Determination of atrazine, desethyl atrazine and desisopropyl atrazine in environmental water samples using hollow fiber-protected liquid-phase microextraction and high performance liquid chromatography

A new method based on hollow fiber-protected liquid-phase microextraction (LPME) was developed for the simultaneous determination of atrazine, desethyl atrazine and desisopropyl atrazine in environmental water samples. In LPME, analytes were extracted into 1-octanol immobilized in the micropores of a poly(vinylidene fluoride) porous hollow fiber membrane, and back extracted into the acceptor (4 M HCl) filled in the lumen of the hollow fiber. After LPME, the analytes trapped in the acceptor were analyzed with high-performance liquid chromatography after neutralization. The effect of extraction factors such as sample pH, acceptor pH, salinity, extraction time, stirring rate, and humic acid were studied. Under the optimized conditions, the limits of detection and relative standard deviations were respectively in the range of 0.5–1.0 μg L⁻¹ and 3.9–4.7% (n = 5). The proposed method was applied to determine atrazine, desethyl atrazine and desisopropyl atrazine in wastewater and groundwater samples. The three analytes were below the limits of detection, but good relative spiked recoveries over 90.1 ± 5.9% at 5 μg L⁻¹ spiked level were obtained.     

Evaluation of a complete HPLC solvent optimization system involving piece-wise quadratic modelling

Summary Interpretive methods are accepted to give the best possible results for selectivity optimization in HPLC. However the methods are very complex, and most work so far has been detailed academic studies. This paper describes an evaluation of a complete integrated system incorporating peak labelling, modelling of retention behaviour and calculation of response surfaces, with particular emphasis on the retention modelling. The peak labelling section has been discussed previously.A piece-wise quadratic function is investigated for the modelling of retention times across an isoeluotropic plane to effect selectivity optimization in HPLC. This requires 10 data-points on the isoeluotropic plane. The predicted global optimum and local optima are evaluated by comparison of calculated and experimental retention data, for a nine component sample. Seven interstitial points, distributed across the whole plane between the data-points, are similarly evaluated for a related sample. The typical error (in retention time) is less than 2%, often 1%, and the maximum error is 4.2%. At the global optimum the error was found be less than 1.3% for all 9 peaks.     

Polynuclear manganese grids and clusters—A magnetic perspective

High nuclearity paramagnetic, spin-coupled transition metal clusters and grids are fascinating chemists and physicists partly because of their structural beauty, and the challenge of creating them, but also because of their novel physical properties. Magnetic interactions between the spin centers are a primary focus. This review will examine a selection of Mn(II) polynuclear grids and clusters, with nuclearities in the range Mn₄ to Mn₉. Theoretical treatments of the magnetic properties are discussed, and approaches to solving the exchange problem for ‘large’ spin systems related to computational difficulties. A freely available software package (MAGMUN4.1) is presented as a means of dealing simply with spin-coupled clusters in general, and symmetry reduction methods are discussed briefly as a means of dealing with ‘large’ spin systems.     

氮杂冠醚研究Ⅶ、双仲胺型氮杂冠醚对过渡金属离子的选择性萃取作用

合成了五种新型双仲胺型氦杂冠醚，研究了它们对过渡金属离子进行液—液萃取，并用原子吸收法测定其浓度。实验结果表明：这类冠醚对Ａｇ￣＋、Ｐｄ￣（２＋）、和Ｐｔ￣（４＋）等贵金属离子有较强的选择配位性能，对选择性分离这些金属离子有重要的意义。     

The calculation of retention and selectivity in reversed-phase liquid chromatography II. Methanol-water eluents

Summary To calculate retention in reversed-phase, high-performance liquid chromatography a method based on the molecular structure of the analyte and the characteristics of sorbents and mobile phases has been employed. Characteristics of different ODS-columns in water-methanol eluents have been determined.     

Theoretical study of the effect of frit quality on chromatography using computational fluid dynamics

Summary Frits at both ends of a chromatographic column, especially for a preparative column, have significant influence on the flow distribution within the column and thus the column efficiency. However, frits have received little attention from chromatographers in the past. Here a theoretical study was conducted with the aid of CFD software FLUENT to investigate the effect of frits on the performance of homogeneous and heterogeneous chromatographic columns. A dimensionless number,FQ, was applied to characterize frit quality. This study visualized how frit quality affects the flow distribution and the concentration band, the shape of eluted pulse at the colum exit and column efficiency. Simulation results show that the development length of the flow distribution is related toFQ but has nothing to do with the packing heterogeneity. The curvature of the concentration band in a column depends onFQ and packing quality. This study shows column efficiency can be improved significantly by increasingFQ and/or frit permeability.     

Non isothermal heat capacities and chemical reactions using a modulated DSC

An evaluation of measurements of heat capacities by modulated differential scanning calorimetry, MDSC is presented. Heat capacities were obtained from 130 to 550 K by a non isothermal technique in which a periodic modulation was added to the linear heating rate. Effects of amplitude and period of modulation, sample weight, sample type, pan type, and cell imbalance are described. Results are compared with those obtained using the isothermal technique. Heat capacity could be measured well into the decomposition region and separated from the non reversing signal due to chemical reaction (degradation), thus allowing a precise detection of onsets of the thermal degradation. This additional information will aid in the interpretation of the degradation chemistry, a field vital for the petroleum-industry.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayPart of this paper was presented at the 23rd Conference of the North American Thermal Analysis Society, Toronto, Canada, September 25–28, 1994.The author (MVN) acknowledges the experimental assistance provided by J. Balogh of Exxon Research and Engineering Company, Linden. Helpful discussions with A. Boller of the University of Tennessee at Knoxville, Dr. Y. Jin, General Electrical, and Dr. S. Sauerbrunn formerly of TA Instruments are also acknowledged.     

Characterisation of Tokaj wines based on free amino acids and biogenic amines using ion-exchange chromatography

Summary Tokaj wines (Szamorodni and Aszu wines) of Hungarian origin were investigated on the basis of free amino acids and biogenic amines. The separation and determination of these compounds was performed by an amino acid analyser equipped with an ion-exchange resin column. The total amount of free amino acids and biogenic amines was higher in Aszu wines than in Szamorodni wines. The main amino acids were proline and arginine, while the major biogenic amines were tyramine and putrescine. The free amino acid and biogenic amine content of Aszu wines depended on the vineyards the wines originated from. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

LC–MS Determination and Pharmacokinetic Study of a Novel Sulfonylurea: Potential Hypoglycemic Agent in Rat Plasma

To support preclinical pharmacokinetic investigation of 1-[4-[2-(4-bromobenzene-sulfonaminoethyl)phenylsufonyl]-3-(trans-4-methylcyclohexyl)urea (G004), a rapid, sensitive and specific high-performance liquid chromatography–electrospray ionization mass spectrometry (LC–ESI-MS) method was developed and validated. Glibenclamide was employed as internal standard. After liquid–liquid extraction the analyte was analyzed on a Kromasil C₁₈ column (150 × 2.0 mm i.d.) with a mobile phase consisted of acetonitrile–water (0.05% acetic acid), 30:70 (v/v). The flow rate was 0.2 mL min⁻¹. Detection was performed on a quadrupole mass spectrometer using an electrospray ionization interface and the selected-ion monitoring (SIM) mode. The retention time was about 3.5 and 4.2 min for Glibenclamide and G004, respectively. The assay was linear over the concentration range of 2.0–500.0 ng mL⁻¹. Extraction Recovery of G004 in rat plasma was more than 87%. The intra- and inter-assay precision was lower than 11.5% (CV). This validated method was successfully applied to the pharmacokinetics of G004 in rats.     

Uniqueness and clustering properties of Gibbs states for classical and quantum unbounded spin systems

We consider quantum unbounded spin systems (lattice boson systems) in -dimensional lattice space Z. Under appropriate conditions on the interactions we prove that in a region of high temperatures the Gibbs state is unique, is translationally invariant, and has clustering properties. The main methods we use are the Wiener integral representation, the cluster expansions for zero boundary conditions and for general Gibbs state, and explicitly -dependent probability estimates. For one-dimensional systems we show the uniqueness of Gibbs states for any value of temperature by using the method of perturbed states. We also consider classical unbounded spin systems. We derive necessary estimates so that all of the results for the quantum systems hold for the classical systems by straightforward applications of the methods used in the quantum case.