Dynamical Crossover and Breakdown of the Stokes−Einstein Relation in Confined Water and in Methanol-Diluted Bulk Water

2010 ◽  
Vol 114 (5) ◽  
pp. 1870-1878 ◽  
Author(s):  
Francesco Mallamace ◽  
Caterina Branca ◽  
Carmelo Corsaro ◽  
Nancy Leone ◽  
Jeroen Spooren ◽  
...  
Keyword(s):  
Bulk Water ◽  
Einstein Relation ◽  
Confined Water ◽  
Dynamical Crossover

The dynamical crossover phenomenon in bulk water, confined water and protein hydration water

2012 ◽  
Vol 24 (6) ◽  
pp. 064103 ◽  
Author(s):  
Francesco Mallamace ◽  
Carmelo Corsaro ◽  
Piero Baglioni ◽  
Emiliano Fratini ◽  
Sow-Hsin Chen
Keyword(s):  
Bulk Water ◽  
Protein Hydration ◽  
Hydration Water ◽  
Confined Water ◽  
Dynamical Crossover

scholarly journals Water Thermodynamics and Its Effects on the Protein Stability and Activity

Biophysica ◽  
2021 ◽  
Vol 1 (4) ◽  
pp. 413-428
Author(s):  
Francesco Mallamace ◽  
Domenico Mallamace ◽  
Sow-Hsin Chen ◽  
Paola Lanzafame ◽  
Georgia Papanikolaou
Keyword(s):  
Dynamic Properties ◽  
Einstein Relation ◽  
Protein Hydration ◽  
Hydration Water ◽  
Confined Water ◽  
Scientific Interest ◽  
Transport Parameters ◽  
Glass Forming ◽  
Protein Properties ◽  
Dynamical Crossover

We discuss a phenomenon regarding water that was until recently a subject of scientific interest: i.e., the dynamical crossover, from the fragile to strong glass forming material, for both bulk and protein hydration water. Such crossover is characterized by a temperature TL in which significant dynamical changes like the decoupling (or the violation of the Stokes-Einstein relation) of homologous transport parameters, e.g., the density relaxation time τ and the viscosity η, occur in the system. On this respect we considered the dynamic properties of water-protein systems. More precisely, we focused our study on proteins and their hydration water, as far as bulk and confined water. In order to clarify the effects of the water dynamical crossover on the protein properties we considered and discussed in a comparative way previous and new experimental data, obtained from different techniques and molecular dynamic simulation (MD). We pointed out the reasons for different dynamical findings from the use of different experimental techniques.

scholarly journals Water confined in solutions of biological relevance

2020 ◽  
Vol 92 (10) ◽  
pp. 1563-1574
Author(s):  
Marie-Claire Bellissent-Funel
Keyword(s):  
Aqueous Solutions ◽  
Bulk Water ◽  
Biological Macromolecules ◽  
Organic Solutes ◽  
Confined Water ◽  
The Past ◽  
Structure And Dynamics ◽  
Biological Relevance ◽  
The Stability

AbstractIn many relevant situations, water is not in its bulk form but instead attached to some substrates or filling some cavities. We shall call water in the latter environment confined water as opposed to bulk water. It is known that the confined water is essential for the stability and the function of biological macromolecules. In this paper, we provide a review of the experimental and computational advances over the past decades concerning the understanding of the structure and dynamics of water confined in aqueous solutions of biological relevance. Examples involving water in solution of organic solutes (cryoprotectants such as dimethylsulfoxide (DMSO), sugars such as trehalose) are provided.

Some Considerations on Confined Water: The Thermal Behavior of Transport Properties in Water-Glycerol and Water-Methanol Mixtures

MRS Advances ◽  
2016 ◽  
Vol 1 (26) ◽  
pp. 1891-1902 ◽  
Author(s):  
Francesco Mallamace ◽  
Carmelo Corsaro ◽  
Domenico Mallamace ◽  
Cirino Vasi ◽  
Sebastiano Vasi ◽  
...  
Keyword(s):  
Hydrophobic Interactions ◽  
Molar Fraction ◽  
Relaxation Times ◽  
Confined Water ◽  
Self Diffusion ◽  
Excess Value ◽  
Water Glycerol ◽  
System Properties ◽  
Dynamical Crossover

ABSTRACTWe discuss recent literature data on the relaxation times (the primary tα), viscosity, and self-diffusion in water-glycerol and water-methanol mixtures across a wide temperature range from the stable water phase to the deep supercooled regime (373–147K). In particular, to clarify the role of hydrophilicity interactions (the hydrogen bonds) and hydrophobic interactions we study the mixture in terms of the water molar fraction (XW) with fixed temperatures at 5K steps across the entire composition range, and we find a marked deviation from the ideal thermodynamic behavior of the transport functions. This deviation is strongly T and XW dependent and spans values that range from two orders of magnitude at the highest temperature to more than five in the deeply supercooled regime (more precisely, at ≃200K). We analyze these deviations in terms of how the measured values differ from ideal values and find that the hydrogen-bonding water network dominates system properties up to XW = 0.3. We also examine an Arrhenius plot of the maximum excess value (Δtα(T) vs. 1/T) and find two significant changes due to water: one at the dynamical crossover temperature (TL ≃ 225K, i.e., the locus of the Widom line), and one at T ≃ 315K (the water isothermal compressibility χT minimum).

scholarly journals Anomalously low dielectric constant of confined water

Science ◽  
2018 ◽  
Vol 360 (6395) ◽  
pp. 1339-1342 ◽  
Author(s):  
L. Fumagalli ◽  
A. Esfandiar ◽  
R. Fabregas ◽  
S. Hu ◽  
P. Ares ◽  
...  
Keyword(s):  
Dielectric Constant ◽  
Bulk Water ◽  
Dead Layer ◽  
Low Dielectric Constant ◽  
Interfacial Water ◽  
Confined Water ◽  
Low Dielectric ◽  
Out Of Plane ◽  
Atomically Flat ◽  
Rotational Freedom

The dielectric constant ε of interfacial water has been predicted to be smaller than that of bulk water (ε ≈ 80) because the rotational freedom of water dipoles is expected to decrease near surfaces, yet experimental evidence is lacking. We report local capacitance measurements for water confined between two atomically flat walls separated by various distances down to 1 nanometer. Our experiments reveal the presence of an interfacial layer with vanishingly small polarization such that its out-of-plane ε is only ~2. The electrically dead layer is found to be two to three molecules thick. These results provide much-needed feedback for theories describing water-mediated surface interactions and the behavior of interfacial water, and show a way to investigate the dielectric properties of other fluids and solids under extreme confinement.

scholarly journals Ice-like water supports hydration forces and eases sliding friction

2016 ◽  
Vol 2 (8) ◽  
pp. e1600763 ◽  
Author(s):  
Nishad Dhopatkar ◽  
Adrian P. Defante ◽  
Ali Dhinojwala
Keyword(s):  
Sliding Friction ◽  
Water Structure ◽  
Water Layer ◽  
Bulk Water ◽  
Interfacial Water ◽  
Confined Water ◽  
Surfactant Monolayers ◽  
Sum Frequency ◽  
Charged Surfaces ◽  
Hydration Forces

The nature of interfacial water is critical in several natural processes, including the aggregation of lipids into the bilayer, protein folding, lubrication of synovial joints, and underwater gecko adhesion. The nanometer-thin water layer trapped between two surfaces has been identified to have properties that are very different from those of bulk water, but the molecular cause of such discrepancy is often undetermined. Using surface-sensitive sum frequency generation (SFG) spectroscopy, we discover a strongly coordinated water layer confined between two charged surfaces, formed by the adsorption of a cationic surfactant on the hydrophobic surfaces. By varying the adsorbed surfactant coverage and hence the surface charge density, we observe a progressively evolving water structure that minimizes the sliding friction only beyond the surfactant concentration needed for monolayer formation. At complete surfactant coverage, the strongly coordinated confined water results in hydration forces, sustains confinement and sliding pressures, and reduces dynamic friction. Observing SFG signals requires breakdown in centrosymmetry, and the SFG signal from two oppositely oriented surfactant monolayers cancels out due to symmetry. Surprisingly, we observe the SFG signal for the water confined between the two charged surfactant monolayers, suggesting that this interfacial water layer is noncentrosymmetric. The structure of molecules under confinement and its macroscopic manifestation on adhesion and friction have significance in many complicated interfacial processes prevalent in biology, chemistry, and engineering.

scholarly journals Crystalline Hydrogen Bond of Water Molecules Confined in a Metal-Organic Framework

2021 ◽  
Author(s):  
Jinhee Bae ◽  
Sun Ho Park ◽  
Dohyun Moon ◽  
Nak Cheon Jeong
Keyword(s):  
Hydrogen Bond ◽  
Metal Organic Framework ◽  
Bulk Water ◽  
Coordination Bond ◽  
Ex Situ ◽  
Water Molecules ◽  
Confined Water ◽  
Metal Organic ◽  
Cu Bonding ◽  
Organic Framework

Abstract Hydrogen bond (H-bond) of water molecules confined in nanopores is of particular interest because it is expected to exhibit chemical features different from bulk water molecules due to its interaction with the wall lining the pores. Herein, we show a crystalline behavior of hydrogen-bonded water molecules residing in the nanocages of a paddlewheel metal-organic framework, providing in situ and ex situ synchrotron single-crystal X-ray diffraction and Raman spectroscopy studies. The crystalline H-bond is demonstrated by proving the vibrational chain connectivity arising between hydrogen bonding and paddlewheel Cu−Cu bonding in sequentially connected Cu–Cu⋅⋅⋅⋅⋅coordinating H2O⋅⋅⋅⋅⋅H-bonded H2O and proving the spatial ordering of H-bonded water molecules at room temperature, where they are anticipated to be disordered with a high degree of freedom in their molecular motions. Additionally, we show a substantial distortion of the paddlewheel Cu2+ centers that arises simultaneously with water coordination. Also, we suggest the dynamic coordination bond character of the H-bond of the confined water molecules, by which an H-bond transitions to a coordination bond at the Cu2+ center instantaneously after dissociating a previously coordinated water molecule.

Structure and Dynamics of Water Adsorbed in Carbon Nanotubes: A Joint Neutron-Scattering and Molecular-Dynamics Study

2004 ◽  
Vol 840 ◽  
Author(s):  
Nicolas R. de Souza ◽  
Alexander I. Kolesnikov ◽  
Chun-Keung Loong ◽  
Alexander P. Moravsky ◽  
Raouf O. Loutfy ◽  
...  
Keyword(s):  
Molecular Dynamics ◽  
Hydrogen Bond ◽  
Freezing Point ◽  
Mean Square Displacement ◽  
Anomalous Behavior ◽  
Bulk Water ◽  
Confined Water ◽  
Hydrogen Atoms ◽  
Spatial And Temporal Scales ◽  
Wide Range

ABSTRACTThe advent of nanocarbons, from single- and multiple-walled nanotubes to nanohorns, avails model studies of confined molecules on the nanoscale. Water encapsulated inside the quasi-one-dimensional channels of these materials is expected to exhibit anomalous behavior due to the unique geometry of nanotubes and the weak interaction between the water molecules and the carbon atoms. We have employed neutron small-to-wide angle diffraction, quasielastic and inelastic scattering in conjunction with molecular-dynamics simulations to characterize the structures and dynamics of water adsorbed in open-ended single- and double-walled nanotubes over a wide range of spatial and temporal scales. We find that a square-ice sheet wrapped next to the inner nanotube wall and a water chain in the interior are the key structural elements of nanotube-confined water/ice. This configuration results in a hydrogen-bond connectivity that markedly differs from that in bulk water. This significantly softened hydrogen-bond network manifests in strong energy shifts of the observed and simulated inter- and intra-molecular vibrations. The very large mean-square displacement of hydrogen atoms observed experimentally and the strong anharmonicity inferred from simulations explain the fluid-like behavior at temperatures far below the freezing point of normal water.

Supramolecular Nanotube Hosts for Encapsulation of 10-nm-Scale Objects

2006 ◽  
Vol 922 ◽  
Author(s):  
Toshimi Shimizu
Keyword(s):  
Self Assembly ◽  
Solvent Polarity ◽  
Bulk Water ◽  
Confined Water ◽  
Time Resolved ◽  
Capillary Action ◽  
Aqueous Dispersions ◽  
Hydrogen Bond Networks ◽  
Lipid Nanotube ◽  
Positively Charged

AbstractSupramolecular nanotube hosts with precisely controlled inner or outer diameters have been synthesized by self-assembly of cardanol-based glycolipids, glucopyranosylamide lipids, or glucose-based unsymmetrical bolaamphiphiles. Time-resolved fluorescent measurement using 8-anilinonaphtahalene-1-sulfonate (ANS) as a probe revealed that the water confined in a cardanol-based glycolipid nanotube has relatively lower solvent polarity than bulk water, which corresponds to that of 1-propanol. Extensively developed hydrogen bond networks also characterize the confined water in comparison to the case in bulk water. Encapsulation ability of the glucopyranosylamide lipid nanotube, which depends on capillary action, has been examined by filling the lyophilized lipid nanotubes with aqueous dispersions of gold or silver nanocrystals, ferritin, or magnetic crystals. We have also succeeded in filling the unsymmetrical bolaamphiphile nanotube, which possesses positively charged inner surfaces, with negatively charged polymer beads or ferritin without depending on capillary action.

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