A vibrational probe for local nucleic acid environments: 5-cyano-2'-deoxyuridine.
Nitriles have been shown to be effective vibrational probes of local environments in proteins but have yet to be fully utilized for the study of nucleic acids. The potential utility of 5-cyano-2'-deoxyuridine ( 1) as a probe of local nucleic acid environment was investigated by measuring the dependence of the IR nitrile stretching frequency (nu CN), line shape, and absorbance on solvent and temperature. The nu CN was found to be sensitive to solvent with an observed blue shift of 9.2 cm (-1) in going from THF to water. The dependence of the nitrile IR absorbance band was further investigated in water-THF mixtures. Global line shape analysis, difference FTIR spectroscopy, and singular value decomposition (SVD) were used to show the presence of three distinct local environments around the nitrile group of 1 in these mixtures. A modest blue shift in nu CN was observed upon a hydrogen-bond-mediated heterodimer formation between 2 (a silyl ether analogue of 1) and 2,6-diheptanamido-pyridine ( 3a) in chloroform. The intrinsic temperature dependence of the nu CN was found to be minimal and linear over the temperature range studied. The experimental studies were complemented by density functional theory (DFT) calculations on the dependence of the nitrile stretching frequency on solute-solvent interactions and upon heterodimer formation with model systems.
Watson
Matthew D
MD
Gai
Xin Sonia
XS
Gillies
Anne T
AT
Brewer
Scott H
SH
Fenlon
Edward E
EE
D003857:Deoxyuridine / Q000031:analogs & derivatives* / Q000737:chemistry; D006860:Hydrogen Bonding; D009570:Nitriles / Q000737:chemistry; D009691:Nucleic Acid Denaturation; D009696:Nucleic Acids / Q000737:chemistry* / Q000378:metabolism; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D044366:Transition Temperature; D014732:Vibration
C448390:5-cyano-2'-deoxyuridine; D009570:Nitriles; D009696:Nucleic Acids; D012997:Solvents; D003857:Deoxyuridine