Structure and Undulations of Escin Adsorption Layer at Water Surface Studied by Molecular Dynamics

The saponin escin, extracted from horse chestnut seeds, forms adsorption layers with high viscoelasticity and low gas permeability. Upon deformation, escin adsorption layers often feature surface wrinkles with characteristic wavelength. In previous studies, we investigated the origin of this behavior and found that the substantial surface elasticity of escin layers may be related to a specific combination of short-, medium-, and long-range attractive forces, leading to tight molecular packing in the layers. In the current study, we performed atomistic molecular dynamics simulations of 441 escin molecules in a dense adsorption layer with an area per molecule of 0.49 nm2. We found that the surfactant molecules are less submerged in water and adopt a more upright position when compared to the characteristics determined in our previous simulations with much smaller molecular models. The number of neighbouring molecules and their local orientation, however, remain similar in the different-size models. To maintain their preferred mutual orientation, the escin molecules segregate into well-ordered domains and spontaneously form wrinkled layers. The same specific interactions (H-bonds, dipole–dipole attraction, and intermediate strong attraction) define the complex internal structure and the undulations of the layers. The analysis of the layer properties reveals a characteristic wrinkle wavelength related to the surface lateral dimensions, in qualitative agreement with the phenomenological description of thin elastic sheets.

Effects of Environmental Factors on the Leaching and Immobilization Behavior of Arsenic from Mudstone by Laboratory and In Situ Column Experiments

Hydrothermally altered rocks generated from underground/tunnel projects often produce acidic leachate and release heavy metals and toxic metalloids, such as arsenic (As). The adsorption layer and immobilization methods using natural adsorbents or immobilizer as reasonable countermeasures have been proposed. In this study, two sets of column experiments were conducted, of which one was focused on the laboratory columns and other on the in situ columns, to evaluate the effects of column conditions on leaching of As from excavated rocks and on adsorption or immobilization behavior of As by a river sediment (RS) as a natural adsorbent or immobilizer. A bottom adsorption layer consisting of the RS was constructed under the excavated rock layer or a mixing layer of the excavated rock and river sediment was packed in the column. The results showed that no significant trends in the adsorption and immobilization of As by the RS were observed by comparing laboratory and in situ column experiments because the experimental conditions did not influence significant change in the leachate pH which affects As adsorption or immobilization. However, As leaching concentrations of the in situ experiments were higher than those of the laboratory column experiments. In addition, the lower pH, higher Eh and higher coexisting sulfate ions of the leachate were observed for the in situ columns, compared to the results of the laboratory columns. These results indicate that the leaching concentration of As became higher in the in situ columns, resulting in higher oxidation of sulfide minerals in the rock. This may be due to the differences in conditions, such as temperature and water content, which induce the differences in the rate of oxidation of minerals contained in the rock. On the other hand, since the leachate pH affecting As adsorption or immobilization was not influenced significantly, As adsorption or immobilization effect by the RS were effective for both laboratory and in situ column experiments. These results indicate that both in situ and laboratory column experiments are useful in evaluating leaching and adsorption of As by natural adsorbents, despite the fact that the water content which directly affects the rate of oxidation is sensitive to weathering conditions.

Galvanic corrosion inhibition from aspect of bonding orbital theory in Cu/Ru barrier CMP

In this report, the galvanic corrosion inhibition between Cu and Ru metal films is studied, based on bonding orbital theory, using pyridinecarboxylic acid groups which show different affinities depending on the electron configuration of each metal resulting from a π-backbonding. The sp2 carbon atoms adjacent to nitrogen in the pyridine ring provide π-acceptor which forms a complex with filled d-orbital of native oxides on Cu and Ru metal film. The difference in the d-orbital electron density of each metal oxide leads to different π-backbonding strength, resulting in dense or sparse adsorption on native metal oxides. The dense adsorption layer is formed on native Cu oxide film due to the full-filled d-orbital electrons, which effectively suppresses anodic reaction in Cu film. On the other hand, only a sparse adsorption layer is formed on native Ru oxide due to its relatively weak affinity between partially filled d-orbital and pyridine groups. The adsorption behaviour is investigated through interfacial interaction analysis and electrochemical interaction evaluation. Based on this finding, the galvanic corrosion behaviour between Cu and Ru during chemical mechanical planarization (CMP) processing has been controlled.

Peculiarities of alginic acid hydration in the air and in hydrophobic organic environment

The effect of the medium on the parameters of water bound to the surface of alginic acid powder was studied by low-temperature 1H NMR spectroscopy. The aim of this work was to study the effect of hydrophobic environment on the binding of water with alginic acid and to compare the parameters of the interfacial layers of water in air, in chloroform and chloroform with the addition of hydrochloric acid. It is shown that when adsorbed on the surface (500 mg/g H2O), most of it is strongly bound. It is shown that for most dispersed systems, when replacing the air with chloroform, the interfacial energy of water increases from 11.8 to 15.2 kJ/mol, which is due to the capability of weakly polar organic molecules to diffuse on the surface of solid particles, thereby reducing the interaction energy with the adsorbed surface water clusters. It is concluded that chloroform molecules cannot diffuse on the surface of alginic acid particles and affect only the structure of water clusters localized in the outer adsorption layer. In the presence of hydrochloric acid on the surface of alginic acid, a system of water clusters is formed, most of which does not dissolve hydrochloric acid, and the radii of these clusters is 2 nm, which are likely to form in the gaps between the polymer chains of polysaccharide.