Application of matrix solid-phase dispersion and high-performance liquid chromatography for determination of sulfonamides in honey.

A novel method for simultaneous determination of 8 sulfonamide residues (sulfathiazole, sulfapyridine, sulfadiazine, sulfamerazine, sulfamonome-thoxine, sulfachloropyridazine, sulfamethoxazole, and sulfadimethoxine) in honey samples by high-performance liquid chromatography (HPLC) has been developed on the basis of precolumn derivatization with 9-fluorenylmethyl-chloroformate (FMOC-Cl). Sulfonamide residues in honey samples were extracted and purified by matrix solid-phase dispersion with C18 as the solid support. The residues were derivatized by FMOC-CI, and the FMOC-sulfonamide derivatives were further purified by solid-phase extraction with silica gel as the solid support prior to HPLC analysis. The average recoveries for most sulfonamide compounds at different spiking levels (from 10 to 250 microg/kg) were > 70% with relative standard deviations < 16%, and their limits of detection were 4.0 microg/kg. The established analytical method has high sensitivity and repeatability and can be applicable for determining the sulfonamide residues in various honey matrixes.

Morphology Effect of Vertical Graphene on the High Performance of Supercapacitor Electrode.

Graphene and its composites are widely investigated as supercapacitor electrodes due to their large specific surface area. However, the severe aggregation and disordered alignment of graphene sheets hamper the maximum utilization of its surface area. Here we report an optimized structure for supercapacitor electrode, i.e., the vertical graphene sheets, which have a vertical structure and open architecture for ion transport pathway. The effect of morphology and orientation of vertical graphene on the performance of supercapacitor is examined using a combination of model calculation and experimental study. Both results consistently demonstrate that the vertical graphene electrode has a much superior performance than that of lateral graphene electrode. Typically, the areal capacitances of a vertical graphene electrode reach 8.4 mF/cm(2) at scan rate of 100 mV/s; this is about 38% higher than that of a lateral graphene electrode and about 6 times higher than that of graphite paper. To further improve its performance, a MnO2 nanoflake layer is coated on the surface of graphene to provide a high pseudocapacitive contribution to the overall areal capacitance which increases to 500 mF/cm(2) at scan rate of 5 mV/s. The reasons for these significant improvements are studied in detail and are attributed to the fast ion diffusion and enhanced charge storage capacity. The microscopic manipulation of graphene electrode configuration could greatly improve its specific capacitance, and furthermore, boost the energy density of supercapacitor. Our results demonstrate that the vertical graphene electrode is more efficient and practical for the high performance energy storage device with high power and energy densities.

Chemically-doped graphene with improved surface plasmon characteristics: an optical near-field study.

One of the most fascinating and important merits of graphene plasmonics is their tunability over a wide range. While chemical doping has proven to be a facile and effective way to create graphene plasmons, most of the previous studies focused on the macroscopic behaviors of the plasmons in chemically-doped graphene and little was known about their nanoscale responses and related mechanisms. Here, to the best of our knowledge, we present the first experimental near-field optical study on chemically-doped graphene with improved surface plasmon characteristics. By using a scattering-type scanning near-field optical microscope (s-SNOM), we managed to show that the graphene plasmons can be tuned and improved using a facile chemical doping method. Specifically, the plasmon interference patterns near the edge of the monolayer graphene were substantially enhanced via nitric acid (HNO3) exposure. The plasmon-related characteristics can be deduced by analyzing such plasmonic fringes, which exhibited a longer plasmon wavelength and reduced plasmon damping rate. In addition, the local carrier density and therefore the Fermi energy level (EF) of graphene can be obtained from the plasmonic nano-imaging, which indicated that the enhanced plasmon oscillation originated from the injection of free holes into graphene by HNO3. These findings were further corroborated by theoretical calculations using density functional theory (DFT). We believe that our findings provide a clear nanoscale picture on improving graphene plasmonics by chemical doping, which will be helpful for optimizing graphene plasmonics and for elucidating the mechanisms of two-dimensional light confinement by atomically thick materials.

A novel approach for simultaneous determination of 2-mercaptobenzimidazole and derivatives of 2-thiouracil in animal tissue by gas chromatography/mass spectrometry.

A novel approach for determination of 2-mercaptobenzimidazole (MBI) and other thyreostatic residues in animal tissues by gas chromatography/mass spectrometry (GC/MS) in selected ion monitoring mode was developed. The analytes in animal tissues (including hypothyroid, pork muscle and beef samples) were extracted by acetonitrile, and then purified by a matrix solid-phase dispersion (MSPD) procedure after the extraction residues had been dissolved in water. The thyreostatic residues were derivatized by pentafluorobenzyl bromide (PFBBr) under strong basic conditions and then N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) before GC/MS analysis. Different kinds of solid supports with various polarities for the MSPD procedure were investigated, and it was found that silica gel was suitable for the purpose. The average recoveries of the thyreostatic drugs in animal tissues ranged from 71.5-96.9% with the relative standard deviations below 10%. By using the developed method, the limits of detection were 10 microg/kg for MBI; 5 microg/kg for 6-phenyl-2-thiouracil; and 2 microg/kg for 2-thiouracil, 6-methyl-2-thiouracil and 6-propyl-2-thiouracil. The stability of the thyreostatic drugs in spiked animal tissues was tested, and the results showed that the thyreostatic drugs did not decompose within 3 months if the sample was stored in darkness below -20 degrees C.

Determination of sulphonamides in animal tissues by high performance liquid chromatography with pre-column derivatization of 9-fluorenylmethyl chloroformate.

A novel approach for simultaneous determination of 12 sulphonamides (sulphadiazine, sulphamethazine, sulphathiazole, sulphadimethoxine, sulphamerazine, sulphapyridine, sulphamethoxazole, suphamethizole, sulphaquinoxaline, sulphameter, sulphamonomethoxine, and sulphachloropyridazine) in animal tissues (swine muscle and liver, chicken muscle, beef muscle) by HPLC with UV detection has been developed. A pre-column derivatization of the sulphonamide compounds with 9-fluorenylmethyl chloroformate (FMOC-Cl) has been proposed and the reaction conditions have been optimized. The FMOC-sulphonamide derivatives were purified by SPE with silica gel as solid support prior to HPLC separation. The limits of detection for the sulphonamide compounds were greatly improved after the derivatization and purification step for the derivatives. Sulphonamide residues in animal tissues were extracted by acetonitrile and purified by solid phase extraction with C(18) as the solid support. The method developed has high sensitivity and good repeatability, and the average recoveries for most of the sulphonamides at various spiking levels were above 70% with relative standard deviations below 13.7%. The limits of detection for most sulphonamides can reach 3-5 microg/kg.