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1.
Pharm Biol ; 60(1): 621-626, 2022 Dec.
Article in English | MEDLINE | ID: mdl-35289238

ABSTRACT

CONTEXT: Tucatinib (CYP2C8 substrate) and quercetin (CYP2C8 inhibitor) are two common drugs for the treatment of cancer. However, the effect of quercetin on the metabolism of tucatinib remains unknown. OBJECTIVE: We validated a sensitive method to quantify tucatinib levels in rat plasma based on ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), which was successfully employed to explore the effect of quercetin on tucatinib pharmacokinetics in rats. MATERIALS AND METHODS: An Acquity UPLC BEH C18 column was applied to achieve the separation of tucatinib and internal standard (IS) talazoparib after protein precipitation with acetonitrile. Then, we used this assay to investigate the effect of different doses of quercetin (25, 50 and 100 mg/kg) on the exposure of orally administered tucatinib (30 mg/kg) in 24 Sprague-Dawley (SD) rats, which were randomly divided into three quercetin pre-treated groups and one control group (n = 6). RESULTS: Our developed assay was verified in all aspects of bioanalytical method validation, involving lower limit of quantification (LLOQ), selectivity, accuracy and precision, calibration curve, extraction recovery, matrix effect and stability. After pre-treatment with 100 mg/kg quercetin, AUC0→t, AUC0→∞ and Cmax of tucatinib were remarkably increased by 75.4%, 75.8% and 59.1% (p < 0.05), respectively, while CLz/F was decreased significantly by 47.3% (p < 0.05) when compared with oral administration of 30 mg/kg tucatinib alone. This change is dose-dependent. CONCLUSIONS: This study will help better understand the pharmacokinetic properties of tucatinib with concurrent use with quercetin, and more clinical verifications were inspired to confirm whether this interaction has clinical significance in humans.


Subject(s)
Chromatography, High Pressure Liquid/methods , Oxazoles/pharmacokinetics , Pyridines/pharmacokinetics , Quercetin/pharmacology , Quinazolines/pharmacokinetics , Tandem Mass Spectrometry/methods , Animals , Antineoplastic Agents/administration & dosage , Antineoplastic Agents/analysis , Antineoplastic Agents/pharmacokinetics , Area Under Curve , Dose-Response Relationship, Drug , Drug Interactions , Limit of Detection , Male , Oxazoles/administration & dosage , Oxazoles/analysis , Pyridines/administration & dosage , Pyridines/analysis , Quercetin/administration & dosage , Quinazolines/administration & dosage , Quinazolines/analysis , Rats , Rats, Sprague-Dawley
2.
Inhal Toxicol ; 32(4): 177-187, 2020 03.
Article in English | MEDLINE | ID: mdl-32408835

ABSTRACT

Background: Marijuana blunts, which are tobacco cigar wrappers filled with marijuana, are commonly smoked in the US as a means of cannabis use. The use of marijuana blunts presents toxicity concerns because the smoke contains both marijuana-related and tobacco-related chemicals. Thus, it is important to understand the chemical composition of mainstream smoke (MSS) from marijuana blunts. This study demonstrates the ability to detect and identify chemical constituents exclusively associated with blunt MSS in contrast to tobacco cigar MSS (designated as 'new exposures') through non-targeted chemical analysis.Methods: Samples collected separately from blunt MSS and tobacco cigar MSS were analyzed using two-dimensional gas chromatography-time-of-flight mass spectrometry (GC × GC-TOFMS).Results and Discussion: Two new exposures, which likely represent only a subset of all new exposures, were identified by evaluating the data from thousands of detected signals and then confirming selected compound identities in analyses using authentic chemical standards. The two confirmed new exposures, mellein and 2-phenyl-2-oxazoline, are not cannabinoids and, to the best of our knowledge, have not been previously reported in association with cannabis, tobacco, or smoke of any kind. In addition, we detected and quantified three phenols (2-, 3-, and 4-ethylphenol) in blunt MSS. Given the toxicity of phenols, quantifying the levels of other phenols could be pursued in future research on blunt MSS.Conclusion: This study shows the power and utility of GC × GC-TOFMS as a methodology for non-targeted chemical analysis to identify new chemical exposures in blunt MSS and to provide data to guide further investigations of blunt MSS.


Subject(s)
Cannabis , Nicotiana , Smoke/analysis , Gas Chromatography-Mass Spectrometry , Marijuana Smoking , Ochratoxins/analysis , Oxazoles/analysis , Phenols/analysis , Tobacco Products
3.
Ecotoxicol Environ Saf ; 192: 110287, 2020 Apr 01.
Article in English | MEDLINE | ID: mdl-32036102

ABSTRACT

An environmentally-friendly and fast analytical method for the stereoselective determination of etoxazole was developed and then applied to estimate stereoselective bioaccumulation and elimination in zebrafish using SFC-MS/MS. Optimal enantioseparation conditions were determined using a Chiralpak IG-3 column and CO2/MeOH mobile phase (80/20, v/v), at 3.0 mL/min within 1 min, 30°Me and 18 MPa. A modified QuEChERS method was developed for zebrafish sample pretreatment, and mean recoveries were 88.43-110.12% with relative standard deviations ranging from 0.32 to 5.34%. The enantioselectives of etoxazole enantiomers in zebrafish during uptake and depuration phases were evaluated. Significant enantioselective bioaccumulation was observed, with preferential accumulation of (-)-R-etoxazole compared to its antipode, during uptake at both low and high exposure concentrations. The toxic effects of etoxazole on zebrafish were further explored, and activities of antioxidant enzymes were determined in liver of zebrafish. Significant changes were observed in the SOD and GST activities and in the MDA levels, which indicated the occurrence of oxidative stress in liver of zebrafish. The toxic effects exhibited time- and dose-dependent properties. These results can facilitate the accurate risk evaluation of etoxazole and provide basic knowledge for further study of biotoxicity mechanisms.


Subject(s)
Chromatography, Supercritical Fluid/methods , Oxazoles/chemistry , Oxazoles/toxicity , Oxidative Stress , Tandem Mass Spectrometry/methods , Water Pollutants, Chemical/chemistry , Animals , Antioxidants/metabolism , Bioaccumulation , Liver/drug effects , Liver/enzymology , Oxazoles/analysis , Oxazoles/pharmacokinetics , Stereoisomerism , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/toxicity , Zebrafish/metabolism
4.
J Environ Sci Health B ; 55(8): 712-718, 2020.
Article in English | MEDLINE | ID: mdl-32515641

ABSTRACT

The degradation under field conditions and the residue behavior of etoxazole during juicing and purée making was evaluated. Etoxazole residues were determined by HPLC-UV at six different Pre Harvest Intervals (PHIs) as to estimate the degradation of residue in fruits. Samples with significant residues were processed and residue were determined after juicing and purée making. The effect of washing was also estimated. Processing Factors (PFs) for etoxazole after each step were less than 1 and the PFs of the overall processes were lower than 0.85 for washing fruits, 0.13 for juice and 0.04 for purée. The studied processes could obviously reduce the pesticide residues that are present in the raw strawberries. Uncertainties in the use of the PFs were identified due to the potential formation of metabolites during the processes.


Subject(s)
Food Contamination/analysis , Food-Processing Industry/methods , Fragaria/chemistry , Oxazoles/analysis , Chromatography, High Pressure Liquid , Egypt , Fruit/chemistry , Pesticide Residues/analysis
5.
Environ Monit Assess ; 191(8): 517, 2019 Jul 27.
Article in English | MEDLINE | ID: mdl-31352622

ABSTRACT

The dissipation and residual levels of etoxazole and pyridaben in Goji berry under open field conditions were determined by using GC-NPD (gas chromatography with nitrogen and phosphorus detector) with modified QuEChERS method. At fortification levels of 0.01, 1, and 5 mg/kg in Goji berry, it was shown that recoveries were ranged from 80.40 to 100.9% with relative standard deviation of the method (RSD) for repeatability ranged from 2.20 to 4.25%. The limit of quantification (LOQ) of the method was 0.01 mg/kg. The dissipation rates of etoxazole and pyridaben were described by using first-order kinetics and its half-life, as they are 7.13 days, 5.77 days, and 5.99 days (etoxazole) and 1.02 day, 0.67 day, 1.02 day (pyridaben). The terminal residues of etoxazole and pyridaben were below the European maximum residue limit (MRL, 0.1 mg/kg) in Goji berry when measured 7 days after the final application, which suggested that the use of these insecticides was safe for humans. This study would help in providing the basic information for developing regulation to guard a safe use of etoxazole and pyridaben in Goji berry and prevent health problem from consumers.


Subject(s)
Environmental Monitoring/methods , Lycium/metabolism , Oxazoles/analysis , Pesticide Residues/analysis , Pyridazines/analysis , China , Half-Life , Humans , Kinetics , Lycium/growth & development , Oxazoles/metabolism , Pesticide Residues/metabolism , Pyridazines/metabolism , Tibet
6.
Nutr Neurosci ; 20(1): 40-48, 2017 Jan.
Article in English | MEDLINE | ID: mdl-25238165

ABSTRACT

BACKGROUND: Seed oils are used as cosmetics or topical treatment for wounds, allergy, dandruff, and other purposes. Natural antioxidants from plants were recently reported to delay the onset or progress of various neurodegenerative conditions. Over one thousand cultivars of Punica granatum (Punicaceae) are known and some are traditionally used to treat various ailments. AIM: The effect of pomegranate oil on 3-nitropropionic acid- (3-NP) induced cytotoxicity in rat pheochromocytoma (PC12) neuronal cells was analyzed in this study. Furthermore, the analysis of unsaturated fatty acid composition of the seed oil of pomegranate by gas chromatography-electron impact mass spectrometry (GC-MS) was done. RESULTS: GC-MS study showed the presence of 6,9-octadecadiynoic acid (C18:2(6,9)) as a major component (60%) as 4,4-dimethyloxazoline derivative. The total extractable oil with light petroleum ether by Soxhlet from the dry seed of P. granatum was 4-6%. The oil analyzed for 48.90 ±â€Š1.50 mg gallic acid equivalents/g of oil, and demonstrated radical-scavenging-linked antioxidant activities in various in vitro assays like the DPPH (2,2-diphenyl-l-picrylhydrazyl, % IP = 35.2 ± 0.9%), ABTS (2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid), % IP 2.2 ± 0.1%), and ß-carotene bleaching assay (% IP = 26 ± 3%), respectively, which could be due the possible role of one methylene interrupted diynoic acid system for its radical-scavenging/antioxidant properties of oil. The oil also reduced lipid peroxidation, suppressed reactive oxygen species, extracellular nitric oxide, lactate/pyruvate ratio, and lactase dehydrogenase generated by 3-NP- (100 mM) induced neurotoxicity in PC12 cells, and enhanced the levels of enzymatic and non-enzymatic antioxidants at 40 µg of gallic acid equivalents. CONCLUSION: The protective effect of pomegranate seed oil might be due to the ability of an oil to neutralize ROS or enhance the expression of antioxidant gene and the exact mechanism of action yet to be elucidated.


Subject(s)
Lythraceae/chemistry , Neurons/drug effects , Neuroprotective Agents/metabolism , Oxidative Stress , Plant Oils/metabolism , Seeds/chemistry , Animals , Antioxidants/chemistry , Antioxidants/metabolism , Antioxidants/therapeutic use , Cell Line, Tumor , Cell Survival/drug effects , Dietary Supplements/analysis , Ethnopharmacology , Linoleic Acids/analysis , Lipid Peroxidation/drug effects , Lythraceae/growth & development , Medicine, Traditional , Neurons/metabolism , Neuroprotective Agents/chemistry , Neuroprotective Agents/therapeutic use , Neurotoxicity Syndromes/prevention & control , Nitro Compounds/antagonists & inhibitors , Nitro Compounds/toxicity , Oman , Oxazoles/analysis , Oxidants/antagonists & inhibitors , Oxidants/toxicity , Oxidative Stress/drug effects , Plant Oils/chemistry , Plant Oils/therapeutic use , Propionates/antagonists & inhibitors , Propionates/toxicity , Rats , Reactive Oxygen Species/antagonists & inhibitors , Reactive Oxygen Species/metabolism , Seeds/growth & development
7.
Biosci Biotechnol Biochem ; 81(2): 343-349, 2017 Feb.
Article in English | MEDLINE | ID: mdl-27710213

ABSTRACT

Pyrrolothiazolate formed by the Maillard reaction between l-cysteine and d-glucose has a pyrrolothiazole skeleton as a chromophore. We searched for a Maillard pigment having a pyrrolooxazole skeleton formed from l-threonine or l-serine instead of l-cysteine in the presence of d-glucose. As a result, two novel yellow pigments, named pyrrolooxazolates A and B, were isolated from model solutions of the Maillard reaction containing l-threonine and d-glucose, and l-serine and d-glucose, respectively, and identified as (2R,3S,7aS)-2,3,7,7a-tetrahydro-6-hydroxy-2,5,7a-trimethyl-7-oxo-pyrrolo[2,1-b]oxazole-3-calboxylic acid and (3S,7aS)-2,3,7,7a-tetrahydro-6-hydroxy-5,7a-dimethyl-7-oxo-pyrrolo[2,1-b]oxazole-3-calboxylic acid by instrumental analyses. These compounds were pyrrolooxazole derivatives carrying a carboxy group, and showed the absorption maxima at 300-360 nm under acidic and neutral conditions and at 320-390 nm under alkaline conditions.


Subject(s)
Glucose/chemistry , Maillard Reaction , Oxazoles/chemistry , Pigments, Biological/chemistry , Serine/chemistry , Threonine/chemistry , Oxazoles/analysis , Oxazoles/isolation & purification , Pigments, Biological/analysis , Pigments, Biological/isolation & purification
8.
J Infect Dis ; 212(11): 1827-34, 2015 Dec 01.
Article in English | MEDLINE | ID: mdl-26014799

ABSTRACT

Improved biomarkers are needed for tuberculosis. To develop tests based on products secreted by tubercle bacilli that are strictly associated with viability, we evaluated 3 bacterial-derived, species-specific, small molecules as biomarkers: 2 mycobactin siderophores and tuberculosinyladenosine. Using liquid chromatography-tandem mass spectrometry, we demonstrated the presence of 1 or both mycobactins and/or tuberculosinyladenosine in serum and whole lung tissues from infected mice and sputum, cerebrospinal fluid (CSF), or lymph nodes from infected patients but not uninfected controls. Detection of the target molecules distinguished host infection status in 100% of mice with both serum and lung as the target sample. In human subjects, we evaluated detection of the bacterial small molecules (BSMs) in multiple body compartments in 3 patient cohorts corresponding to different forms of tuberculosis. We detected at least 1 of the 3 molecules in 90%, 71%, and 40% of tuberculosis patients' sputum, CSF, and lymph node samples, respectively. In paucibacillary forms of human tuberculosis, which are difficult to diagnose even with culture, detection of 1 or more BSM was rapid and compared favorably to polymerase chain reaction-based detection. Secreted BSMs, detectable in serum, warrant further investigation as a means for diagnosis and therapeutic monitoring in patients with tuberculosis.


Subject(s)
Biomarkers/analysis , Mycobacterium tuberculosis/chemistry , Oxazoles/analysis , Tuberculosis/diagnosis , Adenosine/analogs & derivatives , Adenosine/analysis , Animals , Bacterial Typing Techniques , Chromatography, Liquid , Humans , Lung/microbiology , Mice , Mycobacterium tuberculosis/isolation & purification , Sputum/microbiology , Tandem Mass Spectrometry
9.
Anal Bioanal Chem ; 407(24): 7511-6, 2015 Sep.
Article in English | MEDLINE | ID: mdl-26297455

ABSTRACT

A sensitive and specific LC-MS/MS method was developed and validated for simultaneous determination of 2-amino-2-(2-(4'-(2-propyloxazol-4-yl)-[1,1'-biphenyl]-4-yl)ethyl)propane-1,3-diol (SYL930) and its active phosphate metabolite (SYL930-P) in rat blood using SYL927, an analogue of SYL930 as the internal standard. Blood samples were prepared by a simple protein precipitation with acetonitrile. The chromatographic separation was performed on a ZorbaxSB-C18 column (3.5 µm, 2.1 × 100 mm) with a gradient mobile phase of methanol/water containing 0.1 % formic acid (v/v) at a flow rate of 0.2 mL/min. The detection was carried out on a triple quadrupole tandem mass spectrometer equipped with electrospray ionization (ESI) in multiple reactions monitoring mode (MRM). The monitored transitions were 381.2 → 364.2 for SYL930, 461.2 → 334.2 for SYL930-P, and 367.1 → 350.4 for the internal standard, respectively. Good linearity was obtained for the analytes over the range of 0.2-100 ng/mL for SYL930 and 0.5-100 ng/mL for SYL930-P. The lower limits of quantitation (LLOQs) for SYL930 and SYL930-P were 0.2 and 0.5 ng/mL, respectively. The intra-day and inter-day precisions (RSD, %) of analytes were within 9.87 %, and the accuracy (RE, %) ranged from -7.04 to 13.15 %. The mean recoveries for two compounds in rat blood were 87.9-109 %. The analytes were proved to be stable during all sample storage, preparation, and analytic procedures. The validated method was successfully applied to pharmacokinetic and PK/PD studies of SYL930 and SYL930-P in rats after oral administration of SYL930. Graphical Abstract Quantitative determination of SYL930 and its active phosphorylated metabolite in rat blood by LCMS/MS and application to PK/PD analysis.


Subject(s)
Chromatography, Liquid/methods , Oxazoles/analysis , Propane/analogs & derivatives , Tandem Mass Spectrometry/methods , Animals , Oxazoles/metabolism , Oxazoles/pharmacokinetics , Phosphorylation , Propane/analysis , Propane/metabolism , Propane/pharmacokinetics , Rats
10.
Analyst ; 139(9): 2137-43, 2014 May 07.
Article in English | MEDLINE | ID: mdl-24618890

ABSTRACT

The interplay between the entropically and enthalpically favored products of peptide fragmentation is probed using a combined experimental and theoretical approach. These b2 ion products can take either an oxazolone or diketopiperazine structure. Cleavage after the second amide bond is often a favorable process because the products are small ring structures that are particularly stable. These structures are structurally characterized by action IRMPD spectroscopy and semi-quantified using gas-phase hydrogen-deuterium exchange. The formation of the oxazolone and diketopiperazine has been thought to be largely governed by the identity of the first two residues at the N-terminus of the peptide. We show here that the length of the precursor peptide and identity of the third residue play a significant role in the formation of the diketopiperazine structure in peptides containing an N-terminal asparagine residue. This is additionally the first instance showing an N-terminal residue with an amide side chain can promote formation of the diketopiperazine b2 ion structure.


Subject(s)
Diketopiperazines/analysis , Oxazoles/analysis , Peptides/chemistry , Spectrophotometry, Infrared/methods , Mass Spectrometry
11.
Environ Sci Technol ; 48(6): 3310-8, 2014 Mar 18.
Article in English | MEDLINE | ID: mdl-24471759

ABSTRACT

The Rayleigh equation is frequently used to describe isotope fractionation as a function of conversion. In this article we propose to draw a parallel between isotope and enantiomeric enrichments and derive a set of conditions that allow the use of the Rayleigh approach to describe the enantiomeric enrichment-conversion dependencies. We demonstrate an implementation of the Rayleigh equation for the enantioselective enzymatic hydrolysis of Mecoprop-methyl, Dichlorprop-methyl, and dimethyl-methylsuccinate by lipases from Pseudomonas fluorescens, Pseudomonas cepacia, and Candida rugosa. The data obtained for all the studied reactions gave good fits to the Rayleigh equation, with a linear regression R(2) > 0.96. In addition to that, our analysis of four microcosm studies on the hydrolysis of the individual enantiomers of Dichloroprop methyl, Lactofen, Fenoxaprop-ethyl, and Metalaxyl reported in the literature by other research groups revealed a suitability of the Rayleigh dependence. Two dimensional plots describing the isotope fractionation versus enantiomeric enrichment are demonstrated for all studied cases. Processes not accompanied by enantiomeric enrichment (acid and base hydrolysis) and by isotope enrichment (transesterification) are demonstrated, their 2-D plots are either horizontal or vertical which can illuminate concealed degradation pathways.


Subject(s)
2-Methyl-4-chlorophenoxyacetic Acid/analogs & derivatives , Environmental Monitoring/methods , Isotopes/analysis , Oxazoles/analysis , Propionates/analysis , Soil Pollutants/analysis , 2-Methyl-4-chlorophenoxyacetic Acid/analysis , 2-Methyl-4-chlorophenoxyacetic Acid/chemistry , 2-Methyl-4-chlorophenoxyacetic Acid/metabolism , Algorithms , Biodegradation, Environmental , Bioreactors , Isotopes/chemistry , Isotopes/metabolism , Lipase/metabolism , Oxazoles/chemistry , Oxazoles/metabolism , Propionates/chemistry , Propionates/metabolism , Soil Pollutants/chemistry , Stereoisomerism
12.
Biomed Chromatogr ; 28(6): 767-73, 2014 Jun.
Article in English | MEDLINE | ID: mdl-24861742

ABSTRACT

A major modification to the QuEChERS (quick, easy, cheap, effective, rugged and safe) method was developed for the analysis of etoxazole in red pepper using gas chromatography coupled with a nitrogen-phosphorus detector. Etoxazole was extracted with acetonitrile, partitioned with magnesium sulfate and purified with a solid-phase extraction cartridge. The method showed good linearity with a determination coefficient (R(2) ) of 0.998 for the 0.02-2.0 mg/L concentration range. The method was validated using blank red pepper spiked at 0.2 and 1.0 mg/kg, and the average recovery rate was 74.4-79.1% with relative standard deviations <5% for intra- and inter-day precision. The limits of detection and quantification were 0.007 and 0.02 mg/kg, respectively. The developed method was successfully applied to field-incurred samples, and the presence of etoxazole residues was confirmed using gas chromatography/mass spectrometry.


Subject(s)
Capsicum/chemistry , Oxazoles/analysis , Oxazoles/isolation & purification , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Solid Phase Extraction/methods , Chromatography, Gas/instrumentation , Chromatography, Gas/methods , Food Contamination/analysis
13.
J AOAC Int ; 97(6): 1701-6, 2014.
Article in English | MEDLINE | ID: mdl-25632446

ABSTRACT

A direct injection LC/MS/MS method for the determination of the pesticide oxadixyl in wines was developed and validated. A sample divert valve was used to deliver the fraction that contained oxadixyl to the mass spectrometer's electrospray ionization source. Oxadixyl was monitored and quantitated using two transitions in multiple reaction monitoring mode. The method demonstrated recoveries of 99.2 ± 2.0 and 96.7± 5.2% for red and white wines, respectively, a linearity range of 2-20 µg/L, LOD at 0.7 µg/L, LOQ of 2.0 µg/L, and precision values of 8.2% (RSDr) and 6.2% (RSDR). Direct injection of the wine onto a C18 ultra-performance LC column allowed automation and high throughput screening. Benefits of this approach includeminimal sample preparation, short (3 min) run times, and the use of matrix-matched calibration standards, which minimize the matrix effect due to interferences from wine phenolics, sugars, and various other components. The method's performance characteristics were not statistically different for white and red wines. An additional interlaboratory validation study involved 12 laboratories and demonstrated gooddata agreement with HorRat values ranging from 0.23 to 0.52.


Subject(s)
Acetamides/analysis , Chromatography, High Pressure Liquid/methods , Oxazoles/analysis , Tandem Mass Spectrometry/methods , Wine/analysis , Limit of Detection , Spectrometry, Mass, Electrospray Ionization/methods
14.
Bull Environ Contam Toxicol ; 93(6): 775-80, 2014 Dec.
Article in English | MEDLINE | ID: mdl-25236328

ABSTRACT

The extensive use of plant protection products in urban and rural pest control obliges to develop valid analytical methods for their successful and reliable quality control. An analytical procedure for the simultaneous determination of famoxadone and cymoxanil, by reversed phase high performance liquid chromatography based on the use of a monolithic C18 column has been developed and validated. The method involved the extraction of the active ingredients by sonication of the sample with acetonitrile and direct injection on a reversed phase liquid chromatographic system. The repeatability of the method expressed as relative standard deviation (%RSD), was lower than 1 % for both compounds. The limits of quantification for famoxadone and cymoxanil were 10 and 16 µg mL(-1) respectively. The new method involves a considerable reduction in time for both sample preparation and analysis. The proposed analytical procedure is accurate and precise.


Subject(s)
Acetamides/analysis , Chromatography, High Pressure Liquid , Environmental Monitoring/methods , Pesticides/analysis , Chromatography, High Pressure Liquid/instrumentation , Methacrylates/analysis , Oxazoles/analysis , Strobilurins
15.
J Pharm Biomed Anal ; 246: 116225, 2024 Aug 15.
Article in English | MEDLINE | ID: mdl-38761519

ABSTRACT

We developed and validated a bioanalytical assay to quantify delamanid and its key metabolite (DM-6705) in breast milk and aimed to quantify the secretion of these compounds in breast milk. Due to the hydrophobic nature of the analytes, special care was taken during sample preparation to prevent the formation of fatty deposits during protein precipitation. This was followed by online solid phase extraction and liquid chromatography with tandem mass spectrometry for detection. A Restek Viva BiPh C18 column (1.0 mm×50 mm, 5 µm) was used for extraction while chromatographic separation was performed using a Waters Xterra MS C18 (2.1 mm×100 mm, 5 µm) analytical column with an isocratic mobile phase consisting of acetonitrile, methanol, and 5 mM ammonium carbonate. The mass spectrometric detection of the analytes was performed using an AB Sciex 3200 mass spectrometer employing electrospray ionisation in the positive mode with multiple reaction motoring of the relevant precursor and product ions. Delamanid-d4 and OPC-14714 were used as internal standards. A quadratic (weighted 1/x concentration) regression was used to fit calibration curves for delamanid and DM-6705 over the concentration range of 10.0 - 1000 ng/mL. The intra- and inter-day validation accuracies of the quality control samples were between 92.1% and 98.3% for delamanid, and 97.0% and 102.8% for DM-6705. The percentage coefficient of variation (precision) was less than 7.8%. To our knowledge, this is the first report describing the concentrations of delamanid and DM-6705 in the breast milk of patients treated for rifampicin-resistant tuberculosis.


Subject(s)
Milk, Human , Tandem Mass Spectrometry , Tandem Mass Spectrometry/methods , Milk, Human/chemistry , Humans , Female , Oxazoles/analysis , Chromatography, Liquid/methods , Solid Phase Extraction/methods , Reproducibility of Results , Limit of Detection , Calibration , Chromatography, High Pressure Liquid/methods , Guanidines
16.
J Environ Sci Health B ; 48(5): 331-5, 2013.
Article in English | MEDLINE | ID: mdl-23431971

ABSTRACT

A method for determination of etoxazole residues in apples, strawberries and green beans was developed and validated. The analyte was extracted with acetonitrile from foodstuff and a charcoal-celite cartridge was used for clean-up of raw extracts. Reversed phase high performance liquid chromatography with photodiode array detector (HPLC-DAD) was used for the determination and quantification of etoxazole residues in the studied samples. The calibration graphs of etoxazole in a solvent or three blank matrixes were linear within the tested intervals 0.01-2 mg L(-1), with correlation coefficient of determination >0.999. The combined solid phase extraction (SPE) clean-up and the chromatographic method steps were sensitive and reliable for simultaneous determination of etoxazole residues in the studied samples. The average recoveries of etoxazole in the tested foodstuffs were between 93.4 to 102% at spiking levels of 0.01, 0.10, and 0.50 mg kg(-1), with relative standard deviations ranging from 2.8 to 4.7%, in agreement with directives for method validation in residue analyses. The limit of detection (LOD) of the HPLC-DAD system was 100 pg. The limit of quantification of the entire method was 0.01 mg kg(-1).


Subject(s)
Chromatography, High Pressure Liquid/methods , Fruit/chemistry , Oxazoles/analysis , Oxazoles/isolation & purification , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Solid Phase Extraction/methods , Vegetables/chemistry , Food Contamination/analysis
17.
J Environ Sci Health B ; 48(5): 324-30, 2013.
Article in English | MEDLINE | ID: mdl-23431970

ABSTRACT

The persistence of fenoxaprop ethyl {Ethyl (RS)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy) phenoxy] propionate} herbicide and its active metabolite fenoxaprop acid was investigated in soil and wheat crop. Fenoxaprop acid was prepared by alkaline hydrolysis of fenoxaprop ethyl. A HPLC method was developed in which fenoxaprop ethyl herbicide and its acid metabolite showed sharp single peak at 6.44 and 2.61 min respectively. The sensitivity of the method for ester and acid was 2 and 1 ng respectively with limit of detection of 0.1 and 0.05 µg mL(-1). The recovery of fenoxaprop ethyl and fenoxaprop acid from soil, wheat straw and grain ranged between 73.8-80.2%. In a field experiment fenoxaprop ethyl (Puma super® 10 EC) when applied to wheat crop at the rate of 120 g and 240 g a.i. ha(-1) as post emergence spray, fenoxaprop ethyl converted to fenoxaprop acid. Residues of fenoxaprop ethyl and acid dissipated in soil with a half-life of 0.5 and 7.3 days, respectively. At harvest no detectable residues of fenoxaprop ethyl or acid were observed in soil, wheat grain and straw samples.


Subject(s)
Herbicides/analysis , Oxazoles/analysis , Propionates/analysis , Soil Pollutants/analysis , Triticum/chemistry , Chromatography, High Pressure Liquid , Environmental Monitoring , Herbicides/metabolism , India , Oxazoles/metabolism , Propionates/metabolism , Soil/analysis , Soil Pollutants/metabolism , Triticum/metabolism , Tropical Climate
18.
J Sep Sci ; 34(11): 1236-43, 2011 Jun.
Article in English | MEDLINE | ID: mdl-21504065

ABSTRACT

A simple and enantioselective method for the determination of famoxadone enantiomers in spinach using reversed-phase HPLC-MS/MS is presented. Famoxadone residues in spinach were extracted with acetonitrile and an aliquot was cleaned up with PSA (primary and secondary amine, Si-(CH(2))(3)-NH-(CH(2))(2)-NH(2)) and C(18) sorbent, which were powder material. Chiral stationary phase (CSP), cellulose tris(3,5-dimethylphenylcarbamate), was successfully applied to separate two enantiomers using methanol/formic acid-ammonium acetate buffer as mobile phase. The MS/MS fragmentation pathway of ammonium adduct famoxadone molecules ion at m/z 392 was analyzed and an odd electron fragment ion at m/z 238 was observed. Excellent linearity was achieved for each enantiomer over a range of concentrations from 0.5 to 1500 µg/L with coefficients more than 0.99. Average recoveries at five different levels (1, 2.5, 12.5, 250 and 1250 µg/kg, for each enantiomer) ranged from 80.8 to 96.5% with RSD of 4.8-13.4%. The famoxadone enantiomers LODs in spinach were determined to be both 0.3 µg/kg with LOQs of 1 µg/kg. Based on this method, the dissipation process of famoxadone enantiomers in spinach under open field and greenhouse conditions was characterized, providing guidance to the proper and safe use of this fungicide in agriculture.


Subject(s)
Oxazoles/analysis , Spinacia oleracea/chemistry , Chromatography, High Pressure Liquid , Methacrylates/analysis , Molecular Structure , Spectrometry, Mass, Electrospray Ionization , Stereoisomerism , Strobilurins , Tandem Mass Spectrometry
19.
Bull Environ Contam Toxicol ; 87(6): 653-6, 2011 Dec.
Article in English | MEDLINE | ID: mdl-21959994

ABSTRACT

A sensitive and effective analytical method for the determination of hymexazol in cucumber and soil samples by gas chromatography with a flame photometric detector was developed. This method was validated with fortified at three different levels of 0.2, 1.0 and 5.0 mg/kg. Average recoveries obtained from cucumber and soil samples at three fortified levels were 94.0%-107.8% with relative standard deviations (RSDs) of less than 11.4%. Limits of quantification (LOQ) in cucumber and soil were 0.2 mg/kg. The method was successfully applied to determine hymexazol in real samples of cucumber and soil under open fields.


Subject(s)
Chromatography, Gas/methods , Cucumis sativus/chemistry , Environmental Monitoring/methods , Oxazoles/analysis , Soil Pollutants/analysis , Soil/chemistry , Guidelines as Topic , Pesticide Residues/analysis , Soil/analysis
20.
Bull Environ Contam Toxicol ; 87(1): 50-3, 2011 Jul.
Article in English | MEDLINE | ID: mdl-21533830

ABSTRACT

A method for residue analysis of fenoxaprop-P-ethyl and its metabolite (i.e., fenoxaprop-P) was developed using high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). This method was then used to evaluate the residual level and dissipation rate of fenoxaprop-P-ethyl and fenoxaprop-P in the soil and wheat. The half-life of fenoxaprop-P-ethyl in wheat plants and soil was 1.50, 2.36 days in Beijing, and 2.28, 1.79 days in Hubei, respectively. The ultimate residues of the two compounds were undetected in soil, wheat grain and stem at the harvest time, suggesting that fenoxaprop-P-ethyl could be safely used in wheat crops with an appropriate dosage and application.


Subject(s)
Herbicides/metabolism , Oxazoles/metabolism , Pesticide Residues/analysis , Propionates/metabolism , Soil Pollutants/metabolism , Soil/chemistry , Triticum/chemistry , China , Chromatography, High Pressure Liquid , Edible Grain/chemistry , Half-Life , Herbicides/analysis , Oxazoles/analysis , Pesticide Residues/metabolism , Plant Stems/chemistry , Propionates/analysis , Soil Pollutants/analysis , Tandem Mass Spectrometry
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