The exchange of chloro and ethoxy groups upon the addition of dimethylchlorosilane to vinyldimethylethoxysilane

The addition of dimethylchlorosilane to vinyldimethylethoxysilane in the presence of chloroplatinic acid yielded 1,2-bis(dimethylchlorosilyl)ethane, 1-(dimethylchlorosilyl)-2-(dimethylethoxysilyl)ethane and 1,2-bis(dimethylethoxysilyl)ethane. The formation of three products is explained on the basis of chloro-ethoxy exchange reactions. Equilibration of the dimethylchlorosilane-vinyldimethylethoxysilane system was investigated using ¹H NMR and gas-liquid chromatography. The equilibrium constants indicated near random behavior for the substituent exchange.     

Preparation of oriented titanium phosphate and tin phosphate/polyaniline hybrid films by electrochemical deposition

The preparation of hybrid films of metal (Ti and Sn) phosphate nanosheets and polyaniline by simultaneous electrophoretic and electrolytic deposition was performed in an acetonitrile solvent. Emeraldine polyaniline was intercalated between the phosphate nanosheets with a monolayer arrangement. The obtained hybrid films were several tens of micrometers in thickness. The ratio of incorporated polyaniline to metal phosphate in the hybrid films reaches to around 0.45 and 0.30 at suitable concentrations of tetrabutylammonium hydroxide (TBAOH). These amounts correspond with occupancy of polyaniline in the interlayer gallery of several tens percent. Fractions of voids in a horizontal direction were around 22 and 1% in titanium phosphate/polyaniline and tin phosphate/polyaniline hybrid films, respectively. Thus, anodic electrodeposition makes it possible to form thick films of intercalation compounds of alpha-titanium and tin phosphates with polyaniline. These hybrid films were examined for redox activity. The cyclic voltammetry results of these films confirmed that the hybrid films have redox activity by polyaniline. For these voltammograms, the maximum current was observed in the tin phosphate/polyaniline hybrid deposited for 15 min. The redox activity of these hybrids possibly depends on the mesoscopic texture of the film, especially on the amount of voids in a horizontal direction.     

层状α-氢型磷酸氢锆混合二氧化硅的交流电导

1 引言无定形和多晶粉末层状α-水合磷酸氢锆是一种固体质子电解质.多晶粉末层状α-水合磷酸氢锆的电导率随结晶度的提高而明显降低,但是其电导表观活化能相同而和结晶度无关.电导主要是由质子沿着微晶的水合表面迁移所致.因此,增大水合表面有可能提高多晶粉末层状α-磷酸氢锆的电导率.α-磷酸氢锆的层状结构由层间的磷氧基形成氢键     

含1,2-双(3,5-二氧哌嗪-1)乙烷和(±)-1,2-双(3,5-二氧哌嗪-1)丙烷低聚物的合成

<正> 将低分子药物或有药理活性的基团,通过高分子化,所得的高分子药物,具有较高的为细胞吞噬或胞饮等活性,并期望它们在体内崩解缓释,与相应的低分子药物相比,可以发挥长效、低毒的优点。 1,2双-(3,5-二氧哌嗪-1)乙烷和(±)1,2双(3,5-二氧哌嗪-1)丙烷,是临床使用     

Tris-(8-hydroxy-quinoline) aluminium/zirconium phosphate: a novel hybrid assembly with strong luminescence and prolonged lifetime

A novel hybrid assembly of tris-(8-hydroxy-quinoline) aluminium intercalated into modified α-zirconium phosphate in aqueous media was fabricated successfully, resulting in the dramatically enhanced greenish-blue-light emission and prolonged excited-state lifetime.     

Synthesis of α,ω-bis-1,5,3-dithiazepanes and their fungicidal properties

A procedure was developed for preparative synthesis of α,ω-bis-1,5,3-dithiazepanes by heterocyclization of aliphatic α,ω-diamines with N,N,N′,N′-tetramethylmethanediamine and 1,2-ethanedithiol. The fungicidal activity of 1,2-bis(1,5,3-dithiazepan-3-yl)ethane and 3,3′-(3,6-dioxaoctane-1,8-diyl)bis-1,5,3-dithiazepane toward microscopic fungi affecting agricultural plants was studied.     

2]pseudorotaxane formation with N-benzylanilinium axles and 24-crown-8 ether wheels

[reaction: see text] As a hybrid of the N,N-dibenzylammonium and 1,2-bis(pyridinium)ethane axles, various N-benzylanilinium cations were investigated as suitable axles for the formation of [2]pseudorotaxanes with the 24-membered crown ethers 24C8 and DB24C8. The effect of electron-donating OCH(3) and electron-withdrawing CF(3) groups on both the anilinium and benzyl aromatic rings was studied. Formation constants and structural details were compared to the [2]pseudorotaxanes formed by the two aforementioned dibenzylammonium and 1,2-bis(pyridinium)ethane axles.     

Facile Fabrication of Monolayered Hollow Submicrospheres of PANI on Surfaces of Modified Polymer Films

Summary: A novel strategy was developed in order to prepare monolayered polyaniline (PANI) submicrospheres on polymer substrates. The strategy involved two main steps, i.e., photografting of acrylate acid (AA) onto the surface of a polypropylene (PP) film, and subsequent oxidative polymerization of aniline on the grafted surface. It was found that the PANI monolayered hollow submicrospheres were immobilized on the surface of the PP film when the molar ratio of AA to aniline was about 1:1.6. A possible formation mechanism of the hollow PANI submicrosphere iss discussed.     

Rhodium-catalyzed α-methylthiolation reaction of unactivated ketones using 1,2-diphenyl-2-methylthio-1-ethanone for the methylthio transfer reagent

In the presence of catalytic amounts of RhH(PPh₃)₄, 1,2-bis(diphenylphosphino)ethane (dppe), and dimethyl disulfide, ketones without α-activating groups were α-methylthiolated with 1,2-diphenyl-2-methylthio-1-ethanone giving α-methylthio ketones. The reaction of unsymmetrical ketones proceeded at the more substituted carbons. The initial formation of kinetic α-methylthiolated products followed by their rearrangement to thermodynamic products was observed in the reaction of α-phenyl ketones. Aldehydes, phenylacetate, and phenylacetonitrile were also α-methylthiolated under these conditions.     

Rhodium-catalyzed organothio exchange reaction of α-organothioketones with disulfides

RhH(PPh(3))(4) and 1,2-bis(diphenylphosphino)ethane (dppe) catalyzed the organothio exchange reaction of α-organothioketones and organic disulfides. The reaction was affected by the structure of the substrate: α-phenylthio and α-alkylthio aryl ketones reacted effectively with diaryl and dialkyl disulfides; α-phenylthio dialkyl ketones reacted with diaryl disulfides but not with dialkyl disulfides; diaryl disulfides with electron-donating p-substituents were more reactive than those with electron-withdrawing p-substituents.     

Branched [n]rotaxanes (n = 2-4) from multiple dibenzo-24-crown-8 ether wheels and 1,2-bis(4,4'-dipyridinium)ethane axles

To investigate the possibility of incorporating the 1,2-bis(pyridinium)ethane[subset or is implied by]24C8 [2]pseudorotaxane motif into dendrimer like macromolecules, a series of branched [n]rotaxanes were prepared employing multiple dibenzo-24-membered crown ether wheels with various aromatic core structures and the 1,2-bis(4,4'-dipyridinium)ethane axle. Yields of branched [2]-, [3]- and [4]rotaxanes were dependent on the size of the core and the relative proximity of the crown ethers arranged around the core unit.     

聚苯胺膜电极在苯胺单体聚合反应中的电催化性能

自从第一个导电高聚物掺碘的聚乙炔问世以来［1］,人们又陆续开发研制了聚 苯胺(PAn)、聚吡咯和聚噻吩等导电高分子材料. 在众多的导电高分子材料中,聚苯胺以其原 料廉价易得,制备方法简便,导电性能优良,耐高温及抗氧化性能良好等优点而成为最具应用 前景的品种之一. 迄今为止,有关聚苯胺的链结构,掺杂反应,以及导电机理等基础理论方面 的研究已有大量的文献和综述报道［2～6］. 这些基础理论的研究为其应用研究奠定 了坚实的基础. 早在60年代,人们就发现,聚苯胺对氧化亚氮分解及丁二烯异构化反应具有独 特的催化作用;同时,聚苯胺具有超出几何表面的活性表面,故可对某些反应具有选择性的催 化作用. 因此,人们开始研究聚苯胺膜电极对某些电极反应的电催化性能［7～12］. 我国科学工作者在这一领域也做了许多有益的工作,如董绍俊等［13］研究了聚苯胺 膜修饰电极对抗坏血酸的电催化氧化,罗维忠等［14］研究了聚苯胺膜电极对Fe(Ⅱ) 和Sb(Ⅲ)的电催化作用. 本文主要讨论了扫描速度、苯胺单体浓度及温度对聚苯胺膜电极在 苯胺单体聚合过程中电催化性能的影响,为利用聚苯胺处理含苯胺废水提供了一定的理论依 据.     

Copper(II) complexes of a series of polypyridine ligands possessing a 1,2-bis(2-pyridyl)ethane common moiety: incorporation and hydrolysis of phosphate esters

Two tetradentate ligands 1,2-bis[2-((dimethylamino)methyl)-6-pyridyl]ethane (L1) and 1,2-bis[2-(N-piperidinomethyl)-6-pyridyl]ethane (L2) and a hexadentate ligand 1,2-bis(2-((methyl(pyridylmethyl)amino)methyl)-6-pyridyl)ethane (L3) were prepared as part of a series of new polypyridine ligands possessing a 1,2-bis(2-pyridyl)ethane common moiety. L1 and L2 form mononuclear Cu(II) complexes [Cu(L)(Cl)](ClO4) [L = L1 (1) and L2 (2)], respectively. L3 forms a dinuclear Cu(II) complex [Cu2(L3)((PhO)2PO2)2](ClO4)2 (3) or a hexanuclear Cu(II) complex [Cu6(L3)3((PhO)PO3)4](ClO4)4 (4) in the presence of (PhO)2PO2- monoanion or (PhO)PO3(2-) dianion, respectively. The structures of 1-4 were determined by X-ray analysis. The structures in solution were investigated by means of FAB and CSI MS spectrometers. The structural flexibility of the common 1,2-bis(2-pyridyl)ethane moiety and of the pendant groups allows complexes 1-4 to adapt to the various structures. Each Cu ion in 1 and 2 adopts a square pyramidal geometry with one Cl ion and two pendant groups (L1 and L2) binding in a bis-bidentate chelate mode. There is no steric repulsion between the pendant groups, so that the ligands specifically stabilize the mononuclear structures. L3 binds two Cu(II) ions with two pendant groups in tridentate chelate modes and, with the incorporation of phosphate esters, various dinuclear units are formed in 3 and 4. In 4, a dinuclear unit of [Cu2(L3)]4+ links two dinuclear units of [Cu2(L3)(PhOPO3)2] with four (mu3)-1,3-PhOPO3(2-) bridges. The hydrolytic activity of 2 and a dicopper(II) complex of L3 was examined with tris(p-nitrophenyl) phosphate (TNP) as a substrate.     

Conducting polymer films fabricated by oxidative graft copolymerization of aniline on poly(acrylic acid) grafted poly(ethylene terephthalate) surfaces

A conductive polyaniline/poly(ethylene terephthalate) (PANI/PET) composite film was fabricated via the oxidative graft copolymerization of aniline (ANI) onto the plasma-induced poly(acrylic acid) (PAAc) grafted PET surface. The attenuated total reflectance Fourier transform infrared spectroscopy spectra (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) results confirmed that PANI was successfully grafted onto the surface of the PAAc-g-PET films. The effects of the experimental conditions on the percentage of PANI grafted onto the PAAc-g-PET films were extensively investigated. A very high grafting percentage of ANI can be obtained through the acid-base reaction between the aniline monomer and PAAc on the PAAc-g-PET surface at high temperature. As a result, the grafting percentage of PANI can be increased to as high as 12.18 wt %, which causes the surface resistance of the PANI-g-PAAc-g-PET film to be reduced to about 1000 Omega/sq. We predicted that this is because of the high flexibility of the PAAc molecular chains and high solubility of aniline, both of which facilitate the binding of aniline to PAAc during this high temperature acid-base reaction. It was observed by atomic force microscopy (AFM) that the PANI-modified PET surface exhibits higher size irregularity and surface roughness, which further indicated that a much greater number of aniline molecules can be reactively bonded to and distributed along the grafted AAc chains and that the PANI-g-PAAc-g-PET surface resulting from the sequential oxidative graft copolymerization can possess higher electrical conductivity.     

Polyimides containing oxyethylene units

Four aromatic dinitro compounds containing oxyethylene units 1,2-bis(4-nitrophenoxy)ethane, bis(2)-(4-nitrophenoxy)ethyl ether, 1,2-bis(2)-(4-nitrophenoxy)ethoxy)ethane, and bis(2-(2-(4-nitrophenoxy)ethoxy)ethyl) ether were prepared by an aromatic nucleophilic substitution reaction that involved 1-fluoro-4-nitrobenzene and the appropriate oxyethylene glycol. Each of the dinitro compounds could be reduced chemically or catalytically to produce the diamines 1,2-bis(4-aminophenoxy)ethane, bis(2-(4-amino-phenoxy)ethyl ether, 1,2-bis(2-(4-aminophenoxy)ethoxy)ethane, and bis(2-(2-(4-aminophenoxy)ethoxy)ethyl) ether. Polymerization of the diamines was carried out in m-cresol with toluene as an azeotroping agent. Polymides derived from 5,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis-1,3-isobenzofuradione exhibited good solubility in chlorinated solvents, glass transition temperatures as low as 140°C, as evidenced by viscous flow, and good thermal stability; a 5% weight loss generally occured at greater than 450°C. Isothermal aging studies conducted at 600°F(315°C) for 200 h indicated that weight loss is directly related to oxyalkylene chain length–10% for the shortest and 50% for the longest chain.     

自支撑三维功能化石墨烯/聚苯胺电极材料的制备及超级电容性能

采用水热法制备了三维石墨烯(3D-G),并以十八胺(ODA)为接枝剂对部分还原的氧化石墨烯进行氨基化处理,再利用原位聚合法在氨基化石墨烯表面生长聚苯胺,制备了十八胺功能化石墨烯/聚苯胺(G-ODA/PANI).对材料进行了结构表征、电化学性能分析和材料结构的比电容贡献分析.结果显示,电极材料的电容贡献大部分体现为材料的表面电容,G-ODA/PANI电极片在1 A/g电流密度时的比电容最高可达1080 F/g,是未功能化石墨烯/聚苯胺电极材料(G/PANI)的2.57倍,且循环稳定性也有很大的提高,循环10000周后的比容量保持率为90.8%,比G/PANI高9.6%.     

Synthesis, molecular structures, and chemistry of some new palladium(II) and platinum(II) complexes with pentafluorophenyl ligands

A series of palladium(II) and platinum(II) complexes possessing pentafluorophenyl ligands of the general formula [M(L-L)(C6F5)Cl][space](M = Pd 3; L-L=tmeda (N,N,N',N',-tetramethylethylenediamine) a; 1,2-bis(2,6-dimethylphenylimino)ethane) b; dmpe (1,2-bis(dimethylphosphino)ethane) c; dcpe (1,2-bis(dicyclohexylphosphino)ethane) d; Pt ; L-L=tmeda a; 1,2-bis[3,5-bis(trifluoromethyl)phenylimino]-1,2-dimethylethane b; dmpe c; dcpe d) were readily synthesized from the dimer [M(C6F5)(tht)(mu-Cl)2] (M=Pd 1b, Pt 2b; tht=tetrahydrothiophene) and the corresponding bidentate ligand. In the case of palladium, the corresponding iodo analogues (6a-c) were readily synthesized in a one-pot reaction from [Pd2(dba)3], iodopentafluorobenzene, and the appropriate ligand. The platinum complexes 4c-d were then converted to the water complexes [Pt(L-L)(C6F5)(OH2)]OTf (L-L =dmpe 7a; dcpe 7b)via reaction with AgOTf in the presence of water. Attempts to convert the palladium complexes 3c-d to the corresponding water complexes resulted in the disproportionation of the intermediate water complex to form [Pd(L-L)(C6F5)2] (L-L=dmpe 8) or [Pd(L-L)2][OTf]2(L-L=dcpe 9). Upon standing in solution for prolonged periods, complex 7a undergoes an identical disproportionation reaction to the Pd analogues to form [Pt(L-L)(C6F5)2] (L-L=dmpe 10). Complexes 4c and 4d were converted to the corresponding hydrides (11b-c, respectively) using two different hydride sources: 11a was formed by the reaction of with NaBH4 in refluxing THF, while 11b was synthesized in near quantitative yield using [Cp2ZrH2] in refluxing THF. Attempts to synthesize eta2-tetrafluorobenzyne complexes [Pt(L-L)(C6F4)] (L-L=dmpe, dcpe) from reaction of 11a-b with butyllithium were unsuccessful. The molecular structures of 3a,4a, 4c, 4d, 6b, 7a, 8, 11b and have been determined by X-ray crystallographic studies, and are discussed.     

低温合成樟脑磺酸掺杂聚苯胺微管的电化学电容行为

在低温条件下合成了长约为2-3 μm, 外径约为300-400 nm 的樟脑磺酸掺杂聚苯胺微管. 扫描电镜(SEM)和透射电镜(TEM)显示, 生成的聚苯胺微管管径受樟脑磺酸浓度的影响, 高浓度的掺杂剂有利于管状聚苯胺的形成. 采用交流阻抗、循环伏安、恒流充放电等测试技术对不同产物的电化学电容行为进行了研究, 结果表明, 苯胺单体与樟脑磺酸的摩尔比为1:1时所得掺杂态聚苯胺电极具有较好的循环稳定性, 单电极比电容达到522 F·g-1.     

聚苯胺/聚砜复合材料的制备及其超级电容性能

通过化学聚合法,制备出盐酸掺杂聚苯胺（PANI）,将其与聚砜（PSF）溶液混合,定量滴加到玻碳电极上制得PANI/PSF复合膜电极。 采用扫描电子显微镜、红外光谱以及X射线衍射对其结构和形貌进行表征。 根据循环伏安曲线、恒电流充放电曲线和电化学阻抗,研究了其作为电极的超级电容性能。 结果表明,多孔结构的PANI/PSF复合材料具有良好的电容性能,其比电容可达到497 F/g,并且该超级电容器具有较小的内阻和较好的循环稳定性。     

MnO_2/聚苯胺复合材料的电化学电容

以P123为模板剂,软模板法制备出纳米MnO2.酸性条件下引入苯胺并聚合,得到了MnO2/聚苯胺复合材料.X射线衍射(XRD)、红外光谱(IR),扫描电子显微镜(SEM)表征观察样品的结构、形貌.循环伏安、交流阻抗、恒电流充放电等测试MnO2/聚苯胺电极的电化学性能.结果表明:引入苯胺改变了样品纳米MnO2的形貌.MnO2/聚苯胺电极比容量高达190.8F·g-1,500次循环电极比容量仅衰减4.7%,库仑效率均保持在97%以上.