{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T05:16:08Z","timestamp":1788412568858,"version":"build-2803163510"},"reference-count":33,"publisher":"American Chemical Society (ACS)","issue":"24","license":[{"start":{"date-parts":[[2021,9,8]],"date-time":"2021-09-08T00:00:00Z","timestamp":1631059200000},"content-version":"vor","delay-in-days":365,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_ccbyncnd_termsofuse.html"}],"funder":[{"DOI":"10.13039\/na","name":"EU Horizon 2020","doi-asserted-by":"publisher","award":["731077"],"award-info":[{"award-number":["731077"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2020,12,15]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Polybutadiene (PB) and polyisoprene (PI), the two most common polydienes (PD), are involved in a large number of materials and used in a wide variety of applications. The characterization of these polymers by mass spectrometry (MS) continues to be very challenging due to their high insolubility and the difficulty to ionize them. In this work, a cross-metathesis reaction was used to generate end-functionalized acetoxy ionizable oligomers for the structural deciphering of different commercial PB and PI samples. A cross-metathesis reaction was carried out between polymers and the Z-1,4-diacetoxy-2-butene as a chain transfer agent in dichloromethane using a Hoveyda\u2013Grubbs second-generation catalyst. Well-defined acetoxy telechelic structures were obtained and analyzed by Fourier transform ion cyclotron resonance (FTICR) high-resolution MS. However, after depolymerization, low molar mass polyolefins contained some units with different configurations, suggesting an olefin isomerization reaction due to the decomposition of the catalyst. The addition of an electron-deficient reagent such as 2,6-dichloro-1,4-benzoquinone suppressed this isomerization in the case of both Z- and E-PB and PI. Ion mobility spectrometry-mass spectrometry (IMS-MS) and energy-resolved tandem mass spectrometry (ERMS) analyses confirmed a successful isomerization suppression. For comparing the results obtained by depolymerization with classical methods for polymer analysis, pyrolysis-comprehensive two-dimensional gas chromatography\/mass spectrometry (Py-GC \u00d7 GC\u2013MS), atmospheric solid analysis probe (ASAP), and direct inlet probe-atmospheric pressure chemical ionization (DIP-APCI) analyses were performed on the same polymers. This strategy can be applied on a variety of synthetic and natural not yet characterized polymers.<\/jats:p>","DOI":"10.1021\/acs.analchem.0c02650","type":"journal-article","created":{"date-parts":[[2020,9,8]],"date-time":"2020-09-08T10:57:16Z","timestamp":1599562636000},"page":"15736-15744","source":"Crossref","is-referenced-by-count":10,"title":["Regio- and Stereo-Specific Chemical Depolymerization\nof High Molecular Weight Polybutadiene and Polyisoprene for Their\nAnalysis by High-Resolution Fourier Transform Ion Cyclotron Resonance\nMass Spectrometry: Comparison with Pyrolysis-Comprehensive Two-Dimensional\nGas Chromatography\/Mass Spectrometry, Atmospheric Solid Analysis Probe,\nDirect Inlet Probe-Atmospheric Pressure Chemical Ionization Mass Spectrometry,\nand Ion Mobility Spectrometry-Mass Spectrometry"],"prefix":"10.1021","volume":"92","author":[{"given":"Ziad","family":"Mahmoud","sequence":"first","affiliation":[{"name":"Universite\u0301 Lille, CNRS, USR 3290, MSAP, Miniaturisation pour la Synthe\u0300se l\u2019Analyse et la Prote\u0301omique , ,","place":["Lille, France, F-59 000"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fabrice","family":"Bray","sequence":"additional","affiliation":[{"name":"Universite\u0301 Lille, CNRS, USR 3290, MSAP, Miniaturisation pour la Synthe\u0300se l\u2019Analyse et la Prote\u0301omique , ,","place":["Lille, France, F-59 000"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marie","family":"Hubert-Roux","sequence":"additional","affiliation":[{"name":"Normandie Universite\u0301, Universite\u0301 de Rouen, UMR 6014, CNRS, COBRA, Chimie organique et bioorganique, Re\u0301activite\u0301 et Analyse , ,","place":["Mont-Saint-Aignan Cedex, France, 76821"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6508-8566","authenticated-orcid":true,"given":"Michel","family":"Sablier","sequence":"additional","affiliation":[{"name":"Muse\u0301um National d\u2019Histoire Naturelle, USR 3224, CNRS, Centre de Recherche sur la Conservation , 36, rue Geoffroy Saint-Hilaire , ,","place":["Paris, France, 75005"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2406-5664","authenticated-orcid":true,"given":"Carlos","family":"Afonso","sequence":"additional","affiliation":[{"name":"Normandie Universite\u0301, Universite\u0301 de Rouen, UMR 6014, CNRS, COBRA, Chimie organique et bioorganique, Re\u0301activite\u0301 et Analyse , ,","place":["Mont-Saint-Aignan Cedex, France, 76821"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3266-8860","authenticated-orcid":true,"given":"Christian","family":"Rolando","sequence":"additional","affiliation":[{"name":"Universite\u0301 Lille, CNRS, USR 3290, MSAP, Miniaturisation pour la Synthe\u0300se l\u2019Analyse et la Prote\u0301omique , ,","place":["Lille, France, F-59 000"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2020,9,8]]},"reference":[{"key":"2026090300244281600_cit1","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/j.aca.2016.05.024","article-title":"Polymer architectures\nvia mass spectrometry and hyphenated\ntechniques: A review","volume":"932","author":"Crotty","year":"2016","journal-title":"Anal. Chim. Acta"},{"key":"2026090300244281600_cit2","doi-asserted-by":"publisher","first-page":"599","DOI":"10.1039\/b9py00347a","article-title":"Mass spectrometry\nin polymer chemistry: a state-of-the-art up-date","volume":"1","author":"Gruendling","year":"2010","journal-title":"Polym. Chem."},{"key":"2026090300244281600_cit3","doi-asserted-by":"publisher","first-page":"527","DOI":"10.1021\/cr9901081","article-title":"Mass Spectrometry\nof Polymers and Polymer Surfaces","volume":"101","author":"Hanton","year":"2001","journal-title":"Chem. Rev."},{"key":"2026090300244281600_cit4","volume-title":"Pyrolysis-gas Chromatography:\nMass Spectrometry Of Polymeric Materials","author":"Peter","year":"2018"},{"key":"2026090300244281600_cit5","doi-asserted-by":"publisher","first-page":"2743","DOI":"10.1021\/ac020214u","article-title":"Mass spectrometry of chemical polymers","volume":"74","author":"McEwen","year":"2002","journal-title":"Anal. Chem."},{"key":"2026090300244281600_cit6","doi-asserted-by":"publisher","first-page":"7826","DOI":"10.1021\/ac051470k","article-title":"Analysis\nof solids, liquids, and\nbiological tissues using solids probe introduction at atmospheric\npressure on commercial LC\/MS instruments","volume":"77","author":"McEwen","year":"2005","journal-title":"Anal.\nChem."},{"key":"2026090300244281600_cit7","doi-asserted-by":"crossref","DOI":"10.1002\/9780470567234","volume-title":"MALDI Mass Spectrometry\nfor Synthetic Polymer Analysis","author":"Li","year":"2009"},{"key":"2026090300244281600_cit8","doi-asserted-by":"publisher","first-page":"7778","DOI":"10.1021\/ac801198g","article-title":"Direct Probe-Atmospheric\nPressure Chemical Ionization Mass Spectrometry of Cross-Linked Copolymers\nand Copolymer Blends","volume":"80","author":"Whitson","year":"2008","journal-title":"Anal. Chem."},{"key":"2026090300244281600_cit9","doi-asserted-by":"publisher","first-page":"355","DOI":"10.1016\/j.jaap.2011.07.008","article-title":"Direct probe CI-MS and APCI-MS for direct materials\nanalysis","volume":"92","author":"Lattimer","year":"2011","journal-title":"J. Anal. Appl. Pyrolysis"},{"key":"2026090300244281600_cit10","doi-asserted-by":"publisher","first-page":"1664","DOI":"10.1021\/ma991157i","article-title":"Microstructures of butadiene copolymers\ndetermined\nby ozonolysis\/MALDI mass spectrometry","volume":"33","author":"Zoller","year":"2000","journal-title":"Macromolecules"},{"key":"2026090300244281600_cit11","doi-asserted-by":"publisher","first-page":"295","DOI":"10.1016\/j.polymdegradstab.2018.06.019","article-title":"Controlled degradation of polyisoprene\nand polybutadiene: A comparative study of two methods","volume":"154","author":"Berto","year":"2018","journal-title":"Polym. Degrad. Stab."},{"key":"2026090300244281600_cit12","doi-asserted-by":"publisher","first-page":"1661","DOI":"10.1021\/acs.biomac.7b00364","article-title":"Olefin\nCross-Metathesis in Polymer\nand Polysaccharide Chemistry: A Review","volume":"18","author":"Dong","year":"2017","journal-title":"Biomacromolecules"},{"key":"2026090300244281600_cit13","doi-asserted-by":"publisher","first-page":"7117","DOI":"10.1016\/j.tet.2004.05.124","article-title":"Olefin\nmetathesis","volume":"60","author":"Grubbs","year":"2004","journal-title":"Tetrahedron"},{"key":"2026090300244281600_cit14","doi-asserted-by":"publisher","first-page":"3760","DOI":"10.1002\/anie.200600680","article-title":"Olefin-metathesis\ncatalysts for the preparation of molecules and materials (Nobel lecture)","volume":"45","author":"Grubbs","year":"2006","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090300244281600_cit15","doi-asserted-by":"publisher","first-page":"696","DOI":"10.1021\/acssuschemeng.6b01777","article-title":"Controlled\nMetathetic Depolymerization of Natural Rubber in Ionic Liquids: From\nWaste Tires to Telechelic Polyisoprene Oligomers","volume":"5","author":"Mouawia","year":"2017","journal-title":"ACS Sustainable Chem. Eng."},{"key":"2026090300244281600_cit16","doi-asserted-by":"publisher","first-page":"1057","DOI":"10.1002\/macp.200400416","article-title":"Metathetic selective\ndegradation of polyisoprene: low-molecular-weight telechelic oligomer\nobtained from both synthetic and natural rubber","volume":"206","author":"Solanky","year":"2005","journal-title":"Macromol. Chem. Phys."},{"key":"2026090300244281600_cit17","doi-asserted-by":"publisher","first-page":"441","DOI":"10.1021\/ol702624n","article-title":"Increased Efficiency in Cross-Metathesis\nReactions of Sterically Hindered Olefins","volume":"10","author":"Stewart","year":"2008","journal-title":"Org.\nLett."},{"key":"2026090300244281600_cit18","doi-asserted-by":"publisher","first-page":"658","DOI":"10.1002\/rcm.7823","article-title":"Interactive\nvan Krevelen diagrams \u2013 Advanced visualisation of mass spectrometry\ndata of complex mixtures","volume":"31","author":"Kew","year":"2017","journal-title":"Rapid Commun. Mass\nSpectrom."},{"key":"2026090300244281600_cit19","doi-asserted-by":"publisher","first-page":"103","DOI":"10.1016\/j.polymer.2018.07.071","article-title":"Accessible\nmicrostructures of polybutadiene by anionic polymerization","volume":"153","author":"Forens","year":"2018","journal-title":"Polymer"},{"key":"2026090300244281600_cit20","doi-asserted-by":"publisher","first-page":"17160","DOI":"10.1021\/ja052939w","article-title":"Prevention of Undesirable\nIsomerization during Olefin Metathesis","volume":"127","author":"Hong","year":"2005","journal-title":"J. Am.\nChem. Soc."},{"key":"2026090300244281600_cit21","doi-asserted-by":"publisher","first-page":"215","DOI":"10.1016\/0020-7381(82)80026-0","article-title":"Energy-resolved\ntandem and fourier-transform\nmass spectrometry","volume":"44","author":"McLuckey","year":"1982","journal-title":"Int. J. Mass Spectrom. Ion\nPhys."},{"key":"2026090300244281600_cit22","doi-asserted-by":"publisher","first-page":"37","DOI":"10.1016\/0020-7381(82)80037-5","article-title":"Energy-resolved\ncollision-induced dissociation in tandem\nmass spectrometry","volume":"44","author":"Fetterolf","year":"1982","journal-title":"Int. J. Mass Spectrom. Ion\nPhys."},{"key":"2026090300244281600_cit23","doi-asserted-by":"publisher","first-page":"131","DOI":"10.1016\/0010-2180(96)00253-2","article-title":"Flash pyrolysis\nof hydroxyl-terminated polybutadiene\n(HTPB) I: Analysis and implications of the gaseous products","volume":"106","author":"Arisawa","year":"1996","journal-title":"Combust. Flame"},{"key":"2026090300244281600_cit24","doi-asserted-by":"publisher","first-page":"326","DOI":"10.1021\/ma990423p","article-title":"Primary pyrolysis\nproducts of hydroxy-terminated polybutadiene","volume":"33","author":"Ganesh","year":"2000","journal-title":"Macromolecules"},{"key":"2026090300244281600_cit25","doi-asserted-by":"publisher","first-page":"3197","DOI":"10.1002\/pol.1981.170191214","article-title":"Thermal decomposition\nof polybutadienes by pyrolysis\ngas chromatography","volume":"19","author":"Radhakrishnan","year":"1981","journal-title":"J. Polym. Sci., Polym. Chem.\nEd."},{"key":"2026090300244281600_cit26","doi-asserted-by":"publisher","first-page":"9349","DOI":"10.1021\/ac302109q","article-title":"Atmospheric Solid Analysis\nProbe\u2013Ion Mobility Mass Spectrometry of Polypropylene","volume":"84","author":"Barre\u0300re","year":"2012","journal-title":"Anal. Chem."},{"key":"2026090300244281600_cit27","doi-asserted-by":"publisher","first-page":"1133","DOI":"10.1007\/s13361-019-02194-7","article-title":"Fundamental\nStudies of New Ionization\nTechnologies and Insights from IMS-MS","volume":"30","author":"Trimpin","year":"2019","journal-title":"J. Am.\nSoc. Mass Spectrom."},{"key":"2026090300244281600_cit28","doi-asserted-by":"publisher","first-page":"4524","DOI":"10.1039\/c2an35556f","article-title":"Evaluating\nAtmospheric pressure Solids\nAnalysis Probe (ASAP) mass spectrometry for the analysis of low molecular\nweight synthetic polymers","volume":"137","author":"Smith","year":"2012","journal-title":"Analyst"},{"key":"2026090300244281600_cit29","doi-asserted-by":"publisher","first-page":"41","DOI":"10.1002\/pol.1972.110100108","article-title":"Thermal degradation of 1,4-polyisoprene and 1,4-polybutadiene","volume":"10","author":"Golub","year":"1972","journal-title":"J. Polym. Sci., Part B: Polym. Lett."},{"key":"2026090300244281600_cit30","doi-asserted-by":"publisher","first-page":"53","DOI":"10.1016\/S0378-3820(00)00073-4","article-title":"Studies on the thermal degradation\nof polybutadiene","volume":"67","author":"Chen","year":"2000","journal-title":"Fuel Process. Technol."},{"key":"2026090300244281600_cit31","doi-asserted-by":"publisher","first-page":"2071","DOI":"10.1016\/S0016-2361(02)00147-3","article-title":"Studies on the thermal\ndegradation of cis-1, 4-polyisoprene","volume":"81","author":"Chen","year":"2002","journal-title":"Fuel"},{"key":"2026090300244281600_cit32","doi-asserted-by":"publisher","first-page":"4667","DOI":"10.1021\/ma8021234","article-title":"Understanding\nof the Plasticizing\nEffects of Glycerol and PEG 400 on Chitosan Films Using Solid-State\nNMR Spectroscopy","volume":"42","author":"Domja\u0301n","year":"2009","journal-title":"Macromolecules"},{"key":"2026090300244281600_cit33","doi-asserted-by":"publisher","first-page":"325","DOI":"10.1016\/S0021-9673(00)00647-6","article-title":"Polymer\nadditive analysis by pyrolysis\u2013gas chromatography: IV. Antioxidants","volume":"891","author":"Wang","year":"2000","journal-title":"J. Chromatogr. A"}],"container-title":["Analytical Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.analchem.0c02650","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/ancham\/article-pdf\/92\/24\/15736\/67130608\/acs.analchem.0c02650.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/ancham\/article-pdf\/92\/24\/15736\/67130608\/acs.analchem.0c02650.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T04:29:45Z","timestamp":1788409785000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/ancham\/article\/92\/24\/15736\/827261\/Regio-and-Stereo-Specific-Chemical"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,9,8]]},"references-count":33,"journal-issue":{"issue":"24","published-online":{"date-parts":[[2020,9,8]]},"published-print":{"date-parts":[[2020,12,15]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.analchem.0c02650","relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv.12478469.v1","asserted-by":"object"}]},"ISSN":["0003-2700","1520-6882"],"issn-type":[{"value":"0003-2700","type":"print"},{"value":"1520-6882","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,9,8]]}}}