The Dramatic Effect of Water Structure on Hydration Forces and the Electrical Double Layer

Forces between hydrophilic surfaces mediated by water are important in various systems from lipid membranes and solid surfaces to colloids and macromolecules, first discovered as a significant addition to DLVO forces at the nanoscale. These “hydration forces” have been studied in great detail experimentally using osmotic stress measurements, surface force apparatus, and AFM, and they have also been the subject of multiple theories and simulations. One spectacular feature observed in experimental and simulation studies was the nonmonotonic, oscillatory decay in the forces between atomically smooth surfaces. Forces between “rougher” surfaces exhibit only quasi-exponential, monotonic decay. Here we revisit this hydration force problem by exploring the consequences of an extended phenomenological Landau–Ginzburg approach that describes nonlocal correlations in water, linking them with the key features of the wave-number k-dependent nonlocal dielectric function of water. With corresponding boundary conditions, this theory predicts the observed oscillatory decay in hydration force between ideally flat surfaces, the oscillatory mode disappearing with just a tiny roughness of the surfaces (of mean height ca. of the size of a water molecule). This study also brings an important side message. Explanation of these observations appears only possible under an assumption of two modes of polarization in water, consistent with the behavior of the response function, i.e., Lorentzian at small k and resonance-like at higher k. This resolves the “force oscillation–non-oscillation” paradigm, which is a strong, although indirect indication of the existence of these two modes. We also consider other important subjects, such as how the distribution of ions near a charged surface reacts to the propensity for overscreening oscillations due to polarized water. This is important not only for the interactions between charged surfaces but also for the fundamental understanding of the structure of the electrical double layer at electrochemical interfaces. We show that even in dilute electrolytes, the distribution of ions in the vicinity of the polarized interface follows, although not literally, preferential positions corresponding to the potential wells caused by “resonance” water layering. For a sharp interface, the theory predicts that the decaying spatial oscillation profiles extend over a 1 to 2 nm distance from the interface. With the smearing of the interface and the corresponding suppression of the resonance water layering, oscillations in the spatial distribution of ions subside, resulting in a familiar Gouy–Chapman–Stern picture. At longer distances from the interface, whether smeared or not, the ion distribution profiles become Gouy–Chapman-like. The effect of the boundary conditions on water polarization at the interface goes beyond a trivial shift of the potential of zero charge. We show that they can dramatically affect the ion distribution near the charged surface. Last, but not least, we study how the interfacial water layering influences the double layer capacitance and show the effect of the boundary conditions on the slopes of Parsons–Zobel plots, resolving some recently discussed puzzles

Satellite-derived bathymetry in optically complex waters using a model inversion approach and Sentinel-2 data

This study presents an assessment of a model inversion approach to derive shallow water bathymetry in optically complex waters, with the aim of both understanding localised capability and contributing to the global evaluation of Sentinel-2 for coastal monitoring. A dataset of 12 Sentinel-MSI images, in three different study areas along the Irish coast, has been analysed. Before the application of the bathymetric model two atmospheric correction procedures were tested: Deep Water Correction (DWC) and Case 2 Regional Coastal Color (C2RCC) processor. DWC outperformed C2RCC in the majority of the satellite images showing more consistent results. Using DWC for atmospheric correction before the application of the bathymetric model, the lowest average RMSE was found in Dublin Bay (RMSE ¼ 1.60, bias ¼ \u100000 0.51), followed by Mulroy Bay (RMSE ¼ 1.66, bias ¼ 1.30) while Brandon Bay showed the highest average error (RMSE ¼ 2.43, bias ¼ 1.86). However, when the optimal imagery selection was considered, depth estimations with a bias less than 0.1 m and a spread of 1.40 m were achieved up to 10 m. These results were comparable to those achieved by empirical tuning methods, despite not relying on any in situ depth data. This conclusion is of particular relevance as model inversion approaches might allow future modifications in crucial parts of the processing chain leading to improved results. Atmospheric correction, the selection of optimal images (e.g. low turbidity), the definition of suitably limited ranges for the per-pixel occurrence of optical constituents (phytoplankton, CDOM, backscatter) and seabed reflectances, in combination with the understanding of the specifics characteristics at each particular site, were critical steps in the derivation of satellite bathymetry

Modulation of the equilibrative nucleoside transporter by inhibitors of DNA synthesis.

Expression of the equilibrative, S-(p-nitrobenzyl)-6-thioinosine (NBMPR)-sensitive nucleoside transporter (es), a component of the nucleoside salvage pathway, was measured during unperturbed growth and following exposure to various antimetabolites at growth-inhibitory concentrations. The probe 5-(SAENTA-x8)-fluorescein is a highly modified form of adenosine incorporating a fluorescein molecule. It binds. with high affinity and specificity to the (es) nucleoside transporter at a 1:1 stoichiometry, allowing reliable estimates of es expression by flow cytometry. Using a dual labelling technique which combined the vital DNA dye Hoechst-33342 and 5-(SAENTA-x8)-fluorescein, we found that surface expression of es approximately doubled between G1 and G2 + M phases of the cell cycle. To address the question of whether es expression could be modulated in cells exposed to drugs which inhibit de novo synthesis of nucleotides, cells were exposed to antimetabolite drugs having different modes of action. Hydroxyurea and 5-fluorouracil (5-FU), which inhibit the de novo synthesis of DNA precursors, produced increases in the expression of es. In contrast, cytosine arabinoside (ara-C) and aphidicolin, which directly inhibit DNA synthesis, produced no significant increase in es expression. Thymidine (TdR), which is an allosteric inhibitor of ribonucleotide reductase that depletes dATP, dCTP and dGTP pools while repleting the dTTP pool, had no significant effect on es expression. These data suggest that surface expression of the es nucleoside transporter is regulated by a mechanism which is sensitive to the supply of deoxynucleotides. Because 5-FU (which specifically depletes dTTP pools) causes a large increase in expression whereas TdR (which depletes all precursors except dTTP) does not, this mechanism might be particularly sensitive to dTTP pools