Use of flow injection multisite detection as a novel approach for blank signal correction in a spectrophotometric determination

A flow injection multisite detection system was developed for correction of the sample blank in a colorimetric determination. By using detector relocation, a single spectrophotometer is used for the sequential reading of the sample blank and of the colored product; the sample crosses the flow cell to measure intrinsic absorption, the color reagent is subsequently added, and the flow cell is relocated to provide the reading of the resulting plug. The subsequent detector relocation immediately after peak maximum increases the determination frequency. This strategy was tested in the colorimetric determination of iron in soil samples based on the reaction of Fe (II) with 1,10-phenanthroline after reduction of Fe (III) to Fe (II) by ascorbic acid. The results obtained for 15 soil extracts were in good agreement with those obtained by the reference procedure. Relative standard deviations better than 4% were obtained, with a sampling rate of 30/h.     

A versatile set up for implementing different flow analysis approaches: Spectrophotometric determination of nickel in steel alloys

An arrangement capable of implementing the four principal types of flow analysis processes, monosegmented flow analysis (MSFA), flow injection analysis with multicommutation and binary sampling (FIA-MBS), flow injection analysis with sandwich sampling (FIA-SS) and sequential injection analysis (SIA) is described. The core of the flow manifold is a six-way solenoid valve that is assembled together with three three-way solenoid valves in order to provide a versatile flow network. Software was written in VisualBasic 3.0 to give a friendly working structure allowing the user to easily choose the flow variables and the kind of flow system. The reliability of the flow set up for implementation of the four flow analysis systems was evaluated by means of the spectrophotometric determination of nickel in steel alloys, based on the formation of a colored complex with dimethylglyoxime (DMG). The performances of the four different flow methodologies were compared. The reagent consumptions per determination were 4.0 mg of triethanolamine, 6.0 mg of potassium persulfate and 0.6 mg of DMG. When the flow set up was instructed through the software to implement MSFA, FIA-MBS, and FIA-SS approaches, a sampling frequency of 40 samples/h was obtained, while 30 samples could be processed per hour in the SIA mode. The precisions, evaluated as the relative standard deviation of ten determinations were 0.7%, 1.6%, 1.8% and 3.1% for the MFSA, FIA-MBS, FIA-SS and SIA systems, respectively. The results for determination of nickel in steel alloys presented good agreement with the reference method (ICP OES), showing no significant difference at a confidence level of 95%.     

Detection of zeptomolar concentrations of alkaline phosphatase based on a tyrosinase and horse-radish peroxidase bienzyme biosensor

A bienzyme biosensor based on tyrosinase and horse-radish peroxidase is described in a flow injection analysis and cyclic voltammetry for measurement of phenol. Tyrosinase and horse-radish peroxidase were immobilized on the surface of a glassy carbon electrode by bovine serum albumin and glutaric dialdehyde. Phenol was oxidized by tyrosinase and horse-radish peroxidase via catechol to o-quinone in the presence of oxygen and hydrogen peroxide. The o-quinone was reduced to produce catechol (the substrate recycling) on the electrode surface. The enhanced sensitivity of the bienzyme electrode to phenol was observed in the flow injection system comparing with tyrosinase and horse-radish peroxidase monoenzyme electrodes. The mechanisms for enhanced amperometric response to phenol of bienzyme electrode were discussed. The biosensor was used to detect alkaline phosphatase (ALP). A detection limit of 1.4×10⁻¹⁵ M ALP (140 zmol/100 μl) was obtained after 1 h incubation with phenyl phosphate.     

流动注射分光光度法测定砷的研究

本文采用自行设计制造的氢化物发生及吸收装置,将流动注射技术同氢化物发生分光光度法结合在一起,设计了一种不使用载气的流动注射分析系统并对该系统的测定条件进行了实验研究,实验用HNO_3-AgNO_3-聚乙烯醇-乙醇混合液作吸收液,结果证明该系统具有操作简便,成本低廉,分析速度快(30次/小时),灵敏度高,重现性好及线性范围可调的优点。     

Flow injection spectrophotometric determination of tetracycline in a pharmaceutical preparation by complexation with aluminium(III).

A rapid flow injection (FI) spectrophotometric procedure for tetracycline determination is described. It is based on the injection of a 100 microl sample solution containing tetracycline into merged streams of aluminium(III) chloride (0.01 mol 1(-1)) and Tris-buffer in the presence of KCl (0.06 mol l(-1)), pH 7.0, with the same optimum flow rate of 3.2 ml min(-1). A yellow Al(III)-tetracycline complex was monitored at 376 nm. The flow injection system and the experimental conditions were optimized by means of the univariate method. The procedure was applied to the determination of tetracycline in pharmaceutical preparations with a high sampling rate of at least 165 h(-1). A high precision with a relative standard deviation was obtained less than 0.72 and 0.30% of 5.0 and 10 microg ml(-1) (n=11), respectively. The detection limit (3sigma) and the quantification limit (10sigma) were 0.07 and 0.72 mg l(-1), respectively. There were no interference effects from traditional excipients in the dosage forms when the method was applied to pharmaceutical preparations. The matrix effect could be reduced by the standard addition method.     

Tandem on-line dialysis with a double and single dialyser in flow injection dialysis — Simultaneous determination of calcium and high chloride in industrial effluents

The on-line double membrane dialyser described previously was coupled in series to a single dialyser in the manifold of a flow injection system to include the determination of samples with a high chloride content simultaneously with calcium in industrial effluents from a single sample injection. 50 μl of industrial effluent samples are injected into a carrier stream and are simultaneously dialysed in the double on-line dialyser for chloride and calcium. The dialysed chloride sample zones are further directed to a second dialyser that is incorporated in series with the first dialyser. This enables laboratories to determine samples with a very high chloride content up to 60 g/l simultaneously with calcium by using an automated tandem on-line dialysis technique. The fast and reliable fully automated two-component flow injection procedure operated at a sampling frequency of 90 samples per hour and the results obtained for chloride and calcium in industrial effluents compared well with those obtained by standard methods.     

Selective determination of orthophosphate and total inorganic phosphates in detergents by flow injection photometric method

A flow injection photometric system was developed for the determination of orthophosphate and total inorganic phosphates in detergents. While orthophosphate was directly determined in the presence of other phosphates by utilizing the kinetic discrimination of flow injection analysis, total inorganic phosphates was analyzed after on-line hydrolysis of polyphosphates in 2.5 mol l(-1) sulfuric acid for 50 s under 145 degrees C. Sodium dodecyl sulfate (SDS) was added to mask the interference of non-ionic surfactants. The detection limits and the sampling rates were 2.5 mg l(-1) P(2)O(5) and 40 h(-1) for total inorganic phosphates, and 1.0 mg l(-1) P(2)O(5) and 80 h(-1) for orthophosphate determination. The proposed method was applied to analyze orthophosphate and total inorganic phosphates in washing powders. The experimental results are in good agreement with those obtained by the Chinese national standard methods.     

flow injection systems wiht inductively-coupled argon plasma atomic emission spectrometry: Part 2. The generalized standard addition method

In multicomponent analysis by inductively-coupled argon plasma emission spectrometry, the generalized standard addition method is useful in overcoming matrix and/or spectral interferences. As this method requires many standard additions, it becomes cumbersome when done manually if many elements are to be determined. By using a flow injection system, the standard addtion manipulations required can be significantly simplified and completed within a shorter period of time with much less sample material. A flow injection system with merging zones is used to demonstrate the method for analyses of a Ni/Cu/Zn standard and of alloys. The reproducibility of measurements of the injected sample, with or without additions of standards is always better than 99%. The results obtained compare well with those obtained by the manual procedure and also with those obtained by atomic absorption spectrometry.     

Flow injection turbidimetric determination of thiamine in pharmaceutical formulations using silicotungstic acid as precipitant reagent

A simple flow injection system is proposed for the determination of thiamine in pharmaceutical formulations. The determination is based on the precipitation reaction of thiamine with silicotungstic acid in acidic medium to form a thiamine silicotungstate suspension that is measured at 420 nm. Adding 0.05% (w/v) poly(ethyleneglycol) in the carrier solution (0.5 mol l(-1) hydrochloric acid), an improvement in the sensitivity, repeatability and baseline stability of the flow injection system was obtained. The calibration graph was linear in the thiamine concentration range from 5.0x10(-5) to 3.0x10(-4) mol l(-1) with a detection limit of 1.0x10(-5) mol l(-1). The relative standard deviations for ten successive measurements of 1.0x10(-4) mol l(-1) and 2.5x10(-4) mol l(-1) thiamine were less than 1% and an analytical frequency of 90 h(-1) was obtained.     

Nonmonotonic Transient Potential Signals with an 18‐Crown‐6 based Ion‐Selective Electrode in a Flow‐Injection System

The dynamic potential response of an 18‐crown‐6 based ion‐selective electrode towards Li⁺, Na⁺, K⁺ and Ca²⁺, in a flow‐injection system is studied. Different double nonmonotonic transient signals are obtained for the different ions. The influence of the flow‐injection variables and of ion concentration on the signals is studied. Two signal parameters, the relative return rates, are found to be characteristic for each ion and are constant for a concentration range of 1–3 decades. The nonmomotonic transient signals obtained are explained by reference to the theoretical models reported.     

Oscillatory control of sample dispersion in a continuous flow system

A new strategy for the instrumental control of sample dispersion in continuous flow systems is presented. The method is based on shaking a loosely held straight reactor while the sample travels through the flow injection manifold. This external disturbance yields a sample transport more similar to the plug flow type because of the changes promoted on the flow pattern. Up to a three-fold increase in peak height, a comparable reduction in peak width and a more Gaussian peak profile are observed when the signals obtained with the shaken reactor are compared with those obtained with the same reactor but static. Improvements in the analytical performance as a function of different operational variables are shown for systems with or without a chemical reaction. Analytical implications and possible uses are discussed since this strategy allows the control of dispersion by simply selecting the frequency and amplitude of oscillation.     

Detectability of testosterone esters and estradiol benzoate in bovine hair and plasma following pour-on treatment

The abuse of synthetic esters of natural steroids such as testosterone and estradiol in cattle fattening and sports is hard to detect via routine urine testing. The esters are rapidly hydrolysed in vivo into substances which are also endogenously present in urine. An interesting alternative can be provided by the analysis of the administered synthetic steroids themselves, i.e., the analysis of intact steroid esters in hair by liquid chromatography tandem mass spectrometry (LC/MS/MS). However, retrospective estimation of the application date following a non-compliant finding is hindered by the complexity of the kinetics of the incorporation of steroid esters in hair. In this study, the incorporation of intact steroid esters in hair following pour-on treatment has been studied and critically compared with results from intramuscular treatment. To this end animals were pour-on treated with a hormone cocktail containing testosterone cypionate, testosterone decanoate and estradiol benzoate in different carriers. The animals were either treated using injection and pour-on application once or three times having 1 week between treatments using injection and pour-on application. Animals were slaughtered from 10–12 weeks after the last treatment. Both hair and blood plasma samples were collected and analysed by LC/MS/MS. From the results, it is concluded that after single treatment the levels of steroid esters in hair drop to CCβ levels (5–20 μg/kg) after 5–7 weeks. When treatment is repeated two times, the CCβ levels are reached after 9–11 weeks. Furthermore, in plasma, no steroid esters were detected; not even at the low microgramme per litre level but—in contrast with the pour-on application—after i.m. injection, significant increase of 17β-testosterone and 17β-estradiol were observed. These observations suggest that transport of steroid esters after pour-on application is not only performed by blood but also by alternative fluids in the animal so probably the steroid esters are already hydrolysed and epimerized before entering the blood.     

Rapid determination of protein in plant material by flow injection spectrophotometry with trinitrobenzenesulfonic acid

The rapid determination of protein in plant material based on spectrophotometric determination of amino acids in protein hydrolysates with trinitrobenzenesulfonic acid has been adapted to flow injection analysis. With the manifold described, a routine sampling rate of 120 samples/h is possible, though this, as well as sensitivity, can easily be varied. The method was calibrated against the Kjeldahl method and a good correlation was obtained between the two methods over a wide range of protein values for beans.     

Flow injection analysis : Part III. Comparison of continuous flow spectrophotometry and potentiometry for the rapid determination of the total nitrogen content in plant digests

The Berthelot reaction for the determination of ammonia by formation of indophenol blue, has been adapted to continuous flow spectrophotometry and the effects of acidity, temperature, ethanol content and sampling rate have been investigated; optimal conditions are described for the determination of nitrogen in Kjeldahl digests. Comparison of results obtained by this method, the air-gap electrode and classical distillation show no statistical difference at the 1% level, but the flow injection technique can be run at a much higher sampling rate (110–180 samples per h) than any other method and uses as little as 0.3 ml of digest per analysis.     

Flow injection spectrophotometric determination of cyanide by the phenolphthalin method

The phenolphthalin method for the determination of cyanide has been modified and adapted to a continuous flow system based on the flow injection principle. Aqueous cyanide samples are injected into a carrier stream (0.001 M NaOH), which is then merged with the combined reagent stream of phenolphthalin and carbonate buffer (pH 10.3), and the mixture is passed through an on-line cupric sulfide packed column. The resulting phenolphthalein (the oxidized form of phenolphthalin) is measured in a flow-through spectrophotometer at 552 nm, to determine the cyanide content. The chemical factors and flow injection analysis (FIA) variables influencing the system are discussed. The calibration graph is linear from 0.6 to 4.3 ppm cyanide. At a sampling rate of about 70 samples h(-1) with 50 mul sample injections, precision was about 1% relative S.D.     

Total steroid profiling with capillary GC. Details on sample preparation

The accuracy and reproducibility of steroid and steroid conjugate determinations using capillary GC are evaluated. It is possible to analyze many unconjugated steroids, steroid sulfates, and some steroid glucuronides simultaneously, simply by using group fractionation based on successive hydrolysis and solvent extraction steps. However, a reliable determination of corticosteroid glucuronides can only be obtained after previous isolation of the glucuronides as a group, with ion exchange chromatography. In complex chromatograms, the combined use of nitrogen specific detection and flame ionization detection facilitates peak identification.     

Screening method for linear alkylbenzene sulfonates in sediments based on water Soxhlet extraction assisted by focused microwaves with on-line preconcentration/derivatization/detection

A screening method for linear alkylbenzene sulfonates (LAS) in sediments has been developed. Soxhlet extraction with water assisted by focused microwaves provides recoveries better (>90%) than obtained by conventional Soxhlet extraction (70-80%). Coupling of the extractor with an on-line preconcentration/derivatization/detection manifold through a flow injection (FI) interface allows a fully automated screening approach. A yes/no answer can be obtained in less than 2 h (for the whole analytical process), a short time compared with the at least 24 h of Soxhlet extraction (without final detection). Due to the use of water as leaching agent, the proposed method is environmentally friendly.     

Mathematical modelling of sequential determinations by flow-injection sandwich techniques

Preliminary results obtained in the evaluation of a mathematical model for flow-injection systems, including chemical kinetics, with an eight-way injection valve are presented. The use of this kind of injection valve permits the insertion of the sample bolus between two different reagent solutions (sandwich techniques). The model considers the system as a tubular reactor with axially dispersed plug flow. As an example for systems with chemical reaction, the enzymatic determination of glucose was chosen. The parameters of the model (dispersion coefficients and reaction rate constants) were experimentally evaluated by using a tracer or by unidirectional optimization, respectively. The effect of different parameters of the flow system on the analytical signal for one analyte and one reagent was simulated, and the model results are compared with experimental data obtained under the same conditions.