In-syringe dispersive liquid-liquid microextraction using deep eutectic solvent as disperser: Determination of chromium (VI) in beverages. 2020

Andrey Shishov, and Pavel Terno, and Leonid Moskvin, and Andrey Bulatov
Department of Analytical Chemistry, Institute of Chemistry, Saint-Petersburg University, Saint Petersburg State University, SPbSU, SPbU, 7/9 Universitetskaya Nab., St. Petersburg, 199034, Russia. Electronic address: a.y.shishov@spbu.ru.

A novel approach for dispersive liquid-liquid microextraction based on the use of deep eutectic solvent as a disperser was presented for the first time. The procedure was automated based on an in-syringe flow system coupled with UV-Vis detection and demonstrated by the determination of chromium (VI) in beverages. This analytical task was used as a proof-of-concept example. The automated extraction procedure involved the aspiration of aqueous sample into a syringe pump with homogeneous mixture of extraction solvent (1-oсtanol) and deep eutectic solvent (tetrabutylammonium bromide - formic acid) containing color-forming reagent (1,5-diphenylcarbazide). This led to decomposition of deep eutectic solvent in aqueous phase resulting in dispersion of extraction solvent, oxidation of 1,5-diphenylcarbazide to 1,5- diphenylcarbazone in the presence of chromium (VI), and formation of colored chromium (III) complex with 1,5-diphenylcarbazone and its fast extraction. In this case composition of deep eutectic solvent played a key role for analyte extraction. Tetrabutylammonium bromide promoted mass transfer between aqueous phase and the extraction solvent droplets as a salting out agent, bromide ion acted as an ion-pare agent for analyte complex extraction, formic acid provided required pH value for analyte complex formation. Under the optimal conditions the limit of detection, calculated from a blank test based on 3s, was 0.2 μg L-1. The automated dispersive liquid-liquid microextraction using deep eutectic solvent as disperser can be considered as an available, efficient, rapid and environmentally friendly sample pretreatment approach.

UI MeSH Term Description Entries
D002253 Carbonated Beverages Drinkable liquids combined with or impregnated with CARBON DIOXIDE. Carbonated Drinks,Soda Pop,Soft Drinks,Beverage, Carbonated,Beverages, Carbonated,Carbonated Beverage,Carbonated Drink,Drink, Carbonated,Drink, Soft,Drinks, Carbonated,Drinks, Soft,Pop, Soda,Pops, Soda,Soda Pops,Soft Drink
D002857 Chromium A trace element that plays a role in glucose metabolism. It has the atomic symbol Cr, atomic number 24, and atomic weight 52. According to the Fourth Annual Report on Carcinogens (NTP85-002,1985), chromium and some of its compounds have been listed as known carcinogens.
D005506 Food Contamination The presence in food of harmful, unpalatable, or otherwise objectionable foreign substances, e.g. chemicals, microorganisms or diluents, before, during, or after processing or storage. Food Adulteration,Adulteration, Food,Adulterations, Food,Contamination, Food,Contaminations, Food,Food Adulterations,Food Contaminations
D005561 Formates Derivatives of formic acids. Included under this heading are a broad variety of acid forms, salts, esters, and amides that are formed with a single carbon carboxy group. Formic Acids,Acids, Formic
D000067030 Fruit and Vegetable Juices The liquids extracted from plants. Fruit Juices,Vegetable Juices,Fruit Juice,Juice, Fruit,Juice, Vegetable,Juices, Fruit,Juices, Vegetable,Vegetable Juice
D000068220 Prunus avium A plant species in the family ROSACEAE. It is the source of the sweet cherry fruit. Black Cherry,Pie Cherry,Prunus cerasus,Prunus serotina,Sour Cherry,Sweet Cherries,Sweet Cherry Tree,Black Cherries,Cherries, Black,Cherries, Pie,Cherries, Sour,Cherries, Sweet,Cherry Tree, Sweet,Cherry Trees, Sweet,Cherry, Black,Cherry, Pie,Cherry, Sour,Cherry, Sweet,Pie Cherries,Sour Cherries,Sweet Cherry,Sweet Cherry Trees,Tree, Sweet Cherry,Trees, Sweet Cherry
D000644 Quaternary Ammonium Compounds Derivatives of ammonium compounds, NH4+ Y-, in which all four of the hydrogens bonded to nitrogen have been replaced with hydrocarbyl groups. These are distinguished from IMINES which are RN Quaternary Ammonium Compound,Ammonium Compound, Quaternary,Ammonium Compounds, Quaternary,Compound, Quaternary Ammonium
D012997 Solvents Liquids that dissolve other substances (solutes), generally solids, without any change in chemical composition, as, water containing sugar. (Grant & Hackh's Chemical Dictionary, 5th ed) Solvent
D013056 Spectrophotometry, Ultraviolet Determination of the spectra of ultraviolet absorption by specific molecules in gases or liquids, for example Cl2, SO2, NO2, CS2, ozone, mercury vapor, and various unsaturated compounds. (McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed) Ultraviolet Spectrophotometry
D013594 Syringes Instruments used for injecting or withdrawing fluids. (Stedman, 25th ed) Hypodermic Syringes,Syringe, Karman,Hypodermic Syringe,Karman Syringe,Syringe,Syringe, Hypodermic,Syringes, Hypodermic

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