哒嗪并四硫富瓦烯—氨基酸二素体的合成、凝胶化及其凝胶性质研究

发布时间：2018-03-05 08:35

本文选题：四硫富瓦烯　切入点：凝胶因子　出处：《延边大学》2017年硕士论文　论文类型：学位论文

【摘要】：超分子凝胶,是凝胶因子分子通过氢键,π-π堆积,疏水作用力,范德华力,静电作用力,金属配位键,电荷转移(CT)等非共价键作用力,通过分子自组装形成纳米纤维结构包裹溶剂的物质。在材料科学领域得到了广泛的关注。在超分子凝胶中,低分子量凝胶因子是最典型的小分子。由于其精确的分子量有很大的优势,比如分子易被修饰调控,多样化的纳米结构和多种刺激响应的特性。非共价键作用力较弱并且是可逆的,因此这些超分子凝胶能够通过机械力,光,热,化学刺激进行灵活的调控。因此,超分子凝胶在光捕获材料,组织工程,记忆器件,药物释放,太阳能光伏等得到了广泛的应用。作为最著名的π电子给体的四硫富瓦烯TTF以及它的衍生物自组装通过π-π堆积、S…S等作用作为金属晶体和超分子态被广泛的研究,在以往的文献报道中,基于TTF的凝胶因子均以直线型居多,而基于TTF的T型有机凝胶因子却很少有报道过。本文设计并合成一系列哒嗪并四硫富瓦烯连接氨基酸单元的T型有机凝胶因子。它们的凝胶性质在多种有机溶剂中被研究。在这些衍生物中,连接甘氨酸和苯丙氨酸的凝胶因子在极性溶剂和芳香溶剂中能够很好的形成凝胶。有趣的是在这些凝胶因子中,通过超声小于20 S或者零点冷却下能够达到溶液到凝胶的转变,除了带有色氨酸集团的凝胶因子。实验结果显示,这些凝胶因子通过自组装都能够形成长有弹性的三维网状螺旋纳米纤维结构长度超过几十微米。形成的凝胶可以达到凝胶到溶胶的可逆性转变,通过多重刺激,比如温控,超声,化学氧化还原等。重要的是,凝胶能够在甲苯中与C60形成二组分凝胶,观测形貌是螺旋纳米纤维结构。EPR数据说明,二组分凝胶驱动力并不是π-π堆积和S-S作用,而是MPDTTF单元与C60电荷给受的相互作用力。同时由于相邻的发色团呈J型聚集凝胶表现很强的凝胶诱导荧光增强的性质,加入C60后荧光发生了猝灭。此外,凝胶在室温下实现了很好的相选择凝胶化,凝胶凝胶能够从水相吸附阳离子染料,表明在治理污水方面有潜在的应用价值。
[Abstract]:Supramolecular gels are non-covalent bonding forces such as hydrogen bonds, 蟺-蟺 stacking, hydrophobic forces, van der Waals forces, electrostatic forces, metal coordination bonds, charge transfer CTs, etc. The formation of solvent-coated substances with nanofiber structures through molecular self-assembly has received extensive attention in material science. In supramolecular gels, Low molecular weight gel factor is the most typical small molecule. Because its precise molecular weight has great advantage, for example, the molecule is easy to be modified and regulated, The noncovalent bond forces are weak and reversible, so these supramolecular gels can be flexibly regulated by mechanical forces, light, heat, and chemical stimuli. Supramolecular gels in photocapture materials, tissue engineering, memory devices, drug release, Solar photovoltaic has been widely used in many fields. TTF, the most famous 蟺 electron donor, and its derivatives are widely studied as metal crystals and supramolecular states through 蟺-蟺 stacking S... S. In previous literature reports, the gel factors based on TTF were mostly linear. However, T-type organic gel factors based on TTF have been rarely reported. In this paper, a series of T-type organic gel factors with pyridazine and tetrathiafulvalene-linked amino acid units have been designed and synthesized. Their gel properties are found in many organic solvents. In these derivatives, The gel factors that connect glycine to phenylalanine can form gels well in polar solvents and aromatic solvents. Interestingly, the solution to gel transition can be achieved through ultrasonic cooling at less than 20 S or 00:00. Except for the gel factor with tryptophan group. These gel factors are self-assembled to form long, elastic, three-dimensional reticulated helical nanofibers that are more than tens of microns in length. The resulting gel can achieve a reversible transition from gel to sol, through multiple stimuli, such as temperature control, Ultrasonic, chemical redox, etc. The important thing is that the gel can form a two-component gel with C60 in toluene. The observed morphology is helical nanofiber structure. EPR data show that the driving force of the two-component gel is not 蟺-蟺 piling and S-S interaction. It is the interaction force between the MPDTTF unit and the C60 charge, and the fluorescence quenching occurs after the addition of C60 because the adjacent chromophore exhibits a strong gel induced fluorescence enhancement in the form of a J-shaped agglomerate gel. The gel can adsorb cationic dyes from aqueous phase at room temperature, which indicates that it has potential application value in wastewater treatment.
【学位授予单位】：延边大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O648.17

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