Search results for "molecule"
showing 10 items of 5162 documents
The Silica-Water Interface: How the Silanols Determine the Surface Acidity and Modulate the Water Properties.
2015
Silica is the most abundant metal oxide and the main component of the Earth's crust. Its behavior in contact with water plays a critical role in a variety of geochemical and environmental processes. Despite its key role, the details of the aqueous silica interface at the microscopic molecular level are still elusive. Here we provide such a detailed understanding of the molecular behavior of the silica-water interface, using density functional theory based molecular dynamics (DFTMD) simulations, where a consistent treatment of the electronic structure of solvent and surface is provided. We have calculated the acidity of the silanol groups at the interface directly from the DFTMD simulations,…
Compounds of tungsten(VI) with citric acid: A spectrophotometric, polarimetric and hydrogen-1, carbon-13 N.M.R. study of the formation and interconve…
1986
Tungsten(VI)-citrate complexes, which occur in aqueous solution, were studied by polarimetric and absorbance measurements. The pH of the medium is the principal variable controlling complex formation and interconversion equilibria. At high pH (>6), the stable complexes are monomers with 1∶2 and 1∶1 stoichiometry, depending on the tungsten(VI)-citrate ratio, while at lower pH two different dinuclear complexes are formed. The intervals of existence of these species with the pH, the number of equivalents of acid necessary for their formation, as well as the conditional stability constant, have also been calculated. The structure of these compounds have been investigated by1H and13C-n.m.r. spec…
Physical origin of Na+/Cl− selectivity of tight junctions between epithelial cells. Nonlocal electrostatic approach
2020
Abstract Tight junctions (TJs) of epithelial cells play a key role in regulation of the ion exchange between NaCl solutions separated by the layer of these cells. Their functioning is based on a strong difference in the permeabilities of these channels for Na+ and Cl− ion migrational fluxes owing to specific properties of the protein network inside TJs. It has been assumed in this study that this phenomenon originates from combination of two effects related to this specific TJ protein (claudin) which segments are partially located inside the TJ space. First, their ionogenic groups create a negative charge distributed inside TJs, thus inducing a difference between the Na+ and Cl− concentrati…
Ab Initio Liquid Water Dynamics in Aqueous TMAO Solution
2015
Ab initio molecular dynamics (AIMD) simulations in trimethylamine N-oxide (TMAO)-D2O solution are employed to elucidate the effects of TMAO on the reorientational dynamics of D2O molecules. By decomposing the O-D groups of the D2O molecules into specific subensembles, we reveal that water reorientational dynamics are retarded considerably in the vicinity of the hydrophilic TMAO oxygen (O(TMAO)) atom, due to the O-D···O(TMAO) hydrogen-bond. We find that this reorientational motion is governed by two distinct mechanisms: The O-D group rotates (1) after breaking the O-D···O(TMAO) hydrogen-bond, or (2) together with the TMAO molecule while keeping this hydrogen-bond intact. While the orientatio…
Reversible Cluster Formation of Colloidal Nanospheres by Interparticle Photodimerization
2004
Crosslinked spherical nanoparticles based on trimethoxysilane monomers have been prepared by polycondensation in aqueous emulsion. These particles have been labeled chemically at their surface region with two different types of organic dye molecules (cinnamate, coumarin), which both are well known for their ability to undergo a reversible photodimerization if irradiated with light of a suitable wavelength. Upon irradiation of dilute solutions of these nanoparticles with UV light, the photodimerization of labels belonging to different colloidal nanoparticles caused the formation of large colloidal clusters consisting of chemically bound individual nanospheres. This process has been quantitat…
Mixed aggregates based on tetronic-fluorinated surfactants for selective oils capture
2015
Abstract An aqueous star-like copolymer solution was titrated with perfluoro carboxylic acids at various compositions to prepare a polymeric surfactant composed of fluorinated nano-domains. The copolymer is X-shaped where each arm contains ethylene oxide and propylene oxide repetitive units linked to a central ethylenediamine group. The aggregation behavior of the hybrid macromolecule was studied from the physico-chemical point of view by changing parameters like temperature and composition. The solubilization of perfluorinated and hydrogenated alcohols in mixed self-assembled structure revealed that a selectivity toward the fluorinated moiety can be done. The self-assembled structures are …
Solubilization control by redox-switching of polysoaps
2008
Reversible changes in the self-organization of polysoaps may be induced by controlling their charge numbers via covalently bound redox moieties. This is illustrated with two viologen polysoaps, which in response to an electrochemical stimulus, change their solubility and aggregation in water, leading from homogeneously dissolved and aggregated molecules to collapsed ones and vice verse. Using the electrochemical quartz crystal microbalance (EQCM), it could be shown that the reversibility of this process is better than 95% in 16 cycles.
Probing the internal environment of PVP networks generated by irradiation with different sources
2010
Poly(N-vinyl-2-pyrrolidone) (PVP) hydrogels have been synthesised from the aqueous solutions of the same linear polymer by two different radiation sources: electron beams and UV rays. The present investigation couples conventional hydrogel characterisation techniques with the study of the partition equilibria, fluorescence behaviour and release of two different molecular probes, 1-anilino-8-naphthalene sulphonate (ANS) and Thioflavin T (ThT). The two probes have comparable molecular weight and different structural and optical properties. The chemical networks produced upon irradiation in different experimental conditions presented quite distinctive mechanical spectra, yielded to different…
Single Molecule Spectroscopy of Oriented Recombinant Trimeric Light Harvesting Complexes of Higher Plants
2002
The bleaching dynamics of reconstituted single light-harvesting chlorophyll a/b investigated. The complexes containing one histidine6 tag per monomeric subunit were immobilised predominantly in a defined orientation with their symmetry axis perpendicular to a Ni-ion-containing surface allowing for the first time the examination of single LHCIIb in an aqueous environment. Most complexes exhibit photobleaching in one step, indicating coupling between the monomeric subunits leading to an energy transfer between adjacent subunits. Differences in bleaching behaviour between these and previous observations with single LHCIIb are discussed.
VIOLURATO COMPLEXES OF Cr(III). SYNTHESIS AND CHARACTERIZATION. PROTONATION-DEPROTONATION EQUILIBRIA OF THE COORDINATED LIGANDS. EVIDENCE OF THE COOR…
1982
Abstract The formation of violurato complexes of Cr(III) has been studied in aqueous solution. Two compounds, [Cr(H2V)3].5H2O and Na[Cr(H2V)2(OH)2].4H2O have been synthesized and characterized. [Cr(H2V)3] behaves in aqueous solution as a triprotic acid but it can also add a proton yielding [Cr(H2V)2(H3V)]+. The acidity constants of this species have been determined: pKa1 =3.32, pKa2 =4.25, pKa3 =4.83 and pKa4 =6.99 (25°C, 0.1 M NaC1O4). [Cr(H2V)2(OH)2]− undergoes a deprotonation of the two H2V− ligands and a protonation of the hydroxo ligands. The acidity constants of [Cr(H2V)2(H2O)2]+ have been also determined: pKa1 =3.5, pKa2 =4.6, pKa3 =7.1 and pKa4 =9.2 (25°C, 0.1 M NaC1O4). The coordin…