Kinetic Study of [2]Pseudorotaxane Formation with an Asymmetrical Thread

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• 作者：Miguel Quiroga ; Mercedes Parajó ; Pedro Rodríguez-Dafonte ; Luis García-Río
• 刊名：Langmuir
• 出版年：2016
• 出版时间：June 28, 2016
• 年：2016
• 卷：32
• 期：25
• 页码：6367-6375
• 全文大小：450K
• 年卷期：0
• ISSN：1520-5827

文摘

Kinetic and thermodynamic studies on cyclodextrin (CD)-based [2]pseudorotaxane formation have been carried out by a combination of NMR and calorimetric techniques using bolaform surfactants as axles. Experimental evidence of the formation of an external complex between the trimethylammonium head groups of the axle and the external hydrogen atoms of α-cyclodextrin (α-CD) is reported. Inclusion of this external complex in the reaction pathway allows us to explain the kinetic behavior as well as the nonlinear dependence of the observed rate constant on CD concentrations. The equilibrium constant for [2]pseudorotaxane formation is strongly affected by the spacer length of the axle. This effect is a consequence of increasing rotaxane stability because the threading rate constant is almost independent of the spacer length, but dethreading strongly decreases on increasing the axle size. Using a nonsymmetrical axle with tripropyl and trimethylammonium cations precludes CD threading by the large head side. CDs will thread this asymmetrical bolaform by both their wide and narrow sides, yielding two isomeric [2]pseudorotaxanes. Threading by the wide side of the CD is 60% more favorable than that by the narrow one, but dethreading rate constants are the same for both isomers.