Measurement of dioxygen by electrocatalytic reduction on microelectrodes modified with Nafion and methyl viologen

Nafion/methyl viologen (MV) has been chemically modified on a gold disk microelectrode (GDME). The electrochemistry of the Nafion/MV modified GDME is investigated by cyclic voltammetry (CV). Linear sweep voltammetry (LSV) and differential pulse amperometry (DPA) show that the Nafion/MV modified GDME exhibits very high electrocatalytic activity toward dioxygen reduction with good reproducibility and high sensitivity. The electrocatalytic peak current is found to be linear with the dioxygen concentration in the range of 3.44x10(-7) to 2.59x10(-4) mol l(-1) (at 25 degrees C), with a correlation coefficient of 0.9978. The detection limit (signal/noise=3) is calculated to be 0.19 mumol l(-1). The response time of the microsensor for dioxygen measurement is less than 15 s. For ten parallel measurements for 8.50 mumol l(-1) dioxygen, the relative standard deviation (RSD) is found to be 2.7%. The sensitivity of the microsensor is 0.17 nA mumol(-1) l(-1). This microsensor has been successfully employed to measure the concentration of dioxygen in real samples. The quantity of dioxygen, released from the three kinds of chloroplasts of plant leaves under different illumination, is monitored by the Nafion/MV modified gold microsensor. In order to survey the dioxygen concentration in vivo, a Nafion/MV modified carbon fiber microelectrode (CFME) is fabricated by a modification procedure similar to that of the Nafion/MV GDME. As a preliminary test, the dioxygen levels in the different areas of rat brain are determined by the Nafion/MV modified carbon fiber microsensors. The mechanism of the catalytic reaction is also addressed.     

Phage-display selection of a human single-chain fv antibody highly specific for melanoma and breast cancer cells using a chemoenzymatically synthesized G(M3)-carbohydrate antigen

Overexpression of the cell-surface glycosphingolipid G(M3) is associated with a number of different cancers, including those of the skin, colon, breast, and lung. Antibodies against the G(M3) epitope have potential application as therapeutic agents in the treatment of these cancers. We describe the chemoenzymatic synthesis of two G(M3)-derived reagents and their use in the panning of a phage-displayed human single-chain Fv (scFv) antibody library derived from the blood of cancer patients. Three scFv-phage clones, GM3A6, GM3A8, and GM3A15, were selected for recombinant expression and were characterized using BIAcore and flow cytometry. BIAcore measurements using the purified, soluble scFvs yielded dissociation constants (K(d)) ranging from 4.2 x 10(-7) to 2.1 x 10(-5) M. Flow cytometry was used to evaluate the ability of each scFv to discriminate between normal human cells (human dermal fibroblast, HDFa), melanoma cells (HMV-1, M21, and C-8161), and breast cancer cells (BCM-1, BCM-2, and BMS). GM3A6 displayed cross-reactivity with normal cells, as well as tumor cells, and GM3A15 possessed little or no binding activity toward any of the cell lines tested. However, GM3A8 bound to five of the six tumor cell lines and showed no measurable reactivity against the HDFa cells. Hence, we have demonstrated that a synthetic G(M3) panning reagent can be used to isolate a fully human scFv that is highly specific for native G(M3) on the surface of tumor cells. The result is a significant step toward effective immunotherapies for the treatment of cancer.     

单态铝酸根离子与单态硅酸根离子反应的研究

研究了碱性条件下单态铝酸根离与单态硅酸根离子的反应。实验结果表明，生成的硅铝酸盐沉淀与溶液中的Ａｌ，Ｓｉ以及ＯＨ＾－浓义有关。反应过程中存在过饱和现象，反应体系的ＯＨ＾－浓度反应物Ｓｉ／Ａｌ比影响过饱和时间和过饱和区。     

X射线荧光分析中熔融制样条件的研究

本文研究了熔融制样时熔融温度、熔融时间和脱模剂的加入量对分析结果的影响。研究结果表明,随着熔融温度的升高和熔融时间的加长,分析结果的总值将随之增大。相反,脱模剂量的增加会使分析结果降低。通过对熔融样品时产生的升华物的研究,发现在熔触过程中,四硼酸锂比样品以更大的比例逸出熔融体,从而造成了样品在分析圆片中的相对浓缩。而且在高温熔融时,钾和钠比样品中的其他元素例如硅、铝、铁、钛、钙、镁等更易于逸失。制样条件的不同引起样品和熔剂逸失的比例会有变化,它直接影响测定的结果,这证明了在X射线荧光光谱分析中保持制样条件一致的重要性。     

催化光度法测定痕量甲醛

基于磷酸介质中甲醛催化溴酸钾氧化溴甲酚紫的褪色反应 ,建立了测定痕量甲醛的方法。方法的检出限为 1.0× 10 - 5g·L- 1,线性范围为 0 .0 2 0～ 0 .4 8μg·ml- 1,方法简便 ,用于空气中测定痕量甲醛 ,结果满意。     

相反转技术制备环氧树脂水基体系——相反转过程的流变行为研究

对高乳化剂浓度下的相反转发展过程的流变行为进行了应力扫描、动态频率扫描实验表征．结果表明，乳化剂浓度较高时，体系发生完全相反转；体系在相反转点前为Ｗ／Ｏ结构，其粘度几乎不随剪切应力的改变而改变，表现为牛顿流体行为；体系在相反转点后为Ｏ／Ｗ结构，具有很高的粘弹性，并且在较高剪切应力下表现为典型的假塑性．这是由于高分子水基微粒间通过其表面覆盖的表面活性剂与水形成氢键而产生了一种静态结构，此结构在较高剪切应力作用下破坏而导致假塑性．     

Physical properties and electrochemical performance of LiMn2O4 cathode materials prepared by a precipitation method

LiMn₂O₄ powder for lithium-ion batteries was prepared by a precipitation method, and the effects of calcination temperature on the physical properties and electrochemical performance of the samples were investigated by various methods. The results of X-ray diffraction (XRD) showed that the lattice parameter (a) and the unit cell volume (v) decrease with the increasing calcination temperature, and the LiMn₂O₄ sample calcined at 750°C has smaller particle size and higher crystallinity than other samples. The results of the electrochemical experiments showed that the sample calcined at 750°C has larger peak currents, higher initial capacity, and better cycling capability, because of its lower charge-transfer resistance and larger diffusion coefficient of Li⁺ ions than those of other samples.     

STUDIES ON THE SPHERULITE FORMATION IN MELT CAST POLYCAPROLACTONE BASED POLYURETHANES

A series of PCL/MDI/BDO segmented polyurethanes have been synthesized by two-step method in solution.The hard segment content ranges from 10% to 48% by weight, and the molecular weight of PCL diols is 1500. Hard segment spherulites have been observed in compression molded specimens of all of the samples except the one of the lowest hard segment content. The difficulty in sphernlite formation was explained as only in a small temperature range,the microphase separation rate may be faster than the crystallization rate and all these processes are very slow due to the hydrogen bonding between hard and soft segments and the interactions between hard segments themselves. PCL soft segments of molecular weight 1500 is still crystallizable and may form different crystalline superstructures.     

Novel dual inhibitors against FP-2 and PfDHFR as potential antimalarial agents: Design,synthesis and biological evaluation

A series of novel 2,4-diaminopyrimidine-modified compounds was designed and synthesized. Compound 14 showed micromolar dual inhibitory effect on both FP-2 and PfDHFR, and potential inhibition to the proliferation of P. falciparum 3D7 strain and chloroquine-resistant P. falciparum Dd2 strain.     

Homolysis of the Ln-N (Ln = Yb, Eu) bond. Synthesis, structural characterization and catalytic activity of ytterbium(II) and europium(II) complexes with methoxyethyl functionalized indenyl ligands

The interaction of methoxyethyl functionalized indene compounds (C(9)H(6)-1-R-3-CH(2)CH(2)OMe, R =t-BuNHSiMe(2)(1), Me(3)Si (2), H (3)) with [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5)) produced a series of new ytterbium(II) and europium(II) complexes via tandem silylamine elimination/homolysis of the Ln-N (Ln=Yb, Eu) bond. Treatment of the lanthanide(III) amides [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5) with 2 equiv. of, 1,2 and 3, respectively, produced, after workup, the ytterbium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Yb(II) (6), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Yb(II) (7), (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Yb(II)(8) and the corresponding europium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Eu(II)(9), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Eu(II)(10) and (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Eu(II)(11) in moderate to good yield. In contrast, interaction of the corresponding indene compounds 1, 2 or 3 with the lanthanide amides [(Me(3)Si)(2)N](3)Ln (Ln = Yb, Eu) was not observed, while addition of 0.5 equiv. of anhydrous LiCl to the corresponding reaction mixture produced, after workup, the corresponding ytterbium(II) or europium(II) complexes. All the new compounds were fully characterized by spectroscopic and elemental analyses. The structures of complexes, and were determined by single-crystal X-ray analyses. The catalytic activity of all the ytterbium(II) and europium(II) complexes on MMA polymerization was examined. It was found that all the ytterbium(II) and europium(II) complexes can function as single-component MMA polymerization catalysts. The temperature, solvent and ligand effects on the catalytic activity were studied.