含空间位阻侧链取代炔烃的合成及其催化聚合

设计并合成了具有较大空间位阻侧链的取代炔烃2-炔丙氧基-1,4-对苯二甲酸二甲酯单体,分别采用WCl6,WCl6-SnPh4和[Rh(nbd)Cl]2催化体系使其聚合,考察了不同催化剂对聚合的影响.采用红外光谱和核磁共振等技术对单体及聚合物结构进行了表征,并用紫外光谱和荧光光谱研究了所得聚合物的光学性能.结果表明,使用[Rh(nbd)Cl]2催化剂时得到的聚合物是高反式结构,荧光光谱中除了侧基的350 nm发射峰外,还在429 nm处存在较弱的共轭主链发射.使用WCl6-SnPh4催化体系得到的聚合物由于较高的顺式含量,主要是侧基的发射,而较大侧基位阻使主链共轭降低.尽管存在较短的间隔基,引入较大空间位阻侧基仍然迫使聚合物主链扭曲,顺式结构中侧基空间位阻的影响更大.     

含吡啶端基9,10-双芳基蒽共轭分子的合成、聚集诱导荧光增强及双光子诱导荧光

通过Heck反应合成了2个以吡啶为端基的9,10-双芳基蒽共轭分子9,10-二{4-{4-[N,N-二(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽(4Py-PAA)和9,10-二{4-{4-[N,N-二(2-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽(2Py-PAA),化合物结构经过1H NMR,13C NMR,HRMS-MALDI-TOF确证.测定了化合物在不同极性溶剂中的紫外吸收光谱、荧光光谱、荧光寿命及量子产率,测算了4Py-PAA和2Py-PAA的偶极矩.通过循环伏安法研究了它们的前线轨道能级.测定了4Py-PAA和2Py-PAA的固体荧光光谱、固体荧光量子产率及在不同含水量的水/THF混合溶液中的荧光光谱.实验发现4Py-PAA在THF溶液中发出蓝绿色荧光,固体时发出红色荧光,在含水量为70%的水/THF混合溶剂中发出黄色荧光,荧光强度是纯四氢呋喃(THF)的3倍,呈现聚集荧光增强性质.在800 nm飞秒激光下采用双光子诱导荧光参比法测定了4Py-PAA和2Py-PAA在THF溶液中的双光子吸收截面分别为193和101 GM.实验结果表明含有2位和4位吡啶端基9,10-双芳基蒽共轭分子具有良好的荧光发射性能及双光子吸收性质.     

N-(4-羟基苯基)马来酰亚胺的合成及其光谱分析

利用对氨基酚和马来酸酐反应制取N-(4-羟基苯基)马来酰亚胺(HPM),并采用红外光谱及核磁光谱对其结构进行了表征.研究了HPM在甲醇、四氢呋喃及二氯甲烷3种溶剂中的紫外光谱.结果发现,在这3种溶剂中,HPM在210～250 nm范围内的吸收峰对溶剂极性及溶液浓度敏感;而275 nm左右的吸收峰在各种极性不同溶剂中位置...     

含二乙炔类共轭聚合物的合成及性能研究

在以CuCl和四甲基乙二胺(TMEDA)作为催化剂和邻二氯苯作溶剂条件下,以二-(4-乙炔苯基)-4-辛氧基苯胺(M1)和3, 6-双(乙炔基)-N-辛基咔唑(M2)作为单体,通过Glaser-Hay氧化偶联反应合成了含有咔唑和三苯胺结构单元的聚芳烃二乙炔共轭聚合物.采用红外光谱、核磁共振谱、热失重分析、紫外吸收光谱和荧光光谱等方法对聚合物进行结构表征与性能测试.所得到的聚合物都溶于普通的有机溶剂(如四氢呋喃、二氯甲烷、氯仿、甲苯等).结果表明,聚合物具有优异的热稳定性,热失重5 %时,分解温度在400℃以上;在光激发的条件下,聚合物在二氯甲烷溶液中发射蓝光.     

螺二芴基可溶性共聚物的合成及发光性能

以9,9'-螺二芴和不同链长的二烷氧基苯为单体, 以FeCl3为催化剂, 采用化学氧化法合成了一系列聚合物发光材料. 溶解度测试表明, 共聚物在二氯甲烷、四氢呋喃(THF)、氯仿等极性溶剂中具有良好的溶解性. 利用核磁共振氢谱(1H NMR)、傅里叶变换红外(FT-IR)光谱、紫外-可见(UV-Vis)光谱和荧光(PL)光谱研究了共聚物的化学结构和发光性能, 结果表明共聚物在二甲基亚砜(DMSO)中均发射蓝色荧光, 最大吸收和荧光发射峰分别为356和413 nm. 以硫酸奎宁溶液作为参比, 测得共聚物的荧光量子效率为0.69至0.77. 通过循环伏安法(CV)测得所合成的三种共聚物的最高占有分子轨道(HOMO)能级均位于-5.85至-5.69 eV之间.     

9-戊基咔唑-3,6-双-(炔苯基-4-甲酸乙酯)的合成与双光子特性研究

采用钯催化的碳碳偶合反应合成了9-戊基咔唑-3,6-双-(炔苯基-4-甲酸乙酯)(I).进一步研究了化合物I在四氢呋喃和40%四氢呋喃水溶液中的光物理性质,结果显示,化合物I在40%四氢呋喃水溶液中的紫外吸收峰位置与其四氢呋喃溶液相比没有发生明显移动,它在40%四氢呋喃水溶液中的单光子荧光发射峰出现在453 nm,较其在四氢呋喃溶液的发射有42 nm红移,其荧光量子效率为0.44.用波长为660 nm飞秒激光激发时,化合物I在40%四氢呋喃水溶液中的双光子荧光发射最大峰红移至489 nm,其双光子吸收截面值为251GM,比其在四氢呋喃溶液中的截面(151 GM)增强了60%.     

α，ω-二羧基-甲基丙烯酸丁酯低聚物的合成及MS分析

利用传统自由基聚合法，在四氢呋喃溶液中自由基引发聚合甲基丙烯酸丁酯单体而得到ω-羧基-甲基丙烯酸丁酯低聚物(CTBMA)(分子量在1500左右)；利用CTBMA末端酯基的反应特性，在二氧六环／水／KOH混合溶液中皂化CTBMA，使之转化为α，ω-羧基甲基丙烯酸丁酯低聚物(di-CTBMA)；研究了溶剂的类别、反应时间等反应条件对皂化产物结构的影响；利用MALDI-TOF-MS及LSIMS对皂化各阶段产物进行了分析监测．实验表明，在适当的皂化条件下，CTBMA皂化时主要为末端酯基转化为羧基，相应得到的产物di-CTMBA具有很好的结构特性，其官能团度(functionality)接近2．     

水溶性荧光共轭聚合物MPS-PPV的聚合新方法及其荧光波长调控的研究

在NaOH/C2H5OH/DMF溶液中,实现了水溶性阴离子荧光共轭聚合物聚-[5-甲氧基-2-(3-磺酰化丙氧基)-1,4-苯撑乙烯](MPS-PPV)单体的快速聚合并提高了聚合产率。通过改变溶液中NaOH的浓度,实现了对聚合物荧光发射波长的调控。对聚合物进行了元素分析、红外光谱以及分子量的表征,并探讨了不同聚合条件下得到的MPS-PPV的荧光和紫外光谱变化。研究了过氧化氢对MPS-PPV荧光的影响,为基于荧光聚合物的新型传感器的研制提供了新思路。     

a,ω-二羧基-甲基丙烯酸丁酯低聚物的合成及MS分析

利用传统自由基聚合法,在四氢呋喃溶液中自由基引发聚合甲基丙烯酸丁酯单体而得到ω-羧基-甲基丙烯酸丁酯低聚物(CTBMA)(分子量在1500左右);利用CTBMA末端酯基的反应特性,在二氧六环/水/KOH混合溶液中皂化CTBMA,使之转化为α,ω-羧基甲基丙烯酸丁酯低聚物(di-CTBMA);研究了溶剂的类别、反应时间等反应条件对皂化产物结构的影响;利用MALDI-TOF-MS及LSIMS对皂化各阶段产物进行了分析监测.实验表明,在适当的皂化条件下,CTBMA皂化时主要为末端酯基转化为羧基,相应得到的产物di-CTMBA具有很好的结构特性,其官能团度(functionality)接近2.     

间位聚亚吡啶基亚乙炔基共轭聚电解质的合成与溶液光物理性质

合成了单体1,4-双(3-磺酰化丙氧基)-2,5-二碘苯与2,6-二乙炔基吡啶,利用Heck-Sonogashira偶联反应制备了间位聚亚吡啶基亚乙炔基共轭聚电解质m-PPYPE-SO3Na,对单体以及聚合物进行了红外光谱与核磁氢谱表征.测试了该共轭聚电解质m-PPYPE-SO3Na的紫外-可见吸收光谱与荧光发射光谱.研究了该共轭聚电解质的溶液光物理性质,发现该聚电解质具有荧光发射的溶剂依赖性以及浓度依赖性,在水溶液中存在聚集.在聚合物溶液浓度为1×10-6mol/L左右时,聚集发射基本消失,说明此时在溶液中聚合物的聚集程度已经比较低.该聚电解质在水溶液中与表面活性剂之间存在一定的相互作用,加入非离子型高分子表面活性剂聚乙烯吡咯烷酮(PVP)的聚合物水溶液荧光显著增强,表明该表面活性剂破坏聚电解质的聚集.该共轭聚电解质的溶液光物理性质表明其具有成为水溶性荧光探针的应用潜力.     

旋光聚[乙烯-alt-R-N-(1-苯乙基)马来酰胺酸]的合成及静电自组装

以聚(乙烯-alt-马来酸酐)为原料,通过与R-(+)-α-苯乙胺的酰胺化反应,合成了一种新型的旋光聚电解质聚[乙烯-alt-R-N-(1-苯乙基)马来酰胺酸],利用红外吸收光谱、紫外吸收光谱、核磁共振氢谱和旋光度数据对其结构进行表征.聚[乙烯-alt-R-N-(1-苯乙基)马来酰胺酸]与聚二甲基二烯丙基氯化铵(PDDA)逐层静电自组装过程的紫外跟踪测试结果表明,带相反电荷的聚电解质间能够形成稳定增长的自组装膜,多层膜组装量随双层数指数增大.     

N,N′-二-(2-吡啶基)苝四羧酸二酰亚胺的合成及性能研究

合成了N,N′ 二 (2 吡啶基)四羧酸二酰亚胺,并纯化、调晶.对产物进行了元素分析和IR光谱研究(环状二酰亚胺的CO以双峰1708.8cm-1、1664 5cm-1).α晶型产物溶液的紫外可见光谱(最大吸收波长为526.00nm)和荧光光谱(最大发射波长为538.0nm)存在很好的镜像对称关系.薄膜紫外可见光谱图在450—570nm范围内,α晶型比β晶型有较强的吸收峰.X粉末衍射也反映出α晶型在2θ为25.5°、26.3°上的衍射峰强度分别为1954、2603.α、β晶型分别作为电荷产生材料制得的功能分离型有机光导体,在光源波长λ=532nm曝光下,测得含α的感光体达到饱和电位的时间45s、半衰曝光量5.7μJ/cm2、残余电位22V等数据.测得含β的感光体达到饱和电位的时间49s、半衰曝光量9.9μJ/cm2、残余电位22V等性能数值.     

Polymerization of coordinated monomers. IX. Charge-transfer spectrum of the system composed of metal halide,polar vinyl monomer,and electron-donating monomer

The 1:2 stannic chloride–methyl methacrylate complex, the 1:2 stannic chloride–acrylonitrile complex, the ethylaluminum dichloride–methyl methacrylate complex, and the ethylaluminum dichloride–acrylonitrile complex exhibit charge-transfer absorption bands in the wavelength region longer than 300 nm with electron-donating compounds such as mesitylene, styrene, toluene, and butadiene. The absorption spectrum of the mixture of either methyl methacrylate or acrylonitrile with the electron-donating compound is, however, a superpostion of the spectra of the components without any additional absorption. Methyl isobutylate, 3-butenyl methyl ketone, and propionitrile show no charge-transfer absorption bands with the electron-donating compound, even in the presence of a metal halide. Both the presence of the C-C double bond conjugating with the polar group and the coordination of the polar group to a metal halide are essential for an electron-accepting monomer to exhibit a charge-transfer absorption with the electron-donating compound. Continuous variation plots with the use of the charge-transfer band definitely show a 1:1 interaction between the methyl methacrylate coordinated to stannic chloride and styrene, resulting in the determination of the equilibrium constants for the charge-transfer complex formation in methylene chloride: 0.21 l./mole at 25°C and 0.67 l./mole at ?50°C. The charge-transfer absorption is attributed to a ternary molecular complex composed of a metal halide, a polar vinyl monomer, and an electron-donating monomer.     

脉冲激光法连续制备纳米钴乙醇溶胶的研究

纳米钴因其优异的磁性能在磁记录材料 [1]、超顺磁材料 [2 ]、巨磁材料 [3 ]和雷达吸波 [4 ]方面具有重要应用 .金属钴有面心立方、密排六方和非晶态 3种结构 [5] .目前 ,用等离子加热及碳电弧法制备的纳米钴粉基本上都是面心立方结构 [6] .Gibson等 [7]用超声化学方法获得了密     

Vibronic line shapes of PTCDA oligomers in helium nanodroplets

Oligomers of the organic semiconductor 3,4,9,10-perylene-tetracarboxylic-dianhydride, C(24)H(8)O(6) (PTCDA) are studied by means of helium nanodroplet isolation spectroscopy. In contrast to the monomer absorption spectrum, which exhibits clearly separated, very sharp absorption lines, it is found that the oligomer spectrum consists of three main peaks having an apparent width orders of magnitude larger than the width of the monomer lines. Using a simple theoretical model for the oligomer, in which a Frenkel exciton couples to internal vibrational modes of the monomers, these experimental findings are nicely reproduced. The three peaks present in the oligomer spectrum can already be obtained taking only one effective vibrational mode of the PTCDA molecule into account. The inclusion of more vibrational modes leads to quasicontinuous spectra, resembling the broad oligomer spectra.     

MMA/MAh共聚物的合成及其凝胶聚合物电解质性能

从聚甲基丙烯酸甲酯型凝胶聚合物电解质存在的问题出发,设计制备一种甲基丙烯酸甲酯/共聚马来酸酐型凝胶聚合物电解质.采用溶液聚合法,以偶氮二异丁腈(AIBN)为引发剂,甲基丙烯酸甲酯(MMA)、顺丁烯二酸酐(MAh)为单体,其MMA与MAh单体摩尔配比为1∶1,合成了P(MMA-co-MAh)共聚物;采用凝胶色谱(GPC)、傅立叶红外光谱(FTIR)、核磁共振(MNR)、示差扫描量热法(DSC)、热失重分析(TGA)、X-射线衍射分析(XRD)对所合成共聚物的结构进行了表征.结果表明,合成的共聚物为无规非晶型聚合物,其数均分子量Mn为6.40×104,共聚物中MMA与MAh链段摩尔比大约为8∶1,热分解温度为300℃,玻璃化转变温度(Tg)为121.3℃.以P(MMA-co-MAh)共聚物为树脂基体,环状碳酸1,2-丙二酯(PC)为增塑剂,LiClO4为电解质盐,制备了凝胶聚合物电解质(GPE),当共聚物含量为45 wt%时,GPE具有好的成膜性,其室温离子电导率为3.0×10-5S/cm.     

Interaction of phospholipids with rhodamine 6G in toluene.

Upon interaction of various glycerophospholipids with Rhodamine 6G in toluene, a typical difference spectrum with an absorption maximum at approximately 515 nm is obtained . This spectrum is obtained with phosphatidylcholine only after treatment with NaCl, which presumably weakens intra- and/or inter-molecular electrostatic binding between the negatively charged phosphate moiety and the protonated nitrogen in this molecule. Absorption at 515 nm was linear for all of the phospholipids investigated from a concentration of approximately 1.2 microM up to at least 50 microM. The highest extinction coefficient was obtained for diphosphatidylglycerol (251 mM-1 cm-1) and all of the compounds tested, with the exception of phosphatidylethanolamine, demonstrated extinction coefficients higher than that of palmitic acid. Thus, the absorption spectrum which results from the interaction of purified glycerophospholipids with Rhodamine 6G in organic solvent is a sensitive measure of the amount of phospholipid present.     

Nanostructured Hybrid Systems with Rhodamine 6G

We synthesized hybrid materials by sol-gel process, using: methyltriethoxysilane, tetraetylorthosilicate and vinyltriethoxysilane, in the presence of Rhodamine 6G. It was synthesized as well organic-inorganic hybrids with addition of tetraisopropyl orthotitanate and maleic anhydride UV-VIS spectra of dye show two absorption peaks at 499 nm (dimer) and 530 nm (monomer). Evaluating FTIR spectra of hybrid films, it was observed a band at 1077 cm^?1, characteristic of the asymmetric Si-O-Si stretching vibration in oligomer. Fluorescence spectra show that tetraisopropyl orthotitanate presence in the composites modifies the nature of the inorganic matrix and affects the interaction with the added dye.     

A MORPHOLOGICAL STUDY OF POLY（DIVINYLBENZENE-co-ACRYLIC ACID） IN CROSSLINKING PRECIPITATION POLYMERIZATION

Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.     

Research on successive preparation of nano-FeNi alloy and its ethanol sol by pulsed laser ablation

Since Ogale et al.[1,2] firstly prepared metastable matter by pulsed laser ablation at the solid target sub-merged in liquid, there has been a great interest in it. Tokura et al.[3] prepared carbon films in the water by pulsed laser ablation. Zheng et al.[4—6] prepared nano and cluster matters with different shapes through pulsed laser ablation at interface of liquid and solid target. Yang et al.[7,8] prepared cube nano-nitride boron crystalloid and nano-diamond crystalloid with the same meth…