Search results for "Pulsed EPR"
showing 10 items of 21 documents
Rigid Core and Flexible Terminus
2012
The structure of the major light-harvesting chlorophyll a/b complex (LHCII) was analyzed by pulsed EPR measurements and compared with the crystal structure. Site-specific spin labeling of the recombinant protein allowed the measurement of distance distributions over several intra- and intermolecular distances in monomeric and trimeric LHCII, yielding information on the protein structure and its local flexibility. A spin label rotamer library based on a molecular dynamics simulation was used to take the local mobility of spin labels into account. The core of LHCII in solution adopts a structure very similar or identical to the one seen in crystallized LHCII trimers with little motional freed…
Structural analysis of Cu(II) ligation to the 5'-GMP nucleotide by pulse EPR spectroscopy.
2007
JBIC Journal of Biological Inorganic Chemistry, 12 (6)
Interaction of Novel Metal Complexes with DNA: Synthetic and Structural Aspects
2009
Metal ions bind to nucleic acids at various positions. This binding can be modulated by using metal complexes with appropriate ligands. Novel mono- and especially dinuclear metal complexes could be a powerful tool to detect rare, but still physiologically relevant, forms of DNA, e.g. the left-handed Z-DNA. In this review, our recent research activities in this area of bioinorganic chemistry are summarized. A special emphasis is laid on the synthetic challenges that arose upon the synthesis of the polyamine ligands. Further, some rather unusual approaches to elucidate the solution structure of copper bound to guanosine monophosphate with the help of pulsed EPR techniques like ENDOR and HYSC…
Pulse EPR methods for studying chemical and biological samples containing transition metals
2006
This review discusses the application of pulse EPR to the characterization of disordered systems, with an emphasis on samples containing transition metals. Electron nuclear double-resonance (ENDOR), electron-spin-echo envelope-modulation (ESEEM), and double electron-electron resonance (DEER) methodologies are outlined. The theory of field modulation is outlined, and its application is illustrated with DEER experiments. The simulation of powder spectra in EPR is discussed, and strategies for optimization are given. The implementation of this armory of techniques is demonstrated on a rich variety of chemical systems: several porphyrin derivatives that are found in proteins and used as model s…
X-Ray Diffraction and Multifrequency EPR Study of Radiation-Induced Room Temperature Stable Radicals in Octacalcium Phosphate.
2020
Octacalcium phosphate (OCP) {Ca8H2(PO4)6×5H2O] has attracted increasing attention over the last decade as a transient intermediate to the biogenic apatite for bone engineering and in studies involving the processes of pathological calcification. In this work, OCP powders obtained by hydrolysis of dicalcium phosphate dehydrate were subjected to X- and γ-ray irradiation and studied by means of stationary and pulsed electron paramagnetic resonance at 9, 36 and 94 GHz microwave frequencies. Several types of paramagnetic centers were observed in the investigated samples. Their spectroscopic parameters (components of the g and hyperfine tensors) were determined. Based on the extracted parameters,…
Effects of temperature on electron paramagnetic resonance of dangling oxygen bonds in amorphous silicon dioxide
2011
The properties of electron paramagnetic resonance (EPR) signal of oxygen dangling bonds in amorphous SiO2 ("non-bridging oxygen hole centers", NBOHC) in excimer laser-irradiated amorphous SiO2 were studied in the temperature range 20K to 295K. NBOHCs strongly affect optical and chemical properties of amorphous SiO2 -based (nano) structures and their surfaces. The behaviour of their EPR signal is complicated due to a nearly degenerate electronic ground state. It was found that EPR signal has a non-Curie (~1/T) T-dependence down to 40K, indicating that EPR-based concentration estimates routinely obtained at T = 77K underestimate the center concentrations at least by a factor of 1.7. The estim…
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…
Pulsed EPR determination of water accessibility to spin-labeled amino acid residues in LHCIIb.
2009
Membrane proteins reside in a structured environment in which some of their residues are accessible to water, some are in contact with alkyl chains of lipid molecules, and some are buried in the protein. Water accessibility of residues may change during folding or function-related structural dynamics. Several techniques based on the combination of pulsed electron paramagnetic resonance (EPR) with site-directed spin labeling can be used to quantify such water accessibility. Accessibility parameters for different residues in major plant light-harvesting complex IIb are determined by electron spin echo envelope modulation spectroscopy in the presence of deuterated water, deuterium contrast in …
Determination of New Radical Species in Ammonium Tartrate Dosimeters by CW- and Pulsed-EPR Techniques
2015
Samples of ammonium tartrate irradiated with doses of about 0.1–1 kGy by different beams of ionizing radiation (60Co–γ, 19 MeV protons and 62 MeV per nucleon carbon ions) were studied by continuous-wave electron paramagnetic resonance (cw-EPR) and by pulse-EPR techniques. Careful analysis of the cw-EPR and of the echo-detected EPR spectra allowed the identification of a second radical in the system besides the already known radical formed at high temperature by an hydrogen elimination at C(2) position [M. Brustolon et al., Res. Chem. Int 4:359, 1996]. The spectrum of the radical is compatible with that of a radical obtained by hydroxyl elimination.