Force-Reactivity Property of a Single Monomer Is Sufficient To Predict the Micromechanical Behavior of Its Polymer

被引:90
作者
Akbulatov, Sergey [1 ]
Tian, Yancong [1 ]
Boulatov, Roman [1 ]
机构
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
基金
美国国家科学基金会;
关键词
RING-OPENING REACTIONS; EXTENSION;
D O I
10.1021/ja301928d
中图分类号
O6 [化学];
学科分类号
070301 [无机化学];
摘要
We demonstrate an accurate prediction of the micromechanical behavior of a single chain of cydopropanated polybutadiene, which is governed by rapid isomerization of the cyclopropane moieties at similar to 1.2 nN, from the force rate correlation of this reaction measured in a small series of increasingly strained macrocycles. The data demonstrate that a single physical quantity, force, uniquely defines the dynamics across length scales from >100 to <1 nm and that strain imposed through molecular design and that imposed by micromanipulation techniques have equivalent effects on the kinetics of a chemical reaction. This represents a new method of screening potential monomers for applications in stress-responsive materials that could also facilitate atomistic interpretations of single-molecule force experiments.
引用
收藏
页码:7620 / 7623
页数:4
相关论文
共 18 条
[1]
[Anonymous], 2011, J MAT CHEM, V21, P8217
[2]
[Anonymous], DIR MATT EN 5 CHALL
[3]
Mechanical Control of Nanomaterials and Nanosystems [J].
Ariga, Katsuhiko ;
Mori, Taizo ;
Hill, Jonathan P. .
ADVANCED MATERIALS, 2012, 24 (02) :158-176
[4]
Mechanochemically triggered bond formation in solid-state polymers [J].
Black, Ashley L. ;
Orlicki, Joshua A. ;
Craig, Stephen L. .
JOURNAL OF MATERIALS CHEMISTRY, 2011, 21 (23) :8460-8465
[5]
From molecular mechanochemistry to stress-responsive materials [J].
Black, Ashley L. ;
Lenhardt, Jeremy M. ;
Craig, Stephen L. .
JOURNAL OF MATERIALS CHEMISTRY, 2011, 21 (06) :1655-1663
[6]
Force-Transformed Free-Energy Surfaces and Trajectory-Shooting Simulations Reveal the Mechano-Stereochemistry of Cyclopropane Ring-Opening Reactions [J].
Dopieralski, Przemyslaw ;
Ribas-Arino, Jordi ;
Marx, Dominik .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (31) :7105-7108
[7]
Probing the relation between force - Lifetime - and chemistry in single molecular bonds [J].
Evans, E .
ANNUAL REVIEW OF BIOPHYSICS AND BIOMOLECULAR STRUCTURE, 2001, 30 :105-128
[8]
Solvolytic ring-opening reactions of cyclopropyl bromides.: An assessment of the Woodward-Hoffmann-DePuy rule [J].
Faza, ON ;
López, CS ;
Alvarez, R ;
de Lera, AR .
JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (26) :9002-9010
[9]
The Entropic and Enthalpic Contributions to Force-Dependent Dissociation Kinetics of the Pyrophosphate Bond [J].
Hermes, Matthew ;
Boulatov, Roman .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (50) :20044-20047
[10]
Chemomechanics: chemical kinetics for multiscale phenomena [J].
Huang, Zhen ;
Boulatov, Roman .
CHEMICAL SOCIETY REVIEWS, 2011, 40 (05) :2359-2384