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

Autor:	Ronald G. Lawler, Sho-ichi Iwamatsu, Nobuyuki Shibata, Michael Frunzi, Anne M. Baldwin, Nicholas J. Turro
Rok vydání:	2011
Předmět:	Solvent Dissociation constant chemistry.chemical_compound Properties of water Fullerene chemistry Proton NMR Physical chemistry Organic chemistry Nuclear magnetic resonance spectroscopy Physical and Theoretical Chemistry Spectroscopy Equilibrium constant
Zdroj:	The Journal of Physical Chemistry A. 115:735-740
ISSN:	1520-5215 1089-5639
Popis:	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) × 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,ass) = 27 kJ mol(-1), E(a,diss) = 50 kJ mol(-1)). The equilibrium constants and thermodynamic parameters in various solvents (benzene-d(6), 1,2-dichlorobenzene-d(4), and dimethylsulfoxide-d(6)) were estimated using 1D-(1)H NMR spectroscopy. The parameters were dependent on the polarity of the solvent; ΔH depended linearly on the solvent polarity, becoming increasingly unfavorable as polarity increased. Mixtures of polar dimethylsulfoxide-d(6) in less polar 1,1,2,2-tetrachloroethane-d(2) showed a similar trend.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::b049c436c718b93e83d914e0e5de97a1 https://doi.org/10.1021/jp110832m Zobrazit plný text záznamu