Statistical mechanics of hard spheres: validity of the basic relations of the scaled particle theory for frozen structures

In a previous article (J. Math. Phys. 36(201),1995), an equation of state for a hard sphere system was derived from the basic relations of the scaled particle theory without making use of some specific properties of the fluid state; they were only involved in the calculation of the two parameters which appear in that equation. In a later article (Z. f. Phys. B 102(255), 1997) it was therefore used to describe the glassy states, assuming tacitly that the basic relations of the scaled particle theory not only hold for the fluid state, but also for frozen structures. That assumption shall now be discussed in more detail and it will be shown that the basic relations are valid for all possible states of the system.     

Validation of the CALUX bioassay for PCDD/F analyses in human blood plasma and comparison with GC-HRMS

Following the dioxin crisis of 1999, several studies were conducted to assess the impact of this crisis on the dioxin body burden in the Belgian population. The Scientific Institute of Public Health identified a population from whom plasma samples were available and from whom, during the follow up survey, plasma samples were obtained in 2000. In total, 496 samples were collected for GC-HRMS and CALUX analyses to verify statistical assessment conclusions. This study was seen as an opportunity to validate the CALUX bioassay for biological sample analysis and to compare toxic equivalency (TEQ) values obtained by the reference GC-HRMS technique and by the screening method. This article focuses on the validation results of the CALUX bioassay for the analyses of the dioxin fractions of blood plasma. The sample preparation is based on a liquid–liquid extraction, followed by an acid silica in series with an activated carbon clean-up. A good recovery (82%) and reproducibility (coefficient of variation less than 25%) were found for this method. Based on 341 plasma samples, a significant correlation was established between the bioassay and chemical method (R = 0.64). However, a proportional systematic error was observed when the results obtained with the CALUX bioassay were regressed with the results from the GC-HRMS analyses. The limit of quantification (LOQ) used to calculate TEQ values from the GC-HRMS determinations, the use of the relative potency values instead of the toxic equivalent factor and the potential of CALUX bioassay to measure all compounds with affinity for the AhR may partly explain this proportional systematic error. Nevertheless, the present results suggest that the CALUX bioassay could be a promising valid screening method for human blood plasma analyses.     

Quantitative determination of p-aminosalicylic acid and its degradation product m-aminophenol in pellets by ion-pair high-performance liquid chromatography applying the monolithic Chromolith Speedrod RP-18e column

An ion-pair high performance liquid chromatographic method was developed for the simultaneous determination of p-aminosalicylic acid (PAS) and its degradation product m-aminophenol (MAP) in a newly developed multiparticular drug delivery system. Owing to the concentration differences of PAS and MAP, acetanilide and sulfanilic acid were used as internal standards, respectively. The separation was performed on a Chromolith SpeedROD RP-18e column, a new packing material consisting of monolithic rods of highly porous silica. The mobile phase composition was of 20 mm phosphate buffer, 20 mm tetrabutylammonium hydrogen sulphate and 16% (v/v) methanol adjusted to pH 6.8, at a flow-rate of 1.0 mL/min, resulting in a run-time of about 6 min. Detection was by UV at 233 nm. The method was validated and proved to be useful for stability testing of the new dosage form. Separation efficiency was compared between the new packing material Chromolith SpeedROD RP-18e and the conventional reversed-phase cartridge LiChroCART 125-4 (5 microm). A robustness test was carried out on both columns and different separation parameters (retention, resolution, run time, temperature) were determined.     

Determination of glutathione in human blood by high performance thin layer chromatography with fluorescence detection

A rapid, simple and sensitive method is presented for the determination of reduced glutathione in human blood. The samples are treated with trichloroacetic acid and derivatized with ammonium 7-fluorebenzo-2-oxa-1,3-diazole-4-sulphonate followed by high-performance thin-layer chromatography with fluorodensitometric measurements. The determined levels of glutathione in blood were 1.1±0.174 mM, achieving detection limits in the low nanograms per spot range.     

Determination of fluoxetine and norfluoxetine in rat brain microdialysis samples following intraperitoneal fluoxetine administration

Fluoxetine (FLX) and the N-desmethyl metabolite, norfluoxetine (NFLX) in rat brain microdialysis samples were determined by high-performance liquid chromatography (HPLC) with fluorescence detection using pre-column derivatization with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F). In vitro experiment showed that the relative recovery of FLX across microdialysis membrane was enhanced by adding β-cyclodextrin (β-CD) or β-CD polymer to microdialysis perfusion fluid. The perfusion fluid containing β-CD polymer, which has polymeric glyceryl linkers attached to the hydroxyl group, gave the better recovery with satisfactory precisions. Using 1% β-CD polymer in Ringer’s solution as the perfusate, in vivo rat brain microdialysis experiment on intraperitoneal administration of FLX (10 mg/kg) to rats was carried out. The fluorescence peaks of FLX and NFLX appeared later than 30 min after the administration of FLX, and then, gradually increased with time. Two hours later, FLX reached a plateau level, but NFLX slowly increased, and at 24-48 h, NFLX levels were higher than FLX levels. These data suggest that long distributions of FLX and the potent metabolite, NFLX, in brain contributed to the long-term drug actions in vivo.     

Fluorimetric determination of mebendazole and flubendazole in pharmaceutical dosage forms after alkaline hydrolysis

The selective and very sensitive fluorimetric determination of mebendazole and flubendazole is based on alkaline hydrolysis and adsorption on Whatman 42 filter paper. Limits of detection are 0.1 μg ml^?1 and 0.5 μg ml^?1, respectively, with linear response sponse up to 10 μg ml^?1 and 50 μg ml^t?1. The fluorescence produced is very stable (λ_em = 460 nm) and the method is applicable to anthelmintic pharmaceutical preparations.     

Invariance of activity coefficients for the hydrogen ion with charge-type of fluorescent indicators in aqueous-methanol solutions

Steady-state fluorimetric pH titrations of three fluorescent indicators of differing charge-type were carried out in aqueous methanol solutions containing up to 64 mol% methanol. The plot of the ratio of the relative fluorescence efficiency of the indicator acid to that of its conjugate base versus the product of the formal hydrogen ion concentration and the appropriate Bronsted kinetic activity factor gives straight lines for titrations in each mixed solvent, just as it does in water, but only if the constant terms in the Bronsted factor are modified to account for the bulk dielectric constant in each solvent. The product of the formal charges on the proton and the particular conjugate base studied in each titration must also be included in the Bronsted factor. This supports the hypothesis that a valid operational pH can be defined and kinetic parameters related to proton transfer can be extracted from the fluorimetric titrations in mixed solvents.     

SiGe differential transimpedance amplifier with 50-GHz bandwidth

InP and SiGe technologies are both attractive for design of circuits operating at 40 GB/s and beyond. In this paper, we describe a fully differential SiGe transimpedance amplifier (TIA) suitable for differential phase-shift keying applications. The TIA exhibits 49 dB-/spl Omega/ transimpedance, greater than 50-GHz bandwidth, and input-referred current noise less than 30 pA//spl radic/Hz. For comparison, we have also developed a similar TIA in an InP double-heterostructure bipolar transistor technology. The InP TIA had 48 dB-/spl Omega/ transimpedance and 49-GHz bandwidth.     

Chemiluminescence determination of tiopronin and its metabolite 2-mercaptopropionic acid in human urine by HPLC coupled with flow injection

Summary In previous pharmacokinetic studies tiopronin, a drug used for effective treatment of cystinuria and rheumatoid arthritis, and its metabolite 2-mercaptopropionic acid were analysed by conventional liquid chromatography with pre- and post-column derivatization and UV detection. Now a novel HPLC-coupled chemiluminescence-flow-injection analysis (CL-FIA) method has been developed for the determination of tiopronin and 2-mercaptopropionic acid in urine. The method is based on chemiluminescence from a Ce(IV) oxidation system sensitized by quinine, as proposed earlier by this group, and flow-injection analysis. The method, which has the advantages of high sensitivity and selectivity, simple sample treatment and prompt production of results, has also been preliminarily adapted for pharmacokinetic study of tiopronin in urine.