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环糊精-离子液体基自组装体的构建及机理探索

Construction and mechanism of supramolecular self-assemblies based on cyclodextrin and ionic liquid

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【作者】 孟丹施建峰沈兴海

【Author】 Dan Meng;Jianfeng Shi;Xinghai Shen;Beijing National Laboratory for Molecular Sciences (BNLMS), Department of Applied Chemistry,College of Chemistry and Molecular Engineering, Peking University;

【机构】 北京大学化学与分子工程学院放射化学与辐射化学重点学科实验室北京分子科学国家实验室

【摘要】 环糊精与离子液体具有丰富的超分子行为。我们合成了一种包含1-十二烷基-3-甲基咪唑和十二烷基磺酸根的双两亲性的长链离子液体(简称C12mimDSN)。C12mimDSN与β-CD不仅可以在水中产生丰富的自组装行为,而且可以在各种有机溶剂中分别组装成囊泡和凝胶。我们通过DLS、负染色电镜、冷冻刻蚀等表征自组装体的尺寸和形貌。结果发现,低浓度的C12mimDSN@β-CD在有机溶剂中依然会形成囊泡。而高浓度的C12mimDSN@β-CD在DMF、DMSO中会形成有机凝胶。我们通过TGA、DSC对凝胶的热稳定性进行了分析,利用质谱和1H-1H ROESY谱探索C12mimDSN@β-CD自组装机理。初步实验结果表明C12mimDSN与β-CD的包合比例为1:2。在自组装过程中,静电作用、疏溶剂作用以及咪唑头基、环糊精和DMF/DMSO间的氢键都起到了重要的作用。我们还进一步探索了C12mimDSN与β-CD在DMF-H2O或DMSO-H2O的混合溶剂中所形成配合物C12mimDSN@2β-CD和C12mimDSN@3β-CD间的转换。

【Abstract】 Cyclodextrin and ionic liquid can generate various of supramolecular behaviors. We have synthesized a kind of biamphiphilic ionic liquid consisting of 1-dodecyl-3-methylimidazolium and dodecyl sulfonate(C12mimDSN).C12mimDSN itself can form vesicles and gel in acqeous and organic medium.DLS、Negative-Staining TEM and FF TEM was measured to obtain the size and the morphology of the self-assemblies. As a result, Vesicles can be formed in diluted C12mimDSN and β-CD organic solvent. The solution will turn into white gel in a concentrated C12mimDSN and β-CD organic solvent. We have analysed the thermostability of the organic gel with TGA and DSC and explored the self-assemble mechanism of C12mimDSN@β-CD with MS and 1H-1H ROESY spectrum. The results show that the inclusion complex is C12mimDSN@β-CD.The electronic interaction,the hydrophobic interaction and the H-bond between imidazolium headgroup,β-CD and DMF or DMSO are the driving force for the self-assembly. Besides,we try to get the gradual change between C12mimDSN@2β-CD and C12mimDSN@3β-CD in the DMF-H2O or DMSO- H2O solvent.

【关键词】 环糊精自组装体囊泡凝胶
  • 【会议录名称】 中国化学会第30届学术年会摘要集-第二十四分会:超分子组装与软物质材料
  • 【会议名称】中国化学会第30届学术年会-第二十四分会:超分子组装与软物质材料
  • 【会议时间】2016-07-01
  • 【会议地点】中国辽宁大连
  • 【分类号】O641.3
  • 【主办单位】中国化学会
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