Search results for "bond"
showing 10 items of 3527 documents
2D and 3D coordination polymers based on 2,2′-bipyrimidine and cyanide bridging ligands incorporating coordinated and guest ammonia molecules. Synthe…
2005
The coordination polymers {[Ni(CN)4]2[(Ni(NH3)2)2(bpym)]·2H2O}n1 and {[Cu2(CN)2(bpym)]·NH3}n2 have been prepared from the reactions of M(NO3)2·nH2O [Cu(II), n = 3 and M = Ni(II), n = 6] with NaCN and bpym (2,2′-bipyrimidine) in concentrated aqueous ammonia, respectively. The structure of 1 is made of bipyrimidine bridged centrosymmetric dinuclear [Ni(NH3)2(μ-bpym)Ni(NH3)2] fragments connected by four [Ni(CN)4]2− anions giving rise to a 2D framework. Layers, which adopt a stair-like conformation, are stacked with an ABAB… repeat pattern. Water molecules are located in the interlayer space and are involved in hydrogen bond interactions with the non-bridging cyanide groups of the [Ni(CN)4]2− a…
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,…
Synthesis, Characterization, and X-ray Crystal Structures of Cyclam Derivatives. 8. Thermodynamic and Kinetic Appraisal of Lead(II) Chelation by Octa…
2005
En route toward the development of hybrid organic−inorganic extracting materials incorporating lead-selective chelators and their implementation in water purification processes, the lead(II) binding properties of three N-carbamoylmethyl-substituted 1,4,8,11-tetraazacyclotetradecanes (cyclams) have been fully investigated by spectroscopic (IR, UV−vis, MALDI-TOF MS, 1H and 13C NMR), X-ray crystallographic, potentiometric, and kinetic methods. Solution NMR studies revealed that the Pb2+ ion is entrapped in a molecular cage constituted by the four macrocyclic nitrogen and four amidic oxygen atoms. Protonation and lead binding constants determined in aqueous solution were shown to be linearly de…
Proton Transfer versus Hydrogen Bonding: The Reduction of Ubiquinone Q2Incorporated in a Self-Assembled Monolayer in Unbuffered Aqueous Solution
2014
The electrochemical reduction of ubiquinone Q2 (UQ2) in unbuffered aqueous media was investigated over a pH range of 2 to 11, and the results were compared to those obtained in our previous work in buffered solutions. The short isoprene chains of UQ2 were incorporated in a self-assembled monolayer. Analysis of the mechanism and a study in D2O solutions allowed us to demonstrate the important role of hydrogen bonding in the stabilization of the reduced species, also in water. If the concentration of H+ is low relative to that of the quinone, the electrochemical reaction does not proceed through proton-coupled electron transfer, as it does in buffered medium or at low pH values (pH<4.4). We p…
Cobalt Metal-Organic Framework Based on Layered Double Nanosheets for Enhanced Electrocatalytic Water Oxidation in Neutral Media
2020
A new cobalt metal-organic framework (2D-Co-MOF) based on well-defined layered double cores that are strongly connected by intermolecular bonds has been developed. Its 3D structure is held together by π-π stacking interactions between the labile pyridine ligands of the nanosheets. In aqueous solution, the axial pyridine ligands are exchanged by water molecules, producing a delamination of the material, where the individual double nanosheets preserve their structure. The original 3D layered structure can be restored by a solvothermal process with pyridine, so that the material shows a "memory effect"during the delamination-pillarization process. Electrochemical activation of a 2D-Co-MOF@Nafi…
Polyacrylates in aqueous solution. The dependence of protonation on molecular weight, ionic medium and ionic strength
2003
Abstract The protonation constants of polyacrylates with different molecular weights ( W =2000–750 000 Da) were determined in different ionic media (alkali metal chlorides and nitrates, tetraalkylammonium chlorides), at 25 °C, by potentiometric measurements (H + –glass electrode). Literature data were also considered. Different models used to analyse protonation data were compared: the first was the modified Henderson–Hasselbalch two-parameter equation, and the second was the three-parameter equation proposed by Hogfeldt. The dependence on the ionic strength of the different supporting electrolytes and all the protonation parameters involved in the two models showed the trend Et 4 N + ≫Li +…
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.
Structural and Vibrational Study of a New Mixed Dipotassium Hydrogenselenate Dihydrogenphosphate K2(HSeO4)1.5 (H2PO4)0.5.
2006
Abstract Ongoing studies of the KHSeO4–KH2PO4 system, aimed at developing novel proton conducting solids, resulted in the new compound K2(HSeO4)1.5(H2PO4)0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals have been prepared by slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by X-ray single analysis (performed at room temperature), which revealed that K2(HSeO4)1.5(H2PO4)0.5 (KHSeP) crystallizes in space group P 1 ¯ with lattice parameters: a = 7.417(3) A, b = 7.668(2) A, c = 7.744(5) A, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. The compound has a unit cell volume 416.8(3) A3 and two formula unit…
Conformational investigations of bis(α-aminoalkyl)phosphinic acids and studies of the stability of their complexes with Cu(II)
2008
Abstract Conformational investigations of a group of bis(α-aminoalkyl)phosphinic acids were performed by use of NMR spectroscopy and theoretical calculations. In the case of one of the studied compounds, substituted with aminobenzyl and amino(p-chlorobenzyl) moieties, a pH-dependent equilibrium between conformers, stabilized by intermolecular hydrogen bonds was observed. Potentiometric studies proved that these molecules formed stable complexes with copper(II) ions, where stoichiometry was 1:1 and 1:2 depending on pH of their aqueous solution.
Uranium(VI) sequestration by polyacrylic and fulvic acids in aqueous solution
2011
Stability data on the formation of dioxouranium(VI) species with polyacrylic (PAA) and fulvic acids (FA) are reported with the aim to define quantitatively the sequestering capacity of these high molecular weight synthetic and naturally occurring ligands toward uranium(VI), in aqueous solution. Investigations were carried out at t = 25 °C in NaCl medium at different ionic strengths and in absence of supporting electrolyte for uranyl–fulvate (\( {{\text{UO}}_{2}}^{2+} \)–FA) and uranyl–polyacrylate (\( {{\text{UO}}_{ 2}}^{ 2+ } \)–PAA, PAA MW 2 kDa) systems, respectively. The experimental data are consistent with the following speciation models for the two systems investigated: (i) UO2(FA1),…