0000000000024779
AUTHOR
M. Catalá Icardo
A tandem-flow assembly for the chemiluminometric determination of hydroquinone
A direct chemiluminescent procedure for determination of hydroquinone based on the emergent flow methodology known as multicommutation or tandem-flow is presented for first time. The manifold was based on a set of three channels and three solenoid valves; and, the determination was performed at 60degreesC and at flow-rate of 7.5 ml min(-1). The complete cycle lasted 35 s, which resulted in a sample flow trough of 103 h(-1). The chemical process was the hydroquinone oxidation with the system sulphuric acid-potassium permanganate; and the light emission was clearly enhanced by the presence of quinine sulphate and benzalkonium chloride reaching a detection limit of 30 Rg l(-1). The dynamic int…
Selective chlorine determination by gas diffusion in a tandem flow assembly and spectrophotometric detection with o-dianisidine
Abstract A fast, selective, sensitive and automated method for determination of free chlorine in industrial formulations and water samples is proposed. The automation of the flow assembly is based on the “tandem flow” approach, which uses a set of solenoid valves acting as independent switches. The operating cycle for obtaining a typical analytical transient signal can easily be programmed by means of friendly software running in the Windows environment. The manifold is provided with a gas diffusion unit which permits the removal of interfering species as well as concentrating the chlorine. The determination of chlorine is performed on the basis of the oxidation of o-dianisidine as the colo…
Theoretical prediction of the chemiluminescence behaviour of the ergot alkaloids
Abstract The present manuscript is dealing with the application of molecular connectivity calculations to predict the chemiluminescent behaviour of ergot alkaloids when they react with common strong oxidants in liquid phase. Twenty compounds were theoretically studied by means of a discriminant equation formerly published, being 19 of them predicted as chemiluminescent with a high probability. Empirical confirmation of the chemiluminometric behaviour is performed with the few soluble and commercially available ergot alkaloids. On the basis of these results, a new FIA-direct chemiluminescent method is proposed for the determination of the ergot presenting the higher light emission, the pharm…
Molecular connectivity as a relevant new tool for predicting analytical behavior: A survey of chemiluminescence and chromatography
Abstract We present a critical presentation and discussion on molecular connectivity applied to analytical fields, giving special attention to predicting the chemiluminescent behavior of pharmaceuticals and pesticides. Molecular connectivity has been largely applied to predict the therapeutic effects of pharmaceuticals and rarely to predictions in analytical chemistry – basically to chromatographic processes and recently to liquid-phase chemiluminescence.
FI-chemiluminometric study of thiazides by on-line photochemical reaction
The present manuscript deals with a simple and sensitive flow-injection method for the chemiluminescent determination of thiazides. The method is based on the on-line photodegradation and chemiluminescent determination of the resulting photo-fragments. The on-line photodegradation is performed in basic medium by using a photoreactor consisting of a 550 cm long x 0.8 mm ID piece of PTFE tubing helically coiled around an 8 W low-pressure mercury lamp. The determination of the photo-irradiated thiazides is performed by a chemiluminescent oxidative reaction with Ce(IV) in sulphuric acid medium. A heterogeneous group of thiazides (indapamide, metolazone, hydroflumethiazide, chlorthalidone and be…
Enhanced flow-injection–chemiluminometric determination of sulphonamides by on-line photochemical reaction
Abstract The viability of the tandem photochemical reaction-chemiluminescence detection has been studied for an heterogeneous group of sulphonamides (sulphamethoxazole, sulphadiazine, sulphamerazine, sulphamethoxypyridazine, sulphacetamide, sulphadimidine, sulphanilamide, sulphathiazole and sulphaguanidine) using sulphamethoxazole (whose chemiluminescent behaviour has not been previously reported) as a test substance. The ‘on-line’ photochemical-reaction of sulphonamides provides an enhancing influence on the chemiluminometric response of the drugs during their oxidation by potassium permanganate in sulphuric acid medium (sulphamethoxazole, sulphacetamide, sulphadimidine and sulphanilamide …
Automated simultaneous triple dissolution profiles of two drugs, sulphamethoxazole-trimethoprim and hydrochlorothiazide-captopril in solid oral dosage forms by a multicommutation flow-assembly and derivative spectrophotometry.
This article deals with the simultaneous determination of three dissolution profiles with the aid of the new and emerging continuous-flow methodology known as multicommutation. This methodology is based on a flow network of a set of solenoid valves controlled by the computer and acting as independent multicommutators to allow the easy and automated control of flowing solutions. The obtained three dissolution profiles from one dosage form are the whole formulation profile or "global profile" recommended by pharmacopoeias, and, at same time, are recorded two "individual" profiles from two drugs present in the formulation. This is the second attempt to obtain simultaneously three dissolution p…
In situ generation of Co(II) by use of a solid-phase reactor in an FIA assembly for the spectrophotometric determination of penicillamine
[EN] A flow injection analysis (FIA) manifold for the determination of penicillamine in pharmaceutical preparations is proposed. The manifold includes a solid-phase reactor for the in situ production of the derivatizing reagent, Co(II) ion, which forms a coloured complex with penicillamine in an alkaline medium. The reactor is prepared by natural immobilization of cobalt carbonate on a polymer matrix, which endows it with a high mechanical and microbiological stability. The cobalt released by passage of a 5 x 10(-4) Mol l(-1) sulphuric acid stream at a flow-rate of 2.3 ml min(-1) is merged with a volume of 314 mu l of sample containing penicillamine in ammonium-ammonia buffer at pH 9.5 to m…
FI-on line photochemical reaction for direct chemiluminescence determination of photodegradated chloramphenicol.
Abstract A new, simple, clean and selective flow injection strategy based on the tandem photochemical reaction-chemiluminescence detection was applied to the determination of chloramphenicol. The determination is based on the on-line photodegradation of the drug in a glycine buffer at pH 8.8 by using a photoreactor consisting of 697 cm×0.5 mm PTFE tubing helically coiled around an 8 W low-pressure mercury lamp. Photodegradated chloramphenicol is detected by direct chemiluminescence of resulting photo-fragments and their subsequent reaction with potassium permanganate in sulfuric acid medium as oxidant. The method allows the chemiluminescence determination of compounds which do not exhibit n…
Analytical strategy photodegradation/chemiluminescence/continuous-flow multicommutation methodology for the determination of the herbicide Propanil
The present paper is dealing with an analytical strategy based on coupling photodegradation, chemiluminescence and multicommutation continuous-flow methodology for the determination of the pesticide Propanil, a common herbicide. The pesticide solution is inserted as small segments sequentially alternated with segments of the solution for adjusting the suitable medium for the photodegradation. Both flow-rates (sample and medium) are adjusted to required time for photodegradation, 2.0 min; and then, the resulting solution is also sequentially inserted as segments alternated with segments of the oxidizing solutions system, 1.00 x 10(-4) mol 1(-1) potassium permanganate in 2.00 mol 1(-1) sulphu…
Photochemical-chemiliminometric determination of aldicarb in a fully automated multicommutation based flow-assembly
[EN] A sensitive and fully automated method for determination of aldicarb in technical formulations (Temik) and mineral waters is proposed. The automation of the flow-assembly is based on the multicommutation approach, which uses a set of solenoid valves acting as independent switchers. The operating cycle for obtaining a typical analytical transient signal can be easily programmed by means of a home-made software running in the Windows environment. The manifold is provided with a photoreactor consisting of a 150 cm long x 0.8 mm i.d. piece of PTFE tubing coiled around a 20 W low-pressure mercury lamp. The determination of aldicarb is performed on the basis of the iron(III) catalytic minera…
Flow‐Injection Chemiluminescent Determination of Thiamine in Pharmaceutical Samples by On‐line Photodegradation
Abstract A simple, sensitive, and precise method for the determination of thiamine hydrochloride in a flow‐injection system is described. The method is based on the UV irradiation of thiamine in acid medium. Then, the photo‐fragments are oxidized by permanganate in acid medium, and the resultant chemiluminescent intensity is measured. The optimum conditions for the photoreaction and for the chemiluminescence emission were investigated. The method allows the determination of thiamine, over the range 0.05(LOD)–84 mg · l−1, with a throughput of 30 h−1, and a RSD (n, 20) at 20 and 0.5 mg · l−1 of the thiamine level of 2.5 and 1.3%, respectively. The method was applied to pharmaceutical preparat…
Selective flow-injection biamperometric determination of sulfur-containing amino acids and structurally related compounds
Abstract A simple and selective flow-injection method for the determination of cysteine and methionine is proposed. The method is based on the reaction of the amino acid with chloramine-T and the subsequent reaction of the excess of chloramine-T with an acidic solution of iodide producing a stoichiometric amount of tri-iodide (diminution of the flow-injection analysis (FIA) peak) which is determined biamperometrically using two platinum electrodes polarized at 100 mV. The calibration graph is linear up to 10 μg ml−1 of cysteine and 30 μg ml−1 of methionine; the limit of detection is 0.06 and 0.1 μg ml−1; the repeatability (also as percent of a series of 70 continuous FIA peaks of 5 μg ml−1 …
Determination of nitrite by inhibition of the chemiluminescence of acriflavine in a flow-injection assembly
The indirect determination of nitrite was performed with a flow-injection assembly on the basis of the inhibition of the analytical output obtained in a luminometer by oxidation of acriflavine. The acriflavine solution merged with the nitrite and the resulting mixture was injected into a pure water stream. This solution merged with the oxidant solution (potassium permanganate in sulfuric acid medium) and the resulting chemiluminiscence was affected (inhibited) by the presence of nitrite after reaction with the aminoacridine. The method was applicable over the range 10–800 μg l−1 of nitrite with a correlation coefficient of 0.9960. The relative standard deviation was 1.4% and the throughput …
‘In situ’ preparation of nitrous acid solutions by photoreduction in a flow assembly for analysis of pharmaceuticals
The solutions of nitrite ion, or nitrous acid, are frequently used as reagent in different analytical procedures and in pharmaceutical analysis. The low stability of the aqueous solutions of this reagent implies the tedious work of freshly prepared solutions every day and being kept in the refrigerator. In this paper, a photoreactor formed by a low pressure mercury lamp and nesting in a continuous-flow manifold is studied, tested, and proposed for the in situ reduction of nitrate solution into nitrite. The conversion into nitrite is reproducible and it has been successfully applied to determination of different drugs, mostly from the sulphonamide family, in an FIA assembly.
Photo-Induced Luminescence
The present paper is a critical review dealing with the characteristics, reaction mechanisms and photoproducts, instrumentation and analytical applications of the photo-induced either chemiluminescence or fluorescence. Special attention is paid to the determination of pesticides by continuous-flow methodologies. The paper is divided into several sections covering the most relevant published papers.
FIA-Chemiluminescence Determination of Acridine Yellow
Abstract The direct determination of yellow acridine is performed by a FIA assembly on the basis of the oxidation of the acridine. The acridine solution is injected into a pure water stream. This solution merges with the oxidant solution (KMnO4 in sulfuric acid medium) and the resulting chemiluminescence allows the method to be applied over the range 0.01–100 mg L−1 of acridine with a correlation coefficient of 0.9997. The relative standard deviation (%) is 1.6 and the sample throughput 60 h−1. The influence of foreign substances is also tested. The new method is applied to the determination of yellow acridine in waste waters.
Flow injection biamperometric determination of chloramine-T in environmental, pharmaceutical and veterinary samples
Abstract A flow injection assembly for the determination of chloramine-T is proposed. The sample (213 μl) is inserted into the carrier, de-ionized water flowing at 4.1 ml min−1. This carrier merges with a mixture of potassium iodide and sulphuric acid, and the resulting solution flows to the flow cell through a reactor 66 cm long. The chloramine-T oxidises the iodide to tri-iodide. The resulting iodide/iodine ratio is biamperometrically tested. The calibration graph is linear up to 65 μg ml−1 chloramine-T; the limit of detection is 0.5 μg ml−1; the relative standard deviation (r.s.d) of the calibration slope is 2.8% for a series of eight independent calibrations. The r.s.d. of a series of 7…
Three simultaneous dissolution profiles on a solid pharmaceutical formulation by a FIA manifold provided with a single spectrophotometric detector.
This article deals with the simultaneous determination of three dissolution profiles in the same pharmaceutical formulation. The officially proposed procedure from the pharmacopoeias is adapted to the FIA methodology to obtain the officially recommended profile or "global profile", and two "individual" profiles, corresponding to dissolution rate of two different active principles present in the formulation; both drugs have overlapped UV-vis spectra. The simultaneous determination of several profiles is based on the derivative spectra and the zero crossing mathematical procedure for the "individual" profiles of an active principle; the "global" profile of the formulation is obtained from the…
Multicommutation as a powerful new analytical tool
This review presents the state of the art of the emerging continuous-flow methodology based on solenoid valves. This uses flow networks to deliver sample and reagent solutions by controlling the time of flow through the ON/OFF modes of solenoid valves and takes advantage of existing flow injection analysis (FIA) or sequential injection analysis (SIA) device or manifold configurations. It allows one to insert a single plug of sample (or reagent) into the carrier or carrier-reagent stream, mimicking the approaches of FIA or SIA. In addition to the modes used in FIA and SIA, the methodology provides a different mode, based on delivery of a series of alternating sequential insertions of very sm…
Flow spectrophotometric determination of ammonium ion
Abstract A flow procedure is proposed for the determination of ammonium ion. The sample in basic medium is forced through a solid-phase reactor containing immobilized AgCl on polymeric pearl beads. The released Ag + , complexed with the ammonia, gives a blue ternary complex with the aid of bromopyrogallol red and 1,10-phenanthroline which is spectrophotometrically monitored at 636 nm. The calibration graph is linear over the range 1–20 μg ml −1 ammonium ion, detection limit ( s / n = 3) 0.35 μg ml −1 and relative standard deviation (slope) 1.9 % ( n = 7). The sample throughput is 48 h −1 . The influence of foreign compounds is studied and the procedure is applied to ammonium ion determi…
A Fully Automated Assembly Using Solenoid Valves for the Photodegradation and Chemiluminometric Determination of the Herbicide Chlorsulfuron
Abstract This paper presents a new photochemiluminescent system for the determination of chlorsulfuron in water samples. The light from a low‐pressure mercury lamp is used as a clean, reproducible, and inexpensive “reagent” for the derivation of the pesticide, performed in glycine buffer at pH 9.5. Then, the photo‐products from irradiation are oxidized by permanganate in sulfuric acid solution. The oxidation reaction was favored by using high temperatures. A comparative study and discussion about the use of polyphosphoric acid instead of sulfuric acid in the oxidation reaction is also presented. The use of solenoid valves allows for the easy, complete automation of the process with low samp…