Macromolecular Recognition of Cyclodextrin: Inversion of Selectivity of β-Cyclodextrin toward Adamantyl Groups Induced by Macromolecular Chains.

Macromolecular Recognition of Cyclodextrin: Inversion of Selectivity of β-Cyclodextrin toward Adamantyl Groups Induced by Macromolecular Chains.
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DOI:
10.1002/marc.200900283
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发表时间:
2009-10
影响因子:
4.6
通讯作者:
Daisuke Taura;Yosuke Taniguchi;A. Hashidzume;A. Harada
Daisuke Taura;Yosuke Taniguchi;A. Hashidzume;A. Harada
中科院分区:
化学3区
文献类型:
--
作者:
Daisuke Taura;Yosuke Taniguchi;A. Hashidzume;A. Harada

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本文用几种NMR技术研究了β-环糊精(β-CD)与马来酸钠-金刚烷基(Ad)和-金刚烷基苯基(AdPh)乙烯基醚交替共聚物(pAdMA和pAdPhMA)的相互作用。通过对聚合物和模型化合物的表观缔合常数(K)进行比较,发现模型化合物和聚合物体系中β-CD对Ad和AdPh的选择性存在差异。这种现象通过圆二色谱和2D NMR描述如下; β-CD/AdPh模型系统的最稳定包合物对于相应的聚合物系统是极其不稳定的,因为与相邻AdPh部分之间的疏水相互作用的竞争。
Interaction of β-cyclodextrin (β-CD) with alternating copolymers (pAdMA and pAdPhMA) of sodium maleate with adamantyl (Ad) and with adamantylphenyl (AdPh) vinyl ether has been investigated by several NMR techniques. Comparing the apparent association constants (K) for the polymers with the K for the model compounds, which are determined by the analysis of (1) H NMR and isothermal titration calorimetry data, respectively, the selectivities of β-CD toward Ad and AdPh moieties are contrasting for the model and polymer systems. This phenomenon is described by circular dichroism and 2D NMR as follows; the most stable inclusion complex for the β-CD/AdPh model system is extremely destabilized for the corresponding polymer system because of competition with hydrophobic interaction between neighboring AdPh moieties.