一种含螺吡喃和肉桂酸酯双光功能基团的光致变色染料的合成与性能

合成了一种含有光致聚合肉桂酸酯基团的新型光致变色螺吡喃染料,研究其与普通螺吡喃染料在不同高分子材料中的光致变色和热退色过程(PMMA和PVCi).通过UV-Vis光谱、NMR谱和IR光谱研究了新型染料中的肉桂酸酯基团的光致聚合过程,考察了其对螺吡喃结构的光致变色显色体热稳定性的影响.     

含席夫碱基的螺吡喃双功能光致变色材料的合成及性质

设计合成了一系列含席夫碱基的螺吡喃双功能光致变色材料4a~4n. 通过1H NMR, IR和HRMS对其结构进行了表征. 研究了化合物在几种溶剂和PMMA膜中的光致变色性质, 研究了化合物4a在甲醇中, 以及化合物4a和4f在高分子介质聚甲基丙烯酸甲酯(PMMA)中的消色过程. 结果表明, 化合物4e在PMMA膜中光照后呈现出与其它化合物不同的颜色, 为罕见的绿色. 化合物4a在二氯甲烷溶液中有良好的荧光性能. 所合成的新型含席夫碱基的螺吡喃双功能光致变色材料在甲醇、二氯甲烷和环己烷溶液中及在PMMA膜中均表现出良好的光致变色性质.     

光致变色聚合物研究进展

本文主要介绍了9类光致变色聚合物的研究状况,包括光致变色螺吡喃聚合物、螺噁嗪聚合物、二芳基乙烯光致变色聚合物、偶氮苯类光致变色聚合物、苯氧基萘并萘醌光致变色聚合物、俘精酰亚胺光致变色共聚物、硫靛光致变色共聚物、双硫腙光致变色聚合物以及二氢吲嗪光致变色聚合物等.讨论了聚合物的合成、光致变色性质、影响聚合物性质的因素,并对光致变色聚合物未来的研究重点和方向作了展望.     

光致变色聚合物研究进展

本文主要介绍了9类光致变色聚合物的研究状况,包括光致变色螺吡喃聚合物、螺嗪聚合物、二芳基乙烯光致变色聚合物、偶氮苯类光致变色聚合物、苯氧基萘并萘醌光致变色聚合物、俘精酰亚胺光致变色共聚物、硫靛光致变色共聚物、双硫腙光致变色聚合物以及二氢吲嗪光致变色聚合物等。讨论了聚合物的合成、光致变色性质、影响聚合物性质的因素,并对光致变色聚合物未来的研究重点和方向作了展望。     

含BOC保护基团的螺吡喃类化合物的合成及其光致变色性能的研究

合成了5-[N-(叔丁氧甲酰基)氨基]-1,3,3-三甲基-6′-硝基吲哚啉螺吡喃(BOCSPI)和5-[N-(叔丁氧甲酰基)氨基]-1,3,3-三甲基-6′-硝基-8′-甲氧基吲哚啉螺吡喃(BOCSPII)两种光致变色化合物,采用紫外-可见光谱法研究了其在溶液和以不同质量比掺杂在聚甲基丙烯酸甲酯(PMMA)膜中的光致变色性能.研究表明螺吡喃的高掺杂量不利于其开环和闭环态的转化,BOCSPII分子中的甲氧基有利于有色开环体的部花菁的稳定.     

光致变色聚合物研究进展

本文主要介绍了9类光致变色聚合物的研究状况，包括光致变色螺吡喃聚合物、螺噁嗪聚合物、二芳基乙烯光致变色聚合物、偶氮苯类光致变色聚合物、苯氧基萘并萘醌光致变色聚合物、俘精酰亚胺光致变色共聚物、硫靛光致变色共聚物、双硫腙光致变色聚合物以及二氢吲嗪光致变色聚合物等。讨论了聚合物的合成、光致变色性质、影响聚合物性质的因素，并对光致变色聚合物未来的研究重点和方向作了展望。     

光致变色含氟丙烯酸酯涂层的制备及性能

选取十二烷基硫酸钠(SDS),辛基苯基聚氧乙烯醚(OP-10)为复合乳化剂,过硫酸钾(KPS)为引发剂,将2-(全氟己基)乙基甲基丙烯酸酯(PFM)与丙烯酸酯类单体采用预乳化-半连续种子乳液聚合法进行乳液共聚,再将羟基螺吡喃(SPOH)与乳液进行物理共混,制得光致变色含氟丙烯酸酯乳液。 通过多种表征手段研究丙烯酸正丁酯(n-BA)和甲基丙烯酸甲酯(MMA)软硬单体的质量比,SPOH的用量对聚合反应和乳胶膜性能的影响。 结果表明,加入含氟单体后乳胶膜与水、油的接触角提高,热稳定性提高;加入SPOH的质量分数为1.25%时,乳胶膜具有较好的光致变色性能。     

新型含氮杂环螺吡喃化合物的合成及性能研究

为了改善螺吡喃的光致变色性能,提高这一系列化合物的耐疲劳度,在螺吡喃吲哚啉环的氮原子上通过短碳链引入含氮杂环基团,成功合成了1'-(3-N-杂环基丙基)-3',3'-二甲基-6-硝基螺[吲哚啉-2,2'(2H)苯并吡喃](4a～4f).这一系列新的化合物.用核磁共振氢谱、碳谱、红外光谱和元素分析对这些化合物进行结构表征.通过紫外吸收光谱研究化合物在不同溶液(乙醇、二氯甲烷和环己烷)中和不同高分子膜(PMMA和PVB)中的变色性质.进一步对化合物4a在不同溶液中的动力学性质,以及在PMMA膜和PVB膜中的热消色动力学性质进行了研究,拟合计算并比较了消色过程的动力学常数.最后,又将化合物4a和不含含氮杂环的螺吡喃母体进行比较,发现耐疲劳度有很大提高.     

吲哚啉苯并螺呲喃类化合物的合成和应用

吲(口朶)啉苯并螺吡喃类化合物具有明显的光致变色性能。我们合成了6′-碘-1,3,3-三甲基吲(口朶)啉-2-螺环-2′-苯并吡喃及一些不同取代的吲(口朶)啉苯并螺吡喃化合物并对其色变性能进行了初步探讨。用这些化合物与光致抗蚀干膜G11胶制成了一种新型光致变色抗蚀干膜。将底片覆盖在此膜上,经紫外线照射后呈现出明显的色差,显示出的图象可保留24小时以上。     

双功能螺吡喃螺噁嗪类光致变色化合物研究进展

光致变色材料在光学镜头、光学信息存储、光分子开关等方面具有广泛的应用.双功能光致变色材料的合成与应用研究越来越受关注.综述了以螺吡喃、螺噁嗪为光致变色基团的双功能光致变色化合体系的研究进展,主要介绍了具有荧光性能、与金属离子络合性能的光致变色体系的研究进展以及应用.     

New types of multifunctional liquid crystalline photochromic copolymers for optical data recording and storage

A new family of multifunctional chiral‐photochromic liquid crystalline (LC) copolymers containing mesogenic, chiral and photoactive groups were synthesized. The new principles of photo‐regulation of the helical supramolecular structure and optical properties of the binary and ternary chiral‐photochromic LC polymers based on the change of helical twisting power of the chiral‐photochromic monomer units, the dual photochromism and photochemical spectral gap burning were developed. It was shown, that the introduction of small amount of low‐molar‐mass chiral‐photochromic dopants in chiral LC copolymers having different helix signs followed by light irradiation permits one to twist or untwist the helical supramolecular structure. The synthesized polymers are shown to be promising candidates for colour data recording and storage.     

两亲性嵌段共聚物PS-b-PMAA的合成与胶束化行为研究

利用原子转移自由基聚合法(ATRP)得到了分子量可控、分子量分布接近1.1的聚苯乙烯-b-聚甲基丙烯酸叔丁酯(PS-b-PtBMA)嵌段共聚物, 进而在酸性条件下由水解反应得到了两亲性的聚苯乙烯-b-聚甲基丙烯酸 (PS-b-PMAA)嵌段共聚物．用GPC, FTIR和¹H-NMR等对产物的分子量和组成进行了表征．使PS-b-PMAA在选择性溶剂中进行自组装, 通过激光光散射和透射电子显微镜研究了影响其胶束化行为的因素与胶束形态, 并初步探讨了胶束形成的机理, 发现通过控制嵌段共聚物的链段长度之比可得到空心球形的高分子胶束．     

Synthesis and characterization of styrene/isoprene/ethylene oxide block copolymers

Poly(ethylene oxide/isoprene/styrene/isoprene/ethylene oxide) block copolymers were synthesized using potassium–napthalene catalyst in tetrahydrofuran. The dynamic and thermal properties and water absorption of these tri-block copolymers were determined and related to their bulk morphology.     

Synthesis and characterization of particles consisting of a biodegradable poly(l-lactide) core and a functional hydrophilic shell

Block copolymers consisting of poly(solketal acrylate) and poly(l-lactide) were synthesized by combination of atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP) technique. Block copolymerization has been done by two different pathways, simultaneously and sequentially by using a dual functional initiator. Well defined block copolymers were obtained by sequential block copolymerization first implementing ROP of l-lactide followed by ATRP of solketal acrylate. After hydrolysis of the solketal acrylate segments hydrophilic poly(2,3-dihydroxypropyl acrylate) blocks were obtained. The amphiphilic block copolymers were able to self-organize in aqueous solution. Aggregation behavior was studied by means of dynamic and static light scattering. Time dependent enzymatic and hydrolytic degradation of the poly(l-lactide) cores was detected by dynamic light scattering. If enzymatic solutions were used the degradation process proceeded faster and was completed within 4000 min.     

Synthesis and drug release properties of novel pH- and temperature-sensitive copolymers based on a hyperbranched polyether core

Multi-arm star amphiphilic hyperbranched copolymers with poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) shell and hyperbranched poly(3-ethyl-3-(hydroxymethyl)oxetane) (HBPO) core were synthesized by reversible addition?Cfragmentation chain transfer method. The hyperbranched copolymers were further modified by succinic anhydride (SUC) to obtain the novel pH- and thermosensitive hyperbranched copolymer HBPO-star-PDMAEMAs-SUC. The composition and morphology of synthesized copolymers were investigated by ¹H NMR, dynamic light scattering, and transmission electron microscopy. These copolymers exhibited phase transitions in response to pH and temperature. The pH-dependent release properties of the drug-loaded micelles were also investigated using indomethacin (IND) as a model drug. The IND-loaded micelles displayed a rapid drug release at an alkaline pH.     

Shape memory effects of poly(ethylene terephthalate-co-ethylene succinate) random copolymers

Random copolymers based on terephthalate acid, succinic acid and ethylene glycol, with thermally induced shape memory, were synthesized via melt polycondensation. The chemical structures of these poly(ethylene terephthalate-co-ethylene succinate) copolymers (PET-co-ES) were ascertained by ¹H NMR spectroscopy. The thermal and viscoelastic characteristics of these copolymers were studied in terms of the succinic acid content using differential scanning calorimetry and dynamic mechanical analysis. The shape memory effects of the copolymers were examined using the strain test. The experimental results suggested that all copolymers exhibited shape memory above the glass transition temperature and that the highest shape recovery rate was 90%. The shape recovery rates of all test samples declined with the number of cycles. This decrease in the shape recovery rate may result from the change in the degree of polymer orientation and/or crystallinity during repeated testing.     

Self-organization behavior of methacrylate-based amphiphilic di- and triblock copolymers

Amphiphilic di- and triblock copolymers having different hydrophilic-to-hydrophobic block length ratio were synthesized using ATRP. The self-assembly behavior of these AB and ABA block copolymers consisting of poly(n-butyl methacrylate) (B) and poly(2,2-(dimethylaminoethyl methacrylate) (A) was investigated using a combination of dynamic light scattering, negative-stain transmission electron microscopy, cryoelectron microscopy, and atomic force microscopy. Two populations of self-organized structures in aqueous solution, micelles and compound micelles, were detected for diblock copolymers. Triblock copolymers assembled into vesicular structures of uniform sizes. Furthermore it was found that these vesicles tended to compensate the high curvature by additional organization of the polymer chains outside of the membrane. The chain hydrophilicity of the polymers appeared to have a critical impact on the self-assembly response toward temperature change. The self-reorganization of the polymers at different temperatures is discussed.     

Synthesis of gold nanoparticle necklaces using linear-dendritic copolymers

Linear-dendritic copolymers containing hyperbranched poly(citric acid) and linear poly(ethylene glycol) blocks (PCA-PEG-PCA) were used as reducing and capping agents to synthesize and support gold nanoparticles (AuNPs). PCA-PEG-PCA copolymers with 1758, 1889 and 3446 molecular weights, called A1, A2 and A3 through this work, respectively, were synthesized using 2, 5, and 10 citric acid/PEG molar ratios. The diameter of A1, A2 and A3 in a fresh water solution was investigated using dynamic light scattering (DLS) and it was between 1.8 and 2.8 nm. AuNPs were simply synthesized and supported by addition a boiling aqueous solution of HAuCl₄ to aqueous solutions of A1, A2 and A3. Supported AuNPs were stable in water for several months and agglomeration was not occurred. The loading capacity of A1, A2 and A3 and the size of synthesized AuNPs were investigated using UV spectroscopy and transmission electron microscopy (TEM). It was found that the loading capacity of PCA-PEG-PCA copolymers depend on the concentration of copolymers and the size of their poly(citric acid) parts directly. For example average loading capacities for 400 μM concentration of A1, A2 and A3 were 32.24, 37.4 and 41.52 μM, respectively, and average loading capacities for 400, 200 and 100 μM concentration of A1 were 32.24, 20.28 and 9.1 μM, respectively. Interestingly there was a reverse relation between the size of synthesized AuNPs and size of poly(citric acid) parts of PCA-PEG-PCA copolymers.     

京尼平交联低聚乙烯亚胺智能基因载体的制备与表征

使用京尼平与分子量为1800的超支化低聚乙烯亚胺在70％的乙醇溶液中反应,合成了具有荧光的交联型聚合物.利用核磁、凝胶渗透色谱、粒度仪、zeta电位仪和凝胶阻滞电泳对聚合物载体及其与DNA复合物颗粒进行了表征.研究表明,聚合物载体与DNA复合物颗粒粒径为120 ～150 nm,zeta电位为+20～25 mV,聚合物/...