DOI: 10.1073/pnas.1807208115
论文题名: Computational discovery of chemically patterned surfaces that effect unique hydration water dynamics
作者: Monroe J.I. ; Scott Shell M.
刊名: Proceedings of the National Academy of Sciences of the United States of America
ISSN: 0027-8424
出版年: 2018
卷: 115, 期: 32 起始页码: 8093
结束页码: 8098
语种: 英语
英文关键词: computational inverse design
; hydration dynamics
; interfaces
; Molecular dynamics simulations
; water
Scopus关键词: methane
; water
; algorithm
; Article
; catalysis
; chemically patterned surface
; computer analysis
; controlled study
; diffusion
; entropy
; hydration
; hydrogen bond
; hydrophilicity
; molecular dynamics
; priority journal
; solid
; surface property
; thermodynamics
英文摘要: The interactions of water with solid surfaces govern their apparent hydrophobicity/hydrophilicity, influenced at the molecular scale by surface coverage of chemical groups of varied nonpolar/polar character. Recently, it has become clear that the precise patterning of surface groups, and not simply average surface coverage, has a significant impact on the structure and thermodynamics of hydration layer water, and, in turn, on macroscopic interfacial properties. Here we show that patterning also controls the dynamics of hydration water, a behavior frequently thought to be leveraged by biomole-cules to influence functional dynamics, but yet to be generalized. To uncover the role of surface heterogeneities, we couple a genetic algorithm to iterative molecular dynamics simulations to design the patterning of surface functional groups, at fixed coverage, to either minimize or maximize proximal water diffusivity. Optimized surface configurations reveal that clustering of hydrophilic groups increases hydration water mobility, while dispersing them decreases it, but only if hydrophilic moieties interact with water through directional, hydrogen-bonding interactions. Remarkably, we find that, across different surfaces, coverages, and patterns, both the chemical potential for inserting a methane-sized hydrophobe near the interface and, in particular, the hydration water orientational entropy serve as strong predictors for hydration water diffusivity, suggesting that these simple thermodynamic quantities encode the way surfaces control water dynamics. These results suggest a deep and intriguing connection between hydration water thermodynamics and dynamics, demonstrating that subnanometer chemical surface patterning is an important design parameter for engineering solid−water interfaces with applications spanning separations to catalysis. © 2018 National Academy of Sciences. All rights reserved. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/163681
Appears in Collections: 气候变化与战略
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作者单位: Monroe, J.I., Department of Chemical Engineering, University of California, Santa Barbara, CA 93106; Scott Shell, M., Department of Chemical Engineering, University of California, Santa Barbara, CA 93106
Recommended Citation:
Monroe J.I.,Scott Shell M.. Computational discovery of chemically patterned surfaces that effect unique hydration water dynamics[J]. Proceedings of the National Academy of Sciences of the United States of America,2018-01-01,115(32)