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Measurement of the helix opening rate in Z-DNA by 1H nuclear magnetic resonance relaxation spectroscopy
Authors:P Bendel
Affiliation:1. Magnetic Resonance Center—CERM, University of Florence, Via Luigi Sacconi 6, 50019 Sesto Fiorentino, Florence, Italy;2. Department of Biomedical, Experimental and Clinical Sciences “Mario Serio”, University of Florence, Viale Morgagni 50, 50134, Florence, Italy;1. Slovenian NMR Institute, National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia;2. Institute of Microbiology and Immunology, Faculty of Medicine, University of Ljubljana, Ljubljana, Zaloška 4, SI-1000 Ljubljana, Slovenia;3. Department of Biochemistry, Institute of Chemistry, Faculty of Sciences, P. J. Safarik University, 04001 Kosice, Slovakia;4. EN-FIST Center of Excellence, SI-1000 Ljubljana, Slovenia;5. Faculty of Chemistry and Chemical Technology, University of Ljubljana, SI-1000 Ljubljana, Slovenia
Abstract:The exchange rate of the hydrogen-bonded guanine imino protons N(1) in the high-salt form of Poly(dG-dC) was measured by following the non-selective inversion-recovery of their 1H NMR signal at 360 MHz, in the temperature range between 77 degrees C and 90 degrees C. In a 4.5M NaCl solution, Poly(dG-dC) is believed to adapt the left-handed Z-conformation, and the results reported here represent the first quantitative measurements of this rate process for Z-DNA by Nuclear Magnetic Resonance, complementing previous measurements made by tritium exchange at 0 degrees C (Ramstein, J. and Leng, M. (1980) Nature 288, 413-414). The results confirm that this process is much slower in the Z-form, compared to the B-structure, and that this difference in rates results mainly from a large decrease in the entropy of activation for Z-DNA.
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