Home About us Contact
|
Home About us Contact | ||
|
|
||
Liquid-liquid Extraction (liquid-liquid + extraction)
Selected AbstractsResolution of Racemic N -Benzyl ,-Amino Acids by Liquid-Liquid Extraction: A Practical Method Using a Lipophilic Chiral Cobalt(III) Salen Complex and Mechanistic StudiesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 7 2008Pawel Dzygiel Abstract The efficient resolution of racemic N -benzyl ,-amino acids (N -Bn-AA) has been achieved by a liquid-liquid extraction process using the lipophilic chiral salen,cobalt(III) complex [CoIII(3)(OAc)]. As a result of the resolution by extraction, one enantiomer (S) of the N -benzyl ,-amino acid predominated in the aqueous phase, while the other enantiomer (R) was driven into the organic phase by complexation to cobalt. The complexed amino acid (R) was then quantitatively released by a reductive (CoIII,,,CoII) counter-extraction with aqueous sodium dithionite or L -ascorbic acid in methanol. Thereductive cleavage allowed to recover the [CoII(3)] complex in good yield, which could be easily re-oxidized to[CoIII(3)(OAc)] with air/AcOH and reused with essentially no loss of reactivity and selectivity. Investigation on the nitrogen substitution indicates that the presence of a single benzyl group on the amino acid nitrogen is important to obtain high enantioselectivity in the extraction process. The kinetic vs. thermodynamic nature of the resolution process was also investigated with an enantiomeric exchange experiment, which shows that the liquid-liquid extraction with [CoIII(3)(OAc)] is an equilibrium process operating under thermodynamic control. In the absence of a suitable crystal structure of the [CoIII(3)(N -Bn-AA)] complexes, computational and spectroscopic studies were used to investigate how the N -benzyl ,-amino acids are accommodated in the "binding pocket" of the chiral cobalt complex. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Purification of Fluorous Mitsunobu Reactions by Liquid-Liquid ExtractionADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 12-13 2006Dennis Abstract Solvent tuning and partition coefficient measurements have identified suitable reagent and solvent combinations for the purification of fluorous Mitsunobu reaction products. The crude reaction mixtures are partitioned between 2/1 HFE-7100/FC-72 and DMF/10,% water to provide reagent (fluorous) and product (organic) fractions. [source] Liquid chromatography/tandem triple-quadrupole mass spectrometry for determination of paclitaxel in rat tissuesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2006Xinyong Tong A liquid chromatography/tandem triple-quadrupole mass spectrometry assay to quantify paclitaxel in rat tissue homogenates containing taxol or paclitaxel nanoliposome (PTX-NLP) was developed and validated. Liquid-liquid extraction with tert -butyl methyl ether was used for tissue sample preparation and docetaxel was used as the internal standard. Paclitaxel and docetaxel were separated on a 200,mm,×,4.6,mm,×,5,µm C18 column and quantified using a triple-quadrupole mass spectrometer operating in positive ion electrospray selective reaction monitoring mode (ESI+ -SRM) with a total run time of 6.0,min. The peak area of the m/z 876.3,,,307.9 transition of paclitaxel is measured versus that of the m/z 830.3,,,549.1 transition of docetaxel to generate the standard curves. The standard curves were linear over the concentration range of 0.2008,2008,ng/mL for different tissues. The method had high extraction recovery (>90%) and accuracy (>90%) with the intra-day and inter-day precision <15%. Frozen stability, freeze/thaw stability, extraction stability and solution stability at ambient temperature were examined, which indicated the tissue samples should be extracted within 5 days and avoid being frozen and thawed repeatedly over 5 times. Extracted samples after evaporation could be stored at ,20°C for 20 days without drug degradation and no degradation was also observed after solution samples were left to stand at ambient temperature for 24,h. This assay was used to support an in vivo biodistribution study of PTX-NLP in rats. Copyright © 2006 John Wiley & Sons, Ltd. [source] Temporal indication of cannabis use by means of THC glucuronide determinationDRUG TESTING AND ANALYSIS, Issue 11-12 2009Ute Mareck Abstract According to the regulations of the World Anti-Doping Agency (WADA), the use of cannabinoids is forbidden in competition. In doping controls, the detection of cannabinoid misuse is based on the analysis of the non-psychoactive metabolite 11-nor-9-carboxy-delta-9-tetrahydrocannabinol (carboxy-THC). The determination of values greater than 15 ng/mL in urine represents an adverse analytical finding; however, no accurate prediction of the time of application is possible as the half-life of carboxy-THC ranges between three and four days. Consequently the detection of carboxy-THC in doping control urine samples collected in competition might also result from cannabis use in out-of-competition periods. The analysis of the glucuronide of the pharmacologically active delta 9-tetrahydrocannabinol (THC-gluc) may represent a complementary indicator for the detection of cannabis misuse in competition. An assay for the determination of THC-gluc in human urine was established. The sample preparation consisted of liquid-liquid extraction of urine specimens, and extracts were analysed by liquid chromatography/tandem mass spectrometry (LC-MS/MS). Authentic doping-control urine samples as well as specimens obtained from a controlled smoking study were analysed and assay characteristics such as specificity, detection limit (0.1 ng/mL), precision (>90%), recovery (,80%), and extraction efficiency (90%) were determined. Copyright © 2010 John Wiley & Sons, Ltd. [source] Application of FAIMS to anabolic androgenic steroids in sport drug testingDRUG TESTING AND ANALYSIS, Issue 11-12 2009Sven Guddat Abstract Mass spectrometric identification of anabolic androgenic steroids challenges standard doping-control methods. To reveal a doping offence the presence of prohibited anabolic androgenic steroids at trace levels in the picogram-per-millilitre range must be confirmed as reliable. Human urine samples containing epitrenbolone, metandienone metabolite (17, -hydroxymethyl-17,-methyl-18-norandrost-1,4,13-trien-3-one), stanozolol, 16,-hydroxystanozolol and 4,-hydroxystanozolol were analysed using LC-FAIMS-MS/MS. These substances are prohibited in sport according to World Anti-Doping Agency (WADA) regulations. Glucuronides were hydrolysed and prepared by liquid-liquid extraction. Excellent recovery and precision were obtained for all compounds. Linear calibration results for epitrenbolone and metandienone metabolite were obtained and concentration information could be determined in the ranges of reliable response between 750,1200 and 100,600 pg/mL, respectively. Limits of detection were estimated at 25 pg/mL (stanozolol), 50 pg/mL (metandienone metabolite, 16,-hydroxystanozolol), 100 pg/mL (4,-hydroxystanozolol) and 500 pg/mL (epitrenbolone). The assay was applied to doping-control samples. For all analytes, LC-FAIMS-MS/MS resulted in excellent interference removal, which effectively extends the post-dose detection time. Copyright © 2009 John Wiley & Sons, Ltd. [source] Quantitation of talinolol and other ,-blockers by capillary electrophoresis for in vitro drug absorption studiesELECTROPHORESIS, Issue 15 2003Bilal Awadallah Abstract A capillary zone electrophoresis method is described for the enantioseparation of talinolol using heptakis(2,3-diacetyl-6-sulfo)-,-cyclodextrin (HDAS-,-CD) as a chiral selector. After liquid-liquid extraction of talinolol from physiological solution, electrokinetic injection was employed to improve the sensitivity. The use of a coated capillary was necessary to achieve stable and reproducible enantioseparations. A baseline separation of the talinolol enantiomers was achieved in less than 10 min using 100 mM phosphate solution as background electrolyte and pH 3.5, at the presence of 3.0 mM HDAS-,-CD and at 20°C. In addition, this analytical condition proved to be useful for the enantioseparation of a number of other ,-blocking agents such as alprenolol, atenolol, bisoprolol, celiprolol, metipranolol, oxprenolol, and sotalol. For determing talinolol, the method could be validated in terms of precision, accuracy and linearity, and was found to be suitable in determination of talinolol enantiomers in highly diluted samples obtained from in vitro experiments. [source] A TRLFS Study on the Complexation of CmIII and EuIII with 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine in Water/Methanol MixtureEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2010Sascha Trumm Abstract The complexation of CmIII and EuIII with 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPr-BTP) in water/methanol solution is studied. 1:3 complexes [M(nPr-BTP)3]3+ form from the solvated metal ions upon addition of ligand. The conditional stability constants are log,K = 14.4 and log,K = 11.9. For both metal ions the complexation reaction is both enthalpy and entropy driven. ,H is 10.1 kJ/mol more negative than ,H, whereas the entropy difference is small. The difference in ,G between the formation of the CmIII and EuIII complexes is in good agreement with nPr-BTP's selectivity in liquid-liquid extraction. [source] Resolution of Racemic N -Benzyl ,-Amino Acids by Liquid-Liquid Extraction: A Practical Method Using a Lipophilic Chiral Cobalt(III) Salen Complex and Mechanistic StudiesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 7 2008Pawel Dzygiel Abstract The efficient resolution of racemic N -benzyl ,-amino acids (N -Bn-AA) has been achieved by a liquid-liquid extraction process using the lipophilic chiral salen,cobalt(III) complex [CoIII(3)(OAc)]. As a result of the resolution by extraction, one enantiomer (S) of the N -benzyl ,-amino acid predominated in the aqueous phase, while the other enantiomer (R) was driven into the organic phase by complexation to cobalt. The complexed amino acid (R) was then quantitatively released by a reductive (CoIII,,,CoII) counter-extraction with aqueous sodium dithionite or L -ascorbic acid in methanol. Thereductive cleavage allowed to recover the [CoII(3)] complex in good yield, which could be easily re-oxidized to[CoIII(3)(OAc)] with air/AcOH and reused with essentially no loss of reactivity and selectivity. Investigation on the nitrogen substitution indicates that the presence of a single benzyl group on the amino acid nitrogen is important to obtain high enantioselectivity in the extraction process. The kinetic vs. thermodynamic nature of the resolution process was also investigated with an enantiomeric exchange experiment, which shows that the liquid-liquid extraction with [CoIII(3)(OAc)] is an equilibrium process operating under thermodynamic control. In the absence of a suitable crystal structure of the [CoIII(3)(N -Bn-AA)] complexes, computational and spectroscopic studies were used to investigate how the N -benzyl ,-amino acids are accommodated in the "binding pocket" of the chiral cobalt complex. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Representativeness of Apple Aroma Extract Obtained by Vacuum Hydrodistillation: Comparison of Two Concentration TechniquesJOURNAL OF FOOD SCIENCE, Issue 8 2003E. Mehinagic ABSTRACT: Vacuum hydrodistillation, which is a very gentle work-up procedure, has never been used for the extraction of apple aroma. During the concentration of aroma that follows vacuum hydrodistillation, some very volatile components can be lost. The aim of this study was to compare 2 different concentration techniques, liquid-liquid extraction and solid phase extraction, to obtain an apple aroma extract as close as possible to fresh apple. After the elimination of solvent from the extract by gas chromatography, the study of the odor characteristics of solvent-free extracts was made possible. Vacuum hydrodistillation was convenient for fresh apples. [source] Designer drug 2,4,5-trimethoxyamphetamine (TMA-2): Studies on its metabolism and toxicological detection in rat urine using gas chromatographic/mass spectrometric techniquesJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 9 2006Andreas H. Ewald Abstract Studies are described on the metabolism and the toxicological detection of the amphetamine-derived designer drug 2,4,5-trimethoxyamphetamine (TMA-2) in rat urine using gas chromatographic/mass spectrometric (GC/MS) techniques. The identified metabolites indicated that TMA-2 was metabolized by oxidative deamination to the corresponding ketone followed by reduction to the corresponding alcohol, O -demethylation followed by oxidative deamination, and finally O,O -bis-demethylation. All metabolites carrying hydroxy groups were found to be partly excreted in urine as glucuronides and/or sulfates. The authors' systematic toxicological analysis (STA) procedure using full-scan GC/MS after acid hydrolysis, liquid-liquid extraction, and microwave-assisted acetylation allowed the detection, in rat urine, of an intake of TMA-2 that corresponds to a common drug users' dose. Assuming similar metabolism, the described STA procedure in human urine should be suitable as proof of an intake of TMA-2. Copyright © 2006 John Wiley & Sons, Ltd. [source] Extractive bioconversion in a four-phase external-loop airlift bioreactorAICHE JOURNAL, Issue 7 2000Lidija Sajc The integration of biosynthesis and product separation can increase the productivity of immobilized plant cells in airlift bioreactors. Extractive bioconversion of anthraquinones was studied in an external-loop airlift bioreactor consisting of a riser, a downcomer, and two horizontal sections, while containing alginate-immobilized Frangula alnus cells, a continuous aqueous phase (nutrient solution), dispersed solvent phase (n-hexadecane or silicone oil), and gas bubbles. A simple mathematical model was developed to describe the cocurrent liquid-liquid extraction in the riser section of the bioreactor and to rationalize the measured product concentrations in the aqueous and solvent phase. The model equations were solved analytically in a dimensionless form and used to study the effects of flow conditions, solvent properties, product formation rate, droplet size, and contactor length on the extraction efficiency and product concentration profiles in the continuous and dispersed phase. [source] Instrumental planar chromatographic method for determination of carbamazepine in human serumJOURNAL OF SEPARATION SCIENCE, JSS, Issue 9 2009Sigrid Mennickent Abstract An instrumental planar chromatographic (HPTLC) method for quantification of carbamazepine in human serum was developed using liquid-liquid extraction with dichloromethane, fluorescence activation with perchloric acid 60%/ethanol/water (1:1:1, v/v) and fluorescence detection. Planar chromatographic separation was performed on precoated silica gel F254 HPTLC plates using a mixture of ethyl acetate/toluene/methanol/acetic acid glacial (5:4:0.5:0.5, v/v) as mobile phase. Densitometric detection was done at 366 nm. The method was validated for linearity, precision and accuracy. Linear calibration curves in the range of 3 and 20 ng/,L showed correlation coefficient of 0.998. The intra-assay and inter-assay precision, expressed as the RSD, were in the range of 0.41,1.24% (n = 3) and 2.17,3.17% (n = 9), respectively. The LOD was 0.19 ng, and the LOQ was 0.57 ng. Accuracy, calculated as percentage recovery, was between 98.98 and 101.96%, with a RSD not higher than 1.52%. The method was selective for the active principle tested. In conclusion, the method is useful for quantitative determination of carbamazepine in human serum. [source] Rapid simultaneous determination of codeine and morphine in plasma using LC-ESI-MS/MS: Application to a clinical pharmacokinetic studyJOURNAL OF SEPARATION SCIENCE, JSS, Issue 2 2009Qiongfeng Liao Abstract A rapid and sensitive high-performance LC-MS/MS method was developed and validated for the simultaneous quantification of codeine and its metabolite morphine in human plasma using donepezil as an internal standard (IS). Following a single liquid-liquid extraction with ethyl acetate, the analytes were separated using an isocratic mobile phase on a C18 column and analyzed by MS/MS in the selected reaction monitoring mode using the respective [M+H]+ ions, mass-to-charge ratio (m/z) 300/165 for codeine, m/z 286/165 for morphine and m/z 380/91 for IS. The method exhibited a linear dynamic range of 0.2,100/0.5,250 ng/mL for codeine/morphine in human plasma, respectively. The lower LOQs were 0.2 and 0.5 ng/mL for codeine and its metabolite morphine using 0.5 mL of human plasma. Acceptable precision and accuracy were obtained for concentrations over the standard curve range. A run time of 2.0 min for each sample made it possible to analyze more than 300 human plasma samples per day. The validated LC-MS/MS method was applied to a pharmacokinetic study in which healthy Chinese volunteers each received a single oral dose of 30 mg codeine phosphate. [source] Simultaneous determination of simvastatin and simvastatin acid in human plasma by LC-MS/MS without polarity switch: Application to a bioequivalence studyJOURNAL OF SEPARATION SCIENCE, JSS, Issue 2 2008Bhavin N. Patel Abstract A simple, specific and sensitive LC-MS/MS assay for simultaneous determination of simvastatin (SV) and its active ,-hydroxy acid metabolite, simvastatin acid (SVA) in human plasma was developed using a statin analog as internal standard (IS). The method was validated over a dynamic linear range of 0.20,100.00 ng/mL for SV and 0.10,50.00 ng/mL for SVA with correlation coefficient r , 0.9987 and 0.9989, respectively. The analytes and IS were extracted from 500 ,L aliquots of human plasma via liquid-liquid extraction using methyl tert -butyl ether and separated through an Aquasil C18 column (100 mm×2.1 mm, 5 ,m). Detection of analytes and IS was done by MS/MS with a turbo ion spray interface operating in positive ion and selective reaction monitoring acquisition mode. The total chromatographic run time was 3.0 min. Flash freezing of the aqueous phase was an added advantage during liquid-liquid extraction, which considerably reduced time and labour. The method was extensively validated for its accuracy, precision, recovery, stability studies and matrix effect. The method was successfully used for bioequivalence study of 40 mg SV tablet formulation in 12 human subjects under fasting condition. [source] Determination of tribromophenol and pentachlorophenol and its metabolite pentachloroanisole in Asparagus officinalis by gas chromatography/mass spectrometryJOURNAL OF SEPARATION SCIENCE, JSS, Issue 9-10 2003Claudia Mardones Abstract A GC-MS method was developed and optimized for simultaneous determination of pentachlorophenol (PCP), 2,4,6-tribromophenol (TBP), and pentachloroanisole (PCA) residues in the edible part of Asparagus officinalis. For this purpose, two procedures were evaluated: the direct separation of PCP, TBP, and PCA and the separation of acetyl-PCP, acetyl-TBP, and non-acetylated PCA. Better sensitivity and quantitative results, especially for PCP, were obtained after acetylation. The residues of PCP and TBP were extracted as phenolates and acetylated in a carbonate solution. Acetylated compounds were extracted by liquid-liquid extraction with hexane, while PCA was directly leached with this solvent. The proposed method allows the rapid quantification of traces of PCP, TBP, and PCA in a concentration ranging between 1.0 and 8.0 ng mL,1 in solution (corresponding to 0.3 and 8.0 ,g kg,1 in asparagus). In this concentration range, typical recoveries for PCA, TBP, and PCP from asparagus samples were 59%, 86%, and 97% respectively (RSDs 3,7%). [source] Cover Picture: QSAR Comb.MOLECULAR INFORMATICS, Issue 8-9 2006Fluorous molecules are lipophobic and hydrophobic, they can be selectively separated by liquid-liquid extraction with fluorous solvents, solid-phase extraction and HPLC with fluorous silica gel. The cover picture highlights some representative structures of fluorous catalysts, reagents, scavengers, and protecting groups which have been developed for fluorous synthesis and reported in this special issue. [source] Quantification of alkylresorcinols in human plasma by liquid chromatography/tandem mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 5 2010Alastair B. Ross Alkylresorcinols (AR) are of interest as biomarkers of wholegrain wheat and rye intake in epidemiological studies and are currently mainly measured by gas chromatography/mass spectrometry (GC/MS) after labour-intensive sample preparation including liquid-liquid extraction, solid-phase extraction (SPE) and chemical derivatization. This manuscript describes and validates an alternative approach based on normal-phase liquid chromatography/tandem mass spectrometry for the quantification of alkylresorcinols in human plasma. The method requires neither SPE nor chemical derivatization and has a shortened run time compared to GC/MS. Normal- and reversed-phase columns and various mobile phases were evaluated with and without previous SPE of the samples. Normal-phase chromatography allowed separation of AR from the interfering triacylglycerols, diacylglycerols and sterols and enabled detection of AR even without SPE of the samples. The described method has instrumental lower limits of detection in the 25,75 pg range, and lower limits of quantification in the 75,250 pg range. Pooled human plasma and 2H4 -nonadecylresorcinol (internal standard) was applied to calibrate the method in the 20,12,000,nM range. The overall method showed intra-batch precision of 8.6% and an averaged accuracy of 100.2%. Applications for diverse human plasma samples are presented and are compared with the results determined by GC/MS. Based on the presented data; this method requiring less sample preparation is suggested for further evaluation as an alternative to GC/MS for analysis of biomarkers of wholegrain wheat and rye intake in epidemiological studies. Copyright © 2010 John Wiley & Sons, Ltd. [source] Determination of nitrogen-15 isotope fractionation in tropine: evaluation of extraction protocols for isotope ratio measurement by isotope ratio mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 24 2009Roland Molinié N -Demethylation of tropine is an important step in the degradation of this compound and related metabolites. With the purpose of understanding the reaction mechanism(s) involved, it is desirable to measure the 15N kinetic isotope effects (KIEs), which can be accessed through the 15N isotope shift (,,15N) during the reaction. To measure the isotope fractionation in 15N during tropine degradation necessitates the extraction of the residual substrate from dilute aqueous solution without introducing artefactual isotope fractionation. Three protocols have been compared for the extraction and measurement of the 15N/14N ratio of tropine from aqueous medium, involving liquid-liquid phase partitioning or silica-C18 solid-phase extraction. Quantification was by gas chromatography (GC) on the recovered organic phase and ,15N values were obtained by isotope ratio measurement mass spectrometry (irm-MS). Although all the protocols used can provide satisfactory data and both irm-EA-MS and irm-GC-MS can be used to obtain the ,15N values, the most convenient method is liquid-liquid extraction from a reduced aqueous volume combined with irm-GC-MS. The protocols are applied to the measurement of 15N isotope shifts during growth of a Pseudomonas strain that uses tropane alkaloids as sole source of carbon and nitrogen. The accuracy of the determination of the 15N/14N ratio is sufficient to be used for the determination of 15N-KIEs. Copyright © 2009 John Wiley & Sons, Ltd. [source] Metabolite identification of small interfering RNA duplex by high-resolution accurate mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2008Yan Zou On-line liquid chromatography/electrospray ionization high-resolution mass spectrometry (LC/ESI-HRMS) using an LTQ-Orbitrap mass spectrometer was employed to investigate the metabolite profiles of a model siRNA duplex designated HBV263. The HBV263 duplex was incubated in rat and human serum and liver microsomes in vitro. The siRNA drug and its metabolites were then extracted using a liquid-liquid extraction followed by solid-phase extraction (LLE-SPE), and analyzed by LC/ESI-MS. High-resolution accurate mass data enabled differentiation between two possible metabolite sequences with a monoisotopic molecular mass difference of less than 1,Da. ProMass deconvolution software was used to provide semi-automated data processing. In vitro serum and liver microsome incubation samples afforded different metabolite patterns: the antisense strand of the duplex was degraded preferentially in rat and human serum, while the sense strand of the duplex was less stable in rat and human liver microsomes. Copyright © 2008 John Wiley & Sons, Ltd. [source] Liquid chromatography/triple quadrupole tandem mass spectrometry with multiple reaction monitoring for optimal selection of transitions to evaluate nutraceuticals from olive-tree materialsRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 6 2008Rafael Japón Luján Optimal transitions have been selected for the identification and quantitation of the most interesting hydrophilic biophenols in extracts from olive-tree materials, which are of interest because of their nutraceutical properties. The tested materials were extra virgin olive oil, waste from oil production (known as alperujo), and olive-tree materials such as leaves, small branches and fruit stones. The identification and determination steps of the target biophenols are based on liquid chromatography/tandem mass spectrometry (LC/MS/MS) with a triple quadrupole (QQQ) mass detector. The interface between the chromatograph and the QQQ was an electrospray ionization source operated in the negative ion mode. Highly selective identification of the biophenols was confirmed by multiple reaction monitoring (MRM) using the most representative transitions from the precursor ion to the different product ions. Quantitative MS/MS analysis was carried out by optimization and selection of the most sensitive transition for each analyte, which resulted in estimated detection limits of 5.10 to 11.65,ng/mL for the extracts. The biophenols were extracted from the tested samples by different methods: liquid-liquid extraction for virgin olive oil, microwave-assisted leaching for olive leaves, branches and stones, and pressurized liquid leaching for alperujo. This study provides valuable information about the most suitable source for the isolation of each nutraceutical biophenol and enables us to obtain a complete profile of them in Olea Europaea. Copyright © 2008 John Wiley & Sons, Ltd. [source] Determination of paclitaxel in human plasma following the administration of Genaxol or Genetaxyl by liquid chromatography/tandem mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 14 2006Erin R. Gardner A sensitive and specific assay for paclitaxel in plasma has been developed to overcome limitations in previously published assays, using liquid chromatography with tandem mass spectrometric detection. Plasma samples (100,µL) were subjected to liquid-liquid extraction with 1-chlorobutane/acetonitrile (4:1, v/v), with [2H5]paclitaxel employed as the internal standard. Chromatography was carried out with a Waters SymmetryShield C8 column (50,×,2.1 mm, 3.5,µm). The total run time, including equilibration, was 8 min, using a gradient of acetonitrile and 10,mM ammonium formate, pH 4.0. The assay is accurate and precise over the range of 2,2500,ng/mL and has been successfully applied to study the clinical pharmacokinetics of two formulations of paclitaxel, Genaxol and Genetaxyl, given orally and intravenously. Copyright © 2006 John Wiley & Sons, Ltd. [source] Analysis of isotope ratios in vitamin K1 (phylloquinone) from human plasma by gas chromatography/mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2006Kerry S. Jones Vitamin K1 is a fat-soluble vitamin required for the , -carboxylation of vitamin K-dependent proteins. Recent work has suggested an important role for vitamin K1 in bone health beyond its more established function in the control and regulation of blood coagulation. However, current UK recommended intakes do not reflect this recent evidence. The use of stable isotopes provides a powerful tool to investigate vitamin K kinetics, turnover and absorption in man, although published methods have reported difficulties in the extraction and analysis of isotope ratios of vitamin K in human plasma. In this paper, we report a new methodology for the extraction and measurement of isotope ratios in vitamin K1. Sample clean-up is achieved with liquid-liquid extraction, enzyme hydrolysis with lipase and cholesterol esterase, and solid-phase extraction. Isotopic analysis of the pentafluoropropionyl derivative of vitamin K1 is performed by gas chromatography/mass spectrometry (GC/MS). The limit of quantitation is equivalent to at least 0.3,nmol/L and the method is demonstrated to be linear over a range of enrichments. This method provides a robust alternative to previous work requiring the use of semi-preparative high-performance liquid chromatography (HPLC). Copyright © 2006 John Wiley & Sons, Ltd. [source] Automated method for measuring globin adducts of acrylamide and glycidamide at optimized Edman reaction conditions,RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 6 2006Hubert W. Vesper The general population is exposed to acrylamide, a potential human carcinogen, through food and cigarette smoke. The assessment of human exposure to acrylamide is important in the evaluation of health risks associated with this chemical. Hemoglobin adducts of acrylamide (AA-Hb) and its primary metabolite glycidamide (GA-Hb) are established biomarkers of acrylamide exposure and methods to measure these biomarkers using modified Edman reaction are described. Only limited information about the optimal Edman reaction conditions such as pH or temperature is available for these adducts and the existing methods do not allow automation needed in biomonitoring studies. In this study, the yield of Edman products of AA-Hb and GA-Hb between pH 3,10 and at 35,55°C at different time intervals, and the applicability of liquid-liquid extraction on diatomaceous earth for analyte extraction, were assessed and results were used in a new optimized method. The applicability of our optimized method was assessed by comparing results obtained with a convenience sample from 96 individuals with a conventional method. Maximum yield of Edman products was obtained between pH 6,7, heating the reaction solution at 55°C for 2,h resulted in the same yields as with conventional conditions, and use of diatomaceous earth was found suitable for automated analyte extraction. Using these conditions, no difference was observed between our optimized and a conventional method. The median globin adduct values in the convenience sample are 129,pmol/g globin (range: 27,453,pmol/g globin) and 97,pmol/g globin (range: 27,240,pmol/g globin) for AA-Hb and GA-Hb, respectively. The GA-Hb/AA-Hb ratio decreases significantly with increasing AA-Hb values indicating that measurement of AA-Hb as well as GA-Hb are needed to appropriately assess human exposure to acrylamide. Published in 2006 by John Wiley & Sons, Ltd. [source] Simultaneous determination of magnesium lithospermate B, rosmarinic acid, and lithospermic acid in beagle dog serum by liquid chromatography/tandem mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 23 2004Xiaochuan Li A rapid, sensitive and specific isocratic liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed for the simultaneous quantitative determination of magnesium lithospermate B (MLB), rosmarinic acid (RA), and lithospermic acid (LA) in beagle dog serum, with silibinin as internal standard. The serum samples were treated by liquid-liquid extraction and analyzed using LC/MS/MS with a TurboIonSpray source. A short run-time (3,min) fulfilled the need for monitoring serum levels of MLB, RA, and LA in large-scale studies. The calibration curves for MLB, RA, and LA were linear over the ranges 8,2048, 4,1024, and 4,1024,ng/mL, respectively, with coefficients of correlation >0.999. The intra- and inter-day precision (CV) of analysis was <10%, and accuracy ranged from 90,104%. This quantitation method was successfully applied to a pharmacokinetic study of salvianolate administrated by intravenous infusion with dosage of 6,mg/kg in beagle dogs. Copyright © 2004 John Wiley & Sons, Ltd. [source] Analysis of silymarin extracted from a commercial dosage by combining liquid-liquid extraction with negative electrospray tandem mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 23 2004Nadeem Ahmad Khan No abstract is available for this article. [source] Sensitive high-performance liquid chromatography/mass spectrometry method for determination of steviol in rat plasmaRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 1 2004L. Z. Wang The main toxicological concern of stevioside, a highly potent sweetener from S. rebaudiana, is its main metabolite, steviol. To determine very low levels of steviol in in vivo experiments, a sensitive liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (LC/APCI-MS) method was developed for quantifying steviol in rat plasma after oral administration of a single dose of stevioside (0.5,g/kg). The sample preparation uses liquid-liquid extraction with tert -butyl methyl ether in an acidic environment. The retention time of steviol was 10.5 min. The assay was linear over the range 2,1000,ng/mL with a lower limit of detection of 1,ng/mL. The intra- and inter-day precision were <5 and <7%, respectively, and the accuracy was in the range 95,108%. The steviol concentration profile in rat plasma was determined. Copyright © 2003 John Wiley & Sons, Ltd. [source] Quantification of clenbuterol in equine plasma, urine and tissue by liquid chromatography coupled on-line with quadrupole time-of-flight mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 17 2002Fuyu Guan Clenbuterol (CBL) is a potent ,2 -adrenoceptor agonist used for the management of respiratory disorders in the horse. The detection and quantification of CBL can pose a problem due to its potency, the relatively low dose administered to the horse, its slow clearance and low plasma concentrations. Thus, a sensitive method for the quantification and confirmation of CBL in racehorses is required to study its distribution and elimination. A sensitive and fast method was developed for quantification and confirmation of the presence of CBL in equine plasma, urine and tissue samples. The method involved liquid-liquid extraction (LLE), separation by liquid chromatography (LC) on a short cyano column, and pseudo multiple reaction monitoring (pseudo-MRM) by electrospray ionization quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS). At very low concentrations (picograms of CBL/mL), LLE produced better extraction efficiency and calibration curves than solid-phase extraction (SPE). The operating parameters for electrospray QTOF and yield of the product ion in MRM were optimized to enhance sensitivity for the detection and quantification of CBL. The quantification range of the method was 0.013,10,ng of CBL/mL plasma, 0.05,20,ng/0.1,mL of urine, and 0.025,10,ng/g tissue. The detection limit of the method was 13,pg/mL of plasma, 50,pg/0.1,mL of urine, and 25,pg/g of tissue. The method was successfully applied to the analysis of CBL in plasma, urine and various tissue samples, and in pharmacokinetic (PK) studies of CBL in the horse. CBL was quantified for 96,h in plasma and 288,h in urine post-administration of CLB (1.6,µg/kg, 2,×,daily,×,7 days). This method is useful for the detection and quantification of very low concentrations of CBL in urine, plasma and tissue samples. Copyright © 2002 John Wiley & Sons, Ltd. [source] Analysis of pyridoquinoline derivatives by liquid chromatography/atmospheric pressure chemical ionization mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 11 2001Y. Picó A method using liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (LC/APCI-MS) has been developed for the characterization and determination of pyridoquinoline derivatives 4,6-bis(dimethylaminoethylamino)-2,8,10-trimethylpyrido[3,2-g]quinoline, 4,6-bis(dimethylaminoethoxy)-2,8,10-trimethylpyrido[3,2-g]quinoline and 4,6-bis[(dimethylaminoethyl)thio]-2,8,10-trimethylpyrido[3,2-g] quinoline, all with potential antitumor properties. LC separation was performed on a conventional C18 column using a binary mobile phase composed of acetonitrile and 50,mM aqueous ammonium formate at pH 3. The APCI mass spectra obtained showed that proton addition giving [M,+,H]+ was the common mode of ionization to the amino- and thiopyridoquinolines, whereas the alkoxypyridoquinoline was identified by the main formation of the [M,,,(C2H3)N(CH3)2,+,H]+, followed by the [M,+,H]+ ion. The LC separation conditions and MS detection parameters were optimized for the determination. The analytical method was also applied to the determination of these pyridoquinoline derivatives in fetal calf serum using liquid-liquid extraction with dichloromethane. Acceptable recovery values were obtained, ranging between 45 and 98%. Copyright © 2001 John Wiley & Sons, Ltd. [source] Simultaneous RP-HPLC-DAD quantification of bromocriptine, haloperidol and its diazepane structural analog in rat plasma with droperidol as internal standard for application to drug-interaction pharmacokineticsBIOMEDICAL CHROMATOGRAPHY, Issue 7 2010Johnique Billups Abstract A simple and rapid RP-HPLC-DAD method was developed and validated for simultaneous determination of the dopamine antagonists haloperidol, its diazepane analog, and the dopamine agonist bromocriptine in rat plasma, to perform pharmacokinetic drug-interaction studies. Samples were prepared for analysis by acetonitrile (22.0,,g/mL) plasma protein precipitation with droperidol as an internal standard, followed by a double-step liquid-liquid extraction with hexane,:,chloroform (70:30) prior to C-18 separation. Isocratic elution was achieved using a 0.1% (v/v) trifluoroacetic acid in deionized water, methanol and acetonitrile (45/27.5/27.5, v/v/v). Triple-wavelength diode-array detection at the ,max of 245,nm for haloperidol, 254,nm for the diazepane analog and droperidol, and 240,nm for bromocriptine was carried out. The LLOQ of DAL, HAL, and BCT were 45.0, 56.1, and 150,ng/mL, respectively. In rats, the estimated pharmacokinetic parameters (i.e., t1/2, CL, and Vss) of HAL when administered with DAL and BCT were t1/2 = 16.4,min, Vss = 0.541,L/kg for HAL, t1/2 = 28.0,min, Vss = 2.00,L/kg for DAL, and t1/2 = 24.0,min, Vss = 0.106,L/kg for BCT. The PK parameters for HAL differed significantly from those previously reported, which may be an indication of a drug-drug interaction. Copyright © 2009 John Wiley & Sons, Ltd. [source] Lornoxicam pharmacokinetics in the vitreous humor of albino rabbitsACTA OPHTHALMOLOGICA, Issue 2009C TSIKA Purpose To assess the elimination half-life of intravitreal lornoxicam, a non-steroidal anti-inflammatory drug (NSAID). Methods Both eyes of 15 rabbits were intravitreally injected with 250 ,g of commercially available lornoxicam (for intravenous/intramuscular use, Xefo® 8 IV/IM Injection, Nycomed Hellas S.A.). Six eyes were enucleated at time points 0, 1, 2, 6 and 24 hours after the injection was performed. The eyes were immediately frozen at -80°C. The vitreous was eviscerated from the eye and the drug was liquid-liquid extracted from a 0.4 ml sample. Lornoxicam was isolated by a reversed-phase High Performance Liquid Chromatography (HPLC) method at retention time 10.7 min and detected at 372 nm. The data were statistically analyzed in order to evaluate the pharmacokinetic parameters of the drug. Results The recovery of lornoxicam after liquid-liquid extraction was calculated at 69.6% and the limit of determination was 0.1 ,g/ml. Statistical analysis revealed that lornoxicam concentrations followed first-order kinetics with an elimination rate constant of 0.235h-1 and a half-life of 3.0 h. Conclusion The determination of the pharmacokinetic characteristics of intravitreal lornoxicam allows the possibility for further investigation of the drug's intraocular behaviour and therapeutic potential. [source] | ||||||||||||||||||||||||||||