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 ... -  《-》

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 ... -  《-》

Direct-immersion single-drop microextraction and in-drop stirring microextraction for the determination of nanomolar concentrations of lead using automated Lab-In-Syringe technique.

Two operational modes for Lab-In-Syringe automation of direct-immersion single-drop microextraction have been developed and critically compared using lead in drinking water as the model analyte. Dithizone was used in the presence of masking additives as a sensitive chromogenic complexing reagent. The analytical procedure was carried out inside the void of an automatic syringe pump. Normal pump orientation was used to study extraction in a floating drop of a toluene-hexanol mixture. Placing the syringe upside-down allowed the use of a denser-than-water drop of chloroform for the extraction. A magnetic stirring bar was placed inside the syringe for homogenous mixing of the aqueous phase and enabled in-drop stirring in the second configuration while resulting in enhanced extraction efficiency. The use of a syringe as the extraction chamber allowed drop confinement and support by gravitational differences in the syringe inlet. Keeping the stirring rates low, problems related to solvent dispersion such as droplet collection were avoided. With a drop volume of 60 µL, limits of detection of 75 nmol L-1 and 23 nmol L-1 were achieved for the floating drop extraction and the in-drop stirring approaches, respectively. Both methods were characterized by repeatability with RSD typically below 5%, quantitative analyte recoveries, and analyte selectivity achieved by interference masking. Operational differences were critically compared. The proposed methods permitted the routine determination of lead in drinking water to be achieved in less than 6 min.

Šrámková IH ，Horstkotte B ，Fikarová K ，Sklenářová H ，Solich P ... -  《-》

An effervescence-assisted dispersive liquid-liquid microextraction based on three-component deep eutectic solvent for the determination of fluoroquinolones in foods.

An effervescence-assisted dispersive liquid-liquid microextraction approach using three-component deep eutectic solvent based on short-chain and medium-chain carboxylic acids and terpenoid was developed for the first time. The microextraction procedure was applied to the determination of fluoroquinolone antibiotics in foods (milk and shrimp samples) by high-performance liquid chromatography with fluorometric detection. In this microextraction procedure three-component deep eutectic solvent acted as a proton donor agent and an extractant. The carbon dioxide bubbles caused by the fast reaction between precursor of deep eutectic solvent (short-chain carboxylic acid) and effervescent agent (sodium carbonate) promoted the dispersion of the extractant in an aqueous sample phase. Various carboxylic acids were studied as hydrogen bond donors for the formation of deep eutectic solvents and proton donor agents for the generation of CO2 bubbles. Two natural terpenoids (menthol and thymol) were studied as the hydrogen bond acceptors for the formation of three-component solvent. The extraction system based on heptanoic acid and thymol (1:2, mol/mol) containing formic acid (proton donor for generating CO2 bubbles) provided maximum extraction recovery (86-99%) and a higher extraction efficiency of analytes compared to their extraction into individual hydrophobic precursors of the system. The LODs, calculated from the blank tests based on 3σ, were varied from 0.03 to 0.06 μg L-1 and from 0.3 to 0.6 μg kg-1 for fluoroquinolone antibiotics in milk and shrimp samples, respectively. The proposed approach provided effective dispersion of extractant speeding up the extraction process and fast separation of phases without any external energy assistance.

Barbayanov K ，Timofeeva I ，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 《-》