{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,30]],"date-time":"2026-04-30T21:56:07Z","timestamp":1777586167649,"version":"3.51.4"},"reference-count":24,"publisher":"SAGE Publications","issue":"2","license":[{"start":{"date-parts":[[2023,2,16]],"date-time":"2023-02-16T00:00:00Z","timestamp":1676505600000},"content-version":"unspecified","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":["journals.sagepub.com"],"crossmark-restriction":true},"short-container-title":["Eur J Mass Spectrom (Chichester)"],"published-print":{"date-parts":[[2023,4]]},"abstract":"\n The electron ionisation mass spectra of an extensive set of 53 ionised monosubstituted and disubstituted cinnamamides [XC\n 6<\/jats:sub>\n H\n 4<\/jats:sub>\n CH=CHCONH\n 2<\/jats:sub>\n , X = H, F, Cl, Br, I, CH\n 3<\/jats:sub>\n , CH\n 3<\/jats:sub>\n O, CF\n 3<\/jats:sub>\n , NO\n 2<\/jats:sub>\n , CH\n 3<\/jats:sub>\n CH\n 2<\/jats:sub>\n , (CH\n 3<\/jats:sub>\n )\n 2<\/jats:sub>\n CH and (CH\n 3<\/jats:sub>\n )\n 3<\/jats:sub>\n C; and XYC\n 6<\/jats:sub>\n H\n 3<\/jats:sub>\n CH=CHCONH\n 2<\/jats:sub>\n , X = Y = Cl; and X, Y = F, Cl or Br] are reported and discussed. Particular attention is paid to the significance of loss of the substituent, X, from the 2-position, via a rearrangement that is sometimes known as a proximity effect, which has been reported for a range of radical-cations, but is shown in this work to be especially important for ionised cinnamamides. When X is in the 2-position of the aromatic ring, [M \u2013 X]\n +<\/jats:sup>\n is formed to a far greater extent than [M \u2013 H]\n +<\/jats:sup>\n ; in contrast, when X is in the 3-position or 4-position, [M \u2013 H]\n +<\/jats:sup>\n is generally much more important than [M \u2013 X]\n +<\/jats:sup>\n . Parallel trends are found in the spectra of XYC\n 6<\/jats:sub>\n H\n 3<\/jats:sub>\n CH=CHCONH\n 2<\/jats:sub>\n : the signal for [M \u2013 X]\n +<\/jats:sup>\n dominates that for [M \u2013 Y]\n +<\/jats:sup>\n when X is in the 2-position and Y in the 4-position or 5-position, irrespective of the nature of X and Y. Further insight is obtained by studying the competition between expulsion of X\n \u00b7<\/jats:sup>\n and alternative fragmentations that may be described as simple cleavages. Loss of\n \u00b7<\/jats:sup>\n NH\n 2<\/jats:sub>\n results in the formation of a substituted cinnamoyl cation, [XC\n 6<\/jats:sub>\n H\n 4<\/jats:sub>\n CH=CHCO]\n +<\/jats:sup>\n or [XYC\n 6<\/jats:sub>\n H\n 3<\/jats:sub>\n CH=CHCO]\n +<\/jats:sup>\n ; this process competes far less effectively with the proximity effect when X is in the 2-position than when it is in the 3-position or 4-position. Additional information has been obtained by investigating the competition between formation of [M \u2013 H]\n +<\/jats:sup>\n by the proximity effect and loss of CH\n 3<\/jats:sub>\n \u00b7<\/jats:sup>\n by cleavage of a 4-alkyl group to give a benzylic cation, [R\n 1<\/jats:sup>\n R\n 2<\/jats:sup>\n CC\n 6<\/jats:sub>\n H\n 4<\/jats:sub>\n CH=CHCONH\n 2<\/jats:sub>\n ]\n +<\/jats:sup>\n (R\n 1<\/jats:sup>\n , R\n 2<\/jats:sup>\n = H, CH\n 3<\/jats:sub>\n ).\n <\/jats:p>","DOI":"10.1177\/14690667231153777","type":"journal-article","created":{"date-parts":[[2023,2,16]],"date-time":"2023-02-16T03:37:36Z","timestamp":1676518656000},"page":"75-87","update-policy":"https:\/\/doi.org\/10.1177\/sage-journals-update-policy","source":"Crossref","is-referenced-by-count":2,"title":["Proximity effects in the electron ionisation mass spectra of substituted cinnamamides"],"prefix":"10.1177","volume":"29","author":[{"given":"Adam R","family":"Michalik","sequence":"first","affiliation":[{"name":"School of Chemistry and Biosciences, Faculty of Life Sciences, University of Bradford, Bradford, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3409-918X","authenticated-orcid":false,"given":"Nathan W","family":"Fenwick","sequence":"additional","affiliation":[{"name":"School of Chemistry and Biosciences, Faculty of Life Sciences, University of Bradford, Bradford, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Richard","family":"Telford","sequence":"additional","affiliation":[{"name":"School of Chemistry and Biosciences, Faculty of Life Sciences, University of Bradford, Bradford, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Archie W","family":"Johnson","sequence":"additional","affiliation":[{"name":"School of Chemistry and Biosciences, Faculty of Life Sciences, University of Bradford, Bradford, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"William HC","family":"Martin","sequence":"additional","affiliation":[{"name":"School of Chemistry and Biosciences, Faculty of Life Sciences, University of Bradford, Bradford, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1555-7034","authenticated-orcid":false,"given":"Richard D","family":"Bowen","sequence":"additional","affiliation":[{"name":"School of Chemistry and Biosciences, Faculty of Life Sciences, University of Bradford, Bradford, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"179","published-online":{"date-parts":[[2023,2,16]]},"reference":[{"key":"bibr1-14690667231153777","unstructured":"McLafferty F and Ture\u010dek F. 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