Abstract
2D NMR spectroscopy and J coupling constant analysis are applied to resolve the structure of two photoproducts of thymidylyl-(3′→5′)-thymidine. These products are cyclobutane type thymine dimers possessing the cis-syn (the predominant one) and trans-syn geometry. The cis-syn is formed in an ANTI-ANTI conformation about the N-glycosyl linkages and resembles the normal base-stacked configuration. The glycosidic conformation in solution of the 5′ terminal fragment differs from the crystal in which the less common SYN conformation is observed. In this isomer only the sugar pucker of the 3′ terminal fragment is changed substantially with respect to the dinucleotide. The trans-syn isomer is formed in a SYN-ANTI glycosidic conformation. In this isomer the sugar puckers of both deoxyribose rings are affected and a preference for a pure 2′-endo conformation is observed.
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Abbreviations
- dTpdT:
-
2′-deoxythymidylyl-(3′→5′)-2′-deoxythymidine
- dTp[]dT:
-
cyclobutane type photodimers of dTpdT
- dTp- and dTp[]-:
-
their 5' terminal fragments (fragment A)
- -pdT and-[]pdT:
-
their 3′ terminal fragments (fragment B)
- RP-HPLC:
-
reversed-phase high-performance liquid chromatography
- COSY:
-
two-dimensional correlated spectroscopy
- 2D NOE:
-
two-dimensional nuclear Overhauser spectroscopy
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Kemmink, J., Boelens, R. & Kaptein, R. Two-dimensional 1H NMR study of two cyclobutane type photodimers of thymidylyl-(3′→5′)-thymidine. Eur Biophys J 14, 293–299 (1987). https://doi.org/10.1007/BF00254894
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DOI: https://doi.org/10.1007/BF00254894