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To investigate the distribution of flavor components in Luzhou-flavor base baijiu from different aged cellars, the aroma components in 18 samples of Luzhou-flavor base baijiu from three cellars of different ages were identified and quantified by direct injection (DI), liquid-liquid extraction (LLE) or vortex-assisted surfactant-enhanced emulsification liquid-liquid microextraction (VSLLME) combined with gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The differences in flavor among different base baijiu samples was analyzed by chemometrics methods such as principal component analysis (PCA), partial least squares-discriminant analysis (PLS-DA), and Spearman’s correlation coefficient. The results suggested that 151, 154 and 159 volatile compounds were identified in base baijiu from freshly prepared cellar and those aged over 30 and 100 years. In total, 148 aroma compounds were common to the three base baijiu, accounting for 93.1% of the total number of identified compounds. The quantitative analysis of 61 major aroma compounds showed that the concentrations of ethyl caproate, ethyl butyrate, hexanoic acid, butyric acid and acetic acid in base baijiu from each cellar exceeded 100 mg/L. The concentration of ethyl caproate was the highest, ranging from 1 156.4 to 2 142.2 mg/L. Chemometric results indicated that the flavor similarity of base baijiu between the new and over-30-year-old cellars was higher when compared with the cellar aged over 100 years. This findings further strengthen the baijiu industry’s conventional knowledge of the influence of cellar age on the flavor of Luzhou-flavor baijiu.

Abstract Artificial neural networks (ANNs) are biologically inspired algorithms designed to simulate the way in which the human brain processes information. In sample preparation for bioanalysis, liquid–liquid extraction (LLE) represents an important step with the extraction solvent selection is the key laborious step. In the current work, a robust and reliable ANNs model for LLE solvent prediction was generated which could predict the suitable solvent for analyte extraction. The developed ANNs model takes a set of chosen descriptors for the cited analyte as an input and predicts the corresponding Hansen solubility parameters of the suitable extraction solvent as a model output. Then, from the solvent combination’s appendix, the analyst can identify the proposed extraction solvents' combination for the cited analyte easily and efficiently. For the experimental validation of the model prediction capabilities, twenty structurally diverse drugs belonging to different pharmacological classes were extracted from human plasma. The extraction process was performed using the predicted extraction solvent combination for each drug and quantitively estimated by HPLC/UV methods to assess their extraction recovery. The developed LLE solvent prediction model is in- line with the global trend towards green chemistry since it limits the consumption of organic solvents.

In this work, molecular dynamics simulation (MD) was used for studying the liquid-liquid extraction of acetic acid and acetone from water in the presence of nanoparticles. In the next step, the solubility parameter of acetic acid and acetone were predicted at 1 atm and different temperatures along with the solubility parameter of solvents and water at 25 °C and 1 atm. Three pure systems and three systems with different concentration of nanoparticles were investigated to show the effect of cell size or number of molecules on the solubility parameter. With the addition of SiO2 nanoparticles to the solvents, at low concentrations of nanoparticles (0.01–0.1 vol%), the solubility parameter is increased due to the Brownian motion. With the further increase concentration of the nanoparticles, the solubility parameter decreases due to the accumulation of nanoparticles. The difference between the solubility parameter of benzene and acetone was 0.414 (J/cm3)0.5 and 3.13 (J/cm3)0.5, with and without the presence of SiO2 nanoparticles, respectively. Finally, toluene was found to be the best solvent for acetone and acetic acid at silica nanoparticles concentration of 0.062 vol%.

Organochlorine pesticides (OCPs) are persistent organic compounds found in aquatic environments worldwide. A well-validated and well-established analytical method is crucial for detecting OCPs in the environment. In this study, an analytical method for quantifying OCPs in water was developed and evaluated. Here, the range of linearity, reproducibility, uncertainty, specificity, method detection limits (MDL), and special emphasis on detection and quantitation limits were assessed. Recovery studies were performed to measure the accuracy and precision of the method. This method exhibited excellent linearity in the range of 2.5–20 μg/L for all compounds. As none of the targeted compounds was detected in the chromatograms of the blank sample with no baseline noise, the limits of detection (LOD) and limits of quantification (LOQ) were determined using the linear regression method, external calibration curve slope, and laboratory fortified blank-based detection. All compounds showed different LOD and LOQ values, depending on the approach used. In particular, endosulfan sulfate, methoxychlor, endrin ketone, H. epoxide, heptachlor, and 4,4ʹ-DDT exhibited high detection limits. The recovery percentage of the 15 compounds at 5 μg/L spiked concentration was between 50 and 150 %, which is consistent with the accuracy of the APHA method. Except for endosulfan sulfate, the relative standard deviations of all other compounds were below 20 %, indicating good precision. This method has also been applied to real water samples. This validation technique is reliable, sensitive, simple, rapid, easy to comprehend, and reproducible. The application of this method in the real water samples was also conducted. Only α-BHC and γ-Chlordane were detected in the water sample.

Palm stearin-based mono-diacylglycerols (MDAGs) are food emulsifiers that have not yet been widely developed. Monoacylglycerol (MAG) and diacylglycerol (DAG) are the predominant components of MDAGs. Fractionation of MDAGs into MAG and DAG was currently performed by molecular distillation, chromatography, crystallisation or supercritical CO2. In order to reduce production costs and increase production efficiency, a simpler technique for MDAG fractionation is required. A ternary diagram was used to determine the optimum solvent composition for the extraction of MDAGs. Three different extraction methods, i.e. solid-liquid extraction, liquid-liquid extraction and multiple-stage silica-assisted liquid-liquid extraction, were used to fractionate MDAGs. The multiple-stage silica-assisted liquid-liquid extraction provides better separation performance than solid-liquid and liquid-liquid extraction. The extraction method with hexane solvent composition was able to produce DAG-rich fractions with a purity of 81.05% DAG and 16.47% MAG, while the binary solvent composition of hexane:ethanol (8:2) was able to produce MAG-rich fractions with a purity of 13.33% DAG and 83.45% MAG. This extraction method combines two separation mechanisms, i.e. adsorption on silica and solubility in the corresponding solvent. The latter method has the potential for production MAG-rich fraction and DAG-rich fraction. According to their respective functions, each of these fractions can be further developed.

The production and consumption of fruit brandy (rakija) in Bosnia and Herzegovina has a long tradition. The imperative of every brandy producer is to have a quality product that is appealing to the consumer. The aim of our work was to examine the content of C8-C22 fatty acid esters in three samples of domestic fruit brandy (labeled Sample I, II and III). Samples I and II were made from pear, while sample III was from plum. After liquid-liquid extraction, using the solvent system hexane and diethyl ether (1:1), analysis of fatty acid esters was performed using the GC/MS method (gas chromatography with a mass detector). In Sample I and Sample II, eleven C8-C22 fatty acids esters were detected, while in Sample III, eight esters were detected. In Sample I and Sample II, the following fatty acid esters have been identified: Ethyl benzoate, Ethyl octanoate, Ethyl nonanoate, Ethyl decanoate, Ethyl undecanoate, Ethyl dodecanoate, Ethyl tridecanoate, Ethyl tetradecanoate, Ethyl pentadecanoate, Ethyl hexadecanoate, Ethyl eicosanoate. In Sample III the following fatty acid esters have been identified: Ethyl hexanoate, Ethyl benzoate, Ethyl octanoate, Ethyl nonanoate, Ethyl decanoate, Ethyl undecanoate, Ethyl dodecanoate, Ethyl tridecanoate. In all three Samples Ethyl decanoate and Ethyl undecanoate had the highest percentage, which reached up to 11% of the total percentage of detected compounds. As our results show, the developed methodology is effective for the identification of C8-C22 fatty acid esters in fruit brandies, and its further development is needed to be a tool for the quality determination of fruit brandies.

Biogenic waste from waste treatment plants, secondary waste, can be used to produce bio-based carboxylic acids, conventionally produced by chemical synthesis from petroleum-based feedstocks or by synthesis from natural oils. The cascading use of organic residues and wastes to produce bio-based products can contribute to the circular bioeconomy. In the process of biologically treating waste to produce bio-based carboxylic acids, microorganisms already present in the secondary waste use ethanol to convert short-chain into medium-chain carboxylic acids. The medium-chain carboxylic acids were separated from the secondary waste using in-situ extraction (liquid-liquid extraction). In previous studies, laboratory-scale bioreactors without a dispersing function were used. To optimise production and extraction of medium-chain carboxylic acids, the bioreactors were equipped with a device to disperse the extraction solvent in the secondary waste. By increasing the surface area between the phases, the ability to extract the medium-chain carboxylic acids was improved. The study aimed to evaluate the impact of this dispersing process. Production and extraction rates of static bioreactors without dispersing were compared to those of dynamic bioreactors with dispersing on a laboratory scale, using leachate from a composting plant as secondary waste. The results confirmed that dispersion has a positive effect on the process. Dispersing increased the reduction of the nutrient ethanol, the production of medium-chain carboxylic acids in the secondary waste and the extracted medium-chain carboxylic acids.

Introduction: A sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for estimation of bedaquiline (BDQ) in human plasma using the deuterated analogue of the analyte, bedaquiline-d6 (BDQ-d6) as the internal standard. Methods: The plasma sample of 50 µL was extracted by liquid–liquid extraction using methyl tertiary butyl ether (MTBE). The separation was achieved on Zodiac C18 (50 x 4.6 mm, 5 µm) column with a mobile phase consisting of methanol and 5 mM ammonium formate in 0.1 % formic acid (w/v) (90:10, v/v) at a flow rate of 1.0 mL/min. Protonated analyte and internal standard were detected on a triple quadrupole mass spectrometer using multiple reaction monitoring (MRM) mode. Results: The linearity of the method was established in the concentration range of 5–––1800 ng/mL with correlation coefficient, r2 ≥ 0.99. All the validated parameters were found well within the limits. Discussion: The method was applied for the first time to evaluate the pharmacokinetic parameters after single oral dose of BDQ 100 mg under fed conditions in healthy human volunteers, and the results were further authenticated by incurred sample reanalysis.

The removal of nitrogen compounds from fuel via the conventional method, which is hydrodenitrogenation, is costly and involves catalysts and energy-intensive conditions (600 K and 300 atm). Recently, ionic liquids (ILs) have emerged as a promising alternative solvent for the denitrogenation of fuel oil. However, certain ILs are expensive and challenging to synthesize, prompting the exploration of protic ionic liquid (PIL) substitutes, which offer similar advantages to ILs. This study utilized the conductor-like screening model for real solvents (COSMO-RS) to predict the phase equilibria for three PILs—triethylammonium p-toluenesulfonate (TEA-TSA), triethylammonium salicylate (TEA-SA) and triethylammonium benzoate (TEA-BZ)—which were subsequently validated through experimental investigations. Liquid–liquid extraction experiments were conducted at 298 K and 1 atm, with pyrrole (serving as the model nitrogen compound) concentrations in n-hexadecane (representing the model fuel) ranging from 10 to 50 wt%. Additionally, the NRTL model effectively correlated the experimental tie lines. The obtained data indicated that TEA-TSA exhibited superior selectivity and distribution ratio compared to TEA-SA and TEA-BZ. All the ternary systems tested displayed positive slopes, suggesting a higher affinity of nitrogen compounds for the PIL. Supporting this observation, interaction energy (ΔE) and excess enthalpy (HE) were employed. The predicted outcomes revealed that TEA-TSA had high ΔE, and all PILs exhibited negative values of HE. The HE calculation underscored the significance of strong hydrogen bond interactions between pyrrole and the PIL for successful extraction.

Thorium is a radionuclide used in various environmental studies such as dating, sediment movement, soil–plant transfer studies, and contamination of waste from the natural fuel cycle. The liquid–liquid extraction method using tri-n-butyl phosphate (TBP) allows for the separation of Th from the accompanying actinides. However, the separation of Th and U present in the same sample is not trivial. This separation is influenced by the starting acid (HCl or HNO3), the concentration of TBP in an organic solvent, and the concentration of the acid used for re-extracting Th, which is typically HCl. Therefore, it is necessary to study these factors to ensure that the method has sufficient chemical yield and selectivity in complex matrices. This study presents a systematic investigation of the aforementioned parameters, making the necessary variations to select an optimal method for the radiochemical separation of Th. The ideal conditions were obtained using 4 M HCl as the acid prior to extraction, a 1:4 solution of TBP in xylene, and 4 M HCl as the re-extracting agent. The accuracy and precision were studied in four intercomparison exercises conducted in quadruplicate, using the parameters Enumbers, RB(%), and RSD(%) for 232Th and 230Th. The sensitivity of the method was experimentally studied and the limit of detection (LoD) was determined according to ISO 11929:2005. Additionally, the linearity of the method showed that the experimental and theoretical activity concentrations of 232Th and 230Th had slopes of 1 with an intercept close to 0.

This study investigates the unexpected formation of ketoprofen methyl ester (KME) during the routine alkaline liquid–liquid extraction (LLE) process for analyzing basic drugs in horse urine samples using GC–MS analysis. An unidentified peak in the GC–MS chromatogram was observed in certain horse urine samples, identified as KME through mass spectral comparison with in situ synthesized KME. Since the KME is not a metabolite of ketoprofen present in urine, it is proposed that its formation occurs during the LLE process due to the reaction between ketoprofen contained in the urine and methanol used as the solvent of the spiked internal standard. Surprisingly, no artifact was detected when negative quality control horse urine samples (absence of ketoprofen) even when spiked with standard ketoprofen and methanol. Further investigation indicated that the presence of lipase enzymes from bacteria in specific urine samples is the key factor in the formation of the KME artifact. This hypothesis was confirmed when negative quality control horse urines were spiked with ketoprofen, methanol, and a lipase enzyme and the KME artifact was detected. Additionally, the formation of a methyl ester artifact was also detected for flunixin, a carboxylic acid NSAID drug, when negative quality control horse urines were spiked with the drug, methanol, and lipase enzyme. These findings will be valuable for scientists analyzing drugs in urine.

A liquid–liquid extraction pretreatment method using n-hexane as the extractant was developed for the analysis of volatile aroma substances in three flavors (six cola samples, six lemon samples, and six orange samples) of carbonated beverages by gas chromatography–mass spectrometry (GC-MS). Quantitative analysis was conducted using the external standard method. The spiked recovery rate of α-terpineol was used as the evaluation criterion. Single-factor and response surface experiments were conducted to investigate the effects of extraction temperature, extraction time, and solvent-to-sample ratio. The results indicated that the maximum spiked recovery rate of α-terpineol, 81.00%, was achieved at an extraction temperature of 45 °C, extraction time of 30 min, and a solvent-to-sample ratio of 1 mL:15 mL. Thirty-four components were identified by GC-MS on the pretreated samples via the internal standard method. 1,4-Cineole, fenchyl alcohol, borneol, and α-terpineol are covered aroma substances in cola beverages. Two aromatic substances, D-limonene and α-terpineol, were detected in orange juices. α-Terpineol was detected in each lemon-flavor carbonated beverage sample. Going a step further, α-terpineol was detected in all 18 carbonated beverage samples and had high response values. The principal component analysis by functional group classification led to the conclusion that acids, phenols, hydrocarbons, alcohols, and ethers played a major contribution to the aroma of these 18 beverages. Increased separation of target compounds was found using the new pre-treatment methods, resulting in improved analytical resolution and selectivity.

Oxygenated compounds such as acids in bio-oils (BO) have been related to the corrosion of metals and their storage instability when applied as fuels. Therefore, upgrading BO by removing acids (deacidification) can be a valuable technique to reduce corrosivity using specific separation processes. Therefore, the objective of this paper was to evaluate the effect of the water content in the solvent (aqueous methanol), the carboxylic acid content in the BO and extraction temperature on the deacidification process by liquid–liquid extraction (LLE), as well as the effect of the same parameters on the quality of the deacidified BO through physical–chemical and GC-MS analyses. The results show that an increase in the water content (5 to 25%) in the solvent and an increase in the carboxylic acids content (24.38 to 51.56 mg KOH/g) in the BO reduce the solvent’s capacity to extract carboxylic acids while increasing the temperature (25 to 35 °C) of the deacidification process promoted an increase in its capacity to remove them. Consequently, the highest deacidification efficiency (72.65%) is achieved with 5% water in methanol at 25 °C for BO1 (TAN = 24.38 mg KOH/g). Therefore, the deacidification process through LLE using aqueous methanol contributed significantly to BO upgrading.

A separation process by liquid-liquid extraction is a well-known and widespread industrial technology implemented to quantitatively recover valuable chemical elements. In the nuclear industry, such processes have been used for decades to recover uranium and plutonium from spent fuel. The process is non-linear and time constants vary over a wide range. Former studies on a simplified model showed linear controllers such as PID were not adapted to regulate these separation processes. The objective of this study is to propose process monitoring by using available physical models within the PAREX code and to validate the feasibility to monitor a separation process by using directly the PAREX code as a black box. The Predictive Functional Control (PFC) command law manages to monitor non-linear separation processes by liquid-liquid extraction, when using an existing physical model implemented in the PAREX code. An online alignment of the model on process values is necessary to keep the model sufficiently representative to predict the future behaviour of the process. As a reference benchmark, the PID control loop is also simulated with the physical model. The PFC and PID regulations are compared to evaluate the gain of using physical models implemented in the PAREX code. A simulation tool has been developed to implement the PID and Predictive Functional Control (PFC) controllers for separation processes by liquid-liquid extraction. The PFC command law manages to monitor non-linear separation processes, when using a physical model connected to the PAREX code. Even if the PID controller may be locally more efficient, the great strength of the PFC controller is to enable good performances on wider operating conditions, with an easier parametrization. The PFC algorithm is a mean to deal with the process characteristic features, like non-linearity and time constant change. The PFC controller appears to be a good candidate for experimental tests. A mid-term objective is to include the state estimator tool in the control loop to consolidate the controlled variable measurements. These developments may be regarded as an add-on module in a digital factory concept. Results shown in this article are only from simulation. For the sake of data confidentiality, studies with the PAREX code cannot be published and numerical parameters of the process are normalized. These simulations will be validated during further experimental tests.

This work presents the purification of petroleum condensate by removing arsenic ions via liquid-liquid extraction (LLE). Influence of pure and synergistic extractants is investigated. In terms of the practicability, following parameters are examined: the type of extractant, operating time, and temperature. Response surface methodology is used to design parameters such as organic-aqueous ratio and extractant concentration. Under optimal conditions; a mixture of 1 mol/L HCl and 0.02 mol/L thiourea with an organic/aqueous ratio of 1:4 at 323.15 K for 60 min, the extraction of arsenic reached 78.2 %. Further, batch simulation via two-stage counter-current extraction, and estimation by McCabe-Thiele diagram proved to be enhanced arsenic extraction to 95.3 %. Analysis by FTIR show that arsenic ions in petroleum condensate are formed as triphenylarsine compound ((C6H5)3As). The process of arsenic removal proved to be zero-order endothermic, irreversible and spontaneous reaction. The results obtained from the density functional theory (DFT) confirm that arsenic ions react with the synergistic extractant: effectively forming a covalent bond (As–S).

The objective of the method is to allow agitation and fast homogenization of liquid systems in NMR tubes, directly inside the NMR spectrometer. The setup makes it possible to record spectra of samples that are macroscopically not stable, as dispersions of large particles. It makes also possible to fasten the homogeneization of liquid during a reaction or a phase transition. In the present paper, the method has been evaluated using homogeneous liquid extraction (HLLE). This configuration can also be used to introduce gases in different systems to perform various types of experiments. The set up consists in a Teflon tube inserted in the NMR tube bringing gas that yields agitation by bubbling. The gas flow is tuned using an electronically operated valve connected to gas line and to the NMR console. The method details how to reach proper homogenization without any perturbation, as liquid leaks. • An easy method for agitation of liquids inside NMR spectrometers. • The set up can be used for the insertion of gases in the NMR tube inside the spectrometer. • The method allows the study of the mixing of biphasic systems by NMR techniques.

Plant growth regulators (PGRs) are defined as naturally occurring or artificially synthesized compounds. The functions of PGRs mainly include accelerating or delaying seed germination, breaking plant dormancy, stimulating or reducing bud elongation, inducing flowering and fruiting, and affecting the aging process. The application of PGRs has effectively promoted the growth of plants. However, the application concentration of PGRs is more than one millionth. The large amount of abuse and misuse of PGRs in the process of use not only reduces the yield of crops, but also exacerbates their residues in the environment, especially in agricultural products such as fruits and vegetables. So, they are detected in many environmental media like fruits, vegetables, and water. In addition, most PGRs are toxic, and some of them will undergo adsorption, desorption, hydrolysis, photolysis, microbial degradation, and other environmental behaviors after entering the soil. The decomposition products produced by this process are more toxic.In order to comprehensively understand the current status of PGRs pretreatment, analysis and test method, the common pretreatment methods of solid phase extraction and liquid-liquid extraction for typical PGRs in solid substrates such as fruits and vegetables, fertilizers and soil, and in liquid substrates such as water, edible oil and nutrient solution are summarized in this paper, as well as the analysis and testing techniques such as high-performance liquid chromatography (HPLC) and ultra-high performance liquid chromatography (UPLC). Moreover, to reduce the detection limit, high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) is also frequently used. At the same time, considering the strong natural attenuation ability of PGRs and the high toxicity of their intermediates, the advantages, disadvantages and applicability of different testing techniques are systematically summarized, taking into account the special structure and nature of PGRs, in order to fully understand the current status of pretreatment and analytical testing of PGRs and provide literature support for subsequent research on analytical testing, migration transformation, pollution evaluation and treatment of PGRs.Due to many impurities in the sample that can interfere with the detection, the appropriate pretreatment method can improve the accuracy of the test results. However, the sample pretreatment process accounts for more than 70% of the total analysis and test work, and about 50% of the error in the final test results comes from pretreatment. Therefore, establishing a fast, simple, and stable pretreatment method can effectively improve the efficiency and accuracy of analysis and detection. At present, the forms of environmental media detected for PGRs are mainly divided into two types: solid matrix samples (such as fruits, vegetables, fertilizers and soil, etc.) and liquid matrix samples (water, oil and nutrient solution, etc.). The related pretreatment methods are also mostly targeted at these two different forms of environmental media.Solid substrates involving PGRs mainly include fruits and vegetables, fertilizers and soil. Among them, fruits and vegetables are the most frequently detected solid substrates of PGRs, and some PGRs have also been detected in fertilizers, soil and other substrates. The pretreatment process of solid matrix samples can be divided into two parts: extraction and purification. Among them, solid phase extraction is the most commonly used extraction technology, and QuEChERS method is the most widely used purification method.Water, edible oil, and nutrient solution are the most frequently detected liquid substrates of PGRs. At present, liquid-liquid extraction is the most commonly used extraction method for liquid matrix. For the selection of extractants, the octanol-water partition coefficient of PGRs such as gibberellic acid and ethephon is less than 1, which is a strong polar compound and can be extracted by hydrophilic organic solvents such as methanol, ethanol and acetone; the polarity of most other PGRs such as forchlorfenuron and paclobutrazol is relatively weak, but it still belongs to the category of strong polarity compared with other kinds of compounds such as benzene and chloroethane (n-octanol-water partition coefficient>10). Therefore, the extractant can not only use methanol, but also use polar organic solvents such as ethyl acetate and chloroform that are insoluble in water. Although liquid-liquid extraction requires a lot of extractants, the high-water solubility of most PGRs makes them often directly detected by HPLC-MS/MS, which eliminates the complex pretreatment steps such as extraction and purification. In addition, because some PGRs have poor chromatographic characteristics or are not easily detected, the derivatization is also required to convert the components into derivatives suitable for analysis.Analytical and testing technologies mainly include gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), HPLC/UPLC, HPLC-MS/MS, ion chromatography (IC), spectrophotometry (SP), capillary electrophoresis (CE), enzyme-linked immunosorbent assay (ELISA) and electrochemical sensor method.At present, the solubility of most PGRs in water (20℃) is 0.50-10g/L, and the octanol-water partition coefficient of most PGRs is 0-4, with strong hydrophilicity. Therefore, HPLC-MS/MS are applicable to the detection of almost all PGRs. However, HPLC-MS/MS are often used to detect the residues of PGRs in fruits and vegetables, followed by soil and fertilizer, while there are few related studies in natural water. This may be due to the rapid natural decay rate of PGRs in the natural environment, resulting in extremely small amounts of residues in natural water bodies such as surface water and groundwater that cannot be directly detected.GC has the advantages of low cost and easy maintenance, and GC-MS has become a conventional testing technology. However, GC-MS are greatly affected by sample matrix interference and require high pretreatment methods. In addition, due to the influence of the physical and chemical properties of different PGRs (such as abscisic acid and indole acetic acid with a boiling point over 400℃, or forchlorfenuron and cinnamic acid with hydroxyl and carboxyl groups), most PGRs have poor gas chromatographic characteristics and are not easily detected.The order of detection limits of PGRs is GC>HPLC>chromatography-mass spectrometry, and the lowest instrumental detection limit of chromatography-mass spectrometry is 10-5mg/kg. However, the higher solubility and the larger natural attenuation rate of most PGRs lead to the lower detection concentrations in complex environmental substrates such as soil and water, so there is still an urgent need to solve the problem of analytical testing of trace PGRs and its intermediates.In future, PGRs analysis and test method will focus on the analysis and detection of trace PGRs and their intermediates, as well as the development of new materials and technology-based methodologies.

BACKGROUND Hexabromocyclododecanes (HBCDs) have been identified as organic pollutants with the properties of persistence, long-distance migration, bioaccumulation, and biological toxicity. HBCDs have been detected in all kinds of biological and abiotic samples around the world, and have adverse effects on the environment and human body. As a non-invasive biological sample, human milk is a good medium for evaluating the exposure of HBCDs in the human body, and is widely used in the study of the exposure level of HBCDs in various countries, especially in nursing infants and young children. According to the survey, the production and use of HBCDs in Beijing has continued to rise since the use and production restriction of HBCDs in 2016, and the total use of HBCDs in 2019 increased by 60.8% compared with 2018. Therefore, in recent years in Beijing, especially before and after the use and production restriction of HBCDs, the residual characteristics and change trend of HBCDs in breast milk have attracted much attention. OBJECTIVES To investigate the residual characteristics and trends of HBCDs in breast milk in Beijing from 2010 to 2018, evaluate the health risks for infants to intake HBCDs via breastfeeding, and provide basic data support for the scientific use, management, control, and human exposure risk assessment of HBCDs. METHODS Breast milk samples (n=233) were obtained from 85 volunteer donors living in Beijing from 2010 to 2018. All volunteers have been living in Beijing for more than 5 years, are healthy, and do not directly engage in HBCDs production, processing, and other related occupations. Each sample was about 30mL, which was manually collected by volunteers into a 30mL clean glass bottle with a Teflon lined screw cap, and then transferred to a laboratory refrigerator for cryopreservation at -20℃. All volunteers were informed of the objective of this study. Pretreatment was conducted by liquid-liquid extraction and ammonia, ethanol, ether and n-hexane were added in turn. After liquid-liquid extraction, concentrated sulfuric acid sulfonation was combined with solid phase extraction (SPE) to purify the samples. Finally, 200μL methanol was added for constant volume. After centrifugation, the upper layer solution was transferred to a brown sample bottle (including lined tube) for storage. The qualitative and quantitative analysis of HBCDs was performed by Waters UPLC CLASS ultra-high performance liquid phase tandem API 4000 triple quadrupole mass spectrometry(LC-MS/MS). The isotope internal standard method was used for quantitative analysis to reduce the matrix effect. RESULTS The detection rate of HBCDs in breast milk was 100%, indicating that HBCDs have been widespread in the human body. The concentration range of HBCDs was 0.46-93.5ng/g lw (lipid weight), with the average and median values of 7.27ng/g lw and 5.77ng/g lw, respectively. The 95th percentile of high-end exposure was 15.6ng/g lw. There were individual differences in the milk samples. The detection rates of α, β and γ-HBCD in all breast milk samples were 100%, 35.6% and 70.8%, respectively. α-HBCD had the most abundant diastereomers in breast milk samples, accounting for 80.1%, followed by γ-HBCD and β-HBCD in order. There were also a small number of breast milk samples that were dominated by γ-HBCD, accounting for 52.2%-83.5%. Even samples taken by the same volunteer in different months had different major diastereomers. The median EDI of HBCDs via human milk for infant was 20.5ng/kg bw/day, and the 95th percentile value was 71.4ng/kg bw/day, which was comparable to the previous research in Beijing, but higher than Japan, Ghana and other cities in China. CONCLUSIONS Compared with the HBCDs in breast milk from other regions at home and abroad, the level of HBCDs in breast milk in this study is close to the previous research data in Beijing, but higher than that of Shanghai, Shenzhen and other cities in China, as well as higher than the results of recent studies in Japan, the United Kingdom, the United States, Canada, India, the Philippines and some African countries, which may be related to the continuous use of HBCDs in China and the large amount of use. In human breast milk, α-HBCD is the main diastereomers, while in a small number of samples, γ-HBCD is the main diastereomers. The differences in the distribution characteristics of these diastereomers may be due to the differences in the absorption, metabolism and excretion mechanisms among individuals, and the transformation of HBCDs among different isomers in vivo, and the differences in the main external exposure pathways. The level of HBCDs showed an obvious upward trend from 2010 to 2013, reached the highest value of 6.84ng/g lw in 2013, and then decreased slightly and remained constant, which may be related to the production, use and prohibition of HBCDs globally and domestically. The time trend of α-HBCD and HBCDs is basically the same, while the content of β-HBCD and γ-HBCD in breast milk is low, and the change trend is stable with time. The concentration of HBCDs in breast milk changed slowly from 2014 to 2018 but did not show a significant downward trend after the initial ban of HBCDs in China in 2016, which may indicate that there are still a large number of HBCDs in production and use on the market, and human intake of HBCDs through air, dust, diet and other ways does not decrease. The risk assessment results indicate that the Hazard Quotient (HQ) of 99% breast milk samples is less than 1, which indicates that the intake of HBCDs through breast-feeding during lactation would not bring significant health risk to infants, but the HQ value of 1% breast milk samples is greater than 1, which suggests that breastfeeding may bring health risks to infants. More research is needed to further investigate the major sources of exposure and the effect of each potential factor.

Centrifugal contactors (CCs) are a technology candidate for the development of advanced reprocessing flowsheets. While they offer many advantages, such as process intensification, there are still uncertainties regarding their industrial deployment. The presence of particles in the process streams in particular may present a challenge to both performance and operability. Preliminary studies have been undertaken to evaluate the accumulation of particles in the contactors and the effect upon the extraction behaviour of nitric acid. Aluminium oxide (Al2O3) particles were suspended in the aqueous feed solution during the operation of a three-stage, 40 mm diameter CC cascade. The presence of insoluble solid particles in the aqueous feed, up to 7 g/L, were not observed to affect phase separation and entrainment under the experimental conditions investigated. The particles were centrifuged out of solution and accumulated as a thin cake/bed in the rotors of each stage. This work also illustrates that particles do entrain through the cascade. The predominant effect on the rate of accumulation was particle concentration in the aqueous feed solution, and increasing solids loading was observed to have an impact upon the extraction of nitric acid across the cascade.

Though nowadays germanium does not reach the range of popularity of other metals, i.e., rare earth elements, its utility in target industries makes it a strategic metal. Though germanium can be found in a series of raw materials, the principal source for its recovery is from secondary wastes of the zinc industry; also, the recyclability of germanium-bearing waste materials is becoming of interest. In this recovery and due to the size of the target materials, because the diffusion and reaction are to be considered, hydrometallurgy performs a key role in achieving this goal. The present work reviews the most recent applications (2023 and 2024 years) of hydrometallurgical operations on the recovery of germanium from different solid and liquid sources.

A study of the liquid–liquid extraction of ReO4− anions from hydrochloric acid solutions using the ionic liquid Aliquat 336 (QCl: trialkyl(C8–C10)methylammonium chloride) via the well-known method of slope analysis along with the determination of the process parameters is presented. This study employs CCl4, CHCl3 and C6H12 as diluents. This study was carried out at room temperature (22 ± 2) °C and an aqueous/organic volumetric ratio of unity. The ligand effect on the complexation properties of ReO4− is quantitatively assessed in different organic media. The organic extract in chloroform media is examined through 1H, 13C and 15N NMR analysis as well as the HRMS technique and UV-Vis spectroscopy in order to view the anion exchange and ligand coordination in the organic phase solution. Final conclusions are given highlighting the role of the molecular diluent in complexation processes and selectivity involving ionic liquid ligands and various metal s-, p-, d- and f-cations. ReO4− ions have shown one of the best solvent extraction behaviors compared to other ions. For instance, the Aliquat 336 derivative bearing Cl− functions shows strongly enhanced extraction as well as pronounced separation abilities towards ReO4−.

Solvents prepared from natural terpenes (menthol and thymol), as H-bond acceptors, and a series of organic acids (chain lengths of 8, 10, and 14 C atoms), as H-bond donors, were characterized and tested as reaction media for liquid–liquid extraction purposes. Due to their high hydrophobicity, they seem to be promising alternatives to conventional (nonpolar and toxic) solvents, since they possess relatively less toxic, less volatile, and consequently, more environmentally friendly characteristics. Assuming that the equilibrium is established between solvent and analyte during a ligandless procedure, it can be concluded that those nonpolar solvents can efficiently extract nonpolar analytes from the aqueous environment. Previous investigations showed a wide range of applications, including their use as solvents in extractions of metal cations, small molecules, and bioactive compounds for food and pharmaceutical applications. In this work, hydrophobic solvents based on natural terpenes, which showed chemical stability and desirable physicochemical and thermal properties, were chosen as potential reaction media in the liquid–liquid extraction (LLE) procedure for Pb(II) removal from aqueous solutions. Low viscosities and high hydrophobicities of prepared solvents were confirmed as desirable properties for their application. Extraction parameters were optimized, and chosen solvents were applied. The results showed satisfactory extraction efficiencies in simple and fast procedures, followed by low solvent consumption. The best results (98%) were obtained by the thymol-based solvent, thymol–decanoic acid (Thy-DecA) 1:1, followed by L-menthol-based solvents: menthol–octanoic acid (Men-OctA) 1:1 with 97% and menthol–decanoic acid (Men-DecA) 1:1 with 94.3% efficiency.

An ultra-performance liquid chromatography with photodiode array (UPLC-PDA) UV detection method was developed here for the first time for simple, rapid, selective and sensitive quantification of the commonly prescribed selective cyclooxygenase-2 (COX-2) inhibitor etoricoxib in low plasma volumes (50 μL). The method includes protein precipitation followed by liquid–liquid extraction, evaporation and reconstitution. A gradient mobile phase of 75:25 going to 55:45 (v/v) water:acetonitrile (1 mL/min flow rate) was applied. Total run time was 8 min, representing a significant improvement relative to previous reports. Excellent linearity (r2 = 1) was obtained over a wide (0.1–12 µg/mL) etoricoxib concentration range. Short retention times for etoricoxib (4.9 min) and the internal standard trazodone (6.4 min), as well as high stability, recovery, accuracy, precision and reproducibility, and low etoricoxib LOD (20 ng/mL) and LOQ (100 ng/mL), were achieved. Finally, the method was successfully applied to a pharmacokinetic study (single 20 mg/kg orally administered etoricoxib mini-capsule) in rats. In conclusion, the advantages demonstrated in this work make this analytical method both time- and cost-efficient for drug monitoring in pre-clinical/clinical settings.

We summarize advances in lithium recognition receptors, focusing on their use as active reagents in circular processes such as liquid–liquid extraction, an established industrial process that is advantageous due to its large processing capacity and high selectivity. High-performance systems are required, given the increasing demand for effective separation processes for the recovery of valuable substances from spent lithium-ion batteries or the exploration of brines. Hence, the availability of powerful and highly selective receptors is particularly crucial. This mini-review summarizes the development of active receptors for lithium ion extraction and covers advances in receptors for both lithium ions and lithium salts. It discusses various receptor types, ranging from heteroditopic macrocyclic systems to simple β-diketones. The latter achieve particularly high lithium ion extraction yields in the presence of phosphine oxides such as trioctylphosphine oxide. Structural studies employing 4-phosphorylpyrazolone exhibited diverse coordination modes of lithium and represent clear evidence for the synergistic role of the co-ligand on a molecular level.

Accurate models for pulsed sieve tray extraction columns (PSEs) depend on the correct prediction of the drop diameter to estimate extractive mass transfer across the phase boundary. Phenomenologically, the drop diameter is determined by a balance of drop breakage and coalescence. While for most industrial solvent systems, coalescence plays a minor role; breakage is mostly the dominant phenomenon determining the drop diameter. However, most modeling approaches for drop breakage in PSEs are characterized by a trade-off between a broad validity range and good prediction accuracy. To overcome this limitation, we developed a hybrid breakage model for drop breakage in PSEs in which a physical-empirical model basis is enhanced by data-driven parameter estimator models (PEMs). The hybrid model is based on a revised form of Garthe’s breakage model, for which we developed a linear PEM for the model parameters and two data-driven PEMs for dstab and d100, respectively. The hybrid breakage model was validated on 743 experimental data sets and evaluated based on the pull metric. In a sensitivity analysis, the model correctly predicted the breakage probability over a wide range of solvent properties, operating conditions, and sieve tray geometries. In future studies, the hybrid breakage model can be incorporated into extraction column models without an initial parametrization.

Nitrite has been determined using a simple and sensitive spectrophotometric method. The suggested procedure is based on the diazotization reaction of p-bromoaniline in the presence of nitrite ion in a hydrochloric acid media, which produces diazonium salt. This salt is then combined with paracetamol in an ammonium hydroxide medium to produce an orange azo color with a maximum wavelength (λ max.) of 460 nm, molar absorptivity (ε) is 3.8432 x 103 L. mol-l.cm-1, and Beer’s law was established between 0.3-12.0 µg. mL-1. It displays LOD, LOQ, and R2 values of 0.2 µg. mL-1, 0.3 µg. mL-1, and 0.9994 respectively. The dye can be extracted into chloroform. The yellow chloroform extract displays a maximum wavelength (λ max.) of 410 nm, molar absorptivity (ε) is 9.93 x103 L. mol-l.cm-1, and Beer’s law was observed between 0.1-5.0 µg. mL-1. The LOD, LOQ, and R2 values for the suggested extraction procedure were 0.05 µg. mL-1, 0.1 µg. mL-1, and 0.9996, respectively. The suggested method was successfully applied on samples of a human saliva.

Dispersive liquid-liquid microextraction (DLLME) is a novel sample-preparation technique that provides high enrichment factors from the low volume of aqueous samples. This method has gained wide acceptance due to several advantages, including being inexpensive, fast, easy to develop, easy to operate with a high enrichment factor, and consuming low volume of organic solvent, which has made it available to almost all analytical laboratories. This review focuses on the improvements that have been made in the DLLME since its introduction in 2006. In this study, the use of DLLME with simultaneous derivatization of analytes, the combination of DLLME with other sample preparation techniques, and the replacement of toxic chlorinated solvents with low toxicity hydrocarbons, alcohols, and ionic liquids were described. Moreover, this paper seeks to describe the use of DLLME to pre-concentrate metal ions and further modifications of this newly developed technique. It briefly describes the various applications of DLLME for several groups of analytes, including pesticides, drugs, phenols, and other compounds, and finally, some limitations and future trends are anticipated.

Pheromones are the secreted or excreted chemical factor that triggers a social response in members of the same species. Pheromones are chemicals capable of acting outside the body of the secreting individual to impact the behavior of the receiving individual. Terrestrial snails are one of the major pests that cause significant damage to crops. These snails use volatile pheromones to communicate with each other, thereby exchanging various messages between members of their species. Pheromones are able to stimulate message recipients outside the body that produces the message and influence their behavior. Herein, the volatile pheromones that play a major role in the communication between snails of a particular species were investigated. To this end, the pheromones were extracted using liquid phase extraction technique and identified by gas chromatography-mass spectrometry instrument (GC-MS). First, a specific species of the snails were selected, the samples were collected and the pheromones were evaluated. Finally, by comparing the obtained peaks with the reference peaks related to pheromones, the pheromones were identified. The extraction was performed using LLE. The identification was also performed using GC-MS. The results indicated that 2-(3,4-Dimethoxyphenyl)-2-methoxy-N,N-dimethylethanamine, 3,4-Octadiene, 7-methyl-, 2-Pentadecanone- 6,10,14-trimethyl، 4-Hexadecen-6-yne, (E)-، Dimethyl aminomethyl (triethyl) stannane, desmosterol, 2,3-dihydroxypropyl ester, 3,4-Octadiene, 7- methyl- and 4-Methyl-2,5-dimethoxybenzaldehyde are the responsible pheromones. The present study is an experimental study in which the volatile pheromones that play a role in the communication between snails of a particular species were investigated. As a result, the identified pheromones can be used to make pheromone traps.

Separation of aromatics from non-aromatic hydrocarbons was exemplified assuming the liquid-phase extraction process for methylcyclohexane−toluene model mixture separation using the newly tested 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMim][NTf2]) ionic liquid (IL). For this process a separation unit was proposed consisting of separation part represented by a counter-current extraction column and regeneration part including a vacuum evaporator and a vacuum distillation column. Separation of feed composed of 10 mole% of toluene in methylcyclohexane was considered in the designed separation unit. Designed separation efficiency of the unit was based on the following specifications: minimum methylcyclohexane and toluene content in the product streams of 99.5 mole% and the purity of regenerated extraction solvent recycled to the extraction column above 99 mole%.Mathematical model of a counter-current extractor was compiled and its operation was simulated in the Matlab environment. In extractor simulations, proprietary phase equilibrium data were employed. Ternary liquid–liquid equilibrium (LLE) of the methylcyclohexane−toluene−[EMim][NTf2] system was estimated experimentally, from which the model parameters of the original NRTL equation were evauated and used for the ternary phase equilibrium description.Aspen Plus was used to design a separation unit for the title hydrocarbons mixture separation, including the extraction solvent regeneration. Simulation of the proposed separation unit operation was focused not only on its separation efficiency but also on the evaluation of the unit energetic requirements.Results of the unit design calculations (parameters of individual equipment, heat duties) obtained for the tested ionic liquid [EMim][NTf2] were confronted with the simulation results obtained for two ILs recommended in the literature for the non-aromatic–aromatic hydrocarbon mixture separation, namely 1‑butyl‑3-methylimidazolium tetracyanoborate [BMim][TCB] and 1-hexyl-3-methylimidazolium tetracyanoborate [HMim][TCB]. Based on the energetic analysis, the heat integration of the suggested separation unit was carried out for ionic liquid [HMim][TCB], which appeared to be the most efficient extraction solvent among those tested in this study, The heat integration resulted in about 71% reduction of the heat demand of the proposed separation unit.

The misuse of growth-promoting drugs such as beta-2 agonists and steroids is a known problem in farming and sports competitions. Prior to the analysis of biological samples via liquid chromatography (LC)–mass spectrometry (MS) or gas chromatography (GC)–MS, sufficient sample preparation is required to reliably identify or determine the residues of drugs. In practice, broad screening methods are often used to save time and analyze as many compounds as possible. This review was conceptualized to analyze the literature from 2018 until October 2023 for sample preparation procedures applied to animal specimens before LC- or GC-MS analysis. The animals were either used in farming or sports. In the present review, solid phase extraction (SPE) was observed as the dominant sample clean-up technique for beta-2 agonists and steroids, followed by protein precipitation. For the extraction of beta-2 agonists, mixed-mode cation exchanger-based SPE phases were preferably applied, while for the steroids, various types of SPE materials were reported. Furthermore, dispersive SPE-based QuEChERs were utilized. Combinatory use of SPE and liquid–liquid extraction (LLE) was observed to cover further drug classes in addition to beta-2 agonists in broader screening methods.

The conventional hydrodenitrogenation method is expensive and involves the use of catalysts and harsh procedures. In the last few years, ionic liquids (ILs) have gained attention as a promising alternative solvent for fuel oil extractive denitrogenation. In this work, the Conductor-like Screening Model for Real Solvents (COSMO-RS) was used to screen 173 potential ILs as solvents for fuel oil. Two ILs (1-ethyl-3-methylimidazolium dicyanamide ([EMIM][N(CN)2]) and 1-ethyl-3-methylimidazolium methanesulfonate ([EMIM][MeSO3])) were selected for experimental investigation. The experimental liquid–liquid extraction of pyrrole (taken as the model nitrogen compound) from n-hexadecane (the model fuel) was conducted at 298 K and 1 atm with feed concentrations of pyrrole ranging from 10 to 50 wt%, using either the two pure ILs or their mixtures with dimethylformamide or ethylene glycol. Moreover, the NRTL model was effectively used to correlate the experimental tie lines. This work shows that the use of a binary mixture of ILs with a conventional solvent results in good selectivity, but has a low capacity for extracting pyrrole compounds. On the other hand, using an IL-IL mixture exhibits good results for both capacity and selectivity. All the ternary systems tested showed positive slopes, indicating that the nitrogen compounds had a higher affinity for the IL and binary mixture extract phase. In fact, the extraction efficiency for all the systems shows promising results. This characteristic is advantageous, as it requires less solvent to remove nitrogen compounds.

Due to their toxicity and persistence in the environment, phenolic pollutants pose a serious threat to the ecosystem. In this work, the performance of hydrophobic deep eutectic solvents (HDESs) for phenol removal from aqueous effluents is thoroughly investigated using COSMO-RS screening followed by experimental validation. The screening results of 73 HDESs showed that the efficacy of phenol removal is significantly affected by chain length, functional groups, and aromaticity. Trioctylphosphine oxide (TOPO)-based HDESs were found to be the most effective HDESs for phenol elimination combined either with menthol (Men), 1-hexanol (Hex), Decanoic acid (DecA), or Thymol (Thy) all in 1:1 molar ratios. The better phenol elimination abilities of the selected HDESs were confirmed by experimental LLE data obtained at 298.15 K and 101 kPa. In fact, it has been found that there is a positive correlation between extraction efficiency and phenol content. For instance, at a phenol concentration of 7%, TOPO:Men had the highest extraction efficiency (96%). Moreover, the physicochemical properties of the selected HDESs, such as density, viscosity, FTIR, 1HNMR, and TGA, were also measured. The results showed their high thermal stability and low water solubility, which makes them suitable for phenol extraction applications. This study shows that HDESs are capable of removing phenolic contaminants from aqueous effluents in a sustainable and efficient manner and that the selected TOPO-based HDESs are of particular interest for further research and application in phenol removal.

Polyphenols from residual non-food grade Salicornia ramosissima have health-promoting effects in feed, food, or nutraceutical applications. Therefore, the isolation of polyphenols is of interest from a series of environmentally friendly isolation methods with recyclable solvents. The isolation of polyphenols from non-food grade S. ramosissima was investigated using sequential membrane filtration with and without acid pretreatment, liquid–liquid extraction, resin adsorption, and centrifugal partition chromatography (CPC); analyzed by the Folin–Ciocalteu assay for total polyphenols; and finally analyzed using UPLC-TQMS in negative ion-spray mode for detection of 14 polyphenols. Sequential membrane filtration and acid hydrolysis indicated the polyphenols forming complexes with other compounds, retaining the polyphenols in the retentate fraction of large molecular weight cut-off membrane sizes. Conventional liquid–liquid extraction using sequential ethyl acetate and n-butanol showed most polyphenols were extracted, apart from chlorogenic acids, indicating a low isolation efficiency of higher polarity polyphenols. Analysis of the extract after resin adsorption by Amberlite XAD-4 resin showed high efficiency for separation, with 100% of polyphenols adsorbed to the resin after 13 bed volumes and 96.7% eluted from the resin using ethanol. CPC fractionations were performed to fractionate the concentrated extract after resin adsorption. CPC fractionations of the 14 polyphenols were performed using an organic or aqueous phase as a mobile phase. Depending on the mobile phase, different compounds were isolated in a high concentration. Using these easily scalable methods, it was possible to comprehensively study the polyphenols of interest from S. ramosissima and their isolation mechanics. This study will potentially lead the way for the large-scale isolation of polyphenols from S. ramosissima and other complex halophytes. The compounds of the highest concentration after CPC fractionation were isoquercitrin and hyperoside (155.27 mg/g), chlorogenic acid (85.54 mg/g), cryptochlorogenic acid (101.50 mg/g), and protocatechuic acid (398.67 mg/g), and further isolation using CPC could potentially yield novel polyphenol nutraceuticals.

Abstract Background Secondary metabolites have played a key role as starting points for drug development programs due to their often unique features compared with synthetically derived molecules. However, limitations related to the discovery and supply of these molecules by biotechnological means led to the retraction of big pharmaceutical companies from this field. The reasons included problems associated with strain culturing, screening, re-discovery, purification and characterization of novel molecules from natural sources. Nevertheless, recent reports have described technical developments that tackle such issues. While many of these reports focus on the identification and characterization of such molecules to enable subsequent chemical synthesis, a biotechnological supply strategy is rarely reported. This may be because production processes usually fall under proprietary research and/or few processes may meet the requirements of a pharmaceutical development campaign. We aimed to bridge this gap for illudin M—a fungal sesquiterpene used for the development of anticancer agents—with the intention to show that biotechnology can be a vital alternative to synthetic processes dealing with small molecules. Results We used µL-scale models to develop an adsorption and extraction strategy for illudin M recovery from culture supernatant of Omphalotus nidiformis and these findings were successfully transferred into lab-scale. By adsorbing and eluting the product using a fixed resin-bed we reduced the working volume by ~ 90% and removed the aqueous phase from the process. After a washing step, a highly concentrated illudin M fraction was obtained by isocratic elution with 80% methanol. The fraction was dried and extracted using a water/heptane mixture, enriching illudin M in the heptane phase. From heptane illudin M could be instantly crystalized by concentrating the solution, achieving a final purity > 95%. Conclusion We have developed a robust, scalable and low-cost downstream process to obtain highly pure illudin M. By using solid phase extraction we reduced the production of solvent waste. Heptane from the final purification step could be recycled. The reduced amounts of solvents required, and the short purification time render this method a very economic and ecologic alternative to published processes.

Formic acid (FA) is used across the world for a wide variety of applications spanning from chemical production to textile and pharmaceutical industries. FA can be synthesized efficiently from the lignocellulosic biomass constituent carbohydrates by acid hydrolysis in a dilute aqueous reaction media. Since FA forms an azeotrope with water, its purification, water recycle and reuse are vital to establishing a cost-competitive process. In this study, the analytic hierarchy process (AHP) was implemented to determine the desired separation method for isolating FA from a 3 wt.% aqueous solution by considering the advantages and disadvantages of each process. Four parameters named as scalable, quality of the final product, repeatable, and energy consumption were defined as criteria to perform AHP analysis. Furthermore, six alternative approaches namely (i) azeotropic distillation, (ii) extractive distillation with a liquid solvent and (iii) solid salt, (iv) the combination of liquid solvent and solid salt, (v) pressure-swing distillation, and (vi) liquid-liquid extraction (LLE) were examined to decide the most preferred separation method with respect to the goal, which is the desired separation method. The AHP results indicated that the alternative approach, the LLE and the scalable criteria have the highest preference with 39.4% and 54% priority, respectively. The proposed process based on the alternative approach could extract 99% of FA by using diethyl ether. Moreover, an estimated minimum selling price (MSP) of 2.48 $/kg FA with 97.4% purity was achieved by using techno-economic assessment for a typical plant with 1715 ton/day capacity.

The mining of extra-thick coal seams features severe deformation of the stoping roadway and section coal pillars due to the large mining thickness of the coal seams and the intense movement of the overlying strata. The adjacent goaf and secondary mining disturbance in the current working face further challenge the roadway deformation control. This study explores the effect of the overlying strata structural evolution in the fully mechanized caving face of the extra-thick seam on the failure of section roadway and coal pillars. Physical analog modeling was carried out. A MatchID non-contact full-field displacement- and strain-measuring system was used to determine the evolutionary characteristics of the overlying strata breakage in the extra-thick coal seam, including the displacement variation pattern and stress/strain distribution in coal pillars. The results indicated that following the primary mining disturbance in the adjacent working face, the section roadway and coal pillars underwent initial deformation due to the primary mining-induced stress. As the mining of the current working face continued, the section roadway and coal pillars were subjected to secondary mining disturbance to the effect that the structure of the broken overlying strata gradually formed a triangular support structure. Thus, the overlying strata tilted downwards and subsided, forming a layered hanging roof structure. The additional load was then imposed on the stoping roadway and upper part of the section coal pillars. Meanwhile, the overlying strata failure caused a significant increase in the stress within the section coal pillars. Following the secondary mining disturbance, the peak stress reached a maximum of 33.62 KPa, leading to deformation and instability failure of the section roadway and coal pillars. Finally, distinctive evolutionary features of the overlying strata structure in the extra-thick and ordinary coal seams were identified, and their effect on the deformation and failure of the section roadway and coal pillars were analyzed in detail. These findings are considered instrumental in substantiating the deformation control of the stoping roadway and coal pillars in the extra-thick coal seams.

Formic acid (FA) is used across the world for a wide variety of applications spanning from chemical production to textile and pharmaceutical industries. FA can be synthesized efficiently from the lignocellulosic biomass constituent carbohydrates by acid hydrolysis in a dilute aqueous reaction media. Since FA forms an azeotrope with water, its purification, water recycle and reuse are vital to establishing a cost-competitive process. In this study, the analytic hierarchy process (AHP) was implemented to determine the desired separation method for isolating FA from a 3 wt.% aqueous solution by considering the advantages and disadvantages of each process. Four parameters named as scalable, quality of the final product, repeatable, and energy consumption were defined as criteria to perform AHP analysis. Furthermore, six alternative approaches namely (i) azeotropic distillation, (ii) extractive distillation with a liquid solvent and (iii) solid salt, (iv) the combination of liquid solvent and solid salt, (v) pressure-swing distillation, and (vi) liquid-liquid extraction (LLE) were examined to decide the most preferred separation method with respect to the goal, which is the desired separation method. The AHP results indicated that the alternative approach, the LLE and the scalable criteria have the highest preference with 39.4% and 54% priority, respectively. The proposed process based on the alternative approach could extract 99% of FA by using diethyl ether. Moreover, an estimated minimum selling price (MSP) of 2.48 $/kg FA with 97.4% purity was achieved by using techno-economic assessment for a typical plant with 1715 ton/day capacity.

Abstract Dasatinib, a potent oral multi-targeted kinase inhibitor against Src and Bcr-Abl, can decrease inflammatory response in sepsis. A simple and cost-effective method for determination of an effective dose dasatinib was established. This method was validated in human plasma, with the aim of reducing the number of animals used, thus, avoiding ethical problems. Dasatinib and internal standard lopinavir were extracted from 180 uL of plasma using liquid-liquid extraction with methyl tert-butil ether, followed by liquid chromatography coupled to triple quadrupole mass spectrometry in multiple reaction monitoring mode. For the pharmacokinetic study, 1 mg/kg of dasatinib was administered to mice with and without sepsis. The method was linear over the concentration range of 1-98 ng/mL for DAS in mice and human plasma, with r2>0.99 and presented intra- and interday precision within the range of 2.3 - 6.2 and 4.3 - 7.0%, respectively. Further intra- and interday accuracy was within the range of 88.2 - 105.8 and 90.6 - 101.7%, respectively. The mice with sepsis showed AUC0-t = 2076.06 h*ng/mL and Cmax =102.73 ng/mL and mice without sepsis presented AUC0-t = 2128.46 h*ng/mL. Cmax = 164.5 ng/mL. The described analytical method was successfully employed in pharmacokinetic study of DAS in mice.

Amberlite LA-2 was used as an ion exchanger to remove Congo red dye from aqueous solution. The effect of the initial concentration of dye and the initial concentration of Amberlite LA-2 on the efficiency of dye removal from the aqueous phase to the organic phase at different contact times, temperatures and pH values was studied. this research aims to study the potential of using Amberlite LA-2 as an extracting material for Congo red dye removal. UV-visible Spectrophotometer were used to assay the dye concentration in the aqueous solution before and after removal. Distribution coefficients (KD), loading capacity (Z), and extraction efficiency (E%) were computed using experimental data. The maximum extraction efficiency of 99.69 % was obtained with a loading capacity of 384.366 mol/kg. The obtained results also indicated that the removal of dye increases with the increase in the concentration of Amberlite LA-2. The best removal was obtained in a neutral medium (pH = 7), a temperature of 20 oC. A mechanism of extraction by Amberlite LA-2 was also proposed.

Microfluidics based liquid-liquid extraction is emerging as an enabling and powerful technology in radiochemical separations of medically important radioisotopes. In this study, we report the production of high specific activity 64Cu via 64Zn (n, p) 64Cu reaction in a research reactor. A microfluidic continuous flow liquid-liquid extraction system based on the use of dithizone as extractant was developed for efficient separation of miniscule quantity of 64Cu (in ng level) from bulk irradiated Zn target (in g level). The extraction process is completely selective for 64Cu, which could subsequently be retrieved in the desired medium for preparation of radiopharmaceuticals. The overall yield of 64Cu after the separation process was > 85 % and it was obtained with adequately high radionuclidic, radiochemical and chemical purities. Additionally, the effective specific activity of radio chemically separated 64Cu was determined to be 12.2 ± 0.8 GBq/µg, which is quite close to that reported for cyclotron produced no-carrier-added (NCA) 64Cu available commercially. The final 64Cu formulation could be effectively used for preparation of a variety of radiopharmaceuticals with high radiolabeling yields. The promising results obtained in this study open the pathway to achieve continuous and efficient recovery of reactor produced NCA 64Cu from the irradiated target using an automated microfluidic setup.

Liquid–liquid extraction processes, characterized on-line by instrumented microfluidic platform, significantly enhance the development of predictive thermodynamic models, such as ienaics, and lay the foundations for new approaches to improve kinetic models which combine transport and chemistry. Instrumented microfluidics enables precise measurement of free energy of transfer of species at equilibria and their associated characteristic transfer times, faster and more accurately than its batch mode counterpart. Computer controlled and fully automatized, our platform illustrated the kinetic differences of high extraction’s of Ytterbium (Yb) and Iron (Fe), two elements reported as having very different extraction efficiencies due to different molecular forces competing with complexation when modifiers are used together with extractants. Once collected and processed, the kinetics show two distinct behaviors of these two metallic elements: depending on the temperature, Fe could display a very slow extraction profile when compared to Yb.

The phenoxy-amino ligands 2-(((2-(diethylamino)ethyl)amino)methyl)phenol (L1) and 2-(((2-mercaptoethyl)amino)methyl)-phenol (L2) were studied as model chelating agents for liquid-liquid extraction of copper(II), zinc(II), cadmium(II), and lead(II) cations from water using dichloromethane-water biphasic system. The relative affinities of these chelating ligands for copper(II), zinc(II), cadmium(II), and lead(II) by liquid-liquid extraction were found to be in the order copper(II)> zinc(II) > cadmium(II) > lead(II). The ligands L1 and L2 showed binding efficiencies ranging from 78%–97% for copper(II), 75%–91% for zinc(II), 76%–92% for cadmium(II), and 59%–67% for lead(II). The extraction protocol was successfully applied to sewage effluent. HIGHLIGHTS Phenoxy-amino ligands (L1) and (L2) showed good potential as chelating agents for the removal of the heavy metals Cu(II), Zn(II), Pb(II), and Cd(II) from water.; Ligands L1 and L2 demonstrated their potential application in the extraction of Cu(II) and Zn(II) from sewage effluent.; The nature of the metal ion and ligand architecture influenced the extraction ability of the ligands.;

Using environmentally friendly solvents for liquid–liquid extraction offers a promising avenue for promoting sustainability in various industries. Green solvents, including ionic liquids, deep eutectic solvents, supercritical fluids, and bio-based solvents, offer several advantages compared to the traditional solvents of the present time. These solvents possess low toxicity, biodegradability, and reduced environmental impact, making them highly desirable for liquid–liquid extraction processes. Through careful adjustments in composition and physicochemical properties, these solvents can be customized to achieve efficient and selective extraction of desired compounds. Additionally, recent advances in green solvents often contribute to improved energy efficiency, reduced waste production, and the potential for developing novel products with unique characteristics. By embracing green solvents for liquid–liquid extraction, industries can actively contribute to sustainable development, minimize environmental harm, and support the transition towards an eco-friendlier future.

Two new vanadium (V) complexes involving 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR) and tetrazolium cation were studied. The following commercially available tetrazolium salts were used as the cation source: tetrazolium red (2,3,5-triphenyltetrazol-2-ium;chloride, TTC) and neotetrazolium chloride (2-[4-[4-(3,5-diphenyltetrazol-2-ium-2-yl)phenyl]phenyl]-3,5-diphenyltetrazol-2-ium;dichloride, NTC). The cations (abbreviated as TT+ and NTC+) impart high hydrophobicity to the ternary complexes, allowing vanadium to be easily extracted and preconcentrated in one step. The complexes have different stoichiometry. The V(V)–HTAR–TTC complex dimerizes in the organic phase (chloroform) and can be represented by the formula [(TT+)[VO2(HTAR)]]2. The other complex is monomeric (NTC+)[VO2(HTAR)]. The cation has a +1 charge because one of the two chloride ions remains undissociated: NTC+ = (NT2+Cl−)+. The ground-state equilibrium geometries of the constituent cations and final complexes were optimized at the B3LYP and HF levels of theory. The dimer [(TT+)[VO2(HTAR)]]2 is more suitable for practical applications due to its better extraction characteristics and wider pH interval of formation and extraction. It was used for cheap and reliable extraction–spectrophotometric determination of V(V) traces in real samples. The absorption maximum, molar absorptivity coefficient, limit of detection, and linear working range were 549 nm, 5.2 × 104 L mol−1 cm−1, 4.6 ng mL−1, and 0.015–2.0 μg mL−1, respectively.

The release of 1,4-dioxane probably contributes to the deterioration of marine habitats, animal health, and human liver and kidneys. The formulation of 1,4-dioxane in glycols, which has been applied for dehumidifying agents in refineries, may need to be replaced to ensure public health. Further, it is necessary to identify and precisely determine the levels of 1,4-dioxane in glycols for food quality control and environmental safety regulation. The objectives of this study were to validate a liquid–liquid extraction (LLE) method for 1,4-dioxane analysis and to optimize the LLE conditions using a response surface methodology (RSM). With consideration of the food matrix and its applications, polyethylene glycol 200 was used as the model system and analyzed by gas chromatography with flame ionization detection. In the experiments for the optimum extraction temperature and time of 1,4-dioxane in ultrasonic treatment, they were 20 °C and 10 min, respectively. The experimental conditions and results were analyzed by RSM with the Box–Behnken design, and the optimal extraction conditions for the LLE were determined to be coded with three independent variables (sample weight, solvent volume, and centrifugation speed). The amount of 1,4-dioxane increased as the amount of sample increased, whereas the amount of 1,4-dioxane decreased as the amount of solvent increased. This information can help to find the analytical methods for regulating the 1,4-dioxane content and its precise quantification in food products.

The separation of trivalent actinides and lanthanides is a key step in the sustainable development of nuclear energy, and it is currently mainly realized via liquid–liquid extraction techniques. The underlying mechanism is complicated and remains ambiguous, which hinders the further development of extraction. Herein, to better understand the mechanism of the extraction, the contributing factors for the extraction are discussed (specifically, the sulfur-donating ligand, Cyanex301) by combing molecular dynamics simulations and experiments. This work is expected to contribute to improve our systematic understanding on a molecular scale of the extraction of lanthanides and actinides, and to assist in the extensive studies on the design and optimization of novel ligands with improved performance.

Two categories of so-called innovative liquid–liquid extraction systems have recently been added to the classic and well-established category of water/molecular solvent systems: aqueous biphasic systems (ABS) and hydrophobic deep eutectic solvents (DES). Each class displays properties that apparently distinguish it from the other two. However, these three classes seem to be irrelevant because the properties of mutual solubilities in these systems are identical in nature and can be easily understood via a simplified phase diagram. This unifying view is discussed in the light of systems representative of the three categories usually recognised. Two systems are well known in the literature of liquid/liquid extraction of metal ions: (i) H$_{2}$O/HNO$_{3}$/TBP, the archetype of the so-called classical liquid–liquid extraction (ii) H$_{2}$O/Na$_{2}$SO$_{4}$/PEG-4000, considered as an ABS. For the third system, H$_{2}$O/decanoic acid/N$_{4444}$Cl, presented as a hydrophobic DES by its discoverers, new experimental data have been acquired in this work.

Abstract Liquid‐liquid extraction is a complex chemical purification process, which is associated with many thermodynamic and kinetic values. This makes its application in the recycling industry difficult, as it deals with waste streams that have highly variable compositions. In this regard, modelling an extraction process using microfluidics proves to be a useful approach to allow rapid adaptation to such composition changes, if development can be shown to be more accurate, faster, and safer than the classical batch approach with separate analysis. Here, the first automated microfluidic tool integrated with online X‐ray fluorescence (XRF) is reported to study liquid‐liquid extraction processes by enabling metal concentration quantification. The measurement is automated and performed for both aqueous and organic phases to improve accuracy. Overall, this fully automated approach shows that: (i) Thermodynamic and kinetic values associated with these processes can rapidly and efficiently be obtained simultaneously (in less than 13 hours with a resulting liquid use of less than 20 mL). (ii) Numerical simulations are consistent with the experimental data and provide rare insights regarding the respective contributions to the overall kinetic of the extraction system.

In this work, liquid-liquid extraction of phenol from aqueous solutions using primary amine Primene JMT (Primene® JM-T) was investigated. The extraction capability of Primene® JM-T with different diluents, including 3-heptanone, sulfonated kerosene, methyl isobutyl ketone, n-octanol, toluene and petroleum ether was studied. The experimental results indicated that the distribution coefficient of phenol extracted using Primene® JM-T that was diluted in 3-heptanone could reach 101.74 under the pH of 9.2. Moreover, the extraction reaction was exothermic (enthalpy change for the extraction reaction (ΔrHm) was −21.03 kJ/mol). High temperature showed a negative effect on the extraction of phenol. The results also showed that adding mineral salt was conducive to the extraction process, and the extraction efficiency fell in the descending order of: (NH4)2SO4> NaCl > NH4Cl. Two empirical correlations were put forward to quantitatively describe the salting effect. Furthermore, the equilibrium constants of phenol extraction using Primene® JM-T were calculated to be 78.2 L/mol. The phenol was extracted using Primene® JM-T with the possible stoichiometric formula of: [RNH3+⋅PhOH]org, where R represents the alkyl group of the amine.

Objective: An analytical method was established for determination of 13 kinds of bisphenols and alkylphenol compounds in liquid dairy products by salting-out-assisted liquid-liquid extraction coupled with HPLC-MS/MS. Methods: The salting-out-assisted liquid-liquid extraction pre-treatment method was adopted, and the detection was performed in the mode of negative ion source multiple reaction monitoring （MRM） by triple quadrupole mass spectrometry, and quantitative analysis was performed by matrix external standard method. Besides, the effect of extraction solvent type, selection and the usage of salting-out agents on the recoveries were studied and the performance of the method was evaluated. Results: The liquid dairy products were liquid-liquid extracted with acetonitrile as extraction solvent and 0.4 g sodium chloride as salting-out agents. The 13 kinds of phenols had a good linear relationship, and the correlation coefficients were all ＞ 0.99. The standard recovery rates of milk and yoghurt were 81.5% to 118.1% and 80.8% to 107.6%, respectively, and the relative standard deviations were 1.89% to 12.3% and 1.12% to 11.9%. The detection limits were 0.15 to 0.75 μg/kg, and the quantification limits were 0.5 to 2.5 μg/kg. One of the commercially available liquid dairy product was found to contain 4-NP, and the concentrations was 9.28 μg/kg. Conclusion: The established method is suitable for the rapid detection of 13 kinds of bisphenols and alkylphenol compounds in liquid dairy products.