Search results for "physical chemistry"
showing 10 items of 1199 documents
Calcium binding and ionic conduction in single conical nanopores with polyacid chains: model and experiments.
2012
Calcium binding to fixed charge groups confined over nanoscale regions is relevant to ion equilibrium and transport in the ionic channels of the cell membranes and artificial nanopores. We present an experimental and theoretical description of the dissociation equilibrium and transport in a single conical nanopore functionalized with pH-sensitive carboxylic acid groups and phosphonic acid chains. Different phenomena are simultaneously present in this basic problem of physical and biophysical chemistry: (i) the divalent nature of the phosphonic acid groups fixed to the pore walls and the influence of the pH and calcium on the reversible dissociation equilibrium of these groups; (ii) the asym…
A very short uranium-uranium bond: The predicted metastable U22+
2005
Quantum chemical calculations, based on multiconfigurational wave functions and including relativistic effects, show that the U(2)2+ system has a large number of low-lying electronic states with S of 0 to 2 and Lambda ranging from zero to ten. These states share a very small bond length of about 2.30 A, compared to 2.43 A in neutral U2. The Coulomb explosion to 2 U+ lowers the energy by only 1.6 eV and is separated by a broad barrier.
Dynamics of molybdenum nano structure formation on the TiO2(110) surface: A kinetic Monte Carlo approach
2006
Abstract The rutile TiO 2 (1 1 0) surface is a highly anisotropic surface exhibiting “channels” delimited by oxygen rows. In previous experimental and theoretical DFT works we could identify the molybdenum adsorption sites. They are located inside the channels. Moreover, experimental studies have shown that during subsequent annealing after deposition, special molybdenum nano structures can be formed, especially two monolayer high pyramidal chains of atoms. In order to better understand the dynamics of nano structure formation, we present a kinetic Monte Carlo study on diffusion and adsorption of molybdenum atoms on a TiO 2 (1 1 0) surface. A quasi one-dimensional lattice gas model has been…
In silico identification and experimental validation of hits active against KPC-2 β-lactamase
2018
Bacterial resistance has become a worldwide concern, particularly after the emergence of resistant strains overproducing carbapenemases. Among these, the KPC-2 carbapenemase represents a significant clinical challenge, being characterized by a broad substrate spectrum that includes aminothiazoleoxime and cephalosporins such as cefotaxime. Moreover, strains harboring KPC-type β-lactamases are often reported as resistant to available β-lactamase inhibitors (clavulanic acid, tazobactam and sulbactam). Therefore, the identification of novel non β-lactam KPC-2 inhibitors is strongly necessary to maintain treatment options. This study explored novel, non-covalent inhibitors active against KPC-2, …
DNA Photodamage and Repair: Computational Photobiology in Action
2020
DNA is constantly exposed to external and metabolic stress agents, including the solar radiation and in particular the UV portion of the electromagnetic spectrum. Such source of stress can induce photochemical modification of the structure of DNA and of its basic components, i.e. the nucleobases. DNA lesions may ultimately lead to genomic instability, mutations, and even to carcinogenesis. Hence, cells dispose of complex biochemical repair pathways in charge of remove the DNA lesions and avoid their accumulation. In this Chapter, we present the complexity of the DNA lesion chemical and structural space, also complicated by the intricate coupling with the biological relevant signaling pathwa…
EXCITONS, LOCALIZED STATES IN SILICON DIOXIDE AND RELATED CRYSTALS AND GLASSES
2000
The excitons, localized states in crystalline and glassy silicon dioxide, germanium dioxide were studied by photoluminescent and photoelectric experimental methods. Results were compared with analogous investigations of related crystals, such as aluminum and gallium orthophosphates, and of related glasses, such as silica, sodium silicates, germanates, lead and phosphates glasses. Special attention was made to the influence of oxygen deficiency on localized states of glasses, in general, and to the nature of the 7.6 eV band in reduced silica, in particular.
Reactivity of SiCl and SiF groups in SiO2 glass with mobile interstitial O2 and H2O molecules
2007
Reactions of common network-bound halogens in synthetic SiO2 glass, SiCl and SiF groups, with interstitial O2 and H2O molecules incorporated by thermally annealing were studied. It was found that the chemical properties are distinctly different between SiCl and SiF groups. SiCl groups react with interstitial O2 and H2O to form interstitial Cl2 and HCl, respectively. In contrast, formation of interstitial F2 and HF due to the reaction of SiF groups with interstitial O2 and H2O is not observed. The reactivity of SiCl and SiF groups is in accord with the properties and thermodynamic data of their respective analogous compounds, SiCl4 and SiF4.
Photoinduced dissociation of anionic and electron detachment of dianionic gold clusters by use of a laser pointer
2002
Abstract Size-selected anionic and dianionic gold clusters have been stored in a Penning trap and irradiated with the green light of a laser pointer. As examples of special interest, the systems Au 7 − and Au 29 2− have been chosen. In particular, Au 7 − , a small gold cluster with closed electron shell, is observed to decay into Au 6 − and Au 5 − with a decay pathway branching ratio similar to that of Au 9 + . The dianionic cluster Au 29 2− shows electron detachment upon photoexcitation. This observation is in agreement with independent experiments [Stoermer et al., Int. J. Mass Spectrom. 201 (2001) 63], where Au 29 2− is found to be the smallest dianion produced by neutral monomer evapora…
A119Sn Mössbauer spectroscopic study on complexes of di-and tri-organotin(IV) moieties with 2-mercaptoethanesulfonates, in the solid state and in aqu…
1988
The configuration of the bonding environment of tin in the complexes [R2Sn(SCH2CH2SO3)2]2− (R = Me, Ph) and [Me3Sn(SCH2CH2SO3)]− has been determined to be tetrahedral both in the solid state and in aqueous solution (for the methyl derivatives). The coordination number of tin increases to five in aqueous solutions for the Me2Sn(IV) complexes in Hepes buffer (N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid; at least in fivefold excess, at pH 7.4) due to coordination by the tertiary amino nitrogen atom. No effect is detected due to the surfactant 2-hydroxypropylcellulose concerning both coordination to tin and influence on the Mossbauer parameters. The stoichiometry of mixed complex format…
Properties of HO2• radicals induced by γ-ray irradiation in silica nanoparticles
2014
Abstract We report an experimental investigation on the effects of γ -ray irradiation in several types of silica nanoparticles previously loaded with O 2 molecules. They differ in specific surface and average diameter. By electron paramagnetic resonance (EPR) measurements we observe the generation of about 10 18 HO 2 • /cm 3 interstitial radicals. These radicals are induced by reaction of interstitial O 2 molecules with radiolytic H atoms, as previously suggested for O 2 -loaded bulk a-SiO 2 samples. However, at variance with respect to bulk materials, our experimental evidences suggest a different generation process of HO 2 • radical. In fact, by a detailed study of samples exposed to D 2 …