The oxygen reduction reaction at silver electrodes in high chloride media and the implications for silver nanoparticle toxicity

The oxygen reduction reaction (ORR) at neutral pH in various aqueous chloride-containing solutions was investigated voltammetrically. In particular, the ORR was performed in high chloride containing aqueous media including authentic and synthetic seawater under oxygen saturated conditions and compared with that in aqueous nitrate and perchlorate media. The experimental voltammograms revealed a two-electron process forming hydrogen peroxide in low chloride media. In contrast, high concentration chloride solutions, including both synthetic and authentic seawater showed an increase of overpotential, accompanied by a splitting of the voltammetric peak into two one-electron features indicating the formation of superoxide in the first step and its release from the silver-solution interface. The implications for silver nanoparticle toxicology are discussed given the markedly greater toxicity of superoxide over peroxide and the high levels of chloride in biological media as well as in seawater.

Superoxide produced at silver electrode in seawater.     

Remarkably enhanced capacitance of ordered polyaniline nanowires tailored by stepwise electrochemical deposition

A stepwise deposition method was employed to create ordered polyaniline (PANI) nanowires with remarkably enhanced capacitance. Cyclic voltammetry, AC impedance, and galvanostatic charge/discharge cycling were employed to investigate the electrochemical performance of the PANI electrodes. The PANI-deposited electrode exhibits much higher capacitance than those prepared by one-step deposition method, which were mainly contributed from the unique nano structure of PANI and the increased biological, economical, and technical surface areas. The superior capacitive behaviors of the nano PANI electrodes show great potential in preparation of high efficient electrochemical capacitors or rechargeable batteries.     

Detection of environmental chemicals by SPR assay using branched cyclodextrin as sensor ligand

We obtained the association constants Ka of estrogen (E2) and environmental chemicals by the surface plasmon resonance (SPR) assay using the immobilized mono-6-O-α-maltosyl-β-CD (G₂βCD) compared with the immobilized β-CD and the immobilized estrogen receptor (ER). The association behavior of G₂βCD was shown as a ER model compound. The calibration curve was determined by the initial rate of association depending on the various concentrations, and the minimum detectable concentrations in the order of parts per billion were calculated. The SPR assay has advantages that the pre-treatment of the sample is not necessary and the immobilized ligand is stable and useful for the repeated measurement.     

二氧化铈还原表面上水煤气变换反应机理

采用原位红外，程序升温脱附，脉冲表面反应技术研究了ＣｅＯ２还原表面在中温变换反应条件下表面物种的生成及脱附，并根据研究结果归纳出水煤气变换反应机理。     

二(2,4,4-三甲基戊基)膦酸萃取分离稀土元素(Ⅲ)的研究

本文研究了二(2,4,4-三甲基戊基)磷酸(Cyanex 272)的煤油溶液在不同介质(HCI,HNO_3)中对三价混合稀土的萃取分离性能.观测了平衡水相酸度对萃取平衡的影响,由酸度曲线求出相邻元素的平均分离系数,并考察了酸度对反萃取平衡的影响.比较了HCI和HNO_3介质中,Cyanex 272对混合稀土(Ⅲ)的萃取性能.     

四硫富瓦烯为介体的碳纤维束葡萄糖氧化酶微电极的研究

本文研究了一种将电子介体四硫富瓦烯(TTF,Tetrathiafulalene)引入葡萄糖氧化酶微电极的新方法,制成了TTF为介体的碳纤维束葡萄糖氧化酶微电极。该电极制作简单,响应迅速、灵敏,电极寿命可达15天。葡萄糖浓度在1。0×10~(-4)～1.5×10~(-3)mol/L范围内有线性关系。检出限为7×10~(-5)mol/L。用于人体血样中葡萄糖测定获得满意结果。     

两个具有PTP1B抑制活性的4-羟基丁内酯化合物的全合成研究

Two new naturally 4-hydroxylated butenolides were concisely synthesized in excellent enantiomeric purities. An aldol condensation and a Suzuki reaction served successfully as the key steps in the synthesis.     

Polymer-Titanium hybrids obtained by radical polymerization and Sol-Gel process

The possibility to prepare hybrids made by poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA) and/or poly(ethyl acrylate) (PEtA) with TiO₂ was studied. The processes of polymer formation-radical polymerization and sol-gel process for inorganic network —were achieved simultaneously. Due to a high reactivity of titanium isopropoxide (TIP) in the sol-gel process, a complexant comonomer, allyl acetoacetate (AlAcAc), was used. Covalent bonds between polymer and inorganic chains were obtained by addition of trialkoxysilane derivates with vinyl (VTES) or methacryloyl (MPTS) groups. The presence of TIP inhibits the radical polymerization of vinyl acetate (VAc). The PVAc-TiO₂ hybrids were produced by the sol-gel process of TIP in the presence of pre-obtained PVAc. Except for VTES and MPTS, trialkoxysilane derivates with methyl (MeTES), octyl (OTES) and phenyl (PTES) groups were used. The thermal stability of hybrids is strongly affected by TiO₂ presence and by the type of trialkoxysilane derivates. The thermal stability of PVAc hybrids decreases in the presence of TiO₂ inorganic network. The glass transition temperature of polymers increases in the presence of the inorganic network.     

Complexation of well-controlled low-molecular weight polyelectrolytes with antisense oligonucleotides

The influences of polymer-related properties such as molecular weight, charge density, counter ion, and hydrophilic block on the complexation of polyelectrolytes and a fluorescein-labeled oligonucleotide (ON) were investigated. A series of well-defined and well-controlled 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) polymers and block copolymers were prepared using living anionic and radical polymerization methods. Fluorescence measurement was used to reveal the effects of polymer molecular weight, charge density, and counter ion type on the complexation. PolyDMAEMA samples having double molecular weights of the chosen oligonucleotide gave the optimal complexation performance. Kinetic studies showed that high-molecular weight/high-charge density polymer samples produced very stable complexes. The fully charged polyDMAEMA displayed the strongest binding with the ON. These complexes were therefore less sensitive to the changes in the environment. PolyDMAEMA–DMSQ samples had slightly higher complexation ability than polyDMAEMA–MCQ (DMSQ: dimethylsulfate quat; MCQ: methylchloride quat). Both poly(DMAEMA-b-HEMA) and poly(DMAEMA–MCQ-b-PEG) block copolymers showed good complexation ability and steric stability [HEMA: 2-hydroxyethyl methacrylate; PEG: poly(ethylene glycol)]. PEG, but not HEMA block, enhanced the effectiveness of polyDMAEMA–MCQ binding with the ON.     

丙烯环氧化反应的高活性钼催化剂

在钼(Ⅵ),钒(Ⅴ)和钛(Ⅳ)等化合物存在下,丙烯与烷基过氧化氢的环氧化反应比传统的氯醇法有很多优点,其中以钼催化剂的性能最优,但目前报道的催化剂在反应过程中因易分解而降低了活性,并且丙烯与烷基过氧化氢的投料比过大(>3:1),丙烯循环次数过多。前文报道了钼烷基醇胺化合物对环已烯的环氧化反应,本文考察了钼烷基醇胺化合物对丙烯与叔丁基过氧化氢环氧化反应的催化性能。