Supramolecular Solvent-based Microextraction Research Articles

Exploration of supramolecular solvent-based microextraction for crystal violet detecting in water samples

This approach highlights the advantages of supramolecular solvents in a new microextraction model. The distinct properties and behavior of this supramolecular solvent provide enhanced extraction capabilities for detecting crystal violet (CV) in water samples. The methodical experimentation was executed to optimize the critical process parameters, providing maximum efficiency of crystal violet extraction at optimal conditions with pH set at 2.7, 186 μL of extraction solvent, extraction time of 3.5 min, and a salt amount of 3.1 % w/v, yielding the best results. Analytical data from extraction experiments under these optimal conditions demonstrated a high extraction percentage. The extraction model exhibited a linear response within the range of 10–800 ng mL−1 of crystal violet, with a detection limit of 2 ng mL−1. This model enables the measurement of CV in water samples with recovery rates exceeding 97 %, offering a straightforward and accessible approach for analysis.

Primary alcohol-induced coacervation in alkyl polyglucoside micellar solution for supramolecular solvent-based microextraction and chromatographic determination of phthalates in baby food

This study reports for the first time the phenomenon of supramolecular solvent formation based on alkyl polyglucoside as an amphiphile and primary alcohol as a coacervation agent. The physical properties (density, kinematic viscosity, phase diagram for ternary system) of the supramolecular solvent were investigated, and a mechanism for its formation was proposed. A green and simple microextraction procedure for preconcentration and determination of phthalates in baby foods packaged in plastic packaging was developed as proof-of-concept example. The microextraction procedure assumed separation of analytes from solid phase sample in micellar solution of decyl glucoside and in situ formation of supramolecular solvent for analytes preconcentration after addition of n-heptanol. The determination of phthalates in obtained extracts was implemented by high-performance liquid chromatography with UV–Vis detection. The limits of detection, calculated from a blank test based on 3σ, were determined to be 10 μg kg−1 for dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, and di-n-octyl phthalate. The developed procedure did not require filtration of sample suspension, and assumed the use of green and biodegradable substances for the supramolecular solvent formation across a wide pH range.

Supramolecular solvent-based liquid–liquid microextraction (SUPRAS-LLME) of Sudan dyes from food and water samples with HPLC

Utilizing the environmentally friendly technique of supramolecular solvent-based microextraction (SUPRAS-LLME), Sudan I-IV dyes were successfully isolated and enriched from food and natural water samples. The optimization of the microextraction process was carried out by studying the effects of various parameters such as pH (6.0), supramolecular volume (100 μL), tetrahydrofuran (THF) volume (200 μL), ultrasonication temperature (40 °C), and vortex time (1.0 min). Extraction efficiency ranged between 82 % and 109 %, while other analytical parameters such as the limits of detection (LOD) were determined to be 0.23, 0.51, 0.42, and 0.39 μg L−1 for Sudan I, II, III, and IV, respectively. The total figure of merits for the presented SUPRAS-LLME method includes a limits of quantification (LOQ) of 0.78, 1.70, 1.41, and 1.30 μg L−1, a relative standard deviation (RSD%) of 3.4, 6.1, 2.9, and 4.4 (n = 10), a linear range of 5–1000 μg L−1 for all Sudan dyes, a pre-concentration factor (PF) of 15, 10, 10, and 17, and a determination coefficient (R2) of 0.9994, 0.9965, 0.9955, and 0.9946, for Sudan I, II, III, and IV, respectively. The environmental friendliness of the method was confirmed by evaluating the greenness of the method with the AGREE metric tool. A sustainable and environmentally friendly option for the extraction of Sudan dyes from food and water samples is offered by this SUPRAS-LLME method.

Primary Amine-Induced Coacervation in Alkyl Polyglucoside Micellar Solution for Supramolecular Solvent-Based Microextraction

Primary Amine-Induced Coacervation in Alkyl Polyglucoside Micellar Solution for Supramolecular Solvent-Based Microextraction

Highly efficient preconcentration of anti-depressant drugs in biological matrices by conducting supramolecular solvent-based microextraction after dispersive micro solid phase extraction technique

A selective, sensitive, and green sample preparation method was devised by applying a supramolecular solvent-based microextraction (SSME), based on the salting out effect, after conducting the dispersive micro solid phase extraction (Dμ-SPE). The technique was employed for preconcentrative extraction and determination of five anti-depressant drugs in human plasmas and urine samples. The first step was conducted by synthesizing and using a layered double hydroxide-carbon nanotube nanohybrid adsorbent. Multiple interactions betwixt the nanoadsorbent and target analytes, including electrostatic, hydrogen bonding, and π-π interactions and the large surface area of the adsorbent led to an effective performance. In the next step, after emulsification in the presence of supramolecular solvent by ultrasonication, the salting-out effect was applied to separate the extraction phases. At Optimization conditions, wide linearities were obtained, in the ranges of 1.5–3500, 2.0–3500, 1.0–3200, 2.0–3000, and 2.0–3000 ng mL−1 for imipramine, amitriptyline, trimipramine, sertraline, and citalopram, respectively, with low limits of detection ranging from 0.3 to 0.6 ng mL−1. Also, acceptable RSD values (≤8.9%; n = 5) for intra- and inter–day precision were obtained, along with acceptable spiked recoveries (94.5–100.0%) in complex matrices. Overall, the effectiveness of the nanosorbent, ultrasonication, supermolecule green solvents with easy solidification and collection, and elimination of the centrifugation bestowed a highly beneficial method for analyzing anti-depressant drugs.

Environmentally-friendly supramolecular solvent microextraction method for rapid identification of Sudan I–IV from food and beverages

A new ultrasonically assisted supramolecular solvent-based microextraction (UA-SUPRAS-ME) method has been reported. This technique is one of the green methods for rapid microextraction and determination of Sudan I, II, III and IV dyes from food and beverage samples and the study investigated the effects of various parameters such as centrifugation time, 1-octanol volume, pH, supramolecular solvent type, THF volume, ultrasonication time on the optimization of the microextraction process. Addition and recovery of the method were carried out at two different concentrations (10 and 100 ng mL−1) to food and beverage samples and the accuracy of the method was determined. Sudan I dye was detected in red pepper and hot sauce from food samples. Extraction recovery values were found between 90.6 % and 102.5 % which are promising compared to many other methods.

Efficient analyses of triazole fungicides in water, honey and soy milk samples by popping candy-generated CO2 and sugaring-out-assisted supramolecular solvent-based microextraction prior to HPLC determinations.

An enrichment method, namely popping candy-generated CO2 and sugaring-out-assisted supramolecular solvent-based microextraction (PGS-SUPRA), was investigated for the determination of triazole fungicide residues in water, honey and soy milk samples. The extraction process was carried out by adding popping candies into a centrifuge tube. Consequently, rapid dispersion and mass transfer of extractants can be achieved without using dispersants and auxiliary devices, and therefore, the extraction efficiency increased. The extraction parameters affecting the efficiency of the developed method were investigated. The presented method was then analysed by high-performance liquid chromatography. Under the selected condition, the wide linearity of triazole fungicides after preconcentration by the proposed microextraction method ranged from 30 to 1000 μg L-1 for triadimefon and from 90 to 1000 μg L-1 for myclobutanil, tebuconazole and hexaconazole, with a coefficient for determination (R 2) greater than 0.992. The limits of detection (LODs) and limits of quantitation (LOQs) were in the range of 10-30 μg L-1 and 30-90 μg L-1, respectively. The precisions were assessed from the relative standard deviations (RSDs) of the retention time and peak area obtained from intra- (n = 3) and inter-day (n = 3 × 5) experiments, and were greater than 1.66% and 13.52%, respectively. Moreover, the proposed method provided high enhancement factors (EnFs) ranging from 14 to 51 folds. This technique has been prosperously applied for the extraction of fungicide residues in water, honey and soy milk samples with a recovery within the range of 60-114%. Overall, the developed method was found to be advantageous as compared with other sample preparation methods.

Supramolecular solvent-based microextraction probe for fast detection of bisphenols by ambient mass spectrometry

In this study, we investigated for the first time the suitability of supramolecular solvent (SUPRAS)-based microextraction probe for the development of generic and fast sample treatment prior to qualitative analysis by ambient mass spectrometry (AMS) based on ASAP (atmospheric solids analysis probe). SUPRAS are nanostructured liquids formed by the self-assembly of amphiphilic aggregates with multiple binding sites and microenvironments of different polarity for the efficient extraction of multiple compounds. Different types of SUPRAS were evaluated as a simple and single step sample treatment for ASAP. The method was applied to the screening of bisphenol A and structural analogues in thermal paper. Optimal results were achieved with SUPRAS synthesized with 1-decanol in mixtures of ethanol:water. SUPRAS (1.1–2 μL) were loaded onto glass probes and placed in contact with samples for 10 s before ASAP analysis. AMS signal peaks (width: 0.2–0.5 min) were easily integrated and normalized with internal standards (RSD: 2–25%). The method was applied to 62 samples of thermal paper. BPA and BPS were the most widely used, this highlighting the progressive industrial replacement of BPA by BPS.

Synergistic Combination of Facile Thiol-Maleimide Derivatization and Supramolecular Solvent-Based Microextraction for UHPLC-HRMS Analysis of Glutathione in Biofluids.

Glutathione (GSH) is the most abundant non-protein thiol in biofluids, enabling diverse physiological functions. Among the proposed methods for GSH detection, ultra-high-performance liquid chromatography (UHPLC) coupled with high-resolution mass spectrometry (HRMS) has the advantages of high sensitivity and efficiency. In this study, a novel analytical method was developed for the determination of GSH using supramolecular solvent (SUPRAS)-based dispersive liquid–liquid microextraction (DLLME) and UHPLC–HRMS. N-Laurylmaleimide was dissolved in tetrahydrofuran, which served three functions: 1) precipitate the proteins present in the biofluid sample, 2) provide a reaction environment for derivatization, and 3) enable the use of SUPRAS as the dispersing agent. Critical parameters were optimized based on single factor testing and response surface methodology. The established method was validated in terms of linearity, accuracy, precision, and successful quantitative analysis of GSH in saliva, urine, and plasma samples. Experimental results showed that SUPRAS as an extraction solvent was particularly suitable for the extraction of GSH from complex matrices. The current study provides a useful tool for accurate measurements of GSH concentrations, which could potentially be used for clinical diagnostics.

Combination of supramolecular solvent-based microextraction and ultrasound-assisted extraction for cadmium determination in flaxseed flour by thermospray flame furnace atomic absorption spectrometry

This study describes the development of a new analytical method for cadmium determination in flaxseed flour based on ultrasound-assisted extraction combined with supramolecular preconcentration followed by thermospray flame furnace atomic absorption spectrometry. Cadmium from flaxseed flour was extracted by ultrasound-assisted radiation in acid medium (1.5 mol L−1HNO3) followed by liquid–liquid microextraction of the acid extractwith dodecanoic acid/THF supramolecular solvent using diethyl dithiophosphate as a chelating agent. The limit of detection and the analytical curve range were found to be 0.10 μg L−1 and 0.35 to 20.0 μg L−1, respectively. The cadmium concentration in the flaxseed flours was ranged from 0.11 ± 0.04 to 0.79 ± 0.03 µg g−1. The proposed methodis considered simpler, faster, low-cost, and environmentally friendly compared to procedures currently used for the determination of cadmium based on acid digestion and using graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry.

Supramolecular solvent-based microextraction techniques for sampling and preconcentration of heavy metals: A review

Abstract Even very low concentrations of heavy metal pollutants have adverse effects on the environment and on human health. Thus, determining even trace concentrations of heavy metals in various samples has attracted a lot of attention. The conventional analytical methods used for the sampling and analysis of heavy metals have some limitations, including the effects of the matrix and their high detection limits. Thus, various methods are used for the pretreatment and concentration of the target analytes, and these methods are time-consuming, expensive, and require the use of toxic solvents. In recent years, supramolecular solvent-based microextraction (SSME), a green analytical strategy, has been used to determine low concentrations of heavy metals in various matrices. This method has unique features such as high enrichment factor, short extraction time, and rapid analysis. In addition, it is cost effective because it consumes less chemical reagents than other methods. Also, it is ecofriendly, and it has good sensitivity and selectivity. Herein, we presented a comprehensive review of the application of the SSME technique for the analysis of heavy metals in water, food, and biological samples. Also, we have provided the distinctive properties of the SSME technique, discussed the challenges that lie ahead, and addressed the potential future trend.

Supramolecular solvent-based microextraction for the preconcentration of Pb2+ and Cd2+ prior to spectrophotometric detection.

Supramolecular solvent-based dispersive liquid-liquid microextraction technique has been developed as a preconcentration tool for the determination of trace level of Pb2+ and Cd2+. Dodecanol dispersed in tetrahydrofuran has been utilized as a supramolecular-solvent system for the extraction of analytes prior to their quantitative determination with graphite furnace atomic absorption spectrophotometer. Both Pb2+ and Cd2+, which were efficiently extracted by supramolecular solvent system, were complexed with dithizone followed by the addition of supramolecular solvent. The experimental variables that could possibly influence the extraction efficiency, i.e. pH value, temperature, sample volume, centrifugation time, rate of centrifugation, ionic strength, etc. were subjected to the optimization step. An interference study was also conducted to check the selectivity of developed method. Limit of detection calculated for Pb2+ and Cd2+ was 0.015 and 0.061 mg L-1, respectively. The limit of quantification was 0.05 and 0.2 mg L-1 for Pb2+ and Cd2+, respectively. The analytical signal was enhanced to 30 times in case of Pb2+ and 27 times in case of Cd2+. The results obtained revealed that the developed method is rapid, simple, sensitive, and efficient for the determination of both analytes in real water samples.

Supramolecular Solvent-Based Microextraction of Selected Anticonvulsant and Nonsteroidal Anti-Inflammatory Drugs from Sediment Samples.

The increase in the production and consumption of pharmaceuticals increases their presence in the global environment, which may result in direct threats to living organisms. For this reason, there is a need for new methods to analyze drugs in environmental samples. Here, a new procedure for separating and determining selected drugs (diclofenac, ibuprofen, and carbamazepine) from bottom sediment and water samples was developed. Drugs were determined by ultra-high performance liquid chromatography coupled with an ultraviolet detector (UHPLC-UV). In this work, a universal and single-step sample treatment, based on supramolecular solvents (SUPRAS), was proposed to isolate selected anticonvulsants and nonsteroidal anti-inflammatory drugs (NSAIDs) from sediment samples. The following parameters were experimentally selected: composition of the supramolecular solvent (composition THF:H2O (v/v), amount of decanoic acid), volume of extractant, sample mass, extraction time, centrifugation time, and centrifugation speed. Finally, the developed procedure was validated. A Speedisk procedure was also developed to extract selected drugs from water samples. The recovery of analytes using the SUPRAS procedure was in the range of 88.8–115%, while the recoveries of the Speedisk solid-phase extraction procedure ranged from 81.0–106%. The effectiveness of the sorption of the tested drugs by sediment was also examined.

Supramolecular solvent-based microextraction of aryl-phosphate flame retardants in indoor dust from houses and education buildings in Spain

Aryl-phosphate flame retardants (aryl-OPFRs) are flame retardants or plasticizers (among other functions) that can be found in a wide variety of products, from furniture and textiles to cars and electronic equipment. There is an increasing concern about the human exposure to these contaminants due to their ubiquity (as additives they can be easily released from the product to the environment) and potential toxicity. In this study, we investigated the presence of six representative aryl-OPFRs, two well-known aryl-OPFRs (triphenyl phosphate, TPHP and 2-ethylhexyl diphenyl phosphate, EHDPP), two novel aryl-OPFRs (cresyl diphenyl phosphate, CDP and isodecyl diphenyl phosphate, IDPP) and two oligomeric aryl-OPFRs [bisphenol A bis(diphenyl phosphate), BDP and resorcinol bis(diphenyl phosphate, RDP] in indoor dust from houses and education buildings from Spain. Sample treatment was carried out by a novel and simple procedure based on supramolecular solvents (SUPRAS) prior to LC-MS/MS analysis. The median Σaryl-OPFRs was two times higher in classrooms than in houses, being particularly high at University classrooms. The most abundant aryl-OPFR in houses was TPHP (median 497 ng·g−1) while EHDPP (median 407 ng·g−1) and IDPP (median 403 ng·g−1) were dominant in classrooms. This is the first study reporting IDPP, BDP and RDP in different education buildings.

Supramolecular solvent-based microextraction of Sudan Orange G at trace levels for its separation, preconcentration and spectrophotometric determination

ABSTRACT A novel, fast and accurate separation-preconcentration method for supramolecular liquid phase microextraction of sudan orange G dyestuff prior to its UV-vis spectrophotometric determination was developed. Sudan orange G in the model solution was extracted to the supramolecular solvent phase at pH 4.0. Supramolecular solvent used in this study was prepared from tetrahydrofuran (THF) and decanoic acid. Sudan orange G concentration was measured in the UV-Vis spectrophotometer at 380 nm. The sample volume, pH, matrix effect, centrifugation time, ultrasonic bath time, supramolecular solvent volume has been optimised and the work was done under these conditions. The relative standard deviation % value was found below 5%. In this study, the limit of detection (LOD) value and preconcentration factor were found to be 3.4 μgL−1 and 40, respectively. The presented supramolecular liquid phase microextraction procedure was applied to artificial sweat samples and water samples.

Vesicular supramolecular solvent-based microextraction followed by high performance liquid chromatographic analysis of tetracyclines

A simple liquid phase microextraction (LPME) using a vesicular supramolecular solvent (SUPRAS) as the green extraction solvent has been developed for the enrichment of tetracycline antibiotics (TCs) prior to their analysis by reversed phase high performance liquid chromatography. SUPRAS was prepared from a mixture of cationic surfactants: didodecyldimethylammonium bromide (DDAB) and dodecyltrimethylammonium bromide (DTAB) under salt (NaCl) addition for coacervation. The LPME is based on electrostatic interaction between TCs and SUPRAS under salt induced phase separation. Under the optimum conditions, high enrichment factors (EFs) of 48–198, low limits of detection (LODs) in the range of 0.7–3.4 μg L−1 and good precisions with relative standard deviations (RSDs) less than 7.85% were obtained. The applicability of the proposed method was demonstrated for the determination of TCs in milk, egg and honey samples. In addition, morphology, particle sizes and zeta potential of SUPRAS were also investigated.

Determination of Copper Using Supramolecular Solvent-based Microextraction for Food, Spices, and Water Samples Prior to Analysis by Flame Atomic Absorption Spectrometry

Determination of Copper Using Supramolecular Solvent-based Microextraction for Food, Spices, and Water Samples Prior to Analysis by Flame Atomic Absorption Spectrometry

Supramolecular solvent-based microextraction of emerging bisphenol A replacements (colour developers) in indoor dust from public environments

Bisphenol A (BPA) is present in a wide variety of materials and it is a well-known endocrine disruptor that is widespread in indoor and outdoor environments. For this reason, industry has introduced a variety of replacements, such as Bisphenol S (BPS) or Bisphenol F (BPF), and other less known structural analogs, such as BPS-MAE, D-8 or TGSA. These emerging potential contaminants have been identified in thermal paper products, according to recent studies, but their potential toxic effects and their migration into the environment remain unclear. In this study, we report for the first time the presence of emerging BPA replacements in indoor dust from public environments (shops, restaurants, etc.). For this purpose, we optimized a novel supramolecular solvent (SUPRAS)-based microextraction method. SUPRAS are multi-target solvents made up of self-assembled amphiphiles. They offer multiple extraction interactions (dispersion, polar, hydrophobic, etc.) and they constitute excellent candidates to develop generic and fast sample treatment procedures at low cost. By this method, emerging BPA replacements (BPS-MAE, D-8 and TGSA) were detected in dust at median concentrations in the range 6–22 ng g−1 (around ten times lower than BPS) with detection frequencies in the range 50–90%. These results constitute a first insight into the migration of emerging BPA replacements into the environment via indoor dust, which is a common route of human exposure to contaminants.

Assessment of ultrasound-assisted extraction combined with supramolecular solvent-based microextraction for highly sensitive cadmium determination in medicinal plant sample by TS-FF-AAS

A new analytical method exploiting supramolecular solvent-based microextraction (SUPRAS) combined with ultrasound-assisted extraction to preconcentrate cadmium from medicinal plant, with further determination by thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS), is proposed. The proposed method is based on the cadmium ultrasound-assisted extraction from Ginkgo biloba L. leaf samples with diluted acid (0.10 mol L−1 HNO3), followed by the metal complexation with diethyl dithiophosphate and preconcentration using a supramolecular solvent composed of inverted hexagonal aggregates of dodecanoic acid arranged in tetrahydrofuran/water medium. The limits of detection (LOD) and quantification (LOQ) were found to be 0.11 μg L−1 and 0.36 μg L−1, respectively. Intraday and interday precision assessed in terms of relative standard deviations (RSD, %) were lower than 8.50% to 0.70, 1.75 and 5.00 μg L−1 cadmium solutions. The efficiency of ultrasound-assisted extraction was comparable to microwave-assisted digestion and the method accuracy was checked by analysis of certified reference material (Tomato Leaves, SRM 1573a). Samples of Ginkgo biloba L. were analyzed and cadmium contents between 0.21 and 0.33 μg g−1 were found, thereby showing clearly the importance of investigating toxic metals in medicinal plants. The proposed method is simple, highly sensitive, environmentally friendly and has great potential to be applied in the quality control of medicinal plants aiming trace cadmium determination.

Combination of magnetic dispersive micro solid-phase extraction and supramolecular solvent-based microextraction followed by high-performance liquid chromatography for determination of trace amounts of cholesterol-lowering drugs in complicated matrices.

A novel, efficient, rapid, simple, sensitive, selective, and environmentally friendly method termed magnetic dispersive micro solid-phase extraction combined with supramolecular solvent-based microextraction (Mdμ-SPE-SSME) followed by high-performance liquid chromatography (HPLC) with UV detection is introduced for the simultaneous microextraction of cholesterol-lowering drugs in complicated matrices. In the first microextraction procedure, using layered double hydroxide (LDH)-coated Fe3O4 magnetic nanoparticles, an efficient sample cleanup is simply and rapidly provided without the need for time-consuming centrifugation and elution steps. In the first step, desorption of the target analytes is easily performed through dissolution of the LDH-coated magnetic nanoparticles containing the target analytes in an acidic solution. In the next step, an emulsification microextraction method based on a supramolecular solvent is used for excellent preconcentration, ultimately resulting in an appropriate determination of the target analytes in real samples. Under the optimal experimental conditions, the Mdμ-SPE-SSME-HPLC-UV detection procedure provides good linearity in the ranges of 1.0-1500 ng mL-1, 1.5-2000 ng mL-1, and 2.0-2000 ng mL-1 with coefficients of determination of 0.995 or less, low limits of detection (0.3, 0.5, and 0.5 ng mL-1), and good extraction repeatabilities (relative standard deviations below 7.8%, n = 5) in deionized water for rosuvastatin, atorvastatin, and gemfibrozil, respectively. Finally, the proposed method is successfully applied for the determination of the target analytes in complicated matrices. Graphical Abstract Mdμ-SPE-SSME procedure.