Determination of Uric Acid in Human Urine by Ion‐exclusion Chromatography with UV Detection Using Pure Water as Mobile Phase

A simple, rapid and accurate ion‐exclusion chromatographic method coupled with a UV detector for the determination of uric acid in human urine samples has been developed. The separation was carried out on an ion‐exclusion column using only pure water as mobile phase. The detection wavelength was 254 nm and urine sample was injected directly without any pretreatment. Furthermore, the retention behavior of uric acid on the ion‐exclusion column was researched when pure water and 1 mmol·L^?1 HCl were used as mobile phase, respectively. The stability of uric acid was also further investigated within 28 days. In this method, the linear range of the calibration curve for uric acid was 0.25–100 mg·L^?1, and the detection limit calculated at S/N=3 was 0.02 mg·L^?1. The proposed ion‐exclusion chromatographic method has been used for the determination of uric acid in human urine.     

Design,Synthesis, and Insecticidal Activity of 1,5‐Diphenyl‐1‐pentanone Analogues

Three series of novel 1,5‐diphenyl‐1‐pentanone derivatives were designed and synthesized. Their structures were characterized by IR, ¹H NMR techniques, and elemental analysis. The insecticidal activities of the new compounds were preliminarily evaluated. The bioassay results indicated that the compounds X11 – X30 displayed better aphicidal activity against Aphis gossypii than compounds X1 – X10 and the lead compound (E)‐1,5‐diphenyl‐1‐penten‐1‐one ( A ). The inhibitory rates of compounds X6 and X29 were 100% against Plutella xylostella (L.) at 600 mg·L^?1. Compounds X12 , X13, X19 , X24, X25 , X26 and X27 showed higher insecticidal activity against Tetranychus cinnabarinus (Boisduval) at 600 mg·L^?1 than the lead compound ( A ).     

A Simple and Sensitive Method for the Detection of Trace Pb(II) and Cd(II) based on Nafion‐coated Antimony Film Electrode

Nafion‐coated antimony film electrode (NCAFE) was prepared in situ by simultaneously plated antimony with analytes, and applied to the determination of trace Pb(II) and Cd(II) in non‐deaerated solutions by differential pulse anodic stripping voltammetry (DPASV). Various experimental parameters, which influenced the response of the NCAFE to those metals, were thoroughly optimized and discussed. The results indicated that the sensitivity and resistance to surfactants at the NCAFE were remarkably improved with relative to the antimony film electrode (AFE). In the presence of 5 mg·L^?1 gelatin, the peak heights at the NCAFE showed 4‐fold enhancement for Pb and a 9‐fold enhancement for Cd over a bare AFE. Reproducibility of the sensor was satisfactory, and the relative standard deviations were 4.8% for 20 μg·L^?1 Pb and 3.2% for 25 μg·L^?1 Cd (n=15) with preconcentration time of 180 s. The determination limits (S/N=3) of this sensor were determined to be 0.15 μg·L^?1 for Pb and 0.30 μg·L^?1 for Cd with accumulation time of 300 s. The NCAFE was successfully applied to determining Pb(II) and Cd(II) in vegetable and water samples with satisfactory results.     

基于T-T碱基错配的荧光传感器特异性检测汞离子

在本文中,我们研制了一种基于T-T碱基错配特异性键合汞离子的荧光传感器用于汞离子的检测。该传感器由两条分别标记了荧光基团（F）和淬灭基团（Q）的DNA探针组成,并且含有两对用于结合汞离子的T-T错配碱基。当汞离子存在时,两条探针之间形成T-Hg2+-T结构,作用力增强,从而拉近了荧光基团与淬灭基团之间的距离,发生能量转移,使荧光信号在一定程度上被淬灭。在优化的条件下,我们使用该传感器对汞离子进行检测,动力学响应范围为50nM到1000nM,线性相关方程为y= 5281.13 - 1650.56 lg[Hg2+] ( R2 = 0.985),检测下限为79nM。此外,我们还考察了该传感器的选择性,当用其它干扰离子（浓度都为1.0µM）代替待测离子进行实验时,没有发生明显的荧光淬灭,说明该传感器具有较高的选择性。该传感器的构建为汞离子的检测提供了一条快速、简便的新途径。     

A Highly Selective and Sensitive Fluorescent Probe Recognition for Co2+ in Aqueous Media Based on 8‐Hydroxyquinolin‐2‐carbaldehyde‐2‐pyridylformylhydrazone Derivative

A new (8‐hydroxyquinolin‐2‐yl)methylene picolinohydrazide derivative ( L ) has been successfully synthesized and characterized. The probe L displays high selectivity to Co²⁺ in CH₃CN/HEPES (1:1, Ｖ/Ｖ, 10 mmol·L^?1, pH=7.4) with a fluorescence "ON‐OFF" response. The Co²⁺ ion recognition event possesses some distinct features including rapid response, high selectivity and sensitivity, good anti‐interference ability and being applicable within a wide pH range. Based on job's plot and ESI‐MS studies, the 1:1 binding mode was proposed. The binding constant of L and Co²⁺ is 1.63×10⁸ L·mol^?1 and the detection limit is 1.15 µmol·L^?1. Natural water samples experiments revealed that probe L can be potentially applied to the detection of Co²⁺ in real environment.     

Rapid Determination of Free Amino Acids in Milk by Microchip Electrophoresis Coupled with Laser‐induced Fluorescence Detection

A simple and sensitive method for determination of free amino acids in milk by microchip electrophoresis (MCE) coupled with laser‐induced fluorescence (LIF) detection was developed. Seven kinds of standard amino acids were derivated with sulfoindocyanine succinimidyl ester (Cy5) and then perfectly measured by MCE‐LIF within 150 s. The parameters of MCE separation were carefully investigated to obtain the optimal conditions: 100 mmol·L^?1 sodium borate solution (pH 10.0) as running buffer solution, 0.8 kV as injection voltage, 2.2 kV as separation voltage etc. The linear range of the detection of amino acids was from 0.01 µmol·L^?1 to 1.0 µmol·L^?1 and the detection limit was as low as about 1.0 nmol·L^?1. This MCE‐LIF method was applied to the measurements of free amino acids in actual milk samples and satisfactory experimental results were achieved.     

Preparation of l‐phenylalanine‐imprinted solid‐phase extraction sorbent by Pickering emulsion polymerization and the selective enrichment of l‐phenylalanine from human urine

A novel l‐ phenylalanine molecularly imprinted solid‐phase extraction sorbent was synthesized by the combination of Pickering emulsion polymerization and ion‐pair dummy template imprinting. Compared to other polymerization methods, the molecularly imprinted polymers thus prepared exhibit a high specific surface, large pore diameter, and appropriate particle size. The key parameters for solid‐phase extraction were optimized, and the result indicated that the molecularly imprinted polymer thus prepared exhibits a good recovery of 98.9% for l‐ phenylalanine. Under the optimized conditions of the procedure, an analytical method for l‐ phenylalanine was well established. By comparing the performance of the molecularly imprinted polymer and a commercial reverse‐phase silica gel, the obtained molecularly imprinted polymer as an solid‐phase extraction sorbent is more suitable, exhibiting high precision (relative standard deviation 3.2%, n = 4) and a low limit of detection (60.0 ± 1.9 nmol·L^?1) for the isolation of l‐ phenylalanine. Based on these results, the combination of the Pickering emulsion polymerization and ion‐pair dummy template imprinting is effective for preparing selective solid‐phase extraction sorbents for the separation of amino acids and organic acids from complex biological samples.     

Electrochemical Sensor for Sensitive Determination of Ga(III) Ion Based on β‐Cyclodextrin Incorporated Multi‐walled Carbon Nanotubes and Imprinted Sol‐gel Composite Film

A novel sensor for detection of trace gallium ion [Ga(III)] was created by stepwise modification of a gold electrode with β‐cyclodextrin (β‐CD)/multi‐walled carbon nanotubes (MWCNTs) and an ion imprinted polymer (IIP). The sensor surface morphology was characterized by scanning electron microscopy. The electrochemical performance of the imprinted sensor was investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The sensor displayed excellent selectivity towards the target Ga(III) ion. Meanwhile, the introduced MWCNTs displayed noticeable catalytic activity, and β‐CD demonstrated significant enrichment capacity. A linear calibration curve was obtained covering the concentration range from 5.0×10^?8 to 1.0×10^?4 mol·L^?1, with a detection limit of 7.6×10^?9 mol·L^?1. The proposed sensor was successfully applied to detect Ga(III) in real urine samples.     

Study on Determination of Chemical Oxygen Demand in Water with Ion Chromatography

A new method for determining chemical oxygen demand （COD） value in water using ion chromatography coupled with nano TiO2-K2S2O8 co-existing system was described. The photocatalytic oxidation system and nano TiO2-K2S2O8 co-existing system could degrade the organic compounds in water. All sulfur-containing species in the reactive solution were eventually transformed to sulfate which could be determined by conductivity detector in ion chromatography. The change of conductivity of sulfate was proportional to COD value. The optimal experimental conditions and the mechanism of the detection were discussed. The application range was 10.0-300.0 mg·L^-1 and the lowest limit of detection was 3.5 mg·L^-1. It was considered that the value obtained could be reliably correlated with the COD value obtained using the conventional methods.     

Synthesis,Insecticidal Assay and Molecular Docking Study of Novel Neonicotinoids N‐Oxide Analogues

Eight novel neonicotinoids N‐oxide analogues were designed and synthesized. All the compounds have been identified by ¹H NMR and HRMS. The N‐oxide analogues exhibit high insecticidal activity against cowpea aphids (Aphis craccivora) at 250 mg·L^?1. The influence of N‐oxide formation on the biological activity was elucidated by computational chemical study, and it indicated that the water bridge hydrogen bonding network was broken due to the influence of the O atom connected with the pyridine ring.     

Direct Electrochemistry and Electrocatalysis of Hemoglobin Based on Nafion‐Room Temperature Ionic Liquids‐Multiwalled Carbon Nanotubes Composite Film

A robust and effective composite film combined the benefits of Nafion, room temperature ionic liquid (RTIL) and multi‐wall carbon nanotubes (MWNTs) was prepared. Hemoglobin (Hb) was successfully immobilized on glassy carbon electrode surface by entrapping in the composite film. Direct electrochemistry and electrocatalysis of immobilized Hb were investigated in detail. A pair of well‐defined and quasi‐reversible redox peaks of Hb was obtained in 0.10 mol·L^?1 pH 7.0 phosphate buffer solution (PBS), indicating that the Nafion‐RTIL‐MWNTs film showed an obvious promotion for the direct electron transfer between Hb and the underlying electrode. The immobilized Hb exhibited an excellent electrocatalytic activity towards the reduction of H₂O₂. The catalysis current was linear to H₂O₂ concentration in the range of 2.0×10^?6 to 2.5×10^?4 mol·L^?1, with a detection limit of 8.0×10^?7 mol·L^?1 (S/N=3). The apparent Michaelis‐Menten constant (K_m^app) was calculated to be 0.34 mmol·L^?1. Moreover, the modified electrode displayed a good stability and reproducibility. Based on the composite film, a third‐generation reagentless biosensor could be constructed for the determination of H₂O₂.     

Removal of Lead (II) Ions by Poly(2‐octadecyl butanedioic acid): Isothermal and Kinetic Studies

Poly(2‐octadecyl‐butanedioic acid), prepared from polyanhydride PA‐18, possesses novel heavy metal adsorption characteristics. The adsorption capacity of this water insoluble polymer for lead (II) was substantially higher than other heterogeneous adsorbants and is equivalent to those obtained with homogeneous sorbants. The polymer exhibited pseudo‐second‐order kinetics and nearly complete adsorption of lead occurred in 15 min with initial lead (II) concentrations greater than 100 mg · L^?1. Adsorptive behavior was accurately predicted by the Dubinin‐Radushkevich isotherm model. The mean free energy of adsorption of lead (II) onto poly(2‐octadecyl‐butanedioic acid) was determined to be 31.6 kJ · mol^?1, suggesting an ion exchange component to the adsorption mechanism. Gibb's free energy values for this process indicate that it is spontaneous. Adsorption was relatively independent of pH in the range of 3–5, due to the utilization of the sodium carboxylate form of the chelating groups, and was not influenced by high Na⁺ concentration and moderate concentrations (up to 200 mg · L^?1) of Ca⁺². Lead (II) solutions containing 2000 mg · L^?1 Ca⁺² did reduce the adsorption of 2000 mg · L^?1 lead (II) by 28%.     

Synthesis,Bioactivities and Structure Activity Relationship of N‐4‐Methyl‐1,2,3‐thiadiazole‐5‐carbonyl‐N′‐phenyl Ureas

Twenty nine novel N‐4‐methyl‐1,2,3‐thiadiazole‐5‐carbonyl‐N′‐phenyl ureas were designed and synthesized, and their structures were confirmed by proton nuclear magnetic resonance (¹H NMR), infra red spectroscopy (IR) and high‐resolution mass spectroscopy (HRMS). Compounds V‐9 , V‐11 , V‐12 , V‐15 , V‐19 , V‐21 , V‐22 and V‐24 exhibit excellent activity against Culex pipiens pallens. Compounds V‐12 and V‐22 present good insecticidal activity against Plutella xylostella L. Their median lethal concentrations (LC₅₀) are 164.15 and 89.69 mg·L^?1, respectively. Compound V‐11 also has potential wide spectrum of fungicide activity. Its median effective concentrations (EC₅₀) detected from 3.82 µg·mL^?1 against Physalospora piricola to 31.60 µg·mL^?1 against Cercospora arachidicola. Compounds V‐15 and V‐24 show outstanding induction activities as same as positive controls TDL and ningnanmycin, furthermore V‐24 has the highest induction activity of 41.85%±4.43%. To elucidate the structure activity relationship in these compounds, a 3D‐QSAR model has been built. The established model showed a reliable predicting ability with q² values of 0.643 and r² values of 0.982.     

Optimization and validation of an ion‐pair RP‐HPLC‐UV method for the determination of total free iodine in rabbit plasma: application to a pharmacokinetic study

An ion‐pair reverse‐phase high performance liquid chromatographic method with UV–vis detection has been developed for the determination of total free iodine in rabbit plasma after vaginal administration of povidone–iodine (PVP‐I). Sample preparation was done by protein precipitation with acetonitrile in 96‐well format and aspirin was used as the internal standard. The 100 µL sodium thiosulfate solution (5 g L^?1) was added to 100 µL plasma sample before protein precipitation, to convert the total free iodine in plasma to iodide (I^?). Separation was performed on a C₁₈ column (200 × 4.6 mm i.d., 5 µm). The mobile phase consisting of a mixture of water phase (containing 10 mmol L^?1 18‐crown‐6 ether, 5 mmol L^?1 octylamine and 5 mmol L^?1 sodium dihydrogen phosphate, pH adjusted to 6.0 with phosphoric acid) and acetonitrile in the ratio 70:30 (v/v) was delivered isocraticly at a flow rate of 1.0 mL min^?1. The method was sensitive with a lower limit of quantification of 0.005 µg mL^?1, with good linearity (r² > 0.9990) over the linear range of 0.005–2 µg mL^?1. All the validation data, such as linearity, accuracy and precision, were within the required limits. The method was successfully applied to study the pharmacokinetic of PVP–I in rabbits after vaginal administration. Copyright © 2009 John Wiley & Sons, Ltd.     

Novel Amperometric Sensor Based on Rigid Near‐Percolation Composite

A novel amperometric sensor based on a rigid graphite‐epoxy composite of which composition is near to the percolation is reported. The electrochemical response of the novel transducer material was evaluated in terms of reproducibility of the fabrication process and reproducibility and repeatability of the analytical signal. The signal to noise ratio was improved. atomic force microscopy (AFM) technique was used to obtain qualitatively information. Amperometric detection of chlorine in water was carried on at a set potential of ?250 mV vs. Ag/AgCl. The developed flow injection analysis (FIA) system responded linearly to chlorine concentration between 0.15 mg L^?1 and 4 mg L^?1with a sensitivity of ?0.20 μA L mg^?1. The proposed system was applied to real samples from swimming‐pool water. No significant difference was observed regarding the standard method.     

Synthesis of statistical glycidyl methacrylate‐n‐vinyl pyrrolidone copolymers and their reaction with naproxen

Free‐radical copolymerization of glycidyl methacrylate (GMA) with N‐vinylpyrrolidone (VPD) was carried out at 50 °C using 3.0 mol · L^?1 of N,N′‐dimethylformamide solution and 9.0 · 10^?3 mol · L^?1 of 2,2′‐azobisisobutyronitrile as an initiator. The modification reaction of GMA‐VPD copolymers with a model bioactive carboxylic acid, 6‐methoxy‐α‐methyl‐2‐naphthaleneacetic acid (naproxen), was studied in the homogeneous phase using basic catalysts. The influence of the type of catalyst and the GMA content was evaluated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1192–1199, 2002     

A New Amperometric Biosensor Based on HRP/Nano-Au/L-Cysteine/Poly（o-Aminobenzoic acid）-Membrane-Modified Platinum Electrode for the Determination of Hydrogen Peroxide

The third generation amperometric biosensor for the determination of hydrogen peroxide （H2O2） has been described. For the fabrication of biosensor, o-aminobenzoic acid （oABA） was first electropolymerized on the surface of platinum （Pt） electrode as an electrostatic repulsion layer to reject interferences. Horseradish peroxidase （HRP） absorbed by nano-scaled particulate gold （nano-Au） was immobilized on the electrode modified with polymerized o-aminobenzoic acid （poABA） with L-cysteine as a linker to prepare a biosensor for the detection of H2O2. Amperometric detection of H2O2 was realized at a potential of ＋20 mV versus SCE. The resulting biosensor exhibited fast response, excellent reproducibility and sensibility, expanded linear range and low interferences. Temperature and pH dependence and stability of the sensor were investigated. The optimal sensor gave a linear response in the range of 2.99×10^-6 to 3.55×10^-3 mol·L^-1 to H2O2 with a sensibility of 0.0177 A·L^-1·mol^-1 and a detection limit （S/N = 3） of 4.3×10^-7 mol·L^-1. The biosensor demonstrated a 95% response within less than 10 s.     

A Sensitive Surface‐enhanced Raman Scattering Method for Determination of Melamine with Aptamer‐modified Nanosilver Probe

The small nanosilver was prepared by the sodium borohydride procedure. The aptamer was used to modify nanosilver to obtain a nanosilver‐aptamer (AgssDNA) SERS probe for the determination of melamine. In pH 6.6 phosphate buffer solution and in the presence of NaCl, the AgssDNA probe specifically combined with melamine to release nanosilver particles that were aggregated to nanosilver clusters, which exhibited SERS effect at 240 cm^?1. When melamine concentration increased, the nanosilver clusters increased, and the SERS intensity at 240 cm^?1 increased. The increased SERS intensity ΔI_{240 cm?1} is linear to melamine concentration in the range of 6.3–403.6 μg·L^?1, with a detection limit of 1.2 μg·L^?1. This assay was applied to determination of melamine in milk, with satisfactory results.     

Synthesis,Nematicidal Activity,and 3D‐QSAR of Novel 1,3,4‐Oxadiazole/ Thiadiazole Thioether Derivatives

Forty one novel 1,3,4‐oxadiazole/thiadiazole thioether derivatives containing phenoxy moiety were designed and synthesized. Bioassay demonstrated that some of them showed remarkable activities against Tylenchulus semipenetrans in vitro and in vivo. Compounds 20 , 21 , 35 and 39 showed excellent lethal activities after treatment for 48 h in vitro, with LC₅₀ values of 13.4 ± 1.8, 11.7 ± 2.5, 13.7 ± 2.4 and 13.3 ± 1.1 mg·L^–1, respectively, which were obviously superior to fosthiazate (49.1 ± 2.8 mg·L^–1) and avermectin (26.6 ± 2.3 mg·L^–1). Compound 21 can effectively control the citrus nematode disease caused by T. semipenetrans at 200 mg·L^–1 in vivo with (68 ± 3)% inhibitory effect, which was even better than that of avermectin ((63 ± 2)%). The CoMFA and CoMSIA models of three‐dimensional quantitative structure‐activity relationships (3D‐QSARs) were established. The compound 33 was designed based on the 3D‐QSAR models with more vigorous nematicidal activities in vitro (LC₅₀ = 9.8 ± 1.4 mg·L^–1) and in vivo ((70 ± 5)%). These results demonstrated that compound 33 can be considered as a potential nematicide.     

Synthesis of β‐Cyclodextrin‐2,4‐dihydroxyacetophenone‐phenylhydrazine and Its Application

A novel host reagent of β‐cyclodextrin‐2,4‐dihydroxyacetophenone‐phenylhydrazine(β‐CDP‐DHPH) was synthesized and characterized by IR and ¹H NMR spectra. A highly selective and sensitive spectrofluorimetric determination of trace amounts of cadmium was proposed based on the reaction between Cd²⁺ and β‐CDP‐DHPH at pH 10.0. The molar ratio of β‐CDP‐DHPH to Cd²⁺ was 1:1. The linear range of this method was 0.56‐120 μg·L^?;1 with a detection limit of 0.20 μg·L^?;1. The interferences of 39 common ions in the determination of cadmium were investigated, and the results showed that the host reagent had a quite high selectivity. This method was rapid and simple in determination of trace amounts of cadmium in mineral, tap and river water.