Search results for "element"
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Interaction of Cd(II) and Ni(II) terpyridine complexes with model polynucleotides: A multidisciplinary approach
2016
Two metal complexes of 2,2′:6′,2′′-terpyridine (terpy), i.e. Cd(terpy)Cl2 and Ni(terpy)Cl2·3H2O, have been prepared and extensively characterized. The interaction of Cd(terpy)Cl2 with synthetic DNA models, poly(dA-dT)·poly(dA-dT) (polyAT) and poly(dG-dC)·poly(dG-dC) (polyGC), has been studied by CD, fluorescence and UV-vis electronic absorption spectroscopy at several metal/polynucleotide–phosphate ratios and for different NaCl concentrations. All the experimental results indicate an intercalative mechanism of interaction. The optimized geometry of the cadmium complex intercalated between the sixth and seventh base pairs of (AT) and (GC) dodecanucleotide duplexes, obtained by quantum mechan…
Conformational Properties of Nickel(II) Octaethylporphyrin in Solution. 2. A Low-Temperature Optical Absorption Spectroscopy Study
1996
We have measured the absorption spectrum of Ni(II) octaethylporphyrin in CH2Cl2 and in a 50% v/v isopentane/ethyl ether mixture as a function of temperature between 150 and 300 K and 40 and 300 K, respectively. The Soret band can be decomposed into two subbands whose frequencies differ by 220 cm-1. By analogy with resonance Raman results (Jentzen et al. J. Phys. Chem. 1996, 100, 14184−14191 (preceding paper)), we attribute the low-frequency subband to a conformer with a nonplanar macrocycle structure, whereas the high-frequency subband is interpreted as resulting from a planar conformer. The subbands' intensity ratios exhibit a solvent-dependent van't Hoff behavior between 300 and 160 K. Cr…
Double-Electron Excitations in L-edges X-ray-Absorption Spectra of W, Ir and Cs Oxide Compounds
1993
Very strong double-electron excitations have been observed for the first time in the W, Ir L 3-edge and Cs L 1,2,3-edges X-ray-absorption spectra of tungsten and iridium oxide thin films and cesium oxide containing glasses. They are expressed as peaks with a width of several electron-volts located at the absorption background above the edge. The positions of these features are in good agreement with atomic calculations in the Z+1 approximation. They can be attributed to the transitions 2p4d → 5d5d for the L 2,3-edges and 2s4d → 6p5d for the L 1-edge with the dipole selection rules for the angular and total angular momentum ΔL=±1, ΔJ=0,±1.
Photochemical generation of E′ centres from Si–H in amorphous SiO2under pulsed ultraviolet laser radiation
2006
In situ optical absorption spectroscopy was used to study the generation of E' centres () in amorphous SiO2 occurring by photo-induced breaking of Si–H groups under 4.7 eV pulsed laser radiation. The dependence on laser intensity of the defect generation rate is consistent with a two-photon mechanism for Si–H rupture, while the growth and saturation of the defects are conditioned by their concurrent annealing due to a reaction with mobile hydrogen arising from the same precursor. A rate equation is proposed to model the kinetics of the defects and is tested on experimental data.
An increased F2-laser damage in ‘wet’ silica glass due to atomic hydrogen: A new hydrogen-related E′-center
2006
Abstract A dramatic increase of F2-laser induced room temperature-stable point defects in ‘wet’ synthetic silica glass occurs when irradiation temperature is lowered to 80 K. Contrary to the predictions based on the established models of defect processes, a large part of defects induced at 80 K remains stable also at the room temperature. The intensities of the laser-induced optical absorption bands of the non-bridging oxygen hole centers (2.0 and 4.8 eV) and E′-centers (5.8 eV) are comparable to those created by neutron irradiation (1018 n/cm2). A growth of infrared absorption peak at 2237 cm−1 indicates creation of silicon hydride (SiH) groups. A study of irradiation dose dependences and …
Effects of high pressure thermal treatments in oxygen and helium atmospheres on amorphous silicon dioxide and its radiation hardness
2009
The effects of thermal treatments at similar to 400 degrees C in oxygen or helium atmospheres at similar to 180 baron the radiation hardness of amorphous SiO(2) are studied. The generation efficiency of several point defects under gamma irradiation is compared to that of the untreated material. All the effects on point defects generation here observed can be explained in terms of changes in the precursor sites. In particular it has been observed that the thermal treatments can change the precursors sites of point defects both through temperature and pressure related processes, not depending on the atmosphere, and through oxygen related processes creating oxygen excess sites. The presence of…
DNA-binding of zinc(II) and nickel(II) salphen-like complexes extrapolated at 1 M salt concentration: Removing the ionic strength bias in physiologic…
2020
Abstract The DNA-binding of two salphen-like metal complexes of nickel(II) (1) and zinc(II) (2) was investigated in different ionic strength solutions by absorption spectroscopy. The data analysis allowed us to obtain the values of their extrapolated DNA-binding constant in physiological conditions, with DNA-binding strength in the order Ni > Zn, and to give relative weight to the electrostatic and non-electrostatic contributions to their DNA-interaction.
Spectroscopic and electrochromical properties of metallophthalocyanines in silicate bulks and thin films prepared by the sol–gel method
2000
Abstract Magnesium phthalocyanine (MgPc) and praseodymium bisphthalocyanine (Pr(Pc) 2 ) have been entrapped in bulks and thin films of porous silicate xerogels prepared via the sol–gel method. The electronic absorption data obtained for the complexes immobilized in bulk sol–gel matrices indicate the formation of complex equilibria between their monomeric forms and respective agglomerates. Thin xerogel films doped with metallophthalocyanines and connecting two slides of transparent ITO electrodes display changes in the absorption spectra caused by varying of the applied voltage. These changes appear to be reversible in certain ranges of the applied voltages.
EXAFS and XANES Studies of CoxMg1−xO Solid Solutions Using a Laboratory EXAFS Spectrometer
1993
Studies of the local electronic structure and the short-range order in solid solutions CoxMg1−xO with x varying from 0.02 to 1.00 are carried out on the CoK-edge X-ray absorption spectra using a laboratory EXAFS spectrometer. A non-monotonous change of the CoO distance in the first coordination shell with a bent at about x = 0.5 is established. The second coordination shell of cobalt is formed by cobalt and magnesium atoms with a distribution close to a statistical one. [Russian Text Ignored.]
Crystallographic and (spectro)electrochemical characterizations of cobalt(II) 10-phenyl-5,15-di-p-tolylporphyrin
2021
International audience; The synthesis, cyclic and rotating disk electrode voltammograms, UV-visible absorption and Xray diffraction analyses of cobalt(II) 10-phenyl-5,15-dip -tolylporphyrin (1-Co) are described. 1-Co was crystallized by slow diffusion of n-hexane into a concentrated CH2Cl2 solution. X-ray diffraction analyses reveals porphyrin aromatic cycle stacking in the crystal, C-H•••π interactions of the CH2Cl2 solvent with the π-system of one tolyl group and Co(II)•••π (porphyrin ring) interactions. The abstraction of 1.0 F/mol during the electrolysis at the first oxidation potential was followed by spectroelectrochemistry. It leads to the Co(II) → Co(III) transformation rather than …