Science.gov

Sample records for lytb epr metallacycles

  1. Inhibition of the Fe4S4 Cluster-containing Protein IspH (LytB): EPR, Metallacycles and Mechanisms

    PubMed Central

    Wang, Ke; Wang, Weixue; No, Joo-Hwan; Zhang, Yonghui; Zhang, Yong; Oldfield, Eric

    2010-01-01

    We report the inhibition of the Aquifex aeolicus IspH enzyme (LytB, (E)-4-hydroxy-3-methyl-but-2-enyl diphosphate reductase, EC 1.17.1.2) by a series of diphosphates and bisphosphonates. The most active species was an alkynyl diphosphate having an IC50 = 0.45 μM (Ki ~ 60 nM), which generated a very large change in the 9 GHz EPR spectrum of the reduced protein. Based on previous work on organometallic complexes, together with computational docking and quantum chemical calculations, we propose a model for alkyne inhibition involving π (or π/σ) “metallacycle” complex formation with the unique 4th Fe in the Fe4S4 cluster. Aromatic species had less activity and for these, we propose an inhibition model based on an electrostatic interaction with the active site E126. Overall, the results are of broad general interest since not only do they represent the first potent IspH inhibitors, they suggest a conceptually new approach to targeting other Fe4S4-cluster containing proteins that are of interest as drug and herbicide targets. PMID:20426416

  2. Substrate recognition and catalysis by LytB, a pneumococcal peptidoglycan hydrolase involved in virulence

    PubMed Central

    Rico-Lastres, Palma; Díez-Martínez, Roberto; Iglesias-Bexiga, Manuel; Bustamante, Noemí; Aldridge, Christine; Hesek, Dusan; Lee, Mijoon; Mobashery, Shahriar; Gray, Joe; Vollmer, Waldemar; García, Pedro; Menéndez, Margarita

    2015-01-01

    Streptococcus pneumoniae is a major cause of life-threatening diseases worldwide. Here we provide an in-depth functional characterization of LytB, the peptidoglycan hydrolase responsible for physical separation of daughter cells. Identified herein as an N-acetylglucosaminidase, LytB is involved also in colonization and invasion of the nasopharynx, biofilm formation and evasion of host immunity as previously demonstrated. We have shown that LytB cleaves the GlcNAc-β-(1,4)-MurNAc glycosidic bond of peptidoglycan building units. The hydrolysis occurs at sites with fully acetylated GlcNAc moieties, with preference for uncross-linked muropeptides. The necessity of GlcN acetylation and the presence of a single acidic moiety (Glu585) essential for catalysis strongly suggest a substrate-assisted mechanism with anchimeric assistance of the acetamido group of GlcNAc moieties. Additionally, modelling of the catalytic region bound to a hexasaccharide tripentapeptide provided insights into substrate-binding subsites and peptidoglycan recognition. Besides, cell-wall digestion products and solubilisation rates might indicate a tight control of LytB activity to prevent unrestrained breakdown of the cell wall. Choline-independent localization at the poles of the cell, mediated by the choline-binding domain, peptidoglycan modification, and choline-mediated (lipo)teichoic-acid attachment contribute to the high selectivity of LytB. Moreover, so far unknown chitin hydrolase and glycosyltransferase activities were detected using GlcNAc oligomers as substrate. PMID:26537571

  3. Structure of Pneumococcal Peptidoglycan Hydrolase LytB Reveals Insights into the Bacterial Cell Wall Remodeling and Pathogenesis*

    PubMed Central

    Bai, Xiao-Hui; Chen, Hui-Jie; Jiang, Yong-Liang; Wen, Zhensong; Huang, Yubin; Cheng, Wang; Li, Qiong; Qi, Lei; Zhang, Jing-Ren; Chen, Yuxing; Zhou, Cong-Zhao

    2014-01-01

    Streptococcus pneumoniae causes a series of devastating infections in humans. Previous studies have shown that the endo-β-N-acetylglucosaminidase LytB is critical for pneumococcal cell division and nasal colonization, but the biochemical mechanism of LytB action remains unknown. Here we report the 1.65 Å crystal structure of the catalytic domain (residues Lys-375–Asp-658) of LytB (termed LytBCAT), excluding the choline binding domain. LytBCAT consists of three structurally independent modules: SH3b, WW, and GH73. These modules form a “T-shaped” pocket that accommodates a putative tetrasaccharide-pentapeptide substrate of peptidoglycan. Structural comparison and simulation revealed that the GH73 module of LytB harbors the active site, including the catalytic residue Glu-564. In vitro assays of hydrolytic activity indicated that LytB prefers the peptidoglycan from the lytB-deficient pneumococci, suggesting the existence of a specific substrate of LytB in the immature peptidoglycan. Combined with in vitro cell-dispersing and in vivo cell separation assays, we demonstrated that all three modules are necessary for the optimal activity of LytB. Further functional analysis showed that the full catalytic activity of LytB is required for pneumococcal adhesion to and invasion into human lung epithelial cells. Structure-based alignment indicated that the unique modular organization of LytB is highly conserved in its orthologs from Streptococcus mitis group and Gemella species. These findings provided structural insights into the pneumococcal cell wall remodeling and novel hints for the rational design of therapeutic agents against pneumococcal growth and thereby the related diseases. PMID:25002590

  4. An in silico structural insights into Plasmodium LytB protein and its inhibition.

    PubMed

    Bhuyan, Rajabrata; Nandy, Suman Kumar; Seal, Alpana

    2015-01-01

    In most of the pathogenic organisms including Plasmodium falciparum, isoprenoids are synthesized via MEP (MethylErythritol 4-Phosphate) pathway. LytB is the last enzyme of this pathway which catalyzes the conversion of (E)-4-hydroxy-3-methylbut-2-en-1-yl diphosphate (HMBPP) into the two isoprenoid precursors: isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP). Since the MEP pathway is not used by humans, it represents an attractive target for the development of new anti-malarial compounds or inhibitors. Here a systematic in silico study has been conducted to get an insight into the structure of Plasmodium lytB as well as its affinities towards different inhibitors. We used comparative modeling technique to predict the three-dimensional (3D) structure of Plasmodium LytB taking Escherichia coli LytB protein (PDB ID: 3KE8) as template and the model was subsequently refined through molecular dynamics (MD) simulation. A large ligand data-set containing diphospate group was subjected for virtual screening against the target using GOLD 5.2 program. Considering the mode of binding and affinities, 17 leads were selected on basis of binding energies in comparison to its substrate HMBPP (Gold.Chemscore.DG: -20.9734 kcal/mol). Among them, five were discarded because of their inhibitory activity towards other human enzymes. The rest 12 potential leads carry all the properties of any "drug like" molecule and the knowledge of Plasmodium LytB-inhibitory mechanism which can provide valuable support for the anti-malarial-inhibitor design in future. PMID:25011618

  5. EPR imaging

    NASA Astrophysics Data System (ADS)

    Eaton, Sandra S.; Eaton, Gareth R.

    Useful EPR imaging has been achieved using simple gradient coils on a standard spectrometer. Resolution of less than 1 mm is possible without deconvolution of the resulting spectra. Examples are presented using DPPH and nitroxyl radicals.

  6. Aggregation-Induced Emission of Platinum(II) Metallacycles and Their Ability to Detect Nitroaromatics.

    PubMed

    Chowdhury, Aniket; Howlader, Prodip; Mukherjee, Partha Sarathi

    2016-05-23

    Two new acceptors containing platinum-carbazole (1) and platinum-triphenylamine (2) backbones with bite angles of 90° and 120°, respectively, have been synthesised and characterised. Reactions of the rigid acceptor 1 with linear dipyridyl-based donors (3 and 4) generated [4+4] self-assembled molecular squares (5 and 6), and similar treatments with acceptor 2 instead of 1 yielded [6+6] self-assembled molecular hexagons (7 and 8). The metallacycles were characterised by multinuclear NMR spectroscopy ((1) H and (31) P) and ESI-MS. The geometries of the metallacycles were optimised by using the PM6 method. When aggregates of the metallacycles were formed by adding hexane solutions in dichloromethane, aggregation-induced emission was observed for metallacycles 5 and 7, and aggregation-caused quenching was observed for metallacycles 6 and 8. The formation of aggregates was verified by dynamic light scattering and TEM analyses. Macrocycles 5 and 7 are white-light emitters in THF. Moreover, their high luminescence in both solution and the solid state was utilised for the recognition of nitroaromatic explosives. PMID:27106871

  7. Vapochromic Behavior of a Chair-Shaped Supramolecular Metallacycle with Ultra-Stability.

    PubMed

    Jiang, Bo; Zhang, Jing; Ma, Jian-Qiu; Zheng, Wei; Chen, Li-Jun; Sun, Bin; Li, Chao; Hu, Bing-Wen; Tan, Hongwei; Li, Xiaopeng; Yang, Hai-Bo

    2016-01-27

    A new discrete supramolecular metallacycle functionalized with an alkynylplatinum(II) bzimpy moiety was successfully prepared via coordination-driven self-assembly, and it displayed a reversible color change in the solid state between yellow and red, triggered by CH2Cl2 vapor or mechanical grinding. Notably, unlike many known vapochromic systems, the obtained vapochromic metallacycle exhibits ultra-stability, with the red color remaining unchanged in air for several months at room temperature or even under vacuum for >1 week. Further investigation revealed that the chair conformation of the metallacyclic scaffold, which was thought to prevent intermolecular steric repulsion between the alkyl chain and triethylphosphine, favored close molecular stacking through intermolecular Pt···Pt and π-π stacking interactions, thus allowing such vapochromic behavior with ultra-stability. PMID:26741405

  8. Five-membered metallacycles of titanium and zirconium--attractive compounds for organometallic chemistry and catalysis.

    PubMed

    Rosenthal, Uwe; Burlakov, Vladimir V; Bach, Marc A; Beweries, Torsten

    2007-05-01

    In these days a renaissance of metallacycles as an increasingly important class of organometallic compounds for synthetic and catalytic applications is evident, making such very attractive for a plethora of investigations. Titanocene and zirconocene bis(trimethylsilyl)acetylene complexes, regarded as three-membered metallacycles (1-metallacyclopropenes), present a rich chemistry towards unsaturated molecules. By elimination of the alkyne these complexes form by reaction with unsaturated compounds five-membered titana- and zirconacycles, all of which are relevant to stoichiometric and catalytic C-C coupling and cleavage reactions of unsaturated molecules. PMID:17471397

  9. Photoinduced transformations of stiff-stilbene-based discrete metallacycles to metallosupramolecular polymers

    PubMed Central

    Yan, Xuzhou; Xu, Jiang-Fei; Cook, Timothy R.; Huang, Feihe; Yang, Qing-Zheng; Tung, Chen-Ho; Stang, Peter J.

    2014-01-01

    Control over structural transformations in supramolecular entities by external stimuli is critical for the development of adaptable and functional soft materials. Herein, we have designed and synthesized a dipyridyl donor containing a central Z-configured stiff-stilbene unit that self-assembles in the presence of two 180° di-Pt(II) acceptors to produce size-controllable discrete organoplatinum(II) metallacycles with high efficiency by means of the directional-bonding approach. These discrete metallacycles undergo transformation into extended metallosupramolecular polymers upon the conformational switching of the dipyridyl ligand from Z-configured (0°) to E-configured (180°) when photoirradiated. This transformation is accompanied by interesting morphological changes at nanoscopic length scales. The discrete metallacycles aggregate to spherical nanoparticles that evolve into long nanofibers upon polymer formation. These fibers can be reversibly converted to cyclic oligomers by changing the wavelength of irradiation, which reintroduces Z-configured building blocks owing to the reversible nature of stiff-stilbene photoisomerization. The design strategy defined here represents a novel self-assembly pathway to deliver advanced supramolecular assemblies by means of photocontrol. PMID:24889610

  10. Hierarchical Self-Assembly of Discrete Organoplatinum(II) Metallacycles with Polysaccharide via Electrostatic Interactions and Their Application for Heparin Detection.

    PubMed

    Chen, Li-Jun; Ren, Yuan-Yuan; Wu, Nai-Wei; Sun, Bin; Ma, Jian-Qiu; Zhang, Li; Tan, Hongwei; Liu, Minghua; Li, Xiaopeng; Yang, Hai-Bo

    2015-09-16

    In recent past years, investigation of hierarchical self-assembly for constructing artificial functional materials has attracted considerable attention. Discrete metallacycles based on coordination bonds have proven to be valid scaffolds to fabricate various supramolecular polymers or smart soft matter through hierarchical self-assembly. Here, we present the first example of the hierarchical self-assembly of discrete metallacycles by taking advantage of the positive charges of the organoplatinum(II) metallacycle skeleton through multiple electrostatic interactions. Heparin, a sulfated glycosaminoglycan polymer that has been widely used as an anticoagulant drug, was selected to induce hierarchical self-assembly because of the existence of multiple negative charges. To investigate the hierarchical self-assembly process, an aggregation-induced emission (AIE) active moiety, tetra-phenylethylene (TPE), was introduced onto the metallacycle via coordination-driven self-assembly. Photophysical studies revealed that the addition of heparin to the tris-TPE metallacycles solution resulted in dramatic fluorescence enhancement, which supported the aggregation between metallacycle and heparin driven by multiple electrostatic interactions. Moreover, the entangled pearl-necklace networks were obtained through hierarchical self-assembly as detected by SEM, TEM, and LSCM experiments. In particular, single bead-like chains were observed in the AFM and TEM images, which provided direct, visual evidence for the aggregation of positively charged metallacycles and negatively charged heparin. More interestingly, further optical study demonstrated that this TPE-decorated metallacycle could function as a turn-on fluorescent probe for heparin detection with high sensitivity and selectivity. Thus, this research presents the first example of counter polyanion-induced hierarchical self-assembly of discrete metallacycles and provides a "proof-of-principle" method for heparin sensing and binding

  11. Self-Assembly of Chiral Metallacycles and Metallacages from a Directionally Adaptable BINOL-Derived Donor.

    PubMed

    Ye, Yang; Cook, Timothy R; Wang, Shu-Ping; Wu, Jing; Li, Shijun; Stang, Peter J

    2015-09-23

    We present the formation of a series of chiral metallacycles and metallacages by the use of a BINOL-derived dicarboxylate as a donor that is capable of affording a variety of coordination angles between its two Lewis basic sites. Two squares, two rhomboids, two tetragonal prisms, and one hexagonal prism were successfully formed when the chiral dicarboxylate donor self-assembled with one of four ditopic Pt(II) complexes, including two bimetallic 180° Pt-based acceptors, a 120° bimetallic Pt-based acceptor, and a 90° mononuclear Pt-based acceptor. Their structures were well characterized by (31)P{(1)H} NMR, ESI-MS, CD, and optical rotation analyses. PMID:26332954

  12. Construction of Smart Supramolecular Polymeric Hydrogels Cross-linked by Discrete Organoplatinum(II) Metallacycles via Post-Assembly Polymerization.

    PubMed

    Zheng, Wei; Chen, Li-Jun; Yang, Guang; Sun, Bin; Wang, Xu; Jiang, Bo; Yin, Guang-Qiang; Zhang, Li; Li, Xiaopeng; Liu, Minghua; Chen, Guosong; Yang, Hai-Bo

    2016-04-13

    Postassembly modification strategy has been successfully employed in the construction of discrete metallosupramolecular assemblies. However, the most known reports have been limited to the simple structural conversion through the easy covalent reactions, thus hindering the development of organometallic functional materials. In this study, we first combined coordination-driven self-assembly and postassembly reversible addition-fragmentation chain-transfer (RAFT) polymerization to produce a new family of star supramolecular polymers containing well-defined metallacycles as cores, which featured typical lower critical solution temperature (LCST) behavior in water because of the existence of poly(N-isopropylacrylamide) (PNIPAAM) moieties. Moreover, the obtained star polymers could further form supramolecular hydrogels cross-linked by discrete hexagonal metallacycles at room temperature without heating-cooling process. Interestingly, the resultant polymeric hydrogels exhibited stimuli-responsive behavior toward temperature and bromide anion as well as self-healing property. We demonstrated that the dynamic nature of Pt-N bonds in the hexagonal metallacycles played an important role in determining the stimuli-responsive and self-healing property of the final soft matters. Thus, merging coordination-driven self-assembly and postassembly polymerization provided a new avenue to the preparation of functional materials containing well-defined, discrete metal-organic assemblies as main scaffolds. PMID:27011050

  13. Regio- and Enantioselective N-Allylations of Imidazole, Benzimidazole, and Purine Heterocycles Catalyzed by Single-Component Metallacyclic Iridium Complexes

    PubMed Central

    Stanley, Levi M.

    2010-01-01

    Highly regio- and enantioselective iridium-catalyzed N-allylations of benzimidazoles, imidazoles, and purines have been developed. N-Allylated benzimidazoles and imidazoles were isolated in high yields (up to 97%) with high branched-to-linear selectivity (up to 99:1) and enantioselectivity (up to 98% ee) from the reactions of benzimidazole and imidazole nucleophiles with unsymmetrical allylic carbonates in the presence of single component, ethylene-bound, metallacyclic iridium catalysts. N-Allylated purines were also obtained in high yields (up to 91%) with high N9:N7 selectivity (up to 96:4), high branched-to-linear selectivity (98:2), and high enantioselectivity (up to 98% ee) under similar conditions. The reactions encompass a range of benzimidazole, imidazole, and purine nucleophiles, as well as a variety of unsymmetrical aryl, heteroaryl, and aliphatic allylic carbonates. Competition experiments between common amine nucleophiles and the heterocyclic nitrogen nucleophiles studied in this work illustrate the effect of nucleophile pKa on the rate of iridium-catalyzed N-allylation reactions. Kinetic studies on the allylation of benzimidazole catalyzed by metallacyclic iridium-phosphoramidite complexes, in combination with studies on the deactivation of these catalysts in the presence of heterocyclic nucleophiles, provide insight into the effects of the structure of the phosphoramidite ligands on the stability of the metallacyclic catalysts. The data obtained from these studies has led to the development of N-allylations of benzimidazoles and imidazoles in the absence of an exogenous base. PMID:19480431

  14. Construction of Endo-Functionalized Two Dimensional Metallacycles via Coordination-Driven Self-Assembly

    PubMed Central

    Ghosh, Koushik; Zheng, Yao-Rong

    2009-01-01

    The synthesis of three endofunctionalized two-dimensional supramolecular metallacycles including two [2 + 2] rhomboids (5 and 6) and a [3 + 3] hexagon (7) is reported. The resulting self-assembled supramolecular structures, containing several nitrobenzyl moieties at their interior surface, have been fully characterized by multinuclear NMR (31P and 1H) and electrospray ionization mass spectrometry. A significant C–H…O hydrogen bonding between the nitrobenzyl acceptor and the edge molecules of the supramolecular architecture is observed in the small rhomboid 5 and this interaction gradually decreases upon the enlargement of the resulting polygonal structures from a small rhomboid 5 through a large rhomboid 6 to a hexagon 7. Molecular modeling with the MMFF force field gives a possible conformation of each self-assembly in different solvents and shows that the hydrophilic nitrobenzyl moiety prefers to be buried in the cavity of the resulting polygonal structures in nonpolar solvents, thus forming hydrogen bonds with the peripheral component building units. PMID:19835395

  15. Towards high-valent uranium compounds from metallacyclic uranium(IV) precursors.

    PubMed

    Bénaud, Olivier; Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

    2011-08-28

    Treatment of [NaUN*(C,N)(2)] [N* = N(SiMe(3))(2); C,N = CH(2)SiMe(2)N(SiMe(3))] with I(2) led to the formation of the larger metallacycle [UN*(N{SiMe(3)}SiMe(2)CH(2)CH(2)SiMe(2)N{SiMe(3)})I] resulting from U-C cleavage and C-C coupling. Reaction of [NaUN*(O,N)(2)] [O,N = OC(=CH(2))SiMe(2)N(SiMe(3))] with I(2) afforded the U(V) complex [Na{UN*(O,N)(2)}(2)(μ-I)] which was converted into the mononuclear azido derivative [NaUN*(O,N)(2)(N(3))]. This latter was not transformed into the neutral U(VI) derivative in the presence of I(2) but afforded [U(V)(N{SiMe(3)}SiMe(2)C{CHI}O)(2)I(THF)], resulting from a cascade of addition, substitution and protonolysis reactions. PMID:21766108

  16. Light-Emitting Superstructures with Anion Effect: Coordination-Driven Self-Assembly of Pure Tetraphenylethylene Metallacycles and Metallacages.

    PubMed

    Yan, Xuzhou; Wang, Ming; Cook, Timothy R; Zhang, Mingming; Saha, Manik Lal; Zhou, Zhixuan; Li, Xiaopeng; Huang, Feihe; Stang, Peter J

    2016-04-01

    Herein, we describe the synthesis of tetraphenylethylene (TPE)-based di-Pt(II) acceptors as shown by X-ray analysis, which are subsequently used to construct pure TPE-based 2D hexagonal metallacycles and 3D drumlike metallacages with three different counteranions via coordination-driven self-assembly. The metallacycles possess alternating TPE donor and acceptor units that arrange 12 pendant phenyl rings along the outer perimeter that provide the basis for the observed aggregation-induced emission (AIE) behavior. The metallacages are similarly constructed from TPE-based building blocks, specifically two donors and four acceptors, resulting in eight freely rotating phenyl rings decorating the prismatic core. The fluorescence of these cages in dilute solution is intensified when hexane is added to CH2Cl2 solutions, indicative of aggregation-induced enhanced emission (AIEE). The influence of the counteranions on the photophysics of the assemblies was investigated. The molar absorption coefficients (ε), fluorescence emission intensities, and quantum yield (ΦF) values of the SCCs with different counteranions in CH2Cl2 follow the order PF6(-) > OTf(-) > NO3(-). The same trend also applies to the AIE characteristics of the SCCs in the aggregated state. The metal-organic materials developed here not only enrich a newly emerging library of self-assembly AIE metallacycles and cages that are promising candidates for turn-on fluorescent sensors and advanced optical devices but also provide an understanding of how structural factors affect the photophysics of AIE-active SCCs. PMID:26982213

  17. Spin labeling EPR.

    PubMed

    Klare, Johann P; Steinhoff, Heinz-Jürgen

    2009-01-01

    Site-directed spin labeling in combination with electron paramagnetic resonance spectroscopy has emerged as an efficient tool to elucidate the structure and conformational dynamics of biomolecules under native-like conditions. This article summarizes the basics as well as recent progress of site-directed spin labeling. Continuous wave EPR spectra analyses and pulse EPR techniques are reviewed with special emphasis on applications to the sensory rhodopsin-transducer complex mediating the photophobic response of the halophilic archaeum Natronomonas pharaonis and the photosynthetic reaction center from Rhodobacter sphaeroides R26. PMID:19728138

  18. Synthesis of the Cortistatin Pentacyclic Core by Alkoxide-Directed Metallacycle-Mediated Annulative Cross-Coupling.

    PubMed

    Aquino, Claudio; Greszler, Stephen N; Micalizio, Glenn C

    2016-06-01

    The pentacyclic core skeleton of the cortistatins has been prepared in a stereoselective fashion by strategic use of an alkoxide-directed metallacycle-mediated annulative cross-coupling. This metal-centered tandem reaction delivers a polyunsaturated hydrindane and establishes the C13 stereodefined quaternary center with high levels of stereocontrol. Subsequent regio- and stereoselective global hydroboration results in the realization of the DE-trans ring fusion and a tertiary alcohol at C8. Establishment of the ABC-tricyclic subunit was then accomplished through phenolic oxidation/trans-acetalization, chemoselective reduction, regioselective cleavage, and intramolecular alkylation at C5. PMID:27193994

  19. Biomedical and Biochemical Applications of Self-Assembled Metallacycles and Metallacages

    PubMed Central

    Vajpayee, Vaishali; Lee, Min Hyung; Chi, Ki-Whan

    2013-01-01

    Conspectus Coordination-driven self-assembly utilizes the spontaneous formation of metal-ligand bonds in solution to drive mixtures of molecular building blocks to single, unique 2D metallacycles or 3D metallacages based on the directionality of the precursors used. The supramolecular coordination complexes (SCCs) obtained via this process are characterized by well-defined internal cavities and facile pre- or post-self-assembly functionalizations. These properties augment the modularity of the directional bonding design strategy to afford structures with unprecedented tunability both spatially and electronically. Over the past decades, a number of synthetic design methodologies have become established which has led to a substantial library of complexes supported by numerous structural studies. More recently, there has been an emergence of research centered on the potential applications of SCCs, which has developed rapidly on the foundations provided by the aforementioned synthetic and structural bodies of work. The necessary presence of metal ions as structural elements for the directional bonding approach can be exploited to provide biological activity to an SCC, particularly for Pt and Ru-based structures. Since these two metals are not only among the most commonly used for coordination-driven self-assembly but are also the basis for a number of small molecule anticancer agents, a growing number of SCCs have been evaluated for their antitumor properties. When the internal cavity of a cage is optimized for guest encapsulation, a second vector for biological activity, namely drug delivery, is unlocked. Since cages can offer both inherent activity due to their metal ions, as well as delivery of exogenous drug molecules, such ensembles are particularly promising chemotherapeutic agents. The non-covalent interactions of SCCs with guest molecules oftentimes manifest photophysical changes to the resulting host/guest complex. Since a metallacage or cycle can be readily

  20. Hemichelation, a way to stabilize electron-unsaturated complexes: the case of T-shaped Pd and Pt metallacycles.

    PubMed

    Werlé, Christophe; Bailly, Corinne; Karmazin-Brelot, Lydia; Le Goff, Xavier-Frédéric; Ricard, Louis; Djukic, Jean-Pierre

    2013-11-27

    A rational method of synthesis of stable neutral T-shaped 14 electron Pd and Pt complexes is proposed. It takes advantage of the ambiphilic character of the tricarbonyl(η(6)-indenyl)chromium anion, of which the main property is to behave as a hemichelating ligand, that is a nonconventional heteroditopic ligand capable of chelating a metal center by way of covalent and noncovalent bonding, thus preserving its unsaturated valence shell. The reaction of the in situ formed tricarbonyl(η(6)-2-methylindenyl)chromium anion with a series of Pd and Pt metallacycles afforded new air-stable and persistent synfacial heterobimetallic complexes in which the metallacycle binds the indenyl fragment via its metal in an η(1) fashion, leaving the fourth coordination site at the chelated metal virtually vacant. The structures of eight of these novel complexes are disclosed, and their bonding features are investigated by an array of theoretical methods based on the density functional theory (NBO, EDA, ETS-NOCV, AIM, NCI region analysis). Theory shows that the formation of these unusual structures of bimetallic synfacial η(1)-indenyl-Pd/Pt complexes is driven thermodynamically by attractive Coulombic occlusion of the fourth vacant coordination site at Pd/Pt centers by the Cr(CO)3 moiety. PMID:24182317

  1. Construction of tetranuclear metallacycles based on half-sandwich Ir, Rh fragments and pyridyl-substituted ligands with different coordinate vectors.

    PubMed

    Fan, Qi-Jia; Zhang, Wen-Ying; Lin, Yue-Jian; Jin, Guo-Xin

    2016-03-21

    A series of organometallic macrocycles have been constructed by two-step reactions of [Cp*M(μ-Cl)Cl]2 (M = Ir, Rh), firstly with AgOTf to abstract chloride ions and then with simple pyridyl-substituted ligands-pyridyldipyrromethene (HL(1)), pyridin-4-yl (1H-pyrrol-2-yl)methanone (HL(2)) and pyridine-4-carbohydrazide (HL(3))-resulting in the formation of the tetranuclear 32-membered metallacycles [(Cp*Ir)(L(1))]4(OTf)4 (2a) and [(Cp*Rh)(L(1))]4(OTf)4 (2b), and the 28-membered metallacycles [(Cp*Ir)(L(2))]4 (OTf)4 (3a), [(Cp*Rh)(L(2))]4(OTf)4 (3b), [(Cp*Ir)(L(3))]4(OTf)4 (4a) and [(Cp*Rh)(L(3))]4(OTf)4 (4b). Four target complexes were characterised by single crystal X-ray analyses, revealing that these metallacycles, constructed from half-sandwich metal corners and pyridyl-substituted linkers, form large ring structures. The observed variation in the metallacyclic geometries was explained on the basis of the structural flexibility of the corner fragments, subtle changes in coordination geometries, and changes in the orientation of the coordinate vectors in the given ligands, as well as different dihedral angles between the two binding fragments in the nonplanar ligands. PMID:26845526

  2. Reactivity of cationic agostic and carbene structures derived from platinum(II) metallacycles.

    PubMed

    Campos, Jesús; Ortega-Moreno, Laura; Conejero, Salvador; Peloso, Riccardo; López-Serrano, Joaquín; Maya, Celia; Carmona, Ernesto

    2015-06-01

    This paper describes the formation of new platinacyclic complexes derived from the phosphine ligands PiPr2 Xyl, PMeXyl2 , and PMe2 Ar Xyl 2 (Xyl=2,6-Me2 C6 H3 and Ar Xyl 2=2,6-(2,6-Me2 C6 H3 )2 -C6 H3 ) as well as reactivity studies of the trans-[Pt(C^P)2 ] bis-metallacyclic complex 1 a derived from PiPr2 Xyl. Protonation of compound 1 a with [H(OEt2 )2 ][BArF ] (BArF =B[3,5-(CF3 )2 C6 H3 ]4 ) forms a cationic δ-agostic structure 4 a, whereas α-hydride abstraction employing [Ph3 C][PF6 ] produces a cationic platinum carbene trans-[Pt{PiPr2 (2,6-CH(Me)C6 H3 }{PiPr2 (2,6-CH2 (Me)C6 H3 }][PF6 ] (8). Compounds 4 a and 8 react with H2 to yield the same 1:3 equilibrium mixture of 4 a and trans-[PtH(PiPr2 Xyl)2 ][BArF ] (6), in which one of the phosphine ligands participates in a δ-agostic interaction. DFT calculations reveal that H2 activation by 8 occurs at the highly electrophilic alkylidene terminus with no participation of the metal. The two compounds 4 a and 8 experience C-C coupling reactions of a different nature. Thus, 4 a gives rise to complex trans-[PtH{(E)-1,2-bis(2-(PiPr2 )-3-MeC6 H3 )CHCH}] (7) that contains a tridentate diphosphine-alkene ligand, through agostic CH oxidative cleavage and C-C reductive coupling steps, whereas the C-C coupling reaction in 8 involves classical migratory insertion of its [PtCH] and [PtCH2 ] bonds promoted by platinum coordination of CO or CNXyl. The mechanisms of the CC bond-forming reactions have also been investigated by computational methods. PMID:25959723

  3. Rapid frequency scan EPR.

    PubMed

    Tseitlin, Mark; Rinard, George A; Quine, Richard W; Eaton, Sandra S; Eaton, Gareth R

    2011-08-01

    In rapid frequency scan EPR with triangular scans, sufficient time must be allowed to insure that the magnetization in the x, y plane decays to baseline at the end of the scan, which typically is about 5T(2) after the spins are excited. To permit relaxation of signals excited toward the extremes of the scan the total scan time required may be much longer than 5T(2). However, with periodic, saw-tooth excitation, the slow-scan EPR spectrum can be recovered by Fourier deconvolution of data recorded with a total scan period of 5T(2), even if some spins are excited later in the scan. This scan time is similar to polyphase excitation methods. The peak power required for either polyphase excitation or rapid frequency scans is substantially smaller than for pulsed EPR. The use of an arbitrary waveform generator (AWG) and cross loop resonator facilitated implementation of the rapid frequency scan experiments reported here. The use of constant continuous low B(1), periodic excitation waveform, and constant external magnetic field is similar to polyphase excitation, but could be implemented without the AWG that is required for polyphase excitation. PMID:21664848

  4. Rapid Frequency Scan EPR

    PubMed Central

    Tseitlin, Mark; Rinard, George A.; Quine, Richard W.; Eaton, Sandra S.; Eaton, Gareth R.

    2011-01-01

    In rapid frequency scan EPR with triangular scans, sufficient time must be allowed to insure that the magnetization in the x,y plane decays to baseline at the end of the scan, which typically is about 5 T2 after the spins are excited. To permit relaxation of signals excited toward the extremes of the scan the total scan time required may be much longer than 5 T2. However, with periodic, saw-tooth excitation, the slow-scan EPR spectrum can be recovered by Fourier deconvolution of data recorded with a total scan period of 5 T2, even if some spins are excited later in the scan. This scan time is similar to polyphase excitation methods. The peak power required for either polyphase excitation or rapid frequency scans is substantially smaller than for pulsed EPR. The use of an arbitrary waveform generator (AWG) and cross loop resonator facilitated implementation of the rapid frequency scan experiments reported here. The use of constant continuous low B1, periodic excitation waveform, and constant external magnetic field is similar to polyphase excitation, but could be implemented without the AWG that is required for polyphase excitation. PMID:21664848

  5. Broadband Transmission EPR Spectroscopy

    PubMed Central

    Hagen, Wilfred R.

    2013-01-01

    EPR spectroscopy employs a resonator operating at a single microwave frequency and phase-sensitive detection using modulation of the magnetic field. The X-band spectrometer is the general standard with a frequency in the 9–10 GHz range. Most (bio)molecular EPR spectra are determined by a combination of the frequency-dependent electronic Zeeman interaction and a number of frequency-independent interactions, notably, electron spin – nuclear spin interactions and electron spin – electron spin interactions, and unambiguous analysis requires data collection at different frequencies. Extant and long-standing practice is to use a different spectrometer for each frequency. We explore the alternative of replacing the narrow-band source plus single-mode resonator with a continuously tunable microwave source plus a non-resonant coaxial transmission cell in an unmodulated external field. Our source is an arbitrary wave digital signal generator producing an amplitude-modulated sinusoidal microwave in combination with a broadband amplifier for 0.8–2.7 GHz. Theory is developed for coaxial transmission with EPR detection as a function of cell dimensions and materials. We explore examples of a doublet system, a high-spin system, and an integer-spin system. Long, straigth, helical, and helico-toroidal cells are developed and tested with dilute aqueous solutions of spin label hydroxy-tempo. A detection limit of circa 5 µM HO-tempo in water at 800 MHz is obtained for the present setup, and possibilities for future improvement are discussed. PMID:23555819

  6. Retrocausal models for EPR

    NASA Astrophysics Data System (ADS)

    Corry, Richard

    2015-02-01

    This paper takes up Huw Price's challenge to develop a retrocausal toy model of the Bell-EPR experiment. I develop three such models which show that a consistent, local, hidden-variables interpretation of the EPR experiment is indeed possible, and which give a feel for the kind of retrocausation involved. The first of the models also makes clear a problematic feature of retrocausation: it seems that we cannot interpret the hidden elements of reality in a retrocausal model as possessing determinate dispositions to affect the outcome of experiments. This is a feature which Price has embraced, but Gordon Belot has argued that this feature renders retrocausal interpretations "unsuitable for formal development", and the lack of such determinate dispositions threatens to undermine the motivation for hidden-variables interpretations in the first place. But Price and Belot are both too quick in their assessment. I show that determinate dispositions are indeed consistent with retrocausation. What is more, I show that the ontological economy allowed by retrocausation holds out the promise of a classical understanding of spin and polarization.

  7. A Suite of Tetraphenylethylene-Based Discrete Organoplatinum(II) Metallacycles: Controllable Structure and Stoichiometry, Aggregation-Induced Emission, and Nitroaromatics Sensing.

    PubMed

    Yan, Xuzhou; Wang, Haoze; Hauke, Cory E; Cook, Timothy R; Wang, Ming; Saha, Manik Lal; Zhou, Zhixuan; Zhang, Mingming; Li, Xiaopeng; Huang, Feihe; Stang, Peter J

    2015-12-01

    Materials that organize multiple functionally active sites, especially those with aggregation-induced emission (AIE) properties, are of growing interest due to their widespread applications. Despite promising early architectures, the fabrication and preparation of multiple AIEgens, such as multiple tetraphenylethylene (multi-TPE) units, in a single entity remain a big challenge due to the tedious covalent synthetic procedures often accompanying such preparations. Coordination-driven self-assembly is an alternative synthetic methodology with the potential to deliver multi-TPE architectures with light-emitting characteristics. Herein, we report the preparation of a new family of discrete multi-TPE metallacycles in which two pendant phenyl rings of the TPE units remain unused as a structural element, representing novel AIE-active metal-organic materials based on supramolecular coordination complex platforms. These metallacycles possess relatively high molar absorption coefficients but weak fluorescent emission under dilute conditions because of the ability of the untethered phenyl rings to undergo torsional motion as a non-radiative decay pathway. Upon molecular aggregation, the multi-TPE metallacycles show AIE-activity with markedly enhanced quantum yields. Moreover, on account of their AIE characteristics in the condensed state and ability to interact with electron-deficient substrates, the photophysics of these metallacycles is sensitive to the presence of nitroaromatics, motivating their use as sensors. This work represents a unification of themes including molecular self-assembly, AIE, and fluorescence sensing and establishes structure-property-application relationships of multi-TPE scaffolds. The fundamental knowledge obtained from the current research facilitates progress in the field of metal-organic materials, metal-coordination-induced emission, and fluorescent sensing. PMID:26550682

  8. EPR, Biology, and Consciousness

    NASA Astrophysics Data System (ADS)

    Goradia, Shantilal

    2006-03-01

    It seems that Darwin, in his concluding remark (1859, p490) ruled out the possibility of cosmic connection to evolution based on the fixed law of gravity, known then. More recent Dirac’s Large Number Hypothesis as described in http://www.arXiv.org/pdf/physics/0210040 v1 raises a possibility that the universal constant of gravity is decreasing and all coupling constants are increasing with time, so reported by some observations. Deeper investigation of the connection between evolution and the variation of the universal constant of gravity seems worthwhile to see if it impacts the passage of time in a stronger (gravitational according to the spirit of the above archive) field and affects the aging process, and explains locality and causality in random evolutionary mutations. If there is no physical locality and causality consistent with the special theory of relativity, there must be some spiritual locality and causality at superluminal speeds to explain the implicit hidden variables. Then there is a question of how to test spiritual locality and causality. Psychic effects and dream signals look promising, if they exist and can be tested with space age technology. This is neither about religion nor about Einstein’s orthodoxy in light of the spirit of EPR. This is about frontiers of science of the new millennium: biology, and consciousness.

  9. Planar microresonators for EPR experiments.

    PubMed

    Narkowicz, R; Suter, D; Stonies, R

    2005-08-01

    EPR resonators on the basis of standing-wave cavities are optimised for large samples. For small samples it is possible to design different resonators that have much better power handling properties and higher sensitivity. Other parameters being equal, the sensitivity of the resonator can be increased by minimising its size and thus increasing the filling factor. Like in NMR, it is possible to use lumped elements; coils can confine the microwave field to volumes that are much smaller than the wavelength. We discuss the design and evaluation of EPR resonators on the basis of planar microcoils. Our test resonators, which operate at a frequency of 14 GHz, have excellent microwave efficiency factors, achieving 24 ns pi/2 EPR pulses with an input power of 17 mW. The sensitivity tests with DPPH samples resulted in the sensitivity value 2.3 x 10(9) spins.G(-1) Hz(-1/2) at 300 K. PMID:15939642

  10. Planar microresonators for EPR experiments

    NASA Astrophysics Data System (ADS)

    Narkowicz, R.; Suter, D.; Stonies, R.

    2005-08-01

    EPR resonators on the basis of standing-wave cavities are optimised for large samples. For small samples it is possible to design different resonators that have much better power handling properties and higher sensitivity. Other parameters being equal, the sensitivity of the resonator can be increased by minimising its size and thus increasing the filling factor. Like in NMR, it is possible to use lumped elements; coils can confine the microwave field to volumes that are much smaller than the wavelength. We discuss the design and evaluation of EPR resonators on the basis of planar microcoils. Our test resonators, which operate at a frequency of 14 GHz, have excellent microwave efficiency factors, achieving 24 ns π/2 EPR pulses with an input power of 17 mW. The sensitivity tests with DPPH samples resulted in the sensitivity value 2.3 × 10 9 spins · G -1Hz -1/2 at 300 K.

  11. Cross-linked supramolecular polymer gels constructed from discrete multi-pillar[5]arene metallacycles and their multiple stimuli-responsive behavior.

    PubMed

    Li, Zhong-Yu; Zhang, Yanyan; Zhang, Chang-Wei; Chen, Li-Jun; Wang, Chao; Tan, Hongwei; Yu, Yihua; Li, Xiaopeng; Yang, Hai-Bo

    2014-06-18

    A new family of discrete hexakis-pillar[5]arene metallacycles with different sizes have been successfully prepared via coordination-driven self-assembly, which presented very few successful examples of preparation of discrete multiple pillar[n]arene derivatives. These newly designed hexakis-pillar[5]arene metallacycles were well characterized with one-dimensional (1-D) multinuclear NMR ((1)H and (31) P NMR), two-dimensional (2-D) (1)H-(1)H COSY and NOESY, ESI-TOF-MS, elemental analysis, and PM6 semiempirical molecular orbital methods. Furthermore, the host-guest complexation of such hexakis-pillar[5]arene hosts with a series of different neutral ditopic guests G1-6 were well investigated. Through host-guest interactions of hexakis-pillar[5]arene metallacycles H2 or H3 with the neutral dinitrile guest G5, the cross-linked supramolecular polymers H2⊃(G5)3 or H3⊃(G5)3 were successfully constructed at the high-concentration region, respectively. Interestingly, these cross-linked supramolecular polymers transformed into the stable supramolecular gels upon increasing the concentrations to a relatively high level. More importantly, by taking advantage of the dynamic nature of metal-ligand bonds and host-guest interactions, the reversible multiple stimuli-responsive gel-sol phase transitions of such polymer gels were successfully realized under different stimuli, such as temperature, halide, and competitive guest, etc. The mechanism of such multiple stimuli-responsive processes was well illustrated by in situ multinuclear NMR investigation. This research not only provides a highly efficient approach to the preparation of discrete multiple pillar[n]arene derivatives but also presents a new family of multiple stimuli-responsive "smart" soft matters. PMID:24571308

  12. A cryogenic receiver for EPR.

    PubMed

    Narkowicz, R; Ogata, H; Reijerse, E; Suter, D

    2013-12-01

    Cryogenic probes have significantly increased the sensitivity of NMR. Here, we present a compact EPR receiver design capable of cryogenic operation. Compared to room temperature operation, it reduces the noise by a factor of ≈2.5. We discuss in detail the design and analyze the resulting noise performance. At low microwave power, the input noise density closely follows the emission of a cooled 50Ω resistor over the whole measurement range from 20K up to room temperature. To minimize the influence of the microwave source noise, we use high microwave efficiency (≈1.1-1.7mTW(-1/2)) planar microresonators. Their efficient conversion of microwave power to magnetic field permits EPR measurements with very low power levels, typically ranging from a few μW down to fractions of nW. PMID:24161681

  13. EPR-based material modelling of soils

    NASA Astrophysics Data System (ADS)

    Faramarzi, Asaad; Alani, Amir M.

    2013-04-01

    In the past few decades, as a result of the rapid developments in computational software and hardware, alternative computer aided pattern recognition approaches have been introduced to modelling many engineering problems, including constitutive modelling of materials. The main idea behind pattern recognition systems is that they learn adaptively from experience and extract various discriminants, each appropriate for its purpose. In this work an approach is presented for developing material models for soils based on evolutionary polynomial regression (EPR). EPR is a recently developed hybrid data mining technique that searches for structured mathematical equations (representing the behaviour of a system) using genetic algorithm and the least squares method. Stress-strain data from triaxial tests are used to train and develop EPR-based material models for soil. The developed models are compared with some of the well-known conventional material models and it is shown that EPR-based models can provide a better prediction for the behaviour of soils. The main benefits of using EPR-based material models are that it provides a unified approach to constitutive modelling of all materials (i.e., all aspects of material behaviour can be implemented within a unified environment of an EPR model); it does not require any arbitrary choice of constitutive (mathematical) models. In EPR-based material models there are no material parameters to be identified. As the model is trained directly from experimental data therefore, EPR-based material models are the shortest route from experimental research (data) to numerical modelling. Another advantage of EPR-based constitutive model is that as more experimental data become available, the quality of the EPR prediction can be improved by learning from the additional data, and therefore, the EPR model can become more effective and robust. The developed EPR-based material models can be incorporated in finite element (FE) analysis.

  14. A simplified apparatus for EPR imaging

    NASA Astrophysics Data System (ADS)

    Jingchuan, Deng; Kuixiang, Wang; Weiqing, Xu

    1996-06-01

    A simple apparatus for sub-surface electron paramagnetic resonance (EPR) imaging of a cut sample is described. A two-dimensional EPR image corresponding to the electron spin-density distribution of the DPPH test sample has been obtained by using a marginally oscillating self-detecting microwave frequency EPR spectrometer. Higher spatial resolution is obtained by using a deconvolution algorithm and the image processing technique of inverse filtering.

  15. Synthesis of the molecular amalgam [{AuHg₂(o-C₆F₄)₃}{Hg₃(o-C₆F₄)₃}]⁻: a rare example of a heterometallic homoleptic metallacycle.

    PubMed

    Lasanta, Tania; López-de-Luzuriaga, José M; Monge, Miguel; Olmos, M Elena; Pascual, David

    2016-04-21

    The preparation of homoleptic heterometallic complexes still remains a challenge. Herein, we report the synthesis and characterization of [Au(PMe3)2][{AuHg2(o-C6F4)3}{Hg3(o-C6F4)3}] (), a gold-mercury homoleptic metallacycle. The crystal structure of displays two [Hg2M(o-C6F4)3] (M = Au(I), Hg(II)) units linked through a short AuHg contact of 3.097(2) Å, the strongest unsupported Au(I)Hg(II) interaction described to date. Theoretical calculations quantify the interaction between the trimetalic units as -199 kJ mol(-1), a surprisingly strong value. PMID:26983855

  16. EPR techniques for space biodosimetry

    SciTech Connect

    Haskell, E.; Hayes, R.; Kenner, G.; Sholom, S.; Chumak, V.

    1996-12-31

    Retrospective dosimetry of tooth enamel has become an increasingly complex and difficult discipline to undertake while still attaining accuracy. The paper provides a review of the major obstacles, advances and pertinent phenomenon associated with low level retrospective dosimetry of human tooth enamel. Also covered is the many sources of error in EPR dosimetry, their potential solutions, as well as the different analysis and scanning techniques in use with their prospective pros and cons. Prospective directions for new approaches, methods, and instruments are also reviewed.

  17. Zinc(II) and cadmium(II) monohydroxide bridged, dinuclear metallacycles: a unique case of concerted double Berry pseudorotation.

    PubMed

    Reger, Daniel L; Pascui, Andrea E; Pellechia, Perry J; Smith, Mark D

    2013-10-01

    The reactions of M(ClO4)2·6H2O [M = Zn(II), Cd(II)] and the ligands m-bis[bis(1-pyrazolyl)methyl]benzene, L(m), or m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene, L(m)*, in the presence of a base yield the hydroxide bridged dinuclear metallacycles [M2(μ-OH)(μ-L)2](ClO4)3, L = L(m), M = Zn(II) (1); L = L(m)*, M = Zn(II) (2), Cd(II) (3). In the solid state, the coordination environment of the metals is distorted trigonal bipyramidal with the bridging hydroxide in an equatorial position and M-O-M angles greater than 161°. The observation of two equal intensity resonances for each type of pyrazolyl-ring hydrogen in the (1)H NMR for all three complexes coupled with the determination of the hydrodynamic radius based on the diffusion coefficient of 1 that matches that observed in the crystal structure, demonstrate this structure is retained in solution. Additional proof of the dinuclear structures in solution is given by the (113)Cd NMR spectrum of [Cd2(μ-OH)(μ-L(m)*)2](ClO4)3 showing (111/113)Cd satellites (J(111)(Cd-)(113)(Cd) = 173 Hz). Complex 1 is dynamic in solution, with the resonances for each type of pyrazolyl-ring hydrogen broadening and averaging at higher temperatures. Detailed variable temperature studies show that ΔG(pz)(‡) = 15.2(±0.2) kcal/mol, ΔH(pz)(‡) = 6.6(±0.1) kcal/mol, and ΔS(pz)(‡) = -28.8(±0.4) cal/mol·K at 25 °C for this process. The same ΔG(‡) value for the dynamic process was also determined by saturation transfer experiments. The most plausible mechanism for this dynamic process, which exchanges the axial and equatorial positions of the pyrazolyl rings in the trigonal bipyramidal arrangement, involves Berry pseudorotation at both metal sites using the bridging oxygen atom as the pivot ligand, coupled with the ring flip of the ligand's phenylene spacer by 180°, a rearrangement process we termed the "Columbia Twist and Flip". This process was shown to be influenced by trace amounts of water in the solvent, with a

  18. Overview of LBB implementation for the EPR

    SciTech Connect

    Cauquelin, C.

    1997-04-01

    This paper presents an overview of the use of leak-before-break (LBB) analysis for EPR reactors. EPR is an evolutionary Nuclear Island of the 4 loop x 1500 Mwe class currently in the design phase. Application of LBB to the main coolant lines and resulting design impacts are summarized. Background information on LBB analysis in France and Germany is also presented.

  19. EPR STUDIES OF THERMALLY STERILIZED VASELINUM ALBUM.

    PubMed

    Ramos, Paweł; Pilawa, Barbara

    2015-01-01

    Electron paramagnetic resonance (EPR) spectroscopy was used for examination of free radicals in thermally treated vaselinum album (VA). Thermal treatment in hot air as sterilization process was tested. Conditions of thermal sterilization were chosen according to the pharmaceutical norms. Vaselinum album was heated at the following conditions (T--temperature, t--time): T = 160°C and t = 120 min, T = 170°C and t = 60 min and T = 180°C and t = 30 min. The aim of this work was to determine concentration and free radical properties of thermally sterilized VA. EPR analysis for VA was done 15 min after sterilization. EPR measurements were done at room temperature. EPR spectra were recorded in the range of microwave power of 2.2-70 mW. g-Factor, amplitudes (A) and line width (ΔBpp) of the spectra were determined. The shape of the EPR spectra was analyzed. Free radical concentration (N) in the heated samples was determined. EPR spectra were not obtained for the non heated VA. EPR spectra were detected for all thermally sterilized samples. The spectra revealed complex character, their asymmetry depends on microwave power. The lowest free radicals concentration was found for the VA sterilized at 180°C during 30 min. EPR spectroscopy is proposed as the method useful for optimization of sterilization process of drugs. PMID:26647625

  20. EPR dosimetry in chemically treated fingernails

    Technology Transfer Automated Retrieval System (TEKTRAN)

    By using EPR measurements of radiation-induced radicals it is possible to utilize human fingernails to estimate radiation dose after-the-fact. One of the potentially limiting factors in this approach is the presence of artifacts due to mechanically induced EPR signals (MIS) caused by mechanical str...

  1. In Vivo EPR For Dosimetry

    PubMed Central

    Swartz, Harold M.; Burke, Greg; Coey, M.; Demidenko, Eugene; Dong, Ruhong; Grinberg, Oleg; Hilton, James; Iwasaki, Akinori; Lesniewski, Piotr; Kmiec, Maciej; Lo, Kai-Ming; Nicolalde, R. Javier; Ruuge, Andres; Sakata, Yasuko; Sucheta, Artur; Walczak, Tadeusz; Williams, Benjamin B.; Mitchell, Chad; Romanyukha, Alex; Schauer, David A.

    2007-01-01

    As a result of terrorism, accident, or war, populations potentially can be exposed to doses of ionizing radiation that could cause direct clinical effects within days or weeks. There is a critical need to determine the magnitude of the exposure to individuals so that those with significant risk have appropriate procedures initiated immediately, while those without a significant probability of acute effects can be reassured and removed from the need for further consideration in the medical/emergency system. In many of the plausible scenarios there is an urgent need to make the determination very soon after the event and while the subject is still present. In vivo EPR measurements of radiation-induced changes in the enamel of teeth is a method, perhaps the only such method, which can differentiate among doses sufficiently for classifying individuals into categories for treatment with sufficient accuracy to facilitate decisions on medical treatment. In its current state, the in vivo EPR dosimeter can provide estimates of absorbed dose with an error approximately ± 50 cGy over the range of interest for acute biological effects of radiation, assuming repeated measurements of the tooth in the mouth of the subject. The time required for acquisition, the lower limit, and the precision are expected to improve, with improvements in the resonator and the algorithm for acquiring and calculating the dose. The magnet system that is currently used, while potentially deployable, is somewhat large and heavy, requiring that it be mounted on a small truck or trailer. Several smaller magnets, including an intraoral magnet are under development, which would extend the ease of use of this technique. PMID:18591988

  2. Homogeneity and EPR metrics for assessment of regular grids used in CW EPR powder simulations.

    PubMed

    Crăciun, Cora

    2014-08-01

    CW EPR powder spectra may be approximated numerically using a spherical grid and a Voronoi tessellation-based cubature. For a given spin system, the quality of simulated EPR spectra depends on the grid type, size, and orientation in the molecular frame. In previous work, the grids used in CW EPR powder simulations have been compared mainly from geometric perspective. However, some grids with similar homogeneity degree generate different quality simulated spectra. This paper evaluates the grids from EPR perspective, by defining two metrics depending on the spin system characteristics and the grid Voronoi tessellation. The first metric determines if the grid points are EPR-centred in their Voronoi cells, based on the resonance magnetic field variations inside these cells. The second metric verifies if the adjacent Voronoi cells of the tessellation are EPR-overlapping, by computing the common range of their resonance magnetic field intervals. Beside a series of well known regular grids, the paper investigates a modified ZCW grid and a Fibonacci spherical code, which are new in the context of EPR simulations. For the investigated grids, the EPR metrics bring more information than the homogeneity quantities and are better related to the grids' EPR behaviour, for different spin system symmetries. The metrics' efficiency and limits are finally verified for grids generated from the initial ones, by using the original or magnetic field-constraint variants of the Spherical Centroidal Voronoi Tessellation method. PMID:24968092

  3. The bis metallacyclic anion [U(N{SiMe3}2)(CH2SiMe2N{SiMe3})2]-.

    PubMed

    Bénaud, Olivier; Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

    2010-09-01

    A series of bis metallacyclic compounds [M(THF)(x)UN*(CH(2)SiMe(2)N{SiMe(3)})(2)](n) [M = Na (2), Li (3), or K (4), N* = N(SiMe(3))(2)] were isolated from reactions of UCl(4) or [UN*(3)Cl] with MN* or by treatment of [UN*(2)(CH(2)SiMe(2)N{SiMe(3)})] (1) or [UN*(3)] with MN*, MH, or LiCH(2)SiMe(3) in tetrahydrofuran (THF). Crystals of 2a x 1/6n-pentane (x = 0), 2b (x = 1), 2c (x = 2), and 4b (x = 1) were obtained by crystallization of 2 and 4 from pentane, and [Na(18-crown-6)(THF)][UN*(CH(2)SiMe(2)N{SiMe(3)})(2)] (2d) and [Na(15-crown-5)][UN*(CH(2)SiMe(2)N{SiMe(3)})(2)] (2e) were formed upon addition of the crown ether. The crystal structures of 2a-2e and 4b exhibit the same [UN*(CH(2)SiMe(2)N{SiMe(3)})(2)] units which are linked to Na or K atoms via methylene or methyl groups, giving either tight cation-anion pairs (2d and 2e) or one-dimensional (1D) or two-dimensional (2D) polymeric compounds with Na or K atoms in bridging position between methylene groups of adjacent units. Reaction of 2 with CO gave the double insertion derivative [Na(2)(THF)U(2)N*(2)(OC{=CH(2)}SiMe(2)N{SiMe(3)})(4)] (5b) and [Na(15-crown-5)UN*(OC{=CH(2)}SiMe(2)N{SiMe(3)})(2)] (5c) in the presence of the crown ether. Thermal decomposition of 5b gave [Na(2)(THF)U(OC{=CH(2)}SiMe(2)N{SiMe(3)})(3)](2) (6), the product of CO insertion into the putative tris metallacycle [Na(2)(THF)(x)U(CH(2)SiMe(2)N{SiMe(3)})(3)]. The crystal structures of 5b, 5c, and 6 show the interaction of the Na atoms with the exocyclic C=CH(2) bonds. Diffusion of CO(2) into a THF solution of 2 led to the formation of [Na(THF)(x)UN*(OC{O}CH(2)SiMe(2)N{SiMe(3)})(2)] (7) which crystallized from pyridine/pentane to give [Na(THF)(2)(py)(2)UN*(OC{O}CH(2)SiMe(2)N{SiMe(3)})(2)] x 0.5 py (8 x 0.5 py), the first crystallographically characterized complex resulting from CO(2) insertion into a M(CH(2)SiMe(2)N{SiMe(3)}) metallacycle. Compound 2 reacted with I(2) to give [UN*(CH(2)SiMe(2)N{SiMe(3)})(N{SiMe(3)}SiMe(2)CH(2)I)] (9) which would

  4. Shared experience in 13 local Danish EPR projects: the Danish EPR Observatory.

    PubMed

    Nøhr, C; Kristensen, M; Andersen, S K; Vingtoft, S; Lippert, S; Berstein, K; Bruun-Rasmussen, M

    2001-01-01

    In 1996 a national strategy for the development of electronic patient records (EPR) for the Danish hospitals and primary care was launched. An element in the strategy was to support a number of regional EPR development projects. The EPR-Observatory has in the two recent years collected data from the regional projects, dealing with the expectations in four areas: 1) Impact on organisational issues, 2) Benefits of EPR, 3) Integration of EPR with other information systems and 4) security aspects of EPR. Among the observations an increasing teamwork and im-proved knowledge about the patient was found. What was expected, but not found, was resistance to EPR, as a result of changes in skills and power. The most obvious benefits are increased data accessibility and improved decision ma-king. The most considerable disadvantage is an enormous growth in discontent with the systems performance and the fact, that all the projects are delayed. Many different types of integration solutions are chosen, because of a lack of a common model for integration. Generally the projects find, that EPJ yields increased security, but logistical problems arise in having the systems running 24 hours 7 days a week. Economical benefits cannot be documented. This relates to the fact, that the regional projects are stand-alone projects. The ongoing growth in discontent with the EPR-systems and the fact, that all the projects are delayed must be subject to further exploration. PMID:11604822

  5. Pulsed EPR Imaging of Nitroxides in Mice

    PubMed Central

    Hyodo, Fuminori; Matsumoto, Shingo; Devasahayam, Nallathamby; Dharmaraj, Christopher; Subramanian, Sankaran; Mitchell, James B.; Krishna, Murali C.

    2012-01-01

    Nitroxides, unlike trityl radicals, have shorter T2s which until now were not detectable by time-domain Electron Paramagnetic Resonance (EPR) spectrometer at 300 MHz pulsed EPR since their phase memory times were shorter than the spectrometer recovery times. In the current version of the time-domain EPR spectrometer with improved spectrometer recovery times, we tested the feasibility of detecting signals from nitroxide radicals. Several nitroxides and the trityl radical Oxo63 were tested. Among the nitroxides evaluated, deuterated 15N-Tempone (15N-PDT) was found to have the longest T2. The signal intensity profile as a function of concentration of these agents was evaluated and a bi-phasic behavior was observed; beyond a nitroxide concentration of 1.5 mM, signal intensity was found to decrease as a result of self-broadening. Imaging experiments were carried out with 15N-PDT in solutions equilibrated with 0, 5, 10 and 21% oxygen using the Single Point Imaging (SPI) modality in EPR. The image intensity in these tubes was found to depend on the oxygen concentration which in turn influences the T2 of 15N-PDT. In vivo experiments were demonstrated with 15N-PDT in anesthetized mice where the distribution and metabolism of 15N-PDT could be monitored. This study, for the first time shows the capability to image a cell-permeable nitroxide in mice using pulsed EPR in the SPI modality. PMID:19157932

  6. EPR study of free radicals in bread

    NASA Astrophysics Data System (ADS)

    Yordanov, Nicola D.; Mladenova, Ralitsa

    2004-05-01

    The features of the recorded EPR spectra of paramagnetic species formed in bread and rusk are reported. The appearance of free radicals in them is only connected with their thermal treatment since the starting materials (flour and grains) exhibit very weak EPR signal. The obtained EPR spectra are complex and indicate that: (i) the relative number of paramagnetic species depends on the temperature and treating time of the raw product; (ii) the g-values are strongly temperature dependent with a tendency to coincide at t≥220 °C. Because of the relatively low (150-220 °C) temperature of thermal treatment, the studied free radicals can be assumed to appear in the course of the browning (Maillard) reaction and not to the carbonization of the material.

  7. Can EPR non-locality be geometrical?

    SciTech Connect

    Ne`eman, Y. |; Botero, A.

    1995-10-01

    The presence in Quantum Mechanics of non-local correlations is one of the two fundamentally non-intuitive features of that theory. The non-local correlations themselves fall into two classes: EPR and Geometrical. The non-local characteristics of the geometrical type are well-understood and are not suspected of possibly generating acausal features, such as faster-than-light propagation of information. This has especially become true since the emergence of a geometrical treatment for the relevant gauge theories, i.e. Fiber Bundle geometry, in which the quantum non-localities are seen to correspond to pure homotopy considerations. This aspect is reviewed in section 2. Contrary-wise, from its very conception, the EPR situation was felt to be paradoxical. It has been suggested that the non-local features of EPR might also derive from geometrical considerations, like all other non-local characteristics of QM. In[7], one of the authors was able to point out several plausibility arguments for this thesis, emphasizing in particular similarities between the non-local correlations provided by any gauge field theory and those required by the preservation of the quantum numbers of the original EPR state-vector, throughout its spatially-extended mode. The derivation was, however, somewhat incomplete, especially because of the apparent difference between, on the one hand, the closed spatial loops arising in the analysis of the geometrical non-localities, from Aharonov-Bohm and Berry phases to magnetic monopoles and instantons, and on the other hand, in the EPR case, the open line drawn by the positions of the two moving decay products of the disintegrating particle. In what follows, the authors endeavor to remove this obstacle and show that as in all other QM non-localities, EPR is somehow related to closed loops, almost involving homotopy considerations. They develop this view in section 3.

  8. Biophysical EPR Studies Applied to Membrane Proteins

    PubMed Central

    Sahu, Indra D; Lorigan, Gary A

    2015-01-01

    Membrane proteins are very important in controlling bioenergetics, functional activity, and initializing signal pathways in a wide variety of complicated biological systems. They also represent approximately 50% of the potential drug targets. EPR spectroscopy is a very popular and powerful biophysical tool that is used to study the structural and dynamic properties of membrane proteins. In this article, a basic overview of the most commonly used EPR techniques and examples of recent applications to answer pertinent structural and dynamic related questions on membrane protein systems will be presented. PMID:26855825

  9. Barium dithionate as an EPR dosemeter.

    PubMed

    Baran, M P; Bugay, O A; Kolesnik, S P; Maksimenko, V M; Teslenko, V V; Petrenko, T L; Desrosiers, M F

    2006-01-01

    Electron paramagnetic resonance (EPR) dosimetry is growing in popularity and this success has encouraged the search for other dosimetric materials. Previous studies of gamma-irradiated barium dithionate (BaS(2)O(6) x 2H(2)O) have shown promise for its use as a radiation dosemeter. This work studies in greater detail several essential attributes of the system. Special attention has been directed to the study of EPR response dependences on microwave power, irradiation temperature, minimum detectable dose and post-irradiation stability. PMID:16565205

  10. Preparation of EPR/silica filler by a co-irradiation method forming PP/EPR/silica nanocomposites

    NASA Astrophysics Data System (ADS)

    Qian, Jun; Dang, Shuaiying; Huang, Zhijuan; Xu, Yongshen

    2012-01-01

    This paper presents a novel approach to prepare ethylene-propylene rubber (EPR)/silica filler by co-irradiation method forming polypropylene (PP)/EPR/silica nanocomposites. The grafting of maleic anhydride (MAH) on EPR was first studied by co-irradiation in the micro-suspension without any chemical initiator, and the effects of MAH concentration and the total co-irradiation dose on the graft degree of MAH were investigated. Then PP/EPR/silica nanocomposites were successfully prepared by blending of PP matrix and EPR/silica filler, which was obtained by co-irradiation using a mixture of EPR/MAH microsuspension in xylene and tetraethoxysilane/KH560 sol in formic acid. FTIR and SEM results showed that the reactions between MAH on EPR chains and KH560 surrounding silica particles were adopted to form the EPR/silica filler with strong bonding and well silica dispersion. Mechanical properties of PP/EPR/silica nanocomposites with different silica contents and the comparisons with PP, PP/EPR and PP/silica films were studied. The rigid silica particles were trapped in EPR shell and well dispersed in PP/EPR/silica nanocomposites with good compatibility and strong interfacial adhesion, achieving overall improvements in stiffness, strength and toughness compared with pure PP.

  11. Advanced tool kits for EPR security.

    PubMed

    Blobel, B

    2000-11-01

    Responding to the challenge for efficient and high quality health care, the shared care paradigm must be established in health. In that context, information systems such as electronic patient records (EPR) have to meet this paradigm supporting communication and interoperation between the health care establishments (HCE) and health professionals (HP) involved. Due to the sensitivity of personal medical information, this co-operation must be provided in a trustworthy way. To enable different views of HCE and HP ranging from management, doctors, nurses up to systems administrators and IT professionals, a set of models for analysis, design and implementation of secure distributed EPR has been developed and introduced. The approach is based on the popular UML methodology and the component paradigm for open, interoperable systems. Easy to use tool kits deal with both application security services and communication security services but also with the security infrastructure needed. Regarding the requirements for distributed multi-user EPRs, modelling and implementation of policy agreements, authorisation and access control are especially considered. Current developments for a security infrastructure in health care based on cryptographic algorithms as health professional cards (HPC), security services employing digital signatures, and health-related TTP services are discussed. CEN and ISO initiatives for health informatics standards in the context of secure and communicable EPR are especially mentioned. PMID:11154968

  12. Clinical EPR: Unique Opportunities and Some Challenges

    PubMed Central

    Swartz, Harold M.; Williams, Benjamin B.; Zaki, Bassem I.; Hartford, Alan C.; Jarvis, Lesley A.; Chen, Eunice; Comi, Richard J.; Ernstoff, Marc S.; Hou, Huagang; Khan, Nadeem; Swarts, Steven G.; Flood, Ann B.; Kuppusamy, Periannan

    2014-01-01

    Electron paramagnetic resonance (EPR) spectroscopy has been well established as a viable technique for measurement of free radicals and oxygen in biological systems, from in vitro cellular systems to in vivo small animal models of disease. However, the use of EPR in human subjects in the clinical setting, although attractive for a variety of important applications such as oxygen measurement, is challenged with several factors including the need for instrumentation customized for human subjects, probe and regulatory constraints. This paper describes the rationale and development of the first clinical EPR systems for two important clinical applications, namely, measurement of tissue oxygen (oximetry), and radiation dose (dosimetry) in humans. The clinical spectrometers operate at 1.2 GHz frequency and use surface loop resonators capable of providing topical measurements up to 1 cm depth in tissues. Tissue pO2 measurements can be carried out noninvasively and repeatedly after placement of an oxygen-sensitive paramagnetic material (currently India ink) at the site of interest. Our EPR dosimetry system is capable of measuring radiation-induced free radicals in the tooth of irradiated human subjects to determine the exposure dose. These developments offer potential opportunities for clinical dosimetry and oximetry, which include guiding therapy for individual patients with tumors or vascular disease, by monitoring of tissue oxygenation. Further work is in progress to translate this unique technology to routine clinical practice. PMID:24439333

  13. EPR: What has it taught us

    NASA Astrophysics Data System (ADS)

    Stapp, H. P.

    1985-05-01

    Eistein, Podoisky, and Rosen (EPR) paper is discussed. The EPR paper was counterproductive for the following reasons: (1) the work was quickly rebutted by Bohr and this rebuttal was accepted my most workers in the field; (2) scientists who adopted the position advocated by Bohr produced, useful theory, whereas those following the course suggested by EPR produced nothing of any certified practical value; (3) it was shown by Bell that the conclusion reached by EPR is incompatible with their assumptions. The behavior of quantum mechanical systems that are very small, yet large enough to influence their environment in ways that appreciably modify their own behavior, vis-a-vis the behavior they would have if isolated was investigated. Because these systems are neither small enough to be treated as isolated between preparation and detection, nor large enough to be treated classically, they do not conform to the format demanded by the Copenhagen interpretation. The behavior of these systems depends on ontological considerations that were irrelevant in the situations covered by the Copenhagen interpretation, and that were systematically ignored in that interpretation. The task of enlarging the scope of quantum theory to cover these new situations, and comparing the empirical consequences of various ontological assumptions is discussed.

  14. Investigation of EPR signals on tooth enamel

    NASA Astrophysics Data System (ADS)

    Pavlenko, A.; Mironova-Ulmane, N.; Polakov, M.; Riekstina, D.

    2007-12-01

    Calcified tissues are involved in continues metabolic process in human organism exchanging a number of chemical elements with environment. The rate of biochemical reactions is tissue dependent and the slowest one at the tooth enamel, the most mineralized tissue of human organism. The long time stability and unique chemical composition make tooth enamel suitable for number of application. The assessment of individual radiation dose by Electron Paramagnetic Resonance (EPR) and evaluations of elemental composition by Instrumentation Neutron Activation Analysis (INAA) are the well known procedures where properties of tooth enamel intensively used. The current work is focused on investigation of EPR signals and determination of chemical composition on several teeth samples having different origin. The EPR spectra and INAA element content of milk tooth, caries tooth, and paradantose tooth have been compared to each other. The results showed that the intensity of EPR signal is much higher for the caries tooth than the for paradantose tooth that is in agreement with depleted Ca content.

  15. Pulsed EPR imaging of nitroxides in mice.

    PubMed

    Hyodo, Fuminori; Matsumoto, Shingo; Devasahayam, Nallathamby; Dharmaraj, Christopher; Subramanian, Sankaran; Mitchell, James B; Krishna, Murali C

    2009-04-01

    Nitroxides, unlike trityl radicals, have shorter T(2)s which until now were not detectable in vivo by a time-domain pulsed Electron Paramagnetic Resonance (EPR) spectrometer at 300 MHz since their phase memory times were shorter than the spectrometer recovery times. In the current version of the time-domain EPR spectrometer with improved spectrometer recovery times, the feasibility of detecting signals from nitroxide radicals was tested. Among the nitroxides evaluated, deuterated (15)N-Tempone ((15)N-PDT) was found to have the longest T(2). The signal intensity profile as a function of concentration of these agents was evaluated and a biphasic behavior was observed; beyond a nitroxide concentration of 1.5mM, signal intensity was found to decrease as a result of self-broadening. Imaging experiments were carried out with (15)N-PDT in solutions equilibrated with 0%, 5%, 10%, and 21% oxygen using the single point imaging (SPI) modality in EPR. The image intensity in these tubes was found to depend on the oxygen concentration which in turn influences the T(2) of (15)N-PDT. In vivo experiments were demonstrated with (15)N-PDT in anesthetized mice where the distribution and metabolism of (15)N-PDT could be monitored. This study, for the first time shows the capability to image a cell-permeable nitroxide in mice using pulsed EPR in the SPI modality. PMID:19157932

  16. RosettaEPR: An Integrated Tool for Protein Structure Determination from Sparse EPR Data

    PubMed Central

    Hirst, Stephanie J.; Alexander, Nathan; Mchaourab, Hassane S.; Meiler, Jens

    2010-01-01

    Site-directed spin labeling electron paramagnetic resonance (SDSL-EPR) is often used for the structural characterization of proteins that elude other techniques, such as X-ray crystallography and nuclear magnetic resonance (NMR). However, high-resolution structures are difficult to obtain due to uncertainty in the spin label location and sparseness of experimental data. Here, we introduce RosettaEPR, which has been designed to improve de novo high-resolution protein structure prediction using sparse SDSL-EPR distance data. The “motion-on-a-cone” spin label model is converted into a knowledge-based potential, which was implemented as a scoring term in Rosetta. RosettaEPR increased the fractions of correctly folded models (RMSDCα < 7.5Å) and models accurate at medium resolution (RMSDCα < 3.5Å) by 25%. The correlation of score and model quality increased from 0.42 when using no restraints to 0.51 when using bounded restraints and again to 0.62 when using RosettaEPR. This allowed for the selection of accurate models by score. After full-atom refinement, RosettaEPR yielded a 1.7Å model of T4-lysozyme, thus indicating that atomic detail models can be achieved by combining sparse EPR data with Rosetta. While these results indicate RosettaEPR’s potential utility in high-resolution protein structure prediction, they are based on a single example. In order to affirm the method’s general performance, it must be tested on a larger and more versatile dataset of proteins. PMID:21029778

  17. EPR-based material modelling of soils considering volume changes

    NASA Astrophysics Data System (ADS)

    Faramarzi, Asaad; Javadi, Akbar A.; Alani, Amir M.

    2012-11-01

    In this paper an approach is presented for developing material models for soils based on evolutionary polynomial regression (EPR), taking into account its volumetric behaviour. EPR is a recently developed hybrid data mining technique that searches for structured mathematical equations (representing the behaviour of a system) using genetic algorithm and the least squares method. Stress-strain data from triaxial test are used to train and develop EPR-based material models for soil. The developed models are compared with some of the well known conventional material models. In particular, the capability of the developed EPR models in predicting volume change behaviour of soils is illustrated. It is also shown that the developed EPR-based material models can be incorporated in finite element (FE) analysis. Two geotechnical examples are presented to verify the developed EPR-based FE model (EPR-FEM). The results of the EPR-FEM are compared with those of a standard FEM where conventional constitutive models are used to describe the material behaviour. The results show that EPR-FEM can be successfully employed to analyse geotechnical engineering problems. The advantages of the proposed EPR models are highlighted.

  18. EPR Steering inequalities with Communication Assistance

    PubMed Central

    Nagy, Sándor; Vértesi, Tamás

    2016-01-01

    In this paper, we investigate the communication cost of reproducing Einstein-Podolsky-Rosen (EPR) steering correlations arising from bipartite quantum systems. We characterize the set of bipartite quantum states which admits a local hidden state model augmented with c bits of classical communication from an untrusted party (Alice) to a trusted party (Bob). In case of one bit of information (c = 1), we show that this set has a nontrivial intersection with the sets admitting a local hidden state and a local hidden variables model for projective measurements. On the other hand, we find that an infinite amount of classical communication is required from an untrusted Alice to a trusted Bob to simulate the EPR steering correlations produced by a two-qubit maximally entangled state. It is conjectured that a state-of-the-art quantum experiment would be able to falsify two bits of communication this way. PMID:26880376

  19. EPR Investigation of Irradiated Curry Powder

    SciTech Connect

    Duliu, O. G.; Ali, S. I.; Georgescu, R.

    2007-04-23

    Gamma-ray irradiated curry powder, a well priced oriental spice was investigated in order to establish the ability of EPR to detect the presence and time stability of free irradiation free-radicals. Accordingly, curry powder aliquots were irradiated with gradually increasing absorbed doses up to 11.3 kGy. The EPR spectra of all irradiated samples show the presence of al last two different species of free radicals, whose concentration increased monotonously with the absorbed doses. A 100 deg. C isothermal annealing of irradiated samples has shown a differential reduction of amplitude of various components of the initial spectra, but even after 3.6 h of thermal treatment, the remaining amplitude represents no less then 30% of the initial ones. The same peculiarities have been noticed after more than one year storage at room temperature, all of them being very useful in establishing the existence of any previous irradiation treatment.

  20. EPR Steering inequalities with Communication Assistance

    NASA Astrophysics Data System (ADS)

    Nagy, Sándor; Vértesi, Tamás

    2016-02-01

    In this paper, we investigate the communication cost of reproducing Einstein-Podolsky-Rosen (EPR) steering correlations arising from bipartite quantum systems. We characterize the set of bipartite quantum states which admits a local hidden state model augmented with c bits of classical communication from an untrusted party (Alice) to a trusted party (Bob). In case of one bit of information (c = 1), we show that this set has a nontrivial intersection with the sets admitting a local hidden state and a local hidden variables model for projective measurements. On the other hand, we find that an infinite amount of classical communication is required from an untrusted Alice to a trusted Bob to simulate the EPR steering correlations produced by a two-qubit maximally entangled state. It is conjectured that a state-of-the-art quantum experiment would be able to falsify two bits of communication this way.

  1. Deconvolution of sinusoidal rapid EPR scans.

    PubMed

    Tseitlin, Mark; Rinard, George A; Quine, Richard W; Eaton, Sandra S; Eaton, Gareth R

    2011-02-01

    In rapid scan EPR the magnetic field is scanned through the signal in a time that is short relative to electron spin relaxation times. Previously it was shown that the slow-scan lineshape could be recovered from triangular rapid scans by Fourier deconvolution. In this paper a general Fourier deconvolution method is described and demonstrated to recover the slow-scan lineshape from sinusoidal rapid scans. Since an analytical expression for the Fourier transform of the driving function for a sinusoidal scan was not readily apparent, a numerical method was developed to do the deconvolution. The slow scan EPR lineshapes recovered from rapid triangular and sinusoidal scans are in excellent agreement for lithium phthalocyanine, a trityl radical, and the nitroxyl radical, tempone. The availability of a method to deconvolute sinusoidal rapid scans makes it possible to scan faster than is feasible for triangular scans because of hardware limitations on triangular scans. PMID:21163677

  2. Deconvolution of Sinusoidal Rapid EPR Scans

    PubMed Central

    Tseitlin, Mark; Rinard, George A.; Quine, Richard W.; Eaton, Sandra S.; Eaton, Gareth R.

    2011-01-01

    In rapid scan EPR the magnetic field is scanned through the signal in a time that is short relative to electron spin relaxation times. Previously it was shown that the slow scan lineshape could be recovered from triangular rapid scans by Fourier deconvolution. In this paper a general Fourier deconvolution method is described and demonstrated to recover the slow scan lineshape from sinusoidal rapid scans. Since an analytical expression for the Fourier transform of the driving function for a sinusoidal scan was not readily apparent, a numerical method was developed to do the deconvolution. The slow scan EPR lineshapes recovered from rapid triangular and sinusoidal scans are in excellent agreement for lithium phthalocyanine, a trityl radical, and the nitroxyl radical, tempone. The availability of a method to deconvolute sinusoidal rapid scans makes it possible to scan faster than is feasible for triangular scans because of hardware limitations on triangular scans. PMID:21163677

  3. Self-testing through EPR-steering

    NASA Astrophysics Data System (ADS)

    Šupić, Ivan; Hoban, Matty J.

    2016-07-01

    The verification of quantum devices is an important aspect of quantum information, especially with the emergence of more advanced experimental implementations of quantum computation and secure communication. Within this, the theory of device-independent robust self-testing via Bell tests has reached a level of maturity now that many quantum states and measurements can be verified without direct access to the quantum systems: interaction with the devices is solely classical. However, the requirements for this robust level of verification are daunting and require high levels of experimental accuracy. In this paper we discuss the possibility of self-testing where we only have direct access to one part of the quantum device. This motivates the study of self-testing via EPR-steering, an intermediate form of entanglement verification between full state tomography and Bell tests. Quantum non-locality implies EPR-steering so results in the former can apply in the latter, but we ask what advantages may be gleaned from the latter over the former given that one can do partial state tomography? We show that in the case of self-testing a maximally entangled two-qubit state, or ebit, EPR-steering allows for simpler analysis and better error tolerance than in the case of full device-independence. On the other hand, this improvement is only a constant improvement and (up to constants) is the best one can hope for. Finally, we indicate that the main advantage in self-testing based on EPR-steering could be in the case of self-testing multi-partite quantum states and measurements. For example, it may be easier to establish a tensor product structure for a particular party’s Hilbert space even if we do not have access to their part of the global quantum system.

  4. W-Band Frequency-Swept EPR

    PubMed Central

    Hyde, James S.; Strangeway, Robert A.; Camenisch, Theodore G.; Ratke, Joseph J.; Froncisz, Wojciech

    2010-01-01

    This paper describes a novel experiment on nitroxide radical spin labels using a multiarm EPR W-band bridge with a loop-gap resonator (LGR). We demonstrate EPR spectroscopy of spin labels by linear sweep of the microwave frequency across the spectrum. The high bandwidth of the LGR, about 1 GHz between 3 dB points of the microwave resonance, makes this new experiment possible. A frequency-tunable yttrium iron garnet (YIG) oscillator provides sweep rates as high as 1.8 × 105 GHz/s, which corresponds to 6.3 kT/s in magnetic field-sweep units over a 44 MHz range. Two experimental domains were identified. In the first, linear frequency sweep rates were relatively slow, and pure absorption and pure dispersion spectra were obtained. This appears to be a practical mode of operation at the present level of technological development. The main advantage is the elimination of sinusoidal magnetic field modulation. In the second mode, the frequency is swept rapidly across a portion of the spectrum, and then the frequency sweep is stopped for a readout period; FID signals from a swept line oscillate at a frequency that is the difference between the spectral position of the line in frequency units and the readout position. If there is more than one line, oscillations are superimposed. The sweep rates using the YIG oscillator were too slow, and the portion of the spectrum too narrow to achieve the full EPR equivalent of Fourier transform (FT) NMR. The paper discusses technical advances required to reach this goal. The hypothesis that trapezoidal frequency sweep is an enabling technology for FT EPR is supported by this study. PMID:20462775

  5. W-band frequency-swept EPR.

    PubMed

    Hyde, James S; Strangeway, Robert A; Camenisch, Theodore G; Ratke, Joseph J; Froncisz, Wojciech

    2010-07-01

    This paper describes a novel experiment on nitroxide radical spin labels using a multiarm EPR W-band bridge with a loop-gap resonator (LGR). We demonstrate EPR spectroscopy of spin labels by linear sweep of the microwave frequency across the spectrum. The high bandwidth of the LGR, about 1 GHz between 3 dB points of the microwave resonance, makes this new experiment possible. A frequency-tunable yttrium iron garnet (YIG) oscillator provides sweep rates as high as 1.8x10(5) GHz/s, which corresponds to 6.3 kT/s in magnetic field-sweep units over a 44 MHz range. Two experimental domains were identified. In the first, linear frequency sweep rates were relatively slow, and pure absorption and pure dispersion spectra were obtained. This appears to be a practical mode of operation at the present level of technological development. The main advantage is the elimination of sinusoidal magnetic field modulation. In the second mode, the frequency is swept rapidly across a portion of the spectrum, and then the frequency sweep is stopped for a readout period; FID signals from a swept line oscillate at a frequency that is the difference between the spectral position of the line in frequency units and the readout position. If there is more than one line, oscillations are superimposed. The sweep rates using the YIG oscillator were too slow, and the portion of the spectrum too narrow to achieve the full EPR equivalent of Fourier transform (FT) NMR. The paper discusses technical advances required to reach this goal. The hypothesis that trapezoidal frequency sweep is an enabling technology for FT EPR is supported by this study. PMID:20462775

  6. Iodide, azide, and cyanide complexes of (N,C), (N,N), and (N,O) metallacycles of tetra- and pentavalent uranium.

    PubMed

    Bénaud, Olivier; Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

    2011-12-01

    In contrast to the neutral macrocycle [UN*(2)(N,C)] (1) [N* = N(SiMe(3))(3); N,C = CH(2)SiMe(2)N(SiMe(3))] which was quite inert toward I(2), the anionic bismetallacycle [NaUN*(N,C)(2)] (2) was readily transformed into the enlarged monometallacycle [UN*(N,N)I] (4) [N,N = (Me(3)Si)NSiMe(2)CH(2)CH(2)SiMe(2)N(SiMe(3))] resulting from C-C coupling of the two CH(2) groups, and [NaUN*(N,O)(2)] (3) [N,O = OC(═CH(2))SiMe(2)N(SiMe(3))], which is devoid of any U-C bond, was oxidized into the U(V) bismetallacycle [Na{UN*(N,O)(2)}(2)(μ-I)] (5). Sodium amalgam reduction of 4 gave the U(III) compound [UN*(N,N)] (6). Addition of MN(3) or MCN to the (N,C), (N,N), and (N,O) metallacycles 1, 4, and 5 led to the formation of the anionic azide or cyanide derivatives M[UN*(2)(N,C)(N(3))] [M = Na, 7a or Na(15-crown-5), 7b], M[UN*(2)(N,C)(CN)] [M = NEt(4), 8a or Na(15-crown-5), 8b or K(18-crown-6), 8c], M[UN*(N,N)(N(3))(2)] [M = Na, 9a or Na(THF)(4), 9b], [NEt(4)][UN*(N,N)(CN)(2)] (10), M[UN*(N,O)(2)(N(3))] [M = Na, 11a or Na(15-crown-5), 11b], M[UN*(N,O)(2)(CN)] [M = NEt(4), 12a or Na(15-crown-5), 12b]. In the presence of excess iodine in THF, the cyanide 12a was converted back into the iodide 5, while the azide 11a was transformed into the neutral U(V) complex [U(N{SiMe(3)}SiMe(2)C{CHI}O)(2)I(THF)] (13). The X-ray crystal structures of 4, 7b, 8a-c, 9b, 10, 12b, and 13 were determined. PMID:22050237

  7. Tetrabromidocuprates(II)-Synthesis, Structure and EPR.

    PubMed

    Zabel, André; Winter, Alette; Kelling, Alexandra; Schilde, Uwe; Strauch, Peter

    2016-01-01

    Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several "onium" cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g‖ and g⊥) of the tensors could be determined and information on the structural changes in the [CuBr₄](2-) anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids. PMID:27104522

  8. EPR study on gamma-irradiated fruits dehydrated via osmosis

    NASA Astrophysics Data System (ADS)

    Yordanov, N. D.; Aleksieva, K.

    2007-06-01

    The shape and time stability of the electron paramagnetic resonance (EPR) spectra of non- and γ-irradiated papaya, melon, cherry and fig samples dehydrated via osmosis are reported. It is shown that non-irradiated samples are generally EPR silent whereas γ-irradiated exhibit "sugar-like" EPR spectra. The recorded EPR spectra are monitored for a period of 7 months after irradiation (stored at low humidity and in the dark). The results suggest longer period of unambiguous identification of the radiation processing of osmose dehydrated fruits. Therefore, the Protocol EN 13708,2001 issued by CEN is fully applicable for the studied fruit samples.

  9. Use of the Frank sequence in pulsed EPR.

    PubMed

    Tseitlin, Mark; Quine, Richard W; Eaton, Sandra S; Eaton, Gareth R; Halpern, Howard J; Ardenkjaer-Larsen, J-H

    2011-04-01

    The Frank polyphase sequence has been applied to pulsed EPR of triarylmethyl radicals at 25 6 MHz (9.1 mT magnetic field), using 256 phase pulses. In EPR, as in NMR, use of a Frank sequence of phase steps permits pulsed FID signal acquisition with very low power microwave/RF pulses (ca. 1.5 mW in the application reported here) relative to standard pulsed EPR. A 0.2 mM aqueous solution of a triarylmethyl radical was studied using a 16 mm diameter cross-loop resonator to isolate the EPR signal detection system from the incident pulses. PMID:21371924

  10. Use of the Frank Sequence in Pulsed EPR

    PubMed Central

    Tseitlin, Mark; Quine, Richard W.; Eaton, Sandra S.; Eaton, Gareth R.; Halpern, Howard J.; Ardenkjaer-Larsen, J.-H.

    2011-01-01

    The Frank polyphase sequence has been applied to pulsed EPR of triarylmethyl radicals at 256 MHz (9.1 mT magnetic field), using 256 phase pulses. In EPR, as in NMR, use of a Frank sequence of phase steps permits pulsed FID signal acquisition with very low power microwave/RF pulses (ca. 1.5 mW in the application reported here) relative to standard pulsed EPR. A 0.2 mM aqueous solution of a triarylmethyl radical was studied using a 16 mm diameter cross loop resonator to isolate the EPR signal detection system from the incident pulses. PMID:21371924

  11. Locations of radical species in black pepper seeds investigated by CW EPR and 9 GHz EPR imaging

    NASA Astrophysics Data System (ADS)

    Nakagawa, Kouichi; Epel, Boris

    2014-10-01

    In this study, noninvasive 9 GHz electron paramagnetic resonance (EPR)-imaging and continuous wave (CW) EPR were used to investigate the locations of paramagnetic species in black pepper seeds without further irradiation. First, lithium phthalocyanine (LiPC) phantom was used to examine 9 GHz EPR imaging capabilities. The 9 GHz EPR-imager easily resolved the LiPC samples at a distance of ∼2 mm. Then, commercially available black pepper seeds were measured. We observed signatures from three different radical species, which were assigned to stable organic radicals, Fe3+, and Mn2+ complexes. In addition, no EPR spectral change in the seed was observed after it was submerged in distilled H2O for 1 h. The EPR and spectral-spatial EPR imaging results suggested that the three paramagnetic species were mostly located at the seed surface. Fewer radicals were found inside the seed. We demonstrated that the CW EPR and 9 GHz EPR imaging were useful for the determination of the spatial distribution of paramagnetic species in various seeds.

  12. EPR: what has it taught us

    SciTech Connect

    Stapp, H.P.

    1985-05-01

    This symposium commemorating the fiftieth anniversary of the paper of Einstein, Podolsky, and Rosen is a fitting place to review what that work and its sequels have taught us. Prima facie, the EPR paper appears to have been exceedingly counter-productive for the following reasons: (1) The work was quickly rebutted by Bohr, and this rebuttal was apparently accepted by most workers in the field. (2) Scientists who adopted the position advocated by Bohr have produced, in the intervening fifty years, a marvelous body of useful theory, whereas those following the course suggested by EPR have produced nothing of any certified practical value. (3) It has been shown by Bell that the conclusion reached by EPR is incompatible with their assumptions. Chemists and physicists have recently begun to examine the behavior of quantum mechanical systems that are very small, yet large enough to influence their environment in ways that appreciably modify their own behavior, vis-a-vis the behavior they would have if isolated. Because these systems are neither small enough to be treated as isolated (or as residing in a classically described environment) between preparation and detection, nor large enough to be treated classically, they do not conform to the format demanded by the Copenhagen interpretation. Indeed, the behavior of these systems depends on ontological considerations that were irrelevant in the situations covered by the Copenhagen interpretation, and that were systematically ignored in that interpretation. Scientists now face the task of enlarging the scope of quantum theory to cover these new situations, and comparing the empirical consequences of various ontological assumptions. 17 refs.

  13. Comparative study of some new EPR dosimeters

    NASA Astrophysics Data System (ADS)

    Alzimami, K. S.; Maghraby, Ahmed M.; Bradley, D. A.

    2014-02-01

    Investigations have been made of four new radiation dosimetry EPR candidates from the same family of materials: sulfamic acid, sulfanillic acid, homotaurine, and taurine. Mass energy attenuation coefficients, mass stopping power values and the time dependence of the radiation induced radicals are compared. Also investigated are the microwave saturation behavior and the effect of applied modulation amplitude on both peak-to-peak line width (WPP) and peak-to-peak signal height (HPP). The dosimeters are characterized by simple spectra and stable radiation-induced radicals over reasonable durations, especially in taurine dosimeters. Sulfamic acid dosimeters possessed the highest sensitivity followed by taurine and homotaurine and sulfanillic.

  14. EPR investigations of gamma-irradiated novolacs

    NASA Astrophysics Data System (ADS)

    Schrödner, M.; Wünsche, P.; Lampe, I. v.

    EPR investigations of γ-irradiated phenol, p-chlorophenol, o-chlorophenol, 3,5-dichlorophenol and p-cresol novolac are presented. The elimination of a chlorine atom from the phenolic ring must be assumed in the case of chlorinated novolacs. The corresponding aryl radical could only be detected in the case of 3,5-dichlorophenol novolac in a large amount. Furthermore phenoxy and cyclohexadienyl radicals were found in the spectra. The radiation chemical as well as the resist sensitivity are enhanced by chlorination but there is no definite correlation between them.

  15. Case Studies in e-RPL and e-PR

    ERIC Educational Resources Information Center

    Cameron, Roslyn; Miller, Allison

    2014-01-01

    The use of ePortfolios for recognition of prior learning (e-RPL) and for professional recognition (e-PR) is slowly gaining in popularity in the VET sector however their use is sporadic across educational sectors, disciplines, educational institutions and professions. Added to this is an array of purposes and types of e-RPL and e-PR models and…

  16. Quantum Encryption Protocol Based on Continuous Variable EPR Correlations

    NASA Astrophysics Data System (ADS)

    He, Guang-Qiang; Zeng, Gui-Hua

    2006-07-01

    A quantum encryption protocol based on Gaussian-modulated continuous variable EPR correlations is proposed. The security is guaranteed by continuous variable EPR entanglement correlations produced by nondegenerate optical parametric amplifier (NOPA). For general beam splitter eavesdropping strategy, the mutual information I(α,epsilon) between Alice and Eve is calculated by employing Shannon information theory. Finally the security analysis is presented.

  17. EPR investigation of some gamma-irradiated excipients

    NASA Astrophysics Data System (ADS)

    Aleksieva, Katerina; Yordanov, Nicola D.

    2012-09-01

    The results of electron paramagnetic resonance (EPR) studies on some excipients: lactose, microcrystalline cellulose (avicel), starch, dioxosilane (aerosil), talc and magnesium stearate before and after gamma-irradiation are reported. Before irradiation, all samples are EPR silent except talc. After gamma-irradiation, they show complex spectra except magnesium stearate, which is EPR silent. Studies show the influence of gamma-irradiation on EPR spectra and stability of gamma-induced radicals. Analysis of the EPR spectrum of gamma-irradiated talc shows that this material is radiation insensitive. Only lactose forms stable-free radicals upon gamma sterilization and can be used for identification of radiation processing for a long time period thereafter.

  18. Identification of gamma-irradiated fruit juices by EPR spectroscopy

    NASA Astrophysics Data System (ADS)

    Aleksieva, K. I.; Dimov, K. G.; Yordanov, N. D.

    2014-10-01

    The results of electron paramagnetic resonance (EPR) study on commercially available juices from various fruits and different fruit contents: 25%, 40%, 50%, and 100%, homemade juices, nectars and concentrated fruit syrups, before and after gamma-irradiation are reported. In order to remove water from non- and irradiated samples all juices and nectars were filtered; the solid residue was washed with alcohol and dried at room temperature. Only concentrated fruit syrups were dried for 60 min at 40 °C in a standard laboratory oven. All samples under study show a singlet EPR line with g=2.0025 before irradiation with exception of concentrated fruit syrups, which are EPR silent. Irradiation of juice samples gives rise to complex EPR spectra which gradually transferred to “cellulose-like” EPR spectrum from 25% to 100% fruit content. Concentrated fruit syrups show typical “sugar-like“ spectra due to added saccharides. All EPR spectra are characteristic and can prove radiation treatment. The fading kinetics of radiation-induced EPR signals were studied for a period of 60 days after irradiation.

  19. EPR paradox, quantum nonlocality and physical reality

    NASA Astrophysics Data System (ADS)

    Kupczynski, M.

    2016-03-01

    Eighty years ago Einstein, Podolsky and Rosen demonstrated that instantaneous reduction of wave function, believed to describe completely a pair of entangled physical systems, led to EPR paradox. The paradox disappears in statistical interpretation of quantum mechanics (QM) according to which a wave function describes only an ensemble of identically prepared physical systems. QM predicts strong correlations between outcomes of measurements performed on different members of EPR pairs in far-away locations. Searching for an intuitive explanation of these correlations John Bell analysed so called local realistic hidden variable models and proved that correlations consistent with these models satisfy Bell inequalities which are violated by some predictions of QM and by experimental data. Several different local models were constructed and inequalities proven. Some eminent physicists concluded that Nature is definitely nonlocal and that it is acting according to a law of nonlocal randomness. According to these law perfectly random, but strongly correlated events, can be produced at the same time in far away locations and a local and causal explanation of their occurrence cannot be given. We strongly disagree with this conclusion and we prove the contrary by analysing in detail some influential finite sample proofs of Bell and CHSH inequalities and so called Quantum Randi Challenges. We also show how one can win so called Bell's game without violating locality of Nature. Nonlocal randomness is inconsistent with local quantum field theory, with standard model in elementary particle physics and with causal laws and adaptive dynamics prevailing in the surrounding us world. The experimental violation of Bell-type inequalities does not prove the nonlocality of Nature but it only confirms a contextual character of quantum observables and gives a strong argument against counterfactual definiteness and against a point of view according to which experimental outcomes are produced

  20. Lorentz symmetry breaking effects on relativistic EPR correlations

    NASA Astrophysics Data System (ADS)

    Belich, H.; Furtado, C.; Bakke, K.

    2015-09-01

    Lorentz symmetry breaking effects on relativistic EPR (Einstein-Podolsky-Rosen) correlations are discussed. From the modified Maxwell theory coupled to gravity, we establish a possible scenario of the Lorentz symmetry violation and write an effective metric for the Minkowski spacetime. Then we obtain the Wigner rotation angle via the Fermi-Walker transport of spinors and consider the WKB (Wentzel-Kramers-Brillouin) approximation in order to study the influence of Lorentz symmetry breaking effects on the relativistic EPR correlations.

  1. EPR study on non- and gamma-irradiated herbal pills

    NASA Astrophysics Data System (ADS)

    Aleksieva, K.; Lagunov, O.; Dimov, K.; Yordanov, N. D.

    2011-06-01

    The results of EPR studies on herbal pills of marigold, hawthorn, yarrow, common balm, tutsan, nettle and thyme before and after gamma-irradiation are reported. Before irradiation all samples exhibit one weak singlet EPR line with a g-factor of 2.0048±0.0005. After irradiation herbal pills could be separated in two groups according to their EPR spectra. Radiation-induced free radicals in pills of marigold, yarrow, nettle, tutsan and thyme could be attributed mainly to saccharide excipients. Tablets of hawthorn and common balm show "cellulose-like" EPR spectrum, superimposed on partly resolved carbohydrate spectrum, due to the active part (herb) and inulin, which is present in the pills as an excipient. Fading study of the radiation-induced EPR signals confirms that sugar radicals are more stable than cellulose species. The reported results show that the presence of characteristic EPR spectra of herbal pills due to excipients or active part can be used as unambiguous proof of radiation processing within 35 or more days after irradiation.

  2. Sensitivity enhancement in pulse EPR distance measurements.

    PubMed

    Jeschke, G; Bender, A; Paulsen, H; Zimmermann, H; Godt, A

    2004-07-01

    Established pulse EPR approaches to the measurement of small dipole-dipole couplings between electron spins rely on constant-time echo experiments to separate relaxational contributions from dipolar time evolution. This requires a compromise between sensitivity and resolution to be made prior to the measurement, so that optimum data are only obtained if the magnitude of the dipole-dipole coupling is known beforehand to a good approximation. Moreover, the whole dipolar evolution function is measured with relatively low sensitivity. These problems are overcome by a variable-time experiment that achieves suppression of the relaxation contribution by reference deconvolution. Theoretical and experimental results show that this approach leads to significant sensitivity improvements for typical systems and experimental conditions. Further sensitivity improvements or, equivalently, an extension of the accessible distance range can be obtained by matrix deuteration or digital long-pass filtering of the time-domain data. Advantages and limitations of the new variable-time experiment are discussed by comparing it to the established analogous constant-time experiment for measurements of end-to-end distances of 5 and 7.5 nm on rod-like shape-persistent biradicals and for the measurement of a broadly distributed transmembrane distance in a doubly spin-labeled mutant of plant light harvesting complex II. PMID:15183350

  3. Pulsed EPR for studying silver clusters

    NASA Astrophysics Data System (ADS)

    Michalik, J.; Wasowicz, T.; Sadlo, J.; Reijerse, E. J.; Kevan, L.

    1996-01-01

    The cationic silver clusters of different nuclearity have been produced by radiolysis of zeolite A and SAPO molecular sieves containing Ag + as exchangeable cations. The pulsed EPR spectroscopy has been applied for studying the local environment of silver cluster in order to understand the mechanism of cluster formation and stabilization. The electron spin echo modulation (ESEM) results on Ag 6n+ cluster in dehydration zeolite A indicate that the hexameric silver is stabilized only in sodalite cages which are surrounded by α-cages containing no water molecules. Trimeric silver clusters formed in hydrated A zeolites strongly interact with water, thus the paramagnetic center can be considered as a cluster-water adduct. In SAPO-molecular sieves, silver clusters are formed only in the presence of adsorbed alcohol molecules. From ESEM it is determined that Ag 4n+ in SAPO-42 is stabilized in α-cages, where it is directly coordinated by two methanol molecules. Dimeric silver, Ag 2+ in SAPO-5 and SAPO-11 is located in 6-ring channels and interacts with three CH 3OH molecules, each in different 10-ring or 12-ring channels. The differences of Ag 2+ stability in SAPO-5 and SAPO-11 are also discussed.

  4. Single-wall carbon nanotubes and peapods investigated by EPR.

    PubMed

    Corzilius, B; Dinse, K-P; Hata, K

    2007-12-14

    Single-wall carbon nanotubes (SWNT) prepared by the "super growth" method developed recently exhibit electron paramagnetic resonance (EPR) signals, which can be attributed to itinerant spins. EPR results indicate very low defect and catalyst concentrations in this superior material. Under these conditions EPR can be used to study details of charge transport properties over a wide temperature range, although the material is still very "heterogeneous" with respect to tube diameter and chirality. Non-resonant microwave absorption in the temperature range below 20 K is indicative for the opening of a small gap at the Fermi energy for tubes of metallic character, which is indicative for a transition into a superconducting state. Using SWNT filled partially with an endohedral spin probe like N@C(60), such "peapods" can be investigated "from the inside". Continuous-wave (cw) and pulsed EPR was used to investigate localization dynamics within the tubes or to check for interaction with itinerant electrons. Using SWNT grown by different methods, the dominant influence of tube diameter on fullerene dynamics was revealed by temperature dependent pulsed EPR experiments. These differences can be correlated with the interactions between the endohedral observer spin and spins on the SWNT. PMID:18167581

  5. Macromolecular therapeutics in cancer treatment: the EPR effect and beyond.

    PubMed

    Maeda, Hiroshi

    2012-12-10

    In this review, I have discussed various issues of the cancer drug targeting primarily related to the EPR (enhanced permeability and retention) effect, which utilized nanomedicine or macromolecular drugs. The content goes back to the development of the first polymer-protein conjugate anticancer agent SMANCS and development of the arterial infusion in Lipiodol formulation into the tumor feeding artery (hepatic artery for hepatoma). The brief account on the EPR effect and its definition, factors involved, heterogeneity, and various methods of augmentation of the EPR effect, which showed remarkably improved clinical outcomes are also discussed. Various obstacles involved in drug developments and commercialization are also discussed through my personal experience and recollections. PMID:22595146

  6. Absorption line CW EPR using an amplitude modulated longitudinal field.

    PubMed

    Fedin, Matvey; Gromov, Igor; Schweiger, Arthur

    2004-11-01

    In standard continuous wave electron paramagnetic resonance (CW-EPR) experiments, the first derivative of absorption lines is detected. This type of a line shape is caused by the magnetic field modulation and is usually an undesired feature, since the sensitivity of CW-EPR drastically decreases with increasing linewidth. A new approach is introduced, which allows for the measurement of absorption line EPR spectra in systems with broad inhomogeneous lines. The method makes use of multiple-photon transitions that are induced in spin systems when a transverse microwave and a longitudinal radio frequency field are simultaneously applied. The absorption lines are obtained by using amplitude modulation of the radio frequency field and slight saturation of the spectral lines. The basics of the new approach are discussed and experimental examples are given. PMID:15504685

  7. Retrospective dosimetry using EPR and TL techniques: a status report

    SciTech Connect

    Haskell, E.H.

    1996-12-31

    Methods of retrospective dosimetry, including luminescence and electron paramagnetic resonance spectroscopy (EPR), rely on measurement of accident dose absorbed by naturally occurring materials - ceramics in the case of both thermoluminescence (TL) and optically stimulated luminescence (OSL) and organic materials and bio- minerals in the case of EPR. Each of these methods relies on measurement of radiation defects resulting from accidental exposure. Since defects also result from natural sources of radiation over the lifetime of a sample, analysis is usually restricted to materials for which the natural dose may be determined and subtracted from the measured cumulative dose. Luminescence dating techniques rely heavily on an accurate assessment of cumulative dose from natural radiation sources, and dating research has provided us with the bulk of our knowledge in this area. Virtually all of the work on natural dose determination can be directly applied to retrospective techniques. With EPR techniques the cumulative dose from diagnostic x- rays is also of importance.

  8. EPR Correlations, Bell Inequalities and Common Cause Systems

    NASA Astrophysics Data System (ADS)

    Hofer-Szabó, Gábor

    2014-03-01

    Standard common causal explanations of the EPR situation assume a so-called joint common cause system that is a common cause for all correlations. However, the assumption of a joint common cause system together with some other physically motivated assumptions concerning locality and no-conspiracy results in various Bell inequalities. Since Bell inequalities are violated for appropriate measurement settings, a local, non-conspiratorial joint common causal explanation of the EPR situation is ruled out. But why do we assume that a common causal explanation of a set of correlation consists in finding a joint common cause system for all correlations and not just in finding separate common cause systems for the different correlations? What are the perspectives of a local, non-conspiratorial separate common causal explanation for the EPR scenario? And finally, how do Bell inequalities relate to the weaker assumption of separate common cause systems?

  9. Determining the Topology of Integral Membrane Peptides Using EPR Spectroscopy

    PubMed Central

    Inbaraj, Johnson J.; Cardon, Thomas B.; Laryukhin, Mikhail; Grosser, Stuart M.

    2008-01-01

    This paper reports on the development of a new structural biology technique for determining the membrane topology of an integral membrane protein inserted into magnetically aligned phospholipid bilayers (bicelles) using EPR spectroscopy. The nitroxide spin probe, 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (TOAC) was attached to the pore-lining transmembrane domain (M2δ) of the nicotinic acetylcholine receptor (AChR) and incorporated into a bicelle. The corresponding EPR spectra revealed hyperfine splittings that were highly dependent on the macroscopic orientation of the bicelles with respect to the static magnetic field. The helical tilt of the peptide can be easily calculated using the hyperfine splittings gleaned from the orientational dependent EPR spectra. A helical tilt of 14° was calculated for the M2δ peptide with respect to the bilayer normal of the membrane, which agrees well with previous 15N solid-state NMR studies. The helical tilt of the peptide was verified by simulating the corresponding EPR spectra using the standardized MOMD approach. This new method is advantageous because: (1) bicelle samples are easy to prepare, (2) the helical tilt can be directly calculated from the orientational-dependent hyperfine splitting in the EPR spectra, and (3) EPR spectroscopy is approximately 1000 fold more sensitive than 15N solid-state NMR spectroscopy; thus, the helical tilt of an integral membrane peptide can be determined with only 100 μg of peptide. The helical tilt can be determined more accurately by placing TOAC spin labels at several positions with this technique. PMID:16848493

  10. Free-radical probes for functional in vivo EPR imaging

    NASA Astrophysics Data System (ADS)

    Subramanian, S.; Krishna, M. C.

    2007-02-01

    Electron paramagnetic resonance imaging (EPRI) is one of the recent functional imaging modalities that can provide valuable in vivo physiological information on its own merit and aids as a complimentary imaging technique to MRI and PET of tissues especially with respect to in vivo pO II (oxygen partial pressure), redox status and pharmacology. EPR imaging mainly deals with the measurement of distribution and in vivo dynamics and redox changes using special nontoxic paramagnetic spin probes that can be infused into the object of investigation. These spin probes should be characterized by simple EPR spectra, preferably with narrow EPR lines. The line width should be reversibly sensitive to the concentration of in vivo pO II with a linear dependence. Several non-toxic paramagnetic probes, some particulate and insoluble and others water-soluble and infusible (by intravenous or intramuscular injection) have been developed which can be effectively used to quantitatively assess tissue redox status, and tumor hypoxia. Quantitative assessment of the redox status of tissue in vivo is important in investigating oxidative stress, and that of tissue pO II is very important in radiation oncology. Other areas in which EPR imaging and oxymetry may help are in the investigation of tumorangiogenesis, wound healing, oxygenation of tumor tissue by the ingestion of oxygen-rich gases, etc. The correct choice of the spin probe will depend on the modality of measurement (whether by CW or time-domain EPR imaging) and the particular physiology interrogated. Examples of the available spin probes and some EPR imaging applications employing them are presented.

  11. EPR studies of gamma-irradiated taurine single crystals

    NASA Astrophysics Data System (ADS)

    Bulut, A.; Karabulut, B.; Tapramaz, R.; Köksal, F.

    2000-04-01

    An EPR study of gamma-irradiated taurine [C 2H 7NO 3S] single crystal was carried out at room temperature. The EPR spectra were recorded in the three at mutually perpendicular planes. There are two magnetically distinct sites in monoclinic lattice. The principle values of g and hyperfine constants for both sites were calculated. The results have indicated the presence of 32ṠO -2 and 33ṠO -2 radicals. The hyperfine values of 33ṠO -2 radical were used to obtain O-S-O bond angle for both sites.

  12. A new causal interpretation of EPR-B experiment

    NASA Astrophysics Data System (ADS)

    Gondran, Michel; Gondran, Alexandre

    2012-12-01

    In this paper we study a two-step version of EPR-B experiment, the Bohm version of the Einstein-Podolsky-Rosen experiment. Its theoretical resolution in space and time enables us to refute the classic "impossibility" to decompose a pair of entangled atoms into two distinct states, one for each atom. We propose a new causal interpretation of the EPR-B experiment where each atom has a position and a spin while the singlet wave function verifies the two-body Pauli equation. In conclusion we suggest a physical explanation of non-local influences, compatible with Einstein's point of view on relativity.

  13. EPR and Primitive Life: Dating and Visualizing the Organic Matter in the Oldest Rocks

    NASA Astrophysics Data System (ADS)

    Binet, L.; Gourier, D.; Skrzypczak-Bonduelle, A.; Delpoux, O.; Derenne, S.

    2007-03-01

    An EPR study of cherts of different ages showed that the age of the embedded fossil organic matter can be estimated from the EPR lineshape of the radicals. Nondestructive 3D visualization of bacterial mats is cherts in also possible by EPR imaging.

  14. A hand-held EPR scanner for transcutaneous oximetry

    NASA Astrophysics Data System (ADS)

    Wolfson, Helen; Ahmad, Rizwan; Twig, Ygal; Blank, Aharon; Kuppusamy, Periannan

    2015-03-01

    Cutaneous (skin) oxygenation is an important prognostic factor for the treatment of chronic wounds, skin cancer, diabetes side effects, and limb amputation. Currently, there are no reliable methods for measuring this parameter. Oximetry, using electron paramagnetic resonance (EPR) spectroscopy, is emerging as a potential tool for clinical oximetry, including cutaneous applications. The problem with EPR oximetry, however, is that the conventional EPR design requires the use of a large magnet that can generate homogeneous field across the sample, making it unattractive for clinical practice. We present a novel approach that makes use of a miniature permanent magnet, combined with a small microwave resonator, to enable the acquisition of EPR signals from paramagnetic species placed on the skin. The instrumentation consists of a hand-held, modular, cylindrical probehead with overall dimensions of 36-mm diameter and 24-mm height, with 150-g weight. The probehead includes a Halbach array of 16 pieces (4×4×8 mm3) of Sm-Co permanent magnet and a loop-gap resonator (2.24 GHz). Preliminary measurements using a Hahn-echo pulse sequence (800 echos in 20 ms) showed a signalto- noise ratio of ~70 compared to ~435 in a homogenous magnet under identical settings. Further work is in progress to improve the performance of the probehead and to optimize the hand-held system for clinical use

  15. Numerical analysis of EPR spectra. 7. The simplex algorithm

    NASA Astrophysics Data System (ADS)

    Beckwith, Athelstan L. J.; Brumby, Steven

    The Simplex algorithm is well suited to the least-squares analysis of highly complex EPR spectra. The application of the algorithm to the analysis of the spectra of benzo[ a]pyrenyl-6-oxy, chloro(methoxycarbonyl)methyl, and cyano(methoxy)methyl free radicals is described.

  16. New ceramic EPR resonators with high dielectric permittivity.

    PubMed

    Golovina, Iryna; Geifman, Ilia; Belous, Anatolii

    2008-11-01

    New EPR resonators were developed by using a ceramic material with a high dielectric constant, epsilon=160. The resonators have a high quality factor, Q=10(3), and enhance the sensitivity of an EPR spectrometer up to 170 times. Some advantages of the new ceramic resonators are: (1) cheaper synthesis and simplified fabricating technology; (2) wider temperature range; and (3) ease of use. The ceramic material is produced with a titanate of complex oxides of rare-earth and alkaline metals, and has a perovskite type structure. The resonators were tested with X-band EPR spectrometers with cylindrical (TE(011)) and rectangular (TE(102)) cavities at 300 and 77K. We discovered that EPR signal strength enhancement depends on the dielectric constant of the material, resonator geometry and the size of the sample. Also, an unusual resonant mode was found in the dielectric resonator-metallic cavity structure. In this mode, the directions of microwave magnetic fields of the coupled resonators are opposite and the resonant frequency of the structure is higher than the frequency of empty metallic cavity. PMID:18815061

  17. Determination of tritium distribution in labeled compounds using EPR spectrometry

    SciTech Connect

    Postolache, C.; Matei, L.; Georgescu, R.

    2008-07-15

    Usually, the tritium distribution in a labeled compound is analyzed by T-NMR spectrometry. NMR equipment is expensive and its sensitivity is lower in comparison to EPR spectrometry. In this paper, the possibility of determining the distribution of tritium in a labeled molecule using self-radiolytic decay processes was analyzed. (authors)

  18. Quantitative Analysis of the Enhanced Permeation and Retention (EPR) Effect

    PubMed Central

    Ulmschneider, Martin B.; Searson, Peter C.

    2015-01-01

    Tumor vasculature is characterized by a variety of abnormalities including irregular architecture, poor lymphatic drainage, and the upregulation of factors that increase the paracellular permeability. The increased permeability is important in mediating the uptake of an intravenously administered drug in a solid tumor and is known as the enhanced permeation and retention (EPR) effect. Studies in animal models have demonstrated a cut-off size of 500 nm - 1 µm for molecules or nanoparticles to extravasate into a tumor, however, surprisingly little is known about the kinetics of the EPR effect. Here we present a pharmacokinetic model to quantitatively assess the influence of the EPR effect on the uptake of a drug into a solid tumor. We use pharmacokinetic data for Doxil and doxorubicin from human clinical trials to illustrate how the EPR effect influences tumor uptake. This model provides a quantitative framework to guide preclinical trials of new chemotherapies and ultimately to develop design rules that can increase targeting efficiency and decrease unwanted side effects in normal tissue. PMID:25938565

  19. Development of a Hybrid EPR/NMR Coimaging System

    PubMed Central

    Samouilov, Alexandre; Caia, George L.; Kesselring, Eric; Petryakov, Sergey; Wasowicz, Tomasz; Zweier, Jay L.

    2010-01-01

    Electron paramagnetic resonance imaging (EPRI) is a powerful technique that enables spatial mapping of free radicals or other paramagnetic compounds; however, it does not in itself provide anatomic visualization of the body. Proton magnetic resonance imaging (MRI) is well suited to provide anatomical visualization. A hybrid EPR/NMR coimaging instrument was constructed that utilizes the complementary capabilities of both techniques, superimposing EPR and proton-MR images to provide the distribution of paramagnetic species in the body. A common magnet and field gradient system is utilized along with a dual EPR and proton-NMR resonator assembly, enabling coimaging without the need to move the sample. EPRI is performed at ~1.2 GHz/~40 mT and proton MRI is performed at 16.18 MHz/~380 mT; hence the method is suitable for whole-body coimaging of living mice. The gradient system used is calibrated and controlled in such a manner that the spatial geometry of the two acquired images is matched, enabling their superposition without additional postprocessing or marker registration. The performance of the system was tested in a series of phantoms and in vivo applications by mapping the location of a paramagnetic probe in the gastrointestinal (GI) tract of mice. This hybrid EPR/NMR coimaging instrument enables imaging of paramagnetic molecules along with their anatomic localization in the body. PMID:17659621

  20. Accurate Extraction of Nanometer Distances in Multimers by Pulse EPR

    PubMed Central

    Valera, Silvia; Ackermann, Katrin; Pliotas, Christos; Huang, Hexian; Naismith, James H.

    2016-01-01

    Abstract Pulse electron paramagnetic resonance (EPR) is gaining increasing importance in structural biology. The PELDOR (pulsed electron–electron double resonance) method allows extracting distance information on the nanometer scale. Here, we demonstrate the efficient extraction of distances from multimeric systems such as membrane‐embedded ion channels where data analysis is commonly hindered by multi‐spin effects. PMID:26865468

  1. EPR investigations of gamma-irradiated ground black pepper

    NASA Astrophysics Data System (ADS)

    Polovka, Martin; Brezová, Vlasta; Staško, Andrej; Mazúr, Milan; Suhaj, Milan; Šimko, Peter

    2006-02-01

    The γ-radiation treatment of ground black pepper samples resulted in the production of three paramagnetic species ( GI- GIII) which arise from a different origin and have different thermal behavior and stability. The axially symmetric spectra can be characterized by the spin Hamiltonian parameters: GI ( g⊥=2.0060, g∥=2.0032; A⊥=0.85 mT, A∥=0.70 mT) and GII ( g⊥=2.0060, g∥=2.0050; A⊥=0.50 mT, A∥=0.40 mT) assigned to carbohydrate radical structures. The parameters of EPR signal GIII ( g⊥=2.0029, g∥=2.0014; A⊥=3.00 mT, A∥=1.80 mT) possessed features characteristic of cellulose radical species. The activation energies, evaluated by Arrhenius analysis, are in order Ea( GI)< Ea( GIII)< Ea( GII). The EPR measurements performed 20 weeks after radiation process confirmed that a temperature increase from 298 to 353 K, caused a significant decrease of integral EPR signal intensity for γ-irradiated samples (˜40%), compared to the reference (non-irradiated) ground black pepper, where a decrease of ˜13% was found. The influence of γ-radiation treatment on the radical-scavenging activities of aqueous and ethanol extracts of black pepper were investigated by both an EPR spin trapping technique and DPPH assay. No changes were detected in either the water or ethanol extracts for a γ-irradiation dose of 10 kGy.

  2. Nonlinear Simulation of the Tooth Enamel Spectrum for EPR Dosimetry

    NASA Astrophysics Data System (ADS)

    Kirillov, V. A.; Dubovsky, S. V.

    2016-07-01

    Software was developed where initial EPR spectra of tooth enamel were deconvoluted based on nonlinear simulation, line shapes and signal amplitudes in the model initial spectrum were calculated, the regression coefficient was evaluated, and individual spectra were summed. Software validation demonstrated that doses calculated using it agreed excellently with the applied radiation doses and the doses reconstructed by the method of additive doses.

  3. New ceramic EPR resonators with high dielectric permittivity

    NASA Astrophysics Data System (ADS)

    Golovina, Iryna; Geifman, Ilia; Belous, Anatolii

    2008-11-01

    New EPR resonators were developed by using a ceramic material with a high dielectric constant, ɛ = 160. The resonators have a high quality factor, Q = 10 3, and enhance the sensitivity of an EPR spectrometer up to 170 times. Some advantages of the new ceramic resonators are: (1) cheaper synthesis and simplified fabricating technology; (2) wider temperature range; and (3) ease of use. The ceramic material is produced with a titanate of complex oxides of rare-earth and alkaline metals, and has a perovskite type structure. The resonators were tested with X-band EPR spectrometers with cylindrical (TE 011) and rectangular (TE 102) cavities at 300 and 77 K. We discovered that EPR signal strength enhancement depends on the dielectric constant of the material, resonator geometry and the size of the sample. Also, an unusual resonant mode was found in the dielectric resonator-metallic cavity structure. In this mode, the directions of microwave magnetic fields of the coupled resonators are opposite and the resonant frequency of the structure is higher than the frequency of empty metallic cavity.

  4. EPR Imaging at a Few Megahertz Using SQUID Detectors

    NASA Technical Reports Server (NTRS)

    Hahn, Inseob; Day, Peter; Penanen, Konstantin; Eom, Byeong Ho

    2010-01-01

    An apparatus being developed for electron paramagnetic resonance (EPR) imaging operates in the resonance-frequency range of about 1 to 2 MHz well below the microwave frequencies used in conventional EPR. Until now, in order to obtain sufficient signal-to-noise radios (SNRs) in conventional EPR, it has been necessary to place both detectors and objects to be imaged inside resonant microwave cavities. EPR imaging has much in common with magnetic resonance imaging (MRI), which is described briefly in the immediately preceding article. In EPR imaging as in MRI, one applies a magnetic pulse to make magnetic moments (in this case, of electrons) precess in an applied magnetic field having a known gradient. The magnetic moments precess at a resonance frequency proportional to the strength of the local magnetic field. One detects the decaying resonance-frequency magnetic- field component associated with the precession. Position is encoded by use of the known relationship between the resonance frequency and the position dependence of the magnetic field. EPR imaging has recently been recognized as an important tool for non-invasive, in vivo imaging of free radicals and reduction/oxidization metabolism. However, for in vivo EPR imaging of humans and large animals, the conventional approach is not suitable because (1) it is difficult to design and construct resonant cavities large enough and having the required shapes; (2) motion, including respiration and heartbeat, can alter the resonance frequency; and (3) most microwave energy is absorbed in the first few centimeters of tissue depth, thereby potentially endangering the subject and making it impossible to obtain adequate signal strength for imaging at greater depth. To obtain greater penetration depth, prevent injury to the subject, and avoid the difficulties associated with resonant cavities, it is necessary to use lower resonance frequencies. An additional advantage of using lower resonance frequencies is that one can use

  5. EPR/PTFE dosimetry for test reactor environments

    SciTech Connect

    Vehar, D.W.; Griffin, P.J.; Quirk, T.J.

    2011-07-01

    The use of Electron Paramagnetic Resonance (EPR) spectroscopy with materials such as alanine is well established as a technique for measurement of ionizing radiation absorbed dose in photon and electron fields such as Co-60, high-energy bremsstrahlung and electron-beam fields [1]. In fact, EPR/Alanine dosimetry has become a routine transfer standard for national standards bodies such as NIST and NPL. In 1992 the Radiation Metrology Laboratory (RML) at Sandia National Laboratories implemented EPR/Alanine capabilities for use in routine and calibration activities at its Co-60 and pulsed-power facilities. At that time it also investigated the usefulness of the system for measurement of absorbed dose in the mixed neutron/photon environments of reactors such as the Sandia Pulsed Reactor and the Annular Core Research Reactor used for hardness testing of electronics. The RML concluded that the neutron response of alanine was a sufficiently high fraction of the overall dosimeter response that the resulting uncertainties in the photon dose would be unacceptably large for silicon-device testing. However, it also suggested that non-hydrogenous materials such as polytetrafluoroethylene (PTFE) would exhibit smaller neutron response and might be useful in mixed environments. Preliminary research with PTFE in photon environments indicated considerable promise, but further development was not pursued at that time. Because of renewed interest in absorbed dose measurements that could better define the individual contributions of photon and neutron components to the overall dose delivered to a test object, the RML has re-initiated the development of an EPR/PTFE dosimetry system. This effort consists of three stages: 1) Identification of PTFE materials that may be suitable for dosimetry applications. It was speculated that the inconsistency of EPR signatures in the earlier samples may have been due to variability in PTFE manufacturing processes. 2) Characterization of dosimetry in

  6. Multifrequency EPR study on freeze-dried fruits before and after X-ray irradiation

    NASA Astrophysics Data System (ADS)

    Yordanov, N. D.; Aleksieva, K.; Dimitrova, A.; Georgieva, L.; Tzvetkova, E.

    2006-09-01

    X-, K- and Q-band EPR studies on lyophilized whole pulp parts of blue plum, apricot, peach, melon as well as achens and pulp separately of strawberry before and after X-ray irradiation are reported. Before irradiation all samples show in X band a weak singlet EPR line with g=2.0030±0.0005, except melon, which is EPR silent. Immediately after irradiation all samples exhibit complex fruit-depending spectra, which decay with time and change to give, in ca. 50 days, an asymmetric singlet EPR line with g=2.0041±0.0005. Only apricot pulp gave a typical "sugar-like" EPR spectrum. Singlet EPR lines recorded after irradiation in X -band are K- and Q-band resolved as typical anisotropic EPR spectra with g=2.0023±0.0003 and g⊥=2.0041±0.0005. In addition, K- and Q-band EPR spectra of all samples show a superposition with the six EPR lines of Mn 2+ naturally present in the fruits. The saturation behavior of the EPR spectra of achens of lyophilized and fresh strawberry is also studied. The differences in g factors of samples before and after X-ray irradiation might be used for the identification of radiation processing of fruits in the case of pulp and the differences in the EPR saturation behavior might be used for the achens of strawberry.

  7. Kinetic Measurements Using EPR Imaging with a Modulated Field Gradient

    NASA Astrophysics Data System (ADS)

    Herrling, Thomas; Fuchs, Jürgen; Groth, Norbert

    2002-01-01

    EPR imaging with modulated field gradient was applied for the investigation of fast diffusion processes. Three different imaging methods are possible: spectral-temporal, spatio-temporal, and spectral-spatial imaging. The time resolution is on the order of seconds and the spatial resolution is in the micrometer region. The efficiency of this imaging technique is demonstrated for the penetration of the spin probe Tempol in the skin of hairless mice biopsies. The skin is normally protected against the penetration of water soluble substances by the horny layer, a resistive thin lipophilic layer. Overcoming this horny layer for water soluble ingredients is one of the main practical problems for the topical application of pharmaceutics which could be investigated by EPR imaging. Different images represent the penetration behavior of the water soluble Tempol in the skin after treatment with the penetration enhancer DMSO (Dimethylsulfoxide) and after removing the horny layer.

  8. EPR dosimetry in a mixed neutron and gamma radiation field.

    PubMed

    Trompier, F; Fattibene, P; Tikunov, D; Bartolotta, A; Carosi, A; Doca, M C

    2004-01-01

    Suitability of Electron Paramagnetic Resonance (EPR) spectroscopy for criticality dosimetry was evaluated for tooth enamel, mannose and alanine pellets during the 'international intercomparison of criticality dosimetry techniques' at the SILENE reactor held in Valduc in June 2002, France. These three materials were irradiated in neutron and gamma-ray fields of various relative intensities and spectral distributions in order to evaluate their neutron sensitivity. The neutron response was found to be around 10% for tooth enamel, 45% for mannose and between 40 and 90% for alanine pellets according their type. According to the IAEA recommendations on the early estimate of criticality accident absorbed dose, analyzed results show the EPR potentiality and complementarity with regular criticality techniques. PMID:15353687

  9. EPR and electronic absorption spectra of copper bearing turquoise mineral

    NASA Astrophysics Data System (ADS)

    Sharma, K. B. N.; Moorthy, L. R.; Reddy, B. J.; Vedanand, S.

    1988-10-01

    Electron paramagnetic resonance and optical absorption spectra of turquoise have been studied both at room and low temperatures. It is concluded from the EPR spectra that the ground state of Cu 2+ ion in turquoise is 2A g(d x2- y2) and it is sited in an elongated rhombic octahedron (D 2π). The observed absorption bands at 14970 and 18354 cm -1 are assigned at 2A g→ 2B 1 g( dx2- y2→ xy) and 2A g→[ su2B 3g(d x 2-y 2→d yz) respectively assuming D 2π symmetry which are inconsistent with EPR studies. The three bands in the NIR region are attributed to combinations of fundamental modes of the H 2O molecule present in the sample.

  10. Numerical analysis of EPR spectra. 8. Relative concentrations

    NASA Astrophysics Data System (ADS)

    Beckwith, Athelstan L. J.; Brumby, Steven

    A method for determining the relative concentrations of paramagnetic species in mixtures by least-squares analysis of the EPR spectra is described. The method is especially useful when the double integration method cannot be used because of overlap between the component spectra. In two examples, the relative steady-state concentrations of free radicals formed during the photolysis of dimethoxymethane/di- tert-butyl peroxide and cyclopropylmethyl methyl ether/di- tert-butyl peroxide/cyclopropane solutions are determined.

  11. Dosimetry Based on EPR Spectral Analysis of Fingernail Clippings

    PubMed Central

    Wilcox, Dean E.; He, Xiaoming; Gui, Jiang; Ruuge, Andres E.; Li, Hongbin; Williams, Benjamin B.; Swartz, Harold M.

    2009-01-01

    Exposure of fingernails and toenails to ionizing radiation creates radicals that are stable over a relatively long period (days to weeks) and characterized by an isotropic EPR signal at g = 2.003 (so-called radiation-induced signal, RIS). This signal in readily obtained fingernail parings has the potential to be used in screening a population for exposure to radiation and determining individual dose to guide medical treatment. However, the mechanical harvesting of fingernail parings also creates radicals and their EPR signals (so-called mechanically-induced signals, MIS) overlap the g ~ 2.0 region, interfering with efforts to quantify the RIS and, therefore, the radiation dose. Careful analysis of the time evolution and power-dependence of the EPR spectra of freshly cut fingernail parings has now resolved the MIS into three major components, including one that is described for the first time. It dominates the MIS soon after cutting, but decays within the first hour, and consists of a unique doublet that can be resolved from the RIS. The MIS obtained within the first few minutes after cutting is consistent among fingernail samples and provides an opportunity to achieve the two important dosimetry objectives. First, perturbation of the initial MIS by the presence of RIS in fingernails that have received a threshold dose of radiation leads to spectral signatures that can be used for rapid screening. Second, decomposition of the EPR spectra from irradiated fingernails into MIS and RIS components can be used to isolate and thus quantify the RIS for determining individual exposure dose. PMID:20065699

  12. Characterization of nuclear waste forms by EPR spectroscopy

    SciTech Connect

    Boatner, L.A.; Abraham, M.M.; Rappaz, M.

    1980-10-01

    Single crystals of LaPO/sub 4/ have been grown with the addition of various amounts of PW-4b simulated waste, and the EPR spectra of Gd/sup 3 +/ in these samples have been compared with that obtained for a pure LaPO/sub 4/ single crystal. The relationship between the average linewidth of two symmetric EPR transitions and their magnetic field separation for pure and PW-4b doped LaPO/sub 4/ crystals are shown quantitatively. These measurements were carried out for four different crystals and two different magnetic field orientations. Since the linewidth of each transition is proportional to its magnetic field separation from the central line, it can be concluded that the line broadening is inhomogeneous (i.e., the line broadening is due to a distribution of line positions with this distribution resulting from a distribution of impurities in the crystal). The sensitivity of Gd/sup 3 +/ linewidths to defects or strains is also under investigation as a means of detecting metamictization phenomena in orthophosphates. Mixed Ln/sub 1-x/An/sub x/PO/sub 4/ crystals, where Ln is a rare earth and An an actinide, have been grown and EPR spectra of Gd/sup 3 +/ in these systems are of considerable interest for detecting radiation damage created by ..cap alpha..-particles or recoil of the daughter nuclei. Although the examples of the application of EPR to waste form characterization described here have emphasized studies of lanthanide orthophosphates, the same techniques can be applied to perovskite, hollandite, zirconolite, etc. single crystals or powders or to amorphous materials.

  13. Implementing Diffie-Hellman key exchange using quantum EPR pairs

    NASA Astrophysics Data System (ADS)

    Mandal, Sayonnha; Parakh, Abhishek

    2015-05-01

    This paper implements the concepts of perfect forward secrecy and the Diffie-Hellman key exchange using EPR pairs to establish and share a secret key between two non-authenticated parties and transfer messages between them without the risk of compromise. Current implementations of quantum cryptography are based on the BB84 protocol, which is susceptible to siphoning attacks on the multiple photons emitted by practical laser sources. This makes BB84-based quantum cryptography protocol unsuitable for network computing environments. Diffie-Hellman does not require the two parties to be mutually authenticated to each other, yet it can provide a basis for a number of authenticated protocols, most notably the concept of perfect forward secrecy. The work proposed in this paper provides a new direction in utilizing quantum EPR pairs in quantum key exchange. Although, classical cryptography boasts of efficient and robust protocols like the Diffie-Hellman key exchange, in the current times, with the advent of quantum computing they are very much vulnerable to eavesdropping and cryptanalytic attacks. Using quantum cryptographic principles, however, these classical encryption algorithms show more promise and a more robust and secure structure for applications. The unique properties of quantum EPR pairs also, on the other hand, go a long way in removing attacks like eavesdropping by their inherent nature of one particle of the pair losing its state if a measurement occurs on the other. The concept of perfect forward secrecy is revisited in this paper to attribute tighter security to the proposed protocol.

  14. Advances in Probes and Methods for Clinical EPR Oximetry

    PubMed Central

    Hou, Huagang; Khan, Nadeem; Jarvis, Lesley A.; Chen, Eunice Y.; Williams, Benjamin B.; Kuppusamy, Periannan

    2015-01-01

    EPR oximetry, which enables reliable, accurate, and repeated measurements of the partial pressure of oxygen in tissues, provides a unique opportunity to investigate the role of oxygen in the pathogenesis and treatment of several diseases including cancer, stroke, and heart failure. Building on significant advances in the in vivo application of EPR oximetry for small animal models of disease, we are developing suitable probes and instrumentation required for use in human subjects. Our laboratory has established the feasibility of clinical EPR oximetry in cancer patients using India ink, the only material presently approved for clinical use. We now are developing the next generation of probes, which are both superior in terms of oxygen sensitivity and biocompatibility including an excellent safety profile for use in humans. Further advances include the development of implantable oxygen sensors linked to an external coupling loop for measurements of deep-tissue oxygenations at any depth, overcoming the current limitation of 10 mm. This paper presents an overview of recent developments in our ability to make meaningful measurements of oxygen partial pressures in human subjects under clinical settings. PMID:24729217

  15. EPR investigation of some traditional oriental irradiated spices

    NASA Astrophysics Data System (ADS)

    Duliu, Octavian G.; Georgescu, Rodica; Ali, Shaban Ibrahim

    2007-06-01

    The 9.50 GHz electron paramagnetic resonance (EPR) spectra of unirradiated and 60Co γ-ray irradiated cardamom ( Elettaria cardamomum L. Maton, Zingiberaceae), ginger (( Zingiber officinale Rosc., Zingiberaceae), and saffron ( Crocus sativus L., Iridaceae) have been investigated at room temperature. All unirradiated spices presented a weak resonance line with g-factors around free-electron ones. After γ-ray irradiation at an absorbed dose of up to 11.3 kGy, the presence of EPR spectra whose amplitude increase monotonously with the absorbed dose has been noticed with all spices. A 100 °C isothermal annealing of 11.3 kGy irradiated samples has shown a differential reduction of amplitude of various components that compose initial spectra, but even after 3.6 h of thermal treatment, the remaining amplitude represents no less then 30% of the initial ones. The same peculiarities have been noticed after 83 days storage at room temperature but after 340 days storage at ambient conditions only irradiated ginger displays a weak signal that differs from those of unirradiated sample. All these factors could be taken into account in establishing at which extent the EPR is suitable to evidence any irradiation treatment applied to these spices.

  16. A Wire Crossed-Loop-Resonator for Rapid Scan EPR

    PubMed Central

    Rinard, George A.; Quine, Richard W.; Biller, Joshua R.; Eaton, Gareth R.

    2011-01-01

    A crossed-loop (orthogonal mode) resonator (CLR) was constructed of fine wire to achieve design goals for rapid scan in vivo EPR imaging at VHF frequencies (in practice, near 250 MHz). This application requires the resonator to have a very open design to facilitate access to the animal for physiological support during the image acquisition. The rapid scan experiment uses large amplitude magnetic field scans, and sufficiently large resonator and detection bandwidths to record the rapidly-changing signal response. Rapid-scan EPR is sensitive to RF/microwave source noise and to baseline changes that are coherent with the field scan. The sensitivity to source noise is a primary incentive for using a CLR to isolate the detected signal from the RF source noise. Isolation from source noise of 44 and 47 dB was achieved in two resonator designs. Prior results showed that eddy currents contribute to background problems in rapid scan EPR, so the CLR design had to minimize conducting metal components. Using fine (AWG 38) wire for the resonators decreased eddy currents and lowered the resonator Q, thus providing larger resonator bandwidth. Mechanical resonances at specific scan frequencies are a major contributor to rapid scan backgrounds. PMID:21603086

  17. Tetrabromidocuprates(II)—Synthesis, Structure and EPR

    PubMed Central

    Zabel, André; Winter, Alette; Kelling, Alexandra; Schilde, Uwe; Strauch, Peter

    2016-01-01

    Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several “onium” cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g‖ and g⊥) of the tensors could be determined and information on the structural changes in the [CuBr4]2− anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids. PMID:27104522

  18. Peptide-membrane Interactions by Spin-labeling EPR

    PubMed Central

    Smirnova, Tatyana I.; Smirnov, Alex I.

    2016-01-01

    Site-directed spin labeling (SDSL) in combination with Electron Paramagnetic Resonance (EPR) spectroscopy is a well-established method that has recently grown in popularity as an experimental technique, with multiple applications in protein and peptide science. The growth is driven by development of labeling strategies, as well as by considerable technical advances in the field, that are paralleled by an increased availability of EPR instrumentation. While the method requires an introduction of a paramagnetic probe at a well-defined position in a peptide sequence, it has been shown to be minimally destructive to the peptide structure and energetics of the peptide-membrane interactions. In this chapter, we describe basic approaches for using SDSL EPR spectroscopy to study interactions between small peptides and biological membranes or membrane mimetic systems. We focus on experimental approaches to quantify peptide-membrane binding, topology of bound peptides, and characterize peptide aggregation. Sample preparation protocols including spin-labeling methods and preparation of membrane mimetic systems are also described. PMID:26477253

  19. VHF EPR analysis of organic sulfur in coal. Technical report, December 1, 1991--February 29, 1992

    SciTech Connect

    Clarkson, R.B.; Belford, R.L.

    1992-08-01

    This is a report of the second quarter of a two-year investigation exploiting electron paramagnetic resonance (EPR), especially novel, very high frequency (VHF) spectroscopy techniques and instrumentation (the only high-modulation W-band EPR spectrometer in the world) developed earlier by these authors, to conduct further qualitative and quantitative studies of heteroatomic organic molecules in coal with particular emphasis on sulfur. New model compounds have been prepared in EPR-active forms and surveyed with X-band EPR. Previous W-band (96 GHz) VHF-EPR work is being extended to studies of these new model compounds as well as to a variety of coal and desulfurized coal samples. Typically, the model compounds under investigation and their analogues are found in coals as stable free radicals which give rise to an EPR signal.

  20. EPR Study of [Cu(Him)4]·2Br Complex

    NASA Astrophysics Data System (ADS)

    Yıldırım, İ.; Karabulut, B.

    2016-04-01

    The single crystal of [Cu(Him)4]·2Br (Him: C3H4N2, imidazole) complex has been investigated at ambient temperature in three mutually perpendicular planes by EPR technique. The magnetic environments of [Cu(Him)4]·2Br complex have been identified by EPR technique. The study reveals the existence of two magnetically inequivalent Cu2+ sites. The principal values of g tensors were obtained. The EPR parameters show that the paramagnetic centers have rhombic symmetry.

  1. In Vivo Imaging of Tissue Physiological Function using EPR Spectroscopy | NCI Technology Transfer Center | TTC

    Cancer.gov

    Electron paramagnetic resonance (EPR) is a technique for studying chemical species that have one or more unpaired electrons.  The current invention describes Echo-based Single Point Imaging (ESPI), a novel EPR image formation strategy that allows in vivo imaging of physiological function.  The National Cancer Institute's Radiation Biology Branch is seeking statements of capability or interest from parties interested in in-licensing an in vivo imaging using Electron paramagnetic resonance (EPR) to measure active oxygen species.

  2. Implementing a new EPR lineshape parameter for organic radicals in carbonaceous matter

    PubMed Central

    2013-01-01

    Background Electron Paramagnetic Resonance (EPR) is a non-destructive, non-invasive technique useful for the characterization of organic moieties in primitive carbonaceous matter related to the origin of life. The classical EPR parameters are the peak-to-peak amplitude, the linewidth and the g factor; however, such parameters turn out not to suffice to fully determine a single EPR line. Results In this paper, we give the definition and practical implementation of a new EPR parameter based on the signal shape that we call the R10 factor. This parameter was originally defined in the case of a single symmetric EPR line and used as a new datation method for organic matter in the field of exobiology. Conclusion Combined to classical EPR parameters, the proposed shape parameter provides a full description of an EPR spectrum and opens the way to novel applications like datation. Such a parameter is a powerful tool for future EPR studies, not only of carbonaceous matter, but also of any substance which spectrum exhibits a single symmetric line. Reproducibility The paper is a literate program—written using Noweb within the Org-mode as provided by the Emacs editor— and it also describes the full data analysis pipeline that computes the R10 on a real EPR spectrum. PMID:23866970

  3. CW EPR and 9 GHz EPR imaging investigation of stable paramagnetic species and their antioxidant activities in dry shiitake mushroom (Lentinus edodes).

    PubMed

    Nakagawa, Kouichi; Hara, Hideyuki

    2016-05-01

    We investigated the antioxidant activities and locations of stable paramagnetic species in dry (or drying) shiitake mushroom (Lentinus edodes) using continuous wave (CW) electron paramagnetic resonance (EPR) and 9 GHz EPR imaging. CW 9 GHz EPR detected paramagnetic species (peak-to-peak linewidth (ΔHpp) = 0.57 mT) in the mushroom. Two-dimensional imaging of the sharp line using a 9 GHz EPR imager showed that the species were located in the cap and shortened stem portions of the mushroom. No other location of the species was found in the mushroom. However, radical locations and concentrations varied along the cap of the mushroom. The 9 GHz EPR imaging determined the exact location of stable paramagnetic species in the shiitake mushroom. Distilled water extracts of the pigmented cap surface and the inner cap of the mushroom showed similar antioxidant activities that reduced an aqueous solution of 0.1 mM 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl. The present results suggest that the antioxidant activities of the edible mushroom extracts are much weaker than those of ascorbic acid. Thus, CW EPR and EPR imaging revealed the location and distribution of stable paramagnetic species and the antioxidant activities in the shiitake mushroom for the first time. PMID:26846304

  4. X- and Q-band EPR studies on fine powders of irradiated plants. New approach for detection of their radiation history by using Q-band EPR spectrometry

    NASA Astrophysics Data System (ADS)

    Yordanov, Nicola D.; Aleksieva, Katerina

    2004-01-01

    X- and Q-band EPR studies after γ-irradiation of some dry spices and aromatic herbs are reported. Before irradiation all samples show only one singlet line in X-band EPR, whereas the Q-band EPR spectrum of the same samples is a superposition of two individual spectra—one corresponding to the above EPR signal, with an anisotropic spectrum, and a second one consisting of six lines due to the Mn 2+ naturally present in plants. The radiation induced EPR signal due to cellulose free radicals was not detected after γ-irradiation, but only the increase of the natural signal present before the irradiation. The fading kinetic of this EPR signal was monitored in three cases—when samples were kept in plastic bags without any special conditioning after irradiation, when samples were covered with paraffin before irradiation and when samples were dried at 60°C for 1 h before irradiation. The studies show that stability of radiation induced EPR signals decreases in the order of: paraffin covered > heated before irradiation > kept at room conditions. The two EPR spectra in the Q-band—one with radiation dependent intensity and a second due to Mn 2+, which is radiation independent allow identification of previous radiation treatment based on the fact that Mn 2+ quantity in the sample is constant whereas the quantity of radiation-induced free radicals is temperature dependent. It was found that for irradiated samples the ratio between EPR intensity of the free radicals and that of Mn 2+ before and after heating decreases with 50-60% whereas for non-irradiated samples it is ca. 10-15%.

  5. EPR investigation of libration motion of spin labeled hemerythrin

    NASA Astrophysics Data System (ADS)

    Takacs, Istvan Mihaly; Mot, Augustin; Silaghi-Dumitrescu, Radu; Damian, Grigore

    2014-09-01

    Reported here are room-temperature continuous wave X-band Electron Paramagnetic Resonance (EPR) spectra of the non-heme di-iron protein hemerythrin (Hr), spin labeled at position 51C in different viscous media, illustrating the mobility and oligomeric recombination tendency of the Phascolopsis gouldii Hr. The mobility of a spin labeled Hr depends on the local viscosity and its connectivity to the nature of the molecular environment (glycerol, PEG4000 and BSA). This provides the basis for a tool useful in directly monitoring Hr in ex vivo samples upon injection within the bloodstream of test animals, for blood substitute research.

  6. EPR, NMR and molecular dynamics in fluoride glasses

    NASA Astrophysics Data System (ADS)

    Silly, G.; Buzaré, J. Y.; Bureau, B.; Legein, C.; Boulard, B.

    1999-11-01

    This paper deals with the method of investigation of local order in Transition Metal Fluoride Glasses that has been developed in the past few years using magnetic resonance techniques associated to molecular dynamics calculations. The results presented here will concern lead fluoride PZG (PbF2-ZnF2-GaF3) glasses of the PbF2-MtIIF2-MtIIIF3 family, but the method remains valid for any other disordered compound. The only limitations are that the sample may be doped with transition metal ions (S⩾1) for EPR measurements or contain quadrupolar nuclei (I⩾1) to perform NMR investigations.

  7. Mn distribution in natural sphalerites: a micronalytical and EPR study

    NASA Astrophysics Data System (ADS)

    di Benedetto, F.; Bernardini, G. P.; Cipriani, C.; Plant, D.; Romanelli, M.; Vaughan, D. J.

    2003-04-01

    Electron Paramagnetic Resonance (EPR) has been successfully applied to determine the local coordination and distribution of transition metal cations in sulphides and sulphosalts (Di Benedetto et al., 2002). Due to its enhanced sensitivity and element-specificity it is one of the best tools to monitor Mn(II) behaviour down to very low concentrations. In order to reach a fuller understanding of the spectroscopic results, a microanalytical study has also been undertaken by means of Electron Microprobe Analysis. Operating conditions were chosen to achieve the lowest possible detection limits, taking into account that Mn can replace Zn in the sphalerite lattice both as a minor and trace element, and that EPR can detect Mn(II) below the ppm range. Six natural samples from the Museo di Storia Naturale, Università di Firenze, were selected to have pure single crystals and avoid magnetically active phases associated with the sphalerite. The Mn concentration determined ranges between 30 and 14300 ppm and Mn content varies considerably within the same sample, leading to differences up to the 50% as compared to the mean value. X-ray images confirm Mn to be distributed with an unusual pattern, unrelated to the other common Zn-replacing cations, Fe and Cd, present in the samples. Powder EPR spectra reveal at least three different Mn(II) signals: two sextets, overlapping in all samples containing Mn as trace element, and a single line, present only in the more concentrated samples. While the latter have been attributed to an inhomogeneous Mn distribution, due to an enhanced Mn-Mn superexchange interaction, the difference between the two sextets, observed by means of EEPR investigations in a synthetic sphalerite (Di Benedetto et al., 2002), appears unrelated to the Mn concentration and may be attributed to small differences in the local coordination of Mn(II) ions. This, in turn, may be explained by the segregation of small amounts of Mn into polytypic domains, features which

  8. A Signal-to-Noise Standard for Pulsed EPR

    PubMed Central

    Eaton, Gareth R.; Eaton, Sandra S; Quine, Richard W.; Mitchell, Deborah; Kathirvelu, Velavan; Weber, Ralph T.

    2010-01-01

    A 2 mm diameter by 10 mm long cylinder of fused SiO2 (quartz) γ-irradiated to 1 kGy with 60Co contains about 2×1016 spins/cm3. It is proposed as a standard for monitoring signal-to-noise (S/N) performance of X-band pulsed EPR spectrometers. This sample yields S/N of about 25 on modern spin echo spectrometers, which permits measurement of both signal and noise under the same conditions with an 8-bit digitizer. PMID:20451433

  9. An EPR Experiment for the Undergraduate Physical Chemistry Laboratory

    NASA Astrophysics Data System (ADS)

    Butera, R. A.; Waldeck, D. H.

    2000-11-01

    An experiment that illustrates the principles of electron paramagnetic resonance spectroscopy in the undergraduate physical chemistry laboratory is described. Students measure the value of g for DPPH and use it to determine the value of g for two inorganic complexes, Cu(acac)2 and VO(acac)2. The students use two instruments: an instructional device that illustrates the principles of EPR and a commercial Varian E4 spectrometer. This approach allows an elucidation of the principles of the method and provides experience with a more sophisticated research-grade instrument.

  10. Geochemical constraints on the source of EPR MORBs

    NASA Astrophysics Data System (ADS)

    Tian, L.; Wang, Z.

    2015-12-01

    Geochemical variations of mid-ocean ridge basalts (MORBs) have long been attributed to the presence of compositionally distinct crustal and mantle components in their sources. The oxygen isotope composition of MORBs was proposed to be a valuable tracer of subducted crustal materials [1] since 18O/16O ratios are strongly fractioned during low-temperature water-rock interactions (e.g. seafloor alteration). Here, we present a study of combined oxygen isotopes, radiogenic isotopes, and trace elements on volcanic lavas sampled at both ridge axes and off-axis seamounts in the northern East Pacific Rise (EPR; 5-15°N). The chemical composition of these lavas ranges from normal-MORB to enriched-MORB, and the newly analyzed 18O/16O ratios of hand-picked fresh glasses from these 53 lavas were measured using laser-fluorination technique, with a typical precision of ±0.08‰ (1σ). Our results show that the δ18OSMOW values of EPR glasses span ~0.64‰ (from 5.08‰ to 5.72‰), with an average value of 5.53(±0.12, 1σ) ‰, which is comparable to results from previous survey of global MORBs (5.52±0.11‰) [1]. Two andesitic glasses show unusually lower δ18O values (5.08‰ and 5.27‰, respectively) and exhibit excess Cl addition ([Cl]>3000ppm), probably indicating an assimilation of seawater-derived component (e.g., saline brines or altered oceanic crust). Previous studies [2, 3, 4, 5] have shown the correlated variations of trace element ratios (e.g. La/Sm, and K2O/TiO2 element ratios) and radiogenic isotope compositions (e.g. 87Sr/86Sr, 143Nd/144Nd, Pb isotope ratios), suggesting the presence of at least two components in the source of EPR MORBs, an enriched component and depleted component. Our results show that δ18O values of these glasses lack statistically-significant correlations with other geochemical indicies in the same sample, suggesting that (1) the source of EPR MORBs has a uniform oxygen isotope composition, (2) the enriched components in the sources

  11. Solution-phase EPR studies of single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Chen, Y.; Chen, J.; Hu, H.; Hamon, M. A.; Itkis, M. E.; Haddon, R. C.

    1999-01-01

    We report EPR studies on pristine, purified, shortened and soluble SWNTs in various solution phases. Some of these samples give rise to strong, sharp EPR signals, and this technique is useful for monitoring the presence of SWNTs in aqueous and organic solvents. The soluble SWNTs carry about 1 unpaired electron per 10000 carbon atoms and give a free electron g-value.

  12. Alcoholic extraction enables EPR analysis to characterize radiation-induced cellulosic signals in spices.

    PubMed

    Ahn, Jae-Jun; Sanyal, Bhaskar; Akram, Kashif; Kwon, Joong-Ho

    2014-11-19

    Different spices such as turmeric, oregano, and cinnamon were γ-irradiated at 1 and 10 kGy. The electron paramagnetic resonance (EPR) spectra of the nonirradiated samples were characterized by a single central signal (g = 2.006), the intensity of which was significantly enhanced upon irradiation. The EPR spectra of the irradiated spice samples were characterized by an additional triplet signal at g = 2.006 with a hyperfine coupling constant of 3 mT, associated with the cellulose radical. EPR analysis on various sample pretreatments in the irradiated spice samples demonstrated that the spectral features of the cellulose radical varied on the basis of the pretreatment protocol. Alcoholic extraction pretreatment produced considerable improvements of the EPR signals of the irradiated spice samples relative to the conventional oven and freeze-drying techniques. The alcoholic extraction process is therefore proposed as the most suitable sample pretreatment for unambiguous detection of irradiated spices by EPR spectroscopy. PMID:25347931

  13. EPR Studies of Gating Mechanisms in Ion Channels

    PubMed Central

    Chakrapani, Sudha

    2015-01-01

    Ion channels open and close in response to diverse stimuli, and the molecular events underlying these processes are extensively modulated by ligands of both endogenous and exogenous origin. In the past decade, high-resolution structures of several channel types have been solved, providing unprecedented details of the molecular architecture of these membrane proteins. Intrinsic conformational flexibility of ion channels critically governs their functions. However, the dynamics underlying gating mechanisms and modulations are obscured in the information from crystal structures. While nuclear magnetic resonance spectroscopic methods allow direct measurements of protein dynamics, they are limited by the large size of these membrane protein assemblies in detergent micelles or lipid membranes. Electron paramagnetic resonance (EPR) spectroscopy has emerged as a key biophysical tool to characterize structural dynamics of ion channels and to determine stimulus-driven conformational transition between functional states in a physiological environment. This review will provide an overview of the recent advances in the field of voltage- and ligand-gated channels and highlight some of the challenges and controversies surrounding the structural information available. It will discuss general methods used in site-directed spin labeling and EPR spectroscopy and illustrate how findings from these studies have narrowed the gap between high-resolution structures and gating mechanisms in membranes, and have thereby helped reconcile seemingly disparate models of ion channel function. PMID:25950970

  14. Double-stacked dielectric resonator for sensitive EPR measurements.

    PubMed

    Jaworski, M; Sienkiewicz, A; Scholes, C P

    1997-01-01

    A new approximate method for predicting the resonant frequencies and for solving the field distribution problem of a cylindrical dielectric resonator (DR) is developed. The model proposed in this paper bridges the gap between rigorous and accurate finite-element or Green function-based numerical methods on the one hand and on the other hand, simple approximate solutions in which the field distribution can be described analytically, but the resulting frequency is accurate within a few percent only. In the method described here, the approximate solution for the microwave field distribution is modified by substituting different values of the radial separation constants inside and outside of the diskshaped DR. The model is generalized for the double-stacked DR structure and enables one to introduce corrections that take into account the presence of the shielding walls and of the cylindrical sample hole. Good agreement is found between experimental and calculated results for both the single and double-stacked structures that are designed around commercially available X-band DRs (9-10 GHz). For the resonant frequency of the lowest transverse-electric TEzero1 delta mode that is commonly used for EPR measurements, the accuracy of the method is better than 1%. Experimentally measured resonator filling factors are also in good agreement with those theoretically estimated. Both the theory and the experimental results suggest that the double-stacked DR structure with finite spacing between the ceramic cylinders is the most suitable for EPR measurements of long lossy samples. PMID:9169212

  15. EPR study of gamma-irradiated single crystal 4-phenylsemicarbazide

    NASA Astrophysics Data System (ADS)

    Sayin, U.; Türkkan, E.; Dereli, Ö.; Yüksel, H.; Birey, M.

    2010-08-01

    Single crystals of 4-phenylsemicarbazide (4PSC) were investigated using an electron paramagnetic resonance (EPR) technique, with γ irradiation of the crystals at different orientations in the magnetic field between temperatures of 120 and 450 K, and the spectra were found to be temperature independent. Taking into consideration the chemical structure and the experimental spectra of the irradiated single crystal 4PSC, we assumed that one or more paramagnetic species were produced, each having an unpaired electron delocalized in the phenyl ring. Pursuant to this assumption, six possible radicals were modeled using the B3LYP/6-311+G(d) level of density-functional theory. EPR parameters were calculated for these modeled radicals using the B3LYP method and TZVP basis set. The calculated hyperfine coupling constants were used as starting points for simulations. The experimental and simulated spectra for each of the three crystallographic axes were well matched for the modeled radical R6. We thus identified the R6 (C 6H 5NH) radical as a paramagnetic species produced in 4PSC. The experimental g-factor and hyperfine coupling constants of the C 6H 5NH radical were found to be anisotropic, with the average values g=2.00431, aNHN(8)=8.85 G, aNHH(9)=16.85 G, ao,pH(14,16,20)=6.47 G, and amH(18,19)=2.80 G.

  16. EPR Spectroscopic Studies of [FeFe]-Hydrogenase Maturation

    PubMed Central

    Suess, Daniel L. M.

    2015-01-01

    Proton reduction and H2 oxidation are key elementary reactions for solar fuel production. Hydrogenases interconvert H+ and H2 with remarkable efficiency and have therefore received much attention in this context. For [FeFe]-hydrogenases, catalysis occurs at a unique cofactor called the H-cluster. In this article, we discuss ways in which EPR spectroscopy has elucidated aspects of the bioassembly of the H-cluster, with a focus on four case studies: EPR spectroscopic identification of a radical en route to the CO and CN− ligands of the H-cluster, tracing 57Fe from the maturase HydG into the H-cluster, characterization of the auxiliary Fe–S cluster in HydG, and isotopic labeling of the CN− ligands of HydA for electronic structure studies of its Hox state. Advances in cell-free maturation protocols have enabled several of these mechanistic studies, and understanding H-cluster maturation may in turn provide insights leading to improvements in hydrogenase production for biotechnological applications. PMID:26508821

  17. W/O microemulsions as dendrimer nanocarriers: an EPR study.

    PubMed

    Rokach, Shifra; Ottaviani, Maria Francesca; Shames, Alexander I; Nir, Ido; Aserin, Abraham; Garti, Nissim

    2012-10-18

    A complex system, based on a dendrimer solubilized in the aqueous core of water-in-oil microemulsion, may combine the advantages of both dendrimers and microemulsions to provide better control of drug release. We report for the first time the use of EPR technique to determine the effect of solubilized dendrimer on the structure of the microemulsion. The solubilized poly(propyleneimine) (PPI-G2) interacts with sodium bis(2-ethylhexyl) sulfosuccinate (AOT). EPR analysis provided information on polarity, microviscosity, and molecular order of the systems. Polarity and microviscosity increased from unloaded water-in-oil microemulsion to the system loaded with 0.2 wt % PPI-G2, but remained unchanged with higher PPI-G2 loads. The degree of order also increased with 0.2 wt % PPI-G2 with only minor additional increase with larger quantities (25 wt %) of PPI-G2. Variations in pH only slightly affected the structure of microemulsion in the absence and presence of the loaded dendrimers. Aliphatic oils with longer lipophilic chains enhanced the structural order of the microemulsion. On increasing water content, polarity and degree of order increased. PPI-G2 dendrimer in small loads is attracted by the negatively charged AOT and thus intercalates in the interface of the droplets. Yet, at higher PPI-G2 loads, the excess molecules are solubilized in the water core. PMID:22989387

  18. Antioxidant properties of tea investigated by EPR spectroscopy.

    PubMed

    Polovka, Martin; Brezová, Vlasta; Stasko, Andrej

    2003-10-01

    The antioxidant properties of green, black and mixed (fruit) tea samples of different origin were investigated by means of EPR spectroscopy. A six line EPR spectrum of solid tea samples indicates the presence of Mn(II) ions and it is superimposed with a sharp singlet line attributed to semiquinone radical species (Delta H(pp)=1 mT; g=2.0022). Antioxidant properties of aqueous tea extracts in H(2)O(2)/NaOH/dimethylsulfoxide system generating reactive radicals (*OH, O(2)*-), *CH(3)) were followed by spin trapping technique. In addition, antioxidant capacity of these samples was assessed using stable radicals 1,1-diphenyl-2-picrylhydrazyl (DPPH) and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPOL). Typically, the highest antioxidant potential to terminate superoxide radicals was found in green teas, followed by black and fruity teas. The pro-oxidant activity of green teas evidenced by spin traps was promoted in samples with higher Mn(II) and ascorbic acid concentrations. Various sources of free radicals used in the antioxidant tests due to their specific action show different termination rates in the presence of the individual tea samples. PMID:14516911

  19. Stochastic excitation and Hadamard correlation spectroscopy with bandwidth extension in RF FT-EPR

    PubMed Central

    Pursley, Randall H.; Kakareka, John; Salem, Ghadi; Devasahayam, Nallathamby; Subramanian, Sankaran; Tschudin, Rolf G.; Krishna, Murali C.; Pohida, Thomas J.

    2012-01-01

    The application of correlation spectroscopy employing stochastic excitation and the Hadamard transform to time-domain Fourier transform electron paramagnetic resonance (FT-EPR) spectroscopy in the radiofrequency (RF) band is described. An existing, time-domain FT-EPR spectrometer system with a Larmor frequency (Lf) of 300 MHz was used to develop this technique by incorporating a pseudo-random pulse sequence generator to output the maximum length binary sequence (MLBS, 10- and 11-bit). Software developed to control the EPR system setup, acquire the signals, and post process the data, is outlined. The software incorporates the Hadamard transform algorithm to perform the required cross-correlation of the acquired signal and the MLBS after stochastic excitation. To accommodate the EPR signals, bandwidth extension was accomplished by sampling at a rate many times faster than the RF pulse repetition rate, and subsequent digital signal processing of the data. The results of these experiments showed that there was a decrease in the total acquisition time, and an improved free induction decay (FID) signal-to-noise (S/N) ratio compared to the conventional coherent averaging approach. These techniques have the potential to reduce the RF pulse power to the levels used in continuous wave (CW) EPR while retaining the advantage of time-domain EPR methods. These methods have the potential to facilitate the progression to in vivo FT-EPR imaging of larger volumes. PMID:12762981

  20. Active cancellation - A means to zero dead-time pulse EPR

    NASA Astrophysics Data System (ADS)

    Franck, John M.; Barnes, Ryan P.; Keller, Timothy J.; Kaufmann, Thomas; Han, Songi

    2015-12-01

    The necessary resonator employed in pulse electron paramagnetic resonance (EPR) rings after the excitation pulse and creates a finite detector dead-time that ultimately prevents the detection of signal from fast relaxing spin systems, hindering the application of pulse EPR to room temperature measurements of interesting chemical or biological systems. We employ a recently available high bandwidth arbitrary waveform generator (AWG) to produce a cancellation pulse that precisely destructively interferes with the resonant cavity ring-down. We find that we can faithfully detect EPR signal at all times immediately after, as well as during, the excitation pulse. This is a proof of concept study showcasing the capability of AWG pulses to precisely cancel out the resonator ring-down, and allow for the detection of EPR signal during the pulse itself, as well as the dead-time of the resonator. However, the applicability of this approach to conventional EPR experiments is not immediate, as it hinges on either (1) the availability of low-noise microwave sources and amplifiers to produce the necessary power for pulse EPR experiment or (2) the availability of very high conversion factor micro coil resonators that allow for pulse EPR experiments at modest microwave power.

  1. Active cancellation - A means to zero dead-time pulse EPR.

    PubMed

    Franck, John M; Barnes, Ryan P; Keller, Timothy J; Kaufmann, Thomas; Han, Songi

    2015-12-01

    The necessary resonator employed in pulse electron paramagnetic resonance (EPR) rings after the excitation pulse and creates a finite detector dead-time that ultimately prevents the detection of signal from fast relaxing spin systems, hindering the application of pulse EPR to room temperature measurements of interesting chemical or biological systems. We employ a recently available high bandwidth arbitrary waveform generator (AWG) to produce a cancellation pulse that precisely destructively interferes with the resonant cavity ring-down. We find that we can faithfully detect EPR signal at all times immediately after, as well as during, the excitation pulse. This is a proof of concept study showcasing the capability of AWG pulses to precisely cancel out the resonator ring-down, and allow for the detection of EPR signal during the pulse itself, as well as the dead-time of the resonator. However, the applicability of this approach to conventional EPR experiments is not immediate, as it hinges on either (1) the availability of low-noise microwave sources and amplifiers to produce the necessary power for pulse EPR experiment or (2) the availability of very high conversion factor micro coil resonators that allow for pulse EPR experiments at modest microwave power. PMID:26507308

  2. The view from the trenches: part 2-technical considerations for EPR screening.

    PubMed

    Nicolalde, Roberto J; Gougelet, Robert M; Rea, Michael; Williams, Benjamin B; Dong, Ruhong; Kmiec, Maciej M; Lesniewski, Piotr N; Swartz, Harold M

    2010-02-01

    There is growing awareness of the need for methodologies that can be used retrospectively to provide the biodosimetry needed to carry out screening and triage immediately after an event in which large numbers of people have potentially received clinically significant doses of ionizing radiation. The general approach to developing such methodologies has been a technology centric one, often ignoring the system integrations considerations that are key to their effective use. In this study an integrative approach for the evaluation and development of a physical biodosimetry technology was applied based on in vivo electron paramagnetic resonance (EPR) dosimetry. The EPR measurements are based on physical changes in tissues whose magnitudes are not affected by the factors that can confound biologically-based assessments. In this study the use of a pilot simulation exercise to evaluate an experimental EPR system and gather stakeholders' feedback early on in the development process is described. The exercise involved: ten non-irradiated participants, representatives from a local fire department; Department of Homeland Security certified exercise evaluators, EPR experts, physicians; and a human factors engineer. Stakeholders were in agreement that the EPR technology in its current state of development could be deployed for the screening of mass casualties. Furthermore, stakeholders' recommendations will be prioritized and incorporated in future developments of the EPR technique. While the results of this exercise were aimed specifically at providing feedback for the development of EPR dosimetry for screening mass casualties, the methods and lessons learned are likely to be applicable to other biodosimetric methods. PMID:20065674

  3. EPR pairing dynamics in Hubbard model with resonant U

    PubMed Central

    Zhang, X. Z.; Song, Z.

    2016-01-01

    We study the dynamics of the collision between two fermions in Hubbard model with on-site interaction strength U. The exact solution shows that the scattering matrix for two-wavepacket collision is separable into two independent parts, operating on spatial and spin degrees of freedom, respectively. The S-matrix for spin configuration is equivalent to that of Heisenberg-type pulsed interaction with the strength depending on U and relative group velocity vr. This can be applied to create distant EPR pair, through a collision process for two fermions with opposite spins in the case of |vr/U| = 1, without the need for temporal control and measurement process. Multiple collision process for many particles is also discussed. PMID:26728282

  4. Carotenoid cation radicals: electrochemical, optical, and EPR study

    SciTech Connect

    Grant, J.L.; Kramer, V.J.; Ding, R.; Kispert, L.D.

    1988-03-30

    The general aim of this investigation is to determine whether carotenoid cation radicals can be produced, and stabilized, electrochemically. Hence, the authors have undertaken a detailed study of the electrooxidation of various carotenoids (..beta..-carotene (I), ..beta..-apo-8'-carotenal (II), and canthaxanthin (III) using the techniques of cyclic voltammetry, controlled-potential electrolysis (cpe) in conjunction with optical spectroscopy, and EPR spectroscopy coupled with in situ electrolysis. They report the successful generation of carotenoid cation radicals via electrochemical oxidation and, furthermore, the stabilization of these radicals for several minutes in CH/sub 2/Cl/sub 2/ and C/sub 2/H/sub 4/Cl/sub 2/ solvents.

  5. EPR Oximetry in Three Spatial Dimensions using Sparse Spin Distribution

    PubMed Central

    Som, Subhojit; Potter, Lee C.; Ahmad, Rizwan; Vikram, Deepti S.; Kuppusamy, Periannan

    2008-01-01

    A method is presented to use continuous wave electron paramagnetic resonance imaging for rapid measurement of oxygen partial pressure in three spatial dimensions. A particulate paramagnetic probe is employed to create a sparse distribution of spins in a volume of interest. Information encoding location and spectral linewidth is collected by varying the spatial orientation and strength of an applied magnetic gradient field. Data processing exploits the spatial sparseness of spins to detect voxels with nonzero spin and to estimate the spectral linewidth for those voxels. The parsimonious representation of spin locations and linewidths permits an order of magnitude reduction in data acquisition time, compared to four-dimensional tomographic reconstruction using traditional spectral-spatial imaging. The proposed oximetry method is experimentally demonstrated for a lithium octa-n-butoxy naphthalocyanine (LiNc-BuO) probe using an L-band EPR spectrometer. PMID:18538600

  6. N-Player Quantum Games in an EPR Setting

    PubMed Central

    Chappell, James M.; Iqbal, Azhar; Abbott, Derek

    2012-01-01

    The -player quantum games are analyzed that use an Einstein-Podolsky-Rosen (EPR) experiment, as the underlying physical setup. In this setup, a player’s strategies are not unitary transformations as in alternate quantum game-theoretic frameworks, but a classical choice between two directions along which spin or polarization measurements are made. The players’ strategies thus remain identical to their strategies in the mixed-strategy version of the classical game. In the EPR setting the quantum game reduces itself to the corresponding classical game when the shared quantum state reaches zero entanglement. We find the relations for the probability distribution for -qubit GHZ and W-type states, subject to general measurement directions, from which the expressions for the players’ payoffs and mixed Nash equilibrium are determined. Players’ payoff matrices are then defined using linear functions so that common two-player games can be easily extended to the -player case and permit analytic expressions for the Nash equilibrium. As a specific example, we solve the Prisoners’ Dilemma game for general . We find a new property for the game that for an even number of players the payoffs at the Nash equilibrium are equal, whereas for an odd number of players the cooperating players receive higher payoffs. By dispensing with the standard unitary transformations on state vectors in Hilbert space and using instead rotors and multivectors, based on Clifford’s geometric algebra (GA), it is shown how the N-player case becomes tractable. The new mathematical approach presented here has wide implications in the areas of quantum information and quantum complexity, as it opens up a powerful way to tractably analyze N-partite qubit interactions. PMID:22606258

  7. Implementing EPR Dosimetry for Life-Threatening Incidents

    PubMed Central

    Flood, Ann Barry; Bhattacharyya, Shayan; Nicolalde, R. Javier; Swartz, Harold M.

    2007-01-01

    Starting with the assumption that a device to detect unplanned radiation exposures is technically superior to current technology, we examine the additional stakeholders and processes that must be considered to move the device from the lab into use. The use is to provide reliable information to triage people for early treatment of exposure to ionizing radiation that could lead to the Acute Radiation Syndrome. The scenario is a major accident or terrorist event that leaves a large number of people potentially exposed, with the resulting need to identify those to treat promptly or not. In vivo EPR dosimetry is the exemplar of such a technique. Three major areas are reviewed: policy considerations, regulatory clearance, and production of the device. Our analysis of policy-making indicates that the current system is very complex, with multiple significant decision-makers who may have conflicting agendas. Adoption of new technologies by policy-makers is further complicated because many sources of expert input already have made public stances or have reasons to prefer current solutions, e.g., some may have conflicts of interest in approving new devices because they are involved with the development or adoption of competing techniques. Regulatory clearance is complicated by not being able to collect evidence via clinical trials of its intended use, but pathways for approval for emergency use are under development by the FDA. The production of the new device could be problematical if the perceived market is too limited, particularly for private manufacturers; for in vivo EPR dosimetry the potential for other uses may be a mitigating factor. Overall we conclude that technical superiority of a technique does not in itself assure its rapid and effective adoption, even where the need is great and the alternatives are not satisfactory for large populations. Many important steps remain to achieve the goals of approval and adoption for use. PMID:18591990

  8. EPR retrospective dosimetry with fingernails: report on first application cases.

    PubMed

    Trompier, Francois; Queinnec, François; Bey, Eric; De Revel, Thierry; Lataillade, Jean Jacques; Clairand, Isabelle; Benderitter, Marc; Bottollier-Depois, Jean-François

    2014-06-01

    For localized irradiation to hands, in case of sources accidentally handled, it is very difficult to estimate the dose distribution by calculation. Doses may reach several tens of grays, and the dose distribution is usually very heterogeneous. Until recently, doses in such situations could be estimated only by analysis of bone biopsies using Electron Paramagnetic Resonance (EPR) spectroscopy. This technique was used previously on surgical wastes or after amputation of a finger. In this case, the dose information was available in one or a few locations on the hand only, due to the limited number of biopsy fragments usually collected. The idea to measure free radicals (FRs) induced by radiation in nails to estimate a dose is not new, but up to now, no application cases were reported. As a matter of fact, the EPR analysis of nails is complex due to the presence of intrinsic signals and parasitic signals induced by the mechanical stress (when nails are collected), which overlaps the radio-induced components. In addition, the radio-induced FRs identified up to now are unstable and very sensitive to humidity. In these conditions, it was difficult to foresee any application for dosimetry with fingernails. Recently, stable radio-induced FRs in nails has been identified and an associated protocol for dose assessment developed. This protocol has been applied by the Institut de Radioprotection et de Sûreté Nucléaire on fingernail samples from victims of three different radiological accidents that occurred between 2008 and 2012 in different places. PMID:24776914

  9. EPR as an analytical tool in assessing the mineral nutrients and irradiated food products-vegetables

    NASA Astrophysics Data System (ADS)

    Prasuna, C. P. Lakshmi; Chakradhar, R. P. S.; Rao, J. L.; Gopal, N. O.

    2008-12-01

    EPR spectral investigations of some commonly available vegetables in south India, which are of global importance like Daucus carota (carrot), Cyamopsis tetragonoloba (cluster beans), Coccinia indica (little gourd) and Beta vulgaris (beet root) have been carried out. In all the vegetable samples a free radical corresponding to cellulose radical is observed. Almost all the samples under investigation exhibit Mn ions in different oxidation states. The temperature variation EPR studies are done and are discussed in view of the paramagnetic oxidation states. The radiation-induced defects have also been assessed by using the EPR spectra of such irradiated food products.

  10. EPR investigation of some desiccated Ascomycota and Basidiomycota gamma-irradiated mushrooms

    NASA Astrophysics Data System (ADS)

    Bercu, V.; Negut, C. D.; Duliu, O. G.

    2010-12-01

    The suitability of the EPR spectroscopy for detection of γ-irradiation in five species of dried mushroom, currently used in gastronomy: yellow morel— Morchella esculenta, (L.) Pers. (Phylum Ascomycota), button mushroom— Agaricus bisporus (J.E.Lange), Agaricus haemorrhoidarius Fr., golden chantarelle— Cantharellus cibarius Fr., as well as oyster mushroom— Pleurotus ostreatus (Jacq. ex Fr.) (Phylum Basidiomycota) is presented and discussed. Although after irradiation at doses up to 11 kGy, all specimens presented well defined EPR spectra, only A. bisporus EPR signal was enough stable to make detection possible after 18 months.

  11. Bell Correlated and EPR States in the Framework of Jordan Algebras

    NASA Astrophysics Data System (ADS)

    Hamhalter, Jan; Sobotíková, Veronika

    2016-03-01

    We study Bell inequalities and EPR states in the context of Jordan algebras. We show that the set of states violating Bell inequalities across two operator commuting nonmodular Jordan Banach algebras is norm dense in the global state space. It generalizes hitherto known results in quantum field theory in several directions. We propose new Jordan quantity for incommensurable observables in a given state, introduce the concept of EPR state for Jordan structures, and study relationship between EPR states and Bell correlated states. Our analysis shows crucial role of spin factors and Pauli spin matrices for studying noncommutative properties of states and observables.

  12. Migration from a prototype ePR for IA-MISS system to alpha version

    NASA Astrophysics Data System (ADS)

    Documet, Jorge R.; Le, Anh; Liu, Brent J.

    2010-03-01

    Last year we presented a paper that describes the design and clinical implementation of an ePR (Electronic Patient Record) system for Image-Assisted Minimally Invasive Spinal Surgery (IA-MISS). The goal of this ePR is to improve the workflow efficiency by providing all the necessary data of a surgical procedure from the preparation stage until the recovery stage. The mentioned ePR has been implemented and installed clinically and it has been in use for more than 16 months. In this paper, we will describe the migration process from a prototype version of the system to a more stable and easily-to-replicate alpha version.

  13. EPR dosimetric properties of 2-methylalanine pellet for radiation processing application

    NASA Astrophysics Data System (ADS)

    Soliman, Y. S.; Ali, Laila I.; Moustafa, H.; Tadros, Soad M.

    2014-09-01

    The dosimetric characteristics of γ-radiation induced free radicals in 2-methylalanine (2MA) pellet dosimeter are investigated using electron paramagnetic resonance (EPR) in the high-dose range of 1-100 kGy. The EPR spectrum of γ-irradiated 2MA exhibits an isotropic EPR signal with seven lines. The dosimeter response is humidity independent in the range of 33-76% relative humidity. The manufactured dosimeter is typically adipose tissue equivalent in the energy level of 0.1-15 MeV. The overall uncertainty (2σ) of the dosimeter is less than 6.9%.

  14. Optimal strategies for tests of EPR-Steering with no detection loophole

    NASA Astrophysics Data System (ADS)

    Evans, David A.; Wiseman, Howard M.

    2014-12-01

    It has been shown in earlier works that the vertices of Platonic solids are good measurement choices for tests of EPR-Steering. Such measurements are regularly spaced, and measurement diversity is a good feature for making EPR-Steering inequalities easier to violate with entangled states. However, such measurements are provably suboptimal. By scrutinising not only the average results, but also the measurement statistics of cheating strategies in a Local Hidden State model, we outline a method for devising optimal strategies for EPR-Steering tests with no detection loophole.

  15. Microwave (EPR) measurements of the penetration depth measurements of high-Tc superconductors

    NASA Technical Reports Server (NTRS)

    Dalal, N. S.; Rakvin, B.; Mahl, T. A.; Bhalla, A. S.; Sheng, Z. Z.

    1991-01-01

    The use is discussed of electron paramagnetic resonance (EPR) as a quick and easily accessible method for measuring the London penetration depth, lambda for the high T sub c superconductors. The method uses the broadening of the EPR signal, due to the emergence of the magnetic flux lattice, of a free radical adsorbed on the surface of the sample. The second moment, of the EPR signal below T sub c is fitted to the Brandt equation for a simple triangular lattice. The precision of this method compares quite favorably with those of the more standard methods such as micro sup(+)SR, neutron scattering, and magnetic susceptibility.

  16. EPR spectroscopy of protein microcrystals oriented in a liquid crystalline polymer medium

    NASA Astrophysics Data System (ADS)

    Caldeira, Jorge; Figueirinhas, João Luis; Santos, Celina; Godinho, Maria Helena

    2004-10-01

    Correlation of the g-tensor of a paramagnetic active center of a protein with its structure provides a unique experimental information on the electronic structure of the metal site. To address this problem, we made solid films containing metalloprotein ( Desulfovibrio gigas cytochrome c3) microcrystals. The microcrystals in a liquid crystalline polymer medium (water/hydroxypropylcellulose) were partially aligned by a shear flow. A strong orientation effect of the metalloprotein was observed by EPR spectroscopy and polarizing optical microscopy. The EPR spectra of partially oriented samples were simulated, allowing for molecular orientation distribution function determination. The observed effect results in enhanced sensitivity and resolution of the EPR spectra and provides a new approach towards the correlation of spectroscopic data, obtained by EPR or some other technique, with the three-dimensional structure of a protein or a model compound.

  17. Preparation and EPR characterization of N@C60 and N@C70 based peapods

    NASA Astrophysics Data System (ADS)

    Corzilius, B.; Gembus, A.; Weiden, N.; Dinse, K.-P.

    2005-09-01

    Using the quartet spin of encased nitrogen atoms as an electron paramagnetic resonance (EPR) probe, it is possible to examine the fullerene/nanotube interactions in a peapod. A purification method is developed which allows low temperature filling of nanotubes with endohedral fullerenes. The paramagnetic impurities of undoped single wall carbon nanotubes (SWNT) are characterized via EPR resulting in a broad superparamagnetic signal of the remaining catalyst particles and a rather narrow signal of carbonaceous material. Comparison of EPR spectra of several nitrogen endohedral doped peapods with their analogues obtained in a solid fullerene matrix shows a significant broadening of N@C60 and N@C70 EPR signals. This broadening is related to a non-vanishing zero-field splitting caused by deformation of the fullerene cage upon encapsulation.

  18. Crystal field effect on EPR and optical absorption properties of natural green zoisite.

    PubMed

    Javier-Ccallata, Henry; Watanabe, Shigueo

    2013-03-01

    In this study the electron paramagnetic resonance (EPR) and optical absorption (OA) of natural crystal of zoisite were investigated after γ ((60)Co) irradiation and high temperature annealing. EPR measurements show that the zoisite from Tefilo Otoni MG Brazil contain Cr(3+), Fe(3+) and Mn(2+) ions and occupy distorted Al(3+) octahedral and tetrahedral sites which are subjected to the action of a strong crystal field in axial direction. Absorption bands which in principle give rise to sets of EPR lines between 500 and 2500 G were found using the deconvolution method. The application of high doses of gamma ray and high temperature annealing has shown no significant effects on EPR and OA spectra. Spin-allowed, spin-forbidden and crystal field parameters were calculated for 3d(3) configuration and interpreted using the spin Hamiltonian formalism containing axial and rhombic terms in low symmetries. PMID:23291113

  19. Variable temperature EPR studies of Illinois No. 6 coal treated with donor and acceptor molecules

    SciTech Connect

    Thompson, R.L.; Rothenberger, K.S.; Retcofsky, H.L.

    1996-10-01

    Variable, temperature EPR studies of Illinois No. 6 coal, its pyridine extract, and samples of each after treatment with known donor and acceptor molecules are reported. The purpose of the study was to explore the origin of the EPR signals near g = 2 and to assess the contribution of certain non-bonded interactions in coal. Curie Law behavior is exhibited for each sample indicating that the EPR signals are dominated by doublet state radicals. No evidence for thermally accessible, low-lying triplet states, such as those found in some charge-transfer complexes, was found. Infrared spectroscopy reveals, however, that some electron density is transferred from the coal after treatment with acceptors such as TCNQ and TCNE. EPR studies of chromat graphic fractions of the pyridine extract (approximately five percent of the whole coal), both untreated and treated with TTF and TCNE, indicated some minor contributions of low-lying triplet states.

  20. Wormhole and entanglement (non-)detection in the ER=EPR correspondence

    NASA Astrophysics Data System (ADS)

    Bao, Ning; Pollack, Jason; Remmen, Grant N.

    2015-11-01

    The recently proposed ER=EPR correspondence postulates the existence of wormholes (Einstein-Rosen bridges) between entangled states (such as EPR pairs). Entanglement is famously known to be unobservable in quantum mechanics, in that there exists no observable (or, equivalently, projector) that can accurately pick out whether a generic state is entangled. Many features of the geometry of spacetime, however, are observables, so one might worry that the presence or absence of a wormhole could identify an entangled state in ER=EPR, violating quantum mechanics, specifically, the property of state-independence of observables. In this note, we establish that this cannot occur: there is no measurement in general relativity that unambiguously detects the presence of a generic wormhole geometry. This statement is the ER=EPR dual of the undetectability of entanglement.

  1. Nitrite binding to globins: linkage isomerism, EPR silence and reductive chemistry

    PubMed Central

    Silaghi-Dumitrescu, Radu; Svistunenko, Dimitri A.; Cioloboc, Daniela; Bischin, Cristina; Scurtu, Florina; Cooper, Chris E.

    2014-01-01

    The nitrite adducts of globins can potentially bind via O- or N- linkage to the heme iron. We have used EPR (electron paramagnetic resonance) and DFT (density functional theory) to explore these binding modes to myoglobin and hemoglobin. We demonstrate that the nitrite adducts of both globins have detectable EPR signals; we provide an explanation for the difficulty in detecting these EPR features, based on uniaxial state considerations. The EPR and DFT data show that both nitrite linkage isomers can be present at the same time and that the two isomers are readily interconvertible in solution. The millisecond-scale process of nitrite reduction by Hb is investigated in search of the elusive Fe(II)-nitrite adduct. PMID:25172022

  2. Characterizing Active Pharmaceutical Ingredient Binding to Human Serum Albumin by Spin-Labeling and EPR Spectroscopy.

    PubMed

    Hauenschild, Till; Reichenwallner, Jörg; Enkelmann, Volker; Hinderberger, Dariush

    2016-08-26

    Drug binding to human serum albumin (HSA) has been characterized by a spin-labeling and continuous-wave (CW) EPR spectroscopic approach. Specifically, the contribution of functional groups (FGs) in a compound on its albumin-binding capabilities is quantitatively described. Molecules from different drug classes are labeled with EPR-active nitroxide radicals (spin-labeled pharmaceuticals (SLPs)) and in a screening approach CW-EPR spectroscopy is used to investigate HSA binding under physiological conditions and at varying ratios of SLP to protein. Spectral simulations of the CW-EPR spectra allow extraction of association constants (KA ) and the maximum number (n) of binding sites per protein. By comparison of data from 23 SLPs, the mechanisms of drug-protein association and the impact of chemical modifications at individual positions on drug uptake can be rationalized. Furthermore, new drug modifications with predictable protein binding tendency may be envisaged. PMID:27460503

  3. EPR investigations of silicon carbide nanoparticles functionalized by acid doped polyaniline

    NASA Astrophysics Data System (ADS)

    Karray, Fekri; Kassiba, Abdelhadi

    2012-06-01

    Nanocomposites (SiC-PANI) based on silicon carbide nanoparticles (SiC) encapsulated in conducting polyaniline (PANI) are synthesized by direct polymerization of PANI on the nanoparticle surfaces. The conductivity of PANI and the nanocomposites was modulated by several doping levels of camphor sulfonic acid (CSA). Electron paramagnetic resonance (EPR) investigations were carried out on representative SiC-PANI samples over the temperature range [100-300 K]. The features of the EPR spectra were analyzed taking into account the paramagnetic species such as polarons with spin S=1/2 involved in two main environments realized in the composites as well as their thermal activation. A critical temperature range 200-225 K was revealed through crossover changes in the thermal behavior of the EPR spectral parameters. Insights on the electronic transport properties and their thermal evolutions were inferred from polarons species probed by EPR and the electrical conductivity in doped nanocomposites.

  4. Einstein locality, EPR locality, and the significance for science of the nonlocal character of quantum theory

    SciTech Connect

    Stapp, H.P.

    1985-10-01

    The immense difference between Einstein locality and EPR locality is discussed. The latter provides a basis for establishing the nonlocal character of quantum theory, whereas the former does not. A model representing Heisenberg's idea of physical reality is introduced. It is nondeterministic and holistic: the objects, measuring devices, and their environment are treated as an inseparable entity, with, however, macroscopically localizable attributes. The EPR principle that no disturbance can propagate faster than light is imposed without assuming any structure incompatible with orthodox quantum thinking. This locality requirement renders the model incompatible with rudimentary predictions of quantum theory. A more general proof not depending on any model is also given. A recent argument that purports to show that quantum theory is compatible with EPR locality is examined. It illustrates the importance of the crucial one-world assumption. The significance for science of the failure of EPR locality is discussed.

  5. EPR spectra induced by gamma-irradiation of some dry medical herbs

    NASA Astrophysics Data System (ADS)

    Yordanov, N. D.; Lagunov, O.; Dimov, K.

    2009-04-01

    The radiation-induced EPR spectra in some medical herbs are reported. The samples studied are: (i) leaves of nettle, common balm, peppermint and thyme; (ii) stalks of common balm, thyme, milfoil, yarrow and marigold; (iii) blossoms of yarrow and marigold; (iv) blossoms and leaves of hawthorn and tutsan; and (v) roots of common valerian, nettle, elecampane (black and white), restharrows and carlina. Before irradiation all samples exhibit one weak anisotropic singlet EPR line with effective g-value of 2.0050±0.0002. The radiation-induced spectra fall into three groups. EPR spectra of irradiated blossoms of yarrow and marigold, stalks of common balm, thyme, tutsan and yarrow as well as roots of common valerian, nettle and elecampane (black and white) show "cellulose-like" EPR spectrum typical for irradiated plants. It is characterized by one intense central line with g=2.0050±0.0005 and two weak satellite lines situated ca. 30 G left and right to it. EPR spectra of gamma-irradiated restharrows and carlina are complex. They may be represented by one triplet corresponding to the "cellulose-like" EPR spectrum, one relatively intense singlet, situated in the center of the spectrum, and five weak additional satellite lines left and right to the center. The last spectrum was assigned as "carbohydrate-like" type. Only one intense EPR singlet with g=2.0048±0.0005 was recorded after irradiation of leaves of nettle and common balm. The lifetime of the radiation-induced EPR spectra was followed for a period of 3 months.

  6. Preparation and applicability of fresh fruit samples for the identification of radiation treatment by EPR

    NASA Astrophysics Data System (ADS)

    Yordanov, Nicola D.; Aleksieva, Katerina

    2009-03-01

    The results of electron paramagnetic resonance (EPR) study on fresh fruits (whole pulp of pears, apples, peaches, apricots, avocado, kiwi and mango) before and after gamma-irradiation are reported using two drying procedures before EPR investigation. In order to remove water from non-irradiated and irradiated samples of the first batch, the pulp of fresh fruits is pressed, and the solid residue is washed with alcohol and dried at room temperature. The fruits of the second batch are pressed and dried in a standard laboratory oven at 40 °C. The results obtained with both drying procedures are compared. All samples under study show a singlet EPR line with g=2.0048±0.0005 before irradiation. Irradiation gives rise to typical "cellulose-like" EPR spectrum featuring one intensive line with g=2.0048±0.0005 and two very weak satellite lines situated 3 mT at left and right of the central line. Only mango samples show a singlet line after irradiation. The fading kinetics of radiation-induced EPR signal is studied for a period of 50 days after irradiation. When the irradiated fruit samples are stored in their natural state and dried just before each EPR measurement, the satellite lines are measurable for less than 17 days of storage. Irradiated fruit samples, when stored dried, lose for 50 days ca. 40% of their radiation-induced radicals if treated with alcohol or ca. 70% if dried in an oven. The reported results unambiguously show that the presence of the satellite lines in the EPR spectra could be used for identification of radiation processing of fresh fruits, thus extending the validity of European Protocol EN 1787 (2000). Foodstuffs—Detection of Irradiated Food Containing Cellulose by EPR Spectroscopy. European Committee for Standardisation. Brussels for dry herbs.

  7. Gamma-irradiated dry fruits. An example of a wide variety of long-time dependent EPR spectra

    NASA Astrophysics Data System (ADS)

    Yordanov, Nicola D.; Pachova, Zdravka

    2006-03-01

    EPR spectra of dry, sugar containing fruits—raisins, sultanas, figs, dates, peaches, blue plums and chokeberry recorded before and after irradiation with gamma-rays, are reported. It is shown that weak singlet EPR line with 2.0031 ± 0.0005 can be recorded before irradiation of seeds, stones or skin of chokeberry, figs and raisins as well as flesh of blue plum, raisins and peaches. EPR signals of various shape are distinguished after irradiation in different parts of the fruits, as well as in randomly cut pieces of them: Seeds of raisins, chokeberry and figs give a singlet line. Stones from blue plums and peaches exhibit typical "cellulose-like" EPR signal consisting of an intense singlet line with g = 2.0033 ± 0.0005 and 2 week satellite lines situated ca. 30 G left and right to it. Stones of dates are the only sample in which "sugar-like" spectrum is recorded. Skin of raisins and figs exhibits "sugar-like" EPR spectrum whereas that of dates and chokeberry—a singlet line. Under the same experimental conditions skin of sultanas, peaches and blue plums are EPR silent. Flesh of raisins, sultanas, figs, dates and peaches exhibits "sugar-like" EPR spectrum, flesh of blue plums gives a singlet EPR line and that of chokeberry is EPR silent. As a result, randomly cut pieces of dry fruits suitable for EPR studies, containing various constituents, exhibit different in shape and intensity EPR spectra. Kinetic studies followed for 1 year on the time stability of all reported EPR signals indicate that intensity ratio between the simultaneously appearing EPR signals in particular fruit varies from 1:20 immediately after irradiation to 1:0.5 at the end of the period. These observations open a new possibility for identification of irradiated fruits - using the magnitude of the intensity ratio to find the approximate date of radiation processing in the first ca. 30-100 days.

  8. Transport de paires EPR dans des structures mesoscopiques

    NASA Astrophysics Data System (ADS)

    Dupont, Emilie

    Dans cette these, nous nous sommes particulierement interesses a la propagation de paires EPR1 delocalisees et localisees, et a l'influence d'un supraconducteur sur le transport de ces paires. Apres une introduction de cette etude, ainsi que du cadre scientifique qu'est l'informatique quantique dans lequel elle s'inscrit, nous allons dans le chapitre 1 faire un rappel sur le systeme constitue de deux points quantiques normaux entoures de deux fils supraconducteurs. Cela nous permettra d'introduire une methode de calcul qui sera reutilisee par la suite, et de trouver egalement le courant Josephson produit par ce systeme transforme en SQUID-dc par l'ajout d'une jonction auxiliaire. Le SQUID permet de mesurer l'etat de spin (singulet ou triplet), et peut etre forme a partir d'autres systemes que nous etudierons ensuite. Dans le chapitre 2, nous rappellerons l'etude detaillee d'un intricateur d'Andreev faite par un groupe de Bale. La matrice T, permettant d'obtenir le courant dans les cas ou les electrons sont separes spatialement ou non, sera etudiee en detail afin d'en faire usage au chapitre suivant. Le chapitre 3 est consacre a l'etude de l'influence du bruit sur le fonctionnement de l'intricateur d'Andreev. Ce bruit modifie la forme du courant jusqu'a aboutir a d'autres conditions de fonctionnement de l'intricateur. En effet, le bruit present sur les points quantiques peut perturber le transport des paires EPR par l'intermediaire des degres de liberte. Nous montrerons que, du fait de l'"intrication" entre la charge de la paire et le bruit, la paire est detruite pour des temps longs. Cependant, le resultat le plus important sera que le bruit perturbe plus le transport des paires delocalisees, qui implique une resonance de Breit-Wigner a deux particules. Le transport parasite n'implique pour sa part qu'une resonance de Breit-Wigner a une particule. Dans le chapitre 4, nous reviendrons au systeme constitue de deux points quantiques entoures de deux fils

  9. EPR and ENDOR studies of point defects in lithium tetraborate crystals

    NASA Astrophysics Data System (ADS)

    Buchanan, Douglas A.

    Lithium tetraborate (Li2B4O7 or LTB) is a promising material for both radiation dosimetry and neutron detection applications. LTB crystals can be grown pure or doped with different impurities including transition-metal and rare-earth ions. Research in this dissertation focuses on undoped LTB crystals and LTB crystals doped with copper and silver. Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) are used to characterize point defects in the lithium tetraborate crystals. Thermoluminescence (TL), photoluminescence (PL), photoluminescence excitation (PLE), and optical absorption (OA) are also used. An intrinsic hole trap associated with lithium vacancies is characterized with EPR and ENDOR and its thermal stability is determined using thermoluminescence. A "perturbed" hole trap due to Ag2+ ions is characterized in doped crystals using EPR data alone. This method is tested on a previously studied hole center where both EPR and ENDOR were used. New x-ray induced centers are identified in copper-doped crystals. These include two Cu 2+ hole centers and two Cu0 electron centers. These centers are characterized with EPR and their thermal stability explains TL peaks in glow curves. Finally, a comprehensive study utilizing EPR, OA, PL, and PLE data provide convincing explanations for the absorption and emission features of silver-doped crystals.

  10. Multi-photon transitions and Rabi resonance in continuous wave EPR.

    PubMed

    Saiko, Alexander P; Fedaruk, Ryhor; Markevich, Siarhei A

    2015-10-01

    The study of microwave-radiofrequency multi-photon transitions in continuous wave (CW) EPR spectroscopy is extended to a Rabi resonance condition, when the radio frequency of the magnetic-field modulation matches the Rabi frequency of a spin system in the microwave field. Using the non-secular perturbation theory based on the Bogoliubov averaging method, the analytical description of the response of the spin system is derived for all modulation frequency harmonics. When the modulation frequency exceeds the EPR linewidth, multi-photon transitions result in sidebands in absorption EPR spectra measured with phase-sensitive detection at any harmonic. The saturation of different-order multi-photon transitions is shown to be significantly different and to be sensitive to the Rabi resonance. The noticeable frequency shifts of sidebands are found to be the signatures of this resonance. The inversion of two-photon lines in some spectral intervals of the out-of-phase first-harmonic signal is predicted under passage through the Rabi resonance. The inversion indicates the transition from absorption to stimulated emission or vice versa, depending on the sideband. The manifestation of the primary and secondary Rabi resonance is also demonstrated in the time evolution of steady-state EPR signals formed by all harmonics of the modulation frequency. Our results provide a theoretical framework for future developments in multi-photon CW EPR spectroscopy, which can be useful for samples with long spin relaxation times and extremely narrow EPR lines. PMID:26295168

  11. Alanine-EPR as a transfer standard dosimetry system for low energy X radiation

    NASA Astrophysics Data System (ADS)

    Khoury, H. J.; da Silva, E. J.; Mehta, K.; de Barros, V. S.; Asfora, V. K.; Guzzo, P. L.; Parker, A. G.

    2015-11-01

    The purpose of this paper is to evaluate the use of alanine-EPR as a transfer standard dosimetry system for low energy X radiation, such as that in RS-2400, which operates in the range from 25 to 150 kV and 2 to 45 mA. Two types of alanine dosimeters were investigated. One is a commercial alanine pellets from Aérial-Centre de Ressources Technologiques, France and one was prepared in our laboratory (LMRI-DEN/UFPE). The EPR spectra of the irradiated dosimeters were recorded in the Nuclear Energy Department of UFPE, using a Bruker EMX10 EPR spectrometer operating in the X-band. The alanine-EPR dosimetry system was calibrated in the range of 20-220 Gy in this X-ray field, against an ionization chamber calibrated at the relevant X-ray energy with traceability to PTB. The results showed that both alanine dosimeters presented a linear dose response the same sensitivity, when the EPR signal was normalized to alanine mass. The total uncertainty in the measured dose was estimated to be about 3%. The results indicate that it is possible to use the alanine-EPR dosimetry system for validation of a low-energy X ray irradiator, such as RS-2400.

  12. EPR and IR spectral investigations on some leafy vegetables of Indian origin

    NASA Astrophysics Data System (ADS)

    Prasuna, C. P. Lakshmi; Chakradhar, R. P. S.; Rao, J. L.; Gopal, N. O.

    2009-09-01

    EPR spectral investigations have been carried out on four edible leafy vegetables of India, which are used as dietary component in day to day life. In Rumex vesicarius leaf sample, EPR spectral investigations at different temperatures indicate the presence of anti-ferromagnetically coupled Mn(IV)-Mn(IV) complexes. EPR spectra of Trigonella foenum graecum show the presence of Mn ions in multivalent state and Fe 3+ ions in rhombic symmetry. EPR spectra of Basella rubra indicate the presence of Mn(IV)-O-Mn(IV) type complexes. The EPR spectra of Basella rubra have been studied at different temperatures. It is found that the spin population for the resonance signal at g = 2.06 obeys the Boltzmann distribution law. The EPR spectra of Moringa oliefera leaves show the presence of Mn 2+ ions. Radiation induced changes in free radical of this sample have also been studied. The FT-IR spectra of Basella rubra and Moringa oliefera leaves show the evidences for the protein matrix bands and those corresponding to carboxylic C dbnd O bonds.

  13. EPR and IR spectral investigations on some leafy vegetables of Indian origin.

    PubMed

    Prasuna, C P Lakshmi; Chakradhar, R P S; Rao, J L; Gopal, N O

    2009-09-15

    EPR spectral investigations have been carried out on four edible leafy vegetables of India, which are used as dietary component in day to day life. In Rumex vesicarius leaf sample, EPR spectral investigations at different temperatures indicate the presence of anti-ferromagnetically coupled Mn(IV)-Mn(IV) complexes. EPR spectra of Trigonella foenum graecum show the presence of Mn ions in multivalent state and Fe(3+) ions in rhombic symmetry. EPR spectra of Basella rubra indicate the presence of Mn(IV)-O-Mn(IV) type complexes. The EPR spectra of Basella rubra have been studied at different temperatures. It is found that the spin population for the resonance signal at g=2.06 obeys the Boltzmann distribution law. The EPR spectra of Moringa oliefera leaves show the presence of Mn(2+) ions. Radiation induced changes in free radical of this sample have also been studied. The FT-IR spectra of Basella rubra and Moringa oliefera leaves show the evidences for the protein matrix bands and those corresponding to carboxylic CO bonds. PMID:19546024

  14. Photosynthetic reaction center of green sulfur bacteria studied by EPR

    SciTech Connect

    Nitschke, W.; Rutherford, A.W. ); Fieler, U. )

    1990-04-24

    Membrane preparations of two species of the green sulfur bacteria Chlorobium have been studied be EPR. Three signals were detected which were attributed to iron-sulfur centers acting as electron acceptors in the photosynthetic reaction center. (1) A signal from a center designated F{sub B}, was photoinduced at 4K. (2) A similar signal, F{sub A}, was photoinduced in addition to the F{sub B} signal upon a short period of illumination at 200 K. (3) Further illumination at 200 K resulted in the appearance of a broad feature at g=1.78. This is attributed to the g{sub x} component of an iron-sulfur center designated F{sub X}. The designations of these signals as F{sub B}, F{sub A}, and F{sub X} are based on their spectroscopic similarities to signals in photosystem I (PS I). The orientation dependence of these EPR signals in ordered Chlorobium membrane multilayers is remarkably similar to that of their PS I homologues. A magnetic interaction between the reduced forms of F{sub B} and F{sub A} occurs, which is also very similar to that seen in PS I. The triplet state of P{sub 840}, the primary electron donor, could be photoinduced at 4 K in samples which had been preincubated with sodium dithionite and methyl viologen and then preilluminated at 200 K. The preillumination reduces the iron-sulfur centers while the preincubation is thought to result in the inactivation of an earlier electron acceptor. Orientation studies of the triplet signal in ordered multilayers indicate that the bacteriochlorophylls which act as the primary electron donor in Chlorobium are arranged with a structural geometry almost identical with that of the special pair in purple bacteria. The Chlorobium reaction center appears to be similar in some respects to both PS I and to the purple bacterial reaction center. This is discussed with regard to the evolution of the different types of reaction centers from a common ancestor.

  15. Calibration of helical tomotherapy machine using EPR/alanine dosimetry

    SciTech Connect

    Perichon, Nicolas; Garcia, Tristan; Francois, Pascal; Lourenco, Valerie; Lesven, Caroline; Bordy, Jean-Marc

    2011-03-15

    Purpose: Current codes of practice for clinical reference dosimetry of high-energy photon beams in conventional radiotherapy recommend using a 10x10 cm{sup 2} square field, with the detector at a reference depth of 10 cm in water and 100 cm source to surface distance (SSD) (AAPM TG-51) or 100 cm source-to-axis distance (SAD) (IAEA TRS-398). However, the maximum field size of a helical tomotherapy (HT) machine is 40x5 cm{sup 2} defined at 85 cm SAD. These nonstandard conditions prevent a direct implementation of these protocols. The purpose of this study is twofold: To check the absorbed dose in water and dose rate calibration of a tomotherapy unit as well as the accuracy of the tomotherapy treatment planning system (TPS) calculations for a specific test case. Method: Both topics are based on the use of electron paramagnetic resonance (EPR) using alanine as transfer dosimeter between the Laboratoire National Henri Becquerel (LNHB) {sup 60}Co-{gamma}-ray reference beam and the Institut Curie's HT beam. Irradiations performed in the LNHB reference {sup 60}Co-{gamma}-ray beam allowed setting up the calibration method, which was then implemented and tested at the LNHB 6 MV linac x-ray beam, resulting in a deviation of 1.6% (at a 1% standard uncertainty) relative to the reference value determined with the standard IAEA TRS-398 protocol. Results: HT beam dose rate estimation shows a difference of 2% with the value stated by the manufacturer at a 2% standard uncertainty. A 4% deviation between measured dose and the calculation from the tomotherapy TPS was found. The latter was originated by an inadequate representation of the phantom CT-scan values and, consequently, mass densities within the phantom. This difference has been explained by the mass density values given by the CT-scan and used by the TPS which were not the true ones. Once corrected using Monte Carlo N-Particle simulations to validate the accuracy of this process, the difference between corrected TPS

  16. Pulsed EPR characterization of encapsulated atomic hydrogen in octasilsesquioxane cages.

    PubMed

    Mitrikas, George

    2012-03-21

    Hydrogen atoms encapsulated in molecular cages are potential candidates for quantum computing applications. They provide the simplest two-spin system where the 1s electron spin, S = 1/2, is hyperfine-coupled to the proton nuclear spin, I = 1/2, with a large isotropic hyperfine coupling (A = 1420.40575 MHz for a free atom). While hydrogen atoms can be trapped in many matrices at cryogenic temperatures, it has been found that they are exceptionally stable in octasilsesquioxane cages even at room temperature [Sasamori et al., Science, 1994, 256, 1691]. Here we present a detailed spin-lattice and spin-spin relaxation study of atomic hydrogen encapsulated in Si(8)O(12)(OSiMe(2)H)(8) using X-band pulsed EPR spectroscopy. The spin-lattice relaxation times T(1) range between 1.2 s at 20 K and 41.8 μs at room temperature. The temperature dependence of the relaxation rate shows that for T < 60 K the spin-lattice relaxation is best described by a Raman process with a Debye temperature of θ(D) = 135 K, whereas for T > 100 K a thermally activated process with activation energy E(a) = 753 K (523 cm(-1)) prevails. The phase memory time T(M) = 13.9 μs remains practically constant between 200 and 300 K and is determined by nuclear spin diffusion. At lower temperatures T(M) decreases by an order of magnitude and exhibits two minima at T = 140 K and T = 60 K. The temperature dependence of T(M) between 20 and 200 K is attributed to dynamic processes that average inequivalent hyperfine couplings, e.g. rotation of the methyl groups of the cage organic substituents. The hyperfine couplings of the encapsulated proton and the cage (29)Si nuclei are obtained through numerical simulations of field-swept FID-detected EPR spectra and HYSCORE experiments, respectively. The results are discussed in terms of existing phenomenological models based on the spherical harmonic oscillator and compared to those of endohedral fullerenes. PMID:22323086

  17. Reactivity of some vanadium oxides: An EPR and XRD study

    SciTech Connect

    Occhiuzzi, Manlio

    2005-05-15

    V{sub 2}O{sub 5}, VO{sub 2} and V{sub 2}O{sub 3} fresh samples and at different times after purchase or preparation (aged samples) were investigated by chemical analysis, redox treatments, XRD and EPR. The ageing process through a reaction with water and oxygen slowly oxidize crystalline VO{sub 2} and V{sub 2}O{sub 3}, leading to a quasi-amorphous phase with bariandite structure (V{sub 10}O{sub 24}.12H{sub 2}O). The role of water is the progressive demolition of the compact structures and formation of hydrated phase. Kinetic study of VO{sub 2} oxidation by O{sub 2} and O{sub 2}+H{sub 2}O mixture indicates that increasing the temperature up to 723K the effect of water becomes less important. The reaction leads to partially oxidized products with decreasing water content: bariandite at room temperature, V{sub 3}O{sub 7}.H{sub 2}O at 383K and V{sub 3}O{sub 7} at 723K. Kinetic investigation of V{sub 2}O{sub 5} reduction by CO at 633-723K showed that the reduction process proceeds trough the formation of V{sup 4+} and of electrons delocalized in the conduction band.

  18. Noise Analysis of EPR Spectrometers with Cryogenic Microwave Preamplifiers

    NASA Astrophysics Data System (ADS)

    Pfenninger, S.; Froncisz, W.; Hyde, J. S.

    Studies are reported on the sensitivity of an EPR spectrometer utilizing a cryogenic preamplifier (0.5 dB noise figure, 35 K equivalent noise temperature). Three cases are considered: (a) resonator matched in a CW experiment, (b) resonator Q spoiled by overcoupling, and (c) resonator matched in pulse experiments. Contributions to the system noise because of losses in the microwave bridge have been determined quantitatively: the equivalent noise temperature of the receiver chain rises from 35 to 100 K. It is suggested that improved system performance can be achieved by cooling major components of the microwave bridge. It is particularly advantageous to cool the load resistor at port 1 of the circulator. Measurements of source noise are reported. This noise contribution becomes increasingly apparent as the system noise is decreased, but can be suppressed by use of loop-gap resonators. Analysis is carried out in a mixed engineering vocabulary of output noise temperature and equivalent noise temperature, which are temperatures referred to the output and input of the circuit, respectively. It is suggested that this is an appropriate analytical approach when there are multiple paths that feed noise to the output of the circuit with different physical temperatures of the input load resistor for each path.

  19. EPR characterisation of platinum nanoparticle functionalised carbon nanotube hybrid materials.

    PubMed

    Dennany, Lynn; Sherrell, Peter; Chen, Jun; Innis, Peter C; Wallace, Gordon G; Minett, Andrew I

    2010-04-28

    The use of nanostructured carbon materials as electrodes for energy storage and conversion is an expanding area of research in recent years. Herein, platinum nanoparticles have been deposited onto both multi-walled and single-walled carbon nanotubes (CNTs) via a microwave assisted polyol reduction method. This interaction has been probed with electron paramagnetic resonance (EPR) and Raman spectroscopies to elucidate the charge/electron transfer interactions between the Pt nanoparticles and the CNTs. Observed shifts in the g factors of the CNTs are indicative of such an electronic interaction, strongly suggesting the covalent attachment of the nanoparticles to the carboxylic groups on the CNTs, formed during the microwave-assisted reduction process. The Pt decorated CNTs show a dramatic increase in electrochemical behaviour in terms of high reversible capacity and relatively stable cycle performance compared to unmodified CNTs increasing their applicability in energy storage devices. For instance, significant increases in the electrochemical double layer capacitance are observed for the CNT-NP composite electrode. PMID:20379504

  20. Boron dose determination for BNCT using Fricke and EPR dosimetry

    SciTech Connect

    Wielopolski, L.; Ciesielski, B.

    1995-02-01

    In Boron Neutron Capture Therapy (BNCT) the dominant dose delivered to the tumor is due to {alpha} and {sup 7}Li charged particles resulting from a neutron capture by {sup 10}B and is referred to herein as the boron dose. Boron dose is directly attributable to the following two independent factors, one boron concentration and the neutron capture energy dependent cross section of boron, and two the energy spectrum of the neutrons that interact with boron. The neutron energy distribution at a given point is dictated by the incident neutron energy distribution, the depth in tissue, geometrical factors such as beam size and patient`s dimensions. To account for these factors can be accommodated by using Monte Carlo theoretical simulations. However, in conventional experimental BNCT dosimetry, e.g., using TLDs or ionization chambers, it is only possible to estimate the boron dose. To overcome some of the limitations in the conventional dosimetry, modifications in ferrous sulfate dosimetry (Fricke) and Electron Paramagnetic Resonance (EPR) dosimetry in alanine, enable to measure specifically boron dose in a mixed gamma neutron radiation fields. The boron dose, in either of the dosimeters, is obtained as a difference between measurements with boronated and unboronated dosimeters. Since boron participates directly in the measurements, the boron dosimetry reflects the true contribution, integral of the neutron energy spectrum with boron cross section, of the boron dose to the total dose. Both methods are well established and used extensively in dosimetry, they are presented briefly here.

  1. Implementation of GPU-Accelerated Back Projection for EPR imaging

    PubMed Central

    Qiao, Zhiwei; Redler, Gage; Epel, Boris; Qian, Yuhua; Halpern, Howard

    2016-01-01

    Electron paramagnetic resonance (EPR) Imaging (EPRI) is a robust method for measuring in vivo oxygen concentration (pO2). For 3D pulse EPRI, a commonly used reconstruction algorithm is the filtered backprojection (FBP) algorithm, in which the backprojection process is computationally intensive and may be time consuming when implemented on a CPU. A multistage implementation of the backprojection can be used for acceleration, however it is not flexible (requires equal linear angle projection distribution) and may still be time consuming. In this work, single-stage backprojection is implemented on a GPU (Graphics Processing Units) having 1152 cores to accelerate the process. The GPU implementation results in acceleration by over a factor of 200 overall and by over a factor of 3500 if only the computing time is considered. Some important experiences regarding the implementation of GPU-accelerated backprojection for EPRI are summarized. The resulting accelerated image reconstruction is useful for real-time image reconstruction monitoring and other time sensitive applications. PMID:26410654

  2. CW- and pulsed-EPR of carbonaceous matter in primitive meteorites: solving a lineshape paradox.

    PubMed

    Delpoux, Olivier; Gourier, Didier; Binet, Laurent; Vezin, Hervé; Derenne, Sylvie; Robert, François

    2008-05-01

    Insoluble organic matter (IOM) of Orgueil and Tagish Lake meteorites are studied by CW-EPR and pulsed-EPR spectroscopies. The EPR line is due to polycyclic paramagnetic moieties concentrated in defect-rich regions of the IOM, with concentrations of the order of 4x10(19) spin/g. CW-EPR reveals two types of paramagnetic defects: centres with S=1/2, and centres with S=0 ground state and thermally accessible triple state S=1. In spite of the Lorentzian shape of the EPR and its narrowing upon increasing the spin concentration, the EPR line is not in the exchange narrowing regime as previously deduced from multi-frequency CW-EPR [L. Binet, D. Gourier, Appl. Magn. Reson. 30 (2006) 207-231]. It is inhomogeneously broadened as demonstrated by the presence of nuclear modulations in the spin-echo decay. The line narrowing, similar to an exchange narrowing effect, is the result of an increasing contribution of the narrow line of the triplet state centres in addition to the broader line of doublet states. Hyperfine sublevel correlation spectroscopy (HYSCORE) of hydrogen and (13)C nuclei indicates that IOM* centres are small polycyclic moieties that are moderately branched with aliphatic chains, as shown by the presence of aromatic hydrogen atoms. On the contrary the lack of such aromatic hydrogen in triplet states suggests that these radicals are most probably highly branched. Paramagnetic centres are considerably enriched in deuterium, with D/H approximately 1.5+/-0.5x10(-2) of the order of values existing in interstellar medium. PMID:18024197

  3. Electronically Tunable Surface-Coil-Type Resonator for L-Band EPR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Hirata, Hiroshi; Walczak, Tadeusz; Swartz, Harold M.

    2000-01-01

    The automatic frequency control (AFC) circuit in conventional electron paramagnetic resonance (EPR) spectrometers automatically tunes the microwave source to the resonance frequency of the resonator. The circuit works satisfactorily for samples stable enough that the geometric relations in the resonance structure do not change in a significant way. When EPR signals are measured during in vivo experiments with small rodents, however, the distance between the signal source and the surface-coil detector can change rapidly. When a conventional AFC circuit keeps the oscillator tuned to the resonator under those conditions, the resultant frequency change may exceed ±5 MHz and markedly shift the position of the EPR signal. Such a shift results in unacceptable effects on the spectra, especially when the experimenter is dealing with narrow EPR lines. The animal movement also causes a mismatching of the resonator and the 50-ohm transmission line. Direct results of this mismatching are increased noise; shifts in the position of the baseline; and a high probability of overdriving the signal preamplifier with consequent loss of the EPR signal. We therefore designed, built, and tested a new surface-coil resonator using varactor diodes for tuning the resonance frequency to the fixed frequency oscillator and for capacitive matching of the resonator to the 50-ohm transmission line. The performance of the automatic matching system was tested in vivo by measuring EPR spectra of lithium phthalocyanine implanted in rats. Stability and sensitivity of the spectrometer were evaluated by measuring EPR spectra with and without the use of the automatic matching system. The overall experimental performance of the spectrometer was found to significantly improve during in vivo experiments using the automatic matching system. Excellent matching between the 50-ohm transmission line and the resonator was maintained under all experimental circumstances that were tested. This should allow us now to

  4. EPR/alanine dosimetry for two therapeutic proton beams

    NASA Astrophysics Data System (ADS)

    Marrale, Maurizio; Carlino, Antonio; Gallo, Salvatore; Longo, Anna; Panzeca, Salvatore; Bolsi, Alessandra; Hrbacek, Jan; Lomax, Tony

    2016-02-01

    In this work the analysis of the electron paramagnetic resonance (EPR) response of alanine pellets exposed to two different clinical proton beams employed for radiotherapy is performed. One beam is characterized by a passive delivery technique and is dedicated to the eyes treatment (OPTIS2 beam line). Alanine pellets were irradiated with a 70 MeV proton beam corresponding to 35 mm range in eye tissue. We investigated how collimators with different sizes and shape used to conform the dose to the planned target volume influence the delivered dose. For this purpose we performed measurements with varying the collimator size (Output Factor) and the results were compared with those obtained with other dosimetric techniques (such as Markus chamber and diode detector). This analysis showed that the dosimeter response is independent of collimator diameter if this is larger than or equal to 10 mm. The other beam is characterized by an active spot-scanning technique, the Gantry1 beam line (maximum energy 230 MeV), and is used to treat deep-seated tumors. The dose linearity of alanine response in the clinical dose range was tested and the alanine dose response at selected locations in depth was measured and compared with the TPS planned dose in a quasi-clinical scenario. The alanine response was found to be linear in the dose in the clinical explored range (from 10 to 70 Gy). Furthermore, a depth dose profile in a quasi-clinical scenario was measured and compared to the dose computed by the Treatment Planning System PSIPLAN. The comparison of calibrated proton alanine measurements and TPS dose shows a difference under 1% in the SOBP and a "quenching" effect up to 4% in the distal part of SOBP. The positive dosimetric characteristics of the alanine pellets confirm the feasibility to use these detectors for "in vivo" dosimetry in clinical proton beams.

  5. Photoionization of phenothiazine: EPR detection of reactions of the polarized solvated electron

    SciTech Connect

    Turro, N.J.; Khudyakov, I.V.; Willigen, H. van

    1995-12-13

    Photoionization of phenothiazine (PTH) and reactions of the solvated electron with some electron acceptors were studied with steady state and time-resolved EPR and transient optical absorption techniques. Time-resolved EPR spectra from the phenothiazine cation radical (PTH{sup .+}) and hydrated electron (e{sub aq}{sup -}) formed in sodium 1-dodecylsulfate (SDS) micellar solution were observed in emission. By contrast, PTH{sup .+} formed by photoionization of PTH in alcohols gives absorptive EPR signals. The spin polarization carried by the hydrated electron in SDS solutions can be transferred effectively to a stable nitroxyl free radical 3-carboxy-2,2,5, 5-tetramethyl-1-pyrrolidinyloxyl (N{sup .-}) present in the bulk aqueous phase. EPR and flash photolysis measurements show that this electron spin polarization transfer process proceeds with a rate which is approximately five times faster than the chemical reaction between e{sub aq}{sup -} and N{sup .-}. The marked difference in rates is attributed to differences in spin-statistical factors and difference in reaction radii for spin exchange compared to reaction. In alcohol solutions of PTH and a nitroxyl stable radical (2,2,6, 6-tetramethylpyperidin-1-oxyl, TEMPO), excitation of PTH also results in emissive polarization of the EPR spectrum of the stable radical. 46 refs., 12 figs.

  6. Site Directed Spin Labeling and EPR Spectroscopic Studies of Pentameric Ligand-Gated Ion Channels.

    PubMed

    Basak, Sandip; Chatterjee, Soumili; Chakrapani, Sudha

    2016-01-01

    Ion channel gating is a stimulus-driven orchestration of protein motions that leads to transitions between closed, open, and desensitized states. Fundamental to these transitions is the intrinsic flexibility of the protein, which is critically modulated by membrane lipid-composition. To better understand the structural basis of channel function, it is necessary to study protein dynamics in a physiological membrane environment. Electron Paramagnetic Resonance (EPR) spectroscopy is an important tool to characterize conformational transitions between functional states. In comparison to NMR and X-ray crystallography, the information obtained from EPR is intrinsically of lower resolution. However, unlike in other techniques, in EPR there is no upper-limit to the molecular weight of the protein, the sample requirements are significantly lower, and more importantly the protein is not constrained by the crystal lattice forces. Therefore, EPR is uniquely suited for studying large protein complexes and proteins in reconstituted systems. In this article, we will discuss general protocols for site-directed spin labeling and membrane reconstitution using a prokaryotic proton-gated pentameric Ligand-Gated Ion Channel (pLGIC) from Gloeobacter violaceus (GLIC) as an example. A combination of steady-state Continuous Wave (CW) and Pulsed (Double Electron Electron Resonance-DEER) EPR approaches will be described that will enable a complete quantitative characterization of channel dynamics. PMID:27403967

  7. Optimization of bicelle lipid composition and temperature for EPR spectroscopy of aligned membranes

    NASA Astrophysics Data System (ADS)

    McCaffrey, Jesse E.; James, Zachary M.; Thomas, David D.

    2015-01-01

    We have optimized the magnetic alignment of phospholipid bilayered micelles (bicelles) for EPR spectroscopy, by varying lipid composition and temperature. Bicelles have been extensively used in NMR spectroscopy for several decades, in order to obtain aligned samples in a near-native membrane environment and take advantage of the intrinsic sensitivity of magnetic resonance to molecular orientation. Recently, bicelles have also seen increasing use in EPR, which offers superior sensitivity and orientational resolution. However, the low magnetic field strength (less than 1 T) of most conventional EPR spectrometers results in homogeneously oriented bicelles only at a temperature well above physiological. To optimize bicelle composition for magnetic alignment at reduced temperature, we prepared bicelles containing varying ratios of saturated (DMPC) and unsaturated (POPC) phospholipids, using EPR spectra of a spin-labeled fatty acid to assess alignment as a function of lipid composition and temperature. Spectral analysis showed that bicelles containing an equimolar mixture of DMPC and POPC homogeneously align at 298 K, 20 K lower than conventional DMPC-only bicelles. It is now possible to perform EPR studies of membrane protein structure and dynamics in well-aligned bicelles at physiological temperatures and below.

  8. Identification of the EPR signal of S₂⁻ in green ultramarine pigments.

    PubMed

    Raulin, Katarzyna; Gobeltz, Noëlle; Vezin, Hervé; Touati, Nadia; Ledé, Bertrand; Moissette, Alain

    2011-05-28

    Green and blue ultramarine pigments are characterized by the sodalite structure Na(6)(Al(6)Si(6)O(24)) and colored inserted species. These chromophores are sulfur species: S(3)(-) (blue) and S(2)(-) (yellow). Both radicals are encapsulated inside the β-cages. They contribute to the EPR spectrum of ultramarine pigments. The well-known strong EPR signal observed in all ultramarine pigments Continuous-Wave (CW) spectra has long been assigned to S(3)(-) (g = 2.029). In contrast, the S(2)(-) contribution is still subject to controversy because its signal in ultramarine pigments was not resolved even at low temperature in CW-EPR experiments. In this study, we identify unambiguously for the first time by CW-EPR and field sweep-echo detected (FS-ED) EPR the signal of S(2)(-) in ultramarine pigments and we determine its tensor components: g(1) = 2.69(6), g(2) = 2.03(4) and g(3) = 1.86(4). PMID:21468420

  9. Determination of methemoglobin in human blood after ionising radiation by EPR

    NASA Astrophysics Data System (ADS)

    Polakovs, M.; Mironova-Ulmane, N.; Pavlenko, A.; Aboltins, A.

    2015-03-01

    In the present work presents results of investigations of radiation influence on blood of patients examined by radio-isotopes diagnosis (Tc99m), blood of Chernobyl clean-up workers and human blood irradiated by LINAC using Electron Paramagnetic Resonance (EPR). The EPR spectroscopy reveals information on electronic states of transition metal ions, particularly Fe3+ in different spin states. It is shown that EPR spectra of blood of patients before examination has signal from metal-protein transferrin (g=4.3) and after administration of radioisotope proves signal of Fe3+ (methemaglobin) in the high spin state (g=6.0). The EPR spectra of Chernobyl liquidator display number of signals including low and high state of ion Fe3+ (g = 2.0 and g=6.0), and transferrin (g=4.3). The EPR spectra of irradiated human blood by LINAC (linear accelerator) have only signal Fe3+ (methemaglobin) in low-spin state with g = 2.0.

  10. Quantitative Interpretation of Multifrequency Multimode EPR Spectra of Metal Containing Proteins, Enzymes, and Biomimetic Complexes.

    PubMed

    Petasis, Doros T; Hendrich, Michael P

    2015-01-01

    Electron paramagnetic resonance (EPR) spectroscopy has long been a primary method for characterization of paramagnetic centers in materials and biological complexes. Transition metals in biological complexes have valence d-orbitals that largely define the chemistry of the metal centers. EPR spectra are distinctive for metal type, oxidation state, protein environment, substrates, and inhibitors. The study of many metal centers in proteins, enzymes, and biomimetic complexes has led to the development of a systematic methodology for quantitative interpretation of EPR spectra from a wide array of metal containing complexes. The methodology is now contained in the computer program SpinCount. SpinCount allows simulation of EPR spectra from any sample containing multiple species composed of one or two metals in any spin state. The simulations are quantitative, thus allowing determination of all species concentrations in a sample directly from spectra. This chapter will focus on applications to transition metals in biological systems using EPR spectra from multiple microwave frequencies and modes. PMID:26478486

  11. EPR in functional structures based on doped (nano, meso)-porous silica and titanium dioxide

    NASA Astrophysics Data System (ADS)

    Kassiba, A.; Makowska-Janusik, M.; Mehdi, A.

    2011-04-01

    EPR investigations are performed on mesoporous silica (SBA15) functionalized by Nickel-cyclam complexes (1,4,8,11-tetraazacyclotetradecane groups chelating nickel ions) and on mesoporous titanium dioxide with nitrogen doping. For functionalized silica, the magnetic behaviour of organometallic groups, their mutual interactions and dispersion in the host matrices are compared with respect to the doping rates and the synthesis procedures. The relaxation processes were analyzed from the thermal evolution of the paramagnetic spin susceptibilities and EPR line-widths. Particularly, some samples show the formation of clusters where phonon assisted one dimensional (1D) ferromagnetic ordering occurs below 45 K. For the mesoporous TiO2, systematic EPR investigations were performed on two main classes of materials with regard to the porosity degrees. The EPR experiments point out the efficiency of EPR method to probe the degree of functionalization of mesoporous silica or the nitrogen doping achievement in TiO2, and in general to give a valuable feedback to improve the synthesis routes of smart materials.

  12. New Developed Cylindrical TM010 Mode EPR Cavity for X-Band In Vivo Tooth Dosimetry

    PubMed Central

    Junwang, Guo; Qingquan, Yuan; Jianbo, Cong; Lei, Ma; Guofu, Dong; Guoshan, Yang; Ke, Wu

    2014-01-01

    EPR tooth in vivo dosimetry is an attractive approach for initial triage after unexpected nuclear events. An X-band cylindrical TM010 mode resonant cavity was developed for in vivo tooth dosimetry and used in EPR applications for the first time. The cavity had a trapezoidal measuring aperture at the exact position of the cavity’s cylindrical wall where strong microwave magnetic field H1 concentrated and weak microwave electric field E1 distributed. Theoretical calculations and simulations were used to design and optimize the cavity parameters. The cavity features were evaluated by measuring DPPH sample, intact incisor samples embed in a gum model and the rhesus monkey teeth. The results showed that the cavity worked at designed frequency and had the ability to make EPR spectroscopy in relative high sensitivity. Sufficient modulation amplitude and microwave power could be applied into the aperture. Radiation induced EPR signal could be observed remarkably from 1 Gy irradiated intact incisor within only 30 seconds, which was among the best in scan time and detection limit. The in vivo spectroscopy was also realized by acquiring the radiation induced EPR signal from teeth of rhesus monkey whose teeth was irradiated by dose of 2 Gy. The results suggested that the cavity was sensitive to meet the demand to assess doses of significant level in short time. This cavity provided a very potential option for the development of X-band in vivo dosimetry. PMID:25222483

  13. New developed cylindrical TM010 mode EPR cavity for X-band in vivo tooth dosimetry.

    PubMed

    Junwang, Guo; Qingquan, Yuan; Jianbo, Cong; Lei, Ma; Guofu, Dong; Guoshan, Yang; Ke, Wu

    2014-01-01

    EPR tooth in vivo dosimetry is an attractive approach for initial triage after unexpected nuclear events. An X-band cylindrical TM010 mode resonant cavity was developed for in vivo tooth dosimetry and used in EPR applications for the first time. The cavity had a trapezoidal measuring aperture at the exact position of the cavity's cylindrical wall where strong microwave magnetic field H1 concentrated and weak microwave electric field E1 distributed. Theoretical calculations and simulations were used to design and optimize the cavity parameters. The cavity features were evaluated by measuring DPPH sample, intact incisor samples embed in a gum model and the rhesus monkey teeth. The results showed that the cavity worked at designed frequency and had the ability to make EPR spectroscopy in relative high sensitivity. Sufficient modulation amplitude and microwave power could be applied into the aperture. Radiation induced EPR signal could be observed remarkably from 1 Gy irradiated intact incisor within only 30 seconds, which was among the best in scan time and detection limit. The in vivo spectroscopy was also realized by acquiring the radiation induced EPR signal from teeth of rhesus monkey whose teeth was irradiated by dose of 2 Gy. The results suggested that the cavity was sensitive to meet the demand to assess doses of significant level in short time. This cavity provided a very potential option for the development of X-band in vivo dosimetry. PMID:25222483

  14. 20 °C, 9 GHz CW-EPR saturation measurements of five selected Alberta coals

    NASA Astrophysics Data System (ADS)

    Kudynska, J.; Buckmaster, H. A.; Duczmal, T.

    1991-12-01

    This paper reports the first determination of the spin-lattice (T_1) and spin-spin (T_2) relaxation times at 20 °C for two subbituminous and three hv bituminous selected Alberta coals using 9 GHz CW-EPR saturation measurements. Argand diagrammatic techniques were used to verify that the lineshapes were Lorentzian since the deviation was less than 4%. Consequently, it was assumed that the CW-EPR spectral resonances could be approximated to homogeneously broadened lineshapes and saturation techniques could be used to determine these relaxation times. The T_1 and T_2 relaxation times are in good agreement with values reported in the literature using saturation measurements, but two orders of magnitude shorter than those obtained using ESE because coal EPR spectral resonances are the unresolved superposition of comparatively narrow homogeneous resonances.

  15. A reinvestigation of EXAFS and EPR spectroscopic measurements of chromium(VI) reduction by coir pith.

    PubMed

    Suksabye, Parinda; Worasith, Niramon; Thiravetyan, Paitip; Nakajima, Akira; Goodman, Bernard A

    2010-08-15

    New measurements using extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) techniques are consistent with Cr in the Cr(III) oxidation state as the main product from the adsorption of Cr(VI) on coir pith. These confirm the previous X-ray measurements, but differ from the results of previous EPR studies, which indicated that Cr(V) was the main form of Cr. The reason for this discrepancy is the presence of a broad signal from Cr(III) in an unsymmetrical environment that was missed previously; the Cr(V) component is in fact only a minor reaction product. As a result of this problem with spectral acquisition and interpretation, some simple recommendations are presented for conducting EPR investigations on natural systems. PMID:20452728

  16. Copper ESEEM and HYSCORE through ultra-wideband chirp EPR spectroscopy

    SciTech Connect

    Segawa, Takuya F.; Doll, Andrin; Pribitzer, Stephan; Jeschke, Gunnar

    2015-07-28

    The main limitation of pulse electron paramagnetic resonance (EPR) spectroscopy is its narrow excitation bandwidth. Ultra-wideband (UWB) excitation with frequency-swept chirp pulses over several hundreds of megahertz overcomes this drawback. This allows to excite electron spin echo envelope modulation (ESEEM) from paramagnetic copper centers in crystals, whereas up to now, only ESEEM of ligand nuclei like protons or nitrogens at lower frequencies could be detected. ESEEM spectra are recorded as two-dimensional correlation experiments, since the full digitization of the electron spin echo provides an additional Fourier transform EPR dimension. Thus, UWB hyperfine-sublevel correlation experiments generate a novel three-dimensional EPR-correlated nuclear modulation spectrum.

  17. Photonic EPR State from Quadratic Waveguide Array with Alternating Positive and Negative Couplings

    NASA Astrophysics Data System (ADS)

    Ying, Yang; Ping, Xu; Liang-Liang, Lu; Shi-Ning, Zhu

    2016-02-01

    We propose the generation of photonic EPR state from quadratic waveguide array. Both the propagation constant and the nonlinearity in the array are designed to possess a periodical modulation along the propagation direction. This ensures that the photon pairs can be generated efficiently through the quasi-phase-matching spontaneous parametric down conversion by holding the spatial EPR entanglement in the fashion of correlated position and anticorrelated momentum. The Schmidt number which denotes the degree of EPR entanglement is calculated and it can approach a high value when the number of illuminated waveguide channels and the length of the waveguide array are properly chosen. These results suggest the quadratic waveguide array as a compact platform for engineering photonic quantum states in a high-dimensional Hilbert space. Supported by the State Key Program for Basic Research in China under Grant No. 2012CB921802, the National Natural Science Foundations of China under Grant Nos. 91321312, 11321063 and 11422438

  18. Copper ESEEM and HYSCORE through ultra-wideband chirp EPR spectroscopy.

    PubMed

    Segawa, Takuya F; Doll, Andrin; Pribitzer, Stephan; Jeschke, Gunnar

    2015-07-28

    The main limitation of pulse electron paramagnetic resonance (EPR) spectroscopy is its narrow excitation bandwidth. Ultra-wideband (UWB) excitation with frequency-swept chirp pulses over several hundreds of megahertz overcomes this drawback. This allows to excite electron spin echo envelope modulation (ESEEM) from paramagnetic copper centers in crystals, whereas up to now, only ESEEM of ligand nuclei like protons or nitrogens at lower frequencies could be detected. ESEEM spectra are recorded as two-dimensional correlation experiments, since the full digitization of the electron spin echo provides an additional Fourier transform EPR dimension. Thus, UWB hyperfine-sublevel correlation experiments generate a novel three-dimensional EPR-correlated nuclear modulation spectrum. PMID:26233121

  19. Fault Current Distribution and Pole Earth Potential Rise (EPR) Under Substation Fault

    NASA Astrophysics Data System (ADS)

    Nnassereddine, M.; Rizk, J.; Hellany, A.; Nagrial, M.

    2013-09-01

    New high-voltage (HV) substations are fed by transmission lines. The position of these lines necessitates earthing design to ensure safety compliance of the system. Conductive structures such as steel or concrete poles are widely used in HV transmission mains. The earth potential rise (EPR) generated by a fault at the substation could result in an unsafe condition. This article discusses EPR based on substation fault. The pole EPR assessment under substation fault is assessed with and without mutual impedance consideration. Split factor determination with and without the mutual impedance of the line is also discussed. Furthermore, a simplified formula to compute the pole grid current under substation fault is included. Also, it includes the introduction of the n factor which determines the number of poles that required earthing assessments under substation fault. A case study is shown.

  20. EPR/alanine pellets with low Gd content for neutron dosimetry.

    PubMed

    Marrale, M; Brai, M; Longo, A; Panzeca, S; Carlino, A; Tranchina, L; Tomarchio, E; Parlato, A; Buttafava, A; Dondi, D; Zeffiro, A

    2014-10-01

    This paper reports on results obtained by electron paramagnetic resonance (EPR) measurements and Monte Carlo (MC) simulation on a blend of alanine added with low content of gadolinium oxide (5 % by weight) to improve the sensitivity to thermal neutron without excessively affecting tissue equivalence. The sensitivity is enhanced by this doping procedure of more an order of magnitude. The results are compared with those obtained with the addition of boric acid (50 % by weight) where boron is in its natural isotopic composition in order to produce low-cost EPR dosemeters. The gadolinium addition influences neutron sensitivity more than the boron addition. The presence of additives does not substantially change the fading of the EPR signal induced by neutrons. The MC simulations agree the experimental results in case of gadolinium addition. PMID:24262924

  1. Saccharides as Prospective Immobilizers of Nucleic Acids for Room-Temperature Structural EPR Studies.

    PubMed

    Kuzhelev, Andrey A; Shevelev, Georgiy Yu; Krumkacheva, Olesya A; Tormyshev, Victor M; Pyshnyi, Dmitrii V; Fedin, Matvey V; Bagryanskaya, Elena G

    2016-07-01

    Pulsed dipolar electron paramagnetic resonance (EPR) spectroscopy is a powerful tool for structural studies of biomolecules and their complexes. This method, whose applicability has been recently extended to room temperatures, requires immobilization of the studied biosystem to prevent averaging of dipolar couplings; at the same time, the modification of native conformations by immobilization must be avoided. In this work, we provide first demonstration of room-temperature EPR distance measurements in nucleic acids using saccharides trehalose, sucrose, and glucose as immobilizing media. We propose an approach that keeps structural conformation and unity of immobilized double-stranded DNA. Remarkably, room-temperature electron spin dephasing time of triarylmethyl-labeled DNA in trehalose is noticeably longer compared to previously used immobilizers, thus providing a broader range of available distances. Therefore, saccharides, and especially trehalose, can be efficiently used as immobilizers of nucleic acids, mimicking native conditions and allowing wide range of structural EPR studies at room temperatures. PMID:27320083

  2. Pulsed EPR of P1 centers in synthetic diamond under bichromatic excitation conditions

    NASA Astrophysics Data System (ADS)

    Fedoruk, G. G.; Saiko, A. P.; Markevich, S. A.; Poklonskaya, O. N.

    2009-03-01

    The dynamics of the interaction of P1 centers in synthetic diamond with a bichromatic radiation, representing microwave (MW) and radio frequency (RF) fields in a configuration characteristic of the stationary EPR spectroscopy with modulated magnetic field, has been studied using the transient nutation technique. It is demonstrated that a thermobaric treatment of the crystal leads to an increase in the phase relaxation time of P1 centers. Additional increase in this relaxation time is observed under the conditions of a nutation resonance, where the RF field frequency is close to the effective Rabi frequency in the MW field. These data are taken into account in considering the inversion of the EPR lines of P1 centers that was recently discovered in the stationary EPR.

  3. Characterization by XRD and electron paramagnetic resonance (EPR) of waste materials from 'Cerro Matoso' Mine (Colombia)

    SciTech Connect

    Hernandez, Y.; Carriazo, J.G.; Almanza, O. . E-mail: oaalmanzam@unal.edu.co

    2006-07-15

    Materials from a mining process, in which ferronickel metal extraction is the principal aim, were studied. The residual solid (scum) obtained in this process leads to large-scale accumulation of a vitreous material (pollutant) which creates an environmental problem. These materials were characterized by EPR, X-ray diffraction and X-ray fluorescence. The results indicate that the analyzed solids are rich in Fe{sub 2}O{sub 3} and NiO among other oxides. The scum material shows diffraction signals corresponding to the minerals enstatite (pyroxene) and {alpha}-alumina. Moreover, the scum EPR analysis showed a broad line around g = 2.1 corresponding to Fe{sup 3+} clusters in a complex glassy matrix. An analysis of EPR at different temperatures was also performed. The objective of this work, as a first exploratory stage, is to develop a better understanding of the residual solids in order to identify potential applications.

  4. Protein rotational dynamics investigated with a dual EPR/optical molecular probe. Spin-labeled eosin.

    PubMed Central

    Cobb, C E; Hustedt, E J; Beechem, J M; Beth, A H

    1993-01-01

    An acyl spin-label derivative of 5-aminoeosin (5-SLE) was chemically synthesized and employed in studies of rotational dynamics of the free probe and of the probe when bound noncovalently to bovine serum albumin using the spectroscopic techniques of fluorescence anisotropy decay and electron paramagnetic resonance (EPR) and their long-lifetime counterparts phosphorescence anisotropy decay and saturation transfer EPR. Previous work (Beth, A. H., Cobb, C. E., and J. M. Beechem, 1992. Synthesis and characterization of a combined fluorescence, phosphorescence, and electron paramagnetic resonance probe. Society of Photo-Optical Instrumentation Engineers. Time-Resolved Laser Spectroscopy III. 504-512) has shown that the spin-label moiety only slightly altered the fluorescence and phosphorescence lifetimes and quantum yields of 5-SLE when compared with 5-SLE whose nitroxide had been reduced with ascorbate and with the diamagnetic homolog 5-acetyleosin. In the present work, we have utilized time-resolved fluorescence anisotropy decay and linear EPR spectroscopies to observe and quantitate the psec motions of 5-SLE in solution and the nsec motions of the 5-SLE-bovine serum albumin complex. Time-resolved phosphorescence anisotropy decay and saturation transfer EPR studies have been carried out to observe and quantitate the microseconds motions of the 5-SLE-albumin complex in glycerol/buffer solutions of varying viscosity. These latter studies have enabled a rigorous comparison of rotational correlation times obtained from these complementary techniques to be made with a single probe. The studies described demonstrate that it is possible to employ a single molecular probe to carry out the full range of fluorescence, phosphorescence, EPR, and saturation transfer EPR studies. It is anticipated that "dual" molecular probes of this general type will significantly enhance capabilities for extracting dynamics and structural information from macromolecules and their functional

  5. Solid state ``self-calibrated'' EPR-dosimeters—advantageous and shortcomings

    NASA Astrophysics Data System (ADS)

    Peimel-Stuglik, Z.; Fabisiak, S.

    2006-03-01

    EPR dosimetry method with α-alanine as radiation sensitive material (RSM) is widely used in high dose dosimetry laboratories. However, it is not suitable for routine industrial applications mainly because of difficult EPR measurement procedure. In order to simplify quantitative EPR dosimetry measurements Yordanov and Gancheva developed so-called "self-calibrated" (sc) dosimeters consists of RSM (α-alanine, sugar, other ones), Mn 2+/MgO as internal EPR intensity standard (IES) and a binder. The aim of this work was to check dosimetric properties of two experimental batches of sc EPR dosimeters with α-alanine and sugar as RSM, Mn 2+/MgO as IES and paraffin as a binder. The percentage content of the components was 60, 5 and 35% (w/w), respectively. It was established that the investigated alanine sc-dosimeters are about two times more sensitive than the sugar ones. The dose-response coefficient, Kdr of sc-alanine dosimeters was stable in all investigated dose range from 1 to 23 kGy. The Kdr-value of sugar sc-dosimeters decreased with the dose what was in a contradiction to the results pointed to the high stability of radiation generated sugar radicals. The observed effect arose probably from the special chemical procedure used for the sc-sugar dosimeters production. The results confirmed an expectation that the position of sc dosimeter in the cavity is not important factor for accurate dose evaluation. It allows to read-out dosimetric signals in shorter time, with lower uncertainty and on less sophisticate EPR-spectrometers than that commonly used till now. The main shortcomings of sc dosimeters are: (a) the limitation of RSM suitable for sc dosimeters to these ones having strictly linear signal to dose characteristic; (b) necessity to assure very good homogeneity of dosimeter material; and (c) the cost of IES present in the amount of some percent in each sc dosimeter.

  6. 75 FR 16203 - Advisory Committee on Reactor Safeguards (ACRS); Meeting of the ACRS Subcommittee on EPR; Notice...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-31

    ... From the Federal Register Online via the Government Publishing Office NUCLEAR REGULATORY COMMISSION Advisory Committee on Reactor Safeguards (ACRS); Meeting of the ACRS Subcommittee on EPR; Notice of Meeting The ACRS Subcommittee on the U.S. Evolutionary Power Reactor (EPR) will hold a meeting on April 20-21, 2010, at 11545 Rockville Pike, T2-...

  7. EPR study of free radicals in some drugs γ-irradiated in the solid state

    NASA Astrophysics Data System (ADS)

    Ambroż, H. B.; Kornacka, E. M.; Marciniec, B.; Ogrodowczyk, M.; Przybytniak, G. K.

    2000-06-01

    A range of drugs in the form of microcrystalline powder was exposed to γ-radiation. EPR measurements proved that all of them contained various paramagnetic species after 4 and 8 weeks of storage. We observed following radical concentrations, stable up to 4 weeks: the highest for ifosfamide — 4.5×10 17 spins per gram and the lowest for nimodipine — 2.1×10 16 spins per gram. Three drugs exhibited very weak EPR signals before irradiation, not detectable quantitatively. Some spectroscopic properties and suggestions concerning possible structure of the radicals are given in our paper.

  8. Pulsed EPR Distance Measurements in Soluble Proteins by Site-directed Spin-labeling (SDSL)

    PubMed Central

    de Vera, Ian Mitchelle S.; Blackburn, Mandy E.; Galiano, Luis; Fanucci, Gail E.

    2015-01-01

    The resurgence of pulsed electron paramagnetic resonance (EPR) in structural biology centers on recent improvements in distance measurements using the double electron-electron resonance (DEER) technique. This unit focuses on EPR-based distance measurements by site-directed spin-labeling (SDSL) of engineered cysteine residues in soluble proteins, with HIV-1 protease used as a model. To elucidate conformational changes in proteins, experimental protocols were optimized and existing data analysis programs were employed to derive distance distribution profiles. Experimental considerations, sample preparation and error analysis for artifact suppression are also outlined here. PMID:24510645

  9. The first international intercomparison of EPR-dosimetry with teeth: first results.

    PubMed

    Chumak, V; Bailiff, I; Baran, N; Bugai, A; Dubovsky, S; Fedosov, I; Finin, V; Haskell, E; Hayes, R; Ivannikov, A; Kenner, G; Kirillov, V; Khamidova, L; Kolesnik, S; Liidja, G; Likhtarev, I; Lippmaa, E; Maksimenko, V; Meijer, A; Minenko, V; Pasalskaya, L; Past, J; Puskar, J; Radchuk, V; Wieser, A

    1996-01-01

    Intercomparison of EPR-dosimetric techniques using tooth enamel had been performed in order to check whether the results produced by different laboratories are consistent and accurate. Participants were supposed to evaluate doses applied to pulverized enamel samples, using routine techniques from their laboratories. The intercomparison has demonstrated a great variety of methods used for dose reconstruction. Peculiarities of experimental approaches are discussed systematically in terms of procedure for recording the EPR-spectra, determination of the amplitude of the radiation induced signal, determination of the dose, and error propagation. PMID:9022185

  10. Use of polyphase continuous excitation based on the Frank sequence in EPR.

    PubMed Central

    Tseitlin, Mark; Quine, Richard W.; Eaton, Sandra S.; Eaton, Gareth R.

    2011-01-01

    Polyphase continuous excitation based on the Frank sequence is suggested as an alternative to single pulse excitation in EPR. The method allows reduction of the source power, while preserving the excitation bandwidth of a single pulse. For practical EPR implementation the use of a cross-loop resonator is essential to provide isolation between the spin system and the resonator responses to the excitation. Provided that a line broadening of about 5% is acceptable, the cumulative turning angle of the magnetization vector generated by the excitation sequence can be quite large and can produce signal amplitudes that are comparable to that achieved with a higher power 90° pulse. PMID:21737326

  11. Use of polyphase continuous excitation based on the Frank sequence in EPR.

    PubMed

    Tseitlin, Mark; Quine, Richard W; Eaton, Sandra S; Eaton, Gareth R

    2011-08-01

    Polyphase continuous excitation based on the Frank sequence is suggested as an alternative to single pulse excitation in EPR. The method allows reduction of the source power, while preserving the excitation bandwidth of a single pulse. For practical EPR implementation the use of a cross-loop resonator is essential to provide isolation between the spin system and the resonator responses to the excitation. Provided that a line broadening of about 5% is acceptable, the cumulative turning angle of the magnetization vector generated by the excitation sequence can be quite large and can produce signal amplitudes that are comparable to that achieved with a higher power 90° pulse. PMID:21737326

  12. EPR, mass, IR, electronic, and magnetic studies on copper(II) complexes of semicarbazones and thiosemicarbazones

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Gupta, Lokesh Kumar

    2005-01-01

    Copper(II) complexes having the general composition Cu(L) 2X 2 [where L = isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC), and 4-aminoacetophenone thiosemicarbazone (LLD) and X = Cl -, 1/2SO 42-] have been synthesized. All the Cu(II) complexes reported here have been characterized by elemental analyses, molar conductance, magnetic moment susceptibility, EI mass, 1H NMR, IR, EPR, and electronic spectral studies. All the complexes were found to have magnetic moments corresponding to one unpaired electrons. The possible geometries of the complexes were assigned on the basis of EPR, electronic, and infrared spectral studies.

  13. EPR evidence of extrinsic symmetry-breaking defects in nominally pure KTaO3

    NASA Astrophysics Data System (ADS)

    Pechenyi, A. P.; Glinchuk, M. D.; Azzoni, C. B.; Scardina, F.; Paleari, A.

    1995-05-01

    EPR measurements on nominally pure (undoped) KTaO3 single crystals at low temperature (4.2 K) are reported. Evidence is brought of impurity defects analyzed through the experimental spin-Hamiltonian parameters. Axial EPR spectra of Fe3+ in different cation positions are detected. An orthorhombic spectrum is found and attributed to Fe3+ substituting for K+ ions and involving nearby potassium vacancies as charge compensators. Manganese impurities are also observed following illumination of the sample to cause a change of the Mn valence state.

  14. EPR study of VO2+ doped glycine zinc sulphate single crystal

    NASA Astrophysics Data System (ADS)

    Prabakaran, R.; Subramanian, P.

    2015-06-01

    Single crystals Of GZS:VO2+ were grown by slow evaporation of solvent at room temperature. The EPR study was carried out at room temperature. Single crystal rotations in each of the three mutually orthogonal planes indicate single site occupation of VO2+ in the lattice. g and A tensors were calculated from the recorded EPR spectra. The principal values of g and A indicates existence of rhombic symmetry around the VO2+ ion. From the direction cosines of the g and A tensors, the locations of VO2+ in the lattice have been identified as substitutional site.

  15. EPR dosimetry of teeth in past and future accidents: a prospective look at a retrospective method

    SciTech Connect

    Haskell, E.H.; Kenner, G.H.; Hayes, R.B.; Chumak, V.; Shalom, S.

    1996-01-01

    Electron paramagnetic resonance spectroscopy (EPR) of tooth enamel is a relatively new technique for retrospective dosimetry that in the past two years has seen increasing effort towards its development and evaluation. Efforts have centered on determining the accuracy which may be achieved with current measurement techniques as well as the minimum doses detectable. The study was focused on evaluating some factors which influence the accuracy of EPR dosimetry of enamel. Reported are studies on sample intercomparisions, instrumental considerations, and effects of dental x-rays, environmental sunlight and ultraviolet radiation.

  16. EPR detection of the flux distribution in ceramic high-T c superconductors

    NASA Astrophysics Data System (ADS)

    Rakvin, B.; Požek, M.; Dulčić, A.

    1989-10-01

    EPR measurements were made on adsorbed diphenyl picrylhydrazil (DPPH) at the surface of a ceramic high- T c superconductor YBa 2Cu 3O 7. A significant broadening of the EPR linewidth was observed below the superconducting transition temperature T c. It is interpreted as a broadening due to the spatial distribution of the flux in the superconducting mixed state which is developed at the resonant magnetic field H 0 (H Cl ≪ H 0 ≪ H C2). The penetration depth of the magnetic field can be determined by this simple technique.

  17. A secure and efficient password-based user authentication scheme using smart cards for the integrated EPR information system.

    PubMed

    Lee, Tian-Fu; Chang, I-Pin; Lin, Tsung-Hung; Wang, Ching-Cheng

    2013-06-01

    The integrated EPR information system supports convenient and rapid e-medicine services. A secure and efficient authentication scheme for the integrated EPR information system provides safeguarding patients' electronic patient records (EPRs) and helps health care workers and medical personnel to rapidly making correct clinical decisions. Recently, Wu et al. proposed an efficient password-based user authentication scheme using smart cards for the integrated EPR information system, and claimed that the proposed scheme could resist various malicious attacks. However, their scheme is still vulnerable to lost smart card and stolen verifier attacks. This investigation discusses these weaknesses and proposes a secure and efficient authentication scheme for the integrated EPR information system as alternative. Compared with related approaches, the proposed scheme not only retains a lower computational cost and does not require verifier tables for storing users' secrets, but also solves the security problems in previous schemes and withstands possible attacks. PMID:23553734

  18. EPR and optical absorption studies of Cu2+ doped lithium maleate dihydrate single crystal

    NASA Astrophysics Data System (ADS)

    Kripal, Ram; Pandey, Shri Devi

    Electron paramagnetic resonance (EPR) study of Cu2+ doped lithium maleate dihydrate single crystal is done at liquid nitrogen temperature (LNT). Four hyperfine lines are observed in all directions, i.e. only a single site is observed. The spin Hamiltonian parameters are determined from EPR spectra: gx=2.100±0.002, gy=2.162±0.002, gz=2.215±0.002, Ax=(55±5)×10-4 cm-1, Ay=(52±5)×10-4 cm-1, Az=(50±5)×10-4 cm-1. The results indicate that the copper ion enters the lattice interstitially. Using the spin Hamiltonian parameters obtained from EPR study the ground state wave function of Cu2+ ion in the lattice is determined. The optical absorption study of Cu2+ doped lithium maleate dihydrate at room temperature is also performed. With the help of optical and EPR data, the nature of bonding in the complex is discussed.

  19. How can EPR spectroscopy help to unravel molecular mechanisms of flavin-dependent photoreceptors?

    PubMed Central

    Nohr, Daniel; Rodriguez, Ryan; Weber, Stefan; Schleicher, Erik

    2015-01-01

    Electron paramagnetic resonance (EPR) spectroscopy is a well-established spectroscopic method for the examination of paramagnetic molecules. Proteins can contain paramagnetic moieties in form of stable cofactors, transiently formed intermediates, or spin labels artificially introduced to cysteine sites. The focus of this review is to evaluate potential scopes of application of EPR to the emerging field of optogenetics. The main objective for EPR spectroscopy in this context is to unravel the complex mechanisms of light-active proteins, from their primary photoreaction to downstream signal transduction. An overview of recent results from the family of flavin-containing, blue-light dependent photoreceptors is given. In detail, mechanistic similarities and differences are condensed from the three classes of flavoproteins, the cryptochromes, LOV (Light-oxygen-voltage), and BLUF (blue-light using FAD) domains. Additionally, a concept that includes spin-labeled proteins and examination using modern pulsed EPR is introduced, which allows for a precise mapping of light-induced conformational changes. PMID:26389123

  20. EPR techniques to probe insertion and conformation of spin-labeled proteins in lipid bilayers.

    PubMed

    Bordignon, Enrica; Polyhach, Yevhen

    2013-01-01

    Electron paramagnetic resonance (EPR) spectroscopy of spin-labeled membrane proteins is a valuable biophysical technique to study structural details and conformational transitions of proteins close to their physiological environment, e.g., in liposomes, membrane bilayers, and nanodiscs. Unlike in nuclear magnetic resonance spectroscopy, having only one or few specific side chains labeled at a time with paramagnetic probes makes the size of the object under investigation irrelevant in terms of technique sensitivity. As a drawback, extensive site-directed mutagenesis is required in order to analyze the properties of the protein under investigation. EPR can provide detailed information on side chain dynamics of large membrane proteins or protein complexes embedded in membranes with an exquisite sensitivity for flexible regions and on water accessibility profiles across the membrane bilayer. Moreover, distances between the two spin-labeled side chains in membrane proteins can be detected with high precision in the 1.5-6 nm range at cryogenic temperatures. The application of EPR to membrane proteins still presents some challenges in terms of sample preparation, sensitivity, and data interpretation; thus no ready-to-go methodological recipes can be given. However this chapter describes the state of the art in the application of nitroxide-based site-directed spin labeling EPR to membrane proteins, with specific focus on the different types of information which can be obtained with continuous wave and pulsed techniques and on the challenges in sample preparation and data analysis for functional and structural membrane protein studies. PMID:23404283

  1. EPR policies for electronics in developing Asia: an adapted phase-in approach.

    PubMed

    Akenji, Lewis; Hotta, Yasuhiko; Bengtsson, Magnus; Hayashi, Shiko

    2011-09-01

    The amount of e-waste is growing rapidly in developing countries, and the health and environmental problems resulting from poor management of this waste have become a concern for policy makers. In response to these challenges, a number of Asian developing countries have been inspired by policy developments in OECD countries, and have drafted legislations based on the principle of extended producer responsibility (EPR). However, the experiences from developed countries show that a successful implementation of EPR policies requires adequate institutions and sufficient administrative capacity. Even advanced countries are thus facing difficulties. This paper concludes from existing literature and from the authors' own observations that there seems to be a mismatch between the typical policy responses to e-waste problems in developing Asia and the capacity for successful implementation of such policies. It also notes that the e-waste situation in developing Asian countries is further complicated by a number of additional factors, such as difficulties in identifying producers, import of used electronic products and e-waste (sometimes illegal), and the existence of a strong informal waste sector. Given these challenges, the authors conclude that comprehensive EPR policy schemes of the kind that have been implemented in some advanced countries are not likely to be effective. The paper therefore proposes an alternative phase-in approach whereby developing Asian countries are able to move gradually towards EPR systems. It argues that this approach would be more feasible, and discusses what could be the key building blocks of each implementation stage. PMID:21730041

  2. Increasing sensitivity of pulse EPR experiments using echo train detection schemes

    NASA Astrophysics Data System (ADS)

    Mentink-Vigier, F.; Collauto, A.; Feintuch, A.; Kaminker, I.; Tarle, V.; Goldfarb, D.

    2013-11-01

    Modern pulse EPR experiments are routinely used to study the structural features of paramagnetic centers. They are usually performed at low temperatures, where relaxation times are long and polarization is high, to achieve a sufficient Signal/Noise Ratio (SNR). However, when working with samples whose amount and/or concentration are limited, sensitivity becomes an issue and therefore measurements may require a significant accumulation time, up to 12 h or more. As the detection scheme of practically all pulse EPR sequences is based on the integration of a spin echo - either primary, stimulated or refocused - a considerable increase in SNR can be obtained by replacing the single echo detection scheme by a train of echoes. All these echoes, generated by Carr-Purcell type sequences, are integrated and summed together to improve the SNR. This scheme is commonly used in NMR and here we demonstrate its applicability to a number of frequently used pulse EPR experiments: Echo-Detected EPR, Davies and Mims ENDOR (Electron-Nuclear Double Resonance), DEER (Electron-Electron Double Resonance|) and EDNMR (Electron-Electron Double Resonance (ELDOR)-Detected NMR), which were combined with a Carr-Purcell-Meiboom-Gill (CPMG) type detection scheme at W-band. By collecting the transient signal and integrating a number of refocused echoes, this detection scheme yielded a 1.6-5 folds SNR improvement, depending on the paramagnetic center and the pulse sequence applied. This improvement is achieved while keeping the experimental time constant and it does not introduce signal distortion.

  3. High-pressure EPR reveals conformational equilibria and volumetric properties of spin-labeled proteins

    PubMed Central

    McCoy, John; Hubbell, Wayne L.

    2011-01-01

    Identifying equilibrium conformational exchange and characterizing conformational substates is essential for elucidating mechanisms of function in proteins. Site-directed spin labeling has previously been employed to detect conformational changes triggered by some event, but verifying conformational exchange at equilibrium is more challenging. Conformational exchange (microsecond–millisecond) is slow on the EPR time scale, and this proves to be an advantage in directly revealing the presence of multiple substates as distinguishable components in the EPR spectrum, allowing the direct determination of equilibrium constants and free energy differences. However, rotameric exchange of the spin label side chain can also give rise to multiple components in the EPR spectrum. Using spin-labeled mutants of T4 lysozyme, it is shown that high-pressure EPR can be used to: (i) demonstrate equilibrium between spectrally resolved states, (ii) aid in distinguishing conformational from rotameric exchange as the origin of the resolved states, and (iii) determine the relative partial molar volume () and isothermal compressibility () of conformational substates in two-component equilibria from the pressure dependence of the equilibrium constant. These volumetric properties provide insight into the structure of the substates. Finally, the pressure dependence of internal side-chain motion is interpreted in terms of volume fluctuations on the nanosecond time scale, the magnitude of which may reflect local backbone flexibility. PMID:21205903

  4. EPR and ENDOR of Nd^3+ in congruent and stoichiometric LiNbO3

    NASA Astrophysics Data System (ADS)

    Grachev, Valentin; Malovichko, Galina; Munro, Mark

    2007-05-01

    Since many years Lithium Niobate (LN) is of great interest for both fundamental science and applications because of the unusual richness of its ferro-, pyro- and piezoelectric properties. Conventional LN crystals, grown from a congruent melt with lithium deficiency, contain some percent of intrinsic defects. Samples grown under special conditions from melts, to which potassium has been added, have reduced contents of intrinsic defects and lower disorder (stoichiometric samples). Both congruent and stoichiometric crystals doped with neodymium were studied with the help of the electron paramagnetic resonance, EPR. Tremendous narrowing of the EPR lines in stoichiometric samples in comparison with congruent ones allowed us to distinguish four non-equivalent centers, as well as line splitting caused by hyperfine interaction of neodymium electrons with nuclear spins of magnetic isotopes ^143Nd and ^145Nd. One of the centers has axial C3 symmetry, whereas others have lowest C1 symmetry due to presence of intrinsic defects or/and charge compensation defects in the near neighborhood of Nd^3+. Narrow EPR lines allowed us also to investigate Electron Nuclear Double Resonance (ENDOR). Structures of the Nd^3+ centers derived from the EPR/ENDOR data and effects produced by micro- and macro-imperfections of LN crystals are discussed. To cite this abstract, use the following reference: http://meetings.aps.org/link/BAPS.2007.NWS07.C1.4

  5. 34 GHz EPR FTIR spectra of chromatographically separated Boscan asphaltene fractions

    SciTech Connect

    Malhotra, V.M. ); Buckmaster, H.A. )

    1989-03-01

    The authors report on their re-examination of the 34 GHz and Fourier transform infrared (FTIR) measurements on three fractions of Boxcan asphaltene separated by the gel permeation chromatography (GPC) technique. The authors attempted to determine various types of vanadium coordination in GPC fractions by their partial combustion and subsequent EPR AND FTIR measurements.

  6. Estimation of the absorbed dose in radiation-processed food. 4. EPR measurements on eggshell

    SciTech Connect

    Desrosiers, M.F.; Le, F.G. ); Harewood, P.M.; Josephson, E.S. ); Montesalvo, M. )

    1993-09-01

    Fresh whole eggs treated with ionizing radiation for Salmonellae control testing. The eggshell was then removed and examined by electron paramagnetic resonance (EPR) spectroscopy to determine if EPR could be used to (1) distinguish irradiated from unirradiated eggs and (2) assess the absorbed dose. No EPR signals were detected in unirradiated eggs, while strong signals were measurable for more than 200 days after irradiation. Although a number of EPR signals were measured, the most intense resonance (g = 2.0019) was used for dosimetry throughout the study. This signal was observed to increase linearly with dose (up to [approximately]6 kGy), which decayed [approximately]20% within the first 5 days after irradiation and remained relatively constant thereafter. The standard added-dose method was used to assess, retrospectively, the dose to eggs processed at 0.2, 0.7, and 1.4 kGy. Relatively good results were obtained when measurement was made on the day the shell was reirradiated; with this procedure estimates were better for shell processed at the lower doses.

  7. DFT calculations of EPR parameters of transition metal complexes: Implications for catalysis

    SciTech Connect

    Saladino, Alexander C.; Larsen, Sarah C.

    2005-07-15

    Transition metal and ligand hyperfine coupling constants for paramagnetic vanadium and copper model complexes have been calculated using DFT methods that are available in commercial software packages. Variations in EPR parameters with ligand identity and ligand orientation are two of the trends that have been investigated with DFT calculations. For example, the systematic variation of the vanadium hyperfine coupling constant with orientation for an imidazole ligand in a VO2+ complex has been observed experimentally and has also been reproduced by DFT calculations. Similarly, changes in the vanadium hyperfine coupling constant with ligand binding have been calculated using model complexes and DFT methods. DFT methods were also used to calculate ligand hyperfine coupling constants in transition metal systems. The variation of the proton hyperfine coupling constant with water ligand orientation was investigated for [VO(H2O)5]2+ and the results were used to interpret high resolution EPR data of VO2+-exchanged zeolites. Nitrogen hyperfine and quadrupole coupling constants for VO2+ model complexes were calculated and compared with experimental data. The computational results were used to enhance the interpretation of the EPR data for vanadium-exchanged zeolites which are promising catalytic materials. The implications of the DFT calculations of EPR parameters with respect to catalysis will be discussed

  8. EPR on Y-ceramics and Bi-vitroceramics doped with S state paramagnetic ions

    NASA Astrophysics Data System (ADS)

    Simon, Simion; Ilonca, Gheorghe; Barbur, Ioan; Ardelean, Ioan; Redac, Radu

    1989-12-01

    The effect of Gd doping and of thermal history on the EPR spectra from Y 1-xGd xBa 2Cu 3O 7-δ ceramics and, for the first time, from Bi 2-xGd xSr 2Ca 2O z vitroceramics was investigated. The results were correlated with the superconducting properties of the studied samples.

  9. Sonoporation enhances liposome accumulation and penetration in tumors with low EPR.

    PubMed

    Theek, Benjamin; Baues, Maike; Ojha, Tarun; Möckel, Diana; Veettil, Seena Koyadan; Steitz, Julia; van Bloois, Louis; Storm, Gert; Kiessling, Fabian; Lammers, Twan

    2016-06-10

    The Enhanced Permeability and Retention (EPR) effect is a highly variable phenomenon. To enhance EPR-mediated passive drug targeting to tumors, several different pharmacological and physical strategies have been evaluated over the years, including e.g. TNFα-treatment, vascular normalization, hyperthermia and radiotherapy. Here, we systematically investigated the impact of sonoporation, i.e. the combination of ultrasound (US) and microbubbles (MB), on the tumor accumulation and penetration of liposomes. Two different MB formulations were employed, and their ability to enhance liposome accumulation and penetration was evaluated in two different tumor models, which are both characterized by relatively low levels of EPR (i.e. highly cellular A431 epidermoid xenografts and highly stromal BxPC-3 pancreatic carcinoma xenografts). The liposomes were labeled with two different fluorophores, enabling in vivo computed tomography/fluorescence molecular tomography (CT-FMT) and ex vivo two-photon laser scanning microscopy (TPLSM). In both models, in spite of relatively high inter- and intra-individual variability, a trend towards improved liposome accumulation and penetration was observed. In treated tumors, liposome concentrations were up to twice as high as in untreated tumors, and sonoporation enhanced the ability of liposomes to extravasate out of the blood vessels into the tumor interstitium. These findings indicate that sonoporation may be a useful strategy for improving drug targeting to tumors with low EPR. PMID:26878973

  10. Recognising Workplace Learning: The Emerging Practices of e-RPL and e-PR

    ERIC Educational Resources Information Center

    Cameron, Roslyn

    2012-01-01

    Purpose: The use of e-portfolios in recognition of prior learning (RPL) processes in workplace and professional practice contexts has attracted little attention in the literature due to its emergent nature. This study seeks to explore the growing incidence of e-portfolio-based RPL (e-RPL) and professional recognition (e-PR) processes in Australia…

  11. Multifrequency Pulsed EPR Studies of Biologically Relevant Manganese(II) Complexes

    PubMed Central

    Stich, T. A.; Lahiri, S.; Yeagle, G.; Dicus, M.; Brynda, M.; Gunn, A.; Aznar, C.; DeRose, V. J.; Britt, R. D.

    2011-01-01

    Electron paramagnetic resonance studies at multiple frequencies (MF EPR) can provide detailed electronic structure descriptions of unpaired electrons in organic radicals, inorganic complexes, and metalloenzymes. Analysis of these properties aids in the assignment of the chemical environment surrounding the paramagnet and provides mechanistic insight into the chemical reactions in which these systems take part. Herein, we present results from pulsed EPR studies performed at three different frequencies (9, 31, and 130 GHz) on [Mn(II)(H2O)6]2+, Mn(II) adducts with the nucleotides ATP and GMP, and the Mn(II)-bound form of the hammerhead ribozyme (MnHH). Through line shape analysis and interpretation of the zero-field splitting values derived from successful simulations of the corresponding continuous-wave and field-swept echo-detected spectra, these data are used to exemplify the ability of the MF EPR approach in distinguishing the nature of the first ligand sphere. A survey of recent results from pulsed EPR, as well as pulsed electron-nuclear double resonance and electron spin echo envelope modulation spectroscopic studies applied to Mn(II)-dependent systems, is also presented. PMID:22190766

  12. Tight binding study of transition ions in silicon and E.P.R. spectra

    NASA Astrophysics Data System (ADS)

    Pecheur, P.; Toussaint, G.

    1983-02-01

    A tight binding scheme is used to study the electronic structure of transition ions in silicon. Self consistency and spin polarization are introduced in a simple way. Results are obtained for interstitial and substitutional Cr, Mn and Fe impurities. They are compared to E.P.R. experiments and cluster Xα results.

  13. Electronic paramagnetic resonance (EPR) for the study of ascorbyl radical and lipid radicals in marine organisms.

    PubMed

    González, Paula Mariela; Aguiar, María Belén; Malanga, Gabriela; Puntarulo, Susana

    2013-08-01

    Electron paramagnetic resonance (EPR) spectroscopy detects the presence of radicals of biological interest, such as ascorbyl radical (A(•)) and lipid radicals. A(•) is easily detectable by EPR even in aqueous solution at room-temperature. Under oxidative conditions leading to changes in total ascorbate (AH(-)) content, the A(•)/AH(-) ratio could be used to estimate early oxidative stress in the hydrophilic milieu. This methodology was applied to a wide range of aquatic systems including algae, sea urchin, limpets, bivalves and fish, under physiological and oxidative stress conditions as well. The A(•)/AH(-) ratio reflected the state of one part of the oxidative defense system and provided an early and simple diagnosis of environmental stressing conditions. Oxidative damage to lipids was assessed by the EPR-sensitive adduct formation that correlates well with cell membrane damage with no interference from other biological compounds. Probe instability, tissue metabolism, and lack of spin specificity are drawback factors for employing EPR for in vivo determination of free radicals. However, the dependability of this technique, mostly by combining it with other biochemical strategies, enhances the value of these procedures as contributors to the knowledge of oxidative condition in aquatic organisms. PMID:23485428

  14. EPR Studies of Spin-Spin Exchange Processes: A Physical Chemistry Experiment.

    ERIC Educational Resources Information Center

    Eastman, Michael P.

    1982-01-01

    Theoretical background, experimental procedures, and analysis of experimental results are provided for an undergraduate physical chemistry experiment on electron paramagnetic resonance (EPR) linewidths. Source of line broadening observed in a spin-spin exchange process between radicals formed in aqueous solutions of potassium peroxylamine…

  15. EPR study of free-radical structure and conformation in pyridoxine hydrochloride single crystal

    NASA Astrophysics Data System (ADS)

    Masiakowski, Jerzy T.; Krzyminiewski, Ryszard; Pietrzak, Jerzy

    1985-05-01

    Numerical analysis of experimental EPR spectra of γ-irradiated single crystals of pyridoxine hydrochloride (vitamin B 6) allowed determination of the structure of the radical formed. Six hyperfine couplings were distinguished. The geometrical model of the radical was found to be in good agreement with the geometry expected from the crystal structure. Semi-empirical INDO and CNDO calculations were performed.

  16. VO2+ ions in zinc lead borate glasses studied by EPR and optical absorption techniques.

    PubMed

    Prakash, P Giri; Rao, J Lakshmana

    2005-09-01

    Electron paramagnetic resonance (EPR) and optical absorption spectra of vanadyl ions in zinc lead borate (ZnO-PbO-B2O3) glass system have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of VO2+ ions. The values of spin-Hamiltonian parameters indicate that the VO2+ ions in zinc lead borate glasses were present in octahedral sites with tetragonal compression and belong to C4V symmetry. The spin-Hamiltonian parameters g and A are found to be independent of V2O5 content and temperature but changing with ZnO content. The decrease in Deltag( parallel)/Deltag( perpendicular) value with increase in ZnO content indicates that the symmetry around VO2+ ions is more octahedral. The decrease in intensity of EPR signal above 10 mol% of V2O5 is attributed to a fall in the ratio of the number of V4+ ions (N4) to the number of V5+ ions (N5). The number of spins (N) participating in resonance was calculated as a function of temperature for VO2+ doped zinc lead borate glass sample and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility was calculated at various temperatures and the Curie constant was evaluated from the 1/chi-T graph. The optical absorption spectra show single absorption band due to VO2+ ions in tetragonally distorted octahedral sites. PMID:16043053

  17. Gamma-irradiated dry fruits. An example of a wide variety of long-time dependent EPR spectra.

    PubMed

    Yordanov, Nicola D; Pachova, Zdravka

    2006-03-13

    EPR spectra of dry, sugar containing fruits--raisins, sultanas, figs, dates, peaches, blue plums and chokeberry recorded before and after irradiation with gamma-rays, are reported. It is shown that weak singlet EPR line with 2.0031+/-0.0005 can be recorded before irradiation of seeds, stones or skin of chokeberry, figs and raisins as well as flesh of blue plum, raisins and peaches. EPR signals of various shape are distinguished after irradiation in different parts of the fruits, as well as in randomly cut pieces of them: As a result, randomly cut pieces of dry fruits suitable for EPR studies, containing various constituents, exhibit different in shape and intensity EPR spectra. Kinetic studies followed for 1 year on the time stability of all reported EPR signals indicate that intensity ratio between the simultaneously appearing EPR signals in particular fruit varies from 1:20 immediately after irradiation to 1:0.5 at the end of the period. These observations open a new possibility for identification of irradiated fruits - using the magnitude of the intensity ratio to find the approximate date of radiation processing in the first ca. 30-100 days. PMID:16497546

  18. Electronic structure of the primary electron donor of Blastochloris viridis heterodimer mutants : high field EPR study.

    SciTech Connect

    Ponomarenko, N. S.; Poluektov, O. G.; Bylina, E. J.; Norris, J. R.; Chemical Sciences and Engineering Division; Univ. of Chicago

    2010-09-01

    High-field electron paramagnetic resonance (HF EPR) has been employed to investigate the primary electron donor electronic structure of Blastochloris viridis heterodimer mutant reaction centers (RCs). In these mutants the amino acid substitution His(M200)Leu or His(L173)Leu eliminates a ligand to the primary electron donor, resulting in the loss of a magnesium in one of the constituent bacteriochlorophylls (BChl). Thus, the native BChl/BChl homodimer primary donor is converted into a BChl/bacteriopheophytin (BPhe) heterodimer. The heterodimer primary donor radical in chemically oxidized RCs exhibits a broadened EPR line indicating a highly asymmetric distribution of the unpaired electron over both dimer constituents. Observed triplet state EPR signals confirm localization of the excitation on the BChl half of the heterodimer primary donor. Theoretical simulation of the triplet EPR lineshapes clearly shows that, in the case of mutants, triplet states are formed by an intersystem crossing mechanism in contrast to the radical pair mechanism in wild type RCs. Photooxidation of the mutant RCs results in formation of a BPhe anion radical within the heterodimer pair. The accumulation of an intradimer BPhe anion is caused by the substantial loss of interaction between constituents of the heterodimer primary donor along with an increase in the reduction potential of the heterodimer primary donor D/D{sup +} couple. This allows oxidation of the cytochrome even at cryogenic temperatures and reduction of each constituent of the heterodimer primary donor individually. Despite a low yield of primary donor radicals, the enhancement of the semiquinone-iron pair EPR signals in these mutants indicates the presence of kinetically viable electron donors.

  19. EPR Methods for Biological Cu(II): L-Band CW and NARS

    PubMed Central

    Bennett, Brian; Kowalski, Jason

    2016-01-01

    Copper has many roles in biology that involve the change of coordination sphere and/or oxidation state of the copper ion. Consequently, the study of copper in heterogeneous environments is an important area in biophysics. EPR is a primary technique for the investigation of paramagnetic copper, which is usually the isolated Cu(II) ion, but sometimes as Cu(II) in different oxidation states of multi-transition ion clusters. The gross geometry of the coordination environment of Cu(II) can often be determined from a simple inspection of the EPR spectrum, recorded in the traditional X-band frequency range (9 – 10 GHz). Identification and quantitation of the coordinating ligand atoms, however, is not so straightforward. In particular, analysis of the superhyperfine structure on the EPR spectrum, to determine the number of coordinated nitrogen atoms, is fraught with difficulty at X-band, despite the observation that the overwhelming number of EPR studies of Cu(II) in the literature have been carried out at X-band. Greater reliability has been demonstrated at S-band (3 – 4 GHz), using the low-field parallel (gz) features. However, analysis relies on clear identification of the outermost superhyperfine line, which has the lowest intensity of all the spectral features. Computer simulations have subsequently indicated that the much more intense perpendicular region of the spectrum can be reliably interpreted at L-band (2 GHz). The present work describes the development of L-band EPR of Cu(II) into a routine method, that is applicable to biological samples. PMID:26478491

  20. Application of EPR spectroscopy to the examination of pro-oxidant activity of coffee.

    PubMed

    Krakowian, Daniel; Skiba, Dominik; Kudelski, Adam; Pilawa, Barbara; Ramos, Paweł; Adamczyk, Jakub; Pawłowska-Góral, Katarzyna

    2014-05-15

    Free radicals present in coffee may be responsible for exerting toxic effects on an organism. The objectives of this work were to compare free radicals properties and concentrations in different commercially available coffees, in solid and liquid states, and to determine the effect of roasting on the formation of free radicals in coffee beans of various origins. The free radicals content of 15 commercially available coffees (solid and liquid) was compared and the impact of processing examined using electron paramagnetic resonance (EPR) spectroscopy at X-band (9.3 GHz). First derivative EPR spectra were measured at microwave power in the range of 0.7-70 mW. The following parameters were calculated for EPR spectra: amplitude (A), integral intensity (I), and line-width (ΔBpp); g-Factor was obtained from resonance condition. Our study showed that free radicals exist in green coffee beans (10(16) spin/g), roasted coffee beans (10(18) spin/g), and in commercially available coffee (10(17)-10(18) spin/g). Free radical concentrations were higher in solid ground coffee than in instant or lyophilised coffee. Continuous microwave saturation indicated homogeneous broadening of EPR lines from solid and liquid commercial coffee samples as well as green and roasted coffee beans. Slow spin-lattice relaxation processes were found to be present in all coffee samples tested, solid and liquid commercial coffees as well as green and roasted coffee beans. Higher free radicals concentrations were obtained for both the green and roasted at 240 °C coffee beans from Peru compared with those originating from Ethiopia, Brazil, India, or Colombia. Moreover, more free radicals occurred in Arabica coffee beans roasted at 240 °C than Robusta. EPR spectroscopy is a useful method of examining free radicals in different types of coffee. PMID:24423509

  1. Digitally generated excitation and near-baseband quadrature detection of rapid scan EPR signals

    PubMed Central

    Quine, Richard W.; Rinard, George A.; Eaton, Sandra S.; Eaton, Gareth R.

    2014-01-01

    The use of multiple synchronized outputs from an AWG provides the opportunity to perform EPR experiments differently than by conventional EPR. We report a method for reconstructing the quadrature EPR spectrum from periodic signals that are generated with sinusoidal magnetic field modulation such as continuous wave (CW), multiharmonic, or rapid scan experiments. The signal is down-converted to an intermediate frequency (IF) that is less than the field scan or field modulation frequency and then digitized in a single channel. This method permits use of a high-pass analog filter before digitization to remove the strong non-EPR signal at the IF, that might otherwise overwhelm the digitizer. The IF is the difference between two synchronized X-band outputs from a Tektronix AWG 70002A arbitrary waveform generator (AWG), one of which is for excitation and the other is the reference for down-conversion. To permit signal averaging, timing was selected to give an exact integer number of full cycles for each frequency. In the experiments reported here the IF was 5 kHz and the scan frequency was 40 kHz. To produce sinusoidal rapid scans with a scan frequency eight times IF, a third synchronized output generated a square wave that was converted to a sine wave. The timing of the data acquisition with a Bruker SpecJet II was synchronized by an external clock signal from the AWG. The baseband quadrature signal in the frequency domain was reconstructed. This approach has the advantages that (i) the non-EPR response at the carrier frequency is eliminated, (ii) both real and imaginary EPR signals are reconstructed from a single physical channel to produce an ideal quadrature signal, and (iii) signal bandwidth does not increase relative to baseband detection. Spectra were obtained by deconvolution of the reconstructed signals for solid BDPA (1,3-bisdiphenylene-2-phenylallyl) in air, 0.2 mM trityl OX63 in water, 15N perdeuterated tempone, and a nitroxide with a 0.5 G partially

  2. Digitally generated excitation and near-baseband quadrature detection of rapid scan EPR signals.

    PubMed

    Tseitlin, Mark; Yu, Zhelin; Quine, Richard W; Rinard, George A; Eaton, Sandra S; Eaton, Gareth R

    2014-10-30

    The use of multiple synchronized outputs from an arbitrary waveform generator (AWG) provides the opportunity to perform EPR experiments differently than by conventional EPR. We report a method for reconstructing the quadrature EPR spectrum from periodic signals that are generated with sinusoidal magnetic field modulation such as continuous wave (CW), multiharmonic, or rapid scan experiments. The signal is down-converted to an intermediate frequency (IF) that is less than the field scan or field modulation frequency and then digitized in a single channel. This method permits use of a high-pass analog filter before digitization to remove the strong non-EPR signal at the IF, that might otherwise overwhelm the digitizer. The IF is the difference between two synchronized X-band outputs from a Tektronix AWG 70002A, one of which is for excitation and the other is the reference for down-conversion. To permit signal averaging, timing was selected to give an exact integer number of full cycles for each frequency. In the experiments reported here the IF was 5kHz and the scan frequency was 40kHz. To produce sinusoidal rapid scans with a scan frequency eight times IF, a third synchronized output generated a square wave that was converted to a sine wave. The timing of the data acquisition with a Bruker SpecJet II was synchronized by an external clock signal from the AWG. The baseband quadrature signal in the frequency domain was reconstructed. This approach has the advantages that (i) the non-EPR response at the carrier frequency is eliminated, (ii) both real and imaginary EPR signals are reconstructed from a single physical channel to produce an ideal quadrature signal, and (iii) signal bandwidth does not increase relative to baseband detection. Spectra were obtained by deconvolution of the reconstructed signals for solid BDPA (1,3-bisdiphenylene-2-phenylallyl) in air, 0.2mM trityl OX63 in water, (15)N perdeuterated tempone, and a nitroxide with a 0.5G partially-resolved proton

  3. Digitally generated excitation and near-baseband quadrature detection of rapid scan EPR signals

    NASA Astrophysics Data System (ADS)

    Tseitlin, Mark; Yu, Zhelin; Quine, Richard W.; Rinard, George A.; Eaton, Sandra S.; Eaton, Gareth R.

    2014-12-01

    The use of multiple synchronized outputs from an arbitrary waveform generator (AWG) provides the opportunity to perform EPR experiments differently than by conventional EPR. We report a method for reconstructing the quadrature EPR spectrum from periodic signals that are generated with sinusoidal magnetic field modulation such as continuous wave (CW), multiharmonic, or rapid scan experiments. The signal is down-converted to an intermediate frequency (IF) that is less than the field scan or field modulation frequency and then digitized in a single channel. This method permits use of a high-pass analog filter before digitization to remove the strong non-EPR signal at the IF, that might otherwise overwhelm the digitizer. The IF is the difference between two synchronized X-band outputs from a Tektronix AWG 70002A, one of which is for excitation and the other is the reference for down-conversion. To permit signal averaging, timing was selected to give an exact integer number of full cycles for each frequency. In the experiments reported here the IF was 5 kHz and the scan frequency was 40 kHz. To produce sinusoidal rapid scans with a scan frequency eight times IF, a third synchronized output generated a square wave that was converted to a sine wave. The timing of the data acquisition with a Bruker SpecJet II was synchronized by an external clock signal from the AWG. The baseband quadrature signal in the frequency domain was reconstructed. This approach has the advantages that (i) the non-EPR response at the carrier frequency is eliminated, (ii) both real and imaginary EPR signals are reconstructed from a single physical channel to produce an ideal quadrature signal, and (iii) signal bandwidth does not increase relative to baseband detection. Spectra were obtained by deconvolution of the reconstructed signals for solid BDPA (1,3-bisdiphenylene-2-phenylallyl) in air, 0.2 mM trityl OX63 in water, 15N perdeuterated tempone, and a nitroxide with a 0.5 G partially

  4. VHF EPR quantitation and speciation of organic sulfur in coal. Technical report, 1 March--31 May 1994

    SciTech Connect

    Clarkson, R.B.; Belford, R.L.

    1994-09-01

    The existence of free electrons in coals` natural state offers a great attraction for Electron Paramagnetic Resonance (EPR) analysis to aid in the study of the structure and composition of coal. This direct and non-destructive approach to coal analysis has been hindered by the problem of resolution using the conventional 9.5 GHz EPR spectrometers. In the past few years, the authors have developed techniques including W-band Very High Frequency EPR spectroscopy as a means of determining the quantity and structure of organic sulfur in native and desulfurized coals. The state-of-the-art 95 GHz (W-band) EPR spectrometer which they have constructed shows a well resolved spectrum including the interaction between unpaired electrons and the heteroatom like sulfur. The spectra also provide quantitative as well as qualitative information regarding different sulfur species. In this quarter, the authors have been concentrating their efforts on developing a new standard protocol in handling and preparing the coal samples for EPR measurements to provide a quantitative comparison between the EPR spectra of coal in the natural state and desulfurized. Sixteen new coal samples, both native and desulfurized, have been provided to us as well as to the University of Kentucky for analysis by XANES. These samples have been run in both laboratories. The results from these samples, which were kept in an oxygen-free environment, are compared to those of 10 previous samples, which were air-oxidized. Significant differences in the EPR spectra of air-oxidized and oxygen free samples are noted; results from Kentucky are not yet available. Desulfurized samples show a significant decrease in organic sulfur as measured by the VHF-EPR method.

  5. Vhf EPR quantitation and speciation of organic sulfur in coal. [Quarterly] technical report, December 1, 1993--February 28, 1994

    SciTech Connect

    Clarkson, R.B.; Belford, R.I.

    1994-06-01

    The existence of free electrons in coals` natural site offers a great attraction for Electron Paramagnetic Resonance (EPR) analysis to aid in the study of the structure and composition of coal. This direct and non-destructive approach to coal analysis has been hindered by the problem of resolution using the conventional 9.5 GHz EPR spectrometers. In the past few years, we have developed techniques including W-band Very High Frequency EPR spectroscopy as a means of determining the quantity and structure of organic sulfur in native and desulfurized coals. The state of the art 95 GHz (W-band) EPR spectrometer which we have constructed shows a well resolved spectrum including the interaction between unpaired electrons and the heteroatom like sulfur. The spectra also provide quantitative as well as qualitative information regarding different sulfur species. In collaboration with researchers at the University of Kentucky, we are also analyzing the result of desulfurization techniques on the presence of various sulfur species in coal. In the past, we have tried to synthesize various model compounds comparing their W-band spectra with other models, the predictions of theoretical models, and with the W-band spectra of coal specimens. In this quarter, we have been concentrating our efforts on developing a new standard protocol in handling and preparing the coal samples for EPR measurements to provide a quantitative comparison between the EPR spectra of coal in the natural state and desulfurized. Ten coal samples, both native and desulfurized, have been provided to us. These samples have been run in both laboratories. The simulation of coal EPR spectra has been carried out using several mathematical models. EPR results now are being compared with XANES data.

  6. Theoretical investigation of the optical and EPR parameters for VO 2+ion in some complexes

    NASA Astrophysics Data System (ADS)

    Kalfaoğlu, Emel; Karabulut, Bünyamin

    2012-04-01

    The molecular orbital coefficients and the EPR parameters of trisodium citrate dihydrate, sodium hydrogen oxalate monohydrate, potassium d-gluconate monohydrate and L-Alanine vanadyl complexes are calculated theoretically. Two d-d transition spectra and EPR parameters for the VO2+ complex are calculated theoretically by using crystal-field theory. The calculated g and A paramaters have indicated that paramagnetic center is axially symmetric. Having the relations of g∥A⊥ for VO2+ ions, it can be concluded that VO2+ ions are located in distorted octahedral sites (C4v) elongated along the z-axis and the ground state of the paramagnetic electron is dxy.

  7. AC susceptibility and EPR investigations of superspin dynamics in magnetite nanoparticles

    NASA Astrophysics Data System (ADS)

    Price, Alex D.

    In this investigation we use two complementary techniques to distinguish between superparamagnetic blocking (SPB) and superspin-glass (SSG) freezing phenomena in magnetite nanoparticles. While these manifestations of the superspin dynamics are fundamentally different, they have similar "signatures", especially in dc-magnetization experiments. Even if ac-susceptibility measurements are employed, careful use of mathematical models to analyze the data are needed to uncover which type of phenomena (SPB or SSG freezing) occurs within the material. Yet, by utilizing electron paramagnetic resonance (EPR) on a 10 nm Fe3O4 nano-powder as well as on a ferrofluid (based on the same nanoparticle ensemble) we found a very distinct difference in the absorption spectra between the two samples, which indicates markedly different EPR signatures from SPB and SSG freezing behaviors.

  8. EPR study of gamma irradiated DL-methionine sulfone single crystals

    NASA Astrophysics Data System (ADS)

    Karabulut, Bünyamin; Yıldırım, İlkay

    2015-12-01

    Electron paramagnetic resonance (EPR) study of gamma irradiated dl-2-amino-4-(Methylsulfonyl) butyric acid (dl-methionine sulfone, hereafter dl-ABA) single crystals and powder was performed at room temperature. It has been found that this compound indicates the existence of C. O2- and N. H2 radicals after γ-irradiation. While g and hyperfine splitting values for the N. H2 radical were observed, for the C. O2- radical, only the g factor was measured. The EPR spectra have shown that N. H2 radical has two groups each having two distinct sites and C. O2- radical has one site. The principal g and hyperfine values for all sites were analyzed.

  9. Identification and dose assessment of irradiated cardamom and cloves by EPR spectrometry

    NASA Astrophysics Data System (ADS)

    Beshir, W. B.

    2014-03-01

    The use of electron paramagnetic resonance spectroscopy to accurately distinguish irradiated from unirradiated cardamom and cloves and assesses the absorbed dose to radiation processed cardamom and cloves are examined. The results were successful for identifying both irradiated and unirradiated cardamom and cloves. Additive reirradiation of cardamom and cloves produces reproducible dose-response functions, which can be used to assess the initial dose by back-extrapolation. Third degree polynomial function was used to fit the EPR signal/dose curves. It was found that this 3rd degree polynomial function provides satisfactory results without correction of decay for free radicals. The stability of the radiation induced EPR signal of irradiated cardamom and cloves were studied over a storage period of almost 8 months.

  10. Analysis of Two-Player Quantum Games in an EPR Setting Using Clifford's Geometric Algebra

    PubMed Central

    Chappell, James M.; Iqbal, Azhar; Abbott, Derek

    2012-01-01

    The framework for playing quantum games in an Einstein-Podolsky-Rosen (EPR) type setting is investigated using the mathematical formalism of geometric algebra (GA). The main advantage of this framework is that the players' strategy sets remain identical to the ones in the classical mixed-strategy version of the game, and hence the quantum game becomes a proper extension of the classical game, avoiding a criticism of other quantum game frameworks. We produce a general solution for two-player games, and as examples, we analyze the games of Prisoners' Dilemma and Stag Hunt in the EPR setting. The use of GA allows a quantum-mechanical analysis without the use of complex numbers or the Dirac Bra-ket notation, and hence is more accessible to the non-physicist. PMID:22279525

  11. Nano-emulsions of fluorinated trityl radicals as sensors for EPR oximetry

    NASA Astrophysics Data System (ADS)

    Charlier, N.; Driesschaert, B.; Wauthoz, N.; Beghein, N.; Préat, V.; Amighi, K.; Marchand-Brynaert, J.; Gallez, B.

    2009-04-01

    This article reports the development and evaluation of two nano-emulsions (F45T-03/HFB and F15T-03/PFOB) containing fluorinated trityl radicals dissolved in perfluorocarbons. Preparation with a high-pressure homogenizer conferred sub-micronic size to both nano-emulsions. In vitro and in vivo EPR spectroscopy showed that the nano-emulsions had much greater oxygen sensitivity than the hydrophilic trityl, CT-03. In vivo experiments in rodents confirmed the ability of the nano-emulsions to follow the changes in oxygen concentration after induced ischemia. Histological evaluation of the tissue injected with the nano-emulsions revealed some acute toxicity for the F45T-03/HFB nano-emulsion but none for the F15T-03/PFOB nano-emulsion. These new formulations should be considered for further EPR oximetry experiments in pathophysiological situations where subtle changes in tissue oxygenation are expected.

  12. Nano-emulsions of fluorinated trityl radicals as sensors for EPR oximetry.

    PubMed

    Charlier, N; Driesschaert, B; Wauthoz, N; Beghein, N; Préat, V; Amighi, K; Marchand-Brynaert, J; Gallez, B

    2009-04-01

    This article reports the development and evaluation of two nano-emulsions (F45T-03/HFB and F15T-03/PFOB) containing fluorinated trityl radicals dissolved in perfluorocarbons. Preparation with a high-pressure homogenizer conferred sub-micronic size to both nano-emulsions. In vitro and in vivo EPR spectroscopy showed that the nano-emulsions had much greater oxygen sensitivity than the hydrophilic trityl, CT-03. In vivo experiments in rodents confirmed the ability of the nano-emulsions to follow the changes in oxygen concentration after induced ischemia. Histological evaluation of the tissue injected with the nano-emulsions revealed some acute toxicity for the F45T-03/HFB nano-emulsion but none for the F15T-03/PFOB nano-emulsion. These new formulations should be considered for further EPR oximetry experiments in pathophysiological situations where subtle changes in tissue oxygenation are expected. PMID:19128993

  13. Characterisation of nanohybrids of porphyrins with metallic and semiconducting carbon nanotubes by EPR and optical spectroscopy.

    PubMed

    Cambré, Sofie; Wenseleers, Wim; Culin, Jelena; Van Doorslaer, Sabine; Fonseca, Antonio; Nagy, Janos B; Goovaerts, Etienne

    2008-09-15

    Single-walled carbon nanotubes (SWCNTs) are noncovalently functionalised with octaethylporphyrins (OEPs) and the resulting nanohybrids are isolated from the free OEPs. Electron paramagnetic resonance (EPR) spectroscopy of cobalt(II)OEP, adsorbed on the nanotube walls by pi-pi-stacking, demonstrates that the CNTs act as electron acceptors. EPR is shown to be very effective in resolving the different interactions for metallic and semiconducting tubes. Moreover, molecular oxygen is shown to bind selectively to nanohybrids with semiconducting tubes. Water solubilisation of the porphyrin/CNT nanohybrids using bile salts, after applying a thorough washing procedure, yields solutions in which at least 99% of the porphyrins are interacting with the CNTs. Due to this purification, we observe, for the first time, the isolated absorption spectrum of the interacting porphyrins, which is strongly red-shifted compared to the free porphyrin absorption. In addition a quasi-complete quenching of the porphyrin fluorescence is also observed. PMID:18712730

  14. Frequency domain Fourier transform THz-EPR on single molecule magnets using coherent synchrotron radiation.

    PubMed

    Schnegg, Alexander; Behrends, Jan; Lips, Klaus; Bittl, Robert; Holldack, Karsten

    2009-08-21

    Frequency domain Fourier transform THz electron paramagnetic resonance (FD-FT THz-EPR) based on coherent synchrotron radiation (CSR) is presented as a novel tool to ascertain very large zero field splittings in transition metal ion complexes. A description of the FD-FT THz-EPR at the BESSY II storage ring providing CSR in a frequency range from 5 cm(-1) up to 40 cm(-1) at external magnetic fields from -10 T to +10 T is given together with first measurements on the single molecule magnet Mn(12)Ac where we studied DeltaM(S) = +/-1 spin transition energies as a function of the external magnetic field and temperature. PMID:19639156

  15. New chemometric approach MCR-ALS to unmix EPR spectroscopic data from complex mixtures

    NASA Astrophysics Data System (ADS)

    Fadel, Maya Abou; de Juan, Anna; Touati, Nadia; Vezin, Hervé; Duponchel, Ludovic

    2014-11-01

    Electron paramagnetic resonance (EPR) spectra of mixtures are often difficult to interpret due to the superposition of spectral contribution of various species present in the complex materials. It is challenging to accurately identify the number of pure compounds present and to extract their pure spectra. In this study, the powerful chemometric method, multivariate curve resolution-alternating least squares (MCR-ALS), is applied to identify different paramagnetic centers. This method is used to simultaneously extract, with no prior knowledge, the pure spectra and the corresponding concentration profiles of all the compounds in the unknown and unresolved mixtures. The goal of our work is to apply, for the first time, this new chemometrics methodology, MCR-ALS, on EPR spectroscopic data in order to characterize a series of distinct but strongly overlapping spectra of various paramagnetic species.

  16. Dating sediment deposits on Montalvanian carvings using EPR and TL methods

    NASA Astrophysics Data System (ADS)

    Sastry, M. D.; Sullasi, Henry S. L.; Camargo, Fabiola; Watanabe, Shigueo; Prous, André P. P.; Silva, Martha M. C.

    2004-01-01

    About 30 years ago a rock shelter with engravings by early settlers was found at Montalvânia, northern end of state of Minas Gerais, Brazil. Lower part of engravings was covered with thin deposit of calcite mixed with quartz grains, due to occasional flood. This mixture of two minerals was dated by thermoluminescence and electron paramagnetic resonance using in both cases, additive method. The accumulated dose DAC, that is, natural radioactivity and cosmic rays radiation dose that induces TL and EPR signal intensity has been found to be around 50 Gy both by TL and EPR methods. The annual radiation dose rate was estimated to be about 1.027 mGy/a from knowledge of uranium, thorium and potassium content determined by inductively coupled plasma-mass spectrometer system. The age of this calcite plus quartz deposits was estimated to be about 50 ka.

  17. Temperature dependent electron paramagnetic resonance (EPR) of SrZrO3

    NASA Astrophysics Data System (ADS)

    Gupta, Santosh K.; Pathak, Nimai; Ghosh, P. S.; Rajeshwari, B.; Natarajan, V.; Kadam, R. M.

    2015-10-01

    SrZrO3 (SZO), a distorted perovskite was synthesized using gel-combustion route employing citric acid as a fuel and ammonium nitrate as oxidizer followed by characterization using X-ray diffraction (XRD) and electron paramagnetic resonance (EPR). Purity of the sample is confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis. Broadening and shift of the resonance field position in EPR spectrum to the lower field was observed as the temperature is lowered; which is the characteristic of ferromagnetic resonance spectra. The value of Curie-Weiss temperature obtained for SZO particles is 8.7 K. The positive sign of the Curie-Weiss temperature indicates that some of the spins are ferromagnetically coupled in this sample. Theoretical investigation using density functional theory (DFT) calculation revealed that Vacancy at zirconium site contribute maximum to the magnetic moment.

  18. EPR experiment and 2-photon interferometry: Report of a 2-photon interference experiment

    NASA Technical Reports Server (NTRS)

    Shih, Y. H.; Rubin, M. H.; Sergienko, A. V.

    1992-01-01

    After a very brief review of the historical Einstein, Podolsky, and Rosen (EPR) experiments, a new two-photon interference type EPR experiment is reported. A two-photon state was generated by optical parametric down conversion. Pairs of light quanta with degenerate frequency but divergent directions of propagation were sent to two independent Michelson interferometers. First and second order interference effectors were studied. Different than other reports, we observed that the second order interference visibility vanished when the optical path difference of the interferometers were much less than the coherence length of the pumping laser beam. However, we also observed that the second order interference behaved differently depending on whether the interferometers were set at equal or different optical path differences.

  19. EPR and magnetic studies of a novel copper metal organic framework (STAM-I)

    NASA Astrophysics Data System (ADS)

    EL Mkami, H.; Mohideen, M. I. H.; Pal, C.; McKinlay, A.; Scheimann, O.; Morris, R. E.

    2012-08-01

    The magnetic interaction between dinuclear copper (II) in a new copper carboxylate compound, STAM-1, has been investigated by means of EPR and SQUID measurements. The powder EPR spectra, measured at 9.80 and 34.5 GHz and at different temperatures, show the typical lines of the triplet state (S = 1), attributed to Cu2+-Cu2+ dimers, in addition of a temperature dependent central lines. The zero field splitting parameters obtained are |Dobs| = 0.337 cm-1 and E ˜ 0. Magnetic susceptibility data, performed in the range 1.8-300 K, shows a strong antiferromagnetic exchange coupling between the Cu2+ centers in the paddle-wheel units with the exchange coupling constant 2J = -334 ± 4 cm-1.

  20. High precision EPR dosimetry as a reference tool for validation of other techniques.

    PubMed

    Chumak, V V; Sholom, S V; Bakhanova, E V; Pasalskaya, L F; Musijachenko, A V

    2005-02-01

    We present here a particular application area for EPR dosimetry with teeth--use as a source of reference dose values for validation/verification of other retrospective dosimetry techniques and existing dose records. The conditions of application of EPR dosimetry in this role as well as practical design of such studies are shown. Particular attention is given to the requirements to the techniques in terms of precision and throughput, as well as to the issue of availability of samples for analysis and practical solution of this problem. Practical application of this approach is illustrated by several examples of completed validation sub-studies, which were performed in the framework of large-scale post-Chernobyl epidemiological studies. PMID:15607440

  1. EPR and polarography of nitroazoles. 6. 3-Nitro-1,2,4-triazoles

    SciTech Connect

    Vakul'skaya, T.I.; Rakhmatulina, T.N.; Pevzner, M.S.; Kofman, T.P.; Lopyrev, V.A.

    1987-09-01

    The electrochemical reduction of eight 3-nitro-1,2,4-triazole derivatives in acetonitrile was investigated by polarography and EPR spectroscopy. Two different signals were recorded in the EPR spectra in the electrochemical reduction of derivative I. The first signal shows up at the potentials of the second wave with a hyperfine structure corresponding to coupling of an unpaired electron with five nitrogen atoms and to a symmetrical distribution of the spin density as shown. Electrochemical generation of the ion radicals was realized in special electrochemical cells that had been previously deoxygenated by successive freezing and thawing of solutions in vacuo and were then filled with argon purified over potassium-sodium alloy.

  2. Special aspects of the temperature dependence of EPR absorption of chemically carbonized polyvinylidene fluoride derivatives

    NASA Astrophysics Data System (ADS)

    Zhivulin, V. E.; Pesin, L. A.; Ivanov, D. V.

    2016-01-01

    The temperature dependences of electron paramagnetic resonance (EPR) absorption of two samples of chemically carbonized derivatives of polyvinylidene fluoride (PVDF) synthesized under different conditions have been measured in the range of 100-300 K. It has been found that the temperature dependence of the integrated intensity of the EPR signal of both samples is nonmonotonic and does not obey the classical Curie dependence characteristic of free radicals. An analytical expression that is consistent with experimental data and suggests the presence of an activation component of paramagnetism in the test samples has been obtained. The presence of a term independent of temperature in this equation also indicates the paramagnetic contribution of free electrons. The magnitude of the activation energy of the singlet-triplet transitions has been evaluated: δ = 0.067 eV. The HYSCORE spectra of chemically carbonized PVDF derivatives have been obtained for the first time.

  3. Theoretical studies of EPR spectra and defect structure for Er3+ center in lithium niobate.

    PubMed

    Chai, Rui-Peng; Kuang, Xiao-Yu; Duan, Mei-Ling; Zhang, Cai-Xia

    2010-09-15

    The optical and EPR spectra of octahedral Er(3+) center in LiNbO(3) have been studied by diagonalizing 364 x 364 complete energy matrices. The new set of crystal-field parameters that can well account for the Stark levels and EPR parameters have been obtained for Er(3+) ions in LiNbO(3). Simultaneously, by simulating the most reliable six-order parameter B(60) obtained, we have presented the evidence that the Er(3+) ions do not occupy the actual Li(+) site, but have a displacement along the C(3)-axis away from the Li(+) center by about 0.0454 nm. The conclusion is well in accord with that drawn by earlier workers. PMID:20541458

  4. Chitosan gallate as a novel potential polysaccharide antioxidant: an EPR study.

    PubMed

    Pasanphan, Wanvimol; Buettner, Garry R; Chirachanchai, Suwabun

    2010-01-11

    A novel biopolymer-based antioxidant, chitosan conjugated with gallic acid (chitosan galloylate, chitosan-GA), is proposed. Electron paramagnetic resonance (EPR) demonstrates a wide range of antioxidant activity for chitosan-GA as evidenced from its reactions with oxidizing free radicals, that is, 1,1-diphenyl-2-picryl-hydrazyl (DPPH), horseradish peroxidase (HRP)-H(2)O(2), carbon-centered alkyl radicals, and hydroxyl radicals. The EPR spectrum of the radical formed on chitosan-GA was attributed to the semiquinone radical of the gallate moiety. The stoichiometry and effective concentration (EC(50)) of the DPPH free radical with chitosan-GA show that the radical scavenging capacity is maintained even after thermal treatment at 100 degrees C for an hour. Although the degree of substitution of GA on chitosan was about 15%, its antioxidant capacity, that is, the reaction with carbon-centered and hydroxyl radicals, is comparable to that of GA. PMID:19889400

  5. Physiological and pathophysiological reactive oxygen species as probed by EPR spectroscopy: the underutilized research window on muscle ageing.

    PubMed

    A Abdel-Rahman, Engy; Mahmoud, Ali M; Khalifa, Abdulrahman M; Ali, Sameh S

    2016-08-15

    Reactive oxygen and nitrogen species (ROS and RNS) play crucial roles in triggering, mediating and regulating physiological and pathophysiological signal transduction pathways within the cell. Within the cell, ROS efflux is firmly controlled both spatially and temporally, making the study of ROS dynamics a challenging task. Different approaches have been developed for ROS assessment; however, many of these assays are not capable of direct identification or determination of subcellular localization of different ROS. Here we highlight electron paramagnetic resonance (EPR) spectroscopy as a powerful technique that is uniquely capable of addressing questions on ROS dynamics in different biological specimens and cellular compartments. Due to their critical importance in muscle functions and dysfunction, we discuss in some detail spin trapping of various ROS and focus on EPR detection of nitric oxide before highlighting how EPR can be utilized to probe biophysical characteristics of the environment surrounding a given stable radical. Despite the demonstrated ability of EPR spectroscopy to provide unique information on the identity, quantity, dynamics and environment of radical species, its applications in the field of muscle physiology, fatiguing and ageing are disproportionately infrequent. While reviewing the limited examples of successful EPR applications in muscle biology we conclude that the field would greatly benefit from more studies exploring ROS sources and kinetics by spin trapping, protein dynamics by site-directed spin labelling, and membrane dynamics and global redox changes by spin probing EPR approaches. PMID:26801204

  6. DUAL FREQUENCY RESONATOR FOR 1.2 GHZ EPR/16.2 MHZ NMR CO-IMAGING

    PubMed Central

    Petryakov, Sergey; Samouilov, Alexandre; Kesselring, Eric; Caia, George L.; Sun, Ziqi; Zweier, Jay L.

    2010-01-01

    The development of a dual frequency resonator that enables both EPR and proton NMR imaging within the same resonator, magnet and gradient system is described. A novel design allows the same resonator to perform both EPR and proton NMR operation without moving resonator cables or switches. The resonator is capable of working at frequencies of 16.18 MHz for proton NMR and 1.2 GHz for EPR and is optimized for isolated rat heart experiments, measuring 22 mm in inner diameter and 19 mm in length. In EPR mode, the resonator functions as a one loop two gap resonator, electrically coupled through a half wavelength inverter. In NMR mode, it functions a single turn coil. Using the same loop for both modalities maximizes filling factor at both frequencies. Placing the tuning and switching controls away from the resonator prevents any inadvertent movement that would cause errors of EPR and NMR co-imaging registration. The resonator enabled good quality EPR and proton MRI of isolated rat hearts with precise registration. PMID:20434379

  7. SINGLE LOOP - MULTI GAP RESONATOR FOR WHOLE BODY EPR IMAGING OF MICE AT 1.2 GHZ

    PubMed Central

    Petryakov, Sergey; Samouilov, Alexandre; Kesselring, Eric; Wasowicz, Tomasz; Caia, George L.; Zweier, Jay L.

    2009-01-01

    For whole body EPR imaging of small animals, typically low frequencies of 250–750 MHz have been used due to the microwave losses at higher frequencies and the challenges in designing suitable resonators to accommodate these large lossy samples. However, low microwave frequency limits the obtainable sensitivity. L-band frequencies can provide higher sensitivity, and have been commonly used for localized in vivo EPR spectroscopy. Therefore, it would be highly desirable to develop an L-band microwave resonator suitable for in vivo whole body EPR imaging of small animals such as living mice. A 1.2 GHz 16 gap resonator with inner diameter of 43 mm and 48 mm length was designed and constructed for whole body EPR imaging of small animals. The resonator has good field homogeneity and stability to animal induced motional noise. Resonator stability was achieved with electrical and mechanical design utilizing a fixed position double coupling loop of novel geometry, thus minimizing the number of moving parts. Using this resonator, high quality EPR images of lossy phantoms and living mice were obtained. This design provides good sensitivity, ease of sample access, excellent stability and uniform B1 field homogeneity for in vivo whole body EPR imaging of mice at 1.2 GHz. PMID:17625940

  8. Spin relaxation measurements using first-harmonic out-of-phase absorption EPR signals: rotational motion effects.

    PubMed

    Livshits, V A; Marsh, D

    2000-07-01

    A recent survey of nonlinear continuous-wave (CW) EPR methods revealed that the first-harmonic absorption EPR signal, detected 90 degrees out of phase with respect to the Zeeman modulation (V(1)(')-EPR), is the most appropriate for determining spin-lattice relaxation enhancements of spin labels (V. A. Livshits, T. Páli, and D. Marsh, 1998, J. Magn. Reson. 134, 113-123). The sensitivity of such V(1)(')-EPR spectra to molecular rotational motion is investigated here by spectral simulations for nitroxyl spin labels, over the entire range of rotational correlation times. Determination of the effective spin-lattice relaxation times is less dependent on rotational mobility than for other nonlinear CW EPR methods, especially at a Zeeman modulation frequency of 25 kHz which is particularly appropriate for spin labels. This relative insensitivity to molecular motion further enhances the usefulness of the V(1)(')-EPR method. Calibrations of the out-of-phase to in-phase spectral intensity (and amplitude) ratios are given as a function of spin-lattice relaxation time, for the full range of spin-label rotational correlation times. Experimental measurements on spin labels in the slow, intermediate, and fast motional regimes of molecular rotation are used to test and validate the method. PMID:10873499

  9. Highly Active Titanocene Catalysts for Epoxide Hydrosilylation: Synthesis, Theory, Kinetics, EPR Spectroscopy.

    PubMed

    Henriques, Dina Schwarz G; Zimmer, Katharina; Klare, Sven; Meyer, Andreas; Rojo-Wiechel, Elena; Bauer, Mirko; Sure, Rebecca; Grimme, Stefan; Schiemann, Olav; Flowers, Robert A; Gansäuer, Andreas

    2016-06-27

    A catalytic system for titanocene-catalyzed epoxide hydrosilylation is described. It features a straightforward preparation of titanocene hydrides that leads to a reaction with low catalyst loading, high yields, and high selectivity of radical reduction. The mechanism was studied by a suite of methods, including kinetic studies, EPR spectroscopy, and computational methods. An unusual resting state leads to the observation of an inverse rate order with respect to the epoxide. PMID:27125466

  10. EPR spin labeling measurements of thylakoid membrane fluidity during barley leaf senescence.

    PubMed

    Jajić, Ivan; Wiśniewska-Becker, Anna; Sarna, Tadeusz; Jemioła-Rzemińska, Małgorzata; Strzałka, Kazimierz

    2014-07-15

    Physical properties of thylakoid membranes isolated from barley were investigated by the electron paramagnetic resonance (EPR) spin labeling technique. EPR spectra of stearic acid spin labels 5-SASL and 16-SASL were measured as a function of temperature in secondary barley leaves during natural and dark-induced senescence. Oxygen transport parameter was determined from the power saturation curves of the spin labels obtained in the presence and absence of molecular oxygen at 25°C. Parameters of EPR spectra of both spin labels showed an increase in the thylakoid membrane fluidity during senescence, in the headgroup area of the membrane, as well as in its interior. The oxygen transport parameter also increased with age of barley, indicating easier diffusion of oxygen within the membrane and its higher fluidity. The data are consistent with age-related changes of the spin label parameters obtained directly by EPR spectroscopy. Similar outcome was also observed when senescence was induced in mature secondary barley leaves by dark incubation. Such leaves showed higher membrane fluidity in comparison with leaves of the same age, grown under light conditions. Changes in the membrane fluidity of barley secondary leaves were compared with changes in the levels of carotenoids (car) and proteins, which are known to modify membrane fluidity. Determination of total car and proteins showed linear decrease in their level with senescence. The results indicate that thylakoid membrane fluidity of barley leaves increases with senescence; the changes are accompanied with a decrease in the content of car and proteins, which could be a contributing factor. PMID:24974331

  11. Electrostatic influence on rotational mobilities of sol-gel-encapsulated solutes by NMR and EPR spectroscopies.

    PubMed

    Wheeler, Korin E; Lees, Nicholas S; Gurbiel, Ryszard J; Hatch, Shelby L; Nocek, Judith M; Hoffman, Brian M

    2004-10-20

    The rotational mobilities of small solute molecules encapsulated in tetramethyl orthosilicate (TMOS) sol-gels have been investigated by EPR spectroscopy of encapsulated nitroxide probes and by high-resolution NMR spectroscopic measurements of transferred NOE's (trNOE's), of T(1)'s, and of T(1)'s in the rotating frame (T(1)rho). The two spectroscopic methods are sensitive to motions on different time scales and hence, are nicely complementary. Suites of neutral, positively, and negatively charged nitroxide probes (EPR) and of simple diamagnetic small molecules (NMR) were selected to disclose influences of electrostatic interactions with the sol-gel walls and to probe the presence of multiple populations of molecules in distinct regions of the sol-gel pores. For neutral and negatively charged solute probes, both techniques disclose a single population with a significantly increased average rotational correlation time, which we interpret at least in part as resulting from exchange between free-volume and transiently immobilized surface populations. The electrostatic attraction between cationic probes and the negatively charged sol-gel walls causes the positively charged probes to be more effectively immobilized and/or causes a greater percentage of probes to undergo this transient immobilization. The EPR spectra directly disclose a population of cationic probes which are immobilized on the X-band EPR time scale: tau(c) greater than or approximately equal 10(-7) s. However, NMR measurements of trNOE's and of T(1)rho demonstrate that this population does exchange with the free-volume probes on the slower time scale of NMR. This approach is equally applicable to the study of solutes within other types of confined spaces, as well. PMID:15479102

  12. Synthesis and EPR Characterization of Exohedrally Perfluoroalkylated Paramagnetic Lanthanum Metallofullerenes: A Fluorous Phase Approach

    NASA Astrophysics Data System (ADS)

    Tagmatarchis, Nikos; Taninaka, Atsushi; Shinohara, Hisanori; Prato, Maurizio

    2002-10-01

    A strategy to chemically derivatize the outer sphere of endohedral metallofullerenes by using a modern organic technique that utilizes a fluorous synthesis-partitioning approach has been developed. The newly synthesized materials were found to be paramagnetic species and were characterized by electron paramagnetic resonance spectroscopy (EPR), laser desorption time-of-flight spectrometry (LD-TOF) and electronic absorption spectroscopy (UV-VIS-NIR). The systematic study of exohedrally derivatized endohedral metallofullerenes should ultimately provide technologically intriguing novel nano-materials.

  13. Ionizable Nitroxides for Studying Local Electrostatic Properties of Lipid Bilayers and Protein Systems by EPR

    PubMed Central

    Voinov, Maxim A.; Smirnov, Alex I.

    2016-01-01

    Electrostatic interactions are known to play one of the major roles in the myriad of biochemical and biophysical processes. In this Chapter we describe biophysical methods to probe local electrostatic potentials of proteins and lipid bilayer systems that is based on an observation of reversible protonation of nitroxides by EPR. Two types of the electrostatic probes are discussed. The first one includes methanethiosulfonate derivatives of protonatable nitroxides that could be used for highly specific covalent modification of the cysteine’s sulfhydryl groups. Such spin labels are very similar in magnetic parameters and chemical properties to conventional MTSL making them suitable for studying local electrostatic properties of protein-lipid interfaces. The second type of EPR probes is designed as spin-labeled phospholipids having a protonatable nitroxide tethered to the polar head group. The probes of both types report on their ionization state through changes in magnetic parameters and a degree of rotational averaging, thus, allowing one to determine the electrostatic contribution to the interfacial pKa of the nitroxide, and, therefore, determining the local electrostatic potential. Due to their small molecular volume these probes cause a minimal perturbation to the protein or lipid system while covalent attachment secure the position of the reporter nitroxides. Experimental procedures to characterize and calibrate these probes by EPR and also the methods to analyze the EPR spectra by least-squares simulations are also outlined. The ionizable nitroxide labels and the nitroxide-labeled phospholipids described so far cover an exceptionally wide pH range from ca. 2.5 to 7.0 pH units making them suitable to study a broad range of biophysical phenomena especially at the negatively charged lipid bilayer surfaces. The rationale for selecting proper electrostatically neutral interface for calibrating such probes and example of studying surface potential of lipid bilayer is

  14. The 9 GHz EPR Imager for Thin Materials: an Application to Surface Detection

    PubMed Central

    Nakagawa, Kouichi; Ohba, Yasunori; Epel, Boris; Hirata, Hitoshi

    2015-01-01

    A 9 GHz EPR imager that is capable of imaging surface area of the thin-materials has been built. The EPR imager resolved samples spaced by 1 mm. The developed TE111 cavity was able to detect easily ~1.1 mM aqueous TEMPOL solution in ~1.0 mm (i.d.) glass capillary placed just above the cavity. The theoretical sensitivity of the TE111 cavity was estimated to be ~1.3-fold in comparison with the JEOL TE011 cavity considering the same quality factor (Q). The sensitivity measured using the TEMPOL solution showed ~0.33 of that for the JEOL cavity, which was in a qualitative agreement with the calculations considering the difference in the filling factors of the cavities. The relatively low measured sensitivity of the TE111 cavity is due to utilization of microwave field leakage from a small hole in the cavity wall. More importantly, the TE111 cavity does not require inserting sample into the inner volume of the cavity as well as placing samples into EPR tubes. Therefore, we can use the maximum imager microwave power to gain the sample signal intensity. PMID:22864516

  15. EPR study of Cu2+ ion doped orotato(nicotinamid)cobalt(II) single crystal

    NASA Astrophysics Data System (ADS)

    Yıldırım, İ.; Karabulut, B.; Büyükgüngör, O.

    2016-01-01

    We have studied the Cu2+ ion doped orotato(nicotinamid)cobalt(II) complex by using EPR spectroscopy and X-ray diffraction. The single crystal is triclinic with the space group P 1 ‾ . The unit cell dimensions of the crystal are a = 7.2785(4) Å, b = 10.2349(5) Å, c = 12.7372(6) Å, α = 69.297(4)°, β = 74.791(4)° and γ = 76.995(4)°, with Z = 2. We analyzed the EPR spectra of both single crystal and powder of the complex at room temperature. EPR analysis indicates the presence of only one Cu2+ site. We obtained the spin Hamiltonian parameters from the single crystal data for the complex. The spin Hamiltonian parameters are gx = 2.032, gy = 2.116, gz = 2.319, Ax = 28 G, Ay = 66 G, Az = 126 G. These data indicate that the symmetry of paramagnetic center is rhombic. We constructed the ground state wave function of the Cu2+ ion.

  16. Analysis of Influenza A Virus NS1 Dimer Interfaces in Solution by Pulse EPR Distance Measurements

    PubMed Central

    2014-01-01

    Pulsed electron–electron double resonance (PELDOR) is an electron paramagnetic resonance (EPR) spectroscopy technique for nanometer distance measurements between paramagnetic centers such as radicals. PELDOR has been recognized as a valuable tool to approach structural questions in biological systems. In this manuscript, we demonstrate the value of distance measurements for differentiating competing structural models on the dimerization of the effector domain (ED) of the non-structural protein 1 (NS1) of the influenza A virus. Our results show NS1 to be well amenable to nanometer distance measurements by EPR, yielding high quality data. In combination with mutants perturbing protein dimerization and in silico prediction based on crystal structures, we can exclude one of two potential dimerization interfaces. Furthermore, our results lead to a viable hypothesis of a NS1 ED:ED interface which is flexible through rotation around the vector interconnecting the two native cysteines. These results prove the high value of pulse EPR as a complementary method for structural biology. PMID:25148246

  17. EPR investigation of gamma irradiated single crystal guaifenesin: A combined experimental and computational study

    NASA Astrophysics Data System (ADS)

    Tasdemir, Halil Ugur; Sayin, Ulku; Türkkan, Ercan; Ozmen, Ayhan

    2016-04-01

    Gamma irradiated single crystal of Guaifenesin (Glyceryl Guaiacolate), an important expectorant drug, were investigated with Electron Paramagnetic Resonance (EPR) spectroscopy between 123 and 333 K temperature at different orientations in the magnetic field. Considering the chemical structure and the experimental spectra of the gamma irradiated single crystal of guaifenesin sample, we assumed that alkoxy or alkyl-type paramagnetic species may be produced by irradiation. Depending on this assumption, eight possible alkoxy and alkyl-type radicals were modeled and EPR parameters of these modeled radicals were calculated using the B3LYP/6-311++G(d,p)-level of density functional theory (DFT). Theoretically calculated values of alkyl-type modeled radical(R3) are in good agreement with experimentally determined EPR parameters of single crystal. Furthermore, simulation spectra which are obtained by using the theoretical initial values are well matched with the experimental spectra. It was determined that a stable Cα •H2αCβHβCγH2γ (R3) alkyl radical was produced in the host crystal as a result of gamma irradiation.

  18. Entanglement conservation, ER=EPR, and a new classical area theorem for wormholes

    NASA Astrophysics Data System (ADS)

    Remmen, Grant N.; Bao, Ning; Pollack, Jason

    2016-07-01

    We consider the question of entanglement conservation in the context of the ER=EPR correspondence equating quantum entanglement with wormholes. In quantum mechanics, the entanglement between a system and its complement is conserved under unitary operations that act independently on each; ER=EPR suggests that an analogous statement should hold for wormholes. We accordingly prove a new area theorem in general relativity: for a collection of dynamical wormholes and black holes in a spacetime satisfying the null curvature condition, the maximin area for a subset of the horizons (giving the largest area attained by the minimal cross section of the multi-wormhole throat separating the subset from its complement) is invariant under classical time evolution along the outermost apparent horizons. The evolution can be completely general, including horizon mergers and the addition of classical matter satisfying the null energy condition. This theorem is the gravitational dual of entanglement conservation and thus constitutes an explicit characterization of the ER=EPR duality in the classical limit.

  19. Bifunctional Spin Labeling of Muscle Proteins: Accurate Rotational Dynamics, Orientation, and Distance by EPR.

    PubMed

    Thompson, Andrew R; Binder, Benjamin P; McCaffrey, Jesse E; Svensson, Bengt; Thomas, David D

    2015-01-01

    While EPR allows for the characterization of protein structure and function due to its exquisite sensitivity to spin label dynamics, orientation, and distance, these measurements are often limited in sensitivity due to the use of labels that are attached via flexible monofunctional bonds, incurring additional disorder and nanosecond dynamics. In this chapter, we present methods for using a bifunctional spin label (BSL) to measure muscle protein structure and dynamics. We demonstrate that bifunctional attachment eliminates nanosecond internal rotation of the spin label, thereby allowing the accurate measurement of protein backbone rotational dynamics, including microsecond-to-millisecond motions by saturation transfer EPR. BSL also allows for accurate determination of helix orientation and disorder in mechanically and magnetically aligned systems, due to the label's stereospecific attachment. Similarly, labeling with a pair of BSL greatly enhances the resolution and accuracy of distance measurements measured by double electron-electron resonance (DEER). Finally, when BSL is applied to a protein with high helical content in an assembly with high orientational order (e.g., muscle fiber or membrane), two-probe DEER experiments can be combined with single-probe EPR experiments on an oriented sample in a process we call BEER, which has the potential for ab initio high-resolution structure determination. PMID:26477249

  20. Tetrachloridocuprates(II)—Synthesis and Electron Paramagnetic Resonance (EPR) Spectroscopy

    PubMed Central

    Winter, Alette; Zabel, André; Strauch, Peter

    2012-01-01

    Ionic liquids (ILs) on the basis of metal containing anions and/or cations are of interest for a variety of technical applications e.g., synthesis of particles, magnetic or thermochromic materials. We present the synthesis and the results of electron paramagnetic resonance (EPR) spectroscopic analyses of a series of some new potential ionic liquids based on tetrachloridocuprates(II), [CuCl4]2−, with different sterically demanding cations: hexadecyltrimethylammonium 1, tetradecyltrimethylammonium 2, tetrabutylammonium 3 and benzyltriethylammonium 4. The cations in the new compounds were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. The EPR hyperfine structure was not resolved. This is due to the exchange broadening, resulting from still incomplete separation of the paramagnetic Cu(II) centers. Nevertheless, the principal values of the electron Zeemann tensor (g║ and g┴) of the complexes could be determined. Even though the solid substances show slightly different colors, the UV/Vis spectra are nearly identical, indicating structural changes of the tetrachloridocuprate moieties between solid state and solution. The complexes have a promising potential e.g., as high temperature ionic liquids, as precursors for the formation of copper chloride particles or as catalytic paramagnetic ionic liquids. PMID:22408411

  1. Cr3+-Doped Yb3Ga5O12 Nanophosphor: Synthesis, Optical, EPR, Studies

    NASA Astrophysics Data System (ADS)

    Singh, Vijay; Sivaramaiah, G.; Rao, J. L.; Singh, N.; Pathak, M. S.; Jirimali, H. D.; Singh, Pramod K.; Srivastava, Anoop K.; Dhoble, S. J.; Mohapatra, M.

    2016-08-01

    Gallium garnets of lanthanides are multifunctional materials especially known for their complicated structure and magnetic properties. In addition, with a suitable transition metal dopant ion, these matrices have been proved to be excellent materials for lasers. In particular, gallium garnet of ytterbium (Yb3Ga5O12) is known to possess excellent properties with regards to these applications. In this connection, Yb3Ga5O12 doped with Cr3+ nanophosphors were synthesized by a solution combustion route. The synthesized material was characterized by powder x-ray diffraction and scanning electron microscopy for phase purity and homogenous morphology. In order to ascertain the oxidation state of the doped ion, diffuse reflectance (DRF), photoluminescence (PL) and electron paramagnetic resonance (EPR) experiments were performed on the sample. The DRF and PL data suggested the stabilisation of the trivalent Cr ion in the matrix. The EPR spectra exhibited two resonance signals with effective g values at g ≈ 7.6 and 4. The EPR data corroborated the DRF and PL results, suggesting the stabilisation of Cr3+ in the matrix at octahedral-type geometries.

  2. Skeletal Muscle Oxygenation Measured by EPR Oximetry Using a Highly Sensitive Polymer-Encapsulated Paramagnetic Sensor.

    PubMed

    Hou, H; Khan, N; Nagane, M; Gohain, S; Chen, E Y; Jarvis, L A; Schaner, P E; Williams, B B; Flood, A B; Swartz, H M; Kuppusamy, P

    2016-01-01

    We have incorporated LiNc-BuO, an oxygen-sensing paramagnetic material, in polydimethylsiloxane (PDMS), which is an oxygen-permeable, biocompatible, and stable polymer. We fabricated implantable and retrievable oxygen-sensing chips (40 % LiNc-BuO in PDMS) using a 20-G Teflon tubing to mold the chips into variable shapes and sizes for in vivo studies in rats. In vitro EPR measurements were used to test the chip's oxygen response. Oxygen induced linear and reproducible line broadening with increasing partial pressure (pO2). The oxygen response was similar to that of bare (unencapsulated) crystals and did not change significantly on sterilization by autoclaving. The chips were implanted in rat femoris muscle and EPR oximetry was performed repeatedly (weekly) for 12 weeks post-implantation. The measurements showed good reliability and reproducibility over the period of testing. These results demonstrated that the new formulation of OxyChip with 40 % LiNc-BuO will enable the applicability of EPR oximetry for long-term measurement of oxygen concentration in tissues and has the potential for clinical applications. PMID:27526163

  3. Moving Difference (MDIFF) Non-adiabatic rapid sweep (NARS) EPR of copper(II)

    PubMed Central

    Hyde, James S.; Bennett, Brian; Kittell, Aaron W.; Kowalski, Jason M.; Sidabras, Jason W.

    2014-01-01

    Non Adiabatic Rapid Sweep (NARS) EPR spectroscopy has been introduced for application to nitroxide-labeled biological samples (AW Kittell et al, (2011)). Displays are pure absorption, and are built up by acquiring data in spectral segments that are concatenated. In this paper we extend the method to frozen solutions of copper-imidazole, a square planar copper complex with four in-plane nitrogen ligands. Pure absorption spectra are created from concatenation of 170 5-gauss segments spanning 850 G at 1.9 GHz. These spectra, however, are not directly useful since nitrogen superhyperfine couplings are barely visible. Application of the moving difference (MDIFF) algorithm to the digitized NARS pure absorption spectrum is used to produce spectra that are analogous to the first harmonic EPR. The signal intensity is about 4 times higher than when using conventional 100 kHz field modulation, depending on line shape. MDIFF not only filters the spectrum, but also the noise, resulting in further improvement of the SNR for the same signal acquisition time. The MDIFF amplitude can be optimized retrospectively, different spectral regions can be examined at different amplitudes, and an amplitude can be used that is substantially greater than the upper limit of the field modulation amplitude of a conventional EPR spectrometer, which improves the signal-to-noise ratio of broad lines. PMID:24036469

  4. Electron paramagnetic resonance (EPR) study of free radicals in irradiated zinc poly methacrylate

    NASA Astrophysics Data System (ADS)

    Galindo, S.; Ureña-Núñez, F.

    2015-06-01

    We report the analysis of the X-band EPR spectrum of the free radical species formed in Zn(II) polymethacrylate (Zn(II) PMA), after degradation was induced in this polymer by 60Co γ- radiation at room temperature. We begin by describing the synthesis and characterization of our samples and its polymerization before applying them several doses to induce degradation. Doses from 10 to 100 kGy in steps of 10 kGy were applied to the samples. At 10 kGy dose, the EPR spectrum shows the superimposed spectra of two species, namely: a typical pattern of an axially symmetrical singlet and a broad symmetric single line. The former can be attributed to peroxide radicals. After applying further doses, the EPR spectra of the samples display a series of superimposed lines on top of the mentioned axial singlet and the broad line. In these spectra, we recognize three sets of lines: a weak doublet, a quartet and quintet in addition to the already detected axially symmetrical line and the broad singlet. These can be assigned to scission radicals trapped in the polymeric matrix.

  5. Semiquinone and ascorbyl radicals in the gut fluids of caterpillars measured with EPR spectrometry.

    PubMed

    Barbehenn, R V; Poopat, U; Spencer, B

    2003-01-01

    The biological activity of phenolic compounds ingested by caterpillars is commonly believed to result from their oxidation, although the products of oxidation have been well-characterized in only a few cases. The initial oxidation products of phenols (semiquinone or phenoxyl radicals) can be measured with electron paramagnetic resonance (EPR) spectrometry. In this study semiquinone radicals formed from tannic acid and gallic acid in the gut fluids of two species of caterpillars were measured. In Orgyia leucostigma, in which ingested phenols are not oxidized, semiquinone radicals were absent or at very low intensities. By contrast, in Malacosoma disstria, in which ingested phenols are oxidized, high semiquinone radical intensities were measured. In the absence of detectable levels of semiquinone radicals, ascorbyl radicals were detected in the EPR spectra instead. High molar ratios of ascorbate to phenols in an artificial diet produced ascorbyl radicals in the midgut fluids of both species, while diets containing low molar ratios produced semiquinone radicals. Similar results were obtained in M. disstria fed the leaves of red oak or sugar maple. The results of this study provide further evidence that ascorbate is an essential antioxidant that prevents the oxidation of phenols in the gut fluids of caterpillars, and demonstrate that EPR spectrometry is a valuable method for determining the degree of oxidative activation of phenols ingested by herbivorous insects. PMID:12459207

  6. Assessment of quality of quartz crystals by EPR and γ-ray diffraction

    NASA Astrophysics Data System (ADS)

    Nienhaus, K.; Stegger, P.; Lehmann, G.; Schneider, J. R.

    1986-03-01

    Natural amethysts from amygdoidal cavities and from fissures as well as synthetic iron-doped quartz crystals of different origins were studied by EPR and γ-ray diffraction. Anisotropic broadening proportional to the slopes of the transitions consistent with a distribution of orientations, most likely due to a mosaic structure, was observed in the EPR spectra of Fe 3+. This broadening was considerably smaller or completely absent in natural amethysts from fissures as well as in a synthetic crystal grown from NH 4F solution. From this broadening average distributions of orientations could be evaluated for substitutional Fe 3+ in good overall agreement with those obtained for the whole crystals by γ-ray diffraction. Thus Fe 3+ is a good probe for the overall quality of the crystals, but the γ-ray diffraction experiments clearly show predominance of a few orientations rather than a random distribution. In the quartz samples of high perfection a hyperfine splitting from an alkali nucleus could be resolved in the EPR spectra of substitutional Fe 3+ at low temperatures and a contribution of vibrations to the minimum linewidths was also observed.

  7. Multifrequency EPR Studies of Manganese Catalases Provide a Complete Description of Proteinaceous Nitrogen Coordination

    PubMed Central

    Stich, Troy A.; Whittaker, James W.; Britt, R. David

    2012-01-01

    Pulse electron paramagnetic resonance (EPR) spectroscopy is employed at two very different excitation frequencies, 9.77 and 30.67 GHz, in the study of the nitrogen coordination environment of the Mn(III)Mn(IV) state of the dimanganese-containing catalases from Lactobacillus plantarum and Thermus thermophilus. Consistent with previous studies, the lower-frequency results reveal one unique histidine nitrogen-Mn cluster interaction. For the first time, a second, more strongly hyperfine-coupled 14N atom is unambiguously observed through the use of higher frequency/higher field EPR spectroscopy. The low excitation frequency spectral features are rationalized as arising from the interaction of a histidine nitrogen that is bound to the Mn(IV) ion, while the higher excitation frequency features are attributed to the histidine nitrogen bound to the Mn(III) ion. These results allow for the computation of intrinsic hyperfine coupling constants, which range from 2.2 to 2.9 MHz, for sp2-hybridized nitrogens coordinating equatorially to high-valent Mn ions. The relevance of these findings is discussed in the context of recent results from analogous higher frequency EPR studies of the Mn cluster in photosystem II and other exchange-coupled transition metal-containing systems. PMID:20055466

  8. A more secure anonymous user authentication scheme for the integrated EPR information system.

    PubMed

    Wen, Fengtong

    2014-05-01

    Secure and efficient user mutual authentication is an essential task for integrated electronic patient record (EPR) information system. Recently, several authentication schemes have been proposed to meet this requirement. In a recent paper, Lee et al. proposed an efficient and secure password-based authentication scheme used smart cards for the integrated EPR information system. This scheme is believed to have many abilities to resist a range of network attacks. Especially, they claimed that their scheme could resist lost smart card attack. However, we reanalyze the security of Lee et al.'s scheme, and show that it fails to protect off-line password guessing attack if the secret information stored in the smart card is compromised. This also renders that their scheme is insecure against user impersonation attacks. Then, we propose a new user authentication scheme for integrated EPR information systems based on the quadratic residues. The new scheme not only resists a range of network attacks but also provides user anonymity. We show that our proposed scheme can provide stronger security. PMID:24760224

  9. Applications of pulsed EPR spectroscopy to structural studies of sulfite oxidizing enzymes

    SciTech Connect

    Klein, Eric L.; Astashkin, Andrei V.; Raitsimring, Arnold M.; Enemark, John H.

    2013-01-01

    Sulfite oxidizing enzymes (SOEs), including sulfite oxidase (SO) and bacterial sulfite dehydrogenase (SDH), catalyze the oxidation of sulfite (SO32-) to sulfate (SO42-). The active sites of SO and SDH are nearly identical, each having a 5-coordinate, pseudo-square-pyramidal Mo with an axial oxo ligand and three equatorial sulfur donor atoms. One sulfur is from a conserved Cys residue and two are from a pyranopterindithiolene (molybdopterin, MPT) cofactor. The identity of the remaining equatorial ligand, which is solvent-exposed, varies during the catalytic cycle. Numerous in vitro studies, particularly those involving electron paramagnetic resonance (EPR) spectroscopy of the Mo(V) states of SOEs, have shown that the identity and orientation of this exchangeable equatorial ligand depends on the buffer pH, the presence and concentration of certain anions in the buffer, as well as specific point mutations in the protein. Until very recently, however, EPR has not been a practical technique for directly probing specific structures in which the solvent-exposed, exchangeable ligand is an O, OH-, H2O, SO32-, or SO42- group, because the primary O and S isotopes (16O and 32S) are magnetically silent (I = 0). This review focuses on the recent advances in the use of isotopic labeling, variable-frequency high resolution pulsed EPR spectroscopy, synthetic model compounds, and DFT calculations to elucidate the roles of various anions, point mutations, and steric factors in the formation, stabilization, and transformation of SOE active site structures.

  10. Are entangled particles connected by wormholes? Evidence for the ER =EPR conjecture from entropy inequalities

    NASA Astrophysics Data System (ADS)

    Gharibyan, Hrant; Penna, Robert F.

    2014-03-01

    If spacetime is built out of quantum bits, does the shape of space depend on how the bits are entangled? The ER =EPR conjecture relates the entanglement entropy of a collection of black holes to the cross sectional area of Einstein-Rosen (ER) bridges (or wormholes) connecting them. We show that the geometrical entropy of classical ER bridges satisfies the subadditivity, triangle, strong subadditivity, and Cadney-Linden-Winter inequalities. These are nontrivial properties of entanglement entropy, so this is evidence for ER =EPR. We further show that the entanglement entropy associated with classical ER bridges has nonpositive tripartite information. This is not a property of entanglement entropy, in general. For example, the entangled four qubit pure state |GHZ4⟩=(|0000⟩+|1111⟩)/√2 has positive tripartite information, so this state cannot be described by a classical ER bridge. Large black holes with massive amounts of entanglement between them can fail to have a classical ER bridge if they are built out of |GHZ4⟩ states. States with nonpositive tripartite information are called monogamous. We conclude that classical ER bridges require monogamous EPR correlations.

  11. Irradiated bivalve mollusks: Use of EPR spectroscopy for identification and dosimetry

    NASA Astrophysics Data System (ADS)

    Alberti, Angelo; Chiaravalle, Eugenio; Fuochi, Piergiorgio; Macciantelli, Dante; Mangiacotti, Michele; Marchesani, Giuliana; Plescia, Elena

    2011-12-01

    High energy radiation treatment of foodstuff for microbial control and shelf-life extension is being used in many countries. However, for consumer protection and information, the European Union has adopted the Directives 1999/2/EC and 1999/3/EC to harmonize the rules concerning the treatment and trade of irradiated foods in EU countries. Among the validated methods to detect irradiated foods the EU directives also include Electron Paramagnetic Resonance (EPR/ESR) spectroscopy.We describe herein the use of EPR for identification of four species of bivalve mollusks, i.e. brown Venus shells (Callista chione), clams (Tapes semidecussatus), mussels (Mytilus galloprovincialis) and oysters (Ostrea edulis) irradiated with 60Co γ-rays. EPR could definitely identify irradiated seashells due to the presence of long-lived free radicals, primarily CO2-, CO33-, SO2- and SO3- radical anions. The presence of other organic free radicals, believed to originate from conchiolin, a scleroprotein present in the shells, was also ascertained. The use of one of these radicals as a marker for irradiation of brown Venus shells and clams can be envisaged. We also propose a dosimetric protocol for the reconstruction of the administered dose in irradiated oysters.

  12. EPR and impedance spectroscopic investigations on lithium bismuth borate glasses containing nickel and vanadium ions.

    PubMed

    Yadav, Arti; Khasa, Satish; Hooda, Ashima; Dahiya, Manjeet S; Agarwal, Ashish; Chand, Prem

    2016-03-15

    Glasses having composition 7NiO∙23Li2O∙20Bi2O3∙50B2O3, 7V2O5∙23Li2O∙20Bi2O3∙50B2O3 and x(2NiO∙V2O5)∙(30-x)Li2O∙50B2O3∙20Bi2O3 (with x=0, 2, 5, 7 & 10 mol%) prepared through melt-quench route are explored by analyzing density, impedance spectroscopy and electron paramagnetic resonance (EPR). It is found that both density and molar volume increase with an increase in substitution of 2NiO∙V2O5 in the base glass matrix. Different dielectric parameters viz. dielectric loss (ε), electrical modulus (M), loss tangent (tanδ) etc. are evaluated and their variations with frequency and temperature are analyzed which reveals that these glasses exhibit a non-Debye relaxation behavior. A phenomenal description of the capacitive behavior is obtained by considering the circuitry as a parallel combination of bulk resistance (Rb) and constant phase element (CPE). The conduction mechanism is found to follow Quantum Mechanical Tunneling (QMT) model. Spin Hamiltonian Parameters (SHPs) and covalency rates are calculated from the EPR spectra of vanadyl ion. The observed EPR spectra confirmed that V(4+) ion exists as vanadyl ion in the octahedral coordination with tetragonal compression. PMID:26748341

  13. Ionizable Nitroxides for Studying Local Electrostatic Properties of Lipid Bilayers and Protein Systems by EPR.

    PubMed

    Voinov, Maxim A; Smirnov, Alex I

    2015-01-01

    Electrostatic interactions are known to play a major role in the myriad of biochemical and biophysical processes. Here, we describe biophysical methods to probe local electrostatic potentials of proteins and lipid bilayer systems that are based on an observation of reversible protonation of nitroxides by electron paramagnetic resonance (EPR). Two types of probes are described: (1) methanethiosulfonate derivatives of protonatable nitroxides for highly specific covalent modification of the cysteine's sulfhydryl groups and (2) spin-labeled phospholipids with a protonatable nitroxide tethered to the polar head group. The probes of both types report on their ionization state through changes in magnetic parameters and degree of rotational averaging, thus, allowing the electrostatic contribution to the interfacial pKa of the nitroxide, and, therefore, the local electrostatic potential to be determined. Due to their small molecular volume, these probes cause a minimal perturbation to the protein or lipid system. Covalent attachment secures the position of the reporter nitroxides. Experimental procedures to characterize and calibrate these probes by EPR, and also the methods to analyze the EPR spectra by simulations are outlined. The ionizable nitroxide labels and the nitroxide-labeled phospholipids described so far cover an exceptionally wide range of ca. 2.5-7.0 pH units, making them suitable to study a broad range of biophysical phenomena, especially at the negatively charged lipid bilayer surfaces. The rationale for selecting proper electrostatically neutral interface for probe calibration, and examples of lipid bilayer surface potential studies, are also described. PMID:26477252

  14. X-ray absorption spectroscopy and EPR studies of oriented spinach thylakoid preparations

    SciTech Connect

    Andrews, J.C. |

    1995-08-01

    In this study, oriented Photosystem II (PS II) particles from spinach chloroplasts are studied with electron paramagnetic resonance (EPR) and x-ray absorption spectroscopy (XAS) to determine more details of the structure of the oxygen evolving complex (OEC). The nature of halide binding to Mn is also studied with Cl K-edge and Mn EXAFS (extended x-ray absorption fine structure) of Mn-Cl model compounds, and with Mn EXAFS of oriented PS II in which Br has replaced Cl. Attention is focused on the following: photosynthesis and the oxygen evolving complex; determination of mosaic spread in oriented photosystem II particles from signal II EPR measurement; oriented EXAFS--studies of PS II in the S{sub 2} state; structural changes in PS II as a result of treatment with ammonia: EPR and XAS studies; studies of halide binding to Mn: Cl K-edge and Mn EXAFS of Mn-Cl model compounds and Mn EXAFS of oriented Br-treated photosystem II.

  15. Dental radiography: tooth enamel EPR dose assessment from Rando phantom measurements

    NASA Astrophysics Data System (ADS)

    Aragno, D.; Fattibene, P.; Onori, S.; Aragno, D.; Fattibene, P.

    2000-09-01

    Electron paramagnetic resonance dosimetry of tooth enamel is now established as a suitable method for individual dose reconstruction following radiation accidents. The accuracy of the method is limited by some confounding factors, among which is the dose received due to medical x-ray irradiation. In the present paper the EPR response of tooth enamel to endoral examination was experimentally evaluated using an anthropomorphic phantom. The dose to enamel for a single exposure of a typical dental examination performed with a new x-ray generation unit working at 65 kVp gave rise to a CO2- signal of intensity similar to that induced by a dose of about 2 mGy of 60Co. EPR measurements were performed on the entire tooth with no attempt to separate buccal and lingual components. Also the dose to enamel for an orthopantomography exam was estimated. It was derived from TLD measurements as equivalent to 0.2 mGy of 60Co. In view of application to risk assessment analysis, in the present work the value for the ratio of the reference dose at the phantom surface measured with TLD to the dose at the tooth measured with EPR was determined.

  16. EPR and impedance spectroscopic investigations on lithium bismuth borate glasses containing nickel and vanadium ions

    NASA Astrophysics Data System (ADS)

    Yadav, Arti; Khasa, Satish; Hooda, Ashima; Dahiya, Manjeet S.; Agarwal, Ashish; Chand, Prem

    2016-03-01

    Glasses having composition 7NiO • 23Li2O • 20Bi2O3 • 50B2O3, 7V2O5 • 23Li2O • 20Bi2O3 • 50B2O3 and x(2NiO • V2O5) • (30 - x)Li2O • 50B2O3 • 20Bi2O3 (with x = 0, 2, 5, 7 & 10 mol%) prepared through melt-quench route are explored by analyzing density, impedance spectroscopy and electron paramagnetic resonance (EPR). It is found that both density and molar volume increase with an increase in substitution of 2NiO • V2O5 in the base glass matrix. Different dielectric parameters viz. dielectric loss (ε), electrical modulus (M), loss tangent (tanδ) etc. are evaluated and their variations with frequency and temperature are analyzed which reveals that these glasses exhibit a non-Debye relaxation behavior. A phenomenal description of the capacitive behavior is obtained by considering the circuitry as a parallel combination of bulk resistance (Rb) and constant phase element (CPE). The conduction mechanism is found to follow Quantum Mechanical Tunneling (QMT) model. Spin Hamiltonian Parameters (SHPs) and covalency rates are calculated from the EPR spectra of vanadyl ion. The observed EPR spectra confirmed that V4 + ion exists as vanadyl ion in the octahedral coordination with tetragonal compression.

  17. EPR study of Cu(2+) ion doped orotato(nicotinamid)cobalt(II) single crystal.

    PubMed

    Yıldırım, I; Karabulut, B; Büyükgüngör, O

    2016-01-01

    We have studied the Cu(2+) ion doped orotato(nicotinamid)cobalt(II) complex by using EPR spectroscopy and X-ray diffraction. The single crystal is triclinic with the space group P1‾. The unit cell dimensions of the crystal are a=7.2785(4)Å, b=10.2349(5)Å, c=12.7372(6)Å, α=69.297(4)°, β=74.791(4)° and γ=76.995(4)°, with Z=2. We analyzed the EPR spectra of both single crystal and powder of the complex at room temperature. EPR analysis indicates the presence of only one Cu(2+) site. We obtained the spin Hamiltonian parameters from the single crystal data for the complex. The spin Hamiltonian parameters are gx=2.032, gy=2.116, gz=2.319, Ax=28G, Ay=66G, Az=126G. These data indicate that the symmetry of paramagnetic center is rhombic. We constructed the ground state wave function of the Cu(2+) ion. PMID:25704568

  18. Modeling EPR powder spectra using numerical diagonalization of the spin hamiltonian

    PubMed

    Morin; Bonnin

    1999-02-01

    A new modeling code, ZFSFIT (standing for Zero Field Splitting FITting), written in FORTRAN 77 is proposed. It is designed for computing and fitting EPR powder spectra described by any spin Hamiltonian including second- and fourth-order ZFS terms (S EPR powder line positions recorded at distinct frequencies improves the accuracy of the refined EPR parameters. Superhyperfine effects as well as broadening effects due to site-to-site distribution of g-, A-, and ZFS parameters are treated using first-order perturbation theory and can also be refined. Parameters for several distinct centers can be fitted simultaneously, allowing quantification of their relative amounts in the sample. After a description of the algorithm, determination of second- and fourth-order ZFS parameters of Cr3+, Mn2+, and Fe3+ centers in low-symmetry sites in minerals are treated, including first evidence of structural Fe3+ centers in alphaAl(OH)3. The code is available without charge to academic users from the authors. Copyright 1999 Academic Press. PMID:9986760

  19. EPR observation of first point defects in cubic boron nitride crystalline powders

    NASA Astrophysics Data System (ADS)

    Nistor, S. V.; Stefan, M.; Schoemaker, D.; Dinca, G.

    2000-05-01

    An X-band electron paramagnetic resonance (EPR) study of nominally pure, diamond-like cubic boron nitride (c-BN) crystalline powders, has led to the first identification of a spectrum attributed to two related paramagnetic species. The composite EPR spectrum can be observed only in dark brown colored powders known to contain excess of boron. It consists of two superimposed lorentzian components, called D1 and D2, centered at g1=2.0063 and g2=2.0084, with peak-to-peak linewidths of 3.3 and 17.9 mT, respectively. The temperature dependence of the integrated intensities, their linewidths and intensity ratio D2/D1 allows one to conclude that the narrow line D1 originates from EPR transitions inside a S=1/2 ground doublet and the broad line D2 from transitions inside the excited levels of another center. Evidence suggests that both centers are boron related paramagnetic species.

  20. EPR and transient capacitance studies on electron-irradiated silicon solar cells

    NASA Technical Reports Server (NTRS)

    Lee, Y. H.; Cheng, L. J.; Mooney, P. M.; Corbett, J. W.

    1977-01-01

    One and two ohm-cm solar cells irradiated with 1 MeV electrons at 30 C were studied using both EPR and transient capacitance techniques. In 2 ohm-cm cells, Si-G6 and Si-G15 EPR spectra and majority carrier trapping levels at (E sub V + 0.23) eV and (E sub V + 0.38) eV were observed, each of which corresponded to the divacancy and the carbon-oxygen-vacancy complex, respectively. In addition, a boron-associated defect with a minority carrier trapping level at (E sub C -0.27) eV was observed. In 1 ohm-cm cells, the G15 spectrum and majority carrier trap at (E sub V + 0.38) eV were absent and an isotropic EPR line appeared at g = 1.9988 (+ or - 0.0003); additionally, a majority carrier trapping center at (E sub V + 0.32) eV, was found which could be associated with impurity lithium. The formation mechanisms of these defects are discussed according to isochronal annealing data in electron-irradiated p-type silicon.

  1. Resolving Conformational and Rotameric Exchange in Spin-Labeled Proteins Using Saturation Recovery EPR

    PubMed Central

    Bridges, Michael D.; Hideg, Kálmán

    2010-01-01

    The function of many proteins involves equilibria between conformational substates, and to elucidate mechanisms of function it is essential to have experimental tools to detect the presence of conformational substates and to determine the time scale of exchange between them. Site-directed spin labeling (SDSL) has the potential to serve this purpose. In proteins containing a nitroxide side chain (R1), multicomponent electron paramagnetic resonance (EPR) spectra can arise either from equilibria involving different conformational substates or rotamers of R1. To employ SDSL to uniquely identify conformational equilibria, it is thus essential to distinguish between these origins of multicomponent spectra. Here we show that this is possible based on the time scale for exchange of the nitroxide between distinct environments that give rise to multicomponent EPR spectra; rotamer exchange for R1 lies in the ≈0.1–1 μs range, while conformational exchange is at least an order of magnitude slower. The time scales of exchange events are determined by saturation recovery EPR, and in favorable cases, the exchange rate constants between substates with lifetimes of approximately 1–70 μs can be estimated by the approach. PMID:20157634

  2. Some plant leaves have orientation-dependent EPR and NMR spectra.

    PubMed

    McCain, D C; Selig, T C; Govindjee; Markley, J L

    1984-02-01

    Proton nuclear magnetic resonance ((1)H NMR) spectra of leaves from 50 plant species were obtained at a spectrometer frequency of 470 MHz. Water present in leaf samples gives rise to characteristic spectral patterns. Most species show only one broad (1)H NMR peak; however, the leaves of some plants display complex, orientation-dependent spectra in which a common three-line pattern is discerned. The pattern varies with the angle between the leaf surface and the external magnetic field. Proton relaxation measurements show the presence of at least two water compartments in the leaves. The compartments are responsible for different components of the spectral pattern. EPR spectra, obtained at 35 GHz and at a temperature of -180 degrees C, of plant leaf sections are dominated by the strong signals of manganous ions. We find that most plant leaves have isotropic Mn(2+) EPR spectra. However, in some species (including ones that exhibit orientation-dependent (1)H NMR spectra) we detect orientation-dependent intensities in the forbidden lines; the spectra indicate that Mn(2+) ions occupy binding sites with axial or lower symmetry on nonrandomly oriented membranes. Both the NMR and the EPR results suggest that the chloroplasts of some plants are preferentially aligned with respect to the leaf surface. PMID:16593413

  3. Response of lithium formate EPR dosimeters at photon energies relevant to the dosimetry of brachytherapy

    SciTech Connect

    Adolfsson, Emelie; Alm Carlsson, Gudrun; Grindborg, Jan-Erik; Gustafsson, Haakan; Lund, Eva; Carlsson Tedgren, Aasa

    2010-09-15

    Purpose: To investigate experimentally the energy dependence of the detector response of lithium formate EPR dosimeters for photon energies below 1 MeV relative to that at {sup 60}Co energies. High energy photon beams are used in calibrating dosimeters for use in brachytherapy since the absorbed dose to water can be determined with high accuracy in such beams using calibrated ion chambers and standard dosimetry protocols. In addition to any differences in mass-energy absorption properties between water and detector, variations in radiation yield (detector response) with radiation quality, caused by differences in the density of ionization in the energy imparted (LET), may exist. Knowledge of an eventual deviation in detector response with photon energy is important for attaining high accuracy in measured brachytherapy dose distributions. Methods: Lithium formate EPR dosimeters were irradiated to known levels of air kerma in 25-250 kV x-ray beams and in {sup 137}Cs and {sup 60}Co beams at the Swedish Secondary Standards Dosimetry Laboratory. Conversions from air kerma free in air into values of mean absorbed dose to the detectors were made using EGSnrc MC simulations and x-ray energy spectra measured or calculated for the actual beams. The signals from the detectors were measured using EPR spectrometry. Detector response (the EPR signal per mean absorbed dose to the detector) relative to that for {sup 60}Co was determined for each beam quality. Results: Significant decreases in the relative response ranging from 5% to 6% were seen for x-ray beams at tube voltages {<=}180 kV. No significant reduction in the relative response was seen for {sup 137}Cs and 250 kV x rays. Conclusions: When calibrated in {sup 60}Co or MV photon beams, corrections for the photon energy dependence of detector response are needed to achieve the highest accuracy when using lithium formate EPR dosimeters for measuring absorbed doses around brachytherapy sources emitting photons in the energy

  4. Nitroxide free radical clearance in the live rat monitored by radio-frequency CW-EPR and PEDRI

    NASA Astrophysics Data System (ADS)

    Alecci, Marcello; Seimenis, Ioannis; McCallum, Stephen J.; Lurie, David J.; Foster, Margaret A.

    1998-07-01

    The use of RF (100 to 300 MHz) PEDRI and CW-EPR techniques allows the in vivo study of large animals such as whole rats and rabbits. Recently a PEDRI instrument was modified to also allow CW-EPR spectroscopy with samples of similar size and under the same experimental conditions. In the present study, this CW-EPR and PEDRI apparatus was used to assess the feasibility of the detection of a pyrrolidine nitroxide free radical (2,2,5,5,-tetramethylpyrrolidine-1-oxyl-3-carboxylic acid, PCA) in the abdomen of rats. In particular, we have shown that after the PCA administration ( b.w.): (i) the PCA EPR linewidth does not show line broadening due to concentration effects; (ii) a similar PCA up-take phase is observed by EPR and PEDRI; and (iii) the PCA half-lives in the whole abdomen of rats measured with the CW-EPR (, , n = 10) and PEDRI (, , n = 4) techniques were not significantly different ( p>0.05). These results show, for the first time, that information about PCA pharmacokinetics obtained by CW-EPR is the same as that from PEDRI under the same experimental conditions.

  5. EPR study of free radicals in cotton fiber for its potential use as a fortuitous dosimeter in radiological accidents

    NASA Astrophysics Data System (ADS)

    Sudprasert, W.; Insuan, P.; Khamkhrongmee, S.

    2015-05-01

    Electron paramagnetic resonance (EPR) spectroscopy was applied to characterize radiation-induced free radicals in the cotton fiber in order to determine the possibility for using cotton as a fortuitous dosimeter in accidental exposures to radiation. Cotton fabrics were irradiated at 0.1, 0.5, 1, 2, 10, 50 and 500 Gy using a 137Cs gamma source. The irradiated samples were then stored in the dark under controlled environmental conditions for 1, 15, 35 and 60 days. The EPR spectra were observed in samples using a Bruker EMX X-band spectrometer equipped with a TE102 rectangular cavity. The EPR signal intensities of irradiated samples were determined from peak-to-peak amplitudes of EPR spectra and compared to those of unirradiated samples. The following optimum parameters were used: 100 kHz modulation frequency, 9.84 GHz microwave frequency, 1.8 mT modulation amplitude, 1.0 mW microwave power, 655 ms time constant, 41 ms conversion time and 41.98 s sweep time. The EPR spectra of unirradiated samples showed a singlet line with g = 2.006 due to pre-existing stable organic radicals in the cotton fibers, whereas those of irradiated samples showed the same pattern with different signal intensities according to the doses. Irradiation increased the signal intensity in a dose dependent manner. The signal intensity exhibited an exponential decay with storage time from 1 to 60 days. Obviously, the degree of fading of EPR intensity did not depend on the absorbed dose from 0.1 - 50 Gy. The maximum fading was about 60% at 60 days of storage for irradiated samples at all doses. However, this post-irradiation signal appeared to be detectable for up to 60 days. The EPR study results indicated the potential of using cotton as a fortuitous dosimeter in radiological accidents.

  6. VHF EPR analysis of organic sulfur in coal. Final technical report, September 1, 1992--August 31, 1993

    SciTech Connect

    Clarkson, R.B.; Belford, R.L.

    1993-12-31

    A direct and non-destructive technique called very High Frequency Electron Paramagnetic Resonance (VHF EPR) utilizing instrumentation and application techniques developed in this laboratory, is proving to be a practical and sensitive analytical method for the organic sulfur in coal. Research during this past year (1992--1993) was very successful in terms of obtaining spectrochemical information on organic sulfur in coal both quantitatively (amount of organic sulfur) and qualitatively (form and distribution of organic sulfur). Starting in this funding year, the authors have begun to develop and use a two-species model (non-exchanging and axially symmetric) for the simulation of VHF EPR coal spectra. Such a model provides quantitative information on the total concentration of sulfur species that can be directly related to the organic sulfur content as measured by conventional chemical methods. Utilizing the newly developed method, they have analyzed the VHF EPR spectra from some sub-bituminous coals containing organic sulfur in the range from 2% to 12% and a number of maceral blends. Excellent quantitative agreement is achieved between VHF EPR results and chemical analyses. In addition, the modelling of VHF EPR spectra of coal provides detailed spectral parameters. These parameters can be related to the molecular structures of the paramagnetic species giving rise to the EPR signals, as demonstrated by our study of the model compounds. The foundation of VHF EPR analysis of aromatic sulfur radicals has been firmly established based on careful investigations of the molecular and electronic structures of the thiophenic model compounds. The results validate the theoretical soundness of the method and carry important practical implications.

  7. Induction of phase II enzymes and hsp70 genes by copper sulfate through the electrophile-responsive element (EpRE): insights obtained from a transgenic zebrafish model carrying an orthologous EpRE sequence of mammalian origin.

    PubMed

    Almeida, Daniela Volcan; Nornberg, Bruna Félix da Silva; Geracitano, Laura A; Barros, Daniela Martí; Monserrat, José Maria; Marins, Luis Fernando

    2010-09-01

    We have evaluated the homology of the electrophile-responsive element (EpRE) core sequence, a binding site for the Nrf2 transcription factor, in the proximal promoters of the mouse and zebrafish glutathione-S-transferase (gst), glutamate cysteine ligase catalytic subunit (gclc) and heat shock protein 70 (hsp70) genes. The EpRE sites identified for both species in the three analyzed genes showed a high similarity with the putative EpRE core sequence. We also produced a transgenic zebrafish model carrying a transgene comprised of the luciferase (luc) reporter gene under transcriptional control of a mouse EpRE sequence. This transgenic model was exposed to copper sulfate, and the reporter gene was significantly activated. The endogenous gst, gclc and hsp70 zebrafish genes were analyzed in the EpRE-Luc transgenic zebrafish and showed an expression pattern similar to that of the reporter transgene used. Our results demonstrate that EpRE is conserved between mouse and zebrafish for detoxification-related genes and that the development of genetically modified models using this responsive element to drive the expression of reporter genes can be an important tool in understanding the action mechanism of aquatic pollutants. PMID:19116768

  8. SU-C-BRD-05: Non-Invasive in Vivo Biodosimetry in Radiotherapy Patients Using Electron Paramagnetic Resonance (EPR) Spectroscopy

    SciTech Connect

    Bahar, N; Roberts, K; Stabile, F; Mongillo, N; Decker, RD; Wilson, LD; Husain, Z; Contessa, J; Carlson, DJ; Williams, BB; Flood, AB; Swartz, HM

    2015-06-15

    Purpose: Medical intervention following a major, unplanned radiation event can elevate the human whole body exposure LD50 from 3 to 7 Gy. On a large scale, intervention cannot be achieved effectively without accurate and efficient triage. Current methods of retrospective biodosimetry are restricted in capability and applicability; published human data is limited. We aim to further develop, validate, and optimize an automated field-deployable in vivo electron paramagnetic resonance (EPR) instrument that can fill this need. Methods: Ionizing radiation creates highly-stable, carbonate-based free radicals within tooth enamel. Using a process similar to nuclear magnetic resonance, EPR directly measures the presence of radiation-induced free radicals. We performed baseline EPR measurements on one of the upper central incisors of total body irradiation (TBI) and head and neck (H&N) radiotherapy patients before their first treatment. Additional measurements were performed between subsequent fractions to examine the EPR response with increasing radiation dose. Independent dosimetry measurements were performed with optically-stimulated luminescent dosimeters (OSLDs) and diodes to more accurately establish the relationship between EPR signal and delivered radiation dose. Results: 36 EPR measurements were performed over the course of four months on two TBI and four H & N radiotherapy patients. We observe a linear increase in EPR signal with increasing dose across the entirety of the tested range. A linear least squares-weighted fit of delivered dose versus measured signal amplitude yields an adjusted R-square of 0.966. The standard error of inverse prediction (SEIP) is 1.77 Gy. For doses up to 7 Gy, the range most relevant to triage, we calculate an SEIP of 1.29 Gy. Conclusion: EPR spectroscopy provides a promising method of retrospective, non-invasive, in vivo biodosimetry. Our preliminary data show an excellent correlation between predicted signal amplitude and delivered

  9. Use of multi-coil parallel-gap resonators for co-registration EPR/NMR imaging

    NASA Astrophysics Data System (ADS)

    Kawada, Yuuki; Hirata, Hiroshi; Fujii, Hirodata

    2007-01-01

    This article reports experimental investigations on the use of RF resonators for continuous-wave electron paramagnetic resonance (cw-EPR) and proton nuclear magnetic resonance (NMR) imaging. We developed a composite resonator system with multi-coil parallel-gap resonators for co-registration EPR/NMR imaging. The resonance frequencies of each resonator were 21.8 MHz for NMR and 670 MHz for EPR. A smaller resonator (22 mm in diameter) for use in EPR was placed coaxially in a larger resonator (40 mm in diameter) for use in NMR. RF magnetic fields in the composite resonator system were visualized by measuring a homogeneous 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy (4-hydroxy-TEMPO) solution in a test tube. A phantom of five tubes containing distilled water and 4-hydroxy-TEMPO solution was also measured to demonstrate the potential usefulness of this composite resonator system in biomedical science. An image of unpaired electrons was obtained for 4-hydroxy-TEMPO in three tubes, and was successfully mapped on the proton image for five tubes. Technical problems in the implementation of a composite resonator system are discussed with regard to co-registration EPR/NMR imaging for animal experiments.

  10. EPR and ab initio calculation study on the EI4 center in 4H- and 6H-SiC

    SciTech Connect

    Carlsson, P.; Son, N. T.; Janzen, E.; Gali, A.; Isoya, J.; Morishita, N.; Ohshima, T.; Magnusson, B.

    2010-12-15

    We present results from electron paramagnetic resonance (EPR) studies of the EI4 EPR center in 4H- and 6H-SiC. The EPR signal of the EI4 center was found to be drastically enhanced in electron-irradiated high-purity semi-insulating materials after annealing at 700-750 deg. C. Strong EPR signals of the EI4 center with minimal interferences from other radiation-induced defects in irradiated high-purity semi-insulating materials allowed our more detailed study of the hyperfine (hf) structures. An additional large-splitting {sup 29}Si hf structure and {sup 13}C hf lines of the EI4 defect were observed. Comparing the data on the hf interactions and the annealing behavior obtained from EPR experiments and from ab initio supercell calculations of different carbon-vacancy-related complexes, we suggest a complex between a carbon vacancy-carbon antisite and a carbon vacancy at the third-neighbor site of the antisite in the neutral charge state, (V{sub C}-C{sub Si}V{sub C}){sup 0}, as a new defect model for the EI4 center.

  11. Complex Dyke Emplacement at the Hyper-Inflated EPR 16°N Segment

    NASA Astrophysics Data System (ADS)

    Dyment, J.; Deschamps, A.; Gente, P.; Agranier, A.; Aquilon-Robles, A.; Benoit, M.; Hémond, Ch.; Janin, M.; Maia, M.; Rodrigues-Leon, L.; Szitkar, F.; Thibaud, R.; Tilot, V.; Parisub Scientific Party

    2010-12-01

    The EPR segment located between 15°22’N and 16°15’N (hereafter referred as EPR 16°N) presents a very wide (~13 km at the widest) and quite shallow (~2300 m) axial dome and is clearly over-inflated with respect to typical magmatically robust segments of the EPR. This segment is located at the intersection of the EPR with the Mathematician seamount chain, suggesting some kind of ridge-hotspot interaction which would account for the over-inflation. As a consequence of such an interaction, it has also been suggested that the ridge axis may episodically relocate further west to maintain the ridge-hotspot connection. Cruise Parisub of R/V L’Atalante took place in March-April 2010 and used Deep Sea Submersible Nautile and Autonomous Underwater Vehicle Aster-X to study this problem. The area was surveyed using L’Atalante new Simrad EM 122 echo-sounder, and a few sea-surface magnetic profiles were added to the existing data set. A higher resolution swath was achieved at a slower speed on the axial dome. AUV Aster-X completed a 30 x 4 km wide survey of the axial zone at an altitude of 70 m, collecting high resolution multibeam bathymetry and imagery, magnetics, and nephelometry. A total of 24 successful Nautile dives was carried out with videos and photos, rock sampling, and magnetic data collection, making an axial cross section up to 300 ka off-axis to investigate the inferred ridge jumps (10 Nautile dives), and a set of along axis dives to identify the active volcanic axis and search for active and fossil hydrothermal sites (13 Nautile dives). During these dives, several active and inactive hydrothermal vents have been discovered. In this presentation, we focus on the AUV survey. Unlike most fast spreading centres, which display one clear axial graben at the summit of the axial dome, the hyper-inflated dome at 16°N presents a complex set of several grabens, among which it is difficult to decipher which one are volcanically active and may be considered as the

  12. High-Frequency EPR and ENDOR Spectroscopy on Semiconductor Quantum Dots

    PubMed Central

    Baranov, Pavel G.; de Mello Donegá, Celso; Schmidt, Jan

    2010-01-01

    It is shown that high-frequency electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy are excellent tools for the investigation of the electronic properties of semiconductor quantum dots (QDs). The great attractions of these techniques are that, in contrast to optical methods, they allow the identification of the dopants and provide information about the spatial distribution of the electronic wave function. This latter aspect is particularly attractive because it allows for a quantitative measurement of the effect of confinement on the shape and properties of the wave function. In this contribution EPR and ENDOR results are presented on doped ZnO QDs. Shallow donors (SDs), related to interstitial Li and Na and substitutional Al atoms, have been identified in this material by pulsed high-frequency EPR and ENDOR spectroscopy. The shallow character of the wave function of the donors is evidenced by the multitude of ENDOR transitions of the 67Zn nuclear spins and by the hyperfine interaction of the 7Li, 23Na and 27Al nuclear spins that are much smaller than for atomic lithium, sodium and aluminium. The EPR signal of an exchange-coupled pair consisting of a shallow donor and a deep Na-related acceptor has been identified in ZnO nanocrystals with radii smaller than 1.5 nm. From ENDOR experiments it is concluded that the deep Na-related acceptor is located at the interface of the ZnO core and the Zn(OH)2 capping layer, while the shallow donor is in the ZnO core. The spatial distribution of the electronic wave function of a shallow donor in ZnO semiconductor QDs has been determined in the regime of quantum confinement by using the nuclear spins as probes. Hyperfine interactions as monitored by ENDOR spectroscopy quantitatively reveal the transition from semiconductor to molecular properties upon reduction of the size of the nanoparticles. In addition, the effect of confinement on the g-factor of SDs in ZnO as well as in CdS QDs

  13. EPR of layered magnetic metal-amino acid salts. II. Cu(L-Met) 2

    NASA Astrophysics Data System (ADS)

    Levstein, P. R.; Steren, C. A.; Gennaro, A. M.; Calvo, R.

    1988-03-01

    Single crystals of bis(L-methioninato)copper(II), Cu(L-Met) 2, were studied by EPR at 9.7 and 33.6 GHz, at 300 K. The position and the peak-to-peak linewidth of the single observed EPR line were measured in three perpendicular planes of the samples. This single resonance is due to the collapse of the resonances of the two magnetically inequivalent copper ions in the lattice caused by the exchange interaction. The components of the molecular g tensor for isolated copper ions were obtained using a model which assumes axial symmetry. The results indicate that the unpaired electron occupies the d( x2 - y2) orbital, and the orientation of the molecule obtained from the EPR data agrees with the crystallographic result. The linewidth data support a model which assumes exchange narrowing of the magnetic dipolar interaction in a two-dimensional magnetic lattice, an incomplete collapse of the hyperfine structure, and a frequency-dependent contribution in the planes where the g factors for the two sites of copper are different. An analysis of this latter contribution, allows to evaluate an exchange coupling constant | J'| = 0.10 K between inequivalent copper neighbors. Besides, the analysis of the hyperfine contribution to the linewidth gives | J| = 0.18 K for the average value of the exchange interaction of one copper ion with its six nearest neighbors within the layer. Concerning the possible superexchange paths between inequivalent copper ions, we suggest they can be of two types: the CuNH…OCu one, involving hydrogen bonds between equatorial nitrogens and equatorial oxygens, and the other consisting of CuOCOCu carboxylate bridges involving apical and equatorial oxygens. They are discussed in view of the experimental results.

  14. Application of Electron Paramagnetic Resonance (EPR) Oximetry to Monitor Oxygen in Wounds in Diabetic Models

    PubMed Central

    Desmet, Céline M.; Lafosse, Aurore; Vériter, Sophie; Porporato, Paolo E.; Sonveaux, Pierre; Dufrane, Denis; Levêque, Philippe; Gallez, Bernard

    2015-01-01

    A lack of oxygen is classically described as a major cause of impaired wound healing in diabetic patients. Even if the role of oxygen in the wound healing process is well recognized, measurement of oxygen levels in a wound remains challenging. The purpose of the present study was to assess the value of electron paramagnetic resonance (EPR) oximetry to monitor pO2 in wounds during the healing process in diabetic mouse models. Kinetics of wound closure were carried out in streptozotocin (STZ)-treated and db/db mice. The pO2 was followed repeatedly during the healing process by 1 GHz EPR spectroscopy with lithium phthalocyanine (LiPc) crystals used as oxygen sensor in two different wound models: a full-thickness excisional skin wound and a pedicled skin flap. Wound closure kinetics were dramatically slower in 12-week-old db/db compared to control (db/+) mice, whereas kinetics were not statistically different in STZ-treated compared to control mice. At the center of excisional wounds, measurements were highly influenced by atmospheric oxygen early in the healing process. In pedicled flaps, hypoxia was observed early after wounding. While reoxygenation occurred over time in db/+ mice, hypoxia was prolonged in the diabetic db/db model. This observation was consistent with impaired healing and microangiopathies observed using intravital microscopy. In conclusion, EPR oximetry using LiPc crystals as the oxygen sensor is an appropriate technique to follow wound oxygenation in acute and chronic wounds, in normal and diabetic animals. Nevertheless, the technique is limited for measurements in pedicled skin flaps and cannot be applied to excisional wounds in which diffusion of atmospheric oxygen significantly affects the measurements. PMID:26659378

  15. Mapping Local Protein Electrostatics by EPR of pH-Sensitive Thiol-Specific Nitroxide† ¶

    PubMed Central

    Voinov, Maxim A.; Ruuge, Andres; Reznikov, Vladimir A.; Grigor’ev, Igor A.; Smirnov, Alex I.

    2013-01-01

    A first thiol-specific pH-sensitive nitroxide spin label of the imidazolidine series -methanethiosulfonic acid S-(1-oxyl-2,2,3,5,5-pentamethylimidazolidin-4-ylmethyl) ester (IMTSL) - has been synthesized and characterized. X- (9 GHz) and W-band (94 GHz) EPR spectral parameters of the new spin label in its free form and covalently attached to an amino acid cysteine and a tripeptide glutathione were studied as a function of pH and solvent polarity. pKa value of protonatable tertiary amino group of the spin label was found to be unaffected by other ionizable groups present in side chains of unstructured small peptides. The W-band EPR spectra were shown to allow for pKa determination from precise g-factor measurements. Is has been demonstrated that high accuracy of pKa determination for pH-sensitive nitroxides could be achieved regardless the frequency of measurements or the regime of spin exchange: fast at X-band and slow at W-band. IMTSL was found to react specifically with a model protein - iso-1-cytochrome c from yeast Saccharomyces cerevisiae - giving EPR spectra very similar to those of the most commonly employed cysteine-specific label MTSL. CD data indicated no perturbations to the overall protein structure upon IMTSL labeling. It was found that for IMTSL, giso correlates linearly with Aiso but the slopes are different for the neutral and charged forms of the nitroxide. This finding was attributed to the solvent effects on the spin density at the oxygen atom of the N–O group and on the excitation energy of the oxygen lone-pair orbital. PMID:18426227

  16. Water accessibility in a membrane-inserting peptide comparing Overhauser DNP and pulse EPR methods

    NASA Astrophysics Data System (ADS)

    Segawa, Takuya F.; Doppelbauer, Maximilian; Garbuio, Luca; Doll, Andrin; Polyhach, Yevhen O.; Jeschke, Gunnar

    2016-05-01

    Water accessibility is a key parameter for the understanding of the structure of biomolecules, especially membrane proteins. Several experimental techniques based on the combination of electron paramagnetic resonance (EPR) spectroscopy with site-directed spin labeling are currently available. Among those, we compare relaxation time measurements and electron spin echo envelope modulation (ESEEM) experiments using pulse EPR with Overhauser dynamic nuclear polarization (DNP) at X-band frequency and a magnetic field of 0.33 T. Overhauser DNP transfers the electron spin polarization to nuclear spins via cross-relaxation. The change in the intensity of the 1H NMR spectrum of H2O at a Larmor frequency of 14 MHz under a continuous-wave microwave irradiation of the nitroxide spin label contains information on the water accessibility of the labeled site. As a model system for a membrane protein, we use the hydrophobic α-helical peptide WALP23 in unilamellar liposomes of DOPC. Water accessibility measurements with all techniques are conducted for eight peptides with different spin label positions and low radical concentrations (10-20 μM). Consistently in all experiments, the water accessibility appears to be very low, even for labels positioned near the end of the helix. The best profile is obtained by Overhauser DNP, which is the only technique that succeeds in discriminating neighboring positions in WALP23. Since the concentration of the spin-labeled peptides varied, we normalized the DNP parameter ɛ, being the relative change of the NMR intensity, by the electron spin concentration, which was determined from a continuous-wave EPR spectrum.

  17. Application of Electron Paramagnetic Resonance (EPR) Oximetry to Monitor Oxygen in Wounds in Diabetic Models.

    PubMed

    Desmet, Céline M; Lafosse, Aurore; Vériter, Sophie; Porporato, Paolo E; Sonveaux, Pierre; Dufrane, Denis; Levêque, Philippe; Gallez, Bernard

    2015-01-01

    A lack of oxygen is classically described as a major cause of impaired wound healing in diabetic patients. Even if the role of oxygen in the wound healing process is well recognized, measurement of oxygen levels in a wound remains challenging. The purpose of the present study was to assess the value of electron paramagnetic resonance (EPR) oximetry to monitor pO2 in wounds during the healing process in diabetic mouse models. Kinetics of wound closure were carried out in streptozotocin (STZ)-treated and db/db mice. The pO2 was followed repeatedly during the healing process by 1 GHz EPR spectroscopy with lithium phthalocyanine (LiPc) crystals used as oxygen sensor in two different wound models: a full-thickness excisional skin wound and a pedicled skin flap. Wound closure kinetics were dramatically slower in 12-week-old db/db compared to control (db/+) mice, whereas kinetics were not statistically different in STZ-treated compared to control mice. At the center of excisional wounds, measurements were highly influenced by atmospheric oxygen early in the healing process. In pedicled flaps, hypoxia was observed early after wounding. While reoxygenation occurred over time in db/+ mice, hypoxia was prolonged in the diabetic db/db model. This observation was consistent with impaired healing and microangiopathies observed using intravital microscopy. In conclusion, EPR oximetry using LiPc crystals as the oxygen sensor is an appropriate technique to follow wound oxygenation in acute and chronic wounds, in normal and diabetic animals. Nevertheless, the technique is limited for measurements in pedicled skin flaps and cannot be applied to excisional wounds in which diffusion of atmospheric oxygen significantly affects the measurements. PMID:26659378

  18. SPIDYAN, a MATLAB library for simulating pulse EPR experiments with arbitrary waveform excitation.

    PubMed

    Pribitzer, Stephan; Doll, Andrin; Jeschke, Gunnar

    2016-02-01

    Frequency-swept chirp pulses, created with arbitrary waveform generators (AWGs), can achieve inversion over a range of several hundreds of MHz. Such passage pulses provide defined flip angles and increase sensitivity. The fact that spectra are not excited at once, but single transitions are passed one after another, can cause new effects in established pulse EPR sequences. We developed a MATLAB library for simulation of pulse EPR, which is especially suited for modeling spin dynamics in ultra-wideband (UWB) EPR experiments, but can also be used for other experiments and NMR. At present the command line controlled SPin DYnamics ANalysis (SPIDYAN) package supports one-spin and two-spin systems with arbitrary spin quantum numbers. By providing the program with appropriate spin operators and Hamiltonian matrices any spin system is accessible, with limits set only by available memory and computation time. Any pulse sequence using rectangular and linearly or variable-rate frequency-swept chirp pulses, including phase cycling can be quickly created. To keep track of spin evolution the user can choose from a vast variety of detection operators, including transition selective operators. If relaxation effects can be neglected, the program solves the Liouville-von Neumann equation and propagates spin density matrices. In the other cases SPIDYAN uses the quantum mechanical master equation and Liouvillians for propagation. In order to consider the resonator response function, which on the scale of UWB excitation limits bandwidth, the program includes a simple RLC circuit model. Another subroutine can compute waveforms that, for a given resonator, maintain a constant critical adiabaticity factor over the excitation band. Computational efficiency is enhanced by precomputing propagator lookup tables for the whole set of AWG output levels. The features of the software library are discussed and demonstrated with spin-echo and population transfer simulations. PMID:26773526

  19. SPIDYAN, a MATLAB library for simulating pulse EPR experiments with arbitrary waveform excitation

    NASA Astrophysics Data System (ADS)

    Pribitzer, Stephan; Doll, Andrin; Jeschke, Gunnar

    2016-02-01

    Frequency-swept chirp pulses, created with arbitrary waveform generators (AWGs), can achieve inversion over a range of several hundreds of MHz. Such passage pulses provide defined flip angles and increase sensitivity. The fact that spectra are not excited at once, but single transitions are passed one after another, can cause new effects in established pulse EPR sequences. We developed a MATLAB library for simulation of pulse EPR, which is especially suited for modeling spin dynamics in ultra-wideband (UWB) EPR experiments, but can also be used for other experiments and NMR. At present the command line controlled SPin DYnamics ANalysis (SPIDYAN) package supports one-spin and two-spin systems with arbitrary spin quantum numbers. By providing the program with appropriate spin operators and Hamiltonian matrices any spin system is accessible, with limits set only by available memory and computation time. Any pulse sequence using rectangular and linearly or variable-rate frequency-swept chirp pulses, including phase cycling can be quickly created. To keep track of spin evolution the user can choose from a vast variety of detection operators, including transition selective operators. If relaxation effects can be neglected, the program solves the Liouville-von Neumann equation and propagates spin density matrices. In the other cases SPIDYAN uses the quantum mechanical master equation and Liouvillians for propagation. In order to consider the resonator response function, which on the scale of UWB excitation limits bandwidth, the program includes a simple RLC circuit model. Another subroutine can compute waveforms that, for a given resonator, maintain a constant critical adiabaticity factor over the excitation band. Computational efficiency is enhanced by precomputing propagator lookup tables for the whole set of AWG output levels. The features of the software library are discussed and demonstrated with spin-echo and population transfer simulations.

  20. Lipid peroxidation and water penetration in lipid bilayers: a W-band EPR study.

    PubMed

    Conte, Elena; Megli, Francesco Maria; Khandelia, Himanshu; Jeschke, Gunnar; Bordignon, Enrica

    2013-02-01

    Lipid peroxidation plays a key role in the alteration of cell membrane's properties. Here we used as model systems multilamellar vesicles (MLVs) made of the first two products in the oxidative cascade of linoleoyl lecithin, namely 1-palmitoyl-2-(13-hydroperoxy-9,11-octadecanedienoyl)-lecithin (HpPLPC) and 1-palmitoyl-2-(13-hydroxy-9,11-octadecanedienoyl)-lecithin (OHPLPC), exhibiting a hydroperoxide or a hydroxy group at position 13, respectively. The two oxidized lipids were used either pure or in a 1:1 molar ratio mixture with untreated 1-palmitoyl-2-linoleoyl-lecithin (PLPC). The model membranes were doped with spin-labeled lipids to study bilayer alterations by electron paramagnetic resonance (EPR) spectroscopy. Two different spin-labeled lipids were used, bearing the doxyl ring at position (n) 5 or 16: γ-palmitoyl-β-(n-doxylstearoyl)-lecithin (n-DSPPC) and n-doxylstearic acid (n-DSA). Small changes in the acyl chain order in the sub-polar region and at the methyl-terminal induced by lipid peroxidation were detected by X-band EPR. Concomitantly, the polarity and proticity of the membrane bilayer in those regions were investigated at W band in frozen samples. Analysis of the g(xx) and A(zz) parameters revealed that OHPLPC, but mostly HpPLPC, induced a measurable increase in polarity and H-bonding propensity in the central region of the bilayer. Molecular dynamics simulation performed on 16-DSA in the PLPC-HpPLPC bilayer revealed that water molecules are statistically favored with respect to the hydroperoxide groups to interact with the nitroxide at the methyl-terminal, confirming that the H-bonds experimentally observed are due to increased water penetration in the bilayer. The EPR and MD data on model membranes demonstrate that cell membrane damage by oxidative stress cause alteration of water penetration in the bilayer. PMID:23036933

  1. Spin relaxation measurements using first-harmonic out-of-phase absorption EPR signals.

    PubMed

    Livshits, V A; Páli, T; Marsh, D

    1998-09-01

    The dependence on spin-lattice (T1) relaxation of the first-harmonic absorption EPR signal (V'1) detected in phase quadrature with the Zeeman modulation has been investigated both theoretically and experimentally for nitroxide spin labels. Spectral simulations were performed by iterative solution of the Bloch equations that contained explicitly both the modulation and microwave magnetic fields (T. Páli, V. A. Livshits, and D. Marsh, 1996, J. Magn. Reson. B 113, 151-159). It was found that, of the various non-linear EPR displays, the first-harmonic out-of-phase V'1-signal, recorded under conditions of partial saturation of the microwave absorption, is particularly favorable for determining spin-lattice relaxation enhancements because of its superior signal intensity and relative insensitivity to spin-spin (T2) relaxation. By varying the Zeeman modulation frequency it is also possible to tune the optimum sensitivity of the V'1-signal to different ranges of the T1-relaxation time. A Zeeman modulation frequency of 25 kHz appears to be particularly suited to spin label applications. Calibrations are given for the dependence on T1-relaxation time of both the amplitude and the second integral of the V'1-signal recorded under standard conditions. Experiments on different spin labels in solution and in membranes demonstrate the practical usable sensitivity of the V'1-signal, even at modulation frequencies of 25 kHz, and these are used to investigate the dependence on microwave field intensity, in comparison with theoretical predictions. The practicable sensitivity to spin-lattice relaxation enhancements is demonstrated experimentally for a spin-labeled membrane system in the presence of paramagnetic ions. The first-harmonic out-of-phase V'1-signal appears to be the non-linear CW EPR method of choice for determining T1-relaxation enhancements in spin-labeled systems. PMID:9740736

  2. Algorithm for selection of optimized EPR distance restraints for de novo protein structure determination

    PubMed Central

    Kazmier, Kelli; Alexander, Nathan S.; Meiler, Jens; Mchaourab, Hassane S.

    2010-01-01

    A hybrid protein structure determination approach combining sparse Electron Paramagnetic Resonance (EPR) distance restraints and Rosetta de novo protein folding has been previously demonstrated to yield high quality models (Alexander et al., 2008). However, widespread application of this methodology to proteins of unknown structures is hindered by the lack of a general strategy to place spin label pairs in the primary sequence. In this work, we report the development of an algorithm that optimally selects spin labeling positions for the purpose of distance measurements by EPR. For the α-helical subdomain of T4 lysozyme (T4L), simulated restraints that maximize sequence separation between the two spin labels while simultaneously ensuring pairwise connectivity of secondary structure elements yielded vastly improved models by Rosetta folding. 50% of all these models have the correct fold compared to only 21% and 8% correctly folded models when randomly placed restraints or no restraints are used, respectively. Moreover, the improvements in model quality require a limited number of optimized restraints, the number of which is determined by the pairwise connectivities of T4L α-helices. The predicted improvement in Rosetta model quality was verified by experimental determination of distances between spin labels pairs selected by the algorithm. Overall, our results reinforce the rationale for the combined use of sparse EPR distance restraints and de novo folding. By alleviating the experimental bottleneck associated with restraint selection, this algorithm sets the stage for extending computational structure determination to larger, traditionally elusive protein topologies of critical structural and biochemical importance. PMID:21074624

  3. XRD and EPR structural investigation of some zinc borate glasses doped with iron ions

    NASA Astrophysics Data System (ADS)

    Stefan, Razvan; Pascuta, Petru; Popa, Adriana; Raita, Oana; Indrea, Emil; Culea, Eugen

    2012-02-01

    Glasses in the system xFe2O3·(100-x) [45ZnO·55B2O3] (0≤x≤10 mol%) have been prepared by melting at 1200 °C and rapidly cooling at room temperature. The obtained samples were submitted to an additional thermal treatment at 570 °C for 12 h in order to relax the glass structure as well as to improve the local order. The as cast and heat treated samples were investigated using X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) measurements. The XRD patterns of all the studied samples show their vitreous nature. Structural modifications occurring in the heat treated samples compared to the untreated ones have been pointed out. EPR spectra of untreated and heat treated samples revealed resonance absorptions centered at g≈2.0, g≈4.3 and g≈6.4. The compositional variation of the line intensity and linewidth of the absorptions from g≈4.3 and g≈2.0 have been interpreted in terms of the variation in the concentration of the Fe3+ ions and the interaction between the iron ions. The EPR spectra of the untreated samples containing 5 mol% Fe2O3 have been studied at different temperatures (110-290 K). The line intensity of the resonance signals decreases with increase in temperature whereas the linewidth is found to be independent of temperature. It was also found that the temperature variation of reciprocal line intensity obeys the Boltzmann law.

  4. Water accessibility in a membrane-inserting peptide comparing Overhauser DNP and pulse EPR methods.

    PubMed

    Segawa, Takuya F; Doppelbauer, Maximilian; Garbuio, Luca; Doll, Andrin; Polyhach, Yevhen O; Jeschke, Gunnar

    2016-05-21

    Water accessibility is a key parameter for the understanding of the structure of biomolecules, especially membrane proteins. Several experimental techniques based on the combination of electron paramagnetic resonance (EPR) spectroscopy with site-directed spin labeling are currently available. Among those, we compare relaxation time measurements and electron spin echo envelope modulation (ESEEM) experiments using pulse EPR with Overhauser dynamic nuclear polarization (DNP) at X-band frequency and a magnetic field of 0.33 T. Overhauser DNP transfers the electron spin polarization to nuclear spins via cross-relaxation. The change in the intensity of the (1)H NMR spectrum of H2O at a Larmor frequency of 14 MHz under a continuous-wave microwave irradiation of the nitroxide spin label contains information on the water accessibility of the labeled site. As a model system for a membrane protein, we use the hydrophobic α-helical peptide WALP23 in unilamellar liposomes of DOPC. Water accessibility measurements with all techniques are conducted for eight peptides with different spin label positions and low radical concentrations (10-20 μM). Consistently in all experiments, the water accessibility appears to be very low, even for labels positioned near the end of the helix. The best profile is obtained by Overhauser DNP, which is the only technique that succeeds in discriminating neighboring positions in WALP23. Since the concentration of the spin-labeled peptides varied, we normalized the DNP parameter ϵ, being the relative change of the NMR intensity, by the electron spin concentration, which was determined from a continuous-wave EPR spectrum. PMID:27208942

  5. Cooper-pair splitter: towards an efficient source of spin-entangled EPR pairs

    NASA Astrophysics Data System (ADS)

    Schonenberger, Christian

    2011-03-01

    In quantum mechanics the properties of two and more particles can be entangled. In basic science pairs of entangled particles, so called Einstein-Podolsky-Rosen (EPR) pairs, play a special role as toy objects for fundamental studies. They provide such things as ``spooky interaction at distance,'' but they also enable secure encoding and teleportation and are thus important for applications in quantum information technology. Whereas EPR pairs of photons can be generated by parametric down conversion (PDC) in a crystal, a similar source for EPR pairs of electrons does not exists yet. In several theory papers, it has been suggested to use a superconductor for this purpose. The superconducting ground state is formed by a condensate of Cooper-pairs which are electron pairs in a spin-singlet state. Since there are many Cooper pairs in a metallic superconductor like Al, the main tasks are to extract Cooper pairs one by one and to split them into different arms. A controlled and efficient splitting is possible if one makes use of Coulomb interaction. This has recently be demonstrated by two groups [2-4] using hybrid quantum-dot devices with both superconducting and normal metal contacts. In the present talk, I will discuss the Cooper-pair splitter results from the Basel-Budapest-Copenhagen team and compare with the other experiments. As an outlook we discuss approaches that aim at entanglement detection. The Cooper pair splitter holds great promises because very large splitting efficiencies approaching 100% and large pair current rates appear feasible. This work has been done by L. Hofstetter, S. Csonka, A. Geresdi, M. Aagesen, J. Nygard and C. Schönenberger

  6. EPR-based approach for the localization of paramagnetic metal ions in biomolecules.

    PubMed

    Abdullin, Dinar; Florin, Nicole; Hagelueken, Gregor; Schiemann, Olav

    2015-02-01

    Metal ions play an important role in the catalysis and folding of proteins and oligonucleotides. Their localization within the three-dimensional fold of such biomolecules is therefore an important goal in understanding structure-function relationships. A trilateration approach for the localization of metal ions by means of long-range distance measurements based on electron paramagnetic resonance (EPR) is introduced. The approach is tested on the Cu(2+) center of azurin, and factors affecting the precision of the method are discussed. PMID:25522037

  7. EPR study of electron bombarded alkali- and alkaline-earth halide crystal surfaces

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Lad, R. A.

    1975-01-01

    An EPR study of electron bombarded LiF, NaCl, KCl, CaF2 and BaF2 polycrystalline surfaces has shown that small metal particles are formed on the surfaces of the crystals. Identification was made from CESR signals. The symmetric line-shape of the signals, even at 77 K, indicated that the particles were less than 0.5 micron in diameter. Signals due to F centers were observed in LiF but not in the other halides. Implications to metal deposition are considered.

  8. Saturation recovery EPR and ELDOR at W-band for spin labels.

    PubMed

    Froncisz, Wojciech; Camenisch, Theodore G; Ratke, Joseph J; Anderson, James R; Subczynski, Witold K; Strangeway, Robert A; Sidabras, Jason W; Hyde, James S

    2008-08-01

    A reference arm W-band (94 GHz) microwave bridge with two sample-irradiation arms for saturation recovery (SR) EPR and ELDOR experiments is described. Frequencies in each arm are derived from 2 GHz synthesizers that have a common time-base and are translated to 94 GHz in steps of 33 and 59 GHz. Intended applications are to nitroxide radical spin labels and spin probes in the liquid phase. An enabling technology is the use of a W-band loop-gap resonator (LGR) [J.W. Sidabras, R.R. Mett, W. Froncisz, T.G. Camenisch, J.R. Anderson, J.S. Hyde, Multipurpose EPR loop-gap resonator and cylindrical TE(011) cavity for aqueous samples at 94 GHz, Rev. Sci. Instrum. 78 (2007) 034701]. The high efficiency parameter (8.2 GW(-1/2) with sample) permits the saturating pump pulse level to be just 5 mW or less. Applications of SR EPR and ELDOR to the hydrophilic spin labels 3-carbamoyl-2,2,5,5-tetra-methyl-3-pyrroline-1-yloxyl (CTPO) and 2,2,6,6,-tetramethyl-4-piperidone-1-oxyl (TEMPONE) are described in detail. In the SR ELDOR experiment, nitrogen nuclear relaxation as well as Heisenberg exchange transfer saturation from pumped to observed hyperfine transitions. SR ELDOR was found to be an essential method for measurements of saturation transfer rates for small molecules such as TEMPONE. Free induction decay (FID) signals for small nitroxides at W-band are also reported. Results are compared with multifrequency measurements of T(1e) previously reported for these molecules in the range of 2-35 GHz [J.S. Hyde, J.-J. Yin, W.K. Subczynski, T.G. Camenisch, J.J. Ratke, W. Froncisz, Spin label EPR T(1) values using saturation recovery from 2 to 35 GHz. J. Phys. Chem. B 108 (2004) 9524-9529]. The values of T(1e) decrease at 94 GHz relative to values at 35 GHz. PMID:18547848

  9. Chemical process to separate iron oxides particles in pottery sample for EPR dating.

    PubMed

    Watanabe, S; Farias, T M B; Gennari, R F; Ferraz, G M; Kunzli, R; Chubaci, J F D

    2008-12-15

    Ancient potteries usually are made of the local clay material, which contains relatively high concentration of iron. The powdered samples are usually quite black, due to magnetite, and, although they can be used for thermoluminescene (TL) dating, it is easiest to obtain better TL reading when clearest natural or pre-treated sample is used. For electron paramagnetic resonance (EPR) measurements, the huge signal due to iron spin-spin interaction, promotes an intense interference overlapping any other signal in this range. Sample dating is obtained by dividing the radiation dose, determined by the concentration of paramagnetic species generated by irradiation, by the natural dose so as a consequence, EPR dating cannot be used, since iron signal do not depend on radiation dose. In some cases, the density separation method using hydrated solution of sodium polytungstate [Na6(H2W12O40).H2O] becomes useful. However, the sodium polytungstate is very expensive in Brazil; hence an alternative method for eliminating this interference is proposed. A chemical process to eliminate about 90% of magnetite was developed. A sample of powdered ancient pottery was treated in a mixture (3:1:1) of HCl, HNO(3) and H(2)O(2) for 4h. After that, it was washed several times in distilled water to remove all acid matrixes. The original black sample becomes somewhat clearer. The resulting material was analyzed by plasma mass spectrometry (ICP-MS), with the result that the iron content is reduced by a factor of about 9. In EPR measurements a non-treated natural ceramic sample shows a broad spin-spin interaction signal, the chemically treated sample presents a narrow signal in g=2.00 region, possibly due to a radical of (SiO(3))(3-), mixed with signal of remaining iron [M. Ikeya, New Applications of Electron Spin Resonance, World Scientific, Singapore, 1993, p. 285]. This signal increases in intensity under gamma-irradiation. However, still due to iron influence, the additive method yielded too

  10. Pentachlorooxotechnetate(VI) anion, (TcOCl/sub 5/): an EPR study

    SciTech Connect

    Kirmse, R.; Stach, J.; Abram, U.

    1985-07-03

    The anion pentachlorooxotechnetate(VI), TcOCl/sub 5//sup -/, has been prepared by reduction of TcO/sub 4//sup -/ with HCl in concentrated H/sub 2/SO/sub 4/ and investigated by means of the EPR technique. The axial symmetric spectrum suggests an in-plane ..pi..-type ground state of the MO of the unpaired electron. The Tc-Cl/sub eq/ bonding properties have been discussed in terms of MO theory, and a comparison has been given to the bonding properties in likely complexes of neighboring elements of Tc.

  11. Two-dimensional Pulsed EPR Studies of Vanadium-Exchanged ZSM-5

    SciTech Connect

    Woodworth, James F.; Bowman, Michael K.; Larsen, Sarah C.

    2004-10-14

    The pulsed electron paramagnetic resonance (EPR) technique of hyperfine sublevel correlation spectroscopy (HYSCORE) was used to obtain structural information about vanadium(VO2+) exchanged ZSM-5. HYSCORE spectra were obtained for vanadium exchanged ZSM-5 before and after dehydration and after adsorption of ammonia. For the hydrated samples, proton hyperfine coupling constants were measured and assigned to equatorial water ligands with orientations perpendicular and parallel to the equatorial plane. Nitrogen hyperfine coupling constants for adsorbed ammonia were also determined from the HYSCORE spectra. The results were compared with previous density functional theory (DFT) calculations of hyperfine coupling constants for vanadyl model complexes.

  12. Identification of periplasmic nitrate reductase Mo(V) EPR signals in intact cells of Paracoccus denitrificans.

    PubMed

    Sears, H J; Bennett, B; Spiro, S; Thomson, A J; Richardson, D J

    1995-08-15

    EPR spectroscopy has been successfully used to detect signals due to molybdenum (V) and ferric iron in intact cells of aerobically grown Paracoccus denitrificans. The signals are ascribed to the catalytic molybdenum centre and to the haem iron of the periplasmic nitrate reductase. These signals are absent from a mutant strain deficient in this enzyme. The Mo(V) signal is due to the High-g Split species which has been well characterized in the purified enzyme. This confirms that the High-g Split is the physiologically relevant signal of a number observed in the previous work on the purified enzyme. PMID:7646461

  13. The influence of dithiothreitol on DNA radiolysis in frozen aqueous solution:. an EPR study

    NASA Astrophysics Data System (ADS)

    Ambroz, H. B.; Kemp, T. J.; Kornacka, E.; Przybytniak, G.

    2002-05-01

    The effect of a thiol, dithiothreitol (DTT), on DNA radiolysis at cryogenic temperatures was investigated by the EPR method. Dithiothreitol repairs up to 30% of DNA radicals, but an increase in the thiol concentration above 10 mM, even up to 1000 mM, does not further enhance the overall level of the repair process. The transfers of paramagnetic centres from both the guanine radical cation, and the allyl radical of thymine, to thiol were observed, while products generated via the reductive pathway remained unaffected.

  14. A Multiparty Controlled Bidirectional Quantum Secure Direct Communication and Authentication Protocol Based on EPR Pairs

    NASA Astrophysics Data System (ADS)

    Chang, Yan; Zhang, Shi-Bin; Yan, Li-Li; Sheng, Zhi-Wei

    2013-06-01

    A multiparty controlled bidirectional quantum secure direct communication and authentication protocol is proposed based on EPR pair and entanglement swapping. The legitimate identities of communicating parties are encoded to Bell states which act as a detection sequence. Secret messages are transmitted by using the classical XOR operation, which serves as a one-time-pad. No photon with secret information transmits in the quantum channel. Compared with the protocols proposed by Wang et al. [Acta Phys. Sin. 56 (2007) 673; Opt. Commun. 266 (2006) 732], the protocol in this study implements bidirectional communication and authentication, which defends most attacks including the ‘man-in-the-middle’ attack efficiently.

  15. Splitting spacetime and cloning qubits: linking no-go theorems across the ER=EPR duality

    NASA Astrophysics Data System (ADS)

    Bao, Ning; Pollack, Jason; Remmen, Grant N.

    2015-11-01

    We analyze the no-cloning theorem in quantum mechanics through the lens of the proposed ER=EPR (Einstein-Rosen = Einstein-Podolsky-Rosen) duality between entanglement and wormholes. In particular, we find that the no-cloning theorem is dual on the gravity side to the no-go theorem for topology change, violating the axioms of which allows for wormhole stabilization and causality violation. Such a duality between important no-go theorems elucidates the proposed connection between spacetime geometry and quantum entanglement.

  16. [Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

    SciTech Connect

    Eyring, E.M.

    1992-01-01

    The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd[sup 3+] + L(ligand), [RuL[sub 5]H[sub 2]O][sup 2+], laser flash photolysis of Mo(CO)[sub 6] + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd[sup 3+] ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO)[sub 6]-2,2'-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

  17. [Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

    SciTech Connect

    Eyring, E.M.

    1992-10-01

    The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd{sup 3+} + L(ligand), [RuL{sub 5}H{sub 2}O]{sup 2+}, laser flash photolysis of Mo(CO){sub 6} + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd{sup 3+} ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO){sub 6}-2,2`-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

  18. Efficient schemes of joint remote preparation with a passive receiver via EPR pairs

    NASA Astrophysics Data System (ADS)

    Ma, Song-Ya; Gao, Cong; Luo, Ming-Xing

    2015-11-01

    Novel schemes are put forward to execute the joint remote preparation of an arbitrary two-qubit state with a passive receiver via EPR pairs as the entangled channel. Compared with the previous protocols, the required multi-particle measurement is simplified and the classical communication cost is reduced. When the number of senders increases, the advantage is more evident. It means that the proposed schemes are more efficient in practice. Project supported by the National Natural Science Foundation of China (Grant Nos. 61201253, 61303039, 61572246, and 61502147) and the Fundamental Research Fund for the Central Universities of China (Grant No. 2682014CX095).

  19. Bidirectional teleportation of a pure EPR state by using GHZ states

    NASA Astrophysics Data System (ADS)

    Hassanpour, Shima; Houshmand, Monireh

    2016-02-01

    In the present paper, a novel bidirectional quantum teleportation protocol is proposed. By using entanglement swapping technique, two GHZ states are shared as a quantum channel between Alice and Bob as legitimate users. In this scheme, based on controlled-not operation, single-qubit measurement, and appropriate unitary operations, two users can simultaneously transmit a pure EPR state to each other, While, in the previous protocols, the users can just teleport a single-qubit state to each other via more than four-qubit state. Therefore, the proposed scheme is economical compared with previous protocols.

  20. 2'-Alkynylnucleotides: A Sequence- and Spin Label-Flexible Strategy for EPR Spectroscopy in DNA.

    PubMed

    Haugland, Marius M; El-Sagheer, Afaf H; Porter, Rachel J; Peña, Javier; Brown, Tom; Anderson, Edward A; Lovett, Janet E

    2016-07-27

    Electron paramagnetic resonance (EPR) spectroscopy is a powerful method to elucidate molecular structure through the measurement of distances between conformationally well-defined spin labels. Here we report a sequence-flexible approach to the synthesis of double spin-labeled DNA duplexes, where 2'-alkynylnucleosides are incorporated at terminal and internal positions on complementary strands. Post-DNA synthesis copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions with a variety of spin labels enable the use of double electron-electron resonance experiments to measure a number of distances on the duplex, affording a high level of detailed structural information. PMID:27409454

  1. EPR Oximetry for Investigation of Hyperbaric O2 Pre-treatment for Tumor Radiosensitization.

    PubMed

    Williams, Benjamin B; Hou, Huagang; Coombs, Rachel; Swartz, Harold M

    2016-01-01

    A number of studies have reported benefits associated with the application of hyperbaric oxygen treatment (HBO) delivered immediately prior to radiation therapy. While these studies provide evidence that pre-treatment with HBO may be beneficial, no measurements of intratumoral pO2 were carried out and they do not directly link the apparent benefits to decreased hypoxic fractions at the time of radiation therapy. While there is empirical evidence and some theoretical basis for HBO to enhance radiation therapy, without direct and repeated measurements of its effects on pO2, it is unlikely that the use of HBO can be understood and optimized for clinical applications. In vivo EPR oximetry is a technique uniquely capable of providing repeated direct measurements of pO2 through a non-invasive procedure in both animal models and human patients. In order to evaluate the ability of pretreatment with HBO to elevate tumor pO2, a novel small animal hyperbaric chamber system was constructed that allows simultaneous in vivo EPR oximetry. This chamber can be placed within the EPR magnet and is equipped with a variety of ports for multiplace gas delivery, thermoregulation, delivery of anesthesia, physiologic monitoring, and EPR detection. Initial measurements were performed in a subcutaneous RIF-1 tumor model in C3H/HeJ mice. The mean baseline pO2 value was 6.0 ± 1.2 mmHg (N = 7) and responses to two atmospheres absolute pressure HBO varied considerably across subjects, within tumors, and over time. When an increase in pO2 was observed, the effect was transient in all but one case, with durations lasting from 5 min to over 20 min, and returned to baseline levels during HBO administration. These results indicate that without direct measurements of pO2 in the tissue of interest, it is likely to be difficult to know the effects of HBO on actual tissue pO2. PMID:27526165

  2. Spin label electron paramagnetic resonance (EPR) studies of Huntington disease erythrocyte membranes.

    PubMed Central

    Fung, L W; Ostrowski, M S

    1982-01-01

    Several spin-label electron paramagnetic resonance (EPR) studies of red cell membranes appear to show abnormalities in some Huntington disease (HD) patients, but not in others. Both studies measure the W/S ratios, presumably under similar conditions, but have different results. We have studied the W/S ratio in some detail to gain a better understanding of this experimental parameter and to determine its potential application in detecting HD abnormalities. Our results offer little encouragement for continued use of W/S as an indication of membrane defect in HD. PMID:6282120

  3. Growth and EPR and optical properties of Li 2B 4O 7 single crystals doped with Co 2+ ions

    NASA Astrophysics Data System (ADS)

    Piwowarska, D.; Kaczmarek, S. M.; Berkowski, M.; Stefaniuk, I.

    2006-05-01

    Li 2B 4O 7 single crystals doped with Co ions were grown by the Czochralski method. The electron paramagnetic resonance (EPR) and optical absorption spectra of Li 2B 4O 7 (LBO) single crystals doped with Co 2+ ions were measured. The EPR spectra could be described by the spin-Hamiltonian with an effective spin of S={1}/{2} in octahedral symmetry. The values of g and A tensors and direction cosines characterizing Co 2+ centers in the LBO crystal were determined for the first time also. The EPR data reveals at least two types of Co 2+ centers. Optical absorption was measured in the range of 200 to 3200 nm for "as-grown" and γ-irradiated samples of Co:Li 2B 4O 7 crystals confirming octahedral coordination of Co 2+ ions and cation vacancies arising in the "as-grown" crystal.

  4. Theoretical investigations of the optical and EPR spectra for trivalent cerium and ytterbium ions in orthorhombic YF3 crystal

    NASA Astrophysics Data System (ADS)

    Liu, Hong-Gang; Zheng, Wen-Chen

    2016-09-01

    The optical spectra and electron paramagnetic resonance (EPR) parameters (g factors and hyperfine structure constants A) for trivalent cerium and ytterbium ions in YF3 crystal with orthorhombic structure are investigated together by the complete diagonalization (of energy matrix) method (CDM). The obtained results are in reasonable agreement with the experimental ones. More importantly, two magnetically nonequivalent centers in YF3 crystal observed in EPR experiments are confirmed and ascribed to their specific positions in a unit cell by our calculations based on superposition model (SPM) analysis. Such identification of local sites with different magnetic properties would help us to understand not only the EPR spectra and magnetic susceptibility of other lanthanide ions doped in crystals with the same structure as YF3 but also the energy transfer scheme between two lanthanide ions occupying such two sites. All results are discussed carefully.

  5. A Hash Based Remote User Authentication and Authenticated Key Agreement Scheme for the Integrated EPR Information System.

    PubMed

    Li, Chun-Ta; Weng, Chi-Yao; Lee, Cheng-Chi; Wang, Chun-Cheng

    2015-11-01

    To protect patient privacy and ensure authorized access to remote medical services, many remote user authentication schemes for the integrated electronic patient record (EPR) information system have been proposed in the literature. In a recent paper, Das proposed a hash based remote user authentication scheme using passwords and smart cards for the integrated EPR information system, and claimed that the proposed scheme could resist various passive and active attacks. However, in this paper, we found that Das's authentication scheme is still vulnerable to modification and user duplication attacks. Thereafter we propose a secure and efficient authentication scheme for the integrated EPR information system based on lightweight hash function and bitwise exclusive-or (XOR) operations. The security proof and performance analysis show our new scheme is well-suited to adoption in remote medical healthcare services. PMID:26349803

  6. EPR and LC-MS studies on the mechanism of industrial dye decolorization by versatile peroxidase from Bjerkandera adusta.

    PubMed

    Baratto, Maria Camilla; Juarez-Moreno, Karla; Pogni, Rebecca; Basosi, Riccardo; Vazquez-Duhalt, Rafael

    2015-06-01

    The mechanisms of industrial dye transformation by versatile peroxidase were elucidated. Purified versatile peroxidase from Bjerkandera adusta was able to decolorize different classes of dyes including azo and phthalocyanines, but unable to transform any of the anthraquinones tested. Kinetic constants for selected dyes were determined and the transformation products were analyzed by EPR spectroscopy and mass spectrometry. The EPR and MS analyses of the enzymatic decolorization products showed the cleavage of the azo bond in azo dyes and the total disruption of the phthalocyaninic ring in phthalocyanine dyes. The EPR analysis on two copper-containing dyes, reactive violet 5 (azo) and reactive blue 72 (phthalocyanine), showed that the transformation can or not break the metal-ion coordination bond according the dye nature. The role of the catalytic Trp172 in the dye transformation by a long-range electron transfer pathway was confirmed and the oxidation mechanisms are proposed and discussed. PMID:25567062

  7. EPR Studies of the Binding Properties, Guest Dynamics, and Inner-Space Dimensions of a Water-Soluble Resorcinarene Capsule.

    PubMed

    Ayhan, Mehmet Menaf; Casano, Gilles; Karoui, Hakim; Rockenbauer, Antal; Monnier, Valérie; Hardy, Micaël; Tordo, Paul; Bardelang, David; Ouari, Olivier

    2015-11-01

    Nitroxide free radicals have been used to study the inner space of one of Rebek's water-soluble capsules. EPR and (1) H NMR spectroscopy, ESI-MS, and DFT calculations showed a preference for the formation of 1:2 complexes. EPR titrations allowed us to determine binding constants (Ka ) in the order of 10(7)  M(-2) . EPR spectral-shape analysis provided information on the guest rotational dynamics within the capsule. The interplay between optimum hydrogen bonding upon capsule formation and steric strain for guest accommodation highlights some degree of flexibility for guest inclusion, particularly at the center of the capsule where the hydrogen bond seam can be barely distorted or slightly disturbed. PMID:26403999

  8. Toward the Fourth Dimension of Membrane Protein Structure: Insight into Dynamics from Spin-labeling EPR Spectroscopy

    PubMed Central

    Mchaourab, Hassane S.; Steed, P. Ryan; Kazmier, Kelli

    2011-01-01

    Trapping membrane proteins in the confines of a crystal lattice obscures dynamic modes essential for interconversion between multiple conformations in the functional cycle. Moreover, lattice forces could conspire with detergent solubilization to stabilize a minor conformer in an ensemble thus confounding mechanistic interpretation. Spin labeling in conjunction with electron paramagnetic resonance (EPR) spectroscopy offers an exquisite window into membrane protein dynamics in the native–like environment of a lipid bilayer. Systematic application of spin labeling and EPR identifies sequence-specific secondary structures, defines their topology and their packing in the tertiary fold. Long range distance measurements (60-80Å) between pairs of spin labels enable quantitative analysis of equilibrium dynamics and triggered conformational changes. This review highlights the contribution of spin labeling to bridging structure and mechanism. Efforts to develop methods for determining structures from EPR restraints and to increase sensitivity and throughput promise to expand spin labeling applications in membrane protein structural biology. PMID:22078555

  9. Characterization of acyl carrier protein and LytB in Babesia bovis apicoplast

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The apicoplast is a highly specialized organelle that mediates required functions in the growth and replication of apicomplexan parasites. Despite structural conservation of the apicoplast among different parasite genera and species, there are also critical differences in the metabolic requirements ...

  10. EPR and optical studies of vanadium doped potassium dihydrogen citrate (C 6H 7KO 7) single crystal

    NASA Astrophysics Data System (ADS)

    Yarbaşi, Zeynep; Karabulut, Abdulhalik; Karabulut, Bünyamin

    2011-09-01

    An EPR and optical studies of VO 2+ doped potassium dihydrogen citrate (PDHC) single crystals have been carried out at room temperature. It crystallizes in triclinic symmetry with the unit cell dimensions: a = 11.343 Å, b = 13.078 Å, c = 6.272 Å, α = 89.79°, β = 94.36°, γ = 104.2°. The angular variation of EPR spectra have shown that two different VO 2+ complexes are located in different chemical environments and each environment contains one magnetically VO 2+ site occupying substitutional position in the lattice and show very high angular dependence.

  11. Relation between EPR spectra and electrical conductivity of Pr 1-xPb xMnO 3 perovskites

    NASA Astrophysics Data System (ADS)

    Cong, B. T.; Yu, S. C.; Tho, N. D.; Chau, N.; Huynh, T. N.; Phan, T. L.

    2006-09-01

    The correlation between structure, Curie temperature ( TC), line width of EPR spectra and electrical conductivity of Pr 1-xPb xMnO 3 ( x=0.1, 0.2, 0.3, 0.4, and 0.5) perovskites is discussed. It was shown that both adiabatic small polaron and variable range hopping models are good for description of conductivity in paramagnetic region but the first one is more suitable for interpretation of temperature dependence of EPR line width in temperature range 1.2 TC< T<1.3 TC.

  12. Optical and EPR spectroscopy of Zn:Cr:ZnSe and Zn:Fe:ZnSe crystals

    NASA Astrophysics Data System (ADS)

    Fedorov, V. V.; Konak, T.; Dashdorj, J.; Zvanut, M. E.; Mirov, S. B.

    2014-11-01

    Optical and EPR characterization of Cr and Fe doped ZnSe crystals annealed in Zn vapor revealed a strong bleaching of the divalent state of transition metal ions. Photo induced EPR kinetics were studied in 20-80 K temperature range. Analysis of time-dependent data reveals Cr1+ signal rise time decreases with increasing temperature. The non-exponential decay of Cr1+ concentration were analyzed using Auger-type recombination process. The photoluminescence quantum yield of Cr2+ ions at 5E(D) → 5T2(D) mid-IR transition excited via chromium ionization process was measured to be close to 100%.

  13. Decision support tools for proton therapy ePR: intelligent treatment planning navigator and radiation toxicity tool for evaluating of prostate cancer treatment

    NASA Astrophysics Data System (ADS)

    Le, Anh H.; Deshpande, Ruchi; Liu, Brent J.

    2010-03-01

    The electronic patient record (ePR) has been developed for prostate cancer patients treated with proton therapy. The ePR has functionality to accept digital input from patient data, perform outcome analysis and patient and physician profiling, provide clinical decision support and suggest courses of treatment, and distribute information across different platforms and health information systems. In previous years, we have presented the infrastructure of a medical imaging informatics based ePR for PT with functionality to accept digital patient information and distribute this information across geographical location using Internet protocol. In this paper, we present the ePR decision support tools which utilize the imaging processing tools and data collected in the ePR. The two decision support tools including the treatment plan navigator and radiation toxicity tool are presented to evaluate prostate cancer treatment to improve proton therapy operation and improve treatment outcomes analysis.

  14. Effect of annealing on EPR spectra of Ti-Si-C-N samples

    NASA Astrophysics Data System (ADS)

    Guskos, N.; Anagnostakis, E. A.; Zolnierkiewicz, G.; Typek, J.; Biedunkiewicz, A.; Guskos, A.; Berczynski, P.

    2012-03-01

    Two nanocrystalline samples of TiC+SiC+20%C (sample 1) and Si3N4+Si(C,N)+Ti(C,N)+1%C (sample 2) were prepared by non-hydrolytic sol-gel method. The latter sample was produced from sample 1, by subjecting it to additional annealing at high temperature. XRD measurements showed the presence of aggregates of cubic SiC+TiC nanoparticles (10 to 30 nm in size). In both samples, a very narrow electron paramagnetic resonance (EPR) line originating from localized magnetic centers was centered at g eff˜2. At T = 130 K, we registered the linewidths Δ H pp = 1.41(2) G and Δ H pp = 2.92(2) G for the sample without and with thermal annealing, respectively. For the non-annealed sample, the resonance line was fitted by a Lorentzian line in the low temperature range, and by a Dysonian line above 70 K, which indicates a significant change in electrical conductivity. Therefore, thermal annealing can significantly improve the transport properties of samples. An analysis of the temperature dependence of the EPR parameters ( g-factor, linewidth, integrated intensity) showed that thermal annealing has a significant impact on the reorientation processes of localized magnetic centers.

  15. Triarylmethyl Labels: Toward Improving the Accuracy of EPR Nanoscale Distance Measurements in DNAs.

    PubMed

    Shevelev, Georgiy Yu; Krumkacheva, Olesya A; Lomzov, Alexander A; Kuzhelev, Andrey A; Trukhin, Dmitry V; Rogozhnikova, Olga Yu; Tormyshev, Victor M; Pyshnyi, Dmitrii V; Fedin, Matvey V; Bagryanskaya, Elena G

    2015-10-29

    Triarylmethyl (trityl, TAM) based spin labels represent a promising alternative to nitroxides for EPR distance measurements in biomolecules. Herewith, we report synthesis and comparative study of series of model DNA duplexes, 5'-spin-labeled with TAMs and nitroxides. We have found that the accuracy (width) of distance distributions obtained by double electron-electron resonance (DEER/PELDOR) strongly depends on the type of radical. Replacement of both nitroxides by TAMs in the same spin-labeled duplex allows narrowing of the distance distributions by a factor of 3. Replacement of one nitroxide by TAM (orthogonal labeling) leads to a less pronounced narrowing but at the same time gains sensitivity in DEER experiment due to efficient pumping on the narrow EPR line of TAM. Distance distributions in nitroxide/nitroxide pairs are influenced by the structure of the linker: the use of a short amine-based linker improves the accuracy by a factor of 2. At the same time, a negligible dependence on the linker length is found for the distribution width in TAM/TAM pairs. Molecular dynamics calculations indicate greater conformational disorder of nitroxide labels compared to TAM ones, thus rationalizing the experimentally observed trends. Thereby, we conclude that double spin-labeling using TAMs allows obtaining narrower spin-spin distance distributions and potentially more precise distances between labeling sites compared to traditional nitroxides. PMID:26011022

  16. Magnesium lactate mixed with EVA polymer/paraffin as an EPR dosimeter for radiation processing application

    NASA Astrophysics Data System (ADS)

    Soliman, Y. S.; Abdel-Fattah, A. A.

    2012-12-01

    The dosimetric characteristics of γ-radiation-induced defects in magnesium lactate (ML) rods (3.5 mm×10 mm) formulated by mixing ML with molten mixtures of paraffin wax and EVA copolymer have been investigated using electron paramagnetic resonance (EPR). The EPR spectrum of irradiated ML rods was characterized by a quartet signal with the spectroscopic splitting g-factor of 2.0048±0.0003 at 0.4 mT. The useful dose range of the rod dosimeter was 100 Gy to 80 kGy. The mass attenuation coefficient, μ/ρ, and the mass energy-absorption coefficient, μen/ρ, versus energy in the range of 10 keV to 20 MeV indicate that the prepared ML dosimeter is typically adipose tissue equivalent overall this energy range. The overall combined uncertainties (at 2σ) associated with routine dose monitoring in the dose range of 0.1-10 kGy and 10-80 kGy were found to be 6.14% and 6.36%, respectively.

  17. Zigzagging causility model of EPR correlations and on the interpretation of quantum mechanics

    SciTech Connect

    de Beauregard, O.C.

    1988-09-01

    Being formalized inside the S-matrix scheme, the zigzagging causility model of EPR correlations has full Lorentz and CPT invariance. EPR correlations, proper or reversed, and Wheeler's smoky dragon metaphor are respectively pictured in a spacetime or in the momentum-energy space, as V-shaped, anti LAMBDA-shaped, or C-shaped ABC zigzags, with a summation at B over virtual states absolute value B>

  18. Fast dynamic electron paramagnetic resonance (EPR) oxygen imaging using low-rank tensors.

    PubMed

    Christodoulou, Anthony G; Redler, Gage; Clifford, Bryan; Liang, Zhi-Pei; Halpern, Howard J; Epel, Boris

    2016-09-01

    Hypoxic tumors are resistant to radiotherapy, motivating the development of tools to image local oxygen concentrations. It is generally believed that stable or chronic hypoxia is the source of resistance, but more recent work suggests a role for transient hypoxia. Conventional EPR imaging (EPRI) is capable of imaging tissue pO2in vivo, with high pO2 resolution and 1mm spatial resolution but low imaging speed (10min temporal resolution for T1-based pO2 mapping), which makes it difficult to investigate the oxygen changes, e.g., transient hypoxia. Here we describe a new imaging method which accelerates dynamic EPR oxygen imaging, allowing 3D imaging at 2 frames per minute, fast enough to image transient hypoxia at the "speed limit" of observed pO2 change. The method centers on a low-rank tensor model that decouples the tradeoff between imaging speed, spatial coverage/resolution, and number of inversion times (pO2 accuracy). We present a specialized sparse sampling strategy and image reconstruction algorithm for use with this model. The quality and utility of the method is demonstrated in simulations and in vivo experiments in tumor bearing mice. PMID:27498337

  19. EPR and magnetic susceptibility investigation of iron-zinc-phosphate glass ceramics

    SciTech Connect

    Popa, A.; Stefan, R.; Bosca, M.; Dan, V.; Pop, V.; Pascuta, P.

    2013-11-13

    (Fe{sub 2}O{sub 3}){sub x}⋅(P{sub 2}O{sub 5}){sub 40}⋅(ZnO){sub 60−x} glass ceramics containing different concentrations of Fe{sub 2}O{sub 3} ranging from 1 to 20 mol% were obtained by heat treatment of glass samples at 650 °C for 2 h. The structural and magnetic properties of these glass ceramics were investigated by means of electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. The EPR spectra of the studied samples revealed absorptions centered at g ≈ 2.0 and 4.3. The compositional variations of the intensity and line width of these absorption lines was interpreted in terms of the variation in Fe{sup 3+} and Fe{sup 2+} ions concentration in the glass ceramics as well as the interaction between the iron ions. The magnetic susceptibility data evidenced the presence of both Fe{sup 3+} and Fe{sup 2+} ions, with their relative content depending on the Fe{sub 2}O{sub 3} concentration. Dipolar and superexchange interactions involving iron ions were revealed depending on the iron content of the sample.

  20. Heavy-ion-induced sucrose radicals investigated using EPR and UV spectroscopy.

    PubMed

    Nakagawa, Kouichi; Karakirova, Yordanka; Yordanov, Nicola D

    2015-05-01

    The potential use of a sucrose dosimeter for estimating both linear energy transfer (LET) and the absorbed dose of heavy ion and X-ray radiation was investigated. The stable free radicals were produced when sucrose was irradiated with heavy ions, such as helium, carbon, silicon and neon ions, and when the X-ray radiation was similar to the obtained electron paramagnetic resonance (EPR) spectra, which were ∼7 mT wide and composed of several hyperfine structures. In addition, the total spin concentration resulting from heavy-ion irradiation increased linearly as the absorbed dose increased, and decreased logarithmically as the LET increased. These empirical relations imply that the LET at a certain dose can be determined from the spin concentration. For sucrose and alanine, both cross-sections following C-ion irradiation with a 50 Gy dose were ∼1.3 × 10(-12) [μm(2)], taking into account the molecular size of the samples. The values of these cross-sections imply that multiple ionizing particles were involved in the production of stable radicals. Furthermore, UV absorbance at 267 nm of an aqueous solution of irradiated sucrose was found to linearly increase with increasing absorbed dose. Therefore, the EPR and UV results suggest that sucrose can be a useful dosimeter for heavy-ion irradiation. PMID:25480828

  1. Structural characterization and EPR spectral studies on mononuclear copper(II) complex of saccharin with ethylnicotinate

    NASA Astrophysics Data System (ADS)

    Uçar, İbrahim; Bozkurt, Esat; Kazak, Canan; Bulut, Ahmet

    2009-02-01

    Mononuclear copper(II) saccharinate (sac) complex containing ethylnicotinate (enc), [Cu(enc) 2(sac) 2(H 2O)]·1.4H 2O has been synthesized and characterized by spectroscopic (IR, UV-vis, EPR), X-ray diffraction technique and electrochemical methods. It crystallizes in the tetragonal crystal systems with space group I4 1cd and Z = 8. The copper(II) ion presents a CuN 4O distorted square pyramidal coordination. Based on EPR and optical absorption studies, spin-Hamiltonian and bonding parameters have been calculated. The g-values, calculated for title complex in polycrystalline state at 298 K and in frozen DMF (110 K), indicate the presence of the unpaired electron in the d orbital. The evaluated metal-ligand bonding parameters showed strong in-plane σ and in-plane π-bonding. Some comparisons with related structures are made and the most important features of its IR spectrum were also discussed. The cyclic voltammogram of the title complex investigated in DMF (dimethylformamide) solution exhibits only metal centred electroactivity in the potential range ±1.25 V vs. Ag/AgCl reference electrode.

  2. Integrity of the reactor coolant boundary of the European pressurized water reactor (EPR)

    SciTech Connect

    Goetsch, D.; Bieniussa, K.; Schulz, H.; Jalouneix, J.

    1997-04-01

    This paper is an abstract of the work performed in the frame of the development of the IPSN/GRS approach in view of the EPR conceptual safety features. EPR is a pressurized water reactor which will be based on the experience gained by utilities and designers in France and in Germany. The reactor coolant boundary of a PWR includes the reactor pressure vessel (RPV), those parts of the steam generators (SGs) which contain primary coolant, the pressurizer (PSR), the reactor coolant pumps (RCPs), the main coolant lines (MCLs) with their branches as well as the other connecting pipes and all branching pipes including the second isolation valves. The present work covering the integrity of the reactor coolant boundary is mainly restricted to the integrity of the main coolant lines (MCLs) and reflects the design requirements for the main components of the reactor coolant boundary. In the following the conceptual aspects, i.e. design, manufacture, construction and operation, will be assessed. A main aspect is the definition of break postulates regarding overall safety implications.

  3. XAS and Pulsed EPR Studies of the Copper Binding Site in Riboflavin Binding Protein

    SciTech Connect

    Smith,S.; Bencze, K.; Wasiukanis, K.; Benore-Parsons, T.; Stemmler, T.

    2008-01-01

    Riboflavin Binding Protein (RBP) binds copper in a 1:1 molar ratio, forming a distinct well-ordered type II site. The nature of this site has been examined using X-ray absorption and pulsed electron paramagnetic resonance (EPR) spectroscopies, revealing a four coordinate oxygen/nitrogen rich environment. On the basis of analysis of the Cambridge Structural Database, the average protein bound copper-ligand bond length of 1.96 Angstroms, obtained by extended x-ray absorption fine structure (EXAFS), is consistent with four coordinate Cu(I) and Cu(II) models that utilize mixed oxygen and nitrogen ligand distributions. These data suggest a CuO3N coordination state for copper bound to RBP. While pulsed EPR studies including hyperfine sublevel correlation spectroscopy and electron nuclear double resonance show clear spectroscopic evidence for a histidine bound to the copper, inclusion of a histidine in the EXAFS simulation did not lead to any significant improvement in the fit.

  4. A 140 GHz pulsed EPR/212 MHz NMR spectrometer for DNP studies

    NASA Astrophysics Data System (ADS)

    Smith, Albert A.; Corzilius, Björn; Bryant, Jeffrey A.; DeRocher, Ronald; Woskov, Paul P.; Temkin, Richard J.; Griffin, Robert G.

    2012-10-01

    We described a versatile spectrometer designed for the study of dynamic nuclear polarization (DNP) at low temperatures and high fields. The instrument functions both as an NMR spectrometer operating at 212 MHz (1H frequency) with DNP capabilities, and as a pulsed-EPR operating at 140 GHz. A coiled TE011 resonator acts as both an NMR coil and microwave resonator, and a double balanced (1H, 13C) radio frequency circuit greatly stabilizes the NMR performance. A new 140 GHz microwave bridge has also been developed, which utilizes a four-phase network and ELDOR channel at 8.75 GHz, that is then multiplied and mixed to obtain 140 GHz microwave pulses with an output power of 120 mW. Nutation frequencies obtained are as follows: 6 MHz on S = 1/2 electron spins, 100 kHz on 1H, and 50 kHz on 13C. We demonstrate basic EPR, ELDOR, ENDOR, and DNP experiments here. Our solid effect DNP results demonstrate an enhancement of 144 and sensitivity gain of 310 using OX063 trityl at 80 K and an enhancement of 157 and maximum sensitivity gain of 234 using Gd-DOTA at 20 K, which is significantly better performance than previously reported at high fields (⩾3 T).

  5. Low-temperature EPR and quantum chemical study of lactone radical cations and their transformations

    NASA Astrophysics Data System (ADS)

    Naumov, S.; Janovský, I.; Knolle, W.; Mehnert, R.; Turin, D. A.

    2005-07-01

    Radical cations of a number of lactones ( β-butyro-, γ-butyro-, γ-valero-, δ-hexano-, δ-valero- and ɛ-capro-) were radiolytically generated in CF 3CCl 3 matrix and investigated by EPR spectroscopy. The primary radical cation of the 4-membered ring β-butyrolactone is unstable even at 77 K and undergoes spontaneous ring opening and fragmentation, leading to the deprotonated neutral (CH 2CHCH 2) rad radical. The stability of the primary carbonyl-centred radical cations of the 5-, 6- and 7-membered lactone rings towards intramolecular H-shift from the C1 in α-position to carbonyl oxygen depends primarily on the ring size, which determines the activation energy of the transformation and distance L(H-O) of the carbonyl oxygen to the nearest H-atom on the ring. The larger the ring, the smaller the L(H-O) and also activation energy of the H-shift, making the transformation of the primary radical cation more feasible. The quantum chemical calculations facilitated the interpretation of the EPR spectra of the secondary radical cations.

  6. Investigating the Structural Properties of Integral Membrane Proteins with Pulsed EPR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lorigan, Gary

    2013-03-01

    Very limited structural and dynamic information on proteins embedded inside a membrane currently exist, because they are difficulty to crystalize. New biophysical/structural biology methods are needed to probe these systems in a lipid bilayer. The Lorigan lab is applying unique hybrid NMR and spin-label EPR spectroscopic techniques to study membrane proteins. Magnetic resonance spectroscopic data of 15N-, 2H-labeled and/or spin-labeled membrane proteins incorporated into vesicles and bicelles will be presented. State-of-the-art pulsed EPR techniques such as Electron Spin Echo Envelope Modulation (ESEEM) spectroscopy, and Double Electron-Electron Resonance (DEER) spectroscopy will be used. The ESEEM technique can determine short to medium range distances (out to about 8 Å) between a site-specific nitroxide spin label and a nearby NMR-active isotopic labeled residue for a variety of different peptides and proteins which ultimately can be used to determine the difference between an α-helical and β-sheet secondary structure. DEER can be used to measure distances between 2 spin labels out to about 70 Å. We have shown a huge improvement is sensitivity with DEER measurements at Q-band when compared to X-band.

  7. EPR monitored redox titration of the cofactors of Saccharomyces cerevisiae Nar1.

    PubMed

    Hagedoorn, Peter-Leon; van der Weel, Laura; Hagen, Wilfred R

    2014-01-01

    Electron Paramagnetic Resonance (EPR) monitored redox titrations are a powerful method to determine the midpoint potential of cofactors in proteins and to identify and quantify the cofactors in their detectable redox state. The technique is complementary to direct electrochemistry (voltammetry) approaches, as it does not offer information on electron transfer rates, but does establish the identity and redox state of the cofactors in the protein under study. The technique is widely applicable to any protein containing an electron paramagnetic resonance (EPR) detectable cofactor. A typical titration requires 2 ml protein with a cofactor concentration in the range of 1-100 µM. The protein is titrated with a chemical reductant (sodium dithionite) or oxidant (potassium ferricyanide) in order to poise the sample at a certain potential. A platinum wire and a Ag/AgCl reference electrode are connected to a voltmeter to measure the potential of the protein solution A set of 13 different redox mediators is used to equilibrate between the redox cofactors of the protein and the electrodes. Samples are drawn at different potentials and the Electron Paramagnetic Resonance spectra, characteristic for the different redox cofactors in the protein, are measured. The plot of the signal intensity versus the sample potential is analyzed using the Nernst equation in order to determine the midpoint potential of the cofactor. PMID:25490157

  8. Effect of thermal treatment on potato starch evidenced by EPR, XRD and molecular weight distribution.

    PubMed

    Bidzińska, Ewa; Michalec, Marek; Pawcenis, Dominika

    2015-12-01

    Effect of heating of the potato starch on damages of its structure was investigated by quantitative electron paramagnetic resonance (EPR) spectroscopy, X-ray diffraction and determination of the molecular weight distribution. The measurements were performed in the temperature range commonly used for starch modifications optimizing properties important for industrial applications. Upon thermal treatment, because of breaking of the polymer chains, diminishing of the average molecular weights occurred, which significantly influences generation of radicals, evidenced by EPR. For the relatively mild conditions, with heating parameters not exceeding temperature 230 °C and time of heating equal to 30 min a moderate changes of both the number of thermally generated radicals and the mean molecular weight of the starch were observed. After more drastic thermal treatment (e.g. 2 h at 230 °C), a rapid increase in the radical amount occurred, which was accompanied by significant reduction of the starch molecular size and crystallinity. Experimentally established threshold values of heating parameters should not be exceeded in order to avoid excessive damages of the starch structure accompanied by the formation of the redundant amount of radicals. This requirement is important for industrial applications, because significant destruction of the starch matrix might annihilate the positive influence of the previously performed intentional starch modification. PMID:26332295

  9. Mössbauer and EPR Study of Reaction Intermediates of Cytochrome P450

    NASA Astrophysics Data System (ADS)

    Schünemann, V.; Trautwein, A. X.; Jung, C.; Terner, J.

    2002-06-01

    We present a complementary Mössbauer and EPR study on reaction intermediates of substrate-free and substrate-bound cytochrome P450cam from Pseudomonas putida prepared by the freeze-quench method from 57Fe-labeled P450cam using peroxy acetic acid as oxidizing agent. When reacting the substrate-free P450cam for 8 ms reaction time the reaction mixture consists of ˜85% of ferric low-spin iron (Fe(III)) with g-factors and hyperfine parameters of the starting material; the remaining ˜15% are identified as ferryl iron (Fe(IV); S Fe=1) by its Mössbauer signature. Parallel to the ferryl iron a tyrosine radical ( S rad=1/2) is formed. The two paramagnetic species are not exchange-coupled; however, they are close enough to significantly influence the (EPR) relaxation behavior of the radical spin. In the case of substrate-bound P450cam only trace amounts of the tyrosine radical are formed within 8 ms (<3%); within the accuracy of Mössbauer spectroscopy (5%) iron(IV) can not be detected. The results point to Tyr-96, which is hydrogen-bonded to the substrate camphor, as the candidate for the observed tyrosine radical.

  10. Influence of crushing and additive irradiation procedures on EPR dosimetry of tooth enamel

    SciTech Connect

    Shalom, S.V.; Chumak, V.V.; Haskell, E.H.; Hayes, R.B.; Kenner, G.H.

    1996-01-01

    The effect of the crushing and additive dose procedures used in EPR dosimetry of enamel was studied on the signals with g-factors of 2. 0045 and g, = 2.0018, g. = 1.9975. Eight fractions, ranging in size from <75 micrometers to 2 mm, were prepared from one tooth. Two cases were investigated: crushing of a non-irradiated sample and of a sample previously irradiated (6 Gy from `Co gamma ray source). In the non-irradiated study, the intensity of the native signal at 2.0045 in by circa 1.75 times as the grain size decreased from maximum to minimum. A small in radiation sensitivity (< 8%) was also observed with decreasing grain size. In the irradiated samples, crushing resulted in slight variations of reconstructed doses from expected values, but the worst possible case (grain sizes < 75 micron) showed that additional errors were less than 10%. The radiation sensitivity of enamel measured immediately after exposure is underestimated. It increases by about 15% in the first month. Based on the decomposition of the observed spectra, a new interpretation of transient signals 1108 is proposed which explains the above phenomena. Recommendations about how to use this interpretation in retrospective EPR dosimetry are given.

  11. Oxidation state of manganese in zinc pyrophosphate: Probed by luminescence and EPR studies

    NASA Astrophysics Data System (ADS)

    Gupta, Santosh K.; Kadam, R. M.; Natarajan, V.; Godbole, S. V.

    2014-04-01

    Zn2P2O7: Mn was synthesized by wet chemical route and characterized by X-ray diffraction (XRD), photoluminescence (PL) and electron paramagnetic resonance (EPR) techniques. Photoluminescence spectrum shows two bands, one at 500 nm (green emission), which is attributed to the 4T1(4G)-6A1(6S) transition of Mn2+ and other centered at 686 nm (red emission) is attributed to the electronic transition between 2E and 4A2 of Mn4+ accompanied with vibronic transitions. EPR spectroscopic studies also confirmed the presence of both Mn2+ and Mn4+ ions in zinc pyrophosphate with difference in the number of fine transitions and g values (Mn4+, S=3/2, three fine transitions and g < 2.00; Mn2+ S=5/2, five fine transitions and g=2.00).Mn2+ is attributed to presence of Mn at 6-ccordinated Zn2+ site whereas Mn4+ is due to presence substitution of Mn4+ at Zn2+ site thereby invoking charge compensation by presence of interstitial oxygen ions around Mn4+ ion or due to substitution of manganese at distorted 5-coordinated zinc site.

  12. Luminescence studies and EPR investigation of solution combustion derived Eu doped ZnO

    NASA Astrophysics Data System (ADS)

    Jagannatha Reddy, A.; Kokila, M. K.; Nagabhushana, H.; Shivakumara, C.; Chakradhar, R. P. S.; Nagabhushana, B. M.; Hari Krishna, R.

    2014-11-01

    ZnO:Eu (0.1 mol%) nanopowders have been synthesized by auto ignition based low temperature solution combustion method. Powder X-ray diffraction (PXRD) patterns confirm the nanosized particles which exhibit hexagonal wurtzite structure. The crystallite size estimated from Scherrer's formula was found to be in the range 35-39 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies reveal particles are agglomerated with quasi-hexagonal morphology. A blue shift of absorption edge with increase in band gap is observed for Eu doped ZnO samples. Upon 254 nm excitation, ZnO:Eu nanopowders show peaks in regions blue (420-484 nm), green (528 nm) and red (600 nm) which corresponds to both Eu2+ and Eu3+ ions. The electron paramagnetic resonance (EPR) spectrum exhibits a broad resonance signal at g = 4.195 which is attributed to Eu2+ ions. Further, EPR and thermoluminescence (TL) studies reveal presence of native defects in this phosphor. Using TL glow peaks the trap parameters have been evaluated and discussed.

  13. Luminescence studies and EPR investigation of solution combustion derived Eu doped ZnO.

    PubMed

    Jagannatha Reddy, A; Kokila, M K; Nagabhushana, H; Shivakumara, C; Chakradhar, R P S; Nagabhushana, B M; Hari Krishna, R

    2014-11-11

    ZnO:Eu (0.1 mol%) nanopowders have been synthesized by auto ignition based low temperature solution combustion method. Powder X-ray diffraction (PXRD) patterns confirm the nanosized particles which exhibit hexagonal wurtzite structure. The crystallite size estimated from Scherrer's formula was found to be in the range 35-39 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies reveal particles are agglomerated with quasi-hexagonal morphology. A blue shift of absorption edge with increase in band gap is observed for Eu doped ZnO samples. Upon 254 nm excitation, ZnO:Eu nanopowders show peaks in regions blue (420-484 nm), green (528 nm) and red (600 nm) which corresponds to both Eu2+ and Eu3+ ions. The electron paramagnetic resonance (EPR) spectrum exhibits a broad resonance signal at g=4.195 which is attributed to Eu2+ ions. Further, EPR and thermoluminescence (TL) studies reveal presence of native defects in this phosphor. Using TL glow peaks the trap parameters have been evaluated and discussed. PMID:24878437

  14. Spin-labelled cyclometallated palladium complexes. EPR study of dynamic processes in coordination sphere

    NASA Astrophysics Data System (ADS)

    Kozhanov, K. A.; Bubnov, M. P.; Abakumov, G. A.; Cherkasov, V. K.

    2012-12-01

    New four-, five- and six-coordinated cyclometallated o-semiquinonato palladium complexes were obtained and characterized in solution by EPR. Interaction of square-planar azaphenyl palladium semiquinonate with mono and bidentate phosphane donors leads to formation of five- and six-coordinated adducts. Typical values of HFC constants on apical and basal phosphorouses are observed for such compounds. In one case the reversible addition of tri-phenyl-phosphane was observed. The coordination mode of pincer ligand (bi- or tridentate) in o-semiquinonato pincer complexes depends on the nature of linker between coordinating group and pincer aryl ring. In the case of sbnd CH2sbnd linker five coordinated complexes are formed. The "swing" and "fan" oscillations are observed for these compounds. Complexes with sbnd Osbnd linker are the first examples of compounds with bidentate bonded phosphorous-based pincer ligand. Most of complexes are unstable and decompose during some hours. Only the application of o-semiquinones as spin labels and using the EPR technique made possible to observe and interpret their structure.

  15. The assessment of future extremes of air temperature to design EPR type power plants

    NASA Astrophysics Data System (ADS)

    Parey, S.; Hoang, T. T. H.; Dacunha-Castelle, D.

    2010-09-01

    EDF projects the construction of new EPR type nuclear power plants in Europe. These installations are likely to run until the second half of the century, and thus, it is necessary to think their dimensioning in taking current knowledge of climate change impact into account. This paper will present the study dedicated to the estimation of future extremes of air temperature by using the statistical extreme value theory. The adopted methodology consists firstly in comparing current climate temperature extremes between local observations and models at the nearest grid point. Then, if the extremes of both series are comparable, future extremes are derived from the modelled series for a future period. In parallel, the link between the evolution of the mean, variance and extremes is studied in the observation series. If a strong link is identified, future extremes are derived from the stationary extremes of the centred and normalised series and the changes in mean and variance given by climate models for the desired future period. The approach will be illustrated with an example of such an evaluation for an EPR project in the United Kingdom.

  16. Hydrogen at zinc vacancy of ZnO: An EPR and ESEEM study

    SciTech Connect

    Son, N. T.; Ivanov, I. G.; Janzén, E.; Isoya, J.; Ohshima, T.

    2014-02-21

    An electron paramagnetic resonance (EPR) spectrum, labeled S1, with small-splitting doublet accompanied by weak satellites is observed in ZnO irradiated with 2 MeV electrons. The obtained structure is shown to be the hyperfine structure due to the dipolar interaction between an unpaired electron spin and a nuclear spin of hydrogen (H). The observation of the nuclear Zeeman frequency of H in electron spin echo envelope modulation experiments further confirmed the presence of a hydrogen atom in S1. From the observed spin-Hamiltonian parameters, S1 is identified to be the partly H-passivated Zn vacancy, V{sub Zn}{sup −}H{sup +}, with the H{sup +} ion making a short O-H bond with only one nearest O neighbor of V{sub Zn} in the basal plane, being off the substitutional site, while the unpaired electron spin, which gives rise to the observed EPR signal, is localized on the p orbital of another O neighbor also in the basal plane.

  17. Membrane transporters studied by EPR spectroscopy: structure determination and elucidation of functional dynamics.

    PubMed

    Mullen, Anna; Hall, Jenny; Diegel, Janika; Hassan, Isa; Fey, Adam; MacMillan, Fraser

    2016-06-15

    During their mechanistic cycles membrane transporters often undergo extensive conformational changes, sampling a range of orientations, in order to complete their function. Such membrane transporters present somewhat of a challenge to conventional structural studies; indeed, crystallization of membrane-associated proteins sometimes require conditions that vary vastly from their native environments. Moreover, this technique currently only allows for visualization of single selected conformations during any one experiment. EPR spectroscopy is a magnetic resonance technique that offers a unique opportunity to study structural, environmental and dynamic properties of such proteins in their native membrane environments, as well as readily sampling their substrate-binding-induced dynamic conformational changes especially through complementary computational analyses. Here we present a review of recent studies that utilize a variety of EPR techniques in order to investigate both the structure and dynamics of a range of membrane transporters and associated proteins, focusing on both primary (ABC-type transporters) and secondary active transporters which were key interest areas of the late Professor Stephen Baldwin to whom this review is dedicated. PMID:27284059

  18. Discriminative EPR detection of NO and HNO by encapsulated nitronyl nitroxides

    PubMed Central

    Bobko, Andrey A.; Ivanov, Alexander; Khramtsov, Valery V.

    2014-01-01

    Nitric oxide, •NO, is one of the most important molecules in the biochemistry of living organisms. By contrast, nitroxyl, NO−, one-electron reduced analog of •NO which exists at physiological conditions in its protonated form, HNO, has been relatively overlooked. Recent data shows that HNO might be produced endogenously and display unique biological effects. However, there is a lack of specific and quantitative methods of detection of endogenous HNO production. Here we present a new method for discriminative •NO and HNO detection by nitronyl nitroxides (NNs) using electron paramagnetic resonance (EPR). It was found that NNs react with •NO and HNO with similar rate constants of about 104 M−1s−1 but yield different products: imino nitroxides and the hydroxylamine of imino nitroxides, correspondingly. An EPR approach for discriminative •NO and HNO detection using liposome-encapsulated NNs was developed. The membrane barrier of liposomes protects NNs against reduction in biological systems while is permeable to both analytes, •NO and HNO. The sensitivity of this approach for the detection of the rates of •NO/HNO generation is about 1 nM/s. The application of encapsulated NNs for real-time discriminative •NO/HNO detection might become a valuable tool in nitric oxide related studies. PMID:23136998

  19. Polymer-iron oxide composite nanoparticles for EPR-independent drug delivery.

    PubMed

    Park, Jinho; Kadasala, Naveen Reddy; Abouelmagd, Sara A; Castanares, Mark A; Collins, David S; Wei, Alexander; Yeo, Yoon

    2016-09-01

    Nanoparticle (NP)-based approaches to cancer drug delivery are challenged by the heterogeneity of the enhanced permeability and retention (EPR) effect in tumors and the premature attrition of payload from drug carriers during circulation. Here we show that such challenges can be overcome by a magnetophoretic approach to accelerate NP delivery to tumors. Payload-bearing poly(lactic-co-glycolic acid) NPs were converted into polymer-iron-oxide nanocomposites (PINCs) by attaching colloidal Fe3O4 onto the surface, via a simple surface modification method using dopamine polymerization. PINCs formed stable dispersions in serum-supplemented medium and responded quickly to magnetic field gradients above 1 kG/cm. Under the field gradients, PINCs were rapidly transported across physical barriers and into cells and captured under flow conditions similar to those encountered in postcapillary venules, increasing the local concentration by nearly three orders of magnitude. In vivo magnetophoretic delivery enabled PINCs to accumulate in poorly vascularized subcutaneous SKOV3 xenografts that did not support the EPR effect. In vivo magnetic resonance imaging, ex vivo fluorescence imaging, and tissue histology all confirmed that the uptake of PINCs was higher in tumors exposed to magnetic field gradients, relative to negative controls. PMID:27310916

  20. Fast 3D Spatial EPR Imaging Using Spiral Magnetic Field Gradient

    PubMed Central

    Deng, Yuanmu; Petryakov, Sergy; He, Guanglong; Kesselring, Eric; Kuppusamy, Periannan; Zweier, Jay L.

    2007-01-01

    Electron paramagnetic resonance imaging (EPRI) provides direct detection and mapping of free radicals. The continuous wave (CW) EPRI technique, in particular, has been widely used in a variety of applications in the fields of biology and medicine due to its high sensitivity and applicability to a wide range of free radicals and paramagnetic species. However, the technique requires long image acquisition periods, and this limits its use for many in vivo applications where relatively rapid changes occur in the magnitude and distribution of spins. Therefore, there has been a great need to develop fast EPRI techniques. We report the development of a fast 3D CW EPRI technique using spiral magnetic field gradient. By spiraling the magnetic field gradient and stepping the main magnetic field, this approach acquires a 3D image in one sweep of the main magnetic field, enabling significant reduction of the imaging time. A direct one-stage 3D image reconstruction algorithm, modified for reconstruction of the EPR images from the projections acquired with the spiral magnetic field gradient, was used. We demonstrated using a home-built L-band EPR system that the spiral magnetic field gradient technique enabled a 4 to 7-fold accelerated acquisition of projections. This technique has great potential for in vivo studies of free radicals and their metabolism. PMID:17267252

  1. Are Free Radicals Involved in IspH Catalysis? An EPR and Crystallographic Investigation

    PubMed Central

    Wang, Weixue; Wang, Ke; Span, Ingrid; Jauch, Johann; Bacher, Adelbert; Groll, Michael; Oldfield, Eric

    2012-01-01

    The [4Fe-4S] protein IspH in the methylerythritol phosphate isoprenoid biosynthesis pathway is an important anti-infective drug target, but its mechanism of action is still the subject of debate. Here, by using electron paramagnetic resonance (EPR) spectroscopy and 2H, 17O, and 57Fe isotopic labeling, we have characterized and assigned two key reaction intermediates in IspH catalysis. The results are consistent with the bioorganometallic mechanism proposed earlier, and the mechanism is proposed to have similarities to that of ferredoxin: thioredoxin reductase, in that one electron is transferred to the [4Fe-4S]2+ cluster, which then performs a formally two-electron reduction of its substrate, generating an oxidized high potential iron-sulfur protein (HiPIP)-like intermediate. The two paramagnetic reaction intermediates observed correspond to the two intermediates proposed in the bioorganometallic mechanism: the early π-complex in which the substrate’s 3-CH2OH group has rotated away from the reduced iron-sulfur cluster, and the next, η3-allyl complex formed after dehydroxylation. No free radical intermediates are observed, and the two paramagnetic intermediates observed do not fit in a Birch reduction-like or ferraoxetane mechanism. Additionally, we show by using EPR spectroscopy and X-ray crystallography that two substrate analogs (4 and 5) follow the same reaction mechanism. PMID:22687151

  2. A loop resonator for slice-selective in vivo EPR imaging in rats.

    PubMed

    Hirata, Hiroshi; He, Guanglong; Deng, Yuanmu; Salikhov, Ildar; Petryakov, Sergey; Zweier, Jay L

    2008-01-01

    A loop resonator was developed for 300 MHz continuous-wave electron paramagnetic resonance (CW-EPR) spectroscopy and imaging in live rats. A single-turn loop (55 mm in diameter) was used to provide sufficient space for the rat body. Efficiency for generating a radiofrequency magnetic field of 38 microT/W(1/2) was achieved at the center of the loop. For the resonator itself, an unloaded quality factor of 430 was obtained. When a 350 g rat was placed in the resonator at the level of the lower abdomen, the quality factor decreased to 18. The sensitive volume in the loop was visualized with a bottle filled with an aqueous solution of the nitroxide spin probe 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (3-CP). The resonator was shown to enable EPR imaging in live rats. Imaging was performed for 3-CP that had been infused intravenously into the rat and its distribution was visualized within the lower abdomen. PMID:18006343

  3. Combining crystallography and EPR: crystal and solution structures of the multidomain cochaperone DnaJ

    SciTech Connect

    Barends, Thomas R. M.; Brosi, Richard W. W.; Steinmetz, Andrea; Scherer, Anna; Hartmann, Elisabeth; Eschenbach, Jessica; Lorenz, Thorsten; Seidel, Ralf; Shoeman, Robert L.; Zimmermann, Sabine; Bittl, Robert; Schlichting, Ilme; Reinstein, Jochen

    2013-08-01

    The crystal structure of the N-terminal part of T. thermophilus DnaJ unexpectedly showed an ordered GF domain and guided the design of a construct enabling the first structure determination of a complete DnaJ cochaperone molecule. By combining the crystal structures with spin-labelling EPR and cross-linking in solution, a dynamic view of this flexible molecule was developed. Hsp70 chaperones assist in a large variety of protein-folding processes in the cell. Crucial for these activities is the regulation of Hsp70 by Hsp40 cochaperones. DnaJ, the bacterial homologue of Hsp40, stimulates ATP hydrolysis by DnaK (Hsp70) and thus mediates capture of substrate protein, but is also known to possess chaperone activity of its own. The first structure of a complete functional dimeric DnaJ was determined and the mobility of its individual domains in solution was investigated. Crystal structures of the complete molecular cochaperone DnaJ from Thermus thermophilus comprising the J, GF and C-terminal domains and of the J and GF domains alone showed an ordered GF domain interacting with the J domain. Structure-based EPR spin-labelling studies as well as cross-linking results showed the existence of multiple states of DnaJ in solution with different arrangements of the various domains, which has implications for the function of DnaJ.

  4. Association of Copper to Riboflavin Binding Protein; Characterization by EPR and XAS

    SciTech Connect

    Smith,S.; Bencze, K.; Wasiukanis, K.; Stemmler, T.; Benore-Parsons, M.

    2008-01-01

    The association of copper to Riboflavin Binding Protein (RBP) from egg white has been studied by electron paramagnetic resonance (EPR) and X-ray absorption (XAS) spectroscopies. The type II site contains a mix of copper I and II in an oxygen rich environment. The association of copper to Riboflavin Binding Protein (RBP) from egg white has been studied by electron paramagnetic resonance (EPR) and X-ray absorption (XAS) spectroscopies in order to provide insight into how this essential protein may transport and store copper in avian embryos. Riboflavin Binding Protein, RBP, purified from avian egg white, has been shown to bind copper in a 1:1 molar ratio when dialyzed against copper(II) [1]. While the egg is a unique environment and quite rich in copper, the mechanisms by which this copper is delivered during development and stored for eventual use remain unclear [2]. Since RBP is already identified in the active transport of the cofactor riboflavin to the egg, evidence of its copper binding ability may suggest an additional role for RBP in the transport and storage of copper.

  5. Heavy-ion-induced sucrose radicals investigated using EPR and UV spectroscopy

    PubMed Central

    Nakagawa, Kouichi; Karakirova, Yordanka; Yordanov, Nicola D.

    2015-01-01

    The potential use of a sucrose dosimeter for estimating both linear energy transfer (LET) and the absorbed dose of heavy ion and X-ray radiation was investigated. The stable free radicals were produced when sucrose was irradiated with heavy ions, such as helium, carbon, silicon and neon ions, and when the X-ray radiation was similar to the obtained electron paramagnetic resonance (EPR) spectra, which were ∼7 mT wide and composed of several hyperfine structures. In addition, the total spin concentration resulting from heavy-ion irradiation increased linearly as the absorbed dose increased, and decreased logarithmically as the LET increased. These empirical relations imply that the LET at a certain dose can be determined from the spin concentration. For sucrose and alanine, both cross-sections following C-ion irradiation with a 50 Gy dose were ∼1.3 × 10−12 [μm2], taking into account the molecular size of the samples. The values of these cross-sections imply that multiple ionizing particles were involved in the production of stable radicals. Furthermore, UV absorbance at 267 nm of an aqueous solution of irradiated sucrose was found to linearly increase with increasing absorbed dose. Therefore, the EPR and UV results suggest that sucrose can be a useful dosimeter for heavy-ion irradiation. PMID:25480828

  6. Oxidation state of manganese in zinc pyrophosphate: Probed by luminescence and EPR studies

    SciTech Connect

    Gupta, Santosh K. Kadam, R. M. Natarajan, V. Godbole, S. V.

    2014-04-24

    Zn{sub 2}P{sub 2}O{sub 7}: Mn was synthesized by wet chemical route and characterized by X-ray diffraction (XRD), photoluminescence (PL) and electron paramagnetic resonance (EPR) techniques. Photoluminescence spectrum shows two bands, one at 500 nm (green emission), which is attributed to the {sup 4}T{sub 1}({sup 4}G)-{sup 6}A{sub 1}({sup 6}S) transition of Mn{sup 2+} and other centered at 686 nm (red emission) is attributed to the electronic transition between {sup 2}E and {sup 4}A{sub 2} of Mn{sup 4+} accompanied with vibronic transitions. EPR spectroscopic studies also confirmed the presence of both Mn2+ and Mn4+ ions in zinc pyrophosphate with difference in the number of fine transitions and g values (Mn{sub 4+}, S=3/2, three fine transitions and g < 2.00; Mn{sup 2+} S=5/2, five fine transitions and g=2.00).Mn{sup 2+} is attributed to presence of Mn at 6-ccordinated Zn{sup 2+} site whereas Mn{sup 4+} is due to presence substitution of Mn{sup 4+} at Zn{sup 2+} site thereby invoking charge compensation by presence of interstitial oxygen ions around Mn{sup 4+} ion or due to substitution of manganese at distorted 5-coordinated zinc site.

  7. An EPR study on tea: Identification of paramagnetic species, effect of heat and sweeteners

    NASA Astrophysics Data System (ADS)

    Bıyık, Recep; Tapramaz, Recep

    2009-10-01

    Tea ( Camellia Sinensis) is the most widely consumed beverage in the world, and is known to be having therapeutic, antioxidant and nutritional effects. Electron paramagnetic resonance (EPR) spectral studies made on the tea cultivated along the shore of Black Sea, Turkey, show Mn 2+ and Fe 3+ centers in green tea leaves and in black tea extract. Dry black tea flakes and dry extract show additional sharp line attributed to semiquinone radical. The origins of the paramagnetic species in black tea are defined and discussed. Effect of humidity and heat are investigated. It is observed that dry extract of black tea melts at 100 °C and the semiquinone radical lives up to 140 °C while Mn 2+ sextet disappears just above 100 °C in tea extract. Natural and synthetics sweeteners have different effects on the paramagnetic centers. White sugar (sucrose) quenches the Mn 2+ and semiquinone lines in black tea EPR spectrum, and glucose, fructose, lactose and maltose quench Fe 3+ line while synthetic sweeteners acesulfam potassium, aspartame and sodium saccharine do not have any effect on paramagnetic species in tea.

  8. Development of In Vivo Tooth EPR for Individual Radiation Dose Estimation and Screening

    PubMed Central

    Williams, Benjamin B.; Dong, Ruhong; Kmiec, Maciej; Burke, Greg; Demidenko, Eugene; Gladstone, David; Nicolalde, Roberto J; Sucheta, Artur; Lesniewski, Piotr; Swartz, Harold M

    2009-01-01

    The development of in vivo EPR has made it feasible to perform tooth dosimetry measurements in situ, greatly expanding the potential for using this approach for immediate screening after radiation exposures. The ability of in vivo tooth dosimetry to provide estimates of absorbed dose has been established through a series of experiments using unirradiated volunteers with specifically irradiated molar teeth placed in situ within gaps in their dentition and in natural canine teeth of patients who have completed courses of radiation therapy for head and neck cancers. Multiple measurements in patients who have received radiation therapy demonstrate the expected heterogeneous dose distributions. Dose response curves have been generated using both populations and, using the current methodology and instrument, the standard error of prediction based on single 4.5 minute measurements is approximately 1.5 Gy for inserted molar teeth and between 2.0 and 2.5 Gy in the more irregularly shaped canine teeth. Averaging of independent measurements can reduce this error significantly to values near 1 Gy. Developments to reduce these errors are underway, focusing on geometric optimization of the resonators, detector positioning techniques, and optimal data averaging approaches. In summary, it seems plausible that the EPR dosimetry techniques will have an important role in retrospective dosimetry for exposures involving large numbers of individuals. PMID:20065702

  9. ODMR and EPR investigations of Fe centers in KTaO3

    NASA Astrophysics Data System (ADS)

    Reyher, H.-J.; Faust, B.; Maiwald, M.; Hesse, H.

    1996-10-01

    The analysis of EPR spectra obtained from iron doped KTaO3 crystals in the as-grown state revealed three dominant iron centers: Fe3+-OI, axial Fe-centers with spin S = 3/2 and rhombic Fe3+. By comparison with data from literature possible assignments for the center with S = 3/2 are discussed. For the rhombic species the temperature dependence of the main parameters of the Spin- Hamiltonian was measured. The result makes it most plausible that only one rhombic iron center exists in KTaO3, in contrast with literature. The understanding of the EPR spectra allows us to assign transitions, observed at very low magnetic fields by optically detected magnetic resonance (ODMR), to this rhombic Fe center. On this basis, the magnetic circular dichroism (MCD) of this defect could be identified using the method of tagged-MCD. This spectrum is compared to the tagged-MCD of Fe3+-O1 and of axial Fe4+ centers, which may be generated metastably by optical charge transfer. Considerably different structures in the MCD spectra of both Fe3+ centers indicate different local surroundings and electronic states.

  10. Dielectric behavior, conduction and EPR active centres in BiVO4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Venkatesan, Rajalingam; Velumani, Subramaniam; Tabellout, Mohamed; Errien, Nicolas; Kassiba, Abdelhadi

    2013-12-01

    Bismuth vanadate (BiVO4) nanomaterials were synthesized by mechano-chemical ball milling method and complementary investigations were devoted to their structures, nanoparticle morphologies and electronic active centres. The dielectric and conductivity behaviour were analysed systematically in wide temperature and frequency ranges to correlate such physical responses with the peculiarities of the samples. Large interfacial polarisations favoured by high specific surfaces of nanoparticles account for a drastic enhancement of the dielectric function in the quasi-static regime. Exhaustive analyses of the dielectric experiments were achieved and account for the main features of dielectric functions and their related relaxation mechanisms. The electrical conductivity is thermally activated with energies in the range 0.1-0.6 eV depending on the sample features. DC conductivity up to 10-3 S/cm was obtained in well crystallized nanoparticles. Vanadium ions reduction was revealed by EPR spectroscopy with higher concentrations of the active centres (V4+) in more agglomerated and amorphous nanopowders. The EPR spectral parameters of V4+ were determined and correlated with the local environments of reduced vanadium ions and the characteristics of their electronic configurations. An insight is also made on the role of active electronic centres (V4+) on the conduction mechanism in nanostructured BiVO4.

  11. A 140 GHz Pulsed EPR/212 MHz NMR Spectrometer for DNP Studies

    PubMed Central

    Smith, Albert A.; Corzilius, Björn; Bryant, Jeffrey A.; DeRocher, Ronald; Woskov, Paul P.; Temkin, Richard J.; Griffin, Robert G.

    2012-01-01

    We described a versatile spectrometer designed for the study of dynamic nuclear polarization (DNP) at low temperatures and high fields. The instrument functions both as an NMR spectrometer operating at 212 MHz (1H frequency) with DNP capabilities, and as a pulsed-EPR operating at 140 GHz. A coiled TE011 resonator acts as both an NMR coil and microwave resonator, and a double balanced (1H, 13C) radio frequency circuit greatly stabilizes the NMR performance. A new 140 GHz microwave bridge has also been developed, which utilizes a four-phase network and ELDOR channel at 8.75 GHz, that is then multiplied and mixed to obtain 140 GHz microwave pulses with an output power of 120 mW. Nutation frequencies obtained are as follows: 6 MHz on S = ½ electron spins, 100 kHz on 1H, and 50 kHz on 13C. We demonstrate basic EPR, ELDOR, ENDOR, and DNP experiments here. Our solid effect DNP results demonstrate an enhancement of 144 and sensitivity gain of 310 using OX063 trityl at 80 K and an enhancement of 157 and maximum sensitivity gain of 234 using Gd-DOTA at 20 K, which is significantly better performance than previously reported at high fields (>3 T). PMID:22975246

  12. Minimization of actinide waste by multi-recycling of thoriated fuels in the EPR reactor

    NASA Astrophysics Data System (ADS)

    Rose, S. J.; Wilson, J. N.; Capellan, N.; David, S.; Guillemin, P.; Ivanov, E.; Méplan, O.; Nuttin, A.; Siem, S.

    2012-02-01

    The multi-recycling of innovative uranium/thorium oxide fuels for use in the European Pressurized water Reactor (EPR) has been investigated. If increasing quantities of 238U, the fertile isotope in standard UO2 fuel, are replaced by 232Th, then a greater yield of new fissile material (233U) is produced during the cycle than would otherwise be the case. This leads to economies of natural uranium of around 45% if the uranium in the spent fuel is multi-recycled. In addition we show that minor actinide and plutonium waste inventories are reduced and hence waste radio-toxicities and decay heats are up to a factor of 20 lower after 103 years. Two innovative fuel types named S90 and S20, ThO2 mixed with 90% and 20% enriched UO2 respectively, are compared as an alternative to standard uranium oxide (UOX) and uranium/plutonium mixed oxide (MOX) fuels at the longest EPR fuel discharge burn-ups of 65 GWd/t. Fissile and waste inventories are examined, waste radio-toxicities and decay heats are extracted and safety feedback coefficients are calculated.

  13. Fast dynamic electron paramagnetic resonance (EPR) oxygen imaging using low-rank tensors

    NASA Astrophysics Data System (ADS)

    Christodoulou, Anthony G.; Redler, Gage; Clifford, Bryan; Liang, Zhi-Pei; Halpern, Howard J.; Epel, Boris

    2016-09-01

    Hypoxic tumors are resistant to radiotherapy, motivating the development of tools to image local oxygen concentrations. It is generally believed that stable or chronic hypoxia is the source of resistance, but more recent work suggests a role for transient hypoxia. Conventional EPR imaging (EPRI) is capable of imaging tissue pO2in vivo, with high pO2 resolution and 1 mm spatial resolution but low imaging speed (10 min temporal resolution for T1-based pO2 mapping), which makes it difficult to investigate the oxygen changes, e.g., transient hypoxia. Here we describe a new imaging method which accelerates dynamic EPR oxygen imaging, allowing 3D imaging at 2 frames per minute, fast enough to image transient hypoxia at the "speed limit" of observed pO2 change. The method centers on a low-rank tensor model that decouples the tradeoff between imaging speed, spatial coverage/resolution, and number of inversion times (pO2 accuracy). We present a specialized sparse sampling strategy and image reconstruction algorithm for use with this model. The quality and utility of the method is demonstrated in simulations and in vivo experiments in tumor bearing mice.

  14. Temperature effects on EPR spectra of a linear chain copper complex-copper calcium acetate hexahydrate

    NASA Astrophysics Data System (ADS)

    De, D. K.

    1981-03-01

    The observed angular dependence of the electron paramagnetic resonance linewidth in the ab and ac planes of CuCa(AC)2, 6H2O in the temperature interval 77K-12K was explained by considering dipolar interactions along with hyperfine and isotropic exchange interactions in these two planes. It was found that this so called linear-chain copper compound can be better described by a three dimensional paramagnet. The exchange interaction is very nearly isotropic with values Jab = 0.0098 cm-1 and Jc = 0.0103 cm-1. The values of the A⊥ derived from the linewidth fit in the ab plane are 14G at 77K and 60.5G at 1.2K. Due to insufficiency of data in the ac plane, the fit was done with the measured value of A∥. Although the exchange interaction has been found to be temperature independent the hyperfine interaction increases very much at low temperatures. The high temperature (300-460K) EPR spectra are quite different from the low temperature spectra. High temperature differential thermal analyses and thermogravimetric analyses have been carried out and corroborated with the EPR findings.

  15. High-field EPR spectroscopy applied to biological systems: characterization of molecular switches for electron and ion transfer.

    PubMed

    Möbius, K; Savitsky, A; Schnegg, A; Plato, M; Fuchst, M

    2005-01-01

    The last decade witnessed a tremendous growth in combined efforts of biologists, chemists and physicists to understand the dominant factors determining the specificity and directionality of transmembrane transfer processes in proteins. A large variety of experimental techniques is being used including X-ray and neutron diffraction, but also time-resolved optical, infrared and magnetic resonance spectroscopy. This is done in conjunction with genetic engineering strategies to construct site-specific mutants for controlled modification of the proteins. As a general perception of these efforts, the substantial influence of weak interactions within the protein and its membrane interfaces is recognized. The weak interactions are subject to subtle changes during the reaction cycle owing to the inherent flexibility of the protein-membrane complex. Specific conformational changes accomplish molecular-switch functions for the transfer process to proceed with optimum efficiency. Characteristic examples of time varying non-bonded interactions are specific H-patterns and/or polarity effects of the microenvironment. The present perception has emerged from the coupling of newly developed spectroscopic techniques - and advanced EPR certainly deserves credit in this respect - with newly developed computational strategies to interpret the experimental data in terms of protein structure and dynamics. By now, the partners of this coupling, particularly high-field EPR spectroscopy and DFT-based quantum theory, have reached a level of sophistication that applications to large biocomplexes are within reach. In this review, a few large paradigm biosystems are surveyed which were explored lately in our laboratory. Taking advantage of the improved spectral and temporal resolution of high-frequency/high-field EPR at 95 GHz/3.4 T and 360 GHz/12.9 T, as compared to conventional X-band EPR (9.5 GHz/0.34 T), three biosystems are characterized with respect to structure and dynamics: (1) Light

  16. Effects of spin transitions degeneracy in pulsed EPR of the fullerene C70 triplet state produced by continuous light illumination.

    PubMed

    Uvarov, Mikhail N; Kulik, Leonid V; Pichugina, Tatiana I; Dzuba, Sergei A

    2011-05-01

    X-band echo-detected electron paramagnetic resonance (ED EPR) spectra of triplet state of fullerene C(70) generated by continuous light illumination were found to correspond below 30K to a non-equilibrium electron spin polarization. Above 30K spectra are characteristic of Boltzmann equilibrium. Spectra were simulated fairly well with zero-field splitting parameters D=153 MHz and E and distributed within the range of 6-42 MHz. The origin of E distribution is attributed to the Jahn-Teller effect, which in glassy matrix is expected to depend on the local surrounding of a fullerene molecule (a so-called E-strain). In the center of ED EPR spectra a narrow hole was observed. With increase of the microwave pulse turning angle this hole transforms into a single narrow absorptive line. Numerical simulations by density matrix formalism confirm that central hole originates from a simultaneous excitation of both allowed electron spin transitions of the triplet (T(0)↔T(+) and T(0)↔T(-)), because of their degeneracy at this spectral position. Also explanations are given why this hole has not been observed in the previously reported experiments on continuous wave EPR and on ED EPR under laser pulse excitation. PMID:21339084

  17. Application of EPR Spectroscopy to Examination of the Effect of Sterilization Process on Free Radicals in Different Herbs.

    PubMed

    Pawłowska-Góral, Katarzyna; Ramos, Paweł; Pilawa, Barbara; Kurzeja, Ewa

    2013-03-01

    Free radicals in the original and sterilized caraway, curry, curcuma and cardamom were studied. An X-band (9.3 GHz) electron paramagnetic resonance (EPR) spectroscopy was the experimental technique. Effect of microwave power in the range of 2.2-70 mW on amplitudes, linewidths, and lineshape parameters of the EPR spectra was tested. Free radicals concentrations in the non- and sterilized herb samples were compared. The aim of this work was to determine properties and concentration of free radicals in steam sterilized caraway, curry, curcuma and cardamom. It was pointed out that free radicals (~10(18) spin/g) exist in both the original and sterilized herbs. Complex free radical system with oxygen and carbon paramagnetic centers characterizes the examined herbs. Homogeneously dipolar broadened EPR spectra were measured for all the tested herbs. Slow spin-lattice relaxation processes exist in the examined samples. Practical usefulness of EPR method in food technology was discussed. PMID:23487576

  18. Testing and linearity calibration of films of phenol compounds exposed to thermal neutron field for EPR dosimetry.

    PubMed

    Gallo, S; Panzeca, S; Longo, A; Altieri, S; Bentivoglio, A; Dondi, D; Marconi, R P; Protti, N; Zeffiro, A; Marrale, M

    2015-12-01

    This paper reports the preliminary results obtained by Electron Paramagnetic Resonance (EPR) measurements on films of IRGANOX® 1076 phenols with and without low content (5% by weight) of gadolinium oxide (Gd2O3) exposed in the thermal column of the Triga Mark II reactor of LENA (Laboratorio Energia Nucleare Applicata) of Pavia (Italy). Thanks to their size, the phenolic films here presented are good devices for the dosimetry of beams with high dose gradient and which require accurate knowledge of the precise dose delivered. The dependence of EPR signal as function of neutron dose was investigated in the fluence range between 10(11) cm(-2) and 10(14) cm(-2). Linearity of EPR response was found and the signal was compared with that of commercial alanine films. Our analysis showed that gadolinium oxide (5% by weight) can enhance the thermal neutron sensitivity more than 18 times. Irradiated dosimetric films of phenolic compound exhibited EPR signal fading of about 4% after 10 days from irradiation. PMID:26242561

  19. 3D printed sample holder for in-operando EPR spectroscopy on high temperature polymer electrolyte fuel cells.

    PubMed

    Niemöller, Arvid; Jakes, Peter; Kayser, Steffen; Lin, Yu; Lehnert, Werner; Granwehr, Josef

    2016-08-01

    Electrochemical cells contain electrically conductive components, which causes various problems if such a cell is analyzed during operation in an EPR resonator. The optimum cell design strongly depends on the application and it is necessary to make certain compromises that need to be individually arranged. Rapid prototyping presents a straightforward option to implement a variable cell design that can be easily adapted to changing requirements. In this communication, it is demonstrated that sample containers produced by 3D printing are suitable for EPR applications, with a particular emphasis on electrochemical applications. The housing of a high temperature polymer electrolyte fuel cell (HT-PEFC) with a phosphoric acid doped polybenzimidazole membrane was prepared from polycarbonate by 3D printing. Using a custom glass Dewar, this fuel cell could be operated at temperatures up to 140°C in a standard EPR cavity. The carbon-based gas diffusion layer showed an EPR signal with a characteristic Dysonian line shape, whose evolution could be monitored in-operando in a non-invasive manner. PMID:27323280

  20. VHF EPR quantitation and speciation of organic sulfur in coal. Technical report, September 1, 1993--November 30, 1993

    SciTech Connect

    Clarkson, R.B.; Belford, R.L.

    1993-12-31

    Over the last few years, we have developed a non-destructive technique called Very High Frequency Electron Paramagnetic Resonance (VHF-EPR) that is proving to be a practical and very sensitive analytical method for the organic sulfur in coal. Already, although still under development, the technique rapidly can quantify organic sulfur, and perhaps provide information on organic oxygen and nitrogen, in typical Illinois coals. At this stage, the precision is not well enough calibrated, and specificity for particular species needs more development. This year`s proposal outlined a 12 month work plan designed to improve and extend the utility of VHF-EPR. Two main goals of the work are: (1) refinement and calibration of organic sulfur analysis, in coals of differing rank, over a concentration range from 0.1% to 5%, and (2) better utilization of VHF-EPR coal spectral data for sulfur speciation. This quarter, goal (1) is being pursued; results will be ready to describe in a future report. Meanwhile, work toward goal (2) has produced detailed information about the VHF-EPR spectral behavior of several comparison compounds -- sulfur -- containing thiophenic fused-ring molecules.

  1. Electron paramagnetic resonance (EPR) study of spin-labeled camptothecin derivatives: a different look of the ternary complex.

    PubMed

    Ricci, Antonio; Marinello, Jessica; Bortolus, Marco; Sánchez, Albert; Grandas, Anna; Pedroso, Enrique; Pommier, Yves; Capranico, Giovanni; Maniero, Anna Lisa; Zagotto, Giuseppe

    2011-02-24

    Camptothecin (CPT) derivatives are clinically effective poisons of DNA topoisomerase I (Top1) able to form a ternary complex with the Top1-DNA complex. The aim of this investigation was to examine the dynamic aspects of the ternary complex formation by means of site-directed spin labeling electron paramagnetic resonance (SDSL-EPR). Two semisynthetic CPT derivatives bearing the paramagnetic moiety were synthesized, and their biological activity was tested. A 22-mer DNA oligonucleotide sequence with high affinity cleavage site for Top1 was also synthesized. EPR experiments were carried out on modified CPT in the presence of DNA, of Top1, or of both. In the last case, a slow motion component in the EPR signal appeared, indicating the formation of the ternary complex. Deconvolution of the EPR spectrum allowed to obtain the relative drug amounts in the complex. It was also possible to demonstrate that the residence time of CPT "trapped" in the ternary complex is longer than hundreds of microseconds. PMID:21254781

  2. The effects of dose and radiation quality on the shape and power saturation of the EPR signal in alanine.

    PubMed

    Ciesielski, B; Wielopolski, L

    1994-10-01

    Variations in the shape and the power saturation of EPR spectra of L-alanine irradiated with photons, electrons, neutrons and protons are reported. It is shown that the ratio of the intensities of the satellite lines attributable to "spin flips" and the central line depend on the EPR microwave power, and it is proposed as a quantitative measure of the signal saturation effect. Dependence of this ratio on the microwave power is affected by the radiation quality and for doses in excess of 10 kGy by the absorbed dose. At high doses of low-LET radiation these changes are attributed to a high local density of free radicals, while for low doses of high-LET radiation these are due to changes induced in the crystal lattice. Consequently, the conventional peak-to-peak amplitude measurement of the EPR signal intensity is inaccurate when used for high doses and for comparison between radiations with different beam quality. The possibility to determine radiation quality from an EPR measurement is discussed. PMID:7938443

  3. 3D printed sample holder for in-operando EPR spectroscopy on high temperature polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Niemöller, Arvid; Jakes, Peter; Kayser, Steffen; Lin, Yu; Lehnert, Werner; Granwehr, Josef

    2016-08-01

    Electrochemical cells contain electrically conductive components, which causes various problems if such a cell is analyzed during operation in an EPR resonator. The optimum cell design strongly depends on the application and it is necessary to make certain compromises that need to be individually arranged. Rapid prototyping presents a straightforward option to implement a variable cell design that can be easily adapted to changing requirements. In this communication, it is demonstrated that sample containers produced by 3D printing are suitable for EPR applications, with a particular emphasis on electrochemical applications. The housing of a high temperature polymer electrolyte fuel cell (HT-PEFC) with a phosphoric acid doped polybenzimidazole membrane was prepared from polycarbonate by 3D printing. Using a custom glass Dewar, this fuel cell could be operated at temperatures up to 140 °C in a standard EPR cavity. The carbon-based gas diffusion layer showed an EPR signal with a characteristic Dysonian line shape, whose evolution could be monitored in-operando in a non-invasive manner.

  4. EPR study of free radicals in non- and gamma-irradiated nutritive supplements containing anthocyanins concentrate from lyophilized red wine

    NASA Astrophysics Data System (ADS)

    Mladenova, Ralitsa B.; Firzov, Cyril; Yordanov, Nicola D.

    2010-09-01

    Nutritive supplements Enoviton, Enoviton C and Enoviton CE containing standardized anthocyanins from lyophilized red wine, vitamins (some of them) and excipients were investigated by EPR spectrometry before and after gamma-irradiation. Non-irradiated samples exhibit one singlet line with g=2.0039±0.0002, most probably due to free radicals from anthocyanins. After irradiation with 10 kGy gamma-rays, tablets of Еnoviton, Еnoviton С and Еnoviton СЕ, all exhibit complex EPR signals centered at a g-value of g=2.0034. The EPR spectrum of irradiated Enoviton is different from that of Еnoviton С or Еnoviton СЕ due to the overlap of the spectra of microcrystalline cellulose and the background singlet spectrum present in all tablets with the EPR resonance due to irradiated ascorbic acid (in Еnoviton С and Еnoviton СЕ). Gamma-induced free radicals exhibit long time stability—for a six months period the intensity of central peak decrease with 30-40%.

  5. Synthesis, EPR and optical spectroscopy of the Cr-doped tetraborate glasses

    NASA Astrophysics Data System (ADS)

    Padlyak, B. V.; Ryba-Romanowski, W.; Lisiecki, R.; Adamiv, V. T.; Burak, Ya. V.; Teslyuk, I. M.

    2012-10-01

    Electron paramagnetic resonance (EPR), optical absorption and photoluminescence spectra as well as luminescence kinetics of the Li2B4O7:Cr and KLiB4O7:Cr tetraborate glasses were investigated at T = 300 K. The Li2B4O7:Cr and KLiB4O7:Cr glasses containing 0.4 and 1.6 mol.% Cr2O3 of high optical quality were obtained from polycrystalline compounds by fast cooling of the melts. The X-band EPR spectroscopy shows that the Cr impurity is incorporated in the tetraborate glass network as isolated Cr3+ centers and Cr3+-Cr3+ pairs coupled by magnetic dipolar and exchange interactions. The EPR spectral parameters (geff and ΔBpp) of both Cr3+ and Cr3+-Cr3+ centers in the Li2B4O7:Cr and KLiB4O7:Cr glasses were measured and analyzed. All transitions in optical absorption, luminescence excitation and emission spectra of these glasses are identified. Broad complex bands that peak near 615, 405, and 350 nm in optical absorption and luminescence excitation spectra correspond to the 4A2g(F) → 4T2g(F), 4A2g(F) → 4T1g(F), and 4A2g(F) → 4T1g(P) spin-allowed transitions of the Cr3+ centers in distorted octahedral sites of the tetraborate glass network. The octahedral (cubic) crystal field strength (10Dq) and Racach parameters (B and C) for Cr3+ centers in Li2B4O7:Cr and KLiB4O7:Cr glasses are estimated. Narrow and broad emission bands in red - NIR regions are assigned to the 2Eg(F) → 4A2g(F) (R1 line) and 4T2g(F) → 4A2g(F) (electron-vibration) transitions, which correspond to the Cr3+ centers in high-field and low-field sites, respectively. All observed emission bands are characterized by non-exponential decay. Measured average lifetimes and local structure of the Cr3+ centers in high-field and low-field sites of the Li2B4O7:Cr and KLiB4O7:Cr glass network have been discussed.

  6. EPR and rheological study of hybrid interfaces in gold-clay-epoxy nanocomposites.

    PubMed

    Angelov, Verislav; Velichkova, Hristiana; Ivanov, Evgeni; Kotsilkova, Rumiana; Delville, Marie-Hélène; Cangiotti, Michela; Fattori, Alberto; Ottaviani, Maria Francesca

    2014-11-11

    With the aim to obtain new materials with special properties to be used in various industrial and biomedical applications, ternary "gold-clay-epoxy" nanocomposites and their nanodispersions were prepared using clay decorated with gold nanoparticles (AuNPs), at different gold contents. Nanocomposites structure was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Rheology and electron paramagnetic resonance (EPR) techniques were used in order to evaluate the molecular dynamics in the nanodispersions, as well as dynamics at interfaces in the nanocomposites. The percolation threshold (i.e., the filler content related to the formation of long-range connectivity of particles in the dispersed media) of the gold nanoparticles was determined to be ϕp = 0.6 wt % at a fixed clay content of 3 wt %. The flow activation energy and the relaxation time spectrum illustrated the presence of interfacial interactions in the ternary nanodispersions around and above the percolation threshold of AuNPs; these interfacial interactions suppressed the global molecular dynamics. It was found that below ϕp the free epoxy polymer chains ratio dominated over the chains attracted on the gold surfaces; thus, the rheological behavior was not significantly changed by the presence of AuNPs. While, around and above ϕp, the amount of the bonded epoxy polymer chains on the gold surface was much higher than that of the free chains; thus, a substantial increase in the flow activation energy and shift in the spectra to higher relaxation times appeared. The EPR signals of the nanocomposites depended on the gold nanoparticle contents and the preparation procedure thus providing a fingerprint of the different nanostructures. The EPR results from spin probes indicated that the main effect of the gold nanoparticles above ϕp, was to form a more homogeneous, viscous and polar clay-epoxy mixture at the nanoparticle surface. The knowledge

  7. Elucidating the design principles of photosynthetic electron-transfer proteins by site-directed spin labeling EPR spectroscopy.

    PubMed

    Ishara Silva, K; Jagannathan, Bharat; Golbeck, John H; Lakshmi, K V

    2016-05-01

    Site-directed spin labeling electron paramagnetic resonance (SDSL EPR) spectroscopy is a powerful tool to determine solvent accessibility, side-chain dynamics, and inter-spin distances at specific sites in biological macromolecules. This information provides important insights into the structure and dynamics of both natural and designed proteins and protein complexes. Here, we discuss the application of SDSL EPR spectroscopy in probing the charge-transfer cofactors in photosynthetic reaction centers (RC) such as photosystem I (PSI) and the bacterial reaction center (bRC). Photosynthetic RCs are large multi-subunit proteins (molecular weight≥300 kDa) that perform light-driven charge transfer reactions in photosynthesis. These reactions are carried out by cofactors that are paramagnetic in one of their oxidation states. This renders the RCs unsuitable for conventional nuclear magnetic resonance spectroscopy investigations. However, the presence of native paramagnetic centers and the ability to covalently attach site-directed spin labels in RCs makes them ideally suited for the application of SDSL EPR spectroscopy. The paramagnetic centers serve as probes of conformational changes, dynamics of subunit assembly, and the relative motion of cofactors and peptide subunits. In this review, we describe novel applications of SDSL EPR spectroscopy for elucidating the effects of local structure and dynamics on the electron-transfer cofactors of photosynthetic RCs. Because SDSL EPR Spectroscopy is uniquely suited to provide dynamic information on protein motion, it is a particularly useful method in the engineering and analysis of designed electron transfer proteins and protein networks. This article is part of a Special Issue entitled Biodesign for Bioenergetics--the design and engineering of electronic transfer cofactors, proteins and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson. PMID:26334844

  8. A multimedia Electronic Patient Record (ePR) system for Image-Assisted Minimally Invasive Spinal Surgery

    PubMed Central

    Documet, Jorge; Le, Anh; Liu, Brent; Chiu, John; Huang, HK

    2009-01-01

    Purpose This paper presents the concept of bridging the gap between diagnostic images and image-assisted surgical treatment through the development of a one-stop multimedia electronic patient record (ePR) system that manages and distributes the real-time multimodality imaging and informatics data that assists the surgeon during all clinical phases of the operation from planning Intra-Op to post-care follow-up. We present the concept of this multimedia ePR for surgery by first focusing on Image-Assisted Minimally Invasive Spinal Surgery as a clinical application. Methods Three clinical Phases of Minimally Invasive Spinal Surgery workflow in Pre-Op, Intra-Op, and Post Op are discussed. The ePR architecture was developed based on the three-phased workflow, which includes the Pre-Op, Intra-Op, and Post-Op modules and four components comprising of the input integration unit, fault-tolerant gateway server, fault-tolerant ePR server, and the visualization and display. A prototype was built and deployed to a Minimally Invasive Spinal Surgery clinical site with user training and support for daily use. Summary A step-by step approach was introduced to develop a multi-media ePR system for Imaging-Assisted Minimally Invasive Spinal Surgery that includes images, clinical forms, waveforms, and textual data for planning the surgery, two real-time imaging techniques (digital fluoroscopic, DF) and endoscope video images (Endo), and more than half a dozen live vital signs of the patient during surgery. Clinical implementation experiences and challenges were also discussed. PMID:20033507

  9. Membrane fluidity profiles as deduced by saturation-recovery EPR measurements of spin-lattice relaxation times of spin labels

    PubMed Central

    Mainali, Laxman; Feix, Jimmy B.; Hyde, James S.; Subczynski, Witold K.

    2011-01-01

    There are no easily obtainable EPR spectral parameters for lipid spin labels that describe profiles of membrane fluidity. The order parameter, which is most often used as a measure of membrane fluidity, describes the amplitude of wobbling motion of alkyl chains relative to the membrane normal and does not contain explicitly time or velocity. Thus, this parameter can be considered as nondynamic. The spin-lattice relaxation rate (T−11) obtained from saturation-recovery EPR measurements of lipid spin labels in deoxygenated samples depends primarily on the rotational correlation time of the nitroxide moiety within the lipid bilayer. Thus, T−11 can be used as a convenient quantitative measure of membrane fluidity that reflects local membrane dynamics. T−11 profiles obtained for 1-palmitoyl-2-(n-doxylstearoyl)phosphatidylcholine (n-PC) spin labels in dimyristoylphosphatidylcholine (DMPC) membranes with and without 50 mol% cholesterol are presented in parallel with profiles of the rotational diffusion coefficient, R⊥, obtained from simulation of EPR spectra using Freed's model. These profiles are compared with profiles of the order parameter obtained directly from EPR spectra and with profiles of the order parameter obtained from simulation of EPR spectra. It is shown that T−11 and R⊥ profiles reveal changes in membrane fluidity that depend on the motional properties of the lipid alkyl chain. We find that cholesterol has a rigidifying effect only to the depth occupied by the rigid steroid ring structure and a fluidizing effect at deeper locations. These effects cannot be differentiated by profiles of the order parameter. All profiles in this study were obtained at X-band (9.5 GHz). PMID:21868272

  10. High fluence ion beam modification of polymer surfaces: EPR and XPS studies

    NASA Astrophysics Data System (ADS)

    Popok, V. N.; Azarko, I. I.; Odzhaev, V. B.; Tóth, A.; Khaibullin, R. I.

    2001-05-01

    Polyethylene, polyamide-6 and polyimide foils implanted with 100 keV B+, P+ and Sb + ions to a fluence range of 10 15-10 17 cm-2 have been studied using the electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) methods. The experimental data allow the comparison of the implantation-induced changes both in a given polymer foil under different ion beam regimes and in different polymers under similar ion-bombardment conditions. The high fluence implantation of boron ions, depositing energy mainly via electronic stopping, was found to be accompanied with the effective formation of π-bonded carbon-rich clusters. By contrast, heavier (phosphorus and antimony) ions, which deposit energy predominantly in nuclear collisions, produced a lower concentration of π-radicals and a less carbonised top surface layer. The peculiarities and main trends of the alterations of the polymer structure and composition induced via electronic and nuclear stopping have also been discussed.

  11. Digital EPR with an arbitrary waveform generator and direct detection at the carrier frequency

    NASA Astrophysics Data System (ADS)

    Tseitlin, Mark; Quine, Richard W.; Rinard, George A.; Eaton, Sandra S.; Eaton, Gareth R.

    2011-12-01

    A digital EPR spectrometer was constructed by replacing the traditional bridge with an arbitrary waveform generator (AWG) to produce excitation patterns and a high-speed digitizer for direct detection of the spin system response at the carrier frequency. Digital down-conversion produced baseband signals in quadrature with very precise orthogonality. Real-time resonator tuning was performed by monitoring the Fourier transforms of signals reflected from the resonator during frequency sweeps generated by the AWG. The capabilities of the system were demonstrated by rapid magnetic field scans at 256 MHz carrier frequency, and FID and spin echo experiments at 1 and 10 GHz carrier frequencies. For the rapid scan experiments the leakage through a cross-loop resonator was compensated by adjusting the amplitude and phase of a sinusoid at the carrier frequency that was generated with another AWG channel.

  12. CW-EPR study of 2,2,4,4-tetramethyl-3-pentanone oxime single crystals

    NASA Astrophysics Data System (ADS)

    Sayin, Ulku; Yuksel, Huseyin; Ozmen, Ayhan; Birey, Mehmet

    2010-12-01

    The electron paramagnetic resonance (EPR) spectra of gamma irradiated single crystals of 2,2,4,4-tetramethyl-3-pentanone oxime (TPO) have been examined between temperatures of 125 and 450 K. The spectra were found to be both dependent on temperature and orientation of single crystals with magnetic field. We attributed radiation damage centers to iminoxy radicals ( RC=N•O). There are two similar group of splitting in the spectra because of conformational isomers (R1, R2) of iminoxy radicals produced by gamma irradiation of TPO. Determined g-factor and hyperfine coupling constants for R1 and R2 conformers were found anisotropic with the average values ( giso) R1=2.01057, ( giso) R2=2.009337, [( aN) iso] R1=28.09 G, [( aN) iso] R2=36.34 G, [( aH) iso] R2=9.15 G, respectively.

  13. Multi-hop teleportation based on W state and EPR pairs

    NASA Astrophysics Data System (ADS)

    Hai-Tao, Zhan; Xu-Tao, Yu; Pei-Ying, Xiong; Zai-Chen, Zhang

    2016-05-01

    Multi-hop teleportation has significant value due to long-distance delivery of quantum information. Many studies about multi-hop teleportation are based on Bell pairs, partially entangled pairs or W state. The possibility of multi-hop teleportation constituted by partially entangled pairs relates to the number of nodes. The possibility of multi-hop teleportation constituted by double W states is after n-hop teleportation. In this paper, a multi-hop teleportation scheme based on W state and EPR pairs is presented and proved. The successful possibility of quantum information transmitted hop by hop through intermediate nodes is deduced. The possibility of successful transmission is after n-hop teleportation. Project supported by the National Natural Science Foundation of China (Grant No. 61571105), the Prospective Future Network Project of Jiangsu Province, China (Grant No. BY2013095-1-18), and the Independent Project of State Key Laboratory of Millimeter Waves, China (Grant No. Z201504).

  14. Etude de la texture des rubans EPR de silicium polycristallin photovoltaïque

    NASA Astrophysics Data System (ADS)

    Chibani, A.; Gauthier, R.; Pinard, P.; Andonov, P.

    1991-09-01

    EPR polysilicon ribbons are obtained from a 5N-6N purity grade silicon powder melting followed by a recrystallization step. Being assigned to the photocell manufacture, we study the texture by X-ray diffraction method to reveal the majority of the crystal orientations and prove the eventual existence of specific orientations adapted to the best photovoltaic conversion efficiencies such as (100), (110) or (111). Moreover, we tested the possibility to induce the (111) orientation with a monocrystalline seed having this orientation. It appears that the crystal growth is essentially anisotropic and that only the orientation of the grains with their (331) planes parallel to the ribbon surface may be considered as dominant after the recrystallization step; finally, the (111) starting seed has an effect only at the recrystallization onset.

  15. Nature of V {sup n+} ions in SnO{sub 2}: EPR and photoluminescence studies

    SciTech Connect

    Ningthoujam, R.S.; Lahiri, Debdutta; Sudarsan, V.; Poswal, H.K.; Kulshreshtha, S.K. . E-mail: kulshres@magnum.barc.ernet.in; Sharma, Surinder M.; Bhushan, Brij; Sastry, M.D.

    2007-07-03

    SnO{sub 2} and 5 at.% V doped SnO{sub 2} samples were prepared by citrate-gel method. From Raman study on vanadium doped SnO{sub 2}, the existence of phase separated V{sub 2}O{sub 5} clusters has been established. EPR study on the V doped sample clearly revealed the existence of V{sup 4+} ions, which are incorporated in SnO{sub 2} lattice and the existence of conduction electrons with g = 1.993. For vanadium doped SnO{sub 2} sample, there is a decrease in luminescence at 400 nm and an increase in activation energy of electrical conduction compared to undoped SnO{sub 2}, and this has been attributed to the decrease in oxygen vacancies brought about by the incorporation of V{sup 5+} in the SnO{sub 2} lattice.

  16. Analyzing three-player quantum games in an EPR type setup.

    PubMed

    Chappell, James M; Iqbal, Azhar; Abbott, Derek

    2011-01-01

    We use the formalism of Clifford Geometric Algebra (GA) to develop an analysis of quantum versions of three-player non-cooperative games. The quantum games we explore are played in an Einstein-Podolsky-Rosen (EPR) type setting. In this setting, the players' strategy sets remain identical to the ones in the mixed-strategy version of the classical game that is obtained as a proper subset of the corresponding quantum game. Using GA we investigate the outcome of a realization of the game by players sharing GHZ state, W state, and a mixture of GHZ and W states. As a specific example, we study the game of three-player Prisoners' Dilemma. PMID:21818260

  17. Photocatalytic removal of soot: unravelling of the reaction mechanism by EPR and in situ FTIR spectroscopy.

    PubMed

    Smits, Marianne; Ling, Yun; Lenaerts, Silvia; Van Doorslaer, Sabine

    2012-12-21

    Photocatalytic soot oxidation is studied on P25 TiO(2) as an important model reaction for self-cleaning processes by means of electron paramagnetic resonance (EPR) and Fourier transform infrared (FTIR) spectroscopy. Contacting of carbon black with P25 leads on the one hand to a reduction of the local dioxygen concentration in the powder. On the other hand, the weakly adsorbed radicals on the carbon particles are likely to act as alternative traps for the photogenerated conduction-band electrons. We find furthermore that the presence of dioxygen and oxygen-related radicals is vital for the photocatalytic soot degradation. The complete oxidation of soot to CO(2) is evidenced by in situ FTIR spectroscopy, no intermediate CO is detected during the photocatalytic process. PMID:23150192

  18. Some comments on the EPR (The reasons why experiments should still be done)

    SciTech Connect

    Piccioni, O.; Wright, B.

    1993-10-01

    The authors believe that much of the contradiction they hear about the Einstein Podoisky Rosen Paradox (EPR), can be framed into the diverse ways of using or misusing the principle of ``collapse,`` (a principle, which according to Wigner, is very attractive, but not very informative). To make their points, they will mainly use the model [Lamehi-Rachti, Mittig, Phys. Rev. D14 (1976)] of two free protons scattering in the well known state of singlet, ud-du = SS, according to the Pauli Principle. (An equivalent description can be done with the polarization of photons.) The authors ask the important question whether, on separation, the two fermions will remain in the state SS, where neither proton has a definite state and the whole two fermion system has exactly zero component in any direction.

  19. POWDERSPEC 2, a library of new programs for efficient simulation of powder EPR spectra

    NASA Astrophysics Data System (ADS)

    Beltrán-López, Virgilio; González-Tovany, L.

    1994-05-01

    POWDERSPEC 2 is a library of Fortran programs, AXIPRO, AXIANI and CUBIC, for simulating second order powder patterns and electron paramagnetic resonance (EPR) spectra of ions in various important crystal field symmetries. These are the following: AXIPRO is for any spin in axial symmetry. It includes the angle-dependent transition probability for S= {5}/{2}. AXIANI is for axial symmetry with axially anisotropic g and A tensors, for S= {3}/{2}. CUBIC is for cubic symmetry, with isotropic hyperfine interaction, for S= {5}/{2}. These programs, like POWDERSPEC, their predecessor for orthorhombic symmetry, run in a few minutes on a PC with numeric co-processor. They are capable of producing very smooth powder patterns and spectra which can be recorded with currently available graph programs such as LOTUS, SIGMAPLOT or GRAPHER.

  20. The influence of additives on beer stability investigated by EPR spectroscopy

    NASA Astrophysics Data System (ADS)

    Brezová, Vlasta; Polovka, Martin; Staško, Andrej

    2002-04-01

    In thermally-accelerated aging followed by EPR spectroscopy of beer samples of various stabilities, free radical 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPOL) was shown to be an effective indicator of the breakdown of a sample's stability, comparable to the commonly used spin trapping agent α-phenyl- N- tert-butylnitrone (PBN). Both indicators were then employed to investigate the influence of additives on beer stability. The addition of L-ascorbic acid (ASC) to the beer samples accelerated the radical processes and a lower stability was found. DL-α-tocopherol (α-TOC) did not influence beer stability significantly (probably due to its limited solubility). Na 2SO 3, described as a very effective stabilizer in experiments with the PBN spin trap, was found not to be effective using the TEMPOL indicator. This is probably due to inhibition in the formation of spin adducts or their degradation by Na 2SO 3.

  1. The influence of additives on beer stability investigated by EPR spectroscopy.

    PubMed

    Brezová, Vlasta; Polovka, Martin; Stasko, Andrej

    2002-04-01

    In thermally-accelerated aging followed by EPR spectroscopy of beer samples of various stabilities, free radical 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPOL) was shown to be an effective indicator of the breakdown of a sample's stability, comparable to the commonly used spin trapping agent alpha-phenyl-N-tert-butylnitrone (PBN). Both indicators were then employed to investigate the influence of additives on beer stability. The addition of L-ascorbic acid (ASC) to the beer samples accelerated the radical processes and a lower stability was found. DL-alpha-tocopherol (alpha-TOC) did not influence beer stability significantly (probably due to its limited solubility). Na2SO3, described as a very effective stabilizer in experiments with the PBN spin trap, was found not to be effective using the TEMPOL indicator. This is probably due to inhibition in the formation of spin adducts or their degradation by Na2SO3. PMID:11993475

  2. Analysis of Hydroperoxides in Solid Polyethylene by MAS (13)C NMR and EPR

    SciTech Connect

    ASSINK,ROGER A.; CELINA,MATHIAS C.; DUNBAR,TIMOTHY D.; ALAM,TODD M.; CLOUGH,ROGER LEE; GILLEN,KENNETH T.

    1999-11-19

    {sup 13}C-enriched polyethylene was subjected to {gamma}-irradiation in the presence of air at 25 and 80 C for total doses ranging from 71 to 355 kGy. Significant quantities of hydroperoxides were detected in the 25 C irradiated sample by {sup 13}C magic angle spinning NMR spectroscopy. This method of detection was performed on the solid polymer and required no chemical derivatization or addition of solvent. The chemical stability and subsequent products of the hydroperoxide species were studied by annealing the irradiated samples in air at temperatures ranging from 22 to 110 C. A time-temperature superposition analysis provided an activation energy of 108 kJ/mol for the hydroperoxide decomposition process. The primary products of hydroperoxide decomposition were ketones and secondary alcohols with lesser amounts of acids and esters. EPR measurements suggest that the reactive hydroperoxide species reside in the amorphous phase of polyethylene, consistent with degradation occurring in the amorphous phase.

  3. VHF EPR determination of the chemical forms of organic sulfur in coal

    SciTech Connect

    Clarkson, R.B.

    1991-01-01

    This program addresses the need for innovative approaches to characterize the organic sulfur in Illinois Basin coals. We have developed a very high frequency electron paramagnetic resonance (EPR) spectrometer operating at the W-band of microwave frequencies (96 GHz). This instrument has shown unique sensitivity to heteroatoms in coal, and we believe the technique can be successfully applied for the non-destructive, direct determination of organic sulfur in coal. Preliminary data from Illinois coals and separated macerals indicate that the method also may be able to distinguish aromatic from aliphatic sulfur, and may be useful in assessing the extent of conjugation in aromatic portions of the coal. These high energy spectroscopic techniques, however invariably suffer from the fact that they are not truly non-destructive. By contrast, the low powers and relatively low energy radiation used in magnetic resonance techniques have virtually no effect on the physical structure or chemical composition of coal.

  4. Information leakage in three-party simultaneous quantum secure direct communication with EPR pairs

    NASA Astrophysics Data System (ADS)

    Wang, Lian-Ying; Chen, Xiu-Bo; Xu, Gang; Yang, Yi-Xian

    2011-04-01

    In 2007, Wang et al. [M. Y. Wang and F. L. Yan, Chin. Phys. Lett. 24 (2007) 2486] proposed a three-party simultaneous quantum secure direct communication (3P-SQSDC) scheme with EPR pairs. Recently, Chong et al. [S. K. Chong and T. Hwang, Opt. Commun. OPTICS-15438 (2010(online))] proposed an enhancement on Wang et al.'s scheme. The communications in Chong et al.'s 3P-SQSDC can be paralleled and thus their scheme has higher efficiency. However, we find that both of the schemes have the information leakage, because the legitimate parties' secret messages have a strong correlation. This kind of security loophole leads to the consequence that any eavesdropper (Eve) can directly conjecture some information about the secrets without any active attack.

  5. Antioxidant Activity of Some Types of White Wines and Juices Investigated by EPR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Petrisor, Dina; Damian, Grigore; Simon, Simion; Hosu, Anamaria; Miclaus, Vasile

    Two types of white wines with different places of provenience, and a few types of commercial and natural juices were chosen for preliminary studies of their antioxidant characteristics by using Electron Paramagnetic Resonance (EPR) spectroscopy. Antioxidant capacity of these samples was assessed using stable free radicals such as nitroxide radical Tempol (2,2,6,6-tetramethyl-4-hydroxypiperidine-oxyl), as a paramagnetic agent. The inhibition by antioxidants of the absorbance of the paramagnetic species was found to decrease in time with different rates, and was correlated to the antioxidant activity of the studied samples. The obtained results permit us to make a brief evaluation of the main antioxidative characteristics of the studied wines and juices samples.

  6. Digital EPR with an arbitrary waveform generator and direct detection at the carrier frequency

    PubMed Central

    Tseitlin, Mark; Quine, Richard W.; Rinard, George A.; Eaton, Sandra S.; Eaton, Gareth R.

    2011-01-01

    A digital EPR spectrometer was constructed by replacing the traditional bridge with an arbitrary waveform generator (AWG) to produce excitation patterns and a high-speed digitizer for direct detection of the spin system response at the carrier frequency. Digital down-conversion produced baseband signals in quadrature with very precise orthogonality. Real-time resonator tuning was performed by monitoring the Fourier transforms of signals reflected from the resonator during frequency sweeps generated by the AWG. The capabilities of the system were demonstrated by rapid magnetic field scans at 256 MHz carrier frequency, and FID and spin echo experiments at 1 and 10 GHz carrier frequencies. For the rapid scan experiments the leakage through a cross-loop resonator was compensated by adjusting the amplitude and phase of a sinusoid at the carrier frequency that was generated with another AWG channel. PMID:21968420

  7. Applicability of EPR/alanine dosimetry for quality assurance in proton eye radiotherapy.

    PubMed

    Michalec, B; Mierzwinska, G; Ptaszkiewicz, M; Sowa, U; Stolarczyk, L; Weber, A

    2014-06-01

    A new quality assurance and quality control method for proton eye radiotherapy based on electron paramagnetic resonance (EPR)/alanine dosimetry has been developed. It is based on Spread-Out Bragg Peak entrance dose measurement with alanine detectors. The entrance dose is well correlated with the dose at the facility isocenter, where, during the therapeutic irradiation, the tumour is placed. The unique alanine detector features namely keeping the dose record in a form of stable radiation-induced free radicals trapped in the material structure, and the non-destructive read-out makes this type of detector a good candidate for additional documentation of the patient's exposure over the therapy course. PMID:24876341

  8. Generation of states maximally entanglement (EPR states) by passing two atoms through two coupled cavities

    NASA Astrophysics Data System (ADS)

    Yabu-uti, B. F. C.; Nohama, F. K.; Roversi, J. A.

    2008-04-01

    We present the results of the interaction of identical two-level atoms with a system formed by two identical coupled cavities via evanescent field. With new bosonic operators (normal nodes), the interaction Hamiltonian between the cavities can be diagonalized. In a particular case, we can eliminate the interaction of the atoms with the nonresonant normal modes reducing the system to the interaction of the atom with a single-mode (like JCM). As an application of this interaction, we analyze the entanglement between distant atoms. We present two related simple procedures to generate two atoms maximally entangled state (EPR pair) interacting (i)successively (atoms passing through the cavities at different moments) and (ii) simultaneously (at the same time) with the coupled cavities system. Moreover, in contrast with other schemes, we can use identical atoms which simplifies in a experiment point of view.

  9. Probehead with interchangeable loop-gap resonators and rf coils for multifrequency EPR/ENDOR

    NASA Astrophysics Data System (ADS)

    Christides, T.; Froncisz, W.; Oles, T.; Hyde, James S.

    1994-01-01

    A probehead employing interchangeable loop-gap resonators and rf coils for multifrequency EPR/ENDOR spectroscopy from 1 to 10 GHz is described. A precision coupling mechanism allows accurate magnetic coupling of the microwaves to the resonators. The Rexolite© support of the resonator acts as a spool for the ENDOR coil. rf fields of 1.0 mT are generated. The coil and resonator can be easily changed to cover the range of 1-10 GHz. Liquid-phase ENDOR spectra of the stable free-radical galvanoxyl and of the spin label TEMPONE (4-oxo-2,2,6,6-tetramethyl-l-piperidine-N-oxyl) dissolved in n-heptane are shown. The ENDOR enhancement for nitrogen from TEMPONE is 15 times larger at 2.3 than at 9.3 GHz due to the rf enhancement.

  10. Combined approaches of EPR and NMR illustrate only one transmembrane helix in the human IFITM3

    PubMed Central

    Ling, Shenglong; Zhang, Chengwei; Wang, Wei; Cai, Xiaoying; Yu, Lu; Wu, Fangming; Zhang, Longhua; Tian, Changlin

    2016-01-01

    Interferon-inducible transmembrane protein IFITM3 was known to restrict the entry of a wide spectrum of viruses to the cytosol of the host. The mechanism used by the protein to restrict viral entry is unclear given the unavailability of the membrane topology and structures of the IFITM family proteins. Systematic site-directed spin labeling (SDSL) and electron paramagnetic resonance (EPR) studies of IFITM3 in detergent micelles identified a single, long transmembrane helix in the C-terminus and an intramembrane segment in the N-terminal hydrophobic region. Solution NMR studies of the same sample verified the secondary structure distribution and demonstrated two rigid regions interacting with the micellar surface. The resulting membrane topology of IFITM3 supports the mechanism of an enhanced restricted membrane hemi-fusion. PMID:27046158

  11. Internal in vitro dosimetry for fish using hydroxyapatite-based EPR detectors.

    PubMed

    Ivanov, D V; Shishkina, E A; Osipov, D I; Razumeev, R A; Pryakhin, E A

    2015-08-01

    A number of aquatic ecosystems were exposed to ionizing radiation as a result of the activities of the Mayak Production Association in the Southern Urals, former Soviet Union, in the 1950s. Currently, fishes inhabiting contaminated lakes are being actively studied. These investigations need dosimetric support. In the present paper the results of a pilot study for elaborating an EPR dosimeter which can be used for internal dosimetry in vitro are described. Biological hydroxyapatite is proposed here to be used as a detecting substance. More specifically, small hydroxyapatite grains are proposed for use as point detectors fixed in a solid matrix. After having been pelletized, the detectors were covered by Mylar and placed in the body of a fish to be stored in the fridge for several months. Application of the detectors for internal fish dosimetry demonstrated that the enamel sensitivity is sufficient for passive detection of ionizing radiation in fishes inhabiting contaminated lakes in the Southern Urals. PMID:25822591

  12. Dielectric Resonator for Ka-Band Pulsed EPR Measurements at Cryogenic Temperatures: Probehead Construction and Applications

    PubMed Central

    Astashkin, A.; Enemark, J. H.; Blank, A.; Twig, Y.; Song, Y.; Meade, T. J.

    2013-01-01

    The construction and performance of a Ka-band pulsed electron paramagnetic resonance (EPR) cryogenic probehead that incorporates dielectric resonator (DR) is presented. We demonstrate that the use of DR allows one to optimize pulsed double electron–electron resonance (DEER) measurements utilizing large resonator bandwidth and large amplitude of the microwave field B1. In DEER measurements of Gd-based spin labels, use of this probe finally allows one to implement the potentials of Gd-based labels in distance measurements. Evidently, this DR is well suited to any applications requiring large B1-fields and resonator bandwidths, such as electron spin echo envelope modulation spectroscopy of nuclei having low magnetic moments and strong hyperfine interactions and double quantum coherence dipolar spectroscopy as was recently demonstrated in the application of a similar probe based on an loop-gap resonator and reported by Forrer et al. (J Magn Reson 190:280, 2008). PMID:23626406

  13. EPR dosimetry teeth in past and future accidents: A prospective look at a retrospective method

    SciTech Connect

    Haskell, E.; Kenner, G.; Hayes, R.; Chumak, V.; Shalom, S.

    1997-03-01

    Accurate assessments of doses received by individuals exposed to radiation from nuclear accidents and incidents such as those at Hiroshima and Nagasaki, the Nevada test site, Cheliabinsk and Mayak are required for epidemiological studies seeking to establish relationships between radiation dose and health effects. One method of retrospective dosimetry which allows for measurement of cumulative gamma ray doses received by exposed individuals is electron paramagnetic resonance spectroscopy (EPR) of tooth enamel. Tooth enamel stores and retains, indefinitely, information on absorbed radiation dose. And teeth are available in every population as a result of dental extraction for medical reasons including periodontal disease and impacted wisdom teeth. In the case of children, deciduous teeth, which are shed between the ages of 7 and 13, can be a very important dosimetric source if documented collection is implemented shortly following an accident.

  14. EPR investigation of the trivalent chromium complexes in SrTiO3

    NASA Astrophysics Data System (ADS)

    Azamat, D. V.; Dejneka, A.; Lančok, J.; Jastrabik, L.; Trepakov, V. A.; Bryknar, Z.; Neverova, E. V.; Badalyan, A. G.

    2014-02-01

    The trivalent chromium centers were investigated by means of electron paramagnetic resonance (EPR) in SrTiO3 single crystals grown using the Verneuil technique. It was shown that the charge compensation of the Cr3+-VO dominant centers in octahedral environment is due to the remote oxygen vacancy located on the axial axis of the center. In order to provide insight into spin-phonon relaxation processes the studies of axial distortion of Cr3+-VO centers have been performed as function of temperature. The analysis of the trigonal Cr3+ centers found in SrTiO3 indicates the presence of the nearest-neighbor strontium vacancy. The next-nearest-neighbor exchange-coupled pairs of Cr3+ in SrTiO3 has been analyzed from the angular variation of the total electron spin of S=2 resonance lines.

  15. An EPR spin probe method for characterizing changes in the accessible regions of coal upon oxidation

    SciTech Connect

    Sady, W.; Kispert, L.D.; Spears, D.R.

    1992-01-01

    Eight Argonne Premium Coal Samples (APCS) were weathered in air and the structural and chemical changes that upon swelling with toluene and pyridine were, examined by an EPR spin probe method developed in this laboratory. Under mild oxidation conditions and swelling with toluene large structural changes were observed for lignite (Beulah-Zap) which suggested the collapse of the coal structure. This did not occur for higher rank coal. Upon oxidation and swelling with toluene and pyridine an increase occurred in the amino substituted spin probe concentration for coals with the carbon percent above 80%. A maximum was found for the creation of 5 {Angstrom} diameter pores upon swelling with pyridine at 85% C.

  16. Electron Paramagnetic Resonance (EPR) Studies of Near-Surface Magnetic Properties of YBCO Thin Films

    NASA Astrophysics Data System (ADS)

    Pugel, D. E.; Xia, Y.-M.; Salamon, M. B.; Greene, L. H.

    2000-03-01

    Several thin film planar tunneling experiments are consistent with a broken time-reversal symmetry (BTRS) state [1-4].To compliment tunneling measurements, we have developed a technique to measure electron paramagnetic resonance (EPR) effects of the near-surface region of a superconductor. Preliminary data are consistent with the spontaneous formation of magnetic moments at low temperature on YBCO thin films and may prove to be an important confirmation of BTRS. 1. Covington,M. et al., Phys. Rev. Lett., 79, 277, (1997). 2. Kashiwaya, S. et al., J. Phys. Chem. Solids, 59, 2034, (1997). 3. Krupke, R. and Deutscher,G., Phys. Rev. Lett., 83, 4634, (1999). 4. Lesueur,J., Grison,X., Aprili,M. and Kontos,T., cond-mat/9909212. -------------------------------------------------------------

  17. Analyzing Three-Player Quantum Games in an EPR Type Setup

    PubMed Central

    Chappell, James M.; Iqbal, Azhar; Abbott, Derek

    2011-01-01

    We use the formalism of Clifford Geometric Algebra (GA) to develop an analysis of quantum versions of three-player non-cooperative games. The quantum games we explore are played in an Einstein-Podolsky-Rosen (EPR) type setting. In this setting, the players' strategy sets remain identical to the ones in the mixed-strategy version of the classical game that is obtained as a proper subset of the corresponding quantum game. Using GA we investigate the outcome of a realization of the game by players sharing GHZ state, W state, and a mixture of GHZ and W states. As a specific example, we study the game of three-player Prisoners' Dilemma. PMID:21818260

  18. Phenylbutazone Oxidation via Cu,Zn-SOD Peroxidase Activity: An EPR Study.

    PubMed

    Aljuhani, Naif; Whittal, Randy M; Khan, Saifur R; Siraki, Arno G

    2015-07-20

    We investigated the effect of Cu,Zn-superoxide dismutase (Cu,Zn-SOD)-peroxidase activity on the oxidation of the nonsteroidal anti-inflammatory drug phenylbutazone (PBZ). We utilized electron paramagnetic resonance (EPR) spectroscopy to detect free radical intermediates of PBZ, UV-vis spectrophotometry to monitor PBZ oxidation, oxygen analysis to determine the involvement of C-centered radicals, and LC/MS to determine the resulting metabolites. Using EPR spectroscopy and spin-trapping with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), we found that the spin adduct of CO3(•-) (DMPO/(•)OH) was attenuated with increasing PBZ concentrations. The resulting PBZ radical, which was assigned as a carbon-centered radical based on computer simulation of hyperfine splitting constants, was trapped by both DMPO and MNP spin traps. Similar to Cu,Zn-SOD-peroxidase activity, an identical PBZ carbon-centered radical was also detected with the presence of both myeloperoxidase (MPO/H2O2) and horseradish peroxidase (HRP/H2O2). Oxygen analysis revealed depletion in oxygen levels when PBZ was oxidized by SOD peroxidase-activity, further supporting carbon radical formation. In addition, UV-vis spectra showed that the λmax for PBZ (λ = 260 nm) declined in intensity and shifted to a new peak that was similar to the spectrum for 4-hydroxy-PBZ when oxidized by Cu,Zn-SOD-peroxidase activity. LC/MS evidence supported the formation of 4-hydroxy-PBZ when compared to that of a standard, and 4-hydroperoxy-PBZ was also detected in significant yield. These findings together indicate that the carbonate radical, a product of SOD peroxidase activity, appears to play a role in PBZ metabolism. Interestingly, these results are similar to findings from heme peroxidase enzymes, and the context of this metabolic pathway is discussed in terms of a mechanism for PBZ-induced toxicity. PMID:26090772

  19. Quantifying the lateral lipid domain properties in erythrocyte ghost membranes using EPR-spectra decomposition.

    PubMed

    Arsov, Zoran; Schara, Milan; Strancar, Janez

    2002-07-01

    Using EPR spectroscopy a typical lateral domain structure was detected in the membranes of spin-labeled bovine erythrocyte ghosts. The spectral parameters were determined by decomposing the EPR spectrum into three spectral components and tuned by a hybrid-evolutionary-optimization method. In our experiments the lateral domain structure and its properties were influenced by the variation in the temperature and by the addition of n-butanol. The specific responses of the particular domain types were detected. For the most-ordered domain type a break was seen in the temperature dependence of its order parameter, while the order parameters of the two less-ordered domain types exhibited a continuous decrease. Below the break-point temperature the alcohol-induced membrane fluidity variation is mainly a consequence of the change in the proportions of the least- and the most-ordered domain type and not the change of the domain-type ordering or dynamics (with n-butanol concentration). On the other hand, the fluidity variation above the break-point temperature arises from both types of changes. Interestingly, the proportion of the domain type that has its order parameter between that of the least- and the most-ordered domain type remains almost constant with concentration as well as with temperature, which implies its stability. Such characterization of the lateral membrane domain structure could be beneficial when considering the lipid-protein interactions, because it can be assumed that the activity of the membrane-bound enzyme depends on the properties of the particular domain type. PMID:12202132

  20. A Combinatorial NMR and EPR Approach for Evaluating the Structural Ensemble of Partially Folded Proteins

    PubMed Central

    Rao, Jampani Nageswara; Jao, Christine C.; Hegde, Balachandra G.; Langen, Ralf; Ulmer, Tobias S.

    2010-01-01

    Partially folded proteins, characterized as exhibiting secondary structure elements with loose or absent tertiary contacts, represent important intermediates in both physiological protein folding and pathological protein misfolding. To aid in the characterization of the structural state(s) of such proteins, a novel structure calculation scheme is presented that combines structural restraints derived from pulsed EPR and NMR spectroscopy. The methodology is established for the protein α-synuclein (αS), which exhibits characteristics of a partially folded protein when bound to a micelle of the detergent sodium lauroyl sarcosinate (SLAS). By combining 18 EPR-derived interelectron spin label distance distributions with NMR-based secondary structure definitions and bond vector restraints, interelectron distances were correlated and a set of theoretical ensemble basis populations was calculated. A minimal set of basis structures, representing the partially folded state of SLAS-bound αS, was subsequently derived by back-calculating correlated distance distributions. A surprising variety of well-defined protein-micelle interactions was thus revealed in which the micelle is engulfed by two differently arranged anti-parallel αS helices. The methodology further provided the population ratios between dominant ensemble structural states, whereas limitation in obtainable structural resolution arose from spin label flexibility and residual uncertainties in secondary structure definitions. To advance the understanding of protein-micelle interactions, the present study concludes by showing that, in marked contrast to secondary structure stability, helix dynamics of SLAS-bound αS correlate with the degree of protein-induced departures from free micelle dimensions. PMID:20524659

  1. Saturation recovery EPR and ELDOR at W-band for spin labels

    PubMed Central

    Froncisz, Wojciech; Camenisch, Theodore G.; Ratke, Joseph J.; Anderson, James R.; Subczynski, Witold K.; Strangeway, Robert A.; Sidabras, Jason W.; Hyde, James S.

    2008-01-01

    A reference-arm W-band (94 GHz) microwave bridge with two sample-irradiation arms for saturation recovery (SR) EPR and ELDOR experiments is described. Frequencies in each arm are derived from 2 GHz synthesizers that have a common time-base and are translated to 94 GHz in steps of 33 and 59 GHz. Intended applications are to nitroxide radical spin labels and spin probes in the liquid phase. An enabling technology is the use of a W-band loop-gap resonator (LGR) (J.W. Sidabras et al., Rev. Sci. Instrum. 78 (2007) 034701). The high efficiency parameter (8.2 GW−1/2 with sample) permits the saturating pump pulse level to be just 5 mW or less. Applications of SR EPR and ELDOR to the hydrophilic spin labels 3-carbamoyl-2,2,5,5-tetra-methyl-3-pyrroline-1-yloxyl (CTPO) and 2,2,6,6,-tetramethyl-4-piperidone-1-oxyl (TEMPONE) are described in detail. In the SR ELDOR experiment, nitrogen nuclear relaxation as well as Heisenberg exchange transfer saturation from pumped to observed hyperfine transitions. SR ELDOR was found to be an essential method for measurements of saturation transfer rates for small molecules such as TEMPONE. Free induction decay (FID) signals for small nitroxides at W-band are also reported. Results are compared with multifrequency measurements of T1e previously reported for these molecules in the range of 2 to 35 GHz (J.S. Hyde et al., J. Phys. Chem. B 108 (2004) 9524–9529). The values of T1e decrease at 94 GHz relative to values at 35 GHz. PMID:18547848

  2. YAlO3:Cr3+ nanophosphor: synthesis, photoluminescence, EPR, dosimetric studies.

    PubMed

    Premkumar, H B; Sunitha, D V; Nagabhushana, H; Sharma, S C; Nagabhushana, B M; Rao, J L; Gupta, Kinshuk; Chakradhar, R P S

    2012-10-01

    YAlO(3):Cr(3+) (0.1 mol%) nanophosphor has been synthesized by low temperature solution combustion method. The X-ray diffraction studies reveal an orthorhombic structure. Transmission electron microscopy reveals that the particles are spherical in shape with nano-size ~40-65 nm. Electron paramagnetic resonance (EPR) spectrum shows a resonance signal with effective g value at g=1.978 which can be attributed to the exchange coupled Cr(3+) ion pairs in weakly distorted sites. The photoluminescence spectrum shows an intense doublet at 677 nm and 694 nm (R lines) assigned to spin-forbidden (2)E(g)→(4)A(2)(g) transition of Cr(3+) ions. EPR and PL studies reveal that the Cr(3+) ions occupy Al(3+) sites in YAlO(3). The interesting feature reported in this work concerns the linearity with gamma dose in the wide range (0.1-6 kGy). Prominent TL glow peaks at 226 °C and 346 °C were observed for both γ and UV-rays respectively. It is observed that the peaks at 226 °C and 346 °C eventually show a linear response up to 5 kGy which makes them a candidate for high dose dosimetry of ionizing radiation. The kinetic parameters namely activation energy (E), order of kinetics (b), frequency factor (s) of undoped and Cr doped samples were determined using Chens glow peak shape method and the results are discussed in detail. PMID:22673389

  3. DAC-board based X-band EPR spectrometer with arbitrary waveform control.

    PubMed

    Kaufmann, Thomas; Keller, Timothy J; Franck, John M; Barnes, Ryan P; Glaser, Steffen J; Martinis, John M; Han, Songi

    2013-10-01

    We present arbitrary control over a homogenous spin system, demonstrated on a simple, home-built, electron paramagnetic resonance (EPR) spectrometer operating at 8-10 GHz (X-band) and controlled by a 1 GHz arbitrary waveform generator (AWG) with 42 dB (i.e. 14-bit) of dynamic range. Such a spectrometer can be relatively easily built from a single DAC (digital to analog converter) board with a modest number of stock components and offers powerful capabilities for automated digital calibration and correction routines that allow it to generate shaped X-band pulses with precise amplitude and phase control. It can precisely tailor the excitation profiles "seen" by the spins in the microwave resonator, based on feedback calibration with experimental input. We demonstrate the capability to generate a variety of pulse shapes, including rectangular, triangular, Gaussian, sinc, and adiabatic rapid passage waveforms. We then show how one can precisely compensate for the distortion and broadening caused by transmission into the microwave cavity in order to optimize corrected waveforms that are distinctly different from the initial, uncorrected waveforms. Specifically, we exploit a narrow EPR signal whose width is finer than the features of any distortions in order to map out the response to a short pulse, which, in turn, yields the precise transfer function of the spectrometer system. This transfer function is found to be consistent for all pulse shapes in the linear response regime. In addition to allowing precise waveform shaping capabilities, the spectrometer presented here offers complete digital control and calibration of the spectrometer that allows one to phase cycle the pulse phase with 0.007° resolution and to specify the inter-pulse delays and pulse durations to ≤ 250 ps resolution. The implications and potential applications of these capabilities will be discussed. PMID:23999530

  4. EPR, optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses

    NASA Astrophysics Data System (ADS)

    De Vicente, F. S.; Santos, F. A.; Simões, B. S.; Dias, S. T.; Siu Li, M.

    2014-12-01

    Antimony phosphate glasses (SbPO) doped with 3 and 6 mol% of Cr3+ were studied by Electron Paramagnetic Resonance (EPR), UV-VIS optical absorption and luminescence spectroscopy. The EPR spectra of Cr3+-doped glasses showed two principal resonance signals with effective g values at g = 5.11 and g = 1.97. UV-VIS optical absorption spectra of SbPO:Cr3+ presented four characteristics bands at 457, 641, 675, and 705 nm related to the transitions from 4A2(F) to 4T1(F), 4T2(F), 2T1(G), and 2E(G), respectively, of Cr3+ ions in octahedral symmetry. Optical absorption spectra of SbPO:Cr3+ allowed evaluating the crystalline field Dq, Racah parameters (B and C) and Dq/B. The calculated value of Dq/B = 2.48 indicates that Cr3+ ions in SbPO glasses are in strong ligand field sites. The optical band gap for SbPO and SbPO:Cr3+ were evaluated from the UV optical absorption edges. Luminescence measurements of pure and Cr3+-doped glasses excited with 350 nm revealed weak emission bands from 400 to 600 nm due to the 3P1 → 1S0 electronic transition from Sb3+ ions. Cr3+-doped glasses excited with 415 nm presented Cr3+ characteristic luminescence spectra composed by two broad bands, one band centered at 645 nm (2E → 4A2) and another intense band from 700 to 850 nm (4T2 → 4A2).

  5. DAC-board based X-band EPR spectrometer with arbitrary waveform control

    PubMed Central

    Kaufmann, Thomas; Keller, Timothy J.; Franck, John M.; Barnes, Ryan P.; Glaser, Steffen J.; Martinis, John M.; Han, Songi

    2013-01-01

    We present arbitrary control over a homogenous spin system, demonstrated on a simple, home-built, electron paramagnetic resonance (EPR) spectrometer operating at 8–10 GHz (X-band) and controlled by a 1 GHz arbitrary waveform generator (AWG) with 42 dB (i.e. 14-bit) of dynamic range. Such a spectrometer can be relatively easily built from a single DAC (digital to analog converter) board with a modest number of stock components and offers powerful capabilities for automated digital calibration and correction routines that allow it to generate shaped X-band pulses with precise amplitude and phase control. It can precisely tailor the excitation profiles “seen” by the spins in the microwave resonator, based on feedback calibration with experimental input. We demonstrate the capability to generate a variety of pulse shapes, including rectangular, triangular, Gaussian, sinc, and adiabatic rapid passage waveforms. We then show how one can precisely compensate for the distortion and broadening caused by transmission into the microwave cavity in order to optimize corrected waveforms that are distinctly different from the initial, uncorrected waveforms. Specifically, we exploit a narrow EPR signal whose width is finer than the features of any distortions in order to map out the response to a short pulse, which, in turn, yields the precise transfer function of the spectrometer system. This transfer function is found to be consistent for all pulse shapes in the linear response regime. In addition to allowing precise waveform shaping capabilities, the spectrometer presented here offers complete digital control and calibration of the spectrometer that allows one to phase cycle the pulse phase with 0.007° resolution and to specify the inter-pulse delays and pulse durations to ≤250 ps resolution. The implications and potential applications of these capabilities will be discussed. PMID:23999530

  6. EPR and (57)Fe ENDOR investigation of 2Fe ferredoxins from Aquifex aeolicus.

    PubMed

    Cutsail, George E; Doan, Peter E; Hoffman, Brian M; Meyer, Jacques; Telser, Joshua

    2012-12-01

    We have employed EPR and a set of recently developed electron nuclear double resonance (ENDOR) spectroscopies to characterize a suite of [2Fe-2S] ferredoxin clusters from Aquifex aeolicus (Aae Fd1, Fd4, and Fd5). Antiferromagnetic coupling between the Fe(II), S = 2, and Fe(III), S = 5/2, sites of the [2Fe-2S](+) cluster in these proteins creates an S = 1/2 ground state. A complete discussion of the spin-Hamiltonian contributions to g includes new symmetry arguments along with references to related FeS model compounds and their symmetry and EPR properties. Complete (57)Fe hyperfine coupling (hfc) tensors for each iron, with respective orientations relative to g, have been determined by the use of "stochastic" continuous wave and/or "random hopped" pulsed ENDOR, with the relative utility of the two approaches being emphasized. The reported hyperfine tensors include absolute signs determined by a modified pulsed ENDOR saturation and recovery (PESTRE) technique, RD-PESTRE-a post-processing protocol of the "raw data" that comprises an ENDOR spectrum. The (57)Fe hyperfine tensor components found by ENDOR are nicely consistent with those previously found by Mössbauer spectroscopy, while accurate tensor orientations are unique to the ENDOR approach. These measurements demonstrate the capabilities of the newly developed methods. The high-precision hfc tensors serve as a benchmark for this class of FeS proteins, while the variation in the (57)Fe hfc tensors as a function of symmetry in these small FeS clusters provides a reference for higher-nuclearity FeS clusters, such as those found in nitrogenase. PMID:22872138

  7. RosettaEPR: Rotamer Library for Spin Label Structure and Dynamics

    PubMed Central

    Alexander, Nathan S.; Stein, Richard A.; Koteiche, Hanane A.; Kaufmann, Kristian W.; Mchaourab, Hassane S.; Meiler, Jens

    2013-01-01

    An increasingly used parameter in structural biology is the measurement of distances between spin labels bound to a protein. One limitation to these measurements is the unknown position of the spin label relative to the protein backbone. To overcome this drawback, we introduce a rotamer library of the methanethiosulfonate spin label (MTSSL) into the protein modeling program Rosetta. Spin label rotamers were derived from conformations observed in crystal structures of spin labeled T4 lysozyme and previously published molecular dynamics simulations. Rosetta’s ability to accurately recover spin label conformations and EPR measured distance distributions was evaluated against 19 experimentally determined MTSSL labeled structures of T4 lysozyme and the membrane protein LeuT and 73 distance distributions from T4 lysozyme and the membrane protein MsbA. For a site in the core of T4 lysozyme, the correct spin label conformation (Χ1 and Χ2) is recovered in 99.8% of trials. In surface positions 53% of the trajectories agree with crystallized conformations in Χ1 and Χ2. This level of recovery is on par with Rosetta performance for the 20 natural amino acids. In addition, Rosetta predicts the distance between two spin labels with a mean error of 4.4 Å. The width of the experimental distance distribution, which reflects the flexibility of the two spin labels, is predicted with a mean error of 1.3 Å. RosettaEPR makes full-atom spin label modeling available to a wide scientific community in conjunction with the powerful suite of modeling methods within Rosetta. PMID:24039810

  8. Spin labeling EPR studies of the properties of oxidized phospholipid-containing lipid vesicles.

    PubMed

    Megli, Francesco M; Russo, Luciana; Conte, Elena

    2009-02-01

    This study aims at characterizing the structure and some properties of phospholipid multi-lamellar vesicles (MLVs) containing the oxidized species gamma-palmitoyl-beta-(9-hydroperoxy-10,12-octadecanedienoyl)-lecithin (HPPLPC), gamma-palmitoyl-beta-(9-hydroxy-10,12-octadecanedienoyl)-lecithin (HOPLPC), gamma-palmitoyl-beta-glutaroyl-lecithin (GlPPC) and gamma-palmitoyl-beta-azelaoyl-lecithin (AzPPC). Sepharose 4B gel-chromatography was used to ensure and check that only MLVs are used in EPR measurements. Gel-solid to gel-liquid transition temperature (Tm), lateral phase separation, fluidity gradient and polarity profile were studied by use of EPR spectroscopy of enclosed n-doxylstearoyl lecithin spin labels. Contrarily to conjugate dienes and normal phospholipids, pure carboxyacyl species yielded aqueous suspensions showing gel-chromatography elution profile resembling that of lysolecithin micelles. Conjugate dienes/DPPC MLVs showed lateral phase separation at room temperature and Tm value lower than pure DPPC MLVs. Pure conjugate dienes MLVs resembled more PLPC MLVs and displayed free miscibility with PLPC in mixed MLVs. Pure HPPLPC MLV bilayer appeared to be slightly more rigid, while that of HOPLPC and the polarity profile of MLVs made of the pure conjugate dienes species were similar to those of normal PLPC. It is concluded that carboxyacyl lecithins in MLVs tend to disrupt vesicle structure, while conjugated dienes lecithins are more able to affect some physical properties of the bilayer, and that DPPC in MLVs enhances these effects while PLPC shows a better compatibility with the lipoperoxides. PMID:18996354

  9. The energy dependence of lithium formate and alanine EPR dosimeters for medium energy x rays

    SciTech Connect

    Waldeland, Einar; Hole, Eli Olaug; Sagstuen, Einar; Malinen, Eirik

    2010-07-15

    Purpose: To perform a systematic investigation of the energy dependence of alanine and lilthium formate EPR dosimeters for medium energy x rays. Methods: Lithium formate and alanine EPR dosimeters were exposed to eight different x-ray beam qualities, with nominal potentials ranging from 50 to 200 kV. Following ionometry based on standards of absorbed dose to water, the dosimeters were given two different doses of approximately 3 and 6 Gy for each radiation quality, with three dosimeters for each dose. A reference series was also irradiated to three different dose levels at a {sup 60}Co unit. The dose to water energy response, that is, the dosimeter reading per absorbed dose to water relative to that for {sup 60}Co {gamma}-rays, was estimated for each beam quality. In addition, the energy response was calculated by Monte Carlo simulations and compared to the experimental energy response. Results: The experimental energy response estimates ranged from 0.89 to 0.94 and from 0.68 to 0.90 for lithium formate and alanine, respectively. The uncertainties in the experimental energy response estimates were typically 3%. The relative effectiveness, that is, the ratio of the experimental energy response to that following Monte Carlo simulations was, on average, 0.96 and 0.94 for lithium formate and alanine, respectively. Conclusions: This work shows that lithium formate dosimeters are less dependent on x-ray energy than alanine. Furthermore, as the relative effectiveness for both lithium formate and alanine were systematically less than unity, the yield of radiation-induced radicals is decreased following x-irradiation compared to irradiation with {sup 60}Co {gamma}-rays.

  10. Synthesis and EPR studies of 2'-deoxyuridines with alkynyl, rodlike linkages.

    PubMed

    Sniady, Adam; Sevilla, Michael D; Meneni, Srinivasarao; Lis, Tadeusz; Szafert, Slawomir; Khanduri, Deepthi; Finke, John M; Dembinski, Roman

    2009-08-01

    Sonogashira coupling of diacetyl 5-ethynyl-2'-deoxyuridine with diacetyl 5-iodo-2'-deoxyuridine gave the acylated ethynediyl-linked 2'-deoxyuridine dimer (3 b; 63%), which was deprotected with ammonia/methanol to give ethynediyl-linked 2'-deoxyuridines (3 a; 79%). Treatment of 5-ethynyl-2'-deoxyuridine (1 a) with 5-iodo-2'-deoxyuridine gave the furopyrimidine linked to 2'-deoxyuridine (78%). Catalytic oxidative coupling of 1 a (O(2), CuI, Pd/C, N,N-dimethylformamide) gave butadiynediyl-linked 2'-deoxyuridines (4; 84 %). Double Sonogashira coupling of 5-iodo-2'-deoxyuridine with 1,4-diethynylbenzene gave 1,4-phenylenediethynediyl-bridged 2'-deoxyuridines (5; 83%). Cu-catalyzed cycloisomerization of dimers 4 and 5 gave their furopyrimidine derivatives. One-electron addition to 1 a, 3 a, and 4 gave the anion radical, the EPR spectra of which showed that the unpaired electron is largely localized at C6 of one uracil ring (17 G doublet) at 77 K. The EPR spectra of the one-electron-oxidized derivatives of ethynediyl- and butadiynediyl-linked uridines 3 a and 4 at 77 K showed that the unpaired electron is delocalized over both rings. Therefore, structures 3 a and 4 provide an efficient electronic link for hole conduction between the uracil rings. However, for the excess electron, an activation barrier prevents coupling to both rings. These dimeric structures could provide a gate that would separate hole transfer from electron transport between strands in DNA systems. In the crystal structure of acylated dimer 3 b, the bases were found in the anti position relative to each other across the ethynyl link, and similar anti conformation was preserved in the derived furopyrimidine-deoxyuridine dinucleoside. PMID:19609983

  11. EPR study of polyaniline synthesized enzymatically in the presence of submicrometer-sized AOT vesicles.

    PubMed

    Rakvin, Boris; Carić, Dejana; Andreis, Mladen; Junker, Katja; Walde, Peter

    2014-02-27

    EPR spectroscopy was used to examine the magnetic properties of two enzymatically synthesized polyaniline (PANI) samples obtained in the presence of submicrometer-sized vesicles formed from sodium bis(2-ethylhexyl)sulfosuccinate (AOT) as templates. PANI-HRPC-AOT was synthesized with horseradish peroxidase isoenzyme C (HRPC) and hydrogen peroxide (H2O2) as oxidant while PANI-TvL-AOT was prepared with Trametes versicolor laccase (TvL) and dioxygen (O2) as oxidant. A commercial conductive sample of the emeraldine salt form of polyaniline (PANI-ES) was also used for comparison in order to correlate the experimental data obtained for PANI-HRPC-AOT and PANI-TvL-AOT with the properties of the well-characterized PANI-ES. It was shown that a model based on the concept of correlated polaronic bands could be applied for the interpretation of the EPR spectra of all three examined samples, although PANI-HRPC-AOT and PANI-TvL-AOT were significantly less conductive than PANI-ES. The magnetic properties of the PANI samples could be related to their conductivities, whereby a low conductivity was ascribed to decreased interchain spin interactions which were detectable from a splitting of the triplet spectrum at low temperatures (5-10 K). The obtained effective distance between the polyaniline chains is larger for enzymatically synthesized PANI than for PANI-ES, most likely mainly due to the presence of AOT which could not be removed completely during the work-up. AOT influences the chain conformation and the average chain-chain distance. PMID:24484357

  12. Rotation Dynamics Do Not Determine the Unexpected Isotropy of Methyl Radical EPR Spectra.

    PubMed

    Benetis, Nikolas P; Dmitriev, Yurij; Mocci, Francesca; Laaksonen, Aatto

    2015-09-01

    A simple first-principles electronic structure computation, further qc (quantum chemistry) computation, of the methyl radical gives three equal hf (hyperfine) couplings for the three protons with the unpaired electron. The corresponding dipolar tensors were notably rhombic and had different orientations and regular magnitude components, as they should, but what the overall A-tensor was seen by the electron spin is a different story! The final g = (2.002993, 2.002993, 2.002231) tensor and the hf coupling results obtained in vacuum, at the B3LYP/EPRIII level of theory clearly indicate that in particular the above A = (-65.19, -65.19, 62.54) MHz tensor was axial to a first approximation without considering any rotational dynamics for the CH3. This approximation was not applicable, however, for the trifluoromethyl CF3 radical, a heavier and nonplanar rotor with very anisotropic hf coupling, used here for comparison. Finally, a derivation is presented explaining why there is actually no need for the CH3 radicals to consider additional rotational dynamics in order for the electron to obtain an axially symmetric hf (hyperfine) tensor by considering the simultaneous dipolar couplings of the three protons. An additional consequence is an almost isotropic A-tensor for the electron spin of the CH3 radical. To the best of our knowledge, this point has not been discussed in the literature before. The unexpected isotropy of the EPR parameters of CH3 was solely attributed to the rotational dynamics and was not clearly separated from the overall symmetry of the species. The present theoretical results allowed a first explanation of the "forbidden" satellite lines in the CH3 EPR spectrum. The satellites are a fingerprint of the radical rotation, helping thus in distinguishing the CH3 reorientation from quantum rotation at very low temperatures. PMID:26262753

  13. Interaction of tetraphenyl-porphyrin derivatives with DPPC-liposomes: an EPR study.

    PubMed

    Voszka, István; Szabó, Zsófia; Csík, Gabriella; Maillard, Philip; Gróf, Pál

    2005-05-13

    The effect of the symmetry and polarity of the porphyrin molecules on their membrane localization and interaction with membrane lipids were investigated by electron paramagnetic resonance (EPR). For this purpose, two glycoconjugated tetraphenyl porphyrin derivatives were selected, respectively, symmetrically and asymmetrically substituted. Small unilamellar liposomes composed of dipalmitoylphosphatidylcholine (DPPC) and spin labeled stearic acids were prepared. The spin probe was located at the 5th or 7th or 12th or 16th position of the hydrocarbon chain in order to monitor various regions of the lipid bilayer. EPR spectra of porphyrin-free and porphyrin-bound liposomes were recorded at various temperatures below and above the phase transition temperature of DPPC. The effect on membrane fluidity proved to be stronger with the asymmetrical porphyrin derivative than with the symmetrical one. The rigidity increased when the spin label was near lipid head groups. The difference observed between control and porphyrin-treated samples when measured below the main lipid transition temperature disappeared at higher temperature. When the spin label was near the end of the hydrophobic tails, the symmetrical porphyrin derivative caused increase in fluidity, while the asymmetrical one slightly decreased it. To explain this phenomenon we propose that the asymmetrical derivative exerts a stronger ordering effect caused by its fluorophenyl group located at the level of the lipid heads, which is attenuated to the hydrophobic tails. The perturbing effect of the symmetric derivative could not lead to similar extent of ordering at the head groups and looses the hydrocarbon chains deeper in the membrane. PMID:15878112

  14. An image-intensive ePR for image-guided minimally invasive spine surgery applications including real-time intra-operative image acquisition, archival, and display

    NASA Astrophysics Data System (ADS)

    Documet, Jorge R.; Le, Anh; Liu, Brent; Huang, H. K.; Chiu, John

    2009-02-01

    Recent developments in medical imaging informatics have improved clinical workflow in Radiology enterprise but gaps remain in the clinical workflow from diagnosis to surgical treatment through post-operative follow-up. One solution to bridge this gap is the development of an electronic patient record (ePR) that integrates key imaging and informatics data during the pre, intra, and post-operative phases of clinical workflow. We present an ePR system based on standards and tailored to the clinical application for image-guided minimally invasive spinal surgery (MISS). The ePR system has been implemented in a clinical environment for a half-year.

  15. Comparing continuous wave progressive saturation EPR and time domain saturation recovery EPR over the entire motional range of nitroxide spin labels.

    PubMed

    Nielsen, Robert D; Canaan, Stephane; Gladden, James A; Gelb, Michael H; Mailer, Colin; Robinson, Bruce H

    2004-07-01

    The measurement of spin-lattice relaxation rates from spin labels, such as nitroxides, in the presence and absence of spin relaxants provides information that is useful for determining biomolecular properties such as nucleic acid dynamics and the interaction of proteins with membranes. We compare X-band continuous wave (CW) and pulsed or time domain (TD) EPR methods for obtaining spin-lattice relaxation rates of spin labels across the entire range of rotational motion to which relaxation rates are sensitive. Model nitroxides and spin-labeled biological species are used to illustrate the potential complications that arise in extracting relaxation data under conditions typical to biological experiments. The effect of super hyperfine (SHF) structure is investigated for both CW and TD spectra. First and second harmonic absorption and dispersion CW spectra of the nitroxide spin label, TEMPOL, are all fit simultaneously to a model of SHF structure over a range of microwave amplitudes. The CW spectra are novel because all harmonics and microwave phases were acquired simultaneously using our homebuilt CW/TD spectrometer. The effect of the SHF structure on the pulsed free induction decay (FID) and pulsed saturation recovery spectrum is shown for both protonated and deuterated TEMPOL. We present novel pulsed saturation recovery measurements on biological molecules, including spin-lattice relaxation rates of spin-labeled proteins and spin-labeled double-stranded DNA. The impact of structure and dynamics on relaxation rates are discussed in the context of each of these examples. Collisional relaxation rates with oxygen and transition metal paramagnetic relaxants are extracted using both continuous wave and time domain methods. The extent of the errors inherent in the CW method and the advantages of pulsed methods for unambiguously measuring collisional relaxation rates are discussed. Spin-lattice relaxation rates, determined by both CW and pulsed methods, are used to determine

  16. Studies of 3He polarization losses during NMR and EPR measurment and Polarized 3He target cell lifetime

    NASA Astrophysics Data System (ADS)

    An, Peibo

    2014-09-01

    The 3He target cell polarized by spin-exchange optical pumping(SEOP) is used as a neutron substitute to study the inner structure of the neutron. In our lab, nuclear-magnetic-resonance(NMR) is used to measure the relative polarization and electron-paramagnetic-resonance(EPR) is used to measure the spin exchange EPR frequency shift parameter of potassium and rubidium in our target cell presented in magnetic fields. The alkali in the cell is used to facilitate the polarization of 3He. The first part of my work presents the study of the polarization losses of the cell during both NMR and EPR. With the help of improved RF coils, we keep the background noise received by pickup coils reasonably low, but three other kinds of losses are inevitable: losses during Adiabatic Fast Passage (AFP) sweep, losses due to flux change caused by different cell orientation with respect to RF fields and physical losses. Fortunately there is only flux change in NMR measurements. The second part of my work presents the study of cell lifetime improvement. The polarization decreases in a process called relaxation exponentially. The lifetime of a cell is how long it can keep its polarization. The typical lifetime of cells produced in our lab is about 22 hours. With a newly designed vacuum system. The 3He target cell polarized by spin-exchange optical pumping(SEOP) is used as a neutron substitute to study the inner structure of the neutron. In our lab, nuclear-magnetic-resonance(NMR) is used to measure the relative polarization and electron-paramagnetic-resonance(EPR) is used to measure the spin exchange EPR frequency shift parameter of potassium and rubidium in our target cell presented in magnetic fields. The alkali in the cell is used to facilitate the polarization of 3He. The first part of my work presents the study of the polarization losses of the cell during both NMR and EPR. With the help of improved RF coils, we keep the background noise received by pickup coils reasonably low, but

  17. Extending the distance range accessed with continuous wave EPR with Gd3+ spin probes at high magnetic fields†

    PubMed Central

    Edwards, Devin T.; Ma, Zhidong; Meade, Thomas J.; Goldfarb, Daniella; Han, Songi

    2014-01-01

    Interspin distances between 0.8 nm and 2.0 nm can be measured through the dipolar broadening of the continuous wave (cw) EPR spectrum of nitroxide spin labels at X-band (9.4 GHz, 0.35 T). We introduce Gd3+ as a promising alternative spin label for distance measurements by cw EPR above 7 Tesla, where the |−1/2〉 to |1/2〉 transition narrows below 1 mT and becomes extremely sensitive to dipolar broadening. To estimate the distance limits of cw EPR with Gd3+, we have measured spectra of frozen solutions of GdCl3 at 8.6 T (240 GHz) and 10 K at concentrations ranging from 50 mM to 0.1 mM, covering a range of average interspin distances. These experiments show substantial dipolar broadening at distances where line broadening cannot be observed with nitroxides at X-band. This data, and its agreement with calculated dipolar-broadened lineshapes, show Gd3+ to be sensitive to distances as long as ~3.8 nm. Further, the linewidth of a bis-Gd3+ complex with a flexible ~1.6 nm bridge is strongly broadened as compared to the mono-Gd3+ complex, demonstrating the potential for application to pairwise distances. Gd-DOTA-based chelates that can be functionalized to protein surfaces display linewidths narrower than aqueous GdCl3, implying they should be even more sensitive to dipolar broadening. Therefore, we suggest that the combination of tailored Gd3+ labels and high magnetic fields can extend the longest interspin distances measurable by cw EPR from 2.0 nm to 3.8 nm. cw EPR data at 260 K demonstrate that the line broadening remains clear out to similar average interspin distances, offering Gd3+ probes as promising distance rulers at temperatures higher than possible with conventional pulsed EPR distance measurements. PMID:23732863

  18. EPR investigation of Cu2+-substituted photosynthetic bacterial reaction centers: evidence for histidine ligation at the surface metal site.

    PubMed

    Utschig, L M; Poluektov, O; Tiede, D M; Thurnauer, M C

    2000-03-21

    The coordination environments of two distinct metal sites on the bacterial photosynthetic reaction center (RC) protein were probed with pulsed electron paramagnetic resonance (EPR) spectroscopy. For these studies, Cu2+ was bound specifically to a surface site on native Fe2+-containing RCs from Rhodobacter sphaeroides R-26 and to the native non-heme Fe site in biochemically Fe-removed RCs. The cw and pulsed EPR results clearly indicate two spectroscopically different Cu2+ environments. In the dark, the RCs with Cu2+ bound to the surface site exhibit an axially symmetric EPR spectrum with g(parallel) = 2.24, A(parallel) = 160 G, g(perpendicular) = 2.06, whereas the values g(parallel) = 2.31, A(parallel) = 143 G, and g(perpendicular) = 2.07 were observed when Cu(2+) was substituted in the Fe site. Examination of the light-induced spectral changes indicate that the surface Cu2+ is at least 23 A removed from the primary donor (P+) and reduced quinone acceptor (QA-). Electron spin-echo envelope modulation (ESEEM) spectra of these Cu-RC proteins have been obtained and provide the first direct solution structural information about the ligands in the surface metal site. From these pulsed EPR experiments, modulations were observed that are consistent with multiple weakly hyperfine coupled 14N nuclei in close proximity to Cu2+, indicating that two or more histidines ligate the Cu2+ at the surface site. Thus, metal and EPR analyses confirm that we have developed reliable methods for stoichiometrically and specifically binding Cu2+ to a surface site that is distinct from the well characterized Fe site and support the view that Cu2+ is bound at or near the Zn site that modulates electron transfer between the quinones QA and QB (QA-QB --> QAQB-) (Utschig, L. M., Ohigashi, Y., Thurnauer, M. C., and Tiede, D. M (1998) Biochemistry 37, 8278-8281) and proton uptake by QB- (Paddock, M. L., Graige, M. S., Feher, G., and Okamura, M. Y. (1999) Proc. Natl. Acad. Sci. U.S.A. 96, 6183

  19. Studies of EPR parameters for Mn5+-doped Ca2(MO4)Cl (M = P, As, V) crystals from a two-mechanism model

    NASA Astrophysics Data System (ADS)

    Wu, Xiao-Xuan; Yu, Xin-Peng; Zheng, Wen-Chen

    2014-12-01

    The EPR parameters (zero-field splitting D and g-factors g//, g⊥) of Mn5+-doped solid state laser materials Ca2(MO4)Cl (M = P, As, V) are calculated from the complete high-order perturbation formulas of EPR parameters based on the two-mechanism model for 3d2 ions in a approximately tetragonal tetrahedron. The model includes the contributions from both the crystal-field (CF) mechanism and the charge-transfer (CT) mechanism (the latter is neglected in crystal field theory). The calculated results suggest that the contribution to EPR parameters due to CT mechanism is important. So, in the cases of high valence state 3dn ions in crystals, the reasonable explanation of EPR parameters should take both CF and CT mechanisms into account.

  20. Cytochrome c-554 from Methylosinus trichosporium OB3b; a protein that belongs to the cytochrome c2 family and exhibits a HALS-Type EPR signal.

    PubMed

    Harbitz, Espen; Andersson, K Kristoffer

    2011-01-01

    A small soluble cytochrome c-554 purified from Methylosinus trichosporium OB3b has been purified and analyzed by amino acid sequencing, mass spectrometry, visible, CD and EPR spectroscopies. It is found to be a mono heme protein with a characteristic cytochrome c fold, thus fitting into the class of cytochrome c(2), which is the bacterial homologue of mitochondrial cytochrome c. The heme iron has a Histidine/Methionine axial ligation and exhibits a highly anisotropic/axial low spin (HALS) EPR signal, with a g(max) at 3.40, and ligand field parameters V/ξ = 0.99, Δ/ξ = 4.57. This gives the rhombicity V/Δ = 0.22. The structural basis for this HALS EPR signal in Histidine/Methionine ligated hemes is not resolved. The ligand field parameters observed for cytochrome c-554 fits the observed pattern for other cytochromes with similar ligation and EPR behaviour. PMID:21789203

  1. Melt spreading code assessment, modifications, and application to the EPR core catcher design.

    SciTech Connect

    Farmer, M. T .; Nuclear Engineering Division

    2009-03-30

    The Evolutionary Power Reactor (EPR) is under consideration by various utilities in the United States to provide base load electrical production, and as a result the design is undergoing a certification review by the U.S. Nuclear Regulatory Commission (NRC). The severe accident design philosophy for this reactor is based upon the fact that the projected power rating results in a narrow margin for in-vessel melt retention by external cooling of the reactor vessel. As a result, the design addresses ex-vessel core melt stabilization using a mitigation strategy that includes: (1) an external core melt retention system to temporarily hold core melt released from the vessel; (2) a layer of 'sacrificial' material that is admixed with the melt while in the core melt retention system; (3) a melt plug in the lower part of the retention system that, when failed, provides a pathway for the mixture to spread to a large core spreading chamber; and finally, (4) cooling and stabilization of the spread melt by controlled top and bottom flooding. The overall concept is illustrated in Figure 1.1. The melt spreading process relies heavily on inertial flow of a low-viscosity admixed melt to a segmented spreading chamber, and assumes that the melt mass will be distributed to a uniform height in the chamber. The spreading phenomenon thus needs to be modeled properly in order to adequately assess the EPR design. The MELTSPREAD code, developed at Argonne National Laboratory, can model segmented, and both uniform and nonuniform spreading. The NRC is thus utilizing MELTSPREAD to evaluate melt spreading in the EPR design. MELTSPREAD was originally developed to support resolution of the Mark I containment shell vulnerability issue. Following closure of this issue, development of MELTSPREAD ceased in the early 1990's, at which time the melt spreading database upon which the code had been validated was rather limited. In particular, the database that was utilized for initial validation consisted

  2. Did the Galápagos plume influence the ancient EPR? : A geochemical study of basaltic rocks from Hole 1256D

    NASA Astrophysics Data System (ADS)

    Park, S.; Maclennan, J.; Teagle, D.; Hauff, F.

    2008-12-01

    IODP Hole 1256D, which is located in Cocos Plate and was drilled during Leg 206 and Exp. 309/312, was generated under the ancient EPR with a super fast spreading rate (~220 mm/yr full rate) at 15 Ma. Hole 1256D is especially important because it penetrated into gabbro via lava and dikes in intact oceanic crust for the first time in the history of ocean drilling. The 1256D core was chemically analyzed to evaluate melting processes and mantle source heterogeneity under the super fast spreading ancient EPR. The chemical data were compared with modern and well-constrained data-sets from the Northern EPR, Southern EPR and Hole 504B which was generated at the ancient Galápagos spreading center. 1256D core has significantly lower incompatible element concentrations than present-day EPR samples, a signature which might typically be interpreted in terms of greater extents of mantle melting under 1256D. However, the crustal thicknesses at 1256D (5-5.5 km) and the EPR (5-7 km) are similar, indicating that the difference of the degree of partial melting is not the cause of relative depletion of 1256D relative to present EPR. Therefore, this difference may be due to mantle source depletion beneath ancient EPR or a departure of the melting regime from the simple mantle corner flow passive upwelling models. Simple physical models of mantle upwelling at various spreading rates or near evolving triple junctions indicate that the melting process alone is not the cause of the relatively depleted signature at 1256D. Instead, we suggest that this mantle source variation might be caused by upwelling of previously depleted Galápagos plume mantle at the paleo-1256D site. Radiogenic isotopes analysis may support this interpretation.

  3. Constraining the Magmatic Budget of the EPR at 9oN Using Broadband Marine MT

    NASA Astrophysics Data System (ADS)

    Key, K. W.; Constable, S. C.

    2003-12-01

    In February 2004 we will be conducting a 60 site broadband magnetotelluric (MT) survey at the Ridge2000 integrated study site (ISS) on the East Pacific Rise (EPR) near 9oN. Broadband marine MT instrumentation developed at Scripps Institution of Oceanography and used extensively by the petroleum industry will allow resolution of electrical conductivity structure at much shallower depths than traditional MT instrument systems. A small aperture (30km) transect of densely spaced MT sites across the ridge at the ISS "bull's eye" focus area at 9o50'N will image the electrical conductivity structure of the crust and shallow mantle in the vicinity of the ridge axis. A large aperture (200km) MT transect across the ridge at 9o30'N will target both crustal and upper mantle conductivity structures. We will also be deep-towing the new Scripps Underwater Electromagnetic Source Instrument (SUESI) to allow for controlled-source EM data which will provide constraints on the shallowest/resistive structures. Key issues we are addressing with our experiment are: 1. What is the distribution, vertical extent and volume fraction of melt present in the mid to lower crust? A dense transect of MT sites near the ridge axis at the ISS "bull's eye" focus area at 9o50'N will delineate the region of crust containing partial melt and constrain the total amount of connected melt present. 2. To what extent does hydrothermal circulation play a role in heat removal from the crust? What link(s) exists between the hydrothermal activity and crustal magma at the ridge axis? How does hydrothermal circulation affect the lateral extent of the crustal melt? A wide array of MT sites will provide estimates of lateral electrical conductivity variations in the crust near the mid-ocean ridge, from which constraints on temperature, porosity and permeability variations in the region surrounding the mid to lower crustal melt accumulations at 9o50'N can be made. 3. To what extent is melt accumulating at the base of

  4. Magnetism and EPR spectra of the two-sublattice manganese chain Mn2(EDTA)ṡ9H2O

    NASA Astrophysics Data System (ADS)

    Borrás-Almenar, J. J.; Coronado, E.; Gómez-García, C. J.; Gatteschi, D.; Zanchini, C.

    1990-05-01

    We report on the magnetic behavior and single-crystal EPR spectra of the chain complex Mn2(EDTA)ṡ9H2O characterized by two different alternating sites for the manganese ions. Magnetic susceptibility data are indicative of weak antiferromagnetic exchange interactions between the manganese ions, showing a maximum of about 3 K. This behavior can be accurately described on the basis of a Heisenberg chain model that assumes classical spins, giving J/k=-0.72 K and g=2.0. The EPR spectra are typically low dimensional, with an angular dependence of the linewidth of the type (3 cos2 θ-1)n (n=4/3 or 2). Nevertheless, such a behavior cannot be reproduced from a one-dimensional model with dipolar broadening. An alternative broadening mechanism arising from single-ion zero-field splitting is then suggested.

  5. EPR characteristics of free radicals in DOPA-melanin-moxifloxacin complexes at ambient level of UVA radiation

    NASA Astrophysics Data System (ADS)

    Beberok, Artur; Zdybel, Magdalena; Pilawa, Barbara; Buszman, Ewa; Wrześniok, Dorota

    2014-01-01

    EPR studies pointed out that o-semiquinone free radicals with g-values 2.0038-2.0040 take part in moxifloxacin-melanin complex formation. The process contributed to increase in free radicals concentration in nonirradiated complexes. This effect was observed for the complexes with 1 × 10-4 M, 1 × 10-3 M and 4 × 10-3 M drug concentrations. UV irradiation contributed to decrease in free radicals concentration in DOPA-melanin complexes with moxifloxacin, besides the complexes with the drug concentration of 1 × 10-4 M. The strongest decrease was observed for DOPA-melanin-moxifloxacin complexes with the drug concentration of 1 × 10-3 M. Homogeneous broadening of EPR lines, strong dipolar interactions and slow spin-lattice relaxation processes characterized all the tested melanin samples.

  6. Investigations of the EPR Parameters and Local Lattice Structure for the Rhombic Cu2+ Centre in TZSH Crystal

    NASA Astrophysics Data System (ADS)

    Li, Chao-Ying; Liu, Shi-Fei; Fu, Jin-Xian

    2016-03-01

    The electron paramagnetic resonance (EPR) parameters [i.e. g factors gi (i=x, y, z) and hyperfine structure constants Ai] and the local lattice structure for the Cu2+ centre in Tl2Zn(SO4)2·6H2O (TZSH) crystal were theoretically investigated by utilising the perturbation formulae of these parameters for a 3d9 ion under rhombically elongated octahedra. In the calculations, the admixture of d orbitals in the ground state and the ligand orbital and spin-orbit coupling interactions are taken into account based on the cluster approach. The theoretical EPR parameters show good agreement with the observed values, and the Cu2+-H2O bond lengths are obtained as follows: Rx≈1.98 Å, Ry≈2.09 Å, Rz≈2.32 Å. The results are discussed.

  7. The EPR study of Mn2+ ion doped DADT single crystal produced under high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Ceylan, Ümit; Tapramaz, Recep

    2016-01-01

    An EPR study on Cu2+ and VO2+ doped di ammonium D-tartrate single crystals has been reported in previous papers, but the same host did not accept Mn2+ ion at the same reaction conditions in previous trials. In this study EPR study of Mn2+ ion doped di ammonium D tartrate single crystal, (DADT) [(NH4)2C4H4O6], produced in a reactor under high pressure and high temperature. The electronic transitions were determined by the optical absorption spectrum. Hyperfine splitting and g values of the Mn2+ ion forming a complex in the lattice were measured from experimental spectra and spin-spin dipolar splitting parameters D and E were found by the spectrum simulation techniques.

  8. α-Tocopherol impact on oxy-radical induced free radical decomposition of DMSO: Spin trapping EPR and theoretical studies

    NASA Astrophysics Data System (ADS)

    Jerzykiewicz, Maria; Ćwieląg-Piasecka, Irmina; Witwicki, Maciej; Jezierski, Adam

    2011-05-01

    EPR spin trapping and theoretical methods such as density functional theory (DFT) as well as combined DFT and quadratic configuration interaction approach (DFT/QCISD) were used to identify the radicals produced in the reaction of oxy-radicals and dimethyl sulfoxide (DMSO) in the presence and absence of α-tocopherol. Additionally, the mixtures of α-tocopherol with linolenic acid and glyceryl trilinoleate as well as bioglycerols (glycerol fractions from biodiesel production) were tested. α-Tocopherol inhibited oxidation of the main decomposition product of DMSO, •CH 3 to •OCH 3 but did not prevent the transformation process of N-t-butyl- α-phenylnitrone (PBN) into 2-methyl-2-nitrosopropane (MNP). Theoretical investigations confirmed the structures of proposed spin adducts and allowed to correlate the EPR parameters observed in the experiment with the spin adducts electronic structure.

  9. Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis

    SciTech Connect

    Lu, Qingquan; Zhang, Jian; Peng, Pan; Zhang, Guanghui; Huang, Zhiliang; Yi, Hong; Miller, Jeffrey T.; Lei, Aiwen

    2015-05-26

    An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(II) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(I) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(II) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfones are synthesized with good to excellent yields under mild conditions.

  10. Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis

    DOE PAGESBeta

    Lu, Qingquan; Zhang, Jian; Peng, Pan; Zhang, Guanghui; Huang, Zhiliang; Yi, Hong; Miller, Jeffrey T.; Lei, Aiwen

    2015-05-26

    An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(II) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(I) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(II) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfonesmore » are synthesized with good to excellent yields under mild conditions.« less

  11. EPR investigation of thermal decay of radiation-induced species of benzoic acid and its sodium and potassium salts.

    PubMed

    Tuner, Hasan; Kayıkçı, Mehmet Ali

    2015-05-01

    The structural and kinetic features of the radiation-induced radicals of benzoic acid and its sodium and potassium salts were investigated using electron paramagnetic resonance (EPR) spectroscopy. Two main different radicals were found to be responsible for the measured spectra of the irradiated samples. It is concluded that these two radicals have a structure similar to that of cyclohexadienyl-type (CHD) and benzyl-type (BNZ) radicals. The relative contributions of the CHD and BNZ radicals to the measured peak-to-peak amplitude and to the total spectra were calculated. The room-temperature stability of the EPR signals and the decay kinetic features of the radiation-induced radicals derived from annealing at high temperatures were determined. PMID:25744174

  12. EPR, FTIR, and FAB mass spectrometric investigation of reaction of H atoms with C 60 in a cyclohexane matrix

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    1993-03-01

    Hydrogen atoms have been reacted with C 60 in a cyclohexane matrix at 77 K in a rotating cryostat. Species HC 60, H 2 n + 1 C 60, and H 2 nC 60 have been identified by EPR, FTIR and FAB mass spectrometry. HC 60 has the magnetic parameters aH(1) = 92.9 ± 0.5 MHz and g = 2.00218 ± 0.00004. These values are compared to the deuterium and muonium analogs. Reasons for the isotope effect in the hydrogen and muon hyperfine interactions of HC 60 and MuC 60 are discussed. The narrow line widths of the EPR transitions of H 2 n + 1C 60 may be associated with globe-trotting hydrogen atoms. C 60 acts as a H atom sponge at high atom fluxes and H 2 nC 60s with n as large as 17 have been identified.

  13. A comparison of antioxidative capacities of fruit juices, drinks and nectars, as determined by EPR and UV-vis spectroscopies.

    PubMed

    Bartoszek, Mariola; Polak, Justyna

    2016-01-15

    The differences in the Trolox Equivalent Antioxidant Capacity (TEAC) values at the same incubation time obtained by two different techniques: electron paramagnetic resonance (EPR) spectroscopy and ultraviolet visible (UV-vis) spectroscopy, which use the same antioxidant-free radical reaction mechanism, were determined for fruit juices, nectars and drinks. For this study, the stable free radical 1,1-Diphenyl-2-picryl-hydrazyl (DPPH(•)) was used. The antioxidant capacity was presented in Trolox Equivalents, e.g., μM trolox per 100 ml of sample. All of the studied fruit juices, drinks and nectars showed antioxidative properties. Dependencies between TEAC values and the percent fruit content and sample color were observed for the studied beverages. It was found that EPR spectroscopy is the more adequate method for determining TEAC values for these kinds of samples. PMID:26433341

  14. A comparison of antioxidative capacities of fruit juices, drinks and nectars, as determined by EPR and UV-vis spectroscopies

    NASA Astrophysics Data System (ADS)

    Bartoszek, Mariola; Polak, Justyna

    2016-01-01

    The differences in the Trolox Equivalent Antioxidant Capacity (TEAC) values at the same incubation time obtained by two different techniques: electron paramagnetic resonance (EPR) spectroscopy and ultraviolet visible (UV-vis) spectroscopy, which use the same antioxidant-free radical reaction mechanism, were determined for fruit juices, nectars and drinks. For this study, the stable free radical 1,1-Diphenyl-2-picryl-hydrazyl (DPPH•) was used. The antioxidant capacity was presented in Trolox Equivalents, e.g., μM trolox per 100 ml of sample. All of the studied fruit juices, drinks and nectars showed antioxidative properties. Dependencies between TEAC values and the percent fruit content and sample color were observed for the studied beverages. It was found that EPR spectroscopy is the more adequate method for determining TEAC values for these kinds of samples.

  15. Using EPR spectroscopy as a unique probe of molecular-scale reorganization and solvation in self-assembled gel-phase materials.

    PubMed

    Caragheorgheopol, Agneta; Edwards, William; Hardy, John G; Smith, David K; Chechik, Victor

    2014-08-01

    We describe the synthesis of spin-labeled bis-ureas which coassemble with bis-urea gelators and report on self-assembly as detected using electron paramagnetic resonance spectroscopy (EPR). Specifically, EPR detects the gel-sol transition and allows us to quantify how much spin-label is immobilized within the gel fibers and how much is present in mobile solvent pools-as controlled by temperature, gelator structure, and thermal history. EPR is also able to report on the initial self-assembly processes below the gelation threshold which are not macroscopically visible and appears to be more sensitive than NMR to intermediate-sized nongelating oligomeric species. By studying dilute solutions of gelator molecules and using either single or double spin-labels, EPR allows quantification of the initial steps of the hierarchical self-assembly process in terms of cooperativity and association constant. Finally, EPR enables us to estimate the degree of gel-fiber solvation by probing the distances between spin-labels. Comparison of experimental data against the predicted distances assuming the nanofibers are only composed of gelator molecules indicates a significant difference, which can be assigned to the presence of a quantifiable number of explicit solvent molecules. In summary, EPR provides unique data and yields powerful insight into how molecular-scale mobility and solvation impact on assembly of supramolecular gels. PMID:25017326

  16. Effect of nitrogen dioxide on the EPR property of lithium octa-n-butoxy 2,3-naphthalocyanine (LiNc-BuO) microcrystals.

    PubMed

    Pandian, Ramasamy P; Dang, Vinh; Manoharan, Periakaruppan T; Zweier, Jay L; Kuppusamy, Periannan

    2006-07-01

    Lithium octa-n-butoxy-naphthalocyanine (LiNc-BuO) is a stable free radical that can be detected by electron paramagnetic resonance (EPR) spectroscopy. Previously we have reported that microcrystals of LiNc-BuO exhibit a single sharp EPR peak, whose width varies linearly with the partial pressure of paramagnetic molecules such as oxygen and nitric oxide. In this report, we present the effect of nitrogen dioxide (NO2), which is also a paramagnetic molecule, on the EPR properties of LiNc-BuO. The gas-sensing property of LiNc-BuO is attributed to the open molecular framework of the crystal structure which is arranged with wide channels capable of accommodating large molecules such as NO2. The EPR linewidth of LiNc-BuO was highly sensitive to the partial pressure of NO2 in the gas mixture. The line-broadening was quick and reversible in the short-term for low concentration of NO2. However, the EPR signal intensity decreased with time of exposure, apparently due to a reaction of NO2 with LiNc-BuO crystals to give diamagnetic products. The results suggested that LiNc-BuO may be a useful probe for the determination of trace amounts of NO2 using EPR spectroscopy. PMID:16690337

  17. Stochastic Liouville equation studies of FT-EPR spectra of singlet-triplet mixing photo-chemically generated radical pair system.

    PubMed

    Hanaishi, Ryuji

    2008-07-01

    A stochastic Liouville equation (SLE) was numerically solved to obtain pulsed Fourier-transform (FT) EPR spectra on a radical pair system created in a photo-induced chemical reaction. Numerical calculations were applied to the photo-chemical reaction of deuterated acetone and 2-propanol at low temperatures. In this reaction system, the antiphase structures of the EPR signals, so called spin-correlated radical pair (SCRP) signals of two identical isopropyl ketyl radicals and spin-polarized free isopropyl ketyl radicals were observed by FT-EPR and continuous wave time-resolved (CW TR) EPR techniques. In the present work, FT-EPR spectra of the antiphase structure signals of the radical pair themselves as well as spin-polarized free radical signals were simulated. Additionally, rising behavior of free radical signals polarized by the radical pair mechanism (RPM) was also clarified. Furthermore two-dimensional (2D) FT-EPR nutation spectra were simulated in the both cases with and without the radical pairs by the use of SLE. In these simulations, strong DC components in the nutation frequency dimension, were well reproduced as was obtained in experiments. It was shown that relaxation during the microwave pulse was essential for the appearance of the DC components. PMID:18486510

  18. European Pressurized water Reactor (EPR) SAR ATWS Accident Analyses by using 3D Code Internal Coupling Method

    SciTech Connect

    Gagner, Renata; Lafitte, Helene; Dormeau, Pascal; Stoudt, Roger H.

    2004-07-01

    Anticipated Transients Without Scram (ATWS) accident analyses make part of the Safety Analysis Report of the European Pressurized water Reactor (EPR), covering Risk Reduction Category A (Core Melt Prevention) events. This paper deals with three of the most penalizing RRC-A sequences of ATWS caused by mechanical blockage of the control/shutdown rods, regarding their consequences on the Reactor Coolant System (RCS) and core integrity. A new 3D code internal coupling calculation method has been introduced. (authors)

  19. EPR studies on the organization of self-assembled spin-labeled organic monolayers adsorbed on GaAs.

    PubMed

    Ruthstein, Sharon; Artzi, Reit; Goldfarb, Daniella; Naaman, Ron

    2005-02-01

    Characterizing the structure and dynamic properties of a single monolayer is a challenge due to the minute amount of material that is probed. Here, EPR spectroscopy is used for investigating the spatial and temporal organization of self-assembled monolayers of 5- and 16-doxyl stearic acid (5 DSA and 16 DSA, respectively) adsorbed on a GaAs substrate. The results are complemented with FTIR and ellipsometery measurements, which provide the evidence for the formation of monolayers. Moreover, a comparison with the FTIR spectrum of a monolayer of stearic acid shows that the monolayers of the spin labeled molecules are less packed due to the hindrance introduced by the labeling group. The EPR spectra provide a new insight on the ordering in the layer and more interestingly, it reveals the time dependence of the organization. For 5DSA, with the spin-label group situated close to the substrate, the EPR spectrum immediately after adsorption is poorly resolved and dominated by the spin-exchange interaction between neighboring molecules. As time increases (up to 1 week) the resolution of the 14N hyperfine coupling increases, revealing a better organized monolayer where the molecules are more homogenously spaced. Moreover, the spectrum of the layer, after reaching equilibrium, shows that there is no motional freedom near the GaAs surface. Orientation dependence measurements on the equilibrated sample show the presence of a preferred orientation of the molecules, although with a wide distribution. The spectrum of the 16DSA monolayer, where the nitroxide spin label is situated at the end of the chain, far from the surface, also showed a poorly resolved spectrum at short times, but unlike 5DSA, it did not exhibit any time dependence. Through EPR line-shape simulations and by comparison with FTIR results, the differences between 5DSA and 16DSA were attributed to difference in coverage caused by the bulky spin label near the surface in the case of 5DSA. PMID:19785139

  20. Theoretical study of the multiline EPR signal from the S2 state of the oxygen evolving complex of photosystem II

    PubMed Central

    Bonvoisin, Jacques; Blondin, Geneviève; Girerd, Jean-Jacques; Zimmermann, Jean-Luc

    1992-01-01

    The Oxygen evolving complex of plant photosystem II is made of a manganese cluster that gives rise to a low temperature EPR multiline signal in the S2 oxidation state. The origin of this EPR signal has been addressed with respect to the question of the magnetic couplings between the electron and nuclear spins of the four possible Mn ions that make up this complex. Considering Mn(III) and Mn(IV) as the only possible oxidation states present in the S2 state, and no large anisotropy of the magnetic tensors, the breadths of the EPR spectra calculated for dimers and trimers with S = ½ have been compared with that of the biological site. It is concluded that neither a dinuclear nor a trinuclear complex made of Mn(III) and Mn(IV) can be responsible for the multiline signal; but that, by contrast, a tetranuclear Mn complex can be the origin of this signal. The general shape of the experimental spectrum, its particular hyperfine pattern, the positions of most of the hyperfine lines and their relative intensities can be fit by a tetramer model described by the following six fitting parameters: g ≈ 1.987, A1 ≈ 122.4 10-4 cm-1, A2 ≈ 87.2 10-4 cm-1, A3 ≈ 81.6 10-4 cm-1, A4 ≈ 19.1 10-4 cm-1 and δH = 24.5 G. A second model described by parameters very close to those given above except for A4 ≈ 77.5 10-4 cm-1 gives an equally good fit. However, no other set of parameters gives an EPR spectrum that reproduces the hyperfine pattern of the S2 multiline signal. This demonstrates that in the S2 state of the oxygen evolving complex, the four manganese ions are organized in a magnetic tetramer. PMID:19431827

  1. Bypassing the EPR effect with a nanomedicine harboring a sustained-release function allows better tumor control

    PubMed Central

    Shen, Yao An; Shyu, Ing Luen; Lu, Maggie; He, Chun Lin; Hsu, Yen Mei; Liang, Hsiang Fa; Liu, Chih Peng; Liu, Ren Shyan; Shen, Biing Jiun; Wei, Yau Huei; Chuang, Chi Mu

    2015-01-01

    The current enhanced permeability and retention (EPR)-based approved nanomedicines have had little impact in terms of prolongation of overall survival in patients with cancer. For example, the two Phase III trials comparing Doxil®, the first nanomedicine approved by the US Food and Drug Administration, with free doxorubicin did not find an actual translation of the EPR effect into a statistically significant increase in overall survival but did show less cardiotoxicity. In the current work, we used a two-factor factorial experimental design with intraperitoneal versus intravenous delivery and nanomedicine versus free drug as factors to test our hypothesis that regional (intraperitoneal) delivery of nanomedicine may better increase survival when compared with systemic delivery. In this study, we demonstrate that bypassing, rather than exploiting, the EPR effect via intraperitoneal delivery of nanomedicine harboring a sustained-release function demonstrates dual pharmacokinetic advantages, producing more efficient tumor control and suppressing the expression of stemness markers, epithelial-mesenchymal transition, angiogenesis signals, and multidrug resistance in the tumor microenvironment. Metastases to vital organs (eg, lung, liver, and lymphatic system) are also better controlled by intraperitoneal delivery of nanomedicine than by standard systemic delivery of the corresponding free drug. Moreover, the intraperitoneal delivery of nanomedicine has the potential to replace hyperthermic intraperitoneal chemotherapy because it shows equal efficacy and lower toxicity. In terms of efficacy, exploiting the EPR effect may not be the best approach for developing a nanomedicine. Because intraperitoneal chemotherapy is a type of regional chemotherapy, the pharmaceutical industry might consider the regional delivery of nanomedicine as a valid alternative pathway to develop their nanomedicine(s) with the goal of better tumor control in the future. PMID:25848266

  2. EPR and optical absorption studies of Cu{sup 2+} ions in alkaline earth alumino borate glasses

    SciTech Connect

    Ramesh Kumar, V.; Rao, J.L. . E-mail: jlrao46@yahoo.co.in; Gopal, N.O.

    2005-08-11

    Electron paramagnetic resonance (EPR) and optical absorption spectra of Cu{sup 2+} ions in alkaline earth alumino borate glasses doped with different concentrations of CuO have been studied. The EPR spectra of all the glasses exhibit the resonance signals, characteristic of Cu{sup 2+} ions present in axially elongated octahedral sites. The number of spins participating in the resonance has been calculated as a function of temperature for calcium alumino borate (CaAB) glass doped with 0.1 mol% of CuO. From the EPR data, the paramagnetic susceptibility ({chi}) was calculated at different temperatures (T) and from the 1/{chi}-T graph, the Curie temperature of the glass has been evaluated. The optical absorption spectra of all the glasses show a single broad band, which has been assigned to the {sup 2}B{sub 1g} {yields} {sup 2}B{sub 2g} transition of the Cu{sup 2+} ions. The variation in the intensity of optical absorption with the ionic radius of the alkaline earth ion has been explained based on the Coulombic forces. By correlating the EPR and optical absorption spectral data, the nature of the in-plane {sigma} bonding between Cu{sup 2+} ion and the ligands is estimated. From the fundamental ultraviolet absorption edges of the glasses, the optical energy gap (E {sub opt}) and the Urbach energy ({delta}E) are evaluated. The variation in E {sub opt} and {delta}E is explained based on the number of defect centers in the glass.

  3. EPR and optical investigations of LaMgAl{sub 11}O{sub 19}:Cr{sup 3+} phosphor

    SciTech Connect

    Singh, Vijay; Sivaramaiah, G.; Rao, J.L.; Kim, S.H.

    2014-12-15

    Graphical abstract: The EPR spectrum of as-prepared LaMgAl{sub 11}O{sub 19}:Cr{sup 3+} phosphor at 110 K. - Highlights: • Using the combustion synthesis, LaMgAl{sub 11}O{sub 19}:Cr{sup 3+} phosphor has been prepared in a few minutes. • Optical investigation indicates that Cr{sup 3+} ions are present in octahedral symmetry. • The EPR signals indicate that exchange coupled Cr{sup 3+}–Cr{sup 3+} ion pairs in weakly distorted sites. - Abstract: The LaMgAl{sub 11}O{sub 19}:Cr{sup 3+} phosphor has been prepared by a low-temperature combustion synthesis method. As-prepared combustion synthesized powder was characterized using powder X-ray diffraction (XRD), diffuse reflectance (DRS), electron paramagnetic resonance (EPR) and photoluminescence (PL) studies. The X-ray diffraction pattern reveals crystalline hexagonal phases. The UV–vis diffuse reflectance spectrum exhibits three broad bands characteristic of Cr{sup 3+} ions in octahedral symmetry. The EPR spectrum exhibits several resonance signals. The signals with the effective g values at g = 4.84, 3.64 and 2.26 have been attributed to the isolated Cr{sup 3+} ions. The signal with the effective g value at g = 1.94 has been attributed to exchange coupled Cr{sup 3+}–Cr{sup 3+} ion pairs. The PL studies exhibit several bands characteristic of Cr{sup 3+} ions in octahedral symmetry.

  4. Uniaxial magnetic anisotropy of square-planar chromium(II) complexes revealed by magnetic and HF-EPR studies.

    PubMed

    Deng, Yi-Fei; Han, Tian; Wang, Zhenxing; Ouyang, Zhongwen; Yin, Bing; Zheng, Zhiping; Krzystek, J; Zheng, Yan-Zhen

    2015-12-28

    Two mononuclear square-planar Cr(II) complexes are reported, exhibiting field-induced slow magnetic relaxation. The axial zero-field splitting parameter was unambiguously determined by both a high-frequency/field electron paramagnetic resonance (HF-EPR) technique and magnetic measurements. This result represents the first observed single-molecule-magnet behavior in the square planar coordination geometry of any metal ions. PMID:26587566

  5. Identification of the Valence and Coordination Environment of the Particulate Methane Monooxygenase Copper Centers by Advanced EPR Characterization

    PubMed Central

    2015-01-01

    Particulate methane monooxygenase (pMMO) catalyzes the oxidation of methane to methanol in methanotrophic bacteria. As a copper-containing enzyme, pMMO has been investigated extensively by electron paramagnetic resonance (EPR) spectroscopy, but the presence of multiple copper centers has precluded correlation of EPR signals with the crystallographically identified monocopper and dicopper centers. A soluble recombinant fragment of the pmoB subunit of pMMO, spmoB, like pMMO itself, contains two distinct copper centers and exhibits methane oxidation activity. The spmoB protein, spmoB variants designed to disrupt one or the other or both copper centers, as well as native pMMO have been investigated by EPR, ENDOR, and ESEEM spectroscopies in combination with metal content analysis. The data are remarkably similar for spmoB and pMMO, validating the use of spmoB as a model system. The results indicate that one EPR-active Cu(II) ion is present per pMMO and that it is associated with the active-site dicopper center in the form of a valence localized Cu(I)Cu(II) pair; the Cu(II), however, is scrambled between the two locations within the dicopper site. The monocopper site observed in the crystal structures of pMMO can be assigned as Cu(I). 14N ENDOR and ESEEM data are most consistent with one of these dicopper-site signals involving coordination of the Cu(II) ion by residues His137 and His139, the other with Cu(II) coordinated by His33 and the N-terminal amino group. 1H ENDOR measurements indicate there is no aqua (HxO) ligand bound to the Cu(II), either terminally or as a bridge to Cu(I). PMID:25059917

  6. Identification of the valence and coordination environment of the particulate methane monooxygenase copper centers by advanced EPR characterization.

    PubMed

    Culpepper, Megen A; Cutsail, George E; Gunderson, William A; Hoffman, Brian M; Rosenzweig, Amy C

    2014-08-20

    Particulate methane monooxygenase (pMMO) catalyzes the oxidation of methane to methanol in methanotrophic bacteria. As a copper-containing enzyme, pMMO has been investigated extensively by electron paramagnetic resonance (EPR) spectroscopy, but the presence of multiple copper centers has precluded correlation of EPR signals with the crystallographically identified monocopper and dicopper centers. A soluble recombinant fragment of the pmoB subunit of pMMO, spmoB, like pMMO itself, contains two distinct copper centers and exhibits methane oxidation activity. The spmoB protein, spmoB variants designed to disrupt one or the other or both copper centers, as well as native pMMO have been investigated by EPR, ENDOR, and ESEEM spectroscopies in combination with metal content analysis. The data are remarkably similar for spmoB and pMMO, validating the use of spmoB as a model system. The results indicate that one EPR-active Cu(II) ion is present per pMMO and that it is associated with the active-site dicopper center in the form of a valence localized Cu(I)Cu(II) pair; the Cu(II), however, is scrambled between the two locations within the dicopper site. The monocopper site observed in the crystal structures of pMMO can be assigned as Cu(I). (14)N ENDOR and ESEEM data are most consistent with one of these dicopper-site signals involving coordination of the Cu(II) ion by residues His137 and His139, the other with Cu(II) coordinated by His33 and the N-terminal amino group. (1)H ENDOR measurements indicate there is no aqua (HxO) ligand bound to the Cu(II), either terminally or as a bridge to Cu(I). PMID:25059917

  7. Influence of Free Radicals Signal from Dental Resins on the Radio-Induced Signal in Teeth in EPR Retrospective Dosimetry

    PubMed Central

    Dos Santos-Goncalvez, Ana Maria; Beun, Sébastien; Leprince, Julian G.; Leloup, Gaëtane; Gallez, Bernard

    2013-01-01

    In case of radiological accident, retrospective dosimetry is needed to reconstruct the absorbed dose of overexposed individuals not wearing personal dosimeters at the onset of the incident. In such a situation, emergency mass triage will be required. In this context, it has been shown that Electron Paramagnetic Resonance (EPR) spectroscopy would be a rapid and sensitive method, on the field deployable system, allowing dose evaluation of a great number of people in a short time period. This methodology uses tooth enamel as a natural dosimeter. Ionising radiations create stable free radicals in the enamel, in a dose dependent manner, which can be detected by EPR directly in the mouth with an appropriate resonator. Teeth are often subject to restorations, currently made of synthetic dimethacrylate-based photopolymerizable composites. It is known that some dental composites give an EPR signal which is likely to interfere with the dosimetric signal from the enamel. So far, no information was available about the occurrence of this signal in the various composites available on the market, the magnitude of the signal compared to the dosimetric signal, nor its evolution with time. In this study, we conducted a systematic characterization of the signal (intensity, kinetics, interference with dosimetric signal) on 19 most widely used composites for tooth restoration, and on 14 experimental resins made with the most characteristic monomers found in commercial composites. Although a strong EPR signal was observed in every material, a rapid decay of the signal was noted. Six months after the polymerization, the signal was negligible in most composites compared to a 3 Gy dosimetric signal in a tooth. In some cases, a stable atypical signal was observed, which was still interfering with the dosimetric signal. PMID:23704875

  8. A DICOM-RT radiation oncology ePR with decision support utilizing a quantified knowledge base from historical data

    NASA Astrophysics Data System (ADS)

    Documet, Jorge R.; Liu, Brent; Le, Anh; Law, Maria

    2008-03-01

    During the last 2 years we have been working on developing a DICOM-RT (Radiation Therapy) ePR (Electronic Patient Record) with decision support that will allow physicists and radiation oncologists during their decision-making process. This ePR allows offline treatment dose calculations and plan evaluation, while at the same time it compares and quantifies treatment planning algorithms using DICOM-RT objects. The ePR framework permits the addition of visualization, processing, and analysis tools, which combined with the core functionality of reporting, importing and exporting of medical studies, creates a very powerful application that can improve the efficiency while planning cancer treatments. Usually a Radiation Oncology department will have disparate and complex data generated by the RT modalities as well as data scattered in RT Information/Management systems, Record & Verify systems, and Treatment Planning Systems (TPS) which can compromise the efficiency of the clinical workflow since the data crucial for a clinical decision may be time-consuming to retrieve, temporarily missing, or even lost. To address these shortcomings, the ACR-NEMA Standards Committee extended its DICOM (Digital Imaging & Communications in Medicine) standard from Radiology to RT by ratifying seven DICOM RT objects starting in 1997 [1,2]. However, they are not broadly used yet by the RT community in daily clinical operations. In the past, the research focus of an RT department has primarily been developing new protocols and devices to improve treatment process and outcomes of cancer patients with minimal effort dedicated to integration of imaging and information systems. Our attempt is to show a proof-of-concept that a DICOM-RT ePR system can be developed as a foundation to perform medical imaging informatics research in developing decision-support tools and knowledge base for future data mining applications.

  9. Activation of C-Cl by ground-state aluminum atoms: an EPR and DFT investigation.

    PubMed

    Joly, Helen A; Newton, Trevor; Myre, Maxine

    2012-01-01

    The reaction of ground-state Al atoms with dichloromethane (CH(2)Cl(2)) in an adamantane matrix at 77 K yielded two mononuclear Al species. The magnetic parameters, extracted from the axial EPR spectrum of Species A/A' (g(1) = 2.0037, g(2) = g(3) = 2.0030, a(Al,1) = 1307 MHz, a(Al,2) = a(Al,3) = 1273 MHz, a(35Cl) = 34 MHz and a(37Cl) = 28 MHz) were assigned to the Al-atom insertion product, ClCH(2)AlCl. Density functional theory (DFT) calculations of the values of the Al and Cl hyperfine interaction (hfi) of the Cl(1)-Cl(2)gauche conformer were in close agreement with the experimental values of ClCH(2)AlCl. The second species, B/B', had identical magnetic parameters to those of ClCH(2)AlCl with the exception that the Al hfi was 15% smaller. Coordination of a ligand, possessing a lone pair of electrons, to the Al atom of the insertion product, [ClCH(2)AlCl]:X, could cause the a(Al) to decrease by 15%. Alternatively, it is possible that the Cl(1)-Cl(2) anti conformer of ClCH(2)AlCl is also isolated in the matrix. Support for the spectral assignments is given by calculation of the nuclear hfi of [ClCH(2)AlCl]:H(2)O and the Cl(1)-Cl(2) anti conformer of ClCH(2)AlCl using a DFT method. The potential energy hypersurface for an Al atom approaching CH(2)Cl(2), calculated at the B3LYP level, suggests that Al atom abstraction of Cl forming AlCl and CH(2)Cl is favoured in the gas phase. When produced in a matrix, the close proximity of AlCl and CH(2)Cl could account for the formation of ClCH(2)AlCl. EPR evidence was also found for the formation of the CHCl(2) radical. PMID:22086441

  10. Coupling of Waveguide and Resonator by Inductive and Capacitive Irises for EPR Spectroscopy

    PubMed Central

    Mett, R.R.; Sidabras, J.W.; Hyde, J.S.

    2009-01-01

    An analytic circuit model for slot coupling from a waveguide to a loop-gap resonator (LGR) in a context of electron paramagnetic resonance (EPR) spectroscopy is presented. The physical dimensions of the waveguide, iris, LGR, and aqueous sample are transformed into circuit values of inductance, capacitance, and resistance. These values are used in a solution of circuit equations that results in a prediction of the rf currents, magnitude and phase, frequency, and magnetic and electric stored energies near critical coupling. The circuit geometry reflects magnetic flux conservation between the iris and LGR as well as modification of the outer loop LGR currents by the iris. Unlike conventional models, coupling is not explicitly based on a mutual inductance between the iris and LGR. Instead, the conducting wall high frequency rf boundary condition is used to define surface currents, regions, and circuit topology with lumped-circuit values of self-inductance, capacitance, and resistance. Match is produced by a combination of self-inductive and capacitive circuit coupling. Two conditions must be met to achieve match. First, the equivalent resistance of the LGR as seen by the iris must be transformed into the waveguide characteristic impedance. This transformation is met at a particular frequency relative to the natural LGR resonance frequency. The frequency shift magnitude is largely determined by the LGR properties, weakly dependent on iris length and placement, and independent of other iris dimensions. The second condition for match is that the iris reactance at this frequency shift must cancel the residual reactance of the LGR. This second condition is sensitive to the iris dimensions. If both conditions are not simultaneously satisfied, overcoupling or undercoupling results. A slotted iris of equal length to the size of the large dimension of the waveguide is found to have many properties opposite to a conventional iris of shorter length. Notably, the magnetic field

  11. In vivo evidence of methamphetamine induced attenuation of brain tissue oxygenation as measured by EPR oximetry

    SciTech Connect

    Weaver, John; Yang, Yirong; Purvis, Rebecca; Weatherwax, Theodore; Rosen, Gerald M.; Liu, Ke Jian

    2014-03-01

    Abuse of methamphetamine (METH) is a major and significant societal problem in the US, as a number of studies have suggested that METH is associated with increased cerebrovascular events, hemorrhage or vasospasm. Although cellular and molecular mechanisms involved in METH-induced toxicity are not completely understood, changes in brain O{sub 2} may play an important role and contribute to METH-induced neurotoxicity including dopaminergic receptor degradation. Given that O{sub 2} is the terminal electron acceptor for many enzymes that are important in brain function, the impact of METH on brain tissue pO{sub 2}in vivo remains largely uncharacterized. This study investigated striatal tissue pO{sub 2} changes in male C57BL/6 mice (16–20 g) following METH administration using EPR oximetry, a highly sensitive modality to measure pO{sub 2}in vivo, in situ and in real time. We demonstrate that 20 min after a single injection of METH (8 mg/kg i.v.), the striatal pO{sub 2} was reduced to 81% of the pretreatment level and exposure to METH for 3 consecutive days further attenuated striatal pO{sub 2} to 64%. More importantly, pO{sub 2} did not recover fully to control levels even 24 h after administration of a single dose of METH and continual exposure to METH exacerbates the condition. We also show a reduction in cerebral blood flow associated with a decreased brain pO{sub 2} indicating an ischemic condition. Our findings suggests that administration of METH can attenuate brain tissue pO{sub 2}, which may lead to hypoxic insult, thus a risk factor for METH-induced brain injury and the development of stroke in young adults. - Highlights: • Explored striatal tissue pO{sub 2}in vivo after METH administration by EPR oximetry. • pO{sub 2} was reduced by 81% after a single dose and 64% after 3 consecutive daily doses. • pO{sub 2} did not recover fully to control levels even 24 h after a single dose. • Decrease in brain tissue pO{sub 2} may be associated with a decrease in

  12. EPR spectroscopic characterization of persistent germyl-substituted Pb(III)- and Sn(III)-radicals.

    PubMed

    Kurzbach, Dennis; Yao, Shenglai; Hinderberger, Dariush; Klinkhammer, Karl W

    2010-07-28

    In this report we present the synthesis and the detailed electron paramagnetic resonance (EPR) spectroscopic characterization of novel trivalent lead- and tin-based radicals comprising sterically demanding germyl substituents. The investigated radicals are derived from the recently reported trihypersilyl-substituted tetryl radicals *PbHyp3 and *SnHyp3. The tetryl radicals *Pb(Ge(SiMe3)3)3 (8), *Pb(Ge(SiMe3)3)2Si(SiMe3)3 (9), *PbGe(SiMe3)3(Si(SiMe3)3)2 (10), and *Sn(Ge(SiMe3)3)3 (11) show substitution patterns derived from stepwise (9, 10) or complete (8, 11) substitution of hypersilyl groups (Hyp = Si(SiMe3)3) in *PbHyp3 and *SnHyp3 by homologous hypergermyl groups (Hge = Ge(SiMe3)3). They were generated through oxidation of the corresponding potassium tetranides KPbR3 and KSnR3 (R = Hyp, Hge), which in turn had been synthesized employing nucleophilic addition of KHyp or KHge to PbHyp2 or to the novel tetrylenes PbHge2 (1) and SnHge2 (12). The gained EPR spectroscopic data give insights into the influence of the substitution pattern on the geometric and electronic properties of the lead-centered species. With an increasing number of germyl substituents, the spin-orbit coupling to the central atom increases resulting in larger g(iso)-values and larger g-anisotropies while the 209Pb hyperfine splitting constants A(iso) decrease. These decreasing splitting constants are indicative of a diminished s-character of the singly occupied molecular orbital (SOMO) and to a molecular geometry running from slightly pyramidal to almost planar. Interestingly, already one germyl substituent (for radical 10) dominates most of the mentioned properties. For stannyl radical 11 a similar trend is seen for the spin-orbit coupling, while the (117/119)Sn hyperfine splittings unexpectedly increase from SnHyp3 to SnHge3. PMID:20532294

  13. Coupling of Waveguide and Resonator by Inductive and Capacitive Irises for EPR Spectroscopy.

    PubMed

    Mett, R R; Sidabras, J W; Hyde, J S

    2009-01-01

    An analytic circuit model for slot coupling from a waveguide to a loop-gap resonator (LGR) in a context of electron paramagnetic resonance (EPR) spectroscopy is presented. The physical dimensions of the waveguide, iris, LGR, and aqueous sample are transformed into circuit values of inductance, capacitance, and resistance. These values are used in a solution of circuit equations that results in a prediction of the rf currents, magnitude and phase, frequency, and magnetic and electric stored energies near critical coupling. The circuit geometry reflects magnetic flux conservation between the iris and LGR as well as modification of the outer loop LGR currents by the iris. Unlike conventional models, coupling is not explicitly based on a mutual inductance between the iris and LGR. Instead, the conducting wall high frequency rf boundary condition is used to define surface currents, regions, and circuit topology with lumped-circuit values of self-inductance, capacitance, and resistance. Match is produced by a combination of self-inductive and capacitive circuit coupling. Two conditions must be met to achieve match. First, the equivalent resistance of the LGR as seen by the iris must be transformed into the waveguide characteristic impedance. This transformation is met at a particular frequency relative to the natural LGR resonance frequency. The frequency shift magnitude is largely determined by the LGR properties, weakly dependent on iris length and placement, and independent of other iris dimensions. The second condition for match is that the iris reactance at this frequency shift must cancel the residual reactance of the LGR. This second condition is sensitive to the iris dimensions. If both conditions are not simultaneously satisfied, overcoupling or undercoupling results. A slotted iris of equal length to the size of the large dimension of the waveguide is found to have many properties opposite to a conventional iris of shorter length. Notably, the magnetic field

  14. Structural defects in natural plastically deformed diamonds: Evidence from EPR spectroscopy

    NASA Astrophysics Data System (ADS)

    Mineeva, R. M.; Titkov, S. V.; Speransky, A. V.

    2009-06-01

    Structural defects formed as a result of plastic deformation in natural diamond crystals have been studied by EPR spectroscopy. The spectra of brown, pink-brown, black-brown, pink-purple, and gray plastically deformed diamonds of type Ia from deposits in Yakutia and the Urals were recorded. The results of EPR spectroscopy allowed us to identify various deformation centers in the structure of natural diamonds and to show that nitrogen centers were transformed under epigenetic mechanical loading. Abundant A centers, consisting of two isomorphic nitrogen atoms located in neighboring structural sites, were destroyed as a result of this process to form a series of N1, N4, W7, M2, and M3 nitrogen centers. Such centers are characterized by an anisotropic spatial distribution and a positive charge, related to the mechanism of their formation. In addition, N2 centers (probably, deformation-produced dislocations decorated by nitrogen) were formed in all plastically deformed diamonds and W10 and W35 centers (the models have not been finally ascertained) were formed in some of them. It has been established that diamonds with various types of deformation-induced color contain characteristic associations of these deformation centers. The diversity of associations of deformation centers indicates appreciable variations in conditions of disintegration of deep-seated rocks, transfer of diamonds to the Earth’s surface, and formation of kimberlitic deposits. Depending on the conditions of mechanical loading, the diamond crystals were plastically deformed by either dislocation gliding or mechanical twinning. Characteristic features of plastic deformation by dislocation gliding are the substantial prevalence of the N2 centers over other deformation centers and the occurrence of the high-spin W10 and W35 centers. The attributes of less frequent plastic deformation by mechanical twinning are unusual localization of the M2 centers and, in some cases, the N1 centers in microtwinned

  15. Metal Binding Studies and EPR Spectroscopy of the Manganese Transport Regulator MntR†

    PubMed Central

    Golynskiy, Misha V.; Gunderson, William A.; Hendrich, Michael P.; Cohen, Seth M.

    2007-01-01

    Manganese transport regulator (MntR) is a member of the diphtheria toxin repressor (DtxR) family of transcription factors that is responsible for manganese homeostasis in Bacillus subtilis. Prior biophysical studies have focused on the metal-mediated DNA binding of MntR [Lieser, S. A., Davis, T. C., Helmann, J. D., and Cohen, S. M. (2003) Biochemistry 42, 12634-12642], as well as metal stabilization of the MntR structure [Golynskiy, M. V., Davis, T. C., Helmann, J. D., and Cohen, S. M. (2005) Biochemistry 44, 3380-3389], but only limited data on the metal-binding affinities for MntR are available. Herein, the metal-binding affinities of MntR were determined by using electron paramagnetic resonance (EPR) spectroscopy, as well as competition experiments with the fluorimetric dyes Fura-2 and Mag-fura-2. MntR was not capable of competing with Fura-2 for the binding of transition metal ions. Therefore, the metal-binding affinities and stoichiometries of Mag-fura-2 for Mn2+, Co2+, Ni2+, Zn2+, and Cd2+ were determined and utilized in MntR/Mag-fura-2 competition experiments. The measured Kd values for MntR metal binding are comparable to those reported for DtxR metal binding [Kd from 10-7 to 10-4 M; D’Aquino, J. A., et al. (2005) Proc. Natl. Acad. Sci. U.S.A. 102, 18408-18413], AntR [a homologue from Bacillus anthracis; Sen, K. I. et al. (2006) Biochemistry 45, 4295-4303], and generally follow the Irving-Williams series. Direct detection of the dinuclear Mn2+ site in MntR with EPR spectroscopy is presented, and the exchange interaction was determined, J = -0.2 cm-1. This value is lower in magnitude than most known dinuclear Mn2+ sites in proteins and synthetic complexes and is consistent with a dinuclear Mn2+ site with a longer Mn···Mn distance (4.4 Å) observed in some of the available crystal structures. MntR is found to have a surprisingly low binding affinity (∼160 μM) for its cognate metal ion Mn2+. Moreover, the results of DNA binding studies in the presence

  16. EPR studies on the kinetics of the α-hydroxyethyl radical generated by Fenton-like chemistry

    NASA Astrophysics Data System (ADS)

    Schubert, Erik; Hett, Tobias; Schiemann, Olav; NejatyJahromy, Yaser

    2016-04-01

    Flow systems, either stopped or continuous, have long been at the core of kinetic studies of chemical reactions. Such flow systems need to be coupled with appropriate spectroscopic or otherwise techniques for the detection of the chemical species studied. If paramagnetic species are formed or consumed during the investigated reaction, electron paramagnetic resonance (EPR) with its nanomolar sensitivity can be the spectroscopic method of choice. However, not much literature is available on the application of EPR to quantitatively study kinetics of chemical reactions in the liquid state. Herein, we report the characterisation of the commercially available mixing resonator ER 4117 MX from BRUKER using the TEMPO-dithionite reaction as a standard. Furthermore, this setup was used to study the kinetics of the Fenton-like system of TiCl3/H2O2 and ethanol forming the α-hydroxyethyl radical. Potential contributions of reactions with O2, H2O2, Ti3+/4+, and self-recombination in the decay of the α-hydroxyethyl radical were investigated and the bimolecular decay was shown to be the dominant decay pathway, with a decay rate constant of 6.6 ×108 M-1 s-1. This study shows the effectiveness and capabilities of EPR as a direct, sensitive and in-situ method in kinetic studies.

  17. Toward increased concentration sensitivity for continuous wave EPR investigations of spin-labeled biological macromolecules at high fields.

    PubMed

    Song, Likai; Liu, Zhanglong; Kaur, Pavanjeet; Esquiaqui, Jackie M; Hunter, Robert I; Hill, Stephen; Smith, Graham M; Fanucci, Gail E

    2016-04-01

    High-field, high-frequency electron paramagnetic resonance (EPR) spectroscopy at W-(∼94GHz) and D-band (∼140GHz) is important for investigating the conformational dynamics of flexible biological macromolecules because this frequency range has increased spectral sensitivity to nitroxide motion over the 100ps to 2ns regime. However, low concentration sensitivity remains a roadblock for studying aqueous samples at high magnetic fields. Here, we examine the sensitivity of a non-resonant thin-layer cylindrical sample holder, coupled to a quasi-optical induction-mode W-band EPR spectrometer (HiPER), for continuous wave (CW) EPR analyses of: (i) the aqueous nitroxide standard, TEMPO; (ii) the unstructured to α-helical transition of a model IDP protein; and (iii) the base-stacking transition in a kink-turn motif of a large 232nt RNA. For sample volumes of ∼50μL, concentration sensitivities of 2-20μM were achieved, representing a ∼10-fold enhancement compared to a cylindrical TE011 resonator on a commercial Bruker W-band spectrometer. These results therefore highlight the sensitivity of the thin-layer sample holders employed in HiPER for spin-labeling studies of biological macromolecules at high fields, where applications can extend to other systems that are facilitated by the modest sample volumes and ease of sample loading and geometry. PMID:26923151

  18. Solid-state EPR strategies for the structural characterization of paramagnetic NO adducts of frustrated Lewis pairs (FLPs)

    SciTech Connect

    Oliveira, Marcos de; Magon, Claudio José; Wiegand, Thomas; Elmer, Lisa-Maria; Sajid, Muhammad; Kehr, Gerald; Erker, Gerhard; Eckert, Hellmut

    2015-03-28

    Anisotropic interactions present in three new nitroxide radicals prepared by N,N addition of NO to various borane-phosphane frustrated Lewis pairs (FLPs) have been characterized by continuous-wave (cw) and pulsed X-band EPR spectroscopies in solid FLP-hydroxylamine matrices at 100 K. Anisotropic g-tensor values and {sup 11}B, {sup 14}N, and {sup 31}P hyperfine coupling tensor components have been extracted from continuous-wave lineshape analyses, electron spin echo envelope modulation (ESEEM), and hyperfine sublevel correlation spectroscopy (HYSCORE) experiments with the help of computer simulation techniques. Suitable fitting constraints are developed on the basis of density functional theory (DFT) calculations. These calculations reveal that different from the situation in standard nitroxide radicals (TEMPO), the g-tensors are non-coincident with any of the nuclear hyperfine interaction tensors. The determination of these interaction parameters turns out to be successful, as the cw- and pulse EPR experiments are highly complementary in informational content. While the continuous-wave lineshape is largely influenced by the anisotropic hyperfine coupling to {sup 14}N and {sup 31}P, the ESEEM and HYSCORE spectra contain important information about the {sup 11}B hyperfine coupling and nuclear electric quadrupolar interaction. The set of cw- and pulsed EPR experiments, with fitting constraints developed by DFT calculations, defines an efficient strategy for the structural analysis of paramagnetic FLP adducts.

  19. EPR and ENDOR Investigation of Rhodosemiquinone in Bacterial Reaction Centers Formed by B-Branch Electron Transfer

    PubMed Central

    Paddock, M. L.; Flores, M.; Isaacson, R.; Shepherd, J. N.

    2010-01-01

    In photosynthetic bacteria, light-induced electron transfer takes place in a protein called the reaction center (RC) leading to the reduction of a bound ubiquinone molecule, QB, coupled with proton binding from solution. We used electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) to study the magnetic properties of the protonated semiquinone, an intermediate proposed to play a role in proton coupled electron transfer to QB. To stabilize the protonated semiquinone state, we used a ubiquinone derivative, rhodoquinone, which as a semiquinone is more easily protonated than ubisemiquinone. To reduce this low-potential quinone we used mutant RCs modified to directly reduce the quinone in the QB site via B-branch electron transfer (Paddock et al. in Biochemistry 44:6920–6928, 2005). EPR and ENDOR signals were observed upon illumination of mutant RCs in the presence of rhodoquinone. The EPR signals had g values characteristic of rhodosemiquinone (gx = 2.0057, gy = 2.0048, gz ∼ 2.0018) at pH 9.5 and were changed at pH 4.5. The ENDOR spectrum showed couplings due to solvent exchangeable protons typical of hydrogen bonds similar to, but different from, those found for ubisemiquinone. This approach should be useful in future magnetic resonance studies of the protonated semiquinone. PMID:20157643

  20. High-frequency, spin-label EPR of nonaxial lipid ordering and motion in cholesterol-containing membranes.

    PubMed

    Gaffney, B J; Marsh, D

    1998-10-27

    The EPR spectra of spin-labeled lipid chains in fully hydrated bilayer membranes of dimyristoyl phosphatidylcholine containing 40 mol % of cholesterol have been studied in the liquid-ordered phase at a microwave radiation frequency of 94 GHz. At such high field strengths, the spectra should be optimally sensitive to lateral chain ordering that is expected in the formation of in-plane domains. The high-field EPR spectra from random dispersions of the cholesterol-containing membranes display very little axial averaging of the nitroxide g-tensor anisotropy for lipids spin labeled toward the carboxyl end of the sn-2 chain (down to the 8-C atom). For these positions of labeling, anisotropic 14N-hyperfine splittings are resolved in the gzz and gyy regions of the nonaxial EPR spectra. For positions of labeling further down the lipid chain, toward the terminal methyl group, the axial averaging of the spectral features systematically increases and is complete at the 14-C atom position. Concomitantly, the time-averaged element of the 14N-hyperfine tensor decreases, indicating that the axial rotation at the terminal methyl end of the chains arises from correlated torsional motions about the bonds of the chain backbone, the dynamics of which also give rise to a differential line broadening of the 14N-hyperfine manifolds in the gzz region of the spectrum. These results provide an indication of the way in which lateral ordering of lipid chains in membranes is induced by cholesterol. PMID:9789019