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}