Nonenzymatic glucose sensing at ruthenium dioxide–poly(vinyl chloride)–Nafion composite electrode

Development of nonenzymatic glucose sensors with high reproducibility and stability is an urgent need to reduce cost of regular diabetic monitoring. Here, we have fabricated ruthenium dioxide–poly(vinyl chloride)–Nafion (RuO₂–PVC–Nafion) composite for direct glucose sensing in sodium hydroxide and phosphate buffer nonenzymatically for the first time. The restricted activity of the RuO₂–PVC film electrode in alkaline pH is extended to neutral pH using Nafion as an outer membrane, which reduces the distance between Ru active sites by bridging effect and improves the electrode stability. The catalytic rate, measured in terms of change of RuO₂ resistance, is similar irrespective of the medium for the high temperature annealed RuO₂ (700 °C), whereas the low temperature annealed RuO₂ (300 °C) is highly sensitive for the change in the pH of the solution. This is revealed by observing large Michaelis–Menten kinetic constant K _M for the RuO₂ (700 °C) than the low temperature annealed RuO₂ (300 °C) due to effective increase in the catalytic active sites similar to oxygen evolution reaction. Contrast to this, the buffer solution does not influence significantly the apparent K _M observed for RuO₂ (300 °C) and has greater impact on the high temperature 500 and 700 °C annealed RuO₂ samples. Cyclic voltammetry, chrono amperommetry, and electrochemical impedance spectroscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction techniques are used for characterization of the sensor behavior. The RuO₂–PVC–Nafion senses glucose selectively in the presence of potential interferences like fructose, galactose, mannose, sucrose, starch, uric acid, ascorbic acid, dopamine, and catechol in NaOH and phosphate buffer. Glucose sensing in the blood serum of the diabetic and nondiabetic patients is made. The results suggest that the RuO₂–PVC–Nafion is a promising candidate for the development of nonenzymatic glucose sensors.     

An on‐line sample pretreatment technique for the HPLC analysis of plant samples

A continuous‐flow, on‐line sample pretreatment technique using a silica gel microsyringe extractor has been developed. All steps including extraction, separation, clean‐up, and concentration occur in the microsyringe. The overall sample pretreatment process takes <10 min per sample. Different polarity chemicals in the plant sample are successively extracted and separated, and analyzed in parallel using HPLC–UV and HPLC–UV–MS/MS. Polycyclic aromatic hydrocarbons, alkylphenols, and plant hormones were determined as model compounds for nonpolar, intermediate polarity, and polar fractions, respectively. All the parameters that influence the extraction and separation efficiency of the microsyringe extractor have been optimized and evaluated. Under the optimized conditions, recoveries of target compounds ranged from 78.4 to 101.9%, the RSD was <12.8% and the square of the correlation coefficient was >0.99. Complex plant samples of Sambucus Mandshurica Kitag have been tested using this method. Fluorene, phenanthrene, pyrene, and plant hormones were detected in all the samples, and concentrations ranged from 24.2–34.9, 43.8–67.1, 25.9–29.2, and 14.5～110.8 ng/g, respectively.     

经Opuntia dilenii haw植物提取液绿色合成制备的纳米铝酸锌的催化性质(英文)

Various nanosized zinc aluminate(ZnAl2O4) samples were prepared by a conventional and a mi- crowave method both with and without using Opuntia dilenii haw plant extract,and were charac- terized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),high resolution scanning electron microscopy(HRSEM),energy dispersion scanning(EDX),temperature dependent conductance measurements, thermoelectric power measurements, ultraviolet-visible (UV-Vis) diffuse reflectance spectroscopy,and photoluminescence spectroscopy.The formation of a pure ZnAl2O4 phase was confirmed by XRD and FT-IR.A change in morphology from nanosized plates to nanosized sheets with,respectively,the conventional and microwave heating methods was clearly shown by HRSEM.UV-Vis diffusion reflectance spectroscopy measured the band gaps of ZnAl2O4 nanosized plates and nanosized sheets as 3.5 and 3.9 eV,respectively.The synthesized ZnAl2O4 was single crystalline and has three photoluminescence emissions at 482,528,and 540 nm.ZnAl2O4 nanosized sheets prepared by the microwave method showed higher catalytic activity for the oxida- tion of benzyl alcohol(85% conversion) than ZnAl2O4 nanosized plates prepared by the convention- al method(60% conversion).     

Application of Polysaccharide Microarray Technology for the Serodiagnosis of Burkholderia pseudomallei Infection (Melioidosis) in Humans

Burkholderia pseudomallei is the causative agent of melioidosis, a bacterial infection endemic in tropical regions including southeast Asia and northern Australia. B. pseudomallei contains structurally unique polysaccharides (capsular polysaccharide and O?antigen saccharides of lipopolysaccharide). A polysaccharide microarray platform was developed by immobilizing these polysaccharides onto glass slides. Employing this microarray, we were able to demonstrate the presence of antibodies to these polysaccharide antigens in the sera of melioidosis patients, but not in serum from nonmelioidosis human subjects. The advantages of this polysaccharide microarray technology over the conventional tests for the serodiagnosis of melioidosis are discussed.     

Syntheses of β- and γ-fluorophenyl cis- and trans-α-methylene-γ-butyrolactones

Preparation of a series of cis-γ-fluorophenyl-β-phenyl-α-methylene-γ-butyrolactones is reported via ‘allylboration’ of fluorobenzaldehydes with (E)-methyl 3-phenyl-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)acrylate. The corresponding trans-γ-fluorophenyl lactones were prepared either (i) via ‘allylboration’ using the (Z)-reagents or (ii) via an indium triflate-mediated isomerization of the cis-products. The difficulty in isomerizing difluorinated cis-products confirms the probable intermediacy of carbocations. Finally, the synthesis of cis-β-fluorophenyl-γ-phenyl-α-methylene-γ-butyrolactones was achieved via an indium-catalyzed allylation–lactonization of aldehydes with (Z)-2-(bromomethyl)-3-(fluorophenyl)acrylates.     

Cooperativity and cluster growth patterns in acetonitrile: A DFT study

Cooperativity in intermolecular interactions and cluster growth patterns of acetonitrile has been studied using M06L density functional theory. Cyclic, ladder‐type, stacked, cross‐stacked, and mixed patterns are studied. Total interaction energy (E_int) and interaction energy per monomer (E_m) show maximum stability and cooperativity in stacked clusters followed by cross‐stacked ones. As cluster size increased, magnitude of E_m showed significant increase. Compared to E_m of dimer (?2.97 kcal/mol), the increase is 2.6‐fold for 27mer . Higher stabilization in larger clusters is attributed to strong cooperativity in intermolecular C? H···N and dipolar interactions. Enhanced cooperativity in stacked structures is supported by atoms‐in‐molecule electron density (ρ) data. Sum of ρ at intermolecular bond critical points is the highest for stacked clusters. Further, area of negative‐valued molecular electrostatic potential is linearly related with E_int and showed the lowest value in stacked followed by cross‐stacked clusters, indicating maximum utilization of lone pair density and maximum cooperativity in such growth patterns. A red shift in the average C? N stretching frequencies with increase in the number of monomers and its direct correlation with E_int in stacked clusters also supported their stability. Further, two known crystal patterns of acetonitrile (α and β) with 16 monomers are optimized and compared with the most stable hexadecamer pattern and are found to show lower values for E_int and E_m compared to the latter. Based on this result, we predict the existence of a third crystal pattern for acetonitrile which will be more ordered and more stable than α and β forms. © 2014 Wiley Periodicals, Inc.     

Triazine interlinked covalent organic polymer as an efficient anti-bacterial agent

Herein, we report the synthesis of new covalent organic polymer comprising triazine and o-tolidine by solvothermal method. The formation of polymer was confirmed by Fourier transform infra red spectroscopy (FT-IR), cross polarization–magic angle spinning nuclear magnetic resonance (NMR), transmission electron microscopy, and scanning electron microscopy. Their antibacterial activity toward S. aureus (gram-positive) and P. aeruginosa (gram-negative) was assessed by the optical density measurements and direct contact method. These results have great significance toward the design of new porous polymers for antibacterial applications.     

DFT analysis: Fe4 cluster and Fe(110) surface interaction studies with pyrrole,furan, thiophene,and selenophene molecules

DFT studies of both the Fe₄ cluster and the Fe(110) surface interaction with pyrrole, furan, thiophene, and selenophene showed that selenophene forms a stabler adsorbate iron complex than the other heterocyclic molecules; this is consistent with the binding energy data that were calculated between the Fe cluster and the Fe(110) surface with the heterocycles. Furthermore, when the adsorption of the compounds with the iron cluster was analyzed by molecular orbital studies, the orbitals of selenophene overlapped more strongly with the Fe atom than that of the other molecules. In TD-DFT, the π → π* peak observed for the molecules disappeared when they formed complexes, and there appeared a charge transfer band (ligand to metal), thus confirming the coordination of these molecules with the cluster. The data suggest that the chemisorption is an exothermic process.     

Monitoring the Transition from Spherical to Polymer‐like Surfactant Micelles Using Small‐Angle X‐Ray Scattering

Despite over a century of modern surfactant science, the kinetic pathways of morphological transitions in micellar systems are still not well understood. This is mainly as a result of the lack of sufficiently fast methods that can capture the structural changes of such transitions. Herein, a simple surfactant system consisting of sodium dodecyl sulfate (SDS) in aqueous NaCl solutions is investigated. Combining synchrotron radiation small‐angle X‐ray scattering (SAXS) with fast stopped‐flow mixing schemes allows monitoring the process where polymer‐like micelles are formed from globular micelles when the salt concentration is suddenly increased. The results show that “worm‐like” micelles are formed by fusion of globular micelles and short cylinders in a fashion that bears similarities to a step‐like polymerization process.