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Sample records for lytb epr metallacycles

  1. LytB1 and LytB2 of Mycobacterium tuberculosis Are Not Genetically Redundant

    PubMed Central

    Brown, Amanda Claire; Kokoczka, Rachel; Parish, Tanya

    2015-01-01

    Mycobacterium tuberculosis synthesises isoprenoid precursors via the MEP/DOXP pathway and at least five enzymes in the pathway (Dxs1, Dxr/IspC, IspD, IspF, and GcpE/IspG) are required for growth in vitro. We investigated the role of LytB (IspH) in M. tuberculosis; M. tuberculosis is unusual in that it has two homologs–LytB1 and LytB2. We were unable to delete the lytB2 gene unless we provided an additional copy elsewhere, demonstrating that this is the essential homolog. We expressed lytB1 from the lytB2 promoter and confirmed that this could not complement for loss of function of lytB2, despite LytB1 possessing all the previously described conserved critical residues. Interestingly the sole LytB homolog of Mycobacterium smegmatis was able to compensate for loss of LytB2 in M. tuberculosis. We tested translational fusions of LytB1 and LytB2 for functionality in M. tuberculosis, but only a fusion with 90% N-terminal LytB2 and 10% C-terminal LytB1 was functional. In order to identify the key difference between the two proteins, site directed mutagenesis was used to change LytB2 residues into their counterparts in LytB1. None of these amino acid substitutions was essential for function and all lytB2 mutant alleles were functional. In contrast, mutation of the key residues for [Fe4S4] cluster formation, as well as a catalytic residue in LytB1 did not result in functional complementation. Thus, although LytB1 and LytB2 are not genetically redundant, this is not dependent on small amino acid changes, but is likely to be a result of major overall structural differences. PMID:26309039

  2. Chiral NH-Controlled Supramolecular Metallacycles.

    PubMed

    Dong, Jinqiao; Tan, Chunxia; Zhang, Kang; Liu, Yan; Low, Paul J; Jiang, Jianwen; Cui, Yong

    2017-02-01

    Chiral NH functionalities-based discrimination is a key feature of Nature's chemical armory, yet selective binding of biologically active molecules in synthetic systems with high enantioselectivity poses significant challenges. Here we report the assembly of three chiral fluorescent Zn6L6 metallacycles from pyridyl-functionalized Zn(salalen) or Zn(salen) complexes. Each of these metallacycles has a nanoscale hydrophobic cavity decorated with six, three, or zero chiral NH functionalities and packs into a three-dimensional supramolecular porous framework. The binding affinity and enantioselectivity of the metallacycles toward α-hydroxycarboxylic acids, amino acids, small molecule pharamaceuticals (l-dopa, d-penicillamine), and chiral amines increase with the number of chiral NH moieties in the cyclic structure. From single-crystal X-ray diffraction, molecular simulations, and quantum chemical calculations, the chiral recognition and discrimination are attributed to the specific binding of enantiomers in the chiral pockets of the metallacycles. The parent metallacycles are fluorescent with the intensity of emission being linearly related to the enantiomeric composition of the chiral biorelevant guests, which allow them to be utilized in chiral sensing. The fact that manipulation of chiral NH functionalities in metallacycles can control the enantiorecognition of biomolecular complexes would facilitate the design of more effective supramolecular assemblies for enantioselective processes.

  3. Occurrence of homologs of the Escherichia coli lytB gene in gram-negative bacterial species.

    PubMed

    Potter, S; Yang, X; Boulanger, M J; Ishiguro, E E

    1998-04-01

    The Escherichia coli LytB protein regulates the activity of guanosine 3',5'-bispyrophosphate synthetase I (RelA). A Southern blot analysis of chromosomal DNA with the E. coli lytB gene as a probe revealed the presence of lytB homologs in all of the gram-negative bacterial species examined but not in gram-positive species. The lytB homologs from Enterobacter aerogenes and Pseudomonas fluorescens complemented the E. coli lytB44 mutant allele.

  4. 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

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

    PubMed

    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

    2015-11-05

    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.

  6. Inhibition of Plasmodium falciparum ispH (lytB) gene expression by hammerhead ribozyme.

    PubMed

    Vinayak, Sumiti; Sharma, Yagya D

    2007-01-01

    The nonmevalonate pathway of isoprenoid biosynthesis in the apicoplast of the human malaria parasite Plasmodium falciparum is distinct from the mevalonate-dependent pathway of humans and thus a good drug target. We describe here the hammerhead ribozyme based cleavage of the ispH (lytB) gene transcript involved in the last step of this nonmevalonate pathway. Using RNA folding program, three hammerhead ribozymes named as RZ(876), RZ(1260), and RZ(1331) were predicted against ispH (lytB) mRNA. Messenger walk screening (RNaseH) assay confirmed the target accessibility for these ribozymes. All three ribozymes cleaved the target RNA in vitro but RZ(876) exhibited the highest catalytic potential (62.92%). Therefore, RZ(876) was chemically synthesized with appropriate chemical modifications to protect it from nuclease attack while using it for in vitro parasite growth inhibition assay. This ribozyme RZ(876) was able to inhibit 87.36% parasite growth at 30 microM concentration compared to the untreated culture. However, an absolute inhibition of 29.41% was achieved compared to the control ribozyme (RZ(ctrl)). Nonetheless, the growth inhibition effect was found to be sequence-specific as indicated by the decreased level of ispH (lytB) transcript after ribozyme treatment. In conclusion, we have identified the ispH (lytB) as a potential target whose transcript can be cleaved by a ribozyme RZ(876).

  7. Immunization with LytB protein of Streptococcus pneumoniae activates complement-mediated phagocytosis and induces protection against pneumonia and sepsis.

    PubMed

    Corsini, Bruno; Aguinagalde, Leire; Ruiz, Susana; Domenech, Mirian; Antequera, María Luisa; Fenoll, Asunción; García, Pedro; García, Ernesto; Yuste, Jose

    2016-12-07

    The cell wall glucosaminidase LytB of Streptococcus pneumoniae is a surface exposed protein involved in daughter cell separation, biofilm formation and contributes to different aspects of the pathogenesis process. In this study we have characterized the antibody responses after immunization of mice with LytB in the presence of alhydrogel as an adjuvant. Enzyme-linked immunosorbent assays measuring different subclasses of immunoglobulin G, demonstrated that the antibody responses to LytB were predominantly IgG1 and IgG2b, followed by IgG3 and IgG2a subclasses. Complement-mediated immunity against two different pneumococcal serotypes was investigated using sera from immunized mice. Immunization with LytB increased the recognition of S. pneumoniae by complement components C1q and C3b demonstrating that anti-LytB antibodies trigger activation of the classical pathway. Phagocytosis assays showed that serum containing antibodies to LytB stimulates neutrophil-mediated phagocytosis against S. pneumoniae. Animal models of infection including invasive pneumonia and sepsis were performed with two different clinical isolates. Vaccination with LytB increased bacterial clearance and induced protection demonstrating that LytB might be a good candidate to be considered in a future protein-based vaccine against S. pneumoniae.

  8. Gondola-shaped tetra-rhenium metallacycles modified evanescent wave infrared chemical sensors for selective determination of volatile organic compounds.

    PubMed

    Huang, Genin Gary; Lee, Chung-Jay; Tsai, Bo-Chan; Yang, Jyisy; Sathiyendiran, Malaichamy; Lu, Kuang-Lieh

    2011-07-15

    Water-stable and cavity-contained rhenium metallacycles were synthesized, and their ability to selectively interact with volatile organic compounds (VOCs) systematically studied using attenuated total reflection infrared (ATR-IR) spectroscopy. Integrating the unique properties of rhenium metallacycles into optical sensing technologies significantly improves selectivity in detecting aromatic compounds. To explore the interaction of rhenium metallacycles with VOCs, the surface of ATR sensing elements was modified with the synthesized rhenium metallacycles and used to detect VOCs. The results indicate that rhenium metallacycles have crown ether-like recognition sites, which can selectively interact with aromatic compounds, especially those bearing polar functional groups. The IR absorption bands of rhenium metallacycles shift significantly upon adsorption of aromatic VOCs, revealing a strong interaction between the tetra-rhenium metallacycles and guest aromatic compounds. Optimizing the thickness of the metallacycles coated on the surface of the sensing element led to rapid response in detection. The dynamic range of response was generally up to 30 mg/L with detection limits ca. 30 μg/L. Further studies of the effect of interferences indicate that recovery can be higher than 95% for most of the compounds tested. The results on the flow-cell device indicated that the performances were similar to a static detection system but the detection of VOCs can be largely simplified. Copyright © 2011 Elsevier B.V. All rights reserved.

  9. Luminescent charge-transfer platinum(II) metallacycle.

    PubMed

    Hua, Fei; Kinayyigit, Solen; Rachford, Aaron A; Shikhova, Elena A; Goeb, Sébastien; Cable, John R; Adams, Christopher J; Kirschbaum, Kristin; Pinkerton, A Alan; Castellano, Felix N

    2007-10-15

    The photophysical and electrochemical properties of a platinum(II) diimine complex bearing the bidentate diacetylide ligand tolan-2,2'-diacetylide (tda), Pt(dbbpy)(tda) [dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine] (1), are compared with two reference compounds, Pt(dbbpy)(C[triple bond]CPh)(2) (2) and Pt(dppp)tda [dppp = 1,3-bis(diphenylphosphino)propane] (3), respectively. The X-ray crystal structure of 1 is reported, which illustrates the nearly perfect square planarity exhibited by this metallacycle. Chromophore 2 possesses low-lying charge-transfer excited states analogous to 1, whereas structure 3 lacks such excited states but features a low-lying platinum-perturbed tda intraligand triplet manifold. In CH(2)Cl(2), 1 exhibits a broad emission centered at 562 nm at ambient temperature, similar to 2, but with a higher photoluminescence quantum yield and longer excited-state lifetime. In both instances, the photoluminescence is consistent with triplet-charge-transfer excited-state parentage. The rigidity imposed by the cyclic diacetylide ligand in 1 leads to a reduction in nonradiative decay, which enhances its room-temperature photophysical properties. By comparison, 3 radiates highly structured tda-localized triplet-state phosphorescence at room temperature. The 77 K emission spectrum of 1 in 4:1 EtOH/MeOH becomes structured and is quantitatively similar to that measured for 3 under the same conditions. Because the 77 K spectra are nearly identical, the emissions are assigned as (3)tda in nature, implying that the charge-transfer states are raised in energy, relative to the (3)tda levels in 1 in the low-temperature glass. Nanosecond transient absorption spectrometry and ultrafast difference spectra were determined for 1-3 in CH(2)Cl(2) and DMF at ambient temperature. In 1 and 2, the major absorption transients are consistent with the one-electron reduced complexes, corroborated by reductive spectroelectrochemical measurements performed at room temperature. As 3

  10. Fluorescent metallacycle-cored polymers via covalent linkage and their use as contrast agents for cell imaging

    PubMed Central

    Zhang, Mingming; Li, Shuya; Yan, Xuzhou; Zhou, Zhixuan; Saha, Manik Lal; Wang, Yu-Cai; Stang, Peter J.

    2016-01-01

    The covalent linkage of supramolecular monomers provides a powerful strategy for constructing dynamic polymeric materials whose properties can be readily tuned either by the selection of monomers or the choice of functional linkers. In this strategy, the stabilities of the supramolecular monomers and the reactions used to link the monomers are crucial because such monomers are normally dynamic and can disassemble during the linking process, leading to mixture of products. Therefore, although noncovalent interactions have been widely introduced into metallacycle structures to prepare metallosupramolecular polymers, metallacycle-cored polymers linked by covalent bonds have been rarely reported. Herein, we used the mild, highly efficient amidation reaction between alkylamine and N-hydroxysuccinimide-activated carboxylic acid to link the pendent amino functional groups of a rhomboidal metallacycle 10 to give metallacycle-cored polymers P1 and P2, which further yielded nanoparticles at low concentration and transformed into network structures as the concentration increased. Moreover, these polymers exhibited enhanced emission and showed better quantum yields than metallacycle 10 in methanol and methanol/water (1/9, vol/vol) due to the aggregation-induced emission properties of a tetraphenylethene-based pyridyl donor, which serves as a precursor for metallacycle 10. The fluorescence properties of these polymers were further used in cell imaging, and they showed a significant enrichment in lung cells after i.v. injection. Considering the anticancer activity of rhomboidal Pt(II) metallacycles, this type of fluorescent metallacycle-cored polymers can have potential applications toward lung cancer treatment. PMID:27647900

  11. 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

  12. Metallacycles or coexistence of isomeric metallacycle and chain: Anion-dependent luminescent Ag complexes of a flexible diaminotriazine-imidazole ligand

    NASA Astrophysics Data System (ADS)

    Mei, Hong-Xin; Zhang, Ting; Wang, Dan-Feng; Huang, Rong-Bin; Zheng, Lan-Sun

    2015-07-01

    Reaction of a flexible ligand 2,4-diamino-6-[2-(2-methyl-1-imidazolyl) ethyl]-1,3,5-triazine (L) with Ag(I) in the presence of different counteranions afforded five complexes, namely, 2[Agn(L)n(NH3)n] · n[Ag2(L)2(NH3)2] · 2n(nds) (1, H2nds = 1,5-naphthalenedisulfonic acid), 2[Agn(L)n] · n[Ag2(L)2(CF3CO2)2] · nCF3CO2 (2), [Ag2(L)2(NH3)2] · 2(ClO4) (3), [Ag2(L)2] · 2(NO3) (4), [Ag2(L)2] · 2(ClO3) (5), which were characterized by element analysis, IR, PXRD and X-ray single-crystal diffraction. Structural analysis reveals that the L ligand take the same bidentate coordination mode in these complexes. The nds anion and the CF3 CO2- anion lead to the coexistence of isomeric metallacycle and helical chain (ring-opening isomers) in the crystals of 1 and 2, while ClO4-, NO3- and ClO3- anions afford dimeric metallacycles in complexes 3-5. Moreover, thermal gravity analysis (TGA) and emissive behaviors of these complexes were investigated.

  13. Studies on the nonmevalonate terpene biosynthetic pathway: Metabolic role of IspH (LytB) protein

    PubMed Central

    Rohdich, Felix; Hecht, Stefan; Gärtner, Katrin; Adam, Petra; Krieger, Cornelia; Amslinger, Sabine; Arigoni, Duilio; Bacher, Adelbert; Eisenreich, Wolfgang

    2002-01-01

    Isopentenyl diphosphate and dimethylallyl diphosphate serve as the universal precursors for the biosynthesis of terpenes. Although their biosynthesis by means of mevalonate has been studied in detail, a second biosynthetic pathway for their formation by means of 1-deoxy-d-xylulose 5-phosphate has been discovered only recently in plants and certain eubacteria. Earlier in vivo experiments with recombinant Escherichia coli strains showed that exogenous 1-deoxy-d-xylulose can be converted into 1-hydroxy-2-methyl-2-(E)-butenyl 4-diphosphate by the consecutive action of enzymes specified by the xylB and ispCDEFG genes. This article describes the transformation of exogenous [U-13C5]1-deoxy-d-xylulose into a 5:1 mixture of [U-13C5]isopentenyl diphosphate and [U-13C5]dimethylallyl diphosphate by an E. coli strain engineered for the expression of the ispH (lytB) gene in addition to recombinant xylB and ispCDEFG genes. PMID:11818558

  14. High Frequency EPR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gatteschi, D.

    EPR has traditionally been used in order to obtain structural information on transition metal compounds, with exciting frequencies in the range 9-35 GHz.The recent availability of high magnetic field has prompted the use of higher frequencies. In this contribution the advantages of using High-Field-High-Frequency EPR (HF EPR) experiments are reviewed. After a brief introduction aiming to recall the fundamentals of EPR spectroscopy, a short description of the experimental apparatus needed to perform HF EPR measurements is provided. The remaining sections report selected examples showing how much information can be obtained by HF EPR spectra. They range from individual ions with integer spin to molecular clusters. Particular attention is devoted to the so called Single Molecule Magnets, SMM, i.e. to molecular clusters which show slow relaxation of the magnetization at low temperature. This effect is due to Ising type magnetic anisotropy which has been efficiently monitored through HF EPR s pectroscopy.

  15. Dendronized organoplatinum(II) metallacyclic polymers constructed by hierarchical coordination-driven self-assembly and hydrogen-bonding interfaces.

    PubMed

    Yan, Xuzhou; Jiang, Bo; Cook, Timothy R; Zhang, Yanyan; Li, Jinying; Yu, Yihua; Huang, Feihe; Yang, Hai-Bo; Stang, Peter J

    2013-11-13

    We describe the efficient preparation of rhomboidal metallacycles that self-assemble upon mixing a donor decorated with 2-ureido-4-pyrimidinone (UPy) with acceptors containing pendant [G1]-[G3] dendrons. The formed rhomboids subsequently polymerize into dendronized organoplatinum(II) metallacyclic polymers through H-bonding UPy interfaces, which possess the structural features of conventional dendronized polymers as well as the dynamic reversibility of supramolecular polymers. Preservation of both properties in a single material is achieved by exploiting hierarchical self-assembly, namely the unification of coordination-driven self-assembly with H-bonding, which provides facile routes to dendronized metallacycles and subsequent high ordering. The supramolecular polymerization defined here represents a novel method to deliver architecturally complex and ordered polymeric materials with adaptive properties.

  16. A solid state highly emissive Cu(i) metallacycle: promotion of cuprophilic interactions at the excited states.

    PubMed

    El Sayed Moussa, M; Evariste, S; Wong, H-L; Le Bras, L; Roiland, C; Le Polles, L; Le Guennic, B; Costuas, K; Yam, V W-W; Lescop, C

    2016-09-15

    The straightforward synthesis of a new Cu(i) metal-rich small metallacycle is presented. This compound is luminescent in the solid state with an emission quantum yield of 72% at room temperature and displays a pronounced reversible red-shift of its emission spectra upon cooling. Quantum chemical calculations reveal that these properties are governed by important geometrical relaxations that imply the formation of cuprophilic interactions at the excited states.

  17. 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

  18. Coordination-Driven Syntheses of Compact Supramolecular Metallacycles toward Extended Metallo-organic Stacked Supramolecular Assemblies.

    PubMed

    Lescop, Christophe

    2017-04-18

    One important concept associated with supramolecular chemistry is supramolecular self-assembly, which deals with the way discrete individual components interact via intermolecular interactions in order to build, upon their spontaneous association, high order functional assemblies. The accumulation of these very simple and localized noncovalent interactions (such as H-bonding, dipole-dipole, hydrophobic/hydrophilic, van der Waals, π-π, π-CH, etc.) is ubiquitous in the complexity of natural systems (such as DNA, proteins, membranes, micelles, etc.). It can also be transposed to the directed synthesis of intricate artificial scaffolds, which have anticipated geometries and properties. Among the synthetic strategies based on this concept, coordination-driven supramolecular chemistry uses the robust, reversible, and directional metal-to-ligand coordinative bond to build discrete metallo-supramolecular architectures. Within the last two decades, coordination-driven supramolecular chemistry has proved to be one of the most powerful contemporary synthetic approaches and has provided a significant number of increasingly complex supramolecular assemblies, which have predetermined sizes and geometries. While much focus has been devoted to architectures bearing internal cavities for host-guest chemistry or to generate specific reactivity, particular attention can also be paid to compact supramolecular assemblies given that their specific structures are characterized by peculiar synthetic guiding rules as well as by alternative long-range self-assembling properties. This Account describes how a preassembled Cu(I) bimetallic clip bearing short intermetallic distances can be used as a U-shaped molecular clip to give general and versatile access to a large variety of original compact supramolecular metallacycles. When this Cu(I) precursor is reacted with various cyano-capped ditopic linkers that have increasing lengths and complexities, specific effects guiding the selective

  19. Dinuclear Metallacycles with Single M-X-M Bridges (X = Cl(-), Br(-); M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)): Strong Antiferromagnetic Superexchange Interactions.

    PubMed

    Reger, Daniel L; Pascui, Andrea E; Foley, Elizabeth A; Smith, Mark D; Jezierska, Julia; Wojciechowska, Agnieszka; Stoian, Sebastian A; Ozarowski, Andrew

    2017-03-06

    A series of monochloride-bridged, dinuclear metallacycles of the general formula [M2(μ-Cl)(μ-L)2](ClO4)3 have been prepared using the third-generation, ditopic bis(pyrazolyl)methane ligands L = m-bis[bis(1-pyrazolyl)methyl]benzene (Lm), M = Cu(II), Zn(II), and L = m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*), M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II). These complexes were synthesized from the direct reactions of M(ClO4)2·6H2O, MCl2, and the ligand, Lm or Lm*, in the appropriate stoichiometric amounts. Three analogous complexes of the formula [M2(μ-Cl)(μ-L)2](BF4)3, L = Lm, M = Cu(II), and L = Lm*, M = Co(II), Cu(II), were prepared from the reaction of [M2(μ-F)(μ-L)2](BF4)3 and (CH3)3SiCl. The bromide-bridged complex [Cu2(μ-Br)(μ-Lm*)2](ClO4)3 was prepared by the first method. Three acyclic complexes, [Co2(μ-Lm)μ-Cl4], [Co2(μ-Lm*)Cl4], and [Co2(μ-Lm*)Br4], were also prepared. The structures of all [M2(μ-X)(μ-L)2](3+) (X = Cl(-), Br(-)) complexes have two ditopic bis(pyrazolyl)methane ligands bridging two metals in a metallacyclic arrangement. The fifth coordination site of the distorted trigonal bipyramidal metal centers is filled by a bridging halide ligand that has an unusual linear or nearly linear M-X-M angle. The NMR spectra of [Zn2(μ-Cl)(μ-Lm*)2](ClO4)3 and especially [Cd2(μ-Cl)(μ-Lm*)2](ClO4)3 demonstrate that the metallacycle structure is maintained in solution. Solid state magnetic susceptibility data for the copper(II) compounds show very strong antiferromagnetic exchange interactions, with -J values of 536 cm(-1) for [Cu2(μ-Cl)(μ-Lm)2](ClO4)3·xCH3CN, 720 cm(-1) for [Cu2(μ-Cl)(μ-Lm*)2](ClO4)3, and 945 cm(-1) for [Cu2(μ-Br)(μ-Lm*)2](ClO4)3·2CH3CN. Smaller but still substantial antiferromagnetic interactions are observed with other first row transition metals, with -J values of 98 cm(-1) for [Ni2(μ-Cl)(μ-Lm*)2](ClO4)3, 55 cm(-1) for [Co2(μ-Cl)(μ-Lm*)2](ClO4)3, and 34 cm(-1) for [Fe2(μ-Cl)(μ-Lm*)2](ClO4

  20. Spiro copper(II)-metallacycles derived from 5-arylaminomethylene-barbituric acids: Synthesis and structural characterization

    NASA Astrophysics Data System (ADS)

    Fırıncı, Erkan; Giziroglu, Emrah; Celepci, Duygu Barut; Söyleyici, Hakan Can; Aygün, Muhittin

    2017-06-01

    Schiff bases derived from 2,4,6-trioxohexahydroprimidine-5-carbaldehyde can behave as chelating ligands. 5-[(2,6-diisopropylphenylamino)-methylene]pyrimidine-2,4,6-trione (LB1) and 1,3-dimethyl-5-[(2-phenoxyphenylamino)-methylene]pyrimidine-2,4,6-trione (LB2) were used as ligand in the synthesis of novel mononuclear five-coordinated copper(II) complexes. The spectroscopic properties of the ligands were detected by FT-IR and NMR. The molecular structure of LB2 was determined by X-ray diffraction which crystallizes in the orthorhombic Pca21 space group. The complexes of Cu(LB1)2 (2) and Cu(LB2)2 (3) were characterized by elemental analysis, FT-IR and X-ray diffraction. The X-ray diffraction studies reveal 2 and 3 contain five-coordinated Cu(II) atom which is surrounded by two nitrogen and three oxygen atoms. The coordination geometry of complexes were examined using the Addison's model. The results show that complex 2 has distorted trigonal bipyramidal geometry, but complex 3 has distorted square pyramidal geometry. Also, the synthesized copper complexes can be regarded as spiro metallacycles in which copper is central spiro atom.

  1. 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.

  2. Broadband transmission EPR spectroscopy.

    PubMed

    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.

  3. 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

  4. EPR study of porous silicon

    NASA Astrophysics Data System (ADS)

    Jishi, Fu; Jinchang, Mao; En, Wu; Yongqiang, Jia; Borui, Zhang; Lizhu, Zhang; Guogang, Qin; Yuhua, Zhang; Genshuan, Wui

    1994-12-01

    An anisotropic EPR signal was observed in porous Si. According to its symmetry and g value, the EPR signal can be attributed to silicon dangling bonds located on the surface of a porous Si skeleton. The evolution of the EPR signal at room temperature in air was measured. The annealing temperature dependence of the EPR and the PL of porous Si in oxygen and the effects of gamma irradiation on the EPR and the PL spectra of porous Si were studied. The changes of the EPR signal and the PL intensity induced in atmosphere by ethyl alcohol and acetone were discovered. The dangling bond is only one of the factors which affect the PL.

  5. Accumulation of a potent γδ T-cell stimulator after deletion of the lytB gene in Escherichia coli

    PubMed Central

    Eberl, Matthias; Altincicek, Boran; Kollas, Ann-Kristin; Sanderbrand, Silke; Bahr, Ute; Reichenberg, Armin; Beck, Ewald; Foster, Donald; Wiesner, Jochen; Hintz, Martin; Jomaa, Hassan

    2002-01-01

    Activation of human Vγ9/Vδ2 T cells by many pathogens depends on the presence of small phosphorylated non-peptide compounds derived from the 2-C-methyl-d-erythritol 4-phosphate (MEP) pathway of isoprenoid biosynthesis. We here demonstrate that in Escherichia coli mutants deficient in lytB, an essential gene of the MEP pathway, a potent Vγ9/Vδ2 T-cell activator accumulates by a factor of approximately 150 compared to wild-type E. coli. The compound responsible for the strong immunogenicity of this E. coli mutant was subsequently characterized and identified as a small pyrophosphorylated metabolite, with a molecular mass of 262 Da, derived from the MEP pathway. Stimulation of human peripheral blood mononuclear cells (PBMC) with extracts prepared from the lytB-deficient E. coli mutant led to upregulation of T-cell activation markers on the surface of Vγ9/Vδ2 T cells as well as proliferation and expansion of Vγ9/Vδ2 T cells. This response was dependent on costimulatory growth factors, such as interleukin (IL)-2, IL-15 and IL-21. Significant levels of interferon-γ (IFN-γ) and tumour necrosis factor-α (TNF-α) were secreted in the presence of IL-2 and IL-15, but not in the presence of IL-21, demonstrating that proliferating phosphoantigen-reactive Vγ9/Vδ2 T cells do not necessarily produce proinflammatory cytokines. PMID:12047749

  6. 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

  7. Self-assembly of dinuclear Pd(ii)/Pt(ii) metallacyclic receptors incorporating N-heterocyclic carbene complexes as corners.

    PubMed

    Marcos, Ismael; Domarco, Olaya; Peinador, Carlos; Fenández, Alberto; Fernández, Jesús J; Vázquez-García, Digna; García, Marcos D

    2017-03-07

    We report herein the self-assembly of a series of new square and rectangular-shaped dinuclear M2L2 metallacycles (M = Pd(ii)/Pt(ii)), receptors self-assembled in water from four different N-monoalkyl-4,4'-bipyridinium derivatives as ligands and square-planar Pd(ii) and Pt(ii) metal centers having the chelating N-heterocyclic carbene 1,1'-di(methyl)-3,3'-methylene-4-diimidazolin-2,2'-diylidene. The concentration-dependent Pd2L2 metallacycles were successfully obtained and characterized by means of NMR experiments in aqueous media. Due to the strong trans effect exerted by the carbene ligands, the synthesis of the Pt2L2 receptors was achieved as well by self-assembly of the components at room temperature in a few hours, in clear contraposition to the harsh reaction conditions usually required for the labilization of other kinetically inert Pt(ii)-N(pyridine) bonds. X-ray diffraction studies of suitable single crystals of two of the obtained receptors offered additional information on the structure of the obtained supramolecules, whose ability as receptors has been explored by the preparation and study of the corresponding inclusion complexes in water with 1,5-dihydroxynaphthalene as the model substrate.

  8. 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.

  9. 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.

  10. Self-assembled copper(II) metallacycles derived from asymmetric Schiff base ligands: efficient hosts for ADP/ATP in phosphate buffer.

    PubMed

    Kumar, Amit; Pandey, Rampal; Kumar, Ashish; Gupta, Rakesh Kumar; Dubey, Mrigendra; Mohammed, Akbar; Mobin, Shaikh M; Pandey, Daya Shankar

    2015-10-21

    Novel asymmetric Schiff base ligands 2-{[3-(3-hydroxy-1-methyl-but-2-enylideneamino)-2,4,6-trimethylphenylimino]-methyl}-phenol (H2L(1)) and 1-{[3-(3-hydroxy-1-methyl-but-2-enylideneamino)-2,4,6-trimethylphenylimino]-methyl}-naphthalen-2-ol (H2L(2)) possessing dissimilar N,O-chelating sites and copper(ii) metallacycles (CuL(1))4 (1) and (CuL(2))4 (2) based on these ligands have been described. The ligands and complexes have been thoroughly characterized by satisfactory elemental analyses, and spectral (IR, (1)H, (13)C NMR, ESI-MS, UV/vis) and electrochemical studies. Structures of H2L(2) and 1 have been unambiguously determined by X-ray single crystal analyses. The crystal structure of H2L(2) revealed the presence of two distinct N,O-chelating sites on dissimilar cores (naphthalene and β-ketoaminato groups) offering a diverse coordination environment. Metallacycles 1 and 2 having a cavity created by four Cu(ii) centres coordinated in a homo- and heteroleptic fashion with respective ligands act as efficient hosts for adenosine-5'-diphosphate (ADP) and adenosine-5'-triphosphate (ATP) respectively, over other nucleoside polyphosphates (NPPs). The disparate sensitivity of these metallacycles toward ADP and ATP has been attributed to the size of the ligands assuming diverse dimensions and spatial orientations. These are attuned for π-π stacking and electrostatic interactions suitable for different guest molecules under analogous conditions, metallacycle 1 offers better orientation for ADP, while 2 for ATP. The mechanism of the host-guest interaction has been investigated by spectral and electrochemical studies and supported by molecular docking studies.

  11. EPR: an Advanced Evolutionary Design

    SciTech Connect

    Czech, Juergen; Bouteille, Francois; Hudson, Greg

    2004-07-01

    This paper presents the main features of the EPR, an evolutionary design product that builds on French N4 plants (Chooz and Civaux) and Konvoi, the most recent reactor series built in Germany. This Franco-German project was driven by a common French and German desire to cooperate in several areas. In January 2001, Framatome SA and Siemens AG merged their nuclear activities to form Framatome ANP with three regional entities in France, Germany and the USA. The recent decision of Teollisuuden Voima Oy (TVO) to select the EPR for construction in Olkiluoto of the fifth Nuclear Power Plant in Finland gave a new impetus to the project. Framatome ANP is committed to put the FOAK EPR in commercial operation on May 1, 2009. This challenging time schedule will set a new reference for 'Generation III +' LWR's. (authors)

  12. Rapid-scan EPR imaging

    NASA Astrophysics Data System (ADS)

    Eaton, Sandra S.; Shi, Yilin; Woodcock, Lukas; Buchanan, Laura A.; McPeak, Joseph; Quine, Richard W.; Rinard, George A.; Epel, Boris; Halpern, Howard J.; Eaton, Gareth R.

    2017-07-01

    In rapid-scan EPR the magnetic field or frequency is repeatedly scanned through the spectrum at rates that are much faster than in conventional continuous wave EPR. The signal is directly-detected with a mixer at the source frequency. Rapid-scan EPR is particularly advantageous when the scan rate through resonance is fast relative to electron spin relaxation rates. In such scans, there may be oscillations on the trailing edge of the spectrum. These oscillations can be removed by mathematical deconvolution to recover the slow-scan absorption spectrum. In cases of inhomogeneous broadening, the oscillations may interfere destructively to the extent that they are not visible. The deconvolution can be used even when it is not required, so spectra can be obtained in which some portions of the spectrum are in the rapid-scan regime and some are not. The technology developed for rapid-scan EPR can be applied generally so long as spectra are obtained in the linear response region. The detection of the full spectrum in each scan, the ability to use higher microwave power without saturation, and the noise filtering inherent in coherent averaging results in substantial improvement in signal-to-noise relative to conventional continuous wave spectroscopy, which is particularly advantageous for low-frequency EPR imaging. This overview describes the principles of rapid-scan EPR and the hardware used to generate the spectra. Examples are provided of its application to imaging of nitroxide radicals, diradicals, and spin-trapped radicals at a Larmor frequency of ca. 250 MHz.

  13. Hierarchical Self-Assembly of Responsive Organoplatinum(II) Metallacycle-TMV Complexes with Turn-On Fluorescence.

    PubMed

    Tian, Ye; Yan, Xuzhou; Saha, Manik Lal; Niu, Zhongwei; Stang, Peter J

    2016-09-21

    Here we report that the rod-like tobacco mosaic virus (TMV), having a negatively charged surface, can be assembled into three-dimensional micrometer-sized bundle-like superstructures via multiple electrostatic interactions with a positively charged molecular "glue", namely, a tetraphenylethylene (TPE)-based discrete organoplatinum(II) metallacycle (TPE-Pt-MC). Due to the nanoconfinement effect in the resultant TMV/TPE-Pt-MC complexes and the aggregation-induced emission (AIE) activity of the TPE units, these hierarchical architectures result in a dramatic fluorescence enhancement that not only provides evidence for the formation of novel metal-organic biohybrid materials but also represents an alternative to turn-on fluorescence. Moreover, the dissociation of these final constructs and subsequent release of individual virus have been achieved by disrupting the TPE-Pt-MC core using tetrabutylammonium bromide (TBAB). This strategy is also compatible with other protein-based nanoparticles such as bacteriophage M13 and ferritin, proving the generality of this approach. Hence, this research will open new routes for the fabrication of functional biohybrid materials involving metal-organic complexes and anisotropically shaped bionanoparticles.

  14. Dinuclear metallacycles with single M-O(H)-M bridges [M = Fe(II), Co(II), Ni(II), Cu(II)]: effects of large bridging angles on structure and antiferromagnetic superexchange interactions.

    PubMed

    Reger, Daniel L; Pascui, Andrea E; Foley, Elizabeth A; Smith, Mark D; Jezierska, Julia; Ozarowski, Andrew

    2014-02-17

    The reactions of M(ClO4)2·xH2O and the ditopic ligands m-bis[bis(1-pyrazolyl)methyl]benzene (Lm) or m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*) in the presence of triethylamine lead to the formation of monohydroxide-bridged, dinuclear metallacycles of the formula [M2(μ-OH)(μ-Lm)2](ClO4)3 (M = Fe(II), Co(II), Cu(II)) or [M2(μ-OH)(μ-Lm*)2](ClO4)3 (M = Co(II), Ni(II), Cu(II)). With the exception of the complexes where the ligand is Lm and the metal is copper(II), all of these complexes have distorted trigonal bipyramidal geometry around the metal centers and unusual linear (Lm*) or nearly linear (Lm) M-O-M angles. For the two solvates of [Cu2(μ-OH)(μ-Lm)2](ClO4)3, the Cu-O-Cu angles are significantly bent and the geometry about the metal is distorted square pyramidal. All of the copper(II) complexes have structural distortions expected for the pseudo-Jahn-Teller effect. The two cobalt(II) complexes show moderate antiferromagnetic coupling, -J = 48-56 cm(-1), whereas the copper(II) complexes show very strong antiferromagnetic coupling, -J = 555-808 cm(-1). The largest coupling is observed for [Cu2(μ-OH)(μ-Lm*)2](ClO4)3, the complex with a Cu-O-Cu angle of 180°, such that the exchange interaction is transmitted through the dz(2) and the oxygen s and px orbitals. The interaction decreases, but it is still significant, as the Cu-O-Cu angle decreases and the character of the metal orbital becomes increasingly d(x(2)-y(2)). These intermediate geometries and magnetic interactions lead to spin Hamiltonian parameters for the copper(II) complexes in the EPR spectra that have large E/D ratios and one g matrix component very close to 2. Density functional theory calculations were performed using the hybrid B3LYP functional in association with the TZVPP basis set, resulting in reasonable agreement with the experiments.

  15. 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. Copyright © 2013 Elsevier Inc. All rights reserved.

  16. NMR investigations of dinuclear, single-anion bridged copper(II) metallacycles: structure and antiferromagnetic behavior in solution.

    PubMed

    Reger, Daniel L; Pascui, Andrea E; Pellechia, Perry J; Ozarowski, Andrew

    2013-11-04

    The nuclear magnetic resonance (NMR) spectra of single-anion bridged, dinuclear copper(II) metallacycles [Cu2(μ-X)(μ-L)2](A)3 (L(m) = m-bis[bis(1-pyrazolyl)methyl]benzene: X = F(-), A = BF4(-); X = Cl(-), OH(-), A = ClO4(-); L(m)* = m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene: X = CN(-), F(-), Cl(-), OH(-), Br(-), A = ClO4(-)) have relatively sharp (1)H and (13)C NMR resonances with small hyperfine shifts due to the strong antiferromagnetic superexchange interactions between the two S = 1/2 metal centers. The complete assignments of these spectra, except X = CN(-), have been made through a series of NMR experiments: (1)H-(1)H COSY, (1)H-(13)C HSQC, (1)H-(13)C HMBC, T1 measurements and variable-temperature (1)H NMR. The T1 measurements accurately determine the Cu···H distances in these molecules. In solution, the temperature dependence of the chemical shifts correlate with the population of the paramagnetic triplet (S = 1) and diamagnetic singlet (S = 0) states. This correlation allows the determination of antiferromagnetic exchange coupling constants, -J (Ĥ = -JŜ1Ŝ2), in solution for the L(m) compounds 338(F(-)), 460(Cl(-)), 542(OH(-)), for the L(m)* compounds 128(CN(-)), 329(F(-)), 717(Cl(-)), 823(OH(-)), and 944(Br(-)) cm(-1), respectively. These values are of similar magnitudes to those previously measured in the solid state (-Jsolid = 365, 536, 555, 160, 340, 720, 808, and 945 cm(-1), respectively). This method of using NMR to determine -J values in solution is an accurate and convenient method for complexes with strong antiferromagnetic superexchange interactions. In addition, the similarity between the solution and solid-state -J values of these complexes confirms the information gained from the T1 measurements: the structures are similar in the two states.

  17. The marriage of metallacycle transfer chemistry with Suzuki-Miyaura cross-coupling to give main group element-containing conjugated polymers.

    PubMed

    He, Gang; Kang, Le; Torres Delgado, William; Shynkaruk, Olena; Ferguson, Michael J; McDonald, Robert; Rivard, Eric

    2013-04-10

    A versatile and general synthetic route for the synthesis of conjugated main group element-based polymers, previously inaccessible by conventional means, is reported. These polymers contain five-membered chalcogenophene rings based on S, Se, and Te, and we demonstrate that optoelectronic properties can be readily tuned via controlled atom substitution chemistry. In addition, regioregular hybrid thiophene-selenophene-tellurophene and selenophene-fluorene copolymers were synthesized to provide a further illustration of the scope of the presented metallacycle transfer/cross-coupling polymerization method.

  18. Background removal procedure for rapid scan EPR.

    PubMed

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

    2009-01-01

    In rapid scan EPR the changing magnetic field creates a background signal with components at the scan frequency and its harmonics. The amplitude of the background signal increases with scan width and is more significant for weak EPR signals such as are obtained in the presence of magnetic field gradients. A procedure for distinguishing this background from the EPR signal is proposed, mathematically described, and tested for various experimental conditions.

  19. Pharmaceutical applications of in vivo EPR

    NASA Astrophysics Data System (ADS)

    Mäder, Karsten

    1998-07-01

    The aim of this article is to discuss the applications of in vivo EPR in the field of pharmacy. In addition to direct detection of free radical metabolites and measurement of oxygen, EPR can be used to characterize the mechanisms of drug release from biodegradable polymers. Unique information about drug concentration, the microenvironment (viscosity, polarity, pH) and biodistribution (by localized measurement or EPR Imaging) can be obtained.

  20. EPR in B physics and elsewhere

    SciTech Connect

    Lipkin, H.J. ||

    1997-09-01

    The application of Einstein-Podolsky-Rosen correlations in {Upsilon}(4s) {yields} B{anti B} decays to research in CP violation is the first and probably only use of EPR as a technique for research in new physics. Elsewhere highly sophisticated EPR projects question EPR and test its predictions to look for violations of quantum mechanics, hidden variables, Bell`s inequalities, etc.

  1. 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.

  2. 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.

  3. CO2 Stimuli-Responsive, Injectable Block Copolymer Hydrogels Cross-Linked by Discrete Organoplatinum(II) Metallacycles via Stepwise Post-Assembly Polymerization.

    PubMed

    Zheng, Wei; Yang, Guang; Shao, Nannan; Chen, Li-Jun; Ou, Bo; Jiang, Shu-Ting; Chen, Guosong; Yang, Hai-Bo

    2017-10-04

    Supramolecular polymeric gels cross-linked by well-defined, discrete metal-organic macrocycles (MOMs) or metal-organic cages have become a prevailing topic within the field of supramolecular self-assembly. However, the realization of supramolecular polymeric hydrogels cross-linked by discrete organometallic architectures with good biocompatibility is still a great challenge. Herein, we present the successful preparation of CO2 stimuli-responsive, injectable block copolymer hydrogels cross-linked by discrete organoplatinum(II) metallacycles. Through the combination of coordination-driven self-assembly and stepwise post-assembly polymerization, star block copolymers (SBCPs) containing well-defined hexagonal metallacycles as cores were successfully prepared, which featured CO2 stimuli-responsive properties including CO2-triggered morphology transition and CO2-induced thermoresponsive behavior. Interestingly, the resultant SBCPs were capable of forming supramolecular hydrogels with MOMs as junctions near physiological temperature, which allowed the realization of a reversible gel-to-sol transformation through the removal and addition of CO2. More importantly, the resultant supramolecular hydrogels presented good cytocompatibility in vitro. Therefore, this study provides a new strategy for the construction of new "smart" supramolecular hydrogels with promising applications as biological materials.

  4. 3-Rhoda-1,2-diazacyclopentanes: a series of novel metallacycle complexes derived from C-N functionalization of ethylene.

    PubMed

    Drover, Marcus W; Beh, Daniel W; Kennepohl, Pierre; Love, Jennifer A

    2014-10-06

    Rh-containing metallacycles, [(TPA)Rh(III)(κ(2)-(C,N)-CH2CH2(NR)2-]Cl; TPA = N,N,N,N-tris(2-pyridylmethyl)amine have been accessed through treatment of the Rh(I) ethylene complex, [(TPA)Rh(η(2)-CH2CH2)]Cl ([1]Cl) with substituted diazenes. We show this methodology to be tolerant of electron-deficient azo compounds including azo diesters (RCO2N=NCO2R; R = Et [3]Cl, R = iPr [4]Cl, R = tBu [5]Cl, and R = Bn [6]Cl) and a cyclic azo diamide: 4-phenyl-1,2,4-triazole-3,5-dione (PTAD), [7]Cl. The latter complex features two ortho-fused ring systems and constitutes the first 3-rhoda-1,2-diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N-N coordination followed by insertion of ethylene into a [Rh]-N bond. In terms of reactivity, [3]Cl and [4]Cl successfully undergo ring-opening using p-toluenesulfonic acid, affording the Rh chlorides, [(TPA)Rh(III)(Cl)(κ(1)-(C)-CH2CH2(NCO2R)(NHCO2R)]OTs; [13]OTs and [14]OTs. Deprotection of [5]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end-on coordinated diazene [(TPA)Rh(III)(κ(2)-(C,N)-CH2CH2(NH)2-](+) [16]Cl, a hitherto unreported motif. Treatment of [16]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)Rh(III)(κ(2)-(C,N)-CH2CH2(NAc)2-](+), [17]Cl. Treatment of [1]Cl with AcN=NAc did not give the Rh-N insertion product, but instead the N,O-chelated complex [(TPA)Rh(I)(κ(2)-(O,N)-CH3(CO)(NH)(N=C(CH3)(OCH=CH2))]Cl [23]Cl, presumably through insertion of ethylene into a [Rh]-O bond.

  5. EPR dosimetry in chemically treated fingernails

    USDA-ARS?s Scientific Manuscript database

    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...

  6. 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.

  7. 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

  8. Time-resolved pulsed EPR: microwave and optical detection

    SciTech Connect

    Trifunac, A.D.; Smith, J.P.

    1981-01-01

    Time-resolved pulsed EPR spectrometers are described. EPR spectra, kinetic profiles, and relaxation studies are used to illustrate some capabilities of the pulsed EPR experiment. Optical detection of time-resolved EPR spectra of radical ion pairs is used to study radical-ion recombination kinetics, recombination pathways, and the structure of radical anions and cations. 17 figures.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Theoretical EPR study of 6-Mercaptopurine

    NASA Astrophysics Data System (ADS)

    Tasdemir, Halil Ugur; Türkkan, Ercan

    2017-02-01

    6-Mercaptopurine is important antineoplastics agent and it is used for immuno - suppressive and anti - inflammatory. Experimental EPR parameters of 6-Mercaptopurine molecules powder were studied in the literature. The aim of this study EPR parameters of 6 - Mercaptopurine molecules were calculated with theoretical calculations and define the possible radicals of 6 - Mercaptopurine molecules. Firstly the X-ray structure of 6-Mercaptopurine molecules were found in the literature (1). EPR parameters and possible radicals of 6 - Mercaptopurine molecules were calculated from this X-ray structure. Possible radicals of gamma-irradiated 6-Mercaptopurine molecules were constituted. EPR parameters of possible radicals were calculated with B3LYP/6-311++ G (d,p) basis set in DFT methods for 6 - Mercaptopurine molecules.

  11. Perspectives of shaped pulses for EPR spectroscopy

    NASA Astrophysics Data System (ADS)

    Spindler, Philipp E.; Schöps, Philipp; Kallies, Wolfgang; Glaser, Steffen J.; Prisner, Thomas F.

    2017-07-01

    This article describes current uses of shaped pulses, generated by an arbitrary waveform generator, in the field of EPR spectroscopy. We show applications of sech/tanh and WURST pulses to dipolar spectroscopy, including new pulse schemes and procedures, and discuss the more general concept of optimum-control-based pulses for applications in EPR spectroscopy. The article also describes a procedure to correct for experimental imperfections, mostly introduced by the microwave resonator, and discusses further potential applications and limitations of such pulses.

  12. Investigation of radical locations in various sesame seeds by CW EPR and 9-GHz EPR imaging.

    PubMed

    Nakagawa, K; Hara, H

    2015-01-01

    We investigated the location of radical in various sesame seeds using continuous-wave (CW) electron paramagnetic resonance (EPR) and 9-GHz EPR imaging. CW EPR detected persistent radicals (single line) for various sesame seeds. The EPR linewidth of black sesame seeds was narrower than that of the irradiated white sesame seeds. A very small signal was detected for the white sesame seeds. Two-dimensional (2D) imaging using a 9-GHz EPR imager showed that radical locations vary for various sesame seeds. The paramagnetic species in black sesame seeds were located on the seed coat (skin) and in the hilum region. The signal with the highest intensity was obtained from the hilum part. A very low-intensity image was observed for the white sesame seeds. In addition, the 2D imaging of the irradiated white sesame seeds showed that free radicals were located throughout the entire seed. For the first time, CW EPR and 9-GHz EPR imaging showed the exact location of radical species in various sesame seeds.

  13. Protocol for emergency EPR dosimetry in fingernails.

    PubMed

    Trompier, F; Kornak, L; Calas, C; Romanyukha, A; Leblanc, B; Mitchell, C A; Swartz, H M; Clairand, I

    2007-08-01

    There is an increased need for after-the-fact dosimetry because of the high risk of radiation exposures due to terrorism or accidents. In case of such an event, a method is needed to make measurements of dose in a large number of individuals rapidly and with sufficient accuracy to facilitate effective medical triage. Dosimetry based on EPR measurements of fingernails potentially could be an effective tool for this purpose. This paper presents the first operational protocols for EPR fingernail dosimetry, including guidelines for collection and storage of samples, parameters for EPR measurements, and the method of dose assessment. In a blinded test of this protocol application was carried out on nails freshly sampled and irradiated to 4 and 20 Gy; this protocol gave dose estimates with an error of less than 30%.

  14. Spin entanglement, decoherence and Bohm's EPR paradox.

    PubMed

    Cavalcanti, E G; Drummond, P D; Bachor, H A; Reid, M D

    2009-10-12

    We obtain criteria for entanglement and the EPR paradox for spin-entangled particles and analyse the effects of decoherence caused by absorption and state purity errors. For a two qubit photonic state, entanglement can occur for all transmission efficiencies. In this case, the state preparation purity must be above a threshold value. However, Bohm's spin EPR paradox can be achieved only above a critical level of loss. We calculate a required efficiency of 58%, which appears achievable with current quantum optical technologies. For a macroscopic number of particles prepared in a correlated state, spin entanglement and the EPR paradox can be demonstrated using our criteria for efficiencies eta > 1/3 and eta > 2/3 respectively. This indicates a surprising insensitivity to loss decoherence, in a macroscopic system of ultra-cold atoms or photons.

  15. 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.

  16. Using rapid-scan EPR to improve the detection limit of quantitative EPR by more than one order of magnitude.

    PubMed

    Möser, J; Lips, K; Tseytlin, M; Eaton, G R; Eaton, S S; Schnegg, A

    2017-08-01

    X-band rapid-scan EPR was implemented on a commercially available Bruker ELEXSYS E580 spectrometer. Room temperature rapid-scan and continuous-wave EPR spectra were recorded for amorphous silicon powder samples. By comparing the resulting signal intensities the feasibility of performing quantitative rapid-scan EPR is demonstrated. For different hydrogenated amorphous silicon samples, rapid-scan EPR results in signal-to-noise improvements by factors between 10 and 50. Rapid-scan EPR is thus capable of improving the detection limit of quantitative EPR by at least one order of magnitude. In addition, we provide a recipe for setting up and calibrating a conventional pulsed and continuous-wave EPR spectrometer for rapid-scan EPR. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Using rapid-scan EPR to improve the detection limit of quantitative EPR by more than one order of magnitude

    NASA Astrophysics Data System (ADS)

    Möser, J.; Lips, K.; Tseytlin, M.; Eaton, G. R.; Eaton, S. S.; Schnegg, A.

    2017-08-01

    X-band rapid-scan EPR was implemented on a commercially available Bruker ELEXSYS E580 spectrometer. Room temperature rapid-scan and continuous-wave EPR spectra were recorded for amorphous silicon powder samples. By comparing the resulting signal intensities the feasibility of performing quantitative rapid-scan EPR is demonstrated. For different hydrogenated amorphous silicon samples, rapid-scan EPR results in signal-to-noise improvements by factors between 10 and 50. Rapid-scan EPR is thus capable of improving the detection limit of quantitative EPR by at least one order of magnitude. In addition, we provide a recipe for setting up and calibrating a conventional pulsed and continuous-wave EPR spectrometer for rapid-scan EPR.

  18. Teaching the EPR Paradox at High School?

    ERIC Educational Resources Information Center

    Pospiech, Gesche

    1999-01-01

    Argues the importance of students at university and in the final years of high school gaining an appreciation of the principles of quantum mechanics. Presents the EPR gedanken experiment (thought experiment) as a method of teaching the principles of quantum mechanics. (Author/CCM)

  19. 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.

  20. Monitoring enzymatic ATP hydrolysis by EPR spectroscopy.

    PubMed

    Hacker, Stephan M; Hintze, Christian; Marx, Andreas; Drescher, Malte

    2014-07-14

    An adenosine triphosphate (ATP) analogue modified with two nitroxide radicals is developed and employed to study its enzymatic hydrolysis by electron paramagnetic resonance spectroscopy. For this application, we demonstrate that EPR holds the potential to complement fluorogenic substrate analogues in monitoring enzymatic activity.

  1. 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

  2. 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.

  3. EPR spectroscopy of nitrite complexes of methemoglobin.

    PubMed

    Schwab, David E; Stamler, Jonathan S; Singel, David J

    2010-07-19

    The chemical interplay of nitrogen oxides (NO's) with hemoglobin (Hb) has attracted considerable recent attention because of its potential significance in the mechanism of NO-related vasoactivity regulated by Hb. An important theme of this interplay-redox coupling in adducts of heme iron and NO's-has sparked renewed interest in fundamental studies of FeNO(x) coordination complexes. In this Article, we report combined UV-vis and comprehensive electron paramagnetic resonance (EPR) spectroscopic studies that address intriguing questions raised in recent studies of the structure and affinity of the nitrite ligand in complexes with Fe(III) in methemoglobin (metHb). EPR spectra of metHb/NO(2)(-) are found to exhibit a characteristic doubling in their sharper spectral features. Comparative EPR measurements at X- and S-band frequencies, and in D(2)O versus H(2)O, argue against the assignment of this splitting as hyperfine structure. Correlated changes in the EPR spectra with pH enable complete assignment of the spectrum as deriving from the overlap of two low-spin species with g values of 3.018, 2.122, 1.45 and 2.870, 2.304, 1.45 (values for samples at 20 K and pH 7.4 in phosphate-buffered saline). These g values are typical of g values found for other heme proteins with N-coordinated ligands in the binding pocket and are thus suggestive of N-nitro versus O-nitrito coordination. The positions and shapes of the spectral lines vary only slightly with temperature until motional averaging ensues at approximately 150 K. The pattern of motional averaging in the variable-temperature EPR spectra and EPR studies of Fe(III)NO(2)(-)/Fe(II)NO hybrids suggest that one of two species is present in both of the alpha and beta subunits, while the other is exclusive to the beta subunit. Our results also reconfirm that the affinity of nitrite for metHb is of millimolar magnitude, thereby making a direct role for nitrite in physiological hypoxic vasodilation difficult to justify.

  4. Full cycle rapid scan EPR deconvolution algorithm

    NASA Astrophysics Data System (ADS)

    Tseytlin, Mark

    2017-08-01

    Rapid scan electron paramagnetic resonance (RS EPR) is a continuous-wave (CW) method that combines narrowband excitation and broadband detection. Sinusoidal magnetic field scans that span the entire EPR spectrum cause electron spin excitations twice during the scan period. Periodic transient RS signals are digitized and time-averaged. Deconvolution of absorption spectrum from the measured full-cycle signal is an ill-posed problem that does not have a stable solution because the magnetic field passes the same EPR line twice per sinusoidal scan during up- and down-field passages. As a result, RS signals consist of two contributions that need to be separated and postprocessed individually. Deconvolution of either of the contributions is a well-posed problem that has a stable solution. The current version of the RS EPR algorithm solves the separation problem by cutting the full-scan signal into two half-period pieces. This imposes a constraint on the experiment; the EPR signal must completely decay by the end of each half-scan in order to not be truncated. The constraint limits the maximum scan frequency and, therefore, the RS signal-to-noise gain. Faster scans permit the use of higher excitation powers without saturating the spin system, translating into a higher EPR sensitivity. A stable, full-scan algorithm is described in this paper that does not require truncation of the periodic response. This algorithm utilizes the additive property of linear systems: the response to a sum of two inputs is equal the sum of responses to each of the inputs separately. Based on this property, the mathematical model for CW RS EPR can be replaced by that of a sum of two independent full-cycle pulsed field-modulated experiments. In each of these experiments, the excitation power equals to zero during either up- or down-field scan. The full-cycle algorithm permits approaching the upper theoretical scan frequency limit; the transient spin system response must decay within the scan

  5. EPR Severe Accident Threats and Mitigation

    SciTech Connect

    Azarian, G.; Kursawe, H.M.; Nie, M.; Fischer, M.; Eyink, J.; Stoudt, R.H.

    2004-07-01

    Despite the extremely low EPR core melt frequency, an improved defence-in-depth approach is applied in order to comply with the EPR safety target: no stringent countermeasures should be necessary outside the immediate plant vicinity like evacuation, relocation or food control other than the first harvest in case of a severe accident. Design provisions eliminate energetic events and maintain the containment integrity and leak-tightness during the entire course of the accident. Based on scenarios that cover a broad range of physical phenomena and which provide a sound envelope of boundary conditions associated with each containment challenge, a selection of representative loads has been done, for which mitigation measures have to cope with. This paper presents the main critical threats and the approach used to mitigate those threats. (authors)

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. EPR Investigation of Irradiated Curry Powder

    NASA Astrophysics Data System (ADS)

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

    2007-04-01

    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° 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.

  11. Core Monitoring System for TSN EPR Reactors

    SciTech Connect

    Pfeiffer, Maxime

    2015-07-01

    In the context of Chinese (TSN) EPR reactors project, a new on-line support system was introduced to give information, either continuously or upon request, to the plant operators about some advanced physics parameters corresponding to the current state of the nuclear core. This document provides a description of the functions that are available and the advantages provided by using their results. For each function the Human Machine Interface (HMI) is illustrated. (authors)

  12. Seventy Years of the EPR Paradox

    NASA Astrophysics Data System (ADS)

    Kupczynski, Marian

    2006-11-01

    In spite of the fact that statistical predictions of quantum theory (QT) can only be tested if large amount of data is available a claim has been made that QT provides the most complete description of an individual physical system. Einstein's opposition to this claim and the paradox he presented in the article written together with Podolsky and Rosen in 1935 inspired generations of physicists in their quest for better understanding of QT. Seventy years after EPR article it is clear that without deep understanding of the character and limitations of QT one may not hope to find a meaningful unified theory of all physical interactions, manipulate qubits or construct a quantum computer.. In this paper we present shortly the EPR paper, the discussion, which followed it and Bell inequalities (BI). To avoid various paradoxes we advocate purely statistical contextual interpretation (PSC) of QT. According to PSC a state vector is not an attribute of a single electron, photon, trapped ion or quantum dot. A value of an observable assigned to a physical system has only a meaning in a context of a particular physical experiment PSC does not provide any mental space-time picture of sub phenomena. The EPR paradox is avoided because the reduction of the state vector in the measurement process is a passage from a description of the whole ensemble of the experimental results to a particular sub-ensemble of these results. We show that the violation of BI is neither a proof of the completeness of QT nor of its non-locality. Therefore we rephrase the EPR question and ask whether QT is "predictably "complete or in other words does it provide the complete description of experimental data. To test the "predictable completeness" it is not necessary to perform additional experiments it is sufficient to analyze more in detail the existing experimental data by using various non-parametric purity tests and other specific statistical tools invented to study the fine structure the time-series.

  13. 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

  14. CW-EPR Spectral Simulations: Solid State.

    PubMed

    Stoll, Stefan

    2015-01-01

    This chapter summarizes the core concepts underlying the simulation of EPR spectra from biological samples in the solid state, from a user perspective. The key choices and decisions that have to be made by a user when simulating an experimental EPR spectrum are outlined. These include: the choice of the simulation model (the network of spins and the associated spin Hamiltonian), the dynamic regime (solid, liquid, slow motion), the level of theory used in the simulation (matrix diagonalization, perturbation theory, etc.), the treatment of orientational order and disorder (powder, crystal, partial ordering), the inclusion of the effects of structural disorder (strains), the effects of other line broadening mechanisms (unresolved hyperfine couplings, relaxation), and the inclusion of experimental distortions (field modulation, power saturation, filtering). Additionally, the salient aspects of utilizing least-squares fitting algorithms to aid the analysis of experimental spectra with the help of simulations are outlined. Although drawing from the experience gained from implementing EasySpin and from interacting with EasySpin's user base, this chapter applies to any EPR simulation software.

  15. Structural, photoluminescence, and theoretical DFT studies of gold(I) and silver(I) metallacycle dinuclear complexes of 1-methylbenzimidazolediphenyl phosphine (MBDP) ligand

    NASA Astrophysics Data System (ADS)

    Jenkins, Darkus E.; Assefa, Zerihun

    2017-04-01

    The synthesis and structural characterization of the bridging ligand, 1-methyl benzimidazole diphenylphosphine (MBDP) and its coordination with Au(I) and Ag(I) metal ions is reported. Two ligands coordinate to the metal ions in head to tail fashion forming a metallacycle coordination consisting of strong M-M bonding interaction with Ausbnd Au = 2.808 and Agsbnd Ag = 3.017 Å. Linear coordination is observed for the gold, while the silver shows distorted tetrahedral arrangement. X-ray crystal data of [(MBDP)2Au2](CH3CN)(BF4)2 (2) crystallizes in the monoclinic system with the space group of P21/n with cell constants of a = 8.9993 (8) Å, b = 19.6166 (18) Å, c = 13.4484 (12) Å, β = 100.966 (2)°, R = 0.026, and Rw = 0.064. The structure of [(MBDP)2(CH3CN)4Ag2](BF4)2, (3) crystallizes in the P (-)1 space group and the unit cell is a = 10.5423 (10) Å, b = 10.7638 (10) Å, c = 12.3530 (12) Å; α = 88.592 (3)°, β = 73.097 (3)°, γ = 84.422 (3)°, V = 1334.8 (2) Å3 with Z = 1, R = 0.034 and Rw = 0.093. The coordinating ligand as well as both dinuclear compounds reported here are luminescent in the near UV region. As supported by the DFT theoretical work, the emission is suggested to be primarily ligand based π- π* transition.

  16. 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.

  17. 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.

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

    PubMed

    Nakagawa, Kouichi; Epel, Boris

    2014-10-15

    In this study, noninvasive 9GHz 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 9GHz EPR imaging capabilities. The 9GHz EPR-imager easily resolved the LiPC samples at a distance of ∼2mm. Then, commercially available black pepper seeds were measured. We observed signatures from three different radical species, which were assigned to stable organic radicals, Fe(3+), and Mn(2+) complexes. In addition, no EPR spectral change in the seed was observed after it was submerged in distilled H2O for 1h. 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 9GHz EPR imaging were useful for the determination of the spatial distribution of paramagnetic species in various seeds. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. 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.

  20. 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.

  1. 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…

  2. Three key concerns for a successful EPR deployment and usage.

    PubMed

    Janols, Rebecka; Gôrranson, Bengt; Sandblad, Bengt

    2011-01-01

    The health care environment is unique because of the large and complex organisation with a traditional hierarchic structure that is governed by laws and regulations. This paper examines how a large Swedish health care organisation work with usability issues regarding Electronic Patient Record (EPR) deployment and usage. EPR systems have great impact on work environment and clinical work routines will not be performed in the same way as before. This paper analyse how the EPR management and core business understand their EPR responsibilities and work with usability aspects at different levels in the organisations. The paper reveals that there is a conflict about responsibility between EPR management and core business management. The reasons for the confusion are contradictive understanding of what an EPR system is, an IT system or a tool for the core business to perform better health care work. This leads to that care staff's experience regarding the EPR system's usability, is not being listened to within the organisation. Three key concerns for a successful EPR deployment and usage are identified and further analysed; education, evaluation and support & improvement ideas.

  3. EPR study on tomatoes before and after gamma-irradiation

    NASA Astrophysics Data System (ADS)

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

    2009-09-01

    The results from the EPR studies on fresh, air-dried and lyophilized tomato samples before and after gamma-irradiation are reported. Before irradiation fresh and air-dried tomatoes exhibit one singlet EPR line characterized with common g-factor of 2.0048±0.0005, whereas freeze-dried tomato does not show any EPR spectrum. After irradiation, a typical "cellulose-like" triplet EPR spectrum appears in all samples, attributed to cellulose free radicals, generated by gamma-irradiation. It consists of intense central line with g=2.0048±0.0005 and two weak satellite lines separated ca. 3 mT left and right of it. In air-dried and lyophilized tomatoes the "cellulose-like" EPR spectrum is superimposed by an additional partly resolved carbohydrate spectrum. Fading measurements of the radiation-induced EPR signals indicate that the intensity of the EPR spectra of air-dried and freeze-dried tomato are reduced to about 50% after 50 days, whereas those of fresh irradiated tomatoes kept at 4 °C fade completely in 15 days. The reported results unambiguously show that the presence of two satellite lines in the EPR "cellulose-like" spectra of tomato samples can be used for identification of radiation processing.

  4. EPR-based distance measurements at ambient temperature

    NASA Astrophysics Data System (ADS)

    Krumkacheva, Olesya; Bagryanskaya, Elena

    2017-07-01

    Pulsed dipolar (PD) EPR spectroscopy is a powerful technique allowing for distance measurements between spin labels in the range of 2.5-10.0 nm. It was proposed more than 30 years ago, and nowadays is widely used in biophysics and materials science. Until recently, PD EPR experiments were limited to cryogenic temperatures (T < 80 K). Recently, application of spin labels with long electron spin dephasing time at room temperature such as triarylmethyl radicals and nitroxides with bulky substituents at a position close to radical centers enabled measurements at room temperature and even at physiologically relevant temperatures by PD EPR as well as other approaches based on EPR (e.g., relaxation enhancement; RE). In this paper, we review the features of PD EPR and RE at ambient temperatures, in particular, requirements on electron spin phase memory time, ways of immobilization of biomolecules, the influence of a linker between the spin probe and biomolecule, and future opportunities.

  5. 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.

  6. 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.

  7. 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

  8. Einstein and the Quantum: The Secret Life of EPR

    NASA Astrophysics Data System (ADS)

    Fine, Arthur

    2006-05-01

    Locality, separation and entanglement -- 1930s style. Starting with Solvay 1927, we'll explore the background to the 1935 paper by Einstein, Podolsky and Rosen: how it was composed, the actual argument and principles used, and how the paper was received by Schroedinger, and others. We'll also look at Bohr's response: the extent to which Bohr connects with what Einstein was after in EPR and the extent to which EPR marks a shift in Bohr's thinking about the quantum theory. Time permitting, we will contrast EPR with Bell's theorem.

  9. 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.

  10. EPR of radiation defects in lithium-oxyfluoride glass ceramics

    NASA Astrophysics Data System (ADS)

    Fedotovs, A.; Rogulis, U.; Sarakovskis, A.; Dimitrocenko, L.

    2010-11-01

    We studied oxyfluoride composites based on lithium silicate glasses with yttrium fluorides and rare-earth dopants. The electron paramagnetic resonance (EPR) has been used to obtain information about radiation induced defects in these materials. Spectra have been measured before and after X-ray irradiation at room temperature and at liquid nitrogen temperature. Fluoride crystallites within samples were created by means of thermal treatment at specific temperatures. EPR spectra of radiation induced defects in oxyfluoride glass ceramics, in which crystallites have not been yet created, show no explicit hfs interaction of fluorine nuclei. However, in glass ceramics, which already contains fluoride crystallites, the hfs characteristic to fluorine nuclei appears in the EPR spectra. EPR hyperfine structure could be explained within a model of an F-type centre in YF3 crystalline phase.

  11. Software for evaluation of EPR-dosimetry performance.

    PubMed

    Shishkina, E A; Timofeev, Yu S; Ivanov, D V

    2014-06-01

    Electron paramagnetic resonance (EPR) with tooth enamel is a method extensively used for retrospective external dosimetry. Different research groups apply different equipment, sample preparation procedures and spectrum processing algorithms for EPR dosimetry. A uniform algorithm for description and comparison of performances was designed and implemented in a new computer code. The aim of the paper is to introduce the new software 'EPR-dosimetry performance'. The computer code is a user-friendly tool for providing a full description of method-specific capabilities of EPR tooth dosimetry, from metrological characteristics to practical limitations in applications. The software designed for scientists and engineers has several applications, including support of method calibration by evaluation of calibration parameters, evaluation of critical value and detection limit for registration of radiation-induced signal amplitude, estimation of critical value and detection limit for dose evaluation, estimation of minimal detectable value for anthropogenic dose assessment and description of method uncertainty.

  12. A comparative study of EPR projects in Denmark.

    PubMed

    Andersen, Stig Kjaer; Nøhr, Christian; Vingtoft, Søren; Bernstein, Knut; Rasmussen, Morten Bruun

    2002-01-01

    The EPR-Observatory--a public funded project organization--has monitored Danish EPR-projects with respect to various parameters such as diffusion and diffusion rate, barriers and limitations, experience gained. Furthermore, the Observatory has aggregated and disseminated the results and has established a constructive dialogue between the Danish EPR projects. The Observatory has also focused in the later years on analysis of common frames of reference for EPR systems. The National Board of Health and some of the larger counties have developed such frames. First generation systems have been implemented in a few counties with moderate coverage, but a number of projects developing second generation systems are making progress, and the market situation is quickly maturing. There are still, however, major problems in the practical implementation of the systems.

  13. High-frequency EPR study of crude oils

    NASA Astrophysics Data System (ADS)

    Volodin, M. A.; Mamin, G. V.; Izotov, V. V.; Orlinskii, S. B.

    2013-12-01

    Four different samples of crude oil were studied by means of high-frequency W-band (94 GHz) electron paramagnetic resonance (EPR) spectroscopy with the aim to develop new methods of crude oil quality control. High spectral resolution of W-band allowed to avoid an overlap of spectra contributors. The ratio K between the integral intensity of the low-field EPR component of the vanadyl complexes to that of free radical line was chosen as an attribute of each sample. Using the K-parameters and EPR spectra simulations the crude oil leaking between adjacent horizons is shown. Pulsed EPR experiments allowed detecting free radicals signals only. It is demonstrated that the extracted transverse relaxation time could be used as an additional parameter which characterizes the origin of the crude oil and nature of the oil paramagnetic centers.

  14. Simultaneous acquisition of pulse EPR orientation selective spectra

    NASA Astrophysics Data System (ADS)

    Kaminker, Ilia; Florent, Marc; Epel, Boris; Goldfarb, Daniella

    2011-01-01

    High resolution pulse EPR methods are usually applied to resolve weak magnetic electron-nuclear or electron-electron interactions that are otherwise unresolved in the EPR spectrum. Complete information regarding different magnetic interactions, namely, principal components and orientation of principal axis system with respect to the molecular frame, can be derived from orientation selective pulsed EPR measurements that are performed at different magnetic field positions within the inhomogeneously broadened EPR spectrum. These experiments are usually carried out consecutively, namely a particular field position is chosen, data are accumulated until the signal to noise ratio is satisfactory, and then the next field position is chosen and data are accumulated. Here we present a new approach for data acquisition of pulsed EPR experiments referred to as parallel acquisition. It is applicable when the spectral width is much broader than the excitation bandwidth of the applied pulse sequence and it is particularly useful for orientation selective pulse EPR experiments. In this approach several pulse EPR measurements are performed within the waiting (repetition) time between consecutive pulse sequences during which spin lattice relaxation takes place. This is achieved by rapidly changing the main magnetic field, B0, to different values within the EPR spectrum, performing the same experiment on the otherwise idle spins. This scheme represents an efficient utilization of the spectrometer and provides the same spectral information in a shorter time. This approach is demonstrated on W-band orientation selective electron-nuclear double resonance (ENDOR), electron spin echo envelope modulation (ESEEM), electron-electron double resonance (ELDOR) - detected NMR and double electron-electron resonance (DEER) measurements on frozen solutions of nitroxides. We show that a factors of 3-6 reduction in total acquisition time can be obtained, depending on the experiment applied.

  15. 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.

  16. Emergency EPR and OSL dosimetry with table vitamins and minerals.

    PubMed

    Sholom, S; McKeever, S W S

    2016-12-01

    Several table vitamins, minerals and L-lysine amino acid have been preliminarily tested as potential emergency dosemeters using electron paramagnetic resonance (EPR) and optically stimulated luminescence (OSL) techniques. Radiation-induced EPR signals were detected in samples of vitamin B2 and L-lysine while samples of multivitamins of different brands as well as mineral Mg demonstrated prominent OSL signals after exposure to ionizing radiation doses. Basic dosimetric properties of the radiation-sensitive substances were studied, namely dose response, fading of the EPR or OSL signals and values of minimum measurable doses (MMDs). For EPR-sensitive samples, the EPR signal is converted into units of dose using a linear dose response and correcting for fading using the measured fading dependence. For OSL-sensitive materials, a multi-aliquot, enhanced-temperature protocol was developed to avoid the problem of sample sensitization and to minimize the influence of signal fading. The sample dose in this case is also evaluated using the dose response and fading curves. MMDs of the EPR-sensitive samples were below 2 Gy while those of the OSL-sensitive materials were below 500 mGy as long as the samples are analyzed within 1 week after exposure. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  17. Characterizing rhodopsin signaling by EPR spectroscopy: from structure to dynamics.

    PubMed

    Van Eps, Ned; Caro, Lydia N; Morizumi, Takefumi; Ernst, Oliver P

    2015-09-26

    Electron paramagnetic resonance (EPR) spectroscopy, together with spin labeling techniques, has played a major role in the characterization of rhodopsin, the photoreceptor protein and G protein-coupled receptor (GPCR) in rod cells. Two decades ago, these biophysical tools were the first to identify transmembrane helical movements in rhodopsin upon photo-activation, a critical step in the study of GPCR signaling. EPR methods were employed to identify functional loop dynamics within rhodopsin, to measure light-induced millisecond timescale changes in rhodopsin conformation, to characterize the effects of partial agonists on the apoprotein opsin, and to study lipid interactions with rhodopsin. With the emergence of advanced pulsed EPR techniques, the stage was set to determine the amplitude of structural changes in rhodopsin and the dynamics in the rhodopsin signaling complexes. Work in this area has yielded invaluable information about mechanistic properties of GPCRs. Using EPR techniques, receptors are studied in native-like membrane environments and the effects of lipids on conformational equilibria can be explored. This perspective addresses the impact of EPR methods on rhodopsin and GPCR structural biology, highlighting historical discoveries made with spin labeling techniques, and outlining exciting new directions in the field.

  18. Novel EPR characterization of the antioxidant activity of tea leaves

    NASA Astrophysics Data System (ADS)

    Morsy, M. A.; Khaled, M. M.

    2002-04-01

    Electron paramagnetic resonance (EPR) spectroscopy is utilized to investigate several categories of green and black tea: Twining green tea (TGT), Chinese green tea (CGT), Red-labels black tea (RBT). Basically, two EPR signals from all the studied samples are observed: One of them is a very weak sharp EPR signal with Δ Hpp≅10 G and g-factor=2.00023 superimposed on the other broad signal with Δ Hpp≅550 G and g-factor=2.02489. The broad signal is a characteristic one of manganese(II) complex, while the sharp signal is related to a stable radical of aromatic origin exist in a powder condition. The feature of the manganese EPR signal is attributed to manganese(II) complex and reflected the molecular behavior of Mn(II) in the protein system of the natural leaves. The sharp signal, which is most probably due to a semiquinones radicals, is observed at room temperature and its intensity is remarkably affected by photo degradation of the studied samples. The intensity of manganese(II) EPR signal is found to be related to ageing and disintegration of the tea leaves. Moreover, direct relation between the relative intensity of the semiquinones radical signal and antioxidant activity of the studied samples was also correlated.

  19. Accelerated dynamic EPR imaging using fast acquisition and compressive recovery

    NASA Astrophysics Data System (ADS)

    Ahmad, Rizwan; Samouilov, Alexandre; Zweier, Jay L.

    2016-12-01

    Electron paramagnetic resonance (EPR) allows quantitative imaging of tissue redox status, which provides important information about ischemic syndromes, cancer and other pathologies. For continuous wave EPR imaging, however, poor signal-to-noise ratio and low acquisition efficiency limit its ability to image dynamic processes in vivo including tissue redox, where conditions can change rapidly. Here, we present a data acquisition and processing framework that couples fast acquisition with compressive sensing-inspired image recovery to enable EPR-based redox imaging with high spatial and temporal resolutions. The fast acquisition (FA) allows collecting more, albeit noisier, projections in a given scan time. The composite regularization based processing method, called spatio-temporal adaptive recovery (STAR), not only exploits sparsity in multiple representations of the spatio-temporal image but also adaptively adjusts the regularization strength for each representation based on its inherent level of the sparsity. As a result, STAR adjusts to the disparity in the level of sparsity across multiple representations, without introducing any tuning parameter. Our simulation and phantom imaging studies indicate that a combination of fast acquisition and STAR (FASTAR) enables high-fidelity recovery of volumetric image series, with each volumetric image employing less than 10 s of scan. In addition to image fidelity, the time constants derived from FASTAR also match closely to the ground truth even when a small number of projections are used for recovery. This development will enhance the capability of EPR to study fast dynamic processes that cannot be investigated using existing EPR imaging techniques.

  20. Accelerated dynamic EPR imaging using fast acquisition and compressive recovery.

    PubMed

    Ahmad, Rizwan; Samouilov, Alexandre; Zweier, Jay L

    2016-12-01

    Electron paramagnetic resonance (EPR) allows quantitative imaging of tissue redox status, which provides important information about ischemic syndromes, cancer and other pathologies. For continuous wave EPR imaging, however, poor signal-to-noise ratio and low acquisition efficiency limit its ability to image dynamic processes in vivo including tissue redox, where conditions can change rapidly. Here, we present a data acquisition and processing framework that couples fast acquisition with compressive sensing-inspired image recovery to enable EPR-based redox imaging with high spatial and temporal resolutions. The fast acquisition (FA) allows collecting more, albeit noisier, projections in a given scan time. The composite regularization based processing method, called spatio-temporal adaptive recovery (STAR), not only exploits sparsity in multiple representations of the spatio-temporal image but also adaptively adjusts the regularization strength for each representation based on its inherent level of the sparsity. As a result, STAR adjusts to the disparity in the level of sparsity across multiple representations, without introducing any tuning parameter. Our simulation and phantom imaging studies indicate that a combination of fast acquisition and STAR (FASTAR) enables high-fidelity recovery of volumetric image series, with each volumetric image employing less than 10 s of scan. In addition to image fidelity, the time constants derived from FASTAR also match closely to the ground truth even when a small number of projections are used for recovery. This development will enhance the capability of EPR to study fast dynamic processes that cannot be investigated using existing EPR imaging techniques.

  1. 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.

  2. EPR/Homotaurine: A possible dosimetry system for high doses

    NASA Astrophysics Data System (ADS)

    Maghraby, A.; Salama, E.; Mansour, A.

    2011-12-01

    An EPR investigation of radiation induced radicals in Homotaurine revealed that there are two types of radicals produced after exposure to gamma radiation (60Co). EPR spectra were recorded and analyzed; also the microwave power saturation curves for both radicals were studied. The effect of change in modulation amplitude on peak-to-peak signal height and line width was investigated; this is in addition to the evaluation of energy dependence parameters compared to soft tissue and alanine dosimeters. Response of Homotaurine to different radiation doses (0.5 kGy-50 kGy) was studied and found to follow a linear relationship. Radiation induced radicals in Homotaurine persisted and showed a noticeable stability over 30 days following irradiation. It was found that Homotaurine possesses good dosimetric properties using EPR spectroscopy in high doses and is characterized by its simple spectrum.

  3. Identification and dosimetry of irradiated walnuts (Juglans regia) using EPR

    NASA Astrophysics Data System (ADS)

    Maghraby, A.; Salama, E.; Sami, A.; Mansour, A.; El-Sayed, M.

    2012-03-01

    Electron paramagnetic resonance (EPR) is an easy, fast, and reliable tool for identification of irradiated food. Untreated nuts may encounter hazards of carrying several pathogens or microbial contamination; walnuts are of specific importance due to their nutritional and medicinal values, and hence walnut processing via gamma irradiation is a necessary step. EPR was employed for the identification and dosimetry of Cs-137 gamma-irradiated walnuts (shells and kernels). Several important parameters were studied, such as spectral features, microwave power dependence of signal intensities, and short- and long-term time dependences. Responses of walnut shells and kernels to different radiation doses in the range 0-10 kGy were investigated. Results confirmed that EPR is a suitable tool for the identification and dosimetry of irradiated walnuts using either their shells or only kernels.

  4. Radiation accident dosimetry on plastics by EPR spectrometry.

    PubMed

    Trompier, F; Bassinet, C; Clairand, I

    2010-02-01

    In case of acute exposure to ionizing radiation, the dose absorbed by the victims has to be rapidly and accurately assessed in order to choose an appropriate medical treatment. Tooth enamel and bone biopsies measured by EPR spectrometry are often used as dose indicators, due to the good radiation sensitivity and the stability of EPR radiation-sensitive signals. Nevertheless, the invasive sampling of teeth and bones limits the application of this technique to retrospective dosimetry. Therefore, we have investigated an alternative non-invasive methodology. We have surveyed with EPR spectrometry the dosimetric properties of the plastics that can be found in personal effects such as glasses (CR-39, polycarbonate), mobile phones (PMMA, polycarbonate), watches and buttons. Dose response, signal stability and effects of storage conditions were investigated. Significant signal fading limits the use for radiation accident dosimetry. Few plastics present the required characteristics to be used in case of a radiation accident.

  5. Free radicals and antioxidants at a glance using EPR spectroscopy.

    PubMed

    Spasojević, Ivan

    2011-01-01

    The delicate balance between the advantageous and detrimental effects of free radicals is one of the important aspects of human (patho)physiology. The controlled production of reactive oxygen and nitrogen species has an essential role in the regulation of various signaling switches. On the other hand, imbalanced generation of radicals is highly correlated with the pathogenesis of many diseases which require the application of selected antioxidants to regain the homeostasis. In the era of growing interest for redox processes, electron paramagnetic resonance (EPR) spectroscopy is arguably the best-suited technique for such research due to its ability to provide a unique insight into the world of free radicals and antioxidants. Herein, I present the principles of EPR spectroscopy and the applications of this method in assessing: (i) the oxidative status of biological systems, using endogenous long-lived free radicals (ascorbyl radical (Asc(•)), tocopheroxyl radical (TO(•)), melanin) as markers; (ii) the production of short-lived radicals (hydroxyl radical (OH(•)), superoxide radical anion (O(2)(•-)), sulfur- and carbon-centered radicals), which are implicated in both, oxidative stress and redox signaling; (iii) the metabolism of nitric oxide (NO(•)); (iv) the antioxidative properties of various drugs, compounds, and natural products; (v) other redox-relevant parameter. Besides giving a comprehensive survey of up-to-date literature, I also provide illustrative examples in sufficient detail to provide a means to exploit the potential of EPR in biochemical/physiological/medical research. The emphasis is on the features and characteristics (both positive and negative) relevant for EPR application in clinical sciences. My aim is to encourage fellow colleagues interested in free radicals and antioxidants to expand their base knowledge or methods used in their laboratories with data acquired by EPR or some of the EPR techniques outlined in this review, in order to

  6. Comparison of Continuous Wave, Spin Echo, and Rapid Scan EPR of Irradiated Fused Quartz.

    PubMed

    Mitchell, Deborah G; Quine, Richard W; Tseitlin, Mark; Meyer, Virginia; Eaton, Sandra S; Eaton, Gareth R

    2011-09-01

    The E' defect in irradiated fused quartz has spin lattice relaxation times (T(1)) about 100 to 300 μs and spin-spin relaxation times (T(2)) up to about 200 μs, depending on the concentration of defects and other species in the sample. These long relaxation times make it difficult to record an unsaturated continuous wave (CW) electron paramagnetic resonance (EPR) signal that is free of passage effects. Signals measured at X-band (~9.5 GHz) by three EPR methods: conventional slow-scan field modulated EPR, rapid scan EPR, and pulsed EPR, were compared. To acquire spectra with comparable signal-to-noise, both pulsed and rapid scan EPR require less time than conventional CW EPR. Rapid scan spectroscopy does not require the high power amplifiers that are needed for pulsed EPR. The pulsed spectra, and rapid scan spectra obtained by deconvolution of the experimental data, are free of passage effects.

  7. 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.

  8. Shaped optimal control pulses for increased excitation bandwidth in EPR.

    PubMed

    Spindler, Philipp E; Zhang, Yun; Endeward, Burkhard; Gershernzon, Naum; Skinner, Thomas E; Glaser, Steffen J; Prisner, Thomas F

    2012-05-01

    A 1 ns resolution pulse shaping unit has been developed for pulsed EPR spectroscopy to enable 14-bit amplitude and phase modulation. Shaped broadband excitation pulses designed using optimal control theory (OCT) have been tested with this device at X-band frequency (9 GHz). FT-EPR experiments on organic radicals in solution have been performed with the new pulses, designed for uniform excitation over a significantly increased bandwidth compared to a classical rectangular π/2 pulse of the same B(1) amplitude. The concept of a dead-time compensated prefocused pulse has been introduced to EPR with a self-refocusing of 200 ns after the end of the pulse. Echo-like refocused signals have been recorded and compared to the performance of a classical Hahn-echo sequence. The impulse response function of the microwave setup has been measured and incorporated into the algorithm for designing OCT pulses, resulting in further significant improvements in performance. Experimental limitations and potential new applications of OCT pulses in EPR spectroscopy will be discussed.

  9. Quantitative rapid scan EPR spectroscopy at 258 MHz.

    PubMed

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

    2010-07-01

    Experimental data obtained with an electron paramagnetic resonance (EPR) rapid scan spectrometer were translated through the reverse transfer functions of the spectrometer hardware to the sample position. Separately, theoretical calculations were performed to predict signal and noise amplitudes at the sample position for specified experimental conditions. A comparison was then made between the translated experimental values and the calculated values. Excellent agreement was obtained.

  10. 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.

  11. 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

  12. Metamorphic modifications and EPR dosimetry in tooth enamel.

    PubMed

    Brik, A; Radchuk, V; Scherbina, O; Matyash, M; Gaver, O

    1996-01-01

    It is shown that metamorphic modifications in tooth enamel have an essential influence on the results of EPR dosimetry. The metamorphic modifications in minerals of biological origin proceed more quickly than in usual natural minerals. The approaches which at present are applied for reconstruction of doses connected with Chernobyl accident need additional investigation.

  13. Exploiting EPR in polymer drug conjugate delivery for tumor targeting.

    PubMed

    Modi, Sweta; Prakash Jain, Jay; Domb, A J; Kumar, Neeraj

    2006-01-01

    Treatment of tumor tissue without affecting normal cells has always been formidable task for drug delivery scientists and this task is effectively executed by polymer drug conjugate (PDC) delivery. The novelty of this concept lies in the utilization of a physical mechanism called enhanced permeability and retention (EPR) for targeting tumors. EPR is a physiological phenomenon that is customary for fast growing tumor and solves the problem of targeting the miscreant tissue. PDCs offer added advantages of reduced deleterious effects of anticancer drugs and augmentation of its formulation capability (e.g. Solubility). There are now at least eleven PDCs that have entered phase I/II/III clinical trial as anticancer drugs. PDCs once entered into the tumor tissue, taking advantage of EPR, are endocytosed into the cell either by simple or receptor mediated endocytosis. Various polymeric carriers have been used with hydrolyzable linker arm for conjugation with bioactive moiety. The hydrolyzable linkages of PDC are broken down by acid hydrolyses of lysosomes and releases the drug. High concentrations of the chemotherapeutic agent are maintained near the nucleus, the target site. Passive targeting by PDCs is due to the physiological event of EPR, which is becoming one of the major thrust areas for targeting solid tumors.

  14. EPR Assembly of Microgel for FRET Imaging of Breast Cancer

    DTIC Science & Technology

    2007-04-01

    EPR studies have been completed with polymer-hilyte and polymer-fluorescein conjugates. More exhaustive studies using larger mice population are...PNAs): A new generation of probes for genetic and cytogenetic analyses, Annales De Genetique 2004, 47, 349-358.

  15. 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

  16. 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

  17. 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.

  18. Kinetic measurements using EPR imaging with a modulated field gradient.

    PubMed

    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.

  19. 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.

  20. A sensitive EPR dosimetry system based on sulfamic acid

    NASA Astrophysics Data System (ADS)

    Maghraby, A.

    2007-08-01

    There is a need for a sensitive dosimeter using electron paramagnetic resonance spectroscopy (EPR) for use in medical applications, since with this method non-destructive read-out and dose archival could be achieved. Sulfamic acid as a possible detector substance was investigated before and after irradiation, its EPR spectra were recorded and analyzed, some dosimetric characteristics were studied: microwave power saturation behavior, the effect of modulation amplitude on peak-to-peak signal intensity and the line width. Energy-dependence parameters were compared to soft tissue and alanine, and the response to ionizing radiation was studied, also the decay behavior along 133 days after irradiation is presented. It is found that sulfamic acid possesses high-sensitivity and reasonable signal stability which may make it useful as a sensitive dosimeter for medical applications.

  1. On the computer simulation of the EPR-Bohm experiment

    SciTech Connect

    McGoveran, D.O.; Noyes, H.P.; Manthey, M.J.

    1988-12-01

    We argue that supraluminal correlation without supraluminal signaling is a necessary consequence of any finite and discrete model for physics. Every day, the commercial and military practice of using encrypted communication based on correlated, pseudo-random signals illustrates this possibility. All that is needed are two levels of computational complexity which preclude using a smaller system to detect departures from ''randomness'' in the larger system. Hence the experimental realizations of the EPR-Bohm experiment leave open the question of whether the world of experience is ''random'' or pseudo-random. The latter possibility could be demonstrated experimentally if a complexity parameter related to the arm length and switching time in an Aspect-type realization of the EPR-Bohm experiment is sufficiently small compared to the number of reliable total counts which can be obtained in practice. 6 refs.

  2. Identification and dose assessment of irradiated cumin by EPR spectrometry.

    PubMed

    Abdel-Fattah, A A

    2002-03-01

    The use of electron paramagnetic resonance spectroscopy to accurately distinguish irradiated from unirradiated cumin and assess the absorbed dose to radiation-processed cumin is examined. The results were successful for identifying both irradiated and unirradiated cumin. Additive reirradiation of the cumin produces a reproducible dose response function, which can be used to assess the initial dose by back-extrapolation. Third-degree polynomial and exponential functions were used to fit the EPR signal/dose curves. It was found that the 3rd degree polynomial function provides satisfactory results without correction for decay of free radicals. The exponential fit to the data cannot be used without correction of decay of free radicals. The stability of the radiation-induced EPR signal of irradiated cumin was studied over a storage period of 6 months. The additive reirradiation of some samples was carried out at different storage times (10, 20 and 30 days) after initial irradiation.

  3. Electron beam radiation effects on UHMWPE: an EPR study.

    PubMed

    Brunella, Valentina; Paganini, Maria Cristina

    2011-09-01

    Electron paramagnetic resonance (EPR) technique has been employed to detect and characterise a series of different radical species generated in ultra-high molecular weight polyethylene (UHMWPE) via electron beam irradiation. Three different radical species have been found and assigned on the basis of their EPR spectra and of the related computer simulations. A secondary alkyl species, the prevalent one, is present immediately after irradiation, an allyl species appears only 24 h after irradiation when the alkyl species disappears.The third species, clearly visible at high microwave power only, has been observed for the first time and assigned to a tertiary alkyl carbon radical, whose formation is strictly connected with a Y-shape crosslink and a migration of the unpaired electron on a carbon atom localised in an adjacent position.

  4. Phase Pinning by EPR Probe in Biphenyl Doped with Naphthalene

    NASA Astrophysics Data System (ADS)

    Veron, A.; Emery, J.

    1997-08-01

    The naphthalene Electronic Paramagnetic Resonance probe used to study the phase transitions in biphenyl does not account for the plane wave modulation of the incommensurate phase II. Its EPR spectra yields a phase distribution which looks like a “multi-soliton regime”. Moreover, the splitting between the edge singularities is not symmetrical, in contradiction with a linear one. This behaviour is not exhibited by the phenanthrene EPR probe whose spectra account well enough for the plane wave modulation with a linear coupling to the order parameter. To analyse the defect behaviour of the probe, we first introduce a coupling between the probe and the modulation wave and determine the phase distribution within the phenomenological Landau theory. Furthermore, a calculation based on intermolecular interaction is performed in order to describe the microscopic origin of this distribution and is applied to naphthalene and phenanthrene molecular probes.

  5. A transferability study of the EPR-tooth-dosimetry technique.

    PubMed

    Sholom, S; Chumak, V; Desrosiers, M; Bouville, A

    2006-01-01

    The transferability of a measurement protocol from one laboratory to another is an important feature of any mature, standardised protocol. The electron paramagnetic resonance (EPR)-tooth dosimetry technique that was developed in Scientific Center for Radiation Medicine, AMS, Ukraine (SCRM) for routine dosimetry of Chernobyl liquidators has demonstrated consistent results in several inter-laboratory measurement comparisons. Transferability to the EPR dosimetry laboratory at the National Institute of Standards and Technology (NIST) was examined. Several approaches were used to test the technique, including dose reconstruction of SCRM-NIST inter-comparison samples. The study has demonstrated full transferability of the technique and the possibility to reproduce results in a different laboratory environment.

  6. The Chernobyl accident: EPR dosimetry on dental enamel of children.

    PubMed

    Gualtieri, G; Colacicchi, S; Sgattoni, R; Giannoni, M

    2001-07-01

    The radiation dose on tooth enamel of children living close to Chernobyl has been evaluated by EPR. The sample preparation was reduced to a minimum of mechanical steps to remove a piece of enamel. A standard X-ray tube at low energy was used for additive irradiation. The filtration effect of facial soft tissue was taken into account. The radiation dose for a group of teeth slightly exceeds the annual dose, whereas for another group the dose very much exceeds the annual dose. Since the higher dose is found in teeth whose enamel have much lower EPR sensitivity to the radiation, it can be suggested that for these teeth the native signal could alter the evaluation of the smaller radiation signal.

  7. 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.

  8. 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.

  9. EPR study of spermine interaction with multilamellar phosphatidylcholine liposomes.

    PubMed

    Momo, F; Wisniewska, A; Stevanato, R

    1995-11-22

    The interaction of spermine with egg-yolk phosphatidylcholine liposomes was investigated. The EPR spin labeling technique evidenced that spermine induces modifications of some membrane functions of biological interest like water permeability and is a possible modulator of diffusion processes for charged and polar molecules. The association constant for a hypothesized complex between spermine and the phosphate group of phosphatidylcholine was evaluated by enzymatic methods.

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

    PubMed

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

    2010-04-09

    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.

  11. 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

  12. EPR and magnetism of the nanostructured natural carbonaceous material shungite

    NASA Astrophysics Data System (ADS)

    Augustyniak-Jabłokow, Maria Aldona; Yablokov, Yurii V.; Andrzejewski, Bartłomiej; Kempiński, Wojciech; Łoś, Szymon; Tadyszak, Krzysztof; Yablokov, Mikhail Y.; Zhikharev, Valentin A.

    2010-04-01

    The X-band EPR and magnetic susceptibility in the temperature range 4.2-300 K study of the shungite-I, natural nanostructured material from the deposit of Shunga are reported. Obtained results allow us to assign the EPR signal to conduction electrons, estimate their number, N P, and evaluate the Pauli paramagnetism contribution to shungite susceptibility. A small occupation (~5%) of the localized nonbonding π states in the zigzag edges of the open-ended graphene-like layers and/or on σ ( sp 2+ x ) orbitals in the curved parts of the shungite globules has been also revealed. The observed temperature dependence of the EPR linewidth can be explained by the earlier considered interaction of conduction π electrons with local phonon modes associated with the vibration of peripheral carbon atoms of the open zigzag-type edges and with peripheral carbon atoms cross-linking different nanostructures. The relaxation time T 2 and diffusion time T D are found to have comparable values (2.84 × 10-8 and 1.73 × 10-8 s at 5.2 K, respectively), and similar dependence on temperature. The magnetic measurements have revealed the suppression of orbital diamagnetism due to small amount of large enough fragments of the graphene layers.

  13. 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.

  14. Physical, Optical absorption and EPR studies on fluoro- bismuthate glasses

    NASA Astrophysics Data System (ADS)

    Srinivasu, Ch; Samee, M. A.; Edukondalu, A.; Laxmi Kanth, C.; Rahman, Syed

    2015-02-01

    Glasses of the xLiF-(50-x)Li2O-20SrO-30Bi2O3 system, with 0 <= x <= 20 mole % were studied by EPR and Optical measurements. The changes in both density and molar volume indicate structural modifications occur due to addition of LiF. The glass transition temperatures are observed to decrease with an increase in LiF content in the compositions. The local structure around Cu2+ ions has been examined by means of electron paramagnetic resonance and optical absorption measurements. It is observed that the spin-Hamiltonian parameters calculated from the EPR spectra are influenced by the glass composition. The Cu2+ ions are in well-defined axial sites but subjected to small distortion leading to the broadening of the spectra. The spin-Hamiltonian parameter values indicate that the ground state of Cu2+ is and the site symmetry around Cu2+ ions is tetragonally distorted octahedral. The optical absorption spectra exhibited a broad band corresponding to the d-d transition bands of Cu2+ ion. By correlating EPR and optical absorption data, the bond parameters are evaluated.

  15. Noble Gas Polarimetry Using Rb EPR Frequency Shifts

    NASA Astrophysics Data System (ADS)

    Ma, Z. L.; Jeong, K.; Houghtby, E.; Paskvan, T.; Limes, M. E.; Saam, B.

    2014-05-01

    EPR frequency shifts of optically polarized alkali-metal atoms can be exploited for polarimetry of noble-gas nuclei polarized by spin-exchange optical pumping. Our group recently measured the enhancement factor κ0 = 493 for Rb-129Xe, which characterizes the electron wave-function overlap during collisions and is crucial to the calibration of the frequency-shift for 129Xe polarimetry. This type of polarimetry is useful in several applications involving optically polarized 129Xe; our particular motivation is an in situ measurement of absolute 129Xe polarization within the optical pumping cell of a flow-through 129Xe polarizer. This application has some particular challenges, and we have initially observed some unexpected shifts in the 87Rb EPR frequency measurement on board the polarizer. In effort to disentangle these apparent systematic effects, we have constructed a separate experiment to characterize Rb EPR shifts for both 3He and 129Xe in sealed cells. We present results and analysis of these experiments and discuss implications for using this method in flow-through polarizers. NSF PHY-0855482

  16. 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

  17. 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.

  18. VHF EPR analysis of organic sulfur in coal

    SciTech Connect

    Clarkson, R.B.

    1991-01-01

    This report covers progress made in the first yearly quarter of a two year investigation using novel, very high frequency electron paramagnetic resonance (VHF EPR) spectroscopy techniques and instrumentation (one of only two W-band spectrometers in existence) developed earlier by these authors, to conduct further qualitative and quantitative studies of heteroatomic organic molecules in coal with particular emphasis on sulfur. Previous W-band (96 GHz) work is being extended to studies of new model compounds as well as 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. The preparation of radicals from compounds having widely varying structures and physical properties in a stable environment has long been a very difficult task. To address this problem, the refinement of several new and very useful methods of preparing of these stable free radicals in various glasses, at catalytic surfaces, and in solution, are presented in this first report. Free radical generation was accomplished by both UV photolysis as well as chemical oxidation/reduction techniques. By these methods, over 25 new compounds, often commercially derived from coal extracts, have been prepared and studied by conventional X-band EPR (9 GHz). Several representative W-band spectra are also presented.

  19. Thermally stimulated luminescence and EPR studies on topaz.

    PubMed

    Souza, Divanizia N; de Lima, José Fernandes; Valerio, Mário Ernesto G; Caldas, Linda V E

    2006-08-01

    In the present work, electron paramagnetic resonance (EPR) spectra and thermoluminescence (TL) emission of colourless natural topaz from Santo Antônio do Jacinto, Brazil, was studied as a function of thermal treatment and gamma irradiation dose, focussing on the use of this material as a radiation dosimeter. EPR measurements on "as-received" samples at room temperature provided signals in the region of about 500 at 5,000 G. The signal located around g approximately equal to 2, frequently attributed to (AlO(4))(0), increased with additional gamma dose and disappeared after thermal treatment at 500 degrees C for 1h. Irradiation after thermal treatment recovered this signal. The decay promoted by isochronal thermal treatment showed the (AlO(4))(0) defects to be directly related to the TL glows peaks. The variation of EPR spectrum with annealing temperature prior to irradiation showed that the variation of TL sensitivity is a consequence of the variation of the (AlO(4))(0) population.

  20. Toward 2D and 3D imaging of magnetic nanoparticles using EPR measurements

    SciTech Connect

    Coene, A. Crevecoeur, G.; Dupré, L.; Leliaert, J.

    2015-09-15

    Purpose: Magnetic nanoparticles (MNPs) are an important asset in many biomedical applications. An effective working of these applications requires an accurate knowledge of the spatial MNP distribution. A promising, noninvasive, and sensitive technique to visualize MNP distributions in vivo is electron paramagnetic resonance (EPR). Currently only 1D MNP distributions can be reconstructed. In this paper, the authors propose extending 1D EPR toward 2D and 3D using computer simulations to allow accurate imaging of MNP distributions. Methods: To find the MNP distribution belonging to EPR measurements, an inverse problem needs to be solved. The solution of this inverse problem highly depends on the stability of the inverse problem. The authors adapt 1D EPR imaging to realize the imaging of multidimensional MNP distributions. Furthermore, the authors introduce partial volume excitation in which only parts of the volume are imaged to increase stability of the inverse solution and to speed up the measurements. The authors simulate EPR measurements of different 2D and 3D MNP distributions and solve the inverse problem. The stability is evaluated by calculating the condition measure and by comparing the actual MNP distribution to the reconstructed MNP distribution. Based on these simulations, the authors define requirements for the EPR system to cope with the added dimensions. Moreover, the authors investigate how EPR measurements should be conducted to improve the stability of the associated inverse problem and to increase reconstruction quality. Results: The approach used in 1D EPR can only be employed for the reconstruction of small volumes in 2D and 3D EPRs due to numerical instability of the inverse solution. The authors performed EPR measurements of increasing cylindrical volumes and evaluated the condition measure. This showed that a reduction of the inherent symmetry in the EPR methodology is necessary. By reducing the symmetry of the EPR setup, quantitative images of

  1. Effect of aging on EPR cable electrical performance during LOCA simulations. [Ethylene propylene rubber

    SciTech Connect

    Bustard, L.D.

    1984-01-01

    When exposed to a LOCA environment, some ethylene propylene rubber (EPR) cable materials experience substantial moisture absorption and dimensional changes. These phenomena may contribute to mechanical damage of the cable insulation resulting in electrical degradation. Recent experiments illustrate that the extent of moisture absorption and dimensional changes during an accident simulation are dependent on the EPR product, the accelerated age, and the aging technique employed to achieve that age. Results for several commercial EPR materials are summarized.

  2. 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.

  3. An advanced EPR stopped-flow apparatus based on a dielectric ring resonator

    NASA Astrophysics Data System (ADS)

    Lassmann, Günter; Schmidt, Peter Paul; Lubitz, Wolfgang

    2005-02-01

    A novel EPR stopped-flow accessory is described which allows time-dependent cw-EPR measurements of rate constants of reactions involving paramagnetic species after rapid mixing of two liquid reagents. The EPR stopped-flow design represents a state-of-the-art, computer controlled fluid driving system, a miniresonant EPR structure with an integrated small ball mixer, and a stopping valve. The X-band EPR detection system is an improved version of that reported by Sienkiewicz et al. [Rev. Sci. Instr. 65 (1994) 68], and utilizes a resonator with two stacked ceramic dielectric rings separated by a variable spacer. The resonator with the mode TE( H) 011 is tailored particularly for conditions of fast flowing and rapidly stopped aqueous solutions, and for a high time resolution. The short distance between the ball mixer and the small EPR active volume (1.8 μl) yields a measured dead time of 330 μs. A compact assembly of all parts results in minimization of disturbing microphonics. The computer controlled driving system from BioLogic with two independent stepping motors was optimized for EPR stopped-flow with a hard-stop valve. Performance tests on the EPR spectrometer ESP 300E from BRUKER using redox reactions of nitroxide radicals revealed the EPR stopped-flow accessory as an advanced, versatile, and reliable instrument with high reproducibility.

  4. Dependencies of the radiation sensitivity of human tooth enamel in EPR dosimetry.

    PubMed

    Wieser, A; El-Faramawy, N; Meckbach, R

    2001-05-01

    The EPR dose response of tooth enamel was determined for human molars collected in Egypt. The influence of age, gender and residence of the tooth donors as well as tooth position and sample preparation on EPR sensitivity and its variability over the enamel samples was investigated. The EPR sensitivity and its variability were found to depend only on the sample preparation procedure. The variability in EPR sensitivity of enamel from Egyptian teeth was maximally 10% and the mean sensitivity was in good agreement with that of German teeth.

  5. 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

  6. Optical absorption near infrared and EPR studies of mottramite

    NASA Astrophysics Data System (ADS)

    Lakshmi Reddy, S.; Reddy, K. N. M.; Siva Reddy, G.; Endo, Tamio; Frost, R. L.

    2010-06-01

    Mottramite mineral from Tsumeb Corporation Mine, Tsumeb, Otavi, Namibia, is investigated in this present work. The mineral contains vanadium and copper contents of 22.73% and 16.84% by weight, respectively, as V2O5 and CuO. An electron paramagnetic resonance (EPR) study confirmed the presence of Cu(II) with g = 2.2. The optical absorption spectrum of mottramite indicates that Cu(II) is present in a rhombic environment. Near infrared results are due to water fundamentals.

  7. 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

  8. EPR identification of irradiated Monascus purpureus red pigment

    NASA Astrophysics Data System (ADS)

    Duliu, Octavian G.; Ferdes, Mariana; Ferdes, Ovidiu S.

    2000-01-01

    Fresh red alimentary pigment extracted from Monascus purpureus fungus exhibits an intense EPR line consisting of a single, narrow line, attributed to a quinone radical. When irradiated with 7 MeV electrons or 60Co γ-rays, the amplitude of this line increased with the absorbed dose following a saturation exponential dependency up to 10 kGy. During annealing treatment (isothermal heating at 100°C) the irradiation centers decay exponentially with a half-life time of 2.30 min.

  9. A signal-to-noise standard for pulsed EPR.

    PubMed

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

    2010-07-01

    A 2 mm diameter by 10mm long cylinder of fused SiO2 (quartz) gamma-irradiated to 1 kGy with 60Co contains about 2x10(16) 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.

  10. 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

  11. 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.

  12. Use of Rapid-Scan EPR to Improve Detection Sensitivity for Spin-Trapped Radicals

    PubMed Central

    Mitchell, Deborah G.; Rosen, Gerald M.; Tseitlin, Mark; Symmes, Breanna; Eaton, Sandra S.; Eaton, Gareth R.

    2013-01-01

    The short lifetime of superoxide and the low rates of formation expected in vivo make detection by standard continuous wave (CW) electron paramagnetic resonance (EPR) challenging. The new rapid-scan EPR method offers improved sensitivity for these types of samples. In rapid-scan EPR, the magnetic field is scanned through resonance in a time that is short relative to electron spin relaxation times, and data are processed to obtain the absorption spectrum. To validate the application of rapid-scan EPR to spin trapping, superoxide was generated by the reaction of xanthine oxidase and hypoxanthine with rates of 0.1–6.0 μM/min and trapped with 5-tert-butoxycarbonyl-5-methyl-1-pyrroline-N-oxide (BMPO). Spin trapping with BMPO to form the BMPO-OOH adduct converts the very short-lived superoxide radical into a more stable spin adduct. There is good agreement between the hyperfine splitting parameters obtained for BMPO-OOH by CW and rapid-scan EPR. For the same signal acquisition time, the signal/noise ratio is >40 times higher for rapid-scan than for CW EPR. Rapid-scan EPR can detect superoxide produced by Enterococcus faecalis at rates that are too low for detection by CW EPR. PMID:23870255

  13. Photodegradation of hyaluronic acid: EPR and size exclusion chromatography study.

    PubMed

    Lapcík, L; Chabrecek, P; Stasko, A

    1991-10-15

    Photochemically induced radical reactions involving the lateral sequences and the end macromolecular chain groups of hyaluronic acid in aqueous solutions at 293K were studied by EPR spin trapping technique with DMPO (5,5-dimethylpyrroline-1-oxide). In the first 1-10 minutes of irradiation EPR indicates spin adducts of two carbon centered radicals with the splitting constants of aN = 1.60 mT, aH = 2.51 mT and aN = 1.56 mT, aH = 2.28 mT. After longer irradiation time (over 10 minutes) dominate two further DMPO adducts of radicals centered on hetero-atoms with splitting constants of aN = 1.44 mT, aH = 1.60 mT and of aN = 1.49 mT, aH = 1.49 mT. Simultaneously, molecular weight followed by SEC decreases, suggesting that UV irradiation leads to the breaking of interglycosidic bonds of hyaluronic acid main macromolecular chain.

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

    PubMed

    Suess, Daniel L M; Britt, R David

    2015-09-01

    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 (57)Fe 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.

  15. Radiation induced EPR centers in foodstuffs and inorganic materials.

    PubMed

    Pilbrow, J R; Troup, G J; Hutton, D R; Rosengarten, G; Zhong, Y C; Hunter, C R

    1993-01-01

    EPR investigations of a variety of irradiated materials have provided the potential for useful dosimetry applications. Herbs and spices imported into Australia have been investigated to establish whether or not they have been irradiated. Post-irradiation studies have shown that there is more than one free radical species in most cases which decay rapidly with time. Changes to transition metal ion signals, e.g., Cu2+ or Fe3+, appear to be permanent against further irradiation. Thus if these signals change upon irradiation, the material almost certainly has not previously been irradiated. Power saturation studies of alanine, a favored dosimetry material, suggest two distinguishable types of behavior consistent with the presence of spin-flip transitions. Irradiation of vanadium doped beryl yields stable VO2+ ions which may provide a useful dosimetry material. Dosimetry applications would appear to demand low cost, user friendly, automated EPR spectrometers. A patented option based on a 2.5 GHz microstrip microwave bridge will be described briefly.

  16. EPR properties of synthetic apatites, deorganified dentine, and enamel.

    PubMed

    Kenner, G H; Haskell, E H; Hayes, R B; Baig, A; Higuchi, W I

    1998-05-01

    Electron paramagnetic resonance spectroscopy (EPR) was used to study synthetic hydroxyapatite and approximately 1, 2, and 6% synthetic carbonated apatites, deorganified dentine, and enamel. The carbonated apatites were synthesized by hydrolysis of dicalcium phosphate. Comparisons were made with spectra from enamel and deorganified dentine. Microwave power saturation and dose responses were determined for the synthetic materials. The Marquardt version of the Levenberg decomposition method was used to extract individual signals from the apatite data. Two samples of dentine were irradiated with 25 and 100 Gy, respectively, from a 60Co source. The first sample was then deorganified at 200 degreesC using the Soxhlet extraction technique. A third sample was irradiated with 100 Gy after deorganification. The resulting EPR spectra were then compared. It was determined that the dosimetric signal of 2% synthetic carbonated apatite was approximately the same as that of enamel. It was also verified that the dosimetric signal saturates at about 2% in synthetic carbonated apatites. The study established that the precenters responsible for the dosimetric signal (g perpendicular = 2.0018, g parallel = 1.9985) are preferentially concentrated in the surface-accessible region of the mineral component, as shown by the approximately 80% attenuation of the dosimetric signal in dentine following deorganification. The precenters responsible are not destroyed by the deorganification since the magnitude of the dosimetric signal from the dentine specimen irradiated following deorganification was approximately twice that of the comparable untreated, irradiated sample. Finally, the dose response of 2 and 6% synthetic carbonated apatites was determined.

  17. EPR evidence for maghemitization of magnetite in a tropical soil

    NASA Astrophysics Data System (ADS)

    Fischer, H.; Luster, J.; Gehring, A. U.

    2007-06-01

    Electron paramagnetic spectroscopy (EPR) was used in combination with standard rock magnetic methods to study magnetic minerals in a tropical soil. The susceptibility and hysteresis measurements showed magnetite grains with a Curie temperature near 850 K as the dominant magnetic remanence carriers in the soil. A minor Ti content in the magnetite was found by energy dispersive X-ray analysis. In order to get insight into the weathering status of the magnetite, different chemical treatments, including oxalate and citrate-bicarbonate-dithionite (CBD) extraction, were applied to the soil samples. The hysteretic properties exhibited no significant differences between the untreated and the CBD or oxalate treated samples. By contrast, the comparison of the EPR spectra revealed a significant broadening of the linewidth (δB) and a shift of the g-values (geff) to lower fields after the CBD treatment. Furthermore, the spectral parameters geff and δB exhibited an angular dependence. At low temperature, the CBD treated samples showed a jump in δB between 120 and 100 K, the temperature range characteristic for the Verwey transition in magnetite. The changes in the spectral properties after the CBD treatment, which dissolves ferric oxides, were attributed to the removal of maghemite formed by the oxidation of magnetite, that is, during the maghemitization of the magnetite grains.

  18. 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.

  19. Tooth enamel EPR dosimetry: optimization of EPR spectra recording parameters and effect of sample mass on spectral sensitivity.

    PubMed

    Zhumadilov, Kassym; Ivannikov, Alexander; Skvortsov, Valeriy; Stepanenko, Valeriy; Zhumadilov, Zhaxybay; Endo, Satoru; Tanaka, Kenichi; Hoshi, Masaharu

    2005-12-01

    In order to improve the accuracy of the tooth enamel EPR dosimetry method, EPR spectra recording conditions were optimized. The uncertainty of dose determination was obtained as the mean square deviation of doses, determined with the use of a spectra deconvolution program, from the nominal doses for ten enamel samples irradiated in the range from 0 to 500 mGy. The spectra were recorded at different microwave powers and accumulation times. It was shown that minimal uncertainty is achieved at the microwave power of about 2 mW for a used spectrometer JEOL JES-FA100. It was found that a limit of the accumulation time exists beyond which uncertainty reduction is ineffective. At an established total time of measurement, reduced uncertainty is obtained by averaging the experimental doses determined from recorded spectra following intermittent sample shaking and sample tube rotation, rather than from one spectrum recorded at longer accumulation time. The effect of sample mass on the spectrometer's sensitivity was investigated in order to find out how to make appropriate corrections.

  20. EPR imaging of diffusional processes in biologically relevant polymers

    NASA Astrophysics Data System (ADS)

    Berliner, Lawrence J.; Fujii, Hirotada

    Diffusion processes in biological tissue are important problems for noninvasive investigation. As a model study, this work addresses the diffusion of an electrolyte buffer (Krebs) solution containing a nitroxide spin probe into a cylindrical polyacrylamide gel rod. The nitroxide spin density distribution was imaged at 1.6 GHz in gel cross sections at various time intervals for both homogeneous radial diffusion and inhomogeneous diffusion. A one-dimensional radial diffusion constant was calculated for the nitroxide spin probe, TEMPOL, of 3.7 ± 0.7 × 10 -6 cm 2/s at ambient temperature. The EPR spectrometer, using low-field flat-loop surface coils (H. Nishikawa, H. Fujii, and L. J. Berliner, J. Magn. Reson.62, 79 (1985)), showed minimal dielectric or magnetic losses in sensitity for electrolyte vs nondielectric samples.

  1. 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

  2. DLTS and EPR study of defects in H implanted silicon

    NASA Astrophysics Data System (ADS)

    Mikšić, V.; Pivac, B.; Rakvin, B.; Zorc, H.; Corni, F.; Tonini, R.; Ottaviani, G.

    2002-01-01

    Single crystal CZ Si samples were implanted with hydrogen ions to the dose of 2E16 He ions/cm 2 at room temperature and subsequently annealed in vacuum in the temperature interval from 100 to 900 °C. The aim of the experiment was to determine the conditions for bubble formation within the solid film, which may have important technological application. Defects produced in such samples were studied by deep-level transient spectroscopy (DLTS) and electron paramagnetic resonance (EPR) spectroscopy. It is shown that high dose hydrogen implantation produces vacancy-related and silicon selfinterstitial clusters. The latter are thought to be responsible for the formation of the weak displacement field. The annealing at higher temperatures creates multivacancy-related clusters responsible for the strong displacement field formation.

  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. General and efficient simulation of pulse EPR spectra.

    PubMed

    Stoll, Stefan; Britt, R David

    2009-08-21

    We present a rather general and efficient method of simulating electron-spin echo spectra for spin systems where the microwave frequency does not simultaneously excite EPR transitions that share a common level. The approach can handle arbitrary pulse sequences with microwave pulses of arbitrary length and strength. The signal is computed as a sum over signals from the electron coherence transfer pathways contributing to the detected echo. For each pathway, amplitudes and frequencies of the signal components are computed and used to construct a spectral histogram from which the time-domain signal is obtained. For multinuclear spin systems, the nuclear subspace is factorized to accelerate the computation. The method is also applicable to high electron spin systems with significant zero-field splitting and to pulse electron-nuclear double resonance experiments. The method is implemented in the software package EasySpin, and several illustrative calculations are shown.

  5. 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.

  6. 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.

  7. Prediction of nitroxide spin label EPR spectra from MD trajectories: application to myoglobin.

    PubMed

    Kuprusevicius, Egidijus; White, Gaye; Oganesyan, Vasily S

    2011-01-01

    We report the prediction of motional EPR spectra of the metalloprotein sperm whale myoglobin spin labelled with nitroxide directly from Molecular Dynamics (MD) simulations at the atomistic scale. We show that an accurate simulation of EPR spectra can be achieved from a single MD trajectory which is in excellent agreement with experiment. Simulations have been carried out using a general method reported previously by us for the simulation of EPR spectra form single dynamical trajectories. Our calculations demonstrate the complex nature of the dynamics of a spin label which is a superposition of the fast librational motions around dihedral states, of slow conformational flips among different rotameric states and of the slow rotational diffusion of the protein itself. The MD-EPR methodology reported does not require any additional stochastic modelling using adjustable parameters and opens, for the first time, the prospect of the simulation of EPR spectra entirely from single MD trajectories. Such a technique not only simplifies the interpretation and analysis of EPR spectra but also opens the possibility, for example, of "computer engineering" of spin-labelled proteins with the desired properties prior to actual EPR experiment.

  8. Nuclear spin-lattice relaxation in nitroxide spin-label EPR.

    PubMed

    Marsh, Derek

    2016-11-01

    Nuclear relaxation is a sensitive monitor of rotational dynamics in spin-label EPR. It also contributes competing saturation transfer pathways in T1-exchange spectroscopy, and the determination of paramagnetic relaxation enhancement in site-directed spin labelling. A survey shows that the definition of nitrogen nuclear relaxation rate Wn commonly used in the CW-EPR literature for (14)N-nitroxyl spin labels is inconsistent with that currently adopted in time-resolved EPR measurements of saturation recovery. Redefinition of the normalised (14)N spin-lattice relaxation rate, b=Wn/(2We), preserves the expressions used for CW-EPR, whilst rendering them consistent with expressions for saturation recovery rates in pulsed EPR. Furthermore, values routinely quoted for nuclear relaxation times that are deduced from EPR spectral diffusion rates in (14)N-nitroxyl spin labels do not accord with conventional analysis of spin-lattice relaxation in this three-level system. Expressions for CW-saturation EPR with the revised definitions are summarised. Data on nitrogen nuclear spin-lattice relaxation times are compiled according to the three-level scheme for (14)N-relaxation: T1n=1/Wn. Results are compared and contrasted with those for the two-level (15)N-nitroxide system.

  9. Nuclear spin-lattice relaxation in nitroxide spin-label EPR

    NASA Astrophysics Data System (ADS)

    Marsh, Derek

    2016-11-01

    Nuclear relaxation is a sensitive monitor of rotational dynamics in spin-label EPR. It also contributes competing saturation transfer pathways in T1-exchange spectroscopy, and the determination of paramagnetic relaxation enhancement in site-directed spin labelling. A survey shows that the definition of nitrogen nuclear relaxation rate Wn commonly used in the CW-EPR literature for 14N-nitroxyl spin labels is inconsistent with that currently adopted in time-resolved EPR measurements of saturation recovery. Redefinition of the normalised 14N spin-lattice relaxation rate, b = Wn/(2We), preserves the expressions used for CW-EPR, whilst rendering them consistent with expressions for saturation recovery rates in pulsed EPR. Furthermore, values routinely quoted for nuclear relaxation times that are deduced from EPR spectral diffusion rates in 14N-nitroxyl spin labels do not accord with conventional analysis of spin-lattice relaxation in this three-level system. Expressions for CW-saturation EPR with the revised definitions are summarised. Data on nitrogen nuclear spin-lattice relaxation times are compiled according to the three-level scheme for 14N-relaxation: T1n = 1/Wn. Results are compared and contrasted with those for the two-level 15N-nitroxide system.

  10. N-player quantum games in an EPR setting.

    PubMed

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

    2012-01-01

    The N-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 N-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' N x N payoff matrices are then defined using linear functions so that common two-player games can be easily extended to the N-player case and permit analytic expressions for the Nash equilibrium. As a specific example, we solve the Prisoners' Dilemma game for general N ≥ 2. 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.

  11. X-band rapid-scan EPR of nitroxyl radicals.

    PubMed

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

    2012-01-01

    X-band rapid-scan EPR spectra were obtained for dilute aqueous solutions of nitroxyl radicals (15)N-mHCTPO (4-hydro-3-carbamoyl-2,2,5,5-tetra-perdeuteromethyl-pyrrolin-1-(15)N-oxyl-d(12)) and (15)N-PDT (4-oxo-2,2,6,6-tetra-perdeuteromethyl-piperidinyl-(15)N-oxyl-d(16)). Simulations of spectra for (15)N-mHCTPO and (15)N-PDT agreed well with the experimental spectra. As the scan rate is increased in the rapid scan regime, the region in which signal amplitude increases linearly with B(1) extends to higher power and the maximum signal amplitude increases. In the rapid scan regime, the signal-to-noise for rapid-scan spectra was about a factor of 2 higher than for unbroadened CW EPR, even when the rapid scan spectra were obtained in a mode that had only 4% duty cycle for data acquisition. Further improvement in signal-to-noise per unit time is expected for higher duty cycles. Rapid scan spectra have higher bandwidth than CW spectra and therefore require higher detection bandwidths at faster scan rates. However, when the scan rate is increased by increasing the scan frequency, the increase in noise from the detection bandwidth is compensated by the decrease in noise due to increased number of averages per unit time. Because of the higher signal bandwidth, lower resonator Q is needed for rapid scan than for CW, so the rapid scan method is advantageous for lossy samples that inherently lower resonator Q.

  12. 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

  13. Differential regulation of the Epr3 receptor coordinates membrane-restricted rhizobial colonization of root nodule primordia

    PubMed Central

    Kawaharada, Yasuyuki; Nielsen, Mette W.; Kelly, Simon; James, Euan K.; Andersen, Kasper R.; Rasmussen, Sheena R.; Füchtbauer, Winnie; Madsen, Lene H.; Heckmann, Anne B.; Radutoiu, Simona; Stougaard, Jens

    2017-01-01

    In Lotus japonicus, a LysM receptor kinase, EPR3, distinguishes compatible and incompatible rhizobial exopolysaccharides at the epidermis. However, the role of this recognition system in bacterial colonization of the root interior is unknown. Here we show that EPR3 advances the intracellular infection mechanism that mediates infection thread invasion of the root cortex and nodule primordia. At the cellular level, Epr3 expression delineates progression of infection threads into nodule primordia and cortical infection thread formation is impaired in epr3 mutants. Genetic dissection of this developmental coordination showed that Epr3 is integrated into the symbiosis signal transduction pathways. Further analysis showed differential expression of Epr3 in the epidermis and cortical primordia and identified key transcription factors controlling this tissue specificity. These results suggest that exopolysaccharide recognition is reiterated during the progressing infection and that EPR3 perception of compatible exopolysaccharide promotes an intracellular cortical infection mechanism maintaining bacteria enclosed in plant membranes. PMID:28230048

  14. 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.

  15. 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.

  16. 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.

  17. Spin dynamics effects in submillimeter EPR spectroscopy of impurity thulium ions in synthetic forsterite

    NASA Astrophysics Data System (ADS)

    Solovarov, N. K.; Tarasov, V. F.; Zharikov, E. V.

    2016-07-01

    The specific features of the EPR spectra of Tm3+ impurity ions in synthetic forsterite have been studied by continuous-wave EPR spectroscopy in the frequency range of 270-310 GHz at a temperature of 4.2 K in weak magnetic fields. Narrow resonance signals unrelated to the modulation of the resonance conditions of EPR under the modulation of the external magnetic field have been discovered in measurements at frequencies corresponding to the zero field splitting between the ground and first excited singlet electron states of Tm3+ ions in zero magnetic field. The origin of these narrow lines is discussed.

  18. 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.

  19. User acceptance by individuals of health telematics from distributed EPRs associated with knowledge couplers.

    PubMed

    Scherrer, J R; Spahni, S; Boyer, C

    2000-01-01

    The patient in a hospital bed is also a private individual that might access his or her own Electronic Patient Record (EPR) in association with additional tools that are able to show critical up-to-date knowledge about diagnoses, clinical investigations or treatments. The distributed EPRs are shown here in full production with the DOMED application of DIOGENE 2. Besides, in order to facilitate an easier understanding of the EPRs by the patient, the HON Web Site services are at his or her disposal in this respect at the same terminal.

  20. 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.

  1. EPR tooth dosimetry as a tool for validation of retrospective doses: an end-user perspective.

    PubMed

    Bhat, Mohandas

    2005-02-01

    The US Department of Energy (DOE) is co-funding several studies on health effects of radiation in Southern Urals in Russia and on Chernobyl liquidators in Ukraine. Obtaining dose-response relationships is central to all these studies. In order to validate retrospective doses estimated by various methods, Electron paramagnetic Resonance (EPR) tooth dosimetry, considered by many as a gold standard, was attempted. The EPR technique, however, has some limitations. This paper discusses the potential pitfalls of using EPR tooth dosimetry, and some potential solutions.

  2. EPR spin trapping and DFT studies on structure of active antioxidants in biogycerol

    NASA Astrophysics Data System (ADS)

    Jerzykiewicz, Maria; Ćwieląg-Piasecka, Irmina; Witwicki, Maciej; Jezierski, Adam

    2010-09-01

    Spin trapping EPR spectroscopy and DFT methods were used to investigate the structure of antioxidants present in bioglycerols [glycerol fractions (GF) derived from biodiesel production]. For this purpose the reactions of GF components and their pure reference chemicals with PBN and H2O2 were examined via EPR measurements. The EPR parameters of formed PBN spin adducts indicated the α-tocopherol origin of the trapped radicals. The comparative analysis of experimental and theoretically calculated hyperfine constants for the spin adducts strongly suggests the carbon-centered nature of the radicals generated and trapped by PBN in the bioglycerol systems.

  3. 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.

  4. Radical ions and excited states in radiolysis. Optically detected time resolved EPR

    SciTech Connect

    Trifunac, A.D.; Smith, J.P.

    1981-01-01

    Excited-state production and radical-ion recombination kinetics in pulse-irradiated solutions of aromatic solutes in cyclohexane are studied by a new method of optical detection of time-resolved electron paramagnetic resonance (EPR) spectra. 7 figures.

  5. Comparative EPR studies of free radicals in melanin synthesized by Bacillus weihenstephanensis soil strains

    NASA Astrophysics Data System (ADS)

    Zdybel, Magdalena; Pilawa, Barbara; Drewnowska, Justyna M.; Swiecicka, Izabela

    2017-07-01

    EPR spectroscopy was used to examine the properties of and free radical concentrations in atypical water-soluble melanin-like pigments from Bacillus weihenstephanensis strains. The same EPR spectral shape was observed in bacterial melanins as in eumelanin. The EPR lines were homogeneously broadened. Continuous microwave saturation of the EPR lines indicated slow spin-lattice relaxation processes in the samples. Strong dipolar interactions characterized the tested melanin samples. Higher free radical concentrations were found in bacterial melanin than in synthetic melanin. The free radical concentrations in melanin from B. weihenstephanensis increased in the following order: strain JAS 81/4 < JAS 83/3 < JAS 86/1 < JAS 39/1.

  6. EPR studies of the oxyfluoride glass ceramics using Mn2+ as a paramagnetic probe

    NASA Astrophysics Data System (ADS)

    Fedotovs, A.; Berzins, Dz; Sarakovskis, A.; Rogulis, U.; Doke, G.

    2010-11-01

    In this work, we used Mn2+ as a dopant in the oxyfluoride glasses with various fluoride compounds. Electron paramagnetic resonance (EPR) measurements were carried out before and after a heat treatment of the material. In both cases, a well pronounced hyperfine (hf) structure of the EPR spectra characteristic to the Mn2+ ion have been observed. EPR measurements have also been studied for the separate fluoride counterparts of the oxyfluoride glasses. EPR spectra of the LaF3:Mn2+ and CaF2:Mn2+ powders show that Mn2+ ion has a strong superhyperfine (shf) interaction with surrounding fluorine nuclei, and this shf structure could be observed also in the heat treated glass samples.

  7. Study of dose-response and radical decay curves of gamma irradiated norfloxacin using EPR spectroscopy

    NASA Astrophysics Data System (ADS)

    Sütçü, Kerem; Osmanoǧlu, Yunus Emre

    2017-02-01

    In this study, Electron Paramagnetic Resonance (EPR) spectra of unirradiated and γ-irradiated at doses of 1, 5, 10, 12 and 15 kGy norfloxacin (NOF) were investigated. Before irradiation no EPR signal were observed. After irradiation a weak singlet signal at g = 2.0039 were obtained at room temperature. In order to describe the variation of EPR signal intensity with absorbed radiation dose, several mathematical equations were tried. Increasing irradiation dose up to 15 kGy has increased the signal intensity of the central signal however, no significant changes were observed in g spectroscopic splitting factor. The stability of signal intensity of irradiated NOF was studied over a storage period of 200 days. According to analyses conducted, EPR spectroscopy can be used to distinguish irradiated and unirradiated samples from each other.

  8. Searching for biosignatures using electron paramagnetic resonance (EPR) analysis of manganese oxides.

    PubMed

    Kim, Soon Sam; Bargar, John R; Nealson, Kenneth H; Flood, Beverly E; Kirschvink, Joseph L; Raub, Timothy D; Tebo, Bradley M; Villalobos, Mario

    2011-10-01

    Manganese oxide (Mn oxide) minerals from bacterial sources produce electron paramagnetic resonance (EPR) spectral signatures that are mostly distinct from those of synthetic simulants and abiogenic mineral Mn oxides. Biogenic Mn oxides exhibit only narrow EPR spectral linewidths (∼500 G), whereas abiogenic Mn oxides produce spectral linewidths that are 2-6 times broader and range from 1200 to 3000 G. This distinction is consistent with X-ray structural observations that biogenic Mn oxides have abundant layer site vacancies and edge terminations and are mostly of single ionic species [i.e., Mn(IV)], all of which favor narrow EPR linewidths. In contrast, abiogenic Mn oxides have fewer lattice vacancies, larger particle sizes, and mixed ionic species [Mn(III) and Mn(IV)], which lead to the broader linewidths. These properties could be utilized in the search for extraterrestrial physicochemical biosignatures, for example, on Mars missions that include a miniature version of an EPR spectrometer.

  9. 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.

  10. 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

  11. EPR Paradox, Locality and Completeness of Quantum Theory

    NASA Astrophysics Data System (ADS)

    Kupczynski, M.

    2007-12-01

    The quantum theory (QT) and new stochastic approaches have no deterministic prediction for a single measurement or for a single time-series of events observed for a trapped ion, electron or any other individual physical system. The predictions of QT being of probabilistic character apply to the statistical distribution of the results obtained in various experiments. The Copenhagen interpretation (CI) of QT acknowledged the abstract and statistical character of the predictions of QT but at the same time claimed that a state vector Ψ provided complete description of each individual physical system. The assigning the state vector to an individual physical system together with a postulate of its instantaneous reduction in the measurements was shown by Einstein Podolski and Rosen to lead to so called EPR paradox for the experiments with the entangled pairs of the particles. EPR concluded that a state vector could not provide a complete description of the individual systems and the question arose whether the probabilistic predictions of QT could be derived from some more fundamental spatio-temporal deterministic description of the invisible sub-phenomena by introduction of supplementary parameters. The experimental violation of the Bell inequalities in the spin polarization correlation experiments (SPCE) which were the implementations of Bohm and EPR gedanken experiments eliminated so called local and realistic models of the sub-phenomena. Quite often the violation of these inequalities has been incorrectly interpreted as a proof of the completeness of QT or as the violation of the locality and causality in the micro-world. The local and realistic models overlooked the fact that an experimental outcome is only the information about a particular system-system or system-instrument interaction. Namely the quantum phenomena are described in terms of the probabilities. It is well known that the probability distribution is not an attribute of a dice but it is a characteristic

  12. 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

  13. 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.

  14. EPR Properties of Concentrated NdVO4 Single Crystal System.

    PubMed

    Kaczmarek, S M; Fuks, H; Berkowski, M; Głowacki, M; Bojanowski, B

    Single crystals of NdVO4 were grown by the Czochralski method under ambient pressure in a nitrogen atmosphere. Obtained crystals were transparent with strong violet coloring. Temperature and angular dependences of electron paramagnetic resonance (EPR) spectra of the samples in the 3-103 K temperature range were analyzed applying Dyson like lineshape typically used for concentrated magnetic system. EPR-NMR program was used to find local symmetry and spin-Hamiltonian parameters of neodymium ions.

  15. The EPR detection of foods preserved with the use of ionizing radiation

    NASA Astrophysics Data System (ADS)

    Stachowicz, W.; Burlińska, G.; Michalik, J.; Dziedzic-Gocławska, A.; Ostrowski, K.

    1995-02-01

    Solid constituents extracted from irradiated foods have been examined by the epr (esr) spectroscopy. It has been proved that some epr active species produced by radiation in foods are specific and stable enough to be used for the detection of irradiation treatment. The most promising results have been obtained with bones extracted from frozen raw meat (beef, pork, poultry and fish), with seeds of fruits (dates and figs), with dried mushrooms, gelatin and macaroni.

  16. 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.

  17. Functional EPR imaging of ischemic rat heart: monitoring of tissue oxygenation and pH

    PubMed Central

    Gorodetsky, A.A.; Kirilyuk, I.A.; Khramtsov, V. V; Komarov, D.A.

    2015-01-01

    Purpose EPR imaging in spectral-spatial domain with application of soluble paramagnetic probes provides an opportunity for spatially-resolved functional measurements on living objects. The main purpose of this work was development of EPR methods for visualization of oxygenation and acidosis of ischemic myocardium. Methods EPR oxygen measurements were performed using isotopically substituted 2H,15N-dicarboxyproxyl. The radical has EPR linewidth of 320 mG and oxygen-induced line broadening of 0.53 mG/mmHg providing oxygen sensitivity down to 5 μM. pH measurements were performed using previously developed pH-sensitive imidazoline nitroxide. The radical has EPR spectrum with pH-dependable hyperfine splitting, pK = 6.6, providing pH sensitivity of about 0.05 units in physiological range. Results EPR imaging of isolated and perfused rat hearts were performed in 2D + spectral domain. Spatial resolution of the measurements was about 1.4 mm. Marked tissue hypoxia was observed in ischemic area of the hearts after occlusion of left anterior descending coronary artery. Tissue oxygenation was partly restored upon reperfusion. EPR mapping of myocardial pH indicated acidosis of ischemic area down to pH 6.7 – 6.8. Conclusion This work demonstrates capability of low-field EPR and the nitroxide spin probes for mapping of myocardial oxygenation and pH. The developed approaches might be used for noninvasive investigation of microenvironment on living objects. PMID:26301868

  18. Low-temperature EPR spectra of synthetic diamond and type Ib nanodiamond

    NASA Astrophysics Data System (ADS)

    Vaisnoras, R.; Kulbickas, A.; Kobets, M.; Dergachev, K.; Khatsko, E.

    2013-11-01

    Low-frequency resonance studies of single crystal diamond and type Ib nanodiamond (powder) unirradiated and irradiated by protons at temperatures of 300 and 500 K are reported. EPR spectra typical of paramagnetic nitrogen centers are observed. It is shown that when synthetic diamond crystals are irradiated by protons, additional lines appear in the EPR spectra which can be attributed to radiation induced nitrogen-vacancy centers (NV defects).

  19. In vitro Ca(2+)-dependent maturation of milk-clotting recombinant Epr: minor extracellular protease: from Bacillus licheniformis.

    PubMed

    Ageitos, José Manuel; Vallejo, Juan Andrés; Serrat, Manuel; Sánchez-Pérez, Angeles; Villa, Tomás G

    2013-06-01

    The minor extracellular protease (Epr) is secreted into the culture medium during Bacillus licheniformis, strain USC13, stationary phase of growth. Whereas, B. subtilis Epr has been reported to be involved in swarming; the B. licheniformis protease is also involved in milk-clotting as shown by the curd forming ability of culture broths expressing this protein. The objectives of this study are the characterization of recombinant B. licheniformis Epr (minor extracellular protease) and the determination of its calcium-dependent activation process. In this work, we have cloned and expressed B. licheniformis Epr in Escherichia coli. We were also able to construct a tridimensional model for Epr based on its homology to Thermococcus kodakarensis pro-tk-subtilisin 2e1p, fervidolysin from Fervidobacterium pennivorans 1rv6, and B. lentus 1GCI subtilisin. Recombinant Epr was accumulated into inclusion bodies; after protein renaturation, Epr undergoes an in vitro calcium-dependent activation, similar to that described for tk protease. The recombinant Epr is capable of producing milk curds with the same clotting activity previously described for the native B. licheniformis Epr enzyme although further rheological and industrial studies should be carried out to confirm its real applicability. This work represents for the first time that Epr may be successfully expressed in a non-bacilli microorganism.

  20. OSSA - An optimized approach to severe accident management: EPR application

    SciTech Connect

    Sauvage, E. C.; Prior, R.; Coffey, K.; Mazurkiewicz, S. M.

    2006-07-01

    There is a recognized need to provide nuclear power plant technical staff with structured guidance for response to a potential severe accident condition involving core damage and potential release of fission products to the environment. Over the past ten years, many plants worldwide have implemented such guidance for their emergency technical support center teams either by following one of the generic approaches, or by developing fully independent approaches. There are many lessons to be learned from the experience of the past decade, in developing, implementing, and validating severe accident management guidance. Also, though numerous basic approaches exist which share common principles, there are differences in the methodology and application of the guidelines. AREVA/Framatome-ANP is developing an optimized approach to severe accident management guidance in a project called OSSA ('Operating Strategies for Severe Accidents'). There are still numerous operating power plants which have yet to implement severe accident management programs. For these, the option to use an updated approach which makes full use of lessons learned and experience, is seen as a major advantage. Very few of the current approaches covers all operating plant states, including shutdown states with the primary system closed and open. Although it is not necessary to develop an entirely new approach in order to add this capability, the opportunity has been taken to develop revised full scope guidance covering all plant states in addition to the fuel in the fuel building. The EPR includes at the design phase systems and measures to minimize the risk of severe accident and to mitigate such potential scenarios. This presents a difference in comparison with existing plant, for which severe accidents where not considered in the design. Thought developed for all type of plants, OSSA will also be applied on the EPR, with adaptations designed to take into account its favourable situation in that field

  1. 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.

  2. 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.

  3. Advantageous application of a surface coil to EPR irradiation in overhauser-enhanced MRI.

    PubMed

    Matsumoto, Shingo; Yamada, Kenichi; Hirata, Hiroshi; Yasukawa, Keiji; Hyodo, Fuminori; Ichikawa, Kazuhiro; Utsumi, Hideo

    2007-04-01

    The present study describes the advantageous application of a surface coil to electron paramagnetic resonance (EPR) irradiation in Overhauser-enhanced MRI (OMRI). OMRI is a double-resonance method for imaging free radicals based on the Overhauser effect. Proton NMR images are recorded without and with EPR irradiation of the free radical resonance, which results in a difference proton image that shows signal enhancement in spatial regions that contain the free radical. To obtain good signal enhancement in OMRI, very high RF power and a long EPR irradiation time are required. To improve sensitivity and shorten the image acquisition time, especially for localized (and topical) applications, we developed and tested a surface-coil-type EPR irradiation coil. Theoretical calculations and experimental data showed that EPR irradiation through the surface coil could ameliorate the localized Overhauser enhancement, which was related to the ratio of B(1) surface coil/B(1) volume coil in the region of interest (ROI), as expected. The increased sensitivity could also be converted into a shortened EPR irradiation time, resulting in fast data acquisition. For biomedical applications, the use of a surface coil (as opposed to a conventional volume coil) could decrease the total RF power deposition in the sample required to obtain the same Overhauser enhancement in the ROI.

  4. 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.

  5. 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.

  6. Charge Transfer Processes in OPV Materials as Revealed by EPR Spectroscopy

    DOE PAGES

    Niklas, Jens; Poluektov, Oleg

    2017-03-03

    Understanding charge separation and charge transport at a molecular level is crucial for improving the efficiency of organic photovoltaic (OPV) cells. Under illumination of Bulk Heterojunction (BHJ) blends of polymers and fullerenes, various paramagnetic species are formed including polymer and fullerene radicals, radical pairs, and photoexcited triplet states. Light-induced Electron Paramagnetic Resonance (EPR) spectroscopy is ideally suited to study these states in BHJ due to its selectivity in probing the paramagnetic intermediates. Some advanced EPR techniques like light-induced ENDOR spectroscopy and pulsed techniques allow the determination of hyperfine coupling tensors, while high-frequency EPR allows the EPR signals of the individualmore » species to be resolved and their g-tensors to be determined. In these magnetic resonance parameters reveal details about the delocalization of the positive polaron on the various polymer donors which is important for the efficient charge separation in BHJ systems. Time-resolved EPR can contribute to the study of the dynamics of charge separation, charge transfer and recombination in BHJ by probing the unique spectral signatures of charge transfer and triplet states. Furthermore, the potential of the EPR also allows characterization of the intermediates and products of BHJ degradation.« less

  7. Probing Microenvironment in Ionic Liquids by Time-Resolved EPR of Photoexcited Triplets.

    PubMed

    Ivanov, M Yu; Veber, S L; Prikhod'ko, S A; Adonin, N Yu; Bagryanskaya, E G; Fedin, M V

    2015-10-22

    Unusual physicochemical properties of ionic liquids (ILs) open vistas for a variety of new applications. Herewith, we investigate the influence of microviscosity and nanostructuring of ILs on spin dynamics of the dissolved photoexcited molecules. We use two most common ILs [Bmim]PF6 and [Bmim]BF4 (with its close analogue [C10mim]BF4) as solvents and photoexcited Zn tetraphenylporphyrin (ZnTPP) as a probe. Time-resolved electron paramagnetic resonance (TR EPR) is employed to investigate spectra and kinetics of spin-polarized triplet ZnTPP in the temperature range 100-270 K. TR EPR data clearly indicate the presence of two microenvironments of ZnTPP in frozen ILs at 100-200 K, being manifested in different spectral shapes and different spin relaxation rates. For one of these microenvironments TR EPR data is quite similar to those obtained in common frozen organic solvents (toluene, glycerol, N-methyl-2-pyrrolidone). However, the second one favors the remarkably slow relaxation of spin polarization, being much longer than in the case of common solvents. Additional experiments using continuous wave EPR and stable nitroxide as a probe confirmed the formation of heterogeneities upon freezing of ILs and complemented TR EPR results. Thus, TR EPR of photoexcited triplets can be effectively used for probing heterogeneities and nanostructuring in frozen ILs. In addition, the increase of polarization lifetime in frozen ILs is an interesting finding that might allow investigation of short-lived intermediates inaccessible otherwise.

  8. 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.

  9. EPR, thermo and photoluminescence properties of ZnO nanopowders.

    PubMed

    Jagannatha Reddy, A; Kokila, M K; Nagabhushana, H; Rao, J L; Shivakumara, C; Nagabhushana, B M; Chakradhar, R P S

    2011-10-15

    Nanocrystalline ZnO powders have been synthesized by a low temperature solution combustion method. The photoluminescence (PL) spectrum of as-formed and heat treated ZnO shows strong violet (402, 421, 437, 485 nm) and weak green (520 nm) emission peaks respectively. The PL intensities of defect related emission bands decrease with calcinations temperature indicating the decrease of Zn(i) and V(o)(+) caused by the chemisorptions of oxygen. The results are correlated with the electron paramagnetic resonance (EPR) studies. Thermoluminescence (TL) glow curves of gamma irradiated ZnO nanoparticles exhibit a single broad glow peak at ∼343°C. This can be attributed to the recombination of charge carriers released from the surface states associated with oxygen defects, mainly interstitial oxygen ion centers. The trapping parameters of ZnO irradiated with various γ-doses are calculated using peak shape method. It is observed that the glow peak intensity increases with increase of gamma dose without changing glow curve shape. These two characteristic properties such as TL intensity increases with gamma dose and simple glow curve structure is an indication that the synthesized ZnO nanoparticles might be used as good TL dosimeter for high temperature application.

  10. EPR, thermo and photoluminescence properties of ZnO nanopowders

    NASA Astrophysics Data System (ADS)

    Jagannatha Reddy, A.; Kokila, M. K.; Nagabhushana, H.; Rao, J. L.; Shivakumara, C.; Nagabhushana, B. M.; Chakradhar, R. P. S.

    2011-10-01

    Nanocrystalline ZnO powders have been synthesized by a low temperature solution combustion method. The photoluminescence (PL) spectrum of as-formed and heat treated ZnO shows strong violet (402, 421, 437, 485 nm) and weak green (520 nm) emission peaks respectively. The PL intensities of defect related emission bands decrease with calcinations temperature indicating the decrease of Zn i and V o+ caused by the chemisorptions of oxygen. The results are correlated with the electron paramagnetic resonance (EPR) studies. Thermoluminescence (TL) glow curves of gamma irradiated ZnO nanoparticles exhibit a single broad glow peak at ˜343 °C. This can be attributed to the recombination of charge carriers released from the surface states associated with oxygen defects, mainly interstitial oxygen ion centers. The trapping parameters of ZnO irradiated with various γ-doses are calculated using peak shape method. It is observed that the glow peak intensity increases with increase of gamma dose without changing glow curve shape. These two characteristic properties such as TL intensity increases with gamma dose and simple glow curve structure is an indication that the synthesized ZnO nanoparticles might be used as good TL dosimeter for high temperature application.

  11. 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.

  12. Arbitrary waveform modulated pulse EPR at 200 GHz

    NASA Astrophysics Data System (ADS)

    Kaminker, Ilia; Barnes, Ryan; Han, Songi

    2017-06-01

    We report here on the implementation of arbitrary waveform generation (AWG) capabilities at ∼200 GHz into an Electron Paramagnetic Resonance (EPR) and Dynamic Nuclear Polarization (DNP) instrument platform operating at 7 T. This is achieved with the integration of a 1 GHz, 2 channel, digital to analog converter (DAC) board that enables the generation of coherent arbitrary waveforms at Ku-band frequencies with 1 ns resolution into an existing architecture of a solid state amplifier multiplier chain (AMC). This allows for the generation of arbitrary phase- and amplitude-modulated waveforms at 200 GHz with >150 mW power. We find that the non-linearity of the AMC poses significant difficulties in generating amplitude-modulated pulses at 200 GHz. We demonstrate that in the power-limited regime of ω1 < 1 MHz phase-modulated pulses were sufficient to achieve significant improvements in broadband (>10 MHz) spin manipulation in incoherent (inversion), as well as coherent (echo formation) experiments. Highlights include the improvement by one order of magnitude in inversion bandwidth compared to that of conventional rectangular pulses, as well as a factor of two in improvement in the refocused echo intensity at 200 GHz.

  13. Aluminosilicate glasses structure under electron irradiation: An EPR study

    NASA Astrophysics Data System (ADS)

    Gac, A. Le; Boizot, B.; Jégou, C.; Peuget, S.

    2017-09-01

    To understand the complex oxide glasses behavior under irradiation, 13 simplified aluminosilicate glasses were elaborated, composed of SiO2, Al2O3, Na2O and CaO oxides, which were distributed in 3 series to investigate the influence of Na2O/CaO, Al2O3/SiO2 ratios and Al2O3 content. 2.5 MeV Electron irradiations were performed to obtain bulk irradiated samples by electronic collisions at low stopping power. The influence of dose (from 1.105 up to 4.109 Gy) and chemical composition on the formation of paramagnetic centers have been investigated by electron paramagnetic resonance (EPR) spectroscopy. It has shown that electronic collisions induce production of mainly 3 types of point defects (OHC, Al-OHC, E') in the glassy network, whose content increase up to 1 GGy. The production efficiency of Al-OHC defects is increased when the calcium cations are in charge compensator role around aluminum cations instead of sodium cations. A significant decrease of defects concentration was observed between 1 and 4 GGy for all studied glasses.

  14. Wave Detection Beyond the Standard Quantum Limit via EPR Entanglement

    NASA Astrophysics Data System (ADS)

    Ma, Yiqiu; Miao, Haixing; Pang, Belinda; Evans, Matthew; Zhao, Chunnong; Harms, Jan; Schnabel, Roman; Chen, Yanbei

    2017-01-01

    The Standard Quantum Limit in continuous monitoring of a system is given by the trade-off of shot noise and back-action noise. In gravitational-wave detectors, such as Advanced LIGO, both contributions can simultaneously be squeezed in a broad frequency band by injecting a spectrum of squeezed vacuum states with a frequency-dependent squeeze angle. This approach requires setting up an additional long base-line, low-loss filter cavity in a vacuum system at the detector's site. Here, we show that the need for such a filter cavity can be eliminated, by exploiting EPR-entangled signal and idler beams. By harnessing their mutual quantum correlations and the difference in the way each beam propagates in the interferometer, we can engineer the input signal beam to have the appropriate frequency dependent conditional squeezing once the out-going idler beam is detected. Our proposal is appropriate for all future gravitational-wave detectors for achieving sensitivities beyond the Standard Quantum Limit.

  15. Implementation of GPU-accelerated back projection for EPR imaging.

    PubMed

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

    2015-01-01

    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.

  16. EPR and UV spectral study of gamma-irradiated white and burned sugar, fructose and glucose

    NASA Astrophysics Data System (ADS)

    Yordanov, Nicola D.; Georgieva, Elka

    2004-05-01

    The EPR and UV spectral properties of γ-irradiated white and burned sugar, fructose and glucose are studied with the accent on their suitability as dosimetric materials. It is shown that γ-irradiation of solid samples of white sugar and fructose yields stable EPR spectra whereas glucose signal remains time-dependent even 11 months later. Sugar and glucose exhibit linear EPR dose response in the region 0.44-21 kGy and fructose only up to ca. 10 kGy. The relative radiation sensitivity obtained for sugar and fructose is up to 10 kGy and slightly lower for glucose. Burned saccharides provide 2-3 orders of magnitude lower EPR radiation sensitivity making them not suitable for the proposed designation. According to the UV spectra water solutions of γ-irradiated solid white saccharides show well pronounced absorption bands at 267 and 286 nm for sugar and fructose with time-dependent intensities reaching steady values ca. 11 days after dissolution. The intensities of these absorption bands are in linear relation with the absorbed dose of γ-radiation. Glucose shows low sensitively because irradiation with 5.5 kGy yields only a shoulder at about 260-280 nm with decreasing to ca. 40% intensity in the first few days after dissolution. Excellent correlation between the intensities of the EPR- and UV-absorbed dose response is found for sugar and fructose in the region 0.44-10 kGy. This opens new possibilities for independent calibration the EPR dose response. Finally, the comparison suggests sugar as the best, universal material for EPR- and/or UV-dosimetry in the region 0.44-160 kGy.

  17. 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.

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

    NASA Astrophysics Data System (ADS)

    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 4 × 10 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 13C nuclei indicates that IOM rad 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 ≈ 1.5 ± 0.5 × 10 -2 of the order of values existing in interstellar medium.

  19. Wideband frequency-swept excitation in pulsed EPR spectroscopy

    NASA Astrophysics Data System (ADS)

    Doll, Andrin; Jeschke, Gunnar

    2017-07-01

    Excitation of electron spins with monochromatic rectangular pulses is limited to bandwidths that are smaller than the spectral widths of most organic radicals and much smaller than the spectral widths of transition and rare earth metal ions. With frequency-swept pulses, bandwidths of up to 800 MHz have previously been attained for excitation and detection of spin packets at frequencies of about 9.6 GHz and bandwidths of up to 2.5 GHz in a polarization transfer experiment at frequencies of about 34 GHz. The remaining limitations, mainly due to resonator bandwidth and due to pulse length restrictions are discussed. Flip angles for state-space rotations on passage of a transition can generally be computed from the critical adiabaticity by the Landau-Zener-Stückelberg-Majorana expression. For hyperbolic secant pulses, the Demkov-Kunike model describes excitation for spin packets within and outside the sweep range. Well within the sweep range, the Bloch-Siegert phase shift is proportional to critical adiabaticity to a very good approximation. Because of the dependence of both flip angle and coherence phase on critical adiabaticity, it is advantageous to use pairs of amplitude and frequency modulation functions that provide such offset-independent adiabaticity. Compensation for the resonator response function should restore offset-independent adiabaticity. Whereas resonance offsets and Bloch-Siegert phase can be refocused at certain pulse length ratios, phase dispersion in coupled spin systems cannot generally be refocused. Based on the bandwidth limitations that arise from spin dynamics, requirements are derived for a spectrometer that achieves precise spin control over wide bands. The design of such a spectrometer and hardware characterization by EPR experiments are discussed.

  20. EPR Detection of Cellular and Mitochondrial Superoxide Using Cyclic Hydroxylamines

    PubMed Central

    Dikalov, Sergey I.; Kirilyuk, Igor A.; Voinov, Maxim; Grigor’ev, Igor A.

    2014-01-01

    Superoxide (O2•) has been implicated in the pathogenesis of many human diseases but detection of the O2• radicals in biological systems is limited due to inefficiency of O2• spin trapping and lack of site-specific information. In this work we studied production of extracellular, intracellular and mitochondrial O2• in neutrophils, cultured endothelial cells and isolated mitochondria using new set of cationic, anionic and neutral hydroxylamine spin probes with various lipophilicity and cell permeability. Cyclic hydroxylamines rapidly react with O2• producing stable nitroxides and allowed site-specific O2• detection in intracellular, extracellular and mitochondrial compartments. Negatively charged 1-hydroxy-4-phosphono-oxy-2,2,6,6-tetramethylpiperidine (PP-H) and positively charged 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl-trimethylammonium (CAT1-H) detected only extramitochondrial O2•. Inhibition of EPR signal by SOD2 overexpression showed that mitochondria targeted mitoTEMPO-H detected intramitochondrial O2• both in isolated mitochondria and intact cells. Both 1-hydroxy-3-carboxy-2,2,5,5-tetramethylpyrrolidine (CP-H) and 1-hydroxy-3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine (CM-H) detected increase in cytoplasm O2• stimulated by PMA but only CM-H and mitoTEMPO-H showed increase in rotenone-induced mitochondrial O2•. These data show that new set of hydroxylamine spin probes provide unique information about site-specific production of O2• radical in extracellular or intracellular compartments, cytoplasm or mitochondria. PMID:21128732

  1. 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.

  2. Uncertainty analysis for absorption and first-derivative EPR spectra.

    PubMed

    Tseitlin, Mark; Eaton, Sandra S; Eaton, Gareth R

    2012-11-01

    Electron paramagnetic resonance (EPR) experimental techniques produce absorption or first-derivative spectra. Uncertainty analysis provides the basis for comparison of spectra obtained by different methods. In this study it was used to derive analytical equations to relate uncertainties for integrated intensity and line widths obtained from absorption or first-derivative spectra to the signal-to-noise ratio (SNR), with the assumption of white noise. Predicted uncertainties for integrated intensities and line widths are in good agreement with Monte Carlo calculations for Lorentzian and Gaussian lineshapes. Conservative low-pass filtering changes the noise spectrum, which can be modeled in the Monte Carlo simulations. When noise is close to white, the analytical equations provide useful estimates of uncertainties. For example, for a Lorentzian line with white noise, the uncertainty in the number of spins obtained from the first-derivative spectrum is 2.6 times greater than from the absorption spectrum at the same SNR. Uncertainties in line widths obtained from absorption and first-derivative spectra are similar. The impact of integration or differentiation on SNR and on uncertainties in fitting parameters was analyzed. Although integration of the first-derivative spectrum improves the apparent smoothness of the spectrum, it also changes the frequency distribution of the noise. If the lineshape of the signal is known, the integrated intensity can be determined more accurately by fitting the first-derivative spectrum than by first integrating and then fitting the absorption spectrum. Uncertainties in integrated intensities and line widths are less when the parameters are determined from the original data than from spectra that have been either integrated or differentiated.

  3. EPR detection of cellular and mitochondrial superoxide using cyclic hydroxylamines.

    PubMed

    Dikalov, Sergey I; Kirilyuk, Igor A; Voinov, Maxim; Grigor'ev, Igor A

    2011-04-01

    Superoxide (O₂ⁱ⁻) has been implicated in the pathogenesis of many human diseases, but detection of the O(2)(•-) radicals in biological systems is limited due to inefficiency of O₂ⁱ⁻ spin trapping and lack of site-specific information. This work studied production of extracellular, intracellular and mitochondrial O₂ⁱ⁻ in neutrophils, cultured endothelial cells and isolated mitochondria using a new set of cationic, anionic and neutral hydroxylamine spin probes with various lipophilicity and cell permeability. Cyclic hydroxylamines rapidly react with O₂ⁱ⁻, producing stable nitroxides and allowing site-specific cO₂ⁱ⁻ detection in intracellular, extracellular and mitochondrial compartments. Negatively charged 1-hydroxy-4-phosphono-oxy-2,2,6,6-tetramethylpiperidine (PP-H) and positively charged 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl-trimethylammonium (CAT1-H) detected only extramitochondrial O₂ⁱ⁻. Inhibition of EPR signal by SOD2 over-expression showed that mitochondria targeted mitoTEMPO-H detected intramitochondrial O₂ⁱ⁻ both in isolated mitochondria and intact cells. Both 1-hydroxy-3-carboxy-2,2,5,5-tetramethylpyrrolidine (CP-H) and 1-hydroxy-3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine (CM-H) detected an increase in cytoplasm O₂ⁱ⁻ stimulated by PMA, but only CM-H and mitoTEMPO-H showed an increase in rotenone-induced mitochondrial O₂ⁱ⁻. These data show that a new set of hydroxylamine spin probes provide unique information about site-specific production of the O₂ⁱ⁻ radical in extracellular or intracellular compartments, cytoplasm or mitochondria.

  4. 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.

  5. [Effect of ascorbic acid (vitamin C) on the EPR spectra from the black and red hair].

    PubMed

    Chikvaidze, E; Miminoshvili, A; Gogoladze, T; Kiparoidze, S

    2012-02-01

    The EPR spectra of melanin's free radicals in natural black and red hair have been investigated. It is show that the EPR spectrum of black hair is slightly asymmetric singlet with g=2,0035 and ΔH=0,5 mTl. The EPR spectrum of red hair with g=2,0053 differs from the spectrum of black hair. Under the influence of visible (blue with λ(max)=450 nm) in both types of hair (black and red), the protoinduced free radicals appear, which indicates an increase in the intensity of already existing EPR spectrum of hair. It should be noted that the EPR spectra of red hair from various donors are different. The antioxidant ascorbic acid has the different effect on the photoinduced free radicals. In particular, in the case of black hair, the concentration of photoinduced free radicals is slightly reduced, whereas in red hair, the disappearance of the triplet in the spectrum is observed, and at the same time, the spectrum becomes a singlet, the intensity of which increases sharply.

  6. 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.

  7. Continuous microwave saturation of EPR spectra of melanin complexes at different temperatures

    NASA Astrophysics Data System (ADS)

    Zdybel, Magdalena; Pilawa, Barbara; Buszman, Ewa; Wrzesniok, Dorota; Krzyminiewski, Ryszard; Kruczynski, Zdzislaw

    2011-01-01

    Paramagnetic centers in DOPA-melanin and complexes of DOPA-melanin with netilmicin and Cu(II) were studied by the use of an X-band (9.3 GHz) electron paramagnetic resonance (EPR) spectroscopy. Measurements of continuous microwave saturation of EPR spectra at temperatures: 125 K, 175 K, 225 K, 275 K, were performed. Homogeneous broadening of all the examined EPR spectra was observed. EPR spectra of DOPA-melanin-Cu(II) complexes saturated at higher microwave powers than the others tested melanin samples. Fast spin-lattice relaxation exists in DOPA-melanin-Cu(II) complexes. Slow spin-lattice relaxation processes exist in melanin's paramagnetic centers of DOPA-melanin and its complexes with netilmicin, and its complexes with both netilimicin and Cu(II). EPR spectra of all the tested samples saturated at higher microwave powers with increasing of the measuring temperature. Faster spin-lattice relaxation processes occurs in DOPA-melanin and its complexes with netilmicin and Cu(II) at higher temperature.

  8. Rapid Freeze-Quench EPR Spectroscopy: Improved Collection of Frozen Particles.

    PubMed

    Nami, Faezeh; Gast, Peter; Groenen, Edgar J J

    Rapid freeze-quench (RFQ) in combination with electron paramagnetic resonance (EPR) spectroscopy at X-band is a proven technique to trap and characterize paramagnetic intermediates of biochemical reactions. Preparation of suitable samples is still cumbersome, despite many attempts to remedy this problem, and limits the wide applicability of RFQ EPR. We present a method, which improves the collection of freeze-quench particles from isopentane and their packing in an EPR tube. The method is based on sucking the particle suspension into an EPR tube with a filter at the bottom. This procedure results in a significant reduction of the required volume of reactants, which allows the economical use of valuable reactants such as proteins. The approach also enables the successful collection of smaller frozen particles, which are generated at higher flow rates. The method provides for a reproducible, efficient and fast collection of the freeze-quench particles and can be easily adapted to RFQ EPR at higher microwave frequencies than X-band.

  9. Physically-based biodosimetry using in vivo EPR of teeth in patients undergoing total body irradiation

    PubMed Central

    Williams, Benjamin B.; Dong, Ruhong; Nicolalde, Roberto J.; Matthews, Thomas P.; Gladstone, David J.; Demidenko, Eugene; Zaki, Bassem I.; Salikhov, Ildar K.; Lesniewski, Piotr N.; Swartz, Harold M.

    2014-01-01

    Purpose The ability to estimate individual exposures to radiation following a large attack or incident has been identified as a necessity for rational and effective emergency medical response. In vivo electron paramagnetic resonance (EPR) spectroscopy of tooth enamel has been developed to meet this need. Materials and methods A novel transportable EPR spectrometer, developed to facilitate tooth dosimetry in an emergency response setting, was used to measure upper incisors in a model system, in unirradiated subjects, and in patients who had received total body doses of 2 Gy. Results A linear dose response was observed in the model system. A statistically significant increase in the intensity of the radiation-induced EPR signal was observed in irradiated versus unirradiated subjects, with an estimated standard error of dose prediction of 0.9 + 0.3 Gy. Conclusions These results demonstrate the current ability of in vivo EPR tooth dosimetry to distinguish between subjects who have not been irradiated and those who have received exposures that place them at risk for acute radiation syndrome. Procedural and technical developments to further increase the precision of dose estimation and ensure reliable operation in the emergency setting are underway. With these developments EPR tooth dosimetry is likely to be a valuable resource for triage following potential radiation exposure of a large population. PMID:21696339

  10. Physically-based biodosimetry using in vivo EPR of teeth in patients undergoing total body irradiation.

    PubMed

    Williams, Benjamin B; Dong, Ruhong; Nicolalde, Roberto J; Matthews, Thomas P; Gladstone, David J; Demidenko, Eugene; Zaki, Bassem I; Salikhov, Ildar K; Lesniewski, Piotr N; Swartz, Harold M

    2011-08-01

    The ability to estimate individual exposures to radiation following a large attack or incident has been identified as a necessity for rational and effective emergency medical response. In vivo electron paramagnetic resonance (EPR) spectroscopy of tooth enamel has been developed to meet this need. A novel transportable EPR spectrometer, developed to facilitate tooth dosimetry in an emergency response setting, was used to measure upper incisors in a model system, in unirradiated subjects, and in patients who had received total body doses of 2 Gy. A linear dose response was observed in the model system. A statistically significant increase in the intensity of the radiation-induced EPR signal was observed in irradiated versus unirradiated subjects, with an estimated standard error of dose prediction of 0.9 ± 0.3 Gy. These results demonstrate the current ability of in vivo EPR tooth dosimetry to distinguish between subjects who have not been irradiated and those who have received exposures that place them at risk for acute radiation syndrome. Procedural and technical developments to further increase the precision of dose estimation and ensure reliable operation in the emergency setting are underway. With these developments EPR tooth dosimetry is likely to be a valuable resource for triage following potential radiation exposure of a large population.

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

    PubMed Central

    Petasis, Doros T.; Hendrich, Michael P.

    2016-01-01

    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

  13. Geological and petrologic evolution of seamounts near the EPR based on submersible and camera study

    NASA Astrophysics Data System (ADS)

    Batiza, Rodey; Smith, Terri L.; Niu, Yaoling

    1989-09-01

    Observations from 17 ALVIN dives and 14 ANGUS runs plus laboratory study of basalt samples collected with ALVIN help to constrain the morphologic, volcanic and petrologic evolution of four seamounts near the East Pacific Rise (EPR). Comparison among the four volcanoes provides evidence for a general pattern of near-EPR seamount evolution and shows the importance of sedimentation, mass wasting, hydrothermal activity and other geologic processes that occur on submerged oceanic volcanoes. Seamount 5, closest to the EPR (1.0 Ma) is the youngest seamount and may still be active. Its summit is covered by fresh lavas, recent faults and hydrothermal deposits. Seamount D is on crust 1.55 Ma and is inactive; like seamount 5, it has a breached caldera and is composed exclusively of N-MORB. Seamounts 5 and D represent the last stages of growth of typical N-MORB-only seamounts near the EPR axis. Seamounts 6 and 7 have bumpy, flattish summits composed of transitional and alkalic lavas. These lavas probably represent caldera fillings and caps overlying an edifice composed of N-MORB. Evolution from N-MORB-only cratered edifices to the alkalic stage does not occur on all near-EPR seamounts and may be favored by location on structures with relative-motion-parallel orientation.

  14. The Third International Intercomparison on EPR Tooth Dosimetry: part 2, final analysis.

    PubMed

    Wieser, A; Debuyst, R; Fattibene, P; Meghzifene, A; Onori, S; Bayankin, S N; Brik, A; Bugay, A; Chumak, V; Ciesielski, B; Hoshi, M; Imata, H; Ivannikov, A; Ivanov, D; Junczewska, M; Miyazawa, C; Penkowski, M; Pivovarov, S; Romanyukha, A; Romanyukha, L; Schauer, D; Scherbina, O; Schultka, K; Sholom, S; Skvortsov, V; Stepanenko, V; Thomas, J A; Tielewuhan, E; Toyoda, S; Trompier, F

    2006-01-01

    The objective of the Third International Intercomparison on EPR Tooth Dosimetry was to evaluate laboratories performing tooth enamel dosimetry <300 mGy. Final analysis of results included a correlation analysis between features of laboratory dose reconstruction protocols and dosimetry performance. Applicability of electron paramagnetic resonance (EPR) tooth dosimetry at low dose was shown at two applied dose levels of 79 and 176 mGy. Most (9 of 12) laboratories reported the dose to be within 50 mGy of the delivered dose of 79 mGy, and 10 of 12 laboratories reported the dose to be within 100 mGy of the delivered dose of 176 mGy. At the high-dose tested (704 mGy) agreement within 25% of the delivered dose was found in 10 laboratories. Features of EPR dose reconstruction protocols that affect dosimetry performance were found to be magnetic field modulation amplitude in EPR spectrum recording, EPR signal model in spectrum deconvolution and duration of latency period for tooth enamel samples after preparation.

  15. 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.

  16. 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

  17. A special JMR issue: Methodological advances in EPR spectroscopy and imaging

    NASA Astrophysics Data System (ADS)

    2017-07-01

    Since about five decades, EPR spectroscopy provides important insights into the electronic structure of metalloproteins and transition-metal based catalysts. Somewhat later this spectroscopy was also applied to the study of electron transfer processes, often in radical enzymes. The study of diamagnetic proteins and nucleic acids with site-directed spin labeling (SDSL) techniques became really popular in the 1990s and early in the new millennium. The same applies to applications of pulsed EPR techniques to metalloproteins, although the pioneering work in this field by Mims and Peisach dates back to the early 1970s. Pulsed dipolar spectroscopy for the measurement of distance distributions in the nanometer range has become the major EPR-based tool in structural biology during the past 15 years and is still expanding its scope. EPR (or ESR) imaging may appear to be overshadowed by (nuclear) MRI, as it has not yet found clinical application. However, development of EPR-based imaging modalities has recently gained much momentum as they can provide information that is inaccessible by any established imaging technology.

  18. Radiation sensitivity and EPR dosimetric potential of gallic acid and its esters

    NASA Astrophysics Data System (ADS)

    Tuner, Hasan; Oktay Bal, M.; Polat, Mustafa

    2015-02-01

    In the preset work the radiation sensitivities of Gallic Acid anhydrous and monohydrate, Octyl, Lauryl, and Ethyl Gallate (GA, GAm, OG, LG, and EG) were investigated in the intermediate (0.5-20 kGy) and low radiation (<10 Gy) dose range using Electron Paramagnetic Resonance (EPR) spectroscopy. While OG, LG, and EG are presented a singlet EPR spectra, their radiation sensitivity found to be very different in the intermediate dose range. At low radiation dose range (<10 Gy) only LG is found to be present a signal that easily distinguished from the noise signals. The intermediate and low dose range radiation sensitivities are compared using well known EPR dosimeter alanine. The radiation yields (G) of the interested material were found to be 1.34×10-2, 1.48×10-2, 4.14×10-2, and 6.03×10-2, 9.44×10-2 for EG, GA, GAm, OG, and LG, respectively at the intermediate dose range. It is found that the simple EPR spectra and the noticeable EPR signal of LG make it a promising dosimetric material to be used below 10 Gy of radiation dose.

  19. Irradiation ageing of CSPE/EPR control command electric cables. Correlation between mechanical properties and oxidation

    NASA Astrophysics Data System (ADS)

    Calmet, J. F.; Carlin, F.; Nguyen, T. M.; Bousquet, S.; Quinot, P.

    2002-03-01

    In this paper, correlations between the elongation at break and the oxidation of chlorosulfonated polyethylene and ethylene propylene rubber (EPR) polymers in instrumentation and control cables irradiated at different dose rates are brought to evidence. During irradiation, the following phenomena are observed: an increase of oxygen consumption, a degradation of the mechanical properties and a reduction of the oxidation induction time (OIT) measured for EPR. A correlation between the mechanical properties and the OIT of the EPR has only been established in the case of irradiation at low dose rate. This reveals a difference in the oxidative degradation process at low and high dose rates. This study shows the possibility to assess the ageing of electric cables installed inside nuclear power plants by OIT measurements.

  20. Genetically Encoded Spin Labels for In Vitro and In-Cell EPR Studies of Native Proteins.

    PubMed

    Schmidt, M J; Fedoseev, A; Summerer, D; Drescher, M

    2015-01-01

    Electron paramagnetic resonance (EPR) spectroscopy in combination with site-directed spin labeling (SDSL) is a powerful approach to study the structure, dynamics, and interactions of proteins. The genetic encoding of the noncanonical amino acid spin-labeled lysine 1 (SLK-1) eliminates the need for any chemical labeling steps in SDSL-EPR studies and enables the investigation of native, endogenous proteins with minimal structural perturbation, and without the need to create unique reactive sites for chemical labeling. We report detailed experimental procedures for the efficient synthesis of SLK-1, the expression and purification of SLK-1-containing proteins under conditions that ensure maximal integrity of the nitroxide radical moiety, and procedures for intramolecular EPR distance measurements in proteins by double electron-electron resonance.

  1. Radiation effects on microstructure and EPR signal of yttrium oxide rods

    NASA Astrophysics Data System (ADS)

    Santos, S. C.; Rodrigues, O., Jr.; Campos, L. L.

    2017-02-01

    Designing nanostructured materials with high dosimetric efficiency is a great challenge in radiation dosimetry research. From rare-earth series, yttrium oxide is considered as excellent host matrix for rare-earth ions, leading to formation of advanced functional materials with optical, mechanical, chemical, and thermal properties notably improved. Nevertheless, there is a lack of information which correlates microstructural characteristics and performance of rare earths. This work aims to evaluate the radiation effects on microstructure and EPR signal of Y2O3 rods produced by colloidal processing followed by sintering at 1600°C/4h in air. Ceramic rods were exposed to gamma radiation with doses up to 100kGy. Microstructural and dosimetric characterizations were performed by XRD, SEM and EPR techniques. Yttrium oxide rods as sintered exhibited dense microstructure (96.6% theoretical density) and linear EPR dose response behaviour for wide dose range. These results reveal that yttrium oxide is a promising material for radiation dosimetry.

  2. A password-based user authentication scheme for the integrated EPR information system.

    PubMed

    Wu, Zhen-Yu; Chung, Yufang; Lai, Feipei; Chen, Tzer-Shyong

    2012-04-01

    With the rapid development of the Internet, digitization and electronic orientation are required in various applications of our daily life. For e-medicine, establishing Electronic patient records (EPRs) for all the patients has become the top issue during the last decade. Simultaneously, constructing an integrated EPR information system of all the patients is beneficial because it can provide medical institutions and the academia with most of the patients' information in details for them to make correct decisions and clinical decisions, to maintain and analyze patients' health. Also beneficial to doctors and scholars, the EPR system can give them record linkage for researches, payment audits, or other services bound to be developed and integrated into medicine. To tackle the illegal access and to prevent the information from theft during transmission over the insecure Internet, we propose a password-based user authentication scheme suitable for information integration.

  3. Analysis of Mn2+ EPR spectral shapes for studies of the oxyfluoride glass ceramics

    NASA Astrophysics Data System (ADS)

    Fedotovs, A.; Berzins, Dz; Kiselova, O.; Sarakovskis, A.; Rogulis, U.

    2011-06-01

    We investigated the EPR superhyperfine structure of the Mn2+ ion in the disordered BaF2 crystalline media which tends to crystallize in the oxyfluoride glass-ceramics material. Obtained EPR spectra reveal explicit shf structure due to Mn2+ ion building into the BaF2 lattice showing its usefulness as a probe in orientationally disordered and amorphous structures. Two types with explicit shf structure of Mn2+ ion characteristic EPR spectra were obtained in BaF2 powder samples characteristic with broad (type 1) and narrow (type 2) hyperfine structure lines. Spectra of the ZnF2-BaF2 oxyfluoride glass-ceramics samples revealed explicit fine structure lines.

  4. 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.

  5. Navigating membrane protein structure, dynamics, and energy landscapes using spin labeling and EPR spectroscopy

    PubMed Central

    Claxton, Derek P; Kazmier, Kelli; Mishra, Smriti; Mchaourab, Hassane S

    2017-01-01

    A detailed understanding of the functional mechanism of a protein entails the characterization of its energy landscape. Achieving this ambitious goal requires the integration of multiple approaches including determination of high resolution crystal structures, uncovering conformational sampling under distinct biochemical conditions, characterizing the kinetics and thermodynamics of transitions between functional intermediates using spectroscopic techniques, and interpreting and harmonizing the data into novel computational models. With increasing sophistication in solution-based and ensemble-oriented biophysical approaches such as electron paramagnetic resonance (EPR) spectroscopy, atomic resolution structural information can be directly linked to conformational sampling in solution. Here, we detail how recent methodological and technological advances in EPR spectroscopy have contributed to the elucidation of membrane protein mechanisms. Furthermore, we aim to assist investigators interested in pursuing EPR studies by providing an introduction to the technique, a primer on experimental design, and a description of the practical considerations of the method towards generating high quality data. PMID:26477257

  6. Topology of exchange interactions in copper-nitroxide based molecular magnets studied by EPR

    NASA Astrophysics Data System (ADS)

    Drozdyuk, Irina Yu.; Maryunina, Ksenia Yu.; Sagdeev, Renad Z.; Ovcharenko, Victor I.; Bagryanskaya, Elena G.; Fedin, Matvey V.

    2013-10-01

    Switchable copper-nitroxide based molecular magnets Cu(hfac)2LR ('breathing crystals') have one-dimensional (1D) polymer-chain structure and 1D magnetic motif; however, the directions of polymer and magnetic chains in the crystal do not coincide. In this work we report the detailed electron paramagnetic resonance (EPR) study of the topology of intercluster exchange interactions forming the magnetic chains in a series of breathing crystals. The obtained results provide unambiguous manifestation of 1D magnetic behaviour, which degree correlates with the magnitude of intercluster exchange interaction. Analysis of experimental angular-dependent EPR data allowed us to determine relative orientations of magnetic chains with respect to polymer chains. The obtained angle between them is ≈40-46° for three studied compounds. The comparison of EPR and x-ray diffraction data confirms that 1D magnetic chains are formed by interacting adjacent spin triads of neighbouring polymer chains.

  7. 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.

  8. 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.

  9. 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. © The Author 2013. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  10. 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.

  11. "Assessing the RAFT equilibrium constant via model systems: an EPR study"--response to a comment.

    PubMed

    Meiser, Wibke; Buback, Michael

    2012-08-14

    We have presented an EPR-based approach for deducing the RAFT equilibrium constant, K(eq), of a dithiobenzoate-mediated system [Meiser, W. and Buback M. Macromol. Rapid Commun. 2011, 32, 1490]. Our value is by four orders of magnitude below K(eq) from ab initio calculations for the identical monomer-free system. Junkers et al. [Macromol. Rapid Commun. 2011, 32, 1891] claim that our EPR approach would be model dependent and our data could be equally well fitted by assuming slow addition of radicals to the RAFT agent and slow fragmentation of the so-obtained intermediate radical as well as high cross-termination rate. By identification of all side products, our EPR-based method is shown to be model independent and to provide reliable K(eq) values, which demonstrate the validity of the intermediate radical termination model.

  12. EPR and optical absorption studies of Cr3+ ions in d-gluconic acid monohydrate.

    PubMed

    Kripal, Ram; Singh, Pragya; Govind, Har

    2009-10-01

    EPR studies are carried out on Cr(3+) ions doped in d-gluconic acid monohydrate (C(6)H(12)O(7)*H(2)O) single crystals at 77 K. From the observed EPR spectra, the spin Hamiltonian parameters g, |D| and |E| are measured to be 1.9919, 349 (x 10(-4)) cm(-1) and 113 (x 10(-4)) cm(-1), respectively. The optical absorption of the crystal is also studied at room temperature. From the observed band positions, the cubic crystal field splitting parameter Dq (2052 cm(-1)) and the Racah interelectronic repulsion parameter B (653 cm(-1)) are evaluated. From the correlation of EPR and optical data the nature of bonding of Cr(3+) ion with its ligands is discussed.

  13. EPR approaches to heterogeneous catalysis. The chemistry of titanium in heterogeneous catalysts and photocatalysts

    NASA Astrophysics Data System (ADS)

    Morra, Elena; Giamello, Elio; Chiesa, Mario

    2017-07-01

    Paramagnetic species are often involved in catalytic or photocatalytic reactions occurring at the solid-gas interface of heterogeneous catalysts. In this contribution we will provide an overview of the wealth and breadth of information that can be obtained from EPR in the characterization of paramagnetic species in such systems, illustrating the advantages that modern pulsed EPR methodologies can offer in monitoring the elementary processes occurring within the coordination sphere of surface transition-metal ions. To do so we selected three representative systems, where titanium ions in low oxidation states act as active catalytic sites, trying to outline the methodological approaches which characterize the application of EPR techniques and the questions that can be answered and addressed relative to the characterization of heterogeneous catalytic materials.

  14. EPR approaches to heterogeneous catalysis. The chemistry of titanium in heterogeneous catalysts and photocatalysts.

    PubMed

    Morra, Elena; Giamello, Elio; Chiesa, Mario

    2017-07-01

    Paramagnetic species are often involved in catalytic or photocatalytic reactions occurring at the solid-gas interface of heterogeneous catalysts. In this contribution we will provide an overview of the wealth and breadth of information that can be obtained from EPR in the characterization of paramagnetic species in such systems, illustrating the advantages that modern pulsed EPR methodologies can offer in monitoring the elementary processes occurring within the coordination sphere of surface transition-metal ions. To do so we selected three representative systems, where titanium ions in low oxidation states act as active catalytic sites, trying to outline the methodological approaches which characterize the application of EPR techniques and the questions that can be answered and addressed relative to the characterization of heterogeneous catalytic materials. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. EPR investigation of the gamma radiation response of different types of glasses.

    PubMed

    Gancheva, Veselka; Yordanov, Nicola D; Karakirova, Yordanka

    2006-03-13

    Several types of laboratory glasses such as: "Jena", "Rasotherm", "Thüring" as well as window and windscreen glasses were studied by the method of EPR spectroscopy as possible emergency radiation dosimeters for gamma-ray irradiation. The most appropriate values of modulation amplitude and microwave power were found to obtain best sensitivity for the measured signals. Dose measurements have shown a linear dependence between the EPR signal intensity of radiation created defects in glasses and applied dose in the dose range 50-500 Gy. "Thüring" glass was found to be the most sensitive sample to radiation. The magnitude of window glass absorbed dose was evaluated as the difference between the intensity of its EPR signal recorded after irradiation and the background signal, obtained after thermal relaxation of the former.

  16. EPR and optical absorption studies of Cr 3+ ions in D-gluconic acid monohydrate

    NASA Astrophysics Data System (ADS)

    Kripal, Ram; Singh, Pragya; Govind, Har

    2009-10-01

    EPR studies are carried out on Cr 3+ ions doped in D-gluconic acid monohydrate (C 6H 12O 7·H 2O) single crystals at 77 K. From the observed EPR spectra, the spin Hamiltonian parameters g, | D| and | E| are measured to be 1.9919, 349 (×10 -4) cm -1 and 113 (×10 -4) cm -1, respectively. The optical absorption of the crystal is also studied at room temperature. From the observed band positions, the cubic crystal field splitting parameter Dq (2052 cm -1) and the Racah interelectronic repulsion parameter B (653 cm -1) are evaluated. From the correlation of EPR and optical data the nature of bonding of Cr 3+ ion with its ligands is discussed.

  17. Post-annealing effects on EPR response of irradiated nano-structure hydroxyapatite

    NASA Astrophysics Data System (ADS)

    Dowlatshah, F.; Ziaie, F.; Hajiloo, N.; Amraie, R.; Fathollahi, H.

    2012-12-01

    In this work, the nano-structure hydroxyapatite was synthesized via the hydrolysis method. The produced powders were thermally treatment at different temperatures from 400 to 1200°C. The morphological and chemical analyses were carried out using the Fourier transmission infrared spectroscopy, transmission electron microscopy, and X-ray diffraction system. Then, the samples were irradiated at different absorbed doses from 1 to 80 kGy using 60Co γ -ray. Electron paramagnetic resonance (EPR) responses of the samples were measured at room temperature in air. Subsequently, the variations of EPR signal intensities were constructed as the peak-to-peak signal amplitude and results were compared with those of non-annealed samples. The results show that the EPR responses of non-annealed samples are higher rather than other samples and also are saturated at higher doses in comparison with the others.

  18. EPR studies on branched high-spin arylnitrenes.

    PubMed

    Chapyshev, Sergei V; Korchagin, Denis V; Budyka, Mikhail F; Gavrishova, Tatiana N; Neuhaus, Patrik; Sander, Wolfram

    2012-08-06

    The UV (λ>305 nm) photolysis of triazide 3 in 2-methyl-tetrahydrofuran glass at 7 K selectively produces triplet mononitrene 4 (g=2.003, D(T)=0.92 cm(-1), E(T)=0 cm(-1)), quintet dinitrene 6 (g=2.003, D(Q)=0.204 cm(-1), E(Q)=0.035 cm(-1)), and septet trinitrene 8 (g=2.003, D(S)=-0.0904 cm(-1), E(S) =-0.0102 cm(-1)). After 45 min of irradiation, the major products are dinitrene 6 and trinitrene 8 in a ratio of ∼1:2, respectively. These nitrenes are formed as mixtures of rotational isomers each of which has slightly different magnetic parameters D and E. The best agreement between the line-shape spectral simulations and the experimental electron paramagnetic resonance (EPR) spectrum is obtained with the line-broadening parameters Γ(E(Q))=180 MHz for dinitrene 6 and Γ(E(S))=330 MHz for trinitrene 8. According to these line-broadening parameters, the variations of the angles Θ in rotational isomers of 6 and 8 are expected to be about ±1 and ±3°, respectively. Theoretical estimations of the magnetic parameters obtained from PBE/DZ(COSMO)//UB3LYP/6-311+G(d,p) calculations overestimate the E and D values by 1 and 8 %, respectively. Despite the large distances between the nitrene units and the extended π systems, the zero field splitting (zfs) parameters D are found to be close to those in quintet dinitrenes and septet trinitrenes, where the nitrene centers are attached to the same aryl ring. The large D values of branched septet nitrenes are due to strong negative one-center spin-spin interactions in combination with weak positive two-center spin-spin interactions, as predicted by theoretical considerations. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. EPR oxygen images predict tumor control by a 50 percent tumor control radiation dose

    PubMed Central

    Elas, Martyna; Magwood, Jessica M.; Butler, Brandi; Li, Chanel; Wardak, Rona; Barth, Eugene D.; Epel, Boris; Rubinstein, Samuel; Pelizzari, Charles A.; Weichselbaum, Ralph R.; Halpern, Howard J.

    2013-01-01

    Clinical trials to ameliorate hypoxia as a strategy to relieve the radiation resistance it causes have prompted a need to assay the precise extent and location of hypoxia in tumors. Electron Paramagnetic Resonance oxygen imaging (EPR O2 imaging) provides a non-invasive means to address this need. To obtain a preclinical proof of principle that EPR O2 images could predict radiation control, we treated mouse tumors at or near doses required to achieve 50 percent control (TCD50). Mice with FSa fibrosarcoma or MCa4 carcinoma were subjected to EPR O2 imaging and immediately radiated to a TCD50 or TCD50 ±10 Gy.. Statistical analysis was permitted by collection of ~ 1300 tumor pO2 image voxels, including the fraction of tumor voxels with pO2 less than 10 mm Hg (HF10). Tumors were followed for 90 days (FSa) or 120 days (MCa4) to determine local control or failure. HF10 obtained from EPR images showed statistically significant differences between tumors that were controlled by the TCD50 and those that were not controlled for both FSa and MCa4. Kaplan-Meier analysis of both types of tumors showed ~90% of mildly hypoxic tumors were controlled (HF10<10%), and only 37% (FSA) and 23% (MCa4) tumors controlled if hypoxic. EPR pO2 image voxel distributions in these ~0.5 ml tumors provide a prediction of radiation curability independent of radiation dose. These data confirm the significance of EPR pO2 hypoxic fractions. The ~90% control of low HF10 tumors argue that ½ ml subvolumes of tumors may be more sensitive to radiation and may need less radiation for high tumor control rates. PMID:23861469

  20. High-field EPR study of carotenoid and chlorophyll cation radicals in photosystem II.

    SciTech Connect

    Lakshmi, K. V.; Reifler, M. J.; Brudvig, G. W.; Poluektov, O. G.; Wagner, A. M.; Thurnuaer, M. C.; Chemistry; Yale Univ.

    2000-11-16

    In photosystem II (PS II), chlorophyll, {beta}-carotene, and cytochrome b{sub 559} are alternate electron donors that may be involved in a photoprotection mechanism. The present study describes the use of high-field EPR spectroscopy to characterize the low-temperature photooxidation of Chl{sub z} and Car cofactors in PS II. The EPR signals of the individual species, previously not resolved at X-band frequency (9 GHz), are resolved at higher D-band frequency (130 GHz) in deuterated Synechococcus lividus PS II. Deuteration of PS II results in significant narrowing of the EPR lines, yielding well-resolved EPR spectra of the Car{sup +} and Chl{sub z}{sup +} radicals at 130 GHz. The g tensors of the individual species were determined by EPR spectral simulations. The g tensor determined for the Car{sup +} radical (g{sub xx} = 2.00335, g{sub yy} = 2.00251, g{sub zz} = 2.00227) is similar to that previously observed for a canthaxanthin cation radical but with a slightly rhombic tensor. The Chl{sub z}{sup +} g tensor (g{sub xx} = 2.00312, g{sub yy} = 2.00263, g{sub zz} = 2.00202) is similar to that of a chlorophyll a cation radical. This study shows that both the carotenoid and chlorophyll radicals are generated in PS II by illumination at temperatures from 6 to 190 K and that there is no interconversion of Car{sup +} and Chl{sub z}{sup +} radicals upon dark annealing at temperatures up to 160 K. This study also establishes the feasibility of using deuteration and high-field EPR to resolve previously unresolvable cofactor signals in PS II.

  1. Detection of Redox Imbalance in Normal Lymphocytes with Induced Mitochondrial Dysfunction - EPR Study.

    PubMed

    Georgieva, Ekaterina; Zhelev, Zhivko; Aoki, Ichio; Bakalova, Rumiana; Higashi, Tatsuya

    2016-10-01

    The present study describes a new approach for direct imaging of redox status in live cells using paramagnetic spin-probes, which allows evaluation of the level of oxidative stress due to overproduction of superoxide. The method is based on redox cycling of cell/mitochondria-penetrating nitroxide radicals (e.g. mito-TEMPO) and their electron-paramagnetic resonance (EPR) contrast, which makes them useful molecular sensors for analysis of redox status and oxidative stress in cells and tissues. Oxidative stress was induced in normal human lymphocytes by treatment with 2-methoxyestradiol and rotenone (ME/Rot) at different concentrations. This combination provokes mitochondrial dysfunction, which is accompanied by overproduction of superoxide. The EPR measurements were performed in dynamics on X-Band spectrometer after addition of mito-TEMPO to cell suspensions. The intensity of the EPR signal in untreated cells decreased significantly, which indicates a conversion of paramagnetic mito-TEMPO to its non-contrast diamagnetic form (hydroxylamine - mito-TEMPOH) due to reduction. In ME/Rot-treated cells, the signal decreased more slowly and to a lower level with increasing the concentration of ME/Rot. These data indicate an induction of oxidative stress in the cells in a concentration-dependent manner. A very good positive correlation between the intensity of EPR signal of mito-TEMPO and the intracellular level of superoxide was found, analyzed by conventional dihydroethidium test (R=0.9143, p<0.001). In conclusion, our study demonstrated that cell-penetrating paramagnetic spin-probes, such as mito-TEMPO, are valuable tools for EPR imaging of the superoxide level in live cells, as well as for EPR imaging of mitochondrial dysfunction and metabolic activity, accompanied by superoxide imbalance.

  2. Analysis of the spatial distribution of free radicals in ammonium tartrate by pulse EPR techniques.

    PubMed

    Marrale, Maurizio; Brai, Maria; Barbon, Antonio; Brustolon, Marina

    2009-03-01

    Using pulse electron paramagnetic resonance (EPR) on a series of l(+)-ammonium tartrate (AT) dosimeters exposed to radiations with different linear energy transfer (LET), we assessed the ability of pulse EPR spectroscopy to discriminate the quality of various radiation beams such as (60)Co gamma-ray photons, protons and thermal neutrons at various doses by analyzing the local radical distributions produced by the different beams. We performed two types of pulse EPR investigations: two-pulse electron spin echo decay obtained by varying the microwave power, and a double electron-electron resonance (DEER) study. Both methods provide information about the dipolar interactions among the free radicals and about their spatial distributions. The first method provided information on the instantaneous diffusion and hence the microscopic concentration of the radicals that is compared with the macroscopic one obtained by CW-EPR. The DEER spectra yielded the distributions of distances between pairs of radicals two to five crystal cells apart produced by the same radiation event, a result reported here for the first time. The inter-radical distributions given by the DEER results have been simulated by modeling the radical distributions according to the details of the matter-radiation interactions for the various beams. The results of both types of pulse experiments are strongly dependent on the radiation quality. This was also observed for samples giving indistinguishable CW-EPR spectral profiles. We conclude that the pulse EPR measurements can be valuable tools for distinguishing the LET of the radiation beams, an important parameter for radiobiological considerations.

  3. Application of EPR spectroscopy to identify irradiated Indian medicinal plant products.

    PubMed

    Sanyal, Bhaskar; Chatterjee, S; Variyar, Prasad S; Sharma, Arun

    2012-06-01

    A study of gamma-irradiated Indian medicinal plant products was carried out using electron paramagnetic resonance (EPR) spectroscopy. Improved approaches like high-power measurement, microwave saturation, and thermal behavior of the radicals were explored for detection of irradiation. Aswagandha (Withania somnifera), vairi (Salacia reticulata), amla (Emblica officinalis), haldi (Curcumin longa), and guduchi (Tinospora cordifolia) exhibited a weak singlet at g = 2.005 before irradiation. Aswagandha, immediately after radiation treatment, revealed a complex EPR spectrum characterized by EPR spectrum simulation technique as superposition of 3 paramagnetic centers. One group of signal with organic origin was carbohydrate and cellulose radical and the other was isotropic signal of inorganic origin (g⟂ =2.0044 and g|| = 1.9980). However, other products did not exhibit any radiation-specific signal after irradiation. Power saturation and thermal behavior techniques were not suitable for these products. However, amongst all the 3 approaches, high-power measurement of EPR spectra emerged as a suitable technique in identification of the irradiated aswagandha. Gamma-irradiation confirms hygienic quality and improves shelf life of food and other products. However, there is a lack of international consensus over considering this as a general application and different regulations are being enforced. EPR is one of the most promising techniques to identify irradiated foodstuffs for regulatory requirements but it has many limitations. Improved approaches based on the EPR technique explained in this study may be useful to identify irradiated products and become beneficial to food regulators and food irradiation enterprises to enhance confidence in irradiation technology. © 2012 Institute of Food Technologists®

  4. 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.

  5. Application of jade samples for high-dose dosimetry using the EPR technique.

    PubMed

    Teixeira, Maria Inês; Melo, Adeilson P; Ferraz, Gilberto M; Caldas, Linda V E

    2010-01-01

    The dosimeter characteristics of jade samples were studied for application in high-dose dosimetry. Jade is the common denomination of two silicates: jadeite and actinolite. The EPR spectra of different jade samples were obtained after irradiation with absorbed doses of 100 Gy up to 20 kGy. The jade samples present signals that increase with the absorbed dose (g-factors around 2.00); they can be attributed to electron centers. The EPR spectra obtained for the USA jade samples and their main dosimetric properties as reproducibility, calibration curves and energy dependence were investigated.

  6. 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.

  7. 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.

  8. 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.

  9. EPR study of the effect of terahertz radiation on the albumin conformation dynamics

    NASA Astrophysics Data System (ADS)

    Nemova, Eugenia F.; Cherkasova, Olga P.; Fedorov, Vyacheslav I.

    2010-09-01

    Effect of the preliminary irradiation of bovine serum albumin (BSA) in the terahertz spectral range on the conformation changes revealed with the help of EPR spectroscopy was investigated using the spin probing technique. The formation of the spin probe occurs directly in the aqueous solution of BSA from a nitrone compound (dihydropyrazine dioxide). It was shown that irradiation causes changes in the parameters of the EPR spectrum of the spin probe. An approach to linking the observed changes with the structural characteristics of reaction centres - the functional groups of amino acids comprising BSA - was outlined.

  10. EPR of a free radical in C{sub 60}: Effect of O{sub 2}

    SciTech Connect

    Pace, M.D.; Christidis, T.C.; Yin, J.J.; Milliken, J.

    1992-08-20

    An EPR (electron paramagnetic resonance) signal was detected in C{sub 60} powder (10{sup {minus}4} radical-to-C{sub 60} ratio) and studied by multifrequency (S-, X-, and Q-band) EPR using loop-gap resonators. The signal intensity is dependent on O{sub 2} as demonstrated by spectra recorded from N{sub 2}/O{sub 2} gas flow experiments, vacuum-evacuated (10{sup {minus}4} Torr) C{sub 60} samples, and C{sub 60} heated in air at 250 {degrees}C. 22 refs., 4 figs.

  11. Optical and EPR studies of iron bearing phosphate minerals: satterlyite and gormanite from Yukon Territory, Canada.

    PubMed

    Chandrasekhar, A V; Ramanaiah, M Venkata; Reddy, B J; Reddy, Y P; Rao, P S; Ravikumar, R V S S N

    2003-07-01

    The iron phosphate minerals satterlyite and gormanite have been investigated by EPR and optical absorption studies. The optical results indicate the presence of ferrous and ferric ions in both minerals. In gormanite the site symmetry of Fe(III) is near octahedral whereas in satterlyite it is tetragonally distorted. On the other hand, the Fe(II) ions are in tetragonally distorted octahedral site in both minerals. In satterlyite the EPR results indicate the presence of the ferric ion in a tetragonally distorted state together with a small percentage of Mn(II). Crystal field (Dq) and interelectronic parameters (B and C) are evaluated.

  12. European pressurized water reactor (EPR) - an advanced LWR to fit the needs of European utilities

    SciTech Connect

    Teichel, H.; Pouget-Abadie, X.

    1997-12-01

    The European Pressurized Water Reactor (EPR) is a project for the development of an advanced PWR pursued by Electricite de France and the major German utilities (RWEE, PreussenElektra, BAG et. al.) together with SIEMENS, Framatome and their common subsidiary NPI. In this project, the experience gained through the design, the erection, the commissioning and the operation of the existing PWR in France and Germany are combined and the existing technical solutions were carefully checked before adopted for the EPR. The deep involvement of the future operators since the beginning of the project guarantees an optimized operational behaviour and easy maintainability. 1 fig., 1 tab.

  13. EPR lineshape of Mn in BCCD single crystals in the incommensurate phase

    NASA Astrophysics Data System (ADS)

    Heidler, R.; Metz, H.; Windsch, W.

    1994-10-01

    For the interpretation of the Electron Paramagnetic Resonance (EPR) lineshape of incommensurate phases there exist many theoretical models. We suppose a simple physical model to interpret the lineshape of the Mn(2+) EPR spectrum of the first incommensurate phase of betaine calcium chloride dihydrate (BCCD) and discuss it in comparison with other models. Furthermore, we investigate the critical behavior of BCCD at the normal to incommensurate phase transition on the basis of our model. The influence of the Mn(2+) impurities on the phase sequence of BCCD is investigated by dielectric measurements.

  14. EPR and magnetization of Gd 2BaNiO 5

    NASA Astrophysics Data System (ADS)

    Butera, A.; Causa, M. T.; Tovar, M.; Oseroff, S. B.; Cheong, S.-W.

    1995-02-01

    We report EPR and magnetization for Gd 2BaNiO 5 single crystals. The high-temperature susceptibility gives μeff = 7.9 μB/mol Gd and ΘGd = 11 K ( JGdGd/ kB = 0.6 K). The coupling of 1-D Ni chains through the Gd-Ni interaction induces 3-D antiferromagnetic order with T N ⋍ 55(3) K, indicated by a divergence of the EPR linewidth. A mean field analysis gives JGd-Ni/ kB = 3 K.

  15. EFFECT OF CADMIUM(II) ON FREE RADICALS IN DOPA-MELANIN TESTED BY EPR SPECTROSCOPY.

    PubMed

    Zdybel, Magdalena; Pilawa, Barbara; Chodurek, Ewa

    2015-01-01

    Electron paramagnetic resonance (EPR) spectroscopy may be applied to examine interactions of melanin with metal ions and drugs. In this work EPR method was used to examination of changes in free radical system of DOPA-melanin--the model eumelanin after complexing with diamagnetic cadmium(II) ions. Cadmium(II) may affect free radicals in melanin and drugs binding by this polymer, so the knowledge of modification of properties and free radical concentration in melanin is important to pharmacy. The effect of cadmium(II) in different concentrations on free radicals in DOPA-melanin was determined. EPR spectra of DOPA-melanin, and DOPA-melanin complexes with cadmium(II) were measured by an X-band (9.3 GHz) EPR spectrometer produced by Radiopan (Poznań, Poland) and the Rapid Scan Unit from Jagmar (Krak6w, Poland). The DOPA (3,4-dihydroxyphenylalanine) to metal ions molar ratios in the reaction mixtures were 2:1, 1:1, and 1: 2. High concentrations of o-semiquinone (g ~2.0040) free radicals (~10(21)-10(22) spin/g) characterize DOPA-melanin and its complexes with cadmium(II). Formation of melanin complexes with cadmium(II) increase free radical concentration in DOPA-melanin. The highest free radical concentration was obtained for DOPA-melanin-cadmium(II) (1:1) complexes. Broad EPR lines with linewidths: 0.37-0.73 mT, were measured. Linewidths increase after binding of cadmium(II) to melanin. Changes of integral intensities and linewidths with increasing microwave power indicate the homogeneous broadening of EPR lines, independently on the metal ion concentration. Slow spin-lattice relaxation processes existed in all the tested samples, their EPR lines saturated at low microwave powers. Cadmium(II) causes fastening of spin-lattice relaxation processes in DOPA-melanin. The EPR results bring to light the effect of cadmium(II) on free radicals in melanin, and probably as the consequence on drug binding to eumelanin.

  16. 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.

  17. Fusinite: A coal-derived EPR probe for O[sub 2]. Mechanism and application in vivo and in vitro. [EPR (electron paramagnetic resonance)

    SciTech Connect

    Vahidi, N.

    1993-01-01

    Fusinite, an inertinite coal maceral, exhibits a symmetric and exchange-narrowed electron paramagnetic resonance (EPR) line (g = 2.00276), with a first derivative peak-to-peak linewidth ([Delta]B) which is reversibly broaded by molecular O[sub 2]. To explain the mechanism of this type of broadening, pulse and multifrequency EPR measurements (0.25-250 GHz) were carried out in conjunction with O[sub 2] adsorption isotherm studies. The data suggest that, at ambient temperatures, homogeneous broadening of the EPR line of fusinite probably occurs by the exchange modulation of a group of delocalized unpaired electrons at the surface of fusinite by physical adsorbed O[sub 2]. At temperatures below 260[degrees] K, dipole-dipole mechanism begin to contribute more to the broadening of this component. The possibility of two different classes of sites for interaction with O[sub 2] is discussed. The extent of broadening per unit concentration of molecular oxygen is unusually large. This paramagnetic property of fusinite, combined with its very table physiochemical properties and low toxicity, is of utility for the measurement of the concentration of oxygen or [O[sub 2

  18. EPRS is a critical mTORC1-S6K1 effector that influences adiposity in mice.

    PubMed

    Arif, Abul; Terenzi, Fulvia; Potdar, Alka A; Jia, Jie; Sacks, Jessica; China, Arnab; Halawani, Dalia; Vasu, Kommireddy; Li, Xiaoxia; Brown, J Mark; Chen, Jie; Kozma, Sara C; Thomas, George; Fox, Paul L

    2017-02-16

    Metabolic pathways that contribute to adiposity and ageing are activated by the mammalian target of rapamycin complex 1 (mTORC1) and p70 ribosomal protein S6 kinase 1 (S6K1) axis. However, known mTORC1-S6K1 targets do not account for observed loss-of-function phenotypes, suggesting that there are additional downstream effectors of this pathway. Here we identify glutamyl-prolyl-tRNA synthetase (EPRS) as an mTORC1-S6K1 target that contributes to adiposity and ageing. Phosphorylation of EPRS at Ser999 by mTORC1-S6K1 induces its release from the aminoacyl tRNA multisynthetase complex, which is required for execution of noncanonical functions of EPRS beyond protein synthesis. To investigate the physiological function of EPRS phosphorylation, we generated Eprs knock-in mice bearing phospho-deficient Ser999-to-Ala (S999A) and phospho-mimetic (S999D) mutations. Homozygous S999A mice exhibited low body weight, reduced adipose tissue mass, and increased lifespan, similar to S6K1-deficient mice and mice with adipocyte-specific deficiency of raptor, an mTORC1 constituent. Substitution of the Eprs(S999D) allele in S6K1-deficient mice normalized body mass and adiposity, indicating that EPRS phosphorylation mediates S6K1-dependent metabolic responses. In adipocytes, insulin stimulated S6K1-dependent EPRS phosphorylation and release from the multisynthetase complex. Interaction screening revealed that phospho-EPRS binds SLC27A1 (that is, fatty acid transport protein 1, FATP1), inducing its translocation to the plasma membrane and long-chain fatty acid uptake. Thus, EPRS and FATP1 are terminal mTORC1-S6K1 axis effectors that are critical for metabolic phenotypes.

  19. 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…

  20. 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.

  1. 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.

  2. 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.

  3. A rapid freeze-quench setup for multi-frequency EPR spectroscopy of enzymatic reactions.

    PubMed

    Pievo, Roberta; Angerstein, Brigitta; Fielding, Alistair J; Koch, Christian; Feussner, Ivo; Bennati, Marina

    2013-12-16

    Electron paramagnetic resonance (EPR) spectroscopy in combination with the rapid freeze-quench (RFQ) technique is a well-established method to trap and characterize intermediates in chemical or enzymatic reactions at the millisecond or even shorter time scales. The method is particularly powerful for mechanistic studies of enzymatic reactions when combined with high-frequency EPR (ν≥90 GHz), which permits the identification of substrate or protein radical intermediates by their electronic g values. In this work, we describe a new custom-designed micro-mix rapid freeze-quench apparatus, for which reagent volumes for biological samples as small as 20 μL are required. The apparatus was implemented with homemade sample collectors appropriate for 9, 34, and 94 GHz EPR capillaries (4, 2, and 0.87 mm outer diameter, respectively) and the performance was evaluated. We demonstrate the application potential of the RFQ apparatus by following the enzymatic reaction of PpoA, a fungal dioxygenase producing hydro(pero)xylated fatty acids. The larger spectral resolution at 94 GHz allows the discernment of structural changes in the EPR spectra, which are not detectable in the same samples at the standard 9 GHz frequency.

  4. 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

  5. BCL::MP-fold: Membrane protein structure prediction guided by EPR restraints.

    PubMed

    Fischer, Axel W; Alexander, Nathan S; Woetzel, Nils; Karakas, Mert; Weiner, Brian E; Meiler, Jens

    2015-11-01

    For many membrane proteins, the determination of their topology remains a challenge for methods like X-ray crystallography and nuclear magnetic resonance (NMR) spectroscopy. Electron paramagnetic resonance (EPR) spectroscopy has evolved as an alternative technique to study structure and dynamics of membrane proteins. The present study demonstrates the feasibility of membrane protein topology determination using limited EPR distance and accessibility measurements. The BCL::MP-Fold (BioChemical Library membrane protein fold) algorithm assembles secondary structure elements (SSEs) in the membrane using a Monte Carlo Metropolis (MCM) approach. Sampled models are evaluated using knowledge-based potential functions and agreement with the EPR data and a knowledge-based energy function. Twenty-nine membrane proteins of up to 696 residues are used to test the algorithm. The RMSD100 value of the most accurate model is better than 8 Å for 27, better than 6 Å for 22, and better than 4 Å for 15 of the 29 proteins, demonstrating the algorithms' ability to sample the native topology. The average enrichment could be improved from 1.3 to 2.5, showing the improved discrimination power by using EPR data. © 2015 Wiley Periodicals, Inc.

  6. Broadband sensitivity enhancement of detuned dual-recycled Michelson interferometers with EPR entanglement

    NASA Astrophysics Data System (ADS)

    Brown, Daniel D.; Miao, Haixing; Collins, Chris; Mow-Lowry, Conor; Töyrä, Daniel; Freise, Andreas

    2017-09-01

    We demonstrate the applicability of the EPR entanglement squeezing scheme for enhancing the shot-noise-limited sensitivity of detuned dual-recycled Michelson interferometers. In particular, this scheme is applied to the GEO600 interferometer. The effect of losses throughout the interferometer, arm length asymmetries, and imperfect separation of the signal and idler beams is considered.

  7. Simple group password-based authenticated key agreements for the integrated EPR information system.

    PubMed

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

    2013-04-01

    The security and privacy are important issues for electronic patient records (EPRs). The goal of EPRs is sharing the patients' medical histories such as the diagnosis records, reports and diagnosis image files among hospitals by the Internet. So the security issue for the integrated EPR information system is essential. That is, to ensure the information during transmission through by the Internet is secure and private. The group password-based authenticated key agreement (GPAKE) allows a group of users like doctors, nurses and patients to establish a common session key by using password authentication. Then the group of users can securely communicate by using this session key. Many approaches about GAPKE employ the public key infrastructure (PKI) in order to have higher security. However, it not only increases users' overheads and requires keeping an extra equipment for storing long-term secret keys, but also requires maintaining the public key system. This investigation presents a simple group password-based authenticated key agreement (SGPAKE) protocol for the integrated EPR information system. The proposed SGPAKE protocol does not require using the server or users' public keys. Each user only remembers his weak password shared with a trusted server, and then can obtain a common session key. Then all users can securely communicate by using this session key. The proposed SGPAKE protocol not only provides users with convince, but also has higher security.

  8. 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.

  9. 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

  10. 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…

  11. EPR and O2.- scavenger activity: Cu(II)-peptide complexes as superoxide dismutase models.

    PubMed

    Pogni, R; Baratto, M C; Busi, E; Basosi, R

    1999-03-01

    Several copper(II) complexes with aminoacids and peptides are known to show superoxide dismutase (SOD)-like activity. EPR spectroscopy has proved to be a useful tool for studying the complex equilibria of the copper(II) ion and various ligands of biological importance in solution. In the present work, a variety of copper(II) complexes with di-, tri- and tetra-peptides containing only glycine residues (GG, GGG and GGGG) and others containing a histidyl residue in different positions (HGG, GHG, GGH and GGHG) have been investigated. EPR parameters obtained by extensive use of computer simulation of spectra lead to reliable spin Hamiltonian EPR parameters at both room temperature and in frozen solution. The molecular orbital coefficients computed from the anisotropic EPR data and the d-d electronic energies are used to characterize different arrangements of the complexes. Estimation of the scavenger activity of the complexes due to the particular environment created by the ligands around copper is discussed in the frame of the structure-activity relationship.

  12. Emergency Preservation and Resuscitation for Cardiac Arrest from Trauma (EPR-CAT)

    DTIC Science & Technology

    2014-12-01

    TITLE: Emergency Preservation and Resuscitation for Cardiac Arrest from Trauma (EPR-CAT) PRINCIPAL INVESTIGATOR...SUBTITLE Emergency Preservation and Resuscitation for Cardiac Arrest 5a. CONTRACT NUMBER From Trauma 5b. GRANT NUMBER W81XWH-07-1-0682...SUBJECT TERMS Trauma, hemorrhagic shock, cardiac arrest, cardiopulmonary resuscitation , hypothermia 16. SECURITY CLASSIFICATION OF: 17

  13. Manifestation of Strong Coupling Between Microwave Photons and Spins in the epr Spectrum of Anthracite

    NASA Astrophysics Data System (ADS)

    Fedaruk, R.; Adashkevich, S. V.

    2014-07-01

    The change of the anthracite EPR signal shape that was caused by increasing the sample size was observed by continuous-wave EPR with automatic frequency control locked to the measuring cavity. For large samples (>10 mm3), hysteresis (a difference in the resonant magnetic flux densities when the magnetic field was scanned upwards or downwards) and a bistability (a sharp amplitude change) were observed. A two-peak spectrum for a strongly coupled system formed by an electron-spin ensemble and the cavity microwave field was found by changing the frequency of the microwave oscillator during recording of the EPR signals. The difference in the frequencies of these peaks (Rabi splitting) was a measure of the coupling strength between the spins and the microwave field and increased with increasing sample size. The simultaneous increase of the hysteresis and bistability of the EPR signals provided evidence that these peculiarities were caused by the Rabi splitting. Use of the Rabi splitting to determine the number of electron spins in a sample was proposed.

  14. EPR and photoluminescence study of irradiated anion-defective alumina single crystals

    NASA Astrophysics Data System (ADS)

    Kortov, V. S.; Ananchenko, D. V.; Konev, S. F.; Pustovarov, V. A.

    2017-09-01

    Electron paramagnetic resonance (EPR) and photoluminescence (PL) spectra of anion-defective alumina single crystals were measured. Exposure to a dose 10 Gy-1 kGy causes isotropic EPR signal of a complex form, this signal contains narrow and broad components. At the same time, in the PL spectrum alongside with a band of F+-centers (3.8 eV) an additional emission band with the maximum of 2.25 eV is registered. This band corresponds to aggregate F22+-centers which were create under irradiation. By comparing measurements in EPR and PL spectra with further stepped annealing in the temperature range of 773-1473 K of the samples exposed to the same doses, we were able to conclude that a narrow component of isotropic EPR signal is associated with the formation of paramagnetic F22+-centers under irradiation. A wide component can be caused by deep hole traps which are created by a complex defect (VAl2- - F+) with a localized hole.

  15. Four-channel surface coil array for sequential CW-EPR image acquisition

    NASA Astrophysics Data System (ADS)

    Enomoto, Ayano; Emoto, Miho; Fujii, Hirotada; Hirata, Hiroshi

    2013-09-01

    This article describes a four-channel surface coil array to increase the area of visualization for continuous-wave electron paramagnetic resonance (CW-EPR) imaging. A 776-MHz surface coil array was constructed with four independent surface coil resonators and three kinds of switches. Control circuits for switching the resonators were also built to sequentially perform EPR image acquisition for each resonator. The resonance frequencies of the resonators were shifted using PIN diode switches to decouple the inductively coupled coils. To investigate the area of visualization with the surface coil array, three-dimensional EPR imaging was performed using a glass cell phantom filled with a solution of nitroxyl radicals. The area of visualization obtained with the surface coil array was increased approximately 3.5-fold in comparison to that with a single surface coil resonator. Furthermore, to demonstrate the applicability of this surface coil array to animal imaging, three-dimensional EPR imaging was performed in a living mouse with an exogenously injected nitroxyl radical imaging agent.

  16. Application of EPR retrospective dosimetry for large-scale accidental situation.

    PubMed

    Skvortsov, V G; Ivannikov, A I; Stepanenko, V F; Tsyb, A F; Khamidova, L G; Kondrashov, A E; Tikunov, D D

    2000-05-01

    Above 3000 tooth enamel samples, collected at population of radioactive contaminated territories after Chernobyl accident, the Chernobyl liquidators, the retired military of high radiation risk and the population of control radiation free territories were investigated by EPR spectroscopy method in order to obtain accumulated individual exposure doses. Results of EPR spectra measurements are stored in data bank; enamel samples are also stored in order to provide the possibility to repeat the measurements in future. Statistical analysis of results has allowed to detect the contribution into EPR signal in tooth enamel due to the action of the natural background radiation, and the radioactive contamination of territory. In general, the average doses of external exposure of the population obtained with EPR spectroscopy of teeth enamel are consistent with results based on other methods of direct and retrospective dosimetry. Essential exceeding of the individual doses above the average level within the population groups was observed for some persons. That gave the possibility to detect the individuals with overexposure, which were included into groups for medical monitoring.

  17. 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.

  18. Four-channel surface coil array for sequential CW-EPR image acquisition.

    PubMed

    Enomoto, Ayano; Emoto, Miho; Fujii, Hirotada; Hirata, Hiroshi

    2013-09-01

    This article describes a four-channel surface coil array to increase the area of visualization for continuous-wave electron paramagnetic resonance (CW-EPR) imaging. A 776-MHz surface coil array was constructed with four independent surface coil resonators and three kinds of switches. Control circuits for switching the resonators were also built to sequentially perform EPR image acquisition for each resonator. The resonance frequencies of the resonators were shifted using PIN diode switches to decouple the inductively coupled coils. To investigate the area of visualization with the surface coil array, three-dimensional EPR imaging was performed using a glass cell phantom filled with a solution of nitroxyl radicals. The area of visualization obtained with the surface coil array was increased approximately 3.5-fold in comparison to that with a single surface coil resonator. Furthermore, to demonstrate the applicability of this surface coil array to animal imaging, three-dimensional EPR imaging was performed in a living mouse with an exogenously injected nitroxyl radical imaging agent. Copyright © 2013 Elsevier Inc. All rights reserved.

  19. Partitioning of nitroxides in dispersed systems investigated by ultrafiltration, EPR and NMR spectroscopy.

    PubMed

    Krudopp, Heimke; Sönnichsen, Frank D; Steffen-Heins, Anja

    2015-08-15

    The partitioning behavior of paramagnetic nitroxides in dispersed systems can be determined by deconvolution of electron paramagnetic resonance (EPR) spectra giving equivalent results with the validated methods of ultrafiltration techniques (UF) and pulsed-field gradient nuclear magnetic resonance spectroscopy (PFG-NMR). The partitioning behavior of nitroxides with increasing lipophilicity was investigated in anionic, cationic and nonionic micellar systems and 10 wt% o/w emulsions. Apart from EPR spectra deconvolution, the PFG-NMR was used in micellar solutions as a non-destructive approach, while UF based on separation of very small volume of the aqueous phase. As a function of their substituent and lipophilicity, the proportions of nitroxides that were solubilized in the micellar or emulsion interface increased with increasing nitroxide lipophilicity for all emulsifier used. Comparing the different approaches, EPR deconvolution and UF revealed comparable nitroxide proportions that were solubilized in the interfaces. Those proportions were higher than found with PFG-NMR. For PFG-NMR self-diffusion experiments the reduced nitroxides were used revealing a high dynamic of hydroxylamines and emulsifiers. Deconvolution of EPR spectra turned out to be the preferred method for measuring the partitioning behavior of paramagnetic molecules as it enables distinguishing between several populations at their individual solubilization sites. Copyright © 2015 Elsevier Inc. All rights reserved.

  20. EPR and optical absorption study of Cr 3+-doped ammonium lithium sulphate single crystals

    NASA Astrophysics Data System (ADS)

    Kripal, Ram; Govind, Har

    2008-10-01

    EPR study of Cr 3+-doped ammonium lithium sulphate single crystals is carried out at room temperature. The crystal field and spin Hamiltonian parameters are evaluated from the resonance line positions of different lines observed in the EPR spectra. The spin Hamiltonian parameters are found to be g=2.0003±0.0002, D=(269±2)×10 -4 cm -1 and E=(82±2)×10 -4 cm -1 for site I and g=1.9904±0.0002, D=(251±2)×10 -4 cm -1 and E=(79±2)×10 -4 cm -1 for site II, respectively. EPR data indicate that the site symmetry of Cr 3+ ion in the crystal is distorted octahedron and it enters the lattice substitutionally replacing NH4+ sites and bind to the neighbouring extra Li + vacancies necessary for charge compensation. From optical study, the energy values of different orbital levels are estimated. Further, the bonding parameters are obtained by correlating optical and EPR data and the nature of bonding in the crystal is discussed. The values of Racah parameters ( B and C), crystal field parameter ( Dq) and nephelauxetic parameters ( h and k) are obtained to be B=908, C=3553, Dq=1974 cm -1, h=0.052 and k=0.21.

  1. In Vivo EPR Resolution Enhancement Using Techniques Known from Quantum Computing Spin Technology.

    PubMed

    Rahimi, Robabeh; Halpern, Howard J; Takui, Takeji

    2017-01-01

    A crucial issue with in vivo biological/medical EPR is its low signal-to-noise ratio, giving rise to the low spectroscopic resolution. We propose quantum hyperpolarization techniques based on 'Heat Bath Algorithmic Cooling', allowing possible approaches for improving the resolution in magnetic resonance spectroscopy and imaging.

  2. Radiation Dosimetry of Dental Enamel Using X-Band and Q-Band EPR Spectroscopy

    NASA Astrophysics Data System (ADS)

    de, Tania; Romanyukha, Alex; Pass, Barry; Misra, Prabhakar

    2010-02-01

    Electron paramagnetic resonance (EPR) dosimetry of tooth enamel can be used for individual dose reconstruction following radiation accidents. The purpose of this study was to develop a rapid, minimally invasive technique for obtaining a sample of dental enamel small enough to not disturb the structure and functionality of a tooth and to improve the sensitivity of the spectral signals using X-band (9.4 GHz) and Q-band (34 GHz) EPR spectroscopy. EPR measurements in X-band were performed on 100 mg isotropic powdered enamel samples and Q-band measurements done on 4 mg (1x1x3 mm) enamel biopsy samples. All samples were obtained from discarded teeth collected during normal dental treatment. In order to study the variation of the Radiation-Induced Signal (RIS) at different orientations in the applied magnetic field samples were placed in the resonance cavity for Q-band EPR. In X-band spectra, the RIS is distinct from the ``native'' radiation-independent signal only for doses > 0.5Gy. Q-band, however, resolves the RIS and ``native'' signals and improves sensitivity by a factor of 20 enabling measurements in 2-4 mg tooth enamel samples. )

  3. Longitudinal analysis on utilization of medical document management system in a hospital with EPR implementation.

    PubMed

    Kuwata, Shigeki; Yamada, Hitomi; Park, Keunsik

    2011-01-01

    Document management systems (DMS) have widespread in major hospitals in Japan as a platform to digitize the paper-based records being out of coverage by EPR. This study aimed to examine longitudinal trends of actual use of DMS in a hospital in which EPR had been in operation, which would be conducive to planning the further information management system in the hospital. Degrees of utilization of electronic documents and templates with DMS were analyzed based on data extracted from a university-affiliated hospital with EPR. As a result, it was found that the number of electronic documents as well as scanned documents circulating at the hospital tended to increase. The result indicated that replacement of paper-based documents with electronic documents did not occur. Therefore it was anticipated that the need for DMS would continue to increase in the hospital. The methods used this study to analyze the trend of DMS utilization would be applicable to other hospitals with with a variety of DMS implementation, such as electronic storage by scanning documents or paper preservation that is compatible with EPR.

  4. 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

  5. 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…

  6. Non-uniform sampling in EPR--optimizing data acquisition for HYSCORE spectroscopy.

    PubMed

    Nakka, K K; Tesiram, Y A; Brereton, I M; Mobli, M; Harmer, J R

    2014-08-21

    Non-uniform sampling combined with maximum entropy reconstruction is a powerful technique used in multi-dimensional NMR spectroscopy to reduce sample measurement time. We adapted this technique to the pulse EPR experiment hyperfine sublevel correlation (HYSCORE) and show that experimental times can be shortened by approximately an order of magnitude as compared to conventional linear sampling with negligible loss of information.

  7. BCL::MP-Fold: membrane protein structure prediction guided by EPR restraints

    PubMed Central

    Fischer, Axel W.; Alexander, Nathan S.; Woetzel, Nils; Karakaş, Mert; Weiner, Brian E.; Meiler, Jens

    2016-01-01

    For many membrane proteins, the determination of their topology remains a challenge for methods like X-ray crystallography and nuclear magnetic resonance (NMR) spectroscopy. Electron paramagnetic resonance (EPR) spectroscopy has evolved as an alternative technique to study structure and dynamics of membrane proteins. The present study demonstrates the feasibility of membrane protein topology determination using limited EPR distance and accessibility measurements. The BCL::MP-Fold algorithm assembles secondary structure elements (SSEs) in the membrane using a Monte Carlo Metropolis (MCM) approach. Sampled models are evaluated using knowledge-based potential functions and agreement with the EPR data and a knowledge-based energy function. Twenty-nine membrane proteins of up to 696 residues are used to test the algorithm. The protein-size-normalized root-mean-square-deviation (RMSD100) value of the most accurate model is better than 8 Å for twenty-seven, better than 6 Å for twenty-two, and better than 4 Å for fifteen out of twenty-nine proteins, demonstrating the algorithm’s ability to sample the native topology. The average enrichment could be improved from 1.3 to 2.5, showing the improved discrimination power by using EPR data. PMID:25820805

  8. 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.

  9. 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

  10. Impact of EPR systems on information flow in Finnish health centers.

    PubMed

    Mäkelä, Kari; Virjo, Irma; Aho, Juhani; Kalliola, Pentti; Kurunmäki, Harri; Uusitalo, Leena; Valli, Markku; Ylinen, Suvi

    2013-03-01

    We studied how well healthcare personnel in healthcare centers (HCs) in the South Ostrobothnia region of Finland are able to obtain patient information thorough electronic patient record (EPR) systems. This study followed the changes in availability of patient information during a 7-year period, from 2003 to the end of 2010. The patient group studied focused on those involved in anticoagulant (AC) treatment. A structured questionnaire was sent in 2003 to the staff of 15 HCs. The questionnaire dealt with access and availability of patient information from the EPR. Respondents were asked to rate how often they obtain information concerning AC treatment from various sources. In total, 1,114 questionnaires were sent, and 860 answers were received; the response rate was 77%. A repeat study was conducted in 2010, and 932 responses were obtained (response rate, 56%). Paper-based AC treatment cards carried by the patients were an important information source for 75.0% of the respondents in 2003 and 55.4% in 2010. For all new AC treatments, the EPR was a primary information source for 33.3% of respondents in 2003 and 60.2% in 2010. This study indicated that during the study period there was an improvement in access to EPR but that this did not always improve the overall availability of data. Results show that problems in information flow from secondary care to the HCs persist. Almost half of the patients dealt with in the HCs were affected by at least some problems. In the 7 years covered by this study, EPR systems have become more important as information sources for clinical data, but there is still room for improvement.

  11. Detection of free radicals formed by in vitro metabolism of fluoride using EPR spectroscopy.

    PubMed

    Pawłowska-Góral, Katarzyna; Pilawa, Barbara

    2011-10-01

    In many parts of the globe, where water contains large amount of fluoride, fluorosis is a serious public health problem. It is accompanied by many changes, not only in the bones, but practically in all organs of the body. Since it was discovered that oxidation stress, together with the peroxidation of lipids which accompanies it, results in many diseases, research has been carried out on this aspect of fluorosis. The findings, however, are incomplete and divergent. The aim of our study was to determine the presence of free radicals in hepatocytes exposed to fluoride in concentrations which do not lead to changes in the concentrations of calcium and magnesium ions. Free radical properties of hepatocytes incubated with fluoride were studied by an X-band electron paramagnetic resonance (EPR) spectroscopy. Hepatocytes are paramagnetic and broad unsymmetrical EPR spectra were obtained for them. Oxygen free radicals with g-factor of 2.0032 exist in hepatocytes. The effect of fluoride concentration and the time of incubation on free radicals amount in cells were examined. The amount of free radicals in hepatocytes increases with the increase of fluoride concentration for all the incubation times (10, 30, and 60 min). The amount of free radicals in hepatocytes decreases with the increase of time of incubation for all the used fluoride concentrations (0.002, 0.082, and 0.164 mmol/l). EPR spectra of the studied cells are homogeneously broadened. Continuous microwave saturation of EPR lines indicates that slow spin-lattice relaxation processes exist in the studied cells. Strong dipolar interactions responsible for the broadening (ΔB(pp): 1.45-1.87 mT) of the EPR spectra exist in the hepatocytes.

  12. Concentration of Cu, EPR-detectable Cu, and formation of cupric-ferrocyanide in membranes with pMMO.

    PubMed

    Yuan, H; Collins, M L; Antholine, W E

    1998-12-01

    EPR spectra were obtained for the type 2 Cu(2+) site in particulate methane monooxygenase, pMMO, from membrane fractions of Methylomicrobium album BG8. In addition to the EPR signal with g parallel = 2.24 and A parallel = 185 G found in both cells and membrane fractions, a second EPR signal with g parallel = 2.29 and A parallel = 146 G was found in membrane fractions and attributed to oxidation of cuprous sites. Comparison of EPR-detectable Cu(2+) with total copper determined by atomic absorption suggests that there are two or three EPR-silent coppers for every EPR-detectable copper and that there are approximately four coppers per enzyme composed of the 47, 27, and 25 kDa subunits. Treatment of membrane fractions loaded with pMMO with Fe(CN)6(3-) results in a new EPR signal that is attributed to CuFe(CN)6(2-), not to an intrinsic trimeric copper cluster as previously reported in studies with a related bacterium.

  13. A combined EPR and MD simulation study of a nitroxyl spin label with restricted internal mobility sensitive to protein dynamics

    NASA Astrophysics Data System (ADS)

    Oganesyan, Vasily S.; Chami, Fatima; White, Gaye F.; Thomson, Andrew J.

    2017-01-01

    EPR studies combined with fully atomistic Molecular Dynamics (MD) simulations and an MD-EPR simulation method provide evidence for intrinsic low rotameric mobility of a nitroxyl spin label, Rn, compared to the more widely employed label MTSL (R1). Both experimental and modelling results using two structurally different sites of attachment to Myoglobin show that the EPR spectra of Rn are more sensitive to the local protein environment than that of MTSL. This study reveals the potential of using the Rn spin label as a reporter of protein motions.

  14. 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

  15. 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

  16. 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

  17. Membrane remodeling by amyloidogenic and non-amyloidogenic proteins studied by EPR

    NASA Astrophysics Data System (ADS)

    Varkey, Jobin; Langen, Ralf

    2017-07-01

    The advancement in site-directed spin labeling of proteins has enabled EPR studies to expand into newer research areas within the umbrella of protein-membrane interactions. Recently, membrane remodeling by amyloidogenic and non-amyloidogenic proteins has gained a substantial interest in relation to driving and controlling vital cellular processes such as endocytosis, exocytosis, shaping of organelles like endoplasmic reticulum, Golgi and mitochondria, intracellular vesicular trafficking, formation of filopedia and multivesicular bodies, mitochondrial fusion and fission, and synaptic vesicle fusion and recycling in neurotransmission. Misregulation in any of these processes due to an aberrant protein (mutation or misfolding) or alteration of lipid metabolism can be detrimental to the cell and cause disease. Dissection of the structural basis of membrane remodeling by proteins is thus quite necessary for an understanding of the underlying mechanisms, but it remains a formidable task due to the difficulties of various common biophysical tools in monitoring the dynamic process of membrane binding and bending by proteins. This is largely since membranes generally complicate protein structure analysis and this problem is amplified for structural analysis in the presence of different types of membrane curvatures. Recent EPR studies on membrane remodeling by proteins show that a significant structural information can be generated to delineate the role of different protein modules, domains and individual amino acids in the generation of membrane curvature. These studies also show how EPR can complement the data obtained by high resolution techniques such as X-ray and NMR. This perspective covers the application of EPR in recent studies for understanding membrane remodeling by amyloidogenic and non-amyloidogenic proteins that is useful for researchers interested in using or complimenting EPR to gain better understanding of membrane remodeling. We also discuss how a single

  18. EPR and NMR detection of transient radicals and reaction products. [Radiolysis of methanol and aqueous potassium acetate

    SciTech Connect

    Trifunac, A.D.

    1981-01-01

    Magnetic resonance methods in radiation chemistry are illustrated. The most recent developments in pulsed EPR and NMR studies in pulse radiolysis are outlined with emphasis on the study of transient radicals and their reaction products. 12 figures.

  19. New strategy to identify radicals in a time evolving EPR data set by multivariate curve resolution-alternating least squares.

    PubMed

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

    2016-12-01

    Electron paramagnetic resonance (EPR) spectroscopy is a powerful technique that is able to characterize radicals formed in kinetic reactions. However, spectral characterization of individual chemical species is often limited or even unmanageable due to the severe kinetic and spectral overlap among species in kinetic processes. Therefore, we applied, for the first time, multivariate curve resolution-alternating least squares (MCR-ALS) method to EPR time evolving data sets to model and characterize the different constituents in a kinetic reaction. Here we demonstrate the advantage of multivariate analysis in the investigation of radicals formed along the kinetic process of hydroxycoumarin in alkaline medium. Multiset analysis of several EPR-monitored kinetic experiments performed in different conditions revealed the individual paramagnetic centres as well as their kinetic profiles. The results obtained by MCR-ALS method demonstrate its prominent potential in analysis of EPR time evolved spectra.

  20. 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.

  1. Electronic g-factor measurement from ENDOR-induced EPR patterns: malonic acid and guanine hydrochloride dihydrate.

    PubMed

    Kang, Junseog; Tokdemir, Sibel; Shao, Jun; Nelson, William H

    2003-11-01

    Measurement of electronic g-factors (g) from radicals in irradiated organic crystals is generally difficult because the overall EPR pattern is usually the composite of several components, e.g., from multiple radicals and from multiple magnetic sites. However, when an ENDOR line is fully resolved, the method of ENDOR-induced EPR (EI-EPR, or EIE) in principle permits identification of the EPR pattern from the individual component yielding the line. To examine this method as an approach useful for measuring g, we used it to measure those of known radicals in two different crystal systems. First, to verify correspondence of the EIE and EPR sufficient for using EIE patterns to extract g, we used both EIE and EPR to measure g of (*CH(COOH)(2) from irradiated crystals of malonic acid. Then, to illustrate the procedure applied to a system giving a more complex EPR pattern, we used EIE to measure g of the O6-protonated anion radical of guanine in irradiated guanine.HCl.2H(2)O crystals. EPR results from the malonic acid radical are g(max)=2.00374(2), g(mid)=2.00331(2), and g(min)=2.00234(3); EIE results from the same radical are g(max)=2.00375(2), g(mid)=2.00334(2), and g(min)=2.00238(2), where numbers in parentheses indicate statistical uncertainties in the respective least significant digits. In addition, eigenvectors from the two sets of measurements agree to approximately 1 degrees. Results from the guanine radical are g(max)=2.00490(2), g(mid)=2.00318(4), and g(min)=2.00218(4). (The uncertainties should reliably indicate relative accuracy, while absolute accuracy is within +/-0.0002 as indicated by simultaneous measurement of Cr(3+) in MgO.)

  2. EPR and optical absorption studies on Gd 3+ ions in ammonium hydrogen malonate single crystals

    NASA Astrophysics Data System (ADS)

    Kripal, Ram; Mishra, Indrajeet

    2010-01-01

    X-Band electron paramagnetic resonance (EPR) studies of Gd 3+ ions in ammonium hydrogen malonate single crystals have been done at room temperature. Detailed EPR analysis indicates the presence of four physically equivalent but magnetically inequivalent sites. The zero-field splitting parameters and g factor are determined. The Gd 3+ ion is in 8S state; its levels are split by the action of the crystalline electric field of monoclinic symmetry. The optical absorption spectra of Gd 3+ ions in single crystals of ammonium hydrogen malonate are also recorded at room temperature. The energy levels of the 4f 7 configuration are calculated and compared with those observed experimentally. The values of E1=5854±11, E2=31±0.36, E3=592±3.3 and ζ 4f=1595±25 cm -1 are found to give the best over-all agreement between experimentally observed and calculated levels.

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

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

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

  4. EPR in the USSR: the thorny path from birth to biological and chemical applications.

    PubMed

    Ptushenko, Vasily Vitalievich; Zavoiskaya, Nataliya Evgenievna

    2017-08-25

    In 1944, electron paramagnetic resonance (EPR) was discovered by Evgenii Konstantinovich Zavoisky in the USSR (Union of the Soviet Socialist Republics). Since then, magnetic resonance methods have contributed invaluably to our knowledge in many areas of Life Sciences and Chemistry, and particularly in the area of photosynthesis research. However, the road of the magnetic resonance methods, as well as its acceptance in Life Sciences and Chemistry, was not smooth and prompt in the (former) USSR. We discuss the role played by many including Jakov K. Syrkin, Nikolai N. Semenov, Vladislav V. Voevodsky, Lev A. Blumenfeld, Peter L. Kapitza, and Alexander I. Shalnikov during the early stages of biological and chemical EPR spectroscopy in the USSR.

  5. A low-cost implementation of EPR detection in a dissolution DNP setup

    NASA Astrophysics Data System (ADS)

    Granwehr, Josef; Leggett, James; Köckenberger, Walter

    2007-08-01

    The implementation of electron paramagnetic resonance (EPR) detection in a low-temperature dissolution dynamic nuclear polarization (DNP) setup is presented. Using a coil oriented parallel to the static magnetic field, the change of the longitudinal magnetization of free radicals is measured upon resonant irradiation of an amplitude or frequency modulated microwave (mw) field. The absorption EPR spectrum is measured if the amplitude of the mw field is modulated, whilst the first derivative of the spectrum is obtained with frequency modulation. Using a burst of pulses, it is also possible to perform pump-probe experiments such as saturation-recovery or electron-electron double resonance experiments. Furthermore, the magnetization could be monitored in a time-resolved manner during amplitude modulation, thus making it possible to record its transient as it is approaching an equilibrium value. Experimental examples are shown with frozen solutions of trityl radical and TEMPO, two commonly used radicals for dissolution DNP experiments.

  6. Manifestation of the Hanle effect in submillimeter EPR spectroscopy of thulium impurity ions in synthetic forsterite

    NASA Astrophysics Data System (ADS)

    Tarasov, V. F.; Solovarov, N. K.; Zharikov, E. V.

    2016-10-01

    A signal related to the spin level crossing in a zero magnetic field—the Hanle effect—has been registered for the first time in the EPR spectrum. It has been shown that, in the general case, the shape of the signal is determined by two qualitatively different mechanisms: (i) the interference of unsteady-state contributions to the dynamics of atomic coherences (electric or magnetic quantum transition moments with certain phases) with close frequencies ("beats at a zero frequency") and (ii) the summation of resonant signals determined by the steady-state dynamics of the same atomic coherences. The relaxation time of spin coherences has been determined for the EPR transition of Tm3+ ions in synthetic forsterite.

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

    NASA Astrophysics Data System (ADS)

    Price, Alex D.

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

  8. Investigation of signal fading in lithium formate EPR dosimeters using a new sensitive method

    NASA Astrophysics Data System (ADS)

    Adolfsson, Emelie; Karlsson, Mattias; Alm Carlsson, Gudrun; Carlsson Tedgren, Åsa; Lund, Eva; Olsson, Sara; Gustafsson, Håkan

    2012-04-01

    The aim of this study was to investigate signal fading in lithium formate electron paramagnetic resonance (EPR) dosimeters used for clinical applications in radiotherapy. A new experimental method for determination of signal fading, designed to resolve small changes in signal from slowly decaying unstable radicals, was used. Possible signal fading in lithium formate due to different storage temperatures was also tested. Air humidity was kept at a constant level of 33% throughout the experiments. The conclusion drawn from the investigations was that the EPR signal from lithium formate is stable during at least 1 month after irradiation and is not sensitive to variations in storage temperature <40 °C when kept at a relative air humidity of 33%. This makes lithium formate a suitable dosimeter for transfer dosimetry in clinical audits.

  9. 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.

  10. Analysis of two-player quantum games in an EPR setting using Clifford's geometric algebra.

    PubMed

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

    2012-01-01

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

  11. Improving Conventional Enhanced Permeability and Retention (EPR) Effects; What Is the Appropriate Target?

    PubMed Central

    Kobayashi, Hisataka; Watanabe, Rira; Choyke, Peter L.

    2014-01-01

    Nano-sized therapeutic agents have several advantages over low molecular weight agents such as a larger loading capacity, the ability to protect the payload until delivery, more specific targeting due to multivalency and the opportunity for controlled/sustained release. However, the delivery of nano-sized agents into cancer tissue is problematic because it mostly relies on the enhanced permeability and retention (EPR) effect that depends on the leaky nature of the tumor vasculature and the prolonged circulation of nano-sized agents, allowing slow but uneven accumulation in the tumor bed. Delivery of nano-sized agents is dependent on several factors that influence the EPR effect; 1. Regional blood flow to the tumor, 2. Permeability of the tumor vasculature, 3. Structural barriers imposed by perivascular tumor cells and extracellular matrix, 4. Intratumoral pressure. In this review, these factors will be described and methods to enhance nano-agent delivery will be reviewed. PMID:24396516

  12. The design and integration of retinal CAD-SR to diabetes patient ePR system

    NASA Astrophysics Data System (ADS)

    Wu, Huiqun; Wei, Yufang; Liu, Brent J.; Shang, Yujuan; Shi, Lili; Jiang, Kui; Dong, Jiancheng

    2017-03-01

    Diabetic retinopathy (DR) is one of the serious complications of diabetes that could lead to blindness. Digital fundus camera is often used to detect retinal changes but the diagnosis relies too much on ophthalmologist's experience. Based on our previously developed algorithms for quantifying retinal vessels and lesions, we developed a computer aided detection-structured report (CAD-SR) template and implemented it into picture archiving and communication system (PACS). Furthermore, we mapped our CAD-SR into HL7 CDA to integrate CAD findings into diabetes patient electronic patient record (ePR) system. Such integration could provide more quantitative features from fundus image into ePR system, which is valuable for further data mining researches.

  13. Spin Labeling and Characterization of Tau Fibrils Using Electron Paramagnetic Resonance (EPR).

    PubMed

    Meyer, Virginia; Margittai, Martin

    2016-01-01

    Template-assisted propagation of Tau fibrils is essential for the spreading of Tau pathology in Alzheimer's disease. In this process, small seeds of fibrils recruit Tau monomers onto their ends. The physical properties of the fibrils play an important role in their propagation. Here, we describe two different electron paramagnetic resonance (EPR) techniques that have provided crucial insights into the structure of Tau fibrils. Both techniques rely on the site-directed introduction of one or two spin labels into the protein monomer. Continuous-wave (CW) EPR provides information on which amino acid residues are contained in the fibril core and how they are stacked along the long fibril axis. Double electron-electron resonance (DEER) determines distances between two spin labels within a single protein and hence provides insights into their spatial arrangement in the fibril cross section. Because of the long distance range accessible to DEER (~2-5 nm) populations of distinct fibril conformers can be differentiated.

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

    NASA Astrophysics Data System (ADS)

    Beshir, W. B.

    2014-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Karabulut, Bünyamin; Yıldırım, İlkay

    2015-12-01

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

  16. EPR spectroscopy of chlorpromazine-induced free radical formation in normal human melanocytes.

    PubMed

    Otręba, Michał; Zdybel, Magdalena; Pilawa, Barbara; Beberok, Artur; Wrześniok, Dorota; Rok, Jakub; Buszman, Ewa

    2015-07-01

    The purpose of this study was to estimate the effect of chlorpromazine on free radical concentration in HEMn-DP melanocytes using electron paramagnetic resonance (EPR) spectroscopy. It was found that chlorpromazine at concentrations of 1 × 10(-7) and 1 × 10(-6) M contributed to the formation of free radicals (g values ~2) in a dose-dependent manner. The increase in free radical formation was accompanied by an increase in cytotoxicity, as shown by a tetrazolium assay. Homogeneous broadening of EPR lines, slow spin-lattice relaxation processes, and strong dipolar interactions characterized all the tested cellular samples. The performed examination of free radical formation in cells exposed to different chlorpromazine concentrations confirmed the usefulness of electron paramagnetic resonance spectroscopy to determine the effect of a drug on free radical production in a cellular model system in vitro.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  18. Deep level defects in sublimation-grown 6H silicon carbide investigated by DLTS and EPR

    NASA Astrophysics Data System (ADS)

    Irmscher, K.; Pintilie, I.; Pintilie, L.; Schulz, D.

    2001-12-01

    6H-SiC bulk single crystals grown by physical vapor transport (PVT) were investigated by deep-level transient spectroscopy (DLTS) and electron paramagnetic resonance (EPR). One of the observed deep level defects was identified as isolated tungsten on Si sites by EPR. The electron spin of {1}/{2} could be explained by W 5+ (5d 1). This is equivalent to the single positive charge state of a double donor when taking into account the Fermi level position in the n-type samples. The interpretation is also consistent with the DLTS detection of a W related deep level which showed a behavior of the capture of electrons and holes that hints at a double donor. In addition a tantalum related deep level is tentatively discussed. W and Ta were incorporated on electrically active sites in 6H-SiC only in low concentrations (2-4×10 14 cm -3) during crystal growth by PVT.

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

    PubMed

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

    2005-02-01

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

  20. EPR investigation on radiation-induced graft copolymerization of styrene onto polyethylene: Energy transfer effects

    NASA Astrophysics Data System (ADS)

    Salih, M. A.; Buttafava, A.; Ravasio, U.; Mariani, M.; Faucitano, A.

    2007-08-01

    In this paper, energy transfer phenomena concerning the in-source graft copolymerization of styrene onto LDPE were investigated through the EPR analysis of the radical intermediates. The model solution experiments have shown a substantial deviation of the experimental G (radicals) values with respect to the additivity law, which reflect the negative effect of the styrene monomer concentration on the initiation rate of the graft copolymerization. The EPR measurements performed on polyethylene- co-styrene graft copolymers of various composition following low-temperature vacuum gamma irradiation have confirmed the decrease of the total radical yields with increasing the styrene concentration. The effect was partly attributed to the heterogeneity of the graft copolymer matrix and to the lack of molecular mobility in the solid state at low temperature, which prevents the attainment of the favourable geometrical configurations in intermolecular energy and charge transfer events.

  1. Structure-activity study of thiazides by magnetic resonance methods (NQR, NMR, EPR) and DFT calculations.

    PubMed

    Latosińska, J N

    2005-01-01

    The paper presents a comprehensive analysis of the relationship between the electronic structure of thiazides and their biological activity. The compounds of interest were studied in solid state by the resonance methods nuclear quadrupole resonance (NQR), nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) and quantum chemistry (ab inito and DFT) methods. Detailed parallel analysis of the spectroscopic parameters such as quadrupole coupling constant (QCC) NQR chemical shift (delta), chemical shift anisotropy (CSA), asymmetry parameter (eta), NMR and hyperfine coupling constant (A), EPR was performed and the electronic effects (polarisation and delocalisation) were revealed and compared. Biological activity of thiazides has been found to depend on many factors, but mainly on the physico-chemical properties whose assessment was possible on the basis of electron density determination in the molecules performed by experimental and theoretical methods.

  2. In vivo preclinical cancer and tissue engineering applications of absolute oxygen imaging using pulse EPR

    NASA Astrophysics Data System (ADS)

    Epel, Boris; Kotecha, Mrignayani; Halpern, Howard J.

    2017-07-01

    The value of any measurement and a fortiori any measurement technology is defined by the reproducibility and the accuracy of the measurements. This implies a relative freedom of the measurement from factors confounding its accuracy. In the past, one of the reasons for the loss of focus on the importance of imaging oxygen in vivo was the difficulty in obtaining reproducible oxygen or pO2 images free from confounding variation. This review will briefly consider principles of electron paramagnetic oxygen imaging and describe how it achieves absolute oxygen measurements. We will provide a summary review of the progress in biomedical EPR imaging, predominantly in cancer biology research, discuss EPR oxygen imaging for cancer treatment and tissue graft assessment for regenerative medicine applications.

  3. Cyanide inhibition of cytochrome c oxidase. A rapid-freeze e.p.r. investigation.

    PubMed Central

    Jensen, P; Wilson, M T; Aasa, R; Malmström, B G

    1984-01-01

    The inhibition of cytochrome c oxidase by cyanide, starting either with the resting or the pulsed enzyme, was studied by rapid-freeze quenching followed by quantitative e.p.r. It is found that a partial reduction of cytochrome oxidase by transfer of 2 electron equivalents from ferrocytochrome c to cytochrome a and CuA will induce a transition from a closed to an open enzyme conformation, rendering the cytochrome a3-CuB site accessible for cyanide binding, possibly as a bridging ligand. A heterogeneity in the enzyme is observed in that an e.p.r. signal from the cytochrome a3 3+-HCN complex is only found in 20% of the molecules, whereas the remaining cyanide-bound a3-CuB sites are e.p.r.-silent. PMID:6098268

  4. Optical and EPR spectroscopy studies on haem arginate, a new compound used for treatment of porphyria.

    PubMed

    Sievers, G; Häkli, H; Luhtala, J; Tenhunen, R

    1987-01-01

    A protohaem compound, used for treatment of porphyrias, has been studied to elucidate its state of aggregation. EPR and absorption spectroscopy measurements reveal that 38.3 mM protohaem, dissolved in 40% 1,2-propanediol/10% ethanol/water solution, also containing 153 mM arginine, is partly EPR silent. It exists as high molecular weight aggregates and probably also as mu-oxo-dimers. Dilution in the aqueous alcohol solution dissolves the aggregates first to oligomers and dimers, and finally to monomers (Kdiss = 24 X 10(-6)M). When haem is diluted in 0.9% sodium chloride, a fully monomeric state is not reached even at 1 microM concentration. At 3.5 microM concentration, that used for infusion in patients, the haem is still totally aggregated.

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

    PubMed Central

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

    2012-01-01

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

  6. The defect structure and EPR parameters for Er3+ in molybdates: a complete energy matrices study

    NASA Astrophysics Data System (ADS)

    Li, Cheng-Gang; Kuang, Xiao-Yu; Chai, Rui-Peng; Zhao, Ya-Ru

    2012-12-01

    In this paper, we develop a complete energy matrices approach investigating the defect structure and EPR parameters ( ? , ? , ? and ? ) for Er3+ in molybdates. In this approach, the crystal-field parameters used in the calculations are determined from the superposition model and the structural data for tetragonal distortion. The local distortion angles Δθ = -1.628°, Δθ = -1.843° and Δθ = -2.874° are obtained for Er3+ in SrMoO4, PbMoO4 and CaMoO4 crystals, respectively. Moreover, the influence of the orbital reduction factor k and the local distortion angle Δθ on the EPR parameters is analyzed.

  7. Solid-state NMR and EPR Spectroscopy of Mn(2+) -Substituted ATP-Fueled Protein Engines.

    PubMed

    Wiegand, Thomas; Lacabanne, Denis; Keller, Katharina; Cadalbert, Riccardo; Lecoq, Lauriane; Yulikov, Maxim; Terradot, Laurent; Jeschke, Gunnar; Meier, Beat H; Böckmann, Anja

    2017-02-13

    Paramagnetic metal ions deliver structural information both in EPR and solid-state NMR experiments, offering a profitable synergetic approach to study bio-macromolecules. We demonstrate the spectral consequences of Mg(2+) / Mn(2+) substitution and the resulting information contents for two different ATP:Mg(2+) -fueled protein engines, a DnaB helicase from Helicobacter pylori active in the bacterial replisome, and the ABC transporter BmrA, a bacterial efflux pump. We show that, while EPR spectra report on metal binding and provide information on the geometry of the metal centers in the proteins, paramagnetic relaxation enhancements identified in the NMR spectra can be used to localize residues at the binding site. Protein engines are ubiquitous and the methods described herein should be applicable in a broad context.

  8. Electron paramagnetic resonance (EPR) investigations of lichens - 1: effects of air pollution

    NASA Astrophysics Data System (ADS)

    Jezierski, Adam; Bylinska, Ewa; Seaward, Mark R. D.

    Electron paramagnetic resonance (EPR) investigations were carried out on more than 800 samples of lichens from Lower Silesia, southwest Poland. A statistically confirmed correlation between annual average concentration of sulphur dioxide in the atmosphere and concentration of semiquinone radicals in Hypogymnia physodes thalli was found. Similar results were obtained for Umbilicaria species from the Karkonosze Mountains. Distribution of semiquinone radicals in lichen thalli was also investigated. The action of nitrogen dioxide on Umbilicaria species resulted in the synthesis of iminoxy radicals in the thalli. The intensification of the semiquinone free radical production in lichen thalli from atmospherically polluted environments and the degradation of lichen acids to β-diketone compounds would appear to be parallel processes. The properties of the iminoxyls derived from β-diketones in the lichen matrix (anisotropic spectra at room temperature) and in organic solutions after extraction procedure were also examined by EPR.

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

    NASA Astrophysics Data System (ADS)

    Kalfaoğlu, Emel; Karabulut, Bünyamin

    2012-04-01

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

  10. 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.

  11. EPR Study of Vanadium Ion in Zinc-Boro-Vanadate Glasses

    SciTech Connect

    Renuka, C.; Gowda, V. C. Veeranna; Chakradhar, R. P. S.; Reddy, C. Narayana

    2011-07-15

    This paper describes EPR studies on x V{sub 2}O{sub 5}-(40-x)ZnO-60B{sub 2}O{sub 3}(where x 5, 10, 15 and 20 mol %) glass system. These studies indicate a strong compositional dependent trend and existence of characteristic boro-vanadate groups in these glasses. The EPR spectra show a distinct hyperfine structure of {sup 51}V. Spectral analysis shows that the vanadium is present in the glass as vanadyl ion [VO]{sup 2+} at tetragonally distorted octahedral site. The decrease of A{sub ||} and A{sub perpendicular} with increase of V{sub 2}O{sub 5} concentration suggests an increase in the covalence between the central atom and the surrounding oxygen ligands.

  12. EPR study of phenolic radical stabilization by grafting on SiO 2

    NASA Astrophysics Data System (ADS)

    Panagiota, Stathi; Louloudi, Maria; Deligiannakis, Yiannis

    2009-04-01

    A hybrid [SiO 2-GA] material has been synthesized by grafting Gallic acid (3,4,5-trihydroxybenzoic acid, GA) on SiO 2 via formation of amide bonds between amine groups on aminopropyl-silica and the carboxyl group of GA. The spatial fixation of GA prevents polymerization effects. EPR spectroscopy shows that GA radicals on [SiO 2-GA] show remarkable stability, comparable to that previously observed only for radicals in biological matrices on in soil organic matter. EPR reveals a bundle-like organization of the GA molecules on [SiO 2-GA] material. The relation of these factors to the enhanced radical stability is discussed.

  13. EPR spectroscopy solutions for assessment of decellularization of intrathoracic organs and tissues.

    PubMed

    Gubareva, E A; Kuevda, E V; Dzhimak, S S; Basov, A A; Sotnichenko, A S; Bolotin, S N; Gilevich, I V; Gumenyuk, I S; Macchiarini, P

    2016-03-01

    Using EPR spectroscopy it was established that the determination of the concentration of paramagnetic centers in lyophilized tissues allows indirect evaluation of the quality of decellularization of intrathoracic organs (diaphragm, heart, and lungs), since the content of paramagnetic particles in them can serve as a criterion of cell viability and points to the necessity to repeat decellularization. Experiments in rats showed that the EPR spectra of the native thoracic organs contained paramagnetic centers with g-factor values ranging from 2.007 to 2.011 at a concentration of 10(-8) to 6.62 × 10(-7) mol/g of lyophilized tissue, whereas in all decellularized tissues of the same organs paramagnetic particles were not detected.

  14. Influence of Pb(II) Ions on the EPR Properties of the Semiquinone Radicals of Humic Acids and Model Compounds: High Field EPR and Relativistic DFT Studies

    NASA Astrophysics Data System (ADS)

    Witwicki, Maciej; Jerzykiewicz, Maria; Jaszewski, Adrian R.; Jezierska, Julia; Ozarowski, Andrzej

    2009-11-01

    X-band (9.76 GHz) and high field (416.00 GHz) electron paramagnetic resonance spectroscopy (EPR) was used to study the interactions between Pb(II) ions and semiquinone radicals of natural humic acids and their simple models. The EPR experiments were performed on powder samples. The formation of Pb(II) complexes with the radicals was accompanied by a significant decrease of g parameters as compared to those observed for parent radicals. Two types of complexes were identified depending on the initial concentration of Pb(II) ions. For one of them the anisotropic hyperfine coupling with the 207Pb nucleus was observed. Systematic DFT calculations were carried out for complexes with different forms of radical ligands (L2-•, HL-•, and H2L•) derived from 3,4-dihydroxybenzoic acid representing different ligation schemes. The g parameters calculated for the structure characterized by a significant accumulation of spin density on the Pb atom are strongly deviated from the values observed experimentally. Moreover, a decrease of the spin population on all oxygen atoms as a result of complexation of Pb(II) via carboxyl oxygens and protonation of hydroxyl oxygens is required to reproduce the experimental g parameters.

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

    PubMed Central

    Voinov, Maxim A.; Smirnov, Alex I.

    2016-01-01

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

  16. EPR study of a vinyl-type radical in X-irradiated. beta. -carotene

    SciTech Connect

    Joseph, J.; Samskog, P.O.; Lee, S.H.; Kispert, L.D.

    1985-05-09

    A vinyl-type radical with proton EPR couplings of 68 and 72 G has been observed at -40/sup 0/C as a secondary radical formed when a sample of trans-..beta..-carotene powder is X-ray irradiated at 77 K in the dark and warmed. An INDO/CI calculation suggests that it is due to the loss of a proton from the 15 or 15' position. 22 references, 3 tables.

  17. EPR Studies of Cu2+ in dl-Aspartic Acid Single Crystals

    NASA Astrophysics Data System (ADS)

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

    1999-04-01

    EPR studies of Cu2+ doped dl-Aspartic Acid [NH2CH(CH2COOH)COO] powder and single crystal have been carried out at 113 and 300 K. The principal hyperfine and g values, covalancy parameter, mixing coefficients and Fermi-contact term of the complex were obtained, and the ground-state wavefuntion of the Cu2+ ion in the lattice has been constructed.

  18. [Documentation of electronic patient records (EPRS) in German general practices: a telephone survey].

    PubMed

    Heidenreich, Regine; Himmel, Wolfgang; Böckmann, Harro; Hummers-Pradier, Eva; Kochen, Michael M; Niebling, Wilhelm; Rogausch, Anja; Sigle, Jörg; Wetzel, Dirk; Scheidt-Nave, Christa

    2005-01-01

    In Germany, use and contents of EPRs are largely unknown and expected to be highly variable, due to missing standards. We conducted a telephone survey to describe and compare computer documentation habits in general practices. Specifically, we were interested in: (1) the type of medical data recorded; and (2) which factors influence the extent to which doctors used the EPR while seeing their patients. The sampling frame consisted of family physicians participating in a general practice research project: 32% (145/452) of family physicians in the district of Göttingen, Lower Saxony, and 63% (52/83) of physicians from a quality assurance network of family practices in the district of Freiburg, Baden-Württemberg. With the exception of two practices in Göttingen, all practices (n = 165 of 167) took part in this survey. Diagnoses, digital codes for service fees, and prescriptions were computerized in nearly all practices, although doctors were significantly more involved in Freiburg than in Göttingen. Clinical symptoms and findings were recorded in 80% of Freiburg and 52% of Göttingen practices (p = 0.008). Overall, in 74% of Freiburg and 51% of Göttingen practices, the physicians opened the EPR while seeing patients (p = 0.022). Nearly half of the Göttingen practices (49%) and 24% of the Freiburg practices (p < 0.05) entered digital codes for service fees and diagnoses on paper before entering them electronically. In multivariate models adjusting for sex, target group and training specialty, internet access in the office was independently predictive of 'EPR-activity' (OR: 2.23; 95%-confidence interval: 1.12-4.43). There seems to be room for improvement in terms of degree and intensity of recording of clinically-relevant data. Technical interest, i.e., internet access in the office, seems to enhance electronic documentation activities.

  19. On the anomalous temperature behaviour of the EPR signal of monovalent nickel in hydrogenase.

    PubMed

    Van der Zwaan, J W; Albracht, S P; Fontijn, R D; Mul, P

    1987-12-01

    The dependence on temperature in the range between 4.2 K and 20 K was measured for the EPR signal of monovalent nickel in H2-reduced hydrogenase from Chromatium vinosum and from Methanobacterium thermoautotrophicum. In accordance with measurements on the hydrogenase from Desulfovibrio gigas [Teixeira, M., Moura, I., Xavier, A. V., Huynh, B. H., DerVartanian, D. V., Peck, H. D., Jr, LeGall, J. and Moura, J. J. G. (1985) J. Biol. Chem. 260, 8942-8950; and Cammack, R., Patil, D. S. and Fernandez, V. M. (1985) Biochem. Soc. Trans. 13, 572-578], the enzyme from C. vinosum showed a distinct transformation of the EPR signal of nickel in this temperature region. The light sensitivity did not change. EPR spectra recorded at 9 GHz and at 35 GHz showed that the transformation of the spectrum at 4.2 K is caused by spin coupling to an unknown paramagnet. No coupling was apparent at temperatures above 20 K. At 4.2 K, additional, very broad signals in the region g= 1.2-3, as well as a signal around g = 5, were detected In the enzyme from C. Vinosum, both in the H2-reduced state and in the Ar-reoxidised state. The possible origin of the paramagnetic species responsible for these signals is discussed. The EPR signal of monovalent nickel in the enzyme from M. thermoautotrophicum showed no significant changes in line shape between 4.2 K and 70 K, nor were any additional signals detected. This suggests that in the reduced form of this enzyme similar paramagnetic species might be absent or not reduced.

  20. Emergency Preservation and Resuscitation for Cardiac Arrest from Trauma (EPR CAT)

    DTIC Science & Technology

    2016-12-01

    Award Number: W81XWH-07-1-0682 TITLE: Emergency Preservation and Resuscitation for Cardiac Arrest from Trauma (EPR-CAT) PRINCIPAL INVESTIGATOR...Arrest 5a. CONTRACT NUMBER From Trauma 5b. GRANT NUMBER W81XWH-07-1-0682 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER Patrick...for the trauma surgeons involved in the project has been completed. The Shock Trauma Center of the University of Maryland Medical Center is now open

  1. Managing integration work in an NHS electronic patient record (EPR) project.

    PubMed

    Martin, David; Mariani, John; Rouncefield, Mark

    2007-03-01

    This article uses an ethnographic study of the design and deployment of an electronic patient record (EPR) system in the UK NHS to document some of the difficulties of integrating new IT systems with existing and developing practices, technologies and regulatory requirements. It highlights that 'integration' in this situation produces a variety of different but connected and potentially competing requirements that create difficulties in achieving artful and successful system deployment.

  2. Antiviral properties against HIV of water soluble copper carbosilane dendrimers and their EPR characterization.

    PubMed

    Galan, M; Sanchez-Rodriguez, J; Cangiotti, M; Garcia-Gallego, S; Jimenez, J L; Gomez, R; Ottaviani, M F; Munoz-Fernandez, M A; de la Mata, F J

    2012-01-01

    We describe here the use of anionic carbosilane dendrimers to obtain new copper complexes. UV-Vis and a computer aided analysis of the EPR spectra provided information about the coordination modes of copper depending on the nature of the dendrimer and about the geometry and structure of the complexes in solution. Some of these metallo-dendrimers have been tested "in vitro" as antiviral compounds in the inhibition of HIV infection in pre and post-infection treatment.

  3. EPR study of monomeric and dimeric vanadyl ions in SbVO5

    NASA Astrophysics Data System (ADS)

    Typek, J.; Guskos, N.; Buchowski, D.; Wabia, M.; Filipek, E.

    A new compound, SbVO5 , formed in the V-Sb-O system, has been synthesized and investigated using the electron paramagnetic resonance (EPR) technique. SbVO5 has been prepared by two methods: by heating equimolar mixtures of V2O5 and alpha-Sb2O4 in air and by oxidation of the known phase (SbVO4.5) of rutile type obtained in pure argon at temperatures between 550 degreesC and 650 degreesC. At room temperature only a weak EPR signal from the powder sample of SbVO5 was detected corroborating the absence of bulk V(IV) ions in the structure. Comparison with the CuSO4 reference sample revealed that only 0.02% vanadium ions are EPR active. Intense EPR spectra obtained in the low temperature range, below 100 K, showed a well resolved hyperfine structure typical of isolated vanadium ions in axial symmetry, present as VO2+ species, and a broad line attributed to V4+-O-V5+ bonds. The hyperfine structure lines could be analyzed by an axial spin Hamiltonian with g parallel to =1.9311, g perpendicular to =1.9425 and A parallel to =181x10(-4) cm(-1) , A perpendicular to =54x10(-4) cm(-1) . The spectrum recorded at the lowest obtainable temperature T=3.65 K contains yet another component which is typical of a triplet state indicating the presence of two interacting VO2+ nuclei with spin 1/2 giving a singlet S=0 and a triplet S=1 state. The appearance of a low-field line (Bsimilar to1600 Gs at gapproximate to4) is another diagnostic for the presence of dimeric species and is attributed to the forbidden DeltaM(S) =+/-2 transition.

  4. Emergency Preservation and Resuscitation for Cardiac Arrest from Trauma (EPR-CAT)

    DTIC Science & Technology

    2015-10-01

    Award Number: W81XWH-07-1-0682 TITLE: Emergency Preservation and Resuscitation for Cardiac Arrest from Trauma (EPR-CAT) PRINCIPAL INVESTIGATOR...COVERED (From - To) 26 SEP 2014 – 25 SEP 2015 4. TITLE AND SUBTITLE Emergency Preservation and Resuscitation for Cardiac Arrest 5a. CONTRACT NUMBER From...study. It was felt that patients who arrive at the hospital with a pulse, but then develop cardiac arrest in the operating room , rather than in the

  5. Bismuth germanate as a perspective material for dielectric resonators in EPR spectroscopy

    NASA Astrophysics Data System (ADS)

    Ivanov, Mikhail Y.; Nadolinny, Vladimir A.; Bagryanskaya, Elena G.; Grishin, Yuriy A.; Fedin, Matvey V.; Veber, Sergey L.

    2016-10-01

    High purity bismuth germanate (Bi4(GeO4)3, BGO) is proposed and implemented as an alternative material for dielectric EPR resonators. A significant improvement of the absolute sensitivity can be readily achieved by substituting the alumina insert (ring) by BGO-made one in commercially available X-band EPR probeheads. Four BGO dielectric inserts of 2, 3, 4 and 5 mm inner diameter (ID) were made for comparison with standard 5 mm inner diameter alumina insert. All inserts were introduced into commercial Bruker EPR resonator ER 4118X-MD-5W1, and their performance was investigated. The Q-values of empty resonators, B1 saturation curves and continuous wave EPR spectra of DPPH (2,2-diphenyl-1-picrylhydrazyl) were measured and analyzed in a temperature range 6-300 K. BGO-made resonators were found superior in several important aspects. The background signals arising from BGO are much weaker compared to those of alumina at B = 0-0.6 T and T = 6-300 K; this is especially useful for measuring weak signals in the half-field region, as well as those near the central field. Moreover, mechanical properties of BGO allow easy fabrication of dielectric bodies having various shapes and sizes; in particular, small BGO resonators (e.g. ID = 2 or 3 mm) strongly enhance sensitivity for small samples due to increase of the filling factor. All these advantages have been also inspected in the pulse mode, proving that higher B1 fields and better filling factors can be achieved, contributing to the overall enhancement of the performance.

  6. EPR and ENDOR studies of Fe(II) hemoproteins reduced and oxidized at 77 K.

    PubMed

    Davydov, Roman; Hoffman, Brian M

    2008-03-01

    gamma-irradiation of frozen solutions of Fe(II) hemoproteins at 77 K generates both electron paramagnetic resonance (EPR) active singly reduced and oxidized heme centers trapped in the conformation of the Fe(II) precursors. The reduction products of pentacoordinate (S = 2) Fe(II) globins, peroxidases and cytochrome P450cam show EPR and electron-nuclear double resonance (ENDOR) spectra characteristic of (3d 7) Fe(I) species. In addition, cryoreduced Fe(II) alpha-chains of hemoglobin and myoglobin exhibit an S = 3/2 spin state produced by antiferromagnetic coupling between a porphyrin anion radical and pentacoordinate (S = 2) Fe(II). The spectra of cryoreduced forms of Fe(II) hemoglobin alpha-chains and deoxymyoglobin reveal that the Fe(II) precursors adopt multiple conformational substates. Reduction of hexacoordinate Fe(II) cytochrome c and cytochrome b5 as well as carboxy complexes of deoxyglobins produces only Fe(II) porphyrin pi-anion radical species. The low-valent hemoprotein intermediates produced by cryoreduction convert to the Fe(II) states at T > 200 K. Cryogenerated Fe(III) cytochrome c and cytochrome b5 have spectra similar to these for the resting Fe(III) states, whereas the spectra of the products of cryooxidation of pentacoordinate Fe(II) globins and peroxidases are different. Cryooxidation of CO-Fe(II) globins generates Fe(III) hemes with quantum-mechanically admixed S = 3/2, 5/2 ground states. The trapped Fe(III) species relax to the equilibrium ferric states upon annealing at T > 190 K. Both cryooxidized and reduced centers provide very sensitive EPR/ENDOR structure probes of the EPR-silent Fe(II) state.

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

    PubMed

    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 12h 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.

  8. Effects of Ammonium Dinitramide in Human Liver Slices: An EPR/Spin Trapping Study.

    DTIC Science & Technology

    1995-09-01

    dessicator at ambient temperature protected from light until analyzed. It was very important to keep the samples dry because moisture increases molecular...free radicals such as Superoxide , (02~). The control samples were viable for the period of the study but the ADN treated samples were oxidized by... Superoxide produces tributylstannyl superoxo radicals proposed initiateors of lipid peroxidation: An EPR model system Chem Res. Toxicol. 5: 698 Steel

  9. Applications of in vivo electron paramagnetic resonance (EPR) spectroscopy: measurements of pO2 and NO in endotoxin shock.

    PubMed

    Jackson, S K; Madhani, M; Thomas, M; Timmins, G S; James, P E

    2001-03-31

    Recent developments of EPR instrumentation that allow the use of large tissue samples or whole animals and the ability to image spatially resolved EPR signals has led to novel applications of EPR spectroscopy in vivo. Utilising a 1 GHz EPR spectrometer with a 3.4-cm birdcage resonator, it was possible to detect and measure nitric oxide and oxygen in the livers of mice with lipopolysaccharide (LPS)-induced septic shock. Nitric oxide was detected as the nitric oxide (NO) complex of Fe-diethyldithiocarbamic acid (Fe-DETC) while pO2 was measured from the EPR linewidth of the oxygen-sensitive coal material 'gloxy'. LPS treatment stimulated the production of nitric oxide in the liver and the general circulation and the oxygenation of liver tissue was decreased. Selective placement of the EPR probes allowed images of nitric oxide and oxygen to be obtained in the liver. The spectral and spatial information obtained with this technique will allow improved understanding of the pathophysiology of such diseases.

  10. Scope and limitations of the TEMPO/EPR method for singlet oxygen detection: the misleading role of electron transfer.

    PubMed

    Nardi, Giacomo; Manet, Ilse; Monti, Sandra; Miranda, Miguel A; Lhiaubet-Vallet, Virginie

    2014-12-01

    For many biological and biomedical studies, it is essential to detect the production of (1)O2 and quantify its production yield. Among the available methods, detection of the characteristic 1270-nm phosphorescence of singlet oxygen by time-resolved near-infrared (TRNIR) emission constitutes the most direct and unambiguous approach. An alternative indirect method is electron paramagnetic resonance (EPR) in combination with a singlet oxygen probe. This is based on the detection of the TEMPO free radical formed after oxidation of TEMP (2,2,6,6-tetramethylpiperidine) by singlet oxygen. Although the TEMPO/EPR method has been widely employed, it can produce misleading data. This is demonstrated by the present study, in which the quantum yields of singlet oxygen formation obtained by TRNIR emission and by the TEMPO/EPR method are compared for a set of well-known photosensitizers. The results reveal that the TEMPO/EPR method leads to significant overestimation of singlet oxygen yield when the singlet or triplet excited state of the photosensitizer is efficiently quenched by TEMP, acting as electron donor. In such case, generation of the TEMP(+) radical cation, followed by deprotonation and reaction with molecular oxygen, gives rise to an EPR-detectable TEMPO signal that is not associated with singlet oxygen production. This knowledge is essential for an appropriate and error-free application of the TEMPO/EPR method in chemical, biological, and medical studies.

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

    PubMed Central

    A. Abdel‐Rahman, Engy; Mahmoud, Ali M.; Khalifa, Abdulrahman M.

    2016-01-01

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

  12. 95--670 GHz EPR studies of canthaxanthin radical cation stabilized on a silica-alumina surface

    SciTech Connect

    Konovalova, T.A.; Kispert, L.D.; Krzystek, J.; Tol, J. van; Brunel, L.C.; Bratt, P.J.

    1999-07-15

    The 95--670 GHz EPR measurements at 5 K were performed on canthaxanthin radical cation chemically generated on silica-alumina. The 327 GHz and higher frequency EPR spectra were resolved into two principal components of the g tensor. Spectral simulation indicated this to be the result of g anisotropy where g{sub {parallel}} = 2.0032 and g{sub {perpendicular}} = 2.0023. This type of g tensor is consistent with the theory for polyacene {pi}-radical cations, which states that the g tensor becomes cylindrically symmetric with increasing chain length. This also demonstrates that the symmetrical unresolved EPR line at 9 GHz is due to a carotenoid {pi}-radical cation with electron density distributed throughout the whole chain as predicted by RHF-INDO/SP molecular orbital calculations. The lack of temperature dependence of the EPR line widths over the range of 5--80 K at 327 GHz suggests rapid rotation of methyl groups even at 5 K that averages out the proton couplings from three oriented {beta}-protons. In fact, similar line widths at 5 K were observed at 670 GHz. Simulation of EPR spectra at 95--250 GHz gives only symmetrical unresolved lines. The present work shows that the 327--670 GHz EPR measurements are sufficient to resolve the individual g tensors of C-H containing {pi}-radicals in powder and frozen glasses. Symmetry differences can be deduced from which radical identification can be made.

  13. New pulsed EPR methods and their application to characterize mitochondrial complex I.

    PubMed

    Maly, Thorsten; Zwicker, Klaus; Cernescu, Adrian; Brandt, Ulrich; Prisner, Thomas F

    2009-06-01

    Electron Paramagnetic Resonance (EPR) spectroscopy is the method of choice to study paramagnetic cofactors that often play an important role as active centers in electron transfer processes in biological systems. However, in many cases more than one paramagnetic species is contributing to the observed EPR spectrum, making the analysis of individual contributions difficult and in some cases impossible. With time-domain techniques it is possible to exploit differences in the relaxation behavior of different paramagnetic species to distinguish between them and separate their individual spectral contribution. Here we give an overview of the use of pulsed EPR spectroscopy to study the iron-sulfur clusters of NADH:ubiquinone oxidoreductase (complex I). While FeS cluster N1 can be studied individually at a temperature of 30 K, this is not possible for FeS cluster N2 due to its severe spectral overlap with cluster N1. In this case Relaxation Filtered Hyperfine (REFINE) spectroscopy can be used to separate the overlapping spectra based on differences in their relaxation behavior.

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

    SciTech Connect

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

    2016-07-11

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

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

    DOE PAGES

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

    2016-07-11

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  19. Structural Characterization of Polymer-Clay Nanocomposites Prepared by Co-Precipitation Using EPR Techniques

    PubMed Central

    Kielmann, Udo; Jeschke, Gunnar; García-Rubio, Inés

    2014-01-01

    Polymer-clay nanocomposites (PCNCs) containing either a rubber or an acrylate polymer were prepared by drying or co-precipitating polymer latex and nanolayered clay (synthetic and natural) suspensions. The interface between the polymer and the clay nanoparticles was studied by electron paramagnetic resonance (EPR) techniques by selectively addressing spin probes either to the surfactant layer (labeled stearic acid) or the clay surface (labeled catamine). Continuous-wave (CW) EPR studies of the surfactant dynamics allow to define a transition temperature T* which was tentatively assigned to the order-disorder transition of the surfactant layer. CW EPR studies of PCNC showed that completely exfoliated nanoparticles coexist with agglomerates. HYSCORE spectroscopy in PCNCs showed couplings within the probe −assigned with DFT computations− and couplings with nuclei of the environment, 1H and 23Na for the surfactant layer probe, and 29Si, 7Li, 19F and 23Na for the clay surface probe. Analysis of these couplings indicates that the integrity of the surfactant layer is conserved and that there are sizeable ionic regions containing sodium ions directly beyond the surfactant layer. Simulations of the very weak couplings demonstrated that the HYSCORE spectra are sensitive to the composition of the clay and whether or not clay platelets stack. PMID:28788520

  20. A Rectangular Loop Gap Resonator for EPR Studies of Aqueous Samples

    NASA Astrophysics Data System (ADS)

    Piasecki, Wojciech; Froncisz, Wojciech; Hubbell, Wayne L.

    1998-09-01

    A new rectangular geometry of the loop-gap resonator for the use with a flat cell has been developed. Maxwell's equations for the resonators with two, four, six, and eight gaps have been solved assuming the existence of only the magneticz-component. The formulas obtained were numerically solved for the electric and magnetic field distributions over the cross-sections of the resonators. The presence of a nodal plane for the electric field in the center of the resonator allows the use of a flat cell instead of a capillary for EPR measurements. Using the field distributions obtained, the quality factor and EPR signal amplitude for various shapes and gap numbers for the resonators containing a flat cell filled with water were examined numerically. This allowed finding the geometry that yields the maximum EPR signal intensity. Several X-band resonators were built in order to verify the results obtained theoretically. The experiments confirmed the ability of a novel resonant structure to accommodate a flat cell filled with an aqueous sample. It has been found that the optimum aqueous sample volume for the X-band rectangular loop-gap resonator equals 16 mm3. For a saturable aqueous sample this gives a fourfold improvement in theS/Nratio over the circular 1 mm i.d. loop-gap resonator equipped with 0.6 mm i.d. capillary.

  1. Using EPR spectroscopy to go from the Jahn-Teller effect to nuclear waste disposal

    NASA Astrophysics Data System (ADS)

    Boatner, L. A.

    2003-02-01

    Electron paramagnetic resonance (EPR) spectroscopy is a powerful technique for elucidating the fundamental solid-state-chemical and crystal-field ground-state electronic properties of rare-earth and actinide ions that are incorporated into single-crystal host materials. In the case of rare-earth or rare-earth-like ions that are characterized by a degenerate orbital doublet ground state when placed in a cubic crystal field, EPR has proven to be an extremely valuable approach to the study of various manifestations of the Jahn-Teller (J-T) effect. The contributions of EPR spectroscopy to the study of the J-T effect in ions such as La 2+, Y 2+ and Sc 2+ include the discovery of quadrupolar effects in J-T systems and a verification of Frank Ham's theory of the dynamic J-T effect. Such basic studies can often have unforeseen consequences—like leading to the discovery of new scintillators for gamma-ray detection or the development of a matrix for the disposal of radioactive waste.

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

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

    PubMed

    Wen, Fengtong

    2014-05-01

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

  4. Pulsed EPR Determination of Water Accessibility to Spin-Labeled Amino Acid Residues in LHCIIb

    PubMed Central

    Volkov, A.; Dockter, C.; Bund, T.; Paulsen, H.; Jeschke, G.

    2009-01-01

    Membrane proteins reside in a structured environment in which some of their residues are accessible to water, some are in contact with alkyl chains of lipid molecules, and some are buried in the protein. Water accessibility of residues may change during folding or function-related structural dynamics. Several techniques based on the combination of pulsed electron paramagnetic resonance (EPR) with site-directed spin labeling can be used to quantify such water accessibility. Accessibility parameters for different residues in major plant light-harvesting complex IIb are determined by electron spin echo envelope modulation spectroscopy in the presence of deuterated water, deuterium contrast in transversal relaxation rates, analysis of longitudinal relaxation rates, and line shape analysis of electron-spin-echo-detected EPR spectra as well as by the conventional techniques of measuring the maximum hyperfine splitting and progressive saturation in continuous-wave EPR. Systematic comparison of these parameters allows for a more detailed characterization of the environment of the spin-labeled residues. These techniques are applicable independently of protein size and require ∼10–20 nmol of singly spin-labeled protein per sample. For a residue close to the N-terminus, in a domain unresolved in the existing x-ray structures of light-harvesting complex IIb, all methods indicate high water accessibility. PMID:19186148

  5. US EPR Tests Performed to confirm the Mechanical and Hydraulic Design of the Vessel Internals

    SciTech Connect

    Dolleans, Philippe; Chambrin, Jean-Luc; Muller, Thierry

    2006-07-01

    The EPR is an Evolutionary high-Power Reactor which is based on the best French and German experience of the past twenty years in plant design construction and operation. In the present detailed engineering phase of the plant under construction in Finland (Okiluoto 3) or scheduled in France (Flamanville 3), a few actions are still ongoing mainly to complement equipment validation files. Design and validation of the main EPR components were performed within Framatome ANP's engineering teams and its two Technical Centers located in France and Germany, which develop state of the art methods in the field of thermo hydraulic testing. The Reactor Pressure Vessel internals are mainly derived from components already implemented on presently operating plants, but they differ in some features from the design used in French N4 or German Konvoi. The aim of this paper is to present the tests performed to confirm the hydraulic and mechanical design of the EPR vessel internals. - Four different mock-ups are presented to illustrate these tests: - JULIETTE for the reactor pressure vessel lower internals; - ROMEO for the reactor pressure vessel upper internals; - MAGALY for the design of the skeleton-type control rod guide assembly; - HYDRAVIB for the vibratory response of the reactor pressure vessel lowers internals. (authors)

  6. An EPR investigation of SiOx films with columnar structure

    NASA Astrophysics Data System (ADS)

    Bratus', V.; Indutnyi, I.; Shepeliavyi, P.; Torchynska, T.

    2014-11-01

    The results of electron paramagnetic resonance (EPR) study of obliquely deposited porous SiOx films before and after thermal annealing in vacuum at 950 °C are presented. The low intensity slightly asymmetrical and featureless EPR line with a g-value of 2.0044 and a linewidth of 0.77 mT has been detected in as-sputtered films and attributed to dangling bonds of silicon atoms in amorphous SiOx domains with x=0.8. Successive annealing results in decreasing this line and the appearance of an intense EPR line with g=2.0025, linewidth of 0.11 mT and a hyperfine doublet with 1.6 mT splitting. According to the parameters this spectrum has been attributed to the EX center, a hole delocalized over four non-bridging oxygen atoms grouped around a Si vacancy in SiO2. The impact of chemical treatment before annealing and duration of anneals on the defect system is discussed.

  7. Radiation-induced defects in strontium carbonate rod for EPR dosimetry applications

    NASA Astrophysics Data System (ADS)

    Rushdi, M. A. H.; Abdel-Fattah, A. A.; Soliman, Y. S.

    2017-02-01

    The radiation-induced defects in strontium carbonate (SrCO3) rod dosimeter in the dose range of 2.5 Gy-25 kGy was investigated using electron paramagnetic resonance (EPR) technique. The EPR spectra of γ-irradiated strontium carbonate (SC) rods exhibit a strong EPR signal with the spectroscopic splitting g-factor 2.008 and a weak signal at g-factor 2.003. This signal increases with increasing irradiation dose. The dose-response function has a good linearity in the low dose range of 2.5-500 Gy and slight sub-linearity in the high dose range of 0.5-25 kGy. The dosimeter is nearly humidity independent in the level of 33-77% relative humidity during irradiation. The temperature coefficient of the dose-response function is 0.22% per °C in the temperature range of 20-40 °C. The rod dosimeter exhibits a maximum deviation from water equivalency by 7% in the energy range of 0.3-5 MeV. The overall uncertainty of dose determination using SC dosimeter is 5.2% and 4.54% (2σ) for low and high dose range, respectively.

  8. Non-invasive determination of the irradiation dose in fingers using low-frequency EPR

    NASA Astrophysics Data System (ADS)

    Zdravkova, M.; Crokart, N.; Trompier, F.; Beghein, N.; Gallez, B.; Debuyst, R.

    2004-07-01

    Several reports in the literature have described the effects of radiation in workers who exposed their fingers to intense radioactive sources. The radiation injuries occurring after local exposure to a high dose (20 to 100 Gy) could lead to the need for amputation. Follow-up of victims needs to be more rational with a precise knowledge of the irradiated area that risks tissue degradation and necrosis. It has been described previously that X-band electron paramagnetic resonance (EPR) spectroscopy could be used to assess the dose in irradiated amputated fingers. Here, we propose the use of low-frequency EPR spectroscopy to evaluate non-invasively the absorbed dose. Low-frequency microwaves are indeed less absorbed by water and penetrate more deeply into living material (~10 mm in tissues using 1 GHz spectrometers). This work presents preliminary results obtained with baboon and human fingers compared with human dry phalanxes placed inside a surface-coil resonator. The EPR signal increased linearly with the dose. The ratio of the slopes of the dry bone to whole finger linear regression lines was around 5. The detection limit achievable with the present spectrometer and resonator is around 60 Gy, which is well within the range of accidentally exposed fingers. It is likely that the detection limit could be improved in the future, thanks to further technical spectrometer and resonator developments as well as to appropriate spectrum deconvolution into native and dosimetric signals.

  9. In situ EPR and UV-vis spectroelectrochemistry of hole-transporting organic substrates

    NASA Astrophysics Data System (ADS)

    Rapta, Peter; Fáber, René; Dunsch, Lothar; Neudeck, Andreas; Nuyken, Oskar

    2000-02-01

    A newly developed in situ electron paramagnetic resonance (EPR)/ultraviolet-visible (UV-vis) spectroelectrochemical cell equipped with a laminated indium-tin oxide (ITO) working electrode was used in the investigation of various organic substrates which are potential hole-transporting materials. The experiment demonstrated the possibility of using such a technique for examining redox behavior of conducting polymers (polypyrrole, PPy), oligomers (thiophene dimmer and quarterthiophene) and bis-anilines (N,N,N',N'-tetraphenylbenzidine, TPB). All investigated structures formed stable paramagnetic intermediates in the first oxidation step characterised with UV-vis spectra in the region 400-600 nm. In the second oxidation step EPR-silent di-cationic structures are formed with broad vis bands in the region 600-1000 nm. The measurement of the reference UV-vis spectra direct in the EPR cavity was possible using a specially-constructed non-contacted ITO plate in the spectroelectrochemical cell in the case of polypyrrole.

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

    PubMed Central

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

    2012-01-01

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

  11. UV EFFECTS IN TOOTH ENAMEL AND THEIR POSSIBLE APPLICATION IN EPR DOSIMETRY WITH FRONT TEETH

    PubMed Central

    Sholom, S.; Desrosiers, M.; Chumak, V.; Luckyanov, N.; Simon, S.L.; Bouville, A.

    2009-01-01

    The effects of ultraviolet (UV) radiation on ionizing radiation biodosimetry were studied in human tooth enamel samples using the technique of electron paramagnetic resonance (EPR) in X-band. For samples in the form of grains, UV-specific EPR spectra were spectrally distinct from that produced by exposure to gamma radiation. From larger enamel samples, the UV penetration depth was determined to be in the 60–120 μm range. The difference in EPR spectra from UV exposure and from exposure to gamma radiation samples was found to be a useful marker of UV equivalent dose (defined as the apparent contribution to the gamma dose in mGy that results from UV radiation absorption) in tooth enamel. This concept was preliminarily tested on front teeth from inhabitants of the region of the Semipalatinsk Nuclear Test Site (Kazakhstan) who might have received some exposure to gamma radiation from the nuclear tests conducted there as well as from normal UV radiation in sunlight. The technique developed here to quantify and subtract the UV contribution to the measured tooth is currently limited to cumulative dose measurements with a component of UV equivalent dose equal to or greater than 300 mGy. PMID:20065706

  12. EPR and AM1 study of the structure of the radical anion of {beta}-ionone

    SciTech Connect

    Kruppa, A.I. Leshina, T.V.; Konovalov, V.V.; Kispert, L.D.

    1999-03-11

    The structure of the radical anion of {beta}-ionone has been investigated by EPR and AM1 molecular modeling methods as a part of a study to determine the structure and magnetic properties of intermediates of one-electron transfer reactions of carotenoids. Analysis of the temperature dependence of the EPR spectrum of the radical anion shows that the largest hyperfine coupling of 16 G previously assigned to the 7-H proton should be assigned to the 4-H proton in the axial orientation. The previous assignment failed to account for rate of the cyclohexene ring inversion. Comparing the resolved EPR spectra at various temperatures indicates that the coupling of 7-H proton equals {approx}9.5 G. The structure of the radical anion predicted by AM1 molecular modeling is in agreement with this analysis. From the temperature dependence the rate of the cyclohexene ring inversion in the radical anion at room temperatures is approximately 6 {times} 10{sup 7} s{sup {minus}1} with an activation energy of about 7 kcal/mol.

  13. VHF EPR analysis of organic sulfur in coal. [Quarterly] technical report, September 1--November 20, 1991

    SciTech Connect

    Clarkson, R.B.

    1991-12-31

    This report covers progress made in the first yearly quarter of a two year investigation using novel, very high frequency electron paramagnetic resonance (VHF EPR) spectroscopy techniques and instrumentation (one of only two W-band spectrometers in existence) developed earlier by these authors, to conduct further qualitative and quantitative studies of heteroatomic organic molecules in coal with particular emphasis on sulfur. Previous W-band (96 GHz) work is being extended to studies of new model compounds as well as 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. The preparation of radicals from compounds having widely varying structures and physical properties in a stable environment has long been a very difficult task. To address this problem, the refinement of several new and very useful methods of preparing of these stable free radicals in various glasses, at catalytic surfaces, and in solution, are presented in this first report. Free radical generation was accomplished by both UV photolysis as well as chemical oxidation/reduction techniques. By these methods, over 25 new compounds, often commercially derived from coal extracts, have been prepared and studied by conventional X-band EPR (9 GHz). Several representative W-band spectra are also presented.

  14. Intracellular targeting delivery of liposomal drugs to solid tumors based on EPR effects.

    PubMed

    Maruyama, Kazuo

    2011-03-18

    The success of an effective drug delivery system using liposomes for solid tumor targeting based on EPR effects is highly dependent on both size ranging from 100-200 nm in diameter and prolonged circulation half-life in the blood. A major development was the synthesis of PEG-liposomes with a prolonged circulation time in the blood. Active targeting of immunoliposomes to the solid tumor tissue can be achieved by the Fab' fragment which is better than whole IgG in terms of designing PEG-immunoliposomes with prolonged circulation. For intracellular targeting delivery to solid tumors based on EPR effects, transferrin-PEG-liposomes can stay in blood circulation for a long time and extravasate into the extravascular of tumor tissue by the EPR effect as PEG-liposomes. The extravasated transferrin-PEG-liposomes can maintain anti cancer drugs in interstitial space for a longer period, and deliver them into the cytoplasm of tumor cells via transferrin receptor-mediated endocytosis. Transferrin-PEG-liposomes improve the safety and efficacy of anti cancer drug by both passive targeting by prolonged circulation and active targeting by transferrin.

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

    PubMed Central

    2014-01-01

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

  16. Size Dependent Kinetics of Gold Nanorods in EPR Mediated Tumor Delivery

    PubMed Central

    Tong, Xiao; Wang, Zhantong; Sun, Xiaolian; Song, Jibin; Jacobson, Orit; Niu, Gang; Kiesewetter, Dale O.; Chen, Xiaoyuan

    2016-01-01

    Gold nanorods (AuNR) have been intensively used in nanomedicine for cancer diagnostics and therapy, due to their excellent plasmonic photothermal properties. Tuning the size and aspect ratio of AuNR tailors the localized surface plasmon resonance (LSPR) in the NIR spectrum at which biological tissues are transparent, thus enables specific and effective treatment. The AuNR extravasates into tumor interstitium through enhanced permeation and retention (EPR) effect. Efficient AuNR based cancer therapy requires efficient AuNR tumor delivery. However, the size of AuNR can dramatically affect its blood circulation and tumor accumulation. Here we proposed for the first time a systematic framework to investigate the size-dependent kinetics of AuNRs during EPR mediated tumor delivery. By using 64Cu-labeled AuNRs with positron emission tomography (PET) and kinetic modeling, the in vivo uptake and kinetics of 64Cu-AuNR during its blood circulation, tumor accumulation and elimination were studied both in vitro and in vivo. The results of different sized AuNRs were compared and the optimum size of AuNR was suggested for EPR mediated tumor delivery. Our study provides a better understanding of the in vivo behavior of AuNR, which can help future design of nanomaterials for cancer imaging and therapy. PMID:27698939

  17. Extruded dielectric sample tubes of complex cross section for EPR signal enhancement of aqueous samples

    NASA Astrophysics Data System (ADS)

    Sidabras, Jason W.; Mett, Richard R.; Hyde, James S.

    2017-04-01

    This paper builds on the work of Mett and Hyde (2003) and Sidabras et al. (2005) where multiple flat aqueous sample cells placed perpendicular to electric fields in microwave cavities were used to reduce the RF losses and increase the EPR signal. In this work, we present three novel sample holders for loop-gap resonators (LGRs) and cylindrical cavity geometries. Two sample holders have been commissioned and built by polytetrafluoroethylene (PTFE) extrusion techniques: a 1 mm O.D. capillary with a septum down the middle, named DoubleDee, and a 3.5 mm O.D. star shaped sample holder, named AquaStar. Simulations and experimental results at X-band show that the EPR signal intensity increases by factors of 1.43 and 3.87 in the DoubleDee and AquaStar respectively, over the current TPX 0.9 mm O.D. sample tube in a two-loop-one-gap LGR. Finally, combining the insight gained from the constructed sample holders and finite-element solutions, a third multi-lumen sample holder for a cylindrical TE011 cavity is optimized, named AquaSun, where simulations show an EPR signal intensity increase by a factor of 8.2 over a standard 1 mm capillary.

  18. Extruded dielectric sample tubes of complex cross section for EPR signal enhancement of aqueous samples.

    PubMed

    Sidabras, Jason W; Mett, Richard R; Hyde, James S

    2017-04-01

    This paper builds on the work of Mett and Hyde (2003) and Sidabras et al. (2005) where multiple flat aqueous sample cells placed perpendicular to electric fields in microwave cavities were used to reduce the RF losses and increase the EPR signal. In this work, we present three novel sample holders for loop-gap resonators (LGRs) and cylindrical cavity geometries. Two sample holders have been commissioned and built by polytetrafluoroethylene (PTFE) extrusion techniques: a 1mm O.D. capillary with a septum down the middle, named DoubleDee, and a 3.5mm O.D. star shaped sample holder, named AquaStar. Simulations and experimental results at X-band show that the EPR signal intensity increases by factors of 1.43 and 3.87 in the DoubleDee and AquaStar respectively, over the current TPX 0.9mm O.D. sample tube in a two-loop-one-gap LGR. Finally, combining the insight gained from the constructed sample holders and finite-element solutions, a third multi-lumen sample holder for a cylindrical TE011 cavity is optimized, named AquaSun, where simulations show an EPR signal intensity increase by a factor of 8.2 over a standard 1mm capillary. Copyright © 2017 Elsevier Inc. All rights reserved.

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

    PubMed Central

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

    2014-01-01

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

  20. Studying lipid organization in biological membranes using liposomes and EPR spin labeling

    PubMed Central

    Subczynski, Witold K.; Raguz, Marija; Widomska, Justyna

    2015-01-01

    Summary Electron paramagnetic resonance (EPR) spin-labeling methods provide a unique opportunity to determine the lateral organization of lipid bilayer membranes by discrimination of coexisting membrane domains or coexisting membrane phases. In some cases, the coexisting membrane domains can be characterized by profiles of alkyl chain order, fluidity, hydrophobicity, and oxygen diffusion-concentration product in situ, without the need for their physical separation. This chapter briefly explains how the EPR spin-labeling methods can be used to obtain the above mentioned profiles across the lipid bilayer membranes (liposomes) derived from the lipid extract of certain biological membranes. These procedures will be illustrated by EPR measurements performed for multilamellar liposomes made of the lipid extracts from cortical and nuclear fractions of the fiber cell plasma membranes of a cow eye lens. To elucidate better the major factors that determine membrane properties, the results for eye lens lipid membranes will be compared with those obtained for simple model membranes resembling basic lipid composition of biological membranes. PMID:20013402

  1. EPR-correlated dipolar spectroscopy by Q-band chirp SIFTER.

    PubMed

    Doll, Andrin; Jeschke, Gunnar

    2016-08-17

    While two-dimensional correlation spectra contain more information as compared to one-dimensional spectra, typical spectral widths encountered in electron paramagnetic resonance (EPR) spectroscopy largely restrict the applicability of correlation techniques. In essence, the monochromatic excitation pulses established in pulsed EPR often cannot uniformly excite the entire spectrum. Here, this restriction is alleviated for nitroxide spin labels at Q-band microwave frequencies around 35 GHz. This is achieved by substitution of monochromatic pulses by frequency-swept chirp pulses tailored for uniform excitation. Unwanted interference effects brought by this substitution are analyzed for a pair of electron spins with secular dipolar coupling. Experimentally, the dipole-dipole interaction can be separated from other interactions by a constant-time Zeeman-compensated solid echo sequence called SIFTER. Such SIFTER experiments usually yield a one-dimensional dipolar spectrum. EPR-correlated dipolar spectra can be obtained when the four pulses are replaced by chirp pulses. These two-dimensional spectra encode additional information on the geometrical arrangement of the two spin labels. With the excitation parameters achieved by a home-built Q-band spectrometer capable of frequency-swept excitation, unwanted interference effects can be largely neglected for the examined model compound with a spin-spin distance of 4 nm. The experimentally obtained correlation pattern conforms to the expectation based on the inter-spin geometry of the investigated rigid model compound.

  2. Delocalisation of photoexcited triplet states probed by transient EPR and hyperfine spectroscopy

    NASA Astrophysics Data System (ADS)

    Richert, Sabine; Tait, Claudia E.; Timmel, Christiane R.

    2017-07-01

    Photoexcited triplet states play a crucial role in photochemical mechanisms: long known to be of paramount importance in the study of photosynthetic reaction centres, they have more recently also been shown to play a major role in a number of applications in the field of molecular electronics. Their characterisation is crucial for an improved understanding of these processes with a particular focus on the determination of the spatial distribution of the triplet state wavefunction providing information on charge and energy transfer efficiencies. Currently, active research in this field is mostly focussed on the investigation of materials for organic photovoltaics (OPVs) and organic light emitting diodes (OLEDs). As the properties of triplet states and their spatial extent are known to have a major impact on device performance, a detailed understanding of the factors governing triplet state delocalisation is at the basis of the further development and improvement of these devices. Electron Paramagnetic Resonance (EPR) has proven a valuable tool in the study of triplet state properties and both experimental methods as well as data analysis and interpretation techniques have continuously improved over the last few decades. In this review, we discuss the theoretical and practical aspects of the investigation of triplet states and triplet state delocalisation by transient continuous wave and pulse EPR and highlight the advantages and limitations of the presently available techniques and the current trends in the field. Application of EPR in the study of triplet state delocalisation is illustrated on the example of linear multi-porphyrin chains designed as molecular wires.

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

    PubMed

    Yıldırım, I; Karabulut, B; Büyükgüngör, O

    2016-01-05

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

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

    SciTech Connect

    Andrews, J.C. |

    1995-08-01

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

  5. Aging predictions in nuclear power plants: Crosslinked polyolefin and EPR cable insulation materials

    SciTech Connect

    Gillen, K.T.; Clough, R.L.

    1991-06-01

    In two earlier reports, we derived a time-temperature-dose rate superposition methodology, which, when applicable, can be used to predict cable degradation versus dose rate, temperature and exposure time. This methodology results in long-term predictive capabilities at the low dose rates appropriate to ambient nuclear power plant aging environments. The methodology was successfully applied to numerous important cable materials used in nuclear applications and the extrapolated predictions were verified by comparisons with long-term (7 to 12 year) results for similar or identical materials aged in nuclear environments. In this report, we test the methodology on three crosslinked polyolefin (CLPO) and two ethylene propylene rubber (EPR) cable insulation materials. The methodology applies to one of the CLPO materials and one of the EPR materials, allowing predictions to be made for these materials under low dose-rate, low temperature conditions. For the other materials, it is determined that, at low temperatures, a decrease in temperature at a constant radiation dose rate leads to an increase in the degradation rate for the mechanical properties. Since these results contradict the fundamental assumption underlying time-temperature-dose rate superposition, this methodology cannot be applied to such data. As indicated in the earlier reports, such anomalous results might be expected when attempting to model data taken across the crystalline melting region of semicrystalline materials. Nonetheless, the existing experimental evidence suggests that these CLPO and EPR materials have substantial aging endurance for typical reactor conditions. 28 refs., 26 figs., 3 tabs.

  6. Accelerated cable life testing of EPR-insulated medium voltage distribution cables

    SciTech Connect

    Walton, M.D. ); Bernstein, B.S. ); Smith, J.T. III ); Thue, W.A. , Stuart, FL ); Groeger, J.H. )

    1994-07-01

    This paper presents results aimed at developing a reliable accelerated aging tank test for EPR-insulated cables. Aging was performed at 2 to 4 times rated voltage on load cycling to temperatures of 45 C, 60 C, 75 C, and 90 C at the conductor with water in the conductor strands and outside the cable. Results show that cable failure is more rapid at the highest electrical stress and lowest conductor load cycle temperature. Cables aged at higher temperatures and various levels of electrical stress rarely failed and retained in excess of 40% of their original breakdown strength after 1,500+ days of aging. Aging performed at 90 C load cycle temperature and 4 times rated voltage with air on the outside and water at the conductor of the cable showed more rapid loss of life than with water outside. Results indicate the optimum aging conditions for EPR-insulated cables in the accelerated cable life test (ACLT) differ significantly from those previously observed for XLPE-insulated cables, and that the appropriate test methodology for EPR-insulated cables requires additional study.

  7. Development of next-generation macromolecular drugs based on the EPR effect: challenges and pitfalls.

    PubMed

    Nakamura, Hideaki; Fang, Jun; Jun, Fang; Maeda, Hiroshi

    2015-01-01

    A major problem with conventional antitumor therapeutics is nonselective delivery of cytotoxic drugs to normal vital organs and tissues but little delivery to tumor tissues. Here, the authors describe the tumor selective delivery of antitumor drugs by taking advantage of nano-sized drugs and the means to augment it further. Based on the enhanced permeability and retention (EPR) effect, the mechanism for more efficient universal tumor delivery using macromolecular drugs to cover wider tumor types than single molecular target is discussed. Unique properties of solid tumor vasculature in the tumor tissue are discussed, especially leakiness of the blood vessels and factors involved and impaired clearance of macromolecular drugs from the tumor interstitium via the lymphatic system. The criteria for such macromolecular drugs or nanomedicines for effective accumulation at tumor sites is commented on as well as the importance of long plasma retention time of such drugs and a need to release active principles from nanoparticles at target sites. Methods to augment the EPR effect and tumor delivery (2 - 3 times) and its application to photodynamic therapy are also discussed. Tumor selective delivery of antitumor drugs based on the EPR effect can be accomplished and augmented by modulating the tumor environment. This methodology is favorable not only for tumor therapy but also for tumor imaging.

  8. Enhancement of Tumor-Targeted Delivery of Bacteria with Nitroglycerin Involving Augmentation of the EPR Effect.

    PubMed

    Fang, Jun; Long, Liao; Maeda, Hiroshi

    2016-01-01

    The use of bacteria, about 1 μm in size, is now becoming an attractive strategy for cancer treatment. Solid tumors exhibit the enhanced permeability and retention (EPR) effect for biocompatible macromolecules such as polymer-conjugated anticancer agents, liposomes, and micelles. This phenomenon permits tumor-selective delivery of such macromolecules. We report here that bacteria injected intravenously evidenced a property similar to that can of these macromolecules. Bacteria that can accumulate selectively in tumors may therefore be used in cancer treatment.Facultative or anaerobic bacteria will grow even under the hypoxic conditions present in solid tumors. We found earlier that nitric oxide (NO) was among the most important factors that facilitated the EPR effect via vasodilatation, opening of endothelial cell junction gaps, and increasing the blood flow of hypovascular tumors. Here, we describe the augmentation of the EPR effect by means of nitroglycerin (NG), a commonly used NO donor, using various macromolecular agents in different tumor models. More importantly, we report that NG significantly enhanced the delivery of Lactobacillus casei to tumors after intravenous injection of the bacteria, more than a tenfold increase in bacterial accumulation in tumors after NG treatment. This finding suggests that NG has a potential advantage to enhance bacterial therapy of cancer, and further investigations of this possibility are warranted.

  9. ePR for data grid breast imaging: design and specifications

    NASA Astrophysics Data System (ADS)

    Documet, Jorge R.; Liu, Brent J.

    2010-03-01

    The utilization of breast MRI is increasing in the diagnostic evaluation of suspicious breast findings. As more imaging centers implement dedicated breast MR, the need for managing data on a large scale, nationally and even some times internationally, has become more apparent. Our design proposal is to utilize the data grid for managing the storage of the medical images and an ePR that provides the interface to manage the health data of Breast Cancer Patients. In this paper, we present the data grid for DICOM images and DICOM-SR data and the image-intensive web-based ePR system technologies utilizing the simulation of a three-site dedicated breast MR outpatient centers as the clinical application. The implementation of the two technologies the ePR system together with the Breast Imaging Data Grid (BIDG) can provide a global solution that is portable for the Breast Cancer patient including aggregation of Mammo, US, MR, CAD, BI-RADS, and clinical related reports data to form a powerful platform for data mining and outcomes research.

  10. UV effects in tooth enamel and their possible application in EPR dosimetry with front teeth.

    PubMed

    Sholom, S; Desrosiers, M; Chumak, V; Luckyanov, N; Simon, S L; Bouville, A

    2010-02-01

    The effects of ultraviolet (UV) radiation on ionizing radiation biodosimetry were studied in human tooth enamel samples using the technique of electron paramagnetic resonance (EPR) in X-band. For samples in the form of grains, UV-specific EPR spectra were spectrally distinct from those produced by exposure to gamma radiation. From larger enamel samples, the UV penetration depth was determined to be in the 60-120 mum range. The difference in EPR spectra from UV exposure and from exposure to gamma radiation samples was found to be a useful marker of UV equivalent dose (defined as the apparent contribution to the gamma dose in mGy that results from UV radiation absorption) in tooth enamel. This concept was preliminarily tested on front teeth from inhabitants of the region of the Semipalatinsk Nuclear Test Site (Kazakhstan) who might have received some exposure to gamma radiation from the nuclear tests conducted there as well as from normal UV radiation in sunlight. The technique developed here to quantify and subtract the UV contribution to the measured tooth is currently limited to cumulative dose measurements with a component of UV equivalent dose equal to or greater than 300 mGy.

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

    PubMed Central

    Winter, Alette; Zabel, André; Strauch, Peter

    2012-01-01

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

  12. EPR and optical absorption studies of vanadyl impurity in zinc potassium phosphate hexahydrate single crystal

    NASA Astrophysics Data System (ADS)

    Kripal, Ram; Maurya, Manju; Bajpai, Manisha; Govind, Har

    2009-11-01

    Electron paramagnetic resonance (EPR) study of VO 2+ doped zinc potassium phosphate hexahydrate single crystal is carried out. The angular variation of the spectra is studied in the three crystallographic planes. The principal value of spin Hamiltonian parameters g and A and the direction cosines which principal axes make with the crystallographic axes are determined. The observed values are site I: g∥=1.9664±0.0002, g⊥=1.9973±0.0002, A∥=150±2×10 -4, A⊥=60±2×10 -4 cm -1; site II: g∥=1.9276±0.0002, g⊥=1.9921±0.0002, A∥=155±2×10 -4 and A⊥=62±2×10 -4 cm -1. By comparison of direction cosines of g from EPR with the direction cosines of different bonds obtained from crystal structure data it is ascertained that the VO 2+ ion occupies Zn 2+ substitutional sites. The optical absorption study of the crystal at room temperature is also carried out. The bands observed in the optical absorption spectrum are attributed to d-d transitions. The EPR results together with the optical data are employed to estimate the molecular orbital (MO) coefficients. These MO coefficients (also called bonding coefficients) are further used to discuss the nature of bonding of VO 2+ ion with different ligands in the crystal.

  13. Effects of nerolidol and limonene on stratum corneum membranes: A probe EPR and fluorescence spectroscopy study.

    PubMed

    Mendanha, Sebastião Antonio; Marquezin, Cássia Alessandra; Ito, Amando Siuiti; Alonso, Antonio

    2017-10-30

    The sesquiterpene nerolidol and the monoterpene limonene are potent skin-permeation enhancers that have also been shown to have antitumor, antibacterial, antifungal and antiparasitic activities. Because terpenes are membrane-active compounds, we used electron paramagnetic resonance (EPR) spectroscopy of three membrane spin labels combined with the fluorescence spectroscopy of three lipid probes to study the interactions of these terpenes with stratum corneum (SC) intercellular membranes. An experimental apparatus was developed to assess the lipid fluidity of hydrated SC membranes via the fluorescence anisotropy of extrinsic membrane probes. Both EPR and fluorescence probes indicated that the intercellular membranes of neonatal SC rats undergo a main phase transition at approximately 50°C. Taken together, the results indicated that treatment with 1% nerolidol (v/v) caused large fluidity increases in the more ordered phases of SC membranes and that these effects gradually decreased with increasing temperature. Additionally, compared with (+)-limonene, nerolidol was better able to change the SC membrane dynamics. EPR and fluorescence data suggest that these terpenes act as spacers in lipid packaging and create increased lipid disorder in the more ordered regions and phases of SC membranes, notably leading to a population of probes with less restricted motion. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. An EPR Study on VO2+ and Mn2+ Ions in Some Zeolites

    NASA Astrophysics Data System (ADS)

    Ucun, F.; Köksal, F.

    1996-02-01

    The electron paramagnetic resonance (EPR) of hydrated VOSO4 ·3H2O and MnCl2 · 2H2O, adsorbed on the synthetic zeolites 3A, 4A, 5A and 13X of pore diameters 0.3, 0.4, 0.5, and 1.0 nm, respectively, and the natural zeolites heulandite and clinoptilolite was investigated. The spectra indicated that the coordination structures are VO(H2O)52+ and Mn(H2O)62+ , and that their EPR line widths vary with the pore diameters and the surface areas of the zeolites. The spectra of VO(H2O)52+ in natural zeolites at room temperature display an isotropic behavior and therefore indicate that the water ligands are mobile. The EPR spin Hamiltonian parameters, the molecule orbital constant ß2*2 , and the Fermi contact term Keff were determined and are discussed. The spectra of Mn(H2O)62+ for narrow-pore zeolites indicate the existence of mobile and immobile water, whereas for wide-pore and natural zeolites they indicated the existence of only mobile water. The obtained Mn(H2O)62+ spectra are discussed.

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

    NASA Astrophysics Data System (ADS)

    Gharibyan, Hrant; Penna, Robert F.

    2014-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1986-03-01

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

  17. Free Radical Scavenging Activity of Drops and Spray Containing Propolis-An EPR Examination.

    PubMed

    Olczyk, Pawel; Komosinska-Vassev, Katarzyna; Ramos, Pawel; Mencner, Lukasz; Olczyk, Krystyna; Pilawa, Barbara

    2017-01-13

    The influence of heating at a temperature of 50 °C and UV-irradiation of propolis drops and spray on their free radical scavenging activity was determined. The kinetics of interactions of the propolis samples with DPPH free radicals was analyzed. Interactions of propolis drops and propolis spray with free radicals were examined by electron paramagnetic resonance spectroscopy. A spectrometer generating microwaves of 9.3 GHz frequency was used. The EPR spectra of the model DPPH free radicals were compared with the EPR spectra of DPPH in contact with the tested propolis samples. The antioxidative activity of propolis drops and propolis spray decreased after heating at the temperature of 50 °C. A UV-irradiated sample of propolis drops more weakly scavenged free radicals than an untreated sample. The antioxidative activity of propolis spray increased after UV-irradiation. The sample of propolis drops heated at the temperature of 50 °C quenched free radicals faster than the unheated sample. UV-irradiation weakly changed the kinetics of propolis drops or spray interactions with free radicals. EPR analysis indicated that propolis drops and spray should not be stored at a temperature of 50 °C. Propolis drops should not be exposed to UV-irradiation.

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

    SciTech Connect

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

    2013-01-01

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

  19. Chromium(V) complexes generated in Arthrobacter oxydans bysimulation analysis of EPR spectra

    SciTech Connect

    Codd, Rachel; Lay, Peter A.; Tsibakhashvili, Nelly Ya.; Kalabegishvili, Tamaz L.; Murusidze, Ivane G.; Holman, Hoi-Ying N.

    2006-04-01

    Chromium(V) is an intermediate formed during the reductionof Cr(VI) to Cr(III) compounds by various bacteria. However, little isknown about the nature, localization and reactivity of Cr(V) species inmicrobial systems. Electron paramagnetic resonance (EPR) spectroscopy wasused to study the nature of Cr(V) complexes generated inbasalt-inhabiting Gram-positive Arthrobacter oxydans bacteria afterexposure to high concentrations of Cr(VI). Numerical simulations of theEPR spectroscopic data provide strong evidence for at least two differentdiolato-type oxoCr(V) complexes (I, giso = 1.9801; II, giso = 1.9796)involving bacterial cell wall macromolecules in the Cr(VI) A. oxydanssystem. The relative concentrations of the two oxoCr(V) diolato speciesdiffer when Cr(VI) is incubated with either untreated A. oxydans cells(I:II ~; 50:50) or lyophilized cells (I:II ~; 10:90). Based upon themagnitudes of the proton superhyperfine coupling constants (1H aiso) forspecies I and II, the EPR simulation model is unable to distinguishunambiguously whether the oxoCr(V) diolato species are linear alkoxidesor cyclic diols (carbohydrates). The oxygen-containing functional groupsassociated with teichoic acids are the most likely candidates forcomplexation with the Cr(V) ion.

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

    SciTech Connect

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

    2010-09-15

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

  1. Examination by EPR spectroscopy of free radicals in melanins isolated from A-375 cells exposed on valproic acid and cisplatin.

    PubMed

    Chodurek, Ewa; Zdybel, Magdalena; Pilawa, Barbara; Dzierzewicz, Zofia

    2012-01-01

    Drug binding by melanin biopolymers influence the effectiveness of the chemotherapy, radiotherapy and photodynamic therapy. Free radicals of melanins take part in formation of their complex with drugs. The aim of this work was to determine the effect of the two compounds: valproic acid (VPA) and cisplatin (CPT) on free radicals properties of melanin isolated from A-375 melanoma cells. Free radicals were examined by an X-band (9.3 GHz) electron paramagnetic resonance (EPR) spectroscopy. EPR spectra were measured for the model synthetic eumelanin - DOPA-melanin, the melanin isolated from the control A-375 cells and these cells treated by VPA, CPT and both VPA and CPT. For all the examined samples broad EPR lines (deltaBpp: 0.48-0.68 mT) with g-factors of 2.0045-2.0060 characteristic for o-semiquinone free radicals were observed. Free radicals concentrations (N) in the tested samples, g-factors, amplitudes (A), integral intensities (I) and linewidths (deltaBpp) of the EPR spectra, were analyzed. The EPR lines were homogeneously broadened. Continuous microwave saturation of the EPR spectra indicated that slow spin-lattice relaxation processes existed in all the tested melanin samples. The relatively slowest spin-lattice relaxation processes characterized melanin isolated from A-375 cells treated with both VPA and CPT. The changes of the EPR spectra with increasing microwave power in the range of 2.2-70 mW were evaluated. Free radicals concentrations in the melanin from A-375 cells were higher than in the synthetic DOPA-melanin. The strong increase of free radicals concentration in the melanin from A-375 cells was observed after their treating by VPA. CPT also caused the increase of free radicals concentrations in the examined natural melanin. The free radicals concentration in melanin isolated from A-375 cells treated with both VPA and CPT was slightly higher than those in melanin from the control cells.

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

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

    SciTech Connect

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

    1993-12-31

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

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

    SciTech Connect

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

    2015-06-15

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

  5. EPR and optical studies of VO2+ doped potassium succinate-succinic acid single crystal - Substitutional incorporation

    NASA Astrophysics Data System (ADS)

    Juliet sheela, K.; Radha Krishnan, S.; Shanmugam, V. M.; Subramanian, P.

    2017-03-01

    EPR and optical absorption studies of VO2+ doped potassium succinate-succinic acid (KSSA) single crystal has been examined at room temperature. EPR spectrum shows that well resolved hyperfine lines. The angular variation of the EPR spectra has shown that two different VO2+ complexes are located in different chemical environments. Among the number of sites, two sites have been followed and reported here. From the EPR analysis, spin Hamiltonian parameters g and A tensors and their directional cosines are evaluated. Both the sites experience rhombic crystal field symmetry around the impurity ion. The VO2+ ion entering the site location of potassium ion has coordination of eight oxygen atoms in a distorted dodecahedral arrangement. The Optical absorption spectrum studied at room temperature shows bands corresponding to C4v symmetry. The crystal field parameter and tetragonal field parameters are calculated. From the Optical and EPR data various molecular orbital coefficients are evaluated and the nature of bonding in the crystal is discussed.

  6. Fluoride substitution in the Mn cluster from Photosystem II: EPR and X-ray absorption spectroscopy studies

    NASA Astrophysics Data System (ADS)

    DeRose, Victoria J.; Latimer, Matthew J.; Zimmermann, Jean-Luc; Mukerji, Ishita; Yachandra, Vittal K.; Sauer, Kenneth; Klein, Melvin P.

    1995-05-01

    X-band electron paramagnetic resonance (EPR) and Mn K-edge X-ray fluorescence absorption were used to study the effects of fluoride inhibition on the Mn complex in Photosystem II. The tetrameric Mn complex, responsible for the light-induced oxidation of H 2O to form molecular oxygen, is influenced by treatments in which the naturally occurring chloride salts are removed or replaced. Inhibition of the complex by fluoride is examined by parallel enzyme activity and EPR studies. It is found that, as a function of increasing fluoride concentration, the declining enzymatic activity is paralleled initially by an exchange of the S = 1/2 'multiline' EPR signal for the S > 1/2, 'g = 4' EPR signal in illuminated samples. High concentrations of fluoride induce a broad (≈ 200 G), featureless radical signal in samples which have not been illuminated; subsequent illumination of these samples also generates the g = 4 EPR signal. X-ray absorption studies (XAS) of fluoride-inhibited samples show subtle alterations of the conformation of the Mn complex that are consistent with the presence of two dissimilar pairs of Mn atoms. The halide studies are discussed in terms of structural models for the Mn complex.

  7. A Dynamic Nuclear Polarization spectrometer at 95 GHz/144 MHz with EPR and NMR excitation and detection capabilities.

    PubMed

    Feintuch, Akiva; Shimon, Daphna; Hovav, Yonatan; Banerjee, Debamalya; Kaminker, Ilia; Lipkin, Yaacov; Zibzener, Koby; Epel, Boris; Vega, Shimon; Goldfarb, Daniella

    2011-04-01

    A spectrometer specifically designed for systematic studies of the spin dynamics underlying Dynamic Nuclear Polarization (DNP) in solids at low temperatures is described. The spectrometer functions as a fully operational NMR spectrometer (144 MHz) and pulse EPR spectrometer (95 GHz) with a microwave (MW) power of up to 300 mW at the sample position, generating a MW B(1) field as high as 800 KHz. The combined NMR/EPR probe comprises of an open-structure horn-reflector configuration that functions as a low Q EPR cavity and an RF coil that can accommodate a 30-50 μl sample tube. The performance of the spectrometer is demonstrated through some basic pulsed EPR experiments, such as echo-detected EPR, saturation recovery and nutation measurements, that enable quantification of the actual intensity of MW irradiation at the position of the sample. In addition, DNP enhanced NMR signals of samples containing TEMPO and trityl are followed as a function of the MW frequency. Buildup curves of the nuclear polarization are recorded as a function of the microwave irradiation time period at different temperatures and for different MW powers. Copyright © 2011 Elsevier Inc. All rights reserved.

  8. EPR studies of free radicals decay and survival in gamma irradiated aminoglycoside antibiotics: sisomicin, tobramycin and paromomycin.

    PubMed

    Wilczyński, Sławomir; Pilawa, Barbara; Koprowski, Robert; Wróbel, Zygmunt; Ptaszkiewicz, Marta; Swakoń, Jan; Olko, Paweł

    2012-02-14

    Radiation sterilization technology is more actively used now that any time because of its many advantages. Gamma radiation has high penetrating power, relatively low chemical reactivity and causes small temperature rise. But on the other hand radiosterilization can lead to radiolytic products appearing, in example free radicals. Free radicals in radiative sterilized sisomicin, tobramycin and paromomycin were studied by electron paramagnetic resonance (EPR) spectroscopy. Dose of gamma irradiation of 25kGy was used. Concentrations and properties of free radicals in irradiated antibiotics were studied. EPR spectra were recorded for samples stored in air and argon. For gamma irradiated antibiotics strong EPR lines were recorded. One- and two-exponential functions were fitted to experimental points during testing and researching of time influence of the antibiotics storage to studied parameters of EPR lines. Our study of free radicals in radiosterilized antibiotics indicates the need for characterization of medicinal substances prior to sterilization process using EPR values. We propose the concentration of free radicals and other spectroscopic parameters as useful factors to select the optimal type of sterilization for the individual drug. The important parameters are i.a. the τ time constants and K constants of exponential functions. Time constants τ give us information about the speed of free radicals concentration decrease in radiated medicinal substances. The constant K(0) shows the free radicals concentration in irradiated medicament after long time of storage.

  9. EPR studies of SmBa2Cu3O7-δ/MnFe2O4 superconducting composites

    NASA Astrophysics Data System (ADS)

    Awad, R.; Isber, S.; Abou Aly, A. I.; Abdeen, W.; El-Tahan, A.; El-Maghraby, E. M.; Khalaf, A.; Noureddine, S.

    2017-07-01

    Electron paramagnetic resonance (EPR) studies are carried out on composite samples of SmBa2Cu3O7-δ/(MnFe2O4)x superconductors with 0.00 ≤ x ≤ 0.20 wt% at different temperatures 100K ≤ T ≤ 295K. An EPR signal of Cu2+ ions in the orthorhombic local symmetry is observed. Moreover, the EPR signal intensity increases as the temperature decreases from room temperature down to 100 K. The temperature dependence of g-factors indicates the pseudogap onset temperature (T*), corresponding to the peak of the observed curves between 127 K and 162 K. The number of spins (N) participating in EPR resonance are calculated as a function of both nanosized MnFe2O4 addition and temperature. In particular, it is shown that any EPR signal for SmBa2Cu3O7-δ/(MnFe2O4)x is probably due to small amount of spurious phases typically present in the samples such as BaCuO2. The presence of BaCuO2 is confirmed by magnetization-field (M-H) hysteresis measurements

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

    PubMed

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

    2016-05-21

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    PubMed

    Livshits, V A; Páli, T; Marsh, D

    1998-09-01

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

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

    PubMed Central

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

    2015-01-01

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

  14. High-Field EPR Spectroscopy on Transfer Proteins in Biological Action

    NASA Astrophysics Data System (ADS)

    Möbius, K.; Schnegg, A.; Plato, M.; Fuchs, M. R.; Savitsky, A.

    2006-08-01

    In the last decade joint efforts of biologists, chemists, and physicists were made to understand the dominant factors determining specificity and directionality of transmembrane transfer processes in proteins. Characteristic examples of such factors are time varying specific H-bonding patterns and/or polarity effects of the microenvironment. In this overview, a few large paradigm biosystems are surveyed which have been explored lately in our laboratory. Taking advantage of the improved spectral and temporal resolution of high-frequency/high-field EPR at 95 GHz/3.4 T and 360 GHz/12.9 T, as compared to conventional X-band EPR (9.5 GHz/0.34 T), three transfer proteins in action are characterized with respect to structure and dynamics: (1) light-induced electron-transfer intermediates in wild-type and mutant reaction-centre proteins from photosynthetic bacteria Rhodobacter sphaeroides, (2) light-driven proton-transfer intermediates of site-specifically nitroxide spin-labelled mutants of bacteriorhodopsin proteins from Halobacterium salinarium, (3) refolding intermediates of site-specifically nitroxide spin-labelled mutants of the channel-forming protein domain of Colicin A bacterial toxin produced in Escherichia coli. The information obtained is complementary to that of protein crystallography, solid-state NMR, infrared and optical spectroscopy techniques. A unique strength of high-field EPR is particularly noteworthy: it can provide detailed information on transient intermediates of proteins in biological action. They can be observed and characterized while staying in their working states on biologically relevant time scales.

  15. The unusual magnetic properties of kuramite-stannite pseudobinary series: a SQUID and EPR survey

    NASA Astrophysics Data System (ADS)

    di Benedetto, F.; Evstigneeva, T.; Borgheresi, M.; Caneschi, A.; Romanelli, M.

    2009-06-01

    The magnetic properties of the synthetic Cu3SnS4 (kuramite)-Cu2FeSnS4 (stannite) pseudobinary series were investigated by means of electron paramagnetic resonance (EPR) spectroscopy, at room temperature, and by magnetometry, in the range 2-300 K. The system is particularly complex, from both chemical and crystal chemical points of view, in particular with respect to the metal valence states and the local ordering in the different terms of the series. Nevertheless, recent successes in synthesising nanostructured kuramite foster the interest to ascertain the bulk magnetic properties of these important semiconducting phases. The obtained results allowed to ascertain that a variable lack of local ordering in the Cu3- x Fe x SnS4 ( x < 0.85) samples induce the raise of strong metal-sulphur-metal superexchange interactions, that result in the appearance of marked deviations from the single-ion behaviour, typical for pure stannite. Ferro- and antiferromagnetic interactions are in fact observed at relatively high temperatures (~150 K). A possible role played by Cu(I)-Fe(III) was revealed by the EPR measurements. The Cu-rich terms of the series ( x < 0.1) are characterised by dynamic resonant disorder (i.e. time-evolving delocalisation of the formally divalent valence state for Cu among the nearest neighbouring Cu-sites), in addition to the Cu-Fe-Sn static disorder verified along the whole series. Both factors concurring to a non-periodic arrangement of paramagnetic ions in the lattice have the main effect to drastically broaden the EPR lines.

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

    NASA Astrophysics Data System (ADS)

    Pribitzer, Stephan; Doll, Andrin; Jeschke, Gunnar

    2016-02-01

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

  17. Investigations in quantum games using EPR-type set-ups

    NASA Astrophysics Data System (ADS)

    Iqbal, Azhar

    2006-04-01

    Research in quantum games has flourished during recent years. However, it seems that opinion remains divided about their true quantum character and content. For example, one argument says that quantum games are nothing but 'disguised' classical games and that to quantize a game is equivalent to replacing the original game by a different classical game. The present thesis contributes towards the ongoing debate about quantum nature of quantum games by developing two approaches addressing the related issues. Both approaches take Einstein-Podolsky-Rosen (EPR)-type experiments as the underlying physical set-ups to play two-player quantum games. In the first approach, the players' strategies are unit vectors in their respective planes, with the knowledge of coordinate axes being shared between them. Players perform measurements in an EPR-type setting and their payoffs are defined as functions of the correlations, i.e. without reference to classical or quantum mechanics. Classical bimatrix games are reproduced if the input states are classical and perfectly anti-correlated, as for a classical correlation game. However, for a quantum correlation game, with an entangled singlet state as input, qualitatively different solutions are obtained. The second approach uses the result that when the predictions of a Local Hidden Variable (LHV) model are made to violate the Bell inequalities the result is that some probability measures assume negative values. With the requirement that classical games result when the predictions of a LHV model do not violate the Bell inequalities, our analysis looks at the impact which the emergence of negative probabilities has on the solutions of two-player games which are physically implemented using the EPR-type experiments.

  18. On the zigzagging causility model of EPR correlations and on the interpretation of quantum mechanics

    NASA Astrophysics Data System (ADS)

    de Beauregard, O. Costa

    1988-09-01

    Being formalized inside the S-matrix scheme, the zigzagging causility model of EPR correlations has full Lorentz and CPT invariance. EPR correlations, proper or reversed, and Wheeler's smoky dragon metaphor are respectively pictured in spacetime or in the momentum-energy space, as V-shaped, A-shaped, or C-shaped ABC zigzags, with a summation at B over virtual states |B>

  19. Pulsed EPR Spectroscopy of 33S-Labeled Molybdenum Cofactor in Catalytically Active Bioengineered Sulfite Oxidase

    PubMed Central

    Klein, Eric L.; Belaidi, Abdel Ali; Raitsimring, Arnold M.; Davis, Amanda C.; Krämer, Tobias; Astashkin, Andrei V.; Neese, Frank; Schwarz, Günter; Enemark, John H.

    2014-01-01

    Molybdenum enzymes contain at least one pyranopterin dithiolate (molybdopterin, MPT) moiety that coordinates Mo through two dithiolate (dithiolene) sulfur atoms. For sulfite oxidase (SO), hyperfine interactions (hfi) and nuclear quadrupole interactions (nqi) of magnetic nuclei (I ≠ 0) near the Mo(V) (d1) center have been measured using high-resolution pulsed electron paramagnetic resonance (EPR) methods and interpreted with the help of the density functional theory (DFT) calculations. These have provided important insights about the active site structure and the reaction mechanism of the enzyme. However, it has not been possible to use EPR to probe the dithiolene sulfurs directly since naturally abundant 32S has no nuclear spin (I = 0). Here we describe direct incorporation of 33S (I = 3/2), the only stable magnetic sulfur isotope, into MPT using controlled in vitro synthesis with purified proteins. The electron spin echo envelope modulation (ESEEM) spectra from 33S-labeled MPT in this catalytically active SO variant are dominated by the ‘inter-doublet’ transition arising from the strong nuclear quadrupole interaction, as also occurs for the 33S-labeled exchangeable equatorial sulfite ligand [Klein, E. L., et al., Inorg. Chem. 2012, 51, 1408 – 1418]. The estimated experimental hfi and nqi parameters for 33S (aiso = 3 MHz and e2Qq/h = 25 MHz) are in good agreement with those predicted by DFT. In addition, the DFT calculations show that the two 33S atoms are indistinguishable by EPR and reveal a strong intermixing between their out-of-plane pz orbitals and the dxy orbital of Mo(V). PMID:24387640

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

    Pribitzer, Stephan; Doll, Andrin; Jeschke, Gunnar

    2016-02-01

    Frequency-swept chirp pulses, created with arbitrary waveform generators (AWGs), can achieve inversion over a range of several hundreds of MHz. Such passage pulses provide defined flip angles and increase sensitivity. The fact that spectra are not excited at once, but single transitions are passed one after another, can cause new effects in established pulse EPR sequences. We developed a MATLAB library for simulation of pulse EPR, which is especially suited for modeling spin dynamics in ultra-wideband (UWB) EPR experiments, but can also be used for other experiments and NMR. At present the command line controlled SPin DYnamics ANalysis (SPIDYAN) package supports one-spin and two-spin systems with arbitrary spin quantum numbers. By providing the program with appropriate spin operators and Hamiltonian matrices any spin system is accessible, with limits set only by available memory and computation time. Any pulse sequence using rectangular and linearly or variable-rate frequency-swept chirp pulses, including phase cycling can be quickly created. To keep track of spin evolution the user can choose from a vast variety of detection operators, including transition selective operators. If relaxation effects can be neglected, the program solves the Liouville-von Neumann equation and propagates spin density matrices. In the other cases SPIDYAN uses the quantum mechanical master equation and Liouvillians for propagation. In order to consider the resonator response function, which on the scale of UWB excitation limits bandwidth, the program includes a simple RLC circuit model. Another subroutine can compute waveforms that, for a given resonator, maintain a constant critical adiabaticity factor over the excitation band. Computational efficiency is enhanced by precomputing propagator lookup tables for the whole set of AWG output levels. The features of the software library are discussed and demonstrated with spin-echo and population transfer simulations. Copyright © 2016

  2. Biologic dosimetry for nuclear environments by electron paramagnetic resonance (EPR) methods. Conference paper

    SciTech Connect

    McCreery, M.J.; Swenberg, C.E.; Basso, M.J.; Conklin, J.J.; Hsieh, J.

    1982-06-18

    A number of stable and unstable free radicals are produced by exposure of calcified tissues to ionizing radiation. Identification of the exact molecular nature of these radicals and their kinetic annealing properties awaits further investigation. However, the high stability and the dose-response characteristics of the signal at g = 2.0023 make it very promising for use in biologic dosimetry. A 10-25 mg sample of enamel is enough to determine absorbed dose from 10-10 to the 7th power rads of gamma, X-ray, and accelerated electron exposures. This sample, which is no more than a chip from the ridge of a human tooth, does not expose the living portion of the tooth and so is relatively noninvasive. Investigations to establish a standard method for this procedure and to evaluate neutron dose is in progress. Although the procedures outlined here are relatively noninvasive, this technique affords other approaches that are even less invasive. Unlike optical methods, the sample for EPR analysis does not have to be transparent. It is not even necessary to suspend the sample as a fine powder. As long as the bone or tooth sample is within the dimensional limits of the tuned EPR cavity, it can be analyzed intact. This fact makes in vivo analysis feasible. We are currently making attempts to enlarge the EPR cavity with modification of the corresponding electronic components so that a finger can be analyzed. If this approach is successful, the expedient evaluation of large numbers of casualties might be possible by a method that is noninvasive and nondestructive.

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

    NASA Astrophysics Data System (ADS)

    Schonenberger, Christian

    2011-03-01

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

  4. Single crystal EPR, optical absorption and superposition model study of Cr 3+ doped ammonium dihydrogen phosphate

    NASA Astrophysics Data System (ADS)

    Kripal, Ram; Pandey, Sangita

    2010-06-01

    The electron paramagnetic resonance (EPR) studies are carried out on Cr 3+ ion doped ammonium dihydrogen phosphate (ADP) single crystals at room temperature. Four magnetically inequivalent sites for chromium are observed. No hyperfine structure is obtained. The crystal-field and spin Hamiltonian parameters are calculated from the resonance lines obtained at different angular rotations. The zero field and spin Hamiltonian parameters of Cr 3+ ion in ADP are calculated as: | D| = (257 ± 2) × 10 -4 cm -1, | E| = (79 ± 2) × 10 -4 cm -1, g = 1.9724 ± 0.0002 for site I; | D| = (257 ± 2) × 10 -4 cm -1, | E| = (77 ± 2) × 10 -4 cm -1, g = 1.9727 ± 0.0002 for site II; | D| = (259 ± 2) × 10 -4 cm -1, | E| = (78 ± 2) × 10 -4 cm -1, g = 1.9733 ± 0.0002 for site III; | D| = (259 ± 2) × 10 -4 cm -1, | E| = (77 ± 2) × 10 -4 cm -1, g = 1.973 ± 0.0002 for site IV, respectively. The site symmetry of Cr 3+ doped single crystal is discussed on the basis of EPR data. The Cr 3+ ion enters the lattice substitutionally replacing the NH 4+ sites. The optical absorption spectra are recorded in 195-925 nm wavelength range at room temperature. The energy values of different orbital levels are determined. On the basis of EPR and optical data, the nature of bonding in the crystal is discussed. The calculated values of Racah interelectronic repulsion parameters ( B and C), cubic crystal-field splitting parameter ( Dq) and nephelauxetic parameters ( h and k) are: B = 640, C = 3070, Dq = 2067 cm -1, h = 1.44 and k = 0.21, respectively. ZFS parameters are also determined using Bkq parameters from superposition model.

  5. [Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

    SciTech Connect

    Eyring, E.M.

    1992-01-01

    The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd[sup 3+] + L(ligand), [RuL[sub 5]H[sub 2]O][sup 2+], laser flash photolysis of Mo(CO)[sub 6] + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd[sup 3+] ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO)[sub 6]-2,2'-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

  6. [Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

    SciTech Connect

    Eyring, E.M.

    1992-10-01

    The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd{sup 3+} + L(ligand), [RuL{sub 5}H{sub 2}O]{sup 2+}, laser flash photolysis of Mo(CO){sub 6} + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd{sup 3+} ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO){sub 6}-2,2`-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

  7. Bidirectional teleportation of a pure EPR state by using GHZ states

    NASA Astrophysics Data System (ADS)

    Hassanpour, Shima; Houshmand, Monireh

    2016-02-01

    In the present paper, a novel bidirectional quantum teleportation protocol is proposed. By using entanglement swapping technique, two GHZ states are shared as a quantum channel between Alice and Bob as legitimate users. In this scheme, based on controlled-not operation, single-qubit measurement, and appropriate unitary operations, two users can simultaneously transmit a pure EPR state to each other, While, in the previous protocols, the users can just teleport a single-qubit state to each other via more than four-qubit state. Therefore, the proposed scheme is economical compared with previous protocols.

  8. Nursing documentation with NANDA and NIC in a comprehensive HIS/EPR system.

    PubMed

    Flø, Kåre

    2006-01-01

    DIPS nursing documentation system facilitates that nurses can write several types of notes into the EPR. Within these notes the nurses can register NANDA diagnoses and NIC interventions with nursing activities. To choose NANDA and NIC the nurse can use a search engine, or she can choose a relevant Care plan guideline and pick the suggested diagnoses and interventions from there. Diagnoses and interventions with nursing activities registered are presented in a Care plan. When a nurse writes a note for a patient she will always be presented the Care plan and she can easy evaluate and update the Care plan.

  9. Fault-tolerant controlled deterministic secure quantum communication using EPR states against collective noise

    NASA Astrophysics Data System (ADS)

    Kao, Shih-Hung; Yang, Chun-Wei; Hwang, Tzonelih

    2016-11-01

    This paper proposes two new fault-tolerant controlled deterministic secure quantum communication (CDSQC) protocols based only on Einstein-Podolsky-Rosen (EPR) entangled states. The proposed protocols are designed to be robust against the collective-dephasing noise and the collective-rotation noise, respectively. Compared to the existing fault-tolerant controlled quantum communication protocols, the proposed protocols not only can do without a quantum channel between the receiver and the controller as the state-of-the-art protocols do, but also have the advantage that the number of quantum particles required in the CDSQC protocols is reduced owing to the use of the simplest entangled states.

  10. Application of EPR dosimetry in bone for ex vivo measurements of doses in radiotherapy patients.

    PubMed

    Krefft, K; Drogoszewska, B; Kaminska, J; Juniewicz, M; Wołąkiewicz, G; Jakacka, I; Ciesielski, B

    2014-11-01

    In the present study, bone samples from three patients treated in radiotherapy facilities in Poland were used for the determination of doses absorbed during radiotherapy. The samples were obtained during surgical treatments of patients performed due to medical indications. For the purpose of retrospective dosimetry, sensitivity of the radiation-induced EPR signal was individually calibrated in the samples by re-irradiation of the samples with known doses. The doses reconstructed in bones extracted within 6 months after irradiation were consistent with those calculated by treatment planning systems. The dose reconstructed in the bone removed 6 y after radiotherapy was ∼14% lower than the calculated one.

  11. EPR and optical absorption study of Cu2+ doped lithium sulphate monohydrate (LSMH) single crystals

    NASA Astrophysics Data System (ADS)

    Sheela, K. Juliet; Krishnan, S. Radha; Shanmugam, V. M.; Subramanian, P.

    2016-05-01

    EPR study of Cu2+ doped NLO active Lithium Sulphate monohydrate (Li2SO4.H2O) single crystals were grown successfully by slow evaporation method at room temperature. The principal values of g and A tensors indicate existence of orthorhombic symmetry around the Cu2+ ion. From the direction cosines of g and A tensors, the locations of Cu2+ in the lattice have been identified as interstitial site. Optical absorption confirms the rhombic symmetry and ground state wave function of the Cu2+ ion in a lattice as dx2-y2.

  12. Saturation recovery EPR and ELDOR at W-band for spin labels

    NASA Astrophysics Data System (ADS)

    Froncisz, Wojciech; Camenisch, Theodore G.; Ratke, Joseph J.; Anderson, James R.; Subczynski, Witold K.; Strangeway, Robert A.; Sidabras, Jason W.; Hyde, James S.

    2008-08-01

    A reference arm W-band (94 GHz) microwave bridge with two sample-irradiation arms for saturation recovery (SR) EPR and ELDOR experiments is described. Frequencies in each arm are derived from 2 GHz synthesizers that have a common time-base and are translated to 94 GHz in steps of 33 and 59 GHz. Intended applications are to nitroxide radical spin labels and spin probes in the liquid phase. An enabling technology is the use of a W-band loop-gap resonator (LGR) [J.W. Sidabras, R.R. Mett, W. Froncisz, T.G. Camenisch, J.R. Anderson, J.S. Hyde, Multipurpose EPR loop-gap resonator and cylindrical TE 011 cavity for aqueous samples at 94 GHz, Rev. Sci. Instrum. 78 (2007) 034701]. The high efficiency parameter (8.2 GW -1/2 with sample) permits the saturating pump pulse level to be just 5 mW or less. Applications of SR EPR and ELDOR to the hydrophilic spin labels 3-carbamoyl-2,2,5,5-tetra-methyl-3-pyrroline-1-yloxyl (CTPO) and 2,2,6,6,-tetramethyl-4-piperidone-1-oxyl (TEMPONE) are described in detail. In the SR ELDOR experiment, nitrogen nuclear relaxation as well as Heisenberg exchange transfer saturation from pumped to observed hyperfine transitions. SR ELDOR was found to be an essential method for measurements of saturation transfer rates for small molecules such as TEMPONE. Free induction decay (FID) signals for small nitroxides at W-band are also reported. Results are compared with multifrequency measurements of T1e previously reported for these molecules in the range of 2-35 GHz [J.S. Hyde, J.-J. Yin, W.K. Subczynski, T.G. Camenisch, J.J. Ratke, W. Froncisz, Spin label EPR T 1 values using saturation recovery from 2 to 35 GHz. J. Phys. Chem. B 108 (2004) 9524-9529]. The values of T1e decrease at 94 GHz relative to values at 35 GHz.

  13. Saturation recovery EPR and ELDOR at W-band for spin labels.

    PubMed

    Froncisz, Wojciech; Camenisch, Theodore G; Ratke, Joseph J; Anderson, James R; Subczynski, Witold K; Strangeway, Robert A; Sidabras, Jason W; Hyde, James S

    2008-08-01

    A reference arm W-band (94 GHz) microwave bridge with two sample-irradiation arms for saturation recovery (SR) EPR and ELDOR experiments is described. Frequencies in each arm are derived from 2 GHz synthesizers that have a common time-base and are translated to 94 GHz in steps of 33 and 59 GHz. Intended applications are to nitroxide radical spin labels and spin probes in the liquid phase. An enabling technology is the use of a W-band loop-gap resonator (LGR) [J.W. Sidabras, R.R. Mett, W. Froncisz, T.G. Camenisch, J.R. Anderson, J.S. Hyde, Multipurpose EPR loop-gap resonator and cylindrical TE(011) cavity for aqueous samples at 94 GHz, Rev. Sci. Instrum. 78 (2007) 034701]. The high efficiency parameter (8.2 GW(-1/2) with sample) permits the saturating pump pulse level to be just 5 mW or less. Applications of SR EPR and ELDOR to the hydrophilic spin labels 3-carbamoyl-2,2,5,5-tetra-methyl-3-pyrroline-1-yloxyl (CTPO) and 2,2,6,6,-tetramethyl-4-piperidone-1-oxyl (TEMPONE) are described in detail. In the SR ELDOR experiment, nitrogen nuclear relaxation as well as Heisenberg exchange transfer saturation from pumped to observed hyperfine transitions. SR ELDOR was found to be an essential method for measurements of saturation transfer rates for small molecules such as TEMPONE. Free induction decay (FID) signals for small nitroxides at W-band are also reported. Results are compared with multifrequency measurements of T(1e) previously reported for these molecules in the range of 2-35 GHz [J.S. Hyde, J.-J. Yin, W.K. Subczynski, T.G. Camenisch, J.J. Ratke, W. Froncisz, Spin label EPR T(1) values using saturation recovery from 2 to 35 GHz. J. Phys. Chem. B 108 (2004) 9524-9529]. The values of T(1e) decrease at 94 GHz relative to values at 35 GHz.

  14. EPR assessment of protein sites for incorporation of Gd(III) MRI contrast labels

    PubMed Central

    Lagerstedt, Jens O.; Petrlova, Jitka; Hilt, Silvia; Marek, Antonin; Chung, Youngran; Sriram, Renuka; Budamagunta, Madhu S.; Desreux, Jean F.; Thonon, David; Jue, Thomas; Smirnov, Alex I.; Voss, John C.

    2013-01-01

    We have engineered Apolipoprotein A-I (apoA-I), a major protein constituent of high-density lipoprotein (HDL), to contain DOTA-chelated Gd(III) as an MRI contrast agent for the purpose of imaging reconstituted HDL (rHDL) biodistribution, metabolism, and regulation in vivo. This protein contrast agent was obtained by reacting the thiol-reactive Gd[MTS-ADO3A] label with Cys engineered at four distinct positions (52, 55, 76 and 80) in apoA-I. MRI of infused mice previously showed that the Gd-labeled apoA-I migrates to both the liver and the kidney, the organs responsible for HDL catabolism; however, the contrast properties of apoA-I are superior when the ADO3A moiety is located at position 55, compared to the protein labeled at positions 52, 76 or 80. It is shown here that continuous wave X-band (9 GHz) EPR spectroscopy is capable of detecting differences in the Gd(III) signal when comparing the labeled protein in the lipid-free to the rHDL state. Furthermore, the values of NMR relaxivity obtained for labeled variants in both the lipid-free and rHDL states correlate to the product of the X-band Gd(III) spectral width and the collision frequency between a nitroxide spin label and a polar relaxation agent. Consistent with its superior relaxivity measured by NMR, the rHDL-associated apoA-I containing the Gd[MTS-ADO3A] probe attached to position 55 displays favorable dynamic and water accessibility properties as determined by X-band EPR. While room temperature EPR requires >1 mM Gd(III)-labeled and only >10 μM nitroxide-labeled protein to resolve the spectrum, the volume requirement is exceptionally low (~5μL). Thus, X-band EPR provides a practical assessment for the suitability of imaging candidates containing the site-directed ADO3A contrast probe. PMID:23606429

  15. 2'-Alkynylnucleotides: A Sequence- and Spin Label-Flexible Strategy for EPR Spectroscopy in DNA.

    PubMed

    Haugland, Marius M; El-Sagheer, Afaf H; Porter, Rachel J; Peña, Javier; Brown, Tom; Anderson, Edward A; Lovett, Janet E

    2016-07-27

    Electron paramagnetic resonance (EPR) spectroscopy is a powerful method to elucidate molecular structure through the measurement of distances between conformationally well-defined spin labels. Here we report a sequence-flexible approach to the synthesis of double spin-labeled DNA duplexes, where 2'-alkynylnucleosides are incorporated at terminal and internal positions on complementary strands. Post-DNA synthesis copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions with a variety of spin labels enable the use of double electron-electron resonance experiments to measure a number of distances on the duplex, affording a high level of detailed structural information.

  16. An EPR study on a new triclinic symmetry defect in neutron-irradiated FZ-silicon

    NASA Astrophysics Data System (ADS)

    En, Wu; Shu-xian, Wu; Jin-Chang, Mao; Mao-Xun, Yan; Guo-gang, Qin

    1987-01-01

    A new defect, labled as Si-PK1, has been observed with EPR (Electron Paramagnetic Resonance) in neutron irradiated FZ-Si grown in argon, hydrogen and vacuum. Its symmetry has been determined to be triclinic symmetry, the lowest possible symmetry. Si-PK1 has not been observed in CZ-Si. It is not related to any common impurities in Si, like oxygen, carbon, phosphorus and boron, and it should be an intrinsic defect. Combining with the empirical classification of g tensor, it is concluded that Si-PK1 may be a multi-vacancy cluster.

  17. Anisotropy effects of EPR signals and mechanisms of mass transfer in tooth enamel and bones.

    PubMed

    Brik, A; Haskell, E; Brik, V; Scherbina, O; Atamanenko, O

    2000-05-01

    Peculiarities of the internal construction of tooth enamel and bones that cause anisotropy effects and mass transfer in these objects are described. It is shown that the composition of the mineral component of teeth and bones depends on a mechanical-electrical mechanism, which pumps ions into nanocrystals. Decrease in the efficiency of the mechanical-electrical mechanism results in demineralization of enamel and bones, which progresses most rapidly at a disease of the biomineral or under special conditions, such as in space flights. Effects of signal anisotropy in the practice of retrospective EPR dosimetry are discussed.

  18. A Multiparty Controlled Bidirectional Quantum Secure Direct Communication and Authentication Protocol Based on EPR Pairs

    NASA Astrophysics Data System (ADS)

    Chang, Yan; Zhang, Shi-Bin; Yan, Li-Li; Sheng, Zhi-Wei

    2013-06-01

    A multiparty controlled bidirectional quantum secure direct communication and authentication protocol is proposed based on EPR pair and entanglement swapping. The legitimate identities of communicating parties are encoded to Bell states which act as a detection sequence. Secret messages are transmitted by using the classical XOR operation, which serves as a one-time-pad. No photon with secret information transmits in the quantum channel. Compared with the protocols proposed by Wang et al. [Acta Phys. Sin. 56 (2007) 673; Opt. Commun. 266 (2006) 732], the protocol in this study implements bidirectional communication and authentication, which defends most attacks including the ‘man-in-the-middle’ attack efficiently.

  19. Applicability of EPR/alanine dosimetry for quality assurance in proton eye radiotherapy.

    PubMed

    Michalec, B; Mierzwinska, G; Ptaszkiewicz, M; Sowa, U; Stolarczyk, L; Weber, A

    2014-06-01

    A new quality assurance and quality control method for proton eye radiotherapy based on electron paramagnetic resonance (EPR)/alanine dosimetry has been developed. It is based on Spread-Out Bragg Peak entrance dose measurement with alanine detectors. The entrance dose is well correlated with the dose at the facility isocenter, where, during the therapeutic irradiation, the tumour is placed. The unique alanine detector features namely keeping the dose record in a form of stable radiation-induced free radicals trapped in the material structure, and the non-destructive read-out makes this type of detector a good candidate for additional documentation of the patient's exposure over the therapy course.

  20. Single crystal EPR study on gamma-irradiated NLO material (2-amino-5-nitropyridinium chloride)

    NASA Astrophysics Data System (ADS)

    Dhanuskodi, S.; Manikandan, S.

    2004-03-01

    A semiorganic nonlinear optical (NLO) material 2-amino-5-nitropyridinium chloride (2A5NPCl) was synthesized. Single crystals were grown following the slow evaporation method and characterized by measuring density, TGA, FT-IR, FT-Raman and X-ray diffraction techniques. The electron paramagnetic resonance (EPR) spectra were recorded for gamma-irradiated single crystals of 2A5NPCl. The angular variation studies of the spectra were observed and the principal values of the g-tensor and A-tensor were determined.

  1. In situ EPR studies of reaction pathways in Titania photocatalyst-promoted alkylation of alkenes.

    PubMed

    Rhydderch, Shona; Howe, Russell F

    2015-03-03

    In situ EPR spectroscopy at cryogenic temperatures has been used to observe and identify paramagnetic species produced when titania is irradiated in the presence of reactants used in the photocatalytic alkylation of maleimide with t-butyl carboxylic acid or phenoxyacetic acid. It is shown that maleimide acts as an acceptor of conduction band electrons. Valence band holes oxidise t-butyl carboxylic acid to the t-butyl radical and phenoxyacetic acid to the phenoxyacetic acid radical cation. In the presence of maleimide, the phenoxymethyl radical is formed from phenoxyacetic acid. The relevance of these observations to the mechanisms of titania photocatalyst-promoted alkylation of alkenes is discussed.

  2. Surface loop resonator design for in vivo EPR tooth dosimetry using finite element analysis.

    PubMed

    Pollock, Jennifer D; Williams, Benjamin B; Sidabras, Jason W; Grinberg, Oleg; Salikhov, Ildar; Lesniewski, Piotr; Kmiec, Maciej; Swartz, Harold M

    2010-02-01

    Finite element analysis is used to evaluate and design L-band surface loop resonators for in vivo electron paramagnetic resonance (EPR) tooth dosimetry. This approach appears to be practical and useful for the systematic examination and evaluation of resonator configurations to enhance the precision of dose estimates. The effects of loop positioning in the mouth are examined, and it is shown that the sensitivity to loop position along a row of molars is decreased as the loop is moved away from the teeth.

  3. Study of dental enamel and synthetic hydroxyapatite irradiated by EPR at K-band.

    PubMed

    Santos, A B; Rossi, A M; Baffa, O

    2005-02-01

    In this preliminary work the EPR spectra of a small dental enamel block and a synthetic B-type hydroxyapatite in powder form, both irradiated with gamma rays, were analyzed in K-band. The spectra of the dental enamel block allow the analysis of independent components with different angular orientations, while the study of the dosimetric properties of the synthetic hydroxyapatites showed good performance of this spectrometer. K-band spectra show better resolution when compared to X-band, while using significantly less sample material.

  4. Pentachlorooxotechnetate(VI) anion, (TcOCl/sub 5/): an EPR study

    SciTech Connect

    Kirmse, R.; Stach, J.; Abram, U.

    1985-07-03

    The anion pentachlorooxotechnetate(VI), TcOCl/sub 5//sup -/, has been prepared by reduction of TcO/sub 4//sup -/ with HCl in concentrated H/sub 2/SO/sub 4/ and investigated by means of the EPR technique. The axial symmetric spectrum suggests an in-plane ..pi..-type ground state of the MO of the unpaired electron. The Tc-Cl/sub eq/ bonding properties have been discussed in terms of MO theory, and a comparison has been given to the bonding properties in likely complexes of neighboring elements of Tc.

  5. Investigations of EPR parameters for the trigonal Ti3+-Ti3+ pair in beryl crystal.

    PubMed

    Wang, Fang; Zheng, Wen-Chen

    2007-08-01

    By using the complete diagonalization of energy matrix of 3d1 ions in trigonal symmetry, the EPR parameters (g factors g( parallel), g( perpendicular) and zero-field splitting D) of the trigonal Ti3+-Ti3+ pair in beryl crystal are calculated. In the calculations, the exchange interaction in the Ti3+-Ti3+ pair is taken as the perturbation and the local trigonal distortion in the defect center is considered. The results (which are in agreement with the experimental values) are discussed.

  6. Chemical process to separate iron oxides particles in pottery sample for EPR dating.

    PubMed

    Watanabe, S; Farias, T M B; Gennari, R F; Ferraz, G M; Kunzli, R; Chubaci, J F D

    2008-12-15

    Ancient potteries usually are made of the local clay material, which contains relatively high concentration of iron. The powdered samples are usually quite black, due to magnetite, and, although they can be used for thermoluminescene (TL) dating, it is easiest to obtain better TL reading when clearest natural or pre-treated sample is used. For electron paramagnetic resonance (EPR) measurements, the huge signal due to iron spin-spin interaction, promotes an intense interference overlapping any other signal in this range. Sample dating is obtained by dividing the radiation dose, determined by the concentration of paramagnetic species generated by irradiation, by the natural dose so as a consequence, EPR dating cannot be used, since iron signal do not depend on radiation dose. In some cases, the density separation method using hydrated solution of sodium polytungstate [Na6(H2W12O40).H2O] becomes useful. However, the sodium polytungstate is very expensive in Brazil; hence an alternative method for eliminating this interference is proposed. A chemical process to eliminate about 90% of magnetite was developed. A sample of powdered ancient pottery was treated in a mixture (3:1:1) of HCl, HNO(3) and H(2)O(2) for 4h. After that, it was washed several times in distilled water to remove all acid matrixes. The original black sample becomes somewhat clearer. The resulting material was analyzed by plasma mass spectrometry (ICP-MS), with the result that the iron content is reduced by a factor of about 9. In EPR measurements a non-treated natural ceramic sample shows a broad spin-spin interaction signal, the chemically treated sample presents a narrow signal in g=2.00 region, possibly due to a radical of (SiO(3))(3-), mixed with signal of remaining iron [M. Ikeya, New Applications of Electron Spin Resonance, World Scientific, Singapore, 1993, p. 285]. This signal increases in intensity under gamma-irradiation. However, still due to iron influence, the additive method yielded too

  7. Chemical process to separate iron oxides particles in pottery sample for EPR dating

    NASA Astrophysics Data System (ADS)

    Watanabe, S.; Farias, T. M. B.; Gennari, R. F.; Ferraz, G. M.; Kunzli, R.; Chubaci, J. F. D.

    2008-12-01

    Ancient potteries usually are made of the local clay material, which contains relatively high concentration of iron. The powdered samples are usually quite black, due to magnetite, and, although they can be used for thermoluminescene (TL) dating, it is easiest to obtain better TL reading when clearest natural or pre-treated sample is used. For electron paramagnetic resonance (EPR) measurements, the huge signal due to iron spin-spin interaction, promotes an intense interference overlapping any other signal in this range. Sample dating is obtained by dividing the radiation dose, determined by the concentration of paramagnetic species generated by irradiation, by the natural dose so as a consequence, EPR dating cannot be used, since iron signal do not depend on radiation dose. In some cases, the density separation method using hydrated solution of sodium polytungstate [Na 6(H 2W 12O 40)·H 2O] becomes useful. However, the sodium polytungstate is very expensive in Brazil; hence an alternative method for eliminating this interference is proposed. A chemical process to eliminate about 90% of magnetite was developed. A sample of powdered ancient pottery was treated in a mixture (3:1:1) of HCl, HNO 3 and H 2O 2 for 4 h. After that, it was washed several times in distilled water to remove all acid matrixes. The original black sample becomes somewhat clearer. The resulting material was analyzed by plasma mass spectrometry (ICP-MS), with the result that the iron content is reduced by a factor of about 9. In EPR measurements a non-treated natural ceramic sample shows a broad spin-spin interaction signal, the chemically treated sample presents a narrow signal in g = 2.00 region, possibly due to a radical of (SiO 3) 3-, mixed with signal of remaining iron [M. Ikeya, New Applications of Electron Spin Resonance, World Scientific, Singapore, 1993, p. 285]. This signal increases in intensity under γ-irradiation. However, still due to iron influence, the additive method yielded too

  8. Stability of X-band EPR signals from fingernails under vacuum storage.

    PubMed

    Sholom, Sergey; McKeever, Stephen

    2017-12-01

    EPR signals of different origin have been tested in human finger- and toe-nails with an X-band EPR technique for different conditions of nail storage. Three different signals were identified, namely a singlet at g=2.005, a doublet at g=2.004 with a splitting constant A=1.8 mT, and an anisotropic signal at g1=2.057, g2=2.029 and g3=2.003 (positions of local extrema). All EPR spectra from nails, whether irradiated or mechanically stressed, can be described as a superposition of these three signals. The singlet is responsible for the background signal (BG), is the main component of radiation-induced signals (RIS) for low doses (100 Gy or lower) and also contributes to mechanically-induced signals (MIS). This signal is quite stable under vacuum storage, but can be reduced almost to zero by soaking in water. The behavior of this signal under ambient conditions depends on many factors, such as absorbed dose, air humidity, and ambient illumination intensity at the place of storage. The doublet arises after exposure of nails to high (few hundreds Gy and higher) doses or after mechanical stress of samples. Depending on how this signal was obtained, it may have bulk or surface locations with quite different stability properties. The surface-located doublet (generated on the nail edges during cutting or clipping) is quite unstable and decays over about two hours for samples stored at ambient conditions and within several seconds for samples immersed in water. The volume-distributed doublet decays within a few minutes in water, several hours at ambient conditions and several days in vacuum. The anisotropic signal may also be generated by both ionizing radiation and mechanical stress; this signal is quite stable in vacuum and decays over several days at ambient conditions or a few tens of minutes in water. The reference lines for the above-described three EPR signals were obtained and a procedure of spectra deconvolution was developed and tested on samples exposed to both

  9. Structure of the upper mantle under the EPR from waveform inversion of regional events

    PubMed

    Webb; Forsyth

    1998-05-22

    Waveform inversions of seismograms recorded at the Mantle Electromagnetic and Tomography (MELT) Experiment ocean bottom seismometer array from regional events with paths following the East Pacific Rise (EPR) require that low shear velocities (<3.7 km/s) extend to depths of more than 100 km below the rise axis. Velocities increase with average crustal age along ray paths. The reconciliation of Love and Rayleigh wave data requires that shear flow has aligned melt pockets or olivine crystals, creating an anisotropic uppermost mantle.

  10. EPR analysis of the effects of accelerated carbon ion and fast neutron irradiations on table sugar.

    PubMed

    Mikou, M; Benzina, S; Bischoff, P; Denis, J M; Gueulette, J

    2009-09-01

    Table sugar samples were irradiated with accelerated carbon ions and fast neutrons. Electron paramagnetic resonance (EPR) analysis performed after the irradiation revealed a complex spectrum similar to that observed after gamma-ray irradiations. The total concentration of the paramagnetic centers induced by accelerated carbon ions and neutrons was proportional to the absorbed dose. Good stability of the produced free radicals was observed for a typical period of sugar storage. Sugar was more sensitive to accelerated carbon ions than to neutrons. The results show that table sugar can be a useful material for dosimetry in the case of a radiation accident.

  11. Comparison of local and global angular interpolation applied to spectral-spatial EPR image reconstruction.

    PubMed

    Ahn, Kang-Hyun; Halpern, Howard J

    2007-03-01

    Spectral-spatial images reconstructed from a small number of projections suffer from streak artifacts that are seen as noise, particularly in the spectral dimension. Interpolation in projection space can reduce artifacts in the reconstructed images. The reduction of background artifacts improves lineshape fitting. In this work, we compared the performances of angular interpolation implemented using linear, cubic B-spline, and sinc methods. Line width maps were extracted from 4-D EPR images of phantoms using spectral fitting to evaluate each interpolation method and its robustness to noise. Results from experiment and simulation showed that the cubic B-spline, angular interpolation was preferable to either sinc or linear interpolation methods.

  12. Robust EPR-pairs-based quantum secure communication with authentication resisting collective noise

    NASA Astrophysics Data System (ADS)

    Chang, Yan; Zhang, ShiBin; Li, Jian; Yan, LiLi

    2014-10-01

    This work presents two robust quantum secure communication schemes with authentication based on Einstein-Podolsky-Rosen (EPR) pairs, which can withstand collective noises. Two users previously share an identity string representing their identities. The identity string is encoded as decoherence-free states (termed logical qubits), respectively, over the two collective noisy channels, which are used as decoy photons. By using the decoy photons, both the authentication of two users and the detection of eavesdropping were implemented. The use of logical qubits not only guaranteed the high fidelity of exchanged secret message, but also prevented the eavesdroppers to eavesdrop beneath a mask of noise.

  13. Splitting spacetime and cloning qubits: linking no-go theorems across the ER=EPR duality

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    We analyze the no-cloning theorem in quantum mechanics through the lens of the proposed ER=EPR (Einstein-Rosen = Einstein-Podolsky-Rosen) duality between entanglement and wormholes. In particular, we find that the no-cloning theorem is dual on the gravity side to the no-go theorem for topology change, violating the axioms of which allows for wormhole stabilization and causality violation. Such a duality between important no-go theorems elucidates the proposed connection between spacetime geometry and quantum entanglement.

  14. CW and FT time-resolved EPR investigation of the quenching reaction of the 2-hydroxypropan-2-yl radical

    SciTech Connect

    Ohara, Keishi; Hirota, Noboru; Steren, C.A.; Willigen, H. van

    1996-02-22

    The secondary quenching reactions of the 2-hydroxypropan-2-yl radical produced by photolysis of pyrazine, quinoxaline, and p-benzoquinone in 2-propanol were investigated with time-resolved EPR. The quenching rate constants are 6.6 x 10{sup 6}, 1.2 x 10{sup 8}, and nearly 10{sup 8} s{sup -1} s{sup -1} for pyrazine, quinoxaline, and p-benzoquinone, respectively. The time profiles of the transient EPR signals of pyrazinyl and 2-hydroxypropan-2-yl radicals were measured by FT-EPR and analyzed in detail in terms of a reaction scheme involving the primary hydrogen abstraction reaction and the subsequent quenching reaction. It is found that half of the signal intensity of the pyrazinyl radical arises from polarization transfer accompanying 2-hydroxypropan-2-yl quenching by pyrazine. 14 refs., 5 figs.

  15. A Hash Based Remote User Authentication and Authenticated Key Agreement Scheme for the Integrated EPR Information System.

    PubMed

    Li, Chun-Ta; Weng, Chi-Yao; Lee, Cheng-Chi; Wang, Chun-Cheng

    2015-11-01

    To protect patient privacy and ensure authorized access to remote medical services, many remote user authentication schemes for the integrated electronic patient record (EPR) information system have been proposed in the literature. In a recent paper, Das proposed a hash based remote user authentication scheme using passwords and smart cards for the integrated EPR information system, and claimed that the proposed scheme could resist various passive and active attacks. However, in this paper, we found that Das's authentication scheme is still vulnerable to modification and user duplication attacks. Thereafter we propose a secure and efficient authentication scheme for the integrated EPR information system based on lightweight hash function and bitwise exclusive-or (XOR) operations. The security proof and performance analysis show our new scheme is well-suited to adoption in remote medical healthcare services.

  16. Adsorption-desorption induced structural changes of Cu-MOF evidenced by solid state NMR and EPR spectroscopy.

    PubMed

    Jiang, Yijiao; Huang, Jun; Kasumaj, Besnik; Jeschke, Gunnar; Hunger, Michael; Mallat, Tamas; Baiker, Alfons

    2009-02-18

    Adsorption-desorption induced structural changes of Cu(bpy)(H(2)O)(2)(BF(4)),(bpy) (bpy = 4,4'-bipyridine) [Cu-MOF] have been evidenced by combined NMR and EPR spectroscopy. Upon adsorption of probe molecules even at a few mbar, EPR spectra show that they are activated to form complexes at Cu(II) sites, which results in a change of the Cu-MOF's structure as indicated by a high-field shift of the (11)B MAS NMR. After desorption, both EPR and (11)B MAS NMR spectra evidenced that the structure of the Cu-MOF reversibly shifted to the original state. This observation indicates that MOFs can undergo structural changes during processes where adsorption-desorption steps are involved such as gas storage, separation, and catalysis.

  17. Toward the fourth dimension of membrane protein structure: insight into dynamics from spin-labeling EPR spectroscopy.

    PubMed

    McHaourab, Hassane S; Steed, P Ryan; Kazmier, Kelli

    2011-11-09

    Trapping membrane proteins in the confines of a crystal lattice obscures dynamic modes essential for interconversion between multiple conformations in the functional cycle. Moreover, lattice forces could conspire with detergent solubilization to stabilize a minor conformer in an ensemble thus confounding mechanistic interpretation. Spin labeling in conjunction with electron paramagnetic resonance (EPR) spectroscopy offers an exquisite window into membrane protein dynamics in the native-like environment of a lipid bilayer. Systematic application of spin labeling and EPR identifies sequence-specific secondary structures, defines their topology and their packing in the tertiary fold. Long range distance measurements (60 Å-80 Å) between pairs of spin labels enable quantitative analysis of equilibrium dynamics and triggered conformational changes. This review highlights the contribution of spin labeling to bridging structure and mechanism. Efforts to develop methods for determining structures from EPR restraints and to increase sensitivity and throughput promise to expand spin labeling applications in membrane protein structural biology.

  18. Gadolinium-Activated CaZr4O9 Ultraviolet-B-Emitting Phosphor: A Luminescence and EPR Study

    NASA Astrophysics Data System (ADS)

    Singh, Vijay; Singh, N.; Watanabe, S.; Gundu Rao, T. K.; Pathak, M. S.; Srivastava, A. K.; Singh, P. K.; Dhoble, S. J.

    2017-04-01

    Gadolinium-activated CaZr4O9 ultraviolet-B-emitting phosphor has been prepared by a solution combustion method and characterized using powder x-ray diffraction analysis, electron paramagnetic resonance (EPR), and photoluminescence (PL) spectroscopic techniques. Upon excitation at 274 nm, the emission spectrum exhibits a well-defined ultraviolet B emission band with maximum at 313 nm, corresponding to 6P7/2 → 8S7/2 transition. A characteristic "U"-type EPR spectrum is observed for the powder samples. Doped Gd3+ ion appears to occupy calcium sites in the phosphor lattice. EPR and PL analyses of the sample confirm presence of Gd3+ in the CaZr4O9 host.

  19. Theoretical studies of the local structure and EPR parameters for Cu2+ centers in disodium malonate trihydrate single crystal

    NASA Astrophysics Data System (ADS)

    Chao-Ying, Li; Ying, Huang; Xue-Mei, Zheng

    2015-01-01

    The electron paramagnetic resonance (EPR) parameters (g factors gxx, gyy, gzz and hyperfine structure constants Axx, Ayy, Azz) of the two Cu2+ centers in disodium malonate trihydrate (DSMT) single crystal are theoretically interpreted using the high order perturbation formulas of these parameters for a 3d9 ions in rhombically elongated octahedra. In the calculation, the rhombic crystal-field parameters are determined from the superposition model and the admixture of d-orbitals in the ground state wave function are taking account, the results show that although the admixture of the | d z 2 > state to the ground state wave function is small, it should not be neglected in calculations of the EPR parameters. The theoretical EPR parameters show good agreement with the observed values. The results are discussed.

  20. EPR studies of 5-bromouracil crystal after irradiation with X rays in the bromine K-edge region.

    PubMed

    Yokoya, Akinari; Takakura, Kaoru; Watanabe, Ritsuko; Akamatsu, Ken; Ito, Takashi

    2004-10-01

    Radicals induced in a single crystal of 5-bromouracil (BrUra) by synchrotron soft X rays in the bromine K-edge region (13.461-13.482 keV) were investigated using the X-band EPR method. The crystal was irradiated at three peak energies of the absorption spectrum at room temperature or at 80 K. A hydrogen abstraction radical derived from N1 of the pyrimidine ring was commonly observed for all of the energies used, though with some variation in quantity. Similar characteristics were also observed in the EPR signal for the off-K-edge low-energy (13.42 keV) and (60)Co gamma rays used for comparison. When irradiated at 80 K, a much larger exposure (roughly 10 times) of soft X rays was needed to obtain the same signal intensity as that observed at room temperature. EPR signals were not detectable with gamma irradiation at liquid nitrogen temperature.

  1. Tailored sinc pulses for uniform excitation and artifact-free radio frequency time-domain EPR imaging.

    PubMed

    Devasahayam, N; Murugesan, R; Matsumoto, K; Mitchell, J B; Cook, J A; Subramanian, S; Krishna, M C

    2004-05-01

    A method to generate shaped radiofrequency pulses for uniform excitation of electron spins in time-domain radio frequency (RF) electron paramagnetic resonance (EPR) imaging is presented. A commercial waveform generator was integrated with the transmit arm of the existing time-domain RF-EPR spectrometer to generate tailored excitation pulses with sub-nano second resolution for excitation with a 90 degrees flip-angle. A truncated sinc [sin(x)/x] pulse, tailored to compensate for the Q-profile (RF frequency response) of the resonator, was shown to yield images from phantom objects as well as in vivo images, with minimal distortion. These studies point to the advantages in using shaped sinc pulses to achieve improved uniform excitation over a relatively wide bandwidth region in time-domain RF-EPR imaging (RF-FT-EPRI).

  2. EPR adoption and dual record maintenance in the U.S.: assessing variation in medical systems infrastructure.

    PubMed

    Lorence, Daniel P; Spink, Amanda; Richards, Michael C

    2002-10-01

    The growing adoption of evidence-based medicine in the United States is acting to cause fundamental changes in the delivery of healthcare management services. With the increasing incorporation of electronic patient records (EPRs) into the day-to-day practice of medicine, it necessitates greater dependence on adequate functioning of such resources, as they become more frequently used as a clinical complement in the practice of medicine. Assessing the patterns of adoption of EPRs is likewise of increasing importance, with the recent imposition of uniform government data collection and management requirements. The medium of data storage and maintenance within many organizations is a critical factor in the ultimate delivery of service, with a like need for an integrated, designated medium for the management of data becoming paramount. This study examines, on a nationwide basis, variation in reported adoption of EPRs within U.S. healthcare organizations, and the related maintenance of dual electronic/paper record systems.

  3. Introducing the electronic patient record (EPR) in a hospital setting: boundary work and shifting constructions of professional identities.

    PubMed

    Håland, Erna

    2012-06-01

    Today's healthcare sector is being transformed by several ongoing processes, among them the introduction of new technologies, new financial models and new ways of organising work. The introduction of the electronic patient record (EPR) is representative and part of these extensive changes. Based on interviews with health personnel and office staff in a regional hospital in Norway, and with health administrators and information technology service-centre staff in the region, the article examines how the introduction of the EPR, as experienced by the participants, affects the work practices and boundaries between various professional groups in the healthcare system and discusses the implications this has for the understanding of medical practice. The article shows how the EPR has become part of the professionals' boundary work; expressing shifting constructions of professional identities.

  4. Beyond the EPR: Complementary roles of the hospital-wide electronic health record and clinical departmental systems

    PubMed Central

    2009-01-01

    Background Many hospital departments have implemented small clinical departmental systems (CDSs) to collect and use patient data for documentation as well as for other department-specific purposes. As hospitals are implementing institution-wide electronic patient records (EPRs), the EPR is thought to be integrated with, and gradually substitute the smaller systems. Many EPR systems however fail to support important clinical workflows. Also, successful integration of systems has proven hard to achieve. As a result, CDSs are still in widespread use. This study was conducted to see which tasks are supported by CDSs and to compare this to the support offered by the EPR. Methods Semi-structured interviews with users of 16 clinicians using 15 different clinical departmental systems (CDS) at a Medium-sized University hospital in Norway. Inductive analysis of transcriptions from the audio taped interviews. Results The roles of CDSs were complementary to those of the hospital-wide EPR system. The use of structured patient data was a characteristic feature. This facilitated quality development and supervision, tasks that were poorly supported by the EPR system. The structuring of the data also improved filtering of information to better support clinical decision-making. Because of the high value of the structured patient data, the users put much effort in maintaining their integrity and representativeness. Employees from the departments were also engaged in the funding, development, implementation and maintenance of the systems. Conclusion Clinical departmental systems are vital to the activities of a clinical hospital department. The development, implementation and clinical use of such systems can be seen as bottom-up, user-driven innovations. PMID:19523198

  5. Structure and dynamics of paramagnetic transients by pulsed EPR and NMR detection of nuclear resonance. [Pulse radiolysis of methanol in D/sub 2/O

    SciTech Connect

    Trifunac, A.D.

    1981-01-01

    Structure and dynamics of transient radicals in pulse radiolysis can be studied by time resolved EPR and NMR techniques. EPR study of kinetics and relaxation is illustrated. The NMR detection of nuclear resonance in transient radicals is a new method which allows the study of hyperfine coupling, population dynamics, radical kinetics, and reaction mechanism. 9 figures.

  6. Comparison of antioxidants for combined radiation and thermal aging and superposition of radiation and thermal aging for EPR and XLPE

    NASA Astrophysics Data System (ADS)

    Reynolds, A. B.; Wlodkowski, P. A.

    Thermal and combined thermal and radiation aging of low voltage EPR and XLPE cable insulation with Agerite MA antioxidant and with the ZMTI/Aminox antioxidant system was examined to compare the relative effectiveness of the antioxidant and polymer systems. All provided significant stability with no clear choice of any particular combination being superior to the others. A comparison of degradation from thermal and radiation aging with degradation from combined thermal/radiation aging showed that the damage from the individual aging effects was superposable. This indicates that synergistic effects have little importance for the EPRs and XLPEs tested under the aging conditions observed.

  7. EPR monitored redox titration of the cofactors of Saccharomyces cerevisiae Nar1.

    PubMed

    Hagedoorn, Peter-Leon; van der Weel, Laura; Hagen, Wilfred R

    2014-11-26

    Electron Paramagnetic Resonance (EPR) monitored redox titrations are a powerful method to determine the midpoint potential of cofactors in proteins and to identify and quantify the cofactors in their detectable redox state. The technique is complementary to direct electrochemistry (voltammetry) approaches, as it does not offer information on electron transfer rates, but does establish the identity and redox state of the cofactors in the protein under study. The technique is widely applicable to any protein containing an electron paramagnetic resonance (EPR) detectable cofactor. A typical titration requires 2 ml protein with a cofactor concentration in the range of 1-100 µM. The protein is titrated with a chemical reductant (sodium dithionite) or oxidant (potassium ferricyanide) in order to poise the sample at a certain potential. A platinum wire and a Ag/AgCl reference electrode are connected to a voltmeter to measure the potential of the protein solution A set of 13 different redox mediators is used to equilibrate between the redox cofactors of the protein and the electrodes. Samples are drawn at different potentials and the Electron Paramagnetic Resonance spectra, characteristic for the different redox cofactors in the protein, are measured. The plot of the signal intensity versus the sample potential is analyzed using the Nernst equation in order to determine the midpoint potential of the cofactor.

  8. EPR Monitored Redox Titration of the Cofactors of Saccharomyces cerevisiae Nar1

    PubMed Central

    Hagedoorn, Peter-Leon; van der Weel, Laura; Hagen, Wilfred R.

    2014-01-01

    Electron Paramagnetic Resonance (EPR) monitored redox titrations are a powerful method to determine the midpoint potential of cofactors in proteins and to identify and quantify the cofactors in their detectable redox state. The technique is complementary to direct electrochemistry (voltammetry) approaches, as it does not offer information on electron transfer rates, but does establish the identity and redox state of the cofactors in the protein under study. The technique is widely applicable to any protein containing an electron paramagnetic resonance (EPR) detectable cofactor. A typical titration requires 2 ml protein with a cofactor concentration in the range of 1-100 µM. The protein is titrated with a chemical reductant (sodium dithionite) or oxidant (potassium ferricyanide) in order to poise the sample at a certain potential. A platinum wire and a Ag/AgCl reference electrode are connected to a voltmeter to measure the potential of the protein solution. A set of 13 different redox mediators is used to equilibrate between the redox cofactors of the protein and the electrodes. Samples are drawn at different potentials and the Electron Paramagnetic Resonance spectra, characteristic for the different redox cofactors in the protein, are measured. The plot of the signal intensity versus the sample potential is analyzed using the Nernst equation in order to determine the midpoint potential of the cofactor. PMID:25490157

  9. Electrochemical and EPR characterization of 1,4-dihydropyridines. Reactivity towards alkyl radicals.

    PubMed

    Núñez-Vergara, Luis J; López-Alarcón, C; Navarrete-Encina, P A; Atria, A M; Camargo, C; Squella, J A

    2003-01-01

    This work reports the electrochemical oxidation of a series of three synthesized 4-substituted-1,4-dihydropyridine derivatives in different electrolytic media. Also, an EPR characterization of intermediates and the reactivity of derivatives towards ABAP-derived alkyl radicals are reported. Dynamic, differential pulse and cyclic voltammetry studies on a glassy carbon electrode showed an irreversible single-peak due to the oxidation of the 1,4-dihydropyridine (1,4-DHP) ring via 2-electrons to the corresponding pyridine derivative. Levich plots were linear in different media, indicating that the oxidation process is diffusion-controlled. Calculated diffusion coefficients did not exhibit significant differences between the derivatives in the same medium. The oxidation mechanism follows the general pathway (electron, H+, electron, H+) with formation of an unstable pyridinium radical. One-electron oxidation intermediate was confirmed with controlled potential electrolysis (CPE) and EPR experiments. On applying N-tert-butyl-alpha-phenylnitrone (PBN) and 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as the spin trap, these unstable radical intermediates from the oxidation of 1,4-DHP derivatives were intercepted. The final product of the CPE, i.e. pyridine derivative, was identified by GC-MS technique. Direct reactivity of the synthesized compounds towards alkyl radicals was demonstrated by UV-Vis. spectroscopy and GC-MS technique. Results indicate that these derivatives significantly react with the radicals, even compared with a well-known antioxidant drug such as nisoldipine.

  10. Cluster N1 of complex I from Yarrowia lipolytica studied by pulsed EPR spectroscopy.

    PubMed

    Maly, T; Grgic, L; Zwicker, K; Zickermann, V; Brandt, U; Prisner, T

    2006-04-01

    After reduction with nicotinamide adenine dinucleotide (NADH), NADH:ubiquinone oxidoreductase (complex I) of the strictly aerobic yeast Yarrowia lipolytica shows clear signals from five different paramagnetic iron-sulfur (FeS) clusters (N1-N5) which can be detected using electron paramagnetic resonance (EPR) spectroscopy. The ligand environment and the assignment of several FeS clusters to specific binding motifs found in several subunits of the complex are still under debate. In order to characterize the hyperfine interaction of the surrounding nuclei with FeS cluster N1, one- and two-dimensional electron spin echo envelope modulation experiments were performed at a temperature of 30 K. At this temperature only cluster N1 contributes to the overall signal in a pulsed EPR experiment. The hyperfine and quadrupole tensors of a nitrogen nucleus and the isotropic and dipolar hyperfine couplings of two sets of protons could be determined by numerical simulation of the one- and two-dimensional spectra. The values obtained are in perfect agreement with a ferredoxin-like binding structure by four cysteine amino acid residues and allow the assignment of the nitrogen couplings to a backbone nitrogen nucleus and the proton couplings to the beta-protons of the bound cysteine residues.

  11. Polymer–iron oxide composite nanoparticles for EPR-independent drug delivery

    PubMed Central

    Park, Jinho; Kadasala, Naveen R.; Abouelmagd, Sara A.; Castanares, Mark A.; Collins, David S.; Wei, Alexander; Yeo, Yoon

    2016-01-01

    Nanoparticle (NP)-based approaches to cancer drug delivery are challenged by the heterogeneity of the enhanced permeability and retention (EPR) effect in tumors and the premature attrition of payload from drug carriers during circulation. Here we show that such challenges can be overcome by a magnetophoretic approach to accelerate NP delivery to tumors. Payload-bearing poly(lactic-co-glycolic acid) NPs were converted into polymer–iron-oxide nanocomposites (PINCs) by attaching colloidal Fe3O4 onto the surface, via a simple surface modification method using dopamine polymerization. PINCs formed stable dispersions in serum-supplemented medium and responded quickly to magnetic field gradients above 1 kG/cm. Under the field gradients, PINCs were rapidly transported across physical barriers and into cells and captured under flow conditions similar to those encountered in postcapillary venules, increasing the local concentration by nearly three orders of magnitude. In vivo magnetophoretic delivery enabled PINCs to accumulate in poorly vascularized subcutaneous SKOV3 xenografts that did not support the EPR effect. In vivo magnetic resonance imaging, ex vivo fluorescence imaging, and tissue histology all confirmed that the uptake of PINCs was higher in tumors exposed to magnetic field gradients, relative to negative controls. PMID:27310916

  12. Heavy-ion-induced sucrose radicals investigated using EPR and UV spectroscopy.

    PubMed

    Nakagawa, Kouichi; Karakirova, Yordanka; Yordanov, Nicola D

    2015-05-01

    The potential use of a sucrose dosimeter for estimating both linear energy transfer (LET) and the absorbed dose of heavy ion and X-ray radiation was investigated. The stable free radicals were produced when sucrose was irradiated with heavy ions, such as helium, carbon, silicon and neon ions, and when the X-ray radiation was similar to the obtained electron paramagnetic resonance (EPR) spectra, which were ∼7 mT wide and composed of several hyperfine structures. In addition, the total spin concentration resulting from heavy-ion irradiation increased linearly as the absorbed dose increased, and decreased logarithmically as the LET increased. These empirical relations imply that the LET at a certain dose can be determined from the spin concentration. For sucrose and alanine, both cross-sections following C-ion irradiation with a 50 Gy dose were ∼1.3 × 10(-12) [μm(2)], taking into account the molecular size of the samples. The values of these cross-sections imply that multiple ionizing particles were involved in the production of stable radicals. Furthermore, UV absorbance at 267 nm of an aqueous solution of irradiated sucrose was found to linearly increase with increasing absorbed dose. Therefore, the EPR and UV results suggest that sucrose can be a useful dosimeter for heavy-ion irradiation. © The Author 2014. Published by Oxford University Press on behalf of The Japan Radiation Research Society and Japanese Society for Radiation Oncology.

  13. Heavy-ion-induced sucrose radicals investigated using EPR and UV spectroscopy

    PubMed Central

    Nakagawa, Kouichi; Karakirova, Yordanka; Yordanov, Nicola D.

    2015-01-01

    The potential use of a sucrose dosimeter for estimating both linear energy transfer (LET) and the absorbed dose of heavy ion and X-ray radiation was investigated. The stable free radicals were produced when sucrose was irradiated with heavy ions, such as helium, carbon, silicon and neon ions, and when the X-ray radiation was similar to the obtained electron paramagnetic resonance (EPR) spectra, which were ∼7 mT wide and composed of several hyperfine structures. In addition, the total spin concentration resulting from heavy-ion irradiation increased linearly as the absorbed dose increased, and decreased logarithmically as the LET increased. These empirical relations imply that the LET at a certain dose can be determined from the spin concentration. For sucrose and alanine, both cross-sections following C-ion irradiation with a 50 Gy dose were ∼1.3 × 10−12 [μm2], taking into account the molecular size of the samples. The values of these cross-sections imply that multiple ionizing particles were involved in the production of stable radicals. Furthermore, UV absorbance at 267 nm of an aqueous solution of irradiated sucrose was found to linearly increase with increasing absorbed dose. Therefore, the EPR and UV results suggest that sucrose can be a useful dosimeter for heavy-ion irradiation. PMID:25480828

  14. Analysis of nitroxide spin label motion in a protein protein complex using multiple frequency EPR spectroscopy

    NASA Astrophysics Data System (ADS)

    White, G. F.; Ottignon, L.; Georgiou, T.; Kleanthous, C.; Moore, G. R.; Thomson, A. J.; Oganesyan, V. S.

    2007-04-01

    X- and W-band EPR spectra, at room and low temperatures, are reported for nitroxide spin labels attached to cysteine residues selectively introduced into two proteins, the DNase domain of colicin-E9 and its immunity protein, Im9. The dynamics of each site of attachment on the individual proteins and in the tight DNase-Im9 complex have been analysed by computer simulations of the spectra using a model of Brownian dynamics trajectories for the spin label and protein. Ordering potentials have been introduced to describe mobility of labels restricted by the protein domain. Label mobility varies with position from completely immobilised, to motionally restricted and to freely rotating. Bi-modal dynamics of the spin label have been observed for several sites. We show that W-band spectra are particularly useful for detection of anisotropy of spin label motion. On complex formation significant changes are observed in the dynamics of labels at the binding interface region. This work reveals multi-frequency EPR as a sensitive and valuable tool for detecting conformational changes in protein structure and dynamics especially in protein-protein complexes.

  15. Hydrogen at zinc vacancy of ZnO: An EPR and ESEEM study

    SciTech Connect

    Son, N. T.; Ivanov, I. G.; Janzén, E.; Isoya, J.; Ohshima, T.

    2014-02-21

    An electron paramagnetic resonance (EPR) spectrum, labeled S1, with small-splitting doublet accompanied by weak satellites is observed in ZnO irradiated with 2 MeV electrons. The obtained structure is shown to be the hyperfine structure due to the dipolar interaction between an unpaired electron spin and a nuclear spin of hydrogen (H). The observation of the nuclear Zeeman frequency of H in electron spin echo envelope modulation experiments further confirmed the presence of a hydrogen atom in S1. From the observed spin-Hamiltonian parameters, S1 is identified to be the partly H-passivated Zn vacancy, V{sub Zn}{sup −}H{sup +}, with the H{sup +} ion making a short O-H bond with only one nearest O neighbor of V{sub Zn} in the basal plane, being off the substitutional site, while the unpaired electron spin, which gives rise to the observed EPR signal, is localized on the p orbital of another O neighbor also in the basal plane.

  16. The characteristic photoluminescence and EPR features of superdeep diamonds (São-Luis, Brazil)

    NASA Astrophysics Data System (ADS)

    Yuryeva, Olga P.; Rakhmanova, Mariana I.; Nadolinny, Vladimir A.; Zedgenizov, Dmitry A.; Shatsky, Vladislav S.; Kagi, Hiroyuki; Komarovskikh, Andrey Yu.

    2015-10-01

    Photoluminescence (PL) spectroscopy and electron paramagnetic resonance (EPR) were used for the first time to characterize properties of superdeep diamonds from the São-Luis alluvial deposits (Brazil). The infrared measurements showed the low nitrogen content (>50 of 87 diamonds from this locality were nitrogen free and belonged to type IIa) and simultaneously the extremely high level of nitrogen aggregation (pure type IaB being predominant), which indicates that diamonds under study might have formed under high pressure and temperature conditions. In most cases, PL features excited at various wavelengths (313, 473, and 532 nm) were indicative of different growth and post-growth processes during which PL centers could be formed via interaction between vacancies and nitrogen atoms. The overall presence of the 490.7 nm, H3, and H4 centers in the luminescence spectra attests to strong plastic deformations in these diamonds. The neutral vacancy known as the GR1 center has probably occurred in a number of crystals due to radiation damage in the post-growth period. The 558.5 nm PL center is found to be one of the most common defects in type IIa samples which is accompanied by the EPR center with g-factor of 2.00285. The 536 and 576 nm vibronic systems totally dominated the PL spectra of superdeep diamonds, while none of "normal" diamonds from the Mir pipe (Yakutia) with similar nitrogen characteristics showed the latter three PL centers.

  17. Association of Copper to Riboflavin Binding Protein; Characterization by EPR and XAS

    SciTech Connect

    Smith,S.; Bencze, K.; Wasiukanis, K.; Stemmler, T.; Benore-Parsons, M.

    2008-01-01

    The association of copper to Riboflavin Binding Protein (RBP) from egg white has been studied by electron paramagnetic resonance (EPR) and X-ray absorption (XAS) spectroscopies. The type II site contains a mix of copper I and II in an oxygen rich environment. The association of copper to Riboflavin Binding Protein (RBP) from egg white has been studied by electron paramagnetic resonance (EPR) and X-ray absorption (XAS) spectroscopies in order to provide insight into how this essential protein may transport and store copper in avian embryos. Riboflavin Binding Protein, RBP, purified from avian egg white, has been shown to bind copper in a 1:1 molar ratio when dialyzed against copper(II) [1]. While the egg is a unique environment and quite rich in copper, the mechanisms by which this copper is delivered during development and stored for eventual use remain unclear [2]. Since RBP is already identified in the active transport of the cofactor riboflavin to the egg, evidence of its copper binding ability may suggest an additional role for RBP in the transport and storage of copper.

  18. On the "negative utility" of Ernst Cassirer's philosophy of physics: An application to the EPR argument

    NASA Astrophysics Data System (ADS)

    Stamenkovic, Philippe

    2016-08-01

    This paper tries to reconstruct Ernst Cassirer's potential reception of the EPR argument, as exposed by Einstein in his letter to Cassirer of March 1937. It is shown that, in conformity with his transcendental epistemology taking the conditions of accessibility as constitutive of the quantum object, Cassirer would probably have rejected the argument. Indeed, Cassirer would probably not have subscribed to its separability/local causality presupposition (which goes against his interpretation of the quantum formalism as a self-sufficient condition constitutive of the quantum object, without any reliance on spatial intuition), nor to its completeness requirement (as his partial endorsement of Bohr's complementarity, and his rejection of the Kantian "idea of complete determination", illustrate). By rejecting both of its premises, Cassirer's philosophy of physics thus enables to escape the EPR dilemma, and exhibits what, in Kantian terms, might be called a "negative utility" with respect to physical science. A further investigation of the anti-reductionist utility of Cassirer's systematic philosophy with respect to physics and other "symbolic forms" is finally suggested.

  19. Evaluation of Partial k-space strategies to speed up Time-domain EPR Imaging

    PubMed Central

    Subramanian, Sankaran; Chandramouli, Gadisetti VR; McMillan, Alan; Gullapalli, Rao P; Devasahayam, Nallathamby; Mitchell, James B.; Matsumoto, Shingo; Krishna, Murali C

    2012-01-01

    Narrow-line spin probes derived from the trityl radical have led to the development of fast in vivo time-domain EPR imaging. Pure phase-encoding imaging modalities based on the Single Point Imaging scheme (SPI) have demonstrated the feasibility of 3D oximetric images with functional information in minutes. In this paper, we explore techniques to improve the temporal resolution and circumvent the relatively short biological half-lives of trityl probes using partial k-space strategies. There are two main approaches: one involves the use of the Hermitian character of the k-space by which only part of the k-space is measured and the unmeasured part is generated using the Hermitian symmetry. This approach is limited in success by the accuracy of numerical estimate of the phase roll in the k-space that corrupts the Hermiticy. The other approach is to measure only a judicially chosen reduced region of k-space (a centrosymmetric ellipsoid region) that more or less accounts for >70% of the k-space energy. Both of these aspects were explored in FT-EPR imaging with a doubling of scan speed demonstrated by considering ellipsoid geometry of the k-space. Partial k-space strategies help improve the temporal resolution in studying fast dynamics of functional aspects in vivo with infused spin probes. PMID:23045171

  20. Evaluation of partial k-space strategies to speed up time-domain EPR imaging.

    PubMed

    Subramanian, Sankaran; Chandramouli, Gadisetti V R; McMillan, Alan; Gullapalli, Rao P; Devasahayam, Nallathamby; Mitchell, James B; Matsumoto, Shingo; Krishna, Murali C

    2013-09-01

    Narrow-line spin probes derived from the trityl radical have led to the development of fast in vivo time-domain EPR imaging. Pure phase-encoding imaging modalities based on the single-point imaging scheme have demonstrated the feasibility of three-dimensional oximetric images with functional information in minutes. In this article, we explore techniques to improve the temporal resolution and circumvent the relatively short biological half-lives of trityl probes using partial k-space strategies. There are two main approaches: one involves the use of the Hermitian character of the k-space by which only part of the k-space is measured and the unmeasured part is generated using the Hermitian symmetry. This approach is limited in success by the accuracy of numerical estimate of the phase roll in the k-space that corrupts the Hermiticy. The other approach is to measure only a judicially chosen reduced region of k-space (a centrosymmetric ellipsoid region) that more or less accounts for >70% of the k-space energy. Both of these aspects were explored in Fourier transform-EPR imaging with a doubling of scan speed demonstrated by considering ellipsoid geometry of the k-space. Partial k-space strategies help improve the temporal resolution in studying fast dynamics of functional aspects in vivo with infused spin probes. Copyright © 2012 Wiley Periodicals, Inc.