Liquid-liquid Extraction Technique Research Articles

Comparative evaluation of liquid-liquid extraction and nanosorbent extraction for HPLC-PDA analysis of cabazitaxel from rat plasma

A precise, sensitive, accurate, and validated reverse-phase high-performance liquid chromatography (RP-HPLC) method with a bioanalytical approach was utilized to analyze Cabazitaxel (CBZ) in rat plasma. Comparative research on extraction recoveries was performed between traditional liquid-liquid extraction (LLE) and synthesized graphene oxide (GO) based magnetic solid phase extraction (GO@MSPE). The superparamagnetic hybrid nanosorbent was synthesized using the combination of iron oxide and GO and subsequently applied for extraction and bioanalytical quantification of CBZ from plasma by (HPLC-PDA) analysis. Fourier- transform infrared spectroscopy (FT-IR), particle size, scanning electron microscopy (SEM), and x-ray diffraction (XRD) analysis were employed in the characterization of synthesized GO@MSPE nanosorbent. The investigation was accomplished using a shim pack C18 column (150 mm×4.6 mm, 5 µm) with a binary gradient mobile phase consisting of formic acid: acetonitrile: water (0.1:75:25, v/v/v) at a 0.8 mL/min flow rate, and a λmax of 229 nm. The limits of detection (LOD) and quantitation (LOQ) have been determined to be 50 and 100 ng/mL for both LLE and SPE techniques. The linearity range of the approach encompassed from 100 to 5000 ng/mL and was found to be linear (coefficient of determination > 0.99) for CBZ. The proposed method showed extraction recovery of 76.8–88.4% for the synthesized GO@MSPE and 69.3–77.4% for LLE, suggesting that the proposed bioanalytical approach was robust and qualified for all validation parameters within the acceptable criteria. Furthermore, the developed hybrid GO@MSPE nanosorbent with the help of the proposed RP-HPLC method, showed a significant potential for the extraction of CBZ in bioanalysis.

Evaluating bottle liquid-liquid extraction technique for monitoring residual levels of organochlorine pesticides in wastewater treatment-associated matrices

The gold standard for recovering residual organochlorine pesticides from wastewater and aqueous environmental matrices is the continuous liquid-liquid extraction (CLLE) technique that requires methylene chloride (CH2Cl2) as solvent at its refluxing temperature. In light of a recent USEPA proposed prohibitions and workplace protections for CH2Cl2 (due to its toxicity) and the fact that CLLE requires expensive and hard-to-acquire glassware, an alternative to CLLE as currently practiced is needed. The bottle liquid-liquid extraction (BLLE) technique, demonstrated for extracting semi-volatile organic contaminants from surface water, is potentially a low cost and high throughput alternative for such recovery. BLLE is cheaper and has a smaller laboratory footprint. The technique, performed at ambient temperature in a tightly capped bottle, requires less amount of solvent and contains solvent vapor within the bottle. The latter means less CH2Cl2 is encountered in the workplace. In this study, BLLE was performed directly in 1-L amber sampling bottles and shown to recover 21 organochlorine pesticides as efficiently as CLLE from influents and effluents of two wastewater treatment plants Because no statistical differences were found between CLLE (mean = 77.4, SD = 9.28) and BLLE (mean = 79.1, SD = 14.3); t(22) = 0.548, p(same mean) = 0.58, even though CLLE recovered more pesticides than BLLE by 5.18 ± 8.15%, these techniques are amenable to interchangeable usage. The systematic bias so far detected fits the expression BLLE = 1.4[CLLE] – 35 (r = 0.88). Both CLLE and BLLE recoveries were consistently higher for 4,4′-DDD and lower for aldrin, heptachlor and endrin aldehyde. Diethyl ether addition, as some suggested, did not improve BLLE.Synopsis: There is need to find a cheap, reliable and high throughput technique for purifying SVOCs from aqueous environmental media efficiently. BLLE, a little known technique, fulfils this need.

Understanding the Interaction between Nanomaterials Originated from High-Temperature Processed Starch/Myristic Acid and Human Monocyte Cells.

High-temperature cooking approaches trigger many metabolically undesirable molecule formations, which pose health risks. As a result, nanomaterial formation has been observed while cooking and reported recently. At high temperatures, starch and myristic acid interact and lead to the creation of nanomaterials (cMS-NMs). We used a non-polar solvent chloroform to separate the nanomaterials using a liquid-liquid extraction technique. The physico-chemical characterization was carried out using dynamic light scattering (DLS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and Fourier-transform infrared spectroscopy (FTIR). To determine the biological impact of these nanomaterials using different in vitro assays, including a cell viability assay, microscopic staining, and gene expression analysis, we adopted the THP-1 cell line as an in vitro monocyte model in our study. The TEM images revealed that fabricated cMS nanomaterials are smaller than 100 nm in diameter. There were significant concerns found in the cytotoxicity assay and gene expression analysis. At concentrations of 100-250 µg/mL, the cMS-NMs caused up to 95% cell death. We found both necrosis and apoptosis in cMS-NMs treated THP-1 cells. In cMS-NMs-treated THP-1 cells, we found decreased expression levels in IL1B and NFKB1A genes and significant upregulation in MIF genes, suggesting a negative immune response. These findings strongly suggest that cMS-NMs originated from high-temperature food processing can cause adverse effects on biological systems. Therefore, charred materials in processed foods should be avoided in order to minimize the risk of health complications.

A Review on The Impurity Profile of Pharmaceuticals

A collection of analytical procedures known collectively as “impurity profiling” are intended to detect, identify, clarify the structure of, and quantify both organic and inorganic impurities as well as residual solvents in pharmaceutical formulations and bulk pharmaceuticals. This is the main task of contemporary drug analysis since it is the most effective approach to describe the stability and quality of pharmaceutical formulations and bulk pharmaceuticals. To keep an eye on them, specific analytical techniques must be created. When modifications are made to the synthesis, formulation, or production processes, even if they are done to improve them, new purities could be seen. The identification of impurities in Active Pharmaceutical Ingredients (APIs) and the need for purity are being emphasised by a number of regulatory bodies, including the Canadian Drug and Health Agency (CDHA), the United States Food and Drug Administration (FDA), and the International Conference on Harmonisation (ICH). Pharmaceutical products can contain impurities from a variety of sources, including reagents, heavy metals, ligands, catalysts and other materials like charcoal, filter aids, and the like. Degraded end products from hydrolysis, photolytic cleavage, oxidative degradation, decarboxylation, and other processes can also contain impurities, as can enantiomeric impurities. The various pharmacopoeias, including the Indian, American, and British pharmacopoeias, are gradually adding restrictions to the permissible concentrations of contaminants found in APIs or formulations. Capillary electrophoresis, electron paramagnetic resonance, gas-liquid chromatography, gravimetric analysis, high performance liquid chromatography, solidphase extraction techniques, liquid-liquid extraction techniques, mass spectrometry, ultraviolet spectrometry, infrared spectroscopy, supercritical fluid extraction column chromatography, nuclear magnetic resonance (NMR) spectroscopy, and RAMAN spectroscopy are some of the techniques used to isolate and characterize impurities in pharmaceuticals. Liquid Chromatography (LC)-Mass Spectroscopy (MS), GC-MS, LC-NMR, LC- NMR-MS, and LC-MS are the most frequently used hyphenated techniques for drug impurity profiling. This demonstrates the importance and range of drug impurity profiling in pharmaceutical research.

Aniline-Driven Liquid-Liquid Extraction for Methylamine-Water Separation: Process Simulation and Performance Evaluation

Methylamines are toxic with ammonia-like odor while aniline has a fishy odor. Both aniline and methylamines affect aquatic life and water quality if present in large concentrations in water. Nevertheless, the later, with solubility of 1120 g/L is more soluble in water than the former with solubility of 3.6 g/L at 25. Based on their difference in solubilities, liquid-liquid extraction (LLE) technique can be used to separate or remove the presence of any one of the two pollutants in water. The UNIQUAC property method in Aspen Plus V8.8 was proven to be the best method for the LLE of a water-aniline-methylamine ternary mixture after a single stage partition coefficient analysis with a mixing tank. Adopting the best model for a two-stage separation using ‘Extract’ and ‘RadFrac’ Aspen Plus model units, yielded three separate product streams that are 95.5% methylamine, 86.5% aniline and 100% water. The phase boundary, diagonal tie lines and a constant boiling point of 372.505 K showcased by the ternary phase diagram demonstrated the presence of an azeotrope and the ability of the RadFrac model to separate the mixture easily. Future demonstration on how to separate numerous ternary mixtures is recommended, as the need to treat effluents of many industries containing compounds of varying solubilities may warrant the setting up of a LLE unit.

Detection of 11 carbamate pesticide residues in raw and pasteurized camel milk samples using liquid chromatography tandem mass spectrometry: Method development, method validation, and health risk assessment

This study aimed to use ultra-high-performance liquid chromatography coupled to a triple-quadrupole mass spectrometer to detect 11 carbamate pesticide residues in raw and pasteurized camel milk samples collected from the United Arab Emirates. A method was developed and validated by evaluating limits of detection, limits of quantitation, linearity, extraction recovery, repeatability, intermediate precision, and matrix effect. Due to the high protein and fat content in camel milk, a sample preparation step was necessary to avoid potential interference during analysis. For this purpose, 5 different liquid-liquid extraction techniques were evaluated to determine their efficiency in extracting carbamate pesticides from camel milk. The established method demonstrated high accuracy and precision. The matrix effect for all carbamate pesticides was observed to fall within the soft range, indicating its negligible effect. Remarkably, detection limits for all carbamates were as low as 0.01 μg/kg. Additionally, the coefficients of determination were >0.998, demonstrating excellent linearity. A total of 17 camel milk samples were analyzed, and only one sample was found to be free from any carbamate residues. The remaining 16 samples contained at least one carbamate residue, yet all detected concentrations were below the recommended maximum residue limits set by Codex Alimentarius and the European Union pesticide databases. Nonetheless, it is worth noting that the detected levels of ethiofencarb in 3 samples were close to the borderline of the maximum residue limit. To assess the health risk for consumers of camel milk, the hazard index values of carbofuran, carbaryl, and propoxur were calculated. The hazard index values for these 3 carbamate pesticides were all below 1, indicating that camel milk consumers are not at risk from these residues.

Economic simulation of batch and continuous aqueous two-phase purification for viral products.

Vaccine manufacturing strategies that lower capital and production costs could improve vaccine access by reducing the cost per dose and encouraging localized manufacturing. Continuous processing is increasingly utilized to drive lower costs in biological manufacturing by requiring fewer capital and operating resources. Aqueous two-phase systems (ATPS) are a liquid-liquid extraction technique that enables continuous processing for viral vectors. To date, no economic comparison between viral vector purifications using traditional methods and ATPS has been published. In this work, economic simulations of traditional chromatography-based virus purification were compared to ATPS-based virus purification for the same product output in both batch and continuous modes. First, the modeling strategy was validated by re-creating a viral subunit manufacturing economic simulation. Then, ATPS capital and operating costs were compared to that of a traditional chromatography purification at multiple scales. At all scales, ATPS purification required less than 10% of the capital expenditure compared to chromatography-based purification. At an 11 kg per year production scale, the ATPS production costs were 50% less than purification with chromatography. Other chromatography configurations were explored, and may provide a production cost benefit to ATPS, but the purity and recovery were not experimentally verified. Batch and continuous ATPS were similar in capital and production costs. However, manual price adjustments suggest that continuous ATPS plant-building costs could be less than half that of batch ATPS at the 11 kg per year production scale. These simulations show the significant reduction in manufacturing costs that ATPS-based purification could deliver to the vaccine industry.

A Highly Selective Analytical Method Based on Salt-Assisted Liquid-Liquid Extraction for Trace-Level Enrichment of Multiclass Pesticide Residues in Cow Milk for Quantitative Liquid Chromatographic Analysis.

In this study, a simple, inexpensive, selective, and fast salting-out assisted liquid-liquid extraction (SALLE) technique coupled with high-pressure liquid chromatography-diode array detection (HPLC-DAD) was developed for the extraction, preconcentration, and analysis of trace level seven multiclass pesticide residues in pasteurized and raw cow milk samples. The significant factors that affect the extent to which the target analytes are extracted, such as the type of extraction solvent and its volume, the type and concentration of salting-out salts, the pH of the solution, and the extraction time, have been investigated. Under optimum conditions, the correlation coefficient (r2) was obtained within a range of 0.9982-0.9997 for a broad linear range concentration of 2-1500 ng·mL-1. Reliable sensitivity was achieved with limits of detection (LODs) and limits of quantification (LOQs) ranging from 0.58-2.56 ng·mL-1 and 1.95-8.51 ng·mL-1, respectively. While precision with interday and intraday in terms of relative standard deviations (RSDs) was observed in the range of 1.97 - 7.88% and 4.52 - 8.04%, respectively. The results of the precision studies reveal that good repeatability and reproducibility (RSDs <9) were achieved, thus showing a low variability extraction of the developed method. Finally, the proposed and validated approach was effectively used to extract and determine pesticide residues in real milk matrices; however, the target analytes were not detected in all samples.

Controlling Extraction of Rare Earth Elements Using Functionalized Aryl-vinyl Phosphonic Acid Esters.

Ligands that can discriminate between individual rare earth elements are important for production of these critical elements. A set of aryl-vinyl phosphonic acid ligands for extracting rare earth elements were designed and synthesized under the hypothesis that the strength of the rare earth-ligand interactions could be tuned by changing the dipole moment of the ligand. The ligands were synthesized via a two-step reaction procedure using a Heck coupling reaction to functionalize vinyl phosphonic acid, followed by Steglich esterification to obtain high-purity styryl phosphonic acid monoesters with varying dipole moments along the P-C bond. The metal binding strength and composition of the rare earth complexes formed with these styryl phosphonic acid monoesters were experimentally studied by liquid-liquid extraction techniques, while DFT calculations were performed to determine the dipole moments of the free and complexed ligands and the electronic structure of the complexes formed. All three prepared ligands were much stronger extracting agents for europium(III) than the dialkylphosphonic acids usually used for this separation. However, the order of increasing extraction strength was found to match the order of the decreasing calculated dipole moment along the P-C bond of the three styryl-based ligands, rather than correlating with increasing ligand basicity, as reflected by the pKa of the ligands. These findings suggest that this approach can be used to systematically alter the extraction strength of aromatic phosphonic monoesters for rare earth element purification.

Comprehensive metabolite profiling of trimetazidine in camels using high-resolution accurate mass spectrometry: Implications for doping control.

Trimetazidine and its metabolites are prohibited substances in sports. With a growing number of adverse findings in human athletes, it is crucial to develop doping control strategies that include screening for trimetazidine in animal sports. This study aims to detect and characterize trimetazidine and its metabolites for doping control in camel racing. Camel urine and plasma samples were collected from four healthy animals following a single oral dose of trimetazidine. In vitro investigations were conducted using camel liver samples. Liquid-liquid extraction and solid-phase extraction techniques were employed for the extraction of trimetazidine metabolites from plasma and urine matrices. The metabolites were analyzed using a Thermo Orbitrap Exploris LC-MS system with optimized settings to achieve maximum sensitivity and accurate mass measurements. Comprehensive metabolite profiling of trimetazidine in camels revealed the identification of seven phase I and five phase II metabolites. Phase I metabolites were primarily formed through dealkylation, while phase II metabolites were dominated by glucuronide conjugation of demethylated trimetazidine. The findings provided insights into the distinct metabolic pathways and biotransformation patterns of trimetazidine in camels under the experimental conditions. The developed method enables detection and characterization of trimetazidine and its metabolites in camels. The identified metabolites have the potential to serve as marker metabolites for trimetazidine abuse in camel racing. This study provides valuable insights into the metabolism of trimetazidine in camels.

Recent Advances in the Study of Trivalent Lanthanides and Actinides by Phosphinic and Thiophosphinic Ligands in Condensed Phases.

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.

Seasonal variations in the levels of glyphosate in soil, water and crops from three farm settlements in Oyo state, Nigeria

This study investigated the concentration of glyphosate in water (groundwater and surface), soil (top and sub) on cassava and maize farms within 3 farm settlements (Akufo, Ilora and Otiri Ipapo) from Ido, Oyo and Iseyin Local Government Areas of Oyo state, Nigeria. Samples of Top and sub soil were taken from the farms while water was collected from wells (groundwater) and streams (surface water) around each farm settlement using standard methods. Crops (cassava and Maize) samples were collected from each of the selected farm after harvest. The samples were collected over a six-month period to reflect seasonal variation. The glyphosate levels were determined using HPLC-FLD after liquid-liquid extraction technique for water and soxhlet extraction for soil crops The pH, electrical conductivity (EC), total dissolved solids (TDS) values for groundwater were within the WHO limits while values recorded for surface water were above the WHO limits. The phosphate and nitrate values were high in surface water compared to groundwater. High concentration of the exchangeable cations were recorded at the top soil for all the farms with values ranging from 4.0 ± 0.1 to 8.2 ± 0.0 for Ca2+, 2.9 ± 0.0 to 5.1 ± 0.1 for Mg2+, 0.3 ± 0.2 to 0.55 ± 0.0 for Na+, and 0.32 ± 0.0 to 8.2 ± 0.0 for K+. the residual concentration of glyphosate taken from wells and taps (groundwater) were within the maximum concentration of glyphosate in drinking water (0.7 mgL−1). Glyphosate concentrations observed were higher in soil samples from all farm settlements during wet season compared to dry, higher concentrations were also observed in surface water during wet season (August) compared to dry, with Akufo farm settlement having the highest concentrations of 29.40 ± 0.83 mgL−1. The glyphosate residues were also higher in cassava (0.3 ± 0.0 mgKg−1) compared to maize (0.07 ± 0.08 mgKg−1) across each farm settlement. Generally, the higher concentrations observed during wet season in both soil and water samples were as a result of active farm activities during wet season and run off respectively. If herbicide usage is not properly monitored within these settlements, it can pose a threat to aquatic animals and humans around the settlements, thus a sustainable and conservative farming is advised.

Polyphenolic Composition of Carlina acaulis L. Extract and Cytotoxic Potential against Colorectal Adenocarcinoma and Cervical Cancer Cells.

Carlina acaulis is highly valued in the traditional medicine of many European countries for its diuretic, cholagogue, anthelmintic, laxative, and emetic properties. Moreover, practitioners of natural medicine indicate that it has anti-cancer potential. However, its phytochemistry is still little known. In the present study, the polyphenolic composition of the plant was investigated using ultra-high-performance liquid chromatography coupled with a high-resolution/quadrupole time-of-flight mass spectrometer (UHPLC-HR/QTOF/MS-PDA). The fractionation of the extract was carried out using liquid-liquid extraction and preparative chromatography techniques. Cytotoxicity was assessed based on neutral red and MTT assays. The obtained data showed that the species is rich in chlorogenic acids and C-glycosides of luteolin and apigenin. The total amount of chlorogenic acids was 12.6 mg/g. Among flavonoids, kaempferol dihexosidipentose and schaftoside were the most abundant, reaching approximately 3 mg/g, followed by isoorientin, vitexin-2-O-rhamnoside, and vicenin II, each with a content of approximately 2 mg/g. Furthermore, the cytotoxic potential of the plant against human colorectal adenocarcinoma (HT29) and human cervical cancer (HeLa) cells was investigated using the normal epithelial colon cell line (CCD 841CoTr) as a reference. It has been demonstrated that the ethyl acetate fraction was the most abundant in polyphenolic compounds and had the most promising anticancer activity. Further fractionation allowed for the obtaining of some subfractions that differed in phytochemical composition. The subfractions containing polyphenolic acids and flavonoids were characterized by low cytotoxicity against cancer and normal cell lines. Meanwhile, the subfraction with fatty acids was active and decreased the viability of HeLa and HT29 with minimal negative effects on CCD 841CoTr. The effect was probably linked to traumatic acid, which was present in the fraction at a concentration of 147 mg/g of dried weight. The research demonstrated the significant potential of C. acaulis as a plant with promising attributes, thus justifying further exploration of its biological activity.

Dl-carnitine-based green hydrophobic deep eutectic solvent for the enrichment of bisphenol A in mineral water based on ultrasound-assisted liquid-phase microextraction

A powerful pretreatment technique, ultrasound-assisted dispersive liquid-phase microextraction (USA-DLPME) based on dl-Carnitine-based deep eutectic solvent (DES), has been developed to efficiently enrichment of bisphenol A from mineral water samples. The DES-based USA-DLPME technique demonstrated superior extraction efficiency for bisphenol A compared to established organic solvent-based liquid-liquid extraction techniques. The conditions for the extraction of bisphenol A were predicted using the response surface methodology. The effects of pH (A: 2–10), NaCl concentration (B: 0.2–1.0%w/v), DES volume (C: 30–150 μL), and sonication time (D: 1–5 min) were examined using an experimental design. The extraction recovery of Bisphenol A under optimum conditions was achieved at 99.897% (A = 8, B = 0.4%w/v, C = 120 μL, and D = 5 min). Under these conditions, a wide linear range of 1–600 ng mL−1, an enrichment factor of 81.52, a low detection limit of 0.26 ng mL−1 and a limit of quantification of 0.87 ng mL−1 were obtained. Lastly, the proposed technique was used to accurately and reliably identify bisphenol A in various mineral water samples, yielding relative recoveries in the 92–96% range with RSD≤3%. These findings imply that DESs can be widely and successfully used to extract chemicals from actual materials. DESs are a class of innovative green solvents with the potential to replace organic solvents.

Oliveria decumbens Vent. (Apiaceae): Biological screening and chemical compositions

Ethnopharmacological relevanceOliveria decumbens Vent. (Apiaceae), a single aromatic species in Iran, is traditionally used for healing inflammation, gastrointestinal disorders, and infections. Aim of the studyRegarding the importance of O. decumbens in traditional medicine, we aimed to set out the plant's biological screening and analyze the chemical components of the active fractions. Materials and methodsAir-dried O. decumbens aerial parts were macerated by ethanol:water (70:30). Using a liquid-liquid extraction (LLE) technique, n-hexane, dichloromethane (DCM), ethyl acetate (EtOAc), n-butanol (n-BuOH), and water were successively used to fractionate the crude extract into different portions. Various biological activities were performed on the crude extract, fractions, and some experiments on pure compounds. The bioassays were as follows: antibacterial activity against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Pseudomonas aeruginosa, and Salmonella typhi (using microplate alamar blue assay; MABA), antifungal activity against Aspergillus niger, A. fumigatus, Candida albicans, C. glabarate, Fusarium lini, Microspurum canis, and Trichophyton rubrum (using agar tube dilution method), antileishmanial activity against Leishmania major and L. tropica using a 96-well serial dilution protocol, anti-inflammatory activity using the respiratory burst assay, cytotoxicity against HeLa (cervical cancer) and BJ (normal fibroblast) cells using MTT assay, insecticidal activity against Tribolium castaneum, Sitophilus oryzae, and Rhyzopertha dominica (using the contact toxicity method), larvicidal activity against Aedes aegypti, anti-DPPH• activity, and cytotoxicity against brine shrimp (Artemia salina) in a lethality assay. Eventually, the phytochemicals from the active fractions were studied by gas chromatography coupled with mass spectrometry (GC-MS). ResultsInterestingly, the DCM fraction was the most active, followed by the n-hexane fraction in the biological assays, including antibacterial (>80% inhibition), leishmanicidal (IC50 (L.major) = 29.4 μg/mL, and IC50 (L.tropica) = 30.0 μg/mL), anti-inflammatory (IC50 = 15.8 μg/mL), insecticidal (>80% inhibition), and larvicidal (100% inhibition of A. aegypti) assays. Further GC-MS analysis of the DCM and n-hexane fractions resulted in the characterization of 12 and 14 phytoconstituents, respectively, compared with the NIST library. Thymol and carvacrol were abundant in both fractions. To lesser quantities, the presence of monoterpenoids (p-cymen-8-ol, thymoquinone, 3-hydroxy-β-damascone, and 3-hydroxy-7,8-dihydro-β-ionol), phenylpropanoids (methoxyeugenol, elemicin, and 4-[(1E)-3-hydroxy-1-propenyl]-2-methoxyphanol, simple phenolics (salicylic acid and 4-methoxy-2,3,6-trimethyl-phenol), and a coumarin (6,7-dimethoxy-coumarin) were detected in the DCM fraction. On the other hand, besides a coumarin and monoterpenoids, the fatty acids (tetradecanoid acid, n-hexadecanoic acid, and linolenic acid) and a sesquiterpene (spathulenol) were observed in the n-hexane fraction. The EtOAc fraction scavenged the DPPH• radicals better than other fractions (IC50 = 41.4 μg/mL), while in brine shrimp lethality assay, the crude extract was more active than n-hexane and DCM fractions with LD50 = 385.20, 660.28, and 699.74 μg/mL, respectively. Surprisingly, the crude extract and fractions were ineffective against assayed fungal strains and tested cancer and non-cancer cell lines. ConclusionsOur findings showed that O. decumbens deserves to be a multi-bioactive medicinal plant, besides its ability for cereal protection against pests. To understand the principal mechanism of action, in silico, in vitro, and in vivo experiments may clarify the ambiguities and even figure out the synergistic behavior of the minor secondary metabolites.

A Comparative Analysis of Chemical Constituents and Antioxidant Effects of Dendrobium fimbriatum Hook Fractions with Different Polarities.

The aim of this study was to investigate the chemical composition and antioxidant capacity of various polar fractions obtained from Dendrobium fimbriatum Hook (DH). First, a 90% ethanol-aqueous extract of DH (CF) was subjected to sequential fractionation using different organic solvents, resulting in the isolation of a methylene chloride fraction (DF), an ethyl acetate fraction (EF), an n-butanol fraction (BF), and a remaining water fraction (WF) after condensation. Additionally, the CF was also subjected to column chromatography via a D101 macroreticular resin column, eluted with ethanol-aqueous solution to yield six fractions (0%, 20%, 40%, 60%, 80%, and 100%). UPLC-Q-Exactive Orbitrap-MS/MS analysis identified a total of 47 chemical compounds from these polar fractions, including fatty acids, amino acids, phenolic acids, flavonoids, organic heterocyclic molecules, and aromatic compounds. Moreover, DF, EF, and the 60%, 80%, and 100% ethanol-aqueous fractions had higher total phenol content (TPC) and total flavonoid content (TFC) values and greater 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS-) and 1,1-diphenyl-2-picrylhydrazyl (DPPH)-scavenging abilities. In H2O2-induced HepG2 cells, the aforementioned fractions could increase the activities of antioxidative enzymes NAD(P)H: quinone oxidoreductase 1 (NQO1), superoxide dismutase (SOD), heme oxygenase-1 (HO-1) and catalase (CAT), stimulate glutathione (GSH) synthesis by increasing the activities of glutamic acid cysteine ligase (GCL) and glutathione synthetase (GS), regulate GSH metabolism by increasing glutathione peroxidase (GSH-Px) and glutathione reductase (GR) activities, and reduce levels of reactive oxygen species (ROS) and malondialdehyde (MDA). Furthermore, the antioxidative stress effect of the DH fractions was found to be positively correlated with the activation of nuclear factor-erythroid 2-related factor 2 (Nrf2) protein and the presence of antioxidative chemical constituents. In conclusion, this study highlights the efficacy of both liquid-liquid extraction and macroporous resin purification techniques in the enrichment of bioactive compounds from natural food resources. The comprehensive analysis of chemical constituents and antioxidant effects of different polar fractions from Dendrobium fimbriatum Hook contributes to the understanding of its potential application in functional foods and nutraceuticals.

Lower rim thiacalixarenes derivatives incorporating multiple coordinating carbonyl groups: Synthesis, characterization, ion-responsive ability and DFT computational analysis

Three novel tetra substituted p‑tert-butylthiacalix[4]arene derivatives (3, 4, and 5) with five coordinating carbonyl groups at the lower rims were synthesized. Accordingly, diethyl tetra-t‑butyl‑trihydroxy-tetrathia-tetrabenzenacyclooctaphanyl)oxy)malonate react with ethyl bromoacetate, phenacyl bromide and 2‑chloro-N-(p-tolyl)acetamide, to produce new p‑tert-butylthiacalix[4]arenes in of 60, 90, and 80% yields, respectively. The molecular structures of the products were verified using FT-IR, 1H NMR, and 13C NMR spectroscopy. Metal ions such as Na+, K+, Cs+, Hg2+, Cd2+, Pb2+, Ni2+, Co2+, Cu2+, and Ag+ are easily chelated by the new thiacalixarene derivatives using liquid-liquid extraction technique. These compounds surprisingly show high efficiency in liquid-liquid extraction of alkali, heavy, and transition metal ions. Uptake efficiencies of 71.00% (for Co(II)), 46.00% (for Cu(II), and 15.00% (for Hg(II)) were attained by thiacalixarene 3, 4, and 5. These derivatives were subjected to DFT-based computational analysis with the aim of increasing the efficiency with which thiacalixarene (as a nucleophilic) interacts with the metal ion (3, 4, and 5 in the role of electrophile).

The Selective Separation of Carnosic Acid and Rosmarinic Acid by Solid-Phase Extraction and Liquid-Liquid Extraction: A Comparative Study.

Rosmarinus officinalis leaves (ROLs) are widely used in the food and cosmetics industries due to their high antioxidant activity and fascinating flavor properties. Carnosic acid (CA) and rosmarinic acid (RA) are regarded as the characteristic antioxidant components of ROLs, and the selective separation of CA and RA remains a significant challenge. In this work, the feasibility of achieving the selective separation of CA and RA from ROLs by solid-phase extraction (SPE) and liquid-liquid extraction (LLE) was studied and compared. The experiments suggested that SPE with CAD-40 macroporous resin as the adsorbent was a good choice for selectively isolating CA from the extracts of ROLs and could produce raw CA with purity levels as high as 76.5%. The LLE with ethyl acetate (EA) as the extraction solvent was more suitable for extracting RA from the diluted extracts of ROLs and could produce raw RA with a purity level of 56.3%. Compared with the reported column chromatography and LLE techniques, the developed SPE-LLE method not only exhibited higher extraction efficiency for CA and RA, but can also produce CA and RA with higher purity.

Enhancement of phenol recovery from wastewater by nanofluid utilizing liquid-liquid extraction method in a membrane-based contactor

This study aims to investigate the effect of adding nanoparticles (NPs) to phenol solvent on the recovery of phenol from wastewater by applying the liquid-liquid extraction technique in a contactor of a hollow fiber membrane. The resulting solution, called nanofluid, is composed of dispersed SiO2 nanoparticles in a 10% (v/v) tributyl phosphate (TBP) /kerosene mixture. The solvent loaded with phenol was regenerated using NaOH solution in a stripping hollow fiber membrane contactor. The stability of SiO2 NPs in the nanofluid was also investigated. Furthermore, the influence of operating conditions, such as NPs concentration, organic phase flow rate (Qorg), aqueous phase flow rate (Qaqu), and inlet phenol concentration on extraction efficiency (ηextrac), extraction flux (Jextrac), and stripping efficiency (ηstripp) were evaluated. The results showed that after 24 h, approximately 80% of the initial dispersion of SiO2 NPs into the nanofluid was achieved. Furthermore, it was observed that adding NPs to the TBP/kerosene solution improved ηextrac, Jextrac, and ηstripp. Among the studied NPs concentrations, 0.02 wt% exhibited higher values of ηextrac, Jextrac, and ηstripp. Additionally, it was found that increasing Qorg led to a significant increase in ηextrac and Jextrac, but a decrease in ηstripp. Conversely, increasing Qaqu led to a decrease in both ηextrac and ηstripp, but an increase in Jextrac. At an inlet phenol concentration of 1000 ppm and with Qorg and Qaqu at the same value of 150 mL min−1, the use of a solvent containing 0.02 wt% SiO2 NPs resulted in ηextrac of 97.8% and ηstripp of 97.7%.

Toxicological screening method by HPLC-DAD with local spectral library and "home-made" internal standard

A liquid-liquid extraction technique and HPLC-DAD method using a C18 column, 5μm (150x4.6mm i.d.) were developed for a toxicological drug screening. A home-made “N-acetylparoxetine” is used as internal standard. A local UV spectra library of over 130 drugs and some of their metabolites was created. This library covers the main therapeutic classes involved in intoxication cases. The developed procedure is successfully applied to different biological samples (serum, urine, gastric fluid and post mortem whole blood) and allows rapid and simultaneous detection and identification of a large number of substances and their semi-quantification in serum.