Amphiphilic Core-Shell Nanocarriers Based On Hyperbranched Poly(ester amide)-star-PCL: Synthesis, Characterization, and Potential as Efficient Phase Transfer Agent

Amphiphilic biodegradable star-shaped polymer was conveniently prepared by the Sn(Oct)(2)-catalyzed ring opening polymerization of c-caprolactone (CL) with hyperbranched poly(ester amide) (PEA) as a macroinitiator. Various monomer/initiator ratios were employed to vary the length of the PCL arms. H-1 NMR and FTIR characterizations showed the successful synthesis of star polymer with high initiation efficiency. SEC analysis using triple detectors, RI, light scattering, and viscosity confirmed the controlled manner of polymerization and the star architecture.

Highly Active Carbon-supported PdSn Catalysts for Formic Acid Electrooxidation

PdSn/C catalysts with different atomic ratios of Pd to Sn were synthesised by a NaBH4 reduction method. Electrochemical tests show that the alloy catalysts exhibit significantly higher catalytic activity and stability for formic acid electrooxidation (FAEO) than the Pd/C catalyst prepared with the same method. XRD and TEM indicate that a particle-size effect is not the main cause for the high performance. XPS confirms that Pd is modified by Sn through an electronic effect which can decrease the adsorption strength of poisonous intermediates on Pd and thus promote the FAEO greatly.

Reaction Mechanism of Palladium-Catalyzed Silastannation of Allenes by Density Functional Theory

The reaction mechanism of Pd(O)-catalyzed allenes silastannation reaction is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. For the allene insertion step, the Pd-Si bond is preferred over the Pd-Sn bond. The electronic mechanism of the allene insertion into Pd-Si bond to form sigma-vinylpalladium (terminal-insertion) and sigma-allylpalladium (internal-insertion) insertion products is discussed ill terms of the electron donation and back-donation. It is found that the electron back-donation is significant for both terminal- and internal-insertion. During allene insertion into Pd-Si bond, internal-insertion is preferred over terminal-insertion. By using methylallene, the regio-selectivity for the monosubstituted allene insertion into Pd-Si and Pd-Sn bond is analyzed.

三氧杂环己烷的电化学特性

直接氧化一些有机小分子(如甲醇[1~9]和乙醇[10~14]等)的直接氧化燃料电池作为一种对环境友好的能源越来越引起人们的关注.三氧杂环己烷作为一种可再生的能源,可以从地球上存在的大量天然气中得到,来源广泛,价格低廉.三氧杂环己烷反应的基本结构如Scheme 1所示,相对乙醇而言,三氧杂环己烷不存在任何碳碳键,反应更易进行.目前广泛研究的直接氧化燃料电池均采用液体甲醇和S chem e 1 S tru ctu re of tr ioxane乙醇等作燃料,液体燃料的存储运输存在一定的安全隐患,一旦泄漏发生危险,后果非常严重,而三氧杂环己烷作为一种固体,可以有效地避免上述问题的发生,利于安全的储存和运输.Narayanan等[13]研究了三氧杂环己烷在Pt,Pt-Sn和Pt-Ru电极上的电化学行为及其在燃料电池中的应用.本文研究了三氧杂环己烷在不同浓度、不同温度和不同酸度时于光滑铂电极上的电化学行为,初步分析了三氧杂环己烷的反应机理.1实验部分1.1试剂与仪器采用Potentiostat/GalvanostatModel 273A恒电位仪(美国Princeton Applied Research公司),在传统的三...

吸附在Pt/C催化剂上Eu~(3+)对CO电氧化的促进作用

引言目前影响质子交换膜燃料电池(PEMFC)迅速发展并商业化的主要问题之一是阳极催化剂抗CO的毒化能力。Pt因其对氢的氧化具有高的催化活性而广泛地用作PEMFC的阳极催化剂,也有人研究将其它金属用于PEMFC阳极催化剂,但催化活性要比Pt低得多[1~4]。而Pt作PEMFC的阳极催化剂一个问题是痕量的CO,如10~100ppm就可以使Pt催化剂中毒[5,6]。现在的PEMFC一般用高压氢作为燃料,有很大的不安全性。人们提出用两种方法来解决这个问题,一是用甲醇、甲烷或汽油现场重整制氢作燃料的方法,但用这种制氢方法制得的氢气中含有大量的CO,即使经过纯化,也会含有ppm级的CO。另一个方法是直接用小分子醇类化合物,如甲醇作燃料,被称为直接醇燃料电池(DAFC)[7~11],但醇类化合物在阳极氧化时会有中间产物,如CO的产生,容易使阳极Pt催化剂中毒。因此,研究抗CO中毒的阳极催化剂已成为PEMFC和DAFC中一个很重要的研究课题。许多文章已报道Pt与其它贵金属或过渡金属的合金催化剂,或Pt与过渡金属氧化物的复合催化剂有一定的抗CO中毒能力。如Pt鄄Ru[12~16]、Pt鄄Bi[17]、Pt鄄Sn[17~19]...

Biodegradable amphiphilic triblock copolymer bearing pendant glucose residues: Preparation and specific interaction with Concanavalin A molecules

A novel biodegradable amphiphilic block copolymer PLGG-PEG-PLGG bearing pendant glucose residues is successfully prepared by the coupling reaction of 3-(2-aminoethylthio) propyl-R-D-glucopyranoside with the pendant carboxyl groups of PLGG-PEG-PLGG in the presence of N,N'-carbonyldiimidazole. The polymer PLGG-PEG-PLGG, i.e., poly {(lactic acid)-co-[(glycolic acid)-alt-(L-glutamic acid)]}-block-poly(ethylene glycol)-block-poly{( lactic acid)-co-[( glycolic acid)-alt-(L-glutamic acid)]}, is prepared by ring-opening copolymerization of L-lactide (LLA) with (3s)-benzoxylcarbonylethylmorpholine-2,5-dione (BEMD) in the presence of dihydroxyl PEG with molecular weight of 2000 as macroinitiator and Sn(Oct)(2) as catalyst, and then by catalytic hydrogenation. The glucose-grafted copolymer shows a lower degree of cytotoxicity to ECV-304 cells and improved specific recognition and binding with Concanavalin A (Con A). Therefore, this kind of glucose-grafted copolymer may find biomedical applications.

Determination of ultra-trace concentrations of elements in high purity tellurium by inductively coupled plasma mass spectrometry after Fe(OH)(3) coprecipitation

In this work, a method was established for the determination of impurities in high purity tellurium by inductively coupled plasma mass spectrometry (ICP-MS) after Fe(OH)(3) coprecipitation. After comparison of coprecipitation ability and separation efficiency between Fe(OH), and Al(OH)(3), Fe(OH)(3) was chosen as the precipitate. A separation factor of 160 for 200 mg tellurium was obtained under conditions of pH 9 and 2 mg of Fe3(+). The 13 elements, such as Bi, Sn, Pb, In, Tl, Cd, Cu, Co, Ni, Zn, Ti, Be and Zr, could be almost completely coprecipitated under these conditions. In addition, Te memory effect imposed on the ICP-MS instrument was assessed, as well as Te matrix effect that caused the low recovery of Ga, As, Sb and V in real sample was discussed. Finally, the method was evaluated through recovery test and was applied to practical sample analysis, with detection limits of most of the elements being below 0.15 mug g(-1) and R.S.D. below or at approximately 10%, which indicated that this method could fully satisfy the requirements for analysis of 99.999% similar to 99.9999% high purity Te.

Chemical bond properties and Mossbauer spectroscopy in (La1-xMx)(2)CuO4(M=Ba, Sr)

By using the average band-gap model, the chemical bond properties of (La1-x, M-x)(2)CuO4(M=Ba, Sr) were calculated. The calculated covalencies for Cu-O and La-O bond in the compounds are 0.3 and 0.03 respectively. Mossbauer isomer shifts of Fe-57 doped in La2CuO4 and Sn-119 doped in La2CuO4 were calculated by using the chemical surrounding factor defined by covalency and electronic polarizability. Four valence state tin and three valence iron sites were identified in Fe-57 and Sn-119 doped La2CuO4.

Study of the interaction between lanthanide ions and a supported bilayer lipid membrane by cyclic voltammetry and ac impedance

The interaction of lanthanide ions with a supported bilayer lipid (1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine) membrane (sBLM) was investigated by cyclic voltammetry and ac impedance spectroscopy in this paper, Lanthanide can affect the conformation of the supported bilayer lipid membrane and cause pore formation. Through the pores, Fe(CN)(6)(3) (4) can reach the electrode surface and show its redox behaviour. Furthermore the redox currents or Fe(CN)(6)(3) (4) increased with increasing concentration of lanthanides and leveled off at 1.2 muM for Eu3+. The interaction ability of three lanthanides with sBLM follows the sequence: Eu3+ > Tb3+ > La3+.

Chemical bond properties and Mossbauer spectroscopy in REBa2Cu3O7 (RE = Eu, Y)

By using the chemical bond theory of complex crystals, the chemical bond properties of REBa2Cu3O7 (RE = Eu, Y) were calculated. The calculated covalencies for Cu(1)-O and Cu(2)-O bond in REBa2Cu3O7 compounds are 0.41 and 0.28 respectively. Mossbauer isomer shifts of Fe-57 doped, and Sn-119 doped in REBa2Cu3O7-x were calculated by using the chemical environmental factor, h(e), defined by covalency and electronic polarizability. Four valence state tin ion and iron ion sites were identified in Fe-57 and Sn-119 doped REBa2Cu3O7-x superconductors.

Bonding and Mossbauer isomer shifts in (Tl, Pb)-1223 cuprate

By using the clinical bond theory of dielectric description, the chemical bond parameters of (Tl.Pb) - 1223 was calculated. The results show that the Sr-O, Tl-O, and Ca-O types of bond have higher ionic character and the Cu-O types of bond have more covalent, character. Mossbauer isomer shifts of Fe-57 and Sn-119 doped in (Tl, Pb) -1223 were calculated by using the chemical environmental factor, h, defined by covalency and electronic polarizability. Four valence state tin and three valence iron sites were identified ill Fe-57, and Sn-119 doped (Tl, Pb) -1223 superconductor. We conclude that all of' the Fe atoms substitute the Cu at square planar Cu (H site, whereas Sn prefers to Substitute the square pyramidal Cu (2) site.

碳载Pt-TiO_2阳极催化剂对甲醇氧化的电催化活性和稳定性

近年来,直接甲醇燃料电池（DMFC）由于使用液体燃料而越来越受到重视,但目前DMFC存在的一个普遍的问题是常用的Pt阳极催化剂易被甲醇氧化的中间产物所毒化.因此,一些研究者研究了能抗甲醇氧化的中间产物毒化的Pt二元合金或Pt和过渡金属氧化物复合催化剂,如Pt-Ru[1]、Pt-Sn[2]、Pt-WOx[3]等.考虑至TiO2在酸性溶液中的稳定性,Hamnett研究组[4]和我们研究组[5]发现pt-TiO2/Ti复合电极对甲醇氧化有很好的电催化活性和抗中毒的能力.本文报道了制备能在DMFC中实际使用的碳载Pt-TiO2催化剂（Pt-TiO2/C）的方法和比较了Pt-TiO2/C和Pt/C电极对甲醇氧化的电催化活性和稳定性.用固相法制备含Pt20％的Pt/C催化剂[6],将制得的pt/C催化剂和Ti（OBu）4按摩尔比1:1的比例悬浮在乙醇中,超声波震荡并加水,使Ti（OBu）4完全水解成TiO2,并均匀沉积到Pt/C催化剂上,洗涤,真空干燥,500℃热处理

Synthesis and crystal structure of triphenyltin-2-(1,2-ethylenedithio) methylene-3-oxo-5-aryl-4-pentenicate

Nine triphenyltin - 2 - (1,2 - ethylenedithio) methylene - 3 - oxo - 5 - aryl - 4 - pentenicates were synthesized. The crystal structure of the title compound 3b (C33H28O3S2Sn) was determined by X - ray diffraction analysis. The crystal belongs to triclinic system, space group P(1)overbar with a = 0.9074 (2) nm, b = 1.6809(3)nm, c = 2.1834(4)nm, alpha =77.57(3)degrees, beta = 88.04(3)degrees, gamma = 89.47(3)degrees, V = 3.2503nm(3), Z = 2, R = 0.0592. In crystal of 3b, there exist intramolecular 0-Sn coordination bonds, with carboxylate group acting as a bidentate ligand: Sn(1)-0(1) = 0.2086(5) and Sn(1)-0(2) = 0.2594nm, having a deformed trigonal bipyramidal geometry.

水热沉淀法合成SnO_2纳米晶

用水热沉淀法合成了不同粒径的 Sn O2 纳米晶 ,属于四方晶系 ,空间群为 P4/ mnm。计算表明 :随焙烧温度的升高 ,Sn O2 晶粒度增大 ;而平均晶格畸变率则随晶粒度的增大而减小 ,表明粒子越小晶格畸变越大 ,晶粒发育越不完整。TEM分析结果表明 :所合成的 Sn O2 纳米粒子基本呈球形 ;随焙烧温度的升高 ,Sn O2 粒子的粒径增大。热失重分析表明 :水热沉淀法所合成的 Sn O2 纳米粉末中杂质含量很少 ,纯度高。

Chemical bond properties of REBa2Cu3O7 and its Mossbauer spectroscopy

By using the average bond-gap model, the chemical bond properties of REBa2Cu3O7 were calculated. The calculated covalencies for Cu(1)-O and Cu(2)-O bonds in REBa2Cu3O7 compounds are 0.41 and 0.28 respectively. Mossbauer isomer shifts of Fe-57 doped in EuBa2Cu3O7-x and Sn-119 doped in YBa2Cu3O7-x were calculated by using the chemical surrounding factor, h, defined by covalency and electronic polarizability. The valence states and sites of Fe-57 in EuBa2Cu3O7 and Sn-119 in YBa2Cu3O7-x were identified.