瓜环与紫精衍生物及盐酸丁咯地尔的相互作用研究
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摘要
超分子化学的出现对传统化学提出了很大的挑战,它在催化、分子或离子的分离、环境科学以及生命科学等方面的应用研究对人类的发展具有极其深远的影响。瓜环(cucurbit[n]urils, n=5～8,10,简称CB[n])及其系列同系物是超分子化学领域的一类新型笼状超分子主体,因其结构与性质的特殊性,使瓜环在主客体化学、环境化学、材料化学、纳米化学以及药物等方面的应用研究倍受关注,已发展成为一个重要的研究领域。在以上研究的背景下,本文考察了瓜环与紫精衍生物及盐酸丁咯地尔的相互作用情况。主要内容如下：
1.合成了主体瓜环[n](n=5～8)及客体紫精衍生物(记为C12MV、C7MV、C4MV、C2MV),利用1H NMR、ESI-MS以及UV-vis等现代分析方法,考察了瓜环[n](n=7～8)与紫精衍生物的相互作用；研究了瓜环[8]与紫精衍生物及富电子客体2,6-二萘酚、对二苯酚(记为HN、HB)的相互作用。研究表明：C12MV能与瓜环[7]形成包结比为1：2的三元配合物,与瓜环[8]则能形成稳定的包结比为1：1的配合物。另外,C12MV、C7MV、C4MV、C2MV都可以与HN在瓜环[8]空腔内形成电荷转移的三元配合物。研究首次发现,当HN与瓜环[8]及C12MV(或C7MV)自组装的顺序不同时,所形成的三元配合物的包结模式不同,而短链的C4MV(或C2MV)与瓜环[8]及HN的自组装顺序则不会影响配合物的最终包结模式；最后还考察了C12MV与β-环糊精以及瓜环[7]或瓜环[8]的超分子自组装模式,发现瓜环[8]可以将β-环糊精从C12MV中释放并与C12MV形成稳定的包结物。
2.利用1H NMR、ESI-MS、IR以及UV-vis等分析方法,系统的研究了瓜环[n](n=6～8)与盐酸丁咯地尔(记为DLDE)的相互作用。研究结果表明：瓜环[6]与盐酸丁咯地尔的作用非常弱,而瓜环[7]、瓜环[8]则能与盐酸丁咯地尔分别形成稳定的1：1包结配合物,通过紫外吸收光谱法计算得知瓜环[7]、瓜环[8]与盐酸丁咯地尔分子的包结常数在102～103 L/mol范围内,说明瓜环对盐酸丁咯地尔具有潜在的缓释作用。
Nowadays supramolecular chemistry has become one of the most interesting fields of chemical research, because of their potential applications in many aeras, including catalysis, separation of molecules or ions, environmental sciences and life sciences. Cucurbit[n]turils (n=5～8,10, denoted as CB[n]) and their homologues whose shape resembles a pumpkin have been greatly exploited as supramolecular hosts in the host-guest chemistry, environmental chemistry, materials chemistry, nano-chemistry and many other areas. In this thesis, the supramolecular interactions of cucurbiturils with viologen derivatives and buflomedil have been investigated.
1. The viologen derivatives (denoted as C12MV, C7MV, C4MV and C2MV) were synthesized. The interactions of cucurbit[7,8]uril with these synthetic guests have been investigated by using 1H NMR, ESI-MS and UV-vis spectra. The experimental results revealed that CB[7] can interact with C12MV to form a 2:1 inclusion complex, while CB[8] and C12MV can form a very stable 1:1 inclusion complex. It was found that the electron-rich guests of HN can form a 1:1:1 inclusion complexe with C12MV, C7MV, C4MV and C2MV in the cavity of CB[8], respectively. In case of C12MV and C7MV, the different binding model was formed when HN or CB[8] is added first. Wheras, C4MV and C2MV can form the same 1:1:1 inclusion complex with HN and CB[8] no matter HN or CB[8] is added first. The selected binding ofβ-cyclodextrin (denoted asβ-CD) and CB[8](or CB[7]) with C12MV has also been studied. The CB[7] can form a 1:1:1 inclusion complex withβ-CD and C12MV. Wheras, CB[8] can releaseβ-CD from C12MV to form a U-shaped inclusion complex with C12MV.
2. The host-guest chemistry of systems containing buflomedil(denoted as DLDE) and cucurbit[6,7,8]uril was investigated by 1H NMR, ESI-MS, IR and UV-vis spectra. The experiment results revealed that the size of the cavity of the CB[n] played an important role in the interaction between the host and the guest. Buflomedil could form a stable 1:1 inclusion complex with CB[7] and CB[8], whereas the interaction of Buflomedil with CB[6] was very weak. The inclusion constant of buflomedil with CB[7] and CB[8] is 1.43×103L/mol and 3.76×102 L/mol, respectively. The binding constant which was located between 102～103 L/mol indicate that CB[7] and CB[8] could be used as a potential slow-released agent.
1.合成了主体瓜环[n](n=5～8)及客体紫精衍生物(记为C12MV、C7MV、C4MV、C2MV),利用1H NMR、ESI-MS以及UV-vis等现代分析方法,考察了瓜环[n](n=7～8)与紫精衍生物的相互作用；研究了瓜环[8]与紫精衍生物及富电子客体2,6-二萘酚、对二苯酚(记为HN、HB)的相互作用。研究表明：C12MV能与瓜环[7]形成包结比为1：2的三元配合物,与瓜环[8]则能形成稳定的包结比为1：1的配合物。另外,C12MV、C7MV、C4MV、C2MV都可以与HN在瓜环[8]空腔内形成电荷转移的三元配合物。研究首次发现,当HN与瓜环[8]及C12MV(或C7MV)自组装的顺序不同时,所形成的三元配合物的包结模式不同,而短链的C4MV(或C2MV)与瓜环[8]及HN的自组装顺序则不会影响配合物的最终包结模式；最后还考察了C12MV与β-环糊精以及瓜环[7]或瓜环[8]的超分子自组装模式,发现瓜环[8]可以将β-环糊精从C12MV中释放并与C12MV形成稳定的包结物。
2.利用1H NMR、ESI-MS、IR以及UV-vis等分析方法,系统的研究了瓜环[n](n=6～8)与盐酸丁咯地尔(记为DLDE)的相互作用。研究结果表明：瓜环[6]与盐酸丁咯地尔的作用非常弱,而瓜环[7]、瓜环[8]则能与盐酸丁咯地尔分别形成稳定的1：1包结配合物,通过紫外吸收光谱法计算得知瓜环[7]、瓜环[8]与盐酸丁咯地尔分子的包结常数在102～103 L/mol范围内,说明瓜环对盐酸丁咯地尔具有潜在的缓释作用。
Nowadays supramolecular chemistry has become one of the most interesting fields of chemical research, because of their potential applications in many aeras, including catalysis, separation of molecules or ions, environmental sciences and life sciences. Cucurbit[n]turils (n=5～8,10, denoted as CB[n]) and their homologues whose shape resembles a pumpkin have been greatly exploited as supramolecular hosts in the host-guest chemistry, environmental chemistry, materials chemistry, nano-chemistry and many other areas. In this thesis, the supramolecular interactions of cucurbiturils with viologen derivatives and buflomedil have been investigated.
1. The viologen derivatives (denoted as C12MV, C7MV, C4MV and C2MV) were synthesized. The interactions of cucurbit[7,8]uril with these synthetic guests have been investigated by using 1H NMR, ESI-MS and UV-vis spectra. The experimental results revealed that CB[7] can interact with C12MV to form a 2:1 inclusion complex, while CB[8] and C12MV can form a very stable 1:1 inclusion complex. It was found that the electron-rich guests of HN can form a 1:1:1 inclusion complexe with C12MV, C7MV, C4MV and C2MV in the cavity of CB[8], respectively. In case of C12MV and C7MV, the different binding model was formed when HN or CB[8] is added first. Wheras, C4MV and C2MV can form the same 1:1:1 inclusion complex with HN and CB[8] no matter HN or CB[8] is added first. The selected binding ofβ-cyclodextrin (denoted asβ-CD) and CB[8](or CB[7]) with C12MV has also been studied. The CB[7] can form a 1:1:1 inclusion complex withβ-CD and C12MV. Wheras, CB[8] can releaseβ-CD from C12MV to form a U-shaped inclusion complex with C12MV.
2. The host-guest chemistry of systems containing buflomedil(denoted as DLDE) and cucurbit[6,7,8]uril was investigated by 1H NMR, ESI-MS, IR and UV-vis spectra. The experiment results revealed that the size of the cavity of the CB[n] played an important role in the interaction between the host and the guest. Buflomedil could form a stable 1:1 inclusion complex with CB[7] and CB[8], whereas the interaction of Buflomedil with CB[6] was very weak. The inclusion constant of buflomedil with CB[7] and CB[8] is 1.43×103L/mol and 3.76×102 L/mol, respectively. The binding constant which was located between 102～103 L/mol indicate that CB[7] and CB[8] could be used as a potential slow-released agent.
引文
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