Oxidation of Styrene with Molecular Oxygen in Supercritical CO2

The oxidation of styrene with molecular oxygen catalyzed by PdCl2 CuCl2 has been investigated in supercritical CO2 with a batch reactor. The oxidative system of styrene contains four components at the beginning and seven components during the reaction. The critical temperature, critical pressure, and critical density at different conversions are determined by using a high-pressure view cell. The effect of phase behavior on the conversion and selectivity were studied. Experimental results showed that the critical parameters of the reaction mixture at fixed initial molar ratio changed with the conversion of reactant. The conversion of styrene reached maximum near the critical density of the reaction mixture. Product selectivity also varied with density of reaction mixture and could be tuned to some degree.     

Carbon Paste Electrode for the Potentiometric Flow Injection Analysis of Drotaverine Hydrochloride in Serum and Urine

A carbon paste electrode for drotaverine hydrochloride (DvCl) was prepared and fully characterized in terms of composition, life span, usable pH range, response time and temperature. The electrode was applied to the potentiometric determination of drotaverinium ions in pharmaceutical preparations and biological fluids in steady state and flow injection conditions (FIA). The electrode is based on a mixture of two ion exchangers, namely, drotaverinium-silicotungestate and drotaverinium-tetraphenylborate dissolved in tricresyl phosphate as pasting liquid. The modified electrode showed a near-Nernstian slope of 59.34±2mV over the concentration range of 5.0×10^–7–1.0 × 10^–2M. The electrode exhibits good selectivity for DvCl with respect to a large number of inorganic cations, organic cations, sugars and amino acids. Potentiometric titrations of DvCl with several titrants have been monitored using this modified carbon paste electrode as an end-point indicator electrode. The proposed electrode offers the advantages of simplicity, accuracy, automation feasibility and applicability to turbid and colored samples.     

Multicommuted flow-through fluorescence optosensor for determination of furosemide and triamterene

Multicommutation implemented with flow-through optosensors is a very promising area of research. This recent approach benefits from the advantages of both methods and results in high sensitivity, selectivity, and speed, and little waste generation. This paper reports the simultaneous determination of furosemide and triamterene, two widely used diuretics, by measurement of their native fluorescence. The system has been proved to be useful for determination of both analytes in pharmaceutical preparations and for determination of triamterene in human urine and serum. A minicolumn filled with Sephadex SPC-25 microbeads was used to achieve separation of both analytes before detection in a flow-through cell filled with the same resin. The sensor is linear in the range 50–1200 and 0.4–8 ng mL⁻¹ with detection limits of 15 and 0.1 ng mL⁻¹ for furosemide and triamterene, respectively.     

Comments on the mean spherical approximation for hard-core and soft potentials and an application to the one-component plasma

The thermodynamic properties of the mean spherical (MSA), Percus-Yevick (PY), and hypernetted-chain (HNC) approximations are derived by a simple and unified approach by considering the RPA free-energy functionalF and employing an Ewald-type identity. It is demonstrated that with decreasing relative contribution of the hard-core insertion to the thermodynamic functions, the MSA changes its nature from PY-like to HNC-like, withF changing its role from excess pressure to excess free energy, respectively. It is found that the condition of continuity of the MSA pair functions is equivalent to a stationarity condition forF and leads to thermodynamic consistency between the virial and energy equations of state for the (thus defined) soft-MSA (SMSA), withF playing the role of the excess free energy. It is shown that the PY-compressibility and virial equations of state forD-dimensional hard spheres may be simply obtained one from the other without knowing any details of the solution of the model. Using this relation we find an indication that the PY approximation for hard spheres becomes less accurate with increasing dimensionality. A general variational formulation is presented for the application of the MSA for soft potentials, and results for the one-component plasma are discussed and extended.On sabbatical leave from the Nuclear Research Center-Negev, P.O. Box 9001, Beer Sheva, Israel.     

Simultaneous Determination of Aluminum and Iron in High Salt Content Matrices by Adsorptive Stripping Voltammetry. Application to Dialysis Fluids

A new analytical procedure for the simultaneous determination of aluminum(III) and iron(II) in two kinds of dialysis fluids (peritoneal and hemodialysis fluids) by differential pulse adsorptive stripping voltammetry (DPAdSV) is described. The voltammetric measurements were performed using, as working electrode, a stationary mercury electrode, and a platinum electrode and a Ag|AgCl|KCl_(sat.) electrode as auxiliary and reference electrodes, respectively, employing acetate buffer solutions at different pH as supporting electrolyte. As complexing agents, Solochrome Violet RS, Palatine Chrome Black 6BN, Chromazurol S and Eriochrome Black T were employed. For both elements, the accuracy, expressed as relative recovery R%, was very satisfactory being in the range 94–105%, the precision as repeatability, expressed as relative standard deviation s_r%, was lower than 6%, while the limits of detection were of the order of a few units of μg/L. The analytical voltammetric procedure has been validated by comparison with spectroscopic (graphite furnace atomic absorption spectroscopy, GFAAS) measurements.     

Chromatography with Supercritical Fluids

Chromatography with supercritical fluids unites the features of both gas chromatography and liquid chromatography, yet retains special characteristics of its own. The diffusion coefficient and particularly the viscosity of fluid phases may approach values for low-pressure gases, while the solvent power may be similar to that of liquids. However, with supercritical fluids it is possible to control chromatographic separations very effectively by pressure programming, since the solubility increases with increasing density. Temperature programming, on the other hand, can have the opposite effect to that in gas- or liquid-chromatography since the density decreases with increasing temperature at a given pressure. Supercritical fluid chromatography is primarily of interest for the separation of higher molecular weight compounds. The efficiency of this method of separation is demonstrated on several homologous series. Thus, a styrene oligomer with nominal M_w=2200 can be resolved by a pressure and temperature program into 40 species.     

超临界流体技术在制备药物输送系统中的应用

超临界流体技术以其特有的优点成为引人注目的制备药物细微粒子及控制释放的药物输送系统的方法。本文介绍了超临界流体沉淀技术的概念、进展及相关的应用。     

锂离子选择性微电极在生物体液中的响应

最近几年已报道了几种锂离子选择性电极.本文作者曾研制了以苯基膦酸二辛酯(DOPP)为溶剂,四苯硼酸盐为活性物质的PVC膜锂离子选择电极.本文在此基础上研制了锂离子选择性微电极,比较了以四苯硼酸钾(KTPB)及四苯硼酸钠(NaTPB)为活性物质的锂微电极的性能.同时考察了微电极在细胞内液、血清及生理盐液中对锂离子的响应特性.     

Flow-injection chemiluminescent determination of metoclopramide hydrochloride in pharmaceutical formulations and biological fluids using the [Ru(dipy)(3)(2+)]-permanganate system

A flow-injection (FI) methodology using (2,2′-dipyridyl) ruthenium(II) [Ru(dipy)₃²⁺] chemiluminescence (CL) was developed for the rapid and sensitive determination of metoclopramide hydrochloride. The method is based on the CL reaction of metoclopramide with Ru(dipy)₃²⁺ and KMnO₄ in a sulfuric acid medium. Under the optimum conditions, a calibration graph was obtained over the concentration range 0.005-3.5 μg ml⁻¹ with a limit of detection (S/N=2) of 1 ng ml⁻¹. The correlation coefficient was 0.99993 (n=8) with a relative standard deviation of 0.48% for 10 determinations of 1 μg ml⁻¹ of drug. The method was successfully applied to the determination of metoclopramide in pharmaceutical preparations and biological fluids after IP administration of 25 mg kg⁻¹ dose to rats. The elimination half-life was 2.5±0.4 h.