Structural studies of the photochemically damaged nucleic acid by NMR and molecular modeling = NMR과 분자 모델링에 의한 광손상된 핵산의 구조 연구

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Structural studies of the DNA duplex containing a site specific-photodamaged photoproduct is an essential step toward understanding the molecular mechanism of the mutagenesis and the repair activity of ultraviolet irradiated DNA. The solution structures of two photodamaged DNA, psoralen cross-linked octamer duplex and (6-4) adduct- and Dewar photoproduct- containing decamer duplex, have been elucidated by detailed NMR and molecular modeling. (1) The three dimensional structure of the DNA oligomer $d(5``-GGGTACCC-3``)_2$ cross-linked with 4``-aminomethyl-4,5``,8-trimethylpsoralen(AMT) has been determined by two-dimensional NMR and a relaxation matrix refinement method. NMR data and structural calculation establish that the cross-linking of the psoralen in the B-DNA duplex retains Watson-Crick type hydrogen bonding throughout the duplex although the thymine residue which is cross-linked with psoralen forms a weaker hydrogen bond. The psoralen cross-linking in DNA duplex induces significant change of the local DNA structure, but has no important effect on overall DNA helix. Our observation places an upper limit of 10° on overall DNA bending by psoralen cross-linking, which is consistent with the result of HMT-octamer cross link. (2) The relative biological importance of (6-4) adduct and Dewar photoproduct appears to be dependent on the biological species, dipyrimidine sites, and the local conformational variation induced at the damaged sites. The single- stranded deoxynucleotide 10-mers containing site-specific (6-4) adduct or Dewar photoproduct of thymidylyl (3→5)-thymidine were generated by direct photolysis of d(CGCATTACGC) with UV-C(220-260nm) and UV-B(260-320nm) irradiation. Three-dimensional structures of the duplex Dewar and (6-4) decamers of d(CGCATTACGC)(d(GCGTAATGCG) were determined by NMR spectroscopy and relaxation matrix refinement method. NMR data and structural calculation establish that the hydrogen bonding is absent at the 3``-side of the (6-4) l...
Advisors
Choi, Byong-Seokresearcher최병석researcher
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
1996
Identifier
108922/325007 / 000925398
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 1996.2, [ xvii, 217 p. ]

Keywords

Nucleic acid; Photochemically damaged; Molecular modeling; NMR; Structural analysis; 구조 분석; 핵산; 광손상; 분자 모델링; 핵자기 공명법

URI
http://hdl.handle.net/10203/31442
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=108922&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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