Development of a vortex-assisted switchable-hydrophilicity solvent-based liquid phase microextraction for fast and reliable extraction of Zn (II), Fe (II), Pb (II), and Cd (II) from various baby food products.

This manuscript describes the development of a novel liquid phase microextraction (LPME) method for the extraction and determination of Zn (II), Fe (II), Pb (II), and Cd (II) in various infant/baby food and supplements products. The method is based on vortex-assisted extraction combined with a switchable-hydrophilicity solvent (SHS) sample preparation. The SHS, which undergoes reversible phase changes triggered by pH change, enables selective extraction and easy phase separation. A flame atomic absorption spectroscopy was used in the final determination step. Optimization studies revealed, that the optimal pH of the sample solution (after digestion) during analytes extraction is 5.5. A l-proline is added to the sample (375 mM) to ensure the complexation of the target metal cations. After the complexation step, 750 µL of SHS - a N, N-Dimethylcyclohexylamine along with 0.9 mL of 2 M of acetic acid solution is added (hydrophilicity switch-on stage) and mixed manually to obtain a homogeneous solution. In the last stage, 0.45 mL of 10 M NaOH solution (hydrophilicity switch-off stage) is added to the sample solution and a vortex for 100 s is applied to ensure the effective extraction and separation of the complex containing the analytes. At this stage, a cloudy solution is immediately obtained. Finally, the effective phase separation is obtained at the centrifugation step (4000 rpm for 2 mins). The method limit of detection was as 0.03, 0.009, 0.6, and 0.2 ng/L for Zn (II), Fe (II), Cd (II), and Pb (II) respectively with RSD% below 2.0 %. The analysis of certified reference materials and real samples proved the full applicability of the method for routine analysis, contributing to the field of heavy metal analysis and ensuring the safety of baby products. According to the AGREE methodology, this method can be named as green analytical chemistry method with a score of 0.77.

Alcohol-DES based vortex assisted homogenous liquid-liquid microextraction approach for the determination of total selenium in food samples by hydride generation AAS: Insights from theoretical and experimental studies.

This research article proposes a simple, quick, green and cheap approach for the determination of total selenium in food samples using alcohol-DES based vortex-assisted homogenous liquid-liquid microextraction (alcohol-DES-VA-HLLME) combination with hydride generation atomic absorption spectrometry (HG AAS). Analyte, complexing agent and working pH were Se(IV), Sudan-II and pH 4.0, respectively. In order to analyze the nature of the chemical interaction between Se(IV) ion and Sudan-II ligand, experimental results were supported with computational chemistry tools calculating quantum chemical descriptors like frontier orbital energies, hardness, softness, electronegativity, electrophilicity, nucleophilicity, transferred electron from the ligand to ion, electron donating power, electron accepting power, complexation energy, molecule-ion interaction energy. In addition, the alcohol-DES-VA-HLLME method was earned a good detection limit of 3.5 ng L-1 and a wide calibration curve in the concentration range of 12-300 ng L-1 (r: 0.9981). The validity of the method was evaluated by analyzing the two standard reference material (SRMs). The recoveries and relative standard deviations for 25 and 100 ng L-1 of Se(IV) (N:5) were in the range of 1.2-2.5% and 92.1-103.7% respectively, which proved acceptable. The analytical results showed that the proposed method had important features such as cheapness, green, quick extraction and reuse, which made it attractive for the determination and efficient extraction of total selenium in the food samples.

Towards green analysis of curcumin from tea, honey and spices: Extraction by deep eutectic solvent assisted emulsification liquid-liquid microextraction method based on response surface design.

A fast, cheap and green analytical method was developed for the determination and extraction of curcumin in tea, honey, and spices using deep eutectic solvent-assisted emulsification liquid-liquid micro-extraction (DES-ELLME) coupled to UV-VIS spectrophotometry. Quantitative extraction of curcumin from the sample was obtained by the DES, which was prepared by mixing choline chloride and maltose in a 1:3 molar ratio. Response surface design was used for the optimisation of significant experimental parameters including sample pH, amount of extraction solvent, amount of emulsifier solvent and vortex time. The optimum conditions obtained were pH 4.25, 762.5 µL of DES, 107.5 mL of tetrahydrofuran and 3.4 min vortex time, while keeping centrifugation speed fixed at 4000 rpm, 5 min. Under the extraction conditions obtained, analytical features such as calibration equation, limit of detection, enrichment factor, and linearity were Abs = 6.5 × 10-4 [Curcumin, ng mL-1]-1.2 × 10-5, 0.1 ng mL-1, 114 and 0.4-120 ng mL-1, respectively. Moreover, the repeatability and reproducibility of the DES-ELLME method, expressed as relative standard deviation (RSDs%), varied in the ranges of 1.4-3.0% and 2.0-4.3%, respectively. Finally, the proposed method was successfully applied to the extraction and determination of curcumin from prepared samples. The relative mean recovery ranged from 92.3% to 104.4%.

Vortex assisted-ionic liquid dispersive liquid-liquid microextraction and spectrophotometric determination of quercetin in tea, honey, fruit juice and wine samples after optimization based on response surface methodology.

The aim of our study is to develop a new vortex assisted-ionic liquid dispersive liquid-liquid microextraction (VA-IL-DLLM) method for preconcentration and determination of the quercetin in tea, honey, fruit juice and wine samples by spectrophotometry. The method is based on pH sensitive ion-pair formation between quercetin and rhodamine B at pH 6.5 by donor-acceptor mechanism, and then dispersion of the complex in the fine-drops of ionic liquid (IL). In this context, the effects of pH, concentrations of ion-pairing reagent, the IL, vortex time and dispersive solvent type on the preconcentration process of quercetin were investigated using a 2-level-5-factor central composite half fraction design (CCD) as experimental design for response surface methodology (RSM). Quantitative model was developed to determine the quercetin in food samples, and it is verified by analysis of variance (ANOVA) at a 95% confidence level (P < 0.05). Response surface plots and contour plots obtained by the model are used to determine the interactions of experimental variables. After the optimization, calibration graph was obtained between 35 and 750 µg L-1 with the detection limit of 10.2 µg L-1. The recovery and relative standard deviations (RSD%) were in range of 94-104%, and in range of 2.5-4.2%, respectively. The accuracy and precision of the method were tested by the experimental studies such as recoveries, intermediate precision, trueness and expanded uncertainty. A comparison of the current results to those reported for other studies is also presented.

Development of a chemometric-assisted deep eutectic solvent-based microextraction procedure for extraction of caffeine in foods and beverages.

In this research article, a novel and green deep eutectic solvent-based microextraction (DES-ME) procedure based on chemometric-assisted (CA) optimization was developed for the extraction of caffeine in foods and beverages prior to its spectrophotometric determination. Ultrasound was used to accelerate the extraction of caffeine. Deep eutectic solvents (DES), prepared in an ultrasonic bath at 20-60 min for 60-80°C, were used as extraction solvents. The important experimental variables (pH, DES amount, temperature, sonication time and metal concentration) were modelled and optimized using response surface methodology (RSM) based on central composite design (CCD). Under the optimum conditions, the proposed method allowed the determination of caffeine with limits of detection (LOD, 3sblank/m) and quantification (LOQ, 3sblank/m) of 7.5 and 25.0 µg L-1, respectively. For 40 µg L-1 and 100 µg L-1 of caffeine (n = 5), relative standard deviations (RSDs%) and recoveries% were 1.2-1.6% and 96.7-98.2%, respectively. Validation studies (accuracy, precision, trueness, reliability and selectivity) of the method were performed before the analysis of real samples. The results showed that the combination of the CCD with the DES-ME can be considered as a new perspective for the extraction and determination of caffeine in foods and beverages.