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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. 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

  15. 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

  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. 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

  19. 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...

  20. 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.

  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. 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.

  12. 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.

  13. 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

  14. 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

  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. 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

  19. 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

  20. 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.

  1. 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.

  2. 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

  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. 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.

  3. 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

  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. 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

  6. 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

  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. 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

  15. 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)

  16. 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

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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

  5. 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

  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. 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.

  12. 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

  13. 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

  14. 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

  15. 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

  16. 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.

  17. 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

  18. 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.

  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, 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.

  6. 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

  7. 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.

  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. 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

  14. 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.

  15. 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

  16. 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

  17. 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

  18. 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

  19. 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

  20. 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

  1. 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.

  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. 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.

  4. 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

  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. 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

  7. 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

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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%.

  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. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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

  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. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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

  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. 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

  18. 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.

  19. 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.

  20. 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.

  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. 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

  3. 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

  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. 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

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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.

  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. 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

  15. 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.

  16. 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

  17. 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

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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.

  3. 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.

  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, 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.

  8. 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.

  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 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  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 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.

  19. 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

  20. 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.

  1. 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

  2. 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…

  3. 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

  4. 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.

  5. 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

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. 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…

  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. 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

  19. 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.

  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

    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

  2. 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

  3. 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

  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. 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

  7. 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

  8. 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.

  9. 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.

  10. 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.