含有不同烷氧基侧链的聚对苯乙炔(PPV)衍生物的合成与性能表征

采用强碱去卤缩合法合成了聚(2-甲氧基-5-丁氧基)对苯乙炔(PMOBOPV),聚(2-甲氧基-5-辛氧基)对苯乙炔(PMOCOPV),(2-甲氧基-5-异辛氧基)对苯乙炔(iso-PMOCOPV)和聚(2-甲氧基-5-十二烷氧基)对苯乙炔(PMODOPV)四种含有不同烷氧基侧链的聚对苯乙炔(PPV)的衍生物。利用傅里叶变换红外光谱、核磁共振谱、热失重曲线、紫外-可见光吸收光谱和光致发光光谱对聚合物的结构和性能进行了表征。并通过实验确定了适宜的合成反应条件,例如催化剂和原料配比、叔丁醇钾的用量等。结果表明合成的聚合物具有良好的热稳定性和溶解性,聚合物的紫外吸收波长最大在492nm,荧光光谱的最大发射波长在555nm左右。     

含二噻基哒嗪的聚芳炔类衍生物的合成与性能研究

以四(三苯基磷)钯(Pd(PPh3)4)和CuI作为催化剂,在二异丙胺和四氢呋喃溶液中,采用宽能带的1,4-二乙炔基-2,5-二(十二烷氧基)苯(PE)和窄能带的3,6-双(5′-溴-2′-噻吩)-哒嗪(TPD)以不同配料比合成了一系列新型聚芳炔。长链烷氧基的存在使得此类聚合物在常用的有机溶剂中具有较好的溶解性和成膜性。通过对上述聚合物的紫外-可见吸收、荧光发射及循环伏安等基本性能进行探讨可知,共聚物在THF溶液中的荧光量子效率为51%～61%;随着共聚物中TPD含量的增加,共聚物薄膜的吸收起始波长及荧光发射波长均有红移。聚合物薄膜的最大发射峰位于540～551nm。     

含苯并硒二唑组分的聚对苯撑乙炔类共轭聚合物的合成及性能研究

通过钯催化的Sonagashira偶合反应合成出了3种带有不同链长烷氧基侧链,主链中含有2,1,3-苯并硒二唑纽分的聚苯乙炔类共轭聚合物并对其化学结构进行了表征确认.此类聚合物在常用的有机溶剂中具有较好的溶解性和成膜性.通过紫外可见光谱、荧光光谱、循环伏安等对所得聚合物的基本性能进行了探讨.聚合物P7、P9和P12在溶液状态下的紫外吸收分别为421、450和450nm,相对应最大发射分别位于475、482和481nm;固态下聚合物的吸收分别为433、486和486nm,相对应最大发射为575、583和590nm.聚合物的循环伏安测试表明聚合物P7、P9、P12的起始电位为1.19、1.19、1.18V.聚合物非线性光学性能研究表明取代基为十二碳烷氧基的聚合物显示出了良好的三阶非线性光学性能,其三阶非线性光学系数为3.54×10-12esu.     

新型有机聚合物电致发光材料聚(2,3-二芳基-富马氰)的合成、表征及性能研究

利用标准Suzuki反应条件,通过双(4-溴苯基)富马氰和系列芳香族硼酸酯偶合,得到系列聚(2,3-二芳基富马氰).所获得的4种聚合物的合成收率均超过70%,数均分子量Mn为8400～140000;特性粘数[η]为0.31～0.77dLg-1(甲苯,30℃).聚合物溶于普通有机溶剂,具有良好的成膜性.4种聚合物的甲苯溶液显示相似的UV-vis光谱(λmax=413 nm).荧光光谱显示,甲苯溶液中,聚合物的最大发射波长在约544 nm处,荧光量子收率＞30%.聚合物薄膜的最大发射波长为560 nm.粉末X衍射显示,聚合物在2θ＜7°区产生较强的衍射峰,这些小角区的衍射峰所对应的烷氧基侧链间距d1和烷氧基侧链的碳原子数n显现良好的线性关系.热重分析(TGA)显示,氮气中,聚合物的5%重量损失温度＞340℃.电化学分析(CV)表明,在0.1 M支持电解质[Bu4N]BF4的乙腈溶液中,聚合物薄膜的氧化开始于0.68V(相对于Ag+/Ag电极),最大氧化峰值电位为1.03V;在0～-2.5V区域,聚合物的还原始于-1.34V,并在-1.65和-2.03V处给出两个峰值电位.相应的去还原电位为-1.67和-1.33 V.     

含苯乙炔基共轭单体的合成及荧光性能

通过苯乙炔基锂和氯硅烷的偶合反应合成了系列含苯乙炔基共轭单体(PES)。通过红外光谱(FT-IR)、核磁共振(1H-NMR、13C-NMR、29Si-NMR)、质谱分析(MS)和元素分析(EA)对其结构进行了表征,利用紫外光可见分光光谱(UV-Vis)和光致发光光谱(PL)研究了共轭单体的荧光性能,讨论了不同共轭结构与单体性能之间的依赖关系。结果表明,合成得到的共轭单体易溶于常见的有机溶剂(四氢呋喃、氯仿、丙酮、甲苯等)。而且随着单体结构中共轭程度的增大,紫外吸收光谱的最大吸收峰和荧光光谱的发射峰均发生不同程度的红移。其中,四苯乙炔基硅烷(TPES)由于结构极具对称性且共轭程度最高,发射峰红移至368 nm和738 nm处,在可见光范围内发射红光。     

2，5-二烷氧基取代聚对苯撑热性能研究

采用DSC、TGA、WAXD研究了系列 2 ,5 二烷基取代聚对苯撑 (DAO PPP)的热稳定性、热氧化稳定性、相转变行为。DAO PPP的热分解由两步组成。在热分解温度超过 30 0℃时 ,首先开始发生侧链的断裂 ;温度超过 50 0℃时 ,聚合物主链才发生分解。实验结果表明 ,烷氧基的引入降低了聚合物的热稳定性 ,聚合物中的杂质和结构缺陷对其热稳定性也有一定的影响。在其DSC曲线上 ,没有观察到整个聚合物分子的熔点 ,但可观察到具有较长侧链的聚合物侧链的相转变行为。     

表面活性剂对纳米氧化锌形貌和发光性能的影响

以二水合乙酸锌和氢氧化钠为原料,分别以表面活性剂十六烷基三甲基溴化铵(CTAB)和聚乙烯吡咯烷酮(PVP)为结构导向剂,采用简单的水热法制备了不同形貌的纳米氧化锌。研究了两种表面活性剂对纳米氧化锌形貌和光致发光性能的影响,并探讨了表面活性剂的作用机理。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和室温光致发光光谱(PL)等测试方法对样品的结构、形貌和发光性能进行了表征。结果表明:添加了表面活性剂后,样品形貌和尺寸都更加均匀,紫外发射峰强度相对增加。     

含2-异丙基氨基-4,6-二(3,4-乙撑二氧噻基)-1,3,5-三嗪π-共轭聚合物的合成及性能

以二价钯配合物作为催化剂,将2-异丙基氨基-4,6-二(2′-溴-3,4-乙撑二氧噻基)-1,3,5-三嗪分别与1,4-二乙炔基-2,5-二辛氧基苯、1,4-二乙炔基-2,5-二(十二烷氧基)苯、2,7-二(4,4,5,5-四甲基硼烷基)-9,9-二辛基芴交替共聚合成了3种π-共轭聚合物P1,P2和P3。经傅里叶变换红外光谱、氢核磁共振谱、紫外-可见光谱、荧光光谱、循环伏安法、X射线粉末衍射和凝胶渗透色谱等测试手段对其进行了表征,并对聚合物在CHCl3溶液的酸致变色行为进行了研究。结果表明,得到的聚合物在CHCl3中的紫外-可见最大吸收波长分别在443nm和431nm处出现。在CHCl3溶液中聚合物P1,P2和P3最大发射峰分别位于507nm,511nm和543nm,其聚合物薄膜的最大发射波长分别为573nm,557nm和559nm。与P1和P2相比,P3的酸致变色敏感性高于2个数量级。聚合物P1和P2均在-2.0~0V出现n-掺杂峰。聚合物X射线衍射谱图显示聚合物均有一定的结晶性。     

新型含铱共聚物的合成及表征

利用2-对甲苯基吡啶(ptpy)、对乙烯基苯甲酸(VBA)和三水合氯化铱(IrCl_3·H_2O)配位,得到了铱配合物单体Ir(ptpy)_2(VBA),再将其与乙烯基咔唑共聚制得了一种含铱配合物的新型聚合物.通过元素分析、FT-IR光谱和~1H NMR谱等对Ir(ptpy)-2(VBA)和聚合物的结构进行了表征.凝胶色谱仪(GPC)测试结果表明,聚合物的数均分子量(Mn)为8230.此外还研究了Ir(ptpy)_2(VBA)和聚合物的紫外-可见(UV-vis)吸收光谱和光致发光(PL)光谱.光致发光光谱测试结果表明,聚合物在固态时,主体咔唑基团向客体铱配合物基团有着较为有效的能量转移.聚合物在501nm处有较强的金属配合物三重态的磷光发射峰,是一种绿色磷光材料.     

含Eu络合物掺杂的PMMA光致发光薄膜的制备与表征

制备了稀土Eu3+与4-甲氧基二苯甲酰甲烷(4-methoxy-dibenzoylmethane,MDBM)、邻菲罗啉(Phenan-throline,Phen)的络合物Eu(MDBM)3(Phen)x,并通过IR、UV、FS(荧光光谱)对其进行了表征。将Eu(MDBM)3-(Phen)x掺杂到聚甲基丙烯酸甲酯(PMMA)中,得到了光致发光PMMA薄膜。研究结果表明,该薄膜具有较好的光致发光性能,主要荧光激发峰位于380nm,主要荧光发射峰位于613nm,络合物Eu(MDBM)3(Phen)x掺杂量从0.8%增加到1.2%时,薄膜的荧光发射强度呈持续增强趋势,在613nm波长处发射强度增强了13倍。     

Effect of solvents on the synthesis of nano-size zinc oxide and its properties

The effect of the solvents on particle size and morphology of ZnO is investigated. The optical properties of nano ZnO were studied extensively. During this study, zinc oxalate was prepared in aqueous and organic solvents using zinc acetate and oxalic acid as precursors. The thermo-gravimetric analysis (TGA/DTA) showed formation of ZnO at 400 °C. Nano-size zinc oxide was obtained by thermal decomposition of aqueous and organic mediated zinc oxalate at 450 °C. The phase purity was confirmed by XRD and crystal size determined from transmission electron microscopy (TEM) was found to be 22–25 nm for the aqueous and 14 –17 nm in organic mediated ZnO. Scanning electron microscope (SEM) also revealed different nature of surfaces and microstructures for zinc oxide obtained in aqueous and organic solvents. The UV absorption spectra showed sharp absorption peaks with a blue shift for organic mediated ZnO, due to monodispersity and lower particle size. Sharp peaks and absence of any impurity peaks in photoluminescence spectra (PLS) complement the above observations.     

非晶ZrO2-SiO2系薄膜及微细图形的制备

采用溶胶－凝胶与化学修饰相结合的方法制备了ZrO2-SiO2系薄膜，研究了这种凝胶薄膜的FT－IR光谱特性及随紫外线照射时的变化，发现在1600－1400cm^-1之间有一些与含锆螯合物相关的峰，这些峰值随紫外线照射而减弱，表明这些螯合物发生分解，伴随着螯合物的分解，薄膜的乙醇中的溶解能力也发生变化，利用这特性，紫外光通过掩膜照射凝胶薄膜，用有机溶剂溶洗后，获得凝胶薄膜的微细图形，再进行热处理，消除薄膜中的有机物就可得到非晶质ZrO2-SiO2系薄膜的微细图形。     

乳液聚合条件对聚苯胺性能的影响

以（NH4）2S2O8为催化剂,在非极性溶剂-功能质子酸-水三相体系中,采用乳液聚合方法合成聚苯胺。对乳液聚合与化学氧化溶液聚合合成的聚苯胺性能进行了比较,研究了掺杂酸、氧化剂、反应时间、温度等聚合条件对聚苯胺导电性、溶解性等性能的影响。结果表明,乳液聚合产率高于80%,聚苯胺电导率大于1S/cm,在有机溶剂中的溶解性与用化学氧化合成的聚苯胺比较有明显提高。     

Effects of organic solvents on hyaluronic acid nanoparticles obtained by precipitation and chemical crosslinking

Hyaluronic acid is a hydrophilic mucopolysaccharide composed of alternating units of D-glucuronic acid and N-acetylglucosamine. It is used in many medical, pharmaceutical, and cosmetic applications, as sponges, films, or particle formulations. Hyaluronic acid nanoparticles can be synthesized free of oil and surfactants by nanoprecipitation in organic solvents, followed by chemical crosslinking. The organic solvent plays an important role in particles size and structure. Therefore, this study aimed to investigate the influence of acetone, ethanol, and isopropyl alcohol on the synthesis and physico-chemical properties of hyaluronic acid nanoparticles. Particles were crosslinked with adipic hydrazide and chloride carbodiimide under controlled conditions. The nanoparticles obtained with all three studied solvents were moderately electrostatically stable. Experiments with acetone produced the smallest particle size (120.44 nm) and polydispersity (0.27). The size and polydispersity of hyaluronic acid nanoparticles correlated with the surface tension between water and the organic solvents, not with the thermodynamic affinity of water for the organic solvents.     

Synthesis and properties of a solution-processable truxene derivative for OLED devices

A soluble truxene derivative (TR1) attached with triphenylamine at the peripheral position was designed and synthesized. The structure and purity of TR1 were carefully characterized by 1H NMR, UV/vis and photoluminescent spectroscopy, mass spectroscopy, and thermal analyses. It exhibited good solubility in common organic solvents and good film forming properties. The maximum absorption and emission peaks in THF solution were shown at 358 nm and 415 nm, respectively. Bright blue emission was observed in both solution and solid states under UV excitation. The fluorescent quantum efficiency was 0.46. The best luminous efficiency was found to be 3.65 cd/A with CIE coordinates of (0.163, 0.260) in electroluminescence devices.     

5-氯-3-硝基螺吡喃的合成及对银离子和有机胺的识别

合成并研究了5-氯-3-硝基螺吡喃光谱性质及特异性识别.研究结果表明,5-氯-3-硝基螺吡喃具有溶剂化显色效应,闭环结构SP和开环结构MC分别在非极性和极性溶剂中稳定存在;该螺吡喃能从18种常见金属离子中特异识别出Ag+,且可识别四类共16种有机胺.     

Regenerating optical properties of individual gold nanoparticles in alcoholic solvents without any surfactant

We compared the optical properties of gold nanoparticles (GNPs) in various solvents with those of strawberry-like composite particles (Au/SiO2) consisting of a silica core and single attached GNPs. The results show that Au/SiO2 without any surfactant could regenerate well optical properties of individual GNPs in alcoholic solvents. By the electrophoretic light-scattering measurements, the high dispersibility of Au/SiO2 composite particles dispersed in alcoholic solvents has been demonstrated. In addition, using Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, we proposed a possible mechanism to qualitatively account for the dispersibility of Au/SiO2 in organic solvents such as alcoholic solvents and cyclohexane, which may provide an opportunity to manipulate optical signals of single nanoparticle in organic solvents.     

Conformation transition of Bombyx mori silk protein monitored by time-dependent fourier transform infrared (FT-IR) spectroscopy: effect of organic solvent

The conformation transition from random coil and/or helix to β-sheet of silk protein is the most important step in the formation of silk fiber in nature as well as by artificial spinning. Time-dependent Fourier transform infrared (FT-IR) spectroscopy was used in this research to monitor such a conformation transition process induced by the organic solvents methanol, ethanol, propanol, isopropanol, and acetone. The kinetics of β-sheet formation of regenerated Bombyx mori silk fibroin in these organic solvents was obtained by the Δabsorbance-time curve from the time-dependent difference infrared spectra. The results showed that the conformation transition rate of silk fibroin was methanol > ethanol > acetone > propanol > isopropanol, which is in accordance with the polarity of these organic solvents. In connection with the mechanical properties and morphologies of regenerated silk fibers using these organic solvents as coagulation bath reported in the literature, we may conclude that the conformation transition rate of silk protein in the organic solvent is very important in wet-spinning to produce high-performance regenerated silk fibers.