Determination of breast cancer biomarkers with poly acrylic acid/ MIL-88(Fe)-NH2 hydrogel as a coating for stir bar sorptive extraction.

The Poly acrylic acid/MIL-88(Fe)-NH2 composite material, carefully prepared, is employed as a sorbent for the stir bar. The best formula of the composite was selected by investigation of two parameters including the cross-linker of PAA and MIL-88(Fe)-NH2 content. The prepared stir bar was used for extraction of 2-pentanone, 2-heptanone, ethyl propionate, para-xylene, 1,2,4-trimethylbenzene, o-cresol, m-cresol in urine samples as breast cancer biomarkers with gas chromatography-flame ionization detector. The prepared Poly acrylic acid / MIL-88(Fe)-NH2 as sorbent for the stir bar demonstrate good repeatability of one bar (relative standard deviation (RSD%) < 4.61 %) and satisfactory reproducibility between two bars (RSD% < 6.85 %). The central composite design method was applied for the optimization of extraction parameters. Under the optimum conditions, linear dynamic ranges for compounds were in the acceptable range with correlation coefficients higher than 0.99. Detection limits of them were less than 1.71 µg L-1.

Analytical approaches for determination of COVID-19 candidate drugs in human biological matrices.

Since the outbreak of the COVID-19 pandemic, the use of antiviral and other available drugs has been considered to combat or reduce the clinical symptoms of patients. In this regard, it would be necessary to choose sensitive and selective analytical techniques for pharmacokinetic and pharmacodynamic studies, monitoring of drug concentration in biological fluids, and determination of the most appropriate dose to achieve the desired effect on the disease. In the present study, the analytical techniques based on spectroscopy and chromatography with different detectors for diagnosis and determination of candidate drugs in the treatment of COVID-19 in human biological fluids are reviewed during the period 2015-2022. Moreover, various sample preparation and extraction techniques, are being used for this purpose, such as protein precipitation (PP), solid-phase extraction (SPE), liquid-liquid extraction (LLE), and QuEChERS (quick, easy, cheap, effective, rugged, and safe) are investigated.

Fabrication of a new SPME fiber based on Polyacrylic acid/ MIL-88(Fe)-NH2 composite as a self-healing coating for the analysis of breast cancer biomarkers in the urine sample.

Analysis of cancer biomarkers in the body fluids is a new method for early detection of illness. However, due to the complex matrices of samples, the application of a pre-treatment method is unavoidable before the final analysis by gas chromatography (GC). Solid-phase microextraction (SPME) is a simple and, promising pre-concentration and separation method that its coatings are modified with different materials on the fibers. A new innovative self-healing polyacrylic acid PAA/MIL-88(Fe)-NH2 composite was synthesized as an SPME coating. The parameters including pH, crosslinker, and MIL-88(Fe)-NH2 content were optimized to formulate the composite. The prepared fiber was used to extract 2-pentanone, 2-heptanone, ethyl propionate, p-xylene, 1,2,4-trimethylbenzene, and o-cresol as a biomarker in breast cancer from urine samples. The prepared PAA/MIL-88(Fe)-NH2 SPME fibers demonstrate excellent repeatability (relative standard deviation (RSD%)< 3.4%) and satisfactory reproducibility (RSD%<6.9%). The central composite design method was applied for the optimization of extraction parameters. Under the optimum conditions, linear dynamic ranges for biomarkers were in the acceptable range with correlation coefficients higher than 0.98. The detection limits of them were less down 0.0016 µg L-1. Self-healing ability of fiber coating increased useful lifetime (about 120 times extraction with one fiber) as well as accuracy, reproducibility, and recovery of fibers.

Development, validation, and uncertainty measurement of HPLC-DAD method for determination of some free amino acids in infant formula and medical food products for inborn errors of metabolism.

This research aims at determining some free amino acids in amino acid-based infant formulas and amino acid-modified medical foods for inborn errors of metabolism to prove their quality. A method based on high-performance liquid chromatography and diode array detection was developed and validated. Then, overall uncertainty was estimated by the bottom-up approach. Applying the weighted least squares regression method suggested good linearity with coefficient of determinations ≥ 0.9960. The limits of detection were calculated between 0.01 and 0.28 µg/mL. The most repetitive recovery values were obtained in the range of 91-108%, with RSDs ≤ 15%. The expanded uncertainties were below 20% for most amino acids. The contributions of linear regression and repeatability are two main factors in estimating overall uncertainty. The results offer this method as a simple and easy procedure for analyzing free amino acids in seven powdered medical foods designed for phenylketonuria, maple syrup urine disease, methylmalonic, and propionic acidemia.

Clogging sensitivity of flow distributors designed for radially elongated hexagonal pillar array columns: a computational modelling.

Flow distributor located at the beginning of the micromachined pillar array column (PAC) has significant roles in uniform distribution of flow through separation channels and thus separation efficiency. Chip manufacturing artifacts, contaminated solvents, and complex matrix of samples may contribute to clogging of the microfabricated channels, affect the distribution of the sample, and alter the performance of both natural and engineered systems. An even fluid distribution must be achieved cross-sectionally through careful design of flow distributors and minimizing the sensitivity to clogging in order to reach satisfactory separation efficiency. Given the difficulty to investigate experimentally a high number of clogging conditions and geometries, this work exploits a computational fluid dynamic model to investigate the effect of various design parameters on the performance of flow distributors in equally spreading the flow along the separation channels in the presence of different degrees of clogging. An array of radially elongated hexagonal pillars was selected for the separation channel (column). The design parameters include channel width, distributor width, aspect ratio of the pillars, and number of contact zone rows. The performance of known flow distributors, including bifurcating (BF), radially interconnected (RI), and recently introduced mixed-mode (MMI) in addition to two new distributors designed in this work (MMII and MMIII) were investigated in terms of mean elution time, volumetric variance, asymmetry factors, and pressure drop between the inlet and the monitor line for each design. The results show that except for pressure drop, the channel width and aspect ratio of the pillars has no significant influence on flow distribution pattern in non-clogged distributors. However, the behavior of flow distributors in response to clogging was found to be dependent on width of the channels. Also increasing the distributor width and number of contact zone rows after the first splitting stage showed no improvement in the ability to alleviate the clogging. MMI distributor with the channel width of 3 µm, aspect ratio of the pillars equal to 20, number of exits of 8, and number of contact zones of 3 exhibited the highest stability and minimum sensitivity to different degrees of clogging.

Discrimination between vegetable oil and animal fat by a metabolomics approach using gas chromatography-mass spectrometry combined with chemometrics.

Adulteration of olive oil with the other cheap oils and fats plays an important role in economics and has nutritional benefits. In this work, metabolite profiling was performed using gas chromatography-mass spectrometry to identify and quantify animal fat (lard) adulteration in vegetable oil (olive oil). Principal component analysis could correctly identify and clustering olive oil, sunflower oil, sesame oil, lard, and adulterated samples through the changes in their fatty acid methyl esters (FAMEs) profile. A targeted metabolomics method was then optimized and validated through construction of calibration curves of known FAMSs in olive oil and lard. The method was presented high linearity (R2 > 0.96) and good intra and inter day accuracy and precision (79-101 and 86-102% and 2-7 and 3-7, respectively) for determination of FAMEs. Afterwards the absolute concentration and relative percentage of FAMEs were successfully determined in 12 commercial olive oils and 3 lards samples. Methyl myristate, methyl palmitate, methyl oleate, and methyl stearate were selected as discriminant markers to identify and quantify lard adulteration even at a low level of lard (5%w/w), with errors less than 2% in the comparison of the absolute or relative concentrations of FAMEs using several statistical methods. The proposed methodology allowed us to quantify the FAMEs simultaneously and also could predict small amount of lard in the adulterated olive oil samples.

A vinylpyrrolidone-based thin film microextraction in combination with direct solid-state spectrofluorimetry for determination of sartans in human plasma.

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.

Introduction of electropolymerization of pyrrole as a coating method for stir bar sorptive extraction of estradiol followed by gas chromatography.

In this study, fabrication of a stir bar sorbent is presented by electropolymerization of pyrrole via cyclic voltametry for the first time. The fabricated stir bar was applied as an efficient sorbent for extraction and pre-concentration of trace amounts of estradiol in urine samples through stir bar sorptive extraction (SBSE) method followed by gas chromatography-flame ionization detector. For this purpose, first the surface of stainless steel rod was modified by hyroxide functional group. Then electropolymerization of pyrrole monomers took place on the surface of functionalized steel rod under the optimized conditions including pyrrole concentration of 0.03 mol L-1, equal concentration ratio of pyrrole to sodium dodecyl sulfate, 10 cycles of cyclic voltammetry and potential scan rate of 10 mV s-1. Characterization of the produced sorbent was confirmed by scanning electron microscope imaging and energy-dispersive X-ray and infrared spectroscopy. Evantually, under the optimized conditions, the stir bar sorbent was used for extraction of estradiol from human urine samples. The presented SBSE method showed a good linearity range of 50-700 ng mL-1 with coefficient of determination 0.9910, limit of detection 10 ng mL-1 and theoretical limit of quantification 33 ng mL-1. Moreover, better enrichment factor (87) and extraction recovery (43%) were obtained using the fabricated stir bar compared with two commercial stir bars for estradiol. The intra- and inter-bar relative recoveries were obtained 92.0% and their coefficient of variations were less than 5.4%.

Validated determination of losartan and valsartan in human plasma by stir bar sorptive extraction based on acrylate monolithic polymer, liquid chromatographic analysis and experimental design methodology.

In our previous work, a new monolithic coating based on vinylpyrrolidone-ethylene glycol dimethacrylate polymer was introduced for stir bar sorptive extraction. The formulation of the prepared vinylpyrrolidone-ethylene glycol dimethacrylate monolithic polymer was optimized and the satisfactory quality of prepared coated stir bar was demonstrated. In this work, the prepared stir bar was utilized in combination with ultrasound-assisted liquid desorption, followed by high-performance liquid chromatography with ultraviolet detection for the simultaneous determination of losartan (LOS) and valsartan (VAS) in human plasma samples. In a comparison study, the extraction efficiency of the prepared stir bar was accompanied much higher extraction efficiency than the two commercial stir bars (polydimethylsiloxand and polyacrylate) for both target compounds. In order to improve the desorption efficiency of LOS and VAS, the best values for effective parameters on desorption step were selected systematically. Also, the effective parameters on extraction step were optimized using a Box-Behnken design. Under the optimum conditions, the analytical performance of the proposed method displayed excellent linear dynamic ranges for LOS (24-1000 ng mL-1) and VAS (91-1000 ng mL-1), with correlation coefficients of 0.9998 and 0.9971 and detection limits of 7 and 27 ng mL-1, respectively. The intra- and inter-day recovery ranged from 98 to 117%, and the relative standard deviations were less than 8%. Finally, the proposed technique was successfully applied to the analysis of LOS and VAS at their therapeutic levels in volunteer patient plasma sample. The obtained results were confirmed using liquid chromatography-mass spectrometry. The proposed technique was more rapid than previously reported stir bar sorptive extraction techniques based on monolithic coatings, and exhibited lower detection limits in comparison with similar methods for the determination of LOS and VLS in biological fluids. The obtained results were demonstrated that the lower selectivity of UV in comparison with MS detection was rectified by appropriate sample preparation through proposed extraction method to eliminate as many interfering compounds as possible.

Simple and Sensitive Quantification of Ghrelin Hormone in Human Plasma Using SBSE-HPLC/DAD-MS.

During a decade and more since its discovery, the emerging physiological roles of ghrelin in mammalian are increasingly being introduced, proposing a critical need for its quantification in biological milieu. Here in, a simple and sensitive single-step method for extraction and quantification of ghrelin in human plasma was developed and validated using stir bar sorptive extraction (SBSE) followed by high-performance liquid chromatography (HPLC) with diode array detection (DAD) coupled to mass spectrometry (MS). Influential parameters of SBSE procedure were optimized including extraction and desorption times of 45 and 30 min, respectively; pH of 4; no addition of salt. The sum of peak heights of three most intense selected ions in mass spectrum (844, 1125 and 1686 m/z) related to 4-, 3- and 2-fold-charged ions of ghrelin was used for quantification. Validation parameters containing linear dynamic range, limit of quantification and limit of detection were 0.02-80, 0.02 and 0.007 µg L-1, respectively, and calculated relative standard deviation for peak heights was 6.5% (0.7 µg L-1 standard solution). Mean recovery for ghrelin in spiked plasma samples was 96% ± 3. The efficiency of the SBSE-HPLC/DAD-MS procedure was proved by analysis of plasma samples from obese patients undergoing gastric plication surgery. The suggested methodology would contribute to simple and fast analysis of ghrelin levels in obesity and related diseases and also biochemical cycles in which gherlin is present.

Sorptive thin film microextraction followed by direct solid state spectrofluorimetry: A simple, rapid and sensitive method for determination of carvedilol in human plasma.

A poly acrylate-ethylene glycol (PA-EG) thin film is introduced for the first time as a novel polar sorbent for sorptive extraction method coupled directly to solid-state spectrofluorimetry without the necessity of a desorption step. The structure, polarity, fluorescence property and extraction performance of the developed thin film were investigated systematically. Carvedilol was used as the model analyte to evaluate the proposed method. The entire procedure involved one-step extraction of carvedilol from plasma using PA-EG thin film sorptive phase without protein precipitation. Extraction variables were studied in order to establish the best experimental conditions. Optimum extraction conditions were the followings: stirring speed of 1000 rpm, pH of 6.8, extraction temperature of 60 °C, and extraction time of 60 min. Under optimal conditions, extraction of carvedilol was carried out in spiked human plasma; and the linear range of calibration curve was 15-300 ng mL(-1) with regression coefficient of 0.998. Limit of detection (LOD) for the method was 4.5 ng mL(-1). The intra- and inter-day accuracy and precision of the proposed method were evaluated in plasma sample spiked with three concentration levels of carvedilol; yielding a recovery of 91-112% and relative standard deviation of less than 8%, respectively. The established procedure was successfully applied for quantification of carvedilol in plasma sample of a volunteer patient. The developed PA-EG thin film sorptive phase followed by solid-state spectrofluorimetric method provides a simple, rapid and sensitive approach for the analysis of carvedilol in human plasma.

Preparation of a novel sorptive stir bar based on vinylpyrrolidone-ethylene glycol dimethacrylate monolithic polymer for the simultaneous extraction of diazepam and nordazepam from human plasma.

A new monolithic coating based on vinylpyrrolidone-ethylene glycol dimethacrylate polymer was introduced for stir bar sorptive extraction. The polymerization step was performed using different contents of monomer, cross-linker and porogenic solvent, and the best formulation was selected. The quality of the prepared vinylpyrrolidone-ethylene glycol dimethacrylate stir bars was satisfactory, demonstrating good repeatability within batch (relative standard deviation < 3.5%) and acceptable reproducibility between batches (relative standard deviation < 6.0%). The prepared stir bar was utilized in combination with ultrasound-assisted liquid desorption, followed by high-performance liquid chromatography with ultraviolet detection for the simultaneous determination of diazepam and nordazepam in human plasma samples. To optimize the extraction step, a three-level, four-factor, three-block Box-Behnken design was applied. Under the optimum conditions, the analytical performance of the proposed method displayed excellent linear dynamic ranges for diazepam (36-1200 ng/mL) and nordazepam (25-1200 ng/mL), with correlation coefficients of 0.9986 and 0.9968 and detection limits of 12 and 10 ng/mL, respectively. The intra- and interday recovery ranged from 93 to 106%, and the relative standard deviations were less than 6%. Finally, the proposed method was successfully applied to the analysis of diazepam and nordazepam at their therapeutic levels in human plasma. The novelty of this study is the improved polarity of the stir bar coating and its application for the simultaneous extraction of diazepam and its active metabolite, nordazepam in human plasma sample. The method was more rapid than previously reported stir bar sorptive extraction techniques based on monolithic coatings, and exhibited lower detection limits in comparison with similar methods for the determination of diazepam and nordazepam in biological fluids.

Starmerella orientalis f.a., sp. nov., an ascomycetous yeast species isolated from flowers.

Four strains of a novel ascomycetous yeast species were isolated from flowers in Iran and China. Phylogenetic analysis of the sequences of the ITS region (including 5.8S rRNA gene) and the LSU rRNA gene D1/D2 domains indicated that these strains belong to the Starmerella clade and show divergence from previously described species in this clade. Growth reactions on carbon and nitrogen sources were similar to those observed in related species of the Starmerella clade. Sexual reproduction was not observed after mating tests on different sporulation media. Based on physiological characteristics and phylogeny of rRNA gene sequences, the novel species is most closely related to Candida (iter. nom. Starmerella) powellii and Candida (iter. nom. Starmerella) floricola. It is therefore assigned to the genus Starmerella and described as Starmerella orientalis f.a., sp. nov. The type strain is SAM09T ( = IBRC-M 30204T = CBS 14142T). The MycoBank accession number is MB 814379.

Microwave-assisted extraction of cyclotides from Viola ignobilis.

Cyclotides are an interesting family of circular plant peptides. Their unique three-dimensional structure, comprising a head-to-tail circular backbone chain and three disulfide bonds, confers them stability against thermal, chemical, and enzymatic degradation. Their unique stability under extreme conditions creates an idea about the possibility of using harsh extraction methods such as microwave-assisted extraction (MAE) without affecting their structures. MAE has been introduced as a potent extraction method for extraction of natural compounds, but it is seldom used for peptide and protein extraction. In this work, microwave irradiation was applied to the extraction of cyclotides. The procedure was performed in various steps using a microwave instrument under different conditions. High-performance liquid chromatography (HPLC) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) results show stability of cyclotide structures on microwave radiation. The influential parameters, including time, temperature, and the ratio of solvents that are affecting the MAE potency, were optimized. Optimal conditions were obtained at 20 min of irradiation time, 1200 W of system power in 60 °C, and methanol/water at the ratio of 90:10 (v/v) as solvent. The comparison of MAE results with maceration extraction shows that there are similarities between cyclotide sequences and extraction yields.

Evaluation of a method for the simultaneous quantification of N-nitrosamines in water samples based on stir bar sorptive extraction combined with high-performance liquid chromatography and diode array detection.

A simple, sensitive, and reliable procedure based on stir bar sorptive extraction coupled with high-performance liquid chromatography was applied to simultaneously extract and determine three semipolar nitrosamines including N-nitrosodibutylamine, N-nitrosodiphenylamine, and N-nitrosodicyclohexylamine. To achieve the optimum conditions, the effective parameters on the extraction efficiency including desorption solvent and time, ionic strength of sample, extraction time, and sample volume were systematically investigated. The optimized extraction procedure was carried out by stir bars coated with polydimethylsiloxane. Under optimum extraction conditions, the performance of the proposed method was studied. The linear dynamic range was obtained in the range of 0.95-1000 ng/mL (r = 0.9995), 0.26-1000 ng/mL (r = 0.9988) and both 0.32-100 ng/mL (r = 0.9999) and 100-1000 ng/mL (r = 0.9998) with limits of detection of 0.28, 0.08, and 0.09 ng/mL for N-nitrosodibutylamine, N-nitrosodiphenylamine, and N-nitrosodicyclohexylamine, respectively. The average recoveries were obtained >81%, and the reproducibility of the proposed method presented as intra- and interday precision were also found with a relative standard deviation <6%. Finally, the proposed method was successfully applied to the determination of trace amounts of selected nitrosamines in various water and wastewater samples and the obtained results were confirmed using mass spectrometry.

Determination of Carvedilol Enantiomers in Pharmaceutical Dosages by SBSE-HPLC Based on Diastereomer Formation.

A sensitive, selective and simple method for the simultaneous determination of carvedilol enantiomers in aqueous solution has been developed using stir bar sorptive extraction (SBSE) followed by high-performance liquid chromatography (HPLC) with ultraviolet (UV) detection. This method is based on the reaction of carvedilol enantiomers with (-)-menthyl chloroformate (MCF) after extraction by the SBSE method to produce diastereomeric derivatives. The separation was achieved by use of a C18 analytical column and the influence of mobile phase composition on the enantioseparation of carvedilol was studied. The applicability of two sorptive phases, poly(methyl methacrylate/ethyleneglycol dimethacrylate) (PA-EG) and polydimethylsiloxane, were tested for extraction of carvedilol enantiomers from aqueous samples. The obtained results showed excellent linear dynamic ranges and precisions for each of them. The least limit of detection for (S)- and (R)-carvedilol obtained 8 and 11 µg L(-1), respectively, using the PA-EG sorptive phase. Inter- and intra-mean recoveries were also satisfactory, ranging from 98 to 103%, with coefficient of variation in the range of 1-5% at three fortified levels using a PA-EG coated stir bar. The proposed SBSE (PA-EG)-MCF derivatization-HPLC-UV method was successfully applied to enantioselective analysis of carvedilol in water and pharmaceutical dosages, confirming the application of this method.

Synthesis and characterization of Sr3Al2O6 nanocomposite as catalyst for biodiesel production.

Sr-Al mixed oxides nanocomposite as Sr3Al2O6 was prepared by sol-gel method and used as a basic heterogeneous catalyst for transesterification of soybean oil to methyl esters (biodiesel) by methanol. The prepared catalyst was characterized using X-ray diffraction (XRD), Transmission electron microscope (TEM), thermogravimetric analysis (TGA/DTA), temperature-programmed desorption (TPD) and nitrogen adsorption-desorption techniques. The response surface methodology (RSM) based on the Box-Behnken design was employed to investigate the effects of methanol to oil molar ratio, reaction time, catalyst amount and specifically the effect of interaction between process variables on the conversion of oil to biodiesel. Results from this study revealed that individual as well as bilateral variables interactions significantly affect the yield of biodiesel. With this information, it was found that utilization of methanol to oil molar ratio of 25 and 1.3 wt.% of catalyst within reaction time of 61 min and gave the biodiesel yield of 95.7 ± 0.5%.

Determination of Cefixime by a Validated Stability-Indicating HPLC Method and Identification of its Related Substances by LC-MS/MS Studies.

Cefixime is an important cephalosporin antibiotic that easily decomposes and releases different related substances in preparation and storage steps. The objective of the current study was to develop a simple, precise, and accurate isocratic liquid chromatography (LC) method for the determination of cefixime in the presence of its related substances generated from thermal stress in the bulk drug. The chromatographic conditions were comprised of a reversed-phase C18 column (4.6 × 250 mm, 5 µm) with a mobile phase composed of water: acetonitrile (85:15 v/v, with 0.5% formic acid) and ultraviolet detection (UV). Some thermal degradation products were identified using a proposed liquid chromatography-mass spectrometry method. Five peaks (A, B, C, D, and E impurities based on British Pharmacopoeia) were known and a few unknown peaks appeared in the thermal stress solution of cefixime. The linear regression analysis data for the calibration plot of the LC-UV method showed a good linear relationship in the concentration range 0.9-1000.0 µg mL(-1). The recovery of the optimized method was between 94.6 and 98.4% and the inter- and intra-day relative standard deviations were less than 3.3%. The obtained results shown in the LC-UV proposed method can be conveniently used in a quality control laboratory for routine analysis of cefixime for the assay and related substances, as well as for the evaluation of stability samples of bulk drugs.

Stir bar sorptive extraction and high performance liquid chromatographic determination of carvedilol in human serum using two different polymeric phases and an ionic liquid as desorption solvent.

This article presents a method employing stir bar coated with a film of poly (methyl methacrylate/ethyleneglycol dimethacrylate) (PA-EG) and polydimethylsiloxane (PDMS) in combination with liquid desorption (LD) using ionic liquid, followed by high performance liquid chromatography (HPLC) equipped with ultraviolet (UV) detection for the determination of carvedilol in human serum samples. Stir bar sorptive extraction (SBSE) variables, such as desorption and extraction time and temperature, desorption solvent and pH of the matrix were optimized, in order to achieve suitable analytical sensitivity in a short period of time. Also, the concentration effect of 1-methyl-3-octylimidazolium tetrafluoroborate [Omim][BF4] ionic liquid on the efficiency of LD was investigated. A comparison between PA-EG/SBSE and PDMS/SBSE was made by calculating the experimental recovery and partition coefficient (K), where PA-EG phase demonstrated to be an excellent alternative for the enrichment of the carvedilol from serum samples. The effect of [Omim][BF4] on carryover was studied and no carryover was observed. Under optimized experimental conditions, the analytical performance showed excellent linear dynamic range, with correlation coefficients higher than 0.999 and limits of detection and quantification of 0.3 and 1.0 ng mL(-1), respectively. Intra- and inter-day recovery ranged from 94 to 103% and the coefficients of variations were less than 3.2%. The proposed method was shown to be simple, highly sensitive and suitable for the measurement of trace concentration levels of carvedilol in biological fluid media.

Essential oil composition and antioxidant activities of the various extracts of Tanacetum sonbolii Mozaff. (Asteraceae) from Iran.

This study is designed to examine the chemical composition of the essential oil and antioxidant activities of the different extracts of Tanacetum sonbolii Mozaff. from Iran for the first time. The essential oil was isolated by hydrodistillation and its gas chromatography and gas chromatography-mass spectrometry analyses resulted in the identification of 26 components, representing 96.5% of the oil. The major components were characterised to be α-cadinol (35.3%), globulol (20.1%) and 1,8-cineole (8.6%). Antioxidant activities of the various extracts of the plant were determined by two different test systems; 1,1-diphenyl-2-picrylhydrazyl (DPPH) and ß-carotene-linoleic acid. Also, their total phenolic and flavonoid contents were determined. DPPH radical-scavenging activities of test samples followed the order water > chloroform > ethyl acetate > butanol > BHT > methanol. Moreover, the ethyl acetate extract showed better ß-carotene bleaching capacity than the other extracts and the amount of total phenolics was very high in ethyl acetate extract.