Reducing organic substances from anaerobic decomposition of hydrophytes

Oxidation-reduction properties of surface sediments are tightly associated with the geochemistry of substances, and reducing organic substances (ROS) from hydrophytes residues may play an important role in these processes. In this study, composition, dynamics, and properties of ROS from anaerobic decomposition of Eichhornia crassipes (Mart.) Solms, Potamogenton crispus Linn, Vallisneria natans (Lour.) Hara, Lemna trisulca Linn and Microcystis flos-aquae (Wittr) Kirch were investigated using differential pulse voltammetry (DPV). The type of hydrophytes determined both the reducibility and composition of ROS. At the peak time of ROS production, the anaerobic decomposition of M. flos-aquae produced 6 types of ROS, among which 3 belonged to strongly reducing organic substance (SROS), whereas there were only 3-4 types of ROS from the other hydrophytes, 2 of them exhibiting strong reducibility. The order of potential of hydrophytes to produce ROS was estimated to be: M. flos-aquae > E. crassipes > L. trisulca > P. crispus approximate to V. natans, based on the summation of SROS and weakly reducing organic substances (WROS). The dynamic pattern of SROS production was greatly different from WROS. The total SROS appeared periodic fluctuation with reducibility gradually weakening with incubation time, whereas the total WROS increased with incubation time. Reducibility of ROS from hydrophytes was readily affected by acid, base and ligands, suggesting that their properties were related to these aspects. In addition to the reducibility, we believe that more attention should be paid to the other behaviors of ROS in surface sediments.

Sorptive interaction between goethite and strongly reducing organic substances from anaerobic decomposition of green manures

Strongly reducing organic substances (SROS) and iron oxides exist widely in soils and sediments and have been implicated in many soil and sediment processes. In the present work, the sorptive interaction between goethite and SROS derived from anaerobic decomposition of green manures was investigated by differential pulse voltammetry (DPV). Both green manures, Astragaltus sinicus (Astragalus) and Vicia varia (Vicia) were chosen to be anaerobically decomposed by the mixed microorganisms isolated from paddy soils for 30 d to prepare different SROS. Goethite used in experiments was synthesized in laboratory. The anaerobic incubation solutions from green manures at different incubation time were arranged to react with goethite, in which SROS concentration and Fe(II) species were analyzed. The anaerobic decomposition of Astragalus generally produced SROS more in amount but weaker in reducibility than that of Vicia in the same incubation time. The available SROS from Astragalus that could interact with goethite was 0.69 +/- 0.04, 0.84 +/- 0.04 and 1.09 +/- 0.03 cmol kg(-1) as incubated for 10, 15 and 30 d, respectively, for Vicia, it was 0.12 +/- 0.03, 0.46 +/- 0.02 and 0.70 +/- 0.02 cmol kg(-1). One of the fates of SROS as they interacted with goethite was oxidation. The amounts of oxidizable SROS from Astragalus decreased over increasing incubation time from 0.51 +/- 0.05 cmol kg(-1) at day 10 to 0.39 +/- 0.04 cmol kg(-1) at day 30, but for Vicia, it increased with the highest reaching to 0.58 +/- 0.04 cmol kg(-1) at day 30. Another fate of these substances was sorption by goethite. The SROS from Astragalus were sorbed more readily than those from Vicia, and closely depended upon the incubation time, whereas for those from Vicia, the corresponding values were remarkably less and apparently unchangeable with incubation time. The extent of goethite dissolution induced by the anaerobic solution from Vicia was greater than that from Astragalus, showing its higher reactivity. (c) 2008 Published by Elsevier Ltd.

金属纳米材料的合成，组装及电化学性质的研究

利用Brust的两相法制备了一系列Au纳米粒子，重点选择了三种代表性的硫醇配体：包括电活性的4-二茂铁苯硫酚配体，刚性的琉基一三苯基甲烷配体和树枝状硫醇配体。摸索了实验条件对Au纳米粒子粒径的影响。其中重点研究了电活性配体4-二茂铁苯硫酚包覆的Au纳米粒子的电化学性质，它受表面波控制。制备了梭酸配体包覆的水溶性的Au纳米粒子，讨论了梭酸配体在Au纳米粒子表面构向的不同对电解质诱导的Au纳米粒子聚沉的影响。利用双硫醇与4-二茂铁苯硫酚包覆的Au纳米粒子发生配体交换后，将这种电活性的Au纳米粒子组装在金电极表面。XPS结果证明了这个组装的过程，研究了这种电活性Au纳米粒子在电极表面的电化学行为，包括式量电位，峰峰电位差，覆盖度等等。重点讨论了这种组装在电极表面的Au纳米粒子的式量电位发生负移的原因。制备了水溶性的3一琉基甘油包覆的Au纳米粒子，利用微分脉冲伏安（DPv）技术发现了这种Au纳米粒子在水溶液中的量子化充放电现象。3一琉基甘油在Au纳米粒子表面的特殊结构，即大量存在的分子间氢键，避免了水分子渗入硫醇配体层带来的高介电常数的干扰，试验得到了这种Au纳米粒子的电容值，与经典的导电同心球模型计算的理论值接近。利用水溶性的Au纳米粒子为催化剂，催化一个经典的胶体催化的氧化还原反应：铁氰化钾与硫代硫酸钠之间的反应。其催化反应机理为：胶体金作为电子转移媒介体，铁氰根离子和硫代硫酸根离子在胶体金表面交换电子，促进氧化还原反应的进行．利用该氧化还原反应的速度，计算了电子在金纳米粒子表面的三维自组装膜中的电子转移速度。制备了一种空心CdTe＠Au核一壳结构的复合纳米材料。与传统方法制备的实心CdTe＠Au相比，这种空心的纳米材料仍然保留了cdTe的荧光性能．这种空心材料增加了CdTe导带电子和Au之间的电子传递距离，减弱了Au对CdTe发光的淬灭。这种可发光的空心的半导体一金属核一壳纳米材料，有望在光催化，太阳能电池，表面增强拉曼检测，生物标记等诸多领域获得应用．

鸭瘟病毒gB蛋白N端抗原域的高效表达及其免疫特性

在分析鸭瘟病毒(Duck plague virus,DPV)gB蛋白抗原性的基础上,设计1对引物克隆gB蛋白N端抗原性较好的抗原域编码基因,克隆到表达载体pET32a中,构建了原核表达质粒pET-gB1。将pET-gB1转化到感受态大肠杆菌(Escherichia coli)BL21(DE3)中,经IPTG诱导和SDS-PAGE分析,可见约42.4kD的目的蛋白以包涵体形式表达。Western blot分析发现,表达产物与抗鸭瘟的鼠阳性血清发生特异性反应。将包涵体溶解于8mol/L的尿素中,利用His·Bind试剂盒获得纯化的蛋白,将纯化的蛋白皮下注射免疫小鼠,间接ELISA法测得抗体的效价,MTT法检测免疫小鼠的T淋巴细胞增殖反应能力。结果说明,该融合蛋白能够诱导机体产生较强的体液免疫和细胞免疫。

Electrochemical Detection of Hydrazine Based on Electrospun Palladium Nanoparticle/Carbon Nanofibers

In this work, we developed an electrochemical method for the detection of hydrazine based oil palladium nanoparticle/carbon nanofibers (Pd/CNFs). Pd/CNFs were prepared by electrospinning technique and subsequent thermal treatments. The electrocatalytic behaviors of Pd/CNFs modified glassy carbon electrode (Pd/CNF-GCE) for hydrazine oxidation were evaluated by cyclic voltammetry (CV), an obvious and well-defined oxidation peak appeared at -0.32 V (vs. Ag/AgCl). The mechanism of the oxidation of hydrazine at Pd/CNF-GCE was also studied, which demonstrated an irreversible diffusion-controlled electrode process and a four-electron transfer involved in the overall reaction. Furthermore, the wide linear range, low detection limit, good reproducibility and excellent storage stability were obtained utilizing differential pulse voltammetry (DPV).

钯/碳纳米纤维复合材料修饰电极同时检测邻苯二酚和对苯二酚

利用电纺丝技术制得钯/碳纳米纤维复合材料(Pd/CNFs),并将其用于修饰玻碳电极Pd/CNF-GCE/CME。Pd/CNF-GCE/CME对邻苯二酚和对苯二酚的氧化还原反应具有较高的电催化活性,显著提高了二者电化学反应的可逆性。考察了支持电解质的酸度对邻苯二酚和对苯二酚电化学响应的影响,选用0.1mol/LPBS(pH8.0)作为支持电解质。用微分脉冲伏安(DPV)法对邻苯二酚和对苯二酚进行选择性检测:当混合溶液中存在50μmol/L对苯二酚时,邻苯二酚的氧化峰电流与其浓度在1～90μmol/L范围内呈线性关系,检出限为0.3μmol/L(S/N=3);当存在50μmol/L邻苯二酚时,对苯二酚的氧化峰电流与其浓度在2～100μmol/L范围内呈线性关系,检出限为1.0μmol/L。另外,此修饰电极具有较好的重现性和较强的抗干扰能力。将此修饰电极用于模拟水样中邻苯二酚和对苯二酚的测定,结果令人满意。

Au nanoparticles grafted sandwich platform used amplified small molecule electrochemical aptasensor

We report a sensitively amplified electrochemical aptasensor using adenosine triphosphate (ATP) as a model. ATP is a multifunctional nucleotide thatis most important as a "molecular currency" of intracellular energy transfer. In the sensing process, duplexes consisting of partly complementary strand (PCS1), ATP aptamer (ABA) and another partly complementary strand (PCS2) were immobilized onto Au electrode through the 5'-HS on the PCS1. Meanwhile, PCS2 was grafted with the Au nanoparticles (AuNPs) to amplify the detection signals. In the absence of ATP, probe methylene blue (MB) bound to the DNA duplexes and also bound to guanine bases specifically to produce a strong differential pulse voltammetry (DPV) signal. But when ATP exists, the ABA-PCS2 or ABA-PCS1 part duplexes might be destroyed, which decreased the amount of MB on the electrode and led to obviously decreased DPV signal.

Simultaneous determination of dopamine and ascorbic acid at an in-site functionalized self-assembled monolayer on gold electrode

The in-site functionalization of 4-aminothiophenol (4-ATP) self-assembled monolayer on gold electrode at physiological pH yields a redox active monolayer of 4'-mercapto-N-phenylquinone diimine (MNPD). The functionalized electrode exhibits excellent electrocatalytic responses towards dopamine (DA) and ascorbic acid (AA), reducing the overpotentials by about 0.22 V and 0.34 V, respectively, with greatly enhanced current responses. Due to its different catalytic activities toward DA and AA, the modified electrode resolves the overlapping voltammetric responses of DA and AA into two well-defined voltammetric peaks by differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly related to DA and AA concentration in the ranges of 5.0 x 10-6 - 1.25 x 10-4 M and 8.0 x 10-6 - 1.3 x 10-4 M with correlation coefficient of 0.999 and 0.998, respectively. The detective limits (3sigma) for DA and AA were found to be 1.2 x 10-6 M and 2.4 x 10-6 M, respectively.

IrO2/SnO2 electrodes: prepared by sol-gel process and their electrocatalytic for pyrocatechol

IrO2/SnO2 (10%:90%, molar ratio) electrodes (ITEs) were prepared by the sol-gel method as an alternative to the electrode-position and thermal decomposition process. The electrodes were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), cyclic voltammetry (CV) and electrochemical impedance spectra (EIS). From the results of XRD, oxide films prepared at low temperature were in amorphous state, while hydrous IrO2 crystal and cassiterite phase SnO2 were formed at 300 degreesC or even to 500 degreesC. The highly porous structure was confirmed by AFM. The electrochemical experiments demonstrated that the sol-gel method made the ITEs having a fast electron transfer process with good stability and the optimal preparation temperature was 400 degreesC for the highest electroactivity. Furthermore, the electrocatalysis of pyrocatechol on the electrodes was investigated. A quasi-reversible process occurred and a linear range over three orders magnitude (1 x 10(-2) - 10 mM) was obtained by differential pulse voltammetry (DPV). Meanwhile the detection limit of pyrocatechol was 5 x 10(-3) mM. This study indicated that the sol-gel method was an appropriate route to prepare the IrO2/SnO2 electrodes for the electrocatalytic of pyrocatechol.

A temperature-dependent interaction of neutral red with calf thymus DNA

Neutral red (NR) is used as a probe to study the temperature and concentration dependent interaction of a cationic dye with nucleic acid. A temperature-dependent interaction of NR with calf thymus DNA (CT DNA) has been studied by differential pulse voltammetry (DPV), UV-Visible absorption, circular dichroism (CD) and fluorescence spectroscopy. The experimental results of increasing peak current, changes in the UV-Visible absorption and fluorescence spectra of NR and decreasing the induced circular dichroism (ICD) intensity show that (i) the binding mode of NR molecules is changed from intercalating into DNA base pairs to aggregating along the DNA double helix and (ii) the orientation of NR chromophore in DNA double helix is also changed with the temperature.

Studies of electrochemical quantized capacitance charging of surface ensembles of silver nanoparticles

CTAB-stabilized silver nanoparticles were synthesized by NaBH4 reduction. The as-prepared nanoparticles can be self-assembled on 3-mercaptopropionic acid (MPA) modified gold electrode, which was supported strongly by XPS measurements. Exceptional long-term stability of the as-prepared colloidal silver aqueous solution and the desorption of silver nanoparticle ensemble on MPA after alcohol rinsing proved that these CTAB molecules adsorbed on silver core formed interdigitated bilayer structure. DPV and differential capacitance measurements were performed to characterize the as-prepared silver nanoparticle ensemble. and the interesting quantized capacitance charging behaviors were observed.

肌苷在玻碳电极上的伏安法研究

应用线性扫描伏安法（LSV），微分脉冲伏安法（DPV）和循环伏安法（CV）对肌苷在玻碳电极（GCE）上的阳级伏安行为进行了研究，发现在0．1mol/L磷酸氢二纳溶液中，于1．42V（vs.Ag／AgCl）左右产生一个阳极氧化峰，峰电流与肌苷浓度在5×10-4～8×10-2g/L范围内呈线性关系，峰电位随溶液pH值增加而降低。肌苷在与次黄嘌呤、黄嘌呤、尿酸共存时，可得4个分辨良好的阳极氧化峰，它们的峰电位分别为1．42V、1．07V、0．72V和0．26V。用本法不需分离直接测定了药物针剂和加标尿样。实验结果表明肌苷的电极反应为扩散控制不可逆过程。

In situ infrared spectroelectrochemical studies on adsorption and oxidation of nucleic acids at glassy carbon electrode

The adsorption and oxidation of yeast RNA and herring sperm DNA (HS DNA) at glass carbon (GC) electrode are studied by differential pulse voltammetry (DPV) and in situ FTIR spectroelectrochemistry. Two oxidation peaks of yeast RNA are obtained by DPV, whose peak potentials shift negatively with increasing pH. The peak currents decrease gradually in successive scans and no corresponding reduction peaks occur, thus indicating that the oxidation process of yeast RNA is completely irreversible. The IR bands in the 1200-1800 cm-l range, attributed to the stretching and ring vibrations of nucleic acid bases, show the main spectral changes when the potential is shifted positively, which gives evidence that the oxidation process takes place in the base residues. The oxidation process of HS DNA is similar to that of yeast RNA. The results both from DPV and in situ FTIR spectroelectrochemistry confirm that the guanine and adenine residues can be oxidized at the electrode surface, which is consistent with the oxidation mechanism of nucleic acids proposed previously. (C) 2001 Elsevier Science B.V. All rights reserved.

双嘧达莫在玻碳电极上的阳极伏安法研究

用直流伏安法 (DCV) ,微分脉冲伏安法 (DPV)和循环伏安法 (CV)在玻碳电极 (GCE)上研究了双嘧达莫 (DPM)在不同介质中的阳极伏安行为 ,发现在 0 .0 1mol/LHCl溶液中于 0 6 2V(vs .Ag/AgCl)右左产生一个阳极氧化峰 ,其峰高与浓度的线性方程分别为y =0 0 0 0 4+0 17C(0 .0 5 ～ 1.0mg/L)和y =0 0 5 2 +0 2 2C(0 5～ 10mg/L) ,在此体系中大多数金属离子和 2 0多种有机生化物质不干扰测定。采用该方法可不经分离 ,直接测定药物制剂和尿样中DPM的含量。同时对DPM的电极反应机理进行了探讨

Voltammetric study of vitamin K-3 at interdigitated array microelectrodes

Cyclic voltammetry of Vitamin K-3 (V-K3) was measured with Pt disk electrode, platinum interdigitated array (Pt-IDA) and Au-IDA microelectrodes in single and dual modes. The effects of pH, scan rate and collector potential on the current of generator and collector were studied. The collection efficiency of V-K3 at IDA electrodes was measured. The linear ranges for current response as a function of V-K3 concentration were found to he 10 mu M-1 mM (i(g)) and 1 mu M - 1 mM (i(c)) for the generator and collector of the Pt-IDA electrode, respectively. The effects of waiting time, potential difference and pulse electrolysis time in differential pulse voltammetry (DPV) on the peak current of V-K3 were studied to get the optimal condition at 0.1 M Na2HPO4, pH 11.50 and 11.0 for Au-IDA and Pt-IDA, respectively.