Kinetic determination of lactate dehydrogenase in blood serum by multi-detection with a cyclic flow-injection system

The use of a cyclic flow-injection system for the determination of lactate dehydrogenase (LDH) is proposed. This configuration allows the repeated passage of the reacting plug through the detector resulting in multiple peak recordings. From the data obtained, which correspond to a typical kinetic curve, the required sensitivity can be selected by using procedures based on fixed-time measurements (peak maxima or minima) or reaction-rate measurements (signal increment between two successive maxima or minima). The methods were applied successfully to the determination of LDH in blood sera; the average recovery was 100.9%.     

Simultaneous determination by iterative spectrophotometric detection in a closed flow system

A flow-injection configuration based on a closed flow system which includes a single spectrophotometric detector and allows iterative detection by passage of the reacting plug n times through the same detector is described. The information obtained can be used in the simultaneous determination of species by kinetic methods. The example given is the simultaneous determiantion of iron(III) and cobalt(II) via the EGTA/PAR ligand displacement reaction.     

A photometric detector based on a blue light-emitting diode

The suitability of blue light-emitting diodes as radiation sources in molecular absorption spectroscopy was evaluated. Electronic as well as spectral considerations are discussed. A transducer based on a blue light-emitting diode and a photodiode is described which yields direct absorbance readings by passing the photocurrent to an integrated circuit logarithmic converter. The performance of this device was tested for commonly used spectrophotometric procedures for Cr, Mn, Zn, Fe and Cl and compared with conventional molecular absorption spectroscopy. Also investigated was the application of the transducer as a detector in flow-injection analysis.     

Spectroelectrochemical detector for flow-injection systems and liquid chromatography

Flow-through spectroelectrochemical detectors for flow-injection systems and liquid chromatography are described. The detectors have a rectangular flow channel with a reticulated vitreous carbon working electrode followed by an open optical window. The dead volumes of the cells are 27 μl (liquid chromatography) and 80 μl (flow injection). In situ spectral monitoring of reaction products and intermediates for compounds that are both weakly and highly absorbing is demonstrated by using o-tolidine and N,N,N′,N′-tetramethyl-p-phenylenediamine. As a detector for flow-injection systems, components in two-component mixtures can be quantified. As a detector for liquid chromatography, simultaneous absorbance and electrochemical chromatograms allow more eluting compounds to be identified and quantified. Mixtures of nitro- and chloro-phenols are used to illustrate the simultaneous profiling of spectral and redox properties.     

Development of a polypyrrole-based amperometric detector for the determination of certain anions in water samples

The development of a polypyrrole-based modified electrode for use in the detection of anions in flow-injection analysis and ion chromatography is described. Chloride, nitrate, nitrite, perchlorate, bromide, carbonate, sulphate and phosphate were detected by using flow-injection analysis combined with the polypyrrole-based CME electrochemical detector. All of the anions were detected conveniently and reproducibly over a linear concentration range 1-100 mug/ml. A detection limit of 0.1 mug/ml was obtained for chloride and a limit of 1.0 mug/ml for all of the other anions. Chloride, nitrate, sulphate and phosphate, following separation using ion chromatography, were detected simultaneously by using a conductivity detector and the polypyrrole-based CME electrochemical detector in series. Both methods of detection yielded similar results with comparable sensitivity, linearity and limits of detection. This method was then applied to the analysis of fresh water samples. The electrode was stable over a 2-week period of operation with no evidence of chemical or mechanical deterioration.     

Chemical speciation by flow-injection analysis. A review

Speciation of elements in natural matrices, especially of trace metals, is one of the predominant development trends of modern inorganic analysis. The main part of the conventional speciation procedures is a suitable combination of separation and chemical conversion steps, for which the most appropriate methodology seems to be the use of flow-injection. A shorter time of performance of these operations in flow-injection manifolds is advantageous in terms of avoiding the shift of chemical equilibria during the speciation measurement. Numerous other advantages are also pointed out in this review based on 58 references. Among flow-injection analysis methods published so far for speciation the determination of different oxidation states predominates, while a much smaller number of papers have been published on the determination of the degree of complexation or the determination of organometallic compounds.     

Stereoselective Synthesis and Resolution of P-Chiral Phosphine Chalcogenides.

Abstract

New synthetic methods and resolution procedures securing ready access to the resolved P-chiral phosphinoylethenes, phosphinoylacetates and secondary phosphine oxides of diversified structures have been developed. The methods are based on processes employing stereoselective nucleophilic displacement at phosphorus, asymmetric deprotonation, immolative vinyl and chirality transfer from sulfur to phosphorus, chemical and enzymatic kinetic resolution, resolution via covalent diastereoisomers, as well as direct resolution of racemates by classical resolving agents and by chromatography on chiral stationary phases.     

A Novel Spectrometer for Simultaneous Chemical Analyses

A novel spectrometer incorporating a multichannel detector for simultaneous multi-element atomic emission spectrometry (AES) is described. The spectrometer consists of a multi-bandpass optical filter comprised of a concave and a fiat grating in substractive mode, and a high resolution stage which utilizes an echelle grating and an one inch 1024-channel photodiode array as the detector. Characterization with respect to the spectral resolution, the spectral response, and the capability of multi-element detection demonstrated the systems's potential for simultaneous chemical analyses without moving any mechanical parts. To adjust the system for the analyses of different sets of elements, the corresponding mask is simply placed in position.     

Putting the chemistry back into analytical chemistry

Aspects of the current status of and research in analytical chemistry are briefly discussed and the need for cost effective analytical procedures is emphasized. The present and future of a number of aspects of flow-injection analysis are considered. These include the basic theory, the kinetic features, the control features, time-based methodology, and the coupling of sample pretreatment with instrumentation. Several aspects of this latter topic are considered with particular reference to the flow-injection atomic spectrometry combination. Problems of kinetic mismatch between chemistry, manifold residence, and instrument operation are discussed and some possible solutions proposed including the use of closed loop manifolds.     

Automated measurement of dye coverage in photographic negatives by flow-injection analysis

A system was designed to automate the determination of three image dyes in an instant photographic material. The method involves extracting negative samples with dimethylsulfoxide and filtering the extract, followed by quantitating the dye coverage (dye per unit area of negative) through a spectrophotometric flow-injection procedure. Significant spectral overlap exists among the dyes, and as a result calculation of coverage requires solving three simultaneous equations. A microcomputer and data acquisition system were employed for controlling the detector and flow-injection system, acquiring and integrating the detector response, calculating coverage, producing and displaying control charts, and automatically transferring results to a VAX based corporate database. In addition to automating sample preparation and measurement steps as much as possible, the goal of this project was to automate the data manipulation and transfer steps.     

Kinetic treatment of unsegmented flow systems : Part 1. Subjective and semiquantitative evaluations of flow-injection systems with gradient chamber

A variable-time kinetic model is used to evaluate a single-channel flow-injection system with gradient chamber that has been identified as a continuous-flow titration. A physical model, mathematical equations, computed concentration vs. time profiles, experimental data, and formal definitions are used to identify qualitative and quantitative features of the method that have not been apparent from the titration model for the system. It is shown that determinations can be performed with and without reactant in the flow stream and when reactant is in the flow stream, with and without reactant in the gradient chamber when the sample is introduced. It is shown that lowest concentrations with shortest cycle times can be achieved when determinations are performed without reagent in the gradient chamber initially. Characteristics unique to each of three different data processing options are used to evaluate the validity of equations presented. It is suggested that some methods previously identified as continuous-flow titrations are most accurately identified as variable-time kinetic methods, and it is shown that this semantic differentiation can provide improved insight into the methods and can expand the scope of the methods by suggesting new experimental approaches with potential advantages relative to previously described procedures.     

Simultaneous spectrophotometric determination of copper(II) and zinc(II) based on their kinetic separation in flow-injection systems

Flow-injection methods are developed for the spectrophotometric analysis of binary copper(II) and zinc(II) mixtures. They are based on measurements of a differential kinetic signal caused by ligand-exchange reactions that occur in the flow between the complexes of these metals with the same chromogenic reagent (4-(2-pyridylazo)-resorcinol or zincon) and aminopolycarboxylic acids. Two different approaches are used for the kinetic separation (or masking) of these metals followed by the on-line processing of the recorded signal by regression analysis. One of them is monitoring an indicator reaction in the stopped-flow mode, and the other is recording the separated peaks in the flow-injection system with two reaction zones reaching the detector over certain periods. The optimum detection conditions were found (c _min = 0.03 μg/mL), which allow the detection of the studied metal ions in mixtures in a ratio of no more than 1: 5 with a relative error of no more than 5%, good precision (RSD < 10%, n = 6, P = 0.95), and high throughput (90 h^?1). The developed procedures were tested in the analysis of model mixtures and pharmaceutical preparations.     

Application of a capillary flow cell to sophisticated flow-injection systems

Demands placed on spectrophotometric detectors for use in flow-injection systems are discussed. Based on this background, it is proposed that it is worthwhile investing in high-performance detectors and other hardware to make the best use of the advantages of flow-injection methods. A novel flow cell that utilizes optical fibres to transmit light through a capillary, from and to a photometric detector, was applied in experiments that demonstrated the difference between flow systems with sample and with reagent injection through the application of gradient techniques such as electronic dilution. It is show that it is possible to extend the dynamic range of flow-injection systems using gradient techniques, but not in the case of reagent injection.In another set of experiments, the small illuminated volume of the detector cell (< 1 μl) made it possible to measure directly the segmented stream of aqueous and organic phases in flow-injection extraction without phase separation.The monitoring of a pesticide served as a basis for comparison between classical flow-injection extraction and the novel extraction without phase separation. Although the detection limit is lower in the classical technique, extraction without phase separation has the advantage of allowing simultaneous monitoring of the aqueous and organic phases and eliminating the need for the failure-prone phase separation step. A simple sorting program is introduced as an alternative data analysis scheme for the measurement of peak widths and for the evaluation of data gained from flow-injection extraction without phase separation. It proved to be much faster and considerably simpler to use than previous routines.     

Flow cell within an LED: a proposal for an optical absorption detector

Droplets formed at the tip of a tube under the same conditions possess extreme uniformity of form, volume and weight. These properties of liquid drop formation have been known for a long time and consequently many applications for the drop have been found in instrumentation and chemical analysis methods. In the present paper, we report on the analytical use of a dynamic LED-based flow-through optical absorption detector with optical path length controlled by continuous dropping of a solution. This arrangement consists of a flow cell built within a high-intensity red LED (λ _max = 630 nm). The feasibility of the detector is demonstrated by colorimetric determination of methylene blue, and ammonium by Berthelot’s reaction, in a flow-injection system. For ammonium, the reaction forms a blue dye (indophenol) with a maximum absorption at 630–650 nm. The detection limit, considered as 3 times the signal of the blank, is better than 125 μg l^-1. The small flow cell represents a good combination of optical path length, low volume and fast washout. This detector can be used advantageously in automated methods and can represent a solution to problems of optical detection involving gas bubbles and precipitation of particles in turbidimetric applications.     

Flow-injection analysis with multidetection as a useful technique for metal speciation

The analytical potential of a closed flow-injection system with multidetection by a single detector (for calculation of rate constants, reaction rate, dilution and amplification methods, etc.) is extended to simultaneous determinations for chromium speciation, with injection of the reagent(s) into the sample solution (which acts as the carrier).     

Formation of two reaction zones in flow-injection systems for kinetic determinations of cobalt and nickel

The injection of a large sample volume (ca. 1 ml) into a single-channel flow-injection system was studied with a dye (to examine physical dispersion) and with chemical systems having easily-controlled reaction rates (to examine chemical kinetics). With the dye, the response curve has a central plateau caused by non-mixing of carrier and sample. When a chemical reaction takes place, two peaks are obtained with a central minimum corresponding to little or no mixing and reaction. Comparison of these two types of response provides relationships of analytical interest between response parameters and variables in te flow-injection system. The configuration is used for individual kinetic determinations of cobalt and nickel (2.5–30 μg ml^?1 based on the rate of their complex formation with 2-hydroxybenzaldehyde thiosemicarbazone. Sample injection rates were 15 h^?1 for cobalt and 40 h^?1 for nickel. Differential kinetic determinations of cobalt and nickel in mixtures are based on the increment in peak height (or area) between the two peaks obtained for each injection; sample throughput is 7 h^?.     

路易斯酸碱催化的外消旋体(动态)动力学拆分反应

外消旋体的(动态)动力学拆分反应是制备手性化合物的重要方法之一.反应可以通过酶催化或非酶催化的手段来实现,也可以通过两种方法的有机结合来进行.在非酶催化反应中,路易斯酸碱催化是比较常用的方法,它们被广泛地用于多种外消旋体的(动态)动力学拆分反应中,目前在该领域取得了很大的进展.本文讨论了路易斯酸及路易斯碱催化体系在外消旋体(动态)动力学拆分反应中应用的最新进展.     

Wavelength accuracy testing of UV-visible detectors in liquid chromatography

Summary Wavelength accuracy is an important factor of LC detection which can have serious effects on detector response, analytical results, and inter-laboratory reproducibility. Current wavelength accuracy test procedures for LC detectors have serious limitations or are very elaborate. This paper describes two new test procedures which employ Tb⁺³ and Er⁺³ solutions, these ions have narrow well defined absorption bands, and provide suitable test points throughout the ultraviolet-visible spectrum. These new test methods are fast, simple, applicable to any detector, and cover the spectral regions most frequently employed in LC detection.     

Performance evaluation of mapping and linear imaging FTIR microspectroscopy for the characterisation of paint cross sections

Different Fourier transform infrared microspectroscopic techniques, using attenuated total reflection (ATR) mode and single-element mercury–cadmium–telluride (MCT) detector (mapping) or multielement MCT detector (raster scanning), are compared with each other for the characterisation of inorganic compounds and organic substances in paint cross sections. All measurements have been performed on paint cross sections embedded in potassium bromide, a transparent salt in the mid-infrared region, in order to better identify the organic materials without the interference of the usual embedding resin. The limitations and advantages of the different techniques are presented in terms of spatial resolution, data quality and chemical information achieved. For all techniques, the chemical information obtained is found to be nearly identical. However, ATR mapping performed with a recently developed instrumentation shows the best results in terms of spectral quality and spatial resolution. In fact, thin organic layers (∼10 μm) have been not only identified but also accurately located. This paper also highlights the recent introduction of multielement detectors, which may represent a good compromise between mapping and imaging systems.     

Photochemical derivatization and fluorimetric determination of reserpine in a flow-injection assembly

The fluorimetric flow-injection determination of reserpine was achieved with the drug being derivatized on-line by photoreaction. PTFE tubing was helically coiled around a germicide lamp located between the injection valve and detector. Two analytical procedures are proposed using either dilute acetic acid or pure methanol as the carrier stream. The influence of foreign compounds was studied and the method was applied to the determination of reserpine in pharmaceutical formulations.