Local near field assisted ablation of fused silica

In this contribution we present recent experimental and theoretical results on local near-field assisted laser ablation. Along these lines, we have generated sub-diffraction sized nanostructures on fused silica substrates, exploiting the local near fields of highly ordered triangular gold nanoparticle arrays generated by nanosphere lithography. After preparation, the nanoparticle arrays were irradiated with a single 35 fs long laser pulse with a central wavelength of λ=790 nm. The pulse energy was set to E=3.9 μJ, resulting in a fluence well below the ablation threshold of the fused silica substrates. In addition, 3D electromagnetic simulations using a finite integration technique in time domain have been performed. The simulations demonstrate that indeed the local field in the vicinity of the tips of the triangular nanoparticles overcome the ablation threshold and easily explain the generated nanostructures. Most importantly, the simulations show, that higher order modes contribute to the ablation process. These modes cause ablation along the side edges of the nanoparticles. Finally, we demonstrate, that the optical properties of the triangular nanoparticles, which can be tuned by their morphology, are crucial parameters for the generation of the ablation structures.     

Ultrasound-assisted pseudodigestion for toxic metals determination in fish muscles followed by electrothermal atomic absorption spectrophotometry: multivariate strategy

A simple and efficient procedure for the determination of arsenic (As), cadmium (Cd), and lead (Pb) in the edible parts of freshwater fish by ultrasonic-assisted acid pseudodigestion (USD) was developed. A Plackett-Burman experimental design was used as a multivariate strategy for the evaluation of the effects of several variables at once. Five variables--sonication time, sample mass of muscle tissue, temperature of the ultrasonic bath, mL of nitric acid, and mL of a mixture of acid and oxidant--were regarded as factors. From these studies, certain variables showed up as significant, and they were optimized by a 23+star central composite design, which involved 16 experiments. Optimum values of the variables were selected for the development of USD to determine the contents of As, Cd, and Pb in fish muscles used as pollution bioindicators from Lake Manchar (Sindh, Pakistan). The determination of the 3 toxic metals under study was performed by electrothermal atomic absorption spectrometry. The accuracy of the optimized procedure was evaluated by analysis of certified reference materials BCR 185R bovine liver and by comparison with conventional wet acid digestion methodology. The result obtained by the optimized method showed good agreement with the certified values and sufficiently high recovery. No significant differences were observed for P = 0.05. Relative standard deviation values (average of 10 separate determinations) were 1.21, 5.52, and 5.32% for As, Cd, and Pb, respectively.     

Deficiency zero non-metacyclicp-groups of order less than 1000

There are 49 non-metacyclicp-groups of order less than 1000 with trivial Schur multiplier. In this papar we give a list of deficiency zero presentations for these groups.     

Improved high-performance liquid chromatographic assay method for the enantiomers of ibuprofen.

A rapid, inexpensive and sensitive high-performance liquid chromatographic method for the quantitation of ibuprofen enantiomers from a variety of biological fluids is reported. This method uses a commercially available internal standard and has significantly less interference from endogenous co-extracted solutes than do previously reported methods. The method involves the acid extraction of drug and internal standard [(+/-)-fenoprofen] from the biological fluid with isooctane-isopropanol (95:5) followed by evaporation and derivatization with ethylchloroformate and R-(+)-alpha-phenylethylamine. Excellent linearity was observed between the peak-area ratio and enantiomer concentration (r > 0.99) over a concentration range of 0.25-50 micrograms/ml. This method is suitable for the quantitation of ibuprofen from single-dose pharmacokinetic studies involving either rats or humans.     

Oxidative addition of methyl iodide to a new type of binuclear platinum(II) complex: a kinetic study

A new organodiplatinum(II) complex cis,cis-[Me2Pt(mu-NN)(mu-dppm)PtMe2] (1), in which NN = phthalazine and dppm = bis(diphenylphosphino)methane, is synthesized by the reaction of cis,cis-[Me2Pt(mu-SMe2)(mu-dppm)PtMe2] with 1 equiv of NN. Complex 1 has a 5d(pi)(Pt) --> pi(imine) metal-to-ligand charge-transfer band in the visible region, which was used to easily follow the kinetics of its reaction with MeI. Meanwhile, the complex contains a robust bridging dppm ligand that holds the binuclear integrity during the reaction. A double MeI oxidative addition was observed, as shown by spectrophotometry and confirmed by a low-temperature 31P NMR study. The classical S(N)2 mechanism was suggested for both steps, and the involved intermediates were suggested. Consistent with the proposed mechanism, the rates of the reactions at different temperatures were slower in benzene than in acetone and large negative deltaS values were found in each step. However, some abnormalities were observed in the related rate constants and deltaS values, which were demonstrated to be due to the associative involvement of the polar acetone molecules in the reactions. The rates are almost 6 times slower in the second step as compared to the first step because of the electronic effects transmitted through the ligands and the steric effects.     

High-performance liquid chromatographic analysis of tiaprofenic acid and its metabolites in plasma and urine by direct injection

A rapid, convenient, sensitive and selective reversed-phase high-performance liquid chromatographic method was developed to measure tiaprofenic acid, its reduced and oxidized metabolites and their conjugates in biological fluids. The method involved direct injections of plasma and urine samples into the chromatograph before and after alkaline hydrolysis of the conjugates. Concentrations as low as 0.5 micrograms/ml of the drug in plasma and urine were quantifiable. The method was suitable for analysis of tiaprofenic acid and its metabolites in biological fluids after administration of therapeutic doses. Several other non-steroidal anti-inflammatory drugs which were applied to the system did not interfere with the assay.     

碱性溶液中电聚酪胺-铜草酸盐纳米复合物修饰铜电极电催化甲醇氧化(英文)

A polytyramine-copper oxalate nanocomposite modified copper(PTCOxNMC) electrode prepared by electropolymerization was examined for electrocatalytic activity towards the oxidation of methanol in alkaline solution using cyclic voltammetry and impedance spectroscopy. The prepared PTCOxNMC electrode showed a significantly high response for adsorbed methanol oxidation. The effects of various parameters such as potential scan rate and methanol concentration on the electrocatalytic oxidation at the surface of the PTCOxNMC electrode were investigated. Spectrometry techniques such as Fourier transform infrared spectroscopy and scanning electron microscopy were used to determine the surface physical characteristics of the modified electrode and revealed that the polytyramine-copper oxalate nanocomposite particles were highly dispersed on the surface of the copper electrode with a narrow size up to 40 nm. The very high current density obtained for the catalytic oxidation may have resulted from the high electrode surface area caused by modification with the poly-tyramine-copper oxalate nanocomposite.     

Synthesis of salicylaldehyde-modified mesoporous silica and its application as a new sorbent for separation, preconcentration and determination of uranium by inductively coupled plasma atomic emission spectrometry

A new functionalized mesoporous silica (MCM-41) using salicylaldehyde was utilized for the separation, preconcentration and determination of uranium in natural water by inductively coupled plasma atomic emission spectrometry (ICP-AES).Experimental conditions for effective adsorption of trace levels of U(VI) were optimized. The preconcentration factor was 100 (1.0 mL of elution for a 100 mL sample volume). The analytical curve was linear in the range 2-1000 μg L⁻¹ and the detection limit was 0.5 ng mL⁻¹. The relative standard deviation (R.S.D.) under optimum conditions was 2.5% (n = 10). Common coexisting ions did not interfere with the separation and determination of uranium at pH 5. The sorbent exhibited excellent stability and its sorption capacity under optimum conditions has been found to be 10 mg of uranium per gram of sorbent. The method was applied for the recovery and determination of uranium in different water samples.