NDLI: Thymine photodimer formation in DNA hairpins. Unusual conformations favor (6

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Hariharan, Mahesh Siegmund, Karsten Saurel, Clifton McCullagh, Martin Schatz, George C. Lewis, Frederick D.
Description	Country affiliation: United States Author Affiliation: Hariharan M ( Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, USA. fdl@northwestern.edu.)
Abstract	The photochemical reactions of eleven synthetic DNA hairpins possessing a single TT step either in a base-paired stem or in a hexanucleotide linker have been investigated. The major reaction products have been identified as the cis-syn (2 + 2) adduct and the (6 - 4) adduct on the basis of their spectroscopic properties including 1D and 2D NMR spectra, UV spectra and stability or instability to photochemical cleavage. Product quantum yields and ratios determined by HPLC analysis allow the behaviour of the eleven hairpins to be placed into three groups: Group I in which the (2 + 2) adduct is the major product, as is usually the case for DNA, Group II in which comparable amounts of (2 + 2) and (6 - 4) adducts are formed, and Group III in which the major product is the (6 - 4) adduct. The latter behaviour is without precedent in natural or synthetic DNA and appears to be related to the highly fluxional structures of the hairpin reactants. Molecular dynamics simulation of ground state conformations provides quantum yields and product ratios calculated using a single parameter model that are in reasonable agreement with most of the experimental results. Factors which may influence the observed product ratios are discussed.
File Format	HTM / HTML
ISSN	1474905X
e-ISSN	14749092
DOI	10.1039/c3pp50283j
Journal	Photochemical & Photobiological Sciences
Issue Number	2
Volume Number	13
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2014-02-01
Publisher Place	Great Britain (UK)
Access Restriction	Open
Subject Keyword	Discipline Chemistry Discipline Biology Dna Adducts Chemistry Genetics Dimerization Inverted Repeat Sequences Photochemical Processes Thymine Base Pairing Models, Molecular Quantum Theory Research Support, N.i.h., Extramural Research Support, U.s. Gov't, Non-p.h.s.
Content Type	Text
Resource Type	Article
Subject	Physical and Theoretical Chemistry

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