ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTElectron spin resonance spectra of .gamma.-irradiated or photolyzed arsinesA. R. Lyons and M. C. R. SymonsCite this: J. Am. Chem. Soc. 1973, 95, 11, 3483–3485Publication Date (Print):May 1, 1973Publication History Published online1 May 2002Published inissue 1 May 1973https://pubs.acs.org/doi/10.1021/ja00792a006https://doi.org/10.1021/ja00792a006research-articleACS PublicationsRequest reuse permissionsArticle Views48Altmetric-Citations16LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Seven hyperfine components separated by about 450 G were observed in the e.s.r. spectrum of γ-irradiated triethylarsine at 77 K. This is indicative of two equivalent interacting arsenic atoms, and an analysis of the hyperfine tensor components suggests that the species is the dimer cation (R3As—AsR3)+ with a σ2, σ*1 structure as in VK centres. Similar species are formed in γ-irradiated trialkyl phosphines, but are not formed from phosphonium or arsonium salts, nor from the phosphines or arsines in methanol glasses. Irradiation of Me2PS—PSMe2 gave a similar di-phosphorus radical.The magnitudes of the derived orbital populations for phosphorus or arsenic suggest that, although some flattening of the local pyramidal character of the R3M groups occurs, this is far less than that observed for the monomeric R3M+ radicals.

A wide range of R2ĊXR3 radicals has been prepared, generally in the solid-state, by γ-irradiation of the corresponding alkyl derivatives such as R4Sn, R4Pb, R4P+ hal– and R4As+ hal–. From the magnitudes of the hyperfine coupling to α-protons, methyl protons, and X nuclei, it is concluded that for all these radicals, delocalization onto X is undetectably small, and therefore < ∼1 %.

E.s.r. spectra from poly[(oxycarbonyloxy-p-phenylene)isopropylidene-(p-phenylene)]γ- or u.-v.-irradiated at 77 K showed features characteristic of radical pairs in addition to central features assigned mainly to phenoxy radicals. Their decay on slow annealing has been studied and compared with those of similar radicals and radical pairs in γ-irradiated diphenyl carbonate. In the latter the pairs decay rapidly at temperatures far lower than that required for loss of the non-paired radicals. In contrast, paired and non-paired species showed similar decay characteristics in the polymer. Other aspects of radical pair-trapping and decay are reported and discussed.

A. R. Lyons, G. W. Neilson and M. C. R. Symons, J. Chem. Soc., Chem. Commun., 1972, 507 DOI: 10.1039/C39720000507

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHalogen atom additions to olefins. Electron spin resonance study of the intermediatesA. R. Lyons and M. C. R. SymonsCite this: J. Am. Chem. Soc. 1971, 93, 26, 7330–7331Publication Date (Print):December 1, 1971Publication History Published online1 May 2002Published inissue 1 December 1971https://pubs.acs.org/doi/10.1021/ja00755a043https://doi.org/10.1021/ja00755a043research-articleACS PublicationsRequest reuse permissionsArticle Views38Altmetric-Citations35LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Direct e.s.r. evidence for strong hyperfine interaction with phosphorus, arsenic, or tin atoms β to redical centres is presented, which is linked with the large rate enhancements detected by others when such groups are β to aromatic ring systems; the interaction is shown to be hyperconjugative rather than to involve outer d orbitals.

Radicals of type R2Ċ–X (R = H or alkyl, X = alkyl-substituted Al or P) have been identified in the title systems. Trends in the magnetic parameters are compared with those for other radicals in this general class, and it is concluded that in all cases, spin is transmitted to the group X by spin-polarisation of the C–X σ-bonding electrons and that the sign of Aiso(X) is negative. The weight of evidence is strongly against any significant C–X dπ–pπ bonding in the ground state of these radicals.

A study has been made of the kinetics and mechanism of the triethylaluminium initiated polymerization at 0° of methyl isopropenyl ketone (3-methyl-but-3-ene-2-one) in toluene and tetrahydrofuran. The reaction between triethylaluminium and methyl isopropenyl ketone gives rise to a yellow “ate”-complex which rearranges to the initiating species. A rapid production of linear trimer is followed by a slow polymerization giving rise to a bimodal molecular weight distribution. A coordinate mechanism for the polymerization is proposed.

AbstractThe kinetics and mechanism of the triethylaluminum–methyl isopropenyl ketone complex‐initiated polymerization of methyl isopropenyl ketone (3‐methyl‐3‐butene‐2‐one) in toluene have been studied over a range of temperature. Equimolar quantities of monomer and triethylaluminum were premixed to form the initiator species prior to the addition of the excess monomer for polymerization. Initial and overall reaction rates indicate a first‐order dependence on monomer and initiator concentrations. The overall activation energy for the polymerization is 52 ± 3 kJ/mole. Molecular weight distributions were bimodal, with peaks corresponding to the trimer and high molecular weight material. The kinetic data are consistent with a coordinate polymerization mechanism.

V. M. Clark, D. W. Hutchinson, A. R. Lyons and R. K. Roschnik, J. Chem. Soc. C, 1969, 233 DOI: 10.1039/J39690000233

One person in 5 dies from cancer and in woman about 1 in 4 arises in the breast; hence 1 woman in 20 will develop breast cancer. In Northern Ireland with a population of 1·5 million there are 300 new cases every year; 200 of these may eventually require palliative therapy. Unlike many other cancers recognition that cure is impossible does not always mean early death possibly postponed a little by cytotoxic drugs or other unpleasant procedures. Worthwhile prolongation of life can sometimes be obtained by the alteration of the endocrine milieu by a number of simple measures such as oophorectomy or the administration of androgens, oestrogens, progesterones or corticosteroids alone or in combination. These measures may be the limit of therapeutic endeavour, but sometimes hypophysectomy should be considered. One person in 5 dies from cancer and in woman about 1 in 4 arises in the breast; hence 1 woman in 20 will develop breast cancer. In Northern Ireland with a population of 1·5 million there are 300 new cases every year; 200 of these may eventually require palliative therapy. Unlike many other cancers recognition that cure is impossible does not always mean early death possibly postponed a little by cytotoxic drugs or other unpleasant procedures. Worthwhile prolongation of life can sometimes be obtained by the alteration of the endocrine milieu by a number of simple measures such as oophorectomy or the administration of androgens, oestrogens, progesterones or corticosteroids alone or in combination. These measures may be the limit of therapeutic endeavour, but sometimes hypophysectomy should be considered.

Journal Article A rational approach to hypophysectomy Get access George Edelstyn, George Edelstyn Senior Registrar in Radiotherapy Northern Ireland Radiotherapy Centre and the Department of Neurological Surgery, The Royal Victoria Hospital, Belfast Search for other works by this author on: Oxford Academic Google Scholar Colin Gleadhill, Colin Gleadhill Consultant Neurosurgeon Northern Ireland Radiotherapy Centre and the Department of Neurological Surgery, The Royal Victoria Hospital, Belfast Search for other works by this author on: Oxford Academic Google Scholar Arnold Lyons Arnold Lyons Consultant Radiotherapist Northern Ireland Radiotherapy Centre and the Department of Neurological Surgery, The Royal Victoria Hospital, Belfast Search for other works by this author on: Oxford Academic Google Scholar British Journal of Surgery, Volume 52, Issue 12, December 1965, Pages 953–957, https://doi.org/10.1002/bjs.1800521211 Published: 08 December 2005

1958). In women also, the death-rate from lung cancer has increased considerably. The extensive statistical and epidemiological evidence associating tobacco smoking and lung cancer is clear for all to study. Much attention has been directed to carcinogens produced by tobacco combustion; the possible effects of nicotine on the tissues in relation to cancer should now be investigated. If it were shown that metabolic changes are caused by smoking tobacco, and since it is known that nicotine can pass through the placental circulation, the effects of nicotine on the developing foetus should be studied. Is it possible that cellular changes may be caused in utero which manifest their effects in later life ? In the prevention of lung cancer people should be dissuaded from beginning to smoke and smokers persuaded to stop. This is a great challenge to all, and doctors should help people to overcome a severe form of drug addiction. I have made some practical suggestions to help towards a solution of this problem (Raven, 1957), for I feel that elimination of the tobacco habit could be one of the greatest benefits conferred by preventive medicine.

CancerVolume 10, Issue 6 p. 1275-1280 ArticleFree Access Plasmacytoma of lymph glands M. G. Nelson M.D., M.R.C.P., F.R.C.P.I., D.T.M.&H., M. G. Nelson M.D., M.R.C.P., F.R.C.P.I., D.T.M.&H. Royal Victoria Hospital, Belfast, IrelandSearch for more papers by this authorA. R. Lyons M.D., M.R.C.P., D.M.R.T., A. R. Lyons M.D., M.R.C.P., D.M.R.T. Royal Victoria Hospital, Belfast, IrelandSearch for more papers by this author M. G. Nelson M.D., M.R.C.P., F.R.C.P.I., D.T.M.&H., M. G. Nelson M.D., M.R.C.P., F.R.C.P.I., D.T.M.&H. Royal Victoria Hospital, Belfast, IrelandSearch for more papers by this authorA. R. Lyons M.D., M.R.C.P., D.M.R.T., A. R. Lyons M.D., M.R.C.P., D.M.R.T. Royal Victoria Hospital, Belfast, IrelandSearch for more papers by this author First published: November/December 1957 https://doi.org/10.1002/1097-0142(195711/12)10:6<1275::AID-CNCR2820100625>3.0.CO;2-TCitations: 39AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL References 1 Basset, A., and Scapier, J.: Sur un case d'un plasmocytome cervical. Monde méd. 47: 7– 8, 1937. 2 Hellwig, C. A.: Extramedullary plasma cell tumors as observed in various locations. Arch. Path. 36: 95– 111, 1943. 3 Jackson, H., Jr.; Parker, F., Jr., and Bethea, J. M.: Studies of diseases of lymphoid and myeloid tissues; II, plasmatocytomata and their relation to multiple myelomata. Am. J. M. Sc. 181: 169– 180, 1931. 4 Jequier-Doge, E.; Nicod, J. L., and Chapuis, J. P.: Un cas de plasmocytome à localisation ganglionnaire observé cliniquement pendant plus de 6 ans et contrǒlé anatomiquement. Schweiz. med. Wchnschr. 77: 186– 190, 1947. 5 Lane, S. L.: Plasmacytoma of mandible. Oral Surg., Oral Med. & Oral Path. 5: 434– 442, 1952. 6 Maresch, R.: Über ein plasmazelluläres Lymphogranulom. Verhandl. d. deutsch. path. Gesellsch. 13: 257– 263, 1909. 7 Nelson, M. G., and Lyons, A. R.: Unpublished data. 8 Pearse, A. G. E.: Histochemistry; Theoretical and Applied. London. C. & A. Churchill Ltd. 1953. 9 Rowlands, B., and Shaw, N.: Extramedullary plasmocytoma. Brit. M. J. 1: 1302– 1303, 1954. 10 Simon, M. A., and Eidlow, S.: Plasmacytoma of lymph node; report of case with multiple myeloma. New England J. Med. 243: 335– 338, 1950. Citing Literature Volume10, Issue6November/December 1957Pages 1275-1280 ReferencesRelatedInformation