Ground-State Proton Transfer of 7-Hydroxyquinoline Confined in Biologically Relevant Water Nanopools

被引:32
作者
Park, Sun-Young [1 ]
Kwon, Oh-Hoon [1 ]
Kim, Taeg Gyum [1 ]
Jang, Du-Jeon [1 ]
机构
[1] Seoul Natl Univ, Sch Chem, Seoul 151742, South Korea
基金
新加坡国家研究基金会;
关键词
ACID-BASE REACTIONS; REVERSE MICELLES; SOLVATION DYNAMICS; AEROSOL-OT; 7-HYDROXYQUINOLINE-CENTER-DOT(NH3)(N) CLUSTERS; POLY(2-HYDROXYETHYL METHACRYLATE); AQUEOUS; 7-HYDROXYQUINOLINE; TAUTOMERIZATION DYNAMICS; SUPER PHOTOACIDS; EXCITED SINGLET;
D O I
10.1021/jp903693f
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
The ground-state reverse proton transfer of 7-hydroxyquinoline catalyzed by water confined in AOT reverse micelles has been investigated by measuring time-resolved transient-absorption spectra and kinetic profiles. The transfer time is profoundly retarded in water nanopools compared with that in bulk water (26 mu s) although it diminishes with the size increase of the water nanopool. The spectral-shift time of tautomeric transient absorption agrees well with the proton transfer time. The probe molecule is subject to the local gradient of polarity, whose magnitude is altered with the sizes of water nanopools. Accordingly, the observations made in this study indicate the multidimensional character of reaction coordinates, in which solvent polarization coupled to charge transfer plays a seminal role in the control of overall proton-transfer dynamics. The retardation of proton transfer in water nanopools is ascribed to the increased formation energy of a charge-transferred optimal configuration, which is prerequisite to facile intrinsic proton transfer via tunneling.
引用
收藏
页码:16110 / 16115
页数:6
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