Entropy and dynamics of water in hydration layers of a bilayer

We compute the entropy and transport properties of water in the hydration layer of dipalmitoylphosphatidylcholine bilayer by using a recently developed theoretical scheme two-phase thermodynamic model, termed as 2PT method; S.-T. Lin et al., J. Chem. Phys. 119, 11792 (2003)] based on the translational and rotational velocity autocorrelation functions and their power spectra. The weights of translational and rotational power spectra shift from higher to lower frequency as one goes from the bilayer interface to the bulk. Water molecules near the bilayer head groups have substantially lower entropy (48.36 J/mol/K) than water molecules in the intermediate region (51.36 J/mol/K), which have again lower entropy than the molecules (60.52 J/mol/K) in bulk. Thus, the entropic contribution to the free energy change (T Delta S) of transferring an interface water molecule to the bulk is 3.65 kJ/mol and of transferring intermediate water to the bulk is 2.75 kJ/mol at 300 K, which is to be compared with 6.03 kJ/mol for melting of ice at 273 K. The translational diffusion of water in the vicinity of the head groups is found to be in a subdiffusive regime and the rotational diffusion constant increases going away from the interface. This behavior is supported by the slower reorientational relaxation of the dipole vector and OH bond vector of interfacial water. The ratio of reorientational relaxation time for Legendre polynomials of order 1 and 2 is approximately 2 for interface, intermediate, and bulk water, indicating the presence of jump dynamics in these water molecules. (C) 2010 American Institute of Physics. doi:10.1063/1.3494115]

Slow orientational dynamics of water molecules at a micellar surface

The dynamics of water molecules near an aqueous micellar interface is studied in an atomistic molecular dynamics simulation of cesium pentadecafluorooctanoate (CsPFO) in water. The dipolar orientational time correlation function (tcf) and the translational diffusion of the water molecules are investigated. Results show that both the reorientational and the translational motion of water molecules near the micelle are restricted. In particular, the orientational tcf exhibits a very slow component in the long time which is slower than its bulk value by 2 orders of magnitude. This slow decay seems to be related to the slow decay often observed in experiments. The origin of the slow decay is analyzed.

Dynamics of water at the interface of a small protein, enterotoxin

Fully atomistic molecular dynamics simulations have been carried out to investigate the correlation of biological activity with dynamics of water molecules in an aqueous protein solution of the toxic domain of enterotoxin (PDB ID: 1ETN). This is a small protein of 13 amino acid residues. Our study of this water soluble protein clearly reveals that water dynamics slows down in the hydration layer. Despite this general slowing down, water molecules in the vicinity of the second beta turn of this protein exhibit faster dynamics than those near other regions of the protein. Since this beta turn is believed to play a critical role in the receptor binding of this protein, the faster dynamics of water near the beta turn m ay have biological significance. The collective orientational dynamics of the water molecules in the protein solution exhibits a characteristic long time component of 27 ps, which agrees well with dielectric relaxation experiments.

Relaxation and jump dynamics of water at the mica interface

The orientational relaxation dynamics of water confined between mica surfaces is investigated using molecular dynamics simulations. The study illustrates the wide heterogeneity that exists in the dynamics of water adjacent to a strongly hydrophilic surface such as mica. Analysis of the survival probabilities in different layers is carried out by normalizing the corresponding relaxation times with bulk water layers of similar thickness. A 10-fold increase in the survival times is observed for water directly in contact with the mica surface and a non-monotonic variation in the survival times is observed moving away from the mica surface to the bulk-like interior. The orientational relaxation time is highest for water in the contact layer, decreasing monotonically away from the surface. In all cases the ratio of the relaxation times of the 1st and 2nd rank Legendre polynomials of the HH bond vector is found to lie between 1.5 and 1.9 indicating that the reorientational relaxation in the different water layers is governed by jump dynamics. The orientational dynamics of water in the contact layer is particularly novel and is found to undergo distinct two-dimensional hydrogen bond jump reorientational dynamics with an average waiting time of 4.97 ps. The waiting time distribution is found to possess a long tail extending beyond 15 ps. Unlike previously observed jump dynamics in bulk water and other surfaces, jump events in the mica contact layer occur between hydrogen bonds formed by the water molecule and acceptor oxygens on the mica surface. Despite slowing down of the water orientational relaxation near the surface, life-times of water in the hydration shell of the K ion are comparable to that observed in bulk salt solutions. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4717710]

The dynamics of water in hydrated white bread investigated using quasielastic neutron scattering

Kargl, Florian; Sj?str?m, J.; Fernandez-Alonso, F.; Swenson, J., (2007) 'The dynamics of water in hydrated white bread investigated using quasielastic neutron scattering', Journal of Physics: Condensed Matter 19 pp.415119 RAE2008

Meridional mixing of water masses in the Kuroshio Extension: Origins of North Pacific Intermediate Water anomalies

Senior thesis written for Oceanography 445

A description of water masses in Nootka Sound and estimation of diffusivity and upward velocity in Muchalat Inlet using temperature, salinity and dissolved oxygen

Senior thesis written for Oceanography 445

Distribution of water masses and diapycnal mixing in the Cape Verde Frontal Zone

[EN]The Cape Verde Frontal Zone separates North and South Atlantic Central Waters in the eastern North Atlantic Subtropical Gyre. CTD-O2 and shipboard ADCP data from three hydrographic sections carried out in September 2003 are used to study the structure of the front. Results show the relation between spatial variations of water masses and currents, demonstrating the importance of advection in the distribution of water masses. Diapycnal diffusivities due to double diffusion and vertical shear instabilities are also estimated. Existence of competition between the two processes through the water column is shown. Depth-averaged diffusivities suggest that salt fingering dominates diapycnal mixing, except areas of purest South Atlantic Central Water. Here, double diffusion processes are weak and, consequently, shear of the flow is the main process. Results also show that strong mixing induced by vertical shear is associated with a large intrusion found near the front.

(Table 2) Characteristics of influence of cyclonic and anticyclonic activity of water masses on hydrophysical, hydrochemical, and hydrobiological parameters in the southern part of the Black Sea in September 1996

Characteristics of the spatial structure of vertical synoptic currents were calculated from data of the density field surveys in order to estimate their influence on distribution of chlorophyll a concentration. Comparisons of chlorophyll concentration and vertical currents were implemented for two multidisciplinary surveys in the Black Sea carried out in summer, 1991 and in winter, 1994. The results showed qualitative and quantitative indications of coincidence of characteristics cited and, in particular, significant positive values of the correlation coefficient (0.65 for the summer survey and 0.83 for the winter one).

Properties of water masses, taxa abundance, and isotopic ratios of samples obtained around Svalbard archipelago

The feeding strategies of Calanus hyperboreus, C. glacialis, and C. finmarchicus were investigated in the high-Arctic Svalbard region (77-81 °N) in May, August, and December, including seasons with algal blooms, late- to post-bloom situations, and unproductive winter periods. Stable isotope and fatty acid trophic marker (FATM) techniques were employed together to assess trophic level (TL), carbon sources (phytoplankton vs. ice algae), and diet of the three Calanus species. In addition, population development, distribution, and nutritional state (i.e. storage lipids) were examined to estimate their population status at the time of sampling. In May and August, the vertical distribution of the three Calanus species usually coincided with the maximum algal biomass. Their stable isotope and fatty acid (FA) composition indicated that they all were essentially herbivores in May, when the algal biomass was highest. Their FA composition, however, revealed different food preferences. C. hyperboreus had high proportions of 18:4n3, suggesting that it fed mainly on Phaeocystis, whereas C. glacialis and C. finmarchicus had high proportions of 16:4n1, 16:1n7, and 20:5n3, suggesting diatoms as their major food source. Carbon sources (i.e. phytoplankton vs. ice algae) were not possible to determine solely from FATM techniques since ice-diatoms and pelagic-diatoms were characterised by the same FA. However, the enriched d13C values of C. glacialis and C. finmarchicus in May indicated that they fed both on pelagic- and ice-diatoms. Patterns in absolute FA and fatty alcohol composition revealed that diatoms were the most important food for C. hyperboreus and C. glacialis, followed by Phaeocystis, whereas diatoms, Phaeocystis and other small autotrophic flagellates were equally important food for C. finmarchicus. During periods of lower algal biomass, only C. glacialis exhibited evidence of significant dietary switch, with a TL indicative of omnivory (mean TL=2.4). Large spatial variability was observed in population development, distribution, and lipid store sizes in August. At the northernmost station at the southern margin of the Arctic Ocean, the three Calanus species had similarly low lipid stores as they had in May, suggesting that they ascended later in the year. In December, relatively lipid-rich specimens had TL similar to those during the peak productive season (TL~2.0), suggesting that they were hibernating and not feeding on the available refractory material available at that time of the year. In contrast, lipid-poor specimens in December had substantially high TL (TL=2.5), suggesting that they were active and possibly were feeding.