How to Distinguish Isodesmic from Cooperative Supramolecular Polymerisation

被引:437
作者
Smulders, Maarten M. J. [1 ,2 ]
Nieuwenhuizen, Marko M. L. [1 ,2 ]
de Greef, Tom F. A. [1 ,2 ]
van der Schoot, Paul [3 ]
Schenning, Albertus P. H. J. [1 ,2 ]
Meijer, E. W. [1 ,2 ]
机构
[1] Eindhoven Univ Technol, Lab Macromol & Organ Chem, NL-5600 MB Eindhoven, Netherlands
[2] Eindhoven Univ Technol, Inst Complex Mol Syst, NL-5600 MB Eindhoven, Netherlands
[3] Eindhoven Univ Technol, Grp Theory Polymers & Soft Matter, NL-5600 MB Eindhoven, Netherlands
关键词
self-assembly; polymerization; reaction mechanisms; supramolecular chemistry; UV/Vis spectroscopy; PERYLENE BISIMIDE DYES; NUCLEATION-ELONGATION; HELICAL AGGREGATION; SOLDIERS PRINCIPLE; ROSETTE NANOTUBES; BUILDING-BLOCKS; PI-STACKS; POLYMERS; ASSEMBLIES; ASSOCIATION;
D O I
10.1002/chem.200902415
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
To study the supramolecular polymerisation mechanisms of a self-assembling system, concentration- and temperature-dependent measurements can both be used to probe the transition from the molecular dissolved state to the aggregated state. In this report, both methods are evaluated to determine their effectiveness in identifying and quantifying the self-assembly mechanism for isodesmic and cooperative self-assembling systems. It was found that for a rapid and unambiguous determination of the self-assembly mechanism and its thermodynamic parameters, temperature-dependent measurements are more appropriate. These studies allow the acquisition of a large data set leading to an accurate determination of the self-assembly mechanism and quantification of the different thermodynamic parameters that describe the supramolecular polymerisation. For a comprehensive characterisation, additional concentration-dependent measurements can be performed.
引用
收藏
页码:362 / 367
页数:6
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