Structural evidence of anomeric effects in the anesthetic isoflurane
The conformational and structural properties of the inhalational anesthetic isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. Two conformers of the isolated molecule were identified f...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2011-01, Vol.13 (14), p.6610-6618 |
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| container_title | Physical chemistry chemical physics : PCCP |
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| creator | LESARRI, Alberto VEGA-TORIBIO, Alicia SUENRAM, Richard D BRUGH, Dale J NORI-SHARGH, Davood BOGGS, James E GRABOW, Jens-Uwe |
| description | The conformational and structural properties of the inhalational anesthetic isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. Two conformers of the isolated molecule were identified from the rotational spectrum of the parent and several (37)Cl and (13)C isotopologues detected in natural abundance. The two most stable structures of isoflurane are characterized by an anti carbon skeleton (τ(C(1)-C(2)-O-C(3)) = 137.8(11)° or 167.4(19)°), differing in the trans (AT) or gauche (AG) orientation of the difluoromethyl group. The conformational abundances in the jet were estimated from relative intensity measurements as (AT)/(AG) ≈ 3:1. The structural preferences of the molecule have been rationalized with supporting ab initio calculations and natural-bond-orbital (NBO) analysis, which suggest that the molecule is stabilized by hyperconjugative effects. The NBO analysis of donor-acceptor (LP → σ*) interactions showed that these stereoelectronic effects decrease from the AT to AG conformations, so the conformational preferences can be accounted for in terms of the generalized anomeric effect. |
| doi_str_mv | 10.1039/c0cp02465a |
| format | Article |
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Two conformers of the isolated molecule were identified from the rotational spectrum of the parent and several (37)Cl and (13)C isotopologues detected in natural abundance. The two most stable structures of isoflurane are characterized by an anti carbon skeleton (τ(C(1)-C(2)-O-C(3)) = 137.8(11)° or 167.4(19)°), differing in the trans (AT) or gauche (AG) orientation of the difluoromethyl group. The conformational abundances in the jet were estimated from relative intensity measurements as (AT)/(AG) ≈ 3:1. The structural preferences of the molecule have been rationalized with supporting ab initio calculations and natural-bond-orbital (NBO) analysis, which suggest that the molecule is stabilized by hyperconjugative effects. The NBO analysis of donor-acceptor (LP → σ*) interactions showed that these stereoelectronic effects decrease from the AT to AG conformations, so the conformational preferences can be accounted for in terms of the generalized anomeric effect.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/c0cp02465a</identifier><identifier>PMID: 21384026</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Anesthetics ; Anesthetics - chemistry ; Approximation ; Carbon ; Chemistry ; Ethers ; Exact sciences and technology ; General and physical chemistry ; Isoflurane - chemistry ; Isomerism ; Mathematical analysis ; Microwaves ; Models, Molecular ; Molecular Conformation ; Parents ; Rotation ; Rotational ; Spectrum Analysis ; Thermodynamics</subject><ispartof>Physical chemistry chemical physics : PCCP, 2011-01, Vol.13 (14), p.6610-6618</ispartof><rights>2015 INIST-CNRS</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c417t-b6b6c1000aea11d8d215ec459bb072065c330da99ad964bf11e13767081533b53</citedby><cites>FETCH-LOGICAL-c417t-b6b6c1000aea11d8d215ec459bb072065c330da99ad964bf11e13767081533b53</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=24082024$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/21384026$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>LESARRI, Alberto</creatorcontrib><creatorcontrib>VEGA-TORIBIO, Alicia</creatorcontrib><creatorcontrib>SUENRAM, Richard D</creatorcontrib><creatorcontrib>BRUGH, Dale J</creatorcontrib><creatorcontrib>NORI-SHARGH, Davood</creatorcontrib><creatorcontrib>BOGGS, James E</creatorcontrib><creatorcontrib>GRABOW, Jens-Uwe</creatorcontrib><title>Structural evidence of anomeric effects in the anesthetic isoflurane</title><title>Physical chemistry chemical physics : PCCP</title><addtitle>Phys Chem Chem Phys</addtitle><description>The conformational and structural properties of the inhalational anesthetic isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. Two conformers of the isolated molecule were identified from the rotational spectrum of the parent and several (37)Cl and (13)C isotopologues detected in natural abundance. The two most stable structures of isoflurane are characterized by an anti carbon skeleton (τ(C(1)-C(2)-O-C(3)) = 137.8(11)° or 167.4(19)°), differing in the trans (AT) or gauche (AG) orientation of the difluoromethyl group. The conformational abundances in the jet were estimated from relative intensity measurements as (AT)/(AG) ≈ 3:1. The structural preferences of the molecule have been rationalized with supporting ab initio calculations and natural-bond-orbital (NBO) analysis, which suggest that the molecule is stabilized by hyperconjugative effects. The NBO analysis of donor-acceptor (LP → σ*) interactions showed that these stereoelectronic effects decrease from the AT to AG conformations, so the conformational preferences can be accounted for in terms of the generalized anomeric effect.</description><subject>Anesthetics</subject><subject>Anesthetics - chemistry</subject><subject>Approximation</subject><subject>Carbon</subject><subject>Chemistry</subject><subject>Ethers</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Isoflurane - chemistry</subject><subject>Isomerism</subject><subject>Mathematical analysis</subject><subject>Microwaves</subject><subject>Models, Molecular</subject><subject>Molecular Conformation</subject><subject>Parents</subject><subject>Rotation</subject><subject>Rotational</subject><subject>Spectrum Analysis</subject><subject>Thermodynamics</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2011</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkU1LxEAMhgdR3HX14g-QXkQRqpP57lHWT1jwoJ7LdJrBSj_WTiv47x3d1b3pISQkT15eEkIOgZ4D5dmFo25JmVDSbpEpCMXTjBqx_VtrNSF7IbxSSkEC3yUTBtwIytSUXD0O_eiGsbd1gu9Via3DpPOJbbsG-8ol6D26ISRVmwwvGPsYYh7ipAqdr-Nii_tkx9s64ME6z8jzzfXT_C5dPNzezy8XqROgh7RQhXIQXVi0AKUpGUh0QmZFQTWjSjrOaWmzzJaZEoUHQOBaaWpAcl5IPiMnK91l372N0UjeVMFhXUcP3RjyTHGjOePiX9JIo3UMHsnTP0nQigHj8C16tkJd34XQo8-XfdXY_iMHmn99It98IsJHa92xaLD8RX9OH4HjNWCDs7WPh3RV2HCCGha1-CeCG47x</recordid><startdate>20110101</startdate><enddate>20110101</enddate><creator>LESARRI, Alberto</creator><creator>VEGA-TORIBIO, Alicia</creator><creator>SUENRAM, Richard D</creator><creator>BRUGH, Dale J</creator><creator>NORI-SHARGH, Davood</creator><creator>BOGGS, James E</creator><creator>GRABOW, Jens-Uwe</creator><general>Royal Society of Chemistry</general><scope>IQODW</scope><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>7U5</scope><scope>8FD</scope><scope>L7M</scope><scope>7X8</scope></search><sort><creationdate>20110101</creationdate><title>Structural evidence of anomeric effects in the anesthetic isoflurane</title><author>LESARRI, Alberto ; VEGA-TORIBIO, Alicia ; SUENRAM, Richard D ; BRUGH, Dale J ; NORI-SHARGH, Davood ; BOGGS, James E ; GRABOW, Jens-Uwe</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c417t-b6b6c1000aea11d8d215ec459bb072065c330da99ad964bf11e13767081533b53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2011</creationdate><topic>Anesthetics</topic><topic>Anesthetics - chemistry</topic><topic>Approximation</topic><topic>Carbon</topic><topic>Chemistry</topic><topic>Ethers</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>Isoflurane - chemistry</topic><topic>Isomerism</topic><topic>Mathematical analysis</topic><topic>Microwaves</topic><topic>Models, Molecular</topic><topic>Molecular Conformation</topic><topic>Parents</topic><topic>Rotation</topic><topic>Rotational</topic><topic>Spectrum Analysis</topic><topic>Thermodynamics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>LESARRI, Alberto</creatorcontrib><creatorcontrib>VEGA-TORIBIO, Alicia</creatorcontrib><creatorcontrib>SUENRAM, Richard D</creatorcontrib><creatorcontrib>BRUGH, Dale J</creatorcontrib><creatorcontrib>NORI-SHARGH, Davood</creatorcontrib><creatorcontrib>BOGGS, James E</creatorcontrib><creatorcontrib>GRABOW, Jens-Uwe</creatorcontrib><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>LESARRI, Alberto</au><au>VEGA-TORIBIO, Alicia</au><au>SUENRAM, Richard D</au><au>BRUGH, Dale J</au><au>NORI-SHARGH, Davood</au><au>BOGGS, James E</au><au>GRABOW, Jens-Uwe</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Structural evidence of anomeric effects in the anesthetic isoflurane</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><addtitle>Phys Chem Chem Phys</addtitle><date>2011-01-01</date><risdate>2011</risdate><volume>13</volume><issue>14</issue><spage>6610</spage><epage>6618</epage><pages>6610-6618</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>The conformational and structural properties of the inhalational anesthetic isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. Two conformers of the isolated molecule were identified from the rotational spectrum of the parent and several (37)Cl and (13)C isotopologues detected in natural abundance. The two most stable structures of isoflurane are characterized by an anti carbon skeleton (τ(C(1)-C(2)-O-C(3)) = 137.8(11)° or 167.4(19)°), differing in the trans (AT) or gauche (AG) orientation of the difluoromethyl group. The conformational abundances in the jet were estimated from relative intensity measurements as (AT)/(AG) ≈ 3:1. The structural preferences of the molecule have been rationalized with supporting ab initio calculations and natural-bond-orbital (NBO) analysis, which suggest that the molecule is stabilized by hyperconjugative effects. The NBO analysis of donor-acceptor (LP → σ*) interactions showed that these stereoelectronic effects decrease from the AT to AG conformations, so the conformational preferences can be accounted for in terms of the generalized anomeric effect.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><pmid>21384026</pmid><doi>10.1039/c0cp02465a</doi><tpages>9</tpages><oa>free_for_read</oa></addata></record> |
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| source | MEDLINE; Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Anesthetics Anesthetics - chemistry Approximation Carbon Chemistry Ethers Exact sciences and technology General and physical chemistry Isoflurane - chemistry Isomerism Mathematical analysis Microwaves Models, Molecular Molecular Conformation Parents Rotation Rotational Spectrum Analysis Thermodynamics |
| title | Structural evidence of anomeric effects in the anesthetic isoflurane |
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