Linked Life Data

8374057

Source:http://linkedlifedata.com/resource/pubmed/id/8374057

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
4
pubmed:dateCreated
1993-10-18
pubmed:abstractText
Photolysis of thymidylyl-(3'-->5')-thymidine (TpT) has been previously reported by many workers to lead to only two cyclobutane dimers, the cis-syn and trans-syn-I dimers. This is curious in light of the fact that photolysis of thymidylyl-(3'-->5')-deoxyuridine (TpdU), which has a hydrogen in place of a methyl group at C6 of the 3'-thymidine, produces two trans-syn diastereomers. Recently, we discovered by way of X-ray crystallography that photolysis of the (Rp)-methyl phosphate ester of TpT leads to two trans-syn diastereomers, prompting us to reexamine the photochemistry of TpT. In this paper we show that sensitized photolysis of TpT also leads to the hitherto unknown trans-syn-II diastereomer in 2% yield. We also report the solution-state 1H NMR assignment of the trans-syn-II photodimer of TpT and its (Rp)-methyl phosphate ester by way of 2D homonuclear Hartmann--Hahn experiment, rotating frame nuclear Overhauser effect spectroscopy, and proton-detected 1H-31P correlation spectroscopy. Conformational analysis of three-bond 1H-1H, 1H-31P, and 13C-31P coupling constant data established a close similarity between the solution-state structures of the trans-syn-II photodimer of TpT and its (Rp)-methyl phosphate ester, with the crystal structure of the methyl phosphate ester.
pubmed:grant
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:issn
0893-228X
pubmed:author
pubmed:issnType
Print
pubmed:volume
6
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
561-7
pubmed:dateRevised
2007-11-14
pubmed:meshHeading
pubmed:articleTitle
Identification and structure determination of a third cyclobutane photodimer of thymidylyl-(3'-->5')-thymidine: the trans-syn-II product.
pubmed:affiliation
Department of Chemistry, Washington University, St. Louis, Missouri 63130.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, P.H.S.