寡聚(亚硅基二炔基蒽)电子结构和光谱性质的密度泛函理论研究

Poly(silanylenediethynylanthracene) (PSDEA) exhibits a hole-transporting ability experi-mentally. In order to simulate the property of PSDEA, a series of silanylenediethynylan-thracene oligomers were designed. The structures of these oligomers were optimized by using density function theory at B3LYP/6-31G(d) level. The energy gaps of the oligomers decrease with the increase in the chain length. The energy gaps of the oligomers also de-crease in the presence of the electron-withdrawing group on the anthracene ring. The ¹³C chemical shifts and nucleus independent chemical shifts (NICS) at the anthracene ring center in the oligomers were calculated at B3LYP/6-31G level. The chemical shifts of the carbon atoms connected with the nitryl group changed upfield, compared with those of the carbon atoms without the nitryl group. The aromaticity at the anthracene ring center decreases in the presence of the electron-withdrawing group, whereas increases with the increase in the number of the silanylene units. The most sensitive location for calculating the NICS values is 0.1 nm above the anthracene plane.     

基于贻贝仿生化学的分离功能材料

贻贝仿生的表面化学是近年来材料学、化学、生物医学等领域的交叉研究热点。多巴胺可以作为贻贝足丝蛋白(Mfp)超强黏附特性的模型分子,通过复杂的氧化-自聚和组装,形成多种功能的聚多巴胺(PDA)纳米涂层和纳米粒子,在分离膜、吸附材料、生物医用材料、生物黏结剂等领域有着广阔的应用前景。本研究小组近年来持续开展了基于贻贝仿生化学的分离功能材料制备与结构调控的研究工作,率先将多巴胺表面沉积方法应用于多孔分离膜表面的构建与功能化,提出了多巴胺的自聚-沉积过程模型,进而验证了PDA沉积层的纳滤分离特性,建立了一条简单方便的膜表面功能化与纳滤膜制备新途径。本文主要对基于贻贝仿生化学的分离功能材料,特别是分离膜的研究进展进行综述,并对将来的发展趋势进行展望。     

寡聚(亚硅基二炔基蒽)电子结构和光谱性质的密度泛函理论研究

聚(亚硅基二炔基蒽)(PSDEA)经实验测定具有空穴传输的能力. 为了模拟此高聚物的性质, 设计了一系列亚硅基二炔基蒽(SDEA)的寡聚物,利用密度泛函理论方法在B3LYP/6-31G(d)水平上对其构型进行优化. 寡聚物的能隙随着链长的增加而减少,同时蒽环上吸电基团的存在也使能隙减少. 在B3LYP/6-31G水平上计算寡聚物的¹³C化学位移以及蒽环中心位置的核独立化学位移. 寡聚物中与硝基相连的碳原子的化学位移与未连硝基的寡聚物中相同碳原子的化学位移相比向高场移动. 蒽环中心的芳香性在吸电子基团存在时减弱,但随着亚硅基数目的增加而增强. 用于核独立化学位移计算的最敏感区域是蒽环上方0.1 nm处.