Aqueous purine solutions in the absence and presence of NaCl have been studied by vapor-pressure osmometry and high-resolution proton-magnetic-resonance spectroscopy. The presence of NaCl causes a marked change in the temperature dependence of the molal osmotic coefficient and the chemical shift of the purine resonances when compared with the corresponding quantities in purine solutions containing no added salt. In the absence of salt, the destacking of the purine is gradual as the temperature is increased, whereas there is a sharp decrease in purine stacking at approximately 42 degrees C in the presence of NaCl. This salt-induced destacking of purine is consistent with the previously noted salt-induced bulk water destructuring at temperatures above approximately 42 degrees C. This effect has been deduced from considerations of species profiles in acid-water systems as a function of temperature (Leifer, L., and Inoue, K., manuscript in preparation). The implications of this phenomenon on biological systems at elevated temperatures will be discussed.
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http://dx.doi.org/10.1021/bi00670a002 | DOI Listing |
Photochem Photobiol
September 2008
Department of Chemistry, Temple University, Philadelphia, PA, USA.
Cyclobutylpyrimidine dimers (CPDs) are the major UV photoproduct formed in DNA containing adjacent pyrimidines. These lesions can be repaired by DNA photolyase, a flavoprotein that utilizes blue light in a direct reversal of the cyclobutane ring. Previous studies have shown that the CPD is base flipped into the protein, with concomitant disruption of the substrate around the CPD.
View Article and Find Full Text PDFJ Inorg Biochem
February 2008
Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, Université Paris Descartes, UMR 8601 CNRS, 45, rue des Saints-Pères, 75270 Paris, France.
The lymphoid enhancer-binding factor 1 (LEF-1) recognizes a double-stranded 9 base-pairs (bp) long motif in DNA which is significantly bent upon binding. This bend is centered at two destacked adenines whose geometry closely resembles that of two adjacent guanines crosslinked by the antitumor drug cisplatin. It has been proposed that cisplatin-GG crosslinks could hijack high mobility group (HMG) box containing transcription factors such as LEF-1.
View Article and Find Full Text PDFJ Phys Chem B
September 2007
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA.
Cyclobutylpyrimidine dimers (CPDs) are formed between adjacent pyrimidines in DNA when it absorbs ultraviolet light. CPDs can be directly repaired by DNA photolyase (PL) in the presence of visible light. How PL recognizes and binds its substrate is still not well understood.
View Article and Find Full Text PDFJ Am Chem Soc
May 2007
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52056 Aachen, Germany.
We report the crystal structure of the DNA adenine-N6 methyltransferase, M.TaqI, complexed with DNA, showing the fluorescent adenine analog, 2-aminopurine, flipped out of the DNA helix and occupying virtually the same position in the active site as the natural target adenine. Time-resolved fluorescence spectroscopy of the crystalline complex faithfully reports this state: base flipping is accompanied by the loss of the very short ( approximately 50 ps) lifetime component associated with fully base-stacked 2-aminopurine in DNA, and 2-aminopurine is subject to considerable quenching by pi-stacking interactions with Tyr108 in the catalytic motif IV (NPPY).
View Article and Find Full Text PDFNucleic Acids Res
June 2007
Department of Pharmacology, University of Medicine and Dentistry of New Jersey, Robert Wood Johnson Medical School, 675 Hoes Lane, Piscataway, NJ 08854-5635, USA.
Oxazole-containing macrocycles represent a promising class of anticancer agents that target G-quadruplex DNA. We report the results of spectroscopic studies aimed at defining the mode, energetics and specificity with which a hexaoxazole-containing macrocycle (HXDV) binds to the intramolecular quadruplex formed by the human telomeric DNA model oligonucleotide d(T2AG3)4 in the presence of potassium ions. HXDV binds solely to the quadruplex nucleic acid form, but not to the duplex or triplex form.
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