To what extent can methyl derivatives be regarded as stabilized tautomers of xanthine?
Taking xanthine (Xan) as an example, validity of an approach to experimental investigations of nucleotide bases’ tautomeric equilibrium, based on the use of methyl derivatives corresponding to their prototropic tautomers, was studied by 1H NMR in dimethylsulfoxide (DMSO) and by quantum chemical calc...
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| Veröffentlicht in: | Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Molecular and biomolecular spectroscopy, 2005-11, Vol.62 (1), p.112-114 |
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| container_title | Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy |
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| creator | Platonov, M.O. Samijlenko, S.P. Sudakov, O.O. Kondratyuk, I.V. Hovorun, D.M. |
| description | Taking xanthine (Xan) as an example, validity of an approach to experimental investigations of nucleotide bases’ tautomeric equilibrium, based on the use of methyl derivatives corresponding to their prototropic tautomers, was studied by
1H NMR in dimethylsulfoxide (DMSO) and by quantum chemical calculations at the B3LYP/6-311++G(d,p) level of theory. From
1H NMR spectra of m
7Xan, m
9Xan, Xan and m
3Xan conclusion was made that the N7H tautomeric forms of the last two compounds dominate in solution, which was supported by quantum chemical data. Calculated relative energies of the N9H tautomers of Xan and m
3Xan (8.74 and 9.57
kcal/mol, accordingly) are rather close to the m
9Xan one (9.11
kcal/mol). Nonspecific influence of DMSO modelled by the COSMO algorithm therewith reduces these values by approximately 2–3
kcal/mol. The data obtained imply that methyl derivatives are rather good models of high-energy tautomers of nucleotide bases, if their relative energies are not less than a few kcal/mol. |
| doi_str_mv | 10.1016/j.saa.2004.12.012 |
| format | Article |
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1H NMR in dimethylsulfoxide (DMSO) and by quantum chemical calculations at the B3LYP/6-311++G(d,p) level of theory. From
1H NMR spectra of m
7Xan, m
9Xan, Xan and m
3Xan conclusion was made that the N7H tautomeric forms of the last two compounds dominate in solution, which was supported by quantum chemical data. Calculated relative energies of the N9H tautomers of Xan and m
3Xan (8.74 and 9.57
kcal/mol, accordingly) are rather close to the m
9Xan one (9.11
kcal/mol). Nonspecific influence of DMSO modelled by the COSMO algorithm therewith reduces these values by approximately 2–3
kcal/mol. The data obtained imply that methyl derivatives are rather good models of high-energy tautomers of nucleotide bases, if their relative energies are not less than a few kcal/mol.</description><identifier>ISSN: 1386-1425</identifier><identifier>DOI: 10.1016/j.saa.2004.12.012</identifier><identifier>PMID: 16257701</identifier><language>eng</language><publisher>England: Elsevier B.V</publisher><subject>1H NMR ; Calorimetry ; DFT calculations ; Magnetic Resonance Spectroscopy - methods ; Methyl derivatives ; Models, Molecular ; Molecular Conformation ; Tautomerism ; Xanthine ; Xanthine - chemistry ; Xanthines - chemistry</subject><ispartof>Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy, 2005-11, Vol.62 (1), p.112-114</ispartof><rights>2004 Elsevier B.V.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c351t-a16ba3eca21b903c056586a83ea54a0929b3518f7f4e8c0ad1968cfd046cd1af3</citedby><cites>FETCH-LOGICAL-c351t-a16ba3eca21b903c056586a83ea54a0929b3518f7f4e8c0ad1968cfd046cd1af3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.saa.2004.12.012$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,780,784,3550,27924,27925,45995</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/16257701$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Platonov, M.O.</creatorcontrib><creatorcontrib>Samijlenko, S.P.</creatorcontrib><creatorcontrib>Sudakov, O.O.</creatorcontrib><creatorcontrib>Kondratyuk, I.V.</creatorcontrib><creatorcontrib>Hovorun, D.M.</creatorcontrib><title>To what extent can methyl derivatives be regarded as stabilized tautomers of xanthine?</title><title>Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy</title><addtitle>Spectrochim Acta A Mol Biomol Spectrosc</addtitle><description>Taking xanthine (Xan) as an example, validity of an approach to experimental investigations of nucleotide bases’ tautomeric equilibrium, based on the use of methyl derivatives corresponding to their prototropic tautomers, was studied by
1H NMR in dimethylsulfoxide (DMSO) and by quantum chemical calculations at the B3LYP/6-311++G(d,p) level of theory. From
1H NMR spectra of m
7Xan, m
9Xan, Xan and m
3Xan conclusion was made that the N7H tautomeric forms of the last two compounds dominate in solution, which was supported by quantum chemical data. Calculated relative energies of the N9H tautomers of Xan and m
3Xan (8.74 and 9.57
kcal/mol, accordingly) are rather close to the m
9Xan one (9.11
kcal/mol). Nonspecific influence of DMSO modelled by the COSMO algorithm therewith reduces these values by approximately 2–3
kcal/mol. The data obtained imply that methyl derivatives are rather good models of high-energy tautomers of nucleotide bases, if their relative energies are not less than a few kcal/mol.</description><subject>1H NMR</subject><subject>Calorimetry</subject><subject>DFT calculations</subject><subject>Magnetic Resonance Spectroscopy - methods</subject><subject>Methyl derivatives</subject><subject>Models, Molecular</subject><subject>Molecular Conformation</subject><subject>Tautomerism</subject><subject>Xanthine</subject><subject>Xanthine - chemistry</subject><subject>Xanthines - chemistry</subject><issn>1386-1425</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNp9kEtLAzEUhbNQrFZ_gBvJyl3H3MxMZooLkeILBDfVbbiT3LEp89AkrdVf75QW3Lm6HPjOgfsxdg4iAQHqapkExEQKkSUgEwHygB1DWqoJZDIfsZMQlkIIKKU4YiNQMi8KAcfsbd7zrwVGTptIXeQGO95SXHw33JJ3a4xuTYFXxD29o7dkOQYeIlaucT9DiriKfUs-8L7mG-ziwnV0c8oOa2wCne3vmL3e381nj5Pnl4en2e3zxKQ5xAmCqjAlgxKqqUiNyFVeKixTwjxDMZXTauDKuqgzKo1AC1NVmtqKTBkLWKdjdrnb_fD954pC1K0LhpoGO-pXQauyyAqVwQDCDjS-D8FTrT-8a9F_axB6K1Av9SBQbwVqkHoQOHQu9uOrqiX719jbG4DrHUDDi2tHXgfjqDNknScTte3dP_O_QrSDmA</recordid><startdate>20051101</startdate><enddate>20051101</enddate><creator>Platonov, M.O.</creator><creator>Samijlenko, S.P.</creator><creator>Sudakov, O.O.</creator><creator>Kondratyuk, I.V.</creator><creator>Hovorun, D.M.</creator><general>Elsevier B.V</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20051101</creationdate><title>To what extent can methyl derivatives be regarded as stabilized tautomers of xanthine?</title><author>Platonov, M.O. ; Samijlenko, S.P. ; Sudakov, O.O. ; Kondratyuk, I.V. ; Hovorun, D.M.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c351t-a16ba3eca21b903c056586a83ea54a0929b3518f7f4e8c0ad1968cfd046cd1af3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>1H NMR</topic><topic>Calorimetry</topic><topic>DFT calculations</topic><topic>Magnetic Resonance Spectroscopy - methods</topic><topic>Methyl derivatives</topic><topic>Models, Molecular</topic><topic>Molecular Conformation</topic><topic>Tautomerism</topic><topic>Xanthine</topic><topic>Xanthine - chemistry</topic><topic>Xanthines - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Platonov, M.O.</creatorcontrib><creatorcontrib>Samijlenko, S.P.</creatorcontrib><creatorcontrib>Sudakov, O.O.</creatorcontrib><creatorcontrib>Kondratyuk, I.V.</creatorcontrib><creatorcontrib>Hovorun, D.M.</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Platonov, M.O.</au><au>Samijlenko, S.P.</au><au>Sudakov, O.O.</au><au>Kondratyuk, I.V.</au><au>Hovorun, D.M.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>To what extent can methyl derivatives be regarded as stabilized tautomers of xanthine?</atitle><jtitle>Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy</jtitle><addtitle>Spectrochim Acta A Mol Biomol Spectrosc</addtitle><date>2005-11-01</date><risdate>2005</risdate><volume>62</volume><issue>1</issue><spage>112</spage><epage>114</epage><pages>112-114</pages><issn>1386-1425</issn><abstract>Taking xanthine (Xan) as an example, validity of an approach to experimental investigations of nucleotide bases’ tautomeric equilibrium, based on the use of methyl derivatives corresponding to their prototropic tautomers, was studied by
1H NMR in dimethylsulfoxide (DMSO) and by quantum chemical calculations at the B3LYP/6-311++G(d,p) level of theory. From
1H NMR spectra of m
7Xan, m
9Xan, Xan and m
3Xan conclusion was made that the N7H tautomeric forms of the last two compounds dominate in solution, which was supported by quantum chemical data. Calculated relative energies of the N9H tautomers of Xan and m
3Xan (8.74 and 9.57
kcal/mol, accordingly) are rather close to the m
9Xan one (9.11
kcal/mol). Nonspecific influence of DMSO modelled by the COSMO algorithm therewith reduces these values by approximately 2–3
kcal/mol. The data obtained imply that methyl derivatives are rather good models of high-energy tautomers of nucleotide bases, if their relative energies are not less than a few kcal/mol.</abstract><cop>England</cop><pub>Elsevier B.V</pub><pmid>16257701</pmid><doi>10.1016/j.saa.2004.12.012</doi><tpages>3</tpages></addata></record> |
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| ispartof | Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy, 2005-11, Vol.62 (1), p.112-114 |
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| source | MEDLINE; Access via ScienceDirect (Elsevier) |
| subjects | 1H NMR Calorimetry DFT calculations Magnetic Resonance Spectroscopy - methods Methyl derivatives Models, Molecular Molecular Conformation Tautomerism Xanthine Xanthine - chemistry Xanthines - chemistry |
| title | To what extent can methyl derivatives be regarded as stabilized tautomers of xanthine? |
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