热致可逆变色的聚二炔／稀土离子纳米复合物

将Dy^＋或Sm^＋掺杂到具有层状结构的10,12-二十五碳二炔酸（PCDA）纳米粒子中,得到二炔酸／稀土离子（PCDA-RE）纳米复合物．随后在稍微高于二炔酸熔点的温度下对PCDA—RE纳米复合物进行退火处理,退火后的PCDA—RE纳米复合物发生拓扑聚合反应得到聚二炔酸／稀土离子（PDA-RE）纳米复合物．虽然纯聚二炔酸的热致变色过程是不可逆的,但是PDA—Sm纳米复合物和PDA-Dy纳米复合物分别具有不完全和完全热致可逆变色的性能．研究表明,PDA-RE纳米复合物的层间距为5,4nm,比纯聚二炔酸的层间距（4．7nm）要大．对于PDA—RE纳米复合物,稀土离子和聚二炔酸之间的强相互作用是纳米复合物实现大部分或完全可逆变色的原因．同时退火处理对实现聚二炔酸可逆变色非常重要,因为退火处理消除了材料结构中的所有缺陷,最终促使材料具有热致可逆变色性能．     

多巴胺改性聚二乙炔复合热致变色材料的制备及性能

聚二乙炔变色温度较高且受热构象转变后难以回复,可通过端基改性赋予其热致变色可逆的性能并改变变色温度,以适合应用在人体温度智能传感方面. 采用多巴胺改性二乙炔形成分子间氢键,二乙炔头基处多巴胺聚合形成共价键,254 nm紫外光照形成双聚合体系(Poly-PCDA-PDA),且将改性二乙炔与热塑性聚氨酯(TPU)进行复合. 改性后聚二乙炔相转变点由62 ℃降低至约39 ℃,热致变色温度为35 ℃且能够在蓝-紫相之间发生完全可逆转变,改性二乙炔与TPU的复合制备了稳定性高且能够发生可逆热致变色的薄膜,更符合人体温度环境应用场景. 提供了一种多巴胺取代头基后通过共价键连接进一步改性聚二乙炔的策略,有望在聚二乙炔基人体温度传感材料的研究中起到重要作用.     

以物理力将糖脂引入聚联乙炴基质脂的变色囊泡

囊泡具有与生物膜结构类似的封闭双分子层结构,具有模拟生物膜结构的突出优点,因此受到人们的极大重视．因为它具有胶体粒子的大小尺寸,其表面膜的性质易于控制,具有较大的输送客最以及生物相容性,因此,囊泡在药物的传输、基因治疗、癌症的化学治疗、分子识别、分子光学器件的组装、超细颗粒的制备、太阳能转化及反应性能的控制等领域都具有十分重要的意义．然而,在分子识别及药物输送过程中,由丁蟹池的稳定性差而严重影响其应用．聚合表面活性剂囊泡的出现较好地解决了其稳定性差的问题．在众多的可聚合的表面活性剂单体中,具有联…     

席夫碱及其络合物的可逆热致变色材料

对具有可逆的热致变色的席夫碱及其络合物的分类、合成、变色机理以及发展前景等进行了回顾和探讨。     

聚二乙炔囊泡的制备及其在医疗检测领域的应用

聚二乙炔(Polydiacetylene, PDA)因具有独特的光学及电子特性而受到广泛关注。两亲性共轭二乙炔(Diacetylene, DA)单体在一定条件下可以自组装成囊泡结构,紫外线辐射后,经1,4-加成聚合得到聚合物PDA囊泡。PDA在环境刺激下经历颜色和荧光变化,而PDA囊泡的类细胞膜结构使其具有很好的仿生特性,因此PDA囊泡可以用于细菌、病毒、酶等的检测以及疾病诊断和药物控释。本文介绍了PDA囊泡传感系统的制备以及固相聚合和颜色变化的机理,综述了PDA囊泡传感系统在医疗检测领域的研究和应用进展,并对PDA囊泡传感系统存在的问题和未来发展方向进行了总结和展望。     

基于热致变色微胶囊的科普实验方案

颜色是缤纷世界的重要组成部分,热致变色微胶囊的颜色随温度变化而变化,具有\"可视、可玩、可教\"的特点.本科普实验以热致变色微胶囊制备为切入点,从分子结构选择到微胶囊制备和表征,讲述热致变色现象中的化学原理,提高中学生对生活现象的观察力和探知力.本实验操作过程简单、实验现象贴近生活、实验原理易于推广,可以培养学生的基础操作能力,有利于提高学生从理论到实践的转换水平,提升科创探索的设计和动手能力.     

2种偶氮席夫碱类化合物的合成及其热致变色性质

通过重氮偶合反应制得2种氨基偶氮化合物在经纯化下燥后,与水杨醛的乙醇溶液在60℃反应4 h分别得到2种偶氮席夫碱类目标化合物,通过元素分析、核磁共振氢谱、红外光谱测试技术表征了其结构.紫外光谱测试化合物在DMSO溶液的紫外吸收,在升温速率为1.5℃/min测试时,化合物A和B紫外吸收表现出热致变色性质;在45℃的恒定温度测试时,化合物A在450和348 nm的吸光度值与时间呈线性关系,化合物B在425和356 nm的吸光度值与时间呈线性关系.研究表明,2种偶氮席夫碱类化合物有良好的热致变色性,是性能良好的热致变色材料.     

一个紫精基镉配位聚合物的组装、热致变色和电化学性质

在溶剂热合成条件下,将紫精配体1,1′-二(3-羧基苯基)-(4,4′-联吡啶)二氯化物(H₂bcbpy·2Cl)和KI与金属镉离子配位,成功构筑了一例紫精基热致变色配位聚合物[Cd(bcbpy) I₂]·2H₂O (1),该配合物为一维链状结构且具有热致变色性能。在不同温度刺激下,该配合物由绿色缓慢转变为黄绿色,随着温度的升高,配合物1的颜色逐渐加深,最后变为橘黄色。因此,我们将配合物1制作成了感温变色薄膜。此外,我们还对配合物1进行了电化学测试,结果表明该配合物为半导体材料。     

聚合物囊泡的制备及作为药物载体的研究进展

近年来,国内外对聚合物囊泡的应用研究十分活跃。聚合物囊泡是由密闭双分子层构成的、类似脂质体结构的一类高分子聚集体。与小分子聚集体相比,聚合物囊泡具有稳定性高、通透性可设计、同时负载亲水和疏水性药物以及可进一步功能化修饰等优点,使其在疾病诊断、药物包埋与输送、微反应器等生物医学领域具有广泛的应用。本文介绍了聚合物囊泡的制备方法及作为药物载体的最新研究进展。     

一个紫精基镉配位聚合物的组装、热致变色和电化学性质

在溶剂热合成条件下,将紫精配体1,1''-二(3-羧基苯基)-(4,4''-联吡啶)二氯化物(H₂bcbpy·2Cl)和KI与金属镉离子配位,成功构筑了一例紫精基热致变色配位聚合物[Cd(bcbpy) I₂]·2H₂O (1),该配合物为一维链状结构且具有热致变色性能。在不同温度刺激下,该配合物由绿色缓慢转变为黄绿色,随着温度的升高,配合物1的颜色逐渐加深,最后变为橘黄色。因此,我们将配合物1制作成了感温变色薄膜。此外,我们还对配合物1进行了电化学测试,结果表明该配合物为半导体材料。     

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。     

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.     

Facile synthesis of low-polydispersity block copolymer vesicles by azide-zwitterion cycloaddition

Polycaprolactone with azide (PCL-N₃) and polyethylene glycol with α,β-unsaturated ester (maPEG) as chain-end functional group were synthesized, respectively. Then, facile synthesis of polycaprolactone-block-polyethylene glycol (PCL-b-PEG) amphiphilic copolymer by azide-zwitterion cycloaddition of PCL-N₃ and maPEG, as the first example, was reported. The self-assembly of this amphiphilic copolymer was carried out in deionized water, and then the formation of vesicles was proven by the result of transmission electron microscope (TEM). Grainsize analyzer suggested that the diameter of the vesicles is 305 nm in average and the polydispersity of the vesicles is 0.128. The azide-zwitterion cycloaddition provides a powerful method for the post-functionalization of α,β-unsaturated ester or azide end-functionalized polymers.     

New irreversible thermochromic polydiacetylenes

New diacetylenic compounds are described. These compounds are unfunctionalised, monoalcohols, diols or monoesters and present irreversible thermochromic behaviour. When heated, these diynes change colour from blue to red in temperature ranging between −50 and +75 °C depending on chain lengths. A relationship between the number of atoms and the thermochromism temperature has been highlighted. Moreover, a mechanism of this thermochromic phenomenon is demonstrated based on Raman spectroscopy, ESR and solid NMR.     

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.     

Crystal and Molecular Structure of the bis-Ethyl Urethane of 5,7-Dodecadiyn-1,12,diol (ETCD)

Grown from ethyl acetate solution, the bis-ethylurethane of 5,7-dodecadiyn-1,12-diol is a monoclinic crystal, a = 16.9740(16), b = 4.9770(5), c = 11.0874(11) Å; β = 101.869(6)°; Z = 2; V = 916.63(16) ų. The crystal structure contains two N─H…O hydrogen bonds per molecule and has nearly ideal parameters (d = 4.977 Å, ? = 45.8°, R = 3.477 Å) for solid-state polymerization.     

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 and reversible thermochromism of azobenzene-containing polydiacetylenes

A series of diacetylenic monomers containing azobenzene chromophores with different terminal groups {CH₃-(CH₂)₁₁-CC-CC-(CH₂)₈-COO-(CH₂)₂-O-C₆H₄-NN-C₆H₄-R, where R = NO₂, CN, CH₃ and labeled as 3a, 3b and 3c, respectively} were synthesized and characterized by ¹H NMR. The photo-polymerization of spin-coated films of the monomers was carried out by irradiation at 254 nm under monitoring the optical absorption in the visible region and polymers (P3a-P3c) were obtained as blue films that were no longer soluble in common organic solvents. The thermochromic behavior of the polymers was evaluated with UV, Raman, thermogravimetric analysis, X-ray diffraction and differential scanning calorimetry analyses. It was found from results that all of the polymers were thermally stable and decomposed at temperatures as high as ∼300 °C. By tracing the treatment of samples with heating-cooling cycles, the temperature ranges between the low and the high critical temperature for the red-phase were obtained to be 60-160 °C, 57-162 °C and 50-154 °C for P3a, P3b and P3c, respectively, larger than those reported before for other PDAs. The relationship between characteristics above and the chemical structure of polymers was discussed.     

Synthesis and structural and electronic properties of the octaethylporphyrin-dihexylbithiophene-fullerene derivatives (OEP-DHBTh-C60) connected with diacetylene linkage

Orientational isomers of the octaethylporphyrin-dihexylbithiophene-fullerene derivative (OEP-DHBTh-C₆₀) connected with the diacetylene linkage were synthesized. The electronic and electrochemical properties were studied, proving that the orientation of DHBTh affects not only the electronic structures of OEP-DHBTh-C₆₀ but also their molecular motional behaviors evidently.