Development and Validation of a Sonication-Assisted Dispersive Liquid-Liquid Microextraction Procedure and an HPLC-PDA Method for Quantitative Determination of Zolpidem in Human Plasma and Its Application to Forensic Samples.

The use of z-drugs has increased worldwide since its introduction. Although the prescribing patterns of hypnotics differ among countries, zolpidem is the most widely used z-drug in the world. Zolpidem may be involved in poisoning and deaths. A simple and fast HPLC-PDA method was developed and validated. Zolpidem and the internal standard chloramphenicol were extracted from plasma using a sonication-assisted dispersive liquid-liquid microextraction procedure. The method was validated including selectivity, linearity, precision, accuracy, and recovery. The calibration range (0.15-0.6 µg/mL) covers therapeutic and toxic levels of zolpidem in plasma. The limit of quantification was set at 0.15 µg/mL. Intra- and interday accuracy and precision values were lower than 15% at the concentration levels studied. Excellent recovery results were obtained for all concentrations. The proposed method was successfully applied to ten real postmortem plasma samples. In our series, multiple substances (alcohol and/or other drugs) were detected in most cases of death involving zolpidem. Our analytical method is suitable for routine toxicological analysis.

Edible oil-based switchable-hydrophilicity solvent liquid-liquid microextraction prior to smartphone digital image colorimetry for the determination of total curcuminoids in food samples.

Edible oil-based switchable-hydrophilicity solvent liquid-liquid microextraction was coupled with smartphone digital image colorimetry for the determination of total curcuminoids. Images of the colored extracts were captured in a laboratory-made colorimetric box, which were then split into their red-green-blue channels. Optimum extraction conditions were achieved using 550 µL of almond oil as the extraction solvent and 0.40 M sodium hydroxide for hydrolysis of the oil to the salt of its fatty acid. Phosphoric acid (2.0 mL, 4.0 M) was used as the hydrophilicity-switching trigger, while pH of the sample solution adjusted to 5.50 and extraction time of 1.0 min, were found to be optimum. Optimum detection conditions were achieved at a distance of 7.0 cm from the detection camera, a region of interest of 175 px2, a detection wavelength of 420 nm and 50.0% brightness of the light source. The limit of detection was found to be 0.020 µg mL-1. A good linearity was achieved as indicated by coefficients of determination above 0.9965. The proposed method was used for the determination of total curcuminoids in tea and turmeric samples with percentage relative recoveries of 95.0-105.0% and percentage relative standard deviations below 8.7%.

Microsyringe-based slug-flow microextraction for rapid and accurate determination of antibiotics in highly saline seawater.

BACKGROUND: Extensive use of antibiotics leads to widespread environmental pollution, endangering ecosystems, and human health. It is particularly concerning, posing global threats requiring urgent attention and action. In this regard, the shift to mass spectrometry in determining antibiotics is highly desirable. Significant progress has been made in analyzing and optimizing the sensitivity of high-salt samples. However, the persistence of cumbersome operational procedures presents a significant challenge to this shift. Thus, the persistence of complex operational procedures needs to be addressed. RESULTS: In this study, a rapid and direct method for determining antibiotics in highly saline environmental water samples using microsyringe-based slug-flow microextraction (MSFME)-droplet spray ionization (DSI) mass spectrometry (MS) has been described. The proposed method successfully detected clarithromycin, ofloxacin, and sulfadimidine in seawater within a linear range of 1-1200 ng mL-1, with low limits of detection of 0.19 ng mL-1, 0.17 ng mL-1, and 0.20 ng mL-1, respectively (Signal/Noise = 3). Additionally, spiked real seawater samples of all three antibiotics demonstrated satisfactory recoveries (95.1-107.5%) and precision (RSD≤8.8%). The MSFME-treated high-salt sample (3.5 wt%) showed a mass spectral response intensity 4-5 orders of magnitude higher than the untreated medium-salt sample (0.35 wt%). Furthermore, exploration of the applicability of MSFME showed that it is suitable not only for high-salinity (3.5 wt%) samples but also for salt-free or low-salt and hard water samples rich in calcium and magnesium ions. SIGNIFICANCE: Comparisons with other methods, complex laboratory setups for sample processing are now simplified to a single step, completing the entire process, including desalination and detection, MSFME-DSI-MS provides faster results in less than 1 min while maintaining sensitivity comparable to that of other detection methods. In conclusion, this advancement provides an exceptionally simplified protocol for the rapid, highly sensitive, and quantitative determination of antibiotics in environmental water samples.

Development of an orbital shaker-assisted fatty acid-based switchable solvent microextraction procedure for rapid and green extraction of amoxicillin from complex matrices: Central composite design.

In this study, a cheap, fast and simple orbital shaker-assisted fatty acid-based switchable solvent microextraction (OS-FASS-ME) procedure was developed for the extraction of amoxicillin (AMOX) in dairy products, pharmaceutical samples and wastewater prior to its spectrophotometric analysis. Fatty acid-based switchable solvents were investigated for extracting AMOX. The key factors of the OS-FASS-ME procedure were optimized using a central composite design. The linearity of OS-FASS-ME procedure was in the range 5-600 ng mL-1 with a correlation coefficient of 0.991. In five replicate experiments for 20 ng mL-1 of AMOX solution, the recovery and relative standard deviation were 95.8% and 2.2%, respectively. Limits of detection and quantification were found 1.5 ng mL-1 and 5 ng mL-1, respectively. The accuracy, precision, robustness and selectivity of the OS-FASS-ME procedure were investigated in detail under optimum conditions. The OS-FASS-ME procedure was applied to milk, cheese, wastewater, syrups and tablets. A comparison of the results obtained from the reference method and the OS-FASS-ME method showed that the OS-FASS-ME procedure can be successfully applied to complex matrices.

Determination of 13 potential anti-obesity agents in hair by dispersive liquid-liquid microextraction-assisted UHPLC-MS/MS.

As the adulteration of dietary supplements with synthetic drugs remains a prevalent issue, the inclusion of anti-obesity agents may pose health risks, potentially leading to central nervous system or cardiovascular diseases. However, surveillance studies on the use of anti-obesity agents by the Chinese population are limited. This study aims to establish an efficient and rapid hair pretreatment method using dispersive liquid-liquid microextraction (DLLME) combined with high-speed grinding and develop a sensitive and accurate analytical method employing ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) for detecting 13 potential anti-obesity agents in hair samples. Herein, hair samples were washed sequentially with 0.1% sodium dodecyl sulfate (SDS), water and acetone, and then ground at high speed using 1 mL of an extraction solution (internal standard solution-n-butanol-1.2 mol/L Na2HPO4, pH10.0, 100:400:500, v/v/v for procaterol; internal standard solution-ethyl acetate-1.2 mol/L Na2HPO4, pH8.0, 100:300:600, v/v/v for other 12 anti-obesity agents) while simultaneously performing DLLME. The developed method successfully detected 13 anti-obesity agents within 11 min, including bambuterol, clenbuterol, ractopamine, clorprenaline, formoterol, salbutamol, terbutaline, procaterol, phentermine, bupropion, sibutramine, desmethyl sibutramine, and N,N-didesmethyl sibutramine, which improved the screening efficiency. The calibration curves exhibited good linearity of 0.025-5 ng/mg, achieving correlation coefficients of r ≥ 0.99. The lower limits of quantification (LLOQs) for the analytes were 0.025 ng/mg, demonstrating acceptable levels of accuracy and precision. Recovery rates ranged between 73.30% and 107.47% across the three concentrations of 0.075, 0.375, and 3.75 ng/mg. The validated method was successfully applied to 369 real cases and detected six analytes, including bambuterol, salbutamol, terbutaline, sibutramine, desmethyl sibutramine, and N,N-didesmethyl sibutramine. This method offers several advantages, including simple pretreatment, high extraction efficiency, rapid extraction, solvent economy, and pollution mitigation, making it highly suitable for large-scale surveillance of usage of added anti-obesity agents.

Microextraction techniques for occupational biological monitoring: Basic principles, current applications and future perspectives.

The application of green microextraction techniques (METs) is constantly being developed in different areas including pharmaceutical, forensic, food and environmental analysis. However, they are less used in biological monitoring of workers in occupational settings. Developing valid extraction methods and analytical techniques for the determination of occupational indicators plays a critical role in the management of workers' exposure to chemicals in workplaces. Microextraction techniques have become increasingly important because they are inexpensive, robust and environmentally friendly. This study aimed to provide a comprehensive review and interpret the applications of METs and novel sorbents and liquids in biological monitoring. Future perspectives and occupational indicators that METs have not yet been developed for are also discussed.

Supramolecular deep eutectic solvent: a powerful tool for pre-concentration of trace metals in edible oil.

The utilization of supramolecular deep eutectic solvent eddy-assisted liquid-liquid microextraction utilizing 2-hydroxypropyl ß-cyclodextrin (SUPRADES) has been identified as a successful method for pre-enriching Cu, Zn, and Mn in vegetable oil samples. Determination of each element was conducted by inductively coupled plasma optical emission spectrometry (ICP-OES) after digestion of metal-enriched phases. Various parameters were examined, including the composition of SUPRADES species [2HP-ß-CD: DL-lactic acid], a cyclodextrin mass ratio of 20 wt%, a water bath temperature of 75 °C, an extractor volume of 800 µL, a dispersant volume of 50 µL, and an eddy current time of 5 min. Optimal conditions resulted in extraction rates of 99.6% for Cu, 105.2% for Zn, and 101.5% for Mn. The method exhibits a broad linear range spanning from 10 to 20,000 µg L-1, with determination coefficients exceeding 0.99 for all analytes. Enrichment coefficients of 24, 21, and 35 were observed. Limits of detection ranged from 0.89 to 1.30 µg L-1, while limits of quantification ranged from 3.23 to 4.29 µg L-1. The unique structural characteristics of the method enable the successful determination of trace elements in a variety of edible vegetable oils.

Amine Switchable Hydrophilic Solvent Vortex-Assisted Homogeneous Liquid-Liquid Microextraction and GC-MS for the Enrichment and Determination of 2, 6-DIPA Additive in Biodegradable Film.

2, 6-diisopropylaniline (2, 6-DIPA) is a crucial non-intentionally organic additive that allows the assessment of the production processes, formulation qualities, and performance variations in biodegradable mulching film. Moreover, its release into the environment may have certain effects on human health. Hence, this study developed simultaneous heating hydrolysis-extraction and amine switchable hydrophilic solvent vortex-assisted homogeneous liquid-liquid microextraction for the gas chromatography-mass spectrometry analysis of the 2, 6-DIPA additive and its corresponding isocyanates in poly(butylene adipate-co-terephthalate) (PBAT) biodegradable agricultural mulching films. The heating hydrolysis-extraction conditions and factors influencing the efficiency of homogeneous liquid-liquid microextraction, such as the type and volume of amine, homogeneous-phase and phase separation transition pH, and extraction time were investigated and optimized. The optimum heating hydrolysis-extraction conditions were found to be a H2SO4 concentration of 2.5 M, heating temperature of 87.8 °C, and hydrolysis-extraction time of 3.0 h. As a switchable hydrophilic solvent, dipropylamine does not require a dispersant. Vortex assistance is helpful to speed up the extraction. Under the optimum experimental conditions, this method exhibits a better linearity (0.0144~7.200 µg mL-1 with R = 0.9986), low limit of detection and quantification (0.0033 µg g-1 and 0.0103 µg g-1), high extraction recovery (92.5~105.4%), desirable intra- and inter-day precision (relative standard deviation less than 4.1% and 4.7%), and high enrichment factor (90.9). Finally, this method was successfully applied to detect the content of the additive 2, 6-DIPA in PBAT biodegradable agricultural mulching films, thus facilitating production process monitoring or safety assessments.

Analytical strategy to assess the microbial degradation of poly(butylene-adipate-co-terephthalate)/poly(lactic acid) films.

Plastic is widely used in agricultural applications, but its waste has an adverse environmental impact and a long-term detrimental effect. The development of biodegradable plastics for agricultural use is increasing to mitigate plastic waste. The most commonly used biodegradable plastic is poly(butylene adipate co-terephthalate)/poly(lactic acid) (PBAT/PLA) polymer. In this study, an analytical procedure based on dispersive liquid-liquid microextraction (DLLME) followed by gas chromatography-mass spectrometry (GC-MS) in combination with chemometrics has been optimized to assess the degradation level of PBAT/PLA films by monitoring their characteristic degradation products. Carboxylic acids (benzoic, phthalic, adipic, heptanoic, and octadecanoic acids) and 1,4-butanediol have been found to be potential markers of PBAT/PLA degradation. The DLLME-GC-MS analytical approach has been applied for the first time to assess the degradation efficiency of several microorganisms used as degradation accelerators of PBAT/PLA based on the assigned potential markers. This analytical strategy has shown higher sensitivity and precision than standard techniques, such as elemental analysis, allowing us to detect low degradation levels.

Investigation of use of hydrophilic/hydrophobic NADESs for selective extraction of As(III) and Sb(III) ions in vegetable samples: Air assisted liquid phase microextraction and chemometric optimization.

In this paper, a green, cost-effective sample preparation method based on air assisted liquid phase microextraction (AA-LPME) was developed for the simultaneous extraction of As(III) and Sb(III) ions from vegetable samples using hydrophilic/hydrophobic natural deep eutectic solvents (NADESs). Central composite design was used for the optimization of extraction factors including NADES volume, extraction cycle, pH, and curcumin concentration. Limits of detection for As(III) and Sb(III) were 1.5 ng L-1 and 0.06 ng L-1, respectively. Working ranges for As(III) and Sb(III) were 0.2-300 ng L-1 (coefficient of determination (R2 = 0.9978) and 5-400 ng L-1 (R2 = 0.9996), respectively. Relative standard deviations for As(III) and Sb(III) were 2.2-2.8% and 2.9-3.2%, respectively. Enrichment factor of the method was 184 for As(III) and 172 for Sb(III). The accuracy and precision of the AA-NADES-LPME method were investigated by intraday/interday studies and standard reference material analysis, respectively. Finally, the AA-NADES-LPME method was successfully applied to microwave digested vegetable samples using the standard addition approach and acceptable recoveries were achieved.

Determination of insecticide residues in beverages based on MIL-100(Fe) dispersive solid-phase microextraction in combination with dispersive liquid-liquid microextraction followed by HPLC-MS/MS.

A novel dispersive solid-phase microextraction method based on a metal-organic framework (MIL-100(Fe)) combined with a dispersive liquid-liquid microextraction technique was proposed for the extraction and enrichment of four insecticides in beverages. The qualitative and quantitative analysis of these insecticides was conducted using HPLC-MS/MS. To optimize the extraction process, several parameters were investigated, and the main variables were optimized using CCD-based RSM. The developed method displayed a wide linear range of 1.000-1000 ng/L and R2 values >0.993 for all four calibration curves. The method demonstrated high sensitivity, with LODs and LOQs of 0.3-0.6 ng/L and 0.8-1.0 ng/L, respectively. In addition, the greenness of the proposed method was assessed using the Complex GAPI tool, and the results showed that the proposed method exhibits benefits, such as minimal usage of organic solvents and negligible matrix influence, making it a suitable method for the detection of insecticide residues in beverages.

Development of CO2-switchable deep eutectic solvent-based liquid-liquid microextraction approach: Application in urinary excretion and tissue distribution studies.

BACKGROUND: Pharmacokinetic studies are pivotal in drug development, focusing on absorption, distribution, and excretion of active compounds. Effective sample preparation methods play a crucial role in these studies. Traditional techniques like protein precipitation and liquid-liquid extraction often involve toxic solvents and are time-consuming. Recently, deep eutectic solvent (DES) has emerged as an eco-friendly alternative due to its high efficiency, low cost, and low toxicity. This study introduces a novel sample pretreatment method using CO2-switchable DES in liquid-liquid microextraction (LLME) to enhance speed, accuracy, and sensitivity in complex biological samples analysis. RESULTS: A liquid-liquid microextraction sample pretreatment method based on switchable DES combined with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established for the analysis of urine and tissue samples. The method was optimized through systematic investigation of key parameters, including DES type, volume, molar ratio, pH, vortex time, gas purge time, and salt addition. The resulting procedure exhibited satisfying linearity (r2 ≥ 0.9958), good precision (RSD ≤6.01 %), desirable recovery (52.44%-98.12 %) and matrix effect (86.22%-119.30 %), and the accuracy and precision of stability were within the ±15 % limit. The proven methods were further applied to urinary excretion study and tissue distribution study of Nelumbinis plumula (NP) extract. The results indicated that the total cumulative excretion of liensinine, isoliensinine and neferine in urine within 240 h was 4.96 %, 0.66 % and 0.44 %, respectively. The tissue distribution study showed that alkaloids mainly distribute in liver, kidney, and spleen. SIGNIFICANCE: This research introduces a groundbreaking technique distinguished by its simplicity, speed, cost-effectiveness, and environmental friendliness. This approach, utilizing CO2-switchable DES as an extraction solvent for LLME, integrates deproteinization and removal of interfering molecules into a single step. This integration showcases its efficiency and convenience, demonstrating significant promise for various applications in the analysis of biological samples. Additionally, this study provides the first report on urinary excretion and tissue distribution of alkaloids from NP using a DES-LLME method. These findings offer valuable insights into the in vivo behavior of herbal medicine, enhancing understanding of pharmacological actions and facilitating clinical rational administration.

Determination of pesticide residues in soybeans using QuEChERS followed by deep eutectic solvent-based DLLME preconcentration prior to gas chromatography-mass spectrometry analysis.

A reliable and greener alternative to the usual extraction methods is reported for the determination of pesticide residues in soybeans. This novel approach combines the classical QuEChERS extraction method with a DLLME (dispersive liquid-liquid microextraction) step, utilizing a deep eutectic solvent (DES) - camphor: hexanoic acid (1:1 molar ratio) - as the microextraction solvent. This DES has never been employed in pesticide analysis by gas chromatography-mass spectrometry of complex matrices like soybeans. A Plackett-Burman screening design was employed to optimize sample preparation variables of QuEChERS (amount of sodium chloride and magnesium sulfate, and amount of PSA and C18 sorbents) and DLLME (pH of medium, amount of sodium chloride, and volume of microextraction solvent). This design allowed for a systematic evaluation of the impact of each parameter on the method's performance. The optimized method was evaluated using a certified reference material and commercial samples of soybeans. The method exhibited high accuracy and precision for most of the analytes under study, demonstrating its applicability for pesticide residue analysis in soybeans. To assess the greenness and practicality of the developed method, the Analytical Greenness (AGREE) and Blue Applicability Grade Index (BAGI) metric systems were employed, respectively. Overall, the proposed QuEChERS-DLLME method using a DES solvent is a reliable and greener alternative to conventional extraction methods for the determination of pesticide residues in soybeans. Its high performance, coupled with its environmental friendliness, makes it a promising tool for food safety analysis.

High-throughput semi-automated emulsive liquid-liquid microextraction for detecting SDHI fungicides in water, juice, and alcoholic beverage samples via UHPLC-MS/MS.

Herein, a High-Throughput Semi-automated Emulsive Liquid-Liquid Microextraction (HTSA-ELLME) method was developed to detect Succinate Dehydrogenase Inhibitor (SDHI) fungicides in food samples via UHPLC-MS/MS. The Oil-in-Water (O/W) emulsion comprising a hydrophobic extractant and water was dilutable with the aqueous sample solution. Upon injecting the primary emulsion into the sample solution, a secondary O/W emulsion was formed, allowing SDHI fungicides to be extracted. Subsequently, a NaCl-saturated solution was injected in the secondary O/W emulsion as a demulsifier to rapidly separate the extractant, eliminating the need for centrifugation. A 12-channel electronic micropipette was used to achieve a high-throughput semi-automation of the novel sample pretreatment. The linear range was 0.003-0.3 µg L-1 with R2 > 0.998. The limit of detection was 0.001 µg L-1. The HTSA-ELLME method successfully detected SDHI fungicides in water, juice, and alcoholic beverage samples, with recoveries and relative standard deviations of 82.6-106.9% and 0.8-5.8%, respectively. Unlike previously reported liquid-liquid microextraction approaches, the HTSA-ELLME method is the first to be both high-throughput and semi-automated and may aid in designing pesticide pretreatment processes in food samples.

Discrimination of Diptera order insects based on their saturated cuticular hydrocarbon content using a new microextraction procedure and chromatographic analysis.

The nature and proportions of hydrocarbons in the cuticle of insects are characteristic of the species and age. Chemical analysis of cuticular hydrocarbons allows species discrimination, which is of great interest in the forensic field, where insects play a crucial role in estimating the minimum post-mortem interval. The objective of this work was the differentiation of Diptera order insects through their saturated cuticular hydrocarbon compositions (SCHCs). For this, specimens fixed in 70 : 30 ethanol : water, as recommended by the European Association for Forensic Entomology, were submitted to solid-liquid extraction followed by dispersive liquid-liquid microextraction, providing preconcentration factors up to 76 for the SCHCs. The final organic extract was analysed by gas chromatography coupled with flame ionization detection (GC-FID), and GC coupled with mass spectrometry was applied to confirm the identity of the SCHCs. The analysed samples contained linear alkanes with the number of carbon atoms in the C9-C15 and C18-C36 ranges with concentrations between 0.1 and 125 ng g-1. Chrysomya albiceps (in its larval stage) showed the highest number of analytes detected, with 21 compounds, while Lucilia sericata and Calliphora vicina the lowest, with only 3 alkanes. Non-supervised principal component analysis and supervised orthogonal partial least squares discriminant analysis were performed and an optimal model to differentiate specimens according to their species was obtained. In addition, statistically significant differences were observed in the concentrations of certain SCHCs within the same species depending on the stage of development or the growth pattern of the insect.

Development of a new continuous homogenous liquid phase microextraction procedure based on in-situ preparation of deep eutectic solvent; application in the analysis of aliphatic amines in urine samples by GC-MS.

In the present work, a new microextraction procedure combined with gas chromatography-mass spectrometry has been developed for the analysis of several aliphatic amines from urine sample. The sample preparation method was a continuous homogenous liquid phase microextraction that was based on in-situ preparation of 4-chlorophenol: choline chloride deep eutectic solvent. The deep eutectic solvent was prepared by passing the mixture of related compounds through a syringe barrel filled with exothermic salts (calcium chloride and potassium bromide). The released heat by dissolving the salts and increasing the solution ionic strength assists the formation of the deep eutectic solvent. The influence of various factors on the efficiency of the proposed procedure including salts amount, flow rate, pH, salting-out effect, and extraction solvent volume was studied. The calibration curves were linear broadly over the concentration range of 1.2-250 ng mL-1 with coefficient of determinations ≥0.996. The enrichment factors were in the range of 188-246 and the limits of detection and quantification were 0.16-0.37 and 0.56-1.2 ng mL-1, respectively. Based on the results, the offered method was sensitive, rapid, eco-friendly, and efficient for extracting and determining aliphatic amines in urine samples.

Determination of phenytoin at trace levels in domestic wastewater and synthetic urine samples by gas chromatography-mass spectrometry after its preconcentration by simple liquid-phase microextraction.

This work presents a sensitive and accurate analytical method for the determination of phenytoin at trace levels in domestic wastewater and synthetic urine samples by gas chromatography-mass spectrometry (GC-MS) after the metal sieve-linked double syringe liquid-phase microextraction (MSLDS-LPME) method. A metal sieve was produced in our laboratory in order to disperse water-immiscible extraction solvents into aqueous media. Univariate optimization studies for the selection of proper extraction solvent, extraction solvent volume, mixing cycle, and initial sample volume were carried out. Under the optimum MSLDS-LPME conditions, mass-based dynamic range, limit of quantitation (LOQ), limit of detection (LOD), and percent relative standard deviation (%RSD) for the lowest concentration in calibration plot were figured out to be 100.5-10964.2 µg kg-1, 150.6 µg kg-1, 45.2 µg kg-1, and 9.4%, respectively. Detection power was improved as 187.7-folds by the developed MSLDS-LPME-GC-MS system while enhancement in calibration sensitivity was recorded as 188.0-folds. In the final step of this study, the accuracy and applicability of the proposed system were tested by matrix matching calibration strategy. Percent recovery results for domestic wastewater and synthetic urine samples were calculated as 95.6-110.3% and 91.7-106.6%, respectively. These results proved the accuracy and applicability of the proposed preconcentration method, and the obtained analytical results showed the efficiency of the lab-made metal sieve apparatus.

Developing of an eco-friendly liquid-liquid microextraction method by using menthol-based hydrophobic deep eutectic solvent for determination of basic fuchsin dye: assessment of the greenness profile.

Herein, we aimed to develop a new environmentally friendly liquid-liquid microextraction (LLME) method based on hydrophobic deep eutectic solvent (hDES) synthesized using biodegradable dl-menthol and decanoic acid for the spectrophotometric determination of toxic basic fuchsin dye in environmental water samples. The parameters affecting the extraction efficiency such as pH, mole ratio, and volume of hDES (1:2) and type and volume of organic solvent, sample volume, times of vortex, ultrasonic bath and centrifuge, ionic strength, and matrix effect were investigated and optimized. Under optimal conditions, the calibration curve showed linearity in the range of 7.4-167 µg L-1 with a coefficient of determination of 0.9994. The limit of detection, intra-day and inter-day precision, and recovery values were 2.25 µg L-1, 2.46% and 4.45%, and 105 ± 3%, respectively. The preconcentration and enrichment factors were found to be 30 and 61.5, respectively. The proposed hDES-LLME methodology was successfully applied to the environmental water samples to detect toxic BF dye (95-105%). Finally, the ecological impact of the suggested method was evaluated using the analytical eco-scale (PPS:88), complementary green analytical procedure indexe (ComplexGAPI), and the Analytical GREEnness tool (0.63). The assessment results showed that the presented analytical method can be regarded as a green LLME approach for the determination of the BF in water.

Detection of trace components in Xiangdan injection of Dalbergia odorifera based on microextraction and back-extraction along with bar-form-diagram strategy.

Xiangdan Injection are commonly used traditional Chinese medicine formulations for the clinical treatment of cardiovascular diseases. However, the trace components of Dalbergia odorifera in Xiangdan Injection pose a challenge for evaluating its quality due to the difficulty of detection. This study proposes a technology combining dispersive liquid-liquid microextraction and back-extraction (DLLME-BE) along with Bar-Form-Diagram (BFD) to address this issue. The proposed combination method involves vortex-mixing tetradecane, which has a lower density than water, with the sample solution to facilitate the transfer of the target components. Subsequently, a new vortex-assisted liquid-liquid extraction step is performed to enrich the components of Dalbergia odorifera in acetonitrile. The sample analysis was performed on HPLC-DAD, and a clear overview of the chemical composition was obtained by integrating spectral and chromatographic information using BFD. The combination of BFD and CRITIC-TOPSIS strategies was used to optimize the process parameters of DLLME-BE. The determined optimal sample pre-treatment process parameters were as follows: 200 µL extraction solvent, 60 s extraction time, 50 µL back-extraction solvent, and 90 s back-extraction time. Based on the above strategy, a total of 29 trace components, including trans-nerolidol, were detected in the Xiangdan Injection. This combination technology provides valuable guidance for the enrichment analysis of trace components in traditional Chinese medicines.

The selective extraction of dietary polyamines from chicken breast using the application of a lab-on-a-chip electromembrane and dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

Excessive dietary polyamines (PAs), including putrescine (PUT), spermine (SPM), and spermidine (SPD), have become a worldwide concern due to their carcinogenicity and reduced shelf life. A modern miniaturized on-chip electromembrane extraction (EME) has been applied to extract these compounds from chicken breast samples. This method is based fundamentally on ionic compounds' electrostatic attraction, diffusion, and solubility in the acceptor phase. The chemical structure of polyamines enables their efficient extraction using an electric driving force on a microchip device. HCl solution (0.1 mol L-1) was applied as an aqueous acceptor solvent. Dispersive liquid-liquid microextraction was performed after EME to facilitate joining three-phase EME to GC-MS and improve the merit figures. The total ranges of 3.77-7.89 µg g-1, 3.48-7.02 µg g-1, and 0.78-2.20 µg g-1 were acquired as PUT, SPM and SPD concentrations in chicken breast, respectively. The results demonstrate that the level of PAs in fresh chicken breast samples is not concerning, but it may reduce the quality of chicken meat over time. This novel analytical technique has several advantages: high recovery, substantial quickness, remarkable selectivity, and good enrichment factors. This emerging method could be generalized to other studies to analyze different foodstuffs.