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Hydration Effects on the Microwave Dielectricity in Dry Poly(dA)–Poly(dT) DNA
Atsumasa Hojo1,
Hiroshi Matsui1,2,
Kei Iwamoto1,
Takeshi Yanagimachi1,
Hasanudin Abdrurakhan2,
Masateru Taniguchi3,
Tomoji Kawai3, and
Naoki Toyota1,2
1Physics Department, Graduate School of Science, Tohoku University, Sendai 980-8578
2Center for Interdisciplinary Research, Tohoku University, Sendai 980-8578
3The Institute of Scientific and Industrial Research, Osaka University, Ibaraki, Osaka 567-0047
(Received December 19, 2007; Accepted February 20, 2008; Published April 10, 2008)
Using a microwave cavity-perturbation method, the temperature dependence of the complex dielectric constant (\tildeε=ε1+iε2) at 16.3 GHz is measured on a dry poly(dA)–poly(dT) DNA sample prepared under three-different relative humidity (RH) of 0, 11 and 93%. For RH=0%, the temperature dependence of both ε1 and ε2 are explained by the rotational motion of water molecules electrostatically bonding to the negatively charged phosphate group in the primary hydration shell. The activation-type behavior in ε2 is discussed with a double-well potential for a process that the electric dipole of the hydrated water is thermally rotated to the adjacent phosphate groups. For RH=11%, ε2 takes a broad maximum at 280 K due to the collective motion of water molecules in the primary hydration shell. While these features qualitatively resemble to those of free water, the absolute values are much small due to an extremely small number of hydrated water molecules. Moreover the conformation is expected to be of A form, in which the hydration bridge could be constructed in the major groove via hydrogen bonds as suggested by previous X-ray and neutron diffraction experiments. For RH=93%, in addition to the collective motion of the primary hydration shell, a freezing process of the secondary hydration shell appears. Independently on RH, the hydrated water molecules at low temperatures around 200 K or below are hard to respond to microwave electric fields, and hence both the rotational and collective motions cannot be permitted. Approaching to 420 K, ε2 becomes suppressed converging to the same value. The suppression comes from a thermally induced dehydration resulting in eventual reduction of the hydration density down to 0.1 water molecules per nucleotide as revealed by our previous infrared spectroscopy.
©2008 The Physical Society of Japan
KEYWORDS:
DNA, dielectric constant, relaxation, hydration, microwave, water
URL:
http://jpsj.ipap.jp/link?JPSJ/77/044802/
DOI: 10.1143/JPSJ.77.044802
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