联二炔囊泡的光致聚合、热致变色及应用

物理化学实验为各大高校本科化学教学的主干实验课程之一。虽然各高校的物理化学实验内容已十分丰富,但仍然缺乏将不同章节知识点融会贯通以及与学科前沿密切联系的综合型实验内容。我们根据南开大学郭东升教授课题组发表的一篇有关联二炔程序性响应检测胆碱酯酶的工作设计了“联二炔囊泡的光致聚合、热致变色及应用”的物理化学实验,涉及到联二炔缔合胶体的制备、联二炔的紫外光致聚合反应和聚联二炔的热致变色,进而显示其在防伪领域的潜在应用价值。希望通过此实验,使学生对物理化学中的缔合胶体、光化学、热力学、动力学等章节有更深一步的贯通性掌握,并了解自组装、光聚合、变色材料和防伪等相关研究领域的前沿动态。     

The formation of polymerizable tubules

We have been investigating the crystallization behavior of the phospholipid amphiphile, 1,2 bis (10, 12-tricosadiynol)-sn-glycero-3-phosphocholine, DC_8,9PC, which forms both vesicles and hollow tubules as well as Langmuir Blodgett monolayers and multilayers. This material has polymerizable diacetylene groups in equivalent positions on the two hydrocarbon tails. The direct crystallization from solution of this amphiphile has been studied using different solvent mixtures and temperatures. The Langmuir Blodgett technique was also used to compress and orient the tubules.     

Enormously extended π-electronic conjugation system of dimeric octaethylporphyrin transmitted with anthracene

Based on the fact that anthracene (Anth) possesses much higher similarity in electron-releasing ability to porphyrin nucleus than the other polyacenes, the dimeric octaethylporphyrin (OEP) derivatives 4 and 5 (OEP–Anth–OEP) were synthesized and their structure–property relationships were examined, as compared with related OEP dimers 1–3. Among them, the derivative 4 showed enormously high electronic communication between two terminal OEP rings, potentially providing a suitable unit of the electronic structure for molecular design of the OEP devices operating with less energy and with higher sensitivity to outside stimuli.     

Synthesis and crystallographic characterization of a ‘palladadehydrobenzo[19]annulene’

The trans-palladium bis(σ-acetylide) complex (Et₃P)₂Pd(C₃₀H₁₂) (2) was synthesized from hexane 4 in 77% yield via a simple three-step process. The X-ray crystal structure of 2 shows a strained and warped annulenic core upon insertion of the organometallic fragment. UV-vis data of the molecule suggest limited electronic delocalization throughout the metallacycle.     

Morphology‐Dependent Cell Imaging by Using a Self‐Assembled Diacetylene Peptide Amphiphile

Herein, a novel cationic peptide gemini amphiphile containing diacetylene motifs ( DA₂P ) is presented, which self‐assembles into novel tadpole‐ and bola‐shaped nanostructures at low concentrations and nanofibers at higher concentrations. Interestingly, the DA₂P assemblies can be polymerized into a fluorescent red phase but only during incubation with HeLa cells, most likely owing to the reorganization of the diacetylene chains of DA₂P upon interaction with the cell membrane. The red‐fluorescent polymerized DA₂P assemblies can serve as a novel cell imaging probe. However, only vesicles, tadpole‐ and bola‐shaped DA₂P assemblies can be translocated into HeLa cells, whereas the nanofiber‐like DA₂P assemblies are trapped by the cell membranes and do not enter the cells. Hence, morphology‐dependent cell imaging is observed.     

A modified synthesis of tellurophene using NaBH4 to generate sodium telluride

A modified synthesis of tellurophene by reaction of diacetylene with sodium telluride is described. The primary modification involves the convenient in situ generation of sodium telluride by reduction of tellurium metal with NaBH₄ in water.     

琼脂糖基类丁二炔凝胶剂量计的辐照响应行为

将类丁二炔(10, 12-二十五碳二炔酸)囊泡固载于琼脂糖凝胶制备出了新型辐射变色凝胶复合凝胶材料。利用γ射线辐照研究了所制备凝胶的辐照响应行为,结果显示:当γ辐射剂量在500-2000 Gy内,随着剂量增加,凝胶由无色逐渐变为蓝色,颜色不断加深,采用紫外-可见光分光光度计测试其吸收光谱,发现其主要吸收峰值在660 nm附近,且辐照前后凝胶的吸光度差值与剂量有良好线性关系(相关系数R² =0.9942)。进一步研究表明:所制备的凝胶材料对γ射线和电子束辐照有相同的剂量响应,且无明显的能量和剂量率依赖性;凝胶的辐射后效应较弱,辐照后24 h,吸光度基本恒定;分次辐照对凝胶剂量计准确性的影响极小;凝胶在0-30℃范围内的响应性基本保持稳定;在辐照后48 h内,并未观察到囊泡有明显扩散效应,显示出良好的稳定性。此外,琼脂糖具有价廉、无毒且易制备为任意形状凝胶的优点,因此该凝胶剂量计有望应用于真实场景的三维剂量分布测定。     

新型合偶氮功能团的双炔类衍生物非线性光学性质的理论研究

在SM1和ZINDO方法基础上，按完全态求和公式计算分子二阶非线性光学系数β(ijk)和三阶非线性光学系数γ(ijkl)，并对含偶氛功能团的双快类衍生物的二阶、三阶非线性光学性质进行了系统的理论研究．即在基础上，在分子左端引入推电子基N（CH3）2，右端分别引入推电子基CH2OH、2，5-二氮-4-硫甲苯基，研究取代基变化时β、γ变化的规律．对计算结果所反映的规律性在微观上给予了解释．     

Synthesis and structural and electronic properties of the diacetylene- and ethylene-groups connected octaethylporphyrin(Ni) tetramer

The tetramer of octaethylporphyrin nickel complex [OEP(Ni)], connected with diacetylene and ethylene linkages, was synthesized. Its structural and electronic properties were studied, proving that two constituents of the diacetylene-group connected OEP(Ni) dimer face to each other in s-cis conformation about the ethylene linkage but not so closely as to induce a transannular π-electronic interaction between them.     

Synthesis of New Cheral Macrocyclic Tetraoxo Polyamines Containing Pyridine Ring and Functional Arms

Seven new chiral macrocyclic tetraoxo polyamines containing pyridine ring and functional arms derived from L-histidine, L-alanine, L-leucine and L-phenylalanine, respectively, have been synthesized and characterized by MS, ¹H NMR and elemental analysis.