Headspace in-drop derivatization of carbonyl compounds for their analysis by high-performance liquid chromatography-diode array detection

• Published in: Analytica chimica acta Vol. 632; no. 2; pp. 208 - 215
• Main Authors: Pillai, Aradhana K.K.V., Gautam, Khileshwari, Jain, Archana, Verma, Krishna K.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 26.01.2009; Elsevier
• Subjects: 2,4-Dinitrophenylhydrazones; Aldehydes - analysis; Aldehydes - chemistry; Aldehydes - isolation & purification; Analytic Sample Preparation Methods - methods; Analytical chemistry; Carbonyl compounds; Chemistry; Chromatographic methods and physical methods associated with chromatography; Chromatography, High Pressure Liquid - methods; Exact sciences and technology; Headspace single drop extraction; Hydrazones - chemistry; In-drop derivatization; Ketones - analysis; Ketones - chemistry; Ketones - isolation & purification; Liquid chromatography; Other chromatographic methods; Pharmaceutical Preparations - analysis; Pharmaceutical Preparations - chemistry; Phenylhydrazines - chemistry; Reproducibility of Results; Solvents - chemistry; Substrate Specificity; Temperature; Time Factors; Water - chemistry; Carbonyl compounds; Liquid chromatography; Headspace single drop extraction; In-drop derivatization; 2,4-Dinitrophenylhydrazones; Correlation coefficient; Peak resolution; Microanalysis; HPLC chromatography; Derivatization; Solvent extraction; Organic hydrazine; Chemical enrichment; Accuracy; Sample preparation; Injector; Detection limit; Microextraction; Butanol; Headspace; Diode array; Oxidation; Hydrazone
• ISSN: 0003-2670; 1873-4324
• DOI: 10.1016/j.aca.2008.11.021

A simple and rapid method has been reported for the determination of carbonyl compounds involving sample preparation by headspace single drop microextraction using 1-butanol as extraction solvent containing 2,4-dinitrophenylhydrazine for hydrazone formation, and direct transfer of the drop into the injector for high-performance liquid chromatography with diode array detection. An angle-cut polytetrafluoroethylene sleeve, 3 mm × 0.5 mm, was fixed at the tip of the syringe needle and this allowed the use of 7 μL drop of solvent drop for extraction and derivatization. The procedure has been optimized with respect to suitable solvent for headspace drop formation, drop volume, concentration of reagent, sample temperature, reaction time, and headspace-to-sample volume ratio. The method has been validated when rectilinear relationship was obtained between the amount of analyte and peak area ratio of hydrazones in the range 0.01–15 mg L −1, the correlation coefficient over 0.996–0.999, and the limit of detection in the range 1.7–24.1 μg L −1. Spiked real samples have been analyzed with adequate accuracy, and application has been demonstrated of the method for analysis of carbonyl compounds formed as oxidation products.