2D IR photon echo of azido-probes for biomolecular dynamics.
The vibrations in the azido-, N(3), asymmetric stretching region of 2'-azido-2'-deoxyuridine (N(3)dU) are examined by two-dimensional infrared spectroscopy. In water and tetrahydrofuran (THF), the spectra display a single sharp diagonal peak that shows solvent sensitivity. The frequency-frequency correlation time in water is 1.5 ps, consistent with H-bond making and breaking dynamics. The 2D IR spectrum is reproduced for N(3)dU in water based on a model correlation function and known linear response functions. Its large extinction coefficient, vibrational frequency outside the protein and nucleic acid IR absorption, and sensitivity to water dynamics render -N(3) a very useful probe for 2D IR and other nonlinear IR studies: its signal is ca. 100 times that of nitriles.
Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USA.
Matthew J
MJ
Tucker
Xin Sonia
XS
Gai
Edward E
EE
Fenlon
Scott H
SH
Brewer
Robin M
RM
Hochstrasser
D001386:Azides / Q000737:chemistry*; D003857:Deoxyuridine / Q000031:analogs & derivatives* / Q000737:chemistry; D005663:Furans / Q000737:chemistry*; D006860:Hydrogen Bonding; D056004:Molecular Dynamics Simulation; D009570:Nitriles / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D014867:Water / Q000737:chemistry*
D001386:Azides; D005663:Furans; D009570:Nitriles; D014867:Water; C114286:2'-azido-2'-deoxyuridine; C018674:tetrahydrofuran; D003857:Deoxyuridine