期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 112, 期 2, 页码 172-175出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp711205z
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We report direct observation of an entropic effect in determining the folding of a linear dicarboxylate dianion with a flexible aliphatic chain [-O2C-(CH2)(6)-CO2-] by photoelectron spectroscopy as a function of temperature (18-300 K) and degree of solvation from 1 to 18 water molecules. A folding transition is observed to occur at 16 solvent water molecules at room temperature and at 14 solvent molecules below 120 K due to the entropic effect. The -O2C-(CH2)(6)-CO2-(H2O)(14) hydrated cluster exhibits interesting temperature-dependent behaviors, and its ratio of folded over linear conformations can be precisely controlled as a function of temperature. yielding the enthalpy and entropy differences between the two conformations. A folding barrier is observed at very low temperatures, resulting in kinetic trapping of the linear conformation. The current Work provides a simple model system to study the dynamics and entropic effect in complex systems and may be important for understanding the hydration and conformation changes of biological molecules.
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