mSA-CS双极膜在电还原制备巯基乙酸中的应用

用Ca^2＋改性海藻酸钠(SA), 用戊二醛(GA)改性壳聚糖(CS), 制备mSA-CS聚合物双极膜. 测定膜的红外光谱及机械性能, 并作膜的热重分析. 以扫描电镜观察膜表面和界面层形态. 测定了mCS膜制备溶液的粘度以及mSA, mCS膜的含水率、离子交换容量及酸碱浓度对膜溶胀度的影响. 将mSA-CS双极膜应用于电解还原制备巯基乙酸(TGA). 实验结果表明, 以硫代硫酸钠法合成的TGA和二硫代二乙酸(DTDGA)的混合液作阴极液, TGA初始合成质量分数为4.61%, 电流密度为10 mA•cm^－2下常温电解, 产物巯基乙酸的电流效率达66.7%. 与传统的金属还原法还原DTDGA成TGA相比, 不仅省去了昂贵的金属还原剂的消耗, 而且消除了对环境的污染.     

Ni-mSA-mCS双极膜的制备及其在电合成TGA中的应用

通过用Ca2+改性海藻酸钠(SA)和用戊二醛改性壳聚糖(CS)制备Ni-mSA-mCS(m: modified)双极膜. 镍网预先埋在mSA膜表面作为阴极, 不仅增强了膜的机械性能, 而且降低阴极电解液的IR降, 实现零极距. 测定了膜的红外光谱、电镜扫描、机械性能. 将Ni-mSA-mCS双极膜应用于电还原制备巯基乙酸(TGA). 实验结果表明, 电流密度为10 mA·cm-2, 常温电解, 电流效率可达66.7%. 与传统的Zn还原法相比, 不仅省去了昂贵的金属还原剂的消耗, 而且消除了锌泥对环境的污染.     

mCMC-PEG-CS双极膜在电还原制备巯基乙酸中的应用

以Fe3+改性羧甲基纤维素(CMC)和聚乙二醇(PEG)共混物为阳膜, 以戊二醛改性壳聚糖(CS)和聚乙二醇共混物为阴膜, 制备了mCMC-PEG-CS双极膜, 并将其用作电解还原制备巯基乙酸(TGA)电解槽中阴阳两室间的隔膜. 以硫代硫酸钠法合成的巯基乙酸(TGA)和二硫代二乙酸(DTDGA)混合物为原料, 研究了酸浓度、温度及电解电流密度对电还原DTDGA制备TGA的生成量和电流效率的影响. 实验结果表明, 在TGA初始合成质量分数为2.79%, 电流密度为10 mA/cm2, 35 ℃电解时, 阴极室电还原产物巯基乙酸的电流效率为74.69%, 电解过程中的平均电流效率为54.02%. 与传统的金属还原法还原DTDGA制备的TGA相比, 不仅避免了昂贵的金属还原剂锌的消耗, 而且消除了反应副产物锌泥对环境的污染.     

Photometric determination of thioglycolic acid in cosmetics by using a stopped-flow reverse flow-injection system and the formation of gold nanoparticles

The positive effect of thiol compounds as reducing agents in the synthesis of gold nanoparticles in the presence of a micellar medium of Triton X-100 has been photometrically studied using a reverse flow-injection system which operates in the stopped-flow mode (SF-rFIA). The analytical usefulness of this new system has been assessed by its application to the determination of thioglycolic acid (TGA), which was chosen as the analyte model. The dynamic range of the calibration graph was 5.97–80 μmol L^?1, and the detection limit was 1.73 μmol L^?1. The behaviour of other thiol compounds on the system has been also studied. The precision of the method, expressed as relative standard deviation, ranged between 1.5 and 2.3%. The method was applied to the determination of TGA in several cosmetic samples with acceptable recoveries in all instances, which ranged between 90.32 and 101.46%.     

Synthesis of a PEBAX-1074/ZnO nanocomposite membrane with improved CO_2 separation performance

In this investigation, polymeric nanocomposite membranes(PNMs) were prepared via incorporating zinc oxide(ZnO) into poly(ether-block-amide)(PEBAX-1074) polymer matrix with different loadings. The neat membrane and nanocomposite membranes were prepared via solution casting and solution blending methods, respectively. The fabricated membranes were characterized by field emission scanning electron microscopy(FESEM) to survey cross-sectional morphologies and thermal gravimetric analysis(TGA)to study thermal stability. Fourier transform infrared(FT-IR) and X-ray diffraction(XRD) analyses were also employed to identify variations of the chemical bonds and crystal structure of the membranes, respectively. Permeation of pure gases, CO_2, CH_4 and N_2 through the prepared neat and nanocomposite membranes was studied at pressures of 3–18 bar and temperature of 25 °C. The obtained results showed that the fabricated nanocomposite membranes exhibit better separation performance compared to the neat PEBAX membrane in terms of both permeability and selectivity. As an example, at temperature of 25 °C and pressure of 3 bar, CO_2 permeability, ideal CO_2/CH_4 and CO_2/N_2 selectivity values for the neat PEBAX membrane are 110.67 Barrer, 11.09 and 50.08, respectively, while those values are 152.27 Barrer,13.52 and 62.15 for PEBAX/ZnO nanocomposite membrane containing 8 wt% ZnO.     

Fast analysis of thiocyanate by ion-pair chromatography with direct conductivity detection on a monolithic column

Fast analysis of thiocyanate by ion-pair chromatography using a silica-based monolithic column and direct conductivity detection was carried out. Chromatographic separation was performed on a Chromolith Speed ROD RP-18e using tetrabutylammonium hydroxide （TBA）-phthalic acid-acetonitrile as eluent. The effects of eluent concentration, eluent pH value, column temperature and flow rate on retention time of thiocyanate were investigated. The optimized chromatographic conditions for the determination of thiocyanate were as follows： 0.25 mmol/L TBA-0.18 mmol/L phthalate-7% acetonitrile （pH 5.5） as eluent, column temperature of 30 ℃, and flow rate of 6.0 mL/min. Retention time of thiocyanate was less than 1 min under the conditions. Common anions （Cl^-, NO3 , SO42 and I^- ） did not interfere with the determination of thiocyanate. Detection limit （S/N = 3） of thiocyanate was 0.96 mg/L. Calibration graph between peak area and the concentration of thiocyanate was linear in the range of 2.0- 100.0 mg/L. Relative standard deviation （RSD） of chromatographic peak area was 1.4% （n = 5）. This method has been applied to the determination of thiocyanate in ionic liquids. Recoveries of thiocyanate after spiking were 100.5%.     

四磺酸基铜酞菁-海藻酸钠/壳聚糖双极膜的制备与表征

分别用Fe3+和戊二醛作为交联剂对海藻酸钠(SA)阳离子交换膜和壳聚糖(CS)阴离子交换膜进行改性,制备了四磺酸基铜酞菁(CuTsPc)-海藻酸钠/改性壳聚糖双极膜(CuTsPc-SA/mCSBPM).在海藻酸钠阳膜层中添加四磺酸基铜酞菁,以提高阳膜层的离子交换容量,促进双极膜中间层中水的解离.采用X射线光电子能谱(XPS)对CuTsPc-SA阳离子交换膜进行了表征.实验结果表明,改性后SA阳膜层的离子交换容量、H+透过率均获得提高.与Fe3+改性或二茂铁离子改性的mSA/mCS双极膜相比,CuTsPc-SA/mCS双极膜的阻抗及电阻压降(即膜IR降)均下降.当电流密度为120mA/cm2时槽电压仅为5.6V.当CuTsPc含量为2.5%(质量分数)时CuTsPc-SA/mCS双极膜在H+离子浓度小于8mol/L的酸溶液中具有稳定的工作性能.     

An efficient and facile procedure for synthesis of octyl polyglucoside

Nonionic surfactant alkyl polyglucoside (APG) was prepared by direct glycosidation of alkyl alcohol with glucose in the presence of sulfate acid-silica gel (H_2SO_4/SiO_2) as solid acidic catalyst.The quantity of catalyst was only of 1 wt%,based on the glucose,and the conversion of glucose was close to 100% at 110℃in 1.5h.The product was characterized by FT-IR,mass and ~1H NMR spectra.The degree of polymerization (DP) of the glucose in the product was 1.37,and critical micelle concentration (CMC) of product was only 0.0104 wt%.     

Preparation of anion exchange membrane based on block copolymers. Part II: the effect of the formation of macroreticular structure on the membrane properties

The anion exchange membrane was prepared by conducting the formation of macroreticular structure and the introduction of ion exchange groups to the chloromethylated copolymers simultaneously. The membrane properties are summarized below; 0.9–1.4 Ω cm² for area resistivity in 2 M KCl aqueous solution, 1.46–3.7 meq/g-dry-resin for the ion exchange capacity and 0.68–0.87 for the static transport number. The membrane properties of the membrane prepared by forming the macroreticular structure and the introduction of the ion exchange groups to the chloromethylated copolymers simultaneously (B membrane) had higher performance than that of the membrane prepared by the amination of the chloromethylated copolymers (A membrane). It would be expected that the formation of macroreticular structure in the membrane has an effect on the membrane properties. The chemical stability of B membrane which was determined by the oxidative degradation in 2 M nitric acid, had long lifetime with almost the same value of the area resistivity and ion exchange capacity as before durability test.     

Impedance spectroscopy and conductometric biosensing for probing catalase reaction with cyanide as ligand and inhibitor

In this work, a new biosensor was prepared through immobilization of bovine liver catalase in a photoreticulated poly (vinyl alcohol) membrane at the surface of a conductometric transducer. This biosensor was used to study the kinetics of catalase–H₂0₂ reaction and its inhibition by cyanide. Immobilized catalase exhibited a Michaelis–Menten behaviour at low H₂0₂ concentrations (< 100 mM) with apparent constant K_M^app = 84 ± 3 mM and maximal initial velocity V_M^app = 13.4 μS min^? 1. Inhibition by cyanide was found to be non-competitive and inhibition binding constant K_i was 13.9 ± 0.3 μM. The decrease of the biosensor response by increasing cyanide concentration was linear up to 50 μM, with a cyanide detection limit of 6 μM. In parallel, electrochemical characteristics of the catalase/PVA biomembrane and its interaction with cyanide were studied by cyclic voltammetry and impedance spectroscopy. Addition of the biomembrane onto the gold electrodes induced a significant increase of the interfacial polarization resistance R_P. On the contrary, cyanide binding resulted in a decrease of Rp proportional to KCN concentration in the 4 to 50 μM range. Inhibition coefficient I₅₀ calculated by this powerful label-free and substrate-free technique (24.3 μM) was in good agreement with that determined from the substrate-dependent conductometric biosensor (24.9 μM).     

八羧基铜酞菁修饰海藻酸钠阳膜层制备CuPc(COOH)8-SA/mCS双极膜及其表征

在海藻酸钠(SA)中添加八羧基铜酞菁(CuPc(COOH)₈),并分别用Fe³⁺离子和戊二醛作为交联剂对海藻酸钠-八羧基铜酞菁阳膜层和壳聚糖(CS)阴膜层进行改性,制备了八羧基铜酞菁-海藻酸钠/改性壳聚糖双极膜(CuPc(COOH)₈-SA/mCS BPM)。在海藻酸钠中添加八羧基铜酞菁以促进中间层中水的解离。用FTIR、SEM等对制备的CuPc(COOH)₈-SA/mCS双极膜进行了表征。作为比对,制备了Fe³⁺离子改性的Fe-SA/mCS双极膜和二茂铁(Fc)离子改性的Fc-SA/mCS双极膜。实验结果表明,CuPc(COOH)₈-SA阳离子交换膜的离子交换容量、H⁺离子透过率均获得提高。与Fe³⁺离子改性或二茂铁离子改性的mSA/mCS双极膜相比,CuPc(COOH)₈-SA/mCS双极膜的阻抗、电阻压降(IR降)和溶胀度降低,在H+离子浓度低于8 mol·L^-1的酸溶液中具有稳定的工作性能。     

Electro-reduction of cuprous chloride powder to copper nanoparticles in an ionic liquid

Cyclic voltammetry of the CuCl powder in a cavity microelectrode revealed direct electro-reduction in solid state in 1-butyl-3-methylimidazolium hexafluorophosphate. Potentiostatic electrolysis of the salt powder (attached to a current collector) in the ionic liquid produced Cu nanoparticles as confirmed by X-ray diffraction, energy dispersive X-ray analysis, scanning and transmission electron microscopy. The particle size decreased down to 10 nm when the electrode potential was shifted from −0.9 V to −1.8 V (versus Ag/Ag⁺). The electro-reduction and the nanoparticle formation mechanisms were investigated in the ionic liquid and also in aqueous 0.1 mol L⁻¹ KClO₄ in which larger Cu particles were obtained.     

Simultaneous determination of acetaminophen,dopamine and ascorbic acid using a PbS nanoparticles Schiff base-modified carbon paste electrode

A highly sensitive method was investigated for the simultaneous determination of acetaminophen (AC), dopamine (DA), and ascorbic acid (AA) using a PbS nanoparticles Schiff base-modified carbon paste electrode (PSNSB/CPE). Differential pulse voltammetry peak currents of AC, DA and AA increased linearly with their concentrations within the ranges of 3.30 × 10⁻⁸–1.58 × 10⁻⁴ M, 5.0 × 10⁻⁸–1.2 × 10⁻⁴ M and 2.50 × 10⁻⁶–1.05 × 10⁻³ M, respectively, and the detection limits for AC, DA and AA were 5.36 × 10⁻⁹, 2.45 × 10⁻⁹ and 1.86 × 10⁻⁸ M, respectively. The peak potentials recorded in a phosphate buffer solution (PBS) of pH 4.6 were 0.672, 0.390, and 0.168 V (vs Ag/AgCl) for AC, DA and AA, respectively. The modified electrode was used for the determination of AC, DA, and AA simultaneously in real and synthetic samples.     

Interaction and solubilization of some phenolic antioxidants in Pluronic® micelles

The solubilization of four phenolic antioxidants, namely p-hydroxybenzoic acid (PHBAA), syringic acid, sinapic acid, and quercetin in micelles of an ethylene oxide (EO)–propylene oxide (PO) triblock copolymer Pluronic^® P104 (EO₂₇–PO₆₁–EO₂₇, PPO mol wt = 3540, % PEO = 40) was examined at different temperatures, pHs, and in the presence of sodium chloride. The nano-size core–shell micelles of P104 characterized by dynamic light scattering had hydrodynamic diameter of about 18–20 nm with low polydispersity. Antioxidants induced micellization and micellar growth were observed. The critical micellar concentration (CMC), critical micellar temperature (CMT), cloud point (CP) of P104 decreased due to solubilization and interactions of antioxidants. The solubilization was favored at higher temperature, pH and in the presence of salt and follows the order PHBA > syringic acid > sinapic acid > quercetin which corresponds to the trend in their aqueous solubility. The location of antioxidant in micelles observed from NOESY spectra. Structure and hydrophobicity of antioxidants were found to be governing factors for their interaction and location in the micelles.     

Potentiometric determination of diclofenac in pharmaceutical formulation by membrane electrode based on ion associate with base dye

The characteristics,performance and application of membrane electrode based on ion associate of diclofenac with base dye Safranine T are described.The electrode response to diclofenac has the sensitivity of 47±1.0 mV decade~(-1)over the range of 5×10~(-5)to 5×10~(-2)mol/L at pH 6-12,and the detection limit of 3.2×10~(-5)mol/L.The electrode is easy assembled at a relatively low cost has fast response time(2-4 s)and can be used for a period up to 3.5 months without any considerable divergence in potential.The proposed sensor displayed good selectivity for diclofenac in the presence of different substances.It was used to determine diclofenac in pharmaceuticals by means of the standard addition method.     

Sensitive lactate determination based on acclimated mixed bacteria and palygorskite co-modified oxygen electrode

A sensitive bacteria biosensor was prepared for the detection of trace lactate. The sensitive bioelement, Lactobacillus bulgaricus and Streptococcus thermophilus mixed cultrue, and palygorskite, a perfect matrix for bacteria, was co-immobilized on the surface of oxygen electrode. The biosensor possesses fine selective specificity, good sensitivity and longer operational life time, which were due to the mutual help relationship of symbiotic bacteria and 240 days acclimation with lactate as the carbon source. Hydrodynamic amperometry, an advanced electrochemical method, is suitable for on-line monitoring the concentration change of dissolved oxygen that is closely accompanied with the metabolism of lactate. Electrochemical data show that the current is very sensitive to the changes of the concentration of lactate. The response current was linear with lactic acid concentration in the range from 0 to 300 μmol L^? 1, where the response time is no more than 240 s (R = 0.9952), and the sensitivity was 1.87 mA mol^? 1 L. Experiments show the biosensor is also very useful for long time on-line monitoring of lactate, such as fermentation progress.     

A novel sensitive biosensor for Ca2+ based on electropolymerized melatonin modified electrode

An electropolymerized melatonin modified glassy carbon electrode (EPMT/GCE) was prepared by electrochemically polymerizing of melatonin in a 0.04 mol l^?1 perchloric acid solution. In KCl solution, Ca²⁺ was found to perform a reversible complex reaction on the EPMT/GCE to produce a sharp complex adsorption wave. The configuration of the electropolymerized membrane was characterized by scanning electron microscope and various electrochemical techniques. Based on which, a novel sensitive Ca²⁺ electrochemical sensor was established. The peak current showed a linear relationship with Ca²⁺ concentration in range of 6.2 × 10^?7–1.0 × 10^?4 mol l^?1 with detection limit of 4.5 × 10^?7 mol l^?1. The developed electrochemical sensor has been used for determination of Ca²⁺ in body fluid.     

Glucose biosensor based on new carbon nanotube-gold-titania nano-composites modified glassy carbon electrode

In this paper, a novel biosensor was prepared by immobilizing glucose oxidase （GOx） on carbon nanotube-gold-titania nanocomposites （CNT/Au/TiO2） modified glassy carbon electrode （GCE）. SEM was initially used to investigate the surface morphology of CNT/Au/TiO2 nanocomposites modified GCE, indicating the formation of the nano-porous structure which could readily facilitate the attachment of GOx on the electrode surface. Cyclic voltammogram （CV） and electrochemical impedance spectrum （EIS） were further utilized to explore relevant electrochemical activity on CNT]Au/TiO2 nanocomposites modified GCE. The observations demonstrated that the immobilized GOx could efficiently execute its bioelectrocatalytic activity for the oxidation of glucose. The biosensor exhibited a wider linearity range from 0.1 mmol L-1 to 8 mmol L^-1 glucose with a detection limit of 0.077 mmol L^- 1.     

Stannous-acetylacetonate： A new catalyst for poly（trimethylene terephthalate） synthesis

Stannous-acetylacetonate was prepared efficiently and characterized by 1H NMR and FT-IR. Its catalytic activity for poly(trimethylene terephthalate) (PTT) synthesis was investigated. By this catalyst, the degree of esterification of pure terephthalic acid was up to 91.7% after reaction at 260°C for 2 h, while the intrinsic viscosity and content of ter- minal carboxyl groups of the corresponding PTT polymerized at 260°C, 60 Pa for 2 h was 0.8816 dL/g and 17 mol/t, respectively. Stannous-acetylacetonate was more active and promising than tetrabutyl titanate and stannous octoate for PTT synthesis.     

Optimization of the chemoenzymatic mono-epoxidation of linoleic acid using D-optimal design

Mono-epoxied linoleic acid 9(12)-10(13)-monoepoxy 12(9)-octadecanoic acid (MEOA) was synthesized and optimized by immobilized Candida antarctica lipase (Novozym 435®) using D-optimal design. For optimizing the reaction, response surface methodology (RSM) was employed with four reaction variables such as the effect of amount of hydrogen peroxide (μL), amount of enzyme (w) and reaction time (h). At optimum conditions the experiment to obtain a higher yield% with a medium OOC% of MEOA was predicted at an amount of H₂O₂ μL of 15, Novozym 435® of 0.12 g and 7 h of reaction time. At this condition, the yield of MEOA was 82.14%, 4.91% of OOC and 66.65 mg/g of iodine value (IV). The observed value was reasonably close to the predicted value. Hydrogen peroxide was found to have the most significant effect on the degree of epoxidation OOC% and yield%. The epoxy ring opening (–C–O–C–) has been observed by Fourier Transform Infrared Spectroscopy (FTIR) at 820 cm⁻¹ and the double band (–CC–) at 3009 cm⁻¹. ¹H NMR analyses confirmed that the oxirane ring (–CH–O–CH–) of MEOA at 2.92–3.12 ppm and four signals of methane (–CHCH–) was at 5.38–5.49 ppm while the ¹³C NMR showed the oxirane ring (–C–O–C–) at 54.59–57.29 ppm and the olefinic carbons at 124.02–132.89 ppm.