静电纺丝法制备聚丙烯腈/聚苯胺复合纳米纤维及其表征

利用静电纺丝技术,以聚丙烯腈(PAN)和苯胺(ANI)为前驱物,用过硫酸胺(APS)溶液在低温下缓慢氧化聚合,制备了PAN/PANI复合纳米纤维,直径约500 nm.通过扫描电子显微镜(SEM)、红外光谱(FTIR)、X射线衍射(XRD)和激光拉曼(RAMAN)光谱仪等测试手段对材料的形貌和结构进行了表征.探讨了材料制备过程中影响纤维形貌、尺寸、均匀度的因素和PANI含量对复合纤维导电性能的影响,结果表明,PAN浓度、ANI的加入量和电压是影响纤维特性的主要因素;PANI在PAN基体中呈纳米尺寸分布,复合纳米纤维具有良好的导电性能,导电率可达10-2S/cm.     

静电纺丝制备Tb-PEG+Eu-PEG/PANI/PAN荧光导电相变三功能复合纤维

以聚丙烯腈(PAN)为载体基质、 以铕-聚乙二醇(Eu-PEG)和铽-聚乙二醇(Tb-PEG)为相变荧光材料, 加入掺杂的导电聚苯胺(PANI), 采用静电纺丝技术制得Tb-PEG+Eu-PEG/PANI/PAN复合纤维. 采用扫描电子显微镜(SEM)、 荧光光谱(FL) 仪、 差示扫描量热(DSC)仪及宽频介电松驰谱(BDS)仪等方法对相变荧光导电复合纤维的性能进行分析. 研究结果表明, 复合纤维具备良好的荧光、 相变及导电性能. 在294 nm紫外光激发下, 通过调节Tb-PEG和Eu-PEG的质量比可调节复合纤维的发光强度和颜色, 同时复合纤维的相变温度在5467 ℃之间. 复合纤维的电导率达到10^-6 S/cm, 随着PANI含量的增加, 电导率和介电常数增加. 通过调节Tb-PEG, Eu-PEG和PANI的比例及PEG的分子量, 可以实现复合纤维荧光、 导电及相变性能的可控调整.     

聚乳酸/聚苯胺/富勒烯静电纺丝纤维的制备与表征

以富勒烯C_(60)作为聚苯胺的导电掺杂剂,采用乳液聚合-复合法制备了聚乳酸/聚苯胺/富勒烯复合体系(PLA81/PANI14/C_(60)5),并对其结构和性能进行了表征与理论分析.通过静电纺丝-编织法制备了PLA/PANI/C_(60)导电纤维管.利用555定时器原理设计自制了多谐振荡信号的电刺激装置,将其用于导电纤维管的细胞培养,以考察电刺激作用下导电纤维管上成骨细胞的生长和增殖情况.结果表明,PLA/PANI/C_(60)薄片的电阻率为104Ω·cm数量级;C_(60)能够促进苯胺乳液聚合的链增长,提高聚苯胺产物的聚合度;PLA/PANI/C_(60)纤维管形貌规整,具有良好的亲水性;在18μA/1 Hz/500 ms电刺激的作用下,PLA/PANI/C_(60)纤维对成骨细胞的生长具有明显的促进作用.加载适当电流电刺激能够加强生长因子对成骨细胞的分化作用,有利于促进成骨细胞的生长和繁殖.     

静电纺丝制备荧光导电双功能复合纳米纤维及其表征

采用静电纺丝技术将导电聚苯胺(PANI)和铕/铽稀土配合物掺杂到高分子基质聚乙烯吡咯烷酮(PVP)中,制备出荧光导电复合纳米纤维。用扫描电镜(SEM)、荧光光谱仪(FL)、宽频介电松驰谱仪对荧光导电复合纳米纤维的性能进行分析,结果显示,在270nm紫外光激发下,铕系列与铽系列复合纳米纤维分别发出红光和绿光。同时,复合纳米纤维的电导率可以达到1.18×10~(-6) S/cm,两种复合纳米纤维同时具有优异的荧光性能及良好的导电功能。     

聚苯胺表面修饰芳纶浆粕及其纸基材料的导电性能

通过在芳纶浆粕(AP)表面修饰聚苯胺(PANI)制备了聚苯胺-芳纶浆粕(PANI-AP), 然后与碳纤维(CF)共混, 采用湿法抄纸技术制备导电性能优异的纸基材料(PANI-AP/CP). 对其形貌结构、 导电性能及PANI分布均匀性进行了表征, 并研究了环境湿度、 温度、 pH值及放置时间对PANI-AP/CP导电性能的影响. 研究结果表明, PANI-AP表面粗糙度增加, 结晶度增加, 出现含醌式结构的导电PANI的衍射峰, 说明PANI成功修饰于AP表面. 采用该方法制备的PANI-AP/CP导电性能与分布均匀性均得到提高, 相对于碳纤维纸基材(CP), PANI-AP/CP的电导率为3.937 S/cm, 导电性能提高153.5%. 与PANI原位生长于CP(AP/CP-PANI)相比, PANI-AP/CP的导电性能提高34.6%, 总色差值(DE)降低74.9%.     

含水状态对细菌纤维素/聚苯胺复合凝胶膜制备及性能的影响

以不同含水量细菌纤维素为模板,苯胺单体为原料原位聚合生成聚苯胺,制备出不同含水量细菌纤维素/聚苯胺(HBC/PANI、LBC/PANI及DBC/PANI)复合凝胶膜,系统研究了细菌纤维素凝胶膜含水量和反应时间对苯胺原位聚合以及复合凝胶膜微观形貌、电学性能和力学性能的影响.扫描电镜照片表明聚苯胺均匀包覆在BC纤维上形成导电网络结构;四探针测试表明聚合时间90 min时导电率最高;低含水量加快了聚合反应速度,提高了复合凝胶膜的电导率,而完全干燥则使电导率降低;交流阻抗测试也表明低含水量可以明显提高材料的离子导电性;力学性能测试结果表明了BC/PANI复合凝胶膜具有良好的机械性能,抗拉强度可达0.21 MPa,同时低含水量不会降低复合凝胶膜的力学性能.     

高导热氮化硼/芳纶沉析复合薄膜的制备及性能

利用多巴胺(DA)的氧化自聚合特性, 对六方氮化硼(h-BN)进行表面修饰, 并以多巴胺改性后的氮化硼(h-BN@PDA)为导热填料, 对基体芳纶沉析纤维(AF)进行填充, 通过真空辅助抽滤法制备多巴胺改性氮化硼/芳纶沉析(h-BN@PDA/AF)复合薄膜, 并对其微观形貌、 表面官能团、 导热性能、 绝缘性能及力学性能进行研究. 结果表明, 聚多巴胺(PDA)包覆在h-BN表面, 并引入活性基团, 与AF纤维产生氢键, 改善了两者的界面结合, 显著提高了复合薄膜导热性能及绝缘性能. 当h-BN@PDA含量为70%时, h-BN@PDA/AF复合薄膜的导热系数为1.36 W/(m·K), 与纯芳纶沉析薄膜相比, 导热系数的增幅约为697.65%, 体积电阻率为5.96×10 ¹⁴ Ω·m, 拉伸模量高达287.19 MPa.     

硬脂酸改性β-TCP的分析测定及其PLLA复合纳米纤维膜性能研究

采用硬脂酸对β-磷酸三钙(β-TCP)进行表面改性,并研究了β-TCP与硬脂酸的界面作用,通过透射电子显微镜(TEM)、热重分析仪(TGA)以及X光电子能谱(XPS)对改性前后β-TCP的形貌、热失重和表面基团进行表征;采用静电纺丝法制备不同质量配比的β-TCP/PLLA和改性β-TCP/PLLA复合纳米纤维膜,用扫描电镜(SEM)观察复合膜的形貌,并研究其力学性能。结果表明,硬脂酸包覆在β-TCP表面,改性后的β-TCP具有一定疏水性,硬脂酸的H+可与β-TCP中PO3-4的1个O发生质子化反应形成—OH;硬脂酸改性减轻了β-TCP微粒的团聚,可以得到连续均匀的纤维,改性后的β-TCP/PLLA复合纳米纤维膜的力学性能较改性前有明显提高。     

尺寸可控的聚苯胺复合微球的电纺制备与表征

以十二烷基苯磺酸(DBSA)掺杂的导电聚苯胺与聚乙二醇(PEG)及Fe3O4的混合氯仿溶液,采用静电纺丝(spinning technology)方法制备含Fe3O4纳米颗粒的导电聚苯胺(PANI)/PEG/Fe3O4复合微球.SEM结果表明,电纺所得的PANI/PEG/Fe3O4复合微球结构依赖于PEG聚合物浓度、静...     

原位聚合法制备PANI/PET导电织物及其性能分析

在聚酯纤维基材及其织物表面,原位聚合形成厚度约1~2μm聚苯胺包覆层,制得聚苯胺(PANI)/聚酯(PET)导电织物.PANI层优异的导电性能使之成为有广阔发展前景的柔性电磁屏蔽材料.正交试验分析研究了苯胺单体浓度、氧化剂:苯胺摩尔比、掺杂酸浓度、反应时间对PANI包覆层外观形态、与基体结合牢度以及导电性的影响.实验表明:在经适当前处理的PET基材表面,以苯胺单体浓度为0.25mol/L、氧化剂与苯胺摩尔比为1∶1、掺杂酸浓度0.5 mol/L、反应时间60 min、反应温度为0~20℃时制备的PANI/PET导电织物方阻最小,导电性最好;掺杂酸酸性越强,导电性越好.SEM、FTIR及XRD测试表明涤纶织物表面有均匀连续的聚苯胺膜存在.分析表明聚苯胺分子链中氧化结构与还原结构含量基本相等,说明聚苯胺渗入纤维内部,使纤维无定形区面积增加,结晶度减小.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.