Anomalous water molecules and mechanistic effects of water nanotube clusters confined to molecular porous crystals.
The movement of water molecules in the limited space present within nanoscale regions, which is different from the molecular motion of bulk water, is significantly affected by strong interfacial interactions with the surrounding outer walls. Hence, most of the water molecules that are confined to nanochannel spaces having widths less than ca. 2 nm can generally be classified together as "structural water". Since the motions of such water molecules are limited by interfacial interactions with the outer wall, the nature of structural water, which is strongly influenced by the interactions, will have different characteristics from normal water. For our investigations on the characteristics of structural water, we have developed a nanoporous crystal with a diameter of ca. 1.6 nm; it was constructed from 1-D hydrophilic channels by self-organization of the designed molecules. A tubelike three-layered water cluster, called a water nanotube (WNT), is formed in each internal channel space and is regulated by H-bonds with the outer wall. The WNT undergoes a glass transition (T(g) = 107 K) and behaves as a liquid; it freezes at 234 K and changes into an icelike nanotube cluster. In this study, the structure of the WNT is investigated through neutron structure analysis, and it is observed to stabilize by a mechanistic anchor effect of structural water. Furthermore, from neutron-scattering experiments, it is seen that a few water molecules around the center of the WNT move approximately with the same diffusion constant as those in bulk water; however, the residence time and average jump length are longer, despite the restrictions imposed by the H-bonding with structural water. The behavior of mobile water within a WNT is investigated; this can be used to elucidate the mechanism for the effect of structural water on vital functions on the cell surface.
Tadokoro
Makoto
M
Department of Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162-8601, Japan.
Ohhara
Takashi
T
Ohhata
Yuhki
Y
Suda
Takaaki
T
Miyasato
Yuji
Y
Yamada
Takeshi
T
Kikuchi
Tatsuya
T
Tanaka
Ichiro
I
Kurihara
Kazuo
K
Oguni
Masaharu
M
Nakasuji
Kazuhiro
K
Yamamuro
Osamu
O
Ryota
Kuroki
K
D002152:Calorimetry, Differential Scanning; D003035:Cobalt / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D008968:Molecular Conformation; D043942:Nanotubes / Q000737:chemistry*; D016062:Porosity; D014867:Water / Q000737:chemistry*
D056831:Coordination Complexes; D014867:Water; D003035:Cobalt