Au@Pt纳米粒子催化O2还原反应的电化学研究

以100 nm的Au粒子为核,抗坏血酸为还原剂,H2PtCl6·6H2O为前驱体,合成了Pt包Au核壳结构纳米粒子( Au@ Pt)及其修饰的玻碳(GC)电极(Au@ Pt/GC).采用旋转圆盘电极等常规电化学方法,比较了Au@ Pt/GC和商用碳载铂(Pt/C)修饰的玻碳电极(Pt/C/GC)催化O2还原反应活性及耐甲醇性能,发现Au@ Pt纳米粒子在铂用量很低的情况下,其催化O2还原反应活性仍与商用Pt/C相当,而且还具有优良的耐甲醇性能;其催化O2还原反应机理按O2直接还原成H2O的四电子历程进行.     

蛋白质组学研究中傅立叶变换离子回旋共振质谱数据采集方法的比较

探讨了线性离子阱-傅立叶变换离子回旋共振质谱(LTQ-FT)的数据采集模式对蛋白质组鉴定结果的影响,比较和分析了针对不同复杂程度样本的最佳采集模式.对于α-乳清蛋白4种标准蛋白质酶切肽段混合物的简单体系,在傅立叶变换离子回旋共振腔中选3个最强母离子进行选择离子监测扫描后, 再实施二级碎裂的方法(SIM3) 得到的肽段覆盖率, 分别是直接选10个最强母离子进行二级碎裂(FT10)方法得到的肽段覆盖率的1.5～1.9倍.另外, 对酵母蛋白酶切肽段混合物的复杂体系鉴定时,只采集双电荷和三电荷母离子进行二级扫描的方法(FT10_23)比单电荷、双电荷和三电荷都采集的方法(FT10_123)得到的图谱鉴定成功率提高64.1%.实验还对不同数据采集模式下图谱的特点进行了考察.本研究表明,针对不同复杂程度的样本,应采取不同的质谱数据采集方法.     

Zirconium complexes incorporated with asymmetrical tridentate pincer type mono- and di-anionic pyrrolyl ligands: mechanism and reactivity as catalytic precursors

The reactions of Zr(NR(2))(4) (1, R = Me; 2, R = Et) with an asymmetrical tridentate pincer type pyrrole ligand precursor [C(4)H(2)NH(2-CH(2)NH(t)Bu)(5-CH(2)NMe(2))] and treatment of the derivatives with either PhNCS or PhNCO have been carried out and characterized. Reacting Zr(NR(2))(4) (1, R = Me; 2, R = Et) with [C(4)H(2)NH(2-CH(2)NH(t)Bu)(5-CH(2)NMe(2))] generates Zr[C(4)H(2)N(2-CH(2)N(t)Bu)(5-CH(2)NMe(2))](NR(2))(2) (3, R = Me; 4, R = Et) in high yield along with the elimination of 2 equiv of dimethylamine or diethylamine, respectively. Interestingly, while changing the solvent from Et(2)O to CH(2)Cl(2), the complex Zr[C(4)H(2)N(2-CH(2)N(t)Bu)(5-CH(2)NMe(2))][C(4)H(2)N(2-CH(2)NH(t)Bu)(5-CH(2)NMe(2))]Cl (5) is produced by undergoing C-Cl bond cleavage. Furthermore, reaction of either 3 or 4 with 1 or 2 equiv of PhNCS or PhNCO yields Zr[C(4)H(2)N(2-CH(2)N(t)Bu)(5-CH(2)NMe(2))](NMe(2))[PhNC(NMe(2))S] (6), Zr[C(4)H(2)N(2-CH(2)N(t)Bu)(5-CH(2)NMe(2))](NEt(2))[PhNC(NEt(2))O] (7) and Zr[C(4)H(2)N(2-CH(2)NH(t)Bu)(5-CH(2)NMe(2))][PhNC(NEt(2))O](3) (8), respectively. All the aforementioned complexes were characterized by (1)H and (13)C NMR spectrometry and the molecular structures of 5, 6, and 8 have been determined by single-crystal X-ray diffractometry. Complexes 4, 5, and 7 initiated the ethylene polymerization in the presence of MAO as the co-catalyst.     

Probing double layer structures of Au (111)-BMIPF6 ionic liquid interfaces from potential-dependent AFM force curves

High quality AFM force curves are presented with detailed potential dependent layering behaviors of the ionic liquid molecules, from which charged interior and neutral exterior layers are distinguished. The electric double layer is confined within the interior layers of one to two molecular size within the potential range of up to 1 V negative of the PZC.     

The effect of inorganic particles on slot die coating of poly(vinyl alcohol) solutions

Among various coating processes, slot die coating belongs to a class of pre-metered coating, in which the coating film thickness can be predetermined. In the past, most research works on slot die coating have focused mainly on polymer solutions; very little information is available using suspensions as coating fluids. In this study, the effect of adding TiO2 and SiO2 in aqueous polyvinyl alcohol (PVA) solutions on slot die coating is investigated. It was found that the stable coating window was enlarged with the addition of particles, and its size increased with solids concentration. This is due to the strong interaction between polymer and particles, resulting in a higher viscosity and surface tension. As a result, the upstream coating bead is more stable and the maximum coating speed is extended to a high value, hence the coating window becomes larger. Although both viscosity and surface tension appear to contribute to the stability of coating flow, the effect of surface tension is more dominant. The surface tension of a suspension with porous particles was higher than one with hard solid particles. Consequently, the coating window obtained with the former was significantly larger than the latter. Flow visualization revealed that under the same operating conditions, the upstream dynamic contact angle for the suspension was smaller than for the aqueous polymer solution. This observation could be related to the stability of the upstream coating bead, and hence the coating window. The experimental flow fields were verified numerically with the aid of a numerical simulation package (Flow-3D).     

EU-1分子筛的合成及其在正己烷异构化反应中的催化性能

在不同硅铝比(n_SiO2/n_Al2O3)的合成凝胶(含纯硅凝胶)中引入晶种,合成了纯相的EU-1分子筛。研究了铝源、模板剂和晶种添加量对EU-1分子筛的结晶度、形貌尺寸等的影响;重点研究了不同硅铝比对样品结晶度、晶粒尺寸、酸性、比表面积和孔容等的影响。将合成结果绘制成了纯相EU-1分子筛的合成条件三元图,从三元图可看出,晶种法可显著扩大纯相EU-1分子筛的合成区域。将Pt/H-EU-1用于正己烷异构化反应,结果表明,该催化剂具有优异的正己烷异构化活性及稳定性,对异构烷烃有较高的选择性。     

一种带吡啶悬臂大环异双核Zn（Ⅱ）-Ni（Ⅱ）配合物的合成、晶体结构及其DNA结合/切割性质

合成了一种带吡啶悬臂的不对称大环异双核金属Zn（Ⅱ）-Ni（Ⅱ）配合物[ZnNi （L）]（ClO₄）₂·H₂O （H₂L=3,3''-（（ethane-1,2-diylbis （（pyridin-2-ylmethyl） azanediyl）） bis （methyl ene）） bis （2-hydroxy-5-methylbenzaldehyde））,通过红外光谱、电喷雾质谱、单晶X射线衍射对其结构进行了表征。结果表明Zn（Ⅱ）和Ni（Ⅱ）的配位环境分别为扭曲的三角锥和正四面体。利用紫外光谱、粘度实验和循环伏安法对该配合物与DNA的相互作用模式进行了研究,结果表明配合物与小牛胸腺DNA （CT-DNA）的结合方式为插入模式,其相应的结合常数K_b=1.05×10⁵ L·mol^-1。另外,该配合物对pBR322 DNA有一定的切割作用。     

High Efficiency Red Organic Light-Emitting Diodes Based on Microcavity Structure

We demonstrate high efficiency red organic light-emitting diodes （OLEDs） based on a planar microcavity comprised of a dielectric mirror and a metal mirror. The microcavity devices emitted red light at a peak wavelength of 610nm with a full width at half maximum （FWHM） of 25nm in the forward direction, and an enhancement of about 1.3 factor in electroluminescent （EL） efficiency has been experimentally achieved with respect to the conventional noncavity devices. For microcavity devices with the structure of distributed Bragg reflectors （DBR ） /indium-tin-oxide（ITO） /V2O5 /N2N′-di（naphthalene-1-yl）-N2N′-diphenyl-benzidine（NPB ） / 4-（dicy-anomethylene）-2-t-butyl-6（1,1,7,7-tetrame-thyljulolidyl-9-enyl）-4H-pyran（DCJTB）：tris（8-hydroxyquinoline） aluminium （Alq3）/Alq3/LiF/Al, the maximum brightness arrived at 37000cd/m^2 at a current density of 460.0mA/cm^2, and the current efficiency and power efficiency reach 13.7cd/A at a current density of 0.23 mA/cm^2 and 13.31m/W at a current density of 0.04 mA/cm^2, respectively.     

叶轮机械中的泄漏流与泄漏涡

本文基于非正交曲线坐标及非正交速度分量下完全守恒型的N-S方程,采用整体H型网格,用数值方法研究叶轮机械中的泄漏流动。对于不同的间隙尺寸,对于环壁静止与旋转的不同壁面条件,揭示了泄漏流与通道二次涡相互作用的细节,揭示了泄漏涡的生成与发展过程。     

Synthesis, Crystal Structure and Antibacterial Activity of a New Ternary Copper（Ⅱ） Complex with 2,6-Pyridinedicarboxylic Acid and 1,10-Phenanthroline

A new ternary copper(II) complex,[C 43 H 27 Cu 2 N 7 O 5 ]·[C 14 H 6 CuN 2 O 8 ]·6.5H 2 O,has been synthesized by the reaction of copper sulfate,2,6-pyridinedicarboxylic acid and 1,10-phenanthroline (phen),and characterized by elemental analysis,IR,UV and X-ray single-crystal diffraction.It crystallizes in triclinic,space group P1,with a=14.379(5),b=15.510(5),c=15.835(6),α=78.567(6),β=63.594(6),γ=81.287(6)°,V=3092.1(19)3,C 57 H 46 Cu 3 N 9 O 19.5,M r=1359.54,Z=2,D c=1.446 Mg/m 3,λ(MoKα)=0.71073,μ=1.101 mm-1,F(000)=1362,S=1.071,the final R=0.0718 and wR=0.11960 for 10705 observer reflections (I > 2σ(I)).The structure unit of the title complex consists of a mononuclear part and a di-nuclear part,and the three copper ions show three coordination modes.Each 6-coordinated geometry of the Cu atom is a distorted octahedral coordination geometry.The 3D supramolecular system is formed by the hydrogen bond O-H···O and π-π stacking interaction between neighboring single cells.The antibacterial activity of the title complex is also studied.