{"title":"Mass-spectrometric studies of kinetic characteristics of codeine molecule thermodesorption by non-stationary surface ionization method.","authors":"G T Rakhmanov, D T Usmanov","doi":"10.1177/14690667221136069","DOIUrl":"https://doi.org/10.1177/14690667221136069","url":null,"abstract":"<p><p>The adsorption and surface ionization of codeine molecules С<sub>18</sub>H<sub>21</sub>O<sub>3</sub>N (<i>m/z</i> 299) on the surface of oxidized tungsten have been studied by a non-stationary method of voltage modulation under the same experimental conditions with a high-vacuum mass-spectrometric setup using a \"black chamber\" all walls of which are cooled with liquid nitrogen. For the codeine molecule dissociation with the <math><mo>(</mo><mrow><mrow><mi>C</mi></mrow><mo>-</mo><msub><mrow><mi>C</mi></mrow><mn>1</mn></msub></mrow><msub><mo>)</mo><mrow><mi>β</mi></mrow></msub></math> bond breaking and formation of ionizable radicals, the rate constants <i>K</i><sup>+</sup> and <i>K</i><sup>0</sup>, the activation energy <i>Е</i><sup>+</sup> and <i>Е</i><sup>0</sup> of thermodesorption, and the pre-exponential factors in the continuity equation for the radicals C<sub>9</sub>H<sub>7</sub>N<sup>+</sup>CH<sub>3</sub> (<i>m/z</i> 144) have been defined by surface ionization on the surface of oxidized tungsten <i>W<sub>x</sub>O<sub>y</sub></i>. The results of determining the surface ionization coefficient and estimates of the ionization potentials of these radicals have been presented.</p>","PeriodicalId":520618,"journal":{"name":"European journal of mass spectrometry (Chichester, England)","volume":" ","pages":"127-131"},"PeriodicalIF":1.3,"publicationDate":"2022-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40460477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Bioanalytical method for estimation of procyclidine in human plasma using liquid chromatography-tandem mass spectrometry: Application to pharmacokinetic study.","authors":"Viritha Bezawada, Padma Mogili, Sireesha Dodda, Ramakrishna Gajula","doi":"10.1177/14690667221111153","DOIUrl":"https://doi.org/10.1177/14690667221111153","url":null,"abstract":"<p><p>A rapid, selective and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated for quantification of procyclidine hydrochloride in human plasma using Procyclidine D11 hydrochloride as internal standard. Liquid-liquid extraction technique with methyl tertiary butyl ether was used for the extraction of plasma samples. Chromatographic separation of the analyte and the internal standard from the endogenous components was done on Zodiac C<sub>18</sub> column (50 × 4.6 mm, 5 µm) using a mixture of methanol and 0.1% formic acid in water (70:30, v/v) as mobile phase at a flow rate of 1 mL/min with the run time of 2 min. The detection of the eluents was done using multiple reaction monitoring (MRM) in positive ion mode. Linearity of the method was established in the concentration range of 0.5 to 120 ng/mL. Full validation of the method was done as per USFDA guidelines and the results were well within the acceptance limits. The successful application of the method was done on healthy human subjects under fasting conditions, proving it to be used for bioequivalence and bioavailability (BA/BE) studies of procyclidine.</p>","PeriodicalId":520618,"journal":{"name":"European journal of mass spectrometry (Chichester, England)","volume":" ","pages":"89-93"},"PeriodicalIF":1.3,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40470264","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Differential ionization cross-section of hydrogen bromide.","authors":"Ritu Sharawat, Meenakshi Kumari, Rajeev Kumar, Ravinder Sharma","doi":"10.1177/14690667221129942","DOIUrl":"https://doi.org/10.1177/14690667221129942","url":null,"abstract":"<p><p>In this study, the relative single and double differential ionization cross-section of the hydrogen bromide molecule and their fragmented ions (HBr<sup>+</sup>, Br<sup>+</sup>, H<sup>+</sup>) have been theoretically evaluated. In the single differential ionization cross-sections, the loss of incident electron energies (W) at 100 eV, 200 eV, and 500 eV is calculated. The double differential ionization cross-section of the HBr molecule is determined for secondary electron energy (e) and different incident scattering angles (θ). The differential ionization cross-sections of the hydrogen bromide molecule were investigated for the first time.The derived results of the HBr molecule are not only important in spectrometry but may also be interesting for atmospheric sciences.</p>","PeriodicalId":520618,"journal":{"name":"European journal of mass spectrometry (Chichester, England)","volume":" ","pages":"75-80"},"PeriodicalIF":1.3,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40379256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A simple UPLC-MS/MS assay with a core-shell column for the determination of exemestane in human plasma for clinical application.","authors":"Takuho Ishii, Nana Nojiri, Yuji Mano","doi":"10.1177/14690667221126276","DOIUrl":"https://doi.org/10.1177/14690667221126276","url":null,"abstract":"<p><p>Exemestane is one of the aromatase inhibitors and has been used to treat breast cancer by lowering estrogen levels. Accurate quantification of exemestane is important to set an optimal dose, and thus a simple assay for exemestane is developed by ultra-performance liquid chromatography with tandem mass spectrometer. Exemestane was extracted from human plasma samples (100 μL) by simple protein precipitation with acetonitrile/methanol (1/1, v/v). Interference peaks observed close to the elution of exemestane led us to use a core shell column for higher selectivity instead of totally porous columns. The extracts were chromatographed on CORTECS UPLC C18, under a gradient elution at a flow rate of 0.25 mL/min and detected in the selected reaction monitoring. Validation parameters were assessed in accordance with the bioanalytical guidelines using quality control samples. Exemestane in human plasma was quantifiable from 0.5 to 50 ng/mL with high extraction recovery and minimal matrix effects. Hemolyzed or hyperlipemic plasma did not impact the exemestane assay. Exemestane was stable in human plasma for 392 days at -15°C or below. The developed assay was robust and successfully applied to quantifying exemestane concentrations in human plasma to support a clinical trial.</p>","PeriodicalId":520618,"journal":{"name":"European journal of mass spectrometry (Chichester, England)","volume":" ","pages":"94-103"},"PeriodicalIF":1.3,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40373079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kalpana Talari, Sai Krishna Ganji, Satish Mutyam, Raja Rajeswari Tiruveedula
{"title":"Gas chromatography-mass spectrometric determination of organic acids by ion pair liquid extraction followed by in-situ butylation from aqua feed samples.","authors":"Kalpana Talari, Sai Krishna Ganji, Satish Mutyam, Raja Rajeswari Tiruveedula","doi":"10.1177/14690667221103227","DOIUrl":"https://doi.org/10.1177/14690667221103227","url":null,"abstract":"<p><p>A rapid and sensitive analytical method was developed to quantitatively determine organic acids (OAs) from fish feed samples extracted by ion-pair (IP) solvent extraction, followed by in-situ butylation and gas chromatography-mass spectrometric (GC-MS) analysis. The extraction of OAs was carried out with acetonitrile containing 10 mM tetrabutylammonium hydroxide (TBAH), and the analytes were derivatized to their butyl esters in the injection port of the GC-MS system. The developed method was validated in the range of 1-5000 ng/g, with recoveries ranging from 93-117%. The limit of detection (LOD) and limit of quantification (LOQ) of the method was 1-5 ng/g and 2-10 ng/g, respectively, yielding good linearity (R<sup>2</sup> > 0.9990) and precision with a relative standard deviation less than 10%. The proposed method was successfully applied to analyze OAs in sinking and floating fish feed samples. The analyzed samples showed the presence of benzoic, succinic, fumaric, glutaric, adipic, and phthalic acids in sinking feed samples; and benzoic, succinic, adipic, phthalic acids in floating feed samples, respectively.</p>","PeriodicalId":520618,"journal":{"name":"European journal of mass spectrometry (Chichester, England)","volume":" ","pages":"25-34"},"PeriodicalIF":1.3,"publicationDate":"2022-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40391241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mario Thevis, Hans Geyer, Daniel Bahr, Wilhelm Schänzer
{"title":"Identification of fentanyl, alfentanil, sufentanil, remifentanil and their major metabolites in human urine by liquid chromatography/tandem mass spectrometry for doping control purposes.","authors":"Mario Thevis, Hans Geyer, Daniel Bahr, Wilhelm Schänzer","doi":"10.1255/ejms.761","DOIUrl":"https://doi.org/10.1255/ejms.761","url":null,"abstract":"<p><p>Since January 2005, the list of prohibited substances established by the World Anti-Doping Agency prohibits the opioid agent fentanyl as well as its related drugs in professional and amateur sports. Fast, reliable and robust analytical assays are required that allow the sensitive determination of these compounds or respective metabolites in human urine, and liquid chromatography interfaced to mass spectrometry has proven to be a suitable and powerful tool for drug testing for several years. A screening and confirmation method was developed that enables the identification of fentanyl, alfentanil, remifentanil and sufentanil as well as their N-dealkylated or de-esterified metabolites utilizing solid-phase extraction of a 2 mL urine aliquot followed by LC-electrospray-MS/MS analysis. The procedure was validated in terms of recovery (95.8-104.9%), lower limit of detection (0.5 ng mL-1), specificity and interday precision (3.9-19.8%) for the four opioid drugs and the metabolic product norfentanyl. In addition, the mass spectrometric behavior of fentanyl after electrospray ionization and collision-induced dissociation was studied by synthesis and analysis of structurally related compounds, and dissociation pathways were proposed allowing the characterization of target analytes and corresponding metabolites.</p>","PeriodicalId":520618,"journal":{"name":"European journal of mass spectrometry (Chichester, England)","volume":" ","pages":"419-27"},"PeriodicalIF":1.3,"publicationDate":"2005-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1255/ejms.761","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"25620839","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Structural characterization of phosphatidylcholines by atmospheric pressure photoionization mass spectrometry.","authors":"Arnaud Delobel, David Touboul, Olivier Laprévote","doi":"10.1255/ejms.760","DOIUrl":"https://doi.org/10.1255/ejms.760","url":null,"abstract":"<p><p>The potential of atmospheric pressure photoionization was investigated for the structural analysis of phosphatidylcholine lipids (PCs). [M+H]+ ions of high abundance were obtained, along with several fragment ions. Three of these dissociation products corresponded to quite unusual fragmentation pathways but allowed the determination of both the nature and the position on the glycerol backbone (sn-1 or sn-2) of the fatty acyl chains. The loss of a methyl group from the choline head was also observed. These results suggest a complex ionization mechanism in APPI. However, this method proved to be very powerful for the rapid structural analysis of PC species without using MS/MS experiments.</p>","PeriodicalId":520618,"journal":{"name":"European journal of mass spectrometry (Chichester, England)","volume":" ","pages":"409-17"},"PeriodicalIF":1.3,"publicationDate":"2005-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1255/ejms.760","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"25620838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anna Napoli, Leonardo Di Donna, Giovanni Sindona, Elena Urso
{"title":"Gas-phase chemistry of the negative ions of fully-protected peptides by high-resolution electrospray ionization tandem mass spectrometry.","authors":"Anna Napoli, Leonardo Di Donna, Giovanni Sindona, Elena Urso","doi":"10.1255/ejms.769","DOIUrl":"https://doi.org/10.1255/ejms.769","url":null,"abstract":"<p><p>Fully-protected C-terminal free peptides can be conveniently analyzed by high-resolution electrospray tandem mass spectrometry (ESI-MS/MS) in a quadrupole quadrupole time-of-flight tandem hybrid mass spectrometer, operated in the negative (-) ionizaionization mode. The unusual choice of negative ions in mass spectrometry applications to peptide analysis was needed to obtain exhaustive sequence and structural data. The low-energy collision-induced dissociation (CID) experiments provided, in fact, tandem mass spectra displaying highly diagnostic fragments with a good signal-to-noise ratio. The method is applied to segments of porcine calcitonin (Cal), Cal (1016, 1), Cal (1724, 2) and Cal (2528, 3) whose [M H]- deprotonated molecular ions provided low-energy CID mass spectra which allow the evaluation either of the primary structure of the peptide and of the location of the side-chain protective groups. ESI (+) MS can be conveniently used, in the high resolution mode, to achieve precise information on the elemental composition of the examined peptides.</p>","PeriodicalId":520618,"journal":{"name":"European journal of mass spectrometry (Chichester, England)","volume":" ","pages":"403-8"},"PeriodicalIF":1.3,"publicationDate":"2005-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1255/ejms.769","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"25620837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Chemometric approach to evaluate the parameters affecting electrospray: application of a statistical design of experiments for the study of arginine ionization.","authors":"Laurence Charles, Stéphanie Caloprisco, Salimo Mohamed, Michelle Sergent","doi":"10.1255/ejms.759","DOIUrl":"https://doi.org/10.1255/ejms.759","url":null,"abstract":"<p><p>The effects of different experimental parameters on arginine electrospray ionization have been investigated with response surface modelling design. This chemometric technique allows a study of the effects of selected experimental variables and their interactions on the response of an experiment by performing a limited number of analyses. Six variables were studied: methanol content in the liquid phase, formic acid concentration, electrospray voltage, orifice voltage, mobile phase flow rate, and sheath gas flow rate. Signal abundance and signal-to-noise ratio of the protonated molecule and the protonated dimer were measured from the electrospray mass spectra and these four responses were tested by the design. The factor that exhibits the greatest influence on MH+ abundance is shown to be the liquid flow rate whereas the formation of protonated dimer is mainly controlled by the percentage of methanol in the mobile phase. A strong synergic effect of methanol content and formic acid concentration in the liquid has also been demonstrated in the study of noise level. Moreover, the capabilities of the multicriteria optimization method have been demonstrated through a successful prediction of a set of optimal experimental conditions.</p>","PeriodicalId":520618,"journal":{"name":"European journal of mass spectrometry (Chichester, England)","volume":" ","pages":"361-70"},"PeriodicalIF":1.3,"publicationDate":"2005-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1255/ejms.759","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"25618198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Louisa N Alfazema, Don S Richards, Sylvie Gélébart, John C Mitchell, Martin J Snowden
{"title":"Rapid, accurate and precise quantitative drug analysis: comparing liquid chromatography tandem mass spectrometry and chip-based nanoelectrospray ionisation mass spectrometry.","authors":"Louisa N Alfazema, Don S Richards, Sylvie Gélébart, John C Mitchell, Martin J Snowden","doi":"10.1255/ejms.772","DOIUrl":"https://doi.org/10.1255/ejms.772","url":null,"abstract":"<p><p>We have developed a liquid chromatography tandem mass spectrometry (LC-MS/MS) system capable of achieving better than 2% accuracy, routinely over a wide concentration range of 1800 ng mL-1. We demonstrate that the necessary high precision, high accuracy and rapid analysis can be achieved using LC-MS/MS technology. Automated nanoelectrospray ionisation tandem mass spectrometry (nanoESI-MS/MS) technology can be employed to eliminate the chromatographic step completely. In this paper, nanoESI-MS/MS is evaluated and compared directly with LC-MS/MS for the quantitative analysis of two-test analytes, amitriptyline (ATT) and 5-methoxytryptamine (5-MTT), in aqueous/organic mixture. Calibration curves were found to be linear over a wide concentration range of 1800 ng mL-1 for both analytes using LC-MS/MS. Using nanoESI-MS/MS ATT gave a linear response while 5-MTT gave a non-linear response using nanoESI-MS/MS over the same concentration range as in LC-MS/MS. Accuracy and precision values of quality control samples (QCs) at four concentration levels were analysed in replicates of six at each level using 5-MTT and ATT as test analytes for both techniques. The LC-MS/MS system was capable of achieving accuracy levels of 99.50101.96% for ATT and 100.17100.40% for 5-MTT. Accuracy levels using nanoESI-MS/MS were not comparable to LC-MS/MS, they ranged from 90.09100.18% for ATT and 95.95113.55% for 5-MTT. The precision values obtained for nanoESI-MS/MS were in good agreement with those obtained by LC-MS/MS.</p>","PeriodicalId":520618,"journal":{"name":"European journal of mass spectrometry (Chichester, England)","volume":" ","pages":"393-402"},"PeriodicalIF":1.3,"publicationDate":"2005-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1255/ejms.772","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"25620836","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}