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合成了侧链含烷基链(C7)及偶氮基团(Azo)两个疏水基团修饰的聚合物4,并基于环糊精与两个疏水基团C7、Azo的不同结合能力,制备了含两个识别点的侧链准聚轮烷.首先,在聚合物4的溶液中加入α-环糊精(α-CD),α-CD分别包结在C7及Azo部分,得到了侧链准聚轮烷;第二步,在365 nm的紫外光光照下,聚合物4侧链端基的trans-Azo异构为cis-Azo,α-CD从Azo部分解离,但α-CD仍包结在C7部分,得到了侧链聚轮烷;第三步,在侧链聚轮烷溶液中加入β-环糊精(β-CD),β-CD包结在cis-Azo部分,得到了α-CD、β-CD分别包结两个疏水识别点的侧链准聚轮烷. 相似文献
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超分子体系中的分子识别研究(XXX):有机硒修饰β—环糊精的合?… 总被引:5,自引:0,他引:5
我们曾报道了天然环糊精及一些化学修饰环糊精对氨基酸生物小分子的识别研究[1~3],结果表明,多种弱相互作用协同贡献于环糊精-氨基酸超分子配合物的形成,修饰环糊精取代基的形状及尺寸影响对氨基酸的分子识别和手性识别能力. 相似文献
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氨基酸、多肽的环糊精化学 总被引:7,自引:0,他引:7
本文着重介绍了氨基酸、多肽-环糊精连接物的合成,分子识别和自组装,对环糊精及其衍生物与氨基酸、多肽的包合行为,异构体识别和仿酶合成作了简要概述。 相似文献
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我们曾报道了天然环糊精及一些化学修饰环糊精对氨基酸生物小分子的识别研究[1~3],结果表明,多种弱相互作用协同贡献于环糊精-氨基酸超分子配合物的形成,修饰环糊精取代基的形状及尺寸影响对氨基酸的分子识别和手性识别能力. 相似文献
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环糊精包合作用诱导聚合物自组装的研究进展 总被引:1,自引:0,他引:1
将主客体识别与聚合物自组装相结合,利用环糊精对聚合物的包合作用在溶液中诱导聚合物组装形成结构可控的纳米粒子,形成有别于基于环糊精/聚合物包合作用形成的结晶粉末和超分子水凝胶的新型材料.本文介绍了这种诱导组装方案的研究背景及最新的研究成果,综述了诱导组装的原理、特点及影响因素.研究表明,由这种方案制备的聚合物纳米粒子具有超分子动态可逆的特征,进而显示出对温度和pH等敏感的性质.该类环糊精包合作用诱导组装的聚合物超分子聚集体在生物医学材料方面具有潜在的应用价值,如用作药物和基因的可控传递释放载体. 相似文献
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本文综述了近年来基于环糊精包合作用的超分子水凝胶的研究进展,主要包括:环糊精与线性、星型、接枝、超支化聚合物包合形成的多聚(准)轮烷自组装制备超分子物理凝胶及功能化多聚(准)轮烷经交联反应制备超分子化学凝胶;环糊精、环糊精二聚体及其水溶性聚合物与带疏水性侧基的聚合物经“锁-钥匙”包合作用形成超分子物理凝胶;及其在药物、基因释放载体与组织工程支架中的应用。着重介绍了剪切、温度、pH值、光等刺激-响应性超分子水凝胶的设计与制备。 相似文献
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我们曾报道了天然环糊精及一些化学修饰环糊精对氨基酸生物小分子的识别研究 [1~ 3] ,结果表明 ,多种弱相互作用协同贡献于环糊精 -氨基酸超分子配合物的形成 ,修饰环糊精取代基的形状及尺寸影响对氨基酸的分子识别和手性识别能力 .本文通过亲核取代反应将芳香有机硒基团引入到β-环糊精的 2 -位 (化学结构如下式 ) ,荧光光谱滴定法研究结果表明 ,疏水性取代基的引入扩展了环糊精的分子键合能力 ,但手性识别能力降低 .1 实验部分1 .1 仪器及试剂 荧光光谱采用 JASCO FP- 750荧光光谱仪 ,普通 1 0 mm× 1 0 mm× 40 mm石英样品池 ,在 … 相似文献
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超分子体系中的分子识别桥──连环糊精对模型底物的键合能力及分子选择性 总被引:7,自引:0,他引:7
综述了近年来桥连双环糊精分子识别的研究进展,主要从疏水相互作用、多重识别、尺寸和构型匹配、热力学性质以及环糊精二聚体分子识别的一些应用等方面对研究结果进行了评述. 相似文献
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毛细管电泳环糊精添加剂立体选择性差异的研究 总被引:2,自引:0,他引:2
对在毛细管区带电泳环糊精子性拆分体系中手性药物妥布特罗的分离机理进行了探讨。分别测定了α、β、γ-环糊精和二甲基,三甲基,羟丙基-β-环糊精与药物对缺体形成包结配合物的稳定常数以及手性拆分过程中的热力学函数的变化,并对数据进行了分析。 相似文献
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Summary Four cyclodetrin dimer derivatives were synthesized by linking two single cyclodextrin derivatives with difunctional spacer
at the primary side of cyclodetrin. The separation properties of these cylodextrin dimer derivatives as CGC stationary phases
were investigated and compared with those of the unbridged native cyclodextrin derivative. The results show that two recognition
sites and one link spacer of these cyclodextrin dimer derivatives cooperate in separation and affect the separation of disubstituted
benzene positional isomers. 相似文献
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Manickam MC Annalakshmi S Pitchumani K Srinivasan C 《Organic & biomolecular chemistry》2005,3(6):1008-1012
Multiple recognition by cyclodextrin in a bimolecular reaction, namely bromination of styrene, methyl cinnamate, phenylacetylene and allylbenzene, has been studied. Bromohydrin is obtained as a major product along with dibromide in the bromination of styrene and methyl cinnamate. The percentage of bromohydrin decreases as the cavity size increases. With phenylacetylene, bromophenylacetylene and phenacyl bromide are obtained in addition to the dibromides. In the bromination of cyclodextrin complexes of allylbenzene, the product distribution is the same as in solution bromination. The observed results demonstrate the efficiency of cyclodextrin in stabilizing the open carbocationic intermediate and thus provide chemical evidence for the participation of cyclodextrin hydroxyl groups. 相似文献
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Capillary electrophoresis separation of peptide diastereomers that contain methionine sulfoxide by dual cyclodextrin‐crown ether systems† 下载免费PDF全文
Qingfu Zhu Stefan H. Heinemann Roland Schönherr Gerhard K. E. Scriba 《Journal of separation science》2014,37(23):3548-3554
A dual‐selector system employing achiral crown ethers in combination with cyclodextrins has been developed for the separation of peptide diastereomers that contain methionine sulfoxide. The combinations of the crown ethers 15‐crown‐5, 18‐crown‐6, Kryptofix® 21 and Kryptofix® 22 and β‐cyclodextrin, carboxymethyl‐β‐cyclodextrin, and sulfated β‐cyclodextrin were screened at pH 2.5 and pH 8.0 using a 40/50.2 cm, 50 μm id fused‐silica capillary and a separation voltage of 25 kV. No diastereomer separation was observed in the sole presence of crown ethers, while only sulfated β‐cyclodextrin was able to resolve some peptide diastereomers at pH 8.0. Depending on the amino acid sequence of the peptide and the applied cyclodextrin, the addition of crown ethers, especially the Krpytofix® diaza‐crown ethers, resulted in significantly enhanced chiral recognition. Keeping one selector of the dual system constant, increasing concentrations of the second selector resulted in increased peak resolution and analyte migration time for peptide‐crown ether‐cyclodextrin combinations. The simultaneous diastereomer separation of three structurally related peptides was achieved using the dual selector system. 相似文献
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This account describes our research progress in recent years in the areas of the molecular recognition studies on modified cyclodextrins, including positively charged cyclodextrins, cyclodextrin derivatives with hydrophobic substituent, and dimeric cyclodextrins. Calorimetric titration and various spectrometric techniques were employed to determine the complex stability constants, as well as the thermodynamic parameters, for their inclusion complexation with diverse guest molecules. The results obtained have been discussed from the viewpoint of size/shape‐matching, induced‐fit, geometric compensation, and multiple recognition. Thermodynamically, the compensatory relationship between ΔH and TΔS was found to be exhibited in the inclusion complexation of modified cyclodextrin. 相似文献