Polyethers containing coumarin dimer components in the main chain. I. Synthesis by photopolymerization of 7,7′-(polymethylenedioxy) dicoumarins

Eight 7,7′-(polymethylenedioxy)dicoumarins were successfully synthesized by solution condensation of 7-hydroxycoumarin (umbelliferone) or 7-hydroxy-4-methylcoumarin (4-methylumbelliferone) with various dibromoalkanes. Upon benzophenone-sensitized irradiation with 350 nm light in dichloromethane, the terminal coumarin chromophores dimerize to form polyethers containing coumarin dimer components in the main chain. The configurations of the coumarin dimer linkages were characterized by ¹H-NMR spectra. For unsubstituted dicoumarins, the resulting polyethers consist mainly of syn and anti head-to-head coumarin dimer linkages. However, the configurations are syn and anti head-to-tail for those from 4-methyl-substituted dicoumarins. The highest reduced viscosity is 0.23 dL/g obtained with polyether from 7,7′-(decamethylenedioxy)dicoumarin. The photopolymerization in dichloromethane obeys zero order and first order with respect to coumarin chromophore and benzophenone, respectively. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1749–1758, 1997     

7-羟基-4-甲基香豆素的合成研究

以间苯二酚和乙酰乙酸乙酯为原料,有机酸和固体超强酸作为催化剂,合成了7 -羟基-4-甲基香豆素.实验结果表明:间苯二酚、乙酰乙酸乙酯物质的量比为1:1,催化剂对甲苯磺酸用量为1.5％（物质的量百分比）,85℃下反应2h,产率较高为85.1％.     

Conception and Evaluation of Fluorescent Phosphine-Gold Complexes: From Synthesis to in vivo Investigations

A phosphine gold(I) and phosphine-phosphonium gold(I) complexes bearing a fluorescent coumarin moiety were synthesized and characterized. Both complexes displayed interesting photophysical properties: good molar absorption coefficient, good quantum yield of fluorescence, and ability to be tracked in vitro thanks to two-photon imaging. Their in vitro and in vivo biological properties were evaluated onto cancer cell lines both human and murine and into CT26 tumor-bearing BALB/c mice. They displayed moderate to strong antiproliferative properties and the phosphine-phosphonium gold(I) complex induced significant in vivo anti-cancer effect.     

Precision Nanocluster-Based Toroidal and Supertoroidal Frameworks Using Photocycloaddition-Assisted Dynamic Covalent Chemistry

Atomically precise nanoclusters (NCs) have recently emerged as ideal building blocks for constructing self-assembled multifunctional superstructures. The existing structures are based on various non-covalent interactions of the ligands on the NC surface, resulting in inter-NC interactions. Despite recent demonstrations on light-induced reversible self-assembly, long-range reversible self-assembly based on dynamic covalent chemistry on the NC surface has yet to be investigated. Here, it is shown that Au₂₅ NCs containing thiolated umbelliferone (7-hydroxycoumarin) ligands allow [2+2] photocycloaddition reaction-induced self-assembly into colloidal-level toroids. The toroids upon further irradiation undergo inter-toroidal reaction resulting in macroscopic supertoroidal honey-comb frameworks. Systematic investigation using electron microscopy, atomic force microscopy (AFM), and electron tomography (ET) suggest that the NCs initially form spherical aggregates. The spherical structures further undergo fusion resulting in toroid formation. Finally, the toroids fuse into macroscopic honeycomb frameworks. As a proof-of-concept, a cross-photocycloaddition reaction between coumarin-tethered NCs and an anticancer drug (5-fluorouracil) is demonstrated as a model photo-controlled drug release system. The model system allows systematic loading and unloading of the drug during the assembly and disassembly under two different wavelengths. The results suggest that the dynamic covalent chemistry on the NC surface offers a facile route for hierarchical multifunctional frameworks and photocontrolled drug release.     

非淀粉多糖提高高分支麦芽糊精黏弹特性的研究

高分支麦芽糊精是一种新型的益生元,其中含有相对较多的α-1,6葡萄糖苷键,不易被人体小肠内的消化酶快速水解,进而缓慢释放出葡萄糖,适合作为低升糖指数食品的添加剂。但是其水合物黏弹性小,不能为食品体系增加粘稠性,本研究采用动态流变仪,分别测试了黄原胶、桃胶、香豆胶、刺槐豆胶和魔芋胶五种非淀粉多糖对高分支麦芽糊精的增稠效果,结果表明,糊精与非淀粉多糖按4:1的质量比混合后溶于蒸馏水中,形成5%(w/v)的体系,在剪切速率(γ)为0.1 s_?¹ -300 s_?¹区间内测得的剪切流变曲线均符合Herschel-Bulkley 模型(决定系数R₂ ^>0.99),增稠效果魔芋胶> 刺槐豆胶> 香豆胶> 黄原胶> 桃胶。进一步选取增稠效果适中的香豆胶,进行震荡流变测试。麦芽糊精与香豆胶分别按5:1、4:1、3:1、2:1、1:1的质量比制备5%的水溶液体系,震动频率为0.1-10 Hz,结果表明,在香豆胶含量一定时,储能模量和损耗模量随角频率的增加而增加,损耗角正切tanδ随角频率增加而减小;在角频率一定时,储能模量、损耗模量和损耗角正切tanδ均随着香豆胶含量的增加而减小。在质量比为5:1时,tanδ>1,此时混合体系偏向于粘性液体;在质量比为1:1时,tanδ< 1,此时混合体系偏向于弹性固体。     

微波辐射四氯化锡催化无溶剂合成7-羟基-4-甲基香豆素

以间苯二酚和乙酰乙酸乙酯为原料,以五水四氯化锡为催化剂,采用微波辐射技术,无溶剂合成7-羟基-4-甲基香豆素。探索了不同反应条件对产率的影响。结果表明:当n(间苯二酚)∶n(乙酰乙酸乙酯)为1∶0.8,反应温度为115℃,五水四氯化锡为2.6 g(间苯二酚为0.15 mol),辐射时间为16 min,辐射功率为500 W时,产率可达80.6%。     

香豆素衍生物基荧光型水性聚氨酯的制备及性能

采用“一步法”,以异佛尔酮二异氰酸酯(IPDI)、聚己二酸新戊二醇酯(PNGA)、二羟甲基丙酸(DMPA)为原料,用荧光剂7-氨基-4-三氟甲基香豆素(AFC)对预聚体进行封端,在IPDI、PNGA、DMPA、AFC摩尔比为1:0.45:0.30:0.15条件下,制备出一种具有长期贮存稳定性的新型荧光型水性聚氨酯乳液(WPU-AFC)。其结构通过FTIR和UV证实;同时系统地讨论了空间位阻,温度以及AFC含量等因素对乳液荧光性能的影响。结果表明,制备的WPU-AFC的荧光强度主要受“结构荧光猝灭”影响而不是“浓度荧光猝灭”影响;随着温度的升高,WPU-AFC和AFC的荧光强度均降低;相同条件下,WPU-AFC的荧光强度与AFC相比均有明显增强;此外,随着AFC分子中苯并吡喃环刚性结构在聚氨酯主链的引入,胶膜的热稳定性明显提高。     

SDS对香豆素在SB-16胶束增溶行为影响

为了模拟药物香豆素在十二烷基硫酸钠(SDS)和十六烷基磺基甜菜碱(SB-16)复配体系中的分配规律,采用分子动力学的方法模拟了香豆素分子(C-343)在SB-16水溶液中的增溶行为,在上述溶液的基础上又继续添加了表面活性剂SDS,并研究了SDS对香豆素在SB-16胶束增溶行为影响。研究结果表明,在298 K,101.3 kPa下的平衡条件下,C-343可以自发地增溶到SB-16球形胶束中。SDS分子的烷基尾链部分插入到SB-16球形胶束内部,并在SB-16表面形成一层疏水基团在内,亲水基团在外的SDS分子薄层。C-343分子在SDS分子的疏水作用和静电作用下,从SB-16胶束内部逐步迁移至SDS胶束的外层表面上。从理论证实了添加表面活性剂可以对药物分子在胶束溶液中的增溶与释放过程进行有效控制,以期为该类体系的试验研究提供理论依据。     

4-甲基-8-甲酰基-7-羟基香豆素的合成

香豆素衍生物是药物开发和荧光探针设计的重要中间体。文章以间苯二酚和乙酰乙酸乙酯为起始原料,经Pechmann反应和Duff反应两步合成了4-甲基-8-甲酰基-7-羟基香豆素,并优化了反应条件。     

香豆素类荧光增白剂的研究进展

本文探讨了荧光增白剂的作用机理,概述了合成香豆素类荧光增白剂的经典方法以及几种最新研究成果。认为功能性的香豆类化合物具有巨大的应用潜力,如何简便、高效、绿色地制备此类物质是该领域的研究热点之一。