Armağan Önal

A review of the liquid chromatographic methods for the determination of biogenic amines in foods

Biogenic amines (BAs) are biologically active molecules which have aliphatic (putrescine, cadaverine, spermine, spermidine), aromatic (tyramine, phenylethylamine) or heterocyclic (histamine, tryptamine) structures. They can be detected in raw and processed foods which are formed and degraded through several pathways during the metabolic processes of animals, plants and microorganisms. The identification and quantitation procedures of BAs in food samples are very important, because BAs are considered as the indicators of food quality and freshness. The determination of BAs are commonly achieved by separation techniques such as high-performance liquid chromatography (HPLC), gas chromatography (GC) and capillary electrophoresis (CE). In this article, analysis of BAs in foods were reviewed from 2007 to present.

A Review of Current Methods for the Determination of Acrylamide in Food Products

Acrylamide (AA) is a potentially carcinogenic substance which is formed during heating of food products containing carbohydrates and asparagine. It was first detected in food products in 2002. Since that time, several analytical methods have been made available for the quantification of AA in various foods. Starting from the announcement in 2002, occurrence, formation, chemistry, toxicology, and potential health risk in the human diet have been investigated and methods of analysis have been reviewed in many articles. In this paper, current information and analytical methods for the determination of AA have been reviewed.

Spectrophotometric and HPLC determinations of anti-diabetic drugs, rosiglitazone maleate and metformin hydrochloride, in pure form and in pharmaceutical preparations.

In this study, three spectrophotometric methods and one HPLC method were developed for analysis of anti-diabetic drugs in tablets. The two spectrophotometric methods were based on the reaction of rosiglitazone (RSG) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and bromocresol green (BCG). Linear relationship between the absorbance at lambda(max) and the drug concentration was found to be in the ranges 6.0-50.0 and 1.5-12 microg ml(-1) for DDQ and BCG methods, respectively. The third spectrophotometric method consists of a zero-crossing first-derivative spectrophotometric method for simultaneous analysis of RSG and metformin (MTF) in tablets. The calibration curves were linear within the concentration ranges of 5.0-50 microg ml(-1) for RSG and 1.0-10.0 microg ml(-1) for MTF. The fourth method is a rapid stability-indicating HPLC method developed for the determination of RSG. A linear response was observed within the concentration range of 0.25-2.5 microg ml(-1). The proposed methods have been successfully applied to the tablet analysis.

Spectrophotometric and spectrofluorimetric methods for the determination of pregabalin in bulk and pharmaceutical preparation

Two new, sensitive and selective spectrofluorimetric and spectrophotometric methods have been developed for the determination of the gamma-amino-n-butyric acid derivative pregabalin (PGB) in bulk drug and capsule. Pregabalin, as a primary amine compound, reacts with 7-chloro-4-nitrobenzofurazon (NBD-Cl) which is a highly sensitive fluorogenic and chromogenic reagent used in many investigations. According to this fact, spectrophotometric and spectrofluorimetric methods for the determination of pregabalin in capsules were developed for the first time. The relation between the absorbance at 460 nm and the concentration is rectilinear over the range 0.5-7.0 microg mL(-1). The reaction product was also measured spectrofluorimetrically at 558 nm after excitation at 460 nm. The fluorescence intensity was directly proportional to the concentration over the range 40-400 ng mL(-1). The method was applied successfully to the determination of this drug in pharmaceutical dosage form. The mean recovery for the commercial capsules was 99.93% and 99.96% for spectrophotometric and spectrofluorimetric study, respectively. The suggested procedures could be used for the determination of PGB in pure and capsules being sensitive, simple and selective.

7,7,8,8-Tetracyanoquinodimethane as a new derivatization reagent for high-performance liquid chromatography and thin-layer chromatography: rapid screening of plasma for some antidepressants

Abstract Using 7,7,8,8-tetracyanoquinodimethane (TCNQ) as a new derivatization reagent for HPLC and TLC, novel methods are described to detect secondary amine-bearing antidepressants (paroxetine, desipramine, fluoxetine, nortriptyline, maprotiline). The HPLC method is sensitive enough to detect these drugs in plasma at therapeutic levels whereas the latter has potential to detect them in overdose or forensic cases. The methods are based on purple chromogens formed by the displacement reaction of the drugs with TCNQ. The resulting chromogens are directly separated by either reversed-phase HPLC on a C18 column or TLC on silicagel plates. For HPLC, acetonitrile–water (60:40) was used as mobile phase, with detection at 567 nm and separation in 40 min. For TLC, three developing solvent systems were used. By HPLC, 36 ng ml−1 spiked plasma concentration of the drugs gave easily detectable signals whereas by TLC, detection limits varied mostly between 240 and 480 ng ml−1. The HPLC method was applied to real plasma samples. The methods described are simple and very selective; some metabolites of these antidepressants and a vast number of drugs do not interfere with detection.

A new HPLC method with fluorescence detection for the determination of memantine in human plasma.

A sensitive, selective, simple and fast HPLC method based on the formation of derivative with fluorescamine was developed for the determination of memantine (ME) in human plasma. Separation was achieved on a CN column (200 mm×4.6 mm) using acetonitrile-10 mM orthophosphoric acid containing 1 mL/L triethylamine (45:55, v/v) at a flow rate of 1 mL/min. Emission and excitation wavelengths were 480 and 380 nm, respectively. Amantadine was used as an internal standard. Calibration graphs were rectilinear over the range of 1.0-100.0 ng/mL. Limit of detection and limit of quantification were found to be 0.3 and 1.0 ng/mL, respectively. Intra-day and inter-day relative standard deviation values were found to be <2.03%. Average recovery was also found to be around 94%. Proposed method was applied for the pharmacokinetic study in a healthy volunteer after a single oral administration of 20 mg of ME.

Current Status of Polyamine and Polyamine Analogs Analysis in Cancer Research

The amino-acid-derived polyamines have been associated with cell growth and cancer and their concentrations in malignant tumors are extremely high compared to those in tissues that are histologically normal. Hence, polyamines have been considered as an interesting object for anticancer therapy. Analysis of polyamine levels in biological fluid can possibly provide helpful information on the types of cancer and progression phase of the disease. Numerous modern analytical methods, including high-performance liquid chromatography, gas chromatography, capillary electrophoresis, and other separation techniques have been widely utilized for analysing polyamine levels. In both tissue culture and experimental animal models, polyamine analogues restrain cell growth and destroy malignant cells. Determination of intracellular analogue contents is also crucial, since analogue accumulation is a causal factor for their antitumour effectiveness. In this review, the latest methods reported for polyamines and polyamine analogs in cancer research are discussed.

Spectrofluorimetric determination of tobramycin in human serum and pharmaceutical preparations by derivatization with fluorescamine

A simple, sensitive and selective spectrofluorimetric method has been developed for the determination of tobramycin (TOB) in human serum and pharmaceutical preparations. The method is based on the reaction between the primary amino group of TOB and fluorescamine in borate buffer, pH 8.5, to give a highly fluorescent derivative which is measured at 469 nm after excitation at 388 nm. The fluorescence intensity was directly proportional to the concentration over the range 300-1500 ng/mL, with a limit of detection of 65 ng/mL and limit of quantitation of 215 ng/mL. All variables were investigated to optimize the reaction conditions. The method was validated according to International Conference on Harmonization guidelines in terms of specificity, linearity, limit of detection, limit of quantification, accuracy, precision and robustness. Good recoveries were obtained ranging from 97.4 to 100.64%, indicating that no interference was observed from concomitants usually present in pharmaceutical dosage forms. The method was successfully, applied for the analysis of the drug substance in its pharmaceutical preparations and spiked serum samples.

Determination of Eprosartan Mesylate and Hydrochlorothiazide in Tablets by Derivative Spectrophotometric and High-Performance Liquid Chromatographic Methods

Two new simple and selective assay methods have been presented for the analysis of eprosartan mesylate (EPR) and hydrochlorothiazide (HCT) in pharmaceutical formulations. The first method is based on first-derivative ultraviolet spectrophotometry with zero-crossing measurements at 246 and 279 nm for EPR and HCT, respectively. The assay was linear over the concentration ranges 3.0-14.0 µg/mL for EPR and 1.0-12.0 µg/mL for HCT. The quantification limits for EPR and HCT were found to be 1.148 and 0.581 µg/mL, respectively, while the detection limits were 0.344 µg/mL for EPR and 0.175 µg/mL for HCT. The second method involved isocratic reversed-phase liquid chromatography using a mobile phase composed of acetonitrile-10 mM phosphoric acid (pH 2.5) (40:60, v/v). Olmesartan was used as internal standard and the substances were detected at 272 nm. The linearity ranges were found to be 0.5-30 and 0.3-15.0 µg/mL for EPR and HCT, respectively. The limits of detection were found to be 0.121 µg/mL for EPR and 0.045 µg/mL for HCT. The limits of quantification were found to be 0.405 and 0.148 µg/mL for EPR and HCT, respectively. The proposed methods were successfully applied to the determination of commercially available tablets with a high percentage of recovery and good accuracy and precision.

New spectrophotometric and spectrofluorimetric methods for the determination of angiotensin II receptor antagonists in tablets and plasma

Spectrophotometric and spectrofluorimetric methods for the determination of five Angiotensin II type 1 receptor antagonists in tablets and plasma have been developed and optimized. The spectrophotometric method involves the addition of a measured excess of bromate-bromide in HCl medium and subsequent estimation of the residual bromine by reacting with a fixed amount of methyl orange. The spectrofluorimetric method depends on the oxidation of the drugs with cerium(IV) and subsequent monitoring of the fluorescence of the induced cerium(III) at 365 nm with excitation at 255 nm. Both of the proposed methods were successfully applied to the determination of the investigated drugs in their pure forms and pharmaceutical preparations. Besides, the spectrofluorimetric method was applied to the determination of irbesartan and telmisartan in biological fluids with good accuracy and precision.