3-次甲基（4-丁氧基苯胺）噻吩与吡啶、3-丁基噻吩共聚物的金属配合物催化法合成及性能

通过Schiff-base法合成了侧链含席夫碱的新型噻吩单体2,5-二溴-3-次甲基（4-丁氧基苯胺）噻吩,用Ni（Ⅱ）催化剂[二氯-1,3-双（二苯基磷）丙烷基镍（Ⅱ）]合成了新型共轭共聚物聚[3-次甲基（4-丁氧基苯胺）噻吩-共-3-丁基噻吩]（共聚物Ⅰ）和聚[3-次甲基（4-丁氧基苯胺）噻吩-共-吡啶]（共聚物Ⅱ）。采用FT-IR、1H-NMR对2种共聚物的化学结构进行了表征,利用UV-Vis、PL、循环伏安等测试方法对其进行光、电性能测试。结果表明：共聚物在氯仿溶液中发黄绿光,共聚物Ⅰ和共聚物Ⅱ的最大发射峰分别位于540 nm和516 nm,该类共聚物均具有一定的电化学活性。     

甲苯、2-甲基噻吩和3-甲基噻吩的化学分离方法研究

报道了一种分离甲苯、2-甲基噻吩和3-甲基噻吩的方法。通过氯化反应将沸点非常接近的甲苯、2-甲基噻吩和3-甲基噻吩转化为沸点相差较大的甲苯(111℃)、2-氯-5-甲基噻吩(155℃)和2,5-二氯-3-甲基噻吩(185℃),通过对比实验获得氯代反应的最佳条件为:2-甲基噻吩和3-甲基噻吩与磺酰氯的投料比1∶1. 75,反应温度65℃,反应时间2 h。通过精馏将三者分离并提纯,得到甲苯、高附加值的2-氯-5-甲基噻吩和2,5-二氯-3-甲基噻吩产品;通过催化还原反应将2-氯-5-甲基噻吩和2,5-二氯-3-甲基噻吩分别还原为2-甲基噻吩和3-甲基噻吩,达到完全分离、提纯的目的。     

相转移催化法合成2-氯-3-氯甲基-噻吩及噻康唑

相转移催化法合成2-氯-3-氯甲基-噻吩及噻康唑;相转移催化;氯氯甲基噻吩;氯甲基化;噻康唑     

导电聚合物的现场电导/电化学研究——聚(3-甲基噻吩)和聚噻吩

本文提出一种研究导电聚合物的现场电位、电导测量/电化学方法。该实验方法基于一种可重复使用的玻璃碳-碳纤维组双电极。用该方法研究了聚(3-甲基噻吩)和聚噻吩的现场电位、电导/电化学行为。     

对苯二胺类与2,2′-二噻吩共轭共聚物的金属催化法合成与表征

以1,3-二(二苯基膦)丙烷二氯化镍(Ⅱ)作为催化剂,分别合成了2,2′-二噻吩与N,N′-二氯对苯醌二亚胺和2,5-二甲基-N,N′-二氯对苯醌二亚胺的共轭交替共聚物:聚(N,N′-对苯醌二亚胺-2,2′-二噻吩)和聚(2,5-二甲基-N,N′-对苯醌二亚胺-2,2′-二噻吩)。利用红外光谱、紫外可见光谱、循环伏安等测试方法对这2种共聚物进行了表征和性能研究。结果表明:这2种共聚物分别在263、315、410、261、3214、03 nm处出现了紫外吸收峰,对苯二胺上的甲基对共聚物电化学活性具有一定的影响。     

聚(3-甲基噻吩)的电化学稳定性及电催化行为

用连续循环伏安法研究了电化学法制备的聚(3-甲基噻吩)(PMT)薄膜修饰玻璃碳电极在不同支持电解质溶液中的电化学稳定性。在易嵌入PMT的阴离子存在下, PMT电活性随扫描次数按表现二级反应降低; 在难嵌入PMT的离子存在下, PMT具有良好稳定性; 在含有氯、溴离子的水溶液中, PMT可将卤离子电催化氧化, 并引起PMT电活性迅速下降。光电子能谱分析表明氯已键合到PMT结构上。     

烃基-3-噻吩硫醚的合成

噻吩与溴、锌粉依次发生取代,还原反应生成3-溴噻吩。在-70℃,3-溴噻吩与n-丁基锂反应后,再依次加入硫粉、卤代烃,在常温下分别反应1．5、2．5、2．5、3、3和3．5 h,分别合成甲基-3-噻吩硫醚、乙基-3-噻吩硫醚、丙基-3-噻吩硫醚、丁基-3-噻吩硫醚、烯丙基-3-噻吩硫醚和异丙基-3-噻吩硫醚,收率分别为82％、74％、71％、70％、73%和49％。这些化合物结构都通过IR、1H NMR、13C NMR和MS测试技术进行了表征,并对其进行了初步香味评价。结果表明,它们都具有肉香味的特征。     

1-对硝基苯基-3-甲基-4-(α-噻吩甲酰基)-5-吡唑啉酮的合成

对硝基苯肼与乙酰乙酸乙酯经亲核闭环制得1-对硝基苯基-3-甲基-5-吡唑啉酮(1);1与α-噻吩甲酰氯进行克莱森缩合合成了新化合物——1-对硝基苯基-3-甲基-4-(α-噻吩甲酰基)-5-吡唑啉酮,其结构经1H NMR,13C NMR,IR,MS和元素分析表征。     

纳米结构TiO2/3-甲基噻吩和2-噻吩甲酸共聚物复合膜电极光电化学性能

用光电流作用谱、光电流-电势图等光电化学方法研究了ITO/3-甲基噻吩和2-噻吩甲酸共聚物(CTCMT)膜电极和ITO/TiO₂/CTCMT复合膜电极的光电转换性质.结果表明,CTCMT膜为p型半导体,禁带宽度为2.36eV,价带位置为-5.52eV.在ITO/TiO₂/CTCMT复合膜电极中存在p-n异质结,在一定条件下异质结的存在有利于光生电子-空穴对的分离.CTCMT膜修饰ITO/TiO₂电极可使光电流增强,光电流起始波长红移至600nm以上,使宽禁带半导体电极的光电转换效率得到改善.     

3-烷基噻吩交替共聚物的合成及其电化学性质

通过Heck偶联法合成了4种3-烷基噻吩交替共聚物:聚(2,4-二乙烯基-3-己基噻吩-1,3,4-二唑)(P3HT-OXD)、聚(2,4-二乙烯基-3-辛基噻吩-1,3,4-二唑)(P3OT-OXD)、聚(2,4-二乙烯基-3-己基噻吩-吡啶)(P3HT-Py)和聚(2,4-二乙烯基-3-辛基噻吩-吡啶)(P3OT-Py). 用NMR、GPC等测试技术对其结构进行了表征. 采用循环伏安法、紫外-可见吸收光谱法研究了系列共聚物光电性能. 结果表明,随噻吩环3位取代烷基碳链的增长,聚合物电离能(Ip)减小,带隙(Eg)也随之变窄. 其中,P3OT-OXD的Eg比P3HT-OXD小0.11 eV,P3OT-Py的Eg比P3HT-Py小0.19 eV,在3-烷基噻吩聚合物主链上引入吸电子能力较强的二唑单元,可有效提高共聚物电子亲合能(Ea),对提高电子传输能力,改善电子与空穴注入平衡有积极作用.     

Spectroelectrochemistry of intrinsically conducting furan-3-chlorothiophene copolymers

Electrochemical copolymerization of furan and 3-chlorothiophene was performed at constant electrode potential in a binary solvent system consisting of boron trifluoride diethyl etherate + ethyl ether (BFEE + EE; ratio 1:2) and trifluoroacetic acid (10% by volume). The homopolymers and copolymers obtained were studied with cyclic voltammetry, in situ ultraviolet–visible spectroscopy, in situ resonance Raman spectroscopy, and in situ conductivity measurements. The spectroelectrochemical properties of the copolymers show intermediate features between polyfuran and poly(3-chlorothiophene). The conductivity changes of homo- and copolymer films are almost completely reversible when the potential shift direction is reversed.

Properties of poly(3-halidethiophene)s

The influence of the halogen atom on the intrinsic properties of poly(3-halidethiophene)s has been investigated using experimental and theoretical methodologies. Specifically, the electrochemical, electrical, electronic and morphological properties of poly(3-bromothiophene) have been determined and compared with those recently reported for poly(3-chlorothiophene) [Aradilla et al., Polym. Chem., 2012, 3, 436.]. The electrochemical stability and porosity are smaller for poly(3-bromothiophene) than for poly(3-chlorothiophene) while the π-π* lowest transition energy is higher for the former than for the latter. Moreover, quantum mechanical calculations on model oligomers have evidenced that the conformational properties of poly(3-halidethiophene)s, where the halogen is fluorine, chloride or bromine, are dominated by steric interactions and, therefore, are significantly influenced by the size of the halogen atoms. Both the ionization potential and the π-π* lowest transition energy have been predicted to increase slightly when the π-donor character of the halogen atom decreases, in agreement with experimental observations.     

Synthesis of cationic hyperbranched multiarm copolymer and its application in self-reducing and stabilizing gold nanoparticles

A novel hyperbranched multiarm copolymer of HBPO-star-PDEAEMA with a hydrophobic poly(3-ethyl-3-(hydroxymethyl) oxetane)(HBPO) core and many cationic poly(2-(N,N-diethylamino) ethyl methacrylate)(PDEAEMA) arms has been synthesized through an atom transfer radical polymerization(ATRP) method,and been applied to spontaneously reduce and stabilize gold nanoparticles(AuNPs) in water without other additional agents.The size of the nanoparticles could be effectively controlled at about 4 nm,and the nanoparticles ...     

聚丙烯酸锂与1-丁基-3-甲基咪唑溴离子液体的阳离子交换反应

通过聚丙烯酸锂(PAALi)与1-丁基-3-甲基咪唑溴(BmimBr)离子液体进行阳离子交换, 将1-丁基-3-甲基咪唑阳离子引入到聚丙烯酸锂结构中, 形成了丙烯酸锂(AALi)与1-丁基-3-甲基咪唑丙烯酸盐(BmimAA)离子液体的无规共聚物[P(AALi-BmimAA)]. 研究了反应时间、温度、投料比、反应物浓度及聚丙烯酸锂分子量等对离子交换程度的影响. 对不同离子交换程度时聚合物电导率的研究结果表明, 所有共聚物的电导率均比聚丙烯酸锂的有明显提高, 并且随着阳离子交换程度的增加, 电导率出现极值. 在聚丙烯酸锂的15%水溶液中, 当Bmim+与Li+的投料摩尔比为1∶1时, 在80 ℃下交换反应24 h, 得到的共聚物的Bmim+与Li+摩尔比为0.0387, 其电导率最高, 为1.44×10-8 S/cm, 比聚丙烯酸锂的电导率(1.06×10-11 S/cm)提高了3个数量级. 向此共聚物中掺杂LiTFSI, 电导率再次提高2个数量级, 最高可达2.90×10-6 S/cm.     

ATRP法合成两亲性嵌段共聚物PSt-b-PAA及其在离子液体[BMIM][PF6]中的自组装行为研究

利用原子转移自由基聚合法(ATRP)合成了分子量可控、分子量分布窄的嵌段共聚物聚苯乙烯-b-聚丙烯酸叔丁酯(PSt-b-PtBA), 进而在酸性条件下由水解反应得到了两亲性嵌段共聚物聚苯乙烯-b-聚丙烯酸(PSt-b-PAA), 并通过凝胶渗透色谱(GPC)、傅立叶变换红外光谱(FTIR)、核磁共振(1H NMR)等测试手段对产物进行了表征. 使三种分子量不同的两亲性嵌段共聚物在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM][PF6])中进行自组装, 通过激光粒度分析仪(DLS)和透射电子显微镜(TEM)研究了聚合物在离子液体中自组装的胶束尺寸和结构形态. 当PSt的链段长度一定时, 胶束的形状主要依赖于PAA链的长度. 当PAA链段较长时, 胶束呈球形; 当PAA链段较短时, 则变成不规则的花生状胶束.     

3D inverted opal hydrogel scaffolds with oxygen sensing capability

The measurement of local oxygen level in 3D cell culture is desired but remains as a challenge problem. We developed a 3D cell scaffold with luminescence-based oxygen sensing capability that opens the possibility of 3D mapping of oxygen level during cell growth. Hydrogel inverted opal scaffold was prepared by photo-polymerization of poly(2-hydroxyethyl methacrylate (pHEMA) and poly(methacryloyloxy)ethyl-trimethylammonium chloride (pMEATAC) monomer using close-packed bead assembly as template. Tris(4,7-diphenyl-1,10-phenanthroline)ruthenium chloride (Ru(dpp)(3)), was coated on the pHEMA-pMEATAC 3D scaffolds by layer-by-layer (LBL) assembly. pHEMA-pMEATAC copolymer was coated on top of the Ru(dpp)(3) layer as a protection layer. The fluorescence emission of Ru(dpp)(3) can be dynamically quenched by oxygen. By measuring the emission intensity of the scaffold, the local oxygen level can be monitored. The hydrogel scaffolds are transparent, and thus 3D fluorescence intensity can be mapped by confocal microscopy. Human bone marrow stromal cells HS-5 were successfully cultured on the oxygen sensing scaffold, and the observed Ru(dpp)(3) emission intensity from the scaffold was stronger in cell rich area, which indicates a lower oxygen level due to the consumption of the cells.     

磷酸钙骨水泥/聚肽共聚物生物复合材料力学性能及微观结构

磷酸钙骨水(Calcium Phosphate Cement,CPC)是一种新型的人工骨材料,可用于人体骨缺损的修复,具有良好的生物相容性、骨传导性和骨替代性．然而,磷酸钙骨水泥的抗压强度较低,脆性较大,限制了其应用,因而提高抗压强度和减小其脆性成为CPC研究领域的一个重要课题．目前,普遍采用添加纤维的方法来提高CPC材料的抗压强度和韧性．然而大多数的纤维是非降解性的．     

Effect of SDS on the self-assembly behavior of the PEO-PPO-PEO triblock copolymer (EO)20(PO)70(EO)20

The mixed micellar system comprising the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-based triblock copolymer (EO)(20)(PO)(70)(EO)(20) (P123) and the anionic surfactant sodium dodecyl sulfate (SDS) has been investigated in aqueous media by small-angle neutron scattering (SANS) and viscosity measurements. The aggregation number of the copolymer in the micelles decreases upon addition of SDS, but a simultaneous enhancement in the degree of micellar hydration leads to a significant increase in the micellar volume fraction at a fixed copolymer concentration. This enhancement in the micellar hydration leads to a marked increase in the stability of the micellar gel phase until it is destroyed at very high SDS concentration. Mixed micellar systems with low and intermediate SDS concentrations form the micellar gel phase in much wider temperature and copolymer concentration ranges than the pure copolymer micellar solution. A comparison of the observed results with those for the copolymers (EO)(26)(PO)(40)(EO)(26) (P85) and (EO)(99)(PO)(70)(EO)(99) (F127) suggests that the composition of the copolymers plays a significant role in determining the influence of SDS on the gelation characteristics of the aqueous copolymer solutions. Copolymers with high PO/EO ratios show an enhancement in the stability of the gel phase, whereas copolymers with low PO/EO ratios show a deterioration of the same in the presence of SDS.     

Supramolecular self-assembly and controllable drug release of thermosensitive hyperbranched multiarm copolymers

A novel temperature-responsive hyperbranched multiarm copolymer with a hydrophobic hyperbranched poly(3-ethyl-3-(hydroxymethyl)oxetane)(HBPO) core and thermosensitive poly(N-isopropylacrylamide)(PNIPAM) arms was synthesized via the atom transfer radical polymerization(ATRP) of NIPAM monomers from a hyperbranched HBPO macroinitiator.It was found that HBPO-star-PNIPAM self-assembled into multimolecular micelles(around 60 nm) in water at room temperature according to pyrene probe fluorescence spectrometry,1H N...     

Synthesis of a triblock copolymer: Poly(ethylene glycol)‐poly(alkylene phosphate)‐poly(ethylene glycol) as a modifier of CaCO3 crystallization

Triblock copolymer poly(ethylene glycol)‐poly(alkylene phosphate)‐poly(ethylene glycol) was prepared by first reacting hexamethylene glycol with dimethyl‐H‐phosphonate at conditions of transesterification and then replacing the CH₃OP(O)(H)O‐… end‐groups by monomethyl ether of poly(ethylene glycol). The course of reaction was studied by ³¹P NMR indicating complete conversion. After oxidation the poly(alkylene H‐phosphonate was converted into the final triblock polyphosphate. This triblock copolymer was used as a modifier of CaCO₃ crystallization. Unusual semi open empty spheres resulted, composed of small crystallites of the size (diameter) equal to 40–90 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 650–657, 2005