Transformation of Thioacids into Carboxylic Acids via a Visible-Light-Promoted Atomic Substitution Process.

A visible-light-promoted atomic substitution reaction for transforming thiocacids into carboxylic acids with dimethyl sulfoxide (DMSO) as the oxygen source has been developed, affording various alkyl and aryl carboxylic acids in over 90% yields. The atomic substitution process proceeds smoothly through the photochemical reactivity of the formed hydrogen-bonding adduct between thioacids and DMSO. A DMSO-involved proton-coupled electron transfer (PCET) and the simultaneous generation of thiyl and hydroxyl radicals are proposed to be key steps for realizing the transformation.

Development and application of a needle trap device for time-weighted average diffusive sampling.

A simple, cost-effective analysis combining solventless extraction, thermal desorption, and determination of volatile organic compounds (VOCs) was developed and validated. A needle trap device (NTD) packed with the sorbent Carboxen1000 was used as a time-weighted average (TWA) diffusive sampler to collect target compounds by molecular diffusion and adsorption to the packed sorbent. This process can be described with derivations of Fick's first law of diffusion, which expresses the relation between the TWA concentrations to which the passive sampler is exposed and the mass of analytes adsorbed to the packed sorbent in the sampler. The effects of experimental factors such as temperature, pressure, humidity, and face velocity were taken into account in applying diffusive sampling under nonideal conditions. This study demonstrates that NTD is effective for air analysis of benzene, toluene, ethylbenzene, and o-xylene (BTEX), due to the good adsorption/desorption quality of Carboxen 1000 and to the special geometric shape of the needle with a small cross section avoiding the need for calibration. Storage tests showed good storage stability for BTEX. Verification of the theoretical model showed good agreement between theoretical and experimental sampling rates. Method validation done against NIOSH method 1501, SPME, and NTD active sampling revealed good agreement between those methods. Automated NTD sample introduction to a gas chromatograph facilitates the use of this technology for industrial hygiene applications.

Extraction of formic and acetic acids from aqueous solution by dynamic headspace-needle trap extraction temperature and pH optimization.

A combined method of dynamic headspace-needle trap sample preparation and gas chromatography for the determination of formic and acetic acids in aqueous solution was developed in this study. A needle extraction device coupled with a gas aspirating pump was intended to perform sampling and preconcentration of target compounds from aqueous sample before gas chromatographic analysis. The needle trap extraction (NTE) technique allows for the successful sampling of short chain fatty acids under dynamic conditions while keeping the headspace (HS) volume constant. Two important parameters, including extraction temperature and effect of acidification, have been optimized and evaluated using the needle trap device. The method detection limits for the compounds estimated were 87.2microg/L for acetic acid and 234.8microg/L for formic acid in spite of the low flame ionization detection response for formic acid and its low Henry's law constant in aqueous solution. Precision was determined based on the two real samples and ranged between 4.7 and 10.7%. The validated headspace-needle trap extraction method was also successfully applied to several environmental samples.

Evaluation of methanol-water and acetonitrile-water binary mixtures as eluents for temperature-dependent inclusion chromatography.

In the present study the solubility of beta-cyclodextrin and 2-hydroxypropyl-beta-cyclodextrin at sub-zero and elevated temperatures (-10 and +30 degrees C) for a given composition of methanol/water and acetonitrile/water binary mixtures (Xs = 0.16) was studied. Moreover, the freezing temperature profiles of acetonitrile-based chromatographic mobile phases were measured, and the obtained results were compared with data available in the literature. Furthermore, the effect of the macrocycles concentration on the liquid-phase freezing points was determined. The low solubility of native beta-cyclodextrin in a methanol/water mixture at sub-zero temperature as well as the non-linear behavior of acetonitrile/water mixtures that were observed concerning the freezing point profile are discussed from a practical point of view.

Isocratic separation of ginsenosides by high-performance liquid chromatography on a diol column at subambient temperatures.

An improved high-performance liquid chromatographic method for separation of a number of ginsenosides has been developed. The influence of temperature (from 0 to 25 degrees C) on the retention and separation of the ginsenosides was studied by applying a binary mobile phase (acetonitrile/water, 82:18 v/v) and a diol column (LiChrospher 100 Diol). The column temperature is one of the more important parameters for the retention and separation of the components investigated. Selected thermodynamic parameters, including changes of enthalpy (deltaH degrees) and entropy (deltaS degrees), were estimated from linear van't Hoff plots, and possible retention mechanisms were discussed. Moreover, the best separation conditions were selected based on optimization criteria including maximum retention time (t(R max)), minimum resolution (R(s min)), and relative resolution product (r). Temperature regions close to 14 degrees C offered the highest selectivity and almost equal distribution of the ginsenosides peaks across the chromatogram. Under such isocratic conditions, excellent separation of chromatographic standards and selected ginseng samples was achieved in less than 16 min.