Linear pi-conjugated systems derivatized with C60-fullerene as molecular heterojunctions for organic photovoltaics

This tutorial review covers recent contributions in the area of linear pi-conjugated systems bound to fullerenes in view of their application as active materials in photovoltaic devices. The first part discusses the concepts of double-cable polymer and molecular hetero-junction and presents several examples of chemically or electrochemically synthesized C60-derivatized conjugated polymers. The second and main part of the article concerns the various classes of C60-derivatized pi-conjugated oligomers designed in view of their utilization in single-component photovoltaic devices. Thus, C60-containing pi-conjugated systems such as oligoarylenevinylenes, oligoaryleneethynylenes and oligothiophenes are discussed on the basis of the relationships between molecular structure, photophysical properties and performances of the derived photovoltaic devices. A brief last section presents some recent examples of surface-attached molecular hetero-junctions based on self-assembled monolayers and discusses possible routes for future research.     

Synthesis of Zn/Al mixed-oxide catalyst for carbonylation of glycerol with urea

Zn/Al mixed oxide was prepared by the coprecipitation or the hydrothermal method under different conditions and used as catalyst for synthesis of glycerol carbonate by carbonylation of glycerol with urea. The physical properties of the prepared Zn/Al mixed oxide particles were investigated, as well as their activity as catalyst in the mentioned synthesis. The dried Zn/Al mixed-oxide particles prepared by the coprecipitation method showed higher activity in synthesis of glycerol carbonate than those prepared by the hydrothermal method. The Zn/Al mixed oxide prepared by the coprecipitation method without NaNO₃ showed the highest catalytic activity in synthesis of glycerol carbonate.     

Polyesters,polyurethanes and epoxy resins derived from 2,2′-(1,4-phenylenedivinylene)bis-8-hydroxyquinaldine and 6-(4-hydroxystyryl)-3-hydroxypyridine

New polyesters and polyurethanes as well as diepoxides bearing styrylpyridine segments were prepared utilizing 2,2′-(1,4-phenylenedivinylene)bis-8-hydroxyquinaldine (PBHQ) and 6-(4-hydroxystyryl)-3-hydroxypyridine (HSHP) as starting materials. The polyesters were prepared by reacting PBHQ or HSHP with terephthaloyl dichloride in the presence of an acid acceptor utilizing the solution polycondensation method. The polyurethanes were prepared from the reactions of PBHQ and HSHP with tolylene diisocyanate and methylenebis(4-phenylisocyanate). In addition, model diesters and diurethanes were synthesized by reacting PBHQ and HSHP with benzoyl chloride and phenyl isocyanate, respectively. Model compounds and polymers were characterized by FT-IR and ¹H-NMR spectroscopy as well as by DTA and TGA. Diepoxides were also prepared from the reactions of PBHQ and HSHP with epichlorohydrin which were polymerized in the presence of 4,4′-diaminodiphenylsulfone. The polyesters were the most thermostable polymers obtained. After curing at 240°C for 20 h, they were stable in N₂ up to 345–370°C and afforded anaerobic char yields of 65–75% at 800°C. © 1993 John Wiley & Sons, Inc.     

Polyesters,polyurethanes, and epoxy resin derived from 2,2′-(1,4-phenylenedivinylene)bis-5-hydroxypyridine

2,2′-(1,4-Phenylenedivinylene)bis-5-hydroxypyridine (PBHP) was used as a starting material for preparing new polyesters and polyurethanes as well as a diepoxide-bearing styrylpyridine segments. The diesters were prepared by reacting PBHP with terephthaloyl or adipoyl dichloride utilizing the interfacial polycondensation method. The diesters were prepared from the reaction of PBHP with tolylene diisocyanate or methylenebis(4-phenylisocyanate). In addition, a model diester and diurethane were synthesized by reacting PBHP with benzoyl chloride and phenyl isocyanate, respectively. Both model compounds and polymers were characterized by IR and ¹H-NMR spectroscopy, as well as by DTA and TGA. A diepoxide was also prepared from the reaction of PBHP with epichlorohydrin which was polymerized in the presence of 4,4′-diaminodiphenylsulfone. The polyester derived from PBHP and terephthaloyl dichloride was the most thermostable polymer obtained. It was stable in N₂ up to 355°C and afforded an anaerobic char yield of 59% at 800°C. The thermal stabilities of polymers were improved by curing.     

Structure-activity studies of antitumor agent irofulven (hydroxymethylacylfulvene) and analogues

Many analogues of the antitumor agent irofulven have been readily prepared by replacing the allylic hydroxyl with a variety of nucleophiles. Analogues of acylfulvene (the precursor to irofulven) were also prepared by Michael reaction with acrolein. The toxicity of the analogues was determined, as well as preclinical antitumor activity. Several analogues exhibited good activity in mouse xenografts. Structural requirements for activity are discussed.     

Preparations and properties of uniform size macroporous polymer beads prepared by two-step swelling and polymerization method utilizing divinyl succinate or divinyl adipate as a crosslinking agent

Uniform size macroporous polymer beads were prepared through a typical two-step swelling and polymerization method utilizing divinyl succinate or divinyl adipate as well as ethylene dimethacrylate as crosslinking agents. Stable macroporous polymer beads with good size monodispersity and a slightly nonspherical shape were obtained by homopolymerization of divinyl succinate in cyclohexanol as porogen. BET measurements indicated that the beads prepared by homopolymerization of divinyl succinate and copolymerization of divinyl succinate with vinyl p-tert-butylbenzoate, as well as homopolymerization of ethylene dimethacrylate had relatively large specific surface area. In contrast, copolymerization of divinyl succinate with methyl methacrylate afforded beads having a very small specific surface area. Similarly, all the beads prepared using divinyl adipate had very small specific surface area, while size exclusion chromatography in tetrahydrofuran suggested that these beads acquired a porous structure as a result of swelling. When used as packing materials for high-performance liquid chromatography, the beads prepared with divinyl adipate showed unexpected molecular recognition toward flat solutes in reversed phase liquid chromatography in contrast to those prepared with ethylene dimethacrylate. Copolymerizations with methyl methacrylate led to a decrease in molecular recognition, while those with vinyl p-tert-butylbenzoate enhanced the selectivity. © 1996 John Wiley & Sons, Inc.     

碳纳米管/SnO2复合电极的制备及其电催化性能研究

采用液相沉积法制备碳纳米管(CNTs)/SnO₂复合材料, 并制备成电极, 分别与石墨/SnO₂及活性炭/SnO₂复合电极比较, 考察电催化降解有机废水的性能. 由于CNTs高的比表面积及优良的导电性能, 结合SnO₂良好的催化活性, CNTs/SnO₂复合电极电催化降解有机废水性能优越. 研究发现, CNTs的预处理情况、SnO₂负载量以及煅烧温度对复合电极的电催化性能有重要影响. 当功能化CNTs负载40% SnO₂, 煅烧温度600 ℃时, 所得CNTs/SnO₂复合电极电催化降解有机废水的能力是纯CNTs电极的2倍. 最后, 初步探讨了CNTs/SnO₂复合电极电催化降解有机废水的机理.     

Über die Isomerenverteilung bei der Darstellung substituierter Aryldichlorphosphine mit Aluminiumchlorid

The distribution of isomers at the preparation of substituted aryldichlorophosphines using AlCl₃ was determined by means of IR spectroscopy. The isomers of the methylphenyl- and chlorophenyl dichlorophosphines as well as the 1,4-fluorophenyl dichlorphosphine (prepared for the first time) were prepared by way of the corresponding substituted phenylphosphonic bis(diethylamides). Thus calibration curves were obtained for quantitative evaluation. Alkyl- as well as halogene benzenes yield mainly 1,4-substituted aryl dichlorophosphines. Halogenobenzenes yield little 1,2 and little 1,3 isomers, whereas up to 40% 1,3 isomers with little 1,2 product are obtained from alkylbenzenes. *** DIRECT SUPPORT *** A3615112 00022     

Preparation of ultrafine high density gamma ferric oxide using aerosol OT microemulsions and its characterization

Ultrafine gamma ferric oxide has been prepared by controlled heating of ferrous oxalate at a temperature range of 225° to 300°C in moist air. Ferrous oxalate was prepared both in aqueous as well as in Aerosol OT microemulsion systems. It has been observed that the product is always a mixture of alpha and gamma ferric oxides which were characterized by TGA, DTA and XRD studies. Microemulsion mediated ferrous oxalate was found to yield more gamma ferric oxide than that from ferrous oxalate prepared in aqueous solution. However, the yield of gamma ferric oxide prepared through microemulsion mediated system depends on the size of the microemulsion droplets in which precursors have been participated as well as calcination temperature.     

Synthesis and Antimicrobial Activity of Some Novel Thiazoles, 1,3,4‐Thiadiazines, 1,3,4‐Thiadiazoles Incorporating Coumarin Moiety

Starting from 3‐acetyl‐2H‐chromen‐2‐one and hydrazinecarbothiohydrazide, new functionalized thiazoles, 1,3,4‐thiadiazines, and 1,3,4‐thiadiazoles were prepared. The structures of the compounds prepared were confirmed by both elemental and spectral analyses as well as by alternate synthesis. The antimicrobial activities of the compounds prepared were screened, and the results showed that most of such compounds exhibit considerable activities.     

LaHZSM—5沸石的制备及其裂解性能研究

用常压和水热法制备了具有不同交换度的LaHZSM-5沸石,以XPS、IR、XRD及正十五烷裂解对其进行了表征。结果表明,水热法可获得较高交换度的LaHZSM-5沸石。La~(3+)交换的沸石较相同Si/Al比的HZSM-5沸石活性高,对气体的选择性降低,提高了C_(5～10)馏分的选择性。     

超动态法快速制备毛细管色谱柱的研究

用超动态法快速制出了几种非极性毛细管柱,柱效、涂渍效率分别为3000～4500理论塔板/m和65～85%。研究了超动态法中涂渍压力、涂渍液浓度与容量因子的关系;考察了制柱重复性和液膜厚度均匀性;给出了涂渍一般口径和试涂大口径厚液膜毛细管柱的部分结果。     

Further studies on homopolymers and copolymers resulting from the reaction of polymaleic anhydride with alcohols and amines

Polymaleic anhydride prepared by γ-rays irradiation of maleic anhydride was used as a reactive polymer and reacted with certain long-chain aliphatic amines and/or alcohols as well as with the mesogenic biphenylamine. The homopolymers and copolymers that were prepared, i.e., derivatives of N-alkyl polymaleamic acid, monoesters of polymaleic acid, or mixed amide-ester derivatives, were primarily investigated as far as their property to show thermotropic liquid crystalline character is concerned. By this investigation the structural features for the exhibition of mesomorphism by these polymers were determined.     

Liquid crystalline epoxy resins by polyaddition of diglycidyl ether of 4,4′-dihydroxybiphenyl and difunctional aromatic compounds

This work is a continuation of the authors' earlier investigations of liquid crystalline epoxy resins prepared from diglycidyl ether of 4,4′-dihydroxybiphenyl (DGE-DHBP), which was used as a mesogenic agent, and aliphatic dicarboxylic compounds, which were used as flexible spacers. In this paper, the synthesis and characterization of liquid crystalline epoxy resins, prepared from DGE-DHBP and difunctional aromatic compounds are described. Three series of liquid crystalline epoxy resins were prepared by chain extension of DGE-DHBP with isomeric hydroxybenzoic and benzenedicarboxylic acids as well as diphenols. An isophthalic-terminated polyether was applied to decrease the temperature of phase transitions. The syntheses were carried out by catalytic polyaddition in the melt. Triphenylphosphine was applied as the catalyst. The resulting epoxy resins were investigated by DSC, polarizing microscope as well as by X-ray and IR spectroscopy. The phase transition temperatures and the type of mesophase of the resulting products depend on the character of the functional groups in the chain extender and on the position of the functional groups in the aromatic ring. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 21–29, 1998     

Voltage-assisted capillary LC of peptides using monolithic capillary columns prepared by ring-opening metathesis polymerization

We examined the use of monolithic capillary columns prepared via ring-opening metathesis polymerization (ROMP) for peptide separation in voltage-assisted capillary LC (voltage-assisted CLC). In order to demonstrate their potential for peptide separation, ROMP-derived monoliths with RP properties were prepared. The preparation procedure of monoliths was transferred from ROMP monoliths optimized for CLC. ROMP monoliths were synthesized within the confines of 200 microm id fused-silica capillaries with a length of 37 cm. After optimization of the chromatographic conditions, the separation performance was tested using a well-defined set of artificial peptides as well as two peptidic mixtures resulting from a tryptic digest of BSA as well as a collagenase digest of collagen. ROMP monoliths showed comparable performance to other monolithic separation media in voltage-assisted CLC published so far. Therefore, we conclude that by optimizing the composition of the ROMP monoliths as well as by using the controlled manner of their functionalization, ROMP monoliths bear a great potential in CLC and CEC.     

形貌转录法制备Ag-P(AM-co-MAA)复合微球

以反相悬浮聚合技术合成的丙烯酰胺(AM)和甲基丙烯酸(MAA)共聚高分子微凝胶P(AM-co-MAA)为模板,结合反胶束法制备得到Ag3PO4-P(AM-co-MAA)复合微球,并将其分散于乙醇溶剂中通过化学还原Ag3PO4-P(AM-co-MAA)复合微球制备得到粒径为几十微米,具有表面图案,且结构为核-壳型的Ag-P(AM-co-MAA)复合微球材料.能量散射X射线(EDX)谱表明壳化学组成以金属银为主,核以高分子模板为主;扫描电子显微镜(SEM)观察结果表明银-高分子复合微球的表面形貌与其前驱体类似,且可以通过选择模板、改变模板组成、调整金属难溶银盐沉积量等因素加以调控;X射线衍射(XRD)分析表明前驱体复合微球表面Ag3PO4全部转化为单质银.生物抗菌实验表明该类微球材料对大肠杆菌、金黄色葡萄球菌均具有较强的抑制作用.     

含氟丙烯酸酯共聚物制备超疏水表面及其形成机理的研究

以丙烯酸全氟烷基乙基酯和甲基丙烯酸甲酯为共聚单体, 分别以用微乳液聚合法和溶液聚合法制备的无规共聚物和用可逆加成-断裂链转移制备的嵌段共聚物作为成膜共聚物, 并以1,1,2-三氟三氯乙烷作为溶剂, 采用溶剂挥发成膜法可以直接制备出超疏水膜, 聚合物膜对水的接触角可达160°. 改变聚合物结构和成膜条件, 探讨了该类超疏水膜的形成机理和影响因素. 发现膜的表面形貌和疏水性与共聚物的组成、结构、分子量以及成膜条件密切相关, 随着共聚物中氟含量的增大, 膜的表面形貌都趋于平滑; 而且, 无规共聚物比嵌段共聚物更易形成粗糙度好的膜; 同时, 较大的聚合物分子量和适宜的高的成膜温度都对形成粗糙结构有利.     

具有协同表面配体的水溶性稀土上转换发光纳米材料用于活体淋巴结显像

通过水热法,以油酸和两亲性聚乙烯吡咯烷酮(PVP)为协同表面配体,一步水热合成水溶性稀土上转换发光纳米材料(NaYF4:20％ Yb 1％ Tm).稀土纳米粒径尺寸平均为16 nm,在水溶液中稳定单分散,具有较强上转换发光.具有较低的细胞毒性,可用于上转换发光细胞成像.并进一步用于活体淋巴结显像,表现出高的信噪比.     

Synthesis of double‐layered dendritic carbosilanes used on allyloxy and phenylethynyl groups

Double‐layered dendritic carbosilanes were prepared containing phenylethynyl groups on the peripheral layer as well as propyleneoxy and ethenyl groups in the inner shell. The preparation of the allyloxy group containing dendrimers was made by the reaction of chlorosilylated dendrimers with allylalcohol in the presence of TMED. The dendrimers with ethynyl groups on each terminal arm were obtained by the reaction of the chlorosilyl group containing generations with lithium phenylethynyl. Subsequently, by iterative reactions such as hydrosilation and alkynylation as well as alcoholysis, dendritic macromolecules were generated to the fourth generation with 64 phenylethynyl groups on the peripheral layer. Different branching layers such as propyleneoxy and phenylethenyl groups constructed the inner shell of the fourth generation of the prepared dendrimers. The dendrimers were characterized by the use of nuclear magnetic resonance, infrared, size exclusion chromatography, differential scanning calorimetry, ultraviolet, and elemental analysis. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 764–774, 2000     

Preparation and physicochemical characterisation of functionalised multi-walled carbon nanotubes

A series of new functionalised carbonaceous materials were prepared by means of oxidation and ammoxidation of commercially available multi-walled carbon nanotubes. The effect of oxygen and nitrogen doping on the textural, surface as well as thermal properties of the prepared adsorbents was tested. The materials were characterized by elemental analysis, low-temperature nitrogen sorption, determination of the surface oxygen groups content as well as by coupled thermogravimetric and spectroscopic methods (TG/DSC/MS). Depending of the variant of raw nanotubes modification, the final products were oxygen- and nitrogen-doped materials of medium-developed surface area and mesoporous structure, showing highly diverse acidic-basic character of the surface, from the weakly acidic to slightly alkaline.