A vinylpyrrolidone-ethylene glycol dimethacrylate-acrylic acid thin film was prepared on a polypropylene guard and its formulation was optimized for application in thin film microextraction followed by direct solid-state spectrofluorimetry method. The surface morphology, fluorescence property and extraction performance of the thin film were investigated systematically. The intra- and inter-batch reproducibilities of thin film fabrication were obtained 2.3 and 4.2%, respectively. The lifetime of each prepared thin film was 30 times with a relative standard deviation of less than 1.4%. The developed method was optimized for extraction of some sartans as angiotensin II receptors antagonist (including losartan, valsartan, and olmesartan) which have been used to control hypertension as the main causes of cardiovascular disease. The optimum extraction conditions achieved at 2- (for losartan) and 4- (for valsartan and olmesartan) sample pH, 500-rpm rotation rate and 30-min extraction time for all three analytes. At the optimum conditions, analyses of losartan, valsartan, and olmesartan were validated in the human plasma matrix. Broad linearity ranges with determination coefficients of more than 0.999 were achieved for each calibration curve. Limit of detection of the method was 0.5 ng mL-1 for all three analytes. The intra- and inter-day accuracies and precisions of the developed method were evaluated in spiked plasma samples at three concentration levels of each analyte with high recoveries of 95-101% and relative standard deviations less than 6%. This method provides a simple, sensitive, fast, and high-throughput analysis method with the possibility of effective extraction of at least 40 samples simultaneously without the necessity of protein precipitating, desorption, and solvent evaporation steps.Exosomes are extracellular vesicles that mediate intercellular communication, immune response, and tumour metastasis. However, exosome isolation from the blood is complicated because their size and density are similar to those of blood lipoproteins. Here, we employed field programming frit-inlet asymmetrical flow field-flow fractionation (FIAF4) coupled with multiangle light scattering (MALS) for the effective separation of exosomes from free unbound proteins and lipoproteins present in serum samples using different pre-treatment methods, namely, a commercial exosome isolation kit, ultracentrifugation (UC), and a simple centrifugation followed by ultrafiltration (UF). Sizes of the eluted exosomes, as calculated by MALS signals, approximated well with the results of batch dynamic light scattering of the collected fractions and with the sizes of polystyrene particles. Exosome separation from lipoproteins was validated by western blotting with several markers of exosomes and lipoproteins, followed by proteomic analysis using nanoflow ultrahigh-performance liquid chromatography-electrospray ionisation-tandem mass spectrometry. UC requires relatively large amounts of serum samples (at least 2 mL) but is more efficient at removing lipoproteins. The UF method with a centrifugal concentrator (300 kDa) was found to be more effective in retrieving exosomes with low serum volumes (50 μL). Altogether, this study demonstrates the application of field programming FIAF4 for the isolation/purification of exosomes from proteins and lipoproteins in the serum.Electromembrane extraction (EME) involves transfer of analyte ions from aqueous sample, through a supported liquid membrane (SLM), and into an aqueous acceptor solution under the influence of an external electrical field. In addition to target analyte ions, the sample also contains matrix ions, and both the sample and acceptor contains background buffer ions to control pH. The ratio between the total amount of ions in sample and acceptor defines the ion balance (χ). Previous publications have discussed the impact of ion balance, but conclusions are contradictory. Therefore, the current paper investigated the ion balance in more detail. From a theoretical point of view, low χ-values favor EME; buffer anions at high concentration in the acceptor migrate into the SLM, while target cations enters the SLM from the sample to maintain electroneutrality. A large number of experiments was performed in this paper to investigate the practical impact of ion balance. Twelve basic drugs were used as model analytes (0.0 less then log P less then 5.0), and 2-nitrophenyl octyl ether (NPOE) and NPOE + 5% di(2-ethylhexyl) phosphate (DEHP) were used as SLM. With formate buffer pH 3.75 as sample and acceptor, the impact of χ in the range 0.01-10 was studied without bias from differences in pH. Here model analytes were unaffected by ion balance. Buffers containing propionic, butyric, and valeric acid were also tested. These buffer ions migrated more into the SLM, and affected recoveries in several cases. However, this was due to ion pairing rather than effects of ion balance. https://www.selleckchem.com/products/way-309236-a.html Similar behaviors from sodium chloride and urine samples were observed with different χ-values. Thus, in the systems tested, almost no impact of ion balance was found, and this was attributed to very low partition of background buffer and matrix ions into the SLM. On the other hand, extractions were in several cases influenced by ion pairing phenomena.Despite of increased interest in the application of miniature microplasma atomic spectrometry for environmental analytical chemistry, the amenable element detection range is limited to some metal elements and carbon due to it low power consumption. In this work, the generation of silicon atomic emission (251.6 nm and 288.2 nm) from the organosiloxanes was found possible in a low-temperature, low-power, and compact point discharge. Consequence, a tiny point discharge silicon optical emission spectrometer (μPD-OES) was exploited, and used as a novel GC detector for the determination of various cyclic volatile methyl siloxanes (cVMSs). Under the optimized conditions, the developed system provided limits of detection (LODs) of 0.2 mg L-1, 0.04 mg L-1, 0.03 mg L-1 and 0.02 mg L-1 of Si for hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, respectively. Meanwhile, relative standard deviations (RSDs) of better than 2.3% were obtained. In contrast to gas chromatography mass spectrometer, GC-μPD-OES significantly simplifies the experimental setup with low power consumption and a miniature configuration.
A vinylpyrrolidone-ethylene glycol dimethacrylate-acrylic acid thin film was prepared on a polypropylene guard and its formulation was optimized for application in thin film microextraction followed by direct solid-state spectrofluorimetry method. The surface morphology, fluorescence property and extraction performance of the thin film were investigated systematically. The intra- and inter-batch reproducibilities of thin film fabrication were obtained 2.3 and 4.2%, respectively. The lifetime of each prepared thin film was 30 times with a relative standard deviation of less than 1.4%. The developed method was optimized for extraction of some sartans as angiotensin II receptors antagonist (including losartan, valsartan, and olmesartan) which have been used to control hypertension as the main causes of cardiovascular disease. The optimum extraction conditions achieved at 2- (for losartan) and 4- (for valsartan and olmesartan) sample pH, 500-rpm rotation rate and 30-min extraction time for all three analytes. At the optimum conditions, analyses of losartan, valsartan, and olmesartan were validated in the human plasma matrix. Broad linearity ranges with determination coefficients of more than 0.999 were achieved for each calibration curve. Limit of detection of the method was 0.5 ng mL-1 for all three analytes. The intra- and inter-day accuracies and precisions of the developed method were evaluated in spiked plasma samples at three concentration levels of each analyte with high recoveries of 95-101% and relative standard deviations less than 6%. This method provides a simple, sensitive, fast, and high-throughput analysis method with the possibility of effective extraction of at least 40 samples simultaneously without the necessity of protein precipitating, desorption, and solvent evaporation steps.Exosomes are extracellular vesicles that mediate intercellular communication, immune response, and tumour metastasis. However, exosome isolation from the blood is complicated because their size and density are similar to those of blood lipoproteins. Here, we employed field programming frit-inlet asymmetrical flow field-flow fractionation (FIAF4) coupled with multiangle light scattering (MALS) for the effective separation of exosomes from free unbound proteins and lipoproteins present in serum samples using different pre-treatment methods, namely, a commercial exosome isolation kit, ultracentrifugation (UC), and a simple centrifugation followed by ultrafiltration (UF). Sizes of the eluted exosomes, as calculated by MALS signals, approximated well with the results of batch dynamic light scattering of the collected fractions and with the sizes of polystyrene particles. Exosome separation from lipoproteins was validated by western blotting with several markers of exosomes and lipoproteins, followed by proteomic analysis using nanoflow ultrahigh-performance liquid chromatography-electrospray ionisation-tandem mass spectrometry. UC requires relatively large amounts of serum samples (at least 2 mL) but is more efficient at removing lipoproteins. The UF method with a centrifugal concentrator (300 kDa) was found to be more effective in retrieving exosomes with low serum volumes (50 μL). Altogether, this study demonstrates the application of field programming FIAF4 for the isolation/purification of exosomes from proteins and lipoproteins in the serum.Electromembrane extraction (EME) involves transfer of analyte ions from aqueous sample, through a supported liquid membrane (SLM), and into an aqueous acceptor solution under the influence of an external electrical field. In addition to target analyte ions, the sample also contains matrix ions, and both the sample and acceptor contains background buffer ions to control pH. The ratio between the total amount of ions in sample and acceptor defines the ion balance (χ). Previous publications have discussed the impact of ion balance, but conclusions are contradictory. Therefore, the current paper investigated the ion balance in more detail. From a theoretical point of view, low χ-values favor EME; buffer anions at high concentration in the acceptor migrate into the SLM, while target cations enters the SLM from the sample to maintain electroneutrality. A large number of experiments was performed in this paper to investigate the practical impact of ion balance. Twelve basic drugs were used as model analytes (0.0 less then log P less then 5.0), and 2-nitrophenyl octyl ether (NPOE) and NPOE + 5% di(2-ethylhexyl) phosphate (DEHP) were used as SLM. With formate buffer pH 3.75 as sample and acceptor, the impact of χ in the range 0.01-10 was studied without bias from differences in pH. Here model analytes were unaffected by ion balance. Buffers containing propionic, butyric, and valeric acid were also tested. These buffer ions migrated more into the SLM, and affected recoveries in several cases. However, this was due to ion pairing rather than effects of ion balance. https://www.selleckchem.com/products/way-309236-a.html Similar behaviors from sodium chloride and urine samples were observed with different χ-values. Thus, in the systems tested, almost no impact of ion balance was found, and this was attributed to very low partition of background buffer and matrix ions into the SLM. On the other hand, extractions were in several cases influenced by ion pairing phenomena.Despite of increased interest in the application of miniature microplasma atomic spectrometry for environmental analytical chemistry, the amenable element detection range is limited to some metal elements and carbon due to it low power consumption. In this work, the generation of silicon atomic emission (251.6 nm and 288.2 nm) from the organosiloxanes was found possible in a low-temperature, low-power, and compact point discharge. Consequence, a tiny point discharge silicon optical emission spectrometer (μPD-OES) was exploited, and used as a novel GC detector for the determination of various cyclic volatile methyl siloxanes (cVMSs). Under the optimized conditions, the developed system provided limits of detection (LODs) of 0.2 mg L-1, 0.04 mg L-1, 0.03 mg L-1 and 0.02 mg L-1 of Si for hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, respectively. Meanwhile, relative standard deviations (RSDs) of better than 2.3% were obtained. In contrast to gas chromatography mass spectrometer, GC-μPD-OES significantly simplifies the experimental setup with low power consumption and a miniature configuration.
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