Search results for " spectroscopy"
showing 10 items of 6851 documents
The importance of vibronic perturbations in ferrocytochrome c spectra: a reevaluation of spectral properties based on low-temperature optical absorpt…
2005
We have measured and analyzed the low-temperature (T=10 K) absorption spectrum of reduced horse heart and yeast cytochrome c. Both spectra show split and asymmetric Q(0) and Q(upsilon) bands. The spectra were first decomposed into the individual split vibronic sidebands assignable to B(1g) (nu15) and A(2g) (nu19, nu21, and nu22) Herzberg-Teller active modes due to their strong intensity in resonance Raman spectra acquired with Q(0) and Q(upsilon) excitations. The measured band splittings and asymmetries cannot be rationalized solely in terms of electronic perturbations of the heme macrocycle. On the contrary, they clearly point to the importance of considering not only electronic perturbati…
Endothelium- and nitric oxide-dependent vasorelaxing activities of gamma-butyrobetaine esters: possible link to the antiischemic activities of mildro…
2004
Mildronate [3-(2,2,2-trimethylhydrazine) propionate (THP)] is an antiischemic drug acting mainly via inhibition of fatty acid beta-oxidation. Some effects of the drug cannot be explained by the latter mechanism. We tested the eventual nitric oxide (NO) dependence of the mildronate action. Mildronate, gamma-butyrobetaine (GBB) and GBB methyl ester induced transient increases in nitric oxide (NO) concentrations in rat blood and myocardium. In vitro, these compounds neither modified the activities of purified neuronal and endothelial recombinant nitric oxide synthases (NOSs) nor were able to interact with their active site. GBB induced vasodilatation at high concentrations only (EC50 = 5 x 10(…
Diode laser spectroscopy of the nu(8) band of the SF(5)Cl molecule.
2003
Abstract Diode laser spectra of SF 5 Cl have been recorded in the ν 8 band region at a temperature of ca. 240 K, a pressure of 0.25 mbar and an instrumental bandwidth of ca. 0.001 cm −1 . Four regions have been studied: a first one in the P -branch (906.849–907.687 cm −1 ), a second one in the Q -branch (910.407–910.944 cm −1 ), and two other ones in the R -branch (913.957–914.556 and 917.853–918.705 cm −1 ). The whole ν 1 / ν 8 dyad of SF 5 35 Cl has been previously recorded in the group of Professor H. Burger in Wuppertal, thanks to a Fourier transform infrared spectrometer [J. Mol. Spectrosc. 208 (2001) 169]. These data have thus been combined with our diode laser ones in the aim of refi…
Diastereoselective Synthesis of Dialkylated Bis(phosphino)ferrocenes: Their Use in Promoting Silver-Mediated Nucleophilic Fluorination of Chloroquino…
2017
International audience; The diastereoselective synthesis of dialkylated ferrocenyl bis(phosphane)s bearing aryl, alkyl, and hetero- or polycyclic substituents on the phosphino groups is reported, together with their characterization in the solid state by X-ray structure analysis and in solution by multinuclear NMR spectroscopy. Introduction of various alkyl groups on the ferrocene backbone, namely, tert-butyl, isopropyl, and trimethylsilyl, has a significant influence on the stereoselectivity of the ensuing lithiation/phosphination reactions. Only the introduction of the tert-butyl groups ensures both a high yield and perfect diastereoselectivity, which leads to the exclusive formation of t…
Generalized bloch equations for optical interactions in confined geometries
2005
By combining the field-susceptibility technique with the optical Bloch equations, a general formalism is developed for the investigation of molecular photophysical phenomena triggered by nanometer scale optical fields in the presence of complex environments. This formalism illustrate the influence of the illumination regime on the fluorescence signal emitted by a single molecule in a complex environment. In the saturated case, this signal is proportional to the optical local density of states, while it is proportional to the near-field intensity in the non-saturated case. (C) 2005 Elsevier B.V. All rights reserved.
Bulk spin polarization of magnetite from spin-resolved hard x-ray photoelectron spectroscopy
2021
Physical review / B 104(4), 045129 (1-10) (2021). doi:10.1103/PhysRevB.104.045129
Interplay between local structure, vibrational and electronic properties on CuO under pressure
2020
The electronic and local structural properties of CuO under pressure have been investigated by means of X-ray absorption spectroscopy (XAS) at Cu K edge and ab initio calculations, up to 17 GPa. The crystal structure of CuO consists of Cu motifs within CuO4 square planar units and two elongated apical Cu-O bonds. The CuO4 square planar units are stable in the studied pressure range, with Cu-O distances that are approximately constant up to 5 GPa, and then decrease slightly up to 17 GPa. In contrast, the elongated Cu-O apical distances decrease continuously with pressure in the studied range. An anomalous increase of the mean square relative displacement (EXAFS Debye-Waller, s2) of the elong…
The algebra eigenstates method for some systems with spin-like interactions
2006
International audience; An extension of the algebra eigenstates formalism is proposed to solve the eigenvalue equation for a class of problems involving "spin interactions". The method is detailed for the harmonic oscillator, su(2) and su(1, 1) algebras. Special emphasis is given to the resolution of problems in vibronic spectroscopy involving doubly degenerate electronic states.
High-spin → low-spin relaxation in the two-step spincrossover compound [Fe(pic)3]Cl2EtOH (pic = 2-picolylamine)
1998
Abstract The spin-crossover compound [Fe(pic) 3 ]Cl 2 EtOH (pic = 2-picolylamine) shows an unusual two-step spin transition. This is thought to be caused by specific nearest-neighbour interactions and short-range correlations and requires a theoretical treatment of the elastic interactions between the spin-changing molecules beyond the mean-field approximation. Such short-range correlations also influence the high-spin → low-spin relaxation following the light-induced population of the high-spin state at cryogenic temperatures, leading to characteristic deviations from the predictions of a mean-field treatment. These deviations are directly observable by comparison of the full and unperturb…
Uptake of actinides by calcium silicate hydrate (C-S-H) phases
2018
Abstract The sorption of actinides (Th, U – Am) was studied in dependence of the solid-to-liquid (S/L) ratio (0.5–20.0 g/L) and the calcium-to-silicon (C:S) ratio. The C:S ratio was varied between 1.80 and 0.70 to simulate the changing composition of the C-S-H phases during cement degradation from high to low C:S ratios. The decrease of the calcium content in the C-S-H phases by time is accompanied by a decrease in pH in the corresponding suspensions from 12.6 to 10.2. X-ray photoelectron spectroscopy (XPS) of the C-S-H phases showed an increasing depletion of Ca on the surface with increasing C:S ratio in comparison to the composition of the solid phase as a whole. The sorption experiments…