The presence of antibiotic residues in honey has recently become a growing public health concern due to the overuse of these products in beekeeping and their transfer to the food industry. The aim of this study was to develop and validate a simple, selective and sensitive method for the simultaneous identification and quantification of residues of twenty-two sulfonamides, trimethoprim and dapsone in honey using a rapid and reliable liquid chromatography–tandem mass spectrometry (LC–MS/MS) method. The developed method showed good linearity, specificity, precision (repeatability and intra-laboratory reproducibility) and recovery. The decision limit (CCalpha) ranged between 2.16-22.12 µg/kg for CCα, while the detection capability (CCbeta) was between 2.16- 2.67-27.36 µg/kg. The method proved to be rapid, reliable and effective for the determination of sulfonamides, trimethoprim and dapsone from honey samples. The average recoveries were estimated to be between 70 and 106%. The relative standard deviations (RSDs) were between 6-18%. In practice, the method is essential to check the honey sold on the market and ensure its safety before it reaches the consumer.

The present work describes the optimization and validation of a highly selective and sensitive analytical method using solid phase extraction and liquid chromatography tandem mass spectrometry (SPE LC-MS/MS) for the determination of some frequently prescribed pharmaceuticals in urban wastewater received and treated by Sharjah sewage treatment plant (STP). The extraction efficiency of different SPE cartridges was tested and the simultaneous extraction of pharmaceuticals was successfully accomplished using hydrophilic-lipophilic-balanced reversed phase Waters^® Oasis HLB cartridge (200 mg/ 6 mL) at pH 3. The analytes were separated on an Aquity BEH C₁₈ column (1.7 µm, 2.1 mm x 150 mm) using gradient elution and the mass spectrometric analysis were performed in multiple reactions monitoring (MRM) selecting two precursor ions to produce ion transition for each pharmaceutical using positive electrospray ionization (+ESI) mode. The correlation coefficient values in the linear calibration plot for each target compound exceeded 0.99 and the recovery percentages of the investigated pharmaceuticals were more than 84%. Limit of detection (LOD) varied between 0.1-1.5 ng/L and limit of quantification (LOQ) was 0.3-5 ng/L for all analytes. The precision of the method was calculated as the relative standard deviation (RSD%) of replicate measurements and was found to be in the ranges of 2.2% to 7.7% and 2.2% to 8.6% for inter and intra-day analysis, respectively. All of the obtained validation parameters satisfied the requirements and guidelines of analytical method validation.

Stable-isotope dimethyl labeling is a highly reactive and cost-effective derivatization procedure that could be utilized in proteomics analysis. In this study, a liquid chromatography-tandem mass spectrometry in multiple reaction monitoring mode (LC-MS-MRM) platform for the quantification of kiwi allergens was first developed using this strategy. Three signature peptides for target allergens Act d 1, Act d 5, and Act d 11 were determined and were derivatized with normal and deuterated formaldehyde as external calibrants and internal standards, respectively. The results showed that sample preparation with the phenol method provided comprehensive protein populations. Recoveries at four different levels ranging from 72.5–109.3% were achieved for the H-labeled signature peptides of Act d 1 (SPA1-H) and Act d 5 (SPA5-H) with precision ranging from 1.86–9.92%. The limit of quantification (LOQ) was set at 8 pg mL–1 for SPA1-H and at 4 ng mL–1 for SPA5-H. The developed procedure was utilized to analyze seven kinds of hand-made kiwi foods containing 0.0175–0.0515 mg g–1 of Act d 1 and 0.0252–0.0556 mg g–1 of Act d 5. This study extended the applicability of stable-isotope dimethyl labeling to the economical and precise determination of food allergens and peptides.

To determine promethazine (PMZ) and its metabolites promethazine sulfoxide (PMZSO) and monodesmethyl-promethazine (Nor1PMZ) in swine muscle, fat, kidney, and liver, a sample preparation and high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis method were established and validated. The sample was extracted with 0.1% formic acid-acetonitrile, and the extract was purified with acetonitrile-saturated n-hexane. After concentration by rotary evaporation, the extract was re-dissolved in 0.1% formic acid-water and acetonitrile (80:20, v/v). The HPLC-MS/MS column used was a Waters Symmetry C18 (100 mm × 2.1 mm i.d., 3.5 μm), with 0.1% formic acid-water and acetonitrile as the mobile phase, and the target compounds were determined by positive ion scan and multiple reaction monitoring. PMZ and Nor1PMZ were quantified with deuterated promethazine (PMZ-d6) as the internal standard, while PMZSO was quantified by external standard method. The limits of detection (LOD) and limits of quantification (LOQ) of PMZ and PMZSO in muscle, liver, and kidney spiked samples were 0.05 μg/kg and 0.1 μg/kg, respectively, while those of Nor1PMZ were 0.1 μg/kg and 0.5 μg/kg, respectively. The LOD and LOQ of analytes in fat spiked sample were 0.05 μg/kg and 0.1 μg/kg, respectively. The sensitivity of this method reaches or exceeds its presented in previous reports. The analytes PMZ and PMZSO showed good linearity within the range of 0.1 μg/kg to 50 μg/kg, while Nor1PMZ showed good linearity within the range of 0.5 μg/kg to 50 μg/kg, with correlation coefficients (r) greater than 0.99. The recoveries of the target compounds in the sam-ples were between 81.73% and 107.17%, and the precision ranged from 1.78% to 10.47%. This study developed for the first time an HPLC-MS/MS method for the determination of PMZ and its metabolites PMZSO and Nor1PMZ in four swine edible tissues, comprehensively covered target tissues of monitoring object, which is applicable for monitoring veterinary drug residues in ani-mal-derived foods and ensuring food safety.

An analytical method was established by HPLC-DAD-ELSD with C18-NH2 column tandem for the simultaneous determination of hydrophobic components atractylenolide I, II, III, atractylone and hydrophilic compounds glucose, fructose and sucrose in the dried rhizome of Atractylodes macrocephala Koidz (a natural raw material for health foods, Bai-Zhu aka. in Chinese). The method combines different separation capabilities of reversed-phase liquid chromatography and hydrophilic interaction liquid chromatography, can provide a new choice for the simultaneous determination of hydrophilic and hydrophobic compounds in traditional Chinese medicines and health foods. It provided a reference method for the quality control of Bai-Zhu. The results showed that the linear correlation coefficients of the established column tandem chromatographic method were all greater than 0.9990, the relative standard deviation was 0.1%-2.8%, and the average recovery was 96.7%-103.1%. The contents of atractylenolide I, II, III, atractylone, fructose, glucose, and sucrose in 17 batches of Baizhu were 172.3-759.8 μg/g, 201.4-612.8 μg/g, 160.3-534.2 μg/g, 541.4-8723.1 μg/g, 6.9-89.7 mg/g, 0.7-7.9 mg/g, and 1.2-21.0 mg/g, respectively.

The aquaculture industry has become a sustainable provider of food to humans. Remaining challenges include disease issues, as well as ethical concerns for discomfort and stress among farmed fish. There is a need for reliable biomarkers to monitor welfare in fish, and the stress hormone cortisol has been suggested as a good candidate. This study presents a novel method for measurement of cortisol in fish feces based on enzymatic hydrolysis, liquid-liquid extraction, derivatization, and finally instrumental analysis by liquid chromatography coupled with tandem mass spectrometry. Hydrolysis and extraction conditions were optimized. Cortisol appeared to be mostly conjugated to sulfate and less conjugated to glucuronic acid in the studied samples of feces from farmed Atlantic salmon. The method was suitable for quantification of cortisol after enzymatic deconjugation by either combined glucuronidase and sulfatase activity, or by glucuronidase activity alone. The limit of detection was 0.15 ng/g and the limit of quantification was 0.34 ng/g, and the method was linear (R2>0.997) up to 380 ng/g, for measurement of cortisol in wet feces. Method repeatability and intermediate precision were acceptable, both with a CV of 11%. Stress level was high in fish released into seawater, and significantly reduced after eight days.

Glycosphingolipids (GSL) represent a highly heterogeneous class of lipids with many cellular functions, implicated in a wide spectrum of human diseases. Their isolation, detection, and comprehensive structural analysis is a challenging task due to the structural diversity of GSL molecules. In this work, GSL subclasses are isolated from human plasma using an optimized monophasic ethanol–water solvent system capable to recover a broad range of GSL species. Obtained deproteinized plasma is subsequently purified and concentrated by C18-based solid-phase extraction (SPE). The hydrophilic interaction liquid chromatography (HILIC) coupled to electrospray ionization linear ion trap tandem mass spectrometry (ESI-LIT-MS/MS) is used for GSL analysis in the human plasma extract. Our results provide an in-depth profiling and structural characterization of glycosphingolipid and some phospholipid subclasses identified in the human plasma based on their retention times and the interpretation of tandem mass spectra. The structural composition of particular lipid species is readily characterized based on the detailed interpretation of MS and MS/MS spectra and further confirmed by specific fragmentation behavior following predictable patterns, which yields to the unambiguous identification of 154 GSL species within 7 lipid subclasses and 77 phospholipids representing the highest number of GSL species ever reported in the human plasma. The developed HILIC-ESI-MS/MS method can be used for further clinical and biological research of GSL in the human blood or other biological samples.

Microsamples (collections usually less than 50 µL) have been introduced in pre-clinical, clinical, and research settings to overcome obstacles in sampling via traditional venipuncture. However, venipuncture remains the sampling gold standard for metabolic phenotyping of blood. This pre-sents several challenges in metabolic phenotyping workflows: accessibility for individuals in ru-ral and remote underserved areas (due to the need for trained personnel), the unamenable nature to frequent sampling protocols in longitudinal research (for its invasive nature), and sample col-lection difficulty in the young and elderly. Furthermore, venous sample stability may be compro-mised when temperate conditions necessary for cold-chain transport are beyond control. Alter-natively, research utilising microsamples extends phenotyping possibilities to inborn errors of metabolism, therapeutic drug monitoring, nutrition, as well as sport and anti-doping. Although the application of microsamples in metabolic phenotyping exists, it is still in its infancy, with whole blood being overwhelmingly the primary biofluid collected through the collection method of dried blood spots. Research into metabolic phenotyping of microsamples is limited; however, with advances in commercially available microsampling devices, common barriers such as volumetric inaccuracies and the ‘haematocrit effect’ in dried blood spot microsampling can be overcome. In this review, we provide an overview of the common uses and workflows for mi-crosampling in metabolic phenotyping research. We discuss the advancements in technologies, highlighting key considerations and remaining knowledge gaps for employment of microsamples in metabolic phenotyping research. Supporting the translation of research from the ‘bench to the community’.

One of the research priorities in atmospheric chemistry is to advance our understanding of heterogeneous reactions and their effect on the composition of the troposphere. Chemistry on aqueous surfaces is particularly important in this regard because of their ubiquity and expanse. They range from the surfaces of oceans (360 million km²), cloud and aerosol drops (~10 trillion km²) to the fluids lining the human lung (~200 m²). Typically, ambient air contains reactive gases that may affect human health, influence climate and participate in biogeochemical cycles. Despite their importance, reactions between gases and solutes at air-aqueous interfaces are not well understood. New, surface-specific techniques are required that detect and identify the intermediates and products of such reactions as they happen on liquids. This is a tall order because genuine interfacial reactions are faster than mass diffusion into bulk liquids, and may produce novel species at low concentrations. Herein, we review evidence that validates online pneumatic ionization mass spectrometry of liquid microjets dosed by reactive gases as a technique meeting such requirements. Next, we call attention to results obtained by this approach on reactions of ozone, nitrogen dioxide and hydroxyl radicals with various solutes on aqueous surfaces. The overarching conclusion is that the outermost layers of aqueous solutions are unique media, where equilibria shift and reactions proceed faster than, in some cases along different pathways from the bulk liquids. The fact that the rates and mechanisms of reactions at air-aqueous interfaces may not be deduced from experiments in bulk liquids opens new conceptual frameworks and lines of research, and adds an overlooked dimension to atmospheric chemistry.

The European Union's recent decision to renew the authorization for the use of glyphosate until 15 December 2033 stimulates the scientific discussion all around the world regarding its toxicity or otherwise for humans. Glyphosate is a chemical used by millions of tons in the last 50 years worldwide to drying weeds in cultivated fields, greenhouses, roadsides. Concern has been raised in many quarters about the possible presence in the food chain and the consequent adverse effects on health: both aspects that argue in favor of toxicity and those that instead may indicate limited toxicity of glyphosate are here discussed. The great debate that has been generated requires further investigations and field measurements to understand its fate once dispersed in the environment and its concentration in the food chain. Hence the need for validated analytical methods that are available to analysts in the field. In the present review, methods for the analytical determination of glyphosate and its main metabolite, AMPA, are discussed, with a specific focus on chromatographic techniques applied to cereal products. The experimental procedures are explained in any detail, including cleanup, derivatization, and instrumental conditions to give the laboratories involved enough information to proceed with the implementation of this line of analysis. The prevalent chromatographic methods used are LC-MS/MS, GC-MS/SIM, and GC-MS/MS but sufficient indications are also given to those laboratories that wish to use the simpler HPLC-FLD, HPLC-UV, GC-NPD or GC-FPD techniques for screening purposes. Concentrations from literature measured in wheat, corn, barley, rye, oats, soybean, and cereal-based foods are reported together with the regulatory status in various parts of the world and the accumulation mechanism. As for the accumulation in cereals, available data show that glyphosate tends to accumulate more in wholemeal flours than in refined ones, that its concentration in the product strictly depends on the treatment period (the closer it is to the time of harvesting, the higher the concentration) and that in cold climates the herbicide tends to persist in the soil for a long time.

Tributyltin (TBT) is one of the most toxic anthropogenic compounds introduced into the marine environment. Despite its global ban in 2008, TBT is still a problem of great concern due to its high affinity for particulate matter, providing a direct and potentially persistent route of entry into benthic sediments. Bioremediation strategies may constitute an alternative approach to conventional physicochemical methods, benefiting from the microorganism’s potential to metabolize anthropogenic compounds. In this work, a simple, precise and accurate static headspace gas chromatography method was developed to investigate the ability of TBT degrading microbes in sedimentary microcosms over a period of 120 days. The proposed method was validated for linearity, repeatability, accuracy, specificity, limit of detection and limit of quantification. The method was subsequently successfully applied for the detection and quantification of TBT and degrading compounds in sediment samples on day 0, 30, 60, 90 and 120 of the experiment employing the principles of green chemistry. On day 120 the concentration of TBT remaining in the microcosms ranged between 91.91 ng/g wet wt for the least effective microbial inoculant to 52.73 ng/g wet wt for the most effective microbial inoculant from a stating concentration of 100 ng/g wet wt.

Fabric phase sorptive extraction, an innovative integration of solid phase extraction and solid phase microextraction principles, has been combined with gas chromatography-mass spectrometry for the rapid extraction and determination of nineteen organochlorine pesticides in various fruit juices and water samples. FPSE consolidates the advanced features of sol-gel derived extraction sorbents with the rich surface chemistry of cellulose fabric substrate, which could directly extract target analytes from complex sample matrices and substantially simplifies the sample preparation operation. Important FPSE parameters including sorbent chemistry, extraction time, stirring speed, type and volume of back-extraction solvent and back-extraction time have been optimized. Calibration curves were obtained in the concentration range 0.1-500 ng/mL. Under the optimum conditions, the limits of detection were obtained in the range 0.007-0.032 ng/mL with satisfactory precision (RSD<6%). The relative recoveries obtained by spiking organochlorine pesticides in water and selected juice samples were in the range of 91.56–99.83%. The sorbent sol-gel poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) was applied for the extraction and preconcentration of organochlorine pesticides in aqueous and fruit juice samples prior to analysis with gas chromatography-mass spectrometry. The results demonstrated that the present method is simple, rapid, and precise for the determination of organochlorine pesticides in aqueous samples.

SPME analysis of the scent Ophrys orchids gave the following results: O. apifera: benzyl benzoate, -copaene, caryophyllene, and cyclosativene. O. crabronifera subsp. biscutella: pentadecene, pentadecane, heptadecane, nonadecane, and heinecosane. O. bertolonii subsp. bertolonii: pentadecane, heptadecane and nonadecane. O. passionis subsp. garganica: i-propyl palmitate, caryophyllene, pentadecane, and heptadecane. O. holosericea subsp. apulica: -copaene, pentadecane, caryophyllene, and heptadecane. O. lacaitae: -copaene, pentadecane, heptadecane, and caryophyllene. O. bombyliflora: cyclosativene, pentadecane, and ethyl dodecanoate. O. insectifera: 8-heptadecene, pentadecane, and heptadecane. O. lutea: heptadecane, 8-heptadecene, nonadecane, and docosane. O. tenthredinifera subsp. neglecta: -copaene, caryophyllene, and i-propyl palmitate.

Analysis of liquid biopsy samples can reveal a wealth of molecular as well as cellular entities circulating in various body fluids. These entities include circulating tumor cells, circulating cell-free and tumor DNA, RNA, and proteins. Detection and characterization of this genetic and proteomic material can provide crucial information on tumor characteristics, including its heterogeneity, biology, tumor progression, staging, associated gene mutations and the course of therapy. The increased use of liquid biopsy in clinical oncology offers in non-invasive manner easier tumor sampling and continuous monitoring of the disease evolution through repetitive sampling from cancer patients. The continuous monitoring offered by this method is highly relevant to the assessment of a given therapeutic regime and early detection of markers associated with possible drug resistance, which may develop in the course of the therapy. The use of proteomic approaches, including mass spectrometry-based proteomics for the analysis of biofluids extends for over three decades, yet only in the last few years such methods have found their way to clinical oncology. The non-invasive nature of liquid biopsy and the simple procedures for sample collection made this approach far more attractive than the traditional and well-established tissue biopsy. Such preference becomes more practical in the analysis of solid tumors, particularly in pediatric population. In this review we discuss some works on the emerging role of liquid biopsy analyses in clinical oncology, and how such use allows a better understanding of diagnosis, prognosis, disease evolution and response to therapy of various forms of cancer. We also discuss the role of MS-based methods in the characterization of post-translational modifications of proteins circulating in liquid biopsies.

Fingerprints are essential for human identification and are valuable tools in criminal investigations. The pursuit of new materials for digital printing is expanding, with increasing interest in natural compounds such as bixin, sourced from annatto seeds. Despite its traditional use as a natural dye with medicinal properties, the potential of bixin in papilloscopy remains largely untapped. In this study, we meticulously extracted bixin from annatto seeds and meticulously developed composites incorporating zinc carbonate (bixin/ZnCO3) and kaolinite (bixin/kaolinite). UV-visible spectroscopy was used for characterization, and the extracted bixin showed absorption peaks at 429, 453, and 481 nm, which were very similar to standard peaks at 429, 457, and 487 nm. The two samples also had the same retention times (7.07 min) according to further liquid chromatography analysis. Sweat pores were easier to detect thanks to the effectiveness of the bixin/ZnCO3 and bixin/kaolinite composites in creating high contrast sebaceous and natural latent fingerprints. These results highlight the composites’ potential as novel and fascinating instruments for papilloscopy applications, which might also improve forensic investigations.

Emerging pollutants (EPs) encompass natural or synthetic substances in the environment that pose potential risks but have only recently been recognized or monitored. EPs consist of various categories including pesticides, pharmaceuticals, hormones, mycotoxins, and endocrine disrupting chemicals (EDCs). Through several pathways, EPs can access food, potentially leading to health impacts when their safe concentrations are exceeded. Milk, being a highly nutritious and a heavily consumed food product by many consumers of different ages, is a crucial food matrix where EPs should be regularly monitored. In literature, large number of studies was dedicated for the determination of different EPs in dairy milk, employing different analytical techniques. Chromatographic based techniques were the most prevalent means for analysis of EPs in milk, which demonstrated significant efficiency, sensitivity and accuracy for this specific purpose. Prior to chromatographic analysis, extraction of EPs from a complex matrix like milk, is essential. This review comprehensively covers relevant research papers on extraction and subsequent detection and determination of EPs in milk by chromatographic methods from 2018 and until 2023.

The polysaccharide-based chiral stationary phase (CSP) columns for high-performance liquid chromatography (HPLC) were applied in the separation of liquid crystalline racemic mixtures obtained based on (R,S)-2-octanol and were found to be highly effective in recognizing isomers of minor structural differences. The mobile phase (MP), which consists of acetonitrile (ACN)/water (H2O) at different volume ratios, was used. All measurements were made at room temperature. The order of the elution was also determined. The chromatographic parameters such as resolution - (Rs), selectivity - (α), and the number of theoretical plates, i.e., column efficiency - (N), were determined. The polysaccharide-based CSP columns have unique advantages in separation technology, and this study has shown the potential usefulness of the CSP columns in separating liquid crystalline racemic mixtures belonging to the same homologous series.

A simple and rapid method for the extraction of D-series resolvins (RvD1, RvD2, RvD3, RvD4, RvD5) released into Leibovitz's L-15 complete medium by head kidney cells from Atlantic salmon and further liquid chromatography triple quadrupole mass spectrometry determination is proposed. A three-level factorial design was proposed to select the optimal concentrations of internal standards that were used in the evaluation of the performance parameters such as linear range (0.1-50 ng/mL), limits of detection and quantification (0.05 and 0.1 ng/mL, respectively) and recovery values (98.99±0.00). The optimized method was used to determine the stimulated production of resolvins by head kidney cells exposed to docosahexaenoic acid, and the results indicated that it is possible that the production was controlled by circadian responses.

Vitamin A and E are important during pregnancy, the neonatal period, and childhood. The objective of this study was to assess whether maternal RRR-a-tocopherol supplementation affects serum and breast milk retinol. Serum was collected at baseline and twenty days later, and breast milk, at baseline, and on days 1, 7, and 20 after delivery. After the baseline serum collection, the supplemented group (n=16) received a single 400 IU of RRR-α-tocopherol. The control group (n=18) was only performed collections. Retinol and alpha tocopherol levels were determined by liquid chromatography. Serum retinol and alpha tocopherol at baseline and 20 days after delivery indicated proper vitamin A (> 20 µg/dL) and E (> 516 μg/dL) statuses in the control and supplemented groups (p > 0.05). Colostrum retinol levels on days 1 and 7 after delivery were significantly higher in the supplemented group (p = 0.018 and p = 0.012, respectively). Maternal vitamin E supplementation increased colostrum retinol by 52.23% and 111.2%, 24 hours and 7 days, respectively. However, retinol in mature milk did not differ between the groups (p > 0.05). In conclusion, the supplementation with 400 IU of RRR-α-tocopherol improved vitamin A bioavailability in breast milk.

Sunscreens are topical preparations containing one or more compounds that protect humans from ultraviolet (UV) light. This review focuses on analytical methods, particularly liquid chromatography, aimed at identifying and determining UV filters (UVFs) in environmental and marine biota matrices. A literature review was done using NIH (PubMed and Medline), FDA and EPA databases, Google Scholar, and Federal Regulations. This retrospective literature review is focused on the last five years. UVFs quantification in environmental and biological matrices showed a wide array of methods where liquid chromatography is predominant. The scientific literature identified a large variety of analytical methodologies that are compared in this review, to evaluate the better results in terms of limits of quantification and the possibility to identify as many analytes as possible simultaneously.

Abstract: Filipendula ulmaria, commonly known as meadowsweet, is a wild herbaceous flowering plant widely distributed in Europe. A range of salicylic acid derivatives and flavonol glycosides have been previously associated with the antirheumatic and diuretic properties of F. ulmaria. In the present work, an hydroalcoholic extract of F. ulmaria aerial parts was extensively profiled using an efficient NMR-based dereplication strategy. The approach involves fractionation of the crude extract by centrifugal partition chromatography (CPC), ¹³C NMR analysis of the fractions, 2D-cluster mapping of the whole NMR dataset and finally, structure elucidation using a natural metabolite database, validated by 2D NMR data interpretation and liquid chromatography coupled to mass spectrometry. The chemodiversity of the aerial parts was quite broad, with 28 compounds unambiguously identified, belonging to various biosynthetic classes. The F.ulmaria extract and CPC fractions were screened for their potential to improve skin epidermal barrier function and also skin renewal properties using in vitro assays performed on Normal Human Epidermal Keratinocytes. Fractions containing quercetin, kaempferol glycosides, ursolic acid, pomolic acid, naringenin, β-sitosterol, and tellimagrandins I and II were found to be responsible for the up-regulation of genes related to skin barrier function, epidermal renewal and stress responses. This research is significant as it could provide a natural solution for improving hydration and skin renewal properties.

The research aims to discover the natural occurrence of patulin (PAT) in selected citrus fruits from the central cities of Punjab and Pakistan's Northern cities. Total 2970 samples of twelve citrus fruits; kinnow, orange, grapefruits, bitter orange, mausami, red blood, pineapple, sweet orange, rough lime, sweet lime, kagzi lime and lemon were examined using liquid chromatography fitted with UV detector. The limit of detection (LOD) and quantification limit was 0.04 and 0.12 µg/kg, respectively. The results have shown that 56% of samples of citrus fruits from Punjab's central cities, Pakistan, were discovered to be infected from PAT. The elevated amounts of PAT ranging from 0.04 to 1150 µg/kg were found in citrus fruit samples from Multan cities. Furthermore, 31.7% of samples of citrus fruits from Northern cities of Pakistan were discovered to be infected with PAT, and the elevated amounts were found ranging from 0.04-320 µg/kg from Swat city. About 22.1% of samples of citrus fruits have levels of PAT greater than the suggested limits established by the European Union (EU). PAT's dietary intake levels ranged from 0.10-1.11 µg/kg bw/day from the central cities of Punjab, Pakistan, and 0.13-1.93 µg/kg bw/day were documented from Northern cities of Pakistan.

The research aims to discover the natural occurrence of patulin (PAT) in selected citrus fruits from the central cities of Punjab and Pakistan's Northern cities. Total 2970 samples of twelve citrus fruits; kinnow, orange, grapefruits, bitter orange, mausami, red blood, pineapple, sweet orange, rough lime, sweet lime, kagzi lime and lemon were examined using liquid chromatography fitted with UV detector. The limit of detection (LOD) and quantification limit was 0.04 and 0.12 µg/kg, respectively. The results have shown that 56% of samples of citrus fruits from Punjab's central cities, Pakistan, were discovered to be infected from PAT. The elevated amounts of PAT ranging from 0.04 to 1150 µg/kg were found in citrus fruit samples from Multan cities. Furthermore, 31.7% of samples of citrus fruits from Northern cities of Pakistan were discovered to be infected with PAT, and the elevated amounts were found ranging from 0.04-320 µg/kg from Swat city. About 22.1% of samples of citrus fruits have levels of PAT greater than the suggested limits established by the European Union (EU). PAT's dietary intake levels ranged from 0.10-1.11 µg/kg bw/day from the central cities of Punjab, Pakistan, and 0.13-1.93 µg/kg bw/day were documented from Northern cities of Pakistan

Ketogenic diet (KD) is getting in the focus as auxiliary cancer therapy, since it provides sufficient energy supply for healthy cells, while impairing energy production in tumor cells underlying the Warburg effect. Thereby, it can assist in inhibiting tumor growth and simultaneously counteract cachexia, which is frequently observed in cancer patients under chemotherapy. In order to provide molecular evidence for the proposed synergistic inhibition of tumor growth, we applied untargeted quantitative metabolome analysis on a breast cancer xenograft mouse model. Healthy mice and such bearing breast cancer xenografts and receiving chemotherapy were compared after treatment with control diet and KD. Metabolomic profiling was performed on plasma samples, applying high-performance liquid chromatography coupled to tandem mass spectrometry. Statistical analysis revealed metabolic fingerprints comprising numerous significantly regulated features in the group of mice bearing breast cancer. This fingerprint disappeared after treatment with KD, resulting in recovery to the metabolic status observed in healthy mice receiving control diet. Moreover, amino acid metabolism as well as fatty acid transport were found to be affected by both, the tumor and the applied KD. Our results provide clear evidence of a significant molecular effect of KD in the context of tumor growth inhibition.

Dicarbonyls are electrophiles able to generate the so-called advanced glycation end-products (AGEs). Human exposure occurs via ingestion (e.g., food), inhalation (e.g., electronic cigarettes) and dysregulation of endogenous metabolic pathways (e.g., glycolysis). Biological systems can prevent AGEs formation via enzymatic and nonenzymatic reactions. However, the continuous exposure to dicarbonyls may cause the depletion of endogenous substrates and the beginning of AGEs accumulation (i.e., carbonylation). Since this process has been associated with multiple disorders, several studies advocated the use of dicarbonyl binders as food preservatives or as drugs aimed at mitigating carbonylation damages. As reported for other toxicants (e.g., HNE, acrolein), the screening of selective and potent binders can be performed by measuring the residual amount of a selected dicarbonyl substrate, upon its incubation with candidate binders. Unfortunately, naturally occurring dicarbonyls are poorly responsive to many detectors (e.g., UV or MS). For this reason, most of the screening methods that have been reported to date relies on indirect quantification upon derivatization. However, this strategy can potentially lead to inaccurate results since the tested compounds can affect the derivatization yield. Therefore, we herein reported the use of benzylglyoxal (BGO) as a convenient, UV responsive, dicarboyl surrogate. By using BGO as a substrate, we setup an easy and cheap chromatographic assay for the direct measurement of the binding activity towards dicarbonyls, without derivatization. The method was qualified by assessing the binding ability of some known dicarbonyl binders, obtaining results consistent with literature.

In this study, GC–IMS was used to analyze the volatile component and flavor profiles of Crassostrea gigas individuals of different ploidy and gender. Principal component analysis was used to explore overall differences in flavor profiles and a total of 54 volatile compounds were identified. The total volatile flavor contents in edible parts of tetraploid oysters were significantly higher than in diploid and triploid oysters. The concentrations of ethyl (E)-2-butenoate and 1-penten-3-ol were significantly higher of triploid oysters than in diploid and tetraploid oysters. In addition, the volatile compounds propanoic acid, ethyl propanoate, 1-butanol, butanal, and 2-ethyl furan were significantly higher in females than in males. The volatile compounds p-methyl anisole, 3-octanone, 3-octanone, and (E)-2-heptenal were present in higher levels in male than in female oysters. Overall, different ploidy and gender of oysters were being presented with different sensory characteristics, providing new insights for understanding the flavor characteristics of oysters.

A multi-tool analytical practice was used for characterization of 16^th century carpet manufactured in Cairo. Mild extraction method with hydrofluoric acid enabled isolation of intact flavonoids and their glycosides, anthraquinones, tannins and indigoids from fibre samples. High-performance liquid chromatography coupled to spectroscopic and mass spectrometric detectors was used for identification of natural dyes present in the historical samples. Weld, young fustic and brazilwood were identified as the dye sources in yellow thread samples. Red fibres have been colored with lac dye, whereas green fibre shades were obtained with indigo and weld. Tannin-containing plant material in combination with indigo and weld were used to obtain brown hue of thread. Four uncommon and thus-far unknown dye components were also found in the historical samples. These compounds probably represent unique fingerprint of dyed threads from this region. Scanning electron microscopy with energy-dispersive X-ray detector (SEM-EDS) and Fourier transformation infrared spectroscopy (FT-IR) were used for identification and characterization of substrates and mordants present in the historical carpet. Carbon and oxygen were detected in large quantities as a part of the wool protein. The presence of aluminum, iron and calcium indicated their usage as mordants. FT-IR analysis showed bands characteristic to woolen fibres and SEM micrographs definite structure of wool.

Microbial competition within plant tissues affects invading pathogens' fitness. Metabolomics is a great tool for studying their biochemical interactions by identifying accumulated metabolites. Xylella fastidiosa, a Gram-negative bacterium causing Pierce's disease (PD) in grapevines, secretes various virulence factors including cell wall degrading enzymes, adhesion proteins, and quorum sensing molecules. These factors, along with outer membrane vesicles, contribute to its pathogenicity. Previous studies demonstrated that co-inoculating X. fastidiosa with Paraburkholderia phytofirmans strain PsJN suppressed PD symptoms. Here, we further investigated the interaction between the phytopathogen and the endophyte by analyzing the exometabolome of wild-type X. fastidiosa and a diffusible signaling factor (DSF) mutant lacking quorum sensing, cultivated with 20% P. phytofirmans spent media. LC-MS and MAGI were used to detect and map metabolites to genomes revealing a total of 121 metabolites, of which 25 were further investigated. These metabolites potentially relate to host adaptation, virulence, and pathogenicity. Notably, this study presents the first comprehensive profile of X. fastidiosa in the presence of P. phytofirmans spent media. The results highlight that P. phytofirmans and the absence of a functional quorum sensing affect the ratios of glutamine to glutamate (Gln:Glu) in X. fastidiosa. Additionally, two compounds with plant metabolism and growth properties, 2-Aminoisobutyric acid and Gibberellic Acid, were downregulated when X. fastidiosa interacted with P. phytofirmans. These findings suggest that P. phytofirmans-mediated disease suppression involves modulation of the exometabolome of X. fastidiosa, impacting plant immunity.

Compound-specific isotope analysis (CSIA) can provide unique insights into the cycling of elements including carbon and nitrogen. One approach for CSIA is the use of high-performance liquid chromatography (HPLC) to separate compounds of interest, followed by analysis of these compounds using an elemental analyzer coupled to an isotope ratio mass spectrometer. A key component of this technique is the fraction collector, which automatically collects compounds as they are separated by HPLC. Here we present a fraction collector which is a simple adaptation of a 3D printer, and thus can be easily adopted by any laboratory already equipped for HPLC. In addition to the much lower cost compared to commercial alternatives, this adaptation has the advantage for CSIA that the 3D-printer is able to heat the collected fractions, which is not true for many commercial fraction collectors. Heating allows faster evaporation of the solvent, so that the dried compounds can be measured by EA-IRMS immediately. The procedure can be repeated consecutively so that dilute solutions can have the compounds concentrated for analysis. Any computer-controlled HPLC can be integrated to the fraction collector used here by means of AutoIt.

Saussurea neoserrata Nakai offers a reliable and efficient source of antioxidants that can help alleviate adverse skin reactions triggered by air pollutants. Air pollutants, such as particulate matter (PM), have the ability to infiltrate the skin and contribute to the higher occurrence of cardiovascular, cerebrovascular, and respiratory ailments. Individuals with compromised skin barriers are particularly susceptible to the impact of PM since it can be absorbed more readily through the skin. This study investigated the impact of protocatechuic acid and syringin, obtained from the n-BuOH extract of S. neoserrata Nakai, on the release of PGE₂ and PGD₂ induced by PM₁₀. Additionally, it examined the gene expression of enzymes involved in the synthesis of PGE₂ and PGD₂ in human keratinocytes. The findings of this research highlight the potential of utilizing safe and efficient plant-derived antioxidants in dermatological and cosmetic applications to mitigate the negative skin reactions caused by exposure to air pollution.

A novel polyphenol‑coated CoFe₂O₄ system was synthesized as a magnetic adsorbent by chemical oxidative polymerization process for magnetic solid-phase extraction of lawsone. The synthesized nanoadsorbent showed a spherical morphology with diameters under 50 nm by scanning electron microscopy images. The extraction efficiency of this adsorbent was studied towards the extraction of lawsone from saline aqueous solution in dispersion mode. Major parameters including the type and volume of desorption solvent, amount of sorbent, desorption time, extraction time, extraction temperature, ionic strength and pH were optimized. Under the optimum conditions the relative standard deviation in 0.005 µg mL^-1 (inter-day n = 6; intra-day: n = 6; and adsorbent to adsorbent n = 4) were obtained as 5.2, 8.07 and 11.7%, respectively. A linear calibration curve in the range of 0.003–0.5 µg mL^-1 with R² = 0.993 was obtained. The limit of detection and limit of quantification of the method were 0.001 µg mL^-1 and 0.003 µg mL^-1, respectively. The relative recovery percentages were in range of 90-96.4% for henna leaves, henna shampoo, and henna dermal lotion real samples.

Vitamin D has previously been quantified in some plants and algae, particularly in leaves of the Solanaceae family. We measured the vitamin D content of Australian native food plants and Australian-grown edible seaweed. Using liquid chromatography with triple quadrupole mass spectrometry, 13 samples (including leaf, fruit and seed) were analysed in duplicate for vitamin D₂, vitamin D₃, 25-hydroxyvitamin D₂ and 25-hydroxyvitamin D₃. Five samples contained vitamin D₂: raw wattleseed (Acacia victoriae) (0.03 µg/100 g dry weight (DW)); fresh and dried lemon myrtle (Backhousia citriodora) leaves (0.03 and 0.24 µg/100 g DW, respectively); dried leaves and berries of Tasmanian mountain pepper (Tasmannia lanceolata) (0.67 and 0.05 µg/100 g DW, respectively). Fresh kombu (Lessonia corrugata) contained vitamin D₃ (0.01 µg/100 g DW). Detected amounts were low; however, it is possible that exposure to ultraviolet radiation may increase the vitamin D content of plants and algae if vitamin D precursors are present.

To better understand the shape memory materials and self-healing materials, a new series of liquid-crystalline shape memory polyurethane (LC-SMPU) composites, named SMPU-OOBAm, were successfully prepared by incorporating 4-octyldecyloxybenzoic acid (OOBA) into the PEG-based SMPU. The effect of OOBA on the structure, morphology and properties has been carefully investigated. The results demonstrate that SMPU-OOBAm have liquid crystalline properties, triple-shape memory properties and self-healing properties. The incorporated OOBA promotes the crystallizability of both soft and hard segments of SMPU, and the crystallization rate of the hard segment of SMPU decreases when the OOBA-content increases. Additionally, the SMPU-OOBAm forms a two-phase separated structure (SMPU phase and OOBA phase), and it shows two-step modulus changes upon heating. Therefore, the SMPU-OOBAm shows triple-shape memory behavior, and the shape recovery ratio decreases with an increase in the OOBA content. Finally, SMPU-OOBAm shows self-healing properties. The new mechanism can be ascribed to the heating-induced “bleeding” of OOBA in the liquid crystalline state and the subsequent re-crystallization upon cooling. This successful combination of liquid crystalline properties, triple-shape memory properties and self-healing properties make the SMPU-OOBAm composites with many promise applications in smart optical devices, smart electronic devices and smart sensors.

Hypoxic-ischemic encephalopathy (HIE) is one of the most common causes of childhood disability. Hypothermic therapy is currently the only approved neuroprotective approach. However, early diagnosis of HIE can be challenging, especially in the first hours after birth when the decision to treat with hypothermic therapy is critical. Differentiating HIE from other neonatal conditions, such as sepsis, further complicates the diagnosis. This study investigated the utility of a metabolomic-based approach using the NeoBase 2 MSMS kit to diagnose HIE using dry blood stains in a Rice-Vannucci model of HIE in rats. We evaluated the diagnostic accuracy of this method between 3 and 6 hours after the onset of HIE, including in the context of systemic inflammation and concomitant hypothermic therapy. Discriminant analysis revealed several metabolite patterns associated with HIE. A logistic regression model using glycine levels achieved high diagnostic accuracy with areas under the curve (AUC) of 0.94 at 3 hours and 0.96 at 6 hours after the onset of HIE. In addition, orthogonal partial least squares discriminant analysis, which included five metabolites, achieved 100% sensitivity and 80% specificity within 3 hours of HIE. These results highlight the significant potential of the NeoBase 2 MSMS kit for the early diagnosis of HIE and could improve patient management and outcomes in this serious illness.

Two interesting compounds such as quaternary ammonium lignin(QAL) and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (P507) were synthesized as ionic liquids(QP-ILs) for the extraction of metal ions. The extraction behavior of Co(II) and Ni(II) from chloride solution was compared between QP-ILs and P507. The results showed that the extraction rates of Co(II) and Ni(II) in the two solutions varied with the extraction conditions, but QP-ILs has stronger extractability for cobalt than P507, while Ni is on the contrary. Under the same conditions, the Co/Ni separation performance(βCo/Ni) in QP-ILs is superior to that in p507. At pH4.0, 55℃, concentration of 20%, extraction time of 10 minutes, the βCo/Ni of QP-ILs reached to 2703, while that of P507 was only 164. In conclusion, QP-ILs was more efficient than P507 for separating Co from mixed solutions.

High circulating concentrations of the gut microbiota-derived metabolite trimethylamine N-oxide (TMAO) are significantly associated with the risk of obesity and type 2 diabetes (T2D). We aimed at evaluating the impact of glycemic control and bariatric surgery on circulating concentrations of TMAO and its microbiota-dependent intermediate, γ-butyrobetaine (γBB), in newly diagnosed T2D patients and morbidly obese subjects. An additional experiment was carried out in eight male C57BL/6J mice fed a Western-type diet for twelve weeks. The strategy for glycemic control in the T2D patients significantly improved the HbA1c concentrations without producing changes in the estimated glomerular filtration rate. However, the plasma TMAO and γBB concentrations were significantly increased following the glycemic control in T2D patients. Bariatric surgery was very effective in reducing weight in obese subjects. Nevertheless, the surgery reduced plasma γBB concentrations without affecting TMAO concentrations and the estimated glomerular filtration rate. Neither diet-induced obesity nor insulin resistance were associated with circulating TMAO and γBB concentrations in mice. Our findings do not support that glycemic control or bariatric surgery improve the circulating concentrations of TMAO in newly diagnosed T2D and morbidly obese patients. The contribution of antidiabetic drugs to gut microbiota composition could explain TMAO elevations in treated T2D subjects.

Lipophilicity can be measured with different methods, such as Shake-Flask or liquid chromatography. HPLC presents the advantage of overcoming solubility issues and therefore extending the range of lipophilicity to high values. A specific HPLC method, called ELogD, had been developed 20 years ago on a C₁₆-amide stationary phase, enhancing hydrophobic and hydrogen bond interactions to mimic octanol-water partition. The emergence of novel stationary phases added to the need for a less complex mobile phase has led to the development of a new HPLC assay called alphaLogD, applicable to neutral and basic compounds at pH 7.4, that combines superficially porous particles, a high number of equilibriums between solutes and stationary phase, and results in a lower number of isocratic methods to determine the logk’_w at a higher throughput. Statistical studies have been run to successfully evaluate the alphaLogD method compared to the Shake-Flask method and to allow this lipophilicity measurement into the so-called Beyond-Rule-of-5-molecules space.

Bisphenol F (BPF) and bisphenol S (BPS) are increasingly used as substitutes for bisphenol A (BPA) in the plastic industry, driven by concerns over the adverse effects of BPA. However, there is a lack of infor-mation on the extent of exposure to these chemicals in children. This study aims to assess the extent of BPA, BPF, and BPS exposure and determine factors that influence such exposure. A group of Thai children (age 6-13 years, n=358) were recruited between October 2019-2020. Two first morning void was collected one week apart. Demographic and exposure-related information was gathered. Urinary concentrations of bisphenols were analyzed by liquid-chromatography and tandem mass spectrometry. Correlation between bisphenol concentrations and various factors was determined using generalized estimating equations with linear model. BPA, BPF, and BPS were detected at 79.6%, 31.0%, and 16.8%, with geometric mean (GM) concentrations of 1.41, 0.013, and 0.014 ng/mL respectively. Younger children aged < 10 years exhibited 1.3-1.6 times higher GM levels of all bisphenols compared to older children. Exposure to food stored in plas-tic containers were associated with higher levels of BPF and BPS. In conclusion, BPA was the most fre-quently detected bisphenol in urine samples from Thai children, followed by BPF and BPS.

The early diagnosis of mastitis represents an essential factor for a prompt detection of the animal for further actions. In fact, if not culled, infected cows must be segregated from the milking herd and milked last, or milked with separate milking units. Besides microbiological analysis, the somatic cell count (SCC) commonly used as predictor of intramammary infection, frequently lead to a misclassification of milk samples. To overcome these limitations, more specific biomarkers are continuously evaluated. Total amino acid content increases significantly in mastitic milk compared to normal one. Bovine mastitis can arise as a result of infection of the mammary gland by Staphylococcus aureus. Multiplication of this bacterium within the mammary gland is required for infection to persist. S. aureus requires branched-chain amino acids (BCAAs: isoleucine, leucine, valine) for protein synthesis, branched-chain fatty acids synthesis and environmental adaptation by responding to their availability via transcriptional regulators. The importance of BCAAs for S. aureus physiology necessitates that it either synthesize them or scavenge them from the environment. Increase of BCAAs in composite milk has been postulated to be linked to mammary infection by S. aureus. In the present work, we demonstrated, by a direct ion-pairing reversed-phase method based on the use of the evaporative light-scattering detector (IP-RP-HPLC-ELSD), applied to 65 composite cow milk samples, a correlation between the concentration of isoleucine and leucine and S. aureus load.

Osteoarthritis (OA) is a pathology of great impact worldwide which its physiopathology is not completely known and usually diagnosed by imaging techniques performed at advanced stages of the disease. The aim of this study was to evaluate early serum metabolome changes and identify the main metabolites involved in an inflammatory OA animal model. The study was performed with thirty rats, OA in all animals was induced by intra-articular injection of monoiodoacetate into the knee joint. Blood samples were taken from all animals and analyzed by mass spectrometry before OA induction, and 28, 56 and 84 days following induction. Histological study confirmed OA in all samples. The results of this study allow the identification of several changes in the serum metabolome over time, including organic acids, benzenoids, heterocyclic compounds and lipids at T28, organic acids at T56 and lipid classes at T84. We conclude that OA induces serological changes in the metabolome and, more specifically, 18 metabolites which could serve as potential biomarkers. However, it was not possible to establish a relationship between the identified metabolites and the time at which the samples were taken. Therefore, these findings should be confirmed in future OA studies.

Sheep’s milk is a significant source of nucleotides monophosphate (NMPs) but can also contain undesirable residues from veterinary drugs, posing a potential human health risk. This study introduces a novel application of 2D-LC, in heart-cutting mode, for the simultaneous determination of nucleotides and veterinary drug residues in sheep’s milk. Two-dimensional liquid chromatography (2D-LC) allows for the separation of these compounds in a single chromatographic run despite their differing physicochemical properties. The proposed method separates six veterinary drug residues and five NMPs in a single injection. The compounds were separated using a C18 reversed-phase column in the first dimension and a Primesep SB analytical column in the second dimension. The method performance was evaluated in terms of linearity range, detection and quantification limits, matrix effects, precision, and accuracy. The results demonstrated good linearity and sensitivity, with quantification limits allowing for the quantification of veterinary drugs at the maximum residue level and nucleotides at typical levels found in milk samples. The method has been successfully applied to the analysis of sheep’s milk samples acquired from local supermarkets, with recoveries within a range of 70-119 % and 82-117 % for veterinary residues and NMPs, respectively.

Bat feces were reported in ancient Chinese medicine books to have the effect of reducing heat and improving eyesight, but the mechanism of vision improvement still needs further research. To this end, we used 2,2-diphenyl-1-picrylhydrazyl (DPPH) and liquid chromatography/tandem mass spectrometry (LC/MS/MS) to analyze the antioxidant capacity of and the types of vitamins in bat feces. We hoped to screen the pharmacological components of bat feces, and to explain the role that these components may play in the treatment of visual deterioration. Our results found that bat feces had a good antioxidant capacity and mainly contain vitamins B1 (thiamine), B2 (riboflavin), B3 (nicotinamide), B3 (nicotinic acid), and B5 (pantothenic acid). Although these vitamins may help maintain the health of the optic nerve and cornea, the vitamin content of bat feces is low, but the heavy metal content is high, as shown using inductively coupled plasma mass spectrometry (ICP-MS) analysis. Therefore, we suggest that the use of bat feces as traditional Chinese medicine to improve vision should be strictly restricted.

The study of exogenous metabolites of algae-bacterial communities in the laboratory accumulative culture obtained from natural river water was done using gas chromatography-mass spectrometry. Exometabolites of the algae-bacterial community (including microalgae and cyanobacteria) in the culture medium were represented by saturated, unsaturated, and aromatic hydrocarbons, carboxylic acids, phenolic, and terpene compounds and their derivatives. Possible biological activities of the discovered exometabolites are considered. The study has demonstrated that an increase in the number of main groups of microorganisms, along with changes in the composition of algae and cyanobacteria, are responsible for the increase in the composition and concentration of metabolites in the microecosystem's culture medium after one month of cultivation. The presence of octacosane in high concentration (0.0603 mg/l; 23.78% of the total content of low molecular weight organic compounds) by the end of exposure accumulative culture is associated with the strong development of the cyanobacterium Gloeocapsa sp. in the presence of diatom algae of the genus Navicula and green algae of the genera Chlorella and Scenedesmus. Due to the need to comprehend the ecological and biochemical mechanisms of the formation and functioning of algae-bacterial communities, as well as to predict potential paths of transformation and evolution of aquatic ecosystems, the specificity of exometabolite complexes of algae and microorganisms, as well as their allelopathic and other biochemical interactions in freshwater ecosystems, requires further serious study.

Pyrethroid pesticides (PYRs) as the third most widely used pesticides, following organophosphorus and carbamate pesticides, which are of significant importance in the analysis and detection of vegetables. However, the current pretreatment technology for PYRs confronts challenges of difficult separation and low enrichment efficiency, resulting in a cumbersome and time-consuming pretreatment process with poor selectivity. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed to simultaneously purify and enrich five PYRs in vegetables, with the magnetic covalent organic framework nanomaterial COF-SiO2@Fe3O4 as an adsorbent. The COF-SiO2@Fe3O4 was prepared by a simple solvothermal conditions method, using Fe3O4 as magnetic core, benzidine and 3,3,5,5-tetraaldehyde biphenyl as two building units. COF-SiO2@Fe3O4 could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on extraction efficiency was investigated to optimize the MSPE conditions, including adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00–100 μg·kg-1 (1.00–100 μg·kg-1 for bifenthrin and 2.5–100 μg·kg-1 for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3–1.5 μg·kg-1, and the limits of quantification (LOQs) were 0.9–4.5 μg·kg-1. The recoveries were 80.2–116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO2@Fe3O4, NH2-SiO2@Fe3O4 and Fe3O4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO2@Fe3O4 was an efficient and rapid selective adsorbent for PYRs. This method holds promising prospects for the determination of PYRs in real samples.

The naturally occurring dipeptide carnosine (β alanyl L histidine) specifically attenuates tumor growth. Here, we asked whether other small imidazole containing compounds also affect viability of tumor cells without affecting non-malignant cells, and whether formation of histamine is involved. Patient-derived fibroblasts and glioblastoma cells were treated with carnosine, L alanyl L histidine (LA-LH), ß alanyl L alanine, L histidine, histamine, imidazole, β alanine and L alanine. Cell viability was assessed by cell-based assays and microscopy. The intracellular release of L histidine and formation of histamine was investigated by High Performance Liquid Chromatography coupled Mass Spectrometry. Whereas carnosine and LA LH inhibited tumor cell growth with minor effects on fibroblasts, L-histidine, histamine and imidazole affected viability in both cell types. Compounds without imidazole moiety did not diminish viability. In the presence of LA LH but not in the presence of carnosine a significant rise of intracellular amounts of histidine was detected in all cells. Formation of histamine was not detectable in the presence of carnosine, LA LH or histidine. In conclusion, the imidazole moiety of carnosine contributes to its anti-neoplastic effect, which is also seen in the presence of histidine and LA LH. Despite histamine had a strong effect on cell viability, formation of histamine is not responsible for the effects on cell viability of carnosine, LA LH and histidine.

Alterations in the carnitine shuttle system may be an indication of the presence of cancer. As such, in-depth analyses of this pathway in different malignant tumors could be important for the detec-tion and treatment of this disease. The current study aims to assess the profiles of carnitine and acylcarnitines in gliomas with respect to their grade, the presence of isocitrate dehydrogenase (IDH) mutations, and 1p/19q co-deletion. Brain tumors obtained from 19 patients were sampled on-site using solid-phase microextraction (SPME) immediately following excision. Analytes were desorbed and then analyzed via liquid chromatography-high resolution mass spectrometry. The results showed that SPME enabled the extraction of carnitine and 22 acylcarnitines. An analysis of the correlation factor revealed presence of two separate clusters: short-chain and long chain car-nitine esters. Slightly higher carnitine and acylcarnitine concentrations were observed in the higher malignancy tumor samples (high vs low grade), and in those samples with worse projected clinical outcomes (without vs with IDH mutation; without vs with 1p/19q co-deletion). Thus, the proposed chemical biopsy approach offers a simple solution for on-site sampling that enables sample preservation, thus supporting comprehensive multi-method analyses.

Objective: Lipids are secreted into milk as bilayer-coated structures: milk lipid globules (MLGs). Adipophilin (ADRP) and perilipin 3 (TIP47) are associated with MLGs in human breast milk; however, the role of these proteins in milk lipid secretion is not fully understood. The aim of the study was to investigate levels of ADRP, TIP47 and total lipid content in human breast milk, their mutual correlations and dynamics during lactation. Research Methods & Procedures: Milk samples from 22 healthy lactating women (Caucasian, Central European) were collected at five time points during lactation (1–3, 12–14, 29–30, 88–90 and 178–180 days postpartum). Mass spectrometry-based method was used for quantification of ADRP and TIP47 in the samples. The gravimetric method was used to determine milk total lipid content. Results: We observed distinctive trends in ADRP, TIP47 levels and lipid content in human breast milk during the first 6 months of lactation. We also found a significant association between lipid content and ADRP, lipid content and TIP47, and ADRP and TIP47 concentrations in breast milk at all sampling points. Moreover, we derived an equation for estimating the mean lipid content of milk based on ADRP concentration in human breast milk. Conclusions: A mass spectrometry-based method was developed for quantifying ADRP and TIP47 in human breast milk. Strong mutual correlations were found between ADRP, TIP47 and total lipid content in human breast milk.

Extracellular vesicles (EVs) are cell-derived membranous particles secreted by all cell types into the extracellular milieu. EVs carry, protect, and transport a wide array of bioactive cargoes to recipient/target cells. EVs regulate physiological and pathophysiological processes in recipient cells and are important in therapeutics/drug delivery. Despite these great attributes of EVs, an efficient protocol for EV separation from biofluids is lacking. Numerous techniques have been adapted for the separation of EVs with size exclusion chromatography (SEC)-based methods being the most promising. Here, we review the SEC protocols used for EV separation, and discuss opportunities for significant improvements, such as the development of novel particle purification liquid chromatography (PPLC) system capable of tandem purification and characterization of biological and synthetic particles with near-single vesicle resolution. Finally, we identify future perspectives and current issues to make PPLC a tool capable of providing a unified, automated, adaptable, yet simple and affordable particle separation resource.

Short chain quinones (SCQs) have been identified as potential drug candidates against mitochondrial dysfunction, which is largely dependent on their reversible redox characteristics of the active quinone core. We recently synthesized a SCQ library of > 148 naphthoquinone derivatives and identified 16 compounds with enhanced cytoprotection compared to the clinically used benzoquinone idebenone. One of the major drawbacks of idebenone is its high metabolic conversion in the liver, which significantly restricts is therapeutic activity. Therefore, this study assessed the metabolic stability of the 16 identified naphthoquinone derivatives 1-16 using hepatocarcinoma cells in combination with an optimized reverse-phase liquid chromatography (RP-LC) method. Most of the derivatives showed significantly better stability than idebenone over 6 hours (p < 0.001). By extending the side-chain of SCQs, increased stability for some compounds was observed. Metabolic conversion from the derivative 3 to 5 and reduced idebenone metabolism in the presence of 5 were also observed. These results highlight the therapeutic potential of naphthoquinone-based SCQs and provide essential insights for future drug design, prodrug therapy and polytherapy, respectively.

Nitraria tangutorum Bobrov is a berry shrub with white flowers and red fruits, which grows in the deserts in the Tibetan Plateau, Mongolia, and western China. Its fruit N. tangutorum fruit (NTF) contains various bioactive compounds, with anti-fatigue, anti-inflammatory, and neuroprotective functions. However, the high saccharide content of NTF makes it unsuitable for diabetic patients. In this study, we fermented NTF to obtain N. tangutorum fermented juice (NTJ), and N. tangutorum fermented residue (NTR), which are suitable for diabetics to consume. We characterized the bioactive compounds in NTF, NTR, and NTJ, and found that fermentation increased the diversity of bioactive compounds, and greatly reduced sucrose, glucose, and fructose content while generating trehalose, which has the potential to manage blood glucose levels. Further, NTJ displays anti-diabetic potential due to various compounds anti-diabetic properties. This study provides a basis for further clinical research on NTJ's anti-diabetic function in humans.

Introduction. Grilling more and more sophisticated dishes is often a popular activity. Marshmallows are confectionery products popular among children and teenagers worldwide. They are available in many supermarkets ready to be grilled. As such, grilled marshmallows can be a source of exposure to harmful compounds, including carcinogenic polycyclic aromatic hydrocarbons (PAHs). Method. PAHs analysis in marshmallows grilled under different conditions included the dilution stage with deionized water and liquid-liquid extraction with cyclohexane and solid- phase extraction (SPE on silica gel columns). PAH fractions were initially analyzed via planar chromatography (HPTLC-high performance thin layer chromatography) and PAH concentrations were determined via GC-MS/MS (gas chromatography with a tandem mass detector) using the selective reaction monitoring (SRM) mode. This study on the consumption of grilled marshmallows was conducted among approximately 300 children and adolescents. Results. The preliminary results of HPTLC and GC-MS/MS analysis indicated that “raw” marshmallows did not contain PAHs. However, the obtained data suggested a high exposure of young people to carcinogenic PAHs from grilled marshmallows. Carcinogenic BaP was determined in all samples and constituted, on average, 36% of total PAH4. Conclusions. The profile of PAH concentrations in the extracts isolated from various grilled types of marshmallows was very similar (r 2 &gt; 0.8), regardless of the grilling method. Compared to the white sugar confection, the higher concentrations of PAHs were determined in multicolored marshmallows. The lack of social awareness about the exposure to carcinogenic substances is alarming.

Materials based on platinum metals with very good catalytic activity were tested in the reduction of p–nitrophenol (pNP) to p–aminophenol (pAP). The majority of presented catalytic materials are based on the adsorption of p–nitrophenol on the surface of the catalyst simultaneously with molecular hydrogen, coming from sodium borohydride in an aqueous medium, which reduces it. In the present paper, a catalytic material based on osmium dispersed in n–decanol or n–dodecanol is presented, which also works as an emulsion membrane, for the absorption of p–nitrophenol and molecular hydrogen at the n–alcohol aqueous solution interface. The hydrogenation of p–nitrophenol is carried out in a reaction and separation column in which the acid receiving phase emulsion is dispersed in the osmium nanodispersion, in n–alcohols. This emulsion circulates from the base of the column to its upper part in co-current or counter-current with the source phase consisting of p–nitrophenol and sodium borohydride. Experiments show that the circulation of counter-current phases is superior to that in co-current, and the emulsion based on n–decanol is more efficient than the one based on n–dodecanol. The increase in the pH difference between the source and receiving phases leads to the increase in the conversion of p–nitrophenol to p–aminophenol. The efficiency of separation of the reaction product in the receiving phase is lower than the conversion at the same operating time. The apparent catalytic rate constant (kapp) of the new catalytic material based on the emulsion membrane with nanodispersion of osmium nanoparticles (0.1×10−3 for n–dodecanol and 0.9×10−3 for n-decanol) is lower by an order of magnitude compared to those based on adsorption on catalysts from platinum metal group. The advantage of the tested membrane catalytic material is that it extracts p–aminophenol in the acid receiving phase. The paper proposes a mechanism of the studied reduction system.

In this work a series of experiments on the retention of B1 (riboflavin), B2 (thiamine) and B3 (nicotinic acid) vitamins in the HILIC and RPLC conditions have been performed involving the effects of organic modifier type and content, pH of the eluent, and buffering salt (ammonium acetate) concentration in the mobile phase, as well as temperature of the system. For the needs of this studies three columns of different features have been chosen: Acclaim™ Mixed-Mode HILIC-1 (Dionex), Eurospher II 100-5 HILIC (Knauer) and the RPLC column Nucleodur® C18 Gravity – SB (Macherey –Nagel). The influence of acetonitrile and methanol content in the eluent and process temperature have been tested and basing on that the most promising systems have been selected regarding the possible separation of the vitamins mixture. Both pH and buffering salt concentrations in the eluent have been adjusted in order to indicate the most effective system which turned out to be the one involving the Nucleodur column and the eluent with 90% methanol, at pH 6 and Cbuff = 20 mmol/dm3 that enables separation of the mixture within the time as short as 2.5 minutes at 1.0 mL/s flowrate in isocratic conditions.

Firefighters Protective Clothing consist of several layers of different properties and functions. The layers create barriers against dangerous outer factor. However, they are also barriers to transport of sweat produced by human organism. It causes that very often sweat in the form of vapor is not transferred effectively from the human organism through the FPC to environment. This leads to sweat condensation on the skin of the FPC user causing his discomfort. In order to ensure as good as possible physiological comfort of firefighter while firefighting and other rescue actions it is necessary to take into consideration the transport of condensed sweat in the multilayer textile set creating the FPC. In the presented work four variants of multilayer textile sets for the FPC have been tested in the aspect of liquid moisture transport. Measurement was performed by means of the Moisture Management Tester (MMT290) – innovative instrument manufactured by the SDL Atlas. Obtained results showed that the transfer of sweat in liquid form occurs only in the inner, next to skin layer of the multilayer sets for the FPC.

A hydrophilic silica-based stationary phase with surface bound N-acetylglucosamine (GlcNAc-silica) was prepared in house and characterized physically via Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) and chromatographically over a wide range of mobile phase compositions. While both FTIR and TGA confirmed the attachment of the GlcNAc ligands to the silica surface, the chromatographic evaluation of the GlcNAc-silica with polar and slightly polar standard solutes (e.g., sugars, nucleic acid fragments, phenolic and benzoic acid derivatives) yielded the typical hydrophilic interaction liquid chromatography (HILIC) behaviors in the sense that retention increased with increased solute’s polarity and the organic content (i.e., acetonitrile) of the hydro-organic mobile phase (i.e., ACN-rich mobile phase). Sugars derivatized with 1-naphthylamine (1-NA) and 2-aminoanthrcene (2-AA) such as xylose, glucose and short chains maltooligosaccharides constituted the most polar species for HILIC retention evaluation, and in addition the maltooligosaccharides offered a polar homologous series for gauging the hydrophilicity of the GlcNAc-silica in analogy with alkylbenzene homologous series and other nonpolar homologous for evaluating the hydrophobicity of non-polar stationary phases. On the other hand, the benzoic acid and phenolic acid derivatives were the probe solutes for evaluating the HILIC retention dependence of ionizable solutes on the pH of the mobile phase. Similarly, the nucleobase and nucleoside weak basic solutes as well as some typical cyclic nucleotide acidic solutes allowed the examination of the dependence of solute retention on the pH of the mobile as well as the polarity of the species.

This paper reports a novel fabric phase sorptive extraction-high performance liquid chromatography-ultra violet detection (FPSE-HPLC-UV) method for the simultaneous extraction and analysis of four phenyltin derivatives that include triphenyltin hydroxide, triphenyltin acetate, triphenyltin chloride and tetraphenyltin in environmental water (agricultural waste water and municipal waste water) and canned food samples. The selected analytes were well resolved by Waters Nova pack C18 column (3.9 x 150 mm, 4 µm particle size) in isocratic elution mode within 15 minutes. The new microextraction media has been analytically evaluated using phenyltin derivatives as model compounds. The factors affecting the extraction efficiency of FPSE have been evaluated and the optimum extraction conditions were determined. Under these optimum conditions, the limits of detection (LODs) for sol-gel C18 coated fabric phase sorptive extraction (FPSE) media in combination with HPLC-UV for the analysis of the phenyltin derivatives were in the range of 10-100 ng/mL with high precision (low relative standard deviation) at 10 ng/mL concentration with good absolute recoveries. To the best of our knowledge, this is the first FPSE extraction procedure applied to environmental water and canned food samples for the simultaneous determination of phenyltin derivatives and could be readily adopted as a rapid and robust green analytical tool for routine environmental and food analytical laboratories.

Lactoperoxidase (LP), which is a high-value minor whey protein, has recently drawn extensive attention from research scientists and industry due to its multi-function and potential therapeutic applications. In this study, the separation and optimization of two similar-sized proteins, LP and lactoferrin (LF) were investigated using strong cation exchange column chromatography. Optimization was started with central composite design based experiments to characterize the importance of different decision variables. The three variables used in the optimization were flow rate, length of gradient and final salt concentration in the linear elution gradient step. The obtained empiric functional model represented the effect of the significant factors on the yield as the objective function. Afterwards, the calibrated mechanistic model was employed to predict accurate optimal set of variables. The optimal operating points were found and the results were compared with validation experiments. Predictions respecting yield confirmed a very good agreement with experimental results while keeping purity, a product quality characteristic, equal or above to a predefined value.

The chiral optical Tamm state (COTS) is a special localized state at the interface of a handedness-preserving mirror and a structurally chiral medium such as a cholesteric liquid crystal or a chiral sculptured thin film. The spectral behavior of COTS, observed as reflection resonances, is described by the temporal coupled-mode theory. Mode coupling is different for two circular light polarizations because COTS has a helix structure replicating that of the cholesteric. The mode coupling for co-handed circularly polarized light exponentially attenuates with the cholesteric layer thickness since the COTS frequency falls into the stop band. Cross-handed circularly polarized light freely goes through the cholesteric layer and can excite COTS when reflected from the handedness-preserving mirror. The coupling in this case is proportional to anisotropy of the cholesteric and theoretically it is only anisotropy of magnetic permittivity that can ultimately cancel this coupling. These two couplings being equal results in a polarization crossover (the Kopp--Genack effect) for which a linear polarization is optimal to excite COTS. The corresponding cholesteric thickness and scattering matrix for COTS are generally described by simple expressions.

Man-made shallow fishponds in the Czech Republic have been facing a high eutrophication since 1950s. Anthropogenic eutrophication and feeding of fish have strongly affected the physico-chemical properties of water and its aquatic community composition leading to harmful algal bloom formation. In our current study, we have characterised the phytoplankton community across three hypertrophic ponds to assess the phytoplankton dynamics during the vegetation season. We microscopically identified and quantified 29 cyanobacterial taxa comprised of non-toxigenic and toxigenic species. Further, a detailed cyanopeptides (CNPs) profiling was performed using molecular networking analysis of liquid chromatography tandem mass spectrometry (LC–MS/MS) data coupled with dereplication strategy. This MS networking approach coupled with dereplication on online global natural product social networking (GNPS) web platform led us to putatively identify forty CNPs: fourteen anabaenopeptins, ten microcystins, five cyanopeptolins, six microginins, two cyanobactins, a dipeptide radiosumin, a cyclooctapeptide planktocyclin and epidolastatin12. We have applied the binary logistic regression to estimate the CNPs producer by correlating the GNPS data with the species abundance. Usage of The combination of molecular networking and dereplication on online global natural product social networking (GNPS) web platform has proved as a valuable approach for rapid and simultaneous detection of high number of peptides, and rapidly assessing the risk for harmful bloom.

Proteomics in respiratory allergic diseases has such a battery of techniques and programs that one would almost think that there is nothing impossible to find, invent or mold. All these resources that we document here, are involved in solving problems in allergic diseases, both diagnostic, prognostic, treatment and immunotherapy development. The main perspectives, according to this version, are in three strands and / or lockout immunological system: 1) In blocking the diapedesis of cells involved, 2) modifications and blocking of paratopes and epitopes being understood by modifications to antibodies, antagonism or blocking them and 3) blocking FcεR1 receptors to prevent specific IgEs from sticking to mast cells and basophils. These tools and targets in the allergic landscape are, in our view, the prospects in the field.

Unmetamorphosed carbonaceous chondrites provide important information concerning the formation and evolution of organic matter, such as amino acids. However, terrestrial contamination remains a valid concern when investigating the organic inventory of meteorites that have fallen to Earth. Accordingly, JAXA’s Hayabusa2 and NASA’s OSIRIS-REx have been launched with the task of returning uncontaminated C-type asteroid material to Earth. The successful Hayabusa2 mission has a very limited sample size (5.4 g). Therefore, many conventional compound specific techniques will struggle to detect amino acids above detection limit with available sample amounts (~several mg to 10’s of mg) being much smaller than those typically used. Here a novel method utilizing ultrahigh performance liquid chromatography-Orbitrap-mass spectrometry is validated and applied to very small meteorite samples, thus providing an approach that can overcome the small sample size constraints of sample return missions. The method is highly sensitive, enabling the detection of amino acids in the carbonaceous chondrites Murchison (2.28 mg) and Orgueil (2.30 mg). Furthermore, quantitation was possible for many of the detected amino acids in Murchison and Orgueil. Using the data presented here, both the amino acid reservoirs of Murchison and Orgueil and the potential application of this method to sample return samples are discussed.

Circulating tumor cells (CTCs) are cells released from the primary tumor and intravasate into the blood or lymphatic vessels, where they are transported to distant sites and act as seeds that initiate cancer metastases. Recent advances in CTC research have shown their relevance as prognostic markers for early and metastatic disease detection, predictive biomarkers for relapse, and response to medical intervention or therapy. The rapidly evolving landscape of CTC biology has opened new avenues for understanding cancer progression, metastasis, and treatment response. Additionally, translating these findings into clinical applications holds promise for improving cancer diagnostics, prognosis, and personalized therapeutic strategies. This review discusses the significance of CTCs in cancer research and their associated challenges. We explore recent developments in the detection and characterization of CTCs and their implications in cancer research and clinical practice.

Advances in reconfigurable liquid-based reconfigurable antennas are enabling new possibilities to fulfil the requirements of more advanced wireless communication systems. In this review, a comparative analysis of various state-of-the-art concepts and techniques for designing reconfigurable antennas using liquid is presented. First, the electrical properties of different liquids at room temperature commonly used in reconfigurable antennas are identified. This is followed by a discussion of various liquid actuation techniques in enabling high frequency reconfigurability. Next, liquid-based reconfigurable antennas in literature used to achieve the different types of reconfiguration will be critically reviewed. These include frequency-, polarization-, radiation pattern- and compound reconfigurability. The current concepts of liquid-based reconfigurable antennas can be classified broadly into three basic approaches: altering the physical (and electrical) dimensions of antennas using liquid, applying liquid-based sections as reactive loads; and implementation of liquids as dielectric resonators. Each concept and their design approaches will be examined, outlining their benefits, limitations, and possible future improvements.

: To improve the efficiency of rhizobial inoculation operations and address the current situation of rhizobial inoculation being labor-intensive, a spraying and control system for variable rate application (VRA) of liquid rhizobia was developed. The system can accurately regulate the spraying rate of liquid rhizobia according to the desired rate of rhizobia by incremental Proportional Integral Derivative (PID) closed-loop control algorithm, making it particularly suitable for precise spraying with small amounts. In the laboratory experiment of precise flow control, variation coefficient of spraying nozzle from 0.10 MP to 0.20 MP pressure were no more than 1.2%. A clear linear relationship was observed between the spraying rate and pressure. The maximum response time was 1.93 seconds, while the average response time was 1.62 seconds when controlling the spraying system for small amounts. Field trial was conducted in Heilongjiang Agricultural Xianghe Farm of China. Average seeds number and 100-seed weight of soybean plant with rhizobia inoculation treatment were better than control group, and average yield of spraying liquid rhizobia agent with full base fertilizer increased by 232.5 kg/hm2, representing a significant 7.4% improvement over the control group. The results of these trails clearly showed the positive effect of the spraying and control system for liquid rhizobial inoculation, which has superior to existing inoculation manners, and provides an important technical support for the widespread adoption of rhizobia technology.

Waste glycerol can be subjected to various processing operations, including purification and re-fining, to obtain glycerol of appropriate purity. In addition, alternative methods of utilising waste glycerol are also being sought, e.g. by converting it into other valuable chemical products or biofuels. Therefore, various technologies are being developed to utilise this type of waste effectively and sustainably. The production of value-added products from waste glycerol is an important issue that determines the improvement of the economic viability of biofuel production and corresponds to the model of a waste-free and emission-free circular economy. This paper characterised the mechanisms and evaluated the efficiency of existing methods of microbiological utilisation of waste glycerol into liquid biofuels, including biodiesel, bioethanol and biobutanol, and identified further directions for the production of value-added products. In addition, a bibliographical analysis of publications re-lated to the production of liquid fuels and economically valuable products from glycerol was carried out, the progress of research and application work was assessed and directions for future research were identified.

On the system Au(III)-HCl-A324H⁺Cl^-, liquid-liquid extraction experiments were used to define the extraction equilibrium and the corresponding extraction constant, and the facilitated transport of this precious metal, from HCl solutions, across a flat-sheet supported liquid membrane was investigated, using the ionic liquid as carrier, as a function of hydrodynamic conditions, concentration of gold(III) (0.01-0.1 g/L), and HCl (0.5-6 M) in the feed phase, and carrier concentration (0.023-0.92 M) in the membrane. An uphill transport equation was derived considering aqueous feed boundary layer diffusion and membrane diffusion as controlling steps. The aqueous diffusional resistance (Δf) and the membrane diffusional resistance (Δm) were estimated from the proposed equation, being their values 241 s/cm an 9730 s/cm, respectively. The performance of the present carrier was compared against results yielded by other ionic liquids, and also it was investigated the influence that other metals had on gold(III) transport both from binary or quaternary solutions. Gold was finally recovered from receiving solutions as zero valent gold nanoparticles.

Computational fluid dynamics (CFD) has, in the last decade, being an essential problem solving tool in industries such as pharmaceutical, pulp, petrochemical as well as Oil and Gas processing. The use of CFD for mixer design is unpopular in many countries in Africa. Therefore, this study investigates the characteristics of Brine-Surfactant mixing in a horizontal pipeline using CFD. The CFD is conducted by AnsysFluent software (licensed). A T-junction pipe is created and meshed with unstructured tetrahedral elements using design modeler. Discretization is done by Finite Volume Method (FVM), cell-centered scheme with Second-Order Upwind Scheme. The pressure term is introduced into the continuity equation by SIMPLE (Semi-Implicit Method for Pressure Linked Equations) algorithm. The kinetic epsilon model, also known as k-e model is administered to define the properties of the fluid and geometry, such as velocity, species mole fraction, pipe diameter. The boundary conditions is selected based on filed data. The rate of fluid flow in the primary region is 650 bbl/day at 400psi in 4in diameter pipeline, which is 100m long. The numerical simulation was based upon the governing equations such s continuity, Navier’s stoke, energy as well as specie transport equations. The findings shows that higher concentration results in increased mixing time, while 2% conc. of surfactant reaches homogeneity in 20 minutes at 72 meters of the pipe length. The result validated with field detail and the empirical result from literature, and is consistent. This study provide insight on industrial mixer design, chemical injection system, as well as gas pipeline design and optimization, especially in multiphase scale transport.

An extensive thermodynamic study of N-methylformamide (CAS RN: 123-39-7) and N,N-dimethylformamide (CAS RN: 68-12-2), is presented in this work. The liquid heat capacities of N-methylformamide were measured by Tian–Calvet calorimetry in the temperature interval (250 – 300) K. The vapor pressures for N-methylformamide and N,N-dimethylformamide were measured using static method in the temperature range 238 K to 308 K. The ideal-gas thermo-dynamic properties were calculated using a combination of the density functional theory (DFT) and statistical thermodynamics. A consistent thermodynamic description was developed using the method of simultaneous correlation, where the experimental and selected titerature data for vapor pressures, vaporization enthalpies, and liquid phase heat capacities and calculated ide-al-gas heat capacities are treated together to ensure overall thermodynamic consistency of the results. Resulting vapor pressure equation is valid from the triple point to the normal boiling point temperature.

Liquid-liquid phase separation (LLPS) of proteins has been found ubiquitously in eukaryotic cells, critical in the controlling of many biological processes through forming a temporary condensed phase with different bimolecular components. TDP-43 is recruited to stress granules in cells and is the main component of TDP-43 granules and proteinaceous amyloid inclusions in patients with amyotrophic lateral sclerosis (ALS). TDP-43 low complexity domain (LCD) is able to demix in solution forming the protein condensed droplets. The molecular interactions regulating its LLPS were investigated at the protein fusion equilibrium stage, where the droplets stopped growing. We found the molecules in the droplet were still liquid-like but with enhanced intermolecular helix-helix interaction in the LCD. The protein would start to aggregate after about 200 minutes of lag time and aggregate slower than at the condition when the protein does not phase separate or the molecules have a reduced intermolecular helical interaction. A structural transition intermediate towards protein aggregation was also discovered involving a decrease of the intermolecular helix-helix interaction and a reduction in the helicity. Therefore, LLPS and the intermolecular helical interaction could help maintain the stability of TDP-43 LCD.

Guava (Psidium guajava L.) is a common fruit tree that grows in several tropical and subtropical parts of the world. The aim of this study was to employ the use of liquid-liquid fractionation to investigative the comparative antibacterial potential of crude extracts of Guava leaves and bark against selected food isolates; Escherichia coli, Pseudomonas aeruginosa, Streptococcus pneumonia, Bacillus cereus and Staphylococcus aureus. The phytochemical analysis of the extract showed presence of tannin, phenol, flavonoid and terpenoid in all extract, while steroid and saponin were absent in some. The agar diffusion method was employed for the assessment of the sensitivity of the extracts. The ethyl acetate and aqueous fractions from the stem bark acetone extract generally showed better antimicrobial activity compared with other extracts from leaves. The extract was active both against gram positive bacteria (Bacillus cereus and Streptococcus pneumonia) and gram negative bacteria (Escherichia coli, Pseudomonas aeruginosa, , Bacillus cereus and Staphylococcus aureus) at varying zone of inhibition. The results of the study showed the potential of identifying novel antibacterial agent from P. guajava bark and leaves while optimising the potential application for treatment in traditional medicine.

Abstract：Objective: To compare the effects of fermentation on the chemical composition of Gastrodia Tuder Halimasch Powder, and to provide a basis for the processing, processing and clinical application of this medicinal material. Methods: UHPLC-Q-Orbitrap HRMS was used to identify compound structure by comparing excimer ions, characteristic fragment ions and reference substances, and referring to relevant literature and database search. The main differential components were screened by orthogonal partial least squares-discriminant analysis (OPLS-DA), and the differential components were quantitatively studied by high performance liquid chromatography, and the differences in the types and contents of chemical components before and after fermentation were compared. Results: A total of 77 compounds were identified or preliminarily derived after fermentation, including 21 terpenes, 18 organic acids, 9 flavonoids, 7 nucleosides, 6 amides, 4 amino acids, 2 pyrrolidone derivatives, 2 sterols, 2 alkaloids and 6 others.Through high performance liquid chromatography, it was found that the content of daidzein genistein and ergosterol was significantly increased after fermentation, and a new component ergosterol was produced. Compared with Gastrodia Tuder Halimasch Powder before fermentation, the content of genistin and other components was significantly reduced, and there may be a process of genistin conversion to genistein.Conclusion: The fermentation process will have a certain influence on the types and contents of the chemical components of Gastrodia Tuder Halimasch Powder, and ergosterol, genistein and .daidzein may be the main pharmacodynamic components, which can provide a useful reference for the clinical rational application, quality control and mechanism of action of Gastrodia Tuder Halimasch Powder.

Food analysis demands fast methods for routine control and high throughput of samples. Chromatographic separation enables simultaneous determination of numerous compounds in complex matrices, several approaches increasing separation efficiency and speed of analysis were involved. In this work, modern types of column with monolithic rod or superficially porous particles were employed and compared for determination of eight synthetic food dyes, their chromatographic performance was evaluated. During method optimization, cyano stationary phase Chromolith Performance CN 100 × 4.6 mm and Ascentis Express ES-CN 100 × 4.6 mm, 5 µm were selected for the separation of polar colorants. The separation was performed by gradient elution of acetonitrile/methanol and 2% water solution of ammonium acetate at flow rate 2.0 ml min-1. Mobile phase composition and the gradients were optimized in order to enable efficient separation on both columns. The method using fused-core particle column provided higher separation efficiency, narrow peaks of analytes resulted in increased peak capacity and shortening of analysis time. After the validation, the method was applied for analysis of colored beers, soft drinks and candies.

The separation of microparticles with respect to different properties such as size and material is a research field of great interest. Dielectrophoresis, a phenomenon which is capable of addressing multiple particle properties at once, can be used to perform a chromatographic separation. However, the selectivity of current dielectrophoretic particle chromatography (DPC) techniques is limited. Here we show a new approach for DPC based on differences in the dielectrophoretic mobilities and the crossover frequencies of polystyrene particles. Both differences are addressed by modulating the frequency of the electric field to generate positive and negative dielectrophoretic movement to achieve multiple trap and release cycles of the particles. A chromatographic separation of different particle sizes revealed a voltage dependency of this method. Additionally, we showed the frequency bandwidth influence on separation using one example. The DPC method developed was tested with model particles but offers possibilities to separate a broad range of plastic and metal microparticles or cells and to overcome currently existing limitations in selectivity.

We report herein the synthesis of siloxane-functionalized CBP molecules (4,4’-bis(carbazole)-1,1′-biphenyl) for liquid optoelectronic applications. The room-temperature liquid state is obtained through a convenient functionalization of the molecules with heptamethyltrisiloxane chains via hydrosilylation of alkenyl spacers. The synthesis comprises screening of metal-catalyzed methodologies to introduce alkenyl linkers into carbazoles (Stille and Suzuki Miyaura cross-couplings), incorporate the alkenylcarbazoles to dihalobiphenyls (Ullmann coupling), and finally introduce the siloxane chains. The used conditions allowed the synthesis of the target compounds, despite the high reactivity of the alkenyl moieties bound to π-conjugated systems toward undesired side reactions such as polymerization, isomerization, and hydrogenation. The features of these solvent-free liquid CBP derivatives make them potentially interesting for fluidic optoelectronic applications.

Glycosyl inositol phospho ceramides (GIPCs) are the major sphingolipids on earth as they account for a considerable fraction of the total lipids in plants and fungi which in turn represent a large portion of the biomass on earth. Despite their obvious importance, GIPC analysis remains challenging due to the lack of commercial standards and automated annotation software. In this work, we introduce a novel GIPC glycolipidomics workflow based on reversed-phase ultra-high pressure liquid chromatography coupled to high-resolution mass spectrometry. For the first time, automated GIPC assignment was performed using the open-source software Lipid Data Analyzer based on platform-independent decision rules. Four different plant samples (salad, spinach, raspberry, strawberry) were analyzed and revealed 64 GIPCs based on accurate mass, characteristic MS2 fragments and matching retention times. Relative quantification using lactosyl ceramide for internal standardization revealed GIPC t18:1/h24:0 as the most abundant species in all plants. Depending on the plant sample, GIPCs contained mainly amine, N-acetylamine or hydroxyl residues. Most GIPCs revealed a Hex-HexA-IPC core and contained a ceramide part with a trihydroxylated t18:0 or t18:1 long chain base and hydroxylated fatty acid chains ranging from 16 to 26 carbon atoms in length (h16:0 – h26:0). Interestingly, six GIPCs containing t18:2 were observed in raspberry, which was not reported so far. The presented workflow supports the characterization of different plant samples by automatic GIPC assignment potentially leading to the identification of new GIPCs. For the first time, automated high‑throughput profiling of these complex glycolipids is possible by liquid chromatography-high-resolution mass spectrometry and subsequent automated glycolipid annotation based on decision rules.

Affinity chromatography on procainamide-Sepharose has been an important step in the purification of butyrylcholinesterase (BChE) and acetylcholinesterase (AChE) since its introduction in 1978. The procainamide affinity gel has limitations. In the present report a new affinity gel called Hupresin^® was evaluated for its ability to purify truncated, partly-deglycosylated human butyrylcholinesterase (rHuBChE) expressed in a stably transfected CHO cell line. We present a detailed example of the purification of rHuBChE secreted into 3940 mL of serum-free culture medium. The starting material contained 13,163 units of BChE activity (20.9 mg). rHuBChE was purified to homogeneity in a single step by passage over 82 mL of Hupresin^® and elution with 0.1 M tetramethylammonium bromide in 20 mM TrisCl pH 7.5. The fraction with the highest specific activity of 630 units/mg contained 11 mg of BChE. Hupresin^® is superior to procainamide-Sepharose for purification of BChE, but is not suitable for purifying native AChE because Hupresin^® binds AChE so tightly that AChE is desorbed with denaturing solvents such as 50% acetonitrile or 1% trifluoroacetic acid. Procainamide-Sepharose will continue to be useful for purification of AChE.

In this study, we test the performance of a compact gas chromatograph with photoionization detector (GC-PID) and optimize the configuration to detect ambient (sub-ppb) levels of benzene, toluene, ethylbenzene, and xylene isomers (BTEX). The GC-PID system was designed to serve as a relatively inexpensive (~$10k) and field-deployable air toxic screening tool alternative to conventional benchtop GCs. The instrument uses ambient air as a carrier gas, and consists of a Tenax-GR trap preconcentrator, a gas sample valve, two capillary columns, and a photoionization detector (PID) with a small footprint and low power requirement. The performance of the GC-PID has been evaluated in terms of system linearity and sensitivity in field conditions. The BTEX-GC system demonstrated the capacity to detect BTEX at levels as high as 500 ppb with a linear calibration range of 0-100 ppb. A detection limit lower than 1 ppb was found for all BTEX compounds with a sampling volume of 1 L. No significant drift in the instrument was observed. A time-varying calibration technique was established that requires minimal equipment for field operations and optimizes the sampling procedure for field measurements. With an analysis time of less than 15 minutes, the compact GC-PID is ideal for field deployment of background and polluted atmospheres for near-real time measurements of BTEX. The results highlight the application of the compact and portable GC-PID for community monitoring and screening of air toxics.

Background: Cell-free DNA (cfDNA) analysis has become a promising tool for diagnosis, prognosis and monitoring of lymphoma cases. Until now, research in this area has mainly focused in aggressive lymphomas with scanty information from other lymphoma subtypes. Methods: We selected 256 patients diagnosed with lymphomas including a large variety of B-cell and T-cell non-Hodgkin and Hodgkin lymphomas and quantified cfDNA from plasma at the time of diagnosis. We further selected 49 large B cell lymphomas (LBCL) and analyzed cfDNA levels at diagnosis (pre-therapy) and after therapy. In addition, we performed NGS in cfDNA and tissue in this cohort of LBCL. Results: Lymphoma patients showed a statistically significant higher cfDNA concentration than healthy controls (mean 53.0 ng/mL vs 5.6 ng/mL, p <0.001). The cfDNA concentration correlated with lymphoma subtype, lactate dehydrogenase, International Prognostic Index (IPI) score, Ann Arbor (AA) and B-symptoms. In 49 LBCL cases, the cfDNA concentration decreased after therapy in cases who achieved complete response (CR), and increased in non-responders. The median cfDNA at diagnosis of patients who achieved CR and later relapsed was higher (81.5 ng/mL) compared with levels of those who did not (38.6 ng/mL). A concordance of 84% was observed between NGS results in tumor and cfDNA samples. Higher VAF in cfDNA correlated with advanced stage and bulky disease. Conclusions: cfDNA analysis can be easily performed in almost all lymphoma cases. The cfDNA concentration correlated with the characteristics of aggressiveness of the lymphomas and in LBCL with the response achieved after therapy. These results support the utility of cfDNA analysis as a complementary tool in the management of lymphoma patients.

New TLC-densitometric method have been developed for the identification and quantification of paracetamol (PA), propyphenazone (PP) and caffeine (C) of Saridon tablets using the NP-TLC technique combined with densitometry. This method allows for the simultaneous determination of PA, PP, and C in the same sample. Among all tested chromatographic conditions, the mixture consisting of chloroform + toluene + ethyl acetate + ethanol + acetic acid (18:18:7.5:5.0:0.3, v/v) and silica gel 60F254 plate proved to be the most effective for the separation of three tested active pharmaceutical ingredients (APIs) and substances related to paracetamol. The fully validation of the proposed NP-TLC method proves that it is specific, precise, accurate, robust and sensitive. The percentage content in relation to the content declared by the manufacturer is for propyphenazone 99.8%, paracetamol 101.6% and caffeine 100.8%, which are in accordance with pharmacopoeial requirements. The results presented indicate the possibility of using the developed method in the routine control of pharmaceutical preparations containing these APIs. The proposed method is economical and more sensitive compared to the previously proposed planar methods for the simultaneously determination of PA, PP and CAPIs. Will be an What is more, the presented method may be anaxcellent excellent economical alternative when HPLC method is unavailable for such determination.

High-throughput screening of samples is the strategy of choice to detect occupational exposure biomarkers, yet it requires user-friendly apparatus that gives relatively prompt results while ensuring high degrees of selectivity, precision, accuracy and automation, particularly in preparation processes. In the last 10 years, miniaturization has attracted much attention in analytical chemistry and has driven solvent and sample savings and easier automation, the latter thanks to the introduction on the market of three axis autosampler. In light of the above, this contribution describes a novel user-friendly solid-phase microextraction (SPME) off- and on-line platform coupled with gas chromatography triple quadrupole-mass spectrometry to determine urinary 1- and 2-hydroxy-napthalene, 9-hydroxy-phenantrene, 1-hydroxy-pyrene, 3- and 9-hydroxy-benzoantracene and 3-hydroxy-benzo[a]pyrene, metabolites of the related polycyclic aromatic hydrocarbons. In this new procedure chromatography’s sensitivity is combined with the user-friendliness of N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide on-fiber SPME derivatization previous direct immersion sampling, to which is added the quantitative accuracy afforded using specific isotope-labelled internal standards. The detection limits for the seven OH-PAHs were ranged from 0.28 to 1.87 ng/L. Intra-(from 2.5 to 3.0%) and inter-session (from 2.4 to 3.9%) repeatability was also evaluated. This method serves to identify suitable risk-control strategies for occupational hygiene conservation programs

The transport of indium(III), from HCl solutions, across a supported liquid membrane in flat-sheet configuration was investigated, being the carrier the ionic liquid HA324H⁺Cl^- (derived from the tertiary amine Hostarex A324 and hydrochloric acid). Different variables affecting the metal transport: hydrodynamic conditions in the source and receiving phases, metal and HCl concentrations in the source phase, and carrier concentration in the membrane phase, were investigated. Also the transport of indium(III) using carriers of various nature: ionic liquids, alcohol, ketone, phosphine oxide, etc., was compared. The metal transport was modelled describing the transport mechanism as: diffusion across the source diffusion layer, a fast interfacial chemical reaction, and diffusion of the InCl₄^--carrier complex through the membrane support. Diffusional parameters for the transport of indium(III), from the experimental data and the model, were estimated.

This study employs the FLACS code to analyze hydrogen leakage, vapor dispersion, and subsequent explosions. Utilizing pseudo-source models, a liquid pool model, and a hybrid model combining both, we investigate dispersion processes for varying leak mass flow rates (0.225 kg/s and 0.73 kg/s) in a large open space. We also evaluate explosion hazards based on overpressure and impulse effects on humans. The computational results, compared with experimental data, demonstrated reasonable hydrogen vapor cloud concentration predictions, especially aligned with the wind direction. For higher mass flow rate of 0.73 kg/s, the pseudo-source model and hybrid model proved appropriate, while the liquid pool model was more suitable for lower mass flow rate of 0.225 kg/s. Regarding explosion analyses using overpressure-impulse diagram, higher mass flow rates leaded to potentially fatal overpressure and impulse effects on humans. However, lower mass flow rates may cause severe eardrum damage at the maximum overpressure point.

In this work, we proposed a novel design of microfluidic mixer utilizing the amplified Marangoni chaotic advection induced by AC continuous electrowetting of a metal droplet situated in electrolyte solution, due to the linear and quadratic voltage-dependence of flow velocity at small or large voltages, respectively. Unlike previous researchers exploiting the unidirectional surface stress with DC bias at droplet/medium interface for pumping of electrolyte where the resulting flow rate is linearly proportional to the field intensity, dominance of another kind of dipolar flow pattern caused by local Marangoni stress at the drop surface in sufficiently intense AC electric field is demonstrated by both theoretical analysis and experimental observation, which exhibits a quadratic growth trend as a function of the applied voltage. The dipolar shear stress merely appears at larger voltages and greatly enhances the mixing performance by inducing chaotic advection between the neighboring laminar flow. The mixer design developed herein, on the basis of amplified Marangoni chaotic advection around a liquid metal droplet at larger AC voltages, has great potential for chemical reaction and MEMS actuator applications, because of generating high-throughput and excellent mixing performance at the same time.

Melting, solidification and viscosity properties of a multicomponent Fe-Cu-Nb-Mo-Si-B alloys with low aluminum addition up to 0.42 at.% Al were studied using an oscillating cup viscometer. It is shown that melting and solidification are divided into two stages with a knee point at 1461 K. The temperature dependences of the liquid fraction between the liquidus and solidus temperatures during melting and solidification are calculated. It has been proven that aluminum accelerates the processes of melting and solidification and leads to an increase in liquidus and solidus temperatures. In the liquid state at temperatures above 1700 K in an alloy with a low aluminum content, the activation energy of viscous flow increases. This growth was associated with the liquid – liquid structure transition caused by the formation of large clusters based on the metastable Fe23B6 phase. Aluminum atoms attract iron and boron atoms and contribute to the formation of clusters based on the Fe2AlB2 phase and metastable phases of a higher order.

Background: Circulating rare cells participate in breast cancer evolution as systemic components of the disease and thus, are a source of theranostic information. Exploration of cancer-associated rare cells is in its infancy. We determined the validity of a rare-cell detection platform and demonstrated the usefulness of a certain rare cell subset as a novel approach to characterize the breast cancer system. Methods: Linearity of the Rarmax® platform was established using a spike-in approach. The platform includes red blood cell lysis, leukocyte depletion and high-resolution fluorescence image recording. Rare cell analysis was conducted on 28 samples (before and after surgery) from 14 patients with breast cancer, 20 healthy volunteers and 9 non-cancer control volunteers. In-depth identification of rare cells, including circulating tumor cells, endothelial-like cells, erythroblasts and inflammation-associated cells, was performed using a phenotype and morphology-based classification system. Results: The platform performed linearly over a range of 5-950 spiked cells, with an average recovery of 84.6%. Circulating epithelial and endothelial-like cell subsets have been demonstrated to be associated with or independent of cancer with tumor presence. Furthermore, certain cell patterns may be associated with treatment-related adverse effects. The sensitivity in detecting tumor-presence and cancer-associated abnormality before surgery was 50% and 85.7%, respectively and the specificity was 100% and 96.6%, respectively. Conclusion: The present study supports the idea of a cancer-associated rare cell abnormality to represent tumor entities as well as systemic cancer. The latter is independent of the apparent clinical cancer.

The ionic liquid A327H+Cl- is generated by reaction of the tertiary amine A327 (industrial mixture of tri-octil and tri-decyl amines) and hydrochloric acid solutions. Further, the extraction of Au(III) by A327H+Cl- ionic liquid under various variables, including metal and ionic liquid concentrations, has been investigated. Results indicate that A327H+AuCl4- is formed, by an exothermic (ΔHº= -3 kJ/mol) reaction, in the organic solution. Aqueous ionic strength influences the formation constants values and the specific interaction theory (SIT) is used to estimate the interaction coefficient between AuCl4- and H+. Gold (III) is stripped using thiocyanate media, and from the strip solutions, gold is precipitated as gold nanoparticles.

The transport of indium(III), from HCl solutions, across a supported liquid membrane in flat-sheet configuration was investigated, being the carrier the ionic liquid HA324H+Cl- (derived from the tertiary amine Hostarex A324 and hydrochloric acid). Different variables affecting the metal transport: hydrodynamic conditions in the source and receiving phases, metal and HCl concentrations in the source phase, and carrier concentration in the membrane phase, were investigated. Also the transport of indium(III) using carriers of various nature: ionic liquids, alcohol, ketone, phosphine oxide and phosphoric ester, was compared. The metal transport was modelled describing the transport mechanism as: diffusion across the source diffusion layer, a fast interfacial chemical reaction, and diffusion of the InCl4--carrier complex through the membrane support. Diffusional parameters for the transport of indium(III), from the experimental data and the model, were estimated.

Chemical analysis of the organic components in beers has applications to quality control, authenticity and improvements to the flavor characteristics and brewing process. This study aims to show the complementary nature of two instrumental techniques which in combination can identify and quantify the majority of organic components in a beer sample. Nuclear Magnetic Resonance (NMR) was used to provide concentrations of twenty five different organic compounds including alcohols, organic acids, carbohydrates, and amino acids. Calorie content was also estimated for the samples. NMR data for ethanol concentrations were validated by comparison to a Fourier Transform Infrared Spectrometry (FTIR) method. Headspace Solid-Phase Microextraction (SPME) Gas Chromatography Mass Spectrometry (GCMS) was used to identify a range of volatile compounds such as alcohols, esters and hop derived aroma compounds. A simple and inexpensive conversion of a Gas Chromatography Flame Ionization Detector (GC FID) instrument to allow the use of Solid-Phase Microextraction was found to be useful for the quantification of volatile esters.

The Jiangmen Underground Neutrino Observatory (JUNO) is a 20 kton liquid scintillator multi-purpose underground detector, under construction near the chinese city of Jiangmen, with data taking expected to start in 2021. The main goal of the experiment is the neutrino mass hierarchy determination, with more than three sigma significance, and the high precision neutrino oscillation parameters measurements, detecting electron anti-neutrinos, emitted from two near-by (baseline of about 53 km) nuclear power plants. Besides, the unprecedented liquid scintillator type detector performance in target mass, energy resolution, energy calibration precision and low-energy threshold, features a rich physics program for the detection of low-energy astrophysical neutrinos, such as galactic core-collapse supernova neutrinos, solar neutrinos and geo-neutrinos.

Notwithstanding the fact that there is some improvement for an earlier detection of patients with lung cancer, the majority of them still present with a late-stage disease at the time of diagnosis. Next to the most frequently used factors affecting the prognosis of lung cancer patients (stage, performance and age) the recent application of biomarkers obtained by liquid profiling gained more acceptance. In our study we aimed to answer these questions: i) is the quantification of free-circulating methylated PTGER4 and SHOX2 plasma DNA an useful method for the therapy monitoring and is this also possible for patients treated with different therapy regimens?, and ii) is this approach possible when blood drawing tubes are used which allow for a delayed processing of blood samples? Baseline values for mPTGER4 and mSHOX2 do not allow for a clear discrimination between different response groups. In contrast the combination of the methylation values for both genes show a clear difference between responders vs non-responders at the time of re-staging. Additionally, blood drawing into tubes stabilizing the sample give researchers more flexibility.

The binding affinity of trastuzumab and pertuzumab to HER2 has been studied using both experimental and in-silico methods. The experiments were conducted using the antibodies in their complete IgG form, as used in clinical therapy, and the extracellular domain of the HER2 protein in solution. This approach provides a precise, reproducible, and reliable view of the interaction between them in physiological conditions. Dynamic light scattering and size exclusion chromatography coupled with tetra detection were utilized to characterize the protein complexes, measure their concentrations, and calculate the equilibrium free binding energy, ΔGbind. In addition, PRODIGY, a QSAR-like model with excellent predictive ability, was employed to obtain in-silico ΔGbind estimations. The results obtained indicate that pertuzumab exhibits a slightly higher binding affinity to HER2 than trastuzumab. The difference in binding affinity was explained based on the contribution of the different interfacial contact (IC) descriptors to the ΔGbind value estimated by the PRODIGY model. Furthermore, experiments revealed that the pertuzumab IgG antibody binds preferentially to two HER2 proteins, one per Fab fragment, while trastuzumab mainly forms a monovalent complex. This finding was interpreted based on a geometrical model that identified steric crowding in the trastuzumab-HER2 complex as compared to the pertuzumab-HER2 complex.

(200 words) Imidazolium ionic liquids containing acetylacetone, thenoyltrifluoroacetone, or 8-hydroxyquinoline, respectively, were used as the extracting agents for the separation of traces of iron (III) from its aqueous solutions with or without citric and oxalic acids. The results show that 8-hydroxyquinoline in imidazolium ionic liquids extract iron quantitatively from all the tested solutions including complexing ones, regardless indications of unexpected iron behavior/speciation.

In recent years, growing attention has been directed towards the potential of plant extracts as great therapeutic agents in controlling oxidative stress and inflammation. Gymnema inodorum (Lour.) Decne, an indigenous plant locally grown in Northern Thailand, is known for its anti-diabetic activity. This study aims to explore the antioxidant properties and phenolic profile of column chromatographic fractionated G. inodorum leaf extract. The ethanolic-reflux extracts of G. inodorum leaves were subjected to column chromatography for the isolation of bioactive molecules. Total phenolic and flavonoid content were assessed using Folin–Ciocalteu and aluminium chloride colorimetric methods, respectively. Total antioxidant activity was evaluated by employing different antioxidant assays, including 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic)acid (ABTS) scavenging assay and ferric reducing antioxidant power (FRAP) assay. High-Performance Liquid Chromatography (HPLC) with a C18 column was employed to determine the level of gymnemic acid, while Liquid Chromatography Quadrupole Time-of-Flight/Mass Spectrometry (LC-QTOF/MS) was used to identify potential phenolic compounds. The three separated fractions indicating A, B, and C, exhibited remarkable antioxidant activity, with total phenolic content of 0.294 ± 0.056, 0.085 ± 0.039, and 0.227 ± 0.041 mg QE/mL, and total flavonoid content of 0.274 ± 0.050, 0.309 ± 0.110, and 0.384 ± 0.007 mg QE/mL, respectively. Fraction A exhibited the highest DPPH and ABTS scavenging activity, while fraction C demonstrated significantly higher ferric-reducing power. HPLC analysis revealed a highest concentration of gymnemic acid in fraction C (0.393 ± 0.003 mg/g) compared to fraction A (0.159 ± 0.003 mg/g) and fraction B (0.142 ± 0.000 mg/g). The LC-QTOF/MS phenolic screening showed seven potential phenolic compounds in fraction A, seven compounds in fraction B, and four compounds in Fraction C. A significant relationship is found between antioxidant potential and total phenolic content, suggesting that phenolic compounds are the major contributors to the antioxidant activity of G. inodorum.

Molten LiCl-KCl salt and liquid cadmium are proposed as the electrolyte and the reactive cathode for the electrorefining of spent nuclear fuels. Corrosion testing of existing alloys is mandatory to ensure the service life of the electrorefiner vessel and electrode assemblies. Haynes C276, Inconel 600, AISI 316L stainless steel, and 42CrMo low alloy steel were exposed to LiCl-KCl melt at 500°C for 500 h in an argon atmosphere. All alloys suffered from dissolution attacks with the presence of oxide islands or porous oxide layer on the surface. AISI 316L, T91 steel and tungsten specimens were also submitted to corrosion tests in liquid cadmium at 500°C for 120 h. Corrosion of AISI 316L and T91 stainless steel were predominated by chemical oxidation with additional severe Ni dealloying occurred on AISI 316L. Tungsten only suffered from dissolution attack in comparison.

Separation of polyethylene glycols (PEGs) into single homologs by reversed-phase chromatography is investigated experimentally and theoretically. The used core-shell column is shown to achieve baseline separation of PEG homologs up to molar weights of at least 5000 g/mol. A detailed study is performed elucidating the role of the operating conditions temperature, eluent composition, and degree of polymerization of the polymer. Applying Martin's rule yields a simple model for retention times that holds for a wide range of conditions. In combination with relations for column efficiency, the role of the operating conditions is discussed and separations are predicted for analytical-scale chromatography. Finally, the approach is included in an efficient process model based on discrete convolution, which is demonstrated to predict with high accuracy also advanced operating modes with arbitrary injection profiles.

The genetic code evolved by parallel tracks of chaotic and ordered processes. Liquid-liquid phase separation (hydrogels), a chaotic process, constructs diverse membraneless compartments within cells, resulting in regulated hydration and sequestration and concentration of reaction components. Hydrogels relate to chaotic amyloid fiber production. We propose that polyglycine and related hydrogels (i.e. GADV; G is glycine), phase separations, membraneless droplets and amyloid accretions organized protocell domains to drive the earliest evolution of the genetic code and the pre-life to cellular life transition. By contrast, evolution of tRNA, tRNAomes, aminoacyl-tRNA synthetases and translation systems followed highly ordered and systematic pathways, described by well-defined mechanisms and rules. The pathway of evolution of aminoacyl-tRNA synthetases, which tracked evolution of the genetic code, is clarified. Hydrogels and amyloids form a chaotic component, therefore, that complemented otherwise systematic processes. We describe with detail a pre-life world in which hydrogels and amyloids provided the selections of the first life.

Though nowadays germanium do not reach the range of popularity than other metals, i.e. rare earth elements, its utility in target industries makes of it also a strategic metal. Though germanium can be find in a series of raw materials, the principal source for its recovery is from secondary wastes of the zinc industry, and also, the recycle of germanium-bearing waste materials is becoming of interest. In this recovery, Hydrometallurgy is performing a key role to the successful achievement of 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.

This study presents the encapsulation of two amino acid-based ionic liquids (AAILs), 1-Ethyl-3-methylimidazolium glycine [Emim][Gly] and 1-Ethyl-3-methylimidazolium alanine [Emim][Ala], in a highly porous metal organic framework (MOF-177), to generate state-of-the-art composites for post-combustion CO2 capture. The thermogravimetric analysis (TGA) demonstrated a successful encapsulation of the AAILs, consequently dramatically reducing the composites' surface area and pore volume. Both [Emim] [Gly]@MOF-177 and [Emim][Ala]@MOF-177 had close to 3 times the CO2 uptake of MOF-177 at 20 wt.% loading, 0.2 bar, and 303 K. Additionally, 20-[Emim][Gly]@MOF-177 and 20-[Emim] [Ala]@MOF-177 enhanced their CO2/N2 selectivity from 5 (pristine MOF-177) to 13 and 11, respectively.

In this work, we explore the intrinsic disorder status of the three members of the synuclein family of proteins - α-, β-, and γ-synucleins. We also analyzed the peculiarities of the amino acid sequences and modeled 3D structures of the human synuclein family members to find potential effects of pathological mutations. Furthermore, we conducted a comparative sequence-based analysis of the synuclein proteins from various evolutionary distant species and evaluated their levels of intrinsic disorder using a set of commonly used bioinformatics tools. Next, we conducted a detailed functional disorder analysis of the proteins in the interactomes of the human synuclein family members using various web-based disorder analysis and prediction tools, such as RIDAO, D2P2 and FuzDrop. We identify that the interactome of human α-synuclein has relatively higher levels of intrinsic disorder, as compared to the interactomes of human β- and γ- synucleins. These observations highlight the critical importance of intrinsic disorder of human α-synuclein and its interactors in neuronal processes as compared to other proteins of the synuclein family.

The positive impact of nature on human health has been explored by researchers. Although studies have indicated that olfaction and odors have an impact on both memory and health, re-search on the odor perception in relation to perceived health is scarce. A recent study found that the naturenatural scent from stem cuttings and potted plants of a specific rose-scented geranium Pelargonium graveolens, ‘Dr. Westerlund,’Westerlund’ had positive effects on stress-related mental disorders. reduction. Essential oils from many Pelargonium species, in particular ‘Dr. Westerlund’, are known to have phytochemical properties and pharmacological activities. No study has, so far, explored and identified the chemical com-pounds and the sensory perception of these compounds in stem cuttings and the potted ´Dr. Westerlund´ plantplants. Such knowledge would be an important contribution forto an increased understanding of the effects of plants’ chemical odor properties on human well-being and link this to the expressed perceived scents. Resulting sensory profiles of P.This study aimed to identify the sensory profile and suggest responsible chemical compounds of Pelargonium graveolens ´Dr. Westerlund´ as a potted plant and as stem cuttings were reported, as well as´. The sensory and chemical analysis results revealed sensory profiles of Pelargonium graveolens ´Dr. Westerlund´s, and suggestions for the chemical compounds that are attributed to the sensory profiles. Further studies are recommended to investigate the odor experience of scented pelargonium species in relation to various levels ofcorrelation between volatile com-pounds and possible stress hormones. reduction in humans.