Analysis of citrates and benzoates used in poly(vinyl chloride) by supercritical fluid extraction and gas chromatography

Supercritical fluid extraction (SFE) has been demonstrated to be a useful tool in the determination of additives in polymeric materials. This paper describes the determination of some citrates and benzoates in poly(vinyl chloride) blended with 33–34% of plasticizer using off-line SFE followed by gas chromatography. Experimental factors affecting SFE have been studied by gravimetric analysis, followed by analysis of the extracts using a gas chromatograph equipped with a flame ionization detector. The extraction process is governed by the solubility of the plasticizers in the supercritical fluid or by their diffusion through the polymer matrix, which depend on the pressure and temperature used. Maximum extraction (>99%) is obtained at pressures and temperatures higher than 40 MPa and 80 °C, respectively. Due to purge losses, the collection efficiency of plasticizers into a liquid solvent ranges from 85 to 90%. The applicability of the SFE method is demonstrated using real samples and comparing the results with those obtained by conventional Soxhlet extraction.     

Use of SPE—TLC for Quality Control of Rhodiola rosea Extracts

SPE and TLC have been used for qualitative and quantitative analysis of salidroside, rosavin, rosarin, and rosin in commercially available dry extracts from Rhodiola rosea roots. The best separation of all the compounds was achieved on silica gel TLC plates with ethyl acetate—methanol—water, 77 + 13 + 10 (v/v), as mobile phase. UV detection was performed at λ = 215 nm for salidroside and at λ= 245 nm for the rosavins (rosavin, rosarin, and rosin). Detection limits for salidroside and the rosavins were 90 ng and 60 ng per spot, respectively. Results from quantitative analysis confirmed the manufacturer’s declaration of the amounts of salidroside and the rosavins in the extracts.

     

Aggregation des menschlichen Serumalbumins unter den Bedingungen der W ärmedenaturierung

Ohne Zusammenfassung     

Phase Analysis of the Binary System of Cryolite (Na3AlF6) and Sodium Metasilicate (Na2SiO3)

The phase analysis of cryolite (Na₃AlF₆) and sodium metasilicate (Na₂SiO₃) was performed by thermal analysis. The eutectic system with a region of two immiscible substances at a concentration of Na₂SiO₃ between 42.8 and 46.3 mol‐% was identified and the eutectic temperature determined to (886±2) °C. Based on the results of mass‐loss measurements, it was assumed that the introduced Na₂SiO₃ reacts with Na₃AlF₆ due to the formation of some nonvolatile stable compounds. The stable reaction products were identified by X‐ray diffraction analysis and IR spectroscopy of the spontaneously cooled samples, which established the formation of NaF and stable amorphous aluminosilicate compounds.     

Validation of the thermodynamic model of inorganic arsenic in non polluted river waters of the Basque country (Spain)

The thermodynamic model of inorganic arsenic was validated by comparing the predicted As(III) concentration with the experimentally determined one in several river waters samples of the Basque Country (Spain) collected in two sampling campaigns: spring and autumn 2000. This model takes into account the acid-base equilibria of As(III) and As(V) together with the redox equilibria between the H₃AsO₃ and H₃AsO₄ species. A correct prediction of As(III) concentration requires the knowledge of the total concentration of arsenic, pH, redox potential (referred to hydrogen electrode), and ionic strength values of the solution. The estimation of the activity coefficients of the arsenic species was performed by means of the Modified Bromley’s Methodology (MBM).In order to perform the experimental As(III) determination, an analytical method was implemented by using an ion exchange separation of As(III)/As(V) on a continuous FIA-IE-HG-AAS system. The total arsenic concentration was determined together with total concentration of the main alkaline or alkaline-earth metals and anions in the natural waters. Temperature compensated measurements of the pH and redox potentials were made in-situ at the sampling sites.For both seasonal campaigns, the agreement between predicted and experimental As(III) is really high for those samples belonging to non polluted river waters.     

Asymmetric hetero Diels-Alder as an access to carbacephams.

A short and efficient asymmetric synthesis of the (6R,7S)-7-tert-butoxycarbonylamino-2-ketocarbacepham is described. The key step involves the hetero Diels-Alder reaction of the benzylimine derived from the enantiomer of Garner's aldehyde with Danishefsky's diene.     

Arsenic Speciation Analysis in Solutions Treated with Zeolites

Experiments have been carried out to study the behaviour of organoarsenicals treated with zeolites by means of speciation analysis. IC-ICP-MS was applied to identify and quantify arsenite, arsenate and the following organoarsenicals: monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), trimethylarsine oxide (TMAO), tetramethylarsonium bromide (TMA⁺), arsenobetaine (AsB) and arsenocholine (AsC). Zeolites loaded with ferrous ions did not significantly increase the retention of inorganic arsenic species compared to the native zeolites, while there was a ten-fold removal of arsenate relating to arsenite. The formation of As(V) and DMA in the leachates containing clinoptilolites and mordenites was confirmed in the presence of natural and synthetic zeolites. Arsenobetaine and arsenocholine yielded higher levels of arsenate than the methylated species.     

Ab-initio molecular dynamics based on non-local density functional procedure with Gaussian basis; study of structural and temperature behaviour of metallic clusters

An ab-initio molecular dynamics procedure without precalculation of the Born-Oppenheimer energy surface based on an iterative non-local density functional method employing Gaussian atomic basis has been developed. Analytical gradients are calculated and used for the propagation of nuclei. Sufficiently long trajectories can be calculated at an acceptable computational cost, allowing for analysis of dynamical behaviour of small metallic clusters. This is illustrated on an example of the Li₈ cluster. Temperature behaviour of different type of isomers has been investigated. Calculated power spectra allow to identify the presence of more than one isomeric forms along the given trajectories.     

Sol-Gel Processing of PbZrO3 Thin Films

PbZrO₃ (PZ) thin films have been prepared by 2-methoxyethanol route from lead oxide or lead acetate and zirconium n-butoxide. The use of lead oxide as lead source and the seeding layer of TiO₂ on Pt/TiO₂/SiO₂/Si substrate facilitate the formation of the perovskite phase.     

Evaluation of a purge-and-trap injection system for capillary gas chromatography-microwave induced plasma-atomic emission spectrometry for the determination of volatile selenium compounds in water

A method is presented for the selective determination of the volatile selenium species dimethylselenide and dimethyldiselenide, using a commercially available purge-and-trap injection system coupled to capillary gas chromatography-microwave induced plasma-atomic emission spectrometry. The efficiency of the purging step was evaluated and the parameters affecting the purge and trap processes were optimized. The method was applied to the determination of volatile selenium compounds in lake water. Relative detection limits of 2ng/l for dimethylselenide and dimethyldiselenide, corresponding to an absolute detection limit of 10 pg, were achieved.