Deep eutectic solvents with low viscosity for automation of liquid-phase microextraction based on lab-in-syringe system: Separation of Sudan dyes.

In the work limitations of deep eutectic solvents in the flow-based analysis are discussed. Deep eutectic solvents based on terpenes and fatty acids with low viscosity were studied as extraction solvents for liquid-liquid microextraction into a lab-in-syringe system for the first time. As a result an automated deep eutectic solvent-based microextraction approach was proposed. The procedure involved aspiration of deep eutectic solvent (based on terpene and fatty acid) and aqueous sample solution followed by phases mixing by a magnetic stirrer inside a syringe of flow system. After phase separation the extract phase was transferred from the syringe into a vial followed by analysis by a high-performance liquid chromatography with diode-array detection. The determination of Sudan I, Sudan II and Sudan III in chili-based sauces was considered as an analytical task. The mass-transfer intensification performed by the magnetic stirring inside the syringe allowed to perform fast (2 min) and efficient (extraction recoveries 87-95%) extraction. The limits of detection, calculated from a blank test based on 3σ, were from 0.003 to 0.005 mg kg-1, RSD was <9%. The microextraction procedure did not involve the use of hazardous organic solvents, only 100 μL of natural deep eutectic solvent was required for dyes preconcentration.

Shishov A ，Pochivalov A ，Dubrovsky I ，Bulatov A ... -  《-》

Lab-In-Syringe automation of deep eutectic solvent-based direct immersion single drop microextraction coupled online to high-performance liquid chromatography for the determination of fluoroquinolones.

Lab-In-Syringe direct immersion single drop microextraction is proposed as an automated sample pretreatment methodology and coupled online to HPLC with fluorescence detection for the determination of fluoroquinolones in environmental waters. For the first time, a drop of a natural deep eutectic solvent (NADES), synthesized from hexanoic acid and thymol, has been used as an extractant in automated single-drop microextraction. The extraction procedure was carried out within the 5 mL void of an automatic syringe pump. A 9-position head valve served the aspiration of all required solutions, air, waste disposal, and hyphenation with the HPLC instrument. Sample mixing during extraction was done by a magnetic stirring bar placed inside the syringe. Only 60 μL of NADES were required omitting toxic classical solvents and improving the greenness of the proposed methodology. By direct injection, linear working ranges between 0.1 and 5 μg L-1 were achieved for all fluoroquinolones. The limit of quantification values and enrichment factors ranged from 20 ng L-1 to 30 ng L-1 and 35 to 45, respectively. Accuracies obtained from the analysis of spiked surface water and wastewater treatment plant effluent analysis at two concentration levels (0.5 and 4 μg L-1) ranged from 84.6% to 119.7%, with RSD values typically <3%.

Yıldırım S ，Cocovi-Solberg DJ ，Uslu B ，Solich P ，Horstkotte B ... -  《-》

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

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.

Shishov A ，Terno P ，Moskvin L ，Bulatov A ... -  《-》

Automated liquid-liquid microextraction and determination of sulfonamides in urine samples based on Schiff bases formation in natural deep eutectic solvent media.

In this work, an automated liquid-liquid microextraction procedure for the determination of sulfonamides (sulfamethoxazole, sulfamethazine and sulfapyridine) in urine samples using natural deep eutectic solvent is presented for the first time. The mechanism for extraction of sulfonamides was based on the formation of colored Schiff bases in the presence of vanillin, which acted as a derivatization reagent and precursor of natural deep eutectic solvent (an extractant). In this procedure, thymol was used as both media for Schiff bases formation and as a second precursor of the natural deep eutectic solvent. The formation of the Schiff bases was confirmed by mass spectrometry. A Lab-In-Syringe concept was applied for the automation of the microextraction procedure. The procedure involved mixing the sample and natural deep eutectic solvent into a syringe of a flow system, formation and microextraction of colored Schiff base followed by UV-Vis detection. Under optimal automated conditions the limits of detection, calculated from a blank test based on 3s (sigma) were 0.06, 0.1, and 0.06 mg L-1 for sulfapyridine, sulfamethoxazole and sulfamethazine. The proposed automated procedure permitted the routine determination of one drug (sulfamethoxazole, sulfamethazine or sulfapyridine) in urine samples to be achieved in less than 10 min.

Shakirova F ，Shishov A ，Bulatov A 《-》

Nonionic surfactants based hydrophobic deep eutectic solvents for liquid-liquid microextraction of Sudan dyes in tomato chili sauces.

A new type of high-density hydrophobic deep eutectic solvents (DESs) were synthesized with nonionic surfactants as hydrogen bond acceptors and hexafluoroisopropanol (HFIP) as hydrogen bond donor. Brij-35 was selected as the optimal nonionic surfactant for the preparation of Brij-35-HFIP-DES (molar ratio 1:20). A vortex-assisted DES-based liquid-liquid microextraction method was proposed for determination of Sudan dyes in tomato chili sauces. The whole pretreatment process only needs 5 min and 1.1 mL of organic solvent. The method with HPLC-DAD shows high efficiency (enrichment factors 89-176 and extraction rates 61.0-74.6%) and good performance with linearity (R ≥ 0.9997) in 0.04-2 μg g-1 range, detection limits of 0.0045-0.0118 μg g-1, recoveries of 91.6-104.5% and intra-/inter-day precision below 8.0%. A "DES in water in DES" aggregate microstructure was observed in DES-rich phase. The proposed method is simple, quick, eco-friendly, and suits for the efficient extraction and accurate determination of Sudan dyes in tomato chili sauces.

Chen J ，Li X ，Huang A ，Deng W ，Xiao Y ... -  《-》