Search results for "Paramagnetic"

1974

The formation and behaviour of radiation-induced free radicals in statistical copolymers of ethoxyvinylthiomethane (1a) with N-vinylpyrrolidone (2) (1:2,5) and of ethylthiovinylthiomethane (1b) with 2 (1:3,5) has been studied using electron spin resonance spectroscopy. After a γ-irradiation of the copolymers at 77K Cα-radicals in the vinylpyrrolidone moieties could be detected. Investigations on the behaviour of these radicals with an annealing procedure revealed that only in the copolymer (3b) with the dithioacetal group a transfer reaction of hydrogen atoms to the Cα-radicals in the vinylpyrrolidone moieties occurs. This process may be regarded as a repair mechanism. Es wurde die Bildung …

Similarity and Specificity of Chlorophyll b Triplet State in Comparison to Chlorophyll a as Revealed by EPR/ENDOR and DFT Calculations

2019

An investigation of the photoexcited triplet state of chlorophyll (Chl) b has been carried out by means of electron nuclear double resonance, both in a frozen organic solvent and in a protein environment provided by the water-soluble chlorophyll protein of Lepidium virginicum. Density functional theory calculations have allowed the complete assignment of the observed hyperfine couplings corresponding to the methine protons and the methyl groups, leading to a complete picture of the spin density distribution of the triplet state in the tetrapyrrole macrocycle. The triplet-state properties of Chl b are found to be similar, in many respects, to those previously reported for Chl a, although som…

Accessibility of Protein-Bound Chlorophylls Probed by Dynamic Electron Polarization

2018

The possibility to probe the accessibility of sites of proteins represents an important point to explore their interactions with specific substrates in solution. The dynamic electron polarization of nitroxide radicals induced by excited triplet states of organic molecules is a phenomenon that is known to occur in aqueous solutions. The interaction within the radical-triplet pair causes a net emissive dynamic electron polarization of the nitroxide radical, that can be detected by means of time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy. We have exploited this effect to prove the accessibility of chlorophylls bound to a protein, namely, the water-soluble chlorophyll protei…

Early folding events during light harvesting complex II assembly in vitro monitored by pulsed electron paramagnetic resonance

2016

Efficient energy transfer in the major light harvesting complex II (LHCII) of green plants is facilitated by the precise alignment of pigments due to the protein matrix they are bound to. Much is known about the import of the LHCII apoprotein into the chloroplast via the TOC/TIC system and its targeting to the thylakoid membrane but information is sparse about when and where the pigments are bound and how this is coordinated with protein folding. In vitro, the LHCII apoprotein spontaneously folds and binds its pigments if the detergent-solubilized protein is combined with a mixture of chlorophylls a and b and carotenoids. In the present work, we employed this approach to study apoprotein fo…

Localization of the N-terminal Domain in Light-harvesting Chlorophyll a/b Protein by EPR Measurements

2005

The conformational distribution of the N-terminal domain of the major light-harvesting chlorophyll a/b protein (LHCIIb) has been characterized by electron-electron double resonance yielding distances between spin labels placed in various domains of the protein. Distance distributions involving residue 3 near the N terminus turned out to be bimodal, revealing that this domain, which is involved in regulatory functions such as balancing the energy flow through photosystems (PS) I and II, exists in at least two conformational states. Models of the conformational sub-ensembles were generated on the basis of experimental distance restraints from measurements on LHCIIb monomers and then checked f…

Electron paramagnetic resonance (EPR) spin trapping of biological nitric oxide

2007

Nitric oxide (NO) is a free radical species with multiple physiological functions. Because of low concentrations and short half-life of NO, its direct measurement in living tissues remains a difficult task. Electron paramagnetic resonance (EPR) spin trapping is probably one of the best suitable platforms for development of new methods for quantification of biological NO. The most reliable EPR-based approaches developed so far are based on the reaction of NO with various iron complexes, both intrinsic and exogenously applied. This review is focused on the current state and perspectives of EPR spin trapping for experimental and clinical NO biology.

Stable mononuclear lead(III) compound: a lead-centered radical.

2006

Stability of E' centers induced by 4.7eV laser radiation in SiO2

2007

The kinetics of E' centers (silicon dangling bonds) induced by 4.7eV pulsed laser irradiation in dry fused silica was investigated by in situ optical absorption spectroscopy. The stability of the defects, conditioned by reaction with mobile hydrogen of radiolytic origin, is discussed and compared to results of similar experiments performed on wet fused silica. A portion of E' and hydrogen are most likely generated by laser-induced breaking of Si-H precursors, while an additional fraction of the paramagnetic centers arise from another formation mechanism. Both typologies of E' participate to the reaction with H_2 leading to the post-irradiation decay of the defects. This annealing process is…

Structural relaxation of E_gamma centers in amorphous silica

2002

We report experimental evidence of the existence of two variants of the E' gamma centers induced in silica by gamma rays at room temperature. The two variants are distinguishable by the fine features of their line shapes in paramagnetic resonance spectra. These features suggest that the two E' gamma differ for their topology. We find a thermally induced interconversion between the centers with an activation energy of about 34 meV. Hints are also found for the existence of a structural configuration of minimum energy and of a metastable state.

Optical absorption induced by UV laser radiation in Ge-doped amorphous silica probed by in situ spectroscopy

2007

We studied the optical absorption induced by 4.7eV pulsed laser radiation on Ge-doped a-SiO2 synthesized by a sol-gel technique. The absorption spectra in the ultraviolet spectral range were measured during and after the end of irradiation with an in situ technique, evidencing the growth of an absorption signal whose profile is characterized by two main peaks near 4.5eV and 5.7eV and whose shape depends on time. Electron spin resonance measurements performed ex situ a few hours after the end of exposure permit to complete the information acquired by optical absorption by detection of the paramagnetic Ge(1) and Ge-E' centers laser-induced in the samples.