Terminal Diazirines Enable Reverse Polarization Transfer from 15 N 2 Singlets
Diazirine moieties are chemically stable and have been incorporated into biomolecules without impediment of biological activity. The N labeled diazirines are appealing motifs for hyperpolarization supporting relaxation protected states with long-lived lifetimes. The (-CH N ) diazirine groups investi...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2019-08, Vol.58 (32), p.11118-11124 |
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| container_title | Angewandte Chemie International Edition |
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| creator | Zhang, Guannan Colell, Johannes F P Glachet, Thomas Lindale, Jacob R Reboul, Vincent Theis, Thomas Warren, Warren S |
| description | Diazirine moieties are chemically stable and have been incorporated into biomolecules without impediment of biological activity. The
N
labeled diazirines are appealing motifs for hyperpolarization supporting relaxation protected states with long-lived lifetimes. The (-CH
N
) diazirine groups investigated here are analogues to methyl groups, which provides the opportunity to transfer polarization stored on a relaxation protected (-CH
N
) moiety to
H, thus combining the advantages of long lifetimes of
N polarization with superior sensitivity of
H detection. Despite the proximity of
H to
N nuclei in the diazirine moiety,
N T
times of up to (4.6±0.4) min and singlet lifetimes T
of up to (17.5±3.8) min are observed. Furthermore, we found terminal diazirines to support hyperpolarized
H
singlet states in CH
groups of chiral molecules. The singlet lifetime of
H singlets is up to (9.2±1.8) min, thus exceeding
H T
relaxation time (at 8.45 T) by a factor of ≈100. |
| doi_str_mv | 10.1002/anie.201904026 |
| format | Article |
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N
labeled diazirines are appealing motifs for hyperpolarization supporting relaxation protected states with long-lived lifetimes. The (-CH
N
) diazirine groups investigated here are analogues to methyl groups, which provides the opportunity to transfer polarization stored on a relaxation protected (-CH
N
) moiety to
H, thus combining the advantages of long lifetimes of
N polarization with superior sensitivity of
H detection. Despite the proximity of
H to
N nuclei in the diazirine moiety,
N T
times of up to (4.6±0.4) min and singlet lifetimes T
of up to (17.5±3.8) min are observed. Furthermore, we found terminal diazirines to support hyperpolarized
H
singlet states in CH
groups of chiral molecules. The singlet lifetime of
H singlets is up to (9.2±1.8) min, thus exceeding
H T
relaxation time (at 8.45 T) by a factor of ≈100.</description><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201904026</identifier><identifier>PMID: 31168901</identifier><language>eng</language><publisher>Germany: Wiley-VCH Verlag</publisher><subject>Azirines - chemistry ; Chemical Sciences ; Medicinal Chemistry ; Molecular Structure ; Nitrogen Isotopes ; Organic chemistry</subject><ispartof>Angewandte Chemie International Edition, 2019-08, Vol.58 (32), p.11118-11124</ispartof><rights>2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1411-692d3d08d6f73baa8990e84a6ff3cc67577c89000575b8b8f3406a45f09d37eb3</citedby><cites>FETCH-LOGICAL-c1411-692d3d08d6f73baa8990e84a6ff3cc67577c89000575b8b8f3406a45f09d37eb3</cites><orcidid>0000-0001-9020-344X ; 0000-0002-1474-4065 ; 0000-0001-6779-9978 ; 0000-0002-5114-1116 ; 0000-0001-7272-5375 ; 0000-0001-8458-2076 ; 0000-0001-9298-5115</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/31168901$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://normandie-univ.hal.science/hal-02173605$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Zhang, Guannan</creatorcontrib><creatorcontrib>Colell, Johannes F P</creatorcontrib><creatorcontrib>Glachet, Thomas</creatorcontrib><creatorcontrib>Lindale, Jacob R</creatorcontrib><creatorcontrib>Reboul, Vincent</creatorcontrib><creatorcontrib>Theis, Thomas</creatorcontrib><creatorcontrib>Warren, Warren S</creatorcontrib><title>Terminal Diazirines Enable Reverse Polarization Transfer from 15 N 2 Singlets</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Diazirine moieties are chemically stable and have been incorporated into biomolecules without impediment of biological activity. The
N
labeled diazirines are appealing motifs for hyperpolarization supporting relaxation protected states with long-lived lifetimes. The (-CH
N
) diazirine groups investigated here are analogues to methyl groups, which provides the opportunity to transfer polarization stored on a relaxation protected (-CH
N
) moiety to
H, thus combining the advantages of long lifetimes of
N polarization with superior sensitivity of
H detection. Despite the proximity of
H to
N nuclei in the diazirine moiety,
N T
times of up to (4.6±0.4) min and singlet lifetimes T
of up to (17.5±3.8) min are observed. Furthermore, we found terminal diazirines to support hyperpolarized
H
singlet states in CH
groups of chiral molecules. The singlet lifetime of
H singlets is up to (9.2±1.8) min, thus exceeding
H T
relaxation time (at 8.45 T) by a factor of ≈100.</description><subject>Azirines - chemistry</subject><subject>Chemical Sciences</subject><subject>Medicinal Chemistry</subject><subject>Molecular Structure</subject><subject>Nitrogen Isotopes</subject><subject>Organic chemistry</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNo9kE1LAzEQhoMotlavHiVXD1tnks3HHkutVqgfaD0v2d1EI_tRklqwv94t1Z7mZXjeYXgIuUQYIwC7Ma23YwaYQQpMHpEhCoYJV4of9znlPFFa4ICcxfjV81qDPCUDjih1Bjgkj0sbGt-amt56s_XBtzbSWWuK2tJXu7EhWvrS1Sb4rVn7rqXLYNrobKAudA1FQZ8oo2--_ajtOp6TE2fqaC_-5oi8382W03myeL5_mE4WSYkpYiIzVvEKdCWd4oUxOsvA6tRI53hZSiWUKvv3AIQShS604ylIkwoHWcWVLfiIXO_vfpo6XwXfmPCTd8bn88ki3-2AoeISxAZ7drxny9DFGKw7FBDyncN85zA_OOwLV_vC6rtobHXA_6XxX0M1atU</recordid><startdate>20190805</startdate><enddate>20190805</enddate><creator>Zhang, Guannan</creator><creator>Colell, Johannes F P</creator><creator>Glachet, Thomas</creator><creator>Lindale, Jacob R</creator><creator>Reboul, Vincent</creator><creator>Theis, Thomas</creator><creator>Warren, Warren S</creator><general>Wiley-VCH Verlag</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>1XC</scope><orcidid>https://orcid.org/0000-0001-9020-344X</orcidid><orcidid>https://orcid.org/0000-0002-1474-4065</orcidid><orcidid>https://orcid.org/0000-0001-6779-9978</orcidid><orcidid>https://orcid.org/0000-0002-5114-1116</orcidid><orcidid>https://orcid.org/0000-0001-7272-5375</orcidid><orcidid>https://orcid.org/0000-0001-8458-2076</orcidid><orcidid>https://orcid.org/0000-0001-9298-5115</orcidid></search><sort><creationdate>20190805</creationdate><title>Terminal Diazirines Enable Reverse Polarization Transfer from 15 N 2 Singlets</title><author>Zhang, Guannan ; Colell, Johannes F P ; Glachet, Thomas ; Lindale, Jacob R ; Reboul, Vincent ; Theis, Thomas ; Warren, Warren S</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1411-692d3d08d6f73baa8990e84a6ff3cc67577c89000575b8b8f3406a45f09d37eb3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Azirines - chemistry</topic><topic>Chemical Sciences</topic><topic>Medicinal Chemistry</topic><topic>Molecular Structure</topic><topic>Nitrogen Isotopes</topic><topic>Organic chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zhang, Guannan</creatorcontrib><creatorcontrib>Colell, Johannes F P</creatorcontrib><creatorcontrib>Glachet, Thomas</creatorcontrib><creatorcontrib>Lindale, Jacob R</creatorcontrib><creatorcontrib>Reboul, Vincent</creatorcontrib><creatorcontrib>Theis, Thomas</creatorcontrib><creatorcontrib>Warren, Warren S</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zhang, Guannan</au><au>Colell, Johannes F P</au><au>Glachet, Thomas</au><au>Lindale, Jacob R</au><au>Reboul, Vincent</au><au>Theis, Thomas</au><au>Warren, Warren S</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Terminal Diazirines Enable Reverse Polarization Transfer from 15 N 2 Singlets</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2019-08-05</date><risdate>2019</risdate><volume>58</volume><issue>32</issue><spage>11118</spage><epage>11124</epage><pages>11118-11124</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Diazirine moieties are chemically stable and have been incorporated into biomolecules without impediment of biological activity. The
N
labeled diazirines are appealing motifs for hyperpolarization supporting relaxation protected states with long-lived lifetimes. The (-CH
N
) diazirine groups investigated here are analogues to methyl groups, which provides the opportunity to transfer polarization stored on a relaxation protected (-CH
N
) moiety to
H, thus combining the advantages of long lifetimes of
N polarization with superior sensitivity of
H detection. Despite the proximity of
H to
N nuclei in the diazirine moiety,
N T
times of up to (4.6±0.4) min and singlet lifetimes T
of up to (17.5±3.8) min are observed. Furthermore, we found terminal diazirines to support hyperpolarized
H
singlet states in CH
groups of chiral molecules. The singlet lifetime of
H singlets is up to (9.2±1.8) min, thus exceeding
H T
relaxation time (at 8.45 T) by a factor of ≈100.</abstract><cop>Germany</cop><pub>Wiley-VCH Verlag</pub><pmid>31168901</pmid><doi>10.1002/anie.201904026</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0001-9020-344X</orcidid><orcidid>https://orcid.org/0000-0002-1474-4065</orcidid><orcidid>https://orcid.org/0000-0001-6779-9978</orcidid><orcidid>https://orcid.org/0000-0002-5114-1116</orcidid><orcidid>https://orcid.org/0000-0001-7272-5375</orcidid><orcidid>https://orcid.org/0000-0001-8458-2076</orcidid><orcidid>https://orcid.org/0000-0001-9298-5115</orcidid></addata></record> |
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| source | MEDLINE; Wiley Online Library Journals Frontfile Complete |
| subjects | Azirines - chemistry Chemical Sciences Medicinal Chemistry Molecular Structure Nitrogen Isotopes Organic chemistry |
| title | Terminal Diazirines Enable Reverse Polarization Transfer from 15 N 2 Singlets |
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