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两亲性三聚氰胺型单分子层溶解于水相亚相中时非表面活性嘧啶衍生物的分子识别动力学:一种理论方法。

Molecular recognition kinetics of nonsurface active pyrimidine derivatives dissolved in the aqueous subphase by an amphiphilic melamine type monolayer: A theoretical approach.

作者信息

Fainerman V B, Vollhardt D, Aksenenko E V, Liu F

机构信息

Medical Physicochemical Centre, Donetsk Medical University, 16 Ilych Avenue, Donetsk 83003, Ukraine.

出版信息

J Phys Chem B. 2005 Jul 28;109(29):14137-43. doi: 10.1021/jp0515986.

DOI:10.1021/jp0515986
PMID:16852775
Abstract

Experimental studies show a drastic change of the characteristic features (Pi-A isotherms, morphology of the condensed phase domains) of the 2C11H23-melamine monolayers by molecular recognition of the pyrimidine derivatives uracil and thymine, largely affected by the reaction kinetics of the recognition process. A new approximate additive theoretical model is introduced for describing the molecular recognition kinetics. The theoretical approach is based on two assumptions: (i) first-order reaction kinetics for the molecular recognition of the nonsurface active pyrimidine derivatives dissolved in the aqueous subphase by the melamine type monolayer and (ii) applicability of the Pi-A isotherm equations derived previously for the description of melamine type monolayers in the fluid (gaseous, LE) state and the phase transition region to the condensed state. The rate constants for the molecular recognition reaction between the melamine type monolayer and the dissolved thymine and uracil are estimated, which are roughly proportional to the bulk concentrations of the pyrimidine derivatives and depend only slightly on the temperature. The theoretical estimates agree satisfactorily with the experimental results obtained under various conditions (Pi = const and dA/dt = const). This fact supports the validity of the first model proposed for the interfacial molecular recognition kinetics with nonsurface active substrates dissolved in the aqueous subphase by complementary hydrogen bonding.

摘要

实验研究表明,嘧啶衍生物尿嘧啶和胸腺嘧啶通过分子识别作用,使2C11H23-三聚氰胺单层膜的特征特性(π-A等温线、凝聚相域的形态)发生了剧烈变化,这在很大程度上受识别过程反应动力学的影响。引入了一种新的近似加和理论模型来描述分子识别动力学。该理论方法基于两个假设:(i)三聚氰胺型单层膜对溶解在水亚相中的非表面活性嘧啶衍生物进行分子识别的一级反应动力学;(ii)先前推导的用于描述三聚氰胺型单层膜在流体(气态、LE)状态和凝聚态相变区域的π-A等温线方程的适用性。估算了三聚氰胺型单层膜与溶解的胸腺嘧啶和尿嘧啶之间分子识别反应的速率常数,这些常数大致与嘧啶衍生物的本体浓度成正比,且仅略微依赖于温度。理论估算结果与在各种条件下(π = 常数和dA/dt = 常数)获得的实验结果令人满意地吻合。这一事实支持了所提出的第一个模型的有效性,该模型用于描述通过互补氢键与溶解在水亚相中的非表面活性底物进行的界面分子识别动力学。

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