Ya-Qi Jiang

Polypyrrole/graphene composite‐coated fiber for the solid‐phase microextraction of phenols

A polypyrrole (Ppy)/graphene (G) composite was developed and applied as a novel coating for use in solid-phase microextraction (SPME) coupled with gas chromatography (GC). The Ppy/G-coated fiber was prepared by electrochemically polymerizing pyrrole and G on a stainless-steel wire. The extraction efficiency of Ppy/G-coated fiber for five phenols was the highest compared with the fibers coated with either Ppy or Ppy/graphene oxide (GO) using the same method preparation. Significantly, compared with various commercial fibers, the extraction efficiency of Ppy/G-coated fiber is better than or comparable to 85 μm CAR/PDMS fiber (best extraction efficiency of phenol, o-cresol, and m-cresol in commercial fibers) and 85 μm polyacrylate (PA) fiber (best extraction efficiency of 2,4-dichlorophenol and p-bromophenol in commercial fibers). The effects of extraction and desorption parameters such as extraction time, stirring rate, and desorption temperature and time on the extraction/desorption efficiency were investigated and optimized. The calibration curves were linear from 10 to 1000 μg/L for o-cresol, m-cresol, p-bromophenol, and 2,4-dichlorophenol, and from 50 to 1000 μg/L for phenol. The detection limits were within the range 0.34-3.4 μg/L. The single fiber and fiber-to-fiber reproducibilities were <8.3 (n=7) and 13.3% (n=4), respectively. The recovery of the phenols spiked in natural water samples at 200 μg/L ranged from 74.1 to 103.9% and the relative standard deviations were <3.7%.

Characterization of ormosil film for dissolved oxygen-sensing

Abstract An organically modified silicate (ormosil) as a matrix for the fabrication of dissolved oxygen-sensing film was produced. The process included taking tetramethoxysilane (TMOS) and dimethyldimethoxysilane (DiMe-DMOS) as precursor and running a reaction at 60xa0°C in an open vial, which accelerates hydrolysis and condensation and results in the formation of emulsion. The film doped with tris-(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) ([Ru(dpp) 3 ] 2+ ) as an oxygen indicator exhibited a good linear relationship, fast response time, long-term stability and enhanced sensitivity to dissolved oxygen after optimizing the sol–gel processing parameters. The properties and the oxygen-sensing behavior of the film were investigated. The results presented here emphasized the significance of ormosil as a matrix for dissolved oxygen-sensing.

A novel non-enzymatic ECL sensor for glucose using palladium nanoparticles supported on functional carbon nanotubes

A novel non-enzymatic electrochemiluminescence (ECL) sensor based on palladium nanoparticles (PdNPs)-functional carbon nanotubes (FCNTs) was discovered for glucose detection. PdNPs were homogeneously modified on FCNTs using a facile spontaneous redox reaction method. Their morphologies were characterized by transmission electron microscopy (TEM). Based on ECL experimental results, the PdNPs-FCNTs-Nafion film modified electrode displayed high electrocatalytic activity towards the oxidation of glucose. The free radicals generated by the glucose oxidation reacted with the luminol anion (LH(-)), and enhanced the ECL signal. Under the optimized conditions, the linear response of ECL intensity to glucose concentration was valid in the range from 0.5 to 40 micromol L(-1) (r(2)=0.9974) with a detection limit (S/N=3) of 0.09 micromol L(-1). In addition, the modified electrode presented high resistance towards the poisoning of chloride ion, high selectivity and long-term stability. In order to verify the sensor reliability, it was applied to the determination of glucose in glucose injection samples. The results indicated that the proposed approach provided a highly sensitive, more facile method with good reproducibility for glucose determination, promising the development of a non-enzymatic ECL glucose sensor.

A facile synthesis of palladium nanoparticles supported on functional carbon nanotubes and its novel catalysis for ethanol electrooxidation

In this study, a novel material, palladium nanoparticles-carboxylic functional carbon nanotubes (PdNPs-CFCNTs), based on PdNPs supported on CFCNTs was synthesized by a facile spontaneous redox method. The material reveals high electrochemical activity and excellent catalytic characteristic for alcohol electrooxidation on a glassy carbon electrode (GCE) in an alkaline medium. The preparation mechanism was studied by the galvanic cell effect between PdCl(4)(2-) and functional defect sites on CFCNTs. Results from UV-visible absorption spectroscopy and electrochemical impedance spectroscopy revealed that the reduction of PdCl(4)(2-) to metallic Pd was successfully achieved. Morphologies of PdNPs supporting on CFCNTs (PdNPs-CFCNTs) were also characterized by transmission electron micrograph. PdNPs-CFCNTs with the best electrocatalytic characteristics were obtained under the condition as: the weight ratio of Pd to CFCNTs was kept at 2:1, the temperature was kept at 70 degrees C in the synthesis, and the scan rate of the applied potential was selected at 60 mV s(-1). The results indicate that PdNPs-CFCNTs could be a great potential material in direct ethanol fuel cells and ethanol sensors.

Optical biosensor for the determination of BOD in seawater

An automatic sensing system was developed using an optical BOD sensing film. The sensing film consists of an organically modified silicate (ORMOSIL) film embedded with an oxygen-sensitive Ru complex. A multi-microorganisms immobilization method was developed for the BOD sensing film preparation. Three different kinds of microorganisms, Bacillus licheniformis, Dietzia maris and Marinobacter marinus from seawater, were immobilized on a polyvinyl alcohol ORMOSILs. After preconditioning, the BOD biosensor could steadily perform well up to 10 months. The linear fluctuant coefficients (R(2)) in the range of 0.3-40mgL(-1) was 0.985 when a glucose/glutamate BOD standard was applied. The reproducible response for the BOD sensing film could be obtained within +/-2.3% of the mean value in a series of 10 samples in 5.0mgL(-1) BOD standard GGA solution. The effects of temperature, pH and sodium chloride concentration on the two microbial films were studied as well. The BOD sensing system was tested and applied for the BOD determination of seawater.

A novel electrochemiluminescence sensor based on bis(2,2 '-bipyridine)-5-amino-1,10-phenanthroline ruthenium(II) covalently combined with graphite oxide

This communication reports a novel electrochemiluminescence (ECL) sensor based on covalently linking bis(2,2-bipyridine)-5-amino-1,10-phenanthroline ruthenium(II) (Ru(II)-NH2) with graphite oxide (GO) on a glassy carbon electrode. 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride and N-hydroxy-succinimide were applied to activate the carboxyl groups on the GO surface and catalyze the formation of amido link between Ru(II)-NH2 and carboxyl groups on GO. The composite film was characterized using atomic force microscopy, transmission electron microscopy and Fourier transform infrared absorption spectroscopy. Based on ECL experimental results, the composite film modified electrode displayed high electrochemical activity towards the oxidation of 2-(dibutylamino) ethanol (DBAE). Under optimized conditions, the linear response of ECL intensity to DBAE concentration was valid in the range 6.0×10(-7)-2.0×10(-4) mol L(-1) (r2=0.9948) with a detection limit (S/N=3) of 5.0×10(-8) mol L(-1). Furthermore, the ECL sensor presented good characteristics in terms of stability and reproducibility, promising the development of ECL sensors for biologically important compounds.

PH- and mol-ratio dependent tungsten(VI) - citrate speciation from aqueous solutions: syntheses, spectroscopic properties and crystal structures

Abstract Investigation of the aqueous coordination chemistry for citrate and tungsten(VI) resulted in the isolation of three new monomeric and dimeric tungsten(VI) citrate NaK3[W2O5(Hcit)2]·4H2O (1), (Hphen)3[WO2(H2cit)(Hcit)]·6H2O (2) and K4[WO3(cit)]·2H2O (3), (H4citue605citric acid). The three complexes have been characterized by elemental analyses, IR and NMR spectroscopies. The IR and NMR spectra are consistent with monomeric species or a monooxo-bridged dinuclear structure as revealed by single crystal X-ray diffraction study. The dimeric anion of complex 1 contains a bent (O2W)O(WO2) core with an angle of Wue5f8Obue5f8W 162.3(3)°. Each citrate ligand is tridentately coordinated to one tungsten atom through the α-alkoxyl, α-carboxyl, and one β-carboxyl group, making each metal atom six-coordinate and forming a mesomer with configuration of ΔSΛR. The mononuclear tungstate 2 consists of a cis-dioxo partially protonated citrato tungstate(VI) anion and three phenanthrolinium cations. The W(VI) atom is coordinated by two acid oxo groups and two bidentate citrate ligands through α-alkoxyl and α-carboxyl groups, while the other two β-carboxyl or carboxylic groups remain free. The tungsten atom in the complex 3 forms an octahedral coordination with three fac-oxo groups and one tridentate citrate, in which the later is coordinated through the α-alkoxyl and α-carboxyl groups, and much more weakly by one of the two terminal β-carboxyl groups [2.348(4) A]. Interconversion of citrato tungstate(VI) with pH value and the molar ratio of the reactant are discussed.

An in situ applicable colorimetric Cu2+ sensor using quantum dot quenching

In this study, a rapid, convenient and in situ applicable Cu2+ sensor was constructed based on a luminescent layer immobilizing Ru(bpy)3Cl2 with a maximum wavelength of 600 nm, which was taken as the reference background light. The luminescence intensity of the layer was kept constant and isolated from the oxygen change in the solution due to the hybrid polyacrylonitrile–dimethylsulfoxide used in the immobilization of the Ru(bpy)3Cl2. The CdTe quantum dot (QD) luminescence, with a maximum wavelength of 520 nm, was quenched to different degrees depending on the Cu2+ concentration in the solution. Using a commercial camera, different colors could be captured in different Cu2+ concentrations. This color change was caused by the composite light with stable luminescence from the Ru(bpy)3Cl2 layer and the changeable fluorescence of the CdTe QDs. Sensor characteristics, including the co-existing ions, oxygen content, temperature effect, and sensor stability, were investigated.

Complexation between vanadium(V) and citrate: spectroscopic and structural characterization of a dinuclear vanadium(V) complex

Investigation of the aqueous coordination chemistry for citrate and vanadium(V) resulted in the isolation and characterization of a dinuclear vanadium(V) citrato complex (1) Na2K2[VO2(Hcit)]2 · 9H2O. Complex (1) is an intermediate between the fully deprotonated and diprotonated citrate vanadate. It may represent an early mobilized precursor in the biosynthesis of FeV-co, as well as a relevant model in the proton transport relay process between P-cluster pair to M-cluster pair. The complex has been characterized by elemental analyses and i.r. spectroscopy. Its i.r. spectra are consistent with a oxo-bridged dinuclear structure as revealed by a single crystal X-ray diffraction study.

A New Conformation of a Water Hexamer Chain and its Reversible Formation/Removal in the Host Channel by Gas–Solid Reaction

A new type of cyclic water hexamer chain was found to occupy the host channel of a supramolecule, formulated as [Zn(bdc)en·3(H2O)] n (1) [H2bdc=1,3-benzenedicarboxylic acid; en=ethylenediamine] and characterized by X-ray crystallography. As each water molecule was only involved in hydrogen bonding, facile removal of the lattice water was anticipated. The hydrogen-bonded water chain was completely removed by heating 1 at 96°C, forming the dehydrated solid [Zn(bdc)en] n (2). Interestingly, complex 1 can be regenerated in water vapor by a gas–solid reaction.