Quantitative assessment of the reliability of identification by high-performance liquid chromatography-mass spectrometry

At present, mass spectrometry (MS) is the most reliable method for identification but there is not yet a quantitative equation describing this fact. In this investigation an approach to the quantitative assessment of the reliability of identification by MS is proposed which is useful for determination of the selectivity and the validation of analytical methods. Mass spectra of the analytes are presented as maps in which the characteristic ions and their intensities are used for identification. A formula for the quantitative expression of the significance of these parameters to the reliability and the identification is given. The contribution of the resolution of MS instruments or their possibilities of a multiple fragmentation to the reliability of the identification is shown. This approach makes it possible to compare the reliability of identification with different MS instruments. Despite the small contribution of the separation of the chromatographic column compared to the MS separation, the role of the column in the identification is very important to distinguish isomers because their MS spectra are similar.     

Evolved-gas zeeman flame atomic absorption spectrometry for the determination of arsenic compounds

An evolved-gas separation/flame Zeeman atomic absorption spectrometric approach is demonstrated for the speciation and determination of arsenic in oyster tissue. No digestion is needed and separation of inorganic arsenic compounds having similar boiling points is achieved. A stoichiometric or air-rich acetylene/air flame for atomic absorption spectrometry is not generally suitable for arsenic determination because of severe ultraviolet absorption interference at 193.7 nm and low sensitivity; polarized flame Zeeman atomic absorption spectrophotometry with a fuel-rich flame is suitable for the detection of traces of arsenic. The evolved-gas separation/Zeeman atomic absorption approach is simple, based on commercially available instrumentation, and useful for the selective determination of major arsenic compounds. Data are given to demonstrate optimal conditions and to show application to oyster tissue.     

Analytical solution of Poisson–Boltzmann equation for interacting plates of arbitrary potentials and same sign

Efficient calculation of electrostatic interactions in colloidal systems is becoming more important with the advent of such probing techniques as atomic force microscopy. Such practice requires solving the nonlinear Poisson–Boltzmann equation (PBE). Unfortunately, explicit analytical solutions are available only for the weakly charged surfaces. Analysis of arbitrarily charged surfaces is possible only through cumbersome numerical computations. A compact analytical solution of the one-dimensional PBE is presented for two plates interacting in symmetrical electrolytes. The plates can have arbitrary surface potentials at infinite separation as long they have the same sign. Such a condition covers a majority of the colloidal systems encountered. The solution leads to a simple relationship which permits determination of surface potentials, surface charge densities, and electrostatic pressures as a function of plate separation H for different charging scenarios. An analytical expression is also presented for the potential profile between the plates for a given separation. Comparison of these potential profiles with those obtained by numerical analysis shows the validity of the proposed solution.     

On the determination of the point of fracture initiation by the load separation criterion in J-testing of ductile polymers

The application of an experimental approach based on the load separation criterion for the determination of the point of fracture initiation in a fracture test on a ductile polymer was critically examined. To this aim, the fracture process outlined by the application of this method was related to that described by the visual analysis of the fracture surfaces obtained in fracture tests on nominally identical specimens, in which different levels of crack extension were produced. The material examined was an acrylonitrile-butadiene-styrene (ABS) resin, and the fracture tests were performed at low loading rate on single-edge notched in bending specimens.The results demonstrated that this load separation criterion based methodology is a promising approach for the determination of the point of fracture initiation, and for material fracture resistance, J_Ic, evaluation. The method also has experimental simplicity and a high degree of repeatability.     

Saving time when measuring BET isotherms

The measurement of adsorption isotherms and the determination of surface properties of a solid by means of the BET equation usually takes a lot of time as it involves measurement of several dynamic adsorption curves each at a given gas pressure. Two different timesaving approaches are suggested: (a) the beginning of a single dynamic curve is considered and (b) the beginnings of a number of different dynamic curves is considered. Approach (a) is less time consuming than approach (b), where approach (b) yields more accurate estimates of the BET-parameters. A discussion is given of the possibilities of using the time saving procedure of J?ntti for the two approaches.     

Obtaining surface tension from contact angle data by the individual representation approach

Young equation is the fundamental equation of wetting theory in which the connection among the surface tensions, \(\gamma _{{\varphi \psi }} \) and the contact angle, θ _L, are given. The surface tension of solid surfaces, however, cannot be obtained directly from the Young equation. In this paper, the application of the individual representation theory is demonstrated for the determination of surface tensions of solids (or any phase pair) using experimentally obtained contact angle data. According to this approach, the state of the interfacial layers depends upon, by definition, the properties of the bulk phases in every heterogeneous system, and thus, it complements the traditional capillary theory.     

The polarographic determination of indium in zinc-base alloys : The determination of indium in mazak alloys

In this paper, the development of a co-precipitation method for the separation of indium from zinc alloys is described and a method for the determination of indium down to 0.5 p.p.m. in mazak alloys is presented. Results obtained in trials of this method are given and the final conclusions regarding this and previously developed methods are included.     

Computer-assisted transposition of conditions in high-performance thin-layer chromatography to high-performance liquid chromatography for the separation of pesticides

Summary A computer-assisted method is presented for mobile phase selection for the optimal separation of pesticides by HPTLC and HPLC. The system is based on a plot of solute retention value and separation criterion vs. binary mobile phase composition for graphic optimization. The result of HPTLC can be transposed to HPLC for optimal separation. The transposition equation is given.     

Chiral separation of amino acids and peptides by capillary electrophoresis

Chiral separation of amino acids and peptides by capillary electrophoresis (CE) is reviewed regarding the separation principles of different approaches, advantages and limitations, chiral recognition mechanisms and applications. The direct approach details various chiral selectors with an emphasis on cyclodextrins and their derivatives, antibiotics and chiral surfactants as the chiral selectors. The indirect approach deals with various chiral reagents applied for diastereomer formation and types of separation media such as micelles and polymeric pseudo-stationary phases. Many derivatization reagents used for high sensitivity detection of amino acids and peptides are also discussed and their characteristics are summarized in tables. A large number of relevant examples is presented illustrating the current status of enantiomeric and diastereomeric separation of amino acids and peptides. Strategies to enhance the selectivity and optimize separation parameters by the application of experimental designs are described. The reversal of enantiomeric elution order and the effects of organic modifiers on the selectivity are illustrated in both direct and indirect methods. Some applications of chiral amino acid and peptide analysis, in particular, regarding the determination of trace enantiomeric impurities, are given. This review selects more than 200 articles published between 1988 and 1999.     

Separation and determination of the sulph-hydryl flotation collectors using ion-interaction chromatography

Summary This paper discusses simple and practical methods for the separation and determination of various sulph-hydryl flotation reagents by ion-interaction chromatography. Physical and chemical parameters such as column length, the support, and the constituents of the mobile phase and their respective concentrations were considered. A set of capacity factors, determined for a given set of conditions, is used to assist in the design of separation methods. The developed methodology enables the determination of various sulph-hydryl compounds in a given mixture of flotation reagents, distinction between compounds with the same functionality, and the separation of structural isomers of a particular compound. The applicability of the methods was demonstrated by the analysis of some commercial flotation reagents, as well as samples generated in an investigation of synergism of the sulp-hydryl collectors.     

Role of the cure kinetics in morphology control at phase separation of curing multicomponent thermosets and a criterion of equilibrium

The formation of heterophase polymers via phase separation in the course of curing reaction in a blend of a thermosetting oligomer with a rubber modifier is considered. The interference of thermodynamic and kinetic factors that define the morphology of the material being formed is discussed. The need for a kinetic theory of cure-induced phase separation is established, and an approach of this kind is proposed. On the basis of this approach a simple quantitative criterion of deflection of the phase-separating system from the thermodynamic equilibrium is given.     

Determination of enantiomeric excess by capillary electrophoresis

Capillary electrophoresis (CE) is becoming an established method for the determination of chiral trace impurities. This paper provides an overview of the state of the art of CE for such determinations. Detection limits of 0.1% impurity is widely accepted as a minimum requirement for chiral trace impurity determinations. This can be relatively easily achieved with CE. However, determination of lower concentrations requires careful optimization of the separation system. Four factors that are of particular significance for trace enantiomeric determinations: resolution, limit of detection, linear range and type of detection, are discussed. Further, the advantages and disadvantages of derivatization in this context are treated as well as the separation approach, ie., direct chiral separation or separation after the formation of diastereomers. It is concluded that the limit of impurity detection can be about 0.05% when UV detection is employed. Using laser-induced fluorescence detection, a quantitative determination at the 0.005% level is often possible.     

Fast choice of separation conditions for analyses by capillary zone electrophoresis using an information system Xemic

An information system Xemic applicable in analytical chemistry is described and its use in capillary electrophoresis for searching suitable separation conditions is demonstrated. This system is capable to provide suitable separation conditions even for analytes for which no electrophoretic experiments have been published so far. The system works with a database of components of anionic character the analyses of which have been performed, published in reviewed scientific journals, and included into a database created by an expert. Moreover, the system learned to search also in abstracts or complete scientific articles to find articles dealing with the determination of a substance in a given sample matrix. When no experiments have been published so far for a defined substance in a specific matrix, Xemic shows the separation conditions for determination of the substance regardless of the matrix. When no response can be found for the analyte of interest at all, the system Xemic works like an expert in the field and searches chemically similar substances and offers a series of substances the physicochemical properties of which are close to the followed analyte with respect to the behavior in the electric field, and shows working conditions for their analysis. Thus, the analyst puts only the order in the form of a given analyte in a given matrix and obtains a recommendation of a separation system that should enable to perform a successful separation. The system is not rigid and enables the operator to change the importance of individual attributes used in similarity search so as to obtain a broader or narrower group of similar components. With a certain probability the analyte of interest can be successfully analyzed under separation conditions that suited for the analysis of the most similar substances in the given matrix.     

A highly efficient capillary electrophoresis-based method for size determination of water-soluble CdSe/ZnS core-shell quantum dots

This paper describes a highly efficient method for size determination of water-soluble CdSe/ZnS core-shell quantum dots (QDs) by capillary electrophoresis (CE) using polymer additive as sieving medium. The influence of some factors, such as kinds and concentrations of the sieving medium, pH, concentrations of the background electrolyte (BGE) and applied voltage, on the separation of QDs was investigated. Under the optimal separation conditions, four different sized QDs were successfully separated, and the relative standard deviation (RSD) of the migration times for these QDs was below 1.013%. In addition, an equation was fit by taking into account the correlation existing between the electrophoretic mobilities and the sizes of a set of QDs. The feasibility of this equation to measure the sizes of other QDs was confirmed by comparison with the sizes obtained by transmission electron microscopy (TEM) experiment. This work offers a novel method for size determination of QDs, and provides an important reference on the study of QDs based on CE.     

Dedicated mother wavelet in the determination of antimony in the presence of copper

In this paper, a new signal-processing procedure is applied to the optimization of voltammetric determination of antimony in the presence of copper and the parallel determination of these two elements. The proposed numerical algorithm for the separation of the overlapping peaks utilizes the continuous wavelet transform and the inverse continuous wavelet transform. As the base function, the specially defined dedicated mother wavelet is used. In its construction the ideal, simulated voltammetric peak is intensively exploited. This approach, corresponding to the wavelet theory, gives satisfactory signals separation, even in the cases when they constitute one peak. The possibility of Sb(III) determination is presented in the case of different distances between copper and antimony peaks and also in 10-, 20- and 50-fold excesses of Cu. The parallel determination of Cu(II) and Sb(III) is possible even in the case of a 10-fold excess of copper. The quality of the obtained results fulfills the requirements of validation.     

Bioanalysis of erythromycin 2'-ethylsuccinate in plasma using phase-system switching continuous-flow fast atom bombardment liquid chromatography-mass spectrometry

A specific method for the determination of erythromycin 2'-ethylsuccinate (EM-ES) in plasma is described. The method involves a liquid-liquid extraction procedure followed by the analysis of extracts using phase-system switching (PSS) continuous-flow fast atom bombardment (CF-FAB) liquid chromatography-mass spectrometry (LC-MS). In PSS EM-ES is enriched after analytical separation on a short trapping column, from which it is desorbed to the LC-MS interface. In this way, favourable mobile phases can be used for the LC separation and for the MS detection. Using the PSS approach a flow-rate reduction from 1.0 ml/min in the LC system to 15 microliters/min going into the mass spectrometer was achieved without splitting. The determination limit for EM-ES was 0.1 microgram/ml.     

Separation of the Isotopes of Uranium by the Separation Nozzle Process

The separation nozzle process is based on the partial spatial separation of components of different mass in an expanding supersonic jet stream. The process is of especial interest for the separation of uranium isotopes. Details of a systematic experimental determination of the most favorable operating conditions for such a separation are given and the construction and testing of a closed circulation system, the basic unit of a ten membered pilot cascade separator for uranium isotope separation, is described. The optimum values of the specific cost factors obtained experimentally for the separation nozzle process are compared with the corresponding values estimated for the gaseous diffusion process.     

Thermodynamics and statistical mechanics of the ideally polarisable electrode: Gibbs isotherm and surface tension

A definition of the ideally polarisable electrode which allows a general statistical mechanical treatment is given, comparisons with the usual thermodynamic approach being made. It is shown that, with this definition, the system behaves as a pure capacitance to an imposed alternating potential of sufficiently low frequency. The equilibrium states of the system are described by the grand canonical distribution. Thermodynamic functions, given in terms of the grand canonical partition function, can be computed in molecular terms. In particular, general expressions for the surface tension and the pressure are obtained, and compared to those proposed by various authors. The separation of the pressure into electrical and non-electrical parts is analyzed. Expressions are given for the electrochemical potentials of charged and of dipolar species. With these microscopic definitions, the Gibbs adsorption isotherms and the Lippmann equation are derived. For several simple models, including that of Gouy and Chapman for an ionic solution and a metal electrode, these relations are explicity considered. The inadmissability, in a coherent model, of reducing the solvent to a medium of fixed dielectric constant, is emphasized.     

泡沫塑料动态快速分离富集金方法的研究

本文系统研究了泡沫塑料动态快速分离富集金的方法。对泡沫塑料柱的处理方法,再生及主要共存离子干扰的消除等均做了较详细的研究。提出了一种简便,不控速的金分离富集的方法。该法用于分析0.051～3.59g/t四种不同含量的金标样,结果与推荐值吻合,5次分析结果,相对标准偏差<5％,同时,可用泡沫塑料柱当天连续使用分析拿标样,回收率为93％—109％。     

Application of Iso-Selective Gradient Elution for the Separation of Selected Phthalates

Abstract

In this paper, the overlapping resolution mapping scheme was applied to the gradient HPLC separation of selected phthalates. The procedure employs a minimum of seven experiments for the determination of the optimum mobile phase gradient for the desired separation. In the present work, solvent systems for iso-selective multisolvent gradient elution were used. The overlapping resolution mapping procedure was found to be a rapid and systematic approach for optimizing HPLC separations.