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以N-(2-羟基-1-萘基)亚甲基-(S)-α-苯基乙胺为模型分子,考察了脱质子前后该手性Schiff碱溶液手光性质的变化,利用DFT计算探讨手光信号反转机理.结果表明,手光反转源于分子内氢键的断裂与形成及伴随的C—C单键旋转所引起的构象转变,且前后2种构象处于拟对映关系.这一发现意味着通过单键旋转操控分子构象转变可作为构建手性开关的一种有效途径.在此基础上设计、合成了苯乙烯型手性功能单体(VNP)及相应的光学活性聚合物.由于邻位基团的协同效应,聚合物的手光性质对酸碱刺激表现出比单体更灵敏的响应性和可重复性.当循环加入H+和OH-时,聚合物溶液的CD信号(382 nm处的Cotton效应)以“ON”-“OFF”方式发生可逆转变,以此为输出信号可无损耗重复至少5次,实现了通过酸碱调控的无损输出的新型聚合物基手性开关.此外,基于该手性开关体系构建了典型的“禁阻”(IHIBIT)分子逻辑门.
The photoluminescence properties of the chiral Schiff base solution before and after deprotonation were investigated by using N- (2-hydroxy-1-naphthyl) methylene- (S) -α-phenylethylamine as a model molecule. The results show that the hand light reversal results from the intramolecular hydrogen bond rupture and formation and the conformational transition caused by the accompanying C-C single bond rotation, and the two conformations before and after are in the pseudo-enantiopure This finding means that the manipulation of molecular conformational transitions by single-bond rotation can be used as an effective way to construct chiral switchs.On the basis of this, we designed and synthesized styrene-based chiral functional monomers (VNP) and corresponding optics Reactive Polymers Due to the synergistic effect of ortho-groups, the light-sensitive nature of the polymer shows more responsiveness and repeatability to acid-base stimulation than the monomer.When H + and OH- are cyclically added, the polymer solution The CD signal (Cotton effect at 382 nm) reverses in the “ON ” - “OFF ” fashion so that the output signal can be repeated at least 5 times without loss, achieving lossless output via acid-base regulation Of the new polymer-based chiral switch.In addition, based on the chiral switch system to build a typical “forbid ” (IHIB IT) Molecular logic gate.