Structure and orientation of water molecules at model hydrophobic surfaces with curvature: From graphene sheets to carbon nanotubes and fullerenes

Alarcón, L. M.; Malaspina, David C.; Schulz, Erica P.; Frechero, M.A.; Appignanesi, Gustavo A.

doi:10.1016/j.chemphys.2011.07.019

Cited by 40 publications

(46 citation statements)

References 44 publications

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“…In the latter case, the interface becomes orientationally disordered, a tendency that gets exacerbated with the decrease in curvature radius. 20 On the other hand, bulk hydrophobic interfaces have been reported to be basic. 21 The concept of functionalized episteric water is introduced in this work and the results invite a revision of the purported elementary steps in biochemical reactions.…”

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confidence: 99%

Communication: Chemical functionality of interfacial water enveloping nanoscale structural defects in proteins

Fernández

2014

The Journal of Chemical Physics

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Building upon a non-Debye multiscale treatment of water dielectrics, this work reveals the biochemical role of interfacial water enveloping nanoscale structural defects in soluble proteins, asserting its role as a chemical base. This quasi-reactant status is already implied by the significant concentration of structural defects in the vicinity of an enzymatically active site, delineating their role as promoters or enhancers of catalytic activity.

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confidence: 99%

Communication: Chemical functionality of interfacial water enveloping nanoscale structural defects in proteins

Fernández

2014

The Journal of Chemical Physics

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“…The behavior of water at interfaces and under nanoconfinement is quite different from that at bulk conditions, as many experimental and theoretical studies have demonstrated (Huang and Chandler 2000;Huang et al 2003;Bizzarri and Cannistraro 2002;Vitkup et al 2000;Choudhury and Montgomery Pettitt 2005;Stanley et al 2007;Giovambattista et al 2008;Rasaiah et al 2008;Berne et al 2009;Malaspina et al 2010;Alarcón et al 2011;Gelman Constantin et al 2011;Accordino et al 2012a, c;Schulz et al 2011). However, the picture of (nano) confined water is still far from being complete (Giovambattista et al 2012;Rasaiah et al 2008;Berne et al 2009;Schulz et al 2011;Alarcón et al 2014).…”

Section: Introductionmentioning

confidence: 92%

“…Thus, since in complex realistic systems both geometry and chemistry affect its hydration properties, it becomes convenient to first separate them by focusing in simple systems to study the role of geometry to then consider more realistic contexts like, for example, proteins and phospholipid membranes. In this section we review our computational work on model hydrophobic surfaces: a graphene sheet, single-walled carbon nanotubes of different radii and C 60 and C 20 fullerenes (Malaspina et al 2010;Alarcón et al 2011;Accordino et al 2011aAccordino et al , 2012aGelman Constantin et al 2011;Schulz et al 2011). Given the chemical similarity between the three kinds of systems under study, the hydration of the graphene sheet should constitute the limit of infinite curvature radius for both the nanotubes and the fullerenes.…”

Section: Hydration and Geometrymentioning

confidence: 99%

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Hydration and Nanoconfined Water: Insights from Computer Simulations

Alarcón

Fris

Morini

et al. 2015

Subcellular Biochemistry

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The comprehension of the structure and behavior of water at interfaces and under nanoconfinement represents an issue of major concern in several central research areas like hydration, reaction dynamics and biology. From one side, water is known to play a dominant role in the structuring, the dynamics and the functionality of biological molecules, governing main processes like protein folding, protein binding and biological function. In turn, the same principles that rule biological organization at the molecular level are also operative for materials science processes that take place within a water environment, being responsible for the self-assembly of molecular structures to create synthetic supramolecular nanometrically-sized materials. Thus, the understanding of the principles of water hydration, including the development of a theory of hydrophobicity at the nanoscale, is imperative both from a fundamental and an applied standpoint. In this work we present some molecular dynamics studies of the structure and dynamics of water at different interfaces or confinement conditions, ranging from simple model hydrophobic interfaces with different geometrical constraints (in order to single out curvature effects), to self-assembled monolayers, proteins and phospholipid membranes. The tendency of the water molecules to sacrifice the lowest hydrogen bond (HB) coordination as possible at extended interfaces is revealed. This fact makes the first hydration layers to be highly oriented, in some situations even resembling the structure of hexagonal ice. A similar trend to maximize the number of HBs is shown to hold in cavity filling, with small subnanometric hydrophobic cavities remaining empty while larger cavities display an alternation of filled and dry states with a significant inner HB network. We also study interfaces with complex chemical and geometrical nature in order to determine how different conditions affect the local hydration properties. Thus, we show some results for protein hydration and, particularly, some preliminary studies on membrane hydration. Finally, calculations of a local hydrophobicity measure of relevance for binding and self-assembly are also presented. We then conclude with a few words of further emphasis on the relevance of this kind of knowledge to biology and to the design of new materials by highlighting the context-dependent and non-additive nature of different non-covalent interactions in an aqueous nanoenvironment, an issue that is usually greatly overlooked.

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“…1), as indicated in [9] for fully hydrogenated graphene. By contrast, water in contact with pure graphene appears to present preferentially a lone electron pair to the surface [17]. In essence, we compute the interfacial tension arising from the hydrogen bonding frustration of interfacial water, and take into account the fact that this tension is minimized by the adsorbed hydroxide ions, whose dangling donated proton is 88.3% less frustrated than the water counterpart (Fig.…”

Section: Theory/calculationsmentioning

confidence: 98%

Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces

Fernández

2015

Physics Letters A

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Structure and orientation of water molecules at model hydrophobic surfaces with curvature: From graphene sheets to carbon nanotubes and fullerenes

Cited by 40 publications

References 44 publications

Communication: Chemical functionality of interfacial water enveloping nanoscale structural defects in proteins

Communication: Chemical functionality of interfacial water enveloping nanoscale structural defects in proteins

Hydration and Nanoconfined Water: Insights from Computer Simulations

Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces

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