black Bldg,David Brewster Rd, Edinburgh EH9 3FJ, Midlothian, Scotland

[2] Afton Chem Ltd, London Rd, Bracknell RG12 2UW, Berks, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 26期

基金：

英国工程与自然科学研究理事会;

关键词：

cooperativity; hydrogen bonds; noncovalent interactions; supramolecular chemistry; MOLECULAR TORSION BALANCES; FACE AROMATIC INTERACTIONS; PROTEIN-FOLDING MODELS; CH-PI INTERACTIONS; ARENE INTERACTIONS; WATER CHAINS; LIQUID WATER; RECOGNITION; BINDING; ENERGY;

D O I：

10.1002/anie.201703757

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Chains of hydrogen bonds such as those found in water and proteins are often presumed to be more stable than the sum of the individual H bonds. However, the energetics of cooperativity are complicated by solvent effects and the dynamics of intermolecular interactions, meaning that information on cooperativity typically is derived from theory or indirect structural data. Herein, we present direct measurements of energetic cooperativity in an experimental system in which the geometry and the number of H bonds in a chain were systematically controlled. Strikingly, we found that adding a second H-bond donor to form a chain can almost double the strength of the terminal H bond, while further extensions have little effect. The experimental observations add weight to computations which have suggested that strong, but short-range cooperative effects may occur in H-bond chains.

引用

页码：7658 / 7662

页数：5

共 78 条

[51] AB-INITIO STUDY OF COOPERATIVITY IN WATER CHAINS - BINDING-ENERGIES AND ANHARMONIC FREQUENCIES [J].