Kinetics and Solvent-Dependent Thermodynamics of Water Capture by a Fullerene-Based Hydrophobic Nanocavity

被引：16

作者：

Frunzi, Michael ^{[1
]}

Baldwin, Anne M. ^{[1
]}

Shibata, Nobuyuki ^{[2
]}

Iwamatsu, Sho-Ichi ^{[2
]}

Lawler, Ronald G. ^{[3
]}

Turro, Nicholas J. ^{[1
]}

机构：

[1] Columbia Univ, Dept Chem, New York, NY 10027 USA

[2] Nagoya Univ, Grad Sch Environm Studies, Chikusa Ku, Nagoya, Aichi 4648601, Japan

[3] Brown Univ, Dept Chem, Providence, RI 02912 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2011年 / 115卷 / 05期

基金：

美国国家科学基金会; 日本学术振兴会;

关键词：

MOLECULES; ENCAPSULATION; NANOTUBES; CHEMISTRY; CLUSTERS; CAVITIES; BINDING; METHANE; NMR;

D O I：

10.1021/jp110832m

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Kinetic and thermodynamic properties of water encapsulation from organic solution by an open-cage [60]fullerene derivative have been investigated. 2D exchange NMR spectroscopy (EXSY) measurements were employed to determine the association and dissociation constants at 300 330 K (k(a) = 4.3 M-1 x s(-1) and k(d) = 0.42 s(-1) at 300 K) in 1,1,2,2-tetrachloroethane-d(2) as well as the activation energies (E-a,E-ass = 27 kJ mol(-1) E-a,E-diss 50 kJ mol(-1)). The equilibrium constants and thermodynamic parameters in various solvents (benzene-d(6), 1,2-dichlorobenzene-d(4), and dimethylsulfwdde-d(6)) were estimated using 1D-H-1 NMR spectroscopy. The parameters were dependent on the polarity of the solvent; Delta H depended linearly on the solvent polarity, becoming increasingly unfavorable as polarity increased. Mixtures of polar dimethylsulfoxide-do in less polar 1,1,2,2-tetrachloroethane-d(2) showed a similar trend.

引用

页码：735 / 740

页数：6

共 40 条

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