H. Urabe et al., LOW-FREQUENCY RAMAN-SPECTRA OF LYSOZYME CRYSTALS AND ORIENTED DNA FILMS - DYNAMICS OF CRYSTAL WATER, Biophysical journal, 74(3), 1998, pp. 1533-1540
We observed low-frequency Raman spectra of tetragonal lysozyme crystal
s and DNA films, with varying water content of the samples. The spectr
a are fitted well by sums of relaxation modes and damped harmonic osci
llators in the region from similar to 1 cm(-1) to 250 cm(-1). The rela
xation modes are due to crystal water, and the distribution of relaxat
ion times is determined. In wet samples, the relaxation time of a smal
l part of the water molecules is a little longer than that of bulk wat
er. The relaxation time of a considerable part of the crystal water, w
hich belongs mainly to the secondary hydration shell, is an order of m
agnitude longer than that of bulk water. Furthermore, the relaxation t
ime of some water molecules in the primary hydration shell of semidry
samples is shorter than we expected. Thus we have shown that low-frequ
ency Raman measurements combined with properly oriented samples can gi
ve specific information on the dynamics of hydration water in the ps r
ange. On the other hand, we concluded, based on polarized Raman spectr
a of lysozyme crystals, that the damped oscillators correspond to esse
ntially intramolecular vibrational modes.