Recently, we have found a reversible transition between the dispersion and aggregation states of solute molecules in aqueous solutions confined in nanoscale geometry, where solutes exhibit distinct behavior in a new a...Recently, we have found a reversible transition between the dispersion and aggregation states of solute molecules in aqueous solutions confined in nanoscale geometry, where solutes exhibit distinct behavior in a new association state from that in the dispersion and aggregation states observed usually in macroscopic systems. However, it remains unknown whether this new association state of solute molecules found in nanoconfined systems would vanish with the system size increasing and approaching the macroscopic scale. Here, we achieve the phase diagram of solute association states by making the analyses of Gibbs free energy of solutes in nanoconfined aqueous solutions in detail. In the phase diagram, we observe a closed regime with a finite system size of nanoconfined aqueous solutions and a solute concentration range, only in which there exists the new association state of solutes with the reversible transition between the aggregation and dispersion states, and there indeed exists an upper limit of the system size for the new association state, around several tens nanometers. These findings regarding the intimate connection between the system size and the solute association behavior provides the comprehensive understanding of the association dynamics of solutes in nanoconfined environment.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos. 11290164 and11574339)the National Science Fund for Outstanding Young Scholars (Grant No. 11422542)Shanghai Supercomputer Center of China and Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase)
文摘Recently, we have found a reversible transition between the dispersion and aggregation states of solute molecules in aqueous solutions confined in nanoscale geometry, where solutes exhibit distinct behavior in a new association state from that in the dispersion and aggregation states observed usually in macroscopic systems. However, it remains unknown whether this new association state of solute molecules found in nanoconfined systems would vanish with the system size increasing and approaching the macroscopic scale. Here, we achieve the phase diagram of solute association states by making the analyses of Gibbs free energy of solutes in nanoconfined aqueous solutions in detail. In the phase diagram, we observe a closed regime with a finite system size of nanoconfined aqueous solutions and a solute concentration range, only in which there exists the new association state of solutes with the reversible transition between the aggregation and dispersion states, and there indeed exists an upper limit of the system size for the new association state, around several tens nanometers. These findings regarding the intimate connection between the system size and the solute association behavior provides the comprehensive understanding of the association dynamics of solutes in nanoconfined environment.
