On-line extraction and determination of carbofuran in raw milk by direct HPLC injection on an ISRP column

Summary A method has been developed for extraction and determination of carbofuran in milk. The method involved direct injection of raw milk on to a human serum albumin dimethyloctyl-silica gel (HSA-C₈) column and the use of 80:20 (v/v) 0.01 M phosphate buffer pH 5.5-acetonitrile as mobile phase. UV spectrophotometric detection was performed at 220 nm. Identification was based on retention time. Quantification was performed by automatic peak-area determination and was calibrated by use of an external standard.     

Critical evaluation of gas standards based on hydrogen

Summary Six commercial hydrogen standards containing helium, oxygen, nitrogen, methane and carbon dioxide at trace levels were analyzed by gas chromatography, for periods up to 105 days. The concentrations, in the range of 0–120 μmol mol⁻¹, were stable (with the exception of oxygen) but often significantly different from the certified values provided by the suppliers, especially for helium, oxygen and nitrogen. Concurrently, some experiments were carried out to verify the stability of gas mixtures based on hydrogen stored in cylinders submitted to different chemical and physical treatments. The causes that led to the deviations observed, as well as the decreases in oxygen, are discussed. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996.     

Pulsed-Field-Gradient Measurements of Time-Dependent Gas Diffusion

Pulsed-field-gradient NMR techniques are demonstrated for measurements of time-dependent gas diffusion. The standard PGSE technique and variants, applied to a free gas mixture of thermally polarized xenon and O₂, are found to provide a reproducible measure of the xenon diffusion coefficient (5.71 × 10⁻⁶m²s⁻¹for 1 atm of pure xenon), in excellent agreement with previous, non-NMR measurements. The utility of pulsed-field-gradient NMR techniques is demonstrated by the first measurement of time-dependent (i.e., restricted) gas diffusion inside a porous medium (a random pack of glass beads), with results that agree well with theory. Two modified NMR pulse sequences derived from the PGSE technique (named the Pulsed Gradient Echo, or PGE, and the Pulsed Gradient Multiple Spin Echo, or PGMSE) are also applied to measurements of time dependent diffusion of laser polarized xenon gas, with results in good agreement with previous measurements on thermally polarized gas. The PGMSE technique is found to be superior to the PGE method, and to standard PGSE techniques and variants, for efficiently measuring laser polarized noble gas diffusion over a wide range of diffusion times.     

Gas-liquid chromatography of perfluorocarboxylic thioesters

Perfluorocarboxylic thioesters R_FC(O)SR (R_F=CF₃(CF₂)_j, R=CH₃(CH₂)_i, i andj=0–5) were studied for the first time by GLC on packed columns using SE-30, SKTFT-50X, and XE-60 as the stationary phase. The values of thermodynamics functions of sorption were calculated. The correlations between these functions and the molecular structures as well as the conditions of analysis were established. The insertion of the S atom into the molecules of derivatives of perfluorocarboxylic acids causes a decrease in the contribution of the orientation interaction and an increase in the dispersion interaction of thioesters with the stationary phases compared to esters and amides of perfluorocarboxylic acids studied previously. For Part 1, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1165–1168, June, 1997.     

Radio-Frequency Hexamethyldisiloxane Plasma Deposition: A Comparison of Plasma- and Deposit-Chemistry

This study reports on the effect of input power to hexamethyldisiloxane (HMDSO) plasmas. The power dependence of the plasma-phase species and of the surface chemistry (of the deposits) has been investigated. Neutral and positive molecular species were detected within the plasma using mass spectrometry (MS). Secondary ion mass spectrometry (SIMS) was used to probe the molecular structure of the deposits. The elemental composition of the surface was determined by XPS and the deposition rate was monitored using a vibrating quartz crystal microbalance. Neutral and cationic molecules of mass greater than HMDSO were detected in the plasma. Their formation through ion-molecule reactions is proposed. Changes in the relative concentration of plasma-phase species follow those seen in molecular species detected at the deposit surface. Thus, we believe that the molecular structure of the deposits can be related to the species present in the plasma. While traditionally the dominant mechanism in deposit formation is assumed to be free radical combinations, we propose other possibilities involving cations with the aim of putting forward a new perspective on plasma polymerization mechanisms and thereby stimulating discussion.     

Pulsed gas lenses

The concept of a pulsed gas lens is proposed. Potential applications are envisaged and preliminary experiments with pulsed ray refraction are reported.     

Isomer effects on transport properties of polyesters based on bisphenol-A

Pure gas sorption and transport properties of polyesters based on bisphenol-A and both pure isophthalic and pure terephthalic acid chloride were obtained for He, N₂, O₂, CH₄, and CO₂ at 35°C. The polymers were synthesized in our laboratory and amorphous films were prepared with a specialized solvent casting procedure. The polymer containing m-phenylene groups shows higher permselectivity for most of the gas pairs. The ideal selectivity of O₂/N₂ was increased by 33% when p-phenylene units were replaced by m-phenylene ones. On the other hand, the polyester containing only p-phenylene groups, shows higher permeability to all the gases studied. The polymer based on pure terephthalic acid chloride has a 75% higher oxygen permeability and a 1.1-fold higher carbon dioxide permeability than the isophthalic acid derivative. The polyester containing meta-phenylene units has lower T_g, higher permselectivity, lower permeability, lower fractional free volume (FFV), and lower d-spacing. The values of FFV, and lower d-spacing. The values of FFV and d-spacing were only slightly different between the two isomers. Moreover, for the sub-T_gγ transition the maximum in tan δ occured at essentially the same temperature (?55°C). The polymer with a higher concentration of p-phenylene units shows somewhat larger area under the γ-peak, indicating slightly more sub-T_g motion. The Distribution of FFV is considered to be the determining factor for the differences in transport properties observed. © 1993 John Wiley & Sons, Inc.     

高密度氩气的原子间相互作用与状态方程

本文从高密度气体的原子间相互作用出发进行思考,在修改范德瓦耳方程的基础上,提出了一种新的适用于高密度气体的状态方程,并用以对氩气临界区的等温压缩线进行计算,结果与实验值很符合.     

Automated derivatization for on-line solid-phase extraction-gas chromatography; phenolic compounds

An automated system for derivaatization was coupled on-line with solid-phase extraction-gas-chromatography (SPE-GC). The system was optimized for the determination of phenol and chlorinated phenols in aqueous samples. The test analytes were acetylated with acetic anhydride; proper buffering of the sample was a critical factor. Next, the phenol acetates were enriched on a SPE cartridge and transferred to a GC; two appraoaches were studied. In the first approach, the derivatives were enriched on disposable C18 cartridges (ASPEC type) and desorbed with methylacetate. Aan aliquot of the final eluate was injected on-line the GC by means of a loop-type interface. In the second approach, trace enrichment was performed on 10 × 2 mm i.d. LC-type precolumn packed with polystyrenedivinylbenzene copolymer (PLRP-S) this precolumn was dried with a mitrogen purge and the phenol acetates were desorbed with ethyl acetate which was injectedon-line into the retention gap of the GC under partially concurrent solvent evaporation (PCSE) conditions. The Derivatization-SPE-GC system which was based on the loop-type interface has the advantage of simplicity and easy operation, the main drawback is the impossibility to determine phenol acetates which elute prior to trichlorophenol acetates. With the derivatization-SPE-GC approach using PCSE-based desorption, even the most volatile analyte of the test series, phenol acetate, can be determined successfully. The entire procedure, including the derivatization step, was fully automated and integrated in one set-up. The precision data for the integrated on-line derivatization-SP-FID system were fully satisfactory, with RSD values of 1–12 % at the 1 μg/1 level. When a sample volume of 2.2 ml was analyzed, The detection limits for the chlorinated phenol acetates were in the 0.1–0.3 μg/1 range.