Avoparcin, a new macrocyclic antibiotic chiral run buffer additive for capillary electrophoresis.

Avoparcin, like vancomycin, teicoplanin, and ristocetin A, belongs to the family of macrocyclic glycopeptide antibiotics. These antibiotics have all been used as effective chiral selectors for capillary electrophoresis (CE), thin-layer chromatography (TLC), and high performance liquid chromatography (HPLC). The present work focuses on avoparcin, which has been shown to be an excellent chiral selector for the CE enantioseparation of many N-blocked amino acids, as well as several anti-inflammatory drugs of pharmaceutical importance. The use of avoparcin as a chiral run buffer additive in CE is discussed, as well as the effects of changing experimental parameters, like avoparcin concentration, pH, organic modifiers, etc. Comparisons of enantioseparations of some N-3,5-dinitrobenzoyl-derivatized amino acids, using either avoparcin, ristocetin A, teicoplanin, or vancomycin in the run buffer, are also made. In general, vancomycin had the longest migration times, and ristocetin A the shortest, while avoparcin was intermediate. Generally, at least one of the four chiral selectors produced an excellent separation, while a different macrocyclic antibiotic produced a poor separation. Currently, we see no way to predict which chiral run buffer additive will be best or worst for an individual solute.     

“灰色”分析体系的定性定量分析

已知组成范围的“灰色”分析体系的校正,其首要步骤是鉴定出体系中实际存在的物种.本文对由所有可能存在组分的标准光谱与样品光谱构成的矩阵进行了奇异值分解,根据对应奇异向量的元素判断样品的组成,继而做定量分析.计算机模拟与实际分析表明方法令人满意.     

The determination of gallium in rocks by neutron-activation analysis

Neutron-activation analysis has been applied to the determination of gallium in rocks. The Harwell Pile BEPO has been used as the source of neutrons, and a radiochemical procedure employing carrier chemistry has been utilised to separate the induced gallium activity.

Neutron-activation analyses of gallium in the standard rocks Gl and Wl are reported and compared with results obtained by other analytical methods.     

光谱多元分析的校正模型检验及干扰物的检出

提出了一种在校正模型不确定时分析体系的光谱多元分析方法,首先构造投影阵以检验校正模型的合理性,通过检验可以发现分析体系是否含有其它不纯物,继用不纯物在投影空间中的矢量与可能存在物质的投影光谱进行检索比较,检出不纯物并测出各组份含量.将此法应用于3个分析体系,获得满意的结果.     

Purity assessment for avoparcin

Well-characterized pure-substance reference materials for the use as calibrants are essential to establish the metrological traceability of the results of chemical measurements. Normally, the characterization of this type of reference material is conducted through a thorough purity assessment of the compound concerned. For this reason, studies on purity assessment, especially for neat organic compounds, continues as an important part of work being undertaken by metrological institutions around the world. Among others, the need for certified pure reference standards continues to increase for residues analysis in foods, particularly for those compounds which have been banned for food safety reasons, but their residues in foods are still monitored under food surveillance program in many countries. In this respect, avoparcin serves as a very good example where testing laboratories have difficulties in obtaining traceable and comparable results on determination of avoparcin in food matrix samples due, in part, to the unavailability of certified pure-substance reference material as calibrant. In this study, it was attempted to assess the purity of a commercially available test material of avoparcin using the mass balance approach. The objective of this paper is to share the difficulties encountered during the course of purity assessment and how they were addressed. As expected, the most challenging part of work was to identify and estimate the amount of unknown impurities, both organic and inorganic-related ones, given the chemical structure and properties of avoparcin. For instance, avoparcin exists in two forms in the test material, i.e., α- and β-avoparcin, and they were found to be susceptible to hydrolysis under certain conditions.     

Assessment uncertainty associated to the analysis of organic compounds linked to particulate matter of atmospheric aerosols

Current work has evaluated uncertainty associated to quantification of several organic compounds present in particulate matter of atmospheric aerosols, setting out the stages of analytical procedure that contribute most to the global uncertainty. Several sources of uncertainty have been identified, which were clustered into five main contributions: sampling, extraction, clean-up, derivatization and analysis. A discussion of the main contributions to the overall uncertainty is reported, allowing authors to locate the largest ones and plan future improvements. Combined uncertainties ranged between 10-18% (alkanes), 12-16% (PAHs), 10-18% (alcohols) and 9-21% (acids). The analytical procedure was validated by analysing a standard reference material (SRM1649a, urban dust). Also, the proposed method was applied to the analysis of four samples of particulate matter.     

Determination of metals in thoracic fraction of ambient air particulate matter

The present work deals with the optimization and validation of a method for the quantitative simultaneous ICP determination of metals in ambient air particulate matter. The attention has been focused on the thoracic fraction (PM10) and twelve different metals were chosen on the basis of their toxicity and of their possible use as chemical tracers. The microwave acidic digestion of the samples has been performed in the presence of different reagents and under different conditions and particular attention has been paid to the optimization of the whole analytical procedure and to the evaluation of accuracy and precision related to the single operative steps. The interferences due to the reagents and to the sampling supports have also been evaluated. In addition, the analytical procedure has been checked by examining the equivalence of results related to parallel sampled filters pairs.     

Automated ion-selective measurement of lithium in serum. A practical approach to result-level verification in a two-way method validation

 The Quality Assurance Department of Medix Diacor Labservice evaluated a two-way method validation procedure for serum lithium quantification in therapeutic drug monitoring In the process of a company fusion and rationalization of two considerably large production lines, three independent ion-selective electrode (ISE) methods were surveyed, among many others. While tailoring the new medical laboratory production, subcontracting from a collaborating company was discontinued. Likewise, modernization of the ISE instrumentation was unavoidable to increase throughput and effectiveness. It was important that the new result levels should be comparable both with the former subcontractor's levels and with the levels reported from the previously existing instrumentation. The aim of this study was to evaluate the most crucial performance characteristics of a novel lithium method in comparison to the two ISE test methods being withdrawn. The standardized lithium test method was inspected in terms of linear measurement range, analytical variation, bias, past and on-going proficiency testing, in addition to method comparison, to achieve the desired analytical goals. Fulfilling the accreditation requirements in terms of the introduced method validation parameters is discussed. Received: 19 April 2000 / Accepted: 26 July 2000     

Development and validation of an HPLC-DAD analytical procedure for quality control of damiana (Turnera diffusa), using an antioxidant marker isolated from the plant

Damiana is a shrub used as a dietary supplement and as an additive in several foods. This report presents the first validated analytical method for QC of products made from damiana. Through bioassay-guided fractionation, the compound showing the best antioxidant activity, determined using 2,2-diphenyl-1-picryl-hydrazyl assay in TLC, was purified and identified as 8-C-beta-[6-deoxy-2-O-(alpha-1-rhamnopyranosyl)-xylo- hexopyranos-3-uloside] (Cl50 5.56 g/mL). This is the only natural source from which this compound has been reported, and has been found in all native damiana samples analyzed. Therefore, it was used as a biomarker to develop an HPLC-diode-array detection analytical procedure using the first-order derivative of the chromatograms. Separation was achieved using an AccQ Tag C18 150 x 3.9 mm (4 microm) column, with a gradient of methanol and 0.1% trifluoroacetic acid in water. The method was shown to be accurate, sensitive, and reproducible, providing a useful quantitative means to apply QC to damiana products.     

Use of different anticoagulants for HPLC separation and quantification of the free amino acid content of plasma

Amino acid analysis in plasma samples is a very important and difficult task and could represent a useful tool for preventing the occurrence of some diseases (diabetes, cancer, HIV disease). Even though amino acid analysis has been thoroughly investigated, there are still some steps which are not so clear in this analytical procedure, e.g. the coagulation process of the blood to afford plasma and serum. Various anticoagulants are used in clinical chemistry: in this paper we have investigated three commonly used anticoagulants, heparin, EDTA, and sodium citrate. The blood samples have been divided into three portions and each portion treated with a different anticoagulant. The entire analytical procedure (from blood collection to the coagulation all the way to HPLC analysis) has been extensively investigated; the chromatograms and the amino acid recoveries are reported, and the three anticoagulants compared. Finally, the best anticoagulant has been used to analyze glycemic curves of healthy patients: the behavior of essential amino acids in the different blood samples withdrawn has been studied.     

A versatile algorithm for calculating vapour—liquid equilibria

A versatile algorithm is proposed for solving vapour—liquid equilibrium problems. It has been prepared so that the search procedure is generally applicable with any analytical equation of state and any kind of data. Special attention is paid to the applicability of the method in critical and high-pressure regions. Derivatives of the quantities describing the state of the system can be obtained for any equilibrium state as soon as equilibrium is determined. Results are reported for computing based on the use of a modified Redlich—Kwong equation of state.     

Multicentered Gaussian-based potentials for coarse-grained polymer simulations: Linking atomistic and mesoscopic scales

A new analytical form for bond and angle potentials suitable for obtaining mesoscale effective force fields from target distributions is reported. Applications to realistic coarse-grained models of atactic polystyrene and polyamide-6,6 are described. The potential optimization procedure, despite its simplicity, allows the accurate reproduction of the target atomistic distributions. The procedure has been validated for both bond and angle potentials. Nonbonded numerical potentials have been optimized by pressure-corrected iterative Boltzmann inversion. Thus, the proposed coarse-graining strategy consists of hybrid analytical and numerical contributions to the mesoscale polymer force field. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 871–885, 2005     

Analytical comparison of calorimetric,enzymatic and chemical methods for the quantitative determination of cholic acids

Several methods for the determination of cholic acids have been examined using pure cholic acid as standard. Some analytical aspects have been checked and evaluated. Two methods based on DSC were considered using the detection and measurement of the heats of oxidation and heats of fusion, respectively. The results were compared with those obtained both by the enzymatic method using 3α-hydroxysteroid dehydrogenase as reagent and by a chemical method based on the Pettenkofer reaction. Operative procedures of the last method have been tested and improved with respect to the Irvin procedure in some cases.The discussion is reported in terms of precision, sensitivity and possible fields of application for the examined method.     

Some remarks on the information power and selectivity of analytical processes

The consistency of the equation given by Shannon for the transfer of maximum amount of information in one channel, and the equation deduced by Kaiser for the expression of the information power of analytical methods is shown. The fundamental difference between the maximum amount of information obtainable by an instrument and that by an analytical procedure is reported. In the second case the selectivity of the analytical procedure also has to be taken into consideration.     

丙基格林试剂的合成及其在丁基锡衍生反应中的应用

格林试剂衍生方法是气相色谱与元素选择性检测器分离和测定有机锡化合物样品前处理的一个重要环节。研究了丙基格林试剂的实验室合成及其在丁基锡化合物衍生反应中的应用,为这类化合物监测标准方法的建立提供了基础条件。     

Development of an analytical procedure for evaluation of the protective behaviour of innovative fungal patinas on archaeological and artistic metal artefacts

In the literature, the ability to transform metal compounds into metal oxalates has been reported for different species of fungi. This could be an innovative conservation method for archaeological and artistic metal artefacts. In fact, with a high degree of insolubility and chemical stability even in acid atmospheres (pH 3), metal oxalates provide the surface with good protection. Within the framework of the EU-ARTECH project, different fungal strains have been used to transform existing corrosion patinas on outdoor bronze monuments into copper oxalates, while preserving the physical appearance of these artefacts. Given the promising results obtained with this first attempt, the same approach is now applied within the BAHAMAS (Marie Curie Intra European Fellowship action) project, but extended to other metal substrates, for example iron and silver, which are frequently found in cultural heritage artworks and also encounter several problems of active corrosion. The research is investigating the formation mechanisms and adhesion properties of the newly formed metal oxalates by means of complementary analytical techniques (X-ray diffraction (XRD), FTIR microscopy, Raman microscopy, scanning electron microscopy (SEM-EDS), electrochemical impedance spectroscopy (EIS), colorimetry). For each metal substrate, the most appropriate fungal strain is going to be identified and applied to corroded sheets and the novel fungal treatment compared with those used so far. Treated metal sheets will be monitored during 1-year exposure to different cycles of artificial ageing, to evaluate the corrosion resistance of the fungal patinas obtained. The objective of this contribution is to present the first results achieved so far on naturally corroded bronze sheets during the EU-ARTECH project and the analytical procedure used for the testing of the proposed treatment performances during the BAHAMAS project.     

Determination of tauromustine and its demethylated metabolites in plasma and urine

A sensitive, selective and precise high-performance liquid chromatographic method for simultaneous determination of tauromustine and its demethylated metabolites in plasma and urine has been developed. It is based on solid-phase extraction on C18 sorbent and separation on a semipolar column. The analytical procedure is described in detail. The method has been validated with respect to linearity, recovery, selectivity, precision and detection limit. The stability of the determined substances in various media has also been studied.     

Purification of arsenic contaminated ground water using hydrated manganese dioxide

An analytical methodology has been developed for the separation of arsenic from ground water using inorganic material in neutral medium. The separation procedure involves the quantitative retention of arsenic on hydrated manganese dioxide, in neutral medium. The validity of the separation procedure has been checked by a standard addition method and radiotracer studies. Neutron activation analysis (NAA), a powerful measurement technique, has been used for the quantitative determination of arsenic.     

First derivatives of correlated wave functions by a matrix-oriented method: Preliminary application to molecular dipole and quadrupole moments

A direct, matrix-oriented procedure in the context of the self-consistent electron pairs (SCEP) method has been implemented for the evaluation of first derivatives of the energy of a variational configuration interaction wavefunction. This has been applied in calculating dipole and quadrupole moments of the correlated charge distributions of several small molecules. As already established, the analytical differentiation being carried out yields properties slightly different than those calculated by integration with the one-electron density. The matrix-oriented analytical differentiation is computationally competitive with construction of the one-electron density.