title: Two-Dimensional Infrared Study of Vibrational Coupling between Azide and Nitrile Reporters in a RNA Nucleoside.
abstract: The vibrations in the azide, N3, asymmetric stretching region and nitrile, CN, symmetric stretching region of 2'-azido-5-cyano-2'-deoxyuridine (N3CNdU) are examined by two-dimensional infrared (2D IR) spectroscopy. At earlier waiting times, the 2D IR spectrum shows the presence of both vibrational transitions along the diagonal and off-diagonal cross peaks indicating vibrational coupling. The coupling strength is determined from the off-diagonal anharmonicity to be 66 cm(-1) for the intramolecular distance of ∼7.9 Å, based on a structural map generated for this model system. In addition, the frequency-frequency correlation decay is detected, monitoring the solvent dynamics around each individual probe position. Overall, these vibrational reporters can be utilized in tandem to simultaneously track global structural information and fast structural fluctuations.
authors: Department of Chemistry, University of Nevada , Reno, Nevada 89557, United States.
authors: Andrew J
authors: AJ
authors: Schmitz
authors: Department of Chemistry, University of Nevada , Reno, Nevada 89557, United States.
authors: David G
authors: DG
authors: Hogle
authors: Department of Chemistry, Franklin & Marshall College , Lancaster, Pennsylvania 17604-3003, United States.
authors: Xin Sonia
authors: XS
authors: Gai
authors: Department of Chemistry, Franklin & Marshall College , Lancaster, Pennsylvania 17604-3003, United States.
authors: Edward E
authors: EE
authors: Fenlon
authors: Department of Chemistry, Franklin & Marshall College , Lancaster, Pennsylvania 17604-3003, United States.
authors: Scott H
authors: SH
authors: Brewer
authors: Department of Chemistry, University of Nevada , Reno, Nevada 89557, United States.
authors: Matthew J
authors: MJ
authors: Tucker
mesh_terms: D001386:Azides / Q000737:chemistry*; D009570:Nitriles / Q000737:chemistry*; D011789:Quantum Theory; D012313:RNA / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D014732:Vibration
chemical_list: D001386:Azides; D009570:Nitriles; D012313:RNA