CycloLab Cyclodextrin Research and Development Laboratory Ltd, Illatos 7, Budapest, H-1097 Hungary.
Beilstein J Org Chem. 2014 Dec 16;10:3007-18. doi: 10.3762/bjoc.10.319. eCollection 2014.
The fluorescent tagging of cyclodextrin derivatives enlarges their spectroscopic properties thus generating chemosensors, biological tools for visualization and sophisticated photoresponsive devices. Cyclodextrin polymers, due to the cooperative interactions, exhibit additional properties compared to their monomeric counterpart. These macromolecules can be prepared either in well water-soluble form or as gels of high swelling. Two versatile synthetic strategies for introducing a fluorescent tag (rhodamine, fluorescein, nitrobenzofuran or coumarin) into the water-soluble epichlorohydrin branched cyclodextrin polymers were worked out and compared. The fluorescent labeling was realized in three steps: 1) building in azido moieties, 2) transforming the azido groups into amino groups and 3) coupling the proper fluorescent compound to the amino groups. The other strategy started by functionalization of the monomer prior to the branching. Either the fluorescent-labeled monomer or the intermediate azido derivative of the monomer was branched. Further tuning of the properties of the polymer was achieved via branching of the methylated cyclodextrin derivative. The key intermediates and the fluorescent final products were characterized by various spectroscopic techniques and capillary electrophoresis. The applied synthetic routes were evaluated based on the molecular weight, cyclodextrin content of the products and the efficiency of labeling.
环糊精衍生物的荧光标记扩大了它们的光谱性质，从而产生了用于可视化的化学传感器、生物工具和复杂的光响应器件。与单体相比，环糊精聚合物由于协同相互作用而表现出额外的性质。这些高分子可以制备成水溶性形式或高溶胀的凝胶。设计并比较了两种将荧光标记物（罗丹明、荧光素、硝基苯并呋喃或香豆素）引入水溶性表氯醇支化环糊精聚合物的多功能合成策略。荧光标记分三步进行：1）引入叠氮基团，2）将叠氮基团转化为氨基，3）将合适的荧光化合物偶联到氨基上。另一种策略从单体的功能化开始，然后再进行支化。可以使用荧光标记的单体或单体的中间叠氮衍生物进行支化。通过甲基化环糊精衍生物的支化进一步调整聚合物的性质。关键中间体和荧光最终产物通过各种光谱技术和毛细管电泳进行了表征。基于分子量、产物中环糊精的含量和标记效率对所应用的合成路线进行了评估。
