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Sample records for paramagnetic lanthanideiii-chrysin complexes

  1. Paramagnetic Europium Salen Complex and Sickle-Cell Anemia

    NASA Astrophysics Data System (ADS)

    Wynter, Clive I.; Ryan, D. H.; May, Leopold; Oliver, F. W.; Brown, Eugene; Hoffman, Eugene J.; Bernstein, David

    2005-04-01

    A new europium salen complex, Eu(salen)2NH4, was synthesized, and its composition was confirmed by chemical analysis and infrared spectroscopy. Further characterization was carried out by 151 Eu Mössbauer spectroscopy and magnetic susceptibility measurements. Mössbauer spectroscopic measurements were made at varying temperatures between 9 K and room temperature and a value of Debye temperature of 133 ±5 K was computed. Both Mössbauer and magnetic susceptibility measurements confirmed the paramagnetic behavior of this complex and the trivalent state of the europium ion. In view of the fact that the "odd" paramagnetic molecule NO has been shown to reverse sickling of red blood cells in sickle cell anemia, the interaction between the paramagnetic europium salen complex and sickle cells was examined after incubation with this europium complex and shown to have similar effects.

  2. Paramagnetic Centers in DOPA-Melanin-Dihydrostreptomycin Complexes

    NASA Astrophysics Data System (ADS)

    Buszman, E.; Pilawa, B.; Zdybel, M.; Wrześniok, D.; Grzegorczyk, A.; Wilczok, T.

    2006-08-01

    DOPA-melanin-dihydrostreptomycin complexes with drug concentrations 1×10-4-1×10-2 M were examined by the use of electron paramagnetic resonance spectroscopy at X-band (9.3 GHz). Dihydrostreptomycin was chosen for studies, because this aminoglycoside antibiotic causes strong toxic effects in organism. It was stated that dihydrostreptomycin generates o-semiquinone free radicals with g=2.0038 in melanin. Free radicals formation increases with increase in the antibiotic concentration. Changes of EPR lines with microwave powers pointed out that slow spin-lattice relaxation processes exist in DOPA-melanin and in its complexes with dihydrostreptomycin. The measured EPR lines were homogeneously broadened.

  3. Paramagnetic complexes of magnesium as mediators in enzymatic ATP synthesis: DFT calculations of magnetic parameters

    NASA Astrophysics Data System (ADS)

    Buchachenko, A. L.; Shchegoleva, L. N.; Breslavskaya, N. N.

    2009-11-01

    Magnetic parameters ( g-factors, hyperfine coupling constants a( 25Mg) and a( 31P)) of paramagnetic pyrophosphate and hydrate magnesium complexes, which model those in catalytic site of the ATP synthesizing enzymes, are calculated. Both g-factors and HFС constants a( 31P) of the paramagnetic pyrophosphate magnesium complexes are identical to those of the pyrophosphate radical. It demonstrates that namely terminal PO 3 group of the liganded ADP in the complex Mg 2+(ADP) 3- donates electron to the Mg(HO)n2+ ion in the primary reaction of the ion-radical mechanism of enzymatic ATP synthesis.

  4. 17O NMR study of diamagnetic and paramagnetic lanthanide(III)-DOTA complexes in aqueous solution.

    PubMed

    Fusaro, Luca; Luhmer, Michel

    2014-08-18

    The complexes between the polyaminocarboxylate DOTA ligand and the whole series of stable lanthanide(III) metal ions, except Gd(3+), were studied in aqueous solution by (17)O NMR. For all of the paramagnetic systems, the (17)O NMR signals of both the nonchelating (O1) and chelating (O2) oxygen atoms could be detected, and for some of them, the signals of both the SAP and TSAP (TSAP') conformational isomers were also observed. Line width data analysis reveals that signal broadening is not dominated by paramagnetic relaxation enhancement, as it was believed to be. The data indicate that quadrupole relaxation and, for some complexes, chemical exchange between the SAP and TSAP isomers are the major contributions to the (17)O NMR line width at 25 °C. Besides, the Fermi contact and pseudocontact contributions to the observed lanthanide-induced shifts could be extracted. The (17)O hyperfine coupling constants determined for O2 in the SAP and TSAP isomers are similar to each other and to the values reported for several Gd(III) complexes comprising fast-exchanging ligands. Interestingly, the results suggest that (17)O NMR should prove to be useful for the study of highly paramagnetic Gd(III) complexes of nonlabile ligands.

  5. Monitoring Complex Formation by Relaxation-Induced Pulse Electron Paramagnetic Resonance Distance Measurements.

    PubMed

    Giannoulis, Angeliki; Oranges, Maria; Bode, Bela E

    2017-09-06

    Biomolecular complexes are often multimers fueling the demand for methods that allow unraveling their composition and geometric arrangement. Pulse electron paramagnetic resonance (EPR) spectroscopy is increasingly applied for retrieving geometric information on the nanometer scale. The emerging RIDME (relaxation-induced dipolar modulation enhancement) technique offers improved sensitivity in distance experiments involving metal centers (e.g. on metalloproteins or proteins labelled with metal ions). Here, a mixture of a spin labelled ligand with increasing amounts of paramagnetic Cu(II) ions allowed accurate quantification of ligand-metal binding in the model complex formed. The distance measurement was highly accurate and critical aspects for identifying multimerization could be identified. The potential to quantify binding in addition to the high-precision distance measurement will further increase the scope of EPR applications. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  6. Chemoenzymatic Synthesis of Nonasulfated Tetrahyaluronan with a Paramagnetic Tag for Studying Its Complex with Interleukin-10.

    PubMed

    Köhling, Sebastian; Künze, Georg; Lemmnitzer, Katharina; Bermudez, Marcel; Wolber, Gerhard; Schiller, Jürgen; Huster, Daniel; Rademann, Jörg

    2016-04-11

    Implants and artificial biomaterials containing sulfated hyaluronans have been shown to improve the healing of injured skin and bones. It is hypothesized that these effects are mediated by the binding of sulfated glycosaminoglycans (GAGs) to growth factors and cytokines, resulting in the sequestering of proteins to the wound healing site and in modulated protein activity. Given that no direct synthetic access to sulfated oligohyaluronans has been available, little is known about their protein binding and the structure of the resulting protein complexes. Here, the chemoenzymatic preparation of oligohyaluronans on the gram scale is described. Oligohyaluronans are converted into anomeric azides at the reducing end, enabling the attachment of analytical labels through an anomeric ligation reaction. A nonasulfated tetrahyaluronan-ethylenediaminetetraacetic acid derivative has been produced and used as a paramagnetic tag for the elucidation of the complex of this ligand with interleukin-10 using paramagnetic relaxation enhancement NMR analysis. The metal ion position is resolved with 1.0 Å, enabling a refined structural model of the complex.

  7. Structural Analysis of Protein-RNA Complexes in Solution Using NMR Paramagnetic Relaxation Enhancements.

    PubMed

    Hennig, Janosch; Warner, Lisa R; Simon, Bernd; Geerlof, Arie; Mackereth, Cameron D; Sattler, Michael

    2015-01-01

    Biological activity in the cell is predominantly mediated by large multiprotein and protein-nucleic acid complexes that act together to ensure functional fidelity. Nuclear magnetic resonance (NMR) spectroscopy is the only method that can provide information for high-resolution three-dimensional structures and the conformational dynamics of these complexes in solution. Mapping of binding interfaces and molecular interactions along with the characterization of conformational dynamics is possible for very large protein complexes. In contrast, de novo structure determination by NMR becomes very time consuming and difficult for protein complexes larger than 30 kDa as data are noisy and sparse. Fortunately, high-resolution structures are often available for individual domains or subunits of a protein complex and thus sparse data can be used to define their arrangement and dynamics within the assembled complex. In these cases, NMR can therefore be efficiently combined with complementary solution techniques, such as small-angle X-ray or neutron scattering, to provide a comprehensive description of the structure and dynamics of protein complexes in solution. Particularly useful are NMR-derived paramagnetic relaxation enhancements (PREs), which provide long-range distance restraints (ca. 20Å) for structural analysis of large complexes and also report on conformational dynamics in solution. Here, we describe the use of PREs from sample production to structure calculation, focusing on protein-RNA complexes. On the basis of recent examples from our own research, we demonstrate the utility, present protocols, and discuss potential pitfalls when using PREs for studying the structure and dynamic features of protein-RNA complexes.

  8. Coordination functionalization of graphene oxide with tetraazamacrocyclic complexes of nickel(II): Generation of paramagnetic centers

    NASA Astrophysics Data System (ADS)

    Basiuk, Vladimir A.; Alzate-Carvajal, Natalia; Henao-Holguín, Laura V.; Rybak-Akimova, Elena V.; Basiuk, Elena V.

    2016-05-01

    We describe a novel approach to functionalization of graphene oxide (GO) which allows for a facile generation of paramagnetic centers from two diamagnetic components. Coordination attachment of [Ni(cyclam)]2+ or [Ni(tet b)]2+ tetraazamacrocyclic cations to carboxylic groups of GO takes place under basic conditions in aqueous-based reaction medium. The procedure is very straightforward and does not require high temperatures or other harsh conditions. Changing the coordination geometry of Ni(II) from square-planar tetracoordinated to pseudooctahedral hexacoordinated brings about the conversion from low-spin to high-spin state of the metal centers. Even though the content of tetraazamacrocyclic complexes in functionalized GO samples was found to be relatively low (nickel content of ca. 1 wt%, as determined by thermogravimetric analysis, elemental analysis and energy dispersive X-ray spectroscopy), room temperature magnetic susceptibility measurements easily detected the appearance of paramagnetic properties in GO + [Ni(cyclam)] and GO + [Ni(tet b)] nanohybrids, with effective magnetic moments of 1.95 BM and 2.2 BM for, respectively. According to density functional theory calculations, the main spin density is localized at the macrocyclic complexes, without considerable extension to graphene sheet, which suggests insignificant ferromagnetic coupling in the nanohybrids, in agreement with the results of magnetic susceptibility measurements. The coordination attachment of Ni(II) tetraazamacrocycles to GO results in considerable changes in Fourier-transform infrared and X-ray photoelectron spectra, as well as in GO morphology, as observed by scanning and transmission electron microscopy, atomic force and scanning tunneling microscopy.

  9. Innovative magnetic resonance imaging diagnostic agents based on paramagnetic Gd(III) complexes.

    PubMed

    Aime, Silvio; Dastrù, Walter; Crich, Simonetta Geninatti; Gianolio, Eliana; Mainero, Valentina

    2002-01-01

    Gd(III) complexes are under intense scrutiny as contrast agents for magnetic resonance imaging (MRI). They act by enhancing tissutal proton relaxation rates. Much has already been done in order to get an in-depth understanding of the relationships between structure, dynamics, and contrastographic ability of these paramagnetic complexes. Their potential in the assessment of flow, perfusion, and capillary permeability has already been established. The next challenges are in the field of molecular imaging applications, which would allow the attainment of early diagnosis based on the recognition of specific reporters of the onset of the pathological state. To this end, Gd(III) complexes have to be endowed with improved targeting capabilities by conjugating suitable recognition synthons on their surfaces. Small peptides are candidates of choice for the attainment of this goal. Moreover, the intrinsic low sensitivity of the NMR techniques implies the need to deliver large amounts of contrast agents to the target in order to get its visualization in the resulting images. Highly efficient delivery systems have been identified, which bring a great promise for the development of innovative diagnostic agents based on Gd(III) complexes.

  10. Detection and structural characterization of oxo-chromium(V)-sugar complexes by electron paramagnetic resonance.

    PubMed

    Sala, Luis F; González, Juan C; García, Silvia I; Frascaroli, María I; Van Doorslaer, Sabine

    2011-01-01

    This article describes the detection and characterization of oxo-Cr(V)-saccharide coordination compounds, produced during chromic oxidation of carbohydrates by Cr(VI) and Cr(V), using electron paramagnetic resonance (EPR) spectroscopy. After an introduction into the main importance of chromium (bio)chemistry, and more specifically the oxo-chromium(V)-sugar complexes, a general overview is given of the current state-of-the-art EPR techniques. The next step reviews which types of EPR spectroscopy are currently applied to oxo-Cr(V) complexes, and what information about these systems can be gained from such experiments. The advantages and pitfalls of the different approaches are discussed, and it is shown that the potential of high-field and pulsed EPR techniques is as yet still largely unexploited in the field of oxo-Cr(V) complexes. Subsequently, the discussion focuses on the analysis of oxo-Cr(V) complexes of different types of sugars and the implications of the results in terms of understanding chromium (bio)chemistry.

  11. Spectroscopic and quantum chemical study of the structure of a new paramagnetic dimeric palladium(II,III) complex with creatine

    NASA Astrophysics Data System (ADS)

    Mitewa, Mariana; Enchev, Venelin; Bakalova, Tatyana

    2002-05-01

    The structure and coordination mode of the newly synthesized dimeric paramagnetic Pd(II,III) complex are studied using magneto-chemical, EPR and IR spectroscopic methods. In order to perform reliable assignment of the IR bands, the structure and IR spectrum of the free creatine were calculated using ab initio method. For calculation of the configuration of its deprotonated and doubly deprotonated forms the semiempirical AM1 method was used.

  12. Intermolecular Paramagnetic Relaxation Enhancement (PRE) Studies of Transient Complexes in Intrinsically Disordered Proteins.

    PubMed

    Janowska, Maria K; Baum, Jean

    2016-01-01

    NMR interchain paramagnetic relaxation enhancement (PRE) techniques are a very powerful approach for detecting transient interchain interactions between intrinsically disordered proteins. These experiments, requiring a mixed sample containing a 1:1 ratio of isotope-labeled (15)N protein and natural abundance (14)N protein with a paramagnetic spin label, provide data that is limited to interchain interactions only. Application of these experiments to weakly associated transient species such as those that are present in the very early stages of self-assembly processes will aid our understanding of protein aggregation or fibril formation processes.

  13. [Effect of phenobarbital on the kinetics of the change in the level of paramagnetic metalloprotein complexes in dinitrophenol poisoning].

    PubMed

    Luk'ianchuk, V D

    1985-01-01

    EPR spectroscopy was used to study phenobarbital influence on the kinetics of paramagnetic complexes variability of metal proteins--cytochrome P-450 and iron-sulfur proteins of rat liver in acute oral poisoning with the dinitrophenol pesticides DNOK and dinoseb. It was proved experimentally that the barbiturate favoured marked prevention of the decrease of the content of cytochrome P-450 and iron-sulfur proteins, thereby protecting the detoxifying and energy liver system from dinitrophenol-induced injuries. It is discussed that phenobarbital may act both as an inducer of cytochrome P-450 and iron-sulfur proteins involved in electron transport of the mitochondria.

  14. Diamagnetic molybdenum nitride complexes supported by diligating tripodal triamido-phosphine ligands as precursors to paramagnetic phosphine donors.

    PubMed

    Hatnean, Jillian A; Johnson, Samuel A

    2015-09-07

    The reaction of the ligand precursors P[CH2NHAr(R)]3 () with (Me2N)3Mo[triple bond, length as m-dash]N generated the complexes P(CH2NAr(R))3Mo[triple bond, length as m-dash]N (), where Ar(R) = 3,5-(CH3)2C6H3 (), Ph (), and 3,5-(CF3)2C6H3 (), with (Me2N)3Mo[triple bond, length as m-dash]N generated the complexes P(CH2NAr(R))3Mo[triple bond, length as m-dash]N (). Complex was obtained in poor yield, due to the formation of P(CH2N-3,5-(CF3)2C6H3)2(CH2NH-3,5-(CF3)2C6H3)(NMe2H)(NMe2)Mo[triple bond, length as m-dash]N () as the major product. Reaction of with VMes3THF generated the paramagnetic complexes P(CH2NAr(R))3Mo(μ-N)V(Mes)3 (). The reaction of with Ni(acac)2 generated the Ni(0) complexes Ni[P(CH2NAr(R))3Mo[triple bond, length as m-dash]N]4 () in poor yield. These complexes were synthesized in higher yields from the reaction of with Ni(COD)2, where COD = 1,5-cyclooctadiene. Reaction of either with V(Mes)3THF or with Ni(COD)2 generated the paramagnetic nonanuclear complex Ni[P(CH2NAr(R))3Mo(μ-N)VMes3]4 ().

  15. Relative diffusion of paramagnetic metal complexes of MRI contrast agents in an isotropic hydrogel medium.

    PubMed

    Weerakoon, Bimali Sanjeevani; Osuga, Toshiaki

    2017-03-01

    The observation of molecular diffusion by means of magnetic resonance imaging (MRI) is significant in the evaluation of the metabolic activity of living tissues. Series of MRI examinations were conducted on a diffusion model to study the behaviour of the diffusion process of different-molecular-weight (MW) paramagnetic MRI contrast agents in an isotropic agar hydrogel medium. The model consisted of a solidified 1 % agar gel with an initial concentration of 0.5 mmol/L contrast solution layered on top of the gel. The diffusion process was monitored at pre-determined time intervals of immediately, 1, 6, 9, 23, and 48 h after introduction of the contrast agents onto the agar gel with a T1-weighted spin-echo (SE) pulse sequence. Three types of paramagnetic contrast agents, Gd-DTPA with a MW of 547.57 g/mol, Prohance with a MW of 558.69 g/mol and MnCl2 with a MW of 125.84 g/mol, resulted in an approximate average diffusional displacement ratio of 1:1:2 per hour, respectively, within 48 h of the experiment. Therefore, the results of this study supported the hypothesis that the rate of the diffusion process of MRI contrast agents in the agar hydrogel medium is inversely related to their MWs. However, more repetitions are necessary under various types of experimental conditions and also with various types of contrast media of different MWs for further confirmation and validation of these results.

  16. Slow-Motion Theory of Nuclear Spin Relaxation in Paramagnetic Low-Symmetry Complexes: A Generalization to High Electron Spin

    NASA Astrophysics Data System (ADS)

    Nilsson, T.; Kowalewski, J.

    2000-10-01

    The slow-motion theory of nuclear spin relaxation in paramagnetic low-symmetry complexes is generalized to comprise arbitrary values of S. We describe the effects of rhombic symmetry in the static zero-field splitting (ZFS) and allow the principal axis system of the static ZFS tensor to deviate from the molecule-fixed frame of the nuclear-electron dipole-dipole tensor. We show nuclear magnetic relaxation dispersion (NMRD) profiles for different illustrative cases, ranging from within the Redfield limit into the slow-motion regime with respect to the electron spin dynamics. We focus on S = 3/2 and compare the effects of symmetry-breaking properties on the paramagnetic relaxation enhancement (PRE) in this case with that of S = 1, which we have treated in a previous paper. We also discuss cases of S = 2, 5/2, 3, and 7/2. One of the main objectives of this investigation, together with the previous papers, is to provide a set of standard calculations using the general slow-motion theory, against which simplified models may be tested.

  17. Advantages of paramagnetic chemical exchange saturation transfer (CEST) complexes having slow to intermediate water exchange properties as responsive MRI agents.

    PubMed

    Soesbe, Todd C; Wu, Yunkou; Dean Sherry, A

    2013-07-01

    Paramagnetic chemical exchange saturation transfer (PARACEST) complexes are exogenous contrast agents that have great potential to further extend the functional and molecular imaging capabilities of magnetic resonance. As a result of the presence of a central paramagnetic lanthanide ion (Ln(3+) ≠ La(3+) , Gd(3+) , Lu(3+) ) within the chelate, the resonance frequencies of exchangeable protons bound to the PARACEST agent are shifted far away from the bulk water frequency. This large chemical shift, combined with an extreme sensitivity to the chemical exchange rate, make PARACEST agents ideally suited for the reporting of significant biological metrics, such as temperature, pH and the presence of metabolites. In addition, the ability to turn PARACEST agents 'off' and 'on' using a frequency-selective saturation pulse gives them a distinct advantage over Gd(3+) -based contrast agents. A current challenge for PARACEST research is the translation of the promising in vitro results into in vivo systems. This short review article first describes the basic theory behind PARACEST contrast agents, their benefits over other contrast agents and their applications to MRI. It then describes some of the recent PARACEST research results: specifically, pH measurements using water molecule exchange rate modulation, T2 exchange contrast caused by water molecule exchange, the use of ultrashort TEs (TE < 10 µs) to overcome T2 exchange line broadening and the potential application of T2 exchange as a new contrast mechanism for MRI.

  18. Paramagnetic 3d coordination complexes involving redox-active tetrathiafulvalene derivatives: an efficient approach to elaborate multi-properties materials.

    PubMed

    Pointillart, Fabrice; Golhen, Stéphane; Cador, Olivier; Ouahab, Lahcène

    2013-02-14

    The elaboration of multifunctional materials is a great challenge for the physical chemistry community and the studies of molecular materials exhibiting coexistence or synergy between two or more properties are very active. In particular, molecular compounds displaying electrical conductivity and magnetic interactions are currently the subject of intensive studies. Two approaches are now well-known and are explored. On the one hand, the interactions between mobile electrons of the organic network (π electrons) and localized electrons of paramagnetic transition metal (d electrons) take place through space. On the other hand, these interactions take place through covalent chemical bonds. In the latter, the probability to have significant interaction between π and d electrons is enhanced compared to the first approach. In this perspective article, we will give an overview of the known coordination complexes involving tetrathiafulvalene derivatives as ligands for paramagnetic 3d ions and we will describe their physical properties. If necessary, the coexistence or synergy between electrical conductivity, magnetism and other properties will be highlighted.

  19. Advantages of paramagnetic CEST complexes having slow-to-intermediate water exchange properties as responsive MRI agents

    PubMed Central

    Soesbe, Todd C.; Wu, Yunkou; Sherry, A. Dean

    2012-01-01

    Paramagnetic saturation transfer chemical exchange (PARACEST) complexes are exogenous contrast agents that have great potential to further extend the functional and molecular imaging capabilities of magnetic resonance. Due to the presence of a central paramagnetic lanthanide ion (Ln3+ ≠ La3+, Gd3+, Lu3+) within the chelate, the resonance frequencies of protons and water molecules bound to the PARACEST agent are shifted far away from the bulk water frequency. This large chemical shift combined with an extreme sensitivity to the chemical exchange rate make PARACEST agents ideally suited for reporting significant biological metrics such as temperature, pH, and the presence of metabolites. Also, the ability to turn PARACEST agents “off” and “on” using a frequency selective saturation pulse gives them a distinct advantage over Gd3+-based contrast agents. A current challenge for PARACEST research is translating the promising in vitro results into in vivo systems. This short review article first describes the basic theory behind PARACEST contrast agents, their benefits over other contrast agents, and their applications to magnetic resonance imaging. It then describes some of the recent PARACEST research results. Specifically, pH measurements using water molecule exchange rate modulation, T2-exchange contrast due to water molecule exchange, the use of ultra-short echo times (TE<10 μs) to overcome T2-exchange line-broadening, and the potential application of T2-exchange as a new contrast mechanism for magnetic resonance imaging. PMID:23055299

  20. Solid-state proton NMR of paramagnetic metal complexes: DANTE spin echoes for selective excitation in inhomogeneously broadened lines

    NASA Astrophysics Data System (ADS)

    Carnevale, Diego; Perez Linde, A. J.; Bauer, Gerald; Bodenhausen, Geoffrey

    2013-08-01

    The paramagnetic complex bis(oxazolinylphenyl)amine-Fe(III)Cl2 is investigated by means of solid-state proton NMR at 18.8 T (800 MHz) using magic-angle spinning at 65 kHz. Spin echoes that are excited and refocused by combs of rotor-synchronized pulses in the manner of 'Delays Alternating with Nutation for Tailored Excitation' (DANTE) allow one to characterize different chemical environments that severely overlap in conventional MAS spectra. Such sequences combine two apparently contradictory features: an overall bandwidth exceeding several MHz, and very selective irradiation of a few kHz within inhomogeneously broadened sidebands. The experimental hyperfine interactions correlate well with DFT calculations.

  1. Characterization of Protein-Protein Interfaces in Large Complexes by Solid-State NMR Solvent Paramagnetic Relaxation Enhancements.

    PubMed

    Öster, Carl; Kosol, Simone; Hartlmüller, Christoph; Lamley, Jonathan M; Iuga, Dinu; Oss, Andres; Org, Mai-Liis; Vanatalu, Kalju; Samoson, Ago; Madl, Tobias; Lewandowski, Józef R

    2017-09-06

    Solid-state NMR is becoming a viable alternative for obtaining information about structures and dynamics of large biomolecular complexes, including ones that are not accessible to other high-resolution biophysical techniques. In this context, methods for probing protein-protein interfaces at atomic resolution are highly desirable. Solvent paramagnetic relaxation enhancements (sPREs) proved to be a powerful method for probing protein-protein interfaces in large complexes in solution but have not been employed toward this goal in the solid state. We demonstrate that (1)H and (15)N relaxation-based sPREs provide a powerful tool for characterizing intermolecular interactions in large assemblies in the solid state. We present approaches for measuring sPREs in practically the entire range of magic angle spinning frequencies used for biomolecular studies and discuss their benefits and limitations. We validate the approach on crystalline GB1, with our experimental results in good agreement with theoretical predictions. Finally, we use sPREs to characterize protein-protein interfaces in the GB1 complex with immunoglobulin G (IgG). Our results suggest the potential existence of an additional binding site and provide new insights into GB1:IgG complex structure that amend and revise the current model available from studies with IgG fragments. We demonstrate sPREs as a practical, widely applicable, robust, and very sensitive technique for determining intermolecular interaction interfaces in large biomolecular complexes in the solid state.

  2. Characterization of Protein–Protein Interfaces in Large Complexes by Solid-State NMR Solvent Paramagnetic Relaxation Enhancements

    PubMed Central

    2017-01-01

    Solid-state NMR is becoming a viable alternative for obtaining information about structures and dynamics of large biomolecular complexes, including ones that are not accessible to other high-resolution biophysical techniques. In this context, methods for probing protein–protein interfaces at atomic resolution are highly desirable. Solvent paramagnetic relaxation enhancements (sPREs) proved to be a powerful method for probing protein–protein interfaces in large complexes in solution but have not been employed toward this goal in the solid state. We demonstrate that 1H and 15N relaxation-based sPREs provide a powerful tool for characterizing intermolecular interactions in large assemblies in the solid state. We present approaches for measuring sPREs in practically the entire range of magic angle spinning frequencies used for biomolecular studies and discuss their benefits and limitations. We validate the approach on crystalline GB1, with our experimental results in good agreement with theoretical predictions. Finally, we use sPREs to characterize protein–protein interfaces in the GB1 complex with immunoglobulin G (IgG). Our results suggest the potential existence of an additional binding site and provide new insights into GB1:IgG complex structure that amend and revise the current model available from studies with IgG fragments. We demonstrate sPREs as a practical, widely applicable, robust, and very sensitive technique for determining intermolecular interaction interfaces in large biomolecular complexes in the solid state. PMID:28780861

  3. Motion of subfragment-1 in myosin and its supramolecular complexes: saturation transfer electron paramagnetic resonance.

    PubMed Central

    Thomas, D D; Seidel, J C; Hyde, J S; Gergely, J

    1975-01-01

    Molecular dynamics in spin-labeled muscle proteins was studied with a recently developed electron paramagnetic resonance (EPR) technique, saturation transfer spectroscopy, which is uniquely sensitive to rotational motion in the range of 10(-7)-10(-3) sec. Rotational correlation time (tau2) were determined for a spin label analog of iodoacetamide bound to the subfragment-1 (S-1) region of myosin under a variety of conditions likely to shed light on the molecular mechanism of muscle contraction. Results show that (a) the spin labels are rigidly bound to the isolated S-1 (tau2 = 2 x 10(-7) sec) and can be used to estimate values of tau2 for the S-1 region of the myosin molecule; (b) in solutions of intact myosin, S-1 has considerable mobility relative to the rest of the myosin molecule, the value of tau2 for the S-1 segment of myosin being less than twice that for isolated S-1, while the molecular weights differ by a factor of 4 to 5; (c) in myosin filaments, tau2 increases by a factor of only about 10, suggesting motion of the S-1 regions independent of the backbone of the myosin filament, but slower than that in a single molecule; (d) addition of F-actin to solutions of myosin or S-1 increases tau2 by a factor of nearly 10(3), indicating strong immobilization of S-1 upon binding to actin. Saturation transfer spectroscopy promises to provide an extremely useful tool for the study of the motions of the crossbridges and thin filaments in reconstituted systems and in glycerinated muscle fibers. PMID:168572

  4. High binding yet accelerated guest rotation within a cucurbit[7]uril complex. Toward paramagnetic gyroscopes and rolling nanomachines

    NASA Astrophysics Data System (ADS)

    Casano, G.; Poulhès, F.; Tran, T. K.; Ayhan, M. M.; Karoui, H.; Siri, D.; Gaudel-Siri, A.; Rockenbauer, A.; Jeschke, G.; Bardelang, D.; Tordo, P.; Ouari, O.

    2015-07-01

    The (15-oxo-3,7,11-triazadispiro[5.1.5.3]hexadec-7-yl)oxidanyl, a bis-spiropiperidinium nitroxide derived from TEMPONE, can be included in cucurbit[7]uril to form a strong (Ka ~ 2 × 105 M-1) CB[7]@bPTO complex. EPR and MS spectra, DFT calculations, and unparalleled increased resistance (a factor of ~103) toward ascorbic acid reduction show evidence of deep inclusion of bPTO inside CB[7]. The unusual shape of the CB[7]@bPTO EPR spectrum can be explained by an anisotropic Brownian rotational diffusion, the global tumbling of the complex being slower than rotation of bPTO around its ``long molecular axis'' inside CB[7]. The CB[7] (stator) with the encapsulated bPTO (rotator) behaves as a supramolecular paramagnetic rotor with increased rotational speed of the rotator that has great potential for advanced nanoscale machines requiring wheels such as cucurbiturils with virtually no friction between the wheel and the axle for optimum wheel rotation (i.e. nanopulleys and nanocars).The (15-oxo-3,7,11-triazadispiro[5.1.5.3]hexadec-7-yl)oxidanyl, a bis-spiropiperidinium nitroxide derived from TEMPONE, can be included in cucurbit[7]uril to form a strong (Ka ~ 2 × 105 M-1) CB[7]@bPTO complex. EPR and MS spectra, DFT calculations, and unparalleled increased resistance (a factor of ~103) toward ascorbic acid reduction show evidence of deep inclusion of bPTO inside CB[7]. The unusual shape of the CB[7]@bPTO EPR spectrum can be explained by an anisotropic Brownian rotational diffusion, the global tumbling of the complex being slower than rotation of bPTO around its ``long molecular axis'' inside CB[7]. The CB[7] (stator) with the encapsulated bPTO (rotator) behaves as a supramolecular paramagnetic rotor with increased rotational speed of the rotator that has great potential for advanced nanoscale machines requiring wheels such as cucurbiturils with virtually no friction between the wheel and the axle for optimum wheel rotation (i.e. nanopulleys and nanocars). Electronic

  5. Electron Paramagnetic Resonance Spectroscopy of Vanadium (IV) Complexes and Related Species.

    DTIC Science & Technology

    1980-07-27

    previously stated, a computer programr can be used to apply this correction [89] 1.6.4 Anisotropic SpcC’tra of Vantadum(IV) Complexes If a solution of a...done[29-31, 113,114] . The most thorough work has been published by Oliv6 and Henrici -Oliv6 [29-311 (on complexes VOCI 2L2 produced in solution, but not... Computer programs such as these are necessary in order to make unambiguous assignments of spectral lines in anisotropic and complex isotropic

  6. Elucidating connectivity and metal-binding structures of unlabeled paramagnetic complexes by 13C and 1H solid-state NMR under fast magic angle spinning.

    PubMed

    Wickramasinghe, Nalinda P; Shaibat, Medhat A; Ishii, Yoshitaka

    2007-08-23

    Characterizing paramagnetic complexes in solids is an essential step toward understanding their molecular functions. However, methodologies to characterize chemical and electronic structures of paramagnetic systems at the molecular level have been notably limited, particularly for noncrystalline solids. We present an approach to obtain connectivities of chemical groups and metal-binding structures for unlabeled paramagnetic complexes by 13C and 1H high-resolution solid-state NMR (SSNMR) using very fast magic angle spinning (VFMAS, spinning speed >or=20 kHz). It is experimentally shown for unlabeled Cu(II)(Ala-Thr) that 2D 13C/1H correlation SSNMR under VFMAS provides the connectivity of chemical groups and assignments for the characterization of unlabeled paramagnetic systems in solids. We demonstrate that on the basis of the assignments provided by the VFMAS approach multiple 13C-metal distances can be simultaneously elucidated by a combination of measurements of 13C anisotropic hyperfine shifts and 13C T1 relaxation due to hyperfine interactions for this peptide-Cu(II) complex. It is also shown that an analysis of 1H anisotropic hyperfine shifts allows for the determination of electron-spin states in Fe(III)-chloroprotoporphyin-IX in solid states.

  7. Polynuclear water-soluble dinitrosyl iron complexes with cysteine or glutathione ligands: electron paramagnetic resonance and optical studies.

    PubMed

    Vanin, Anatoly F; Poltorakov, Alexander P; Mikoyan, Vasak D; Kubrina, Lyudmila N; Burbaev, Dosymzhan S

    2010-09-15

    Electron paramagnetic resonance and optical spectrophotometric studies have demonstrated that low-molecular dinitrosyl iron complexes (DNICs) with cysteine or glutathione exist in aqueous solutions in the form of paramagnetic mononuclear (capital EM, Cyrillic-DNICs) and diamagnetic binuclear complexes (B-DNICs). The latter represent Roussin's red salt esters and can be prepared by treatment of aqueous solutions of Fe(2+) and thiols (small er, Cyrilliccapital EN, Cyrillic 7.4) with gaseous nitric oxide (NO) at the thiol:Fe(2+) ratio 1:1. capital EM, Cyrillic-DNICs are synthesized under identical conditions at the thiol:Fe(2+) ratios above 20 and produce an EPR signal with an electronic configuration {Fe(NO)(2)}(7) at g(aver.)=2.03. At neutral pH, aqueous solutions contain both M-DNICs and B-DNICs (the content of the latter makes up to 50% of the total DNIC pool). The concentration of B-DNICs decreases with a rise in pH; at small er, Cyrilliccapital EN, Cyrillic 9-10, the solutions contain predominantly M-DNICs. The addition of thiol excess to aqueous solutions of B-DNICs synthesized at the thiol:Fe(2+) ratio 1:2 results in their conversion into capital EM, Cyrillic-DNICs, the total amount of iron incorporated into M-DNICs not exceeding 50% of the total iron pool in B-DNICs. Air bubbling of cys-capital EM, Cyrillic-DNIC solutions results in cysteine oxidation-controlled conversion of capital EM, Cyrillic-DNICs first into cys-B-DNICs and then into the EPR-silent compound capital HA, Cyrillic able to generate a strong absorption band at 278 nm. In the presence of glutathione or cysteine excess, compound capital HA, Cyrillic is converted into B-DNIC/M-DNIC and is completely decomposed under effect of the Fe(2+) chelator small o, Cyrillic-phenanthroline or N-methyl-d-glucamine dithiocarbamate (MGD). Moreover, MGD initiates the synthesis of paramagnetic mononitrosyl iron complexes with MGD. It is hypothesized that compound capital HA, Cyrillic represents a polynuclear

  8. High binding yet accelerated guest rotation within a cucurbit[7]uril complex. Toward paramagnetic gyroscopes and rolling nanomachines.

    PubMed

    Casano, G; Poulhès, F; Tran, T K; Ayhan, M M; Karoui, H; Siri, D; Gaudel-Siri, A; Rockenbauer, A; Jeschke, G; Bardelang, D; Tordo, P; Ouari, O

    2015-07-28

    The (15-oxo-3,7,11-triazadispiro[5.1.5.3]hexadec-7-yl)oxidanyl, a bis-spiropiperidinium nitroxide derived from TEMPONE, can be included in cucurbit[7]uril to form a strong (K(a)∼ 2 × 10(5) M(-1)) CB[7]@bPTO complex. EPR and MS spectra, DFT calculations, and unparalleled increased resistance (a factor of ∼10(3)) toward ascorbic acid reduction show evidence of deep inclusion of bPTO inside CB[7]. The unusual shape of the CB[7]@bPTO EPR spectrum can be explained by an anisotropic Brownian rotational diffusion, the global tumbling of the complex being slower than rotation of bPTO around its "long molecular axis" inside CB[7]. The CB[7] (stator) with the encapsulated bPTO (rotator) behaves as a supramolecular paramagnetic rotor with increased rotational speed of the rotator that has great potential for advanced nanoscale machines requiring wheels such as cucurbiturils with virtually no friction between the wheel and the axle for optimum wheel rotation (i.e. nanopulleys and nanocars).

  9. Synthesis, Structural Characterization, and Cytotoxic Activity of Novel Paramagnetic Platinum Hematoporphyrin IX Complexes: Potent Antitumor Agents

    PubMed Central

    Gencheva, G.; Tsekova, D.; Gochev, G.; Momekov, G.; Tyuliev, G.; Skumryev, V.; Karaivanova, M.; Bontchev, P. R.

    2007-01-01

    Three novel stable Pt(III) complexes with distorted octahedral structure and (dz2)1 ground state have been obtained in the course of Pt(II)-hematoporphyrin IX ((7,12-bis(1-hydroxyethyl)-3,8,13,17-tetramethyl-21H-23H-porphyn-2,18-dipropionic acid), Hp) interaction in alkaline aqueous medium and aerobic conditions. A redox interaction also takes place together with the complexation process leading to the formation of Pt(III) species and organic radicals. The processes in the reaction system and the structure of the complexes formed cis-[Pt(III)(NH3)2(Hp−3H)(H2O)2]⋅H2O 1, [Pt(III)(Hp−3H)(H2O)2]⋅H2O 2, and [Pt((O,O)Hp−2H)Cl(H2O)3] 3, were studied by UV-Vis, IR, EPR and XPS spectra, thermal (TGS, DSC), potentiometric and magnetic methods. The newly synthesized complexes show promising cytotoxic activity comparable with that of cis-platin in in vitro tests against a panel of human leukemia cell lines. The observed cytotoxicity of the complex 2 against SKW-3 cells (KE-37 derivative) is due to induction of cell death through apoptosis. PMID:18309370

  10. A pair of highly biotolerated diamagnetic and paramagnetic iron(ii) complexes displaying electroneutrality.

    PubMed

    Wang, J; Gondrand, C; Touti, F; Hasserodt, J

    2015-09-21

    A pair of structurally analogous macrocyclic iron(ii) complexes with a magnetic off-on relationship is reported that exhibit electroneutrality at neutral pH and high stability in physiological media. This has been achieved by external charge compensation using nicotinate pendent arms. No contact toxicity was observed for cells up to 4 mM for the low-spin and 2 mM for the high-spin complex. These results are a necessary precursor to the future design of turn-on probes with elevated biotolerance.

  11. [Experimental hemorrhagic stroke: the effect of the peptide preparation cortexin in the formation of Hb-NO-complexes and other blood paramagnetic centers].

    PubMed

    Reutov, V P; Baĭder, L M; Kuropteva, Z V; Krushinskiĭ, A L; Kuzenkov, V S; Moldaliev, Zh T; Granstrem, O K

    2011-01-01

    Using electronic paramagnetic resonance (EPR), we studied the effect of the peptide cortexin on the content of hemoglobin nitrozyl complexes (Hb-NO-complexes) and other paramagnetic centers (transferrin, methemoglobin) in the blood of rats of Krushynsky-Molodkina line in the experimental hemorrhagic stroke induced by acoustic stress. After the acoustic exposure, the level of Hb-NO-complexes have increased by more than 6 times. The intensity of the EPR signal of the plasma peptide transferrin increased by 1,5 times. The level of blood methemoglobin was also elevated, though not significantly, after the acoustic stress. Cortexin substantially reduces the formation of Hb-NO-complexes and, therefore, the level of nitride oxide while the contents of transferrin and methemoglobin remain intact.

  12. The first examples of multiply bonded dirhenium(iii,ii) paramagnetic complexes containing nitrobenzoate ligands: spectroscopic, structural, cytotoxicity and computational studies.

    PubMed

    Mallick, Suman; Ghosh, Mrinal Kanti; Mandal, Suman; Rane, Vinayak; Kadam, Ramakant; Chatterjee, Annesha; Bhattacharyya, Arindam; Chattopadhyay, Swarup

    2017-02-09

    4-Nitrobenzoic acid, 3-nitrobenzoic acid and 4'-nitro[1,1'-biphenyl]-4-carboxylic acid react with the multiply bonded paramagnetic dirhenium(iii,ii) complex Re2(μ-O2CCH3)Cl4(μ-Ph2PCH2PPh2)2 (1) in refluxing ethanol to afford the paramagnetic substitution products of the type Re2(μ-L)Cl4(μ-Ph2PCH2PPh2)2, where L represents the nitrobenzoate ligands [L = 4-nitrobenzoate, 2; 3-nitrobenzoate, 3; 4'-nitro[1,1'-biphenyl]-4-carboxylate, 4]. These are the first examples of paramagnetic dirhenium complexes containing nitrobenzoate ligands. The spectral (UV-vis, IR, and EPR) and electrochemical properties of the complexes are described. The identity of 4 has been established by single-crystal X-ray structure determination (Re-Re distance of 2.2967(4) Å). The electronic structures of the complexes were scrutinized by density functional theory (DFT) calculations. X-band EPR spectral measurements along with the DFT analysis show that the unpaired electron resides in the metal-metal δ* antibonding orbital. The complexes were also screened in vitro for their antiproliferative properties against the human breast cancer cell line MCF-7 by the MTT assay. Flow cytometry analysis showed that the complexes arrested the sub-G0/G1 phase.

  13. Increasing the sensitivity of NMR diffusion measurements by paramagnetic longitudinal relaxation enhancement, with application to ribosome–nascent chain complexes

    PubMed Central

    Cassaignau, Anaïs M. E.; Cabrita, Lisa D.

    2016-01-01

    The translational diffusion of macromolecules can be examined non-invasively by stimulated echo (STE) NMR experiments to accurately determine their molecular sizes. These measurements can be important probes of intermolecular interactions and protein folding and unfolding, and are crucial in monitoring the integrity of large macromolecular assemblies such as ribosome–nascent chain complexes (RNCs). However, NMR studies of these complexes can be severely constrained by their slow tumbling, low solubility (with maximum concentrations of up to 10 μM), and short lifetimes resulting in weak signal, and therefore continuing improvements in experimental sensitivity are essential. Here we explore the use of the paramagnetic longitudinal relaxation enhancement (PLRE) agent NiDO2A on the sensitivity of 15N XSTE and SORDID heteronuclear STE experiments, which can be used to monitor the integrity of these unstable complexes. We exploit the dependence of the PLRE effect on the gyromagnetic ratio and electronic relaxation time to accelerate recovery of 1H magnetization without adversely affecting storage on Nz during diffusion delays or introducing significant transverse relaxation line broadening. By applying the longitudinal relaxation-optimized SORDID pulse sequence together with NiDO2A to 70S Escherichia coli ribosomes and RNCs, NMR diffusion sensitivity enhancements of up to 4.5-fold relative to XSTE are achieved, alongside ~1.9-fold improvements in two-dimensional NMR sensitivity, without compromising the sample integrity. We anticipate these results will significantly advance the use of NMR to probe dynamic regions of ribosomes and other large, unstable macromolecular assemblies. PMID:26253948

  14. Paramagnetic lanthanide(III) complexes as pH-sensitive chemical exchange saturation transfer (CEST) contrast agents for MRI applications.

    PubMed

    Aime, Silvio; Barge, Alessandro; Delli Castelli, Daniela; Fedeli, Franco; Mortillaro, Armando; Nielsen, Flemming U; Terreno, Enzo

    2002-04-01

    The recently introduced new class of contrast agents (CAs) based on chemical exchange saturation transfer (CEST) may have a huge potential for the development of novel applications in the field of MRI. In this work we explored the CEST properties of a series of Lanthanide(III) complexes (Ln = Eu, Dy, Ho, Er, Tm, Yb) with the macrocyclic DOTAM-Gly ligand, which is the tetraglycineamide derivative of DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid). These complexes possess two pools of exchangeable protons represented by the coordinated water and the amide protons. Yb-DOTAM-Gly displays the most interesting CEST properties when its amide N-H resonance (16 ppm upfield H2O signal) is irradiated. Up to 70% suppression of the water signal is obtained at pH 8. As the exchange rate of amide protons is base-catalyzed, Yb-DOTAM-Gly results to be an efficient pH-responsive probe in the 5.5-8.1 pH range. Moreover, a ratiometric method has been set up in order to remove the dependence of the observed pH responsiveness from the absolute concentration of the paramagnetic agent. In fact, the use of a mixture of Eu-DOTAM-Gly and Yb-DOTAM-Gly, whose exchangeable proton pools are represented by the coordinated water (ca. 40 ppm downfield H2O signal at 312K) and amide protons, respectively, produces a pH-dependent CEST effect which is the function of the concentration ratio of the two complexes.

  15. Evaluation of synergistic antioxidant potential of complex mixtures using oxygen radical absorbance capacity (ORAC) and electron paramagnetic resonance (EPR).

    PubMed

    Parker, Tory L; Miller, Samantha A; Myers, Lauren E; Miguez, Fernando E; Engeseth, Nicki J

    2010-01-13

    Previous research has demonstrated that certain combinations of compounds result in a decrease in toxic or pro-oxidative effects, previously noted when compounds were administered singly. Thus, there is a need to study many complex interactions further. Two in vitro techniques [electron paramagnetic resonance (EPR) and oxygen radical absorbance capacity (ORAC) assays] were used in this study to assess pro- and antioxidant capacity and synergistic potential of various compounds. Rutin, p-coumaric acid, abscisic acid, ascorbic acid, and a sugar solution were evaluated individually at various concentrations and in all 26 possible combinations at concentrations found in certain foods (honey or papaya), both before and after simulated digestion. EPR results indicated sugar-containing combinations provided significantly higher antioxidant capacity; those combinations containing sugars and ascorbic acid demonstrated synergistic potential. The ORAC assay suggested additive effects, with some combinations having synergistic potential, although fewer combinations were significantly synergistic after digestion. Finally, ascorbic acid, caffeic acid, quercetin, and urate were evaluated at serum-achievable levels. EPR analysis did not demonstrate additive or synergistic potential, although ORAC analysis did, principally in combinations containing ascorbic acid.

  16. Transmembrane signal transduction in archaeal phototaxis: the sensory rhodopsin II-transducer complex studied by electron paramagnetic resonance spectroscopy.

    PubMed

    Klare, Johann P; Bordignon, Enrica; Engelhard, Martin; Steinhoff, Heinz-Jürgen

    2011-09-01

    Archaeal photoreceptors, together with their cognate transducer proteins, mediate phototaxis by regulating cell motility through two-component signal transduction pathways. This sensory pathway is closely related to the bacterial chemotactic system, which has been studied in detail during the past 40 years. Structural and functional studies applying site-directed spin labelling and electron paramagnetic resonance spectroscopy on the sensory rhodopsin II/transducer (NpSRII/NpHtrII) complex of Natronomonas pharaonis have yielded insights into the structure, the mechanisms of signal perception, the signal transduction across the membrane and provided information about the subsequent information transfer within the transducer protein towards the components of the intracellular signalling pathway. Here, we provide an overview about the findings of the last decade, which, combined with the wealth of data from research on the Escherichia coli chemotaxis system, served to understand the basic principles microorganisms use to adapt to their environment. We document the time course of a signal being perceived at the membrane, transferred across the membrane and, for the first time, how this signal modulates the dynamic properties of a HAMP domain, a ubiquitous signal transduction module found in various protein classes. Copyright © 2011 Elsevier GmbH. All rights reserved.

  17. Eu(III) complexes as anion-responsive luminescent sensors and paramagnetic chemical exchange saturation transfer agents.

    PubMed

    Hammell, Jacob; Buttarazzi, Leandro; Huang, Ching-Hui; Morrow, Janet R

    2011-06-06

    The Eu(III) complex of (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) is studied as a sensor for biologically relevant anions. Anion interactions produce changes in the luminescence emission spectrum of the Eu(III) complex, in the (1)H NMR spectrum, and correspondingly, in the PARACEST spectrum of the complex (PARACEST = paramagnetic chemical exchange saturation transfer). Direct excitation spectroscopy and luminescence lifetime studies of Eu(S-THP) give information about the speciation and nature of anion interactions including carbonate, acetate, lactate, citrate, phosphate, and methylphosphate at pH 7.2. Data is consistent with the formation of both innersphere and outersphere complexes of Eu(S-THP) with acetate, lactate, and carbonate. These anions have weak dissociation constants that range from 19 to 38 mM. Citrate binding to Eu(S-THP) is predominantly innersphere with a dissociation constant of 17 μM. Luminescence emission peak changes upon addition of anion to Eu(S-THP) show that there are two distinct binding events for phosphate and methylphosphate with dissociation constants of 0.3 mM and 3.0 mM for phosphate and 0.6 mM and 9.8 mM for methyl phosphate. Eu(THPC) contains an appended carbostyril derivative as an antenna to sensitize Eu(III) luminescence. Eu(THPC) binds phosphate and citrate with dissociation constants that are 10-fold less than that of the Eu(S-THP) parent, suggesting that functionalization through a pendent group disrupts the anion binding site. Eu(S-THP) functions as an anion responsive PARACEST agent through exchange of the alcohol protons with bulk water. The alcohol proton resonances of Eu(S-THP) shift downfield in the presence of acetate, lactate, citrate, and methylphosphate, giving rise to distinct PARACEST peaks. In contrast, phosphate binds to Eu(S-THP) to suppress the PARACEST alcohol OH peak and carbonate does not markedly change the alcohol peak at 5 mM Eu(S-THP), 15 mM carbonate at p

  18. Paramagnetic oxotungsten(V) complexes containing the hydrotris(3,5-dimethylpyrazol-1-yl)borate ligand.

    PubMed

    Sproules, Stephen; Eagle, Aston A; Taylor, Michelle K; Gable, Robert W; White, Jonathan M; Young, Charles G

    2011-05-16

    Sky-blue Tp*WOCl(2) has been synthesized from the high-yielding reaction of Tp*WO(2)Cl with boron trichloride in refluxing toluene. Dark-red Tp*WOI(2) was prepared via thermal decarbonylation followed by aerial oxidation of Tp*WI(CO)(3) in acetonitrile. From these precursors, an extensive series of mononuclear tungstenyl complexes, Tp*WOXY [X = Cl(-), Y = OPh(-), SPh(-); X = Y = OPh(-), 2-(n-propyl)phenolate (PP(-)), SPh(-), SePh(-); XY = toluene-3,4-dithiolate (tdt(2-)), quinoxaline-2,3-dithiolate (qdt(2-)), benzene-1,2-diselenolate (bds(2-)); Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate], was prepared by metathesis with the respective alkali-metal salt of X(-)/XY(2-) or (NHEt(3))(2)(qdt). The complexes were characterized by microanalysis, mass spectrometry, electrochemistry, IR, electron paramagnetic resonance (EPR), and electronic absorption spectroscopies, and X-ray crystallography (for X = Y = OPh(-), PP(-), SPh(-); XY = bds(2-)). The six-coordinate, distorted-octahedral tungsten centers are coordinated by terminal oxo [W≡O = 1.689(6)-1.704(3) Å], tridentate Tp*, and monodentate or bidentate O/S/Se-donor ligands. Spin Hamiltonian parameters derived from the simulation of fluid-solution X-band EPR spectra revealed that the soft-donor S/Se ligand complexes had larger g values and smaller (183)W hyperfine coupling constants than the less covalent hard-donor O/Cl species. The former showed low-energy ligand-to-metal charge-transfer bands in the near-IR region of their electronic absorption spectra. These oxotungsten(V) complexes display lower reduction potentials than their molybdenum counterparts, underscoring the preference of tungsten for higher oxidation states. Furthermore, the protonation of the pyrazine nitrogen atoms of the qdt(2-) ligand has been examined by spectroelectrochemistry; the product of the one-electron reduction of [Tp*WO(qdtH)](+) revealed usually intense low-energy bands.

  19. Paramagnetic-diamagnetic phase transition accompanied by coordination bond formation-dissociation in the dithiolate complex Na[Ni(pdt)2]·2H2O.

    PubMed

    Takaishi, Shinya; Ishihara, Nozomi; Kubo, Kazuya; Katoh, Keiichi; Breedlove, Brian K; Miyasaka, Hitoshi; Yamashita, Masahiro

    2011-07-18

    Bis(2,3-pyrazinedithiolate)nickel complex Na[Ni(pdt)(2)]·2H(2)O formed one-dimensional stacks of the Ni(pdt)(2) units and showed strong antiferromagnetic interactions along the stacking direction. A first-order phase transition between the paramagnetic and diamagnetic states, which was driven by dimerization of the Ni(pdt)(2) units, accompanied by coordination bond formation, was observed.

  20. Relaxation filtered hyperfine (REFINE) spectroscopy: a novel tool for studying overlapping biological electron paramagnetic resonance signals applied to mitochondrial complex I.

    PubMed

    Maly, Thorsten; MacMillan, Fraser; Zwicker, Klaus; Kashani-Poor, Noushin; Brandt, Ulrich; Prisner, Thomas F

    2004-04-06

    A simple strategy to separate overlapping electron paramagnetic resonance (EPR) signals in biological systems is presented. Pulsed EPR methods (inversion- and saturation-recovery) allow the determination of the T(1) spin-lattice relaxation times of paramagnetic centers. T(1) may vary by several orders of magnitude depending on the species under investigation. These variations can be employed to study selectively individual species from a spectrum that results from an overlap of two species using an inversion-recovery filtered (IRf) pulsed EPR technique. The feasibility of such an IRf field-swept technique is demonstrated on model compounds (alpha,gamma-bisphenylene-beta-phenylallyl-benzolate, BDPA, and 2,2,6,6-tetramethyl-piperidine-1-oxyl, TEMPO) and a simple strategy for the successful analysis of such mixtures is presented. Complex I is a multisubunit membrane protein of the respiratory chain containing several iron-sulfur (FeS) centers, which are observable with EPR spectroscopy. It is not possible to investigate the functionally important FeS cluster N2 separately because this EPR signal always overlaps with the other FeS signals. This cluster can be studied selectively using the IRf field-swept technique and its EPR spectrum is in excellent agreement with previous cw-EPR data from the literature. In addition, the possibility to separate the hyperfine spectra of two spectrally overlapping paramagnetic species is demonstrated by applying this relaxation filter together with hyperfine spectroscopy (REFINE). For the first time, the application of this filter to a three-pulse electron spin-echo envelope modulation (ESEEM) pulse sequence is demonstrated to selectively observe hyperfine spectra on a system containing two paramagnetic species. Finally, REFINE is used to assign the observed nitrogen modulation in complex I to an individual iron-sulfur cluster.

  1. Solution 1H NMR characterization of substrate-free C. diphtheriae heme oxygenase; pertinence for determining magnetic axes in paramagnetic substrate complexes

    PubMed Central

    Du, Zhenming; Unno, Masaki; Matsui, Toshitaka; Ikeda-Saito, Masao; La Mar, Gerd N.

    2010-01-01

    Proton 2D NMR was used to confirm in solution a highly conserved portion of the molecular structure upon substrate loss for the heme oxygenase from the pathogenic bacterium Corynebacterium diphtheriae, HmuO. The chemical shifts for the conserved portion of the structure are assessed as references for the dipolar shifts needed to determine the orientation of the paramagnetic susceptibility tensor, χ, in paramagnetic substrate complexes of HmuO. It is shown that the chemical shifts for the structurally conserved portion of substrate-free HmuO serve as excellent references for residues with only small to moderate sized dipolar shifts in the cyanide-inhibited substrate complex of HmuO, yielding an orientation of χ that is essentially the same as conventionally obtained from large dipolar shifts based on empirical estimates of the diamagnetic reference. The implications of these diamagnetic chemical shifts for characterizing the hydrogen bonding in the physiologically relevant, resting-state, high-spin aquo complex are discussed. The pattern of labile proton exchange in the distal H-bond network of substrate-free HmuO allowed comparison of changes in dynamic stability of tertiary contacts in the substrate-free and substrate-bound HmuO and with the same complexes of human heme oxygenase. PMID:20655112

  2. From a paramagnetic, mononuclear supersulfidonickel(II) complex to a diamagnetic dimer with a four-sulfur two-electron bond.

    PubMed

    Yao, Shenglai; Milsmann, Carsten; Bill, Eckhard; Wieghardt, Karl; Driess, Matthias

    2008-10-15

    The first isolable "side-on" supersulfidonickel(II) complex 1(1) with the elusive S2-. ligand has been synthesized by facile oxidation of the corresponding nickel(I) precursor [LNi] with elemental sulfur. Remarkably, paramagnetic 1(1) associates voluntarily to give the diamagnetic dimer 1(2) with a four-sulfur two-electron bond as proven by X-ray diffraction analysis, spectroscopic measurements (1H NMR, EPR, SQUID), and DFT calculations. Gentle sulfur transfer of 1(1) to Ph3P or its reaction with [LNi] affords solely the genuine disulfide complex 3 having a Ni2(mu-mu2:mu2-S2) core.

  3. Theoretical investigation of paramagnetic NMR shifts in transition metal acetylacetonato complexes: analysis of signs, magnitudes, and the role of the covalency of ligand-metal bonding.

    PubMed

    Pritchard, Ben; Autschbach, Jochen

    2012-08-06

    Ligand chemical shifts are calculated and analyzed for three paramagnetic transition metal tris-acetylacetonato (acac) complexes, namely high-spin Fe(III) and Cr(III), and low-spin Ru(III), using scalar relativistic density functional theory (DFT). The signs and magnitudes of the paramagnetic NMR ligand chemical shifts are directly related to the extent of covalent acac oxygen-to-metal σ donation involving unoccupied metal valence d(σ) acceptor orbitals. The role of delocalization of metal-centered spin density over the ligand atoms plays a minor secondary role. Of particular interest is the origin of the sign and magnitude of the methyl carbon chemical shift in the acac ligands, and the role played by the DFT delocalization error when calculating such shifts. It is found that the α versus β spin balance of oxygen σ donation to metal valence d acceptor orbitals is responsible for the sign and the magnitude of the ligand methyl carbon chemical shift. A problematic case is the methyl carbon shift of Fe(acac)(3). Most functionals produce shifts in excess of 1400 ppm, whereas the experimental shift is approximately 279 ppm. Range-separated hybrid functionals that are optimally tuned for Fe(acac)(3) based on DFT energetic criteria predict a lower limit of about 2000 ppm for the methyl carbon shift of the high-spin electronic configuration. Since the experimental value is based on a very strongly broadened signal it is possibly unreliable.

  4. Synthesis and 1H NMR studies of paramagnetic nickel(II) complexes containing bis(pyrazolyl)methane ligands with dendritic substituents.

    PubMed

    Sánchez-Méndez, Alberto; Benito, Jose María; de Jesús, Ernesto; de la Mata, F Javier; Flores, Juan C; Gómez, Rafael; Gómez-Sal, Pilar

    2006-12-07

    The substituted bis(pyrazolyl)methane ligands RCH(3,5-Me2pz)2(R=SiMe3, CH2Ph, G1, G2, and G3; Gn=Fréchet-type dendritic wedges of generation n) have been prepared starting from H2C(3,5-Me2pz)2. Reaction of these didentate ligands with [NiBr2(DME)] is a straightforward procedure that allows the synthesis of the nickel(II) complexes [NiBr2{RCH(3,5-Me2pz)2}]. The molecular structure of compound (R=CH2Ph) has been determined by X-ray diffraction studies. The nickel centre coordinates two bromine and two nitrogen atoms in a tetrahedral environment, and the metallacycle Ni(NN)2C adopts a boat conformation with the benzyl group in an axial position. 1H NMR studies have been carried out to characterize these paramagnetic nickel compounds in solution. Valuable information about the disposition of the ligands and dendritic wedges in solution has been obtained thanks to the influence of the paramagnetic centre on the proton resonances.

  5. Fluorescence and electron paramagnetic resonance studies of norfloxacin and N-donor mixed-ligand ternary copper(II) complexes: Stability and interaction with SDS micelles.

    PubMed

    Vignoli Muniz, Gabriel S; Incio, Jimmy Llontop; Alves, Odivaldo C; Krambrock, Klaus; Teixeira, Letícia R; Louro, Sonia R W

    2017-08-05

    The stability of ternary copper(II) complexes of a heterocyclic ligand, L (L being 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen)) and the fluorescent antibacterial agent norfloxacin (NFX) as the second ligand was studied at pH7.4 and different ionic strengths. Fluorescence quenching upon titration of NFX with the binary complexes allowed to obtain stability constants for NFX binding, Kb, as a function of ionic strength. The Kb values vary by more than two orders of magnitude when buffer concentration varies from 0.5 to 100mM. It was observed that previously synthesized ternary complexes dissociate in buffer according with the obtained stability constants. This shows that equimolar solutions of NFX and binary complexes are equivalent to solutions of synthesized ternary complexes. The interaction of the ternary copper complexes with anionic SDS (sodium dodecyl sulfate) micelles was studied by fluorescence and electron paramagnetic resonance (EPR). Titration of NFX-loaded SDS micelles with the complexes Cu:L allowed to determine the stability constants inside the micelles. Fluorescence quenching demonstrated that SDS micelles increase the stability constants by factors around 50. EPR spectra gave details of the copper(II) local environment, and demonstrated that the structure of the ternary complexes inside SDS micelles is different from that in buffer. Mononuclear ternary complexes formed inside the micelles, while in buffer most ternary complexes are binuclear. The results show that anionic membrane interfaces increase formation of copper fluoroquinolone complexes, which can influence bioavailability, membrane diffusion, and mechanism of action of the antibiotics. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Magnetic alignment and quadrupolar/paramagnetic cross-correlation in complexes of Na with LnDOTP5-.

    PubMed

    Eliav, Uzi; Shekar, S Chandra; Ling, Wen; Navon, Gil; Jerschow, Alexej

    2012-03-01

    The observation of a double-quantum filtered signal of quadrupolar nuclei (e.g. (23)Na) in solution has been traditionally interpreted as a sign for anisotropic reorientational motion. Ling and Jerschow (2007) have found that a (23)Na double-quantum signal is observed also in solutions of TmDOTPNa(5). Interference effects between the quadrupolar and the paramagnetic interactions have been reported to lead to the appearance of double-quantum coherences even in the absence of a residual quadrupolar interaction. In addition, such processes lead to differential linebroadening effects between the satellite transitions, akin to effects that are well known for dipolar-CSA cross-correlation. Here, we report experiments on sodium in the presence of LnDOTP compounds, where it is shown that these cross-correlation effects correlate well with the pseudo-contact shift. In addition, anisotropic g-values of the lanthanide compounds in question, can also lead to alignment within the magnetic field, and consequently to the appearance of line splitting and double-quantum coherences. The two competing effects are demonstrated and it is concluded that both cross-correlated relaxation and alignment in the magnetic field must be at work in the systems described here. Copyright © 2012 Elsevier Inc. All rights reserved.

  7. Effect of oxygen on free radicals in DOPA-melanin complexes with netilmicin, diamagnetic Zn(II), and paramagnetic Cu(II)

    NASA Astrophysics Data System (ADS)

    Zdybel, Magdalena; Pilawa, Barbara; Buszman, Ewa; Wrześniok, Dorota

    2013-01-01

    Electron paramagnetic resonance (EPR) spectroscopy was used to examine interactions between molecules of oxygen O2 and free radicals of DOPA-melanin and its complexes with netilmicin, Zn(II) and Cu(II). EPR spectra were measured for evacuated samples and then compared to earlier data for the samples in air. The concentrations of free radicals in the evacuated samples were higher than for samples in air. The strongest effect was observed for DOPA-melanin and melanin samples containing Cu(II). Evacuation of DOPA-melanin and DOPA-melanin-Cu(II) samples causes high EPR line broadening. Faster spin-lattice relaxation processes exist in evacuated melanin samples than in samples in air.

  8. Resonance Raman, electron paramagnetic resonance, and density functional theory calculations of a phenolate-bound iron porphyrin complex: electrostatic versus covalent contribution to bonding.

    PubMed

    Das, Pradip Kumar; Dey, Abhishek

    2014-07-21

    Resonance Raman (rR), electron paramagnetic resonance (EPR), and density functional theory (DFT) calculations of a phenolate-bound iron porphyrin complex are reported. The complex is found to exist in a five-coordinate high-spin state in a noncoordinating solvent and in a six-coordinate low-spin state in a coordinating solvent. The vibrations originating from the iron phenolate-bound chromophores reproduced those reported for heme tyrosine active sites in nature. The EPR parameters and iron-pyrrole (Fe-Npyr) vibrations of phenolate, thiolate, and imidazole ligated iron porphyrin complexes indicate that the phenolate axial ligand acts as a π anisotropic ligand, which is more covalent than a neutral imidazole ligand but less covalent than a thiolate axial ligand. While the Fe(III/II) potential of the phenolate compound in a noncoordinating solvent is 500 mV more negative than that of the imidazole-bound complex, it is also 110 mV more negative than that of the thiolate-bound complex. DFT calculations reproduce the geometry and vibrational frequencies and show that while both phenolate and thiolate axial ligands bear π and σ interaction with the ferric center, the former is significantly less covalent than the thiolate. The higher covalency of the thiolate ligand is responsible for the lower Fe-Npyr vibration and higher V/λ (from EPR) of the thiolate-bound complexes relative to those of the phenolate-bound complex, whereas the greater electrostatic stabilization of the Fe(III)-OPh bond is responsible for lowering the Fe(III/II) E° of the phenolate-bound complex relative to that of the thiolate-bound complex in a medium having a reasonable dielectric constant.

  9. PARAMAGNETIC RELAXATION IN CRYSTALS.

    DTIC Science & Technology

    CRYSTALS, PARAMAGNETIC RESONANCE, RELAXATION TIME , CRYSTAL DEFECTS, QUARTZ, GLASS, STRAIN(MECHANICS), TEMPERATURE, NUCLEAR SPINS, HYDROGEN, CALCIUM COMPOUNDS, FLUORIDES, COLOR CENTERS, PHONONS, OXYGEN.

  10. Fluxionality in a paramagnetic seven-coordinate iron(II) complex: a variable-temperature, two-dimensional NMR and DFT study.

    PubMed

    Lonnon, David G; Ball, Graham E; Taylor, Ivan; Craig, Donald C; Colbran, Stephen B

    2009-06-01

    The preparation and detailed characterizations of the high-spin seven-coordinate complexes [M(kappa(7)N-L)](ClO(4))(2) (M = Mn(II), Fe(II); L = N,N,N',N'-tetrakis(2-pyridylmethyl)-2,6-bis(aminomethyl)pyridine) are described. The X-ray crystal structures reveal seven-coordinate metal complex ions. Consideration of continuous shape measures reveals that the coordination environments about the metal ions are better described as having (C(s)) face-capped trigonal prismatic symmetry than (C(2)) pentagonal bipyramidal symmetry. The (S = (5)/(2)) Mn(II) species shows complicated X-band electron paramagnetic resonance (EPR) spectra and broad, unrevealing (1)H NMR spectra. In contrast, the (S = 2) Fe(II) complex is EPR-silent and shows completely interpretable (1)H NMR spectra containing the requisite number of paramagnetically shifted peaks in the range delta +150 to -60. The (13)C NMR spectra are likewise informative. Variable-temperature (1)H NMR spectra show coalescences and decoalescences indicative of an intramolecular process that pairwise-exchanges the nonequivalent pyridylmethyl "arms" of the two bis(pyridylmethyl)amine (bpa) domains. A suite of NMR techniques, including T(1) relaxation measurements and variable-temperature (1)H-(1)H correlation spectroscopy, (1)H-(1)H total correlation spectroscopy, (1)H-(1)H nuclear Overhauser effect spectroscopy/exchange spectroscopy, and (1)H-(13)C heteronuclear multiple-quantum coherence experiments, has been used to assign the NMR spectra and characterize the exchange process. Analysis of the data from these experiments yields the following thermodynamic parameters for the exchange: DeltaH++ = 53.6 +/- 2.8 kJ mol(-1), DeltaS++ = -10.0 +/- 9.8 J K(-1) mol(-1), and DeltaG++ (298 K) = 50.6 kJ mol(-1). Density functional theory (B3LYP) calculations have been used to explore the energetics of possible mechanistic pathways for the underlying fluxional process. The most plausible mechanism found involves dissociation of a

  11. Synthesis, structure, and electrochemical properties of sterically protected molybdenum trihydride redox pairs: a paramagnetic "stretched" dihydrogen complex?

    PubMed

    Baya, Miguel; Houghton, Jennifer; Daran, Jean-Claude; Poli, Rinaldo; Male, Louise; Albinati, Alberto; Gutman, Matthias

    2007-01-01

    Complexes [MoCp(#)(PMe(3))(2)H(3)] (Cp(#)=1,2,4-C(5)H(2)tBu(3), 2 a; C(5)HiPr(4), 2 b) have been synthesized from the corresponding compounds [MoCp(#)Cl(4)] (1 a, 1 b) and fully characterized, including by X-ray crystallography and by a neutron diffraction study for 2 a. Protonation of 2 a led to complex [Mo(1,2,4-C(5)H(2)tBu(3))(PMe(3))(2)H(4)](+) (3 a) in THF and to [Mo(1,2,4-C(5)H(2)tBu(3))(PMe(3))(2)(MeCN)H(2)](+) (4 a) in MeCN. Complex 4 b analogously derives from protonation of 2 b in MeCN, whereas the tetrahydride complex 3 b is unstable. One-electron oxidation of 2 a and 2 b by [FeCp(2)]PF(6) produces the EPR-active 17-electron complexes 2 a(+) and 2 b(+). The former is thermally more stable than the latter and could be crystallographically characterized as the PF(6) (-) salt by X-ray diffraction, providing evidence for the presence of a stretched dihydrogen ligand (H...H=1.36(6) angstroms). Controlled thermal decomposition of 2 a(+) yielded the product of H(2) elimination, the 15-electron monohydride complex [Mo(1,2,4-C(5)H(2)tBu(3))(PMe(3))(2)H]PF(6) (5 a), which was characterized by X-ray crystallography and by EPR spectroscopy at liquid He temperature. The compound establishes an equilibrium with the solvent adduct in THF. An electrochemical study by cyclic voltammetry provides further evidence for a rapid H(2) elimination process from the 17-electron complexes. In contrast to the previously investigated [MoCp*(dppe)H(3)](+) system (dppe=1,2-bis(diphenylphosphino)ethane; Cp*=pentamethylcyclopentadienyl), the decomposition of 2 a(+) by H(2) substitution with a solvent molecule appears to follow a dissociative pathway in MeCN.

  12. Investigation of Phenols Activity in Early Stage Oxidation of Edible Oils by Electron Paramagnetic Resonance and (19)F NMR Spectroscopies Using Novel Lipid Vanadium Complexes As Radical Initiators.

    PubMed

    Drouza, Chryssoula; Dieronitou, Anthi; Hadjiadamou, Ioanna; Stylianou, Marios

    2017-06-21

    A novel dynamic method for the investigation of the phenols activity in early stage oxidation of edible oils based on the formation of α-tocopheryl radicals initiated by oil-soluble vanadium complexes is developed. Two new vanadium complexes in oxidation states V and IV were synthesized by reacting 2,2'-((2-hydroxyoctadecyl)azanediyl)bis(ethan-1-ol) (C18DEA) with [VO(acac)2] and 1-(bis(pyridin-2-ylmethyl)amino)octadecan-2-ol (C18DPA) with VOCl2. Addition of a solution of either complex in edible oils resulted in the formation of α-tocopheryl radical, which was monitored by electron paramagnetic resonance (EPR) spectroscopy. The intensity of the α-tocopheryl signal in the EPR spectra was measured versus time. It was found that the profile of the intensity of the α-tocopheryl signal versus time depends on the type of oil, the phenolic content, and the storage time of the oil. The time interval until the occurrence of maximum peak intensity be reached (tm), the height of the maximum intensity, and the rate of the quenching of the α-tocopheryl radical were used for the investigation of the mechanism of the edible oils oxidation. (19)F NMR of the (19)F labeled phenolic compounds (through trifluoroacetate esters) and radical trap experiments showed that the vanadium complexes in edible oil activate the one electron reduction of dioxygen to superperoxide radical. Superperoxide reacts with the lipids to form alkoperoxyl and alkoxyl lipid radicals, and all these radicals react with the phenols contained in oils.

  13. Design principles and theory of paramagnetic fluorine-labelled lanthanide complexes as probes for (19)F magnetic resonance: a proof-of-concept study.

    PubMed

    Chalmers, Kirsten H; De Luca, Elena; Hogg, Naomi H M; Kenwright, Alan M; Kuprov, Ilya; Parker, David; Botta, Mauro; Wilson, J Ian; Blamire, Andrew M

    2010-01-04

    The synthesis and spectroscopic properties of a series of CF(3)-labelled lanthanide(III) complexes (Ln=Gd, Tb, Dy, Ho, Er, Tm) with amide-substituted ligands based on 1,4,7,10-tetraazacyclododecane are described. The theoretical contributions of the (19)F magnetic relaxation processes in these systems are critically assessed and selected volumetric plots are presented. These plots allow an accurate estimation of the increase in the rates of longitudinal and transverse relaxation as a function of the distance between the Ln(III) ion and the fluorine nucleus, the applied magnetic field, and the re-rotational correlation time of the complex, for a given Ln(III) ion. Selected complexes exhibit pH-dependent chemical shift behaviour, and a pK(a) of 7.0 was determined in one example based on the holmium complex of an ortho-cyano DO3A-monoamide ligand, which allowed the pH to be assessed by measuring the difference in chemical shift (varying by over 14 ppm) between two (19)F resonances. Relaxation analyses of variable-temperature and variable-field (19)F, (17)O and (1)H NMR spectroscopy experiments are reported, aided by identification of salient low-energy conformers by using density functional theory. The study of fluorine relaxation rates, over a field range of 4.7 to 16.5 T allowed precise computation of the distance between the Ln(III) ion and the CF(3) reporter group by using global fitting methods. The sensitivity benefits of using such paramagnetic fluorinated probes in (19)F NMR spectroscopic studies are quantified in preliminary spectroscopic and imaging experiments with respect to a diamagnetic yttrium(III) analogue.

  14. Electron paramagnetic resonance and Mössbauer spectroscopy and density functional theory analysis of a high-spin Fe(IV)-oxo complex.

    PubMed

    Gupta, Rupal; Lacy, David C; Bominaar, Emile L; Borovik, A S; Hendrich, Michael P

    2012-06-13

    High-spin Fe(IV)-oxo species are known to be kinetically competent oxidants in non-heme iron enzymes. The properties of these oxidants are not as well understood as the corresponding intermediate-spin oxidants of heme complexes. The present work gives a detailed characterization of the structurally similar complexes [Fe(IV)H(3)buea(O)](-), [Fe(III)H(3)buea(O)](2-), and [Fe(III)H(3)buea(OH)](-) (H(3)buea = tris[(N'-tert-butylureaylato)-N-ethylene]aminato) using Mössbauer and dual-frequency/dual-mode electron paramagnetic resonance (EPR) spectroscopies. The [Fe(IV)H(3)buea(O)](-) complex has a high-spin (S = 2) configuration imposed by the C(3)-symmetric ligand. The EPR spectra of the [Fe(IV)H(3)buea(O)](-) complex presented here represent the first documented examples of an EPR signal from an Fe(IV)-oxo complex, demonstrating the ability to detect and quantify Fe(IV) species with EPR spectroscopy. Quantitative simulations allowed the determination of the zero-field parameter, D = +4.7 cm(-1), and the species concentration. Density functional theory (DFT) calculations of the zero-field parameter were found to be in agreement with the experimental value and indicated that the major contribution to the D value is from spin-orbit coupling of the ground state with an excited S = 1 electronic configuration at 1.2 eV. (17)O isotope enrichment experiments allowed the determination of the hyperfine constants ((17)O)A(z) = 10 MHz for [Fe(IV)H(3)buea(O)](-) and ((17)O)A(y) = 8 MHz, ((17)O)A(z) = 12 MHz for [Fe(III)H(3)buea(OH)](-). The isotropic hyperfine constant (((17)O)A(iso) = -16.8 MHz) was derived from the experimental value to allow a quantitative determination of the spin polarization (ρ(p) = 0.56) of the oxo p orbitals of the Fe-oxo bond in [Fe(IV)H(3)buea(O)](-). This is the first experimental determination for non-heme complexes and indicates significant covalency in the Fe-oxo bond. High-field Mössbauer spectroscopy gave an (57)Fe A(dip) tensor of (+5.6, +5

  15. Gd(III) complexes as paramagnetic tags: Evaluation of the spin delocalization over the nuclei of the ligand

    NASA Astrophysics Data System (ADS)

    Collauto, A.; Feintuch, A.; Qi, M.; Godt, A.; Meade, T.; Goldfarb, D.

    2016-02-01

    Complexes of the Gd(III) ion are currently being established as spin labels for distance determination in biomolecules by pulse dipolar spectroscopy. Because Gd(III) is an f ion, one expects electron spin density to be localized on the Gd(III) ion - an important feature for the mentioned application. Most of the complex ligands have nitrogens as Gd(III) coordinating atoms. Therefore, measurement of the 14N hyperfine coupling gives access to information on the localization of the electron spin on the Gd(III) ion. We carried out W-band, 1D and 2D 14N and 1H ENDOR measurements on the Gd(III) complexes Gd-DOTA, Gd-538, Gd-595, and Gd-PyMTA that serve as spin labels for Gd-Gd distance measurements. The obtained 14N spectra are particularly well resolved, revealing both the hyperfine and nuclear quadrupole splittings, which were assigned using 2D Mims ENDOR experiments. Additionally, the spectral contributions of the two different types of nitrogen atoms of Gd-PyMTA, the aliphatic N atom and the pyridine N atom, were distinguishable. The 14N hyperfine interaction was found to have a very small isotropic hyperfine component of -0.25 to -0.37 MHz. Furthermore, the anisotropic hyperfine interactions with the 14N nuclei and with the non-exchangeable protons of the ligands are well described by the point-dipole approximation using distances derived from the crystal structures. We therefore conclude that the spin density is fully localized on the Gd(III) ion and that the spin density distribution over the nuclei of the ligands is rightfully ignored when analyzing distance measurements.

  16. Upconverting rare-earth nanoparticles with a paramagnetic lanthanide complex shell for upconversion fluorescent and magnetic resonance dual-modality imaging

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Ji, Lei; Zhang, Bingbo; Yin, Peihao; Qiu, Yanyan; Song, Daqian; Zhou, Juying; Li, Qi

    2013-05-01

    Multi-modal imaging based on multifunctional nanoparticles is a promising alternative approach to improve the sensitivity of early cancer diagnosis. In this study, highly upconverting fluorescence and strong relaxivity rare-earth nanoparticles coated with paramagnetic lanthanide complex shells and polyethylene glycol (PEGylated UCNPs@DTPA-Gd3+) are synthesized as dual-modality imaging contrast agents (CAs) for upconverting fluorescent and magnetic resonance dual-modality imaging. PEGylated UCNPs@DTPA-Gd3+ with sizes in the range of 32-86 nm are colloidally stable. They exhibit higher longitudinal relaxivity and transverse relaxivity in water (r1 and r2 values are 7.4 and 27.8 s-1 per mM Gd3+, respectively) than does commercial Gd-DTPA (r1 and r2 values of 3.7 and 4.6 s-1 per mM Gd3+, respectively). They are found to be biocompatible. In vitro cancer cell imaging shows good imaging contrast of PEGylated UCNPs@DTPA-Gd3+. In vivo upconversion fluorescent imaging and T1-weighted MRI show excellent enhancement of both fluorescent and MR signals in the livers of mice administered PEGylated UCNPs@DTPA-Gd3+. All the experimental results indicate that the synthesized PEGylated UCNPs@DTPA-Gd3+ present great potential for biomedical upconversion of fluorescent and magnetic resonance dual-modality imaging applications.

  17. Paramagnetic Spin Seebeck Effect

    NASA Astrophysics Data System (ADS)

    Wu, Stephen M.; Pearson, John E.; Bhattacharya, Anand

    2015-05-01

    We report the observation of the longitudinal spin Seebeck effect in paramagnetic insulators. By using a microscale on-chip local heater, we generate a large thermal gradient confined to the chip surface without a large increase in the total sample temperature. Using this technique at low temperatures (<20 K ), we resolve the paramagnetic spin Seebeck effect in the insulating paramagnets Gd3Ga5O12 (gadolinium gallium garnet) and DyScO3 (DSO), using either W or Pt as the spin detector layer. By taking advantage of the strong magnetocrystalline anisotropy of DSO, we eliminate contributions from the Nernst effect in W or Pt, which produces a phenomenologically similar signal.

  18. Paramagnetic spin seebeck effect.

    PubMed

    Wu, Stephen M; Pearson, John E; Bhattacharya, Anand

    2015-05-08

    We report the observation of the longitudinal spin Seebeck effect in paramagnetic insulators. By using a microscale on-chip local heater, we generate a large thermal gradient confined to the chip surface without a large increase in the total sample temperature. Using this technique at low temperatures (<20  K), we resolve the paramagnetic spin Seebeck effect in the insulating paramagnets Gd3Ga5O12 (gadolinium gallium garnet) and DyScO3 (DSO), using either W or Pt as the spin detector layer. By taking advantage of the strong magnetocrystalline anisotropy of DSO, we eliminate contributions from the Nernst effect in W or Pt, which produces a phenomenologically similar signal.

  19. Paramagnetic Spin Seebeck Effect

    SciTech Connect

    Wu, Stephen M.; Pearson, John E.; Bhattacharya, Anand

    2015-05-01

    We report the observation of the longitudinal spin Seebeck effect in paramagnetic insulators. By using a microscale on-chip local heater, we generate a large thermal gradient confined to the chip surface without a large increase in the total sample temperature. Using this technique at low temperatures (< 20 K), we resolve the paramagnetic spin Seebeck effect in the insulating paramagnets Gd3Ga5O12 (gadolinium gallium garnet) and DyScO3 (DSO), using either W or Pt as the spin detector layer. By taking advantage of the strong magnetocrystalline anisotropy of DSO, we eliminate contributions from the Nernst effect in W or Pt, which produces a phenomenologically similar signal.

  20. Liquid-crystalline dendrimer Cu(II) complexes and Cu(0) nanoclusters based on the Cu(II) complexes: An electron paramagnetic resonance investigation

    NASA Astrophysics Data System (ADS)

    Domracheva, N. E.; Mirea, A.; Schwoerer, M.; Torre-Lorente, L.; Lattermann, G.

    2007-07-01

    New nanostructured materials, namely, the liquid-crystalline copper(II) complexes that contain poly(propylene imine) dendrimer ligands of the first (ligand 1) and second (ligand 2) generations and which have a columnar mesophase and different copper contents (x = Cu/L), are investigated by EPR spectroscopy. The influence of water molecules and nitrate counterions on the magnetic properties of complex 2 (x = 7.3) is studied. It is demonstrated that water molecules can extract some of the copper ions from dendrimer complexes and form hexaaqua copper complexes with free ions. The dimer spectra of fully hydrated complex 2 (x = 7.3) are observed at temperatures T < 10 K. For this complex, the structure is identified and the distance between the copper ions is determined. It is shown that the nitrate counterion plays the role of a bridge between the hexaaqua copper(II) complex and the dendrimer copper(II) complex. The temperature-induced valence tautomerism attended by electron transport is revealed for the first time in blue dendrimer complexes 1 (x = 1.9) with a dimer structure. The activation energy for electron transport is estimated to be 0.35 meV. The coordination of the copper ion site (NO4) and the structural arrangement of green complexes 1 (x = 1.9) in the columnar mesophase are determined. Complexes of this type form linear chains in which nitrate counterions serve as bridges between copper centers. It is revealed that green complexes 1 (x = 1.9) dissolved in isotropic inert solvents can be oriented in the magnetic field (B 0 = 8000 G). The degree of orientation of these complexes is rather high (S z = 0.76) and close to that of systems with a complete ordering (S z = 1) in the magnetic field. Copper(0) nanoclusters prepared by reduction of complex 2 (x = 7.3) in two reducing agents (NaBH4, N2H4 · H2O) are examined. A model is proposed for a possible location of Cu(0) nanoclusters in a dendrimer matrix.

  1. Unitized paramagnetic salt thermometer

    SciTech Connect

    Abraham, B.M.

    1982-06-01

    The details of construction and assembly of a cerous magnesium nitrate (CMN) paramagnetic thermometer are presented. The thermometer is a small unit consisting of a primary, two secondaries, the salt pill, and thermal links. The thermometer calibration changes very little on successive coolings and is reliable to 35 mK. A typical calibration curve is also presented.

  2. Paramagnetic and Diamagnetic Materials

    ERIC Educational Resources Information Center

    Thompson, Frank

    2011-01-01

    Paramagnetic and diamagnetic materials are now generally known as the "Cinderella" materials of the magnetic world. However, susceptibility measurements made on these materials in the past have revealed many details about the molecular bonding and the atomic structure of the so-called "transition" elements. Indeed, the magnetic moment of neodymium…

  3. Paramagnetic and Diamagnetic Materials

    ERIC Educational Resources Information Center

    Thompson, Frank

    2011-01-01

    Paramagnetic and diamagnetic materials are now generally known as the "Cinderella" materials of the magnetic world. However, susceptibility measurements made on these materials in the past have revealed many details about the molecular bonding and the atomic structure of the so-called "transition" elements. Indeed, the magnetic moment of neodymium…

  4. Demonstrating Paramagnetism Using Liquid Nitrogen.

    ERIC Educational Resources Information Center

    Simmonds, Ray; And Others

    1994-01-01

    Describes how liquid nitrogen is attracted to the poles of neodymium magnets. Nitrogen is not paramagnetic, so the attraction suggests that the liquid nitrogen contains a small amount of oxygen, which causes the paramagnetism. (MVL)

  5. Demonstrating Paramagnetism Using Liquid Nitrogen.

    ERIC Educational Resources Information Center

    Simmonds, Ray; And Others

    1994-01-01

    Describes how liquid nitrogen is attracted to the poles of neodymium magnets. Nitrogen is not paramagnetic, so the attraction suggests that the liquid nitrogen contains a small amount of oxygen, which causes the paramagnetism. (MVL)

  6. Multifrequency pulsed electron paramagnetic resonance on metalloproteins.

    PubMed

    Lyubenova, Sevdalina; Maly, Thorsten; Zwicker, Klaus; Brandt, Ulrich; Ludwig, Bernd; Prisner, Thomas

    2010-02-16

    Metalloproteins often contain metal centers that are paramagnetic in some functional state of the protein; hence electron paramagnetic resonance (EPR) spectroscopy can be a powerful tool for studying protein structure and function. Dipolar spectroscopy allows the determination of the dipole-dipole interactions between metal centers in protein complexes, revealing the structural arrangement of different paramagnetic centers at distances of up to 8 nm. Hyperfine spectroscopy can be used to measure the interaction between an unpaired electron spin and nuclear spins within a distance of 0.8 nm; it therefore permits the characterization of the local structure of the paramagnetic center's ligand sphere with very high precision. In this Account, we review our laboratory's recent applications of both dipolar and hyperfine pulsed EPR methods to metalloproteins. We used pulsed dipolar relaxation methods to investigate the complex of cytochrome c and cytochrome c oxidase, a noncovalent protein-protein complex involved in mitochondrial electron-transfer reactions. Hyperfine sublevel correlation spectroscopy (HYSCORE) was used to study the ligand sphere of iron-sulfur clusters in complex I of the mitochondrial respiratory chain and substrate binding to the molybdenum enzyme polysulfide reductase. These examples demonstrate the potential of the two techniques; however, they also highlight the difficulties of data interpretation when several paramagnetic species with overlapping spectra are present in the protein. In such cases, further approaches and data are very useful to enhance the information content. Relaxation filtered hyperfine spectroscopy (REFINE) can be used to separate the individual components of overlapping paramagnetic species on the basis of differences in their longitudinal relaxation rates; it is applicable to any kind of pulsed hyperfine or dipolar spectroscopy. Here, we show that the spectra of the iron-sulfur clusters in complex I can be separated by this

  7. Acoustic paramagnetic logging tool

    DOEpatents

    Vail, III, William B.

    1988-01-01

    New methods and apparatus are disclosed which allow measurement of the presence of oil and water in geological formations using a new physical effect called the Acoustic Paramagnetic Logging Effect (APLE). The presence of petroleum in formation causes a slight increase in the earth's magnetic field in the vicinity of the reservoir. This is the phenomena of paramagnetism. Application of an acoustic source to a geological formation at the Larmor frequency of the nucleons present causes the paramagnetism of the formation to disappear. This results in a decrease in the earth3 s magnetic field in the vicinity of the oil bearing formation. Repetitively frequency sweeping the acoustic source through the Larmor frequency of the nucleons present (approx. 2 kHz) causes an amplitude modulation of the earth's magnetic field which is a consequence of the APLE. The amplitude modulation of the earth's magnetic field is measured with an induction coil gradiometer and provides a direct measure of the amount of oil and water in the excitation zone of the formation . The phase of the signal is used to infer the longitudinal relaxation times of the fluids present, which results in the ability in general to separate oil and water and to measure the viscosity of the oil present. Such measurements may be preformed in open boreholes and in cased well bores.

  8. Is the photon paramagnetic?

    SciTech Connect

    Perez Rojas, H.; Querts, E. Rodriguez

    2009-05-01

    A photon exhibits a tiny anomalous magnetic moment {mu}{sub {gamma}} due to its interaction with an external constant magnetic field in vacuum through the virtual electron-positron background. It is paramagnetic ({mu}{sub {gamma}}>0) in the whole region of transparency, i.e., below the first threshold energy for pair creation, and has a maximum near this threshold. The photon magnetic moment is different for eigenmodes polarized along and perpendicular to the magnetic field. Explicit expressions are given for {mu}{sub {gamma}} for the cases of photon energies smaller than and closer to the first pair creation threshold. The region beyond the first threshold is briefly discussed.

  9. Paramagnetic propellant orientation

    NASA Technical Reports Server (NTRS)

    Hendricks, R. C.

    1991-01-01

    Deep space or low earth orbital propellant tanks require a fluid orientation system prior to engine firing or transfer. Some propellants such as cryogenic hydrogen, oxygen, and air are paramagnetic and respond to electromagnetic fields. A simple magnetic scheme is described for propellant orientation and a video tape presentation is provided that demonstrates some effects of magnetic fields on liquid air and oxygen in a low gravity simulator using the Leidenfrost phenomenon. When these Leidenfrost drops intersect the field lines, their flight paths are altered, some directly into the poles, some to the edges, and others move out of the field.

  10. Spin-lattice relaxation of ligand nuclei in slowly reorienting paramagnetic complexes in the electronic doublet spin state ( S = {1}/{2}). A theoretical approach for strongly coupled two-spin systems

    NASA Astrophysics Data System (ADS)

    Benetis, Nikolas P.

    In this paper a general theory for treating the spin-lattice relaxation of a ligand nucleus (denoted by I) is derived for a metal complex in a doublet electron spin state ( S = {1}/{2}). The dipole-dipole SI interaction is treated for the case where the electron spin is also strongly coupled to the metal nucleus K. The SK interaction considered here is the hyperfine coupling, both scalar (SC) and dipolar (DD). The present theory is valid for slowly reorienting complexes in solution and can, furthermore, incorporate relaxation effects of the electron spin S, and the metal nucleus K due to processes which are faster than, and independent of, reorientation, i.e., for processes that fulfil the strong narrowing conditions. The effects of chemical exchange of the ligands and of anisotropic reorientation of the complex are also studied. Together with our previous studies of paramagnetic complexes with electron spin S ≧ 1, that have been recently reviewed by J. Kowalewski, L. Nordenskiöld, N. Benetis, and P. O. Westlund, ( Prog. NMR Spectrosc.17, 141 (1985)), the present work completes the elementary relaxation features of ligand nuclei of metal complexes in the slow motional regime. The present theory is shown to be more general than the theory of Bertini and co-workers ( J. Magn. Reson.59 , 213 (1984)), which can be obtained as a limit of the present approach by decoupling the reorientation from the motions of the S-K two spin system. The treatment of a strongly coupled two-spin system is emphasized since it provides a necessary step to the treatment of the relaxation of paramagnetic doublets.

  11. A paramagnetic molecular voltmeter

    NASA Astrophysics Data System (ADS)

    Surek, Jack T.; Thomas, David D.

    2008-01-01

    We have developed a general electron paramagnetic resonance (EPR) method to measure electrostatic potential at spin labels on proteins to millivolt accuracy. Electrostatic potential is fundamental to energy-transducing proteins like myosin, because molecular energy storage and retrieval is primarily electrostatic. Quantitative analysis of protein electrostatics demands a site-specific spectroscopic method sensitive to millivolt changes. Previous electrostatic potential studies on macromolecules fell short in sensitivity, accuracy and/or specificity. Our approach uses fast-relaxing charged and neutral paramagnetic relaxation agents (PRAs) to increase nitroxide spin label relaxation rate solely through collisional spin exchange. These PRAs were calibrated in experiments on small nitroxides of known structure and charge to account for differences in their relaxation efficiency. Nitroxide longitudinal ( R1) and transverse ( R2) relaxation rates were separated by applying lineshape analysis to progressive saturation spectra. The ratio of measured R1 increases for each pair of charged and neutral PRAs measures the shift in local PRA concentration due to electrostatic potential. Voltage at the spin label is then calculated using the Boltzmann equation. Measured voltages for two small charged nitroxides agree with Debye-Hückel calculations. Voltage for spin-labeled myosin fragment S1 also agrees with calculation based on the p K shift of the reacted cysteine.

  12. A Paramagnetic Molecular Voltmeter

    PubMed Central

    Surek, Jack T.; Thomas, David D.

    2008-01-01

    We have developed a general electron paramagnetic resonance (EPR) method to measure electrostatic potential at spin labels on proteins to millivolt accuracy. Electrostatic potential is fundamental to energy-transducing proteins like myosin, because molecular energy storage and retrieval is primarily electrostatic. Quantitative analysis of protein electrostatics demands a site-specific spectroscopic method sensitive to millivolt changes. Previous electrostatic potential studies on macromolecules fell short in sensitivity, accuracy and/or specificity. Our approach uses fast-relaxing charged and neutral paramagnetic relaxation agents (PRAs) to increase nitroxide spin label relaxation rate solely through collisional spin exchange. These PRAs were calibrated in experiments on small nitroxides of known structure and charge to account for differences in their relaxation efficiency. Nitroxide longitudinal (R1) and transverse (R2) relaxation rates were separated by applying lineshape analysis to progressive saturation spectra. The ratio of measured R1 increases for each pair of charged and neutral PRAs measures the shift in local PRA concentration due to electrostatic potential. Voltage at the spin label is then calculated using the Boltzmann equation. Measured voltages for two small charged nitroxides agree with Debye-Hückel calculations. Voltage for spin-labeled myosin fragment S1 also agrees with calculation based on the pK shift of the reacted cysteine. PMID:17964835

  13. Formation of a paramagnetic Al complex and extrusion of Fe during the reaction of (diiminepyridine)Fe with AlR3 (R = Me, Et).

    PubMed

    Scott, Jennifer; Gambarotta, Sandro; Korobkov, Ilia; Knijnenburg, Quinten; de Bruin, Bas; Budzelaar, Peter H M

    2005-12-14

    The reaction of the {2,6-[2,6-(iPr)2PhN=C(CH3)]2(C5H3N)}FeCl2 catalyst precursor with R3Al [R = Me, Et] afforded {2,6-[2,6-(iPr)2PhN=C(CH3)]2(C5H3N)}AlMe2 (1) and [eta4-LAl2Et3(mu-Cl)]Fe-(eta6-C7H8) (2), respectively. These paramagnetic species arises from both transmetalation, during which the strong terdentate ligand loses the Fe center, and reduction. The extent of reduction depends on the nature of the Al alkylating agent. The electrons necessary for the reduction are likely to be provided by cleavage of Fe-C bond of transient low-valent organo-Fe species.

  14. Influence of Ring-Expanded N-Heterocyclic Carbenes on the Structures of Half-Sandwich Ni(I) Complexes: An X-ray, Electron Paramagnetic Resonance (EPR), and Electron Nuclear Double Resonance (ENDOR) Study.

    PubMed

    Pelties, Stefan; Carter, Emma; Folli, Andrea; Mahon, Mary F; Murphy, Damien M; Whittlesey, Michael K; Wolf, Robert

    2016-11-07

    Potassium graphite reduction of the half-sandwich Ni(II) ring-expanded diamino/diamidocarbene complexes CpNi(RE-NHC)Br gave the Ni(I) derivatives CpNi(RE-NHC) (where RE-NHC = 6-Mes (1), 7-Mes (2), 6-MesDAC (3)) in yields of 40%-50%. The electronic structures of paramagnetic 1-3 were investigated by CW X-/Q-band electron paramagnetic resonance (EPR) and Q-band (1)H electron nuclear double resonance (ENDOR) spectroscopy. While small variations in the g-values were observed between the diaminocarbene complexes 1 and 2, pronounced changes in the g-values were detected between the almost isostructural species (1) and diamidocarbene species (3). These results highlight the sensitivity of the EPR g-tensor to changes in the electronic structure of the Ni(I) centers generated by incorporation of heteroatom substituents onto the backbone ring positions. Variable-temperature EPR analysis also revealed the presence of a second Ni(I) site in 3. The experimental g-values for these two Ni(I) sites detected by EPR in frozen solutions of 3 are consistent with resolution on the EPR time scale of the disordered components evident in the X-ray crystallographically determined structure and the corresponding density functional theory (DFT)-calculated g-tensor. Q-band (1)H ENDOR measurements revealed a small amount of unpaired electron spin density on the Cp rings, consistent with the calculated SOMO of complexes 1-3. The magnitude of the (1)H A values for 3 were also notably larger, compared to 1 and 2, again highlighting the influence of the diamidocarbene on the electronic properties of 3.

  15. Characterization of the manganese O2-evolving complex and the iron-quinone acceptor complex in photosystem II from a thermophilic cyanobacterium by electron paramagnetic resonance and X-ray absorption spectroscopy.

    PubMed

    McDermott, A E; Yachandra, V K; Guiles, R D; Cole, J L; Dexheimer, S L; Britt, R D; Sauer, K; Klein, M P

    1988-05-31

    The Mn donor complex in the S1 and S2 states and the iron-quinone acceptor complex (Fe2+-Q) in O2-evolving photosystem II (PS II) preparations from a thermophilic cyanobacterium, Synechococcus sp., have been studied with X-ray absorption spectroscopy and electron paramagnetic resonance (EPR). Illumination of these preparations at 220-240 K results in formation of a multiline EPR signal very similar to that assigned to a Mn S2 species observed in spinach PS II, together with g = 1.8 and 1.9 EPR signals similar to the Fe2+-QA- acceptor signals seen in spinach PS II. Illumination at 110-160 K does not produce the g = 1.8 or 1.9 EPR signals, nor the multiline or g = 4.1 EPR signals associated with the S2 state of PS II in spinach; however, a signal which peaks at g = 1.6 appears. The most probable assignment of this signal is an altered configuration of the Fe2+-QA- complex. In addition, no donor signal was seen upon warming the 140 K illuminated sample to 215 K. Following continuous illumination at temperatures between 140 and 215 K, the average X-ray absorption Mn K-edge inflection energy changes from 6550 eV for a dark-adapted (S1) sample to 6551 eV for the illuminated (S2) sample. The shift in edge inflection energy indicates an oxidation of Mn, and the absolute edge inflection energies indicate an average Mn oxidation state higher than Mn(II). Upon illumination a significant change was observed in the shape of the features associated with 1s to 3d transitions. The S1 spectrum resembles those of Mn(III) complexes, and the S2 spectrum resembles those of Mn(IV) complexes. The extended X-ray absorption fine structure (EXAFS) spectrum of the Mn complex is similar in the S1 and S2 states. Simulations indicate O or N ligands at 1.75 +/- 0.05 A, transition metal neighbor(s) at 2.73 +/- 0.05 A, which are assumed to be Mn, and terminal ligands which are probably N and O at a range of distances around 2.2 A. The Mn-O bond length of 1.75 A and the transition metal at 2.7 A

  16. Paramagnetic resonance and visible spectroscopic properties of binuclear Cu-Cu and Cu-Zn imidazolate-bridged complexes: effective model for active site of superoxide dismutase

    NASA Astrophysics Data System (ADS)

    Patel, R. N.; Kumar, Subodh; Pandeya, K. B.

    2000-12-01

    Syntheses of the imidazolate-bridged heterometallic binuclear copper-zinc complex [(glyala)Cu-im-Zn(glyala)]Na,where H 2glyala=glycylalanine, and im=imidazolate ion, has been achieved. X-band e.p.r and visible absorption spectra of the complex [(glyala)Cu-im-Zn(glyala)]Na at different pH values in frozen solution (50% aqueous DMSO, 77K) show that the imidazolate-bridged complex is stable in the pH range 7.15-10.50.

  17. Nuclear magnetic resonance and optical absorption spectroscopic studies on paramagnetic praseodymium(III) complexes with beta-diketone and heterocyclic amines.

    PubMed

    Ansari, A A; Ahmed, Zubair; Iftikhar, K

    2007-09-01

    The optical absorption spectra of [Pr(acac)(3)(H(2)O)(2)].H(2)O, [Pr(acac)(3)phen.H(2)O] and [Pr(acac)(3)bpy] (where acac is the anion of acetylacetone, phen is 1,10-phenanthroline and bpy is 2,2'-bipyridyl) have been analyzed in the visible region in a series of non-aqueous solvents (methanol, ethanol, isopropanol, chloroform, acetonitrile and pyridine). The complexes display four non-hypersensitive 4f-4f transitions ((3)P(2), (3)P(1)+(1)I(6), (3)P(0) and (1)D(2)) from the (3)H(4) ground state. The band shape of the transitions shows remarkable changes upon dissolving in different solvents. Distinctively different band shapes have been observed for phen and bpy complexes. The phen is more effective in producing changes and the splitting of the bands is more pronounced in phen complex since it is a stronger ligand and leads to stronger Pr-N(phen) bond. The splitting of the bands is indicative of partaking of f-orbitals in bonding. The NMR signals of heterocyclic amines have been shifted to high fields while the resonances due to acetylacetone moiety have moved to low fields which is the consequence of change in geometry of the complexes upon coordination of the heterocyclic amines and reflects the importance of geometric factor (3cos(2)theta-1) in changing sign of the shift and to a good approximation the shifts arise predominantly from the dipolar mechanism. The phen complexes have narrower line width than bpy complexes. The line broadening in the case of bpy complexes is suggestive of exchange between inter-converting forms. The bpy possesses some degree of rotational freedom about C(6)-C(6') bond and the two pyridine rings undergo scissoring motion with respect to each other.

  18. Optical absorption and NMR spectroscopic studies on paramagnetic neodymium(III) complexes with beta-diketone and heterocyclic amines. The environment effect on 4f-4f hypersensitive transitions.

    PubMed

    Ansari, A A; Irfanullah, M; Iftikhar, K

    2007-08-01

    The optical absorption spectra of [Nd(acac)3(H2O)2].H2O, [Nd(acac)3bpy] and [Nd(acac)3phen(H2O)2] (where acac=acetylacetone, bpy=2,2'-bipyridyl and phen=1,10-phenanthroline) complexes in the visible region, in a series of non-aqueous solvents (methanol, ethanol, isopropanol, chloroform, acetonitrile, pyridine, nitrobenzene and dimethylsulphoxide) have been analyzed. The transition 4G(5/2)<--4I(9/2) (Nd-VI) located near the middle of the visible region (17,500 cm(-1)) is hypersensitive. Its behavior is in sharp contrast to many other typically weak and consistently unvaried, normal 4f-4f transitions. The oscillator strength of this transition for the chelate as well as its adducts with phen and bpy in any of the solvent employed is larger than the oscillator strength of Nd3+ aqua-ion. It is most intense in pyridine for all the complexes studied and, therefore, pyridine is the most effective in promoting f-f spectral intensity. The band shape and oscillator strength of the hypersensitive transitions display pronounced changes as compared to Nd3+ aqua-ion. The band shapes of the hypersensitive transitions show remarkable changes on passing from aqueous solution to various non-aqueous solutions, which is the result of change in the environment about the Nd(III) ion in the various solutions and suggests change in the environment about the Nd(III) ion in the various solutions and suggests coordination of solvent molecule(s), in some cases. A comparative account of hypersensitivity in the present complexes with those of other adducts of Nd(beta-diketoenolate)3 with heterocyclic amines is discussed. The NMR signals of heterocyclic amines have been shifted to high fields while the resonances due to acetylacetone moiety have moved to low fields. The paramagnetic shift in the complexes is dipolar in nature.

  19. Paramagnetic nuclear magnetic resonance relaxation and molecular mechanics studies of the chloroperoxidase-indole complex: insights into the mechanism of chloroperoxidase-catalyzed regioselective oxidation of indole.

    PubMed

    Zhang, Rui; He, Qinghao; Chatfield, David; Wang, Xiaotang

    2013-05-28

    To unravel the mechanism of chloroperoxidase (CPO)-catalyzed regioselective oxidation of indole, we studied the structure of the CPO-indole complex using nuclear magnetic resonance (NMR) relaxation measurements and computational techniques. The dissociation constant (KD) of the CPO-indole complex was calculated to be approximately 21 mM. The distances (r) between protons of indole and the heme iron calculated via NMR relaxation measurements and molecular docking revealed that the pyrrole ring of indole is oriented toward the heme with its 2-H pointing directly at the heme iron. Both KD and r values are independent of pH in the range of 3.0-6.5. The stability and structure of the CPO-indole complex are also independent of the concentration of chloride or iodide ion. Molecular docking suggests the formation of a hydrogen bond between the NH group of indole and the carboxyl O of Glu 183 in the binding of indole to CPO. Simulated annealing of the CPO-indole complex using r values from NMR experiments as distance restraints reveals that the van der Waals interactions were much stronger than the Coulomb interactions in the binding of indole to CPO, indicating that the association of indole with CPO is primarily governed by hydrophobic rather than electrostatic interactions. This work provides the first experimental and theoretical evidence of the long-sought mechanism that leads to the "unexpected" regioselectivity of the CPO-catalyzed oxidation of indole. The structure of the CPO-indole complex will serve as a lighthouse in guiding the design of CPO mutants with tailor-made activities for biotechnological applications.

  20. Paramagnetic NMR Relaxation and Molecular Mechanics Studies of Chloroperoxidase-Indole Complex: Insights into the Mechanism of Chloroperoxidase-Catalyzed Regioselective Oxidation of Indole

    PubMed Central

    Zhang, Rui; He, Qinghao; Chatfield, David; Wang, Xiaotang

    2013-01-01

    To unravel the mechanism of CPO-catalyzed regioselective oxidation of indole, the structure of the CPO-indole complex was studied using NMR relaxation measurements and computational techniques. The dissociation constant (KD) of the CPO-indole complex was calculated to be approximately 21 mM. The distances (r) between protons of indole and the heme iron calculated from NMR relaxation measurements and molecular docking revealed that the pyrrole ring of indole is oriented toward the heme with its 2-H pointing directly at the heme iron. Both KD and r values are independent of pH in the range of 3.0–6.5. The stability and structure of the CPO-indole complex are also independent of the concentration of chloride/iodide ion. Molecular docking suggests the formation of a hydrogen bond between the N–H of indole and the carboxyl O of Glu 183 in the binding of indole to CPO. Simulated annealing of the CPO-indole complex using r values from NMR experiments as distance restraints reveals that the van der Waals interactions were much stronger than the Coulomb interactions in indole binding to CPO, indicating that the association of indole with CPO is primarily governed by hydrophobic rather than electrostatic interactions. This work provides the first experimental and theoretical evidence for the long-sought mechanism that leads to the “unexpected” regioselectivity of CPO-catalyzed oxidation of indole. The structure of the CPO-indole complex will serve as a lighthouse in guiding the design of CPO mutants with tailor-made activities for biotechnological applications. PMID:23634952

  1. Synthesis of Lipophilic Paramagnetic Contrast Agents.

    PubMed

    Baker, William C.; Choi, Michael J.; Hill, Daniel C.; Thompson, Julie L.; Petillo, Peter A.

    1999-04-16

    The facile, high-yielding synthesis of a series of macrocycles 7a-k in 75-100% yield is reported. The transformation of these compounds to their carboxymethylated analogues 8a-k in 75-90% yield and subsequent gadolinium complexes 9a-k provides a series of homologous neutral paramagnetic contrast agents (PCAs) with tunable lipophilicity. Alkylated cationic intermediates 6a-k are prepared in yields of 72-94% from glyoxal adduct of cyclen (5) and slight excesses of alkyl iodides. The methodology is selective for monoalkylation and amenable to large-scale synthesis.

  2. Sulfur donor ligand binding to ferric cytochrome P-450-CAM and myoglobin. Ultraviolet-visible absorption, magnetic circular dichroism, and electron paramagnetic resonance spectroscopic investigation of the complexes.

    PubMed

    Sono, M; Andersson, L A; Dawson, J H

    1982-07-25

    The binding of thiol, thiolate, thioether, and disulfide sulfur donor ligands to ferric cytochrome P-450-CAM and myoglobin has been investigated by UV-visible absorption, magnetic circular dichroism (MCD), and EPR spectroscopy. For ferric P-450, the binding of all sulfur donors is competitive with substrate binding. Addition of thiols to P-450 leads to interconvertible thiol or thiolate-bound species depending on the thiol acidity (pKa) and the solution ph; ligation of thiols lowers their pKa by about 4 units. In contrast, only the thiolate-bound form is seen for myoglobin regardless of thiol acidity or solution pH (5.5-11.0), indicating that the heme iron of myoglobin is less electron-rich than that of P-450. Thiolate ligands show much higher affinity (Kd approximately 10(-6) M) for ferric P-450 than do thiols (Kd approximately 10(-3) M). The affinity of thioethers for P-450 (Kd approximately 10(-3) M) is pH-independent (pH 5.5-9.0). The observed disulfide coordination to P-450 represents the first example of disulfide ligation to heme iron; no significant evidence for thioether or disulfide binding to myoglobin is seen. Except for the thiolate complexes, the UV-visible and MCD spectral properties of the other sulfur donor . P-450 complexes are similar to, although distinguishable from, those of native P-450. The ferric P-450 . thiolate complexes exhibit MCD spectra resembling that of ferrous P-450 . CO; both also exhibit unique hyperporphyrin (split Soret) UV-visible spectra. The EPR spectra of all P-450 complexes examined display very narrow spread g-values such as are characteristic of native P-450, indicating that the endogenous cysteinate axial ligand is retained upon complex formation. The dissimilarities observed between P-450 and myoglobin in their reactivity toward sulfur donor ligands at least partly reflect the variation in heme iron electron density resulting from their different endogenous axial ligands and may, in turn, help to explain their

  3. Structure and function of the manganese complex involved in photosynthetic oxygen evolution determined by x-ray adsorption spectroscopy and electron paramagnetic resonance spectroscopy

    SciTech Connect

    Guiles, R.D.

    1988-04-01

    Water is the terminal electron donor in the linear light-driven electron transport chain used by higher plants, cyanobacteria and green algae to fix carbon dioxide. The involvement of a membrane-bound manganese-containing protein complex has been demonstrated at the site of water oxidation within the photosystem II (PSII) reaction center. The photosynthetic oxidation of water to molecular oxygen is believed to involve intermediate S-states (S/sub 0//hor ellipsis/S/sub 4/), of the oxygen evolving complex (OEC). The use of multiline EPR signal associated with Mn and assigned to the S/sub 2/ state has greatly facilitated structural characterization of the OEC. This thesis contains a description of methods used to cryogenically stabilize PSII preparations suitable for x-ray absorption spectroscopy in the S/sub 1/, S/sub 2/ and S/sub 3/ states as well as a state induced by hydroxylamine resembling the S/sub 0/ state of the OEC. Studies of the Mn K-edges of PSII preparations indicate that a light-induced oxidation of Mn occurring during the S/sub 1/ ..-->.. S/sub 2/ state transition corresponds to a formal valence change from Mn(III) to Mn(IV). An analysis of the extended x-ray absorption fine structure (EXAFS) of the Mn complex within PSII preparations poised in the S/sub 1/, S/sub 2/, S/sub 3/ and hydroxylamine-induced S/sub 0/ states indicates that the four manganese present are organized as two di-..mu..-oxo bridged binuclear managanese complexes. An essential component of the analysis of the EXAFS was a parallel analysis of a set of crystallographically characterized multinuclear ..mu..-oxo bridged manganese complexes. Based on conclusions drawn from the analysis of the Mn K-edge and EXAFS of PSII preparations cryogenically stabilized in the S-states described above, a model for the mechanism of photosynthetic water oxidation is presented. 274 refs., 46 figs., 17 tabs.

  4. Charge transfer complexes of fullerenes containing C₆₀˙⁻ and C₇₀˙⁻ radical anions with paramagnetic Co(II)(dppe)₂Cl⁺ cations (dppe: 1,2-bis(diphenylphosphino)ethane).

    PubMed

    Konarev, Dmitri V; Troyanov, Sergey I; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

    2016-04-21

    The reduction of Co(II)(dppe)Cl2 with sodium fluorenone ketyl produces a red solution containing the Co(I) species. The dissolution of C60 in the obtained solution followed by the precipitation of crystals with hexane yields a salt {Co(I)(dppe)2(+)}(C60˙(-))·2C6H4Cl2 and a novel complex {Co(dppe)2Cl}(C60) (). With C70, only the crystals of {Co(dppe)2Cl}(C70)·0.5C6H4Cl2 () are formed. Complex contains zig-zag fullerene chains whereas closely packed double chains are formed from fullerenes in . According to the optical spectra and magnetic data charge transfer occurs in both and with the formation of the Co(II)(dppe)2Cl(+) cations and the C60˙(-) or C70˙(-) radical anions. In spite of the close packing in crystals, C60˙(-) or C70˙(-) retain their monomeric form at least down to 100 K. The effective magnetic moments of and of 1.98 and 2.27μB at 300 K, respectively, do not attain the value of 2.45μB expected for the system with two non-interacting S = 1/2 spins at full charge transfer to fullerenes. Most probably diamagnetic {Co(I)(dppe)2Cl}(0) and neutral fullerenes are partially preserved in the samples which can explain the weak magnetic coupling of spins and the absence of fullerene dimerization in both complexes. The EPR spectra of and show asymmetric signals approximated by several lines with g-factors ranging from 2.0009 to 2.3325. These signals originate from the exchange interaction between the paramagnetic Co(II)(dppe)2Cl(+) cations and the fullerene˙(-) radical anions.

  5. NMR paramagnetic relaxation due to the S=5/2 complex, Fe(III)-(tetra-p-sulfonatophenyl)porphyrin: central role of the tetragonal fourth-order zero-field splitting interaction.

    PubMed

    Schaefle, Nathaniel; Sharp, Robert

    2005-05-08

    The metalloporphyrins, Me-TSPP [Me=Cr(III), Mn(III), Mn(II), Fe(III), and TSPP=meso-(tetra-p-sulfonatophenyl)porphyrin], which possess electron spins S=3/2, 2, 5/2, and 5/2, respectively, comprise an important series of model systems for mechanistic studies of NMR paramagnetic relaxation enhancement (NMR-PRE). For these S>1/2 spin systems, the NMR-PRE depends critically on the detailed form of the zero-field splitting (zfs) tensor. We report the results of experimental and theoretical studies of the NMR relaxation mechanism associated with Fe(III)-TSPP, a spin 5/2 complex for which the overall zfs is relatively large (D approximately = 10 cm(-1)). A comparison of experimental data with spin dynamics simulations shows that the primary determinant of the shape of the magnetic relaxation dispersion profile of the water proton R1 is the tetragonal fourth-order component of the zfs tensor. The relaxation mechanism, which has not previously been described, is a consequence of zfs-induced mixing of the spin eigenfunctions of adjacent Kramers doublets. We have also investigated the magnetic-field dependence of electron-spin relaxation for S=5/2 in the presence of a large zfs, such as occurs in Fe(III)-TSPP. Calculations show that field dependence of this kind is suppressed in the vicinity of the zfs limit, in agreement with observation.

  6. Paramagnetic Precipitates May Raise Supercurrent

    NASA Technical Reports Server (NTRS)

    Collings, E. W.

    1985-01-01

    Addition of Mn to Ti/Nb superconducting alloy increases critical current. Adding Mn to Ti/Nb alloy has little effect on major superconducting phase, but confers strong paramagnetic susceptibility on alpha-phase particles. beta-phase particles become stronger flux pinners, resulting in increase in critical current.

  7. Paramagnetic Precipitates May Raise Supercurrent

    NASA Technical Reports Server (NTRS)

    Collings, E. W.

    1985-01-01

    Addition of Mn to Ti/Nb superconducting alloy increases critical current. Adding Mn to Ti/Nb alloy has little effect on major superconducting phase, but confers strong paramagnetic susceptibility on alpha-phase particles. beta-phase particles become stronger flux pinners, resulting in increase in critical current.

  8. X-Band Electron Paramagnetic Resonance Comparison of Mononuclear Mn(IV)-oxo and Mn(IV)-hydroxo Complexes and Quantum Chemical Investigation of Mn(IV) Zero-Field Splitting.

    PubMed

    Leto, Domenick F; Massie, Allyssa A; Colmer, Hannah E; Jackson, Timothy A

    2016-04-04

    X-band electron paramagnetic resonance (EPR) spectroscopy was used to probe the ground-state electronic structures of mononuclear Mn(IV) complexes [Mn(IV)(OH)2(Me2EBC)](2+) and [Mn(IV)(O)(OH)(Me2EBC)](+). These compounds are known to effect C-H bond oxidation reactions by a hydrogen-atom transfer mechanism. They provide an ideal system for comparing Mn(IV)-hydroxo versus Mn(IV)-oxo motifs, as they differ by only a proton. Simulations of 5 K EPR data, along with analysis of variable-temperature EPR signal intensities, allowed for the estimation of ground-state zero-field splitting (ZFS) and (55)Mn hyperfine parameters for both complexes. From this analysis, it was concluded that the Mn(IV)-oxo complex [Mn(IV)(O)(OH)(Me2EBC)](+) has an axial ZFS parameter D (D = +1.2(0.4) cm(-1)) and rhombicity (E/D = 0.22(1)) perturbed relative to the Mn(IV)-hydroxo analogue [Mn(IV)(OH)2(Me2EBC)](2+) (|D| = 0.75(0.25) cm(-1); E/D = 0.15(2)), although the complexes have similar (55)Mn values (a = 7.7 and 7.5 mT, respectively). The ZFS parameters for [Mn(IV)(OH)2(Me2EBC)](2+) were compared with values obtained previously through variable-temperature, variable-field magnetic circular dichroism (VTVH MCD) experiments. While the VTVH MCD analysis can provide a reasonable estimate of the magnitude of D, the E/D values were poorly defined. Using the ZFS parameters reported for these complexes and five other mononuclear Mn(IV) complexes, we employed coupled-perturbed density functional theory (CP-DFT) and complete active space self-consistent field (CASSCF) calculations with second-order n-electron valence-state perturbation theory (NEVPT2) correction, to compare the ability of these two quantum chemical methods for reproducing experimental ZFS parameters for Mn(IV) centers. The CP-DFT approach was found to provide reasonably acceptable values for D, whereas the CASSCF/NEVPT2 method fared worse, considerably overestimating the magnitude of D in several cases. Both methods were poor in

  9. Effect of the synergistic anion on electron paramagnetic resonance spectra of iron-transferrin anion complexes is consistent with bidentate binding of the anion.

    PubMed Central

    Dubach, J; Gaffney, B J; More, K; Eaton, G R; Eaton, S S

    1991-01-01

    Continuous wave (cw) X-band EPR spectra at approximately 90 K were obtained for iron-transferrin-anion complexes with 18 anions. Each anion had a carboxylate group and at least one other polar moiety. As the second polar group was varied from hydroxyl to carbonyl to amine to carboxylate, the EPR spectra changed from a dominant signal at g' approximately 4.3 with a second smaller peak at g' approximately 9 to a broad signal with intensity between g' approximately 5 and 7. Computer simulation indicated that the changes in the EPR spectra were due to changes in the zero field splitting parameter ratio, E/D, from approximately 1/3 for carbonate anion to approximately 0.04 for malonate anion. Observation of iron-13C coupling in the electron spin echo envelope modulation (ESEEM) for iron transferrin [1-13C]pyruvate indicated that the carboxylate group was bound to the iron. It is proposed that all of the anions behave as bidentate ligands, with coordination to the iron through both the carboxylate and proximal groups, and the carboxyl group serves as a bridge between the iron and a positively charged group on the protein. PMID:1651123

  10. Electron paramagnetic resonance studies in neutron-irradiated silicon

    NASA Astrophysics Data System (ADS)

    Corbett, James W.; Kleinhenz, Richard L.; En, Wu; Zhi-pu, You

    1982-08-01

    Electron paramagnetic resonance studies of neutron-irradiated silicon are surveyed, both as being of interest per se and as related to transmutation doping. The emerging panorama progressing from vacancy- and interstitial-related point defects to agglomerates visible in the electron microscope is described. Intrinsic and impurity-driven partial dissociation of defect complexes is discussed.

  11. Electron Paramagnetic Resonance Retrospective Dosimetry

    SciTech Connect

    Romanyukha, Alex; Trompier, Francois

    2011-05-05

    Necessity for, principles of, and general concepts of the electron paramagnetic resonance (EPR) retrospective dosimetry are presented. Also presented and given in details are examples of EPR retrospective dosimetry applications in tooth enamel, bone, and fingernails with focus on general approaches for solving technical and methodological problems. Advantages, drawbacks, and possible future developments are discussed and an extensive bibliography on EPR retrospective dosimetry is provided.

  12. Site-directed spin labeling electron paramagnetic resonance study of the calcium-induced structural transition in the N-domain of human cardiac troponin C complexed with troponin I.

    PubMed

    Ueki, Shoji; Nakamura, Motoyoshi; Komori, Tomotaka; Arata, Toshiaki

    2005-01-11

    Calcium-induced structural transition in the amino-terminal domain of troponin C (TnC) triggers skeletal and cardiac muscle contraction. The salient feature of this structural transition is the movement of the B and C helices, which is termed the "opening" of the N-domain. This movement exposes a hydrophobic region, allowing interaction with the regulatory domain of troponin I (TnI) as can be seen in the crystal structure of the troponin ternary complex [Takeda, S., Yamashita, A., Maeda, K., and Maeda, Y. (2003) Nature 424, 35-41]. In contrast to skeletal TnC, Ca(2+)-binding site I (an EF-hand motif that consists of an A helix-loop-B helix motif) is inactive in cardiac TnC. The question arising from comparisons with skeletal TnC is how both helices move according to Ca(2+) binding or interact with TnI in cardiac TnC. In this study, we examined the Ca(2+)-induced movement of the B and C helices relative to the D helix in a cardiac TnC monomer state and TnC-TnI binary complex by means of site-directed spin labeling electron paramagnetic resonance (EPR). Doubly spin-labeled TnC mutants were prepared, and the spin-spin distances were estimated by analyzing dipolar interactions with the Fourier deconvolution method. An interspin distance of 18.4 A was estimated for mutants spin labeled at G42C on the B helix and C84 on the D helix in a Mg(2+)-saturated monomer state. The interspin distance between Q58C on the C helix and C84 on the D helix was estimated to be 18.3 A under the same conditions. Distance changes were observed by the addition of Ca(2+) ions and the formation of a complex with TnI. Our data indicated that the C helix moved away from the D helix in a distinct Ca(2+)-dependent manner, while the B helix did not. A movement of the B helix by interaction with TnI was observed. Both Ca(2+) and TnI were also shown to be essential for the full opening of the N-domain in cardiac TnC.

  13. The effect of a paramagnetic metal ion within a molecule: comparison of the structurally identical paramagnetic [3,3-Fe(1,2-C2B9H11)2]- with the diamagnetic [3,3-Co(1,2-C2B9H11)2]- sandwich complexes.

    PubMed

    Cioran, Ana M; Teixidor, Francesc; Viñas, Clara

    2015-02-14

    Derivatives of the ferrabisdicarbollide [3,3'-Fe(1,2-C(2)B(9)H(11))(2)](-) have been produced starting from the zwitterion [3,3'-Fe(8-(OCH(2)CH(2))(2)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))], 1, upon reaction with nucleophiles: alkoxides, halides and hydrosulfide ions HS(-). The result has been the preparation of [3,3'-Fe(8-(OCH(2)CH(2))(2)R/X-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))] (R = OMe, [2](-); OEt, [3](-); OCH(2)CH(2)OCH(3), [4](-); and X = Cl, [5](-); Br, [6](-); I, [7](-); and SH, [8](-)). The reaction behavior of is comparable to the well-studied cobalt equivalent, [3,3'-Co(8-(OCH(2)CH(2))2-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))], and the yields and stability of the resulting complexes are similar. These results are relevant taking into account that [3,3'-Fe(1,2-C(2)B(9)H(11))(2))(-) is a paramagnetic anion. Implications of this are observed in the (11)B-, (1)H and (13)C NMR spectra of [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-) and [3,3'-Fe(1,2-C(2)B(9)H(11))(2)](-) that having identical sandwich molecular structures and the same negative charge have absolutely different widths of the NMR field, between 15 and -25 ppm for [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-) and in the range 150 to -550 ppm for [3,3'-Fe(1,2-C(2)B(9)H(11))(2)](-). The sharpness of both spectra is on the other hand comparable, although no B-H couplings are observed in the Fe metallacarborane or its derivatives. Remarkable is the comparative influence vs. [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-) of replacing Co by Fe on the elements of the cluster layer nearest to the metal. The two equivalent C cluster (Cc) atoms are influenced at 36 840 Hz, the two equivalent B atoms that are adjacent to the two Cc are influenced at 38 157 Hz and the single B that is adjacent to the two B atoms is influenced at 44 062 Hz. Remarkable is the similar influence on B and on C, taking into account that the values have been obtained from two distinct NMR spectra of (11)B and (13)C. The {(11)B-(11)B} COSY NMR and {(1)H

  14. A new paramagnetically shifted imaging probe for MRI

    PubMed Central

    Senanayake, P. Kanthi; Rogers, Nicola J.; Finney, Katie‐Louise N.A.; Harvey, Peter; Funk, Alexander M.; Wilson, J. Ian; O'Hogain, Dara; Maxwell, Ross; Parker, David

    2016-01-01

    Purpose To develop and characterize a new paramagnetic contrast agent for molecular imaging by MRI. Methods A contrast agent was developed for direct MRI detection through the paramagnetically shifted proton magnetic resonances of two chemically equivalent tert‐butyl reporter groups within a dysprosium(III) complex. The complex was characterized in phantoms and imaged in physiologically intact mice at 7 Tesla (T) using three‐dimensional (3D) gradient echo and spectroscopic imaging (MRSI) sequences to measure spatial distribution and signal frequency. Results The reporter protons reside ∼6.5 Å from the paramagnetic center, resulting in fast T 1 relaxation (T 1 = 8 ms) and a large paramagnetic frequency shift exceeding 60 ppm. Fast relaxation allowed short scan repetition times with high excitation flip angle, resulting in high sensitivity. The large dipolar shift allowed direct frequency selective excitation and acquisition of the dysprosium(III) complex, independent of the tissue water signal. The biokinetics of the complex were followed in vivo with a temporal resolution of 62 s following a single, low‐dose intravenous injection. The lower concentration limit for detection was ∼23 μM. Through MRSI, the temperature dependence of the paramagnetic shift (0.28 ppm.K−1) was exploited to examine tissue temperature variation. Conclusions These data demonstrate a new MRI agent with the potential for physiological monitoring by MRI. Magn Reson Med 77:1307–1317, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. PMID:26922918

  15. Magic angle spinning NMR of paramagnetic proteins.

    PubMed

    Knight, Michael J; Felli, Isabella C; Pierattelli, Roberta; Emsley, Lyndon; Pintacuda, Guido

    2013-09-17

    Metal ions are ubiquitous in biochemical and cellular processes. Since many metal ions are paramagnetic due to the presence of unpaired electrons, paramagnetic molecules are an important class of targets for research in structural biology and related fields. Today, NMR spectroscopy plays a central role in the investigation of the structure and chemical properties of paramagnetic metalloproteins, linking the observed paramagnetic phenomena directly to electronic and molecular structure. A major step forward in the study of proteins by solid-state NMR came with the advent of ultrafast magic angle spinning (MAS) and the ability to use (1)H detection. Combined, these techniques have allowed investigators to observe nuclei that previously were invisible in highly paramagnetic metalloproteins. In addition, these techniques have enabled quantitative site-specific measurement of a variety of long-range paramagnetic effects. Instead of limiting solid-state NMR studies of biological systems, paramagnetism provides an information-rich phenomenon that can be exploited in these studies. This Account emphasizes state-of-the-art methods and applications of solid-state NMR in paramagnetic systems in biological chemistry. In particular, we discuss the use of ultrafast MAS and (1)H-detection in perdeuterated paramagnetic metalloproteins. Current methodology allows us to determine the structure and dynamics of metalloenzymes, and, as an example, we describe solid-state NMR studies of microcrystalline superoxide dismutase, a 32 kDa dimer. Data were acquired with remarkably short times, and these experiments required only a few milligrams of sample.

  16. Demonstrations on Paramagnetism with an Electronic Balance.

    ERIC Educational Resources Information Center

    Cortel, Adolf

    1998-01-01

    A paramagnetic substance is attracted by a magnetic field with a force proportional to its magnetic susceptibility which is related to the number of unpaired electrons in the atoms. Data are used to establish oxidation states and bonding properties. Describes a simple setup to demonstrate the paramagnetism of common inorganic compounds. (DKM)

  17. Magnetic flocculation of paramagnetic particles

    SciTech Connect

    Tsouris, C.; Scott, T.C.

    1994-09-01

    An experimental apparatus has been assembled for the flocculation study of paramagnetic particles under the influence of a strong magnetic field. A magnetic field of strength up to 6 T is generated by a cryogenic magnet operating near liquid helium temperatures. Experimental information is obtained from fluctuation and intensity measurements of light passing through a particle suspension located in a uniform magnetic field. Particle flocculation is described by a Brownian flocculation model in which hydrodynamic, van der Waals, double-layer, and magnetic forces are incorporated for the estimation of the particle flocculation rate. A population-balance model is employed in conjunction with the flocculation model to predict the evolution of the particle size and composition or magnetic susceptibility with time. The effects of magnetic-field strength, magnetic susceptibility of the particles, particle size, and zeta potential are investigated. Results show that particle size and magnetic susceptibility each play an important role in the selective flocculation of particles of different properties.

  18. Paramagnetic Ligand Tagging To Identify Protein Binding Sites

    PubMed Central

    2015-01-01

    Transient biomolecular interactions are the cornerstones of the cellular machinery. The identification of the binding sites for low affinity molecular encounters is essential for the development of high affinity pharmaceuticals from weakly binding leads but is hindered by the lack of robust methodologies for characterization of weakly binding complexes. We introduce a paramagnetic ligand tagging approach that enables localization of low affinity protein–ligand binding clefts by detection and analysis of intermolecular protein NMR pseudocontact shifts, which are invoked by the covalent attachment of a paramagnetic lanthanoid chelating tag to the ligand of interest. The methodology is corroborated by identification of the low millimolar volatile anesthetic interaction site of the calcium sensor protein calmodulin. It presents an efficient route to binding site localization for low affinity complexes and is applicable to rapid screening of protein–ligand systems with varying binding affinity. PMID:26289584

  19. Paramagnetic Enhancement of Nuclear Spin-Spin Coupling.

    PubMed

    Cherry, Peter John; Rouf, Syed Awais; Vaara, Juha

    2017-03-14

    We present a derivation and computations of the paramagnetic enhancement of the nuclear magnetic resonance (NMR) spin-spin coupling, which may be expressed in terms of the hyperfine coupling (HFC) and (for systems with multiple unpaired electrons) zero-field splitting (ZFS) tensors. This enhancement is formally analogous to the hyperfine contributions to the NMR shielding tensor as formulated by Kurland and McGarvey. The significance of the spin-spin coupling enhancement is demonstrated by using a combination of density-functional theory and correlated ab initio calculations, to determine the HFC and ZFS tensors, respectively, for two paramagnetic 3d metallocenes, a Cr(II)(acac)2 complex, a Co(II) pyrazolylborate complex, and a lanthanide system, Gd-DOTA. Particular attention is paid to relativistic effects in HFC tensors, which are calculated using two methods: a nonrelativistic method supplemented by perturbational spin-orbit coupling corrections, and a fully relativistic, four-component matrix-Dirac-Kohn-Sham approach. The paramagnetic enhancement lacks a direct dependence on the distance between the coupled nuclei, and represents more the strength and orientation of the individual hyperfine couplings of the two nuclei to the spin density distribution. Therefore, the enhancement gains relative importance as compared to conventional coupling as the distance between the nuclei increases, or generally in the cases where the conventional coupling mechanisms result in a small value. With the development of the experimental techniques of paramagnetic NMR, the more significant enhancements, e.g., of the (13)C(13)C couplings in the Gd-DOTA complex (as large as 9.4 Hz), may eventually become important.

  20. Ultrasensitive proteome analysis using paramagnetic bead technology

    PubMed Central

    Hughes, Christopher S; Foehr, Sophia; Garfield, David A; Furlong, Eileen E; Steinmetz, Lars M; Krijgsveld, Jeroen

    2014-01-01

    In order to obtain a systems-level understanding of a complex biological system, detailed proteome information is essential. Despite great progress in proteomics technologies, thorough interrogation of the proteome from quantity-limited biological samples is hampered by inefficiencies during processing. To address these challenges, here we introduce a novel protocol using paramagnetic beads, termed Single-Pot Solid-Phase-enhanced Sample Preparation (SP3). SP3 provides a rapid and unbiased means of proteomic sample preparation in a single tube that facilitates ultrasensitive analysis by outperforming existing protocols in terms of efficiency, scalability, speed, throughput, and flexibility. To illustrate these benefits, characterization of 1,000 HeLa cells and single Drosophila embryos is used to establish that SP3 provides an enhanced platform for profiling proteomes derived from sub-microgram amounts of material. These data present a first view of developmental stage-specific proteome dynamics in Drosophila at a single-embryo resolution, permitting characterization of inter-individual expression variation. Together, the findings of this work position SP3 as a superior protocol that facilitates exciting new directions in multiple areas of proteomics ranging from developmental biology to clinical applications. PMID:25358341

  1. Solid-State NMR Study of Paramagnetic Bis(alaninato-κ(2)N,O)copper(II) and Bis(1-amino(cyclo)alkane-1-carboxylato-κ(2)N,O)copper(II) Complexes: Reflection of Stereoisomerism and Molecular Mobility in (13)C and (2)H Fast Magic Angle Spinning Spectra.

    PubMed

    Szalontai, Gábor; Csonka, Róbert; Speier, Gábor; Kaizer, József; Sabolović, Jasmina

    2015-05-18

    Solid-state stereochemistry and mobility of paramagnetic copper(II) complexes formed by aliphatic amino acids (l-alanine, d,l-alanine, 1-amino-2-methyl-alanine) and 1-amino(cyclo)alkane-1-carboxylic acids (alkane = propane, butane, pentane, hexane) as bidentate ligands has been studied by (13)C and (2)H solid-state fast magic angle spinning (MAS) NMR spectroscopy. We examined the prospective method to characterize solid-state paramagnetic compounds in a routine way. Both (13)C and (2)H MAS spectra can distinguish d,l and l,l diastereomers of natural and polydeuterated bis([Dn]alaninato)copper(II) (n = 0, 2, 8) complexes with axial and/or equatorial methyl positions (conformations) primarily due to different Fermi-contact (FC) contributions. The three-bond hyperfine couplings clearly show Karplus-like dependence on the torsional angles which turned out to be a useful assignment aid. Density functional theory calculations of the FC term and crystal structures were also used to aid the final assignments. The correlations obtained for bis(alaninato-κ(2)N,O)copper(II) complexes were successfully used to characterize other complexes. The usefulness of the (2)H MAS spectra of the deuterated complexes was underlined. Even the spectra of the easily exchangeable amine protons contained essential stereochemical information. In the case of a dimer structure of bis(1-aminohexane-1-carboxylato-κ(2)N,O)copper(II) both the (13)C and (2)H resolutions were good enough to confirm the presence of the cis and trans forms in the asymmetric unit. With regard to the internal solid-state motions in the crystal lattice, the obtained quadrupolar tensor parameters were similar for the d,l- and l,l-alaninato isomers and also for the cis-trans forms suggesting similar crystal packing effects, static amine deuterons involved in hydrogen bonding, and fast rotating methyl groups.

  2. Protein structure determination with paramagnetic solid-state NMR spectroscopy.

    PubMed

    Sengupta, Ishita; Nadaud, Philippe S; Jaroniec, Christopher P

    2013-09-17

    +)-tagged GB1 mutants to rapidly determine the global protein fold in a de novo fashion. Remarkably, these studies required quantitative measurements of only approximately four or five backbone amide (15)N longitudinal paramagnetic relaxation enhancements per residue, in the complete absence of the usual internuclear distance restraints. Importantly, this paramagnetic solid-state NMR methodology is general and can be directly applied to larger proteins and protein complexes for which a significant fraction of the signals can be assigned in standard 2D and 3D MAS NMR chemical shift correlation spectra.

  3. Dual excitation acoustic paramagnetic logging tool

    DOEpatents

    Vail, W.B. III.

    1989-02-14

    New methods and apparatus are disclosed which allow measurement of the presence of oil and water in geological formations using a new physical effect called the Acoustic Paramagnetic Logging Effect (APLE). The presence of petroleum in formation causes a slight increase in the earth's magnetic field in the vicinity of the reservoir. This is the phenomena of paramagnetism. Application of an acoustic source to a geological formation at the Larmor frequency of the nucleons present causes the paramagnetism of the formation to disappear. This results in a decrease in the earth's magnetic field in the vicinity of the oil bearing formation. Repetitively frequency sweeping the acoustic source through the Larmor frequency of the nucleons present (approx. 2 kHz) causes an amplitude modulation of the earth's magnetic field which is a consequence of the APLE. The amplitude modulation of the earth's magnetic field is measured with an induction coil gradiometer and provides a direct measure of the amount of oil and water in the excitation zone of the formation. The phase of the signal is used to infer the longitudinal relaxation times of the fluids present, which results in the ability in general to separate oil and water and to measure the viscosity of the oil present. Such measurements may be performed in open boreholes and in cased well bores. The Dual Excitation Acoustic Paramagnetic Logging Tool employing two acoustic sources is also described. 6 figs.

  4. Pseudo-spin paramagnetism in graphene

    SciTech Connect

    Koshino, Mikito; Ando, Tsuneya

    2011-12-23

    We calculate the orbital diamagnetic susceptibility of monolayer graphene with an energy gap. The valley pseudo-spin produces paramagnetic susceptibility analogous to contribution from real spin, and explains the origin of a singular orbital magnetism at Dirac point of monolayer graphene.

  5. Paramagnetic ellipsoidal microswimmer in a magnetic field

    NASA Astrophysics Data System (ADS)

    Sandoval, Mario; Fan, Louis; Pak, On Shun

    We study the two-dimensional Brownian dynamics of an ellipsoidal paramagnetic microswimmer moving at low-Reynolds-number and subject to a magnetic field. Its corresponding mean-square displacement tensor showing the effect of particles's shape, activity and magnetic field, on the microswimmer's diffusion is analytically obtained. A comparison among analytical and computational results is also made and we obtain excellent agreement.

  6. Dual excitation acoustic paramagnetic logging tool

    DOEpatents

    Vail, III, William B.

    1989-01-01

    New methods and apparatus are disclosed which allow measurement of the presence of oil and water in gelogical formations using a new physical effect called the Acoustic Paramagnetic Logging Effect (APLE). The presence of petroleum in formation causes a slight increase in the earth's magnetic field in the vicinity of the reservoir. This is the phenomena of paramagnetism. Application of an acoustic source to a geological formation at the Larmor frequency of the nucleous present causes the paramagnetism of the formation to disappear. This results in a decrease in the earth's magnetic field in the vicinity of the oil bearing formation. Repetitively frequency sweeping the acoustic source through the Larmor frequency of the nucleons present (approx. 2 kHz) causes an amplitude modulation of the earth's magnetic field which is a consequence of the APLE. The amplitude modulation of the earth's magnetic field is measured with an induction coil gradiometer and provides a direct measure of the amount of oil and water in the excitation zone of the formation. The phase of the signal is used to infer the longitudinal relaxation times of the fluids present, which results in the ability in general to separate oil and water and to measure the viscosity of the oil present. Such measurements may be preformed in open boreholes and in cased well bores. The Dual Excitation Acoustic Paramagnetic Logging Tool employing two acoustic sources is also described.

  7. Collective modes in cold paramagnetic gases

    SciTech Connect

    Andreeva, T L; Rubin, P L

    2014-02-28

    We have obtained a condition for the emergence of spin waves in paramagnetic gases Re >> ImÂ, which is fulfilled only at temperatures of the order of 1 μK. (laser applications and other topics in quantum electronics)

  8. A comparison of the effects of symmetry and magnetoanisotropy on paramagnetic relaxation in related dysprosium single ion magnets.

    PubMed

    Williams, Ursula J; Mahoney, Brian D; DeGregorio, Patrick T; Carroll, Patrick J; Nakamaru-Ogiso, Eiko; Kikkawa, James M; Schelter, Eric J

    2012-06-07

    Dysprosium complexes of the tmtaa(2-) ligand were synthesized and characterized by X-band EPR and magnetism studies. Both complexes demonstrate magnetoanisotropy and slow paramagnetic relaxation. Comparison of these compounds with the seminal phthalocyanine complex [Dy(Pc)(2)](-) shows the azaannulide complexes are more susceptible to relaxation through non-thermal pathways.

  9. Cut and paste RNA for nuclear magnetic resonance, paramagnetic resonance enhancement, and electron paramagnetic resonance structural studies.

    PubMed

    Duss, Olivier; Diarra Dit Konté, Nana; Allain, Frédéric H-T

    2015-01-01

    RNA is a crucial regulator involved in most molecular processes of life. Understanding its function at the molecular level requires high-resolution structural information. However, the dynamic nature of RNA complicates structure determination because crystallization is often not possible or can result in crystal-packing artifacts resulting in nonnative structures. To study RNA and its complexes in solution, we described an approach in which large multi-domain RNA or protein-RNA complex structures can be determined at high resolution from isolated domains determined by nuclear magnetic resonance (NMR) spectroscopy, and then constructing the entire macromolecular structure using electron paramagnetic resonance (EPR) long-range distance constraints. Every step in this structure determination approach requires different types of isotope or spin-labeled RNAs. Here, we present a simple modular RNA cut and paste approach including protocols to generate (1) small isotopically labeled RNAs (<10 nucleotides) for NMR structural studies, which cannot be obtained by standard protocols, (2) large segmentally isotope and/or spin-labeled RNAs for diamagnetic NMR and paramagnetic relaxation enhancement NMR, and (3) large spin-labeled RNAs for pulse EPR spectroscopy.

  10. Paramagnetic carbon-13 shifts induced by the free radical tempo. 2. Nitrogen heterocycles

    SciTech Connect

    Qui, Z.W.; Grant, D.M.; Pugmire, R.J.

    1984-02-08

    With use of the free radical Tempo as a shift and relaxation reagent, both paramagnetic shifts and spin-lattice relaxation rates of nitrogen heterocycles are reported. Paramagnetic shifts of these compounds are larger than the corresponding shifts of the aromatic hydrocarbons, indicating a stronger interaction between nitrogen heterocyclic compounds and Tempo. Paramagnetic shifts increase with the number of nitrogen atoms per molecule. For pyridine type compounds, both shift and relaxation data show that the stronger interaction is not at the adjacent positions to the nitrogen atoms. It would appear in these heterocyclic complexes with Tempo that the nitrogen atoms tend to orient away from the N-O group in Tempo. In contrast, imidazole and indole exhibit a much stronger interaction with the Tempo due to hydrogen bond formation, and the positions near the N-H group exhibit larger paramagnetic shifts and relaxation rates. An approximate static model involving an indole-Tempo, hydrogen-bond complex accounts for the relaxation data from which both an equilibrium constant of complexation and a hydrogen-bond distance in the indole-Tempo complex could be estimated.

  11. Electron paramagnetic resonance study of doped synthetic crystals of struvite and its zinc analogue

    NASA Astrophysics Data System (ADS)

    Chand, Prem; Agarwal, O. P.

    The electron paramagnetic resonance (EPR) technique has been used to study the Mn 2+ paramagnetic impurity complexes in synthetic struvite (MgNH 4PO 4β6H 2O) and the zinc isomorph (ZnNH 4PO 4β6H 2O). EPR of VO 2+ ion complexes in vanadyl doped crystals of the zinc isomorph of struvite has also been studied. Two differently oriented, but otherwise identical complexes of both Mn 2+ ion and VO 2+ ion are found in these crystals. The spin Hamiltonian parameters indicate a large orthorhombic distortion of the [Mn 2+(H 2O) 6] octahedra and an axial symmetry of the vanadyl complexes. The results indicate that in both manganese and vanadyl complexes, the metal ions have covalent bonding with the ligands.

  12. Paramagnetic atom number and paramagnetic critical pressure of the sc, bcc and fcc Ising nanolattices

    NASA Astrophysics Data System (ADS)

    Şarlı, Numan

    2015-01-01

    The effects of the magnetic atom number in the unit volume on the magnetic properties are investigated by using sc (n=8), bcc (n=9) and fcc (n=14) Ising NLs within the effective field theory with correlations. We find that the magnetic properties expand as the magnetic atom number increases in the unit volume and this expanding constitutes an elliptical path at TC. The effect of the magnetic atom number (n) in the unit volume on the magnetic properties (mp) appear as nscparamagnetic hysteresis curves are directly proportional with the atom number in the unit volume. This proportion is the confirmation that the Curie's constant is directly proportional with the atom number in the unit volume (C α n). Hence, by using the slopes of the paramagnetic hysteresis curves of any nanosystem, it can be predicted that the number of particles in its unit volume. Moreover, the magnetic atoms in the paramagnetic region can be considered as particles in the gas. Because of the absence of an external magnetic field, the spin orientations of these atoms are random and free to rotate. Hence, they act on individually with no mutual interaction between two nearest-neighbor magnetic atoms. Therefore, we use the statistical mechanics form of the ideal gas law in the paramagnetic region and we obtain the critical paramagnetic pressure (PC=npkBTC) of the Ising NLs at TC. We define the paramagnetic magnetic atom number in the unit volume as np=n(1-M(T)).

  13. Reversible Redox Chemistry and Catalytic C(sp(3))-H Amination Reactivity of a Paramagnetic Pd Complex Bearing a Redox-Active o-Aminophenol-Derived NNO Pincer Ligand.

    PubMed

    Broere, Daniël L J; van Leest, Nicolaas P; de Bruin, Bas; Siegler, Maxime A; van der Vlugt, Jarl Ivar

    2016-09-06

    The synthesis, spectroelectrochemical characterization (ultraviolet-visible and nuclear magnetic resonance), solid state structures, and computational metric parameters of three isostructural PdCl(NNO) complexes 1 [PdCl(NNO(ISQ))], 2 {[PdCl(NNO(AP))](-)}, and 5 {[PdCl(NNO(IBQ))](+)} (NNO = o-aminophenol-derived redox-active ligand with a pendant pyridine) with different NNO oxidation states are described. The reduced diamagnetic complex 2 readily reacts with halogenated solvents, including lattice solvent from crystalline pure material, as supported by spectroscopic data and density functional theory calculations. Thorough removal of chlorinated impurities allows for modest catalytic turnover in the conversion of 4-phenylbutyl azide into N-protected 2-phenylpyrrolidine, which is the first example of a palladium-catalyzed radical-type transformation facilitated by a redox-active ligand as well as the first C-H amination mediated by ligand-to-substrate single-electron transfer.

  14. 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

  15. A paramagnetic CEST agent for imaging glucose by MRI.

    PubMed

    Zhang, Shanrong; Trokowski, Robert; Sherry, A Dean

    2003-12-17

    The europium(III) complex of a DOTA-tetraamide ligand (DOTA = 1,4,7,10-tetraazacyclododecane-N,N',N' ',N' ''-tetraacetic acids) containing two phenyl boronate pendent arms binds glucose reversibly with an association constant of 383 M-1 at pH 7. Glucose binding results in slowing of water exchange between a single Eu(III)-bound water molecule and bulk water, and this can be imaged by MRI using chemical exchange saturation transfer (CEST) imaging sequence. This metabolite-responsive paramagnetic CEST agent responds to changes in glucose over the physiologically important range (0-20 mM), and thus it offers the possibility of high-sensitivity MR imaging glucose in tissues using bulk water protons as antenna.

  16. Paramagnetic and Antiferromagnetic Spin Seebeck Effect

    NASA Astrophysics Data System (ADS)

    Wu, Stephen

    We report on the observation of the longitudinal spin Seebeck effect in both antiferromagnetic and paramagnetic insulators. By using a microscale on-chip local heater, it is possible to generate a large thermal gradient confined to the chip surface without a large increase in the total sample temperature. This technique allows us to easily access low temperatures (200 mK) and high magnetic fields (14 T) through conventional dilution refrigeration and superconducting magnet setups. By exploring this regime, we detect the spin Seebeck effect through the spin-flop transition in antiferromagnetic MnF2 when a large magnetic field (>9 T) is applied along the easy axis direction. Using the same technique, we are also able to resolve a spin Seebeck effect from the paramagnetic phase of geometrically frustrated antiferromagnet Gd3Ga5O12 (gadolinium gallium garnet) and antiferromagnetic DyScO3 (DSO). Since these measurements occur above the ordering temperatures of these two materials, short-range magnetic order is implicated as the cause of the spin Seebeck effect in these systems. The discovery of the spin Seebeck effect in these two materials classes suggest that both antiferromagnetic spin waves and spin excitations from short range magnetic order may be used to generate spin current from insulators and that the spin wave spectra of individual materials are highly important to the specifics of the longitudinal spin Seebeck effect. Since insulating antiferromagnets and paramagnets are far more common than the typical insulating ferrimagnetic materials used in spin Seebeck experiments, this discovery opens up a large new class of materials for use in spin caloritronic devices. All authors acknowledge support of the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division. The use of facilities at the Center for Nanoscale Materials, was supported by the U.S. DOE, BES under Contract No. DE-AC02-06CH11357.

  17. Paramagnetic excited vortex states in superconductors

    NASA Astrophysics Data System (ADS)

    Gomes, Rodolpho Ribeiro; Doria, Mauro M.; Romaguera, Antonio R. de C.

    2016-06-01

    We consider excited vortex states, which are vortex states left inside a superconductor once the external applied magnetic field is switched off and whose energy is lower than of the normal state. We show that this state is paramagnetic and develop here a general method to obtain its Gibbs free energy through conformal mapping. The solution for any number of vortices in any cross-section geometry can be read off from the Schwarz-Christoffel mapping. The method is based on the first-order equations used by Abrikosov to discover vortices.

  18. Tuning Paramagnetic Spin Excitations of Single Adatoms

    NASA Astrophysics Data System (ADS)

    Ibañez-Azpiroz, Julen; Dias, Manuel dos Santos; Schweflinghaus, Benedikt; Blügel, Stefan; Lounis, Samir

    2017-07-01

    We predict the existence of paramagnetic spin excitations (PSE) in nonmagnetic single adatoms. Our calculations demonstrate that PSE develop a well-defined structure in the meV region when the adatom's Stoner criterion for magnetism is close to the critical point. We further reveal a subtle tunability and enhancement of PSE by external magnetic fields. Finally, we show how PSE can be detected as moving steps in the d I /d V signal of inelastic scanning tunneling spectroscopy, opening a potential route for experimentally accessing electronic properties of nonmagnetic adatoms, such as the Stoner parameter.

  19. Change in the paramagnetic characteristics of coals during metamorphism

    SciTech Connect

    Bineev, E.A.; Peresun'ko, T.F.

    1983-01-01

    The paper studies the paramagnetic properties of deep-mined coals on samples taken from one seam with a wide spectrum of metamorphism. Changes which take place in the concentration of paramagnetic centres within the various types of coal are related to structural and chemical transformations which occur with progressive coalification. Comparisons of EPR and X-ray structural and elementary analyses produce a picture of those particular paramagnetic centres which are responsible for the wide- and narrow-band EPR signals.

  20. Spin fluctuations in 3d paramagnetic metals

    NASA Astrophysics Data System (ADS)

    Wysocki, Aleksander; Kutepov, Andrey; Antropov, Vladimir

    Spin fluctuations (SFs) in 3d paramagnetic metals were investigated using the linear response formalism within the time dependent density functional theory. An efficient scheme of frequency integration using the Matsubara technique has been implemented and tested. The SFs spectrum in 3d paramagnets is analyzed in real and reciprocal spaces as a function of frequency and temperature. For all materials the SFs are characterized by the coexistence of low and high energy branches which originate from different regions of the Brillouin zone. The low-energy ones can be measured by neutron scattering experiments while the high-energy SFs appear to be more localized. Further, we studied the nature of square of fluctuating magnetic moment in these materials. This work was supported, in part, by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy (DOE), and by the Office of Basic Energy Science, Division of Materials Science and Engineering. The research was performed at Ames Laboratory, which is operated for the U.S. DOE by Iowa State University under contract # DE-AC02-07CH11358.

  1. Spin paramagnetic deformation of a neutron star

    NASA Astrophysics Data System (ADS)

    Suvorov, A. G.; Mastrano, A.; Melatos, A.

    2016-02-01

    Quantum mechanical corrections to the hydromagnetic force balance equation, derived from the microscopic Schrödinger-Pauli theory of quantum plasmas, modify the equilibrium structure and hence the mass quadrupole moment of a neutron star. It is shown here that the dominant effect - spin paramagnetism - is most significant in a magnetar, where one typically has μ _B|B|≳ k_B T_e, where μB is the Bohr magneton, B is the magnetic field, and Te is the electron temperature. The spin paramagnetic deformation of a non-barotropic magnetar with a linked poloidal-toroidal magnetic field is calculated to be up to ˜10 times greater than the deformation caused solely by the Lorentz force. It depends on the degree of Pauli blocking by conduction electrons and the propensity to form magnetic domains, processes which are incompletely modelled at magnetar field strengths. The star becomes more oblate, as the toroidal field component strengthens. The result implies that existing classical predictions underestimate the maximum strength of the gravitational wave signal from rapidly spinning magnetars at birth. Turning the argument around, future gravitational-wave upper limits of increasing sensitivity will place ever-stricter constraints on the physics of Pauli blocking and magnetic domain formation under magnetar conditions.

  2. Density functional calculations of (55)Mn, (14)N and (13)C electron paramagnetic resonance parameters support an energetically feasible model system for the S(2) state of the oxygen-evolving complex of photosystem II.

    PubMed

    Schinzel, Sandra; Schraut, Johannes; Arbuznikov, Alexei V; Siegbahn, Per E M; Kaupp, Martin

    2010-09-10

    Metal and ligand hyperfine couplings of a previously suggested, energetically feasible Mn(4)Ca model cluster (SG2009(-1)) for the S(2) state of the oxygen-evolving complex (OEC) of photosystem II (PSII) have been studied by broken-symmetry density functional methods and compared with other suggested structural and spectroscopic models. This was carried out explicitly for different spin-coupling patterns of the S=1/2 ground state of the Mn(III)(Mn(IV))(3) cluster. By applying spin-projection techniques and a scaling of the manganese hyperfine couplings, computation of the hyperfine and nuclear quadrupole coupling parameters allows a direct evaluation of the proposed models in comparison with data obtained from the simulation of EPR, ENDOR, and ESEEM spectra. The computation of (55)Mn hyperfine couplings (HFCs) for SG2009(-1) gives excellent agreement with experiment. However, at the current level of spin projection, the (55)Mn HFCs do not appear sufficiently accurate to distinguish between different structural models. Yet, of all the models studied, SG2009(-1) is the only one with the Mn(III) site at the Mn(C) center, which is coordinated by histidine (D1-His332). The computed histidine (14)N HFC anisotropy for SG2009(-1) gives much better agreement with ESEEM data than the other models, in which Mn(C) is an Mn(IV) site, thus supporting the validity of the model. The (13)C HFCs of various carboxylates have been compared with (13)C ENDOR data for PSII preparations with (13)C-labelled alanine.

  3. Cu(II)-Based Paramagnetic Probe to Study RNA-Protein Interactions by NMR.

    PubMed

    Seebald, Leah M; DeMott, Christopher M; Ranganathan, Srivathsan; Asare Okai, Papa Nii; Glazunova, Anastasia; Chen, Alan; Shekhtman, Alexander; Royzen, Maksim

    2017-04-03

    Paramagnetic NMR techniques allow for studying three-dimensional structures of RNA-protein complexes. In particular, paramagnetic relaxation enhancement (PRE) data can provide valuable information about long-range distances between different structural components. For PRE NMR experiments, oligonucleotides are typically spin-labeled using nitroxide reagents. The current work describes an alternative approach involving a Cu(II) cyclen-based probe that can be covalently attached to an RNA strand in the vicinity of the protein's binding site using "click" chemistry. The approach has been applied to study binding of HIV-1 nucleocapsid protein 7 (NCp7) to a model RNA pentanucleotide, 5'-ACGCU-3'. Coordination of the paramagnetic metal to glutamic acid residue of NCp7 reduced flexibility of the probe, thus simplifying interpretation of the PRE data. NMR experiments showed attenuation of signal intensities from protein residues localized in proximity to the paramagnetic probe as the result of RNA-protein interactions. The extent of the attenuation was related to the probe's proximity allowing us to construct the protein's contact surface map.

  4. High field electron paramagnetic resonance characterization of electronic and structural environments for paramagnetic metal ions and organic free radicals in Deepwater Horizon oil spill tar balls.

    PubMed

    Ramachandran, Vasanth; van Tol, Johan; McKenna, Amy M; Rodgers, Ryan P; Marshall, Alan G; Dalal, Naresh S

    2015-02-17

    In the first use of high-field electron paramagnetic resonance (EPR) spectroscopy to characterize paramagnetic metal-organic and free radical species from tar balls and weathered crude oil samples from the Gulf of Mexico (collected after the Deepwater Horizon oil spill) and an asphalt volcano sample collected off the coast of Santa Barbara, CA, we are able to identify for the first time the various paramagnetic species present in the native state of these samples and understand their molecular structures and bonding. The two tar ball and one asphalt volcano samples contain three distinct paramagnetic species: (i) an organic free radical, (ii) a [VO](2+) containing porphyrin, and (iii) a Mn(2+) containing complex. The organic free radical was found to have a disc-shaped or flat structure, based on its axially symmetric spectrum. The characteristic spectral features of the vanadyl species closely resemble those of pure vanadyl porphyrin; hence, its nuclear framework around the vanadyl ion must be similar to that of vanadyl octaethyl porphyrin (VOOEP). The Mn(2+) ion, essentially undetected by low-field EPR, yields a high-field EPR spectrum with well-resolved hyperfine features devoid of zero-field splitting, characteristic of tetrahedral or octahedral Mn-O bonding. Although the lower-field EPR signals from the organic free radicals in fossil fuel samples have been investigated over the last 5 decades, the observed signal was featureless. In contrast, high-field EPR (up to 240 GHz) reveals that the species is a disc-shaped hydrocarbon molecule in which the unpaired electron is extensively delocalized. We envisage that the measured g-value components will serve as a sensitive basis for electronic structure calculations. High-field electron nuclear double resonance experiments should provide an accurate picture of the spin density distribution for both the vanadyl-porphyrin and Mn(2+) complexes, as well as the organic free radical, and will be the focus of follow

  5. Paramagnetic Materials for PASER and Tunable RF Absorption

    SciTech Connect

    Antipov, Sergey P.; Schoessow, Paul; Kanareykin, Alexei; Jing Chunguang; Poluektov, Oleg; Gai Wei

    2010-11-04

    We report on the use of paramagnetic active media for the PASER (Particle Acceleration by Stimulated Emission of Radiation) and for dielectric loaded accelerating structures with tunable absorption for high order modes. The dielectric is doped with a material exhibiting high paramagnetic resonance, e.g. ruby with Cr{sup 3+}. The absorption frequency can be tuned by a magnetic field.

  6. Electron Paramagnetic Resonance Study of Pr

    SciTech Connect

    Tezuka, Keitaro; Hinatsu, Yukio

    2001-01-01

    Electron paramagnetic resonance (EPR) spectra of tetravalent praseodymium ions doped in the cubic perovskite compound BaHfO{sub 3} have been measured at 4.2 K. A very large hyperfine interaction with the {sup 141}Pr nucleus was observed in the spectrum of Pr{sup 4+}/ BaHfO{sub 3}. The results were analyzed based on the weak field approximation, and the g value (|g|=0.619) and a hyperfine coupling constant (A=0.0589 cm{sup {minus}1}) were obtained. The measured g value is much smaller than |-10/7|, which indicates that the crystal field effect on the behavior of a 4f electron is large. These g and A values were compared with the EPR results for other f{sup 1} ions in an octahedral crystal field.

  7. Density-functional study of paramagnetic iron

    NASA Astrophysics Data System (ADS)

    Zhang, Hualei; Johansson, Börje; Vitos, Levente

    2011-10-01

    By using density-functional theory in combination with the coherent-potential approximation and the disordered local magnetic moment picture, we demonstrate that the competing high-temperature cubic phases of paramagnetic Fe correspond to two distinct total energy minima in the tetragonal (Bain) configurational space. Both the face-centered-cubic (fcc) and the body-centered-cubic (bcc) lattices are dynamically stable, and at static conditions the fcc structure is found to be the thermodynamically stable phase. The theoretical bcc and fcc bulk parameters are in agreement with the experimental data. Due to the shallow energy minimum around the bcc structure, increasing temperature is predicted to stabilize the bcc (δ) phase against the fcc (γ) one.

  8. Effective optical Faraday rotations of semiconductor EuS nanocrystals with paramagnetic transition-metal ions.

    PubMed

    Hasegawa, Yasuchika; Maeda, Masashi; Nakanishi, Takayuki; Doi, Yoshihiro; Hinatsu, Yukio; Fujita, Koji; Tanaka, Katsuhisa; Koizumi, Hitoshi; Fushimi, Koji

    2013-02-20

    Novel EuS nanocrystals containing paramagnetic Mn(II), Co(II), or Fe(II) ions have been reported as advanced semiconductor materials with effective optical rotation under a magnetic field, Faraday rotation. EuS nanocrystals with transition-metal ions, EuS:M nanocrystals, were prepared by the reduction of the Eu(III) dithiocarbamate complex tetraphenylphosphonium tetrakis(diethyldithiocarbamate)europium(III) with transition-metal complexes at 300 °C. The EuS:M nanocrystals thus prepared were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), inductively coupled plasma atomic emission spectroanalysis (ICP-AES), and a superconducting quantum interference device (SQUID) magnetometer. Enhanced Faraday rotations of the EuS:M nanocrystals were observed around 550 nm, and their enhanced spin polarization was estimated using electron paramagnetic resonance (EPR) measurements. In this report, the magneto-optical relationship between the Faraday rotation efficiency and spin polarization is discussed.

  9. In-situ electron paramagnetic resonance studies of paramagnetic point defects in superconducting microwave resonators

    NASA Astrophysics Data System (ADS)

    Zhang, Shengke; Kopas, Cameron; Wagner, Brian; Queen, Daniel; Newman, N.

    2016-09-01

    The physical nature and concentration of paramagnetic point defects in the dielectrics of superconducting planar microwave resonators have been determined using in-situ electron paramagnetic resonance spectroscopy. To perform this work, the quality factor of parallel plate and stripline resonators was measured as a function of the magnitude of a magnetic-field applied parallel to the electrode surfaces. YBa2Cu3O7-δ thin film electrodes proved to be a preferred choice over Nb and MgB2 because they are readily available and have a small surface resistance (Rs) up to high temperatures (˜77 K) and magnetic fields (i.e., <1 T). Stripline resonators with a widely used high performance microwave dielectric, Co2+-doped Ba(Zn1/3Nb2/3)O3, are shown to have losses dominated by d-electron spin-excitations in exchange-coupled Co2+ point-defect clusters, even in the absence of an applied magnetic field. A significant enhanced microwave loss in stripline and parallel plate resonators is found to correlate with the presence of paramagnetic Mn2+ dopants in Ba(Zn1/3Ta2/3)O3 ceramics and dangling bond states in amorphous Si thin films, although the identification of the dominant loss mechanism(s) in these dielectrics requires further investigation.

  10. Seeing the invisible by paramagnetic and diamagnetic NMR.

    PubMed

    Clore, G Marius

    2013-12-01

    Sparsely populated transient states of proteins and their complexes play an important role in many biological processes including protein-protein and protein-DNA recognition, allostery, conformational selection, induced fit and self-assembly. These states are difficult to study as their low population and transient nature makes them effectively invisible to conventional structural and biophysical techniques. In the present article, I summarize recent NMR developments in our laboratory, including the use of paramagnetic relaxation enhancement, lifetime line broadening and dark-state exchange saturation transfer spectroscopy, that have permitted such sparsely populated states to be detected, characterized and, in some instances, visualized. I illustrate the application of these methods to the elucidation of mechanisms whereby transcription factors locate their specific target sites within an overwhelming sea of non-specific DNA, to the characterization of encounter complexes in protein-protein recognition, to large-scale interdomain motions involved in ligand binding, and to the interaction of monomeric amyloid β-peptide with the surface of amyloid protofibrils and the internal cavity surface of the chaperonin GroEL.

  11. NMR identification of protein surfaces using paramagnetic probes

    SciTech Connect

    Petros, A.M.; Mueller, L.; Kopple, K.D. )

    1990-10-01

    Paramagnetic agents produce line broadening and thus cancellation of anti phase cross-peak components in two-dimensional correlated nulcear magnetic resonance spectra. The specificity of this effect was examined to determine its utility for identifying surface residues of proteins. Ubiquitin and hen egg white lysozyme, for which X-ray crystal structures and proton NMR assignments are available, served as test cases. Two relaxation reagents were employed, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1 oxy and the gadolinium(III) diethylenetriaminepentaacetate complex ion. Correlations were sought between reagent-produced decreases of side-chain cross-peak volumes in double-quantum-filtered proton correlation (DQF-COSY) spectra and the solvent-exposed side-chain surface area of the corresponding residues. The lanthanide complex produced strong effects ascribable to association with carboxylate groups but was not otherwise useful in delineating surface residues. The nitroxyl, on the other hand, produced clear distinctions among the Val, Leu, and Ile residues that generally paralleled side-chain exposure in the crystal, although consistent correlations were not observed with residues of other types. Although an instance of possible specific protein-nitroxyl association was noted, the nitroxyl appears to be a tool for identifying hydrophobic surface residues.

  12. Induced Orbital Paramagnetism and Paratropism in Closed-Shell Molecules

    NASA Astrophysics Data System (ADS)

    Pelloni, Stefano; Lazzeretti, Paolo; Zanasi, Riccardo

    2009-07-01

    Three-dimensional models of the quantum-mechanical current density induced by a uniform magnetic field in the electron cloud have been obtained for closed-shell systems BeH-, BH, and CH+, characterized by induced orbital paramagnetism, and in planar unsaturated hydrocarbons C4H4 and clamped C8H8, exhibiting π paramagnetism. It is shown that, even for these paramagnetic systems, the paramagnetic contributions to magnetic susceptibilities and nuclear magnetic shielding, customarily taken into account in perturbation theory approaches, can formally be eliminated via the procedure of continuous transformation of the origin of the current density-paramagnetic zero. The definition of magnetic response properties can therefore be recast as a sum of two formally "diamagnetic" terms for any molecule, including systems showing strong induced orbital paramagnetism. It is shown that the paramagnetism in the compounds studied arises from the nodal topology of the electronic wave function. In particular, paratropic vortices circulate about stagnation lines at the intersection of nodal surfaces of the highest-occupied zero-order molecular orbital and corresponding first-order orbital.

  13. Induced orbital paramagnetism and paratropism in closed-shell molecules.

    PubMed

    Pelloni, Stefano; Lazzeretti, Paolo; Zanasi, Riccardo

    2009-12-31

    Three-dimensional models of the quantum-mechanical current density induced by a uniform magnetic field in the electron cloud have been obtained for closed-shell systems BeH(-), BH, and CH(+), characterized by induced orbital paramagnetism, and in planar unsaturated hydrocarbons C(4)H(4) and clamped C(8)H(8), exhibiting pi paramagnetism. It is shown that, even for these paramagnetic systems, the paramagnetic contributions to magnetic susceptibilities and nuclear magnetic shielding, customarily taken into account in perturbation theory approaches, can formally be eliminated via the procedure of continuous transformation of the origin of the current density-paramagnetic zero. The definition of magnetic response properties can therefore be recast as a sum of two formally "diamagnetic" terms for any molecule, including systems showing strong induced orbital paramagnetism. It is shown that the paramagnetism in the compounds studied arises from the nodal topology of the electronic wave function. In particular, paratropic vortices circulate about stagnation lines at the intersection of nodal surfaces of the highest-occupied zero-order molecular orbital and corresponding first-order orbital.

  14. Vacancy dynamics in the paramagnetic environment

    NASA Astrophysics Data System (ADS)

    Carlstrom, Johan; Svistunov, Boris; Prokofiev, Nikolay

    We consider the motion of a single vacancy in a magnetic spin-1/2 lattice. Examples of realisations of this model include vacancies in a He3 solid or holes in the t-J model with J=0. This motion is ballistic when spins exhibit ferromagnetic order, with < | r (t) | > growing linearly with time. However in the disordered paramagnet, the motion of the vacancy becomes highly nontrivial, and no exact solution to this outstanding problem is known. This scenario is known as the Brinkman-Rice problem. We report here numerical results for the spatial probability distribution of the vacancy obtained by integrating the time evolution operator through Monte Carlo and averaging over a large number of random spin realisations. We find highly counterintuitive results, with the probability of finding the vacancy at a given site oscillating in time. These results can be verified in experiments with ultra-cold fermions in optical lattice at a temperature high enough that the spins are disordered.

  15. Microstrip resonators for electron paramagnetic resonance experiments.

    PubMed

    Torrezan, A C; Mayer Alegre, T P; Medeiros-Ribeiro, G

    2009-07-01

    In this article we evaluate the performance of an electron paramagnetic resonance (EPR) setup using a microstrip resonator (MR). The design and characterization of the resonator are described and parameters of importance to EPR and spin manipulation are examined, including cavity quality factor, filling factor, and microwave magnetic field in the sample region. Simulated microwave electric and magnetic field distributions in the resonator are also presented and compared with qualitative measurements of the field distribution obtained by a perturbation technique. Based on EPR experiments carried out with a standard marker at room temperature and a MR resonating at 8.17 GHz, the minimum detectable number of spins was found to be 5 x 10(10) spins/GHz(1/2) despite the low MR unloaded quality factor Q0=60. The functionality of the EPR setup was further evaluated at low temperature, where the spin resonance of Cr dopants present in a GaAs wafer was detected at 2.3 K. The design and characterization of a more versatile MR targeting an improved EPR sensitivity and featuring an integrated biasing circuit for the study of samples that require an electrical contact are also discussed.

  16. Magnetoresistance in paramagnetic heavy fermion metals.

    PubMed

    Parihari, D; Vidhyadhiraja, N S

    2009-10-07

    A theoretical study of magnetic field (h) effects on single-particle spectra and the transport quantities of heavy fermion metals in the paramagnetic phase is carried out. We have employed a non-perturbative local moment approach (LMA) to the asymmetric periodic Anderson model within the dynamical mean field framework. The lattice coherence scale ω(L), which is proportional within the LMA to the spin-flip energy scale, and has been shown in earlier studies to be the energy scale at which crossover to single-impurity physics occurs, increases monotonically with increasing magnetic field. The many body Kondo resonance in the density of states at the Fermi level splits into two, with the splitting being proportional to the field itself. For h≥0, we demonstrate adiabatic continuity from the strongly interacting case to a corresponding non-interacting limit, thus establishing Fermi liquid behaviour for heavy fermion metals in the presence of a magnetic field. In the Kondo lattice regime, the theoretically computed magnetoresistance is found to be negative in the entire temperature range. We argue that such a result could be understood at [Formula: see text] by field-induced suppression of spin-flip scattering and at [Formula: see text] through lattice coherence. The coherence peak in the heavy fermion resistivity diminishes and moves to higher temperatures with increasing field. Direct comparison of the theoretical results to the field dependent resistivity measurements in CeB(6) yields good agreement.

  17. Water exchange in plant tissue studied by proton NMR in the presence of paramagnetic centers.

    PubMed

    Bacić, G; Ratković, S

    1984-04-01

    The proton NMR relaxation of water in maize roots in the presence of paramagnetic centers, Mn2+, Mn- EDTA2 -, and dextran-magnetite was measured. It was shown that the NMR method of Conlon and Outhred (1972, Biochem. Biophys. Acta. 288:354-361) can be applied to a heterogenous multicellular system, and the water exchange time between cortical cells and the extracellular space can be calculated. The water exchange is presumably controlled by the intracellular unstirred layers. The Mn- EDTA2 - complex is a suitable paramagnetic compound for complex tissue, while the application of dextran-magnetite is probably restricted to studies of water exchange in cell suspensions. The water free space of the root and viscosity of the cells cytoplasm was estimated with the use of Mn- EDTA2 -. The convenience of proton NMR for studying the multiphase uptake of paramagnetic ions by plant root as well as their transport to leaves is demonstrated. A simple and rapid NMR technique (spin-echo recovery) for continuous measurement of the uptake process is presented.

  18. Water exchange in plant tissue studied by proton NMR in the presence of paramagnetic centers.

    PubMed Central

    Bacić, G; Ratković, S

    1984-01-01

    The proton NMR relaxation of water in maize roots in the presence of paramagnetic centers, Mn2+, Mn- EDTA2 -, and dextran-magnetite was measured. It was shown that the NMR method of Conlon and Outhred (1972, Biochem. Biophys. Acta. 288:354-361) can be applied to a heterogenous multicellular system, and the water exchange time between cortical cells and the extracellular space can be calculated. The water exchange is presumably controlled by the intracellular unstirred layers. The Mn- EDTA2 - complex is a suitable paramagnetic compound for complex tissue, while the application of dextran-magnetite is probably restricted to studies of water exchange in cell suspensions. The water free space of the root and viscosity of the cells cytoplasm was estimated with the use of Mn- EDTA2 -. The convenience of proton NMR for studying the multiphase uptake of paramagnetic ions by plant root as well as their transport to leaves is demonstrated. A simple and rapid NMR technique (spin-echo recovery) for continuous measurement of the uptake process is presented. PMID:6426539

  19. Hydrodynamic instability in a magnetically driven suspension of paramagnetic red blood cells.

    PubMed

    Kashevsky, B E; Zholud, A M; Kashevsky, S B

    2015-09-07

    We investigate the magnetically driven motion in suspensions of paramagnetic particles. Our object is diluted deoxygenated whole blood with paramagnetic red blood cells (RBCs). We use direct observations in a closed vertical Hele-Shaw channel, and a well-defined magnetic force field applied horizontally in the channel plane. At very low cell concentrations, we register single-particle motion mode, track individual cells and determine their hydrodynamic and magnetic characteristics. Above 0.2 volume percent concentration, we observe local swirls and a global transient quasi-periodic vortex structure, intensifying with increasing cell concentration, but surprisingly this does not influence the time and purity of the magnetic extraction of RBCs. Our observations shed light on the behavioral complexity of magnetically driven submagnetic suspensions, an important issue for the emerging microfluidic technology of direct magnetic cell separation and intriguing for the mechanics of particulate soft matter.

  20. Enhancement of T1 and T2 relaxation by paramagnetic silica-coated nanocrystals

    SciTech Connect

    Gerion, D; Herberg, J; Gjersing, E; Ramon, E; Maxwell, R; Gray, J W; Budinger, T F; Chen, F F

    2006-08-28

    We present the first comprehensive investigation on water-soluble nanoparticles embedded into a paramagnetic shell and their properties as an MRI contrast agent. The nanoprobes are constructed with an inorganic core embedded into an ultra-thin silica shell covalently linked to chelated Gd{sup 3+} paramagnetic ions that act as an MRI contrast agent. The chelator contains the molecule DOTA and the inorganic core contains a fluorescent CdSe/ZnS qdots in Au nanoparticles. Optical properties of the cores (fluorescence emission or plasmon position) are not affected by the neither the silica shell nor the presence of the chelated paramagnetic ions. The resulting complex is a MRI/fluorescence probe with a diameter of 8 to 15 nm. This probe is highly soluble in high ionic strength buffers at pH ranging from {approx}4 to 11. In MRI experiments at clinical field strengths of 60 MHz, the QDs probes posses spin-lattice (T{sub 1}) and a spin-spin (T{sub 2}) relaxivities of 1018.6 +/- 19.4 mM{sup -1} s{sup -1} and 2438.1 +/- 46.3 mM{sup -1} s{sup -1} respectively for probes having {approx}8 nm. This increase in relaxivity has been correlated to the number of paramagnetic ions covalently linked to the silica shell, ranging from approximately 45 to over 320. We found that each bound chelated paramagnetic species contributes by over 23 mM{sup -1} s{sup -1} to the total T{sub 1} and by over 54 mM{sup -1} s{sup -1} to the total T{sub 2} relaxivity respectively. The contrast power is modulated by the number of paramagnetic moieties linked to the silica shell and is only limited by the number of chelated paramagnetic species that can be packed on the surface. So far, the sensitivity of our probes is in the 100 nM range for 8-10 nm particles and reaches 10 nM for particles with approximately 15-18 nm in diameter. The sensitivities values in solutions are equivalent of those obtained with small superparamagnetic iron oxide nanoparticles of 7 nm diameter clustered into a 100 nm polymeric

  1. Application of paramagnetic beads for purifying Bacillus anthracis protective antigen.

    PubMed

    Zarzecka, A; Bartoszcze, M

    2006-10-01

    Paramagnetic beads coated with Protein G and Tosylactivated-280 dynabeads have been used to purify Bacillus anthracis protective antigen from a liquid culture. The obtained protein was used in the enzyme-linked immunosorbent assay test to detect B. anthracis protective antigen antibodies in human sera collected from immunized individuals. The purification method using paramagnetic beads is very effective. It is fast, easy and may be carried out practically in any laboratory.

  2. Application of Electron Paramagnetic Resonance to Study of Gallstones

    NASA Astrophysics Data System (ADS)

    Kiselev, S. A.; Tsyro, L. V.; Afanasiev, D. A.; Unger, F. G.; Soloviev, M. M.

    2014-03-01

    We present the results of an electron paramagnetic resonance (EPR) study of mixed cholesterol gallstones. We have established that free radicals are distributed nonuniformly within the interior of the stone. The type and number of paramagnetic centers depend on the pigment content in the selected layer. We show that the parameters of the sextet lines in the EPR spectrum of the pigment are close to the parameters of lines in the spectrum of a brown pigment stone.

  3. Magnetic stabilization and vorticity in submillimeter paramagnetic liquid tubes

    PubMed Central

    Coey, J. Michael D.; Aogaki, Ryoichi; Byrne, Fiona; Stamenov, Plamen

    2009-01-01

    It is possible to suppress convection and dispersion of a paramagnetic liquid by means of a magnetic field. A tube of paramagnetic liquid can be stabilized in water along a ferromagnetic track in a vertical magnetic field, but not in a horizontal field. Conversely, an “antitube” of water can be stabilized in a paramagnetic liquid along the same track in a transverse horizontal field, but not in a vertical field. The stability arises from the interaction of the induced moment in the solution with the magnetic field gradient in the vicinity of the track. The magnetic force causes the tube of paramagnetic liquid to behave as if it were encased by an elastic membrane whose cross-section is modified by gravitational forces and Maxwell stress. Convection from the tube to its surroundings is inhibited, but not diffusion. Liquid motion within the paramagnetic tube, however, exhibits vorticity in tubes of diameter 1 mm or less—conditions where classical pipe flow would be perfectly streamline, and mixing extremely slow. The liquid tube is found to slide along the track almost without friction. Paramagnetic liquid tubes and antitubes offer appealing new prospects for mass transport, microfluidics, and electrodeposition. PMID:19416873

  4. Magnetic stabilization and vorticity in submillimeter paramagnetic liquid tubes.

    PubMed

    Coey, J Michael D; Aogaki, Ryoichi; Byrne, Fiona; Stamenov, Plamen

    2009-06-02

    It is possible to suppress convection and dispersion of a paramagnetic liquid by means of a magnetic field. A tube of paramagnetic liquid can be stabilized in water along a ferromagnetic track in a vertical magnetic field, but not in a horizontal field. Conversely, an "antitube" of water can be stabilized in a paramagnetic liquid along the same track in a transverse horizontal field, but not in a vertical field. The stability arises from the interaction of the induced moment in the solution with the magnetic field gradient in the vicinity of the track. The magnetic force causes the tube of paramagnetic liquid to behave as if it were encased by an elastic membrane whose cross-section is modified by gravitational forces and Maxwell stress. Convection from the tube to its surroundings is inhibited, but not diffusion. Liquid motion within the paramagnetic tube, however, exhibits vorticity in tubes of diameter 1 mm or less--conditions where classical pipe flow would be perfectly streamline, and mixing extremely slow. The liquid tube is found to slide along the track almost without friction. Paramagnetic liquid tubes and antitubes offer appealing new prospects for mass transport, microfluidics, and electrodeposition.

  5. Reconstruction of orientations of a moving protein domain from paramagnetic data

    NASA Astrophysics Data System (ADS)

    Gardner, Richard J.; Longinetti, Marco; Sgheri, Luca

    2005-06-01

    We study the inverse problem of determining the position of the moving C-terminal domain in a metalloprotein from measurements of its mean paramagnetic tensor \\bar\\chi . The latter can be represented as a finite sum involving the corresponding magnetic susceptibility tensor χ and a finite number of rotations. We obtain an optimal estimate for the maximum probability that the C-terminal domain can assume a given orientation, and we show that only three rotations are required in the representation of \\bar\\chi , and that in general two are not enough. We also investigate the situation in which a compatible pair of mean paramagnetic tensors is obtained. Under a mild assumption on the corresponding magnetic susceptibility tensors, justified on physical grounds, we again obtain an optimal estimate for the maximum probability that the C-terminal domain can assume a given orientation. Moreover, we prove that only ten rotations are required in the representation of the compatible pair of mean paramagnetic tensors, and that in general three are not enough. The theoretical investigation is concluded by a study of the coaxial case, when all rotations are assumed to have a common axis. Results are obtained via an interesting connection with another inverse problem, the quadratic complex moment problem. Finally, we describe an application to experimental NMR data.

  6. Predicting paramagnetic 1H NMR chemical shifts and state-energy separations in spin-crossover host-guest systems.

    PubMed

    Isley, William C; Zarra, Salvatore; Carlson, Rebecca K; Bilbeisi, Rana A; Ronson, Tanya K; Nitschke, Jonathan R; Gagliardi, Laura; Cramer, Christopher J

    2014-06-14

    The behaviour of metal-organic cages upon guest encapsulation can be difficult to elucidate in solution. Paramagnetic metal centres introduce additional dispersion of signals that is useful for characterisation of host-guest complexes in solution using nuclear magnetic resonance (NMR). However, paramagnetic centres also complicate spectral assignment due to line broadening, signal integration error, and large changes in chemical shifts, which can be difficult to assign even for known compounds. Quantum chemical predictions can provide information that greatly facilitates the assignment of NMR signals and identification of species present. Here we explore how the prediction of paramagnetic NMR spectra may be used to gain insight into the spin crossover (SCO) properties of iron(II)-based metal organic coordination cages, specifically examining how the structure of the local metal coordination environment affects SCO. To represent the tetrahedral metal-organic cage, a model system is generated by considering an isolated metal-ion vertex: fac-ML3(2+) (M = Fe(II), Co(II); L = N-phenyl-2-pyridinaldimine). The sensitivity of the (1)H paramagnetic chemical shifts to local coordination environments is assessed and utilised to shed light on spin crossover behaviour in iron complexes. Our data indicate that expansion of the metal coordination sphere must precede any thermal SCO. An attempt to correlate experimental enthalpies of SCO with static properties of bound guests shows that no simple relationship exists, and that effects are likely due to nuanced dynamic response to encapsulation.

  7. PASE ( PAramagnetic Signals Enhancement): A New Method for NMR Study of Paramagnetic Proteins

    NASA Astrophysics Data System (ADS)

    Bondon, Arnaud; Mouro, Corinne

    1998-09-01

    A new method for NMR spectra acquisition of paramagnetic proteins is described, based on the simple use of homonuclear broadband decoupling of the diamagnetic region. Several advantages are associated with this method which was applied to one-dimensional spectra, to 1D NOE-difference spectroscopy, and to 2D NOESY. The main advantage is a very flat baseline obtained using the PASE (paramagneticsignalsenhancement) method. Furthermore, the bulky region of the diamagnetic protons being suppressed, clean NOE-difference spectra can be acquired as well as improved 2D NOESY maps. Applications on 1D1H spectrum of bovine liver catalase (MW 230,000), and 1D and 2D on the high-spin form of the myoglobin, used as a model protein, are presented.

  8. Electron paramagnetic resonance study of radiation-induced paramagnetic centers in succinic anhydride single crystal

    NASA Astrophysics Data System (ADS)

    Caliskan, Betul; Caliskan, Ali Cengiz; Er, Emine

    2017-09-01

    Succinic anhydride single crystals were exposed to 60Co-gamma irradiation at room temperature. The irradiated single crystals were investigated at 125 K by Electron Paramagnetic Resonance (EPR) Spectroscopy. The investigation of EPR spectra of irradiated single crystals of succinic anhydride showed the presence of two succinic anhydride anion radicals. The anion radicals observed in gamma-irradiated succinic anhydride single crystal were created by the scission of the carbon-oxygen double bond. The structure of EPR spectra demonstrated that the hyperfine splittings arise from the same radical species. The reduction of succinic anhydride was identified which is formed by the addition of an electron to oxygen of the Csbnd O bond. The g values, the hyperfine structure constants and direction cosines of the radiation damage centers observed in succinic anhydride single crystal were obtained.

  9. Magnetic field controlled composite paramagnetic-diamagnetic colloidal phases.

    PubMed

    Ray, A; Fischer, Th M

    2012-07-19

    We report on differently ordered colloidal phases of a mixture of paramagnetic and diamagnetic colloids subject to a quickly varying time dependent magnetic field. Effectively paramagnetic and effectively diamagnetic colloids are created from paramagnetic and nonmagnetic colloids immersed into a thin film of aqueous ferrofluid. The time-averaged dipole interaction between induced dipoles can be characterized by a uniaxial external precession angle and a biaxial eccentricity characterizing the anisotropy of the external field modulation. The variation of both control parameters causes a sequence of transitions between differently correlated orientation order between the paramagnetic and diamagnetic colloids. We observe the formation of bonds between paramagnets and diamagnets along one or two directions with a staggered order of the magnetic moments. Bonds between similar particles with uniform order of the magnetic moments form along directions orthogonal to bonds between different particles along the staggered directions. When the external precession angle passes the magic angle, the particle order rearranges and staggered directions with bonds between different particles change into uniformly ordered directions with bonds between similar particles and vice versa. The transition in order occurs in two steps with a biaxial phase intervening between the two uniaxial ordering phases.

  10. Perspectives on paramagnetic NMR from a life sciences infrastructure.

    PubMed

    Ravera, Enrico; Parigi, Giacomo; Luchinat, Claudio

    2017-09-01

    The effects arising in NMR spectroscopy because of the presence of unpaired electrons, collectively referred to as "paramagnetic NMR" have attracted increasing attention over the last decades. From the standpoint of the structural and mechanistic biology, paramagnetic NMR provides long range restraints that can be used to assess the accuracy of crystal structures in solution and to improve them by simultaneous refinements through NMR and X-ray data. These restraints also provide information on structure rearrangements and conformational variability in biomolecular systems. Theoretical improvements in quantum chemistry calculations can nowadays allow for accurate calculations of the paramagnetic data from a molecular structural model, thus providing a tool to refine the metal coordination environment by matching the paramagnetic effects observed far away from the metal. Furthermore, the availability of an improved technology (higher fields and faster magic angle spinning) has promoted paramagnetic NMR applications in the fast-growing area of biomolecular solid-state NMR. Major improvements in dynamic nuclear polarization have been recently achieved, especially through the exploitation of the Overhauser effect occurring through the contact-driven relaxation mechanism: the very large enhancement of the (13)C signal observed in a variety of liquid organic compounds at high fields is expected to open up new perspectives for applications of solution NMR. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Magnetic couplings in the chemical shift of paramagnetic NMR.

    PubMed

    Vaara, Juha; Rouf, Syed Awais; Mareš, Jiří

    2015-10-13

    We apply the Kurland-McGarvey (J. Magn. Reson. 1970, 2, 286) theory for the NMR shielding of paramagnetic molecules, particularly its special case limited to the ground-state multiplet characterized by zero-field splitting (ZFS) interaction of the form S·D·S. The correct formulation for this problem was recently presented by Soncini and Van den Heuvel (J. Chem. Phys. 2013, 138, 054113). With the effective electron spin quantum number S, the theory involves 2S+1 states, of which all but one are low-lying excited states, between which magnetic couplings take place by Zeeman and hyperfine interactions. We investigate these couplings as a function of temperature, focusing on both the high- and low-temperature behaviors. As has been seen in work by others, the full treatment of magnetic couplings is crucial for a realistic description of the temperature behavior of NMR shielding up to normal measurement temperatures. At high temperatures, depending on the magnitude of ZFS, the effect of magnetic couplings diminishes, and the Zeeman and hyperfine interactions become effectively averaged in the thermally occupied states of the multiplet. At still higher temperatures, the ZFS may be omitted altogether, and the shielding properties may be evaluated using a doublet-like formula, with all the 2S+1 states becoming effectively degenerate at the limit of vanishing magnetic field. We demonstrate these features using first-principles calculations of Ni(II), Co(II), Cr(II), and Cr(III) complexes, which have ZFS of different sizes and signs. A non-monotonic inverse temperature dependence of the hyperfine shift is predicted for axially symmetric integer-spin systems with a positive D parameter of ZFS. This is due to the magnetic coupling terms that are proportional to kT at low temperatures, canceling the Curie-type 1/kT prefactor of the hyperfine shielding in this case.

  12. Using Paramagnetism to Slow Down Nuclear Relaxation in Protein NMR.

    PubMed

    Orton, Henry W; Kuprov, Ilya; Loh, Choy-Theng; Otting, Gottfried

    2016-12-01

    Paramagnetic metal ions accelerate nuclear spin relaxation; this effect is widely used for distance measurement and called paramagnetic relaxation enhancement (PRE). Theoretical predictions established that, under special circumstances, it is also possible to achieve a reduction in nuclear relaxation rates (negative PRE). This situation would occur if the mechanism of nuclear relaxation in the diamagnetic state is counterbalanced by a paramagnetic relaxation mechanism caused by the metal ion. Here we report the first experimental evidence for such a cross-correlation effect. Using a uniformly (15)N-labeled mutant of calbindin D9k loaded with either Tm(3+) or Tb(3+), reduced R1 and R2 relaxation rates of backbone (15)N spins were observed compared with the diamagnetic reference (the same protein loaded with Y(3+)). The effect arises from the compensation of the chemical shift anisotropy tensor by the anisotropic dipolar shielding generated by the unpaired electron spin.

  13. On Quantum Gravity, Asymptotic Safety, and Paramagnetic Dominance

    NASA Astrophysics Data System (ADS)

    Nink, Andreas; Reuter, Martin

    2015-01-01

    We discuss the conceptual ideas underlying the Asymptotic Safety approach to the nonperturbative renormalization of gravity. By now numerous functional renormalization group studies predict the existence of a suitable nontrivial ultraviolet fixed point. We use an analogy to elementary magnetic systems to uncover the physical mechanism behind the emergence of this fixed point. It is seen to result from the dominance of certain paramagnetic-type interactions over diamagnetic ones. Furthermore, the spacetimes of Quantum Einstein Gravity behave like a polarizable medium with a "paramagnetic" response to external perturbations. Similarities with the vacuum state of Yang-Mills theory are pointed out.

  14. Van vleck paramagnetism in orthorhombic TiO2 (Brookite)

    USGS Publications Warehouse

    Senftle, F.E.; Thorpe, A.N.

    1968-01-01

    The magnetic susceptibility of the orthorhombic form of titanium dioxide has been measured from 5 to 300??K. After deducting the temperature-dependent component, which is probably due to defects or impurities, and the free-ion diamagnetic component, the Van Vleck paramagnetism was estimated to be 33??10-6 emu/mole. Comparison is made between this value and the Van Vleck paramagnetism of strontium titanate and the two tetragonal forms of titanium dioxide: rutile and anatase. ?? 1968 The American Physical Society.

  15. Extrinsic paramagnetic Meissner effect in multiphase indium-tin alloys

    NASA Astrophysics Data System (ADS)

    Chu, Shaoyan; Schwartz, Adam J.; Massalski, Thaddeus B.; Laughlin, David E.

    2006-09-01

    The authors report the observation of a paramagnetic Meissner effect (PME) in a two-phase In-Sn alloy in which the phases become superconducting at different temperatures. This observation has been tested and confirmed by constructing an artificial In-Sn sample in which one phase was deliberately encapsulated in another. The authors conclude that PME is extrinsic, rather than intrinsic, and thus describe it as an extrinsic paramagnetic Meissner effect (EPME). It is expected to occur in multiple-phase samples where more than one phase is superconducting and where a suitable microstructural phase distribution is developed. In such samples EPME can be produced at will.

  16. Magnetic resonance force microscopy with a paramagnetic probe

    DOE PAGES

    Berman, G. P.; Gorshkov, V. N.; Tsifrinovich, V. I.

    2017-04-01

    Here, we consider theoretically extension of magnetic resonance force microscopy (MRFM) replacing a ferromagnetic probe on a cantilever tip (CT) with a paramagnetic one (PMRFM). The dynamics of the interaction between the paramagnetic probe and a local magnetic moment in a sample is analyzed, using a quasi-classical approach. We show that the application of a proper sequence of electromagnetic pulses provides a significant deflection of the CT from the initial equilibrium position. Periodic application of these sequences of pulses results in quasi-periodic CT deflections from the equilibrium, which can be used for detection of the magnetic moment in a sample.

  17. Enhancement of Paramagnetic Relaxation by Photoexcited Gold Nanorods

    PubMed Central

    Wen, Tao; Wamer, Wayne G.; Subczynski, Witold K.; Hou, Shuai; Wu, Xiaochun; Yin, Jun-Jie

    2016-01-01

    Electron spin resonance (ESR) spectroscopy was used to investigate the switchable, light-dependent effects of gold nanorods (GNRs) on paramagnetic properties of nitroxide spin probes. The photoexcited GNRs enhanced the spin-spin and spin-lattice relaxations of nitroxide spin probes. It was shown that molecular oxygen plays the key role in this process. Our results demonstrate that ESR is a powerful tool for investigating the events following photoexcitation of GNRs. The novel light-controlled effects observed for GNRs on paramagnetic properties and activities of surrounding molecules have a number of significant applications where oxygen sensing and oxygen activity is important. PMID:27071507

  18. Electron paramagnetic resonance study of ZnO varistor material.

    PubMed

    Baraki, Raschid; Zierep, Paul; Erdem, Emre; Weber, Stefan; Granzow, Torsten

    2014-03-19

    Matsuoka-type zinc oxide (ZnO) varistor material was synthesized using a conventional solid-state reaction method. X-band electron paramagnetic resonance (EPR) data revealed that Mn ions substitute in the ZnO lattice with a 2+ paramagnetic state. Co ions with either 3+ or 2+ oxidation states are only detectable at cryogenic temperatures. A Cr(3+) EPR signal was strongly suppressed or masked by a Mn(2+) signal. Photoluminescence and electrical results indicated that the varistor sample has fewer intrinsic defects and much higher resistivity as compared to undoped and metal-ion doped ZnO.

  19. Magnetic resonance force microscopy with a paramagnetic probe

    NASA Astrophysics Data System (ADS)

    Berman, G. P.; Gorshkov, V. N.; Tsifrinovich, V. I.

    2017-04-01

    We consider theoretically extension of magnetic resonance force microscopy (MRFM) replacing a ferromagnetic probe on a cantilever tip (CT) with a paramagnetic one (PMRFM). The dynamics of the interaction between the paramagnetic probe and a local magnetic moment in a sample is analyzed, using a quasi-classical approach. We show that the application of a proper sequence of electromagnetic pulses provides a significant deflection of the CT from the initial equilibrium position. Periodic application of these sequences of pulses results in quasi-periodic CT deflections from the equilibrium, which can be used for detection of the magnetic moment in a sample.

  20. Electron paramagnetic resonance study of new paramagnetic centers in microcline-perthites from pegmatites

    NASA Astrophysics Data System (ADS)

    Matyash, I. V.; Bagmut, N. N.; Litovchenko, A. S.; Proshko, V. Ya.

    1982-08-01

    Four new types of paramagnetic centers — NH+ 3, N2-, Al-O-, E 1 — have been detected in microcline perthites from pegmatites in the Ukrainian Shield. Values are tabulated for their g and A tensors and limits of thermal stability determined. The NH+ 3 center substitutes the K+ ion. It occurs naturally in potash feldspars but is intensified by gamma or X-ray irradiation. It is regarded as a radiational development of the more general NH+ 4 ⇄ K+ isomorphism. It disappears after heating to temperatures higher than 470 K. The N2- center is an uncommon example of isomorphous substitution of a bridging oxygen, being located on a O D( m) site between T 2( o) and T 1( m) silicon sites. It is stable to 820 K. The hole center, Al-O-, has been detected on an O A(l) oxygen shared by T 1( o) and T 1( m) tetrahedra. It is stable to 590 K. The E 1 center in these alkali feldspars is similar to the E 1 center in quartz, being an electron trapped in an oxygen vacancy in the O B ( o) position. It is stable to 420 K. The NH+ 3, Al-O- and E 1 centers can be restored from temperatures above their stability limits by gamma radiation. Concentration of centers varies from sample to sample depending on conditions of formation and subsequent history of the minerals.

  1. Cancer detection based on Raman spectra super-paramagnetic clustering

    NASA Astrophysics Data System (ADS)

    González-Solís, José Luis; Guizar-Ruiz, Juan Ignacio; Martínez-Espinosa, Juan Carlos; Martínez-Zerega, Brenda Esmeralda; Juárez-López, Héctor Alfonso; Vargas-Rodríguez, Héctor; Gallegos-Infante, Luis Armando; González-Silva, Ricardo Armando; Espinoza-Padilla, Pedro Basilio; Palomares-Anda, Pascual

    2016-08-01

    The clustering of Raman spectra of serum sample is analyzed using the super-paramagnetic clustering technique based in the Potts spin model. We investigated the clustering of biochemical networks by using Raman data that define edge lengths in the network, and where the interactions are functions of the Raman spectra's individual band intensities. For this study, we used two groups of 58 and 102 control Raman spectra and the intensities of 160, 150 and 42 Raman spectra of serum samples from breast and cervical cancer and leukemia patients, respectively. The spectra were collected from patients from different hospitals from Mexico. By using super-paramagnetic clustering technique, we identified the most natural and compact clusters allowing us to discriminate the control and cancer patients. A special interest was the leukemia case where its nearly hierarchical observed structure allowed the identification of the patients's leukemia type. The goal of this study is to apply a model of statistical physics, as the super-paramagnetic, to find these natural clusters that allow us to design a cancer detection method. To the best of our knowledge, this is the first report of preliminary results evaluating the usefulness of super-paramagnetic clustering in the discipline of spectroscopy where it is used for classification of spectra.

  2. Introduction to Spin Label Electron Paramagnetic Resonance Spectroscopy of Proteins

    ERIC Educational Resources Information Center

    Melanson, Michelle; Sood, Abha; Torok, Fanni; Torok, Marianna

    2013-01-01

    An undergraduate laboratory exercise is described to demonstrate the biochemical applications of electron paramagnetic resonance (EPR) spectroscopy. The beta93 cysteine residue of hemoglobin is labeled by the covalent binding of 3-maleimido-proxyl (5-MSL) and 2,2,5,5-tetramethyl-1-oxyl-3-methyl methanethiosulfonate (MTSL), respectively. The excess…

  3. Electron paramagnetic resonance study of two smectic A liquid crystals.

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Gelerinter, E.; Fishel, D. L.

    1972-01-01

    Study of the molecular ordering in two smectic A liquid crystals using vanadyl acetylacetonate as a paramagnetic probe. The average hyperfine splitting of the spectrum in the smectic A mesophase is measured as a function of the orientation relative to the dc magnetic field of the spectrometer after alignment of the molecules of the liquid crystal.

  4. Paramagnetic-Salt Thermometer With Flux Pump And SQUID's

    NASA Technical Reports Server (NTRS)

    Strayer, Donald M.; Israelsson, Ulf E.

    1993-01-01

    Paramagnetic-salt low-temperature thermometer incorporates improved superconducting magnetic-flux pump, multiple superconducting quantum interference devices as magnetometers, and feedback stabilization of magnetic flux. Requires much smaller initial magnetizing currents and provides improved temperature resolution via suppression of drift in magnetic induction.

  5. Apparatus for magnetic separation of paramagnetic and diamagnetic material

    DOEpatents

    Doctor, R.D.

    1986-07-24

    The present invention relates to methods and apparatus for segregating paramagnetic from diamagnetic particles in particulate material and, in particular, to the open gradient magnetic separation of ash producing components and pyritic sulfur from coal. The apparatus includes a vertical cylinder and a rotatable vertical screw positioned within the cylinder, the screw having a helical blade angled downwardly and outwardly from the axis. Rotation of the vertical screw causes denser particles, which in the case of coal include pyritic sulfur and ash, which are paramagnetic, to migrate to the outside of the screw, and less dense particles, such as the low sulfur organic portion of the coal, which are diamagnetic, to migrate towards the center of the screw. A vibration mechanism attached to the screw causes the screw to vibrate during rotation, agitating and thereby accommodating further segregation of the particles. An open gradient magnetic field is applied circumferentially along the entire length of the screw by a superconducting quadrupole magnet. The open gradient magnetic field further segregates the paramagnetic-particles from the diamagnetic particles. The paramagnetic particles may then be directed from the cylinder into a first storage bin, and the diamagnetic particles, which are suitable for relatively clean combustion, may be directed into a second storage bin. 5 figs.

  6. Apparatus for magnetic separation of paramagnetic and diamagnetic material

    DOEpatents

    Doctor, Richard D.

    1988-01-01

    The present invention relates to methods and apparatus for segregating paramagnetic from diamagnetic particles in particulate material and, in particular, to the open gradient magnetic separation of ash producing components and pyritic sulfur from coal. The apparatus includes a vertical cylinder and a rotatable vertical screw positioned within the cylinder, the screw having a helical blade angled downwardly and outwardly from the axis. Rotation of the vertical screw causes denser particles, which in the case of coal include pyritic sulfur and ash, which are paramagnetic, to migrate to the outside of the screw, and less dense particles, such as the low sulfur organic portion of the coal, which are diamagnetic, to migrate towards the center of the screw. A vibration mechanism attached to the screw causes the screw to vibrate during rotation, agitating and thereby accommodating further segregation of the particles. An open gradient magnetic field is applied circumferentially along the entire length of the screw by a superconducting quadropole magnet. The open gradient magnetic field further segregates the paramagnetic particles from the diamagnetic particles. The paramagnetic particles may then be directed from the cylinder into a first storage bin, and the diamagnetic particles, which are suitable for relatively clean combustion, may be directed into a second storage bin.

  7. Apparatus for magnetic separation of paramagnetic and diamagnetic material

    DOEpatents

    Doctor, R.D.

    1988-10-18

    The present invention relates to methods and apparatus for segregating paramagnetic from diamagnetic particles in particulate material and, in particular, to the open gradient magnetic separation of ash producing components and pyritic sulfur from coal. The apparatus includes a vertical cylinder and a rotatable vertical screw positioned within the cylinder, the screw having a helical blade angled downwardly and outwardly from the axis. Rotation of the vertical screw causes denser particles, which in the case of coal include pyritic sulfur and ash, which are paramagnetic, to migrate to the outside of the screw, and less dense particles, such as the low sulfur organic portion of the coal, which are diamagnetic, to migrate towards the center of the screw. A vibration mechanism attached to the screw causes the screw to vibrate during rotation, agitating and thereby accommodating further segregation of the particles. An open gradient magnetic field is applied circumferentially along the entire length of the screw by a superconducting quadrupole magnet. The open gradient magnetic field further segregates the paramagnetic particles from the diamagnetic particles. The paramagnetic particles may then be directed from the cylinder into a first storage bin, and the diamagnetic particles, which are suitable for relatively clean combustion, may be directed into a second storage bin. 5 figs.

  8. Paramagnetic-Salt Thermometer With Flux Pump And SQUID's

    NASA Technical Reports Server (NTRS)

    Strayer, Donald M.; Israelsson, Ulf E.

    1993-01-01

    Paramagnetic-salt low-temperature thermometer incorporates improved superconducting magnetic-flux pump, multiple superconducting quantum interference devices as magnetometers, and feedback stabilization of magnetic flux. Requires much smaller initial magnetizing currents and provides improved temperature resolution via suppression of drift in magnetic induction.

  9. Introduction to Spin Label Electron Paramagnetic Resonance Spectroscopy of Proteins

    ERIC Educational Resources Information Center

    Melanson, Michelle; Sood, Abha; Torok, Fanni; Torok, Marianna

    2013-01-01

    An undergraduate laboratory exercise is described to demonstrate the biochemical applications of electron paramagnetic resonance (EPR) spectroscopy. The beta93 cysteine residue of hemoglobin is labeled by the covalent binding of 3-maleimido-proxyl (5-MSL) and 2,2,5,5-tetramethyl-1-oxyl-3-methyl methanethiosulfonate (MTSL), respectively. The excess…

  10. The Paramagnetic Pillared Bentonites as Digestive Tract MRI Contrast Agents

    NASA Astrophysics Data System (ADS)

    Mojović, Miloš; Daković, Marko; Omerašević, Mia; Mojović, Zorica; Banković, Predrag; Milutinović-Nikolić, Aleksandra; Jovanović, Dušan

    The increased use of imaging techniques in diagnostic studies, such as MRI, has contributed to the development of the wide range of new materials which could be successfully used as image improving agents. However, there is a lack of such substances in the area of gastrointestinal tract MRI. Many of the traditionally popular relaxation altering agents show poor results and disadvantages provoking black bowel, side effects of diarrhea and the presence of artifacts arising from clumping. Paramagnetic species seem to be potentially suitable agents for these studies, but contrast opacification has been reported and less than 60% of the gastrointestinal tract magnetic resonance scans showed improved delineation of abdominal pathologies. The new solution has been proposed as zeolites or smectite clays (hectorite and montmorillonite) enclosing of paramagnetic metal ions obtained by ion-exchange methods. However, such materials have problems of leakage of paramagnetic ions causing the appearance of the various side-effects. In this study we show that Co+2 and Dy+3 paramagnetic-pillared bentonites could be successfully used as MRI digestive tract non-leaching contrast agents, altering the longitudinal and transverse relaxation times of fluids in contact with the clay minerals.

  11. Studying metal ion-protein interactions: electronic absorption, circular dichroism, and electron paramagnetic resonance.

    PubMed

    Quintanar, Liliana; Rivillas-Acevedo, Lina

    2013-01-01

    Metal ions play a wide range of important functional roles in biology, and they often serve as cofactors in enzymes. Some of the metal ions that are essential for life are strongly associated with proteins, forming obligate metalloproteins, while others may bind to proteins with relatively low affinity. The spectroscopic tools presented in this chapter are suitable to study metal ion-protein interactions. Metal sites in proteins are usually low symmetry centers that differentially absorb left and right circularly polarized light. The combination of electronic absorption and circular dichroism (CD) in the UV-visible region allows the characterization of electronic transitions associated with the metal-protein complex, yielding information on the geometry and nature of the metal-ligand interactions. For paramagnetic metal centers in proteins, electron paramagnetic resonance (EPR) is a powerful tool that provides information on the chemical environment around the unpaired electron(s), as it relates to the electronic structure and geometry of the metal-protein complex. EPR can also probe interactions between the electron spin and nuclear spins in the vicinity, yielding valuable information on some metal-ligand interactions. This chapter describes each spectroscopic technique and it provides the necessary information to design and implement the study of metal ion-protein interactions by electronic absorption, CD, and EPR.

  12. Electron paramagnetic studies of the copper and iron containing soluble ammonia monooxygenase from Nitrosomonas europaea.

    PubMed

    Gilch, Stefan; Meyer, Ortwin; Schmidt, Ingo

    2010-08-01

    Soluble ammonia monooxygenase (AMO) from Nitrosomonas europaea was purified to homogeneity and metals in the active sites of the enzyme (Cu, Fe) were analyzed by electron paramagnetic resonance (EPR) spectroscopy. EPR spectra were obtained for a type 2 Cu(II) site with g(parallel) = 2.24, A(parallel) = 18.4 mT and g(perpendicular) = 2.057 as well as for heme and non heme iron present in purified soluble AMO from N. europaea. A second type 2 Cu(II) EPR signal with g(parallel) = 2.29, A(parallel) = 16.1 mT and g(perpendicular) = 2.03 appeared in the spectrum of the ferricyanide oxidized enzyme and was attributed to oxidation of cuprous sites. Comparison of EPR-detectable Cu(2+) with total copper determined by inductively coupled plasma-mass spectrometry (ICP-MS) suggests that there are six paramagnetic Cu(2+) and three diamagnetic Cu(1+) per heterotrimeric soluble AMO (two paramagnetic and one diamagnetic Cu per alphabetagamma-protomer). A trigonal EPR signal at g = 6.01, caused by a high-spin iron, indicative for cytochrome bound iron, and a rhombic signal at g = 4.31, characteristic of specifically bound Fe(3+) was detectable. The binding of nitric oxide in the presence of reductant resulted in a ferrous S = 3/2 signal, characteristic of a ferrous nitrosyl complex. Inactivation of soluble AMO with acetylene did neither diminish the ferrous signal nor the intensity of the Cu(2+)-EPR signal.

  13. A little spin on the side: solvent and temperature dependent paramagnetism in [Ru(II)(bpy)2(phendione)](2+).

    PubMed

    Schmidt, Robert D; Kent, Caleb A; Concepcion, Javier J; Lin, Wenbin; Meyer, Thomas J; Forbes, Malcolm D E

    2014-12-21

    Solvent and temperature dependent paramagnetism is reported for the complex [Ru(II)(bpy)2(phendione)](PF6)2 (bpy = 2,2'-bipyridine, phendione = 1,10-phenanthroline-5,6-dione), . Magnetometry, (1)H-NMR, EPR and substituent effects confirm that the paramagnetic character is localized on the phendione ligand, and arises due to mixing of the MLCT excited state with an open shell triplet state on the phendione moiety, a process that is most likely driven by aromatization. The stabilized open shell phendione structure, in which the triplet lies lower in energy than the singlet, can then be thermally populated from the ground state of the complex. This process is facilitated by admixture of singlet character from the MLCT state. Paramagnetic behavior is absent in the free phendione ligand, and disappears in the presence of Lewis acids and in the presence of water due to hydrogen bonding (or hydrate formation at sufficient water concentrations). Control experiments rule out the presence of monoradicals such as semiquinone anions. Implications for spin filtering, sensing, and other electronic applications using such structures are discussed.

  14. Dynamics of paramagnetic squares in uniform magnetic fields

    NASA Astrophysics Data System (ADS)

    Du, Di; He, Peng; Zeng, Yongchao; Biswal, Sibani Lisa

    2016-11-01

    The magnetic forces between paramagnetic squares cannot be calculated using a classic dipolar model because the magnetic field distribution is not uniform within square particles. Here, we present the calculation of magnetic forces and torques on paramagnetic squares in a uniform 2-D magnetic field using a Laplace's equation solver. With these calculations, we simulate the variations in equilibrium configurations as a function of number of interacting squares. For example, a single square orients with its diagonal directed to the external field while a system of multiple squares will assemble into chain-like structures with their edges directed to the external field. Unlike chains of spherical magnetic particles, that easily stagger themselves to aggregate, chains consisting of magnetic squares are unable to aggregate due to interchain repulsion.

  15. Biocompatible Collagen Paramagnetic Scaffold for Controlled Drug Release.

    PubMed

    Bettini, Simona; Bonfrate, Valentina; Syrgiannis, Zois; Sannino, Alessandro; Salvatore, Luca; Madaghiele, Marta; Valli, Ludovico; Giancane, Gabriele

    2015-09-14

    A porous collagen-based hydrogel scaffold was prepared in the presence of iron oxide nanoparticles (NPs) and was characterized by means of infrared spectroscopy and scanning electron microscopy. The hybrid scaffold was then loaded with fluorescein sodium salt as a model compound. The release of the hydrosoluble species was triggered and accurately controlled by the application of an external magnetic field, as monitored by fluorescence spectroscopy. The biocompatibility of the proposed matrix was also tested by the MTT assay performed on 3T3 cells. Cell viability was only slightly reduced when the cells were incubated in the presence of the collagen-NP hydrogel, compared to controls. The economicity of the chemical protocol used to obtain the paramagnetic scaffolds as well as their biocompatibility and the safety of the external trigger needed to induce the drug release suggest the proposed collagen paramagnetic matrices for a number of applications including tissue engeneering and drug delivery.

  16. Spin injection and spin transport in paramagnetic insulators

    DOE PAGES

    Okamoto, Satoshi

    2016-02-22

    We investigate the spin injection and the spin transport in paramagnetic insulators described by simple Heisenberg interactions using auxiliary particle methods. Some of these methods allow access to both paramagnetic states above magnetic transition temperatures and magnetic states at low temperatures. It is predicted that the spin injection at an interface with a normal metal is rather insensitive to temperatures above the magnetic transition temperature. On the other hand below the transition temperature, it decreases monotonically and disappears at zero temperature. We also analyze the bulk spin conductance. We show that the conductance becomes zero at zero temperature as predictedmore » by linear spin wave theory but increases with temperature and is maximized around the magnetic transition temperature. These findings suggest that the compromise between the two effects determines the optimal temperature for spintronics applications utilizing magnetic insulators.« less

  17. Spin injection and spin transport in paramagnetic insulators

    SciTech Connect

    Okamoto, Satoshi

    2016-02-22

    We investigate the spin injection and the spin transport in paramagnetic insulators described by simple Heisenberg interactions using auxiliary particle methods. Some of these methods allow access to both paramagnetic states above magnetic transition temperatures and magnetic states at low temperatures. It is predicted that the spin injection at an interface with a normal metal is rather insensitive to temperatures above the magnetic transition temperature. On the other hand below the transition temperature, it decreases monotonically and disappears at zero temperature. We also analyze the bulk spin conductance. We show that the conductance becomes zero at zero temperature as predicted by linear spin wave theory but increases with temperature and is maximized around the magnetic transition temperature. These findings suggest that the compromise between the two effects determines the optimal temperature for spintronics applications utilizing magnetic insulators.

  18. Nuclear spin-lattice relaxation in nanofluids with paramagnetic impurities.

    PubMed

    Furman, Gregory B; Goren, Shaul D; Meerovich, Victor M; Sokolovsky, Vladimir L

    2015-12-01

    We study the spin-lattice relaxation of the nuclear spins in a liquid or a gas entrapped in nanosized ellipsoidal cavities with paramagnetic impurities. Two cases are considered where the major axes of cavities are in orientational order and isotropically disordered. The evolution equation and analytical expression for spin lattice relaxation time are obtained which give the dependence of the relaxation time on the structural parameters of a nanocavity and the characteristics of a gas or a liquid confined in nanocavities. For the case of orientationally ordered cavities, the relaxation process is exponential. When the nanocavities are isotropically disordered, the time dependence of the magnetization is significantly non-exponential. As shown for this case, the relaxation process is characterized by two time constants. The measurements of the relaxation time, along with the information about the cavity size, allow determining the shape and orientation of the nanocavity and concentration of the paramagnetic impurities.

  19. Electron-paramagnetic resonance detection with software time locking.

    PubMed

    Aloisi, Giovanni; Mannini, Matteo; Caneschi, Andrea; Dolci, David; Carlà, Marcello

    2014-02-01

    A setup for electron paramagnetic resonance with narrow band digital detection is described. A low frequency reference tone is added to the radio frequency signal. This reference signal, after digital detection, is used to lock the resonance signal, even in the absence of hardware time locking among the radio frequency generator, the conversion local oscillators, and the sampling stage. Results obtained with 2,2-Diphenyl-1-Pycryl-Hydrazil are presented and discussed.

  20. Main characteristics of a Brayton refrigeration cycle of paramagnetic salt

    NASA Astrophysics Data System (ADS)

    Chen, Lixuan; Yan, Zijun

    1994-02-01

    The characteristics of a magnetic Brayton refrigeration cycle are investigated on the basis of the general equation of state of a simple paramagnetic salt. The refrigeration heat and the coefficient of performance of the magnetic Brayton refrigeration cycle are derived, and the effect of regeneration on the performance is discussed. It is expounded that the magnetic Brayton refrigeration cycle possesses both advantages of the magnetic Ericsson and the magnetic Carnot refrigeration cycles.

  1. Hyperfine Structure and Exchange Narrowing of Paramagnetic Resonance

    DOE R&D Accomplishments Database

    Townes, C. H.; Turkevich, J.

    1950-01-01

    Discussion of electronic paramagnetic resonance for the free radical á, á-diphenyl â-picryl hydrazyl as observed by its effect on the transmission of microwave through a TE{sub 01} cavity with a small amount of the free radical placed approximately on the axis of the cavity; the half-width of this resonance at half maximum absorption was 1.45 oersteds.

  2. Detection of nitric oxide by electron paramagnetic resonance spectroscopy.

    PubMed

    Hogg, Neil

    2010-07-15

    Electron paramagnetic resonance (EPR) spectroscopy has been used in a number of ways to study nitric oxide chemistry and biology. As an intrinsically stable and relatively unreactive diatomic free radical, the challenges of detecting this species by EPR are somewhat different from those of transient radical species. This review gives a basic introduction to EPR spectroscopy and discusses its uses to assess and quantify nitric oxide formation in biological systems.

  3. The role of spinning electrons in paramagnetic phenomena

    NASA Technical Reports Server (NTRS)

    Bose, D. M.

    1986-01-01

    An attempt is made to explain paramagnetic phenomena without assuming the orientation of a molecule or ion in a magnetic field. Only the spin angular momentum is assumed to be responsible. A derivative of the Gurie-Langevin law and the magnetic moments of ions are given as a function of the number of electrons in an inner, incomplete shell. An explanation of Gerlach's experiments with iron and nickel vapors is attempted. An explanation of magnetomechanical experiments with ferromagne elements is given.

  4. A point about electron paramagnetic resonance detection of irradiated foodstuffs

    NASA Astrophysics Data System (ADS)

    Douifi, Leila; Raffi, Jacques; Stocker, Pierre; Dole, François

    1998-12-01

    This paper makes a point about the identification of irradiated foodstuffs by means of electron paramagnetic resonance (EPR) or electron spin resonance (ESR). EPR is the most accurate method for such routine applications since radicals are stabilised for a long time in all (or part of) foods that are in solid and dry states; consequently, EPR can be applied to meat and fish bones, fruit and relative products (from vegetal origin). More details are given for mollusc shells, such as oysters and mussels.

  5. Electron Paramagnetic Resonance Characterization of Membrane Bound Iron-Sulfur Clusters and Aconitase in Plant Mitochondria

    PubMed Central

    Brouquisse, Renaud; Gaillard, Jacques; Douce, Roland

    1986-01-01

    Electron paramagnetic resonance (EPR) characteristics of the iron-sulfur clusters of potato tuber mitochondria have been examined in various subfractions of the mitochondria. We confirm that EPR signals comparable to those of the iron-sulfur proteins of mammalian mitochondria respiratory complexes are also present in plant mitochondria. Two distinct iron-sulfur centers paramagnetic in the oxidized state exhibit signals which differ in their detailed line shape and field position. One of these which is present in the inner membrane corresponds to center S.3. The EPR spectrum of the soluble fraction revealed the presence of another center with a low field maximum at g = 2.03 and is associated with aconitase. The EPR signal observed in the mitochondrial matrix from potato tuber and characteristic of 3Fe cluster is significantly changed in shape after addition of citrate and differs clearly from the spectrum of pig heart mitochondrial aconitase. The aconitase in plant mitochondria differs from that of mammalian mitochondria by several features. PMID:16664783

  6. Electron Paramagnetic Resonance of a Single NV Nanodiamond Attached to an Individual Biomolecule

    NASA Astrophysics Data System (ADS)

    Teeling-Smith, Richelle M.; Jung, Young Woo; Scozzaro, Nicolas; Cardellino, Jeremy; Rampersaud, Isaac; North, Justin A.; Šimon, Marek; Bhallamudi, Vidya P.; Rampersaud, Arfaan; Johnston-Halperin, Ezekiel; Poirier, Michael G.; Hammel, P. Chris

    2016-05-01

    A key limitation of electron paramagnetic resonance (EPR), an established and powerful tool for studying atomic-scale biomolecular structure and dynamics is its poor sensitivity, samples containing in excess of 10^12 labeled biomolecules are required in typical experiments. In contrast, single molecule measurements provide improved insights into heterogeneous behaviors that can be masked by ensemble measurements and are often essential for illuminating the molecular mechanisms behind the function of a biomolecule. We report EPR measurements of a single labeled biomolecule that merge these two powerful techniques. We selectively label an individual double-stranded DNA molecule with a single nanodiamond containing nitrogen-vacancy (NV) centers, and optically detect the paramagnetic resonance of NV spins in the nanodiamond probe. Analysis of the spectrum reveals that the nanodiamond probe has complete rotational freedom and that the characteristic time scale for reorientation of the nanodiamond probe is slow compared to the transverse spin relaxation time. This demonstration of EPR spectroscopy of a single nanodiamond labeled DNA provides the foundation for the development of single molecule magnetic resonance studies of complex biomolecular systems.

  7. Electron Paramagnetic Resonance of a Single NV Nanodiamond Attached to an Individual Biomolecule.

    PubMed

    Teeling-Smith, Richelle M; Jung, Young Woo; Scozzaro, Nicolas; Cardellino, Jeremy; Rampersaud, Isaac; North, Justin A; Šimon, Marek; Bhallamudi, Vidya P; Rampersaud, Arfaan; Johnston-Halperin, Ezekiel; Poirier, Michael G; Hammel, P Chris

    2016-05-10

    Electron paramagnetic resonance (EPR), an established and powerful methodology for studying atomic-scale biomolecular structure and dynamics, typically requires in excess of 10(12) labeled biomolecules. Single-molecule measurements provide improved insights into heterogeneous behaviors that can be masked in ensemble measurements and are often essential for illuminating the molecular mechanisms behind the function of a biomolecule. Here, we report EPR measurements of a single labeled biomolecule. We selectively label an individual double-stranded DNA molecule with a single nanodiamond containing nitrogen-vacancy centers, and optically detect the paramagnetic resonance of nitrogen-vacancy spins in the nanodiamond probe. Analysis of the spectrum reveals that the nanodiamond probe has complete rotational freedom and that the characteristic timescale for reorientation of the nanodiamond probe is slow compared with the transverse spin relaxation time. This demonstration of EPR spectroscopy of a single nanodiamond-labeled DNA provides the foundation for the development of single-molecule magnetic resonance studies of complex biomolecular systems.

  8. Four-component relativistic density functional theory calculations of NMR shielding tensors for paramagnetic systems.

    PubMed

    Komorovsky, Stanislav; Repisky, Michal; Ruud, Kenneth; Malkina, Olga L; Malkin, Vladimir G

    2013-12-27

    A four-component relativistic method for the calculation of NMR shielding constants of paramagnetic doublet systems has been developed and implemented in the ReSpect program package. The method uses a Kramer unrestricted noncollinear formulation of density functional theory (DFT), providing the best DFT framework for property calculations of open-shell species. The evaluation of paramagnetic nuclear magnetic resonance (pNMR) tensors reduces to the calculation of electronic g tensors, hyperfine coupling tensors, and NMR shielding tensors. For all properties, modern four-component formulations were adopted. The use of both restricted kinetically and magnetically balanced basis sets along with gauge-including atomic orbitals ensures rapid basis-set convergence. These approaches are exact in the framework of the Dirac-Coulomb Hamiltonian, thus providing useful reference data for more approximate methods. Benchmark calculations on Ru(III) complexes demonstrate good performance of the method in reproducing experimental data and also its applicability to chemically relevant medium-sized systems. Decomposition of the temperature-dependent part of the pNMR tensor into the traditional contact and pseudocontact terms is proposed.

  9. Experimental Study of Rayleigh-Taylor Instability Using Paramagnetic Fluids

    NASA Astrophysics Data System (ADS)

    Tsiklashvili, Vladimer; Likhachev, Oleg; Jacobs, Jeffry

    2009-11-01

    Experiments that take advantage of the properties of paramagnetic liquids are used to study Rayleigh-Taylor instability. A gravitationally unstable combination of a paramagnetic salt solution and a nonmagnetic solution is initially stabilized by a magnetic field gradient that is produced by the contoured pole-caps of a large electromagnet. Rayleigh-Taylor instability originates with the rapid removal of current from the electromagnet, which results in the heavy liquid falling into the light liquid due to gravity and, thus, mixing with it. The mixing zone is visualized by back-lit photography and is recorded with a digital video camera. For visualization purposes, a blue-green dye is added to the magnetic fluid. The mixing rate of the two liquids is determined from an averaged dye concentration across the mixing layer by means of the Beer-Lambert law. After removal of the suspending magnetic field, the initially flat interface between the two liquids develops a random surface pattern with the dominant length scale well approximated by the fastest growing wavelength in accordance with the viscous linear stability theory. Several combinations of paramagnetic and nonmagnetic solutions have been considered during the course of the research. A functional dependence of the mixing layer growth constant, α, on the properties of the liquids is a primary subject of the present study.

  10. Tris buffer modulates polydopamine growth, aggregation, and paramagnetic properties.

    PubMed

    Della Vecchia, Nicola Fyodor; Luchini, Alessandra; Napolitano, Alessandra; D'Errico, Gerardino; Vitiello, Giuseppe; Szekely, Noemi; d'Ischia, Marco; Paduano, Luigi

    2014-08-19

    Despite the growing technological interest of polydopamine (dopamine melanin)-based coatings for a broad variety of applications, the factors governing particle size, shape, and electronic properties of this bioinspired multifunctional material have remained little understood. Herein, we report a detailed characterization of polydopamine growth, particle morphology, and paramagnetic properties as a function of dopamine concentration and nature of the buffer (pH 8.5). Dynamic Light Scattering data revealed an increase in the hydrodynamic radii (Rh) of melanin particles with increasing dopamine concentration in all buffers examined, especially in phosphate buffer. Conversely, a marked inhibition of particle growth was apparent in Tris buffer, with Rh remaining as low as <100 nm during polymerization of 0.5 mM dopamine. Small angle neutron scattering data suggested formation of bidimensional structures in phosphate or bicarbonate buffers, while apparently three-dimensional fractal objects prevailed in Tris buffer. Finally, electron paramagnetic resonance spectra revealed a broader signal amplitude with a peculiar power saturation decay profile for polydopamine samples prepared in Tris buffer, denoting more homogeneous paramagnetic centers with respect to similar samples obtained in phosphate and bicarbonate buffers. Overall, these results disclose Tris buffer as an efficient modulator of polydopamine buildup and properties for the rational control and fine-tuning of melanin aggregate size, morphology, and free radical behavior.

  11. Holographic model for the paramagnetism/antiferromagnetism phase transition

    NASA Astrophysics Data System (ADS)

    Cai, Rong-Gen; Yang, Run-Qiu

    2015-04-01

    In this paper we build a holographic model of paramagnetism/antiferromagnetism phase transition, which is realized by introducing two real antisymmetric tensor fields coupling to the background gauge field strength and interacting with each other in a dyonic black brane background. In the case without an external magnetic field and in low temperatures, the magnetic moments condense spontaneously in an antiparallel manner with the same magnitude and the time reversal symmetry is also broken spontaneously (if the boundary spatial dimension is more than 2, spatial rotational symmetry is broken spontaneously as well), which leads to an antiferromagnetic phase. In the case with the weak external magnetic field, the magnetic susceptibility density has a peak at the critical temperature and satisfies the Curie-Weiss law in the paramagnetic phase of antiferromagnetism. In the strong external magnetic field case, there is a critical magnetic field Bc in the antiferromagnetic phase: when the magnetic field reaches Bc, the system will return into the paramagnetic phase by a second order phase transition.

  12. Complexity.

    PubMed

    Gómez-Hernández, J Jaime

    2006-01-01

    It is difficult to define complexity in modeling. Complexity is often associated with uncertainty since modeling uncertainty is an intrinsically difficult task. However, modeling uncertainty does not require, necessarily, complex models, in the sense of a model requiring an unmanageable number of degrees of freedom to characterize the aquifer. The relationship between complexity, uncertainty, heterogeneity, and stochastic modeling is not simple. Aquifer models should be able to quantify the uncertainty of their predictions, which can be done using stochastic models that produce heterogeneous realizations of aquifer parameters. This is the type of complexity addressed in this article.

  13. Time-resolved luminescence measurements of the magnetic field effect on paramagnetic photosensitizers in photodynamic reactions

    NASA Astrophysics Data System (ADS)

    Mermut, O.; Bouchard, J.-P.; Cormier, J.-F.; Desroches, P.; Diamond, K. R.; Fortin, M.; Gallant, P.; Leclair, S.; Marois, J.-S.; Noiseux, I.; Morin, J.-F.; Patterson, M. S.; Vernon, M.

    2008-02-01

    The development of multimodal molecular probes and photosensitizing agents for use in photodynamic therapy (PDT) is vital for optimizing and monitoring cytotoxic responses. We propose a combinatorial approach utilizing photosensitizing molecules that are both paramagnetic and luminescent with multimodal functionality to perturb, control, and monitor molecular-scale reaction pathways in PDT. To this end, a time-domain single photon counting lifetime apparatus with a 400 nm excitation source has been developed and integrated with a variable low field magnet (0- 350mT). The luminescence lifetime decay function was measured in the presence of a sweeping magnetic field for a custom designed photosensitizing molecule in which photoinduced electron transfer was studied The photosensitizer studied was a donor-acceptor complex synthesized using a porphyrin linked to a fullerene molecule. The magneto-optic properties were investigated for the free-base photosensitizer complex as well as those containing either diamagnetic (paired electron) or paramagnetic (unpaired electron) metal centers, Zn(II) and Cu(II). The magnetic field was employed to affect and modify the spin states of radical pairs of the photosensitizing agents via magnetically induced hyperfine and Zeeman effects. Since the Type 1 reaction pathway of an excited triplet state photosensitizer involves the production of radical species, lifetime measurements were conducted at low dissolved oxygen concentration (0.01ppm) to elucidate the dependence of the magnetic perturbation on the photosensitization mechanistic pathway. To optimize the magnetic response, a solvent study was performed examining the dependence of the emission properties on the magnetic field in solutions of varying dielectric constants. Lastly, the cytotoxicity in murine tumor cell suspensions was investigated for the novel porphyrin-fullerene complex by inducing photodynamic treatments and determining the associated cell survival.

  14. Hybrid lanthanide nanoparticles with paramagnetic shell coated on upconversion fluorescent nanocrystals.

    PubMed

    Li, Zhengquan; Zhang, Yong; Shuter, Borys; Muhammad Idris, Niagara

    2009-10-20

    Nanoparticles comprising of fluorescent probes and MRI contrast agents are highly desirable for biomedical applications due to their ability to be detected at different modes, optically and magnetically. However, most fluorescent probes in such nanoparticles synthesized so far are down-conversion phosphors such as organic dyes and quantum dots, which are known to display many intrinsic limitations. Here, we report a core-shell hybrid lanthanide nanoparticle consisting of an upconverting lanthanide nanocrystal core and a paramagnetic lanthanide complex shell. These nanoparticles are uniform in size, stable in water, and show both high MR relaxivities and upconversion fluorescence, which may have the potential to serve as a versatile imaging tool for smart detection or diagnosis in future biomedical engineering.

  15. Luminescence, electron paramagnetic resonance, and optical properties of lunar material.

    PubMed

    Geake, J E; Dollfus, A; Garlick, G F; Lamb, W; Walker, C; Steigmann, G A; Titulaer, C

    1970-01-30

    Dust samples have been found to luminesce weakly under proton excitation, but not under ultraviolet. Damage, recovery, and heating effects have been investigated. Chips of breccia show luminescence, from white inclusions only, under ultraviolet and protons. Some rock chips show general luminescence, mainly from plagioclase. No natural or excited thermoluminescence has been found for dust or chips. The electron paramagnetic resonance spectrum shows the same broad Fe(3+) dipole resonance for dust and for some chips; other chips show no response. The polarization characteristics of dust are found to be identical to those of the Sea of Tranquillity, independently of proton damage. Chips show characteristics unlike any part of the lunar surface.

  16. Magnetic refrigeration apparatus with belt of ferro or paramagnetic material

    DOEpatents

    Barclay, John A.; Stewart, Walter F.; Henke, Michael D.; Kalash, Kenneth E.

    1987-01-01

    A magnetic refrigerator operating in the 12 to 77K range utilizes a belt which carries ferromagnetic or paramagnetic material and which is disposed in a loop which passes through the center of a solenoidal magnet to achieve cooling. The magnetic material carried by the belt, which can be blocks in frames of a linked belt, can be a mixture of substances with different Curie temperatures arranged such that the Curie temperatures progressively increase from one edge of the belt to the other. This magnetic refrigerator can be used to cool and liquefy hydrogen or other fluids.

  17. The paramagnetic properties of ferromagnetic mixed-spin chain system

    NASA Astrophysics Data System (ADS)

    Hu, Ai-Yuan; Wu, Zhi-Min; Cui, Yu-Ting; Qin, Guo-Ping

    2015-01-01

    The double-time Green's function method is used to investigate the paramagnetic properties of ferromagnetic mixed-spin chain system within the random-phase approximation and Anderson-Callen's decoupling approximation. The analytic expressions of the transverse susceptibility, longitudinal susceptibility and correlation length are obtained under transverse and longitudinal magnetic field. Using the analytic expressions of the transverse and longitudinal susceptibility to fit the experimental results, our results well agree with experimental data and the results from the high temperature series expansion within a simple Padé approximation.

  18. Viscoelasticity of dynamically self-assembled paramagnetic colloidal clusters.

    PubMed

    Tierno, Pietro; Muruganathan, Ramanathan; Fischer, Thomas M

    2007-01-12

    Paramagnetic particles in a liquid above a solid dynamically self-assemble into two-dimensional (2D) viscoelastic clusters in a processing magnetic field if the precession angle exceeds the magic angle. Hexagonal clusters rotate with a frequency proportional to the precession frequency of the magnetic field. The rotation is explained by viscoelastic shear waves excited in the clusters that can be visualized slightly above the magic angle. The cluster rotation and the visualization of viscoelastic modes are independent techniques to probe the rheological properties of the cluster. We find agreement between both techniques when determining the 2D cluster viscosity eta(c) approximately 10(-11) N s/m.

  19. Electron Paramagnetic Resonance Imaging and Spectroscopy of Polydopamine Radicals.

    PubMed

    Mrówczyński, Radosław; Coy, L Emerson; Scheibe, Błażej; Czechowski, Tomasz; Augustyniak-Jabłokow, Maria; Jurga, Stefan; Tadyszak, Krzysztof

    2015-08-13

    A thorough investigation of biomimetic polydopamine (PDA) by Electron Paramagnetic Resonance (EPR) is shown. In addition, temperature dependent spectroscopic EPR data are presented in the range 3.8-300 K. Small discrepancies in magnetic susceptibility behavior are observed between previously reported melanin samples. These variations were attributed to thermally acitivated processes. More importantly, EPR spatial-spatial 2D imaging of polydopamine radicals on a phantom is presented for the first time. In consequence, a new possible application of polydopamine as EPR imagining marker is addressed.

  20. Magnetic refrigeration apparatus with belt of ferro or paramagnetic material

    DOEpatents

    Barclay, J.A.; Stewart, W.F.; Henke, M.D.; Kalash, K.E.

    1986-04-03

    A magnetic refrigerator operating in the 12 to 77 K range utilizes a belt which carries ferromagnetic or paramagnetic material and which is disposed in a loop which passes through the center of a solenoidal magnet to achieve cooling. The magnetic material carried by the belt, which can be blocks in frames of a linked belt, can be a mixture of substances with different Curie temperatures arranged such that the Curie temperatures progressively increase from one edge of the belt to the other. This magnetic refrigerator can be used to cool and liquefy hydrogen or other fluids.

  1. Multifrequency electron paramagnetic resonance study on deproteinized human bone

    NASA Astrophysics Data System (ADS)

    Strzelczak, Grażyna; Sadło, Jarosław; Danilczuk, Marek; Stachowicz, Wacław; Callens, Freddy; Vanhaelewyn, Gauthier; Goovaerts, Etienne; Michalik, Jacek

    2007-08-01

    Irradiated samples of deproteinized powdered human bone ( femur) have been examined by electron paramagnetic resonance (EPR) spectroscopy in X, Q and W bands. In the bone powder sample only one type of CO 2- radical ion is stabilized in the hydroxyapatite structure in contrast to powdered human tooth enamel, a material also containing hydroxyapatite, widely used for EPR dosimetry and in which a few radicals are stable at room temperature. It is suggested that the use of deproteinized bone for EPR dosimetry could improve the accuracy of dose determination.

  2. Electron paramagnetic resonance in Cu-doped ZnO

    NASA Astrophysics Data System (ADS)

    Buchheit, R.; Acosta-Humánez, F.; Almanza, O.

    2016-04-01

    In this work, ZnO and Cu-doped ZnO nanoparticles (Zn1-xCuxO, x = 3%), with a calcination temperature of 500∘C were synthesized using the sol-gel method. The particles were analyzed using atomic absorption spectroscopy (AAS), X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) at X-band, measurement in a temperature range from 90 K to room temperature. AAS confirmed a good correspondence between the experimental doping concentration and the theoretical value. XRD reveals the presence of ZnO phase in hexagonal wurtzite structure and a nanoparticle size for the samples synthesized. EPR spectroscopy shows the presence of point defects in both samples with g-values of g = 1.959 for shallow donors and g = 2.004 for ionized vacancies. It is important when these materials are required have been used as catalysts, as suggested that it is not necessary prepare them at higher temperature. A simulation of the Cu EPR signal using an anisotropic spin Hamiltonian was performed and showed good coincidence with the experimental spectra. It was shown that Cu2+ ions enter interstitial octahedral sites of orthorhombic symmetry in the wurtzite crystal structure. Temperature dependence of the EPR linewidth and signal intensity shows a paramagnetic behavior of the sample in the measurement range. A Néel temperature TN = 78 ± 19 K was determined.

  3. Paramagnetic ionic liquids for measurements of density using magnetic levitation.

    PubMed

    Bwambok, David K; Thuo, Martin M; Atkinson, Manza B J; Mirica, Katherine A; Shapiro, Nathan D; Whitesides, George M

    2013-09-03

    Paramagnetic ionic liquids (PILs) provide new capabilities to measurements of density using magnetic levitation (MagLev). In a typical measurement, a diamagnetic object of unknown density is placed in a container containing a PIL. The container is placed between two magnets (typically NdFeB, oriented with like poles facing). The density of the diamagnetic object can be determined by measuring its position in the magnetic field along the vertical axis (levitation height, h), either as an absolute value or relative to internal standards of known density. For density measurements by MagLev, PILs have three advantages over solutions of paramagnetic salts in aqueous or organic solutions: (i) negligible vapor pressures; (ii) low melting points; (iii) high thermal stabilities. In addition, the densities, magnetic susceptibilities, glass transition temperatures, thermal decomposition temperatures, viscosities, and hydrophobicities of PILs can be tuned over broad ranges by choosing the cation-anion pair. The low melting points and high thermal stabilities of PILs provide large liquidus windows for density measurements. This paper demonstrates applications and advantages of PILs in density-based analyses using MagLev.

  4. Classical Orbital Paramagnetism in Non-equilibrium Steady State

    NASA Astrophysics Data System (ADS)

    Deshpande, Avinash A.; Kumar, N.

    2017-09-01

    We report the results of our numerical simulation of classical-dissipative dynamics of a charged particle subjected to a non-Markovian stochastic forcing. We find that the system develops a steady-state orbital magnetic moment in the presence of a static magnetic field. Very significantly, the sign of the orbital magnetic moment turns out to be paramagnetic for our choice of parameters, varied over a wide range. This is shown specifically for the case of classical dynamics driven by a Kubo-Anderson type non-Markovian noise. Natural spatial boundary condition was imposed through (1) a soft (harmonic) confining potential, and (2) a hard potential, approximating a reflecting wall. There was no noticeable qualitative difference. What appears to be crucial to the orbital magnetic effect noticed here is the non-Markovian property of the driving noise chosen. Experimental realization of this effect on the laboratory scale, and its possible implications are briefly discussed. We would like to emphasize that the above steady-state classical orbital paramagnetic moment complements, rather than contradicts the Bohr-van Leeuwen (BvL) theorem on the absence of classical orbital diamagnetism in thermodynamic equilibrium.

  5. Different metamagnetism between paramagnetic Ce and Yb isomorphs

    NASA Astrophysics Data System (ADS)

    Miyake, Atsushi; Sato, Yoshiaki; Tokunaga, Masashi; Jatmika, Jumaeda; Ebihara, Takao

    2017-08-01

    To solve the puzzle of metamagnetic phenomena in heavy-fermion systems, we have compared paramagnetic isostructural Ce and Yb systems, CeNi2Ge2 and YbNi2Ge2 , both of which are located near a magnetic instability. The most intriguing result is the discovery of a metamagneticlike anomaly for isomorphic Ce and Yb paramagnetic systems from magnetization measurements in a pulsed magnetic field. Similar to other metamagnets, the metamagnetic transition fields for both compounds are well scaled by the temperature Tχmax, at which the magnetic susceptibility shows a maximum. In addition, for CeNi2Ge2 , a peak of nonlinear susceptibility χ3 appears at approximately Tχmax/2 , as for other heavy-fermion metamagnets. In contrast, YbNi2Ge2 shows only a sign change for χ3 at Tχmax, as observed in itinerant metamagnets located near the ferromagnetic critical point. The metamagnetism of CeNi2Ge2 corresponds to a typical Kondo lattice system, whereas that of YbNi2Ge2 is similar to the nearly ferromagnetic itinerant systems. Other possibilities for the metamagnetic behavior of YbNi2Ge2 are also discussed.

  6. Enhanced paramagnetism of mesoscopic graphdiyne by doping with nitrogen.

    PubMed

    Zhang, Mingjia; Wang, Xiaoxiong; Sun, Huijuan; Wang, Ning; Lv, Qing; Cui, Weiwei; Long, Yunze; Huang, Changshui

    2017-09-14

    The new two-dimensional graphitic material, graphdiyne, has attracted great interest recently due to the superior intrinsic semiconductor properties. Here we investigate the magnetism of pure graphdiyne material and find it demonstrating a remarkable paramagnetic characteristic, which can be attributed to the appearance of special sp-hybridized carbon atoms. On this basis, we further introduce nitrogen with 5.29% N/C ratio into graphdiyne followed by simply annealing in a dopant source and realize a twofold enhancement of saturation moment at 2 K. Associate with the density of states calculation, we investigate the influence of the nitrogen atom doping sites on paramagnetism, and further reveal the important role of doped nitrogen atom on benzene ring in improving local magnetic moment. These results can not only help us deeply understand the intrinsic magnetism of graphdiyne, but also open an efficient way to improve magnetism of graphdiyne by hetero atom doping, like nitrogen doping, which may promote the potential application of graphdiyne in spintronics.

  7. Internalization of paramagnetic phosphatidylserine-containing liposomes by macrophages.

    PubMed

    Geelen, Tessa; Yeo, Sin Yuin; Paulis, Leonie E M; Starmans, Lucas W E; Nicolay, Klaas; Strijkers, Gustav J

    2012-08-28

    Inflammation plays an important role in many pathologies, including cardiovascular diseases, neurological conditions and oncology, and is considered an important predictor for disease progression and outcome. In vivo imaging of inflammatory cells will improve diagnosis and provide a read-out for therapy efficacy. Paramagnetic phosphatidylserine (PS)-containing liposomes were developed for magnetic resonance imaging (MRI) and confocal microscopy imaging of macrophages. These nanoparticles also provide a platform to combine imaging with targeted drug delivery. Incorporation of PS into liposomes did not affect liposomal size and morphology up to 12 mol% of PS. Liposomes containing 6 mol% of PS showed the highest uptake by murine macrophages, while only minor uptake was observed in endothelial cells. Uptake of liposomes containing 6 mol% of PS was dependent on the presence of Ca2+ and Mg2+. Furthermore, these 6 mol% PS-containing liposomes were mainly internalized into macrophages, whereas liposomes without PS only bound to the macrophage cell membrane. Paramagnetic liposomes containing 6 mol% of PS for MR imaging of macrophages have been developed. In vitro these liposomes showed specific internalization by macrophages. Therefore, these liposomes might be suitable for in vivo visualization of macrophage content and for (visualization of) targeted drug delivery to inflammatory cells.

  8. Internalization of paramagnetic phosphatidylserine-containing liposomes by macrophages

    PubMed Central

    2012-01-01

    Background Inflammation plays an important role in many pathologies, including cardiovascular diseases, neurological conditions and oncology, and is considered an important predictor for disease progression and outcome. In vivo imaging of inflammatory cells will improve diagnosis and provide a read-out for therapy efficacy. Paramagnetic phosphatidylserine (PS)-containing liposomes were developed for magnetic resonance imaging (MRI) and confocal microscopy imaging of macrophages. These nanoparticles also provide a platform to combine imaging with targeted drug delivery. Results Incorporation of PS into liposomes did not affect liposomal size and morphology up to 12 mol% of PS. Liposomes containing 6 mol% of PS showed the highest uptake by murine macrophages, while only minor uptake was observed in endothelial cells. Uptake of liposomes containing 6 mol% of PS was dependent on the presence of Ca2+ and Mg2+. Furthermore, these 6 mol% PS-containing liposomes were mainly internalized into macrophages, whereas liposomes without PS only bound to the macrophage cell membrane. Conclusions Paramagnetic liposomes containing 6 mol% of PS for MR imaging of macrophages have been developed. In vitro these liposomes showed specific internalization by macrophages. Therefore, these liposomes might be suitable for in vivo visualization of macrophage content and for (visualization of) targeted drug delivery to inflammatory cells. PMID:22929153

  9. The Bain path of paramagnetic Fe-Cr based alloys

    NASA Astrophysics Data System (ADS)

    Al-Zoubi, N.; Johansson, B.; Nilson, G.; Vitos, L.

    2011-07-01

    Employing the first-principles exact muffin-tin orbital method in combination with the coherent potential approximation, we calculated the total energy and local magnetic moments of paramagnetic Fe-Cr-M (M = Cr, Mn, Fe, Co, Ni) alloys along the tetragonal distortion (Bain) path connecting the body centered cubic (bcc) and the face centered cubic (fcc) structures. The paramagnetic phase is modeled by the disordered local magnetic moment scheme. For all alloys, the local magnetic moments on Fe atoms decrease from the maximum value corresponding to the bcc phase toward the minimum value realized for the fcc phase. Cobalt atoms have non-vanishing local magnetic moments only for tetragonal lattices with c/a < 1.30, whereas the local magnetic moments of Mn show weak crystal structure dependence. We find that Cr stabilizes the bcc lattice and increases the energy barrier as going from the bcc toward the fcc phase. Both Co and Ni favor the fcc lattice and decrease the energy barrier relative to the bcc phase. On the other hand, the tetragonal distortion around the fcc phase is facilitated by Cr and to a somewhat lesser extent also by Ni, but strongly impeded by Co. Manganese has negligible effect on the structural energy difference as well as on the energy barrier along the Bain path. Our findings on the alloying induced softening or hardening of Fe-Cr based alloys against tetragonal distortions are important for understanding the interstitial driven martensitic transformations in alloy steels.

  10. Applications of electron paramagnetic resonance spectroscopy to study interactions of iron proteins in cells with nitric oxide

    NASA Astrophysics Data System (ADS)

    Cammack, R.; Shergill, J. K.; Ananda Inalsingh, V.; Hughes, Martin N.

    1998-12-01

    Nitric oxide and species derived from it have a wide range of biological functions. Some applications of electron paramagnetic resonance (EPR) spectroscopy are reviewed, for observing nitrosyl species in biological systems. Nitrite has long been used as a food preservative owing to its bacteriostatic effect on spoilage bacteria. Nitrosyl complexes such as sodium nitroprusside, which are added experimentally as NO-generators, themselves produce paramagnetic nitrosyl species, which may be seen by EPR. We have used this to observe the effects of nitroprusside on clostridial cells. After growth in the presence of sublethal concentrations of nitroprusside, the cells show they have been converted into other, presumably less toxic, nitrosyl complexes such as (RS) 2Fe(NO) 2. Nitric oxide is cytotoxic, partly due to its effects on mitochondria. This is exploited in the destruction of cancer cells by the immune system. The targets include iron-sulfur proteins. It appears that species derived from nitric oxide such as peroxynitrite may be responsible. Addition of peroxynitrite to mitochondria led to depletion of the EPR-detectable iron-sulfur clusters. Paramagnetic complexes are formed in vivo from hemoglobin, in conditions such as experimental endotoxic shock. This has been used to follow the course of production of NO by macrophages. We have examined the effects of suppression of NO synthase using biopterin antagonists. Another method is to use an injected NO-trapping agent, Fe-diethyldithiocarbamate (Fe-DETC) to detect accumulated NO by EPR. In this way we have observed the effects of depletion of serum arginine by arginase. In brains from victims of Parkinson's disease, a nitrosyl species, identified as nitrosyl hemoglobin, has been observed in substantia nigra. This is an indication for the involvement of nitric oxide or a derived species in the damage to this organ.

  11. In vivo nitric oxide detection in the septic rat brain by electron paramagnetic resonance.

    PubMed

    Suzuki, Y; Fujii, S; Numagami, Y; Tominaga, T; Yoshimoto, T; Yoshimura, T

    1998-03-01

    To detect nitric oxide (NO) in the rat brain during lipopolysaccharide (LPS)-induced sepsis, electron paramagnetic resonance (EPR) was employed with the NO trapping technique, using an iron and N,N-diethyldithiocarbamate (DETC) complex. An X-band (about 9.5 GHz) EPR system detected a triplet signal (g = 2.038) derived from an NO-Fe-DETC complex being superimposed on the g(perpendicular) signal of Cu-DETC complex at liquid nitrogen temperature. The height of the triplet signal peaked seven hours after injection of 40 mg/kg of LPS, and over 25 x 10(4) U/kg of IFN-gamma enhanced the LPS-induced NO formation. Pretreatment with N(G)-monomethyl-L-arginine (NMMA), an NO synthase inhibitor, deleted only the triplet signal. A triplet signal (g(iso) = 2.040, aN = 1.28 mT) derived from the NO-Fe-DETC complex was also observed at ambient temperature. Then, a home-built 700 MHz EPR system was used to detect an NO signal in the septic rat brain in vivo. We successfully monitored the NO-Fe-DETC signal in the head region of a living rat under the condition that provided maximum height of the NO-Fe-DETC signal in the X-band EPR study. Pretreatment with NMMA again deleted the NO-Fe-DETC signal. This is the first EPR observation of endogenous NO in the brain of living rats.

  12. Synthesis and characterization of nanoparticles, consisting of a gadolinium paramagnetic core and a mesoporous silica shell, for controlled delivery of hydrophobic drugs

    NASA Astrophysics Data System (ADS)

    Stefanakis, Dimitrios; Ghanotakis, Demetrios

    2014-01-01

    As a strategy to improve drug delivery systems, paramagnetic gadolinium nanoparticles consisting of a paramagnetic nucleus (Gd2(OH)5NO3) and a mesoporous silica shell were prepared. The novelty of these nanoparticles is that the hydrophobic environment in the pores allows for facile immobilization of drugs that are not freely soluble in water. This was demonstrated by loading the pores of the nanoparticles with either the antibiotic chlortetracycline (ctcl) or the anticancer drug chlorambucil (cmbl). The structural and magnetic properties of the resulting drug-nanoparticle complexes were extensively characterized by various techniques which revealed that they were both paramagnetic and highly ordered, and had an excellent drug-loading capacity. Gradual release of both chlortetracycline and chlorambucil was demonstrated by studying their release profiles. The profiles for both GdSiO-ctcl and GdSiO-cmbl nanoparticles and their paramagnetic properties show that these species are appropriate candidates for controlled drug delivery, particularly in combination with MRI studies.

  13. Specific and Nonspecific Interactions in Ultraweak Protein–Protein Associations Revealed by Solvent Paramagnetic Relaxation Enhancements

    PubMed Central

    2015-01-01

    Weak and transient protein–protein interactions underlie numerous biological processes. However, the location of the interaction sites of the specific complexes and the effect of transient, nonspecific protein–protein interactions often remain elusive. We have investigated the weak self-association of human growth hormone (hGH, KD = 0.90 ± 0.03 mM) at neutral pH by the paramagnetic relaxation enhancement (PRE) of the amide protons induced by the soluble paramagnetic relaxation agent, gadodiamide (Gd(DTPA-BMA)). Primarily, it was found that the PREs are in agreement with the general Hwang-Freed model for relaxation by translational diffusion (J. Chem. Phys.1975, 63, 4017–4025), only if crowding effects on the diffusion in the protein solution are taken into account. Second, by measuring the PREs of the amide protons at increasing hGH concentrations and a constant concentration of the relaxation agent, it is shown that a distinction can be made between residues that are affected only by transient, nonspecific protein–protein interactions and residues that are involved in specific protein–protein associations. Thus, the PREs of the former residues increase linearly with the hGH concentration in the entire concentration range because of a reduction of the diffusion caused by the transient, nonspecific protein–protein interactions, while the PREs of the latter residues increase only at the lower hGH concentrations but decrease at the higher concentrations because of specific protein–protein associations that impede the access of gadodiamide to the residues of the interaction surface. Finally, it is found that the ultraweak aggregation of hGH involves several interaction sites that are located in patches covering a large part of the protein surface. PMID:24969589

  14. Enhanced Wireless Power Transmission Using Strong Paramagnetic Response.

    PubMed

    Ahn, Dukju; Kiani, Mehdi; Ghovanloo, Maysam

    2014-03-01

    A method of quasi-static magnetic resonant coupling has been presented for improving the power transmission efficiency (PTE) in near-field wireless power transmission, which improves upon the state of the art. The traditional source resonator on the transmitter side is equipped with an additional resonator with a resonance frequency that is tuned substantially higher than the magnetic field excitation frequency. This additional resonator enhances the magnetic dipole moment and the effective permeability of the power transmitter, owing to a phenomenon known as the strong paramagnetic response. Both theoretical calculations and experimental results show increased PTE due to amplification of the effective permeability. In measurements, the PTE was improved from 57.8% to 64.2% at the nominal distance of 15 cm when the effective permeability was 2.6. The power delivered to load was also improved significantly, with the same 10 V excitation voltage, from 0.38 to 5.26 W.

  15. Search for exotic short-range interactions using paramagnetic insulators

    DOE PAGES

    Chu, Pinghan; Weisman, E.; Liu, C. -Y.; ...

    2015-05-26

    We describe a proposed experimental search for exotic spin-coupled interactions using a solid-state paramagnetic insulator. The experiment is sensitive to the net magnetization induced by the exotic interaction between the unpaired insulator electrons with a dense, nonmagnetic mass in close proximity. An existing experiment has been used to set limits on the electric dipole moment of the electron by probing the magnetization induced in a cryogenic gadolinium gallium garnet sample on application of a strong electric field. With suitable additions, including a movable source mass, this experiment can be used to explore “monopole-dipole” forces on polarized electrons with unique ormore » unprecedented sensitivity. As a result, the solid-state, nonmagnetic construction, combined with the low-noise conditions and extremely sensitive magnetometry available at cryogenic temperatures could lead to a sensitivity over 10 orders of magnitude greater than exiting limits in the range below 1 mm.« less

  16. Modified Mason number for charged paramagnetic colloidal suspensions.

    PubMed

    Du, Di; Hilou, Elaa; Biswal, Sibani Lisa

    2016-06-01

    The dynamics of magnetorheological fluids have typically been described by the Mason number, a governing parameter defined as the ratio between viscous and magnetic forces in the fluid. For most experimental suspensions of magnetic particles, surface forces, such as steric and electrostatic interactions, can significantly influence the dynamics. Here we propose a theory of a modified Mason number that accounts for surface forces and show that this modified Mason number is a function of interparticle distance. We demonstrate that this modified Mason number is accurate in describing the dynamics of a rotating pair of paramagnetic colloids of identical or mismatched sizes in either high or low salt solutions. The modified Mason number is confirmed to be pseudoconstant for particle pairs and particle chains undergoing a stable-metastable transition during rotation. The interparticle distance term can be calculated using theory or can be measured experimentally. This modified Mason number is more applicable to magnetorheological systems where surface forces are not negligible.

  17. Modified Mason number for charged paramagnetic colloidal suspensions

    NASA Astrophysics Data System (ADS)

    Du, Di; Hilou, Elaa; Biswal, Sibani Lisa

    2016-06-01

    The dynamics of magnetorheological fluids have typically been described by the Mason number, a governing parameter defined as the ratio between viscous and magnetic forces in the fluid. For most experimental suspensions of magnetic particles, surface forces, such as steric and electrostatic interactions, can significantly influence the dynamics. Here we propose a theory of a modified Mason number that accounts for surface forces and show that this modified Mason number is a function of interparticle distance. We demonstrate that this modified Mason number is accurate in describing the dynamics of a rotating pair of paramagnetic colloids of identical or mismatched sizes in either high or low salt solutions. The modified Mason number is confirmed to be pseudoconstant for particle pairs and particle chains undergoing a stable-metastable transition during rotation. The interparticle distance term can be calculated using theory or can be measured experimentally. This modified Mason number is more applicable to magnetorheological systems where surface forces are not negligible.

  18. Paramagnetic colloidal ribbons in a precessing magnetic field.

    PubMed

    Alvarez-Nodarse, R; Quintero, N R; Mertens, F G; Casic, N; Fischer, Th M

    2015-03-01

    We investigate the dynamics of a kink in a damped parametrically driven nonlinear Klein-Gordon equation. We show by using a method of averaging that, in the high-frequency limit, the kink moves in an effective potential and is driven by an effective constant force. We demonstrate that the shape of the solitary wave can be controlled via the frequency and the eccentricity of the modulation. This is in accordance with the experimental results reported in a recent paper [Casic et al., Phys. Rev. Lett. 110, 168302 (2013)], where the dynamic self-assembly and propulsion of a ribbon formed from paramagnetic colloids in a time-dependent magnetic field has been studied.

  19. Search for exotic short-range interactions using paramagnetic insulators

    SciTech Connect

    Chu, Pinghan; Weisman, E.; Liu, C. -Y.; Long, J. C.

    2015-05-26

    We describe a proposed experimental search for exotic spin-coupled interactions using a solid-state paramagnetic insulator. The experiment is sensitive to the net magnetization induced by the exotic interaction between the unpaired insulator electrons with a dense, nonmagnetic mass in close proximity. An existing experiment has been used to set limits on the electric dipole moment of the electron by probing the magnetization induced in a cryogenic gadolinium gallium garnet sample on application of a strong electric field. With suitable additions, including a movable source mass, this experiment can be used to explore “monopole-dipole” forces on polarized electrons with unique or unprecedented sensitivity. As a result, the solid-state, nonmagnetic construction, combined with the low-noise conditions and extremely sensitive magnetometry available at cryogenic temperatures could lead to a sensitivity over 10 orders of magnitude greater than exiting limits in the range below 1 mm.

  20. Collective modes in the paramagnetic phase of the Hubbard model

    NASA Astrophysics Data System (ADS)

    Dao, Vu Hung; Frésard, Raymond

    2017-04-01

    The charge dynamical response function of the Hubbard model is investigated on the square lattice in the thermodynamic limit. The obtained charge-excitation spectra consist of a continuum, a gapless collective mode with anisotropic zero-sound velocity, and a correlation-induced high-frequency mode at ω ≈U . The correlation function is calculated from Gaussian fluctuations around the paramagnetic saddle point within the Kotliar and Ruckenstein slave-boson representation. Its dependence on the on-site Coulomb repulsion U and density is studied in detail. An approximate analytical expression of the high-frequency mode, which holds for any lattice with one atom in the unit cell, is derived. Comparison with numerical simulations, perturbation theory, and the polarization potential theory is carried out. We also show that magnetic instabilities tend to vanish for T ≳t /6 , and finite-temperature phase diagrams are established.

  1. Quantum Paramagnet in a π Flux Triangular Lattice Hubbard Model

    NASA Astrophysics Data System (ADS)

    Rachel, Stephan; Laubach, Manuel; Reuther, Johannes; Thomale, Ronny

    2015-04-01

    We propose the π flux triangular lattice Hubbard model (π THM) as a prototypical setup to stabilize magnetically disordered quantum states of matter in the presence of charge fluctuations. The quantum paramagnetic domain of the π THM that we identify for intermediate Hubbard U is framed by a Dirac semimetal for weak coupling and by 120° Néel order for strong coupling. Generalizing the Klein duality from spin Hamiltonians to tight-binding models, the π THM maps to a Hubbard model which corresponds to the (JH,JK)=(-1 ,2 ) Heisenberg-Kitaev model in its strong coupling limit. The π THM provides a promising microscopic testing ground for exotic finite-U spin liquid ground states amenable to numerical investigation.

  2. Holographic paramagnetism-ferromagnetism phase transition with the nonlinear electrodynamics

    NASA Astrophysics Data System (ADS)

    Zhang, Cheng-Yuan; Wu, Ya-Bo; Zhang, Ya-Nan; Wang, Huan-Yu; Wu, Meng-Meng

    2017-01-01

    In the probe limit, we investigate the nonlinear electrodynamical effects of the both exponential form and the logarithmic form on the holographic paramagnetism-ferromagnetism phase transition in the background of a Schwarzschild-AdS black hole spacetime. Moreover, by comparing the exponential form of nonlinear electrodynamics with the logarithmic form of nonlinear electrodynamics and the Born-Infeld nonlinear electrodynamics which has been presented in Ref. [55], we find that the higher nonlinear electrodynamics correction makes the critical temperature smaller and the magnetic moment harder form in the case without external field. Furthermore, the increase of nonlinear parameter b will result in extending the period of the external magnetic field. Especially, the effect of the exponential form of nonlinear electrodynamics on the periodicity of hysteresis loop is more noticeable.

  3. Egyptian limestone for gamma dosimetry: an electron paramagnetic resonance study

    NASA Astrophysics Data System (ADS)

    Salama, E.

    2014-04-01

    The electron paramagnetic resonance (EPR) properties of limestone from a certain Egyptian site were investigated in order to propose an efficient and low-cost gamma dosimeter. Radiation-induced free radicals were of one type which was produced in the limestone samples at g=2.0066 after exposure to gamma radiation (60Co). EPR spectrum was recorded and analyzed. The microwave power saturation curve and the effect of changing modulation amplitude on peak-to- peak signal height were investigated. The response of limestone to different radiation doses (0.5-20 kGy) was studied. Except for the decrease in signal intensities during the first five hours following irradiation, over the period of two months fair stabilities of signal intensities were noticed. From the current results, it is possible to conclude that natural limestone may be a suitable material for radiation dosimetry in the range of irradiation processing.

  4. Magnetic nanoparticle imaging using multiple electron paramagnetic resonance activation sequences

    SciTech Connect

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

    2015-05-07

    Magnetic nanoparticles play an important role in several biomedical applications such as hyperthermia, drug targeting, and disease detection. To realize an effective working of these applications, the spatial distribution of the particles needs to be accurately known, in a non-invasive way. Electron Paramagnetic Resonance (EPR) is a promising and sensitive measurement technique for recovering these distributions. In the conventional approach, EPR is applied with a homogeneous magnetic field. In this paper, we employ different heterogeneous magnetic fields that allow to stabilize the solution of the associated inverse problem and to obtain localized spatial information. A comparison is made between the two approaches and our novel adaptation shows an average increase in reconstruction quality by 5% and is 12 times more robust towards noise. Furthermore, our approach allows to speed up the EPR measurements while still obtaining reconstructions with an improved accuracy and noise robustness compared to homogeneous EPR.

  5. Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Formanuik, Alasdair; Ariciu, Ana-Maria; Ortu, Fabrizio; Beekmeyer, Reece; Kerridge, Andrew; Tuna, Floriana; McInnes, Eric J. L.; Mills, David P.

    2017-06-01

    Our knowledge of actinide chemical bonds lags far behind our understanding of the bonding regimes of any other series of elements. This is a major issue given the technological as well as fundamental importance of f-block elements. Some key chemical differences between actinides and lanthanides—and between different actinides—can be ascribed to minor differences in covalency, that is, the degree to which electrons are shared between the f-block element and coordinated ligands. Yet there are almost no direct measures of such covalency for actinides. Here we report the first pulsed electron paramagnetic resonance spectra of actinide compounds. We apply the hyperfine sublevel correlation technique to quantify the electron-spin density at ligand nuclei (via the weak hyperfine interactions) in molecular thorium(III) and uranium(III) species and therefore the extent of covalency. Such information will be important in developing our understanding of the chemical bonding, and therefore the reactivity, of actinides.

  6. Liquid-state paramagnetic relaxation from first principles

    NASA Astrophysics Data System (ADS)

    Rantaharju, Jyrki; Vaara, Juha

    2016-10-01

    We simulate nuclear and electron spin relaxation rates in a paramagnetic system from first principles. Sampling a molecular dynamics trajectory with quantum-chemical calculations produces a time series of the instantaneous parameters of the relevant spin Hamiltonian. The Hamiltonians are, in turn, used to numerically solve the Liouville-von Neumann equation for the time evolution of the spin density matrix. We demonstrate the approach by studying the aqueous solution of the Ni2 + ion. Taking advantage of Kubo's theory, the spin-lattice (T1) and spin-spin (T2) relaxation rates are extracted from the simulations of the time dependence of the longitudinal and transverse magnetization, respectively. Good agreement with the available experimental data is obtained by the method.

  7. How paramagnetic and diamagnetic LMOCs detect picric acid from surface water and the intracellular environment: a combined experimental and DFT-D3 study.

    PubMed

    Ghosh, Pritam; Banerjee, Priyabrata

    2016-08-17

    Diamagnetic and Paramagnetic Luminescent Metal Organic Complexes (LMOCs) have been reported for Explosive and Pollutant Nitro Aromatic (epNAC) recognition. The diamagnetic complex shows a highly intense AIE induced by NEt3H(+), which disappears after picric acid recognition and subsequently RET will quench the emission intensity. Radical stabilized paramagnetic LMOCs seem to be active but show lower sensing efficiency in comparison with diamagnetic LMOCs. Solution and solid state spectroscopy studies along with DFT-D3 have been executed to enlighten the host guest interaction. Limit of PA detection is ∼250 ppb with a binding constant of 1.2 × 10(5) M(-1). Time-stepping, i.e. intervening in the problem of picric acid recognition from surface water collected from several places of West Bengal, India, has been performed. Mutagenic picric acid has been successfully detected in an aqueous medium inside both prokaryotic and eukaryotic cells at a ppm level using fluorescence microscopy.

  8. Electron paramagnetic resonance spectral study of [Mn(acs)2(2-pic)2(H2O)2] single crystals

    NASA Astrophysics Data System (ADS)

    Kocakoç, Mehpeyker; Tapramaz, Recep

    2016-03-01

    Acesulfame potassium salt is a synthetic and non-caloric sweetener. It is also important chemically for its capability of being ligand in coordination compounds, because it can bind over Nitrogen and Oxygen atoms of carbonyl and sulfonyl groups and ring oxygen. Some acesulfame containing transition metal ion complexes with mixed ligands exhibit solvato and thermo chromic properties and these properties make them physically important. In this work single crystals of Mn+2 ion complex with mixed ligand, [Mn(acs)2(2-pic)2(H2O)2], was studied with electron paramagnetic resonance (EPR) spectroscopy. EPR parameters were determined. Zero field splitting parameters indicated that the complex was highly symmetric. Variable temperature studies showed no detectable chance in spectra.

  9. Changes in mitochondrial functioning with electromagnetic radiation of ultra high frequency as revealed by electron paramagnetic resonance methods.

    PubMed

    Burlaka, Anatoly; Selyuk, Marina; Gafurov, Marat; Lukin, Sergei; Potaskalova, Viktoria; Sidorik, Evgeny

    2014-05-01

    To study the effects of electromagnetic radiation (EMR) of ultra high frequency (UHF) in the doses equivalent to the maximal permitted energy load for the staffs of the radar stations on the biochemical processes that occur in the cell organelles. Liver, cardiac and aorta tissues from the male rats exposed to non-thermal UHF EMR in pulsed and continuous modes were studied during 28 days after the irradiation by the electron paramagnetic resonance (EPR) methods including a spin trapping of superoxide radicals. The qualitative and quantitative disturbances in electron transport chain (ETC) of mitochondria are registered. A formation of the iron-nitrosyl complexes of nitric oxide (NO) radicals with the iron-sulphide (FeS) proteins, the decreased activity of FeS-protein N2 of NADH-ubiquinone oxidoreductase complex and flavo-ubisemiquinone growth combined with the increased rates of superoxide production are obtained. (i) Abnormalities in the mitochondrial ETC of liver and aorta cells are more pronounced for animals radiated in a pulsed mode; (ii) the alterations in the functioning of the mitochondrial ETC cause increase of superoxide radicals generation rate in all samples, formation of cellular hypoxia, and intensification of the oxide-initiated metabolic changes; and (iii) electron paramagnetic resonance methods could be used to track the qualitative and quantitative changes in the mitochondrial ETC caused by the UHF EMR.

  10. Nickel-Salen supported paramagnetic nanoparticles for 6-His-target recombinant protein affinity purification.

    PubMed

    Rashid, Zahra; Ghahremanzadeh, Ramin; Nejadmoghaddam, Mohammad-Reza; Nazari, Mahboobeh; Shokri, Mohammad-Reza; Naeimi, Hossein; Zarnani, Amir-Hassan

    2017-03-24

    In this research, a simple, efficient, inexpensive, rapid and high yield method for the purification of 6×histidine-tagged recombinant protein was developed. For this purpose, manganese ferrite magnetic nanoparticles (MNPs) were synthesized through a co-precipitation method and then they were conveniently surface-modified with tetraethyl orthosilicate (TEOS) in order to prevent oxidation and form high density of hydroxyl groups. Next, the salen ligand was prepared from condensation reaction of salicylaldehyde and 3-aminopropyl (trimethoxy) silane (APTMS) in 1:1 molar ratio; followed by complexation with Ni(OAc)2.4H2O. Finally, the prepared Ni(II)-salen complex conjugated to silica coated MNPs and MnFe2O4@SiO2@Ni-Salen complex nanoparticles were obtained. The functionalized nanoparticles were spherical with an average diameter around 70nm. The obtained MNPs had a saturation magnetization about 54 emu/g and had super paramagnetic character. These MNPs were used efficiently to enrich recombinant histidine-tagged (His-tagged) protein-A from bacterial cell lysate. In about 45min, highly pure His-tagged recombinant protein was obtained, as judged by SDS-PAGE analysis and silver staining. The amount of target protein in flow through and washing fractions was minimal denoting the high efficiency of purification process. The average capacity of the matrix was found to be high and about 180±15mgg(-1) (protein/MnFe2O4@SiO2@Ni-Salen complex). Collectively, purification process with MnFe2O4@SiO2@Ni-Salen complex nanoparticles is rapid, efficient, selective and whole purification can be carried out in only a single tube without the need for expensive systems.

  11. Uridine-based paramagnetic supramolecular nanoaggregate with high relaxivity capable of detecting primitive liver tumor lesions.

    PubMed

    Bhuniya, Sankarprasad; Moon, Hyeyoung; Lee, Hyunseung; Hong, Kwan Soo; Lee, Sumin; Yu, Dae-Yeul; Kim, Jong Seung

    2011-09-01

    The water soluble uridine-based paramagnetic self-assembled amphiphilic molecules (LGd2-5) with DTTA binding site were synthesized and have been characterized in regard to their T(1) magnetic resonance imaging (MRI) contrast agent (CA) properties. The water proton relaxivities have been measured in phosphate buffered saline (PBS) at 36 °C at 3 different magnetic fields. Among the self-assembled CAs, LGd3 showed unprecedented, high relaxivities of 30.3 and 23.4 mM(-1) s(-1) in PBS solution at 36 °C at 0.47 and 1.41 T, respectively. The non-covalent interactions between the new CAs and human serum albumin (HSA) have been investigated and the relaxivity was further increased by 135-215% depending on alkyl chain lengths. The chemically inertness of these complexes (LGd1, LGd2, LGd3, LGd4) against biologically most abundant metal ion (i.e. Zn(2+)) have shown within the range of commercial DTPA-based CAs. In vivo pharmacokinetics of the complex LGd3 showed highly specific for hepatocytes resulting in increase of contrast noise ratio by ∼240% in T(1)-weighted MR images of mouse liver 2 h after injection of the LGd3. It is capable to detect small hepatocellular carcinoma (HCC) with diameter of 1.5 mm.

  12. Automatic fitting to `powder' EPR spectra of coupled paramagnetic species employing Feynman's theorem

    NASA Astrophysics Data System (ADS)

    Lund, Anders; Gustafsson, Håkan; Maruani, Jean; Shiotani, Masaru

    2006-03-01

    A previous automatic fitting procedure of EPR spectra has been extended with the purpose to characterise coupled paramagnetic complexes in powders and frozen solutions. The theoretical EPR spectra were obtained by matrix diagonalization of a general spin Hamiltonian. A least-squares fitting procedure using analytical derivatives of the calculated spectrum with respect to the spectroscopic, fine structure, nuclear quadrupole, electron-electron, and hyperfine coupling tensors was used to refine those parameters. The powder spectra of matrix isolated rad CF 3 and RCF 2CF 2rad radicals, previously measured at low temperature, were reanalysed with this method. A theoretically modeled complex consisting of a Cu 2+ ion, featuring an axially symmetric g-tensor and 63Cu hyperfine structure anisotropy, and a free radical located at different orientations, with respect to the symmetry axis of the Cu 2+ ion, was examined in order to investigate the possibility to recover the magnetic parameters of the separate units and the magnetic couplings between them.

  13. Amending the anisotropy barrier and luminescence behavior of heterometallic trinuclear linear [M(II) -Ln(III) -M(II) ] (Ln(III) =Gd, Tb, Dy; M(II) =Mg/Zn) complexes by change from divalent paramagnetic to diamagnetic metal ions.

    PubMed

    Das, Sourav; Bejoymohandas, K S; Dey, Atanu; Biswas, Sourav; Reddy, M L P; Morales, Roser; Ruiz, Eliseo; Titos-Padilla, Silvia; Colacio, Enrique; Chandrasekhar, Vadapalli

    2015-04-20

    The sequential reaction of a multisite coordinating compartmental ligand [2-(2-hydroxy-3-(hydroxymethyl)-5-methylbenzylideneamino)-2-methylpropane-1,3-diol] (LH4 ) with appropriate lanthanide salts followed by the addition of [Mg(NO3 )2 ]⋅6 H2 O or [Zn(NO3 )2 ]⋅6 H2 O in a 4:1:2 stoichiometric ratio in the presence of triethylamine affords a series of isostructural heterometallic trinuclear complexes containing [Mg2 Ln](3+) (Ln=Dy, Gd, and Tb) and [Zn2 Ln](3+) (Ln=Dy, Gd, and Tb) cores. The formation of these complexes is demonstrated by X-ray crystallography as well as ESI-MS spectra. All complexes are isostructural possessing a linear trimetallic core with a central lanthanide ion. The comprehensive studies discussed involve the synthesis, structure, magnetism, and photophysical properties on this family of trinuclear [Mg2 Ln](3+) and [Zn2 Ln](3+) heterometallic complexes. [Mg2 Dy](3+) and [Zn2 Dy](3+) show slow relaxation of the magnetization below 12 K under zero applied direct current (dc) field, but without reaching a neat maximum, which is due to the overlapping with a faster quantum tunneling relaxation mediated through dipole-dipole and hyperfine interactions. Under a small applied dc field of 1000 Oe, the quantum tunneling is almost suppressed and temperature and frequency dependent peaks are observed, thus confirming the single-molecule magnet behavior of complexes [Mg2 Dy](3+) and [Zn2 Dy](3+) .

  14. Magnetic resonance studies of isotopically labeled paramagnetic proteins: (2FE-2S) ferredoxins

    SciTech Connect

    Cheng, H.; Xia, B.; Chae, Y.K.; Westler, W.M.; Markley, J.L.

    1994-12-01

    Recent developments in NMR spectroscopy, especially multidimensional, multinuclear NMR techniques, have made NMR the most versatile tool available for studying protein structure and function in solution. Unlike diamagnetic proteins, paramagnetic proteins contain centers with unpaired electrons. These unpaired electrons interact with magnetic nuclei either through chemical bonds by a contact mechanism or through space by a pseudocontact mechanism. Such interactions make the acquisition and analysis of NMR spectra of paramagnetic proteins more challenging than those of diamagnetic proteins. Some NMR signals from paramagnetic proteins are shifted outside the chemical shift region characteristic of diamagnetic proteins; these {open_quotes}hyperfine-shifted{close_quotes} resonances originate from nuclei that interact with unpaired electrons from the paramagnetic center. The large chemical shift dispersion in spectra of paramagnetic proteins makes it difficult to excite the entire spectral window and leads to distortions in the baseline. Interactions with paramagnetic centers shorten T{sub 1} and T{sub 2} relaxation times of nuclei; the consequences are line broadening and lower spectral sensitivity. Scalar (through bond) and dipolar (through space) interactions between pairs of nuclei are what give rise to crosspeak signals in multi-dimensional NMR spectra of small diamagnetic proteins. When such interactions involve a nucleus that is strongly relaxed by interaction with a paramagnetic center, specialized methods may be needed for its detection or it may be completely undetectable by present nD NMR methods.

  15. Paramagnetic Liquid Bridge in a Gravity-Compensating Magnetic Field

    NASA Technical Reports Server (NTRS)

    Mahajan, Milind P.; Tsige, Mesfin; Taylor, P. L.; Rosenblatt, Charles

    1999-01-01

    Magnetic levitation was used to stabilize cylindrical columns of a paramagnetic liquid in air between two solid supports. The maximum achievable length to diameter ratio R(sub max) was approx. (3.10 +/- 0.07), very close to the Rayleigh-Plateau limit of pi. For smaller R, the stability of the column was measured as a function of the Bond number, which could be continuously varied by adjusting the strength of the magnetic field. Liquid bridges supported by two solid surfaces have been attracting scientific attention since the time of Rayleigh and Plateau. For a cylindrical bridge of length L and diameter d, it was shown theoretically that in zero gravity the maximum slenderness ratio R (identically = L/d) is pi. The stability and ultimate collapse of such bridges is of interest because of their importance in a number of industrial processes and their potential for low gravity applications. In the presence of gravity, however, the cylindrical shape of an axisymmetric bridge tends to deform, limiting its stability and decreasing the maximum achievable value of R. Theoretical studies have discussed the stability and possible shapes of axisymmetric bridges. Experiments typically are performed in either a Plateau tank, in which the bridge is surrounded by a density-matched immiscible fluid, or in a space-borne microgravity environment. It has been shown, for example, that the stability limit R can be pushed beyond pi by using flow stabilization, by acoustic radiation pressure, or by forming columns in the presence of an axial electric field. In this work, magnetic levitation was used to simulate a low gravity environment and create quasi-cylindrical liquid columns in air. Use of a magnetic field permits us to continuously vary the Bond number B identically equal to (g)(rho)d(exp 2)/4(sigma), where g is the gravitational acceleration, rho is the density of the liquid, and sigma is the surface tension of the liquid in air. The dimensionless Bond number represents the

  16. Extrinsic Paramagnetic Meissner Effect in Multiphase Indium-Tin Alloys

    SciTech Connect

    Chu, S; Schwartz, A J; Massalski, T B; Laughlin, D E

    2005-12-02

    A well-known effect in superconducting materials below their critical temperatures (T{sub c}) is the reduction to zero of their electrical resistivities. Concomitantly, the materials become perfect diamagnets for small fields. This effect, termed the Meissner Effect, allows for the direct measurement of the transition temperature (T{sub c}) by magnetic techniques such as the superconducting quantum interference device (SQUID). A Paramagnetic Meissner Effect (PME), i.e., the unexpected observation of positive magnetic moment in a superconductor below its critical temperature during field cooling (FC), was first reported in 1989 by Svedlindh et al. (1). The origin of PME in high T{sub c} superconductors has been discussed by numerous investigators as possibly resulting from {pi}-junctions, d-wave behavior, giant vortex states, flux compression, or weak links. In conventional superconductors like Nb, the PME was ascribed to the inhomogeneous nature of such samples, whereby their surface is sufficiently different from the interior and becomes superconducting at a higher temperature than the interior on cooling, thereby trapping the magnetic flux. There remains significant controversy regarding the fundamental origin of the PME. Here, we show that the PME in two-phase and three-phase In-Sn alloys is a property resulting from the morphological distribution of the multiple phases. We propose that PME in these alloys results from microstructural encapsulation of the grains of one superconducting phase inside the grains of another (e.g., the matrix) which has a higher T{sub c}. Hence the PME in this case is extrinsic in nature rather than intrinsic to the material, and could be described as an Extrinsic Paramagnetic Meissner Effect (EPME). It may be expected to occur in multiple-phase alloy samples where more than one of the phases is superconducting, or in nominally single-phase materials where the surface of the specimen, grain boundaries, or other defects have different

  17. Paramagnetic Intermediates Generated by Radical S-Adenosylmethionine (SAM) Enzymes

    PubMed Central

    2015-01-01

    Conspectus A [4Fe–4S]+ cluster reduces a bound S-adenosylmethionine (SAM) molecule, cleaving it into methionine and a 5′-deoxyadenosyl radical (5′-dA•). This step initiates the varied chemistry catalyzed by each of the so-called radical SAM enzymes. The strongly oxidizing 5′-dA• is quenched by abstracting a H-atom from a target species. In some cases, this species is an exogenous molecule of substrate, for example, l-tyrosine in the [FeFe] hydrogenase maturase, HydG. In other cases, the target is a proteinaceous residue as in all the glycyl radical forming enzymes. The generation of this initial radical species and the subsequent chemistry involving downstream radical intermediates is meticulously controlled by the enzyme so as to prevent unwanted reactions. But the manner in which this control is exerted is unknown. Electron paramagnetic resonance (EPR) spectroscopy has proven to be a valuable tool used to gain insight into these mechanisms. In this Account, we summarize efforts to trap such radical intermediates in radical SAM enzymes and highlight four examples in which EPR spectroscopic results have shed significant light on the corresponding mechanism. For lysine 2,3-aminomutase, nearly each possible intermediate, from an analogue of the initial 5′-dA• to the product radical l-β-lysine, has been explored. A paramagnetic intermediate observed in biotin synthase is shown to involve an auxiliary [FeS] cluster whose bridging sulfide is a co-substrate for the final step in the biosynthesis of vitamin B7. In HydG, the l-tyrosine substrate is converted in unprecedented fashion to a 4-oxidobenzyl radical on the way to generating CO and CN– ligands for the [FeFe] cluster of hydrogenase. And finally, EPR has confirmed a mechanistic proposal for the antibiotic resistance protein Cfr, which methylates the unactivated sp2-hybridized C8-carbon of an adenosine base of 23S ribosomal RNA. These four systems provide just a brief survey of the ever-growing set

  18. Paramagnetic intermediates generated by radical S-adenosylmethionine (SAM) enzymes.

    PubMed

    Stich, Troy A; Myers, William K; Britt, R David

    2014-08-19

    A [4Fe-4S](+) cluster reduces a bound S-adenosylmethionine (SAM) molecule, cleaving it into methionine and a 5'-deoxyadenosyl radical (5'-dA(•)). This step initiates the varied chemistry catalyzed by each of the so-called radical SAM enzymes. The strongly oxidizing 5'-dA(•) is quenched by abstracting a H-atom from a target species. In some cases, this species is an exogenous molecule of substrate, for example, L-tyrosine in the [FeFe] hydrogenase maturase, HydG. In other cases, the target is a proteinaceous residue as in all the glycyl radical forming enzymes. The generation of this initial radical species and the subsequent chemistry involving downstream radical intermediates is meticulously controlled by the enzyme so as to prevent unwanted reactions. But the manner in which this control is exerted is unknown. Electron paramagnetic resonance (EPR) spectroscopy has proven to be a valuable tool used to gain insight into these mechanisms. In this Account, we summarize efforts to trap such radical intermediates in radical SAM enzymes and highlight four examples in which EPR spectroscopic results have shed significant light on the corresponding mechanism. For lysine 2,3-aminomutase, nearly each possible intermediate, from an analogue of the initial 5'-dA(•) to the product radical L-β-lysine, has been explored. A paramagnetic intermediate observed in biotin synthase is shown to involve an auxiliary [FeS] cluster whose bridging sulfide is a co-substrate for the final step in the biosynthesis of vitamin B7. In HydG, the L-tyrosine substrate is converted in unprecedented fashion to a 4-oxidobenzyl radical on the way to generating CO and CN(-) ligands for the [FeFe] cluster of hydrogenase. And finally, EPR has confirmed a mechanistic proposal for the antibiotic resistance protein Cfr, which methylates the unactivated sp(2)-hybridized C8-carbon of an adenosine base of 23S ribosomal RNA. These four systems provide just a brief survey of the ever-growing set of radical

  19. Bimetallic cyanide-bridged complexes based on the photochromic nitroprusside anion and paramagnetic metal complexes. Syntheses, structures, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O, [Ni(en)2][Fe(CN)5NO]x3H2O, [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO], and [Mn(5-Brsalen)]2[Fe(CN)5NO].

    PubMed

    Clemente-León, M; Coronado, E; Galán-Mascarós, J R; Gómez-García, C J; Woike, T; Clemente-Juan, J M

    2001-01-01

    The synthesis, crystal structure, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O (1), [Ni(en)2][Fe(CN)5NO]x3H2O (2), [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO] (3), and [Mn(5-Brsalen)]2[Fe(CN)5NO] (4) are presented. 1 crystallizes in the monoclinic space group P2(1)/n (a = 7.407(4) A, b = 28.963(6) A, c = 14.744(5) A, alpha = 90 degrees, beta = 103.26(4) degrees, gamma = 90 degrees, Z = 2). Its structure consists of branched linear chains formed by cis-[Ni(en)2]2+ cations and ferrocyanide and nitroprusside anions. The presence of two kinds of iron(II) sites has been demonstrated by Mössbauer spectroscopy. 2 crystallizes in the monoclinic space group P2(1)/c (a = 11.076(3) A, b = 10.983(2) A, c = 17.018(5) A, alpha = 90 degrees, beta = 107.25(2) degrees, gamma = 90 degrees, Z = 4). Its structure consists of zigzag chains formed by an alternated array of cis-[Ni(en)2]2+ cations and nitroprusside anions. 3 crystallizes in the triclinic space group P1 (a = 8.896(5) A, b = 10.430(5) A, c = 12.699(5) A, alpha = 71.110(5) degrees, beta = 79.990(5) degrees, gamma = 89.470(5) degrees, Z = 1). Its structure comprises neutral trinuclear bimetallic complexes in which a central [Fe(CN)5NO]2- anion is linked to two [Mn(3-MeOsalen)]+ cations. 4 crystallizes in the tetragonal space group P4/ncc (a = 13.630(5) A, c = 21.420(8) A, Z = 4). Its structure shows an extended 2D neutral network formed by cyclic octameric [-Mn-NC-Fe-CN-]4 units. The magnetic properties of these compounds indicate the presence of quasi-isolated paramagnetic Ni2+ and Mn3+. Irradiated samples of the four compounds have been studied by differential scanning calorimetry to detect the existence of the long-lived metastable states of nitroprusside.

  20. A solid state paramagnetic maser device driven by electron spin injection.

    PubMed

    Watts, S M; van Wees, B J

    2006-09-15

    In response to an external, microwave-frequency magnetic field, a paramagnetic medium will absorb energy from the field that drives the magnetization dynamics. Here we describe a new process by which an external spin-injection source, when combined with the microwave field spin pumping, can drive the paramagnetic medium from one that absorbs microwave energy to one that emits microwave energy. We derive a simple condition for the crossover from absorptive to emissive behavior. Based on this process, we propose a solid-state, paramagnetic device in which microwave amplification by stimulated emission of radiation is driven by spin injection.

  1. Monitoring changes of paramagnetically-shifted 31P signals in phospholipid vesicles

    NASA Astrophysics Data System (ADS)

    Joyce, Rebecca E.; Williams, Thomas L.; Serpell, Louise C.; Day, Iain J.

    2016-03-01

    Phospholipid vesicles are commonly used as biomimetics in the investigation of the interaction of various species with cell membranes. In this letter we present a 31P NMR investigation of a simple vesicle system using a paramagnetic shift reagent to probe the inner and outer layers of the lipid bilayer. Time-dependent changes in the 31P NMR signal are observed, which differ whether the paramagnetic species is inside or outside the vesicle, and on the choice of buffer solution used. An interpretation of these results is given in terms of the interaction of the paramagnetic shift reagent with the lipids.

  2. [ESR spectra of paramagnetic centers of ferricytochrome c, induced by UV-radiation at 77 K].

    PubMed

    Artiukhov, V G

    1987-01-01

    Paramagnetic properties of ferricytochrome c aqueous glyceric solutions exposed to UV-light of various wave lengths at 77K have been investigated. Absorption of longwave UV- and visible light by hemin (5-240 min) does not induce the formation of paramagnetic centres in hemoprotein. However absorption of UV-light by chromophorms of a protein component of ferricytochrome c induces the formation of free radicals with a quantum yield of 0.07. During long-term (40 to 200 min) UV-irradiation (260-380 nm) of protein solutions several types of paramagnetic centres including HCO radicals are formed.

  3. [Effect of paramagnetic additives on the spin lattice relaxation of the protons of intracellular water].

    PubMed

    Samuilov, F D; Nikiforova, V I; Nikiforov, E A

    1979-01-01

    Studies of the effects of Mn2+ and Fe3+ paramagnetic ions on spin-lattice relaxation of water protons in plant cells have shown that paramagnetic admixtures which are in the cells under normal conditions (in natural quantities) produce no significant effect on the rate of spin-lattice relation of water protons. On the basis of the investigations of proton, spin-lattice relaxation at increased content of Mn2+ paramagnetic ions in plant cells possible separation of relaxation times T1l and T1s which are corresponded by different water fractions in the cells is shown as well as possible stimation of water quantity in the fractions.

  4. Electron paramagnetic resonance of conduction-band electrons in silicon

    NASA Astrophysics Data System (ADS)

    Young, C. F.; Poindexter, E. H.; Gerardi, G. J.; Warren, W. L.; Keeble, D. J.

    1997-06-01

    The g value of conduction-band electrons in silicon was properly determined by using electron paramagnetic resonance. A linear empirical relationship was first found between the g values and the thermal ionization energies of several well-known group-V substitutional shallow donors in silicon. An extrapolation of the empirical relation to zero ionization energy predicted the g value of conduction-band (CB) electrons, gCB=1.9995, which is slightly but definitely different from that of conduction electrons in the donor-impurity band of degenerate n-type silicon; although both g values have been tacitly accepted to be identical for nearly four decades. The prediction was directly verified by measuring the g value of CB electrons created either by thermal emission from shallow donors in phosphorus-doped silicon at T=125 K and by above-band-gap optical excitation in high-purity p-type silicon at T=3.5 K; the measured g value in both experiments was precisely gCB=1.9995(1). The empirical relation is still not theoretically explained.

  5. Identification of irradiated cashew nut by electron paramagnetic resonance spectroscopy.

    PubMed

    Sanyal, Bhaskar; Sajilata, M G; Chatterjee, Suchandra; Singhal, Rekha S; Variyar, Prasad S; Kamat, M Y; Sharma, Arun

    2008-10-08

    Cashew nut samples were irradiated at gamma-radiation doses of 0.25, 0.5, 0.75, and 1 kGy, the permissible dose range for insect disinfestation of food commodities. A weak and short-lived triplet (g = 2.004 and hfcc = 30 G) along with an anisotropic signal (g perpendicular = 2.0069 and g parallel = 2.000) were produced immediately after irradiation. These signals were assigned to that of cellulose and CO 2 (-) radicals. However, the irradiated samples showed a dose-dependent increase of the central line (g = 2.0045 +/- 0.0002). The nature of the free radicals formed during conventional processing such as thermal treatment was investigated and showed an increase in intensity of the central line (g = 2.0045) similar to that of irradiation. Characteristics of the free radicals were studied by their relaxation and thermal behaviors. The present work explores the possibility to identify irradiated cashew nuts from nonirradiated ones by the thermal behaviors of the radicals beyond the period, when the characteristic electron paramagnetic resonance spectral lines of the cellulose free radicals have essentially disappeared. In addition, this study for the first time reports that relaxation behavior of the radicals could be a useful tool to distinguish between roasted and irradiated cashew nuts.

  6. Introduction to spin label electron paramagnetic resonance spectroscopy of proteins.

    PubMed

    Melanson, Michelle; Sood, Abha; Török, Fanni; Török, Marianna

    2013-01-01

    An undergraduate laboratory exercise is described to demonstrate the biochemical applications of electron paramagnetic resonance (EPR) spectroscopy. The β93 cysteine residue of hemoglobin is labeled by the covalent binding of 3-maleimido-proxyl (5-MSL) and 2,2,5,5-tetramethyl-1-oxyl-3-methyl methanethiosulfonate (MTSL), respectively. The excess spin label is removed by gel-exclusion chromatography. Changes in the mobility of the reporter groups attached to the protein are monitored by EPR spectroscopy. While the spectral parameters of the rigidly attached 5-MSL provide information on the rotation of the whole spin labeled protein, MTSL bound by a more flexible linkage describes the local environment of the cysteine residue in the interior of the protein structure. Students can study the known crystal structure of hemoglobin in comparison to the results they obtain by analyzing the EPR spectra. Overall, the exercise introduces them to laboratory techniques such as protein labeling, gel filtration, EPR spectroscopy, as well as familiarizes them with the online Protein Data Bank as a research resource and PyMOL software as a structure visualization tool. Copyright © 2013 International Union of Biochemistry and Molecular Biology, Inc.

  7. Detection of electron paramagnetic resonance absorption using frequency modulation.

    PubMed

    Hirata, Hiroshi; Kuyama, Toshifumi; Ono, Mitsuhiro; Shimoyama, Yuhei

    2003-10-01

    A frequency modulation (FM) method was developed to measure electron paramagnetic resonance (EPR) absorption. The first-derivative spectrum of 1,1-diphenyl-2-picrylhydrazyl (DPPH) powder was measured with this FM method. Frequency modulation of up to 1.6 MHz (peak-to-peak) was achieved at a microwave carrier frequency of 1.1 GHz. This corresponds to a magnetic field modulation of 57microT (peak-to-peak) at 40.3 mT. By using a tunable microwave resonator and automatic control systems, we achieved a practical continuous-wave (CW) EPR spectrometer that incorporates the FM method. In the present experiments, the EPR signal intensity was proportional to the magnitude of frequency modulation. The background signal at the modulation frequency (1 kHz) for EPR detection was also proportional to the magnitude of frequency modulation. An automatic matching control (AMC) system reduced the amplitude of noise in microwave detection and improved the baseline stability. Distortion of the spectral lineshape was seen when the spectrometer settings were not appropriate, e.g., with a lack of the open-loop gain in automatic tuning control (ATC). FM is an alternative to field modulation when the side-effect of field modulation is detrimental for EPR detection. The present spectroscopic technique based on the FM scheme is useful for measuring the first derivative with respect to the microwave frequency in investigations of electron-spin-related phenomena.

  8. Maximally spaced projection sequencing in electron paramagnetic resonance imaging

    PubMed Central

    Redler, Gage; Epel, Boris; Halpern, Howard J.

    2015-01-01

    Electron paramagnetic resonance imaging (EPRI) provides 3D images of absolute oxygen concentration (pO2) in vivo with excellent spatial and pO2 resolution. When investigating such physiologic parameters in living animals, the situation is inherently dynamic. Improvements in temporal resolution and experimental versatility are necessary to properly study such a system. Uniformly distributed projections result in efficient use of data for image reconstruction. This has dictated current methods such as equal-solid-angle (ESA) spacing of projections. However, acquisition sequencing must still be optimized to achieve uniformity throughout imaging. An object-independent method for uniform acquisition of projections, using the ESA uniform distribution for the final set of projections, is presented. Each successive projection maximizes the distance in the gradient space between itself and prior projections. This maximally spaced projection sequencing (MSPS) method improves image quality for intermediate images reconstructed from incomplete projection sets, enabling useful real-time reconstruction. This method also provides improved experimental versatility, reduced artifacts, and the ability to adjust temporal resolution post factum to best fit the data and its application. The MSPS method in EPRI provides the improvements necessary to more appropriately study a dynamic system. PMID:26185490

  9. Effects of water on fingernail electron paramagnetic resonance dosimetry

    PubMed Central

    Zhang, Tengda; Zhao, Zhixin; Zhang, Haiying; Zhai, Hezheng; Ruan, Shuzhou; Jiao, Ling; Zhang, Wenyi

    2016-01-01

    Electron paramagnetic resonance (EPR) is a promising biodosimetric method, and fingernails are sensitive biomaterials to ionizing radiation. Therefore, kinetic energy released per unit mass (kerma) can be estimated by measuring the level of free radicals within fingernails, using EPR. However, to date this dosimetry has been deficient and insufficiently accurate. In the sampling processes and measurements, water plays a significant role. This paper discusses many effects of water on fingernail EPR dosimetry, including disturbance to EPR measurements and two different effects on the production of free radicals. Water that is unable to contact free radicals can promote the production of free radicals due to indirect ionizing effects. Therefore, varying water content within fingernails can lead to varying growth rates in the free radical concentration after irradiation—these two variables have a linear relationship, with a slope of 1.8143. Thus, EPR dosimetry needs to be adjusted according to the water content of the fingernails of an individual. When the free radicals are exposed to water, the eliminating effect will appear. Therefore, soaking fingernail pieces in water before irradiation, as many researchers have previously done, can cause estimation errors. In addition, nails need to be dehydrated before making accurately quantitative EPR measurements. PMID:27342838

  10. Targeted-ROI imaging in electron paramagnetic resonance imaging

    NASA Astrophysics Data System (ADS)

    Pan, Xiaochuan; Xia, Dan; Halpern, Howard

    2007-07-01

    Electron paramagnetic resonance imaging (EPRI) is a technique that has been used for in vivo oxygen imaging of small animals. In continuous wave (CW) EPRI, the measurement can be interpreted as a sampled 4D Radon transform of the image function. The conventional filtered-backprojection (FBP) algorithm has been used widely for reconstructing images from full knowledge of the Radon transform acquired in CW EPRI. In practical applications of CW EPRI, one often is interested in information only in a region of interest (ROI) within the imaged subject. It is desirable to accurately reconstruct an ROI image only from partial knowledge of the Radon transform because acquisition of the partial data set can lead to considerable reduction of imaging time. The conventional FBP algorithm cannot, however, reconstruct accurate ROI images from partial knowledge of the Radon transform of even dimension. In this work, we describe two new algorithms, which are referred to as the backprojection filtration (BPF) and minimum-data filtered-backprojection (MDFBP) algorithms, for accurate ROI-image reconstruction from a partial Radon transform (or, truncated Radon transform) in CW EPRI. We have also performed numerical studies in the context of ROI-image reconstruction of a synthetic 2D image with density similar to that found in a small animal EPRI. This demonstrates both the inadequacy of the conventional FBP algorithm and the success of BPF and MDFBP algorithms in ROI reconstruction. The proposed ROI imaging approach promises a means to substantially reduce image acquisition time in CW EPRI.

  11. Electron Paramagnetic Resonance studies of x-ray irradiated Nafion

    NASA Astrophysics Data System (ADS)

    Fragoso, Juan; Usher, Timothy

    2007-03-01

    Fuel cells promise a bright future as power sources for a variety of electronic equipment as well as more power demanding elements. Nafion (DuPont's trademark of a sulfonated tetrafluorethylene polymer modified from Teflon) is the heart of Proton Exchange Membrane Fuel Cells (PEMFCs) as well as Direct Methanol Fuel Cells (DMFCs). Fuel cells are used to power electronic equipment on spacecraft, satellites and unpiloted high altitude aircraft, where ionizing radiation can be a concern. Electron Paramagnetic Resonance (EPR) is a spectroscopic technique that is very sensitive to free radicals such as those produced by ionizing radiation therefore EPR can give us a window into the degradation of the Nafion membranes due to the ionizing radiation. Nafion samples were irradiated using a x-ray diffractometer with a copper target operating at 40kV and 55mA for at least 3hrs. X-Band EPR spectroscopy of the irradiated nafion reveals a peak at 3400G with a width of 10G, which decays over time, completely diminishing in a couple of weeks. Preliminary results from the polarization studies on the effects of ionizing radiation will also be presented.

  12. Uniform spinning sampling gradient electron paramagnetic resonance imaging.

    PubMed

    Johnson, David H; Ahmad, Rizwan; Liu, Yangping; Chen, Zhiyu; Samouilov, Alexandre; Zweier, Jay L

    2014-02-01

    To improve the quality and speed of electron paramagnetic resonance imaging (EPRI) acquisition by combining a uniform sampling distribution with spinning gradient acquisition. A uniform sampling distribution was derived for spinning gradient EPRI acquisition (uniform spinning sampling, USS) and compared to the existing (equilinear spinning sampling, ESS) acquisition strategy. Novel corrections were introduced to reduce artifacts in experimental data. Simulations demonstrated that USS puts an equal number of projections near each axis whereas ESS puts excessive projections at one axis, wasting acquisition time. Artifact corrections added to the magnetic gradient waveforms reduced noise and correlation between projections. USS images had higher SNR (85.9 ± 0.8 vs. 56.2 ± 0.8) and lower mean-squared error than ESS images. The quality of the USS images did not vary with the magnetic gradient orientation, in contrast to ESS images. The quality of rat heart images was improved using USS compared to that with ESS or traditional fast-scan acquisitions. A novel EPRI acquisition which combines spinning gradient acquisition with a uniform sampling distribution was developed. This USS spinning gradient acquisition offers superior SNR and reduced artifacts compared to prior methods enabling potential improvements in speed and quality of EPR imaging in biological applications. Copyright © 2013 Wiley Periodicals, Inc.

  13. Uniform Spinning Sampling Gradient Electron Paramagnetic Resonance Imaging

    PubMed Central

    Johnson, David H.; Ahmad, Rizwan; Liu, Yangping; Chen, Zhiyu; Samouilov, Alexandre; Zweier, Jay L.

    2014-01-01

    Purpose To improve the quality and speed of electron paramagnetic resonance imaging (EPRI) acquisition by combining a uniform sampling distribution with spinning gradient acquisition. Theory and Methods A uniform sampling distribution was derived for spinning gradient EPRI acquisition (Uniform Spinning Sampling, USS) and compared to the existing (Equilinear Spinning Sampling, ESS) acquisition strategy. Novel corrections were introduced to reduce artifacts in experimental data. Results Simulations demonstrated that USS puts an equal number of projections near each axis whereas ESS puts excessive projections at one axis, wasting acquisition time. Artifact corrections added to the magnetic gradient waveforms reduced noise and correlation between projections. USS images had higher SNR (85.9±0.8 vs. 56.2±0.8) and lower mean-squared error than ESS images. The quality of the USS images did not vary with the magnetic gradient orientation, in contrast to ESS images. The quality of rat heart images was improved using USS compared to that with ESS or traditional fast-scan acquisitions. Conclusion A novel EPRI acquisition which combines spinning gradient acquisition with a uniform sampling distribution was developed. This USS spinning gradient acquisition offers superior SNR and reduced artifacts compared to prior methods enabling potential improvements in speed and quality of EPR imaging in biological applications. PMID:23475830

  14. Electron paramagnetic resonance calculations for hydrogenated Si surfaces

    NASA Astrophysics Data System (ADS)

    Rohrmüller, M.; Schmidt, W. G.; Gerstmann, U.

    2017-03-01

    Electron paramagnetic resonance (EPR) signatures, more specifically the elements of the electronic g tensor, are calculated within density functional theory for hydrogenated Si(111), Si(001), Si(113), Si(114), Si (11 2 ¯) , and Si(110) surfaces. Thereby both perturbation theory and a more sophisticated Berry phase technique are applied. Specific defects on different surface orientations are shown to reproduce the resonances at g ¯=2.0043 and g ¯=2.0052 measured for hydrogenated microcrystalline silicon: The latter value is argued here to originate from regions with low hydrogen coverage; the resonance at g ¯=2.0043 is shown to appear in positions with dihydride environment, where an H atom is directly bound to the silicon dangling-bond atoms. A third group of EPR signals with considerably larger g ¯ values between 2.006 and 2.009 is predicted for highly symmetric dangling bonds resembling single dangling-bond defects in silicon bulk material. As the exact value depends strongly on local strain, this type of defect can explain a less intense signal with large g strain observed in microcrystalline as well as in amorphous material.

  15. Paramagnetic Manganese in the Atherosclerotic Plaque of Carotid Arteries

    PubMed Central

    Chelyshev, Yury; Ignatyev, Igor; Zanochkin, Alexey; Mamin, Georgy; Sorokin, Boris; Sorokina, Alexandra; Lyapkalo, Natalya; Gizatullina, Nazima; Orlinskii, Sergei

    2016-01-01

    The search for adequate markers of atherosclerotic plaque (AP) instability in the context of assessment of the ischemic stroke risk in patients with atherosclerosis of the carotid arteries as well as for solid physical and chemical factors that are connected with the AP stability is extremely important. We investigate the inner lining of the carotid artery specimens from the male patients with atherosclerosis (27 patients, 42–64 years old) obtained during carotid endarterectomy by using different analytical tools including ultrasound angiography, X-ray analysis, immunological, histochemical analyses, and high-field (3.4 T) pulse electron paramagnetic resonance (EPR) at 94 GHz. No correlation between the stable and unstable APs in the sense of the calcification is revealed. In all of the investigated samples, the EPR spectra of manganese, namely, Mn2+ ions, are registered. Spectral and relaxation characteristics of Mn2+ ions are close to those obtained for the synthetic (nano) hydroxyapatite species but differ from each other for stable and unstable APs. This demonstrates that AP stability could be specified by the molecular organization of their hydroxyapatite components. The origin of the obtained differences and the possibility of using EPR of Mn2+ as an AP stability marker are discussed. PMID:28078287

  16. A direct simulation method for flows with suspended paramagnetic particles

    SciTech Connect

    Kang, Tae Gon; Hulsen, Martien A. Toonder, Jaap M.J. den; Anderson, Patrick D.; Meijer, Han E.H.

    2008-04-20

    A direct numerical simulation method based on the Maxwell stress tensor and a fictitious domain method has been developed to solve flows with suspended paramagnetic particles. The numerical scheme enables us to take into account both hydrodynamic and magnetic interactions between particles in a fully coupled manner. Particles are assumed to be non-Brownian with negligible inertia. Rigid body motions of particles in 2D are described by a rigid-ring description implemented by Lagrange multipliers. The magnetic force, acting on the particles due to magnetic fields, is represented by the divergence of the Maxwell stress tensor, which acts as a body force added to the momentum balance equation. Focusing on two-dimensional problems, we solve a single-particle problem for verification. With the magnetic force working on the particle, the proper number of collocation points is found to be two points per element. The convergence with mesh refinement is verified by comparing results from regular mesh problems with those from a boundary-fitted mesh problem as references. We apply the developed method to two application problems: two-particle interaction in a uniform magnetic field and the motion of a magnetic chain in a rotating field, demonstrating the capability of the method to tackle general problems. In the motion of a magnetic chain, especially, the deformation pattern at break-up is similar to the experimentally observed one. The present formulation can be extended to three-dimensional and viscoelastic flow problems.

  17. Electron Paramagnetic Resonance Characterization of Tetrahydrobiopterin Radical Formation in Bacterial Nitric Oxide Synthase Compared to Mammalian Nitric Oxide Synthase

    PubMed Central

    Brunel, Albane; Santolini, Jérôme; Dorlet, Pierre

    2012-01-01

    H4B is an essential catalytic cofactor of the mNOSs. It acts as an electron donor and activates the ferrous heme-oxygen complex intermediate during Arg oxidation (first step) and NOHA oxidation (second step) leading to nitric oxide and citrulline as final products. However, its role as a proton donor is still debated. Furthermore, its exact involvement has never been explored for other NOSs such as NOS-like proteins from bacteria. This article proposes a comparative study of the role of H4B between iNOS and bsNOS. In this work, we have used freeze-quench to stop the arginine and NOHA oxidation reactions and trap reaction intermediates. We have characterized these intermediates using multifrequency electron paramagnetic resonance. For the first time, to our knowledge, we report a radical formation for a nonmammalian NOS. The results indicate that bsNOS, like iNOS, has the capacity to generate a pterin radical during Arg oxidation. Our current electron paramagnetic resonance data suggest that this radical is protonated indicating that H4B may not transfer any proton. In the 2nd step, the radical trapped for iNOS is also suggested to be protonated as in the 1st step, whereas it was not possible to trap a radical for the bsNOS 2nd step. Our data highlight potential differences for the catalytic mechanism of NOHA oxidation between mammalian and bacterial NOSs. PMID:22828337

  18. Membrane protein-lipid interactions in mixed micelles studied by NMR spectroscopy with the use of paramagnetic reagents.

    PubMed

    Hilty, Christian; Wider, Gerhard; Fernández, César; Wüthrich, Kurt

    2004-04-02

    For solution NMR studies of the structure and function of membrane proteins, these macromolecules have to be reconstituted and solubilized in detergent micelles. Detailed characterization of the mixed detergent/protein micelles is then of key importance to validate the results from such studies, and to evaluate how faithfully the natural environment of the protein in the biological membrane is mimicked by the micelle. In this paper, a selection of paramagnetic probes with different physicochemical properties are used to characterize the 60 kDa mixed micelles consisting of about 90 molecules of the detergent dihexanoylphosphatidylcholine (DHPC) and one molecule of the Escherichia coli outer-membrane protein X (OmpX), which had previously been extensively studied by solution NMR techniques. The observation of highly selective relaxation effects on the NMR spectra of OmpX and DHPC from a water-soluble relaxation agent and from nitroxide spin labels attached to lipophilic molecules, confirmed data obtained previously with more complex NMR studies of the diamagnetic OmpX/DHPC system, and yielded additional novel insights into the protein-detergent interactions in the mixed micelles. The application of paramagnetic probes to the well-characterized OmpX/DHPC system indicates that such probes should be widely applicable as an efficient support of NMR studies of the topology of mixed membrane protein-detergent micelles.

  19. Spintronic detection of interfacial magnetic switching in a paramagnetic thin film of tris(8-hydroxyquinoline)iron(III)

    NASA Astrophysics Data System (ADS)

    Sun, Dali; Kareis, Christopher M.; van Schooten, Kipp J.; Jiang, Wei; Siegel, Gene; Kavand, Marzieh; Davidson, Royce A.; Shum, William W.; Zhang, Chuang; Liu, Haoliang; Tiwari, Ashutosh; Boehme, Christoph; Liu, Feng; Stephens, Peter W.; Miller, Joel S.; Vardeny, Z. Valy

    2017-02-01

    Organic semiconductors find increasing importance in spin transport devices due to the modulation and control of their properties through chemical synthetic versatility. The organic materials have been used as interlayers between two ferromagnet (FM) electrodes in organic spin valves, as well as for magnetic spin manipulation of metal-organic complexes at the molecular level. In the latter, the substrate-induced magnetic switching in a paramagnetic molecule has been evoked extensively but studied by delicate surface spectroscopies. Here we present evidence of the substantial magnetic switching in a thin film of the paramagnetic molecule, tris(8-hydroxyquinoline)iron(III) (Fe q3 ) deposited on a FM substrate, using the magnetoresistance response of electrical spin-injection in an organic spin valve structure, as well as the inverse-spin-Hall effect induced by state-of-art pulsed microwave spin-pumping. We show that interfacial spin control at the molecular level may lead to a macroscopic organic spin transport device, thus bridging the gap between organic spintronics and molecular spintronics.

  20. In vitro neurotoxicity of magnetic resonance imaging (MRI) contrast agents: influence of the molecular structure and paramagnetic ion.

    PubMed

    Bertin, Annabelle; Michou-Gallani, Anne-Isabelle; Gallani, Jean-Louis; Felder-Flesch, Delphine

    2010-08-01

    Interest in contrast agent's (CA) neurotoxicity has greatly increased due to the growing need of new compounds dedicated to brain imaging. Magnetic resonance imaging (MRI) CA have been evaluated by means of different toxicological assays with cultured rat primary neurons (evaluation of neurite specific parameters via immunostaining of the cells and LDH leakage). To determine the potential neurotoxicity of a precise paramagnetic ion in a defined structure (architecture and molecular weight), novel hydrosoluble dendritic Manganese (II) and Gadolinium (III) complexes derived from diethylenetriamine pentaacetic acid (DTPA) have been studied and compared to a linear homologue (same molecular weight) and commercially available low molecular weight MRI CA like Mn-DPDP (Teslascan, GE Healthcare) and Gd-DTPA (Magnevist, Schering). The range of CA concentrations studied was 0.1-10mM, suitable for MRI examinations. This set of experiments allows a toxicity ranking of these reagents as a function of molecular structure and nature of the paramagnetic ion. We could determine that the architecture (linear vs. dendritic) does not play an important role in the in vitro neurotoxicity, whereas the structure of the chelating cage is of greater importance. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  1. 76 FR 67200 - Prospective Grant of Exclusive License: Electron Paramagnetic Resonance Devices and Systems for...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-31

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF HEALTH AND HUMAN SERVICES National Institutes of Health Prospective Grant of Exclusive License: Electron... of use limited to electron paramagnetic resonance devices and systems for oximetry. DATES:...

  2. Small-angle neutron scattering of nanocrystalline gadolinium and holmium with random paramagnetic susceptibility

    NASA Astrophysics Data System (ADS)

    Döbrich, Frank; Bick, Jens-Peter; Birringer, Rainer; Wolff, Matthias; Kohlbrecher, Joachim; Michels, Andreas

    2015-02-01

    A neutron study of nanocrystalline terbium (Balaji G et al 2008 Phys. Rev. Lett. 100 227202) has shown that the randomly oriented anisotropy of the paramagnetic susceptibility tensor may lead to strongly correlated nanoscale spin disorder in the paramagnetic state which can be probed very effectively by magnetic small-angle neutron scattering (SANS). In principle, this scenario is also applicable to other rare-earth metals and the size of the effect is expected to scale with the strength of the anisotropy in the paramagnetic state. Here, we report SANS results (in the paramagnetic state) on nanocrystalline inert-gas condensed samples of Gd and Ho, which represent the cases of low and high anisotropy, respectively.

  3. Microscale Demonstration of the Paramagnetism of Liquid Oxygen with a Neodymium Magnet

    ERIC Educational Resources Information Center

    Mattson, Bruce

    2007-01-01

    A microscale classroom demonstration of the paramagnetic behavior of various samples of liquid oxygen with neodymium magnet is being presented. The experiment should be done with extreme caution, as liquid oxygen reacts violently with organic matters.

  4. Microscale Demonstration of the Paramagnetism of Liquid Oxygen with a Neodymium Magnet

    ERIC Educational Resources Information Center

    Mattson, Bruce

    2007-01-01

    A microscale classroom demonstration of the paramagnetic behavior of various samples of liquid oxygen with neodymium magnet is being presented. The experiment should be done with extreme caution, as liquid oxygen reacts violently with organic matters.

  5. Structural investigation and electron paramagnetic resonance of vanadyl doped alkali niobium borate glasses.

    PubMed

    Agarwal, A; Sheoran, A; Sanghi, S; Bhatnagar, V; Gupta, S K; Arora, M

    2010-03-01

    Glasses with compositions xNb(2)O(5).(30-x)M(2)O.69B(2)O(3) (where M=Li, Na, K; x=0, 4, 8 mol%) doped with 1 mol% V(2)O(5) have been prepared using normal melt quench technique. The IR transmission spectra of the glasses have been studied over the range 400-4000 cm(-1). The changes caused by the addition of Nb(2)O(5) on the structure of these glasses have been reported. The electron paramagnetic resonance spectra of VO(2+) ions in these glasses have been recorded in X-band (9.14 GHz) at room temperature (300 K). The spin Hamiltonian parameters, dipolar hyperfine coupling parameter and Fermi contact interaction parameter have been calculated. It is observed that the resultant resonance spectra contain hyperfine structures (hfs) due to V(4+) ions which exist as VO(2+) ions in octahedral coordination with a tetragonal compression in the present glasses. The tetragonality of V(4+)O(6) complex decreases with increasing concentration of Nb(2)O(5). The 3d(xy) orbit contracts with increase in Nb(2)O(5):M(2)O ratio. Values of the theoretical optical basicity, Lambda(th), have also been reported.

  6. Exploring intrinsically disordered proteins using site-directed spin labeling electron paramagnetic resonance spectroscopy

    PubMed Central

    Le Breton, Nolwenn; Martinho, Marlène; Mileo, Elisabetta; Etienne, Emilien; Gerbaud, Guillaume; Guigliarelli, Bruno; Belle, Valérie

    2015-01-01

    Proteins are highly variable biological systems, not only in their structures but also in their dynamics. The most extreme example of dynamics is encountered within the family of Intrinsically Disordered Proteins (IDPs), which are proteins lacking a well-defined 3D structure under physiological conditions. Among the biophysical techniques well-suited to study such highly flexible proteins, Site-Directed Spin Labeling combined with EPR spectroscopy (SDSL-EPR) is one of the most powerful, being able to reveal, at the residue level, structural transitions such as folding events. SDSL-EPR is based on selective grafting of a paramagnetic label on the protein under study and is limited neither by the size nor by the complexity of the system. The objective of this mini-review is to describe the basic strategy of SDSL-EPR and to illustrate how it can be successfully applied to characterize the structural behavior of IDPs. Recent developments aimed at enlarging the panoply of SDSL-EPR approaches are presented in particular newly synthesized spin labels that allow the limitations of the classical ones to be overcome. The potentialities of these new spin labels will be demonstrated on different examples of IDPs. PMID:26042221

  7. Electron paramagnetic resonance and photochromism of N3V0 in diamond

    NASA Astrophysics Data System (ADS)

    Green, B. L.; Breeze, B. G.; E Newton, M.

    2017-06-01

    The defect in diamond formed by a vacancy surrounded by three nearest-neighbor nitrogen atoms and one carbon atom, {{\\text{N}}3}\\text{V} , is found in the vast majority of natural diamonds. Despite {{\\text{N}}3}{{\\text{V}}0} being the earliest electron paramagnetic resonance spectrum observed in diamond, to date no satisfactory simulation of the spectrum for an arbitrary magnetic field direction has been produced due to its complexity. In this work, {{\\text{N}}3}{{\\text{V}}0} is identified in {{}15}\\text{N} -doped synthetic diamond following irradiation and annealing. The {{}15}{{\\text{N}}3}{{\\text{V}}0} spin Hamiltonian parameters are directly determined and used to refine the parameters for {{}14}{{\\text{N}}3}{{\\text{V}}0} , enabling the latter to be accurately simulated and fitted for an arbitrary magnetic field direction. Study of {{}15}{{\\text{N}}3}{{\\text{V}}0} under excitation with green light indicates charge transfer between {{\\text{N}}3}\\text{V} and {{\\text{N}}\\text{s}} . It is argued that this charge transfer is facilitated by direct ionization of {{\\text{N}}3}{{\\text{V}}-} , an as-yet unobserved charge state of {{\\text{N}}3}\\text{V} .

  8. Ab initio study of the phase stability in paramagnetic duplex steel alloys

    NASA Astrophysics Data System (ADS)

    Pitkänen, H.; Alatalo, M.; Puisto, A.; Ropo, M.; Kokko, K.; Punkkinen, M. P. J.; Olsson, P.; Johansson, B.; Hertzman, S.; Vitos, L.

    2009-01-01

    Duplex stainless steels have many superior properties compared to conventional steels, this being mainly due to their microstructure containing approximately equal amount of ferrite and austenite phases formed by iron, chromium (or Cr equivalent), and nickel (or Ni equivalent). Using computational methods based on first-principles theories, the phase stability of paramagnetic Fe1-c-nCrcNin alloys ( 0.12≤c≤0.32 and 0.04≤n≤0.32 ) at high temperatures (≳1000K) is addressed. It is shown that the stabilization of the ferrite-austenite two-phase field in duplex steels is a result of complex interplay of several competing phenomena. Taking into account only the formation energies yields a complete phase separation, strongly overestimating the two-phase region. The formation energies are calculated to be lower for the austenite than for the ferrite, meaning that the configurational entropy has a more significant impact on the stability field of the austenitic phase. The magnetic and vibrational free energies have opposite effects on the phase stability. Namely, the magnetic entropy favors the ferrite phase, whereas the vibrational free energy stabilizes the austenite phase. Combining the formation energies with the magnetic, vibrational, and configurational free energies, a region of coexistence between the two phases is obtained, in line with former thermodynamic assessments as well as with experimental observations.

  9. Microscopic Sources of Paramagnetic Noise on α-Al2O3 Substrates for Superconducting Qubits

    NASA Astrophysics Data System (ADS)

    Dubois, Jonathan; Lee, Donghwa; Lordi, Vince

    2014-03-01

    Superconducting qubits (SQs) represent a promising route to achieving a scalable quantum computer. However, the coupling between electro-dynamic qubits and (as yet largely unidentified) ambient parasitic noise sources has so far limited the functionality of current SQs by limiting coherence times of the quantum states below a practical threshold for measurement and manipulation. Further improvement can be enabled by a detailed understanding of the various noise sources afflicting SQs. In this work, first principles density functional theory (DFT) calculations are employed to identify the microscopic origins of magnetic noise sources in SQs on an α-Al2O3 substrate. The results indicate that it is unlikely that the existence of intrinsic point defects and defect complexes in the substrate are responsible for low frequency noise in these systems. Rather, a comprehensive analysis of extrinsic defects shows that surface aluminum ions interacting with ambient molecules will form a bath of magnetic moments that can couple to the SQ paramagnetically. The microscopic origin of this magnetic noise source is discussed and strategies for ameliorating the effects of these magnetic defects are proposed. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  10. Time-resolved electron paramagnetic resonance of radical pair intermediates in cryptochromes

    NASA Astrophysics Data System (ADS)

    Biskup, Till

    2013-12-01

    Electron transfer plays a key role in many biological systems, including core complexes of photosynthesis and respiration. As this involves unpaired electron spins, electron paramagnetic resonance (EPR) is the method of choice to investigate such processes. Systems that show photo-induced charge separation and electron transfer are of particular interest, as here the processes can easily be synchronised to the experiment and therefore followed directly over its time course. One particular class of proteins, the cryptochromes, showing charge separation and in turn spin-correlated radical pairs upon excitation with blue light, have been investigated by time-resolved EPR spectroscopy in great detail and the results obtained so far are summarised in this contribution. Highlights include the first observation of spin-correlated radical pairs in these proteins, a fact with great impact on the proposed role as key part of a magnetic compass of migratory birds, as well as the assignment of the radical-pair partners and the unravelling of alternative and unexpected electron transfer pathways in these proteins, giving new insights into aspects of biological electron transfer itself.

  11. Paramagnetic properties of humus acids of podzolic and bog-podzolic soils

    NASA Astrophysics Data System (ADS)

    Lodygin, E. D.; Beznosikov, V. A.; Chukov, S. N.

    2007-07-01

    The contents of free radicals in preparations of humic and fulvic acids extracted from virgin and plowed podzolic, surface gleyic podzolic, and peaty podzolic-gleyic soils were determined. The concentration of paramagnetic centers in the humic acids was 1.5-2 times higher than that in the fulvic acids. The agricultural use decreases the paramagnetic activity of the humus compounds and promotes the accumulation of biothermodynamically stable organic compounds in the plow horizons.

  12. Retrospective Reconstruction of Radiation Doses of Chernobyl Liquidators by Electron Paramagnetic Resonance

    DTIC Science & Technology

    1997-12-01

    Armed Forces Rad I Research Institute Retrospective Reconstruction of Radiation Doses of Chernobyl Liquidators by Electron Paramagnetic Resonance A...of Radiation Doses of Chernobyl Liquidators by Electron Paramagnetic Resonance Authored by Scientific Center of Radiation Medicine Academy of Medical...libraries associated with the U.S. Government’s Depository Library System. Preface On April 26, 1986, Reactor #4 at the Chernobyl Nuclear Power Plant near

  13. Electron paramagnetic resonance dosimetry: Methodology and material characterization

    NASA Astrophysics Data System (ADS)

    Hayes, Robert Bruce

    Electron Paramagnetic Resonance (EPR) methodologies for radiation dose reconstruction are investigated using various dosimeter materials. Specifically, methodologies were developed and used that were intended to improve the accuracy and precision of EPR dosimetric techniques, including combining specimen rotation during measurement, use of an internal manganese standard, instrument stabilization techniques and strict measurement protocols. Characterization and quantification of these improvements were preformed on three specific EPR dosimeter materials. The dosimeter materials investigated using these optimized EPR techniques were Walrus teeth, human tooth enamel and alanine dosimeters. Walrus teeth showed the least desirable properties for EPR dosimetry yielding large native signals and low sensitivity (EPR signal per unit dose). The methods for tooth enamel and alanine resulted in large improvements in precision and accuracy. The minimum detectable dose (MDD) found for alanine was approximately 30 mGy (three standard deviations from the measured zero dose value). This is a sensitivity improvement of 5 to 10 over other specialized techniques published in the literature that offer MDD's in the range of 150 mGy to 300 mGy. The accuracy of the method on tooth enamel was comparable to that typically reported in the literature although the measurement precision was increased by about 7. This improvement in measurement precision enables various applications including dose vs. depth profile analysis and a more nondestructive testing evaluation (where the whole sample need not be additively irradiated in order to calibrate its radiation response). A nondestructive evaluation of numerous samples showed that the method could reconstruct the same doses to within 10 mGy of those evaluated destructively. Doses used for this assessment were in the range of 100 to 250 mGy. The method had sufficient stability to measure tooth enamel samples exhibiting extreme anisotropy with a

  14. Electronic paramagnetic resonance power saturation of wooden samples

    NASA Astrophysics Data System (ADS)

    Brai, Maria; Longo, Anna; Maccotta, Antonella; Marrale, Maurizio

    2009-05-01

    The deterioration of wood used for artifacts of artistic interest involves the production of different free radicals from the macromolecules of the wooden matrix (cellulose, lignin, and hemicellulose). Among the techniques able to provide information about these free radicals, the contribution of electronic paramagnetic resonance (EPR) can be very valuable. In this paper, the study of EPR signals (with g ≈2) of both modern and ancient wooden taxa was undertaken in order to analyze some features of the free radicals in natural wood. In particular, we have studied the microwave power saturation behaviors of seasoned wooden samples from ten species, and we have found remarkable differences between softwoods and hardwoods. These differences can be correlated to dissimilarities in the relaxation times T1 and T2 attributable to the different microscopic structures of the two trees' categories. The method has been also applied to ancient woods belonging to works of art in order to assess the conservation state of these artifacts. The analysis of the saturation curves has been found to be sensitive to the wood decay state. Indeed the deterioration process of the wooden matrix involves a variation of the relaxation times; this could be ascribed to both possible structure modifications and to concentration increments of the free radicals inside ancient woods due to decay induced by natural (biological, chemical, and physical) agents. This analysis method seems to be promising for the characterization of the wooden decay state and, therefore, it could provide valuable diagnostic indications which are necessary for the restoration and conservation of many artifact of historical-artistic-archaeological interest.

  15. Dating carbonaceous matter in archean cherts by electron paramagnetic resonance.

    PubMed

    Bourbin, M; Gourier, D; Derenne, S; Binet, L; Le Du, Y; Westall, F; Kremer, B; Gautret, P

    2013-02-01

    Ancient geological materials are likely to be contaminated through geological times. Thus, establishing the syngeneity of the organic matter embedded in a mineral matrix is a crucial step in the study of very ancient rocks. This is particularly the case for Archean siliceous sedimentary rocks (cherts), which record the earliest traces of life. We used electron paramagnetic resonance (EPR) for assessing the syngeneity of organic matter in cherts that have a metamorphic grade no higher than greenschist. A correlation between the age of Precambrian samples and the shape of their EPR signal was established and statistically tested. As thermal treatments impact organic matter maturity, the effect of temperature on this syngeneity proxy was studied; cyanobacteria were submitted to cumulative short thermal treatment at high temperatures followed by an analysis of their EPR parameters. The resulting carbonaceous matter showed an evolution similar to that of a thermally treated young chert. Furthermore, the possible effect of metamorphism, which is a longer thermal event at lower temperatures, was ruled out for cherts older than 2 Gyr, based on the study of Silurian cherts of the same age and same precursors but various metamorphic grades. We determined that even the most metamorphosed sample did not exhibit the lineshape of an Archean sample. In the hope of detecting organic contamination in Archean cherts, a "contamination-like" mixture was prepared and studied by EPR. It resulted that the lineshape analysis alone does not allow contamination detection and that it must be performed along with cumulative thermal treatments. Such treatments were applied to three Archean chert samples, making dating of their carbonaceous matter possible. We concluded that EPR is a powerful tool to study primitive organic matter and could be used in further exobiology studies on low-metamorphic grade samples (from Mars for example).

  16. Dating Carbonaceous Matter in Archean Cherts by Electron Paramagnetic Resonance

    PubMed Central

    Bourbin, M.; Derenne, S.; Binet, L.; Le Du, Y.; Westall, F.; Kremer, B.; Gautret, P.

    2013-01-01

    Abstract Ancient geological materials are likely to be contaminated through geological times. Thus, establishing the syngeneity of the organic matter embedded in a mineral matrix is a crucial step in the study of very ancient rocks. This is particularly the case for Archean siliceous sedimentary rocks (cherts), which record the earliest traces of life. We used electron paramagnetic resonance (EPR) for assessing the syngeneity of organic matter in cherts that have a metamorphic grade no higher than greenschist. A correlation between the age of Precambrian samples and the shape of their EPR signal was established and statistically tested. As thermal treatments impact organic matter maturity, the effect of temperature on this syngeneity proxy was studied; cyanobacteria were submitted to cumulative short thermal treatment at high temperatures followed by an analysis of their EPR parameters. The resulting carbonaceous matter showed an evolution similar to that of a thermally treated young chert. Furthermore, the possible effect of metamorphism, which is a longer thermal event at lower temperatures, was ruled out for cherts older than 2 Gyr, based on the study of Silurian cherts of the same age and same precursors but various metamorphic grades. We determined that even the most metamorphosed sample did not exhibit the lineshape of an Archean sample. In the hope of detecting organic contamination in Archean cherts, a “contamination-like” mixture was prepared and studied by EPR. It resulted that the lineshape analysis alone does not allow contamination detection and that it must be performed along with cumulative thermal treatments. Such treatments were applied to three Archean chert samples, making dating of their carbonaceous matter possible. We concluded that EPR is a powerful tool to study primitive organic matter and could be used in further exobiology studies on low-metamorphic grade samples (from Mars for example). Key Words: Kerogen—Sedimentary rocks

  17. Magnetothermal Convection in Nonconducting Diamagnetic and Paramagnetic Fluids

    NASA Technical Reports Server (NTRS)

    Edwards, Boyd F.; Gray, Donald D.; Huang, Jie

    1996-01-01

    Nonuniform magnetic fields exert a magnetic body force on electrically nonconducting classical fluids. These include paramagnetic fluids such as gaseous and liquid oxygen and diamagnetic fluids such as helium. Recent experiments show that this force can overwhelm the force of gravity even at the surface of the earth; it can levitate liquids and gases, quench candle flames, block gas flows, and suppress heat transport. Thermal gradients render the magnetic force nonuniform through the temperature-dependent magnetic susceptibility. These thermal gradients can therefore drive magnetic convection analogous to buoyancy-driven convection. This magnetothermal convection can overwhelm convection driven by gravitational buoyancy in terrestrial experiments. The objectives of the proposed ground-based theoretical study are (a) to supply the magnetothermohydrodynamic theory necessary to understand these recent experiments and (b) to explore the consequences of nonuniform magnetic fields in microgravity. Even the linear theory for the onset of magnetothermal convection is lacking in the literature. We intend to supply the linear and nonlinear theory based on the thermohydrodynamic equations supplemented by the magnetic body force. We intend to investigate the effect of magnetic fields on gas blockage and heat transport in microgravity. Since magnetic fields provide a means of creating arbitrary, controllable body force distributions, we intend to investigate the possibility of using magnetic fields to position and control fluids in microgravity. We also intend to investigate the possibility of creating stationary terrestrial microgravity environments by using the magnetic force to effectively cancel gravity. These investigations may aid in the design of space-based heat-transfer, combustion, and human-life-support equipment.

  18. Subtle dynamics of holo glutamine binding protein revealed with a rigid paramagnetic probe.

    PubMed

    Liu, Zhu; Gong, Zhou; Guo, Da-Chuan; Zhang, Wei-Ping; Tang, Chun

    2014-03-11

    Bacterial periplasmic binding proteins (PBPs) are involved in the translocation of small molecules in the periplasm. To unload, the two domains of a PBP open up, allowing the ligand to exit. However, it is not clear whether there are dynamics near the binding site which can facilitate the rapid dissociation of a ligand. To visualize such dynamics, we utilized paramagnetic relaxation enhancement (PRE) NMR and introduced a rigid paramagnetic probe to a PBP, glutamine-binding protein (QBP) with its cognate ligand bound. A paramagnetic Cu(II) ion is sandwiched between an engineered di-histidine motif at a helix and an NTA capping molecule. The afforded paramagnetic probe is so rigid that PRE values calculated from a single structure of holo QBP largely agree with the observed values. The remaining PRE discrepancies, however, manifest dynamics of a loop in the opposite domain from the paramagnetic probe. This loop packs against the glutamine ligand in the holo QBP and undergoes fluctuations upon ligand dissociation, as assessed by steered molecular dynamics simulations. As such, the loop dynamics, occurring for a small population in nanosecond to microsecond time scale, may be related to the ligand dissociation process. The rigid paramagnetic probe described herein can be grafted to other protein systems for structure and dynamics studies.

  19. Paramagnetic nanoparticles as potential MRI contrast agents: characterization, NMR relaxation, simulations and theory.

    PubMed

    Vuong, Quoc Lam; Van Doorslaer, Sabine; Bridot, Jean-Luc; Argante, Corradina; Alejandro, Gabriela; Hermann, Raphaël; Disch, Sabrina; Mattea, Carlos; Stapf, Siegfried; Gossuin, Yves

    2012-12-01

    Paramagnetic nanoparticles, mainly rare earth oxides and hydroxides, have been produced these last few years for use as MRI contrast agents. They could become an interesting alternative to iron oxide particles. However, their relaxation properties are not well understood. Magnetometry, (1)H and (2)H NMR relaxation results at different magnetic fields and electron paramagnetic resonance are used to investigate the relaxation induced by paramagnetic particles. When combined with computer simulations of transverse relaxation, they allow an accurate description of the relaxation induced by paramagnetic particles. For gadolinium hydroxide particles, both T(1) and T(2) relaxation are due to a chemical exchange of protons between the particle surface and bulk water, called inner sphere relaxation. The inner sphere is also responsible for T(1) relaxation of dysprosium, holmium, terbium and erbium containing particles. However, for these latter compounds, T(2) relaxation is caused by water diffusion in the field inhomogeneities created by the magnetic particle, the outer-sphere relaxation mechanism. The different relaxation behaviors are caused by different electron relaxation times (estimated by electron paramagnetic resonance). These findings may allow tailoring paramagnetic particles: ultrasmall gadolinium oxide and hydroxide particles for T(1) contrast agents, with shapes ensuring the highest surface-to-volume ratio. All the other compounds present interesting T(2) relaxation performance at high fields. These results are in agreement with computer simulations and theoretical predictions of the outer-sphere and static dephasing regime theories. The T(2) efficiency would be optimum for spherical particles of 40-50 nm radius.

  20. Characterisation and evaluation of paramagnetic fluorine labelled glycol chitosan conjugates for (19)F and (1)H magnetic resonance imaging.

    PubMed

    De Luca, Elena; Harvey, Peter; Chalmers, Kirsten H; Mishra, Anurag; Senanayake, P Kanthi; Wilson, J Ian; Botta, Mauro; Fekete, Marianna; Blamire, Andrew M; Parker, David

    2014-02-01

    Medium molecular weight glycol chitosan conjugates have been prepared, linked by an amide bond to paramagnetic Gd(III), Ho(III) and Dy(III) macrocyclic complexes in which a trifluoromethyl reporter group is located 6.5 Å from the paramagnetic centre. The faster relaxation of the observed nucleus allows modified pulse sequences to be used with shorter acquisition times. The polydisperse materials have been characterised by gel permeation chromatography, revealing an average molecular weight on the order of 13,800 (Gd), 14,600 (Dy) and 16,200 (Ho), consistent with the presence of 8.5, 9.5 and 13 complexes, respectively. The gadolinium conjugate was prepared for both a q = 1 monoamide tricarboxylate conjugate (r1p 11.2 mM(-1) s(-1), 310 K, 1.4 T) and a q = 0 triphosphinate system, and conventional contrast-enhanced proton MRI studies at 7 T were undertaken in mice bearing an HT-29 or an HCT-116 colorectal tumour xenograft (17 μmol/kg). Enhanced contrast was observed following injection in the tail vein in tumour tissue, with uptake also evident in the liver and kidney with a tumour-to-liver ratio of 2:1 at 13 min, and large amounts in the kidney and bladder consistent with predominant renal clearance. Parallel experiments observing the (19)F resonance in the holmium conjugate complex using a surface coil did not succeed owing to its high R2 value (750 Hz, 7 T). However, the fluorine signal in the dysprosium triphosphinate chitosan conjugate [R1/R2 = 0.6 and R1 = 145 Hz (7 T)] was sharper and could be observed in vivo at -65.7 ppm, following intravenous tail vein injection of a dose of 34 μmol/kg.

  1. Mapping RNA-protein interactions in ribonuclease P from Escherichia coli using electron paramagnetic resonance spectroscopy.

    PubMed

    Gopalan, V; Kühne, H; Biswas, R; Li, H; Brudvig, G W; Altman, S

    1999-02-09

    Ribonuclease P (RNase P) is a catalytic ribonucleoprotein (RNP) essential for tRNA biosynthesis. In Escherichia coli, this RNP complex is composed of a catalytic RNA subunit, M1 RNA, and a protein cofactor, C5 protein. Using the sulfhydryl-specific reagent (1-oxyl-2,2,5, 5-tetramethyl-Delta3-pyrroline-3-methyl)methanethiosulfonate (MTSL), we have introduced a nitroxide spin label individually at six genetically engineered cysteine residues (i.e., positions 16, 21, 44, 54, 66, and 106) and the native cysteine residue (i.e., position 113) in C5 protein. The spin label covalently attached to any protein is sensitive to structural changes in its microenvironment. Therefore, we expected that if the spin label introduced at a particular position in C5 protein was present at the RNA-protein interface, the electron paramagnetic resonance (EPR) spectrum of the spin label would be altered upon binding of the spin-labeled C5 protein to M1 RNA. The EPR spectra observed with the various MTSL-modified mutant derivatives of C5 protein indicate that the spin label attached to the protein at positions 16, 44, 54, 66, and 113 is immobilized to varying degrees upon addition of M1 RNA but not in the presence of a catalytically inactive, deletion derivative of M1 RNA. In contrast, the spin label attached to position 21 displays an increased mobility upon binding to M1 RNA. The results from this EPR spectroscopy-based approach together with those from earlier studies identify residues in C5 protein which are proximal to M1 RNA in the RNase P holoenzyme complex.

  2. `Rapidly Appearing' molybdenum electron-paramagnetic-resonance signals from reduced xanthine oxidase

    PubMed Central

    Bray, R. C.; Vänngård, T.

    1969-01-01

    Further electron-paramagnetic-resonance studies relating to the role of molybdenum in the enzymic mechanisms of xanthine oxidase were carried out. The classification of the various molybdenum signals obtained on reducing the enzyme is briefly discussed. The group of `Rapidly appearing' signals, which are obtained with all substrates within the turnover time and which show interaction with exchangeable protons, were studied in detail. Signals with salicylaldehyde, purine and xanthine in H2O and in 95% D2O were examined at 9 and 35GHz and interpreted with the help of computer simulation. Molybdenum atoms in a number of different chemical environments are involved, each substrate giving rise to two superimposed spectra with slightly different parameters; g values and proton splittings were determined. The spectrum with salicylaldehyde is believed to represent the reduced enzyme alone not in the form of a complex with substrate and its two constituents are believed to represent the two molybdenum atoms bonded slightly differently within the enzyme molecule. With purine and xanthine the spectra are thought to represent complexes of reduced enzyme with substrate molecules. With xanthine one signal-giving species shows coupling to two equivalent protons, whereas in all the other species observed two non-equivalent protons are involved. The origin of the protons is discussed in the light of the direct hydrogen-transfer mechanism implicated earlier for the enzyme. It is concluded that the proton derived from the substrate is located at least 3å from the molybdenum atom with which it interacts. PMID:4310055

  3. Towards Human Oxygen Images with Electron Paramagnetic Resonance Imaging

    PubMed Central

    Epel, Boris; Redler, Gage; Tormyshev, Victor; Halpern, Howard J.

    2016-01-01

    Electron paramagnetic resonance imaging (EPRI) has been used to noninvasively provide 3D images of absolute oxygen concentration (pO2) in small animals. These oxygen images are well resolved both spatially (∼1mm) and in pO2 (1-3 torr). EPRI preclinical images of pO2 have demonstrated extremely promising results for various applications investigating oxygen related physiologic and biologic processes as well as the dependence of various disease states on pO2, such as the role of hypoxia in cancer. Recent developments have been made that help to progress EPRI towards the eventual goal of human application. For example, a bimodal crossed-wire surface coil has been developed. Very preliminary tests demonstrated a 20 dB isolation between transmit and receive for this coil, with an anticipated additional 20dB achievable. This could potentially be used to image local pO2 in human subjects with superficial tumors with EPRI. Local excitation and detection will reduce the specific absorption rate limitations on images and eliminate any possible power deposition concerns. Additionally, a large 9 mT EPRI magnet has been constructed which can fit and provide static main and gradient fields for imaging local anatomy in an entire human. One potential obstacle that must be overcome in order to use EPRI to image humans is the approved use of the requisite EPRI spin probe imaging agent (trityl). While nontoxic, EPRI trityl spin probes have been injected intravenously when imaging small animals, which results in relatively high total body injection doses that would not be suitable for human imaging applications. Work has been done demonstrating the alternative use of intratumoral (IT) injections, which can reduce the amount of trityl required for imaging by a factor of 2000- relative to a whole body intravenous injection. The development of a large magnet that can accommodate human subjects, the design of a surface coil for imaging of superficial pO2, and the reduction of required

  4. Connecting lipoxygenase function to structure by electron paramagnetic resonance.

    PubMed

    Gaffney, Betty J

    2014-12-16

    CONSPECTUS: Lipoxygenase enzymes insert oxygen in a polyunsaturated lipid, yielding a hydroperoxide product. When the acyl chain is arachidonate, with three cis-pentadiene units, 12 positionally and stereochemically different products might result. The plant lipids, linoleate and linolenate, have, respectively, four and eight potential oxygen insertion sites. The puzzle of how specificity is achieved in these reactions grows as more and more protein structures confirm the conservation of a lipoxygenase protein fold in plants, animals, and bacteria. Lipoxygenases are large enough (60-100 kDa) that they provide a protein shell completely surrounding an active site cavity that has the shape of a long acyl chain and contains a catalytic metal (usually iron). This Account summarizes electron paramagnetic resonance (EPR) spectroscopic, and other, experiments designed to bridge the gap between lipid-lipoxygenase interactions in solution and crystal structures. Experiments with spin-labeled lipids give a picture of bound lipids tethered to protein by an acyl chain, but with a polar end emerging from the cavity to solvent exposure, where the headgroup is highly flexible. The location of a spin on the polar end of a lysolecithin was determined by pulsed, dipolar EPR measurements, by representing the protein structure as a five-point grid of spin-labels with coordinates derived from 10 distance determinations between spin pairs. Distances from the lipid spin to each grid site completed a six-point representation of the enzyme with a bound lipid. Insight into the dynamics that allow substrate/product to enter/exit the cavity was obtained with a different set of spin-labeled protein mutants. Once substrate enters the cavity, the rate-limiting step of catalysis involves redox cycling at the metal center. Here, a mononuclear iron cycles between ferric and ferrous (high-spin) forms. Two helices provide pairs of side-chain ligands to the iron, resulting in characteristic EPR

  5. Thermomagnetic phenomena in mesoscopic and paramagnetically limited superconductors

    NASA Astrophysics Data System (ADS)

    Hettinger, Mengling

    The superconducting fluctuation effect, due to droplets of preformed Cooper pairs above the critical temperature Tc, governs the temperature dependence of kinetic coefficients in superconductors at the onset of the phase transition. The transverse thermoelectric response - Nernst effect - is particularly sensitive to the fluctuations, and the large Nernst signal found in the various superconducting materials has raised much debate on its connection to the origin of unconventional superconductivity. In this thesis, we present a systematic study of the electrical and thermomagnetic transport phenomena in mesoscopic and paramagnetically (Pauli) limited superconductors. In the first chapter of this thesis we concentrate on the study of mesoscopic effects on transport in superconductors. We find that long-range phase coherence developing close to Tc triggers a great amplification of mesoscopic fluctuations due to strong pairing correlations. As a result, mesoscopic conductance fluctuations cease to be universal and exhibit pronounced dependence on temperature. Despite the lack of universality, in the sense of random matrix theory classification, we have discovered a different kind of universality in terms of temperature dependence of fluctuating characteristics. We find that mesoscopic fluctuations of conductivity, transversal thermoelectric coefficient and diamagnetic susceptibility consistently display the same scaling with temperature close to Tc. We connect our results to the existing experimental measurements of conductance fluctuations in superconducting films. Experimental verification of the temperature scaling and the overall magnitude of the mesoscopic fluctuations of Nernst coefficient will provide a powerful tool for a better understanding of thermomagnetic transport phenomena in correlated systems. In the second chapter of this thesis we examine the electrical and thermal transport anomalies in the ultra-thin superconducting films in an external in

  6. Paramagnetic resonance studies of defects in titanium dioxide crystals

    NASA Astrophysics Data System (ADS)

    Yang, Shan

    Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) are used to identify and characterize point defects in TiO2 crystals having the rutile structure. Defect production occurs at low temperature during illumination with 442 nm laser light. Spectra with S = 1/2 and S = 1 are assigned to singly ionized and neutral oxygen vacancies, respectively. These oxygen vacancies have their unpaired spins localized on the two neighboring titanium ions aligned along the [001] axis. A Ti3+ ion next to a substitutional Si4+ ion, a Ti3+ self-trapped electron, and a self-trapped hole on the oxygen sublattice are also observed. Fluorine ions substitute for oxygen and are present as unintentional impurities in TiO2 crystals. Isolated singly ionized fluorine donors in an as-grown (fully oxidized) crystal convert to their neutral charge state during exposure to 442 nm laser light at 6 K. These donors return to the singly ionized charge state within a few seconds when the light is removed. In contrast, the neutral fluorine donors are observed at 6 K without photoexcitation after a crystal is reduced at 600 ºC in flowing nitrogen gas. The angular dependences of the EPR and ENDOR spectra provide a complete set of spin-Hamiltonian parameters (principal values are 1.9746, 1.9782, and 1.9430 for the g matrix and -0.23, 0.47, and 5.15 MHz for the 19F hyperfine matrix). These matrices suggest that the unpaired electron is localized primarily on one of the two equivalent neighboring substitutional titanium ions, i.e., the ground state of the neutral fluorine donor in rutile-structured TiO2 is a Ti 3+ ion adjacent to a F- ion. Hydrogen, in the form of an OH- ion, is a shallow donor in TiO2. In the neutral charge state, the unpaired electron forms an adjacent Ti3+ ion. The hydrogen EPR signal cannot be produced in oxidized crystals containing fluorine donors, which suggest that hydrogen is a shallower donor than fluorine in TiO2 (rutile) crystals. The hydrogen EPR

  7. Hyperfine Sublevel Correlation (HYSCORE) Spectra for Paramagnetic Centers with Nuclear Spin I = 1 Having Isotropic Hyperfine Interactions

    SciTech Connect

    Maryasov, Alexander G.; Bowman, Michael K.

    2004-07-08

    It is shown that HYSCORE spectra of paramagnetic centers having nuclei of spin I=1 with isotropic hfi and arbitrary NQI consist of ridges having zero width. A parametric presentation of these ridges is found which shows the range of possible frequencies in the HYSCORE spectrum and aids in spectral assignments and rapid estimation of spin Hamiltonian parameters. An alternative approach for the spectral density calculation is presented that is based on spectral decomposition of the Hamiltonian. Only the eigenvalues of the Hamiltonian are needed in this approach. An atlas of HYSCORE spectra is given in the Supporting Information. This approach is applied to the estimation of the spin Hamiltonian parameters of the oxovanadium-EDTA complex.

  8. Electron paramagnetic resonance studies of Cu 2+ ion in Tetraaqua-di(nicotinamide)Ni(II)-saccharinates single crystals

    NASA Astrophysics Data System (ADS)

    Yerli, Y.; Kazan, S.; Yalçın, O.; Aktaş, B.

    2006-06-01

    X-band (˜9.8 GHz) electron paramagnetic resonance (EPR) measurement at ambient temperature in three mutually perpendicular planes have been carried out on a single crystal of Cu 2+ doped mixed ligand complex of Ni(II) with saccharin and nicotinamide [Ni(Nic) 2(H 2O) 4](sac) 2. The angular dependent spectra showed that the Cu 2+ ion enters Ni 2+ sites in the lattice and distorted local environment of Ni 2+ site. The principal g and A values, covalency parameter ( α' 2), mixing coefficients ( α and β) and Fermi contact term ( K) have been evaluated from the EPR analysis. The ground-state wave function of the Cu 2+ ion has been constructed using the α' 2, α and β values. The nature of the distortion present in the lattice is obtained from the values of the mixing coefficients.

  9. Exploring Structure, Dynamics, and Topology of Nitroxide Spin-Labeled Proteins Using Continuous-Wave Electron Paramagnetic Resonance Spectroscopy.

    PubMed

    Altenbach, Christian; López, Carlos J; Hideg, Kálmán; Hubbell, Wayne L

    2015-01-01

    Structural and dynamical characterization of proteins is of central importance in understanding the mechanisms underlying their biological functions. Site-directed spin labeling (SDSL) combined with continuous-wave electron paramagnetic resonance (CW EPR) spectroscopy has shown the capability of providing this information with site-specific resolution under physiological conditions for proteins of any degree of complexity, including those associated with membranes. This chapter introduces methods commonly employed for SDSL and describes selected CW EPR-based methods that can be applied to (1) map secondary and tertiary protein structure, (2) determine membrane protein topology, (3) measure protein backbone flexibility, and (4) reveal the existence of conformational exchange at equilibrium. © 2015 Elsevier Inc. All rights reserved.

  10. Mechanical membrane for the separation of a paramagnetic constituent from a fluid

    DOEpatents

    Maurice, David

    2017-05-02

    The disclosure provides an apparatus and method for the separation of a paramagnetic component from a mixture using a mechanical membrane apparatus. The mechanical membrane comprises a supporting material having a plurality of pores where each pore is surrounded by a plurality of magnetic regions. The magnetic regions augment a magnetic field on one side of the supporting material while mitigating the field to near zero on the opposite side. In operation, a flow of fluid such as air comprising a paramagnetic component such as O.sub.2 is directed toward the mechanical membrane, and the paramagnetic component is typically attracted toward a magnetic field surrounding a pore while dimagnetic components such as N.sub.2 are generally repelled. As some portion of the fluid passes through the plurality of magnetic apertures to the opposite side of the mechanical membrane, the mechanical membrane generates a fluid enriched in the paramagnetic component. Alternately, the magnetic field may act to repel the paramagnetic component while diamagnetic components such as N.sub.2 are generally unaffected and pass to the opposite side of the mechanical membrane.

  11. High field electron paramagnetic resonance spectroscopy under ultrahigh vacuum conditions—A multipurpose machine to study paramagnetic species on well defined single crystal surfaces

    SciTech Connect

    Rocker, J.; Cornu, D.; Kieseritzky, E.; Hänsel-Ziegler, W.; Freund, H.-J.; Seiler, A.; Bondarchuk, O.

    2014-08-01

    A new ultrahigh vacuum (UHV) electron paramagnetic resonance (EPR) spectrometer operating at 94 GHz to investigate paramagnetic centers on single crystal surfaces is described. It is particularly designed to study paramagnetic centers on well-defined model catalysts using epitaxial thin oxide films grown on metal single crystals. The EPR setup is based on a commercial Bruker E600 spectrometer, which is adapted to ultrahigh vacuum conditions using a home made Fabry Perot resonator. The key idea of the resonator is to use the planar metal single crystal required to grow the single crystalline oxide films as one of the mirrors of the resonator. EPR spectroscopy is solely sensitive to paramagnetic species, which are typically minority species in such a system. Hence, additional experimental characterization tools are required to allow for a comprehensive investigation of the surface. The apparatus includes a preparation chamber hosting equipment, which is required to prepare supported model catalysts. In addition, surface characterization tools such as low energy electron diffraction (LEED)/Auger spectroscopy, temperature programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS) are available to characterize the surfaces. A second chamber used to perform EPR spectroscopy at 94 GHz has a room temperature scanning tunneling microscope attached to it, which allows for real space structural characterization. The heart of the UHV adaptation of the EPR experiment is the sealing of the Fabry-Perot resonator against atmosphere. To this end it is possible to use a thin sapphire window glued to the backside of the coupling orifice of the Fabry Perot resonator. With the help of a variety of stabilization measures reducing vibrations as well as thermal drift it is possible to accumulate data for a time span, which is for low temperature measurements only limited by the amount of liquid helium. Test measurements show that the system can detect paramagnetic

  12. Electron Paramagnetic Resonance Study of Structural Changes in the O Photointermediate of Bacteriorhodopsin

    PubMed Central

    Chen, Deliang; Wang, Jennifer M.; Lanyi, Janos K.

    2007-01-01

    The structural changes of bacteriorhodopsin during its photochemical cycle, as revealed by crystal structures of trapped intermediates, have provided insights to the proton translocation mechanism. Because accumulation of the last photointermediate, O, appears to be hindered by lattice forces in the crystals, the only information about the structure of this state is from suggested analogies with the determined structures of the non-illuminated D85S mutant and wild type bacteriorhodopsin at low pH. We used electron paramagnetic resonance spectroscopy of site-directed spin labels at the extracellular protein surface in membranes to test these models. Spin-spin dipolar interactions in the authentic O state compared to the non-illuminated state revealed that the distance between helices C and F increases by ca. 4 Å, there is no distance change between helices D and F, and the distance between helix D and helix B of the adjacent monomer increases. Further, the mobility changes of single labels indicate that helices E and F move outward from the proton channel at the center of the protein, and helix D tilts inward. The overall pattern of movements suggests that the model at acid pH is a better representation of the O state than D85S. However, the mobility analysis of spin-labels on the B-C interhelical loop indicates that the anti-parallel β-sheet maintains its ordered secondary structure in O, instead of the predicted disorder in the two structural models. During decay of the O state, the last step of the photocycle, a proton is transferred from Asp85 to proton release complex in the extracellular proton channel. The structural changes in O suggest the need of large conformational changes to drive the Arg82 side-chain back to its initial orientation towards Asp85, and to rearrange the numerous water molecules in this region in order to conduct the proton away from Asp85. PMID:17196982

  13. Electron paramagnetic resonance study of structural changes in the O photointermediate of bacteriorhodopsin.

    PubMed

    Chen, Deliang; Wang, Jennifer M; Lanyi, Janos K

    2007-02-23

    The structural changes of bacteriorhodopsin during its photochemical cycle, as revealed by crystal structures of trapped intermediates, have provided insights to the proton translocation mechanism. Because accumulation of the last photointermediate, O, appears to be hindered by lattice forces in the crystals, the only information about the structure of this state is from suggested analogies with the determined structures of the non-illuminated D85S mutant and wild-type bacteriorhodopsin at low pH. We used electron paramagnetic resonance spectroscopy of site-directed spin labels at the extracellular protein surface in membranes to test these models. Spin-spin dipolar interactions in the authentic O state compared to the non-illuminated state revealed that the distance between helices C and F increases by ca 4 Angstroms, there is no distance change between helices D and F, and the distance between helix D and helix B of the adjacent monomer increases. Further, the mobility changes of single labels indicate that helices E and F move outward from the proton channel at the center of the protein, and helix D tilts inward. The overall pattern of movements suggests that the model at acid pH is a better representation of the O state than D85S. However, the mobility analysis of spin-labels on the B-C interhelical loop indicates that the antiparallel beta-sheet maintains its ordered secondary structure in O, instead of the predicted disorder in the two structural models. During decay of the O state, the last step of the photocycle, a proton is transferred from Asp85 to proton release complex in the extracellular proton channel. The structural changes in O suggest the need of large conformational changes to drive the Arg82 side-chain back to its initial orientation towards Asp85, and to rearrange the numerous water molecules in this region in order to conduct the proton away from Asp85.

  14. Pulsed electron paramagnetic resonance spectroscopy powered by a free-electron laser.

    PubMed

    Takahashi, S; Brunel, L-C; Edwards, D T; van Tol, J; Ramian, G; Han, S; Sherwin, M S

    2012-09-20

    Electron paramagnetic resonance (EPR) spectroscopy interrogates unpaired electron spins in solids and liquids to reveal local structure and dynamics; for example, EPR has elucidated parts of the structure of protein complexes that other techniques in structural biology have not been able to reveal. EPR can also probe the interplay of light and electricity in organic solar cells and light-emitting diodes, and the origin of decoherence in condensed matter, which is of fundamental importance to the development of quantum information processors. Like nuclear magnetic resonance, EPR spectroscopy becomes more powerful at high magnetic fields and frequencies, and with excitation by coherent pulses rather than continuous waves. However, the difficulty of generating sequences of powerful pulses at frequencies above 100 gigahertz has, until now, confined high-power pulsed EPR to magnetic fields of 3.5 teslas and below. Here we demonstrate that one-kilowatt pulses from a free-electron laser can power a pulsed EPR spectrometer at 240 gigahertz (8.5 teslas), providing transformative enhancements over the alternative, a state-of-the-art ∼30-milliwatt solid-state source. Our spectrometer can rotate spin-1/2 electrons through π/2 in only 6 nanoseconds (compared to 300 nanoseconds with the solid-state source). Fourier-transform EPR on nitrogen impurities in diamond demonstrates excitation and detection of EPR lines separated by about 200 megahertz. We measured decoherence times as short as 63 nanoseconds, in a frozen solution of nitroxide free-radicals at temperatures as high as 190 kelvin. Both free-electron lasers and the quasi-optical technology developed for the spectrometer are scalable to frequencies well in excess of one terahertz, opening the way to high-power pulsed EPR spectroscopy up to the highest static magnetic fields currently available.

  15. Quasilocal critical nature of cooperative paramagnetic fluctuations in CaRuO3 metal

    NASA Astrophysics Data System (ADS)

    Gunasekera, J.; Harriger, L.; Heitmann, T.; Dahal, A.; Knoll, H.; Singh, D. K.

    2015-06-01

    We report the observation of cooperative paramagnetic fluctuations of Ru4 + spins that coexist with the non-Fermi-liquid state in CaRuO3 perovskite below T ≃21 K. Detailed electrical, magnetic, and neutron scattering measurements reveal that the Ru4 + ions reside in magnetic-field-independent random domains with dynamic properties that are reminiscent of the cooperative paramagnetic fluctuations. The linear (E /T ) scaling of the dynamic susceptibilities and divergence of the mean relaxation time as T →0 K suggest a quasilocal critical nature of the spin fluctuations. We argue that the non-Fermi-liquid behavior arises due to the quantum critical nature of the cooperative paramagnetic fluctuations in CaRuO3.

  16. Structural studies of proteins by paramagnetic solid-state NMR spectroscopy

    PubMed Central

    Jaroniec, Christopher P.

    2015-01-01

    Paramagnetism-based nuclear pseudocontact shifts and spin relaxation enhancements contain a wealth of information in solid-state NMR spectra about electron-nucleus distances on the ~20 Å length scale, far beyond that normally probed through measurements of nuclear dipolar couplings. Such data are especially vital in the context of structural studies of proteins and other biological molecules that suffer from a sparse number of experimentally-accessible atomic distances constraining their three-dimensional fold or intermolecular interactions. This perspective provides a brief overview of the recent developments and applications of paramagnetic magic-angle spinning NMR to biological systems, with primary focus on the investigations of metalloproteins and natively diamagnetic proteins modified with covalent paramagnetic tags. PMID:25797004

  17. Orbital Paramagnetism of a Softly Confined 2DEG Strip in the Extreme Quantum Limit

    NASA Astrophysics Data System (ADS)

    Harrison, Michael J.

    2002-03-01

    The role of surfaces in the orbital magnetism of a noninteracting electron gas of finite size has long been of continuing theoretical interest[1]. More recent experiments on 2DEG heterostructures embodied in gallium-arsenide squares of micron size indicate orbital electronic paramagnetism much larger than Landau diamagnetism[2]. The orbital magnetism in the extreme quantum limit of softly confined 2DEG strips several microns wide with areal electron densities greater than 10^9 per square centimeter is shown to have a large paramagnetic maximum as a function of magnetic field before reverting to negative Landau diamagnetism at sufficiently large fields. A novel fabricated heterostructure, layered with such strips, is described which may exhibit strong bulk paramagnetism. 1. Frank S. Ham,Phys.Rev.92,1113(1953), and references therein. 2. L.P.Levy,D.H.Reich,L.Pfeiffer, and K.West,Physica B 189, 204(1993).

  18. Effect of Paramagnetic Ions on NMR Relaxation of Fluids at Solid Surfaces

    NASA Astrophysics Data System (ADS)

    Foley, I.; Farooqui, S. A.; Kleinberg, R. L.

    Proton NMR longitudinal and transverse relaxation times of water-saturated powder packs have been measured. The powders were a series of synthetic calcium silicates with known concentrations of iron or manganese paramagnetic ions. The rate of water proton relaxation has been found to be linearly proportional to the concentration of paramagnetic ion. The constant of proportionality is used to determine the electron relaxation time of ions at the fluid-solid interface. A substantial relaxivity is found in the absence of paramagnetic ions. Thus the oxide surface itself is an unexpectedly good relaxer of fluid-borne nuclear spins. The results answer some long-standing questions connected with the NMR properties of fluid-saturated sedimentary rocks.

  19. Electron paramagnetic resonance investigation of purified catalyst-free single-walled carbon nanotubes.

    PubMed

    Zaka, Mujtaba; Ito, Yasuhiro; Wang, Huiliang; Yan, Wenjing; Robertson, Alex; Wu, Yimin A; Rümmeli, Mark H; Staunton, David; Hashimoto, Takeshi; Morton, John J L; Ardavan, Arzhang; Briggs, G Andrew D; Warner, Jamie H

    2010-12-28

    Electron paramagnetic resonance of single-walled carbon nanotubes (SWCNTs) has been bedevilled by the presence of paramagnetic impurities. To address this, SWCNTs produced by laser ablation with a nonmagnetic PtRhRe catalyst were purified through a multiple step centrifugation process in order to remove amorphous carbon and catalyst impurities. Centrifugation of a SWCNT solution resulted in sedimentation of carbon nanotube bundles containing clusters of catalyst particles, while isolated nanotubes with reduced catalyst particle content remained in the supernatant. Further ultracentrifugation resulted in highly purified SWCNT samples with a narrow diameter distribution and almost no detectable catalyst particles. Electron paramagnetic resonance (EPR) signals were detected only for samples which contained catalyst particles, with the ultracentrifuged SWCNTs showing no EPR signal at X-band (9.4 GHz) and fields < 0.4 T.

  20. Paramagnetic resonance and susceptibility of ilmenite, FeTiO3 crystal

    NASA Technical Reports Server (NTRS)

    Mcdonald, P. F.; Parasiris, A.; Pandey, R. K.; Gries, B. L.; Kirk, W. P.

    1991-01-01

    Large high-purity single crystals of FeTiO3 with ilmenite structure have been grown from a stoichiometric melt of Fe2O3 and TiO2 under an inert atmosphere using the modified Czochralski technique. Susceptibility and X-band paramagnetic resonance studies have been performed. Susceptibility measurements indicate a Neel temperature of about 59 K. The paramagnetic resonance spectrum for magnetic field perpendicular to the crystal c axis consists of a portion of a single, very intense approximately Lorentzian absorption line with its peak at about 600 G and half width at half maximum almost 1200 G. The absorption extends to zero magnetic field. For magnetic field approximately parallel to the c axis, the paramagnetic absorption is much smaller and may be considered a superposition of two approximately Lorentzian line shapes. The magnetic resonance measurements indicate a weak temperature dependence and large angular anisotropy.

  1. Following lithiation fronts in paramagnetic electrodes with in situ magnetic resonance spectroscopic imaging

    NASA Astrophysics Data System (ADS)

    Tang, Mingxue; Sarou-Kanian, Vincent; Melin, Philippe; Leriche, Jean-Bernard; Ménétrier, Michel; Tarascon, Jean-Marie; Deschamps, Michaël; Salager, Elodie

    2016-11-01

    Li-ion batteries are invaluable for portable electronics and vehicle electrification. A better knowledge of compositional variations within the electrodes during battery operation is, however, still needed to keep improving their performance. Although essential in the medical field, magnetic resonance imaging of solid paramagnetic battery materials is challenging due to the short lifetime of their signals. Here we develop the scanning image-selected in situ spectroscopy approach, using the strongest commercially available magnetic field gradient. We demonstrate the 7Li magnetic resonance spectroscopic image of a 5 mm-diameter operating battery with a resolution of 100 μm. The time-resolved image-spectra enable the visualization in situ of the displacement of lithiation fronts inside thick paramagnetic electrodes during battery operation. Such observations are critical to identify the key limiting parameters for high-capacity and fast-cycling batteries. This non-invasive technique also offers opportunities to study devices containing paramagnetic materials while operating.

  2. Epirubicin loaded super paramagnetic iron oxide nanoparticle-aptamer bioconjugate for combined colon cancer therapy and imaging in vivo.

    PubMed

    Jalalian, Seyed Hamid; Taghdisi, Seyed Mohammad; Shahidi Hamedani, Nasim; Kalat, Seyedeh Alia Moosavian; Lavaee, Parirokh; Zandkarimi, Majid; Ghows, Narjes; Jaafari, Mahmoud Reza; Naghibi, Saeed; Danesh, Noor Mohammad; Ramezani, Mohammad; Abnous, Khalil

    2013-10-09

    Every year a large number of new cases of colorectal cancer are diagnosed in the world. Application of Epirubicin (Epi) in treatment of cancer has been limited due to its cardiotoxicity. Specific delivery of chemotherapy drugs is an important factor in reducing the side effects of drugs used in chemotherapy. Enhanced permeability, retention effect and magnetic resonance (MR) traceability of super paramagnetic iron oxide nanoparticles (SPION) make them a great candidate in cancer therapy and imaging. In this study, Epirubicin-5TR1 aptamer-SPION tertiary complex was evaluated for the imaging and treatment of murine colon carcinoma cells (C26 cells, target). For cytotoxic studies (MTT assay), C26 and CHO-K1 (Chinese hamster ovary cells, nontarget) cells were treated with either Epi or Epi-Apt-SPION tertiary complex. Internalization was evaluated by flow cytometry. Finally, Apt-SPION bioconjugate was used for imaging of cancer in vivo. Flow cytometric analysis showed that the tertiary complex was internalized effectively to C26 cells, but not to CHO-K1 cells. Cytotoxicity of Epi-Apt-SPION tertiary complex also confirmed internalization data. The complex was less cytotoxic in CHO-K1 cells when compared to Epi alone. No significant change in viability between Epi- and complex-treated C26 cells was observed. Magnetic resonance imaging (MRI) indicated a high level of accumulation of the nano-magnets within the tumor site. In conclusion Epi-Apt-SPION tertiary complex is introduced as an effective system for targeted delivery of Epi to C26 cells. Moreover this complex could efficiently detect tumors when analyzed by MRI and inhibit tumor growth in vivo.

  3. Dynamics of paramagnetic agents by off-resonance rotating frame technique

    NASA Astrophysics Data System (ADS)

    Zhang, Huiming; Xie, Yang

    2006-12-01

    Off-resonance rotating frame technique offers a novel tool to explore the dynamics of paramagnetic agents at high magnetic fields ( B0 > 3 T). Based on the effect of paramagnetic relaxation enhancement in the off-resonance rotating frame, a new method is described here for determining the dynamics of paramagnetic ion chelates from the residual z-magnetizations of water protons. In this method, the dynamics of the chelates are identified by the difference magnetization profiles, which are the subtraction of the residual z-magnetization as a function of frequency offset obtained at two sets of RF amplitude ω1 and pulse duration τ. The choices of ω1 and τ are guided by a 2-D magnetization map that is created numerically by plotting the residual z-magnetization as a function of effective field angle θ and off-resonance pulse duration τ. From the region of magnetization map that is the most sensitive to the alteration of the paramagnetic relaxation enhancement efficiency R1 ρ/ R1, the ratio of the off-resonance rotating frame relaxation rate constant R1 ρ verse the laboratory frame relaxation rate constant R1, three types of difference magnetization profiles can be generated. The magnetization map and the difference magnetization profiles are correlated with the rotational correlation time τR of Gd-DTPA through numerical simulations, and further validated by the experimental data for a series of macromolecule conjugated Gd-DTPA in aqueous solutions. Effects of hydration water number q, diffusion coefficient D, magnetic field strength B0 and multiple rotational correlation times are explored with the simulations of the magnetization map. This method not only provides a simple and reliable approach to determine the dynamics of paramagnetic labeling of molecular/cellular events at high magnetic fields, but also a new strategy for spectral editing in NMR/MRI based on the dynamics of paramagnetic labeling in vivo.

  4. Susceptibility cancellation of a microcoil wound with a paramagnetic-liquid-filled copper capillary.

    PubMed

    Takeda, Kazuyuki; Takasaki, Tomoya; Takegoshi, K

    2015-09-01

    Even though microcoils improve the sensitivity of NMR measurement of tiny samples, magnetic-field inhomogeneity due to the bulk susceptibility effect of the coil material can cause serious resonance-line broadening. Here, we propose to fabricate the microcoil using a thin, hollow copper capillary instead of a wire and fill paramagnetic liquid inside the capillary, so as to cancel the diamagnetic contribution of the copper. Susceptibility cancellation is demonstrated using aqueous solution of NiSO4. In addition, the paramagnetic liquid serves as coolant when it is circulated through the copper capillary, effectively transferring the heat generated by radiofrequency pulses.

  5. Paramagnetic closed-shell molecules: the isoelectronic series CH , BH and BeH-

    NASA Astrophysics Data System (ADS)

    Fowler, P. W.; Steiner, E.

    Coupled Hartree-Fock calculations predict CH+, like its isoelectronic analogue BH, to be paramagnetic. The calculated magnetizability has components χ∥(CH+) = - 1·44 and χ⊥(CH+) = + 10·54 a.u. with a mean value χ(CH+) = + 6·55 a.u. (5·17 × 10-28 J T-2). Predicted nuclear shieldings are σ(C) = - 1250 ppm and σ(H) = + 34·1 ppm. The isolated BeH- anion is predicted to lie on the diamagnetic/paramagnetic borderline, but when placed in a crystal lattice is likely to be weakly diamagnetic.

  6. Direction-dependent freezing of diamagnetic colloidal tracers suspended in paramagnetic ionic liquids.

    PubMed

    Passow, Christopher; Fischer, Birgit; Sprung, Michael; Köckerling, Martin; Wagner, Joachim

    2014-07-01

    The dynamic behavior of an inverse ferrofluid consisting of diamagnetic, spherical silica particles suspended in the paramagnetic ionic liquid (EMIm)2[Co(NCS)4] is investigated by means of x-ray photon correlation spectroscopy in the presence of an external magnetic field. Dipole-dipole interactions between the diamagnetic holes in the paramagnetic continuum of the suspending medium induce a direction-dependence of the diffusive motion of the colloidal particles: due to a magnetic repulsion perpendicular to the direction of an external field the diffusive motion of the colloidal particles is selectively frozen in this direction.

  7. Susceptibility cancellation of a microcoil wound with a paramagnetic-liquid-filled copper capillary

    NASA Astrophysics Data System (ADS)

    Takeda, Kazuyuki; Takasaki, Tomoya; Takegoshi, K.

    2015-09-01

    Even though microcoils improve the sensitivity of NMR measurement of tiny samples, magnetic-field inhomogeneity due to the bulk susceptibility effect of the coil material can cause serious resonance-line broadening. Here, we propose to fabricate the microcoil using a thin, hollow copper capillary instead of a wire and fill paramagnetic liquid inside the capillary, so as to cancel the diamagnetic contribution of the copper. Susceptibility cancellation is demonstrated using aqueous solution of NiSO4. In addition, the paramagnetic liquid serves as coolant when it is circulated through the copper capillary, effectively transferring the heat generated by radiofrequency pulses.

  8. Gamma-irradiated ExtraVit M nutritive supplement studied by electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Petrişor, Dina; Damian, Grigore; Simon, Simion

    2008-04-01

    An unirradiated and γ-irradiated nutritive supplement named ExtraVit M was studied by electron paramagnetic resonance (EPR) spectroscopy in order to detect stable paramagnetic species following improvement of hygienic quality by γ-radiation. Free radicals were induced by γ-radiation in the studied samples from low absorbed doses, showing a certain sensibility of these samples to the radiation treatment. The EPR spectrum of irradiated ExtraVit M is typical for drugs or nutritive supplements containing high levels of sugars, vitamin C and cellulose.

  9. Models for Copper Dynamic Behavior in Doped Cadmium dl-Histidine Crystals: Electron Paramagnetic Resonance and Crystallographic Analysis.

    PubMed

    Colaneri, Michael J; Teat, Simon J; Vitali, Jacqueline

    2015-11-12

    Electron paramagnetic resonance and crystallographic studies of copper-doped cadmium dl-histidine, abbreviated as CdDLHis, were undertaken to gain further understanding on the relationship between site structure and dynamic behavior in biological model complexes. X-ray diffraction measurements determined the crystal structure of CdDLHis at 100 and 298 K. CdDLHis crystallizes in the monoclinic space group P21/c with two cadmium complexes per asymmetric unit. In each complex, the Cd is hexacoordinated to two histidine molecules. Both histidines are l in one complex and d in the other. Additionally, each complex contains multiple waters of varying disorder. Single crystal EPR spectroscopic splitting (g) and copper hyperfine (A(Cu)) tensors at room temperature (principal values: g = 2.249, 2.089, 2.050; A(Cu) = -453, -30.5, -0.08 MHz) were determined from rotational experiments. Alignments of the tensor directions with the host structure were used to position the copper unpaired dx(2)-y(2) orbital in an approximate plane made by four proposed ligand atoms: the N-imidazole and N-amino of one histidine, and the N-amino and O-carboxyl of the other. Each complex has two such planes related by noncrystallographic symmetry, which make an angle of 65° and have a 1.56 Å distance between their midpoints. These findings are consistent with three interpretations that can adequately explain previous temperature-dependent EPR powder spectra of this system: (1) a local structural distortion (static strain) at the copper site has a temperature dependence significant enough to affect the EPR pattern, (2) the copper can hop between the two sites in each complex at high temperature, and (3) there exists a dynamic Jahn-Teller effect involving the copper ligands.

  10. Stochastic Liouville equation treatment of the electron paramagnetic resonance line shape of an S-state ion in solution.

    PubMed

    Borel, Alain; Clarkson, R B; Belford, R Linn

    2007-02-07

    The current approaches used for the analysis of electron paramagnetic resonance spectra of Gd3+ complexes suffer from a number of drawbacks. Even the elaborate model of [Rast et al., J. Chem. Phys. 113, 8724 (2000)] where the electron spin relaxation is explained by the modulation of the zero-field splitting (ZFS), by molecular tumbling (the so called static contribution), and deformations (transient contribution), is only readily applicable within the validity range of the Redfield theory [Advances in Magnetic Resonance, edited by J.-S. Waugh (Academic, New York, 1965), Vol. 1, p. 1], that is, when the ZFS is small compared to the Zeeman energy and the rotational and vibrational modulations are fast compared to the relaxation time. Spin labels (nitroxides and transition metal complexes) have been studied for years in systems that violate these conditions. The theoretical framework commonly used in such studies is the stochastic Liouville equation (SLE). The authors shall show how the physical model of Rast et al. can be cast into the SLE formalism, paying special attention to the specific problems introduced by the [Uhlenbeck and Ornstein, Phys. Rev. 36, 823 (1930)] process used to model the transient ZFS. The resulting equations are very general and valid for arbitrary correlation times, magnetic field strength, electron spin S, or symmetry. The authors demonstrate the equivalence of the SLE approach with the Redfield approximation for two well-known Gd3+ complexes.

  11. Electronic and magnetic properties of the paramagnetic Twenty electron Fe(O) sandwich [C6(CH3)6]2 Fe from Mössbauer measurements and molecular orbital calculations

    NASA Astrophysics Data System (ADS)

    Mariot, J. P.; Michaud, P.; Lauer, S.; Astruc, D.; Trautwein, A. X.; Varret, F.

    1983-10-01

    A Mössbauer study of the title paramagnetic Fe(O) complex was carried out from 4.2 K to 250 K. The electric field gradient (EFG) tensor was found to be temperature independent in accordance with the well isolated nature of state3A2g. Measurements in an applied magnetic field of 6 T confirmed the paramagnetic nature (S=1) of the complex and showed the EFG tensor to be negative. From the thermal variation of the hyperfine field we determined the spin hamiltonian constant D=14 K and find the g-value to be close to the free electron value. Semi-empirical molecular orbital (MO) calculations were carried out with a modelized molecule of D6h symmetry; results are in good agreement with the experimental values (for both the electronic and magnetic properties).

  12. Paramagnetic properties of noncentrosymmetric superconductors: application to CePt3Si.

    PubMed

    Samokhin, K V

    2005-01-21

    In a noncentrosymmetric crystal, the Zeeman interaction of the band electrons with an external magnetic field is highly anisotropic in the momentum space, vanishing along some high-symmetry planes. One of the consequences is that the paramagnetic susceptibility in superconductors without inversion symmetry, such as CePt3Si, shows an unusual temperature dependence.

  13. Maxwell's Relations for a van der Waals Gas and a Nuclear Paramagnetic System.

    ERIC Educational Resources Information Center

    Herlihy, James; And Others

    1981-01-01

    Since Maxwell's relations are derived in general form from the first to second laws, and students often wonder what they mean and how they are used, appropriate partition functions for van der Waals gas and the nuclear paramagnetic system are used to obtain entropy expressions and equations of state. (Author/SK)

  14. Non-perturbative magnetic phenomena in closed-shell paramagnetic molecules.

    PubMed

    Tellgren, Erik I; Helgaker, Trygve; Soncini, Alessandro

    2009-07-14

    By means of non-perturbative ab initio calculations, it is shown that paramagnetic closed-shell molecules are characterized by a strongly non-linear magnetic response, whose main feature consists of a paramagnetic-to-diamagnetic transition in a strong magnetic field. The physical origin of this phenomenon is rationalised on the basis of an analytical model based on molecular orbital theory. For the largest molecules considered here, the acepleiadylene dianion and the corannulene dianion, the transition field is of the order of 10(3) T, about one order of magnitude larger than the magnetic field strength currently achievable in experimental settings. However, our simple model suggests that the paramagnetic-to-diamagnetic transition is a universal property of paramagnetic closed-shell systems in strong magnetic fields, provided no singlet-triplet level crossing occurs for fields smaller than the critical transition field. Accordingly, fields weaker than 100 T should suffice to trigger the predicted transition for systems whose size is still well within the (medium-large) molecular domain, such as hypothetical antiaromatic rings with less than one hundred carbon atoms.

  15. The Effect of Electronic Paramagnetism on Nuclear Magnetic Resonance Frequencies in Metals

    DOE R&D Accomplishments Database

    Townes, C. H.; Herring, C.; Knight, W. D.

    1950-09-22

    Observations on the shifts of nuclear resonances in metals ( Li{sup 7}, Na{sup 23}, Cu {sup 63}, Be{sup 9}, Pb{sup 207}, Al{sup 27}, and Ca{sup 69} ) due to free electron paramagnetism; comparison with theoretical values.

  16. 40 CFR 1065.280 - Paramagnetic and magnetopneumatic O2 detection analyzers.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 32 2010-07-01 2010-07-01 false Paramagnetic and magnetopneumatic O2 detection analyzers. 1065.280 Section 1065.280 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Measurement Instruments O2 Measurements §...

  17. Evidence of surface paramagnetism in niobium and consequences for the superconducting cavity surface impedance.

    SciTech Connect

    Prolier, T.; Kharitonov, M.; Pellin, M.; Zasadzinski, J.; Ciovati, G.

    2011-06-01

    The presence of magnetic impurities in native niobium oxides have been confirmed by Point contact spectroscopy (PCT), SQUID magnetometry and Electron paramagnetic resonance (EPR). All niobium (Nb) samples displayed a small impurity contribution to the magnetic susceptibility at low temperatures which exhibited Curie-Weiss behavior, indicative of weakly coupled localized paramagnetic moments. By examining Nb samples with widely varying surface-to-volume ratios (rods, foils, wires, powders) it was found that the impurity contribution is correlated with surface area. Tunneling measurements which use the native oxide layers as barriers exhibit a zero-bias conductance peak which splits in a magnetic field >; 4T, consistent with the Appelbaum-Anderson model for spin flip tunneling. Viewed together the experiments strongly suggest that the native oxides of Nb are intrinsically defective, and consistently exhibit localized paramagnetic moments caused by oxygen vacancies in Nb{sub 2}O{sub 5}. The computation of the surface impedance (R{sub s}) in presence of magnetic impurities in the Shiba approximation reveals the saturation at low temperature of R{sub s}, suggesting that magnetic impurities are responsible for the so-called residual resistance. These properties may have an impact on Nb based superconducting devices and shine a new light on the origin of the paramagnetic Meissner effect (PME).

  18. Electron paramagnetic resonance of natural and gamma-irradiated alunite and kaolin mineral powders

    NASA Astrophysics Data System (ADS)

    Koksal, F.; Koseoglu, R.; Saka, I.; Basaran, E.; Sener, F.

    2004-06-01

    Natural alunite and kaolin minerals obtained from West Anatolia were investigated by electron paramagnetic resonance (EPR) in natural and gamma-irradiated states at room temperature and at 113 K. The paramagnetic centres at ambient temperature in natural alunite were attributed to the (C) over dot H 2OH, (C) over dot O-3(-), (S) over dot O-2(-), (C) over dot O-2(-) and [AlO4 ](0) radicals. In natural kaolin, the paramagnetic centres were attributed to the (C) over dot O-3(-), (S) over dot O-2(-) (C) over dot O-2(-) and [AlO4](0) radicals. The gamma-irradiation does not produce any detectable effects on these radicals. At 113 K, the lines for (C) over dot H2OH could not be observed well, probably due to the anisotropic behaviour of the hyperfine interaction of the methylene protons, but the lines for [AlO4](0) centres were found to be perfectly observable at above 20 mW microwave power in both alunite and kaolin powders before and after gamma-irradiation. The EPR parameters of the observed paramagnetic centres were reported.

  19. Paramagnetic NMR Investigation of Dendrimer-Based Host-Guest Interactions

    PubMed Central

    Wang, Fei; Shao, Naimin; Cheng, Yiyun

    2013-01-01

    In this study, the host-guest behavior of poly(amidoamine) (PAMAM) dendrimers bearing amine, hydroxyl, or carboxylate surface functionalities were investigated by paramagnetic NMR studies. 2,2,6,6-Tetramethylpiperidinyloxy (TEMPO) derivatives were used as paramagnetic guest molecules. The results showed that TEMPO-COOH significantly broaden the 1H NMR peaks of amine- and hydroxyl-terminated PAMAM dendrimers. In comparison, no paramagnetic relaxation enhancement (PRE) was observed between TEMPO-NH2, TEMPO-OH and the three types of PAMAM dendrimers. The PRE phenomenon observed is correlated with the encapsulation of TEMPO-COOH within dendrimer pockets. Protonation of the tertiary amine groups within PAMAM dendrimers plays an important role during this process. Interestingly, the absence of TEMPO-COOH encapsulation within carboxylate-terminated PAMAM dendrimer is observed due to the repulsion of TEMPO-COO- anion and anionic dendrimer surface. The combination of paramagnetic probes and 1H NMR linewidth analysis can be used as a powerful tool in the analysis of dendrimer-based host-guest systems. PMID:23762249

  20. Size-dependent magnetophoresis of native single super-paramagnetic nanoparticles in a microchip.

    PubMed

    Zhang, Peng; Park, Sangyoon; Kang, Seong Ho

    2013-08-25

    Real-time dynamics of native super-paramagnetic nanoparticles (SPMNPs) with different sizes were observed in a microchip at the single-particle level. Based on the optimized magnetic field conditions obtained in the single-nanoparticle study, the SPMNPs were successfully separated and detected within ~15 s from the model polydisperse mixture.

  1. Recharge processes of paramagnetic centers during illumination in nitrogen-doped nanocrystalline titanium dioxide

    NASA Astrophysics Data System (ADS)

    Le, N. T.; Konstantinova, E. A.; Kokorin, A. I.; Kodom, T.; Alonso-Vante, N.

    2015-08-01

    Nitrogen-doped titanium dioxide (N-TiO2) has been investigated by the EPR-technique. Two types of paramagnetic centers - N• and NO•-radicals - were detected in the samples. Both N• and NO•-related centers are recharged during illumination. Band diagrams of TiO2 with N• and NO• radicals energy level position are proposed.

  2. Differences in magnetically induced motion of diamagnetic, paramagnetic, and superparamagnetic microparticles detected by cell tracking velocimetry.

    PubMed

    Jin, Xiaoxia; Zhao, Yang; Richardson, Aaron; Moore, Lee; Williams, P Stephen; Zborowski, Maciej; Chalmers, Jeffrey J

    2008-12-01

    Magnetic separation in biomedical applications is based on differential magnetophoretic mobility (MM) of microparticulate matter in viscous media. Typically, the difference in MM is obtained by selectively labeling the target cells with superparamagnetic iron oxide nanoparticles (SPIONs). We have measured the MM of monodisperse, polystyrene microspheres (PSMs), with and without attached SPIONs as a model of cell motion induced by nanoparticle magnetization, using variable H field and cell tracking velocimetry (CTV). As a model of paramagnetic microparticle motion, the MM measurements were performed on the same PSMs in paramagnetic gadolinium solutions, and on spores of a prokaryotic organism, Bacillus globigii (shown to contain paramagnetic manganese). The CTV analysis was sensitive to the type of the microparticle magnetization, producing a value of MM independent of the applied H field for the paramagnetic species, and a decreasing MM value with an increasing field for superparamagnetic species, as predicted from theory. The SPION-labeled PSMs exhibited a saturation magnetization above H approximately = 64,000 A m(-1) (or 0.08 tesla). Based on those data, the average saturation magnetizations of the SPIONs was calculated and shown to vary between different commercial sources. The results demonstrate sensitivity of the CTV analysis to different magnetization mechanisms of the microparticles.

  3. Differences in magnetically induced motion of diamagnetic, paramagnetic, and superparamagnetic microparticles detected by Cell Tracking Velocimetry

    PubMed Central

    Jin, Xiaoxia; Zhao, Yang; Richardson, Aaron; Moore, Lee; Williams, P. Stephen; Zborowski, Maciej; Chalmers, Jeffrey J.

    2009-01-01

    Magnetic separation in biomedical applications is based on differential magnetophoretic mobility (MM) of microparticulate matter in viscous media. Typically, the difference in MM is obtained by selectively labeling the target cells with superparamagnetic iron oxide nanoparticles(SPIONs). We have measured the MM of monodisperse, polystyrene microspheres (PSMs), with and without attached SPIONs as a model of cell motion induced by nanoparticle magnetization, using variable H field and Cell Tracking Velocimetry (CTV). As a model of paramagnetic microparticle motion, the MM measurements were performed on the same PSMs in paramagnetic gadolinium solutions, and on spores of a prokaryotic organism, Bacillus globigii (shown to contain paramagnetic manganese). The CTV analysis was sensitive to the type of the microparticle magnetization, producing a value of MM independent of the applied H field for the paramagnetic species, and a decreasing MM value with an increasing field for superparamagnetic species, as predicted from theory. The SPION-labeled PSMs exhibited a saturation magnetization above H ≅ 64,000 A m−1 (or 0.08 tesla). Based on those data, the average saturation magnetizations of the SPIONs was calculated and shown to vary between different commercial sources. The results demonstrate sensitivity of the CTV analysis to different magnetization mechanisms of the microparticles. PMID:19082082

  4. An EPR study on tea: Identification of paramagnetic species, effect of heat and sweeteners

    NASA Astrophysics Data System (ADS)

    Bıyık, Recep; Tapramaz, Recep

    2009-10-01

    Tea ( Camellia Sinensis) is the most widely consumed beverage in the world, and is known to be having therapeutic, antioxidant and nutritional effects. Electron paramagnetic resonance (EPR) spectral studies made on the tea cultivated along the shore of Black Sea, Turkey, show Mn 2+ and Fe 3+ centers in green tea leaves and in black tea extract. Dry black tea flakes and dry extract show additional sharp line attributed to semiquinone radical. The origins of the paramagnetic species in black tea are defined and discussed. Effect of humidity and heat are investigated. It is observed that dry extract of black tea melts at 100 °C and the semiquinone radical lives up to 140 °C while Mn 2+ sextet disappears just above 100 °C in tea extract. Natural and synthetics sweeteners have different effects on the paramagnetic centers. White sugar (sucrose) quenches the Mn 2+ and semiquinone lines in black tea EPR spectrum, and glucose, fructose, lactose and maltose quench Fe 3+ line while synthetic sweeteners acesulfam potassium, aspartame and sodium saccharine do not have any effect on paramagnetic species in tea.

  5. Maxwell's Relations for a van der Waals Gas and a Nuclear Paramagnetic System.

    ERIC Educational Resources Information Center

    Herlihy, James; And Others

    1981-01-01

    Since Maxwell's relations are derived in general form from the first to second laws, and students often wonder what they mean and how they are used, appropriate partition functions for van der Waals gas and the nuclear paramagnetic system are used to obtain entropy expressions and equations of state. (Author/SK)

  6. Electron paramagnetic resonance spectral study of [Mn(acs){sub 2}(2–pic){sub 2}(H{sub 2}O){sub 2}] single crystals

    SciTech Connect

    Kocakoç, Mehpeyker; Tapramaz, Recep

    2016-03-25

    Acesulfame potassium salt is a synthetic and non-caloric sweetener. It is also important chemically for its capability of being ligand in coordination compounds, because it can bind over Nitrogen and Oxygen atoms of carbonyl and sulfonyl groups and ring oxygen. Some acesulfame containing transition metal ion complexes with mixed ligands exhibit solvato and thermo chromic properties and these properties make them physically important. In this work single crystals of Mn{sup +2} ion complex with mixed ligand, [Mn(acs){sub 2}(2-pic){sub 2}(H{sub 2}O){sub 2}], was studied with electron paramagnetic resonance (EPR) spectroscopy. EPR parameters were determined. Zero field splitting parameters indicated that the complex was highly symmetric. Variable temperature studies showed no detectable chance in spectra.

  7. ELECTRON PARAMAGNETIC RESONANCE DOSIMETRY FOR A LARGE-SCALE RADIATION INCIDENT

    PubMed Central

    Swartz, Harold M.; Flood, Ann Barry; Williams, Benjamin B.; Dong, Ruhong; Swarts, Steven G.; He, Xiaoming; Grinberg, Oleg; Sidabras, Jason; Demidenko, Eugene; Gui, Jiang; Gladstone, David J.; Jarvis, Lesley A.; Kmiec, Maciej M.; Kobayashi, Kyo; Lesniewski, Piotr N.; Marsh, Stephen D.P.; Matthews, Thomas P.; Nicolalde, Roberto J.; Pennington, Patrick M.; Raynolds, Timothy; Salikhov, Ildar; Wilcox, Dean E.; Zaki, Bassem I.

    2013-01-01

    With possibilities for radiation terrorism and intensified concerns about nuclear accidents since the recent Fukushima Daiichi event, the potential exposure of large numbers of individuals to radiation that could lead to acute clinical effects has become a major concern. For the medical community to cope with such an event and avoid overwhelming the medical care system, it is essential to identify not only individuals who have received clinically significant exposures and need medical intervention but also those who do not need treatment. The ability of electron paramagnetic resonance to measure radiation-induced paramagnetic species, which persist in certain tissues (e.g., teeth, fingernails, toenails, bone, and hair), has led this technique to become a prominent method for screening significantly exposed individuals. Although the technical requirements needed to develop this method for effective application in a radiation event are daunting, remarkable progress has been made. In collaboration with General Electric, and through funding committed by the Biomedical Advanced Research and Development Authority, electron paramagnetic resonance tooth dosimetry of the upper incisors is being developed to become a Food and Drug Administration-approved and manufacturable device designed to carry out triage for a threshold dose of 2 Gy. Significant progress has also been made in the development of electron paramagnetic resonance nail dosimetry based on measurements of nails in situ under point-of-care conditions, and in the near future this may become a second field-ready technique. Based on recent progress in measurements of nail clippings, we anticipate that this technique may be implementable at remotely located laboratories to provide additional information when the measurements of dose on site need to be supplemented. We conclude that electron paramagnetic resonance dosimetry is likely to be a useful part of triage for a large-scale radiation incident. PMID:22850230

  8. New paramagnetic defects in synthetic diamonds grown using nickel catalyst

    NASA Astrophysics Data System (ADS)

    Neves, A. J.; Pereira, R.; Sobolev, N. A.; Nazaré, M. H.; Gehlhoff, W.; Näser, A.; Kanda, H.

    1999-12-01

    We report four new EPR spectra found in high-pressure synthetic diamonds with high nitrogen content, grown using nickel, and annealed at 1600°C. Analyzing the complex spectra around g≈2 two trigonal and two orthorhombic defects, all with S={1}/{2}, were identified from the angular dependence and the different saturation behavior of the transitions. Besides optical and EPR investigations reveal several centers which have been previously ascribed to defects containing nickel and nitrogen. However, nitrogen is not involved in the new centers, since no evidence of an 14N hyperfine structure could be found. Possible relations of the new defects with Ni are discussed.

  9. Electron paramagnetic resonance and quantum-mechanical analysis of binuclear niobium clusters in lithium-niobium phosphate glasses

    NASA Astrophysics Data System (ADS)

    Rakhimov, R. R.; Turney, V. J.; Jones, D. E.; Dobryakov, S. N.; Borisov, Yu. A.; Prokof'ev, A. I.; Aleksandrov, A. I.

    2003-04-01

    Electron paramagnetic resonance (EPR) spectra of Nb4+ ions in Li2O-Nb2O5-P2O5 glasses with different composition of oxide components have been investigated. The EPR spectrum shape analysis of Nb4+ (electron configuration 4d1, electron spin S=1/2) reveals the formation of triplet niobium binuclear complex (total electron spin S=1) in glasses. The amount of Nb4+ ions in glasses reversibly changes with temperature and is explained via the mechanism of electron hopping between niobium ions in clusters. The dependence of the amount of Nb4+ ions upon Li2O content has a maximal character, which implies that small amounts of Li+ ions stabilize the Nb4+ pairs, but cause their disproportionation at higher concentrations of Li+ ions in the glass. Quantum mechanical analysis of electronic and spin states of binuclear niobium clusters has been performed on model binuclear complexes, (HO)3Nb-O-Nb(OH)3, [(HO)3Nb-O-Nb(OH)3]Li+, and [(HO)3Nb-O-Nb(OH)3](Li+)2 that exhibit the reversible disproportionation reaction Nb4+-O-Nb4+⇔Nb3+-O-Nb5+. Triplet states of these complexes (total electron spin S=1) have lower energies than singlet states (S=0), and Li+ ions stabilize the binuclear niobium complex. We have found that electron spin densities on niobium ions change depending upon the shift of the bridging oxygen atom. Application of this theoretical modeling to the analysis of the experimental EPR spectrum in Li2O-Nb2O5-P2O5 glass concludes noncentrosymmetric structure of binuclear niobium complex with ˜0.1 Å offset of the bridging oxygen atom towards one Nb atom.

  10. In Vivo Formation of Electron Paramagnetic Resonance-Detectable Nitric Oxide and of Nitrotyrosine Is Not Impaired during Murine Leishmaniasis

    PubMed Central

    Giorgio, Selma; Linares, Edlaine; Ischiropoulos, Harry; Von Zuben, Fernando José; Yamada, Aureo; Augusto, Ohara

    1998-01-01

    Recent studies have provided evidence for a dual role of nitric oxide (NO) during murine leishmaniasis. To explore this problem, we monitored the formation of NO and its derived oxidants during the course of Leishmania amazonensis infection in tissues of susceptible (BALB/c) and relatively resistant (C57BL/6) mice. NO production was detected directly by low-temperature electron paramagnetic resonance spectra of animal tissues. Both mouse strains presented detectable levels of hemoglobin nitrosyl (HbNO) complexes and of heme nitrosyl and iron-dithiol-dinitrosyl complexes in the blood and footpad lesions, respectively. Estimation of the nitrosyl complex levels demonstrated that most of the NO is synthesized in the footpad lesions. In agreement, immunohistochemical analysis of the lesions demonstrated the presence of nitrotyrosine in proteins of macrophage vacuoles and parasites. Since macrophages lack myeloperoxidase, peroxynitrite is likely to be the nitrating NO metabolite produced during the infection. The levels of HbNO complexes in the blood reflected changes occurring during the infection such as those in parasite burden and lesion size. The maximum levels of HbNO complexes detected in the blood of susceptible mice were higher than those of C57BL/6 mice but occurred at late stages of infection and were accompanied by the presence of bacteria in the cutaneous lesions. The results indicate that the local production of NO is an important mechanism for the elimination of parasites if it occurs before the parasite burden becomes too high. From then on, elevated production of NO and derived oxidants aggravates the inflammatory process with the occurrence of a hypoxic environment that may favor secondary infections. PMID:9453645

  11. Mn(II) Binding and Subsequent Oxidation by the Multicopper Oxidase MnxG Investigated by Electron Paramagnetic Resonance Spectroscopy.

    PubMed

    Tao, Lizhi; Stich, Troy A; Butterfield, Cristina N; Romano, Christine A; Spiro, Thomas G; Tebo, Bradley M; Casey, William H; Britt, R David

    2015-08-26

    The dynamics of manganese solid formation (as MnOx) by the multicopper oxidase (MCO)-containing Mnx protein complex were examined by electron paramagnetic resonance (EPR) spectroscopy. Continuous-wave (CW) EPR spectra of samples of Mnx, prepared in atmosphere and then reacted with Mn(II) for times ranging from 7 to 600 s, indicate rapid oxidation of the substrate manganese (with two-phase pseudo-first-order kinetics modeled using rate coefficients of: k(1obs) = 0.205 ± 0.001 s(-1) and k(2obs) = 0.019 ± 0.001 s(-1)). This process occurs on approximately the same time scale as in vitro solid MnOx formation when there is a large excess of Mn(II). We also found CW and pulse EPR spectroscopic evidence for at least three classes of Mn(II)-containing species in the reaction mixtures: (i) aqueous Mn(II), (ii) a specifically bound mononuclear Mn(II) ion coordinated to the Mnx complex by one nitrogenous ligand, and (iii) a weakly exchange-coupled dimeric Mn(II) species. These findings provide new insights into the molecular mechanism of manganese mineralization.

  12. Super paramagnetic iron oxide nanoparticle modified mancozeb imprinted polymer

    NASA Astrophysics Data System (ADS)

    Kumar, Sunil; Madhuri, Rashmi; Sharma, Prashant K.

    2017-05-01

    An electrochemical sensor for detection of mancozeb from soil and vegetable sample using molecularly imprinted star polymer modified with iron oxide nanoparticles (SPIONs) is described in this work. We have prepared SPIONS by hydrothermal method and modified with vinyl silane to introduce double bond at their surface. The vinyl group modified SPIONs were used to form mancozeb imprinted star polymer (ISP). The ISPs have specific recognition ability high adsorption capacity towards their template molecule and could be easily extracted from complex matrices using a simple magnet. The prepared polymer was well characterized by field emissive scanning electron microscopy (FE-SEM). Under the optimum condition, the prepared sensor shows good response for mancozeb in the range of 5.96 to 222.39 µg L-1 (detection limit=0.98 µg L-1). The proposed sensors have highly selective for detection of mancozeb in soil and vegetable samples also.

  13. Complete series of chiral paramagnetic molecular conductors based on tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) and Chloranilate-bridged heterobimetallic honeycomb layers.

    PubMed

    Atzori, Matteo; Pop, Flavia; Auban-Senzier, Pascale; Clérac, Rodolphe; Canadell, Enric; Mercuri, Maria Laura; Avarvari, Narcis

    2015-04-06

    Electrocrystallization of enantiopure (S,S,S,S)- and (R,R,R,R)-tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) donors, as well as the racemic mixture, in the presence of potassium cations and the tris(chloranilato)ferrate(III) [Fe(Cl2An)3](3-) paramagnetic anion afforded a complete series of chiral magnetic molecular conductors formulated as β-[(S,S,S,S)-TM-BEDT-TTF]3PPh4[K(I)Fe(III)(Cl2An)3]·3H2O (1), β-[(R,R,R,R)-TM-BEDT-TTF]3PPh4[K(I)Fe(III)(Cl2An)3]·3H2O (2), and β-[(rac)-TM-BEDT-TTF]3PPh4[K(I)Fe(III)(Cl2An)3]·3H2O (3). Compounds 1-3 are isostructural and crystallize in triclinic space groups (P1 for 1 and 2, P-1 for 3) showing a segregated organic-inorganic crystal structure, where anionic honeycomb layers obtained by self-assembling of the Λ and Δ enantiomers of the paramagnetic complex with potassium cations alternate with organic layers where the chiral donors are arranged in the β packing motif. Compounds 1-3 show a molecular packing strongly influenced by the topology of the inorganic layers and behave as molecular semiconductors with room-temperature conductivity values of ca. 3 × 10(-4) S cm(-1). The magnetic properties are dominated by the paramagnetic S = 5/2 [Fe(Cl2An)3](3-) anions whose high-spin character is confirmed by magnetic susceptibility measurements. The correlation between crystal structure and conducting behavior has been studied by means of tight-binding band structure calculations which support the observed conducting properties.

  14. Synthesis and characterization of a combined fluorescence, phosphorescence, and electron paramagnetic resonance probe

    NASA Astrophysics Data System (ADS)

    Beth, Albert H.; Cobb, Charles E.; Beechem, Joseph M.

    1992-04-01

    A spin-labeled derivative of eosin was chemically synthesized from 5-aminoeosin and the nitroxide spin label 2,2,5,5-tetramethylpyrrolin-1-oxyl-3-carboxylic acid. Following determination of the chemical identity of the spin-labeled eosin (5-SLE) by FAB mass spectroscopy, its optical and magnetic resonance spectroscopic properties were characterized in aqueous solution and compared to a diamagnetic eosin derivative, 5-acetamido eosin (5- AcE). The visible light absorption maximum of 5-SLE was 518 nm, the same as for 5-AcE. The fluorescence quantum yield of 5-SLE was only reduced by approximately 10% relative to 5-AcE, and the fluorescence lifetime was marginally reduced relative to 5-AcE. The phosphorescence lifetime and yield for 5-SLE were very similar to those for 5-AcE. The phosphorescence yield of 5-SLE bound noncovalently to BSA was reduced by approximately 60% relative to 5-AcE, and the phosphorescence lifetime reduced from approximately 2.4 msec (5-AcE) to 1.6 msec (5-SLE). Reduction of the nitroxide moiety of the 5-SLE with sodium ascorbate resulted in minimal changes in the fluorescence and phosphorescence quantum yields and lifetimes. This indicated that the unpaired electron of the nitroxide spin label did not seriously affect the optical spectroscopic characteristics of the spin-labeled eosin molecule. The quantum yields and lifetimes of 5-SLE were still quite acceptable for time- resolved fluorescence and phosphorescence studies. The electron paramagnetic resonance (EPR) spectrum of 5-SLE in aqueous solution has a lineshape consistent with a molecule the size of 5-SLE undergoing rapid rotational reorientation. When bound to BSA, the EPR spectrum of 5-SLE was broadened to a near slow motion limit for EPR, as expected for the relatively slowly rotating protein-5-SLE complex. Time-resolved phosphorescence anisotropy and saturation transfer EPR (ST-EPR) experiments with samples of 5-SLE bound to BSA in solutions of varying glycerol concentrations at 2

  15. Structure and dynamics in B12 enzyme catalysis revealed by electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Warncke, Kurt

    2009-03-01

    Challenges to the understanding of how protein structure and dynamics contribute to catalysis in enzymes, and the use of time-resolved electron paramagnetic resonance (EPR) spectroscopic techniques to address the challenges, are examined in the context of the coenzyme B12-dependent enzyme, ethanolamine ammonia-lyase (EAL), from Salmonella typhimurium. EAL conducts the homolytic cleavage of the coenzyme cobalt-carbon bond, intraprotein radical migration (5-6 å), and hydrogen atom transfers, which enable the core radical-mediated rearrangement reaction. Thermodynamic and activation parameters are measured in two experimental systems, which were developed to isolate sub-sequences from the multi-step catalytic cycle, as follows: (1) A dimethylsulfoxide (DMSO)/water cryosolvent system is used to prepare the kinetically-arrested enzyme/coenzyme/substrate ternary complex in fluid solution at 230 K.[1] Temperature-step initiated cobalt-carbon bond cleavage and radical pair separation to form the Co(II)-substrate radical pair are monitored by using time-resolved, full-spectrum EPR spectroscopy (234<=T<=250 K).[1] (2) The Co(II)-substrate radical pair is cryotrapped in frozen aqueous solution at T<150 K, and then promoted to react by a temperature step. The reaction of the substrate radical along the native pathway to form the diamagnetic bound products is monitored by using time-resolved, full-spectrum EPR spectroscopy (187<=T<=217 K).[2] High temporal resolution is achieved, because the reactions are dramatically slowed at the low temperatures, relative to the initiation and spectrum acquistion times. The results are combined with high resolution structures of the reactant centers, obtained by pulsed-EPR spectroscopies,[3] and the protein, obtained by structural proteomics[4] and EPR and electron spin echo envelope modulation (ESEEM) in combination with site directed mutagenesis,[5] to approach a molecular level description of protein contributions to catalysis in EAL. [4

  16. DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids

    NASA Astrophysics Data System (ADS)

    Pigliapochi, Roberta; Pell, Andrew J.; Seymour, Ieuan D.; Grey, Clare P.; Ceresoli, Davide; Kaupp, Martin

    2017-02-01

    Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for studying the structural and electronic properties of paramagnetic solids. However, the interpretation of paramagnetic NMR spectra is often challenging as a result of the interactions of unpaired electrons with the nuclear spins of interest. In this work, we extend the formalism of the paramagnetic NMR shielding in the presence of spin-orbit coupling towards solid systems with multiple paramagnetic centers. We demonstrate how the single-ion electron paramagnetic resonance g tensor is defined and calculated in periodic paramagnetic solids. We then calculate the hyperfine tensor and the g tensor with density functional theory to show the validity of the presented model and we further demonstrate how these interactions can be combined to give the overall paramagnetic shielding tensor, σs. The method is applied to a series of olivine-type LiTMPO4 materials (with TM=Mn , Fe, Co, and Ni) and the corresponding 7Li and 31P NMR spectra are simulated. We analyze the effects of spin-orbit coupling and of the electron-nuclear magnetic interactions on the calculated NMR parameters. A detailed comparison is presented between contact and dipolar interactions across the LiTMPO4 series, in which the magnitudes and signs of the nonrelativistic and relativistic components of the overall isotropic shift and shift anisotropy are computed and rationalized.

  17. Shape-, size-, and functional group-selective binding of small organic guests in a paramagnetic coordination cage.

    PubMed

    Turega, Simon; Whitehead, Martina; Hall, Benjamin R; Meijer, Anthony J H M; Hunter, Christopher A; Ward, Michael D

    2013-01-18

    The host-guest chemistry of the octanuclear cubic coordination cage [Co(8)L(12)](16+) (where L is a bridging ligand containing two chelating pyrazolyl-pyridine units connected to a central naphthalene-1,5-diyl spacer via methylene "hinges") has been investigated in detail by (1)H NMR spectroscopy. The cage encloses a cavity of volume of ca. 400 Å(3), which is accessible through 4 Å diameter portals in the centers of the cube faces. The paramagnetism of the cage eliminates overlap of NMR signals by dispersing them over a range of ca. 200 ppm, making changes of specific signals easy to observe, and also results in large complexation-induced shifts of bound guests. The cage, in CD(3)CN solution, acts as a remarkably size- and shape-selective host for small organic guests such as coumarin (K = 78 M(-1)) and other bicyclic molecules of comparable size and shape such as isoquinoline-N-oxide (K = 2100 M(-1)). Binding arises from two independent recognition elements, which have been separately quantified. These are (i) a polar component arising from interaction of the H-bond accepting O atom of the guest with a convergent group of CH protons inside the cavity that lie close to a fac tris-chelate metal center and are therefore in a region of high electrostatic potential; and (ii) an additional component arising from the second aromatic ring (aromatic/van der Waals interactions with the interior surface of the cage and/or solvophobic interactions). The strength of the first component varies linearly with the H-bond-accepting ability of the guest; the second component is fixed at approximately 10 kJ mol(-1). We have also used (1)H-(1)H exchange spectroscopy (EXSY) experiments to analyze semiquantitatively two distinct dynamic processes, viz. movement of the guest into and out of the cavity and tumbling of the guest inside the host cavity. Depending on the size of the guest and the position of substituents, the rates of these processes can vary substantially, and the rates

  18. Responses of Mn2+ speciation in Deinococcus radiodurans and Escherichia coli to γ-radiation by advanced paramagnetic resonance methods

    PubMed Central

    Sharma, Ajay; Gaidamakova, Elena K.; Matrosova, Vera Y.; Bennett, Brian; Daly, Michael J.; Hoffman, Brian M.

    2013-01-01

    The remarkable ability of bacterium Deinococcus radiodurans to survive extreme doses of γ-rays (12,000 Gy), 20 times greater than Escherichia coli, is undiminished by loss of Mn-dependent superoxide dismutase (SodA). D. radiodurans radiation resistance is attributed to the accumulation of low-molecular-weight (LMW) “antioxidant” Mn2+–metabolite complexes that protect essential enzymes from oxidative damage. However, in vivo information about such complexes within D. radiodurans cells is lacking, and the idea that they can supplant reactive-oxygen-species (ROS)–scavenging enzymes remains controversial. In this report, measurements by advanced paramagnetic resonance techniques [electron-spin-echo (ESE)-EPR/electron nuclear double resonance/ESE envelope modulation (ESEEM)] reveal differential details of the in vivo Mn2+ speciation in D. radiodurans and E. coli cells and their responses to 10 kGy γ-irradiation. The Mn2+ of D. radiodurans exists predominantly as LMW complexes with nitrogenous metabolites and orthophosphate, with negligible EPR signal from Mn2+ of SodA. Thus, the extreme radiation resistance of D. radiodurans cells cannot be attributed to SodA. Correspondingly, 10 kGy irradiation causes no change in D. radiodurans Mn2+ speciation, despite the paucity of holo-SodA. In contrast, the EPR signal of E. coli is dominated by signals from low-symmetry enzyme sites such as that of SodA, with a minority pool of LMW Mn2+ complexes that show negligible coordination by nitrogenous metabolites. Nonetheless, irradiation of E. coli majorly changes LMW Mn2+ speciation, with extensive binding of nitrogenous ligands created by irradiation. We infer that E. coli is highly susceptible to radiation-induced ROS because it lacks an adequate supply of LMW Mn antioxidants. PMID:23536297

  19. Responses of Mn2+ speciation in Deinococcus radiodurans and Escherichia coli to γ-radiation by advanced paramagnetic resonance methods.

    PubMed

    Sharma, Ajay; Gaidamakova, Elena K; Matrosova, Vera Y; Bennett, Brian; Daly, Michael J; Hoffman, Brian M

    2013-04-09

    The remarkable ability of bacterium Deinococcus radiodurans to survive extreme doses of γ-rays (12,000 Gy), 20 times greater than Escherichia coli, is undiminished by loss of Mn-dependent superoxide dismutase (SodA). D. radiodurans radiation resistance is attributed to the accumulation of low-molecular-weight (LMW) "antioxidant" Mn(2+)-metabolite complexes that protect essential enzymes from oxidative damage. However, in vivo information about such complexes within D. radiodurans cells is lacking, and the idea that they can supplant reactive-oxygen-species (ROS)-scavenging enzymes remains controversial. In this report, measurements by advanced paramagnetic resonance techniques [electron-spin-echo (ESE)-EPR/electron nuclear double resonance/ESE envelope modulation (ESEEM)] reveal differential details of the in vivo Mn(2+) speciation in D. radiodurans and E. coli cells and their responses to 10 kGy γ-irradiation. The Mn(2+) of D. radiodurans exists predominantly as LMW complexes with nitrogenous metabolites and orthophosphate, with negligible EPR signal from Mn(2+) of SodA. Thus, the extreme radiation resistance of D. radiodurans cells cannot be attributed to SodA. Correspondingly, 10 kGy irradiation causes no change in D. radiodurans Mn(2+) speciation, despite the paucity of holo-SodA. In contrast, the EPR signal of E. coli is dominated by signals from low-symmetry enzyme sites such as that of SodA, with a minority pool of LMW Mn(2+) complexes that show negligible coordination by nitrogenous metabolites. Nonetheless, irradiation of E. coli majorly changes LMW Mn(2+) speciation, with extensive binding of nitrogenous ligands created by irradiation. We infer that E. coli is highly susceptible to radiation-induced ROS because it lacks an adequate supply of LMW Mn antioxidants.

  20. Magneto-induced stress enhancing effect in a colloidal suspension of paramagnetic and superparamagnetic particles dispersed in a ferrofluid medium.

    PubMed

    Liu, Taixiang; Gong, Xinglong; Xu, Yangguang; Xuan, Shouhu

    2014-02-14

    The magneto-induced stress and relative microstructure in a colloidal suspension of paramagnetic and superparamagnetic particles dispersed in a ferrofluid medium is studied using particle-level dynamics simulation. It shows that the stress perpendicular to the direction of an external uniaxial magnetic field can be strongly enhanced by increasing the ratio of paramagnetic particles to approaching that of superparamagnetic particles. The magnetic field-induced net-like or embedded chain-like microstructures formed by paramagnetic and superparamagnetic particles contribute to this stress enhancing effect.

  1. Anisotropy in the paramagnetic phase of RAl/sub 2/ cubic intermetallic compounds (R = Tb, Dy, and Er)

    SciTech Connect

    del Moral, A.; Ibarra, M.R.; Abell, J.S.; Montenegro, J.F.D.

    1987-05-01

    In this paper it is shown that the anisotropy in the paramagnetic phase is a useful characteristic when used to single out high-rank susceptibility tensor components in the paramagnetic regime of cubic crystals. Application of this technique to RAl/sub 2/ compounds (R = Tb,Dy,Er) allows the determination of longitudinal and transverse (in the form of linear combinations) fourth- and sixth-rank paramagnetic susceptibilities. The use of the fourth-rank longitudinal susceptibility allows quadrupolar pair interactions in these compounds to be probed.

  2. Fermi Surfaces in the Antiferromagnetic, Paramagnetic and Polarized Paramagnetic States of CeRh2Si2 Compared with Quantum Oscillation Experiments

    NASA Astrophysics Data System (ADS)

    Pourret, Alexandre; Suzuki, Michi-To; Palaccio Morales, Alexandra; Seyfarth, Gabriel; Knebel, Georg; Aoki, Dai; Flouquet, Jacques

    2017-08-01

    The large quantum oscillations observed in the thermoelectric power in the antiferromagnetic (AF) state of the heavy-fermion compound CeRh2Si2 disappear suddenly when entering in the polarized paramagnetic (PPM) state at Hc ˜ 26.5 T, indicating an abrupt reconstruction of the Fermi surface. The electronic band structure was calculated using [LDA+U] for the AF state taking the correct magnetic structure into account, for the PPM state, and for the paramagnetic state (PM). Different Fermi surfaces were obtained for the AF, PM, and PPM states. Due to band folding, a large number of branches was expected and observed in the AF state. The LDA+U calculation was compared with the previous LDA calculations. Furthermore, we compared both calculations with previously published de Haas-van Alphen experiments. The better agreement with the LDA approach suggests that above the critical pressure pc CeRh2Si2 enters in a mixed-valence state. In the PPM state under a high magnetic field, the 4f contribution at the Fermi level EF drops significantly compared with that in the PM state, and the 4f electrons contribute only weakly to the Fermi surface in our approach.

  3. Electron paramagnetic resonance study of the nuclear spin dynamics in an AlAs quantum well

    NASA Astrophysics Data System (ADS)

    Shchepetilnikov, A. V.; Frolov, D. D.; Nefyodov, Yu. A.; Kukushkin, I. V.; Tiemann, L.; Reichl, C.; Dietsche, W.; Wegscheider, W.

    2016-12-01

    The nuclear spin dynamics in an asymmetrically doped 16-nm AlAs quantum well grown along the [001] direction has been studied experimentally using the time decay of the Overhauser shift of paramagnetic resonance of conduction electrons. The nonzero spin polarization of nuclei causing the initial observed Overhauser shift is due the relaxation of the nonequilibrium spin polarization of electrons into the nuclear subsystem near electron paramagnetic resonance owing to the hyperfine interaction. The measured relaxation time of nuclear spins near the unity filling factor is (530 ± 30) min at the temperature T = 0.5 K. This value exceeds the characteristic spin relaxation times of nuclei in GaAs/AlGaAs heterostructures by more than an order of magnitude. This fact indicates the decrease in the strength of the hyperfine interaction in the AlAs quantum well in comparison with GaAs/AlGaAs heterostructures.

  4. On the Electron Paramagnetic Resonance Studies in Mixed Alkali Borate Glasses

    SciTech Connect

    Padmaja, G.; Reddy, T. Goverdhan; Kistaiah, P.

    2011-10-20

    Mixed alkali effect in oxide based glasses is one of the current research activity and studies on the behavior of spectroscopic parameters in these systems are quite important to understand the basic nature of this phenomenon. EPR studies of mixed alkali glasses Li{sub 2}O-K{sub 2}O-ZnO-B{sub 2}O{sub 3} doped with Fe{sup 3+} and Mn{sup 2+} were carried out at room temperature. The EPR spectra show typical resonances of d{sup 5} system (Fe{sup 3+} and Mn{sup 2+}) in all the measured glass specimens. Evaluated hyperfine constant, number of paramagnetic centers and paramagnetic susceptibility values show deviation from the linearity with the progressive substitution of the Li ion with K in glass network.

  5. Alfven seismic vibrations of crustal solid-state plasma in quaking paramagnetic neutron star

    SciTech Connect

    Bastrukov, S.; Xu, R.-X.; Molodtsova, I.; Takata, J.; Chang, H.-K.

    2010-11-15

    Magneto-solid-mechanical model of two-component, core-crust, paramagnetic neutron star responding to quake-induced perturbation by differentially rotational, torsional, oscillations of crustal electron-nuclear solid-state plasma about axis of magnetic field frozen in the immobile paramagnetic core is developed. Particular attention is given to the node-free torsional crust-against-core vibrations under combined action of Lorentz magnetic and Hooke's elastic forces; the damping is attributed to Newtonian force of shear viscose stresses in crustal solid-state plasma. The spectral formulas for the frequency and lifetime of this toroidal mode are derived in analytic form and discussed in the context of quasiperiodic oscillations of the x-ray outburst flux from quaking magnetars. The application of obtained theoretical spectra to modal analysis of available data on frequencies of oscillating outburst emission suggests that detected variability is the manifestation of crustal Alfven's seismic vibrations restored by Lorentz force of magnetic field stresses.

  6. Aggregation process of paramagnetic particles in fluid in the magnetic field.

    PubMed

    Pei, Ning; Cheng, Xiaoye; Huang, Zheyong; Wang, Xiang; Yang, Kai; Wang, Ye; Gong, Yongyong

    2016-07-01

    Magnetic targeting is a promising therapeutic strategy for localizing systemically delivered magnetic responsive drugs or cells to target tissue, but excessive aggregation of magnetic particles could result in vascular embolization. To analyze the reason for embolization, the attractive process of magnetic particles in magnetic field (MF) was studied in this paper by analyzing the form of the aggregated paramagnetic particles while the particle suspension flowed through a tube, which served as a model of blood vessels. The effects of magnetic flux density and fluid velocity on the formation of aggregated paramagnetic particles were investigated. The number of large aggregated clusters dramatically increased with increment in the magnetic flux density and decreased with increment in the fluid velocity. The analysis of accumulative process demonstrates the MF around initially attracted particles was focused, which induced the formation of clusters and increased the possibility of embolism. Bioelectromagnetics. 37:323-330, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  7. Paramagnetic molecule induced strong antiferromagnetic exchange coupling on a magnetic tunnel junction based molecular spintronics device.

    PubMed

    Tyagi, Pawan; Baker, Collin; D'Angelo, Christopher

    2015-07-31

    This paper reports our Monte Carlo (MC) studies aiming to explain the experimentally observed paramagnetic molecule induced antiferromagnetic coupling between ferromagnetic (FM) electrodes. Recently developed magnetic tunnel junction based molecular spintronics devices (MTJMSDs) were prepared by chemically bonding the paramagnetic molecules between the FM electrodes along the tunnel junction's perimeter. These MTJMSDs exhibited molecule-induced strong antiferromagnetic coupling. We simulated the 3D atomic model analogous to the MTJMSD and studied the effect of molecule's magnetic couplings with the two FM electrodes. Simulations show that when a molecule established ferromagnetic coupling with one electrode and antiferromagnetic coupling with the other electrode, then theoretical results effectively explained the experimental findings. Our studies suggest that in order to align MTJMSDs' electrodes antiparallel to each other, the exchange coupling strength between a molecule and FM electrodes should be ∼50% of the interatomic exchange coupling for the FM electrodes.

  8. Observations of Pauli Paramagnetic Effects on the Flux Line Lattice in CeCoIn5

    SciTech Connect

    Petrovic, C.; White, J.S.; Das, P.; Eskildsen, M.R.; DeBeer-Schmitt, L.; Forgan, E.M.; Bianchi, A.D.; Kenzelmann, M.; Zolliker, M.; Gerber, S.; Gavilano, J.L.; Mesot, J.; Movshovich, R.; E D Bauer, E.D.; Sarrao, J.L.

    2010-02-01

    From small-angle neutron scattering studies of the flux line lattice (FLL) in CeCoIn{sub 5}, with magnetic field applied parallel to the crystal c-axis, we obtain the field and temperature dependence of the FLL form factor (FF), which is a measure of the spatial variation of the field in the mixed state. We extend our earlier work (Bianchi et al 2008 Science 319 177) to temperatures up to 1250 mK. Over the entire temperature range, paramagnetism in the flux line cores results in an increase of the FF with field. Near H{sub c2} the FF decreases again, and our results indicate that this fall-off extends outside the proposed Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) region. Instead, we attribute the decrease to a paramagnetic suppression of Cooper pairing. At higher temperatures, a gradual crossover toward more conventional mixed state behavior is observed.

  9. Lithium naphthalocyanine as a new molecular radical probe for electron paramagnetic resonance oximetry

    NASA Astrophysics Data System (ADS)

    Manivannan, Ayyakkannu; Yanagi, Hisao; Ilangovan, Govindasamy; Kuppusamy, Periannan

    2001-08-01

    A new lithium naphthalocyanine dye aggregate [Li 2Nc][LiNc] is reported as a potential electron paramagnetic resonance (EPR) oximetry probe for accurate measurement of oxygen concentration in biological systems. The Li 2Nc is diamagnetic; however, the LiNc molecule has an unpaired electron and hence is paramagnetic. The aggregate shows a strong and single line EPR signal that is non-saturating at normal EPR power levels. An oxygen-dependent peak-to-peak EPR spectral width ranging from 0.51 G (at pO 2: 0 mmHg) to 26.2 G (at pO 2: 760 mmHg) has been observed. The application of this probe has been demonstrated in the measurement of arterial and venous oxygen tensions in a rat.

  10. Energy of interaction between carbon impurities in paramagnetic γ-iron

    SciTech Connect

    Ponomareva, A. V.; Gornostyrev, Yu. N.; Abrikosov, I. A.

    2015-04-15

    The energies of interaction between carbon impurity atoms in paramagnetic fcc iron (austenite) are calculated using electron density functional theory. Point defects in the paramagnetic matrix are described using a statistical approach that takes into account local magnetic fluctuations and atomic relaxation in the environment of impurity atoms. It is shown that, in addition to local deformations, magnetism significantly contributes to the energies of dissolution and interaction of carbon atoms. The values of the carbon-carbon interaction energy are indicative of a significant repulsion between these atoms in the first and second coordination spheres. The results of calculations are consistent with estimates obtained from experimental data on the activity of carbon impurity atoms in iron.

  11. Paramagnetic Meissner Transitions in Pb Films and the Vortex Compression Model

    NASA Astrophysics Data System (ADS)

    Brandt, D.; Binns, C.; Gurman, S. J.; Torricelli, G.; Gray, D. S. W.

    2011-05-01

    The magnetic flux exclusion known as Meissner effect resulting from a perfectly diamagnetic susceptibility χ=-1 is one of the defining features of type-I superconductivity. More recently some materials have been reported to undergo a transition to a paramagnetic state as they are cooled through their superconducting transition temperature (Svedlindh et al. in Physica C, pp. 162-164, 1989; Li in Phys. Rep. 376:133-223, 2003). This is known as the Paramagnetic Meissner Effect (PME). Here we report the observation of a transition from the Meissner state to a PME state in thin Pb films. We go on to show how simple modifications to the vortex compression model developed by Koshelev and Larkin (Phys. Rev. B 52:13559-13562, 1995) yield magnetization-vs-temperature curves in good qualitative agreement with the magnetization curves reported in the experiment.

  12. Paramagnetic moments in YBa2Cu3O7-δ nanocomposite films

    NASA Astrophysics Data System (ADS)

    Dias, F. T.; Vieira, V. N.; Silva, D. L.; Albino Aguiar, J.; Valadão, D. R. B.; Obradors, X.; Puig, T.; Wolff-Fabris, F.; Kampert, E.

    2014-08-01

    We report on magnetization studies in YBa2Cu3O7-δ thin films with dispersed Ba2YTaO6 nanoparticles. The magnetization measurements were made using a superconducting quantum interference device (SQUID) and a vibrating sample magnetometer (VSM). Magnetic moments were measured as functions temperature using zero-field cooling (ZFC) and field-cooled (FC) prescriptions for magnetic fields up to 10 T applied parallel and perpendicular to the ab planes. A paramagnetic response related to the superconducting state was observed during the FC experiments. This effect, known as paramagnetic Meissner effect (PME), apparently increases when the magnetic field is increased. We discuss our PME results in terms of the strong pinning scenario modulated by Ba2YTaO6 nanoparticles dispersed into the superconducting matrix.

  13. Mechanisms of enhanced orbital dia- and paramagnetism: application to the Rashba semiconductor BiTeI.

    PubMed

    Schober, G A H; Murakawa, H; Bahramy, M S; Arita, R; Kaneko, Y; Tokura, Y; Nagaosa, N

    2012-06-15

    We study the magnetic susceptibility of a layered semiconductor BiTeI with giant Rashba spin splitting both theoretically and experimentally to explore its orbital magnetism. Apart from the core contributions, a large temperature-dependent diamagnetic susceptibility is observed when the Fermi energy E(F) is near the crossing point of the Rashba spin-split conduction bands at the time-reversal symmetry point A. On the other hand, when E(F) is below this band crossing, the susceptibility turns to be paramagnetic. These features are consistent with first-principles calculations, which also predict an enhanced orbital magnetic susceptibility with both positive and negative signs as a function of E(F) due to band (anti)crossings. Based on these observations, we propose two mechanisms for the enhanced paramagnetic orbital susceptibility.

  14. Electron paramagnetic resonance and FT-IR spectroscopic studies of glycine anhydride and betaine hydrochloride

    NASA Astrophysics Data System (ADS)

    Halim Başkan, M.; Kartal, Zeki; Aydın, Murat

    2015-12-01

    Gamma irradiated powders of glycine anhydride and betaine hydrochloride have been investigated at room temperature by electron paramagnetic resonance (EPR). In these compounds, the observed paramagnetic species were attributed to the R1 and R2 radicals, respectively. It was determined that the free electron interacted with environmental protons and 14N nucleus in both radicals. The EPR spectra of gamma irradiated powder samples remained unchanged at room temperature for two weeks after irradiation. Also, the Fourier Transform Infrared (FT-IR), FT-Raman and thermal analyses of both compounds were investigated. The functional groups in the molecular structures of glycine anhydride and betaine hydrochloride were identified by vibrational spectroscopies (FT-IR and FT-Raman).

  15. Longitudinal spin fluctuation contribution to thermal lattice expansion of paramagnetic Fe

    NASA Astrophysics Data System (ADS)

    Dong, Zhihua; Li, Wei; Chen, Dengfu; Schönecker, Stephan; Long, Mujun; Vitos, Levente

    2017-02-01

    Using an efficient first-principles computational scheme for paramagnetic body-centered cubic (bcc) and face-centered cubic (fcc) Fe, we investigate the impact of thermal longitudinal spin fluctuations (LSFs) on the thermal lattice expansion. The equilibrium physical parameters are derived from the self-consistent Helmholtz free energy, in which the LSFs are considered within the adiabatic approximation and the anharmonic lattice vibration effect is included using the Debye-Grüneisen model taking into account the interplay between thermal, magnetic, and elastic degrees of freedom. Thermal LSFs are energetically more favorable in the fcc phase than in the bcc one giving a sizable contribution to the linear thermal expansion of γ -Fe. The present scheme leads to accurate temperature-dependent equilibrium Wigner-Seitz radius, bulk modulus, and Debye temperature within the stability fields of the two phases and demonstrates the importance of thermal spin fluctuations in paramagnetic Fe.

  16. MRI detection of paramagnetic chemical exchange effects in mice kidneys in vivo.

    PubMed

    Vinogradov, Elena; He, Huamei; Lubag, Angelo; Balschi, James A; Sherry, A Dean; Lenkinski, Robert E

    2007-10-01

    In this report, the On resonance PARamagnetic CHemical Exchange Effects (OPARACHEE) method was implemented in vivo using WALTZ-16* as a preparation pulse with a standard spin echo sequence to detect the accumulation and clearance of the TmDOTA-4AmC(-) in mouse kidney. The performance of the technique in vivo is described in terms of the magnitude of the contrast effect versus the bolus agent concentration and signal-to-noise ratio (SNR) levels. The lowest injected concentration of TmDOTA-4AmC(-), 200 microL of a 2-mM stock solution (corresponds to approximately 0.2 mM agent in plasma), reduced the total water signal in the kidney papilla by 45% 3 min after the a bolus injection. The results show that the OPARACHEE methodology employing low-amplitude RF trains can detect paramagnetic exchanging agents in vivo.

  17. Characterization of humic acids from tundra soils of northern Western Siberia by electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Chukov, S. N.; Ejarque, E.; Abakumov, E. V.

    2017-01-01

    Humic acids from polar soils—cryozems (Cryosols), gleyezems (Gleysols), and peat soils (Histosols)—have been studied by electron paramagnetic resonance spectroscopy. First information was acquired on the content of free radicals in humic acids from polar soils for the northern regions of Western Siberia (Gydan Peninsula, Belyi Island). It was found that polar soils are characterized by higher contents of free radicals than other zonal soils. This is related to the lower degree of humification of organic matter and the enhanced hydromorphism under continuous permafrost conditions. The low degree of organic matter humification in the cryolithozone was confirmed by the increased content of free radicals as determined by electron paramagnetic resonance, which indicates a low biothermodynamic stability of organic matter.

  18. Defect introduced paramagnetism and weak localization in two-dimensional metal VSe2.

    PubMed

    Cao, Qiang; Yun, Frank; Sang, Lina; Wang, Xiaolin

    2017-09-27

    We have carried out a detailed investigation of the magnetism, valence state, and magnetotransport in VSe2 bulk single crystals, as well as in laminates obtained by mechanical exfoliation. In sharp contrast to the ferromagnetic behavior reported previously, here, no ferromagnetism could be detected for VSe2 single crystal and laminate from room temperature down to 2 K. Neither did we find the Curie paramagnetism expected due to the 3d1 odd-electronic configuration of covalent V4+ ions. Rather, VSe2 is a non-magnetic alloy without local moment. Only a weak paramagnetic contribution introduced by defects is noticeable below 50 K. A weak localization effect due to defects was also observed in VSe2 single crystals for the first time. © 2017 IOP Publishing Ltd.

  19. Magneto-optical activity at the structural phase transition in paramagnetic KMnF 3

    NASA Astrophysics Data System (ADS)

    Pezzoni, R.; Rigamonti, A.; Torre, S.

    1985-09-01

    The magneto-optical Verdet constant ø has been measured in the paramagnetic phase of KMnF 3 and particularly in the neighbourhood of the cubic-tetragonal phase transition driven by the softening of zone boundary modes. ø is positive and displays a sizeable decrease on cooling, thus indicating the presence of a temperature dependent paramagnetic contribution that, in view of the 6S ground state of the Mn 2+ ion, is attributed to the role of spin-orbit interaction. In a temperature range of about 20K around Tc = 186K, a cusp-shaped anomaly of ø is observed. From the dependence on the wavelength, and by taking into account also EPR linewidth and g measurements and optical absorption spectra, an analysis of the possible mechanisms for the cusp-shaped anomaly is given. It is argued that the enhancement of the critical rotational fluctuations of the MnF 6 octahedra can be responsible for this effect.

  20. Inverse magnetocaloric effect in the uniaxial paramagnet with non-Kramers ions

    NASA Astrophysics Data System (ADS)

    Kokorina, E. E.; Medvedev, M. V.

    2017-03-01

    It has been shown that, in a uniaxial paramagnet with non-Kramers ions with a spin of S = 1 and single-ion anisotropy of the easy-plane type ( DS Z 2 ), there is a low-field (μ0 H ≤ D) and low-temperature ( k B T < 0.68D) region in which the isothermal magnetization along the hard direction H||O Z increases the magnetic entropy by Δ S M ( T, Δ H = H f - H i > 0) > 0 and the adiabatic magnetization along the same direction reduces the sample temperature by Δ T ad( T, Δ H > 0) < 0 (inverse magnetocaloric effect (MCE)). The main features of the inverse MCE in uniaxial paramagnets with large spins ( S = 2, 3, …) of the non-Kramers ions have been discussed.

  1. Anomalous paramagnetic behavior: the role of zero-point electromagnetic fluctuations

    NASA Astrophysics Data System (ADS)

    França, H. M.; Santos, R. B. B.

    1998-02-01

    The interaction of a microscopic magnetic dipole and the inductor of a RLC circuit without batteries, is described using the approach of stochastic electrodynamics. The purpose of this study is to clarify the effects of the current fluctuations on the paramagnetic behaviour of a sample of magnetic material which is close to a thin solenoid. A suppression is predicted in the average magnetization, even in the case in which the circuit temperature is arbitrarily close to the absolute zero.

  2. Exchange enhanced paramagnetism of rare-earth (yttrium)-transition metal compounds

    SciTech Connect

    Burzo, Emil

    2015-12-07

    The magnetic susceptibilities, χ, of R-M and R-M-B exchange enhanced paramagnets where R = Y, La, Lu and M= Co, Ni are analysed. As a general feature, there is a T{sup 2} dependence of χ values at T < 10 K, while for T > T* a Curie-Weiss behavior is shown. The experimental data are discussed in correlation with band structure calculations. The pressure dependence of LuCo{sub 2} magnetic susceptibility is also analysed.

  3. Cavity- and waveguide-resonators in electron paramagnetic resonance, nuclear magnetic resonance, and magnetic resonance imaging.

    PubMed

    Webb, Andrew

    2014-11-01

    Cavity resonators are widely used in electron paramagnetic resonance, very high field magnetic resonance microimaging and also in high field human imaging. The basic principles and designs of different forms of cavity resonators including rectangular, cylindrical, re-entrant, cavity magnetrons, toroidal cavities and dielectric resonators are reviewed. Applications in EPR and MRI are summarized, and finally the topic of traveling wave MRI using the magnet bore as a waveguide is discussed.

  4. The paramagnetic properties of one-dimensional spin-1 single-ion anisotropic ferromagnet

    NASA Astrophysics Data System (ADS)

    Wang, Hai-Jun; Chen, Yuan; Fu, Liang-Jie; Lin, Rui-Na; Song, Chuang-Chuang

    2009-06-01

    One-dimensional single-ion anisotropic ferromagnet with spin-1 is investigated by means of Green's function treatment in this paper. The model Hamiltonian includes a Heisenberg ferromagnetic term, an external magnetic field, and a second-order single-ion anisotropy. The magnetic properties of the system are treated by the random phase approximation for the exchange interaction term and the Anderson-Callen approximation for the anisotropy term. Our paramagnetic results are in agreement with the other theoretical results.

  5. Process and apparatus for preparing textured crystalline materials using anisotropy in the paramagnetic susceptibility

    DOEpatents

    Holloway, Aleksey

    1992-01-07

    The present invention discloses a process and apparatus for forming textures in materials. The process comprises heating a material having an anisotropy in the paramagnetic or diamagnetic susceptibility within a magnetic field. The material is heated to a temperature approaching its melting point while a magnetic field of at least 10.sup.4 Oe is simultaneously applied. The process and apparatus produce highly textured bulk and elongated materials with high current densities below critical superconducting temperatures.

  6. Holographic paramagnetism-ferromagnetism phase transition in the Born-Infeld electrodynamics

    NASA Astrophysics Data System (ADS)

    Wu, Ya-Bo; Zhang, Cheng-Yuan; Lu, Jun-Wang; Fan, Bi; Shu, Shuang; Liu, Yu-Chen

    2016-09-01

    In the probe limit, we investigate the effects of the Born-Infeld electrodynamics on the holographic paramagnetism-ferromagnetism phase transition in the background of a Schwarzschild-AdS black hole spacetime. We find that the presence of Born-Infeld scale parameter b decreases the critical temperature and makes the magnetic moment harder to form in the case of without external field. Furthermore, the increase of b will result in extending the period of the external magnetic field.

  7. Effect of conduction electrons on the paramagnetic susceptibility of rare earth intermetallics

    SciTech Connect

    Zajac, S.; Pesek, F.

    1994-03-01

    The authors have calculated the paramagnetic susceptibility of rare earth intermetallics in the model of the crystal-field split 4F ions interacting with conduction electrons by exchange coupling. Using the thermodynamic perturbation theory they have derived analytical formulae for the susceptibility to the second order. They have developed scheme to simultaneously optimize fitting of crystal-field and coupling parameters to the experimental data.

  8. Determining residual impurities in sapphire by means of electron paramagnetic resonance and nuclear activation analysis

    NASA Astrophysics Data System (ADS)

    Bletskan, D. I.; Bratus', V. Ya.; Luk'yanchuk, A. R.; Maslyuk, V. T.; Parlag, O. A.

    2008-07-01

    Sapphire (α-Al2O3) single crystals grown using the Verneuil and Kyropoulos methods have been analyzed using electron paramagnetic resonance and γ-ray spectroscopy with 12-MeV bremsstrahlung excitation. It is established that uncontrolled impurities in the final sapphire single crystals grown by the Kyropoulos method in molybdenum-tungsten crucibles are supplied both from the initial materials and from the furnace and crucible materials

  9. Exchange enhanced paramagnetism of rare-earth (yttrium)-transition metal compounds

    NASA Astrophysics Data System (ADS)

    Burzo, Emil

    2015-12-01

    The magnetic susceptibilities, χ, of R-M and R-M-B exchange enhanced paramagnets where R = Y, La, Lu and M= Co, Ni are analysed. As a general feature, there is a T2 dependence of χ values at T < 10 K, while for T > T* a Curie-Weiss behavior is shown. The experimental data are discussed in correlation with band structure calculations. The pressure dependence of LuCo2 magnetic susceptibility is also analysed.

  10. Process and apparatus for preparing textured crystalline materials using anisotropy in the paramagnetic susceptibility

    DOEpatents

    Holloway, A.

    1992-01-07

    The present invention discloses a process and apparatus for forming textures in materials. The process comprises heating a material having an anisotropy in the paramagnetic or diamagnetic susceptibility within a magnetic field. The material is heated to a temperature approaching its melting point while a magnetic field of at least 10[sup 4]Oe is simultaneously applied. The process and apparatus produce highly textured bulk and elongated materials with high current densities below critical superconducting temperatures. 6 figs.

  11. Asymptotic freedom and IR freezing in QCD: the role of gluon paramagnetism

    SciTech Connect

    Simonov, Yu. A.

    2011-08-15

    Paramagnetism of gluons is shown to play the basic role in establishing main properties of QCD: IR freezing and asymptotic freedom (AF). Starting with Polyakov background field approach the first terms of background perturbation theory are calculated and shown to ensure not only the classical result of AF but also IR freezing. For the latter only the confining property of the background is needed, and the effective mass entering the IR freezing logarithms is calculated in good agreement with phenomenology and lattice data.

  12. Paramagnet induced signal quenching in MAS-DNP experiments in frozen homogeneous solutions

    NASA Astrophysics Data System (ADS)

    Corzilius, Björn; Andreas, Loren B.; Smith, Albert A.; Ni, Qing Zhe; Griffin, Robert G.

    2014-03-01

    The effects of nuclear signal quenching induced by the presence of a paramagnetic polarizing agent are documented for conditions used in magic angle spinning (MAS)-dynamic nuclear polarization (DNP) experiments on homogeneous solutions. In particular, we present a detailed analysis of three time constants: (1) the longitudinal build-up time constant TB for 1H; (2) the rotating frame relaxation time constant T1ρ for 1H and 13C and (3) T2 of 13C, the transverse relaxation time constant in the laboratory frame. These relaxation times were measured during microwave irradiation at a magnetic field of 5 T (140 GHz) as a function of the concentration of four polarizing agents: TOTAPOL, 4-amino-TEMPO, trityl (OX063), and Gd-DOTA and are compared to those obtained for a sample lacking paramagnetic doping. We also report the EPR relaxation time constants T1S and T2S, the DNP enhancements, ε, and the parameter E, defined below, which measures the sensitivity enhancement for the four polarizing agents as a function of the electron concentration. We observe substantial intensity losses (paramagnetic quenching) with all of the polarizing agents due to broadening mechanisms and cross relaxation during MAS. In particular, the monoradical trityl and biradical TOTAPOL induce ∼40% and 50% loss of signal intensity. In contrast there is little suppression of signal intensity in static samples containing these paramagnetic species. Despite the losses due to quenching, we find that all of the polarizing agents provide substantial gains in signal intensity with DNP, and in particular that the net enhancement is optimal for biradicals that operate with the cross effect. We discuss the possibility that much of this polarization loss can be regained with the development of instrumentation and methods to perform electron decoupling.

  13. Magnetism on the surface of the bulk paramagnetic intermetallic compound YCo2.

    PubMed

    Khmelevskyi, S; Mohn, P; Redinger, J; Weinert, M

    2005-04-15

    Using full-potential electronic structure calculations, we predict that the (111) surface of the cubic Laves phase Pauli paramagnet YCo2 is ferromagnetic. The magnetism of the (111) surface is independent of the termination of the surface, does not extend beyond two Co layers, and is related to the field-induced metamagnetism of the bulk. YCo2 appears to be a prominent candidate to demonstrate the phenomenon of surface-induced itinerant magnetism localized in two dimensions.

  14. Paramagnetic carbon-13 shifts induced by the free radical 2,2,6,6-tetramethylpiperidinyl-1-oxy. 1. Simple aromatic and paraffinic hydrocarbons

    SciTech Connect

    Qiu, Z.W.; Grant, D.M.; Pugmire, R.J.

    1982-05-19

    Using the free radical 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) as a shift reagent, both apparent and true molar paramagnetic shifts of 22 compounds are reported. Paramagnetic shifts increase monotonically with measures of conjugation and aromaticity. The nonalternant hydrocarbons experience greater effects than the corresponding alternant systems. Steric hindrance effects become important factors in various methyl derivatives. As previously supposed the shifts do not appear to relate primarily with either the frontier spin densities or with ..pi..-charge densities. Therefore, the direct charge-transfer or spin delocalization proposals requiring a strong intermolecular interaction of the ..pi..-stacking variety are felt not to be attractive. Linear correlation exists between these and Morishima's data and between the data for TEMPO and 4-OH-TEMPO. In each case TEMPO is more effetive as a shift reagent than the other two nitroxide free radicals. A shift model involving a pseudocontact interaction during the existence of a transient weak complex is supported by these data. 5 figures, 1 table.

  15. Upcycling: converting waste plastics into paramagnetic, conducting, solid, pure carbon microspheres.

    PubMed

    Pol, Vilas Ganpat

    2010-06-15

    The recent tremendous increase in the volume of waste plastics (WP) will have a harmful environmental impact on the health of living beings. Hundreds of years are required to degrade WP in atmospheric conditions. Hence, in coming years, in addition to traditional recycling services, innovative "upcycling" processes are necessary. This article presents an environmentally benign, solvent-free autogenic process that converts various WP [low density polyethylene (LDPE), high density polyethylene (HDPE), polyethylene terephthalate (PET), polystyrene (PS), or their mixtures] into carbon microspheres (CMSs), an industrially significant, value-added product. The thermal dissociation of these individual or mixed WP in a closed reactor under autogenic pressure ( approximately 1000 psi) produced dry, pure powder of CMSs. In this paper, the optimization of process parameters such as the effect of mixing of WP with other materials, and the role of reaction temperature and time are reported. Employing advanced analytical techniques, the atomic structure, composition, and morphology of as-obtained CMSs were analyzed. The room-temperature paramagnetism in CMSs prepared from waste LDPE, HDPE, and PS was further studied by electron paramagnetic resonance (EPR). The conducting and paramagnetic nature of CMSs holds promise for their potential applications in toners, printers, paints, batteries, lubricants, and tires.

  16. Equation of state of paramagnetic CrN from ab initio molecular dynamics

    NASA Astrophysics Data System (ADS)

    Steneteg, Peter; Alling, Björn; Abrikosov, Igor A.

    2012-04-01

    The equation of state for chromium nitride has been debated in the literature in connection with a proposed collapse of its bulk modulus following the pressure-induced transition from the paramagnetic cubic phase to the antiferromagnetic orthorhombic phase [F. Rivadulla , Nature Mater.1476-112210.1038/nmat2549 8, 947 (2009); B. Alling , Nature Mater.1476-112210.1038/nmat2722 9, 283 (2010)]. Experimentally the measurements are complicated due to the low transition pressure, while theoretically the simulation of magnetic disorder represents a major challenge. Here a first-principles method is suggested for the calculation of thermodynamic properties of magnetic materials in their high-temperature paramagnetic phase. It is based on ab initio molecular dynamics and simultaneous redistributions of the disordered but finite local magnetic moments. We apply this disordered local moments molecular dynamics method to the case of CrN and simulate its equation of state. In particular the debated bulk modulus is calculated in the paramagnetic cubic phase and is shown to be very similar to that of the antiferromagnetic orthorhombic CrN phase for all considered temperatures.

  17. Following lithiation fronts in paramagnetic electrodes with in situ magnetic resonance spectroscopic imaging

    PubMed Central

    Tang, Mingxue; Sarou-Kanian, Vincent; Melin, Philippe; Leriche, Jean-Bernard; Ménétrier, Michel; Tarascon, Jean-Marie; Deschamps, Michaël; Salager, Elodie

    2016-01-01

    Li-ion batteries are invaluable for portable electronics and vehicle electrification. A better knowledge of compositional variations within the electrodes during battery operation is, however, still needed to keep improving their performance. Although essential in the medical field, magnetic resonance imaging of solid paramagnetic battery materials is challenging due to the short lifetime of their signals. Here we develop the scanning image-selected in situ spectroscopy approach, using the strongest commercially available magnetic field gradient. We demonstrate the 7Li magnetic resonance spectroscopic image of a 5 mm-diameter operating battery with a resolution of 100 μm. The time-resolved image-spectra enable the visualization in situ of the displacement of lithiation fronts inside thick paramagnetic electrodes during battery operation. Such observations are critical to identify the key limiting parameters for high-capacity and fast-cycling batteries. This non-invasive technique also offers opportunities to study devices containing paramagnetic materials while operating. PMID:27808094

  18. Selective observation of a spinning-sideband manifold of paramagnetic solids by rotation-synchronized DANTE

    NASA Astrophysics Data System (ADS)

    Murakami, Miwa; Arai, Hajime; Uchimoto, Yoshiharu; Ogumi, Zempachi

    2013-06-01

    We examine applicability of rotation-synchronized Delays Alternating with Nutation for Tailored Excitation (rs-DANTE) to a crowded sideband spectrum spreading over a few 100 kHz by the paramagnetic interaction. It is shown that rs-DANTE can be used to excite 6Li spinning sideband manifolds of the three crystallographic Li sites (2b, 4h, and 2c) in a magic-angle spinning (MAS) spectrum of 6Li-enriched Li2MnO3. The observed lineshape is insensitive to rf inhomogeneiety, thus indicating practical applicability of rs-DANTE to a paramagnetic system. Each sideband pattern can be described by the paramagnetic anisotropies evaluated by taking the electron-6Li dipolar interactions into account. The isotropic chemical shift for each site can thus be obtained by comparing the experimental sideband pattern to the calculated one. It is therefore possible by this approach to obtain both isotropic and anisotropic shift information. Further effects of structural disorder in Li2MnO3 on the isotropic shift and the sideband pattern are discussed.

  19. Selective observation of a spinning-sideband manifold of paramagnetic solids by rotation-synchronized DANTE.

    PubMed

    Murakami, Miwa; Arai, Hajime; Uchimoto, Yoshiharu; Ogumi, Zempachi

    2013-06-01

    We examine applicability of rotation-synchronized Delays Alternating with Nutation for Tailored Excitation (rs-DANTE) to a crowded sideband spectrum spreading over a few 100 kHz by the paramagnetic interaction. It is shown that rs-DANTE can be used to excite (6)Li spinning sideband manifolds of the three crystallographic Li sites (2b, 4h, and 2c) in a magic-angle spinning (MAS) spectrum of (6)Li-enriched Li2MnO3. The observed lineshape is insensitive to rf inhomogeneiety, thus indicating practical applicability of rs-DANTE to a paramagnetic system. Each sideband pattern can be described by the paramagnetic anisotropies evaluated by taking the electron-(6)Li dipolar interactions into account. The isotropic chemical shift for each site can thus be obtained by comparing the experimental sideband pattern to the calculated one. It is therefore possible by this approach to obtain both isotropic and anisotropic shift information. Further effects of structural disorder in Li2MnO3 on the isotropic shift and the sideband pattern are discussed. Copyright © 2013 Elsevier Inc. All rights reserved.

  20. Paramagnetic Salt Pill Design for Magnetic Refrigerators Used In-Space Applications

    NASA Astrophysics Data System (ADS)

    Hagmann, C.; Benford, D. J.; Richards, P. L.

    An adiabatic demagnetization refrigerator (ADR) is described which was designed for use in the multiband imaging photometer for the Space Infrared Telescope Facility (SIRTF). This refrigerator was required to cool bolometric detectors for infrared and millimetre waves to 0.1 K. A paramagnetic salt pill with a number of novel features was developed to meet the stringent requirements for an ADR used in space. An unusual paramagnetic salt, chromic caesium alum (CCA), is used to meet the requirement of thermal stability under the bake-out temperatures used in commissioning space cryogenic vacuum systems. The cycle time for the refrigerator has been reduced to almost-equal-to 30 min by attention to thermal time constants and by growing the CCA salt directly on to an array of gold wires. Crystal growing procedures were developed to overcome problems with the low solubility of CCA in water. The salt pill is sealed in stainless steel to retain water of hydration and is constructed of materials which are not corroded by commonly used paramagnetic salts.

  1. Environmentally sensitive paramagnetic and diamagnetic contrast agents for nuclear magnetic resonance imaging and spectroscopy.

    PubMed

    Pacheco-Torres, Jesus; Calle, Daniel; Lizarbe, Blanca; Negri, Viviana; Ubide, Carmen; Fayos, Rosa; Larrubia, Pilar López; Ballesteros, Paloma; Cerdan, Sebastian

    2011-01-01

    Even though alterations in the microenvironmental properties of tissues underlie the development of the most prevalent and morbid pathologies, they are not directly observable in vivo by Magnetic Resonance Imaging (MRI) or Spectroscopy (MRS) methods. This circumstance has lead to the development of a wide variety of exogenous paramagnetic and diamagnetic MRI and MRS probes able to inform non invasively on microenvironmental variables such as pH, pO(2), ion concentration o even temperature. This review covers the fundamentals of environmental contrast and the current arsenal of endogenous and exogenous MRI and MRS contrast enhancing agents available to visualize it. We begin describing the physicochemical background necessary to understand paramagnetic and diamagnetic contrast enhancement with a special reference to novel magnetization transfer and (13)C hyperpolarization strategies. We describe then the main macrocyclic structures used to support the environmentally sensitive paramagnetic sensors, including CEST and PARACEST pH sensitive probes, temperature probes and enzyme activity or gene expression activatable probes. Finally we address the most commonly used diamagnetic contrast agents including imidazolic derivatives to reveal extracellular pH and tissue pO(2) values by MRS. The potential applications of these agents in multimodal and molecular imaging approaches are discussed.

  2. On the explanation of the paramagnetic Meissner effect in superconductor/ferromagnet heterostructures

    NASA Astrophysics Data System (ADS)

    Nagy, B.; Khaydukov, Yu.; Efremov, D.; Vasenko, A. S.; Mustafa, L.; Kim, J.-H.; Keller, T.; Zhernenkov, K.; Devishvili, A.; Steitz, R.; Keimer, B.; Bottyán, L.

    2016-10-01

    An increase of the magnetic moment in superconductor/ferromagnet (S/F) bilayers V(40 nm)/F (\\text{F}=\\text{Fe}(1,~3 \\text{nm}) , Co(3 nm), Ni(3 nm)) was observed using SQUID magnetometry upon cooling below the superconducting transition temperature T C in magnetic fields of 10 Oe to 50 Oe applied parallel to the sample surface. A similar increase, often called the paramagnetic Meissner effect (PME), was observed before in various superconductors and superconductor/ferromagnet systems. To explain the PME effect in the presented S/F bilayers a model based on a row of vortices located at the S/F interface is proposed. According to the model the magnetic moment induced below T C consists of the paramagnetic contribution of the vortex cores and the diamagnetic contribution of the vortex-free region of the S layer. Since the thickness of the S layer is found to be 3-4 times less than the magnetic-field penetration depth, this latter diamagnetic contribution is negligible. The model correctly accounts for the sign, the approximate magnitude and the field dependence of the paramagnetic and the Meissner contributions of the induced magnetic moment upon passing the superconducting transition of a ferromagnet/superconductor bilayer.

  3. Paramagnetic Properties of Fullerene-Derived Nanomaterials and Their Polymer Composites: Drastic Pumping Out Effect

    NASA Astrophysics Data System (ADS)

    Konchits, Andriy A.; Shanina, Bela D.; Krasnovyd, Serhii V.; Burya, Alexander I.; Kuznetsova, Olga Yu

    2017-08-01

    The evolution of paramagnetic properties of the fullerene soot (FS), fullerene black (FB), and their polymer composites Phenylon C-2/FS, FB has been studied using the electron paramagnetic resonance (EPR) method. For the first time, a drastic growth of the EPR signals in the FB, FS, and composite samples was observed under pumping out at temperatures T = 20 ÷ 300 °C, which is attributed to the interaction between carbon defects and adsorbed gas molecules, mainly oxygen. It is shown that the ensemble of paramagnetic centers in the FB, FS, and the composite is heterogeneous. This ensemble consists of three spin subsystems 1, 2, and 3 related with different structural elements. The subsystems give three corresponding contributions, L 1, L 2 and L 3, into the overall contour of the EPR signal. The most intensive and broad signal L 3 is caused by 2D electrons from the surface of carbon flakes. Theoretical calculations of the L 3 signal line shape were carried out, and the decay rate of the integral intensity has been obtained for each component L 1, L 2, and L 3 after the contact of the sample with the ambient air. The signal decay process in the bulk composite samples is much slower due to their low gas permeability at room temperature (RT).

  4. Understanding the NMR shifts in paramagnetic transition metal oxides using density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Carlier, D.; Ménétrier, M.; Grey, C. P.; Delmas, C.; Ceder, G.

    2003-05-01

    The 6,7Li MAS NMR spectra of lithium ions in paramagnetic host materials are extremely sensitive to number and nature of the paramagnetic cations in the Li local environments and large shifts (Fermi contact shifts) are often observed. The work presented in this paper aims to provide a rational basis for the interpretation of the 6,7Li NMR shifts, as a function of the lithium local environment and electronic configuration of the transition metal ions. We focus on the layered rocksalts often found for LiMO2 compounds and on materials that are isostructural with the K2NiF4 structure. In order to understand the spin-density transfer mechanism from the transition metal ion to the lithium nucleus, which gives rise to the hyperfine shifts observed by NMR, we have performed density functional theory (DFT) calculations in the generalized gradient approximation. For each compound, we calculate the spin densities values on the transition metal, oxygen and lithium ions and map the spin density in the M-O-Li plane. Predictions of the calculations are in good agreement with several experimental results. We show that DFT calculations are a useful tool with which to interpret the observed paramagnetic shifts in layered oxides and to understand the major spin-density transfer processes. This information should help us to predict the magnitudes and signs of the Li hyperfine shifts for different Li local environments and t2g vs eg electrons in other compounds.

  5. Mechanics of semiflexible chains formed by poly(ethylene glycol)-linked paramagnetic particles.

    PubMed

    Biswal, Sibani Lisa; Gast, Alice P

    2003-08-01

    Magnetorheological particles, permanently linked into chains, provide a magnetically actuated means to manipulate microscopic fluid flow. Paramagnetic colloidal particles form reversible chains by acquiring dipole moments in the presence of an external magnetic field. By chemically connecting paramagnetic colloidal particles, flexible magnetoresponsive chains can be created. We link the paramagnetic microspheres using streptavidin-biotin binding. Streptavidin coated microspheres are placed in a flow cell and a magnetic field is applied, causing the particles to form chains. Then a solution of polymeric linkers of bis-biotin-poly(ethylene glycol) molecules is added in the presence of the field. These linked chains remain responsive to a magnetic field; however, in the absence of an external magnetic field these chains bend and flex due to thermal motion. The chain flexibility is determined by the length of the spacer molecule between particles and is quantified by the flexural rigidity or bending stiffness. To understand the mechanical properties of the chains, we use a variety of optical trapping experiments to measure the flexural rigidity. Increasing the length of the poly(ethylene glycol) chain in the linker increases the flexibility of the chains.

  6. Sheathless and high throughput sorting of paramagnetic microparticles in a magneto-hydrodynamic microfluidic device.

    PubMed

    Kumar, Vikash; Rezai, Pouya

    2016-08-01

    Sorting of microorganisms and particles from a mixture is critical for numerous biotechnological and medical applications. Several sorting methods such as pinched flow fractionation (PFF), optical sorting, dielectrophoresis, acoustic separation, magnetophoresis and deterministic lateral displacement (DLD) have been reported in literature. But most of these methods lack ideal characteristics of a sorter such as ability to process at high throughput, simple design, non-complicated fabrication method, sheathless operation and high purity in separation. In this paper, we have introduced a novel sorting technique by integrating focusing of magnetic particles in a narrow microchannel with their hydrodynamic separation at a downstream expansion channel which meets majority of the aforementioned characteristics. To achieve this, the sheathless focusing of paramagnetic microparticles in the narrow microchannel and their deflection at the expansion channel were first studied at various flow rates (0.5-5 ml h-1). Then, a mixture of 5 and 11 μm paramagnetic particles was introduced into the device and their separation was examined quantitatively. It was found that the magnetic particles were focused along the wall of channel, however their centers were positioned on two distinct streamlines owing to difference in their sizes. Hence, these two particles were found separated from each other as they flew into the expansion region. This technique of size based separation of paramagnetic particles works at a high throughput of 107 particles per hour and offers more than 98% purity in sorting.

  7. Electron paramagnetic resonance imaging for real-time monitoring of Li-ion batteries

    PubMed Central

    Sathiya, M.; Leriche, J.-B.; Salager, E.; Gourier, D.; Tarascon, J.-M.; Vezin, H.

    2015-01-01

    Batteries for electrical storage are central to any future alternative energy paradigm. The ability to probe the redox mechanisms occurring at electrodes during their operation is essential to improve battery performances. Here we present the first report on Electron Paramagnetic Resonance operando spectroscopy and in situ imaging of a Li-ion battery using Li2Ru0.75Sn0.25O3, a high-capacity (>270 mAh g−1) Li-rich layered oxide, as positive electrode. By monitoring operando the electron paramagnetic resonance signals of Ru5+ and paramagnetic oxygen species, we unambiguously prove the formation of reversible (O2)n− species that contribute to their high capacity. In addition, we visualize by imaging with micrometric resolution the plating/stripping of Li at the negative electrode and highlight the zones of nucleation and growth of Ru5+/oxygen species at the positive electrode. This efficient way to locate ‘electron’-related phenomena opens a new area in the field of battery characterization that should enable future breakthroughs in battery research. PMID:25662295

  8. Electron paramagnetic resonance imaging for real-time monitoring of Li-ion batteries.

    PubMed

    Sathiya, M; Leriche, J-B; Salager, E; Gourier, D; Tarascon, J-M; Vezin, H

    2015-02-09

    Batteries for electrical storage are central to any future alternative energy paradigm. The ability to probe the redox mechanisms occurring at electrodes during their operation is essential to improve battery performances. Here we present the first report on Electron Paramagnetic Resonance operando spectroscopy and in situ imaging of a Li-ion battery using Li2Ru0.75Sn0.25O3, a high-capacity (>270 mAh g(-1)) Li-rich layered oxide, as positive electrode. By monitoring operando the electron paramagnetic resonance signals of Ru(5+) and paramagnetic oxygen species, we unambiguously prove the formation of reversible (O2)(n-) species that contribute to their high capacity. In addition, we visualize by imaging with micrometric resolution the plating/stripping of Li at the negative electrode and highlight the zones of nucleation and growth of Ru(5+)/oxygen species at the positive electrode. This efficient way to locate 'electron'-related phenomena opens a new area in the field of battery characterization that should enable future breakthroughs in battery research.

  9. Following lithiation fronts in paramagnetic electrodes with in situ magnetic resonance spectroscopic imaging.

    PubMed

    Tang, Mingxue; Sarou-Kanian, Vincent; Melin, Philippe; Leriche, Jean-Bernard; Ménétrier, Michel; Tarascon, Jean-Marie; Deschamps, Michaël; Salager, Elodie

    2016-11-03

    Li-ion batteries are invaluable for portable electronics and vehicle electrification. A better knowledge of compositional variations within the electrodes during battery operation is, however, still needed to keep improving their performance. Although essential in the medical field, magnetic resonance imaging of solid paramagnetic battery materials is challenging due to the short lifetime of their signals. Here we develop the scanning image-selected in situ spectroscopy approach, using the strongest commercially available magnetic field gradient. We demonstrate the (7)Li magnetic resonance spectroscopic image of a 5 mm-diameter operating battery with a resolution of 100 μm. The time-resolved image-spectra enable the visualization in situ of the displacement of lithiation fronts inside thick paramagnetic electrodes during battery operation. Such observations are critical to identify the key limiting parameters for high-capacity and fast-cycling batteries. This non-invasive technique also offers opportunities to study devices containing paramagnetic materials while operating.

  10. Upcycling : converting waste plastics into paramagnetic, conducting, solid, pure carbon microspheres.

    SciTech Connect

    Pol, V.

    2010-06-15

    The recent tremendous increase in the volume of waste plastics (WP) will have a harmful environmental impact on the health of living beings. Hundreds of years are required to degrade WP in atmospheric conditions. Hence, in coming years, in addition to traditional recycling services, innovative 'upcycling' processes are necessary. This article presents an environmentally benign, solvent-free autogenic process that converts various WP [low density polyethylene (LDPE), high density polyethylene (HDPE), polyethylene terephthalate (PET), polystyrene (PS), or their mixtures] into carbon microspheres (CMSs), an industrially significant, value-added product. The thermal dissociation of these individual or mixed WP in a closed reactor under autogenic pressure (1000 psi) produced dry, pure powder of CMSs. In this paper, the optimization of process parameters such as the effect of mixing of WP with other materials, and the role of reaction temperature and time are reported. Employing advanced analytical techniques, the atomic structure, composition, and morphology of as-obtained CMSs were analyzed. The room-temperature paramagnetism in CMSs prepared from waste LDPE, HDPE, and PS was further studied by electron paramagnetic resonance (EPR). The conducting and paramagnetic nature of CMSs holds promise for their potential applications in toners, printers, paints, batteries, lubricants, and tires.

  11. Paramagnetic Meissner effect and strong time dependence at high fields in melt-textured high- T C superconductors

    NASA Astrophysics Data System (ADS)

    de Paiva Gouvêa, Cristol; Dias, Fábio Teixeira; das Neves Vieira, Valdemar; da Silva, Douglas Langie; Schaf, Jacob; Wolff-Fabris, Frederik; Rovira, Joan Josep Roa

    2013-05-01

    In this work we report on systematic field-cooled magnetization experiments in melt-textured YBa2Cu3O7- δ samples containing Y211 precipitates. Magnetic fields up to 14 T were applied either parallel or perpendicular to the ab planes and a strong paramagnetic response related to the superconducting state was observed. This effect is known as paramagnetic Meissner effect (PME). The magnitude of the PME increases when the field is augmented. This effect shows a strong paramagnetic relaxation, such that the paramagnetic moment increases as a function of the time. The pinning by the Y211 particles plays a crucial role in the explanation of this effect and our results suggest that the pinning capacity can produce a strong flux compression into the sample, originating the PME and the strong time dependence.

  12. Phosphorus-31 and carbon-13 nuclear magnetic resonance studies of divalent cation binding to phosphatidylserine membranes. Use of cobalt as a paramagnetic probe

    SciTech Connect

    McLaughlin, A.C.

    1982-01-01

    The paramagnetic divalent cation cobalt has large and well-understood effects on NMR signals from ligands bound in the first coordination sphere, i.e., inner-sphere ligands, and the authors have used these effects to identify divalent cation binding sites at the surface of phosphatidylserine membranes. /sup 31/P NMR results show that 13% of the bound cobalt ions are involved in inner-sphere complexes with the phosphodiester group, while /sup 13/C NMR results show that 54% of the bound cobalt ions are involved in unidentate inner sphere complexes with the carboxyl group. No evidence is found for cobalt binding to the carbonyl groups, but proton release studies suggest that 32% of the bound cobalt ions are involved in chelate complexes that contain both the carboxyl and the amine groups. All of the bound cobalt ions can thus be accounted for in terms of inner sphere complexes with the phosphodiester group or the carboxyl group. They suggest that the unidentate inner-sphere complex between cobalt and the carboxyl group of phosphatidylserine and the inner-sphere complex between cobalt and the phosphodiester group of phosphatidylserine provide reasonable models for complexes between alkaline earth cations and phosphatidylserine membranes.

  13. Phosphorus-31 and carbon-13 nuclear magnetic resonance studies of divalent cation binding to phosphatidylserine membranes: use of cobalt as a paramagnetic probe

    SciTech Connect

    McLaughlin, A.C.

    1982-09-28

    The paramagnetic divalent cation cobalt has large and well-understood effects on NMR signals from ligands bound in the first coordination sphere, i.e., inner-sphere ligands, and we have used these effects to identify divalent cation binding sites at the surface of phosphatidylserine membranes. /sup 31/P NMR results show that 13% of the bound cobalt ions are involved in inner-sphere complexes with the phosphodiester group, while /sup 13/C NMR results show that 54% of the bound cobalt ions are involved in unidentate inner sphere complexes with the carboxyl group. No evidence is found for cobalt binding to the carbonyl groups, but proton release studies suggest that 32% of the bound cobalt ions are involved in chelate complexes that contain both the carboxyl and the amine groups. All (i.e., 13% + 54% + 32% = 99%) of the bound cobalt ions can thus be accounted for in terms of inner sphere complexes with the phosphodiester group or the carboxyl group. We suggest that the unidentate inner-sphere complex between cobalt and the carboxyl group of phosphatidylserine and the inner-sphere complex between cobalt and the phosphodiester group of phosphatidylserine provide reasonable models for complexes between alkaline earth cations and phosphatidylserine membranes.

  14. Immiscible phase nucleic acid purification eliminates PCR inhibitors with a single pass of paramagnetic particles through a hydrophobic liquid.

    PubMed

    Sur, Kunal; McFall, Sally M; Yeh, Emilie T; Jangam, Sujit R; Hayden, Mark A; Stroupe, Stephen D; Kelso, David M

    2010-09-01

    Extraction and purification of nucleic acids from complex biological samples for PCR are critical steps because inhibitors must be removed that can affect reaction efficiency and the accuracy of results. This preanalytical processing generally involves capturing nucleic acids on microparticles that are then washed with a series of buffers to desorb and dilute out interfering substances. We have developed a novel purification method that replaces multiple wash steps with a single pass of paramagnetic particles (PMPs) though an immiscible hydrophobic liquid. Only two aqueous solutions are required: a lysis buffer, in which nucleic acids are captured on PMPs, and an elution buffer, in which they are released for amplification. The PMPs containing the nucleic acids are magnetically transported through a channel containing liquid wax that connects the lysis chamber to the elution chamber in a specially designed cartridge. Transporting PMPs through the immiscible phase yielded DNA and RNA as pure as that obtained after extensive wash steps required by comparable purification methods. Our immiscible-phase process has been applied to targets in whole blood, plasma, and urine and will enable the development of faster and simpler purification systems.

  15. Axially uniform magnetic field-modulation excitation for electron paramagnetic resonance in rectangular and cylindrical cavities by slot cutting

    NASA Astrophysics Data System (ADS)

    Sidabras, Jason W.; Richie, James E.; Hyde, James S.

    2017-01-01

    In continuous-wave (CW) Electron Paramagnetic Resonance (EPR) a low-frequency time-harmonic magnetic field, called field modulation, is applied parallel to the static magnetic field and incident on the sample. Varying amplitude of the field modulation incident on the sample has consequences on spectral line-shape and line-height over the axis of the sample. Here we present a method of coupling magnetic field into the cavity using slots perpendicular to the sample axis where the slot depths are designed in such a way to produce an axially uniform magnetic field along the sample. Previous literature typically assumes a uniform cross-section and axial excitation due to the wavelength of the field modulation being much larger than the cavity. Through numerical analysis and insights obtained from the eigenfunction expansion of dyadic Green's functions, it is shown that evanescent standing-wave modes with complex cross-sections are formed within the cavity. From this analysis, a W-band (94 GHz) cylindrical cavity is designed where modulation slots are optimized to present a uniform 100 kHz field modulation over the length of the sample.

  16. Axially uniform magnetic field-modulation excitation for electron paramagnetic resonance in rectangular and cylindrical cavities by slot cutting.

    PubMed

    Sidabras, Jason W; Richie, James E; Hyde, James S

    2017-01-01

    In continuous-wave (CW) Electron Paramagnetic Resonance (EPR) a low-frequency time-harmonic magnetic field, called field modulation, is applied parallel to the static magnetic field and incident on the sample. Varying amplitude of the field modulation incident on the sample has consequences on spectral line-shape and line-height over the axis of the sample. Here we present a method of coupling magnetic field into the cavity using slots perpendicular to the sample axis where the slot depths are designed in such a way to produce an axially uniform magnetic field along the sample. Previous literature typically assumes a uniform cross-section and axial excitation due to the wavelength of the field modulation being much larger than the cavity. Through numerical analysis and insights obtained from the eigenfunction expansion of dyadic Green's functions, it is shown that evanescent standing-wave modes with complex cross-sections are formed within the cavity. From this analysis, a W-band (94GHz) cylindrical cavity is designed where modulation slots are optimized to present a uniform 100kHz field modulation over the length of the sample. Copyright © 2016 Elsevier Inc. All rights reserved.

  17. Investigation of Antioxidant Activity of Pomegranate Juices by Means of Electron Paramagnetic Resonance and UV-Vis Spectroscopy.

    PubMed

    Kozik, Violetta; Jarzembek, Krystyna; Jędrzejowska, Agnieszka; Bąk, Andrzej; Polak, Justyna; Bartoszek, Mariola; Pytlakowska, Katarzyna

    2015-01-01

    Pomegranate fruit (Punica granatum L.) is a source of numerous phenolic compounds, and it contains flavonoids such as anthocyanins, anthocyanidins, cyanidins, catechins and other complexes of flavonoids, ellagitannins, and hydrolyzed tannins. Pomegranate juice shows antioxidant, antiproliferative, and anti-atherosclerotic properties. The antioxidant capacity (TEAC) of the pomegranate juices was measured using electron paramagnetic resonance (EPR) spectroscopy and 1,1-diphenyl-2-picrylhydrazyl (DPPH•) as a source of free radicals, and the total phenolic (TP) content was measured using UV-Vis spectroscopy. All the examined pomegranate juices exhibited relatively high antioxidant properties. The TEAC values determined by means of EPR spectroscopy using Trolox (TE) as a free radical scavenger were in the range of 463.12 to 1911.91 μmol TE/100 mL juice. The TP content measured by the Folin-Ciocalteu method, using gallic acid (GA) as a free radical scavenger, widely varied in the investigated pomegranate juice samples and ranged from 1673.62 to 5263.87 mg GA/1 L juice. The strongest antioxidant properties were observed with the fresh pomegranate juices obtained from the fruits originating from Israel, Lebanon, and Azerbaijan. Correlation analysis of numerical data obtained by means of EPR spectroscopy (TEAC) and UV-Vis spectroscopy (TP) gave correlation coefficient (r)=0.90 and determination coefficient (r2)=0.81 (P<0.05).

  18. One and Two Dimensional Pulsed Electron Paramagnetic Resonance Studies of in vivo Vanadyl Coordination in Rat Kidney

    PubMed Central

    Liboiron, Barry D.; Thompson, Katherine H.; Vera, Erika; Yuen, Violet G.; McNeill, John H.

    2003-01-01

    The biological fate of a chelated vanadium source is investigated by/n vivo spectroscopic methods to elucidate the chemical form in which the metal ion is accumulated. A pulsed electron paramagnetic resonance study of vanadyl ions in kidney tissue, taken from rats previously treated with bis(ethylmaltolato)oxovanadium(IV) (BEOV) in drinking water, is presented. A combined approach using stimulated echo (3-pulse) electron spin echo envelope modulation (ESEEM) and the two dimensional 4-pulse hyperfine sublevel correlation (HYSCORE) spectroscopies has shown that at least some of the VO2+ ions are involved in the coordination with nitrogen-containing ligands. From the experimental spectra, a 4N hyperfine coupling constant of 4.9 MHz and a quadrupole coupling constant of 0.6 + 0.04 MHz were determined, consistent with amine coordination of the vanadyl ions. Study of VO-histidine model complexes allowed for a determination of the percentage of nitrogen-coordinated VO2+ ions in the tissue sample that is found nitrogen-coordinated. By taking into account the bidentate nature of histidine coordination to VO2+ ions, a more accurate determination of this value is reported. The biological fate of chelated versus free (i.e. salts) vanadyl ion sources has been deduced by comparison to earlier reports. In contrast to its superior pharmacological efficacy over VOSO4, BEOV shares a remarkably similar biological fate after uptake into kidney tissue. PMID:18365044

  19. Electron Energy Structure and Electron Paramagnetic Resonance of Binuclear Niobium Molecules in Li-Nb Phosphate Glass Dielectrics

    NASA Astrophysics Data System (ADS)

    Arrington-Peet, Sabrina

    2005-03-01

    Electron paramagnetic resonance (EPR) spectra of Nb4+ ions in lithium-niobium phosphate glass insulators with different composition of oxide components have been studied. The EPR data reveal formation of triplet Nb binuclear complex in Li-Nb glass dielectric. Equilibrium atomic geometries of a model molecule (OH)3-Nb-O-Nb-(OH)3 embedded into Li-Nb phosphate glass are determined by molecular dynamics. The total energy and electron energy structure of the system have been studied by first principles generalized gradient approximation (GGA) method within density functional theory (DFT). Molecular geometry in substantially distorted as a result of external potential of the glass. Total energy analysis of the (OH)3-Nb-O-Nb-(OH)3 molecule embedded into Li-Nb phosphate glass indicates appearance of two non-equivalent atomic geometries with the oxygen atom in --Nb-O-Nb- fragment shifted from its undisturbed symmetrical position. Predicted modifications of electron energy structure of the system are discussed in comparison with measured EPR data.

  20. Paramagnetic-based NMR restraints lift residual dipolar coupling degeneracy in multidomain detergent-solubilized membrane proteins.

    PubMed

    Shi, Lei; Traaseth, Nathaniel J; Verardi, Raffaello; Gustavsson, Martin; Gao, Jiali; Veglia, Gianluigi

    2011-02-23

    Residual dipolar couplings (RDCs) are widely used as orientation-dependent NMR restraints to improve the resolution of the NMR conformational ensemble of biomacromolecules and define the relative orientation of multidomain proteins and protein complexes. However, the interpretation of RDCs is complicated by the intrinsic degeneracy of analytical solutions and protein dynamics that lead to ill-defined orientations of the structural domains (ghost orientations). Here, we illustrate how restraints from paramagnetic relaxation enhancement (PRE) experiments lift the orientational ambiguity of multidomain membrane proteins solubilized in detergent micelles. We tested this approach on monomeric phospholamban (PLN), a 52-residue membrane protein, which is composed of two helical domains connected by a flexible loop. We show that the combination of classical solution NMR restraints (NOEs and dihedral angles) with RDC and PRE constraints resolves topological ambiguities, improving the convergence of the PLN structural ensemble and giving the depth of insertion of the protein within the micelle. The combination of RDCs with PREs will be necessary for improving the accuracy and precision of membrane protein conformational ensembles, where three-dimensional structures are dictated by interactions with the membrane-mimicking environment rather than compact tertiary folds common in globular proteins.

  1. Paramagnetic and diamagnetic pair-breaking effect in electric-field-induced surface superconductivity under parallel magnetic fields

    NASA Astrophysics Data System (ADS)

    Ichioka, Masanori; Nabeta, Masahiro; Tanaka, Kenta K.; Onari, Seiichiro

    2017-07-01

    Electric-field-induced surface superconductivity is studied by Bogoliubov-de Gennes equation under magnetic fields parallel to the surface. We estimate the pair-breaking effects by the paramagnetic Zeeman shift and by diamagnetic screening current. We find that the depth dependences of pair potential, screening current, spin current, and paramagnetic moment under the magnetic fields reflect the multi-gap superconductivity in the sub-band structure.

  2. Electron Paramagnetic Resonance: a tool for in situ detection, imaging and dating of biosignatures in primitive organic matter

    NASA Astrophysics Data System (ADS)

    Gourier, D.; Binet, L.; Vezin, H.

    2012-04-01

    Electron Paramagnetic Resonance (EPR) spectroscopy and imaging are based on the interaction of a microwave electromagnetic field (typically in the GHz range) with electron spins in presence of an external magnetic field. Contrary to UV-visible and Infrared light, microwave radiation can penetrate in most non conducting materials, so that EPR is sensitive to the bulk (and not to the surface) of samples. All the paramagnetic defects, impurities, point defects in the mineral matrix, radicals in carbonaceous matter of an ancient rock can be detected by this technique. As the most ancient traces of life, as old as 3.5 Gy, are recorded as carbonaceous microstructures in siliceous sedimentary structures (cherts), the radical defects of these microstructures can be probed in situ without sample preparation. By using continuous-wave EPR, the fossilized carbonaceous matter can be mapped at the sub-millimeter scale (EPR imaging)[1], and can be dated with respect to the host rock (evolution of the EPR lineshape)[2]. Thus this method could be used for contamination detection (endolithic bacteria, infiltration etc…). By using pulsed-EPR spectroscopy (instead of continuous wave), nuclear magnetic transitions of elements in and around radicals can be detected with a high resolution and sensitivity. We show that specific nuclear transitions for hydrogen (1H and 2D) and 13C (and other nuclei such as 29Si and 31P) can be identified in extraterrestrial carbonaceous matter (meteorites) and in Precambrian and younger cherts. These pulsed techniques provide molecular scale biosignatures for primitive life detection and internal probes to study the history of organic matter in the early solar system [3,4]. Paramagnetic biosignatures are not limited to the organic component of cherts. Specific EPR biosignatures of metal ions can be detected in biominerals such as MnO2 [5] or in molecular V4+ complexes [6]. EPR is thus a potential technique for the search of primitive life on Earth and

  3. Two-dimensional NMR measurement and point dipole model prediction of paramagnetic shift tensors in solids

    SciTech Connect

    Walder, Brennan J.; Davis, Michael C.; Grandinetti, Philip J.; Dey, Krishna K.; Baltisberger, Jay H.

    2015-01-07

    A new two-dimensional Nuclear Magnetic Resonance (NMR) experiment to separate and correlate the first-order quadrupolar and chemical/paramagnetic shift interactions is described. This experiment, which we call the shifting-d echo experiment, allows a more precise determination of tensor principal components values and their relative orientation. It is designed using the recently introduced symmetry pathway concept. A comparison of the shifting-d experiment with earlier proposed methods is presented and experimentally illustrated in the case of {sup 2}H (I = 1) paramagnetic shift and quadrupolar tensors of CuCl{sub 2}⋅2D{sub 2}O. The benefits of the shifting-d echo experiment over other methods are a factor of two improvement in sensitivity and the suppression of major artifacts. From the 2D lineshape analysis of the shifting-d spectrum, the {sup 2}H quadrupolar coupling parameters are 〈C{sub q}〉 = 118.1 kHz and 〈η{sub q}〉 = 0.88, and the {sup 2}H paramagnetic shift tensor anisotropy parameters are 〈ζ{sub P}〉 = − 152.5 ppm and 〈η{sub P}〉 = 0.91. The orientation of the quadrupolar coupling principal axis system (PAS) relative to the paramagnetic shift anisotropy principal axis system is given by (α,β,γ)=((π)/2 ,(π)/2 ,0). Using a simple ligand hopping model, the tensor parameters in the absence of exchange are estimated. On the basis of this analysis, the instantaneous principal components and orientation of the quadrupolar coupling are found to be in excellent agreement with previous measurements. A new point dipole model for predicting the paramagnetic shift tensor is proposed yielding significantly better agreement than previously used models. In the new model, the dipoles are displaced from nuclei at positions associated with high electron density in the singly occupied molecular orbital predicted from ligand field theory.

  4. A study on Si / Al 2 O 3 paramagnetic point defects

    NASA Astrophysics Data System (ADS)

    Kühnhold-Pospischil, S.; Saint-Cast, P.; Hofmann, M.; Weber, S.; Jakes, P.; Eichel, R.-A.; Granwehr, J.

    2016-11-01

    In this contribution, negative charges and electronic traps related to the Si / Al 2 O 3 interface were measured and related to paramagnetic point defects and molecular vibrations. To this end, contactless capacitance voltage measurements, X-band electron paramagnetic resonance (EPR), and infrared spectroscopy were carried out, and their results were compared. A change in the negative charge density and electron trap density at the Si / Al 2 O 3 interface was achieved by adding a thermally grown SiO 2 layer with varying thicknesses and conducting an additional temperature treatment. Using EPR, five paramagnetic moments were detected in Si / ( SiO 2 ) / Al 2 O 3 samples with g values of g 1 = 2.0081 ± 0.0002 , g 2 = 2.0054 ± 0.0002 , g 3 = 2.0003 ± 0.0002 , g 4 = 2.0026 ± 0.0002 , and g 5 = 2.0029 ± 0.0002 . Variation of the Al 2 O 3 layer thickness shows that paramagnetic species associated with g1, g2, and g3 are located at the Si / Al 2 O 3 interface, and those with g4 and g5 are located within the bulk Al 2 O 3 . Furthermore, g1, g2, and g3 were shown to originate from oxygen plasma exposure during Al 2 O 3 deposition. Comparing the g values and their location within the Si / Al 2 O 3 system, g1 and g3 can be attributed to P b 0 centers, g3 to Si dangling bonds (Si-dbs), and g4 and g5 to rotating methyl radicals. All paramagnetic moments observed in this contribution disappear after a 5-min temperature treatment at 450 ° C . The deposition of an additional thermal SiO 2 layer between the Si and the Al 2 O 3 decreases the negative fixed charge density and defect density by about one order of magnitude. In this contribution, these changes can be correlated with a decrease in amplitude of the Si-db signal. P b 0 and the methyl radical signals were less affected by this additional SiO 2 layer. Based on these observations, microscopic models for the negative fixed charge density ( Q tot ) and the interface trap density ( D it ) and the connection between these

  5. Ferromagnetic, dia-/paramagnetic and superparamagnetic components of Aral Sea sediments: significance for paleoenvironmental reconstruction

    NASA Astrophysics Data System (ADS)

    Kosareva, Lina; Nourgaliev, Danis; Kuzina, Dilyara; Spassov, Simo; Fattakhova, Leysan

    2015-04-01

    Modern lake sediments are a unique source of information for climate changes, regionally and globally, because all environmental variations are recorded by these sediments with high resolution. Magnetic minerals are hereby of particular interest, because they occur almost in any environment, because they are susceptible tracing environmental changes, which are closely related to their formation conditions, and because magnetic mineral concentrations in the ppm range can be detected. Our goal is to decipher the magnetic susceptibility signal in lake sediments by decomposing the bulk susceptibility signal of a lake sediment sequence into ferromagnetic (χf), dia-/paramagnetic (χp) and superparamagnetic (χsp) components. Each of these has a different origin: paramagnetic minerals are usually attributed to terrigenous sediment input, ferromagnetics are of biogenic origin, and superparamagnetic minerals may be of either biogenic or terrigenous origin. In sediments, paramagnetic components contribute most to the bulk susceptibility signal, because the ferromagnetic contributions are low. Most sediments of modern lakes contain a lot of organic material and water, which are both diamagnetic. High-field susceptibility changes reflect thus changes in terrigenous input. The latter increases with precipitation which augments the influx of terrigenous material carried by rivers into the lake, consequently the susceptibility increases sharply. However, under certain conditions, such for instance during shrinking water table or withering of tributaries, the lake biota grows stronger and the bacterial activity, including magnetotactic bacteria, increases. This results in an enhanced ferromagnetic component (χf). Superparamagnetic (SP) components may also be formed, but their magnetic grain size is much smaller, i.e. in the order of about 30-40 nm. This abstract presents a new method to discriminate and to quantify the contribution of dia- and paramagnetic, ferromagnetic and

  6. Accurate structure and dynamics of the metal-site of paramagnetic metalloproteins from NMR parameters using natural bond orbitals.

    PubMed

    Hansen, D Flemming; Westler, William M; Kunze, Micha B A; Markley, John L; Weinhold, Frank; Led, Jens J

    2012-03-14

    A natural bond orbital (NBO) analysis of unpaired electron spin density in metalloproteins is presented, which allows a fast and robust calculation of paramagnetic NMR parameters. Approximately 90% of the unpaired electron spin density occupies metal-ligand NBOs, allowing the majority of the density to be modeled by only a few NBOs that reflect the chemical bonding environment. We show that the paramagnetic relaxation rate of protons can be calculated accurately using only the metal-ligand NBOs and that these rates are in good agreement with corresponding rates measured experimentally. This holds, in particular, for protons of ligand residues where the point-dipole approximation breaks down. To describe the paramagnetic relaxation of heavy nuclei, also the electron spin density in the local orbitals must be taken into account. Geometric distance restraints for (15)N can be derived from the paramagnetic relaxation enhancement and the Fermi contact shift when local NBOs are included in the analysis. Thus, the NBO approach allows us to include experimental paramagnetic NMR parameters of (15)N nuclei as restraints in a structure optimization protocol. We performed a molecular dynamics simulation and structure determination of oxidized rubredoxin using the experimentally obtained paramagnetic NMR parameters of (15)N. The corresponding structures obtained are in good agreement with the crystal structure of rubredoxin. Thus, the NBO approach allows an accurate description of the geometric structure and the dynamics of metalloproteins, when NMR parameters are available of nuclei in the immediate vicinity of the metal-site.

  7. Electron paramagnetic resonance and ultraviolet/visible study of compounds I and II in the horseradish peroxidase-H 2O 2-silk fiber reaction system

    NASA Astrophysics Data System (ADS)

    Oliva, C.; Freddi, G.; Repetto, S.; D'Ambrosio, A.

    2003-06-01

    The enzymatic oxidation of silk with H2O2 in the presence of horseradish peroxidase (HRP) has been investigated. Two intermediate complexes have been observed during this reaction. Both can be attributed to Fe4+ ions axially bonded to an oxygen atom and to a porphyrin radical (Prad ). In the most unstable of them, indicated as compound II, the chemical bond between [FeIVO]2+ and Prad was weaker than in the other, indicated as compound I. The former compound disappeared within 1 h of the reaction, at difference with the latter, traces of which were observed even after 3 weeks with dried samples. However, the chemical bond between [FeIVO]2+ and Prad in compound I weakened during the sample ageing. All these phenomena have been enlightened by electron paramagnetic resonance (EPR) and spectrophotometric ultraviolet/visible (UV/Vis) measurements.

  8. Differential effects of cholesterol on acyl chain order in erythrocyte membranes as a function of depth from the surface. An electron paramagnetic resonance (EPR) spin label study.

    PubMed

    Cassera, M B; Silber, A M; Gennaro, A M

    2002-10-16

    The purpose of this work is to analyze the effects of cholesterol modulation on acyl chain ordering in the membrane of human erythrocytes as a function of depth from the surface. Partial cholesterol depletion was achieved by incubation of erythrocytes with liposomes containing saturated phospholipids, or with methyl-beta-cyclodextrin (MbetaCD). Cholesterol enrichment was achieved by incubation with liposomes formed by phospholipids/cholesterol, or with the complex MbetaCD/cholesterol. Acyl chain order was studied with electron paramagnetic resonance spectroscopy (EPR) using spin labels that sense the lipid bilayer at different depths. It is shown that the increase in cholesterol stiffens acyl chains but decreases the interaction among lipid headgroups, while cholesterol depletion causes the opposite behavior. It is likely that the observed cholesterol effects are related to those stabilizing the cholesterol-rich detergent-insoluble membrane domains (rafts), recently shown to exist in erythrocytes.

  9. Temperature dependence of contact and dipolar NMR chemical shifts in paramagnetic molecules

    SciTech Connect

    Martin, Bob; Autschbach, Jochen

    2015-02-07

    Using a recently proposed equation for NMR nuclear magnetic shielding for molecules with unpaired electrons [A. Soncini and W. Van den Heuvel, J. Chem. Phys. 138, 021103 (2013)], equations for the temperature (T) dependent isotropic shielding for multiplets with an effective spin S equal to 1/2, 1, 3/2, 2, and 5/2 in terms of electron paramagnetic resonance spin Hamiltonian parameters are derived and then expanded in powers of 1/T. One simplifying assumption used is that a matrix derived from the zero-field splitting (ZFS) tensor and the Zeeman coupling matrix (g-tensor) share the same principal axis system. The influence of the rhombic ZFS parameter E is only investigated for S = 1. Expressions for paramagnetic contact shielding (from the isotropic part of the hyperfine coupling matrix) and pseudo-contact or dipolar shielding (from the anisotropic part of the hyperfine coupling matrix) are considered separately. The leading order is always 1/T. A temperature dependence of the contact shielding as 1/T and of the dipolar shielding as 1/T{sup 2}, which is sometimes assumed in the assignment of paramagnetic chemical shifts, is shown to arise only if S ≥ 1 and zero-field splitting is appreciable, and only if the Zeeman coupling matrix is nearly isotropic (Δg = 0). In such situations, an assignment of contact versus dipolar shifts may be possible based only on linear and quadratic fits of measured variable-temperature chemical shifts versus 1/T. Numerical data are provided for nickelocene (S = 1). Even under the assumption of Δg = 0, a different leading order of contact and dipolar shifts in powers of 1/T is not obtained for S = 3/2. When Δg is not very small, dipolar and contact shifts both depend in leading order in 1/T in all cases, with sizable contributions in order 1/T{sup n} with n = 2 and higher.

  10. Paramagnetic Defects in Electron-Irradiated Yttria-Stabilized Zirconia: Effect of Yttria Content

    SciTech Connect

    Costantini, Jean-Marc; Beuneu, Francois; Morrison-Smith, Sarah; Devanathan, Ram; Weber, William J

    2011-01-01

    We have studied the effect of the yttria content on the paramagnetic centres in electron-irradiated yttria-stabilized zirconia (ZrO2: Y3+) or YSZ. Single crystals with 9.5 mol% or 18 mol% Y2O3 were irradiated with electrons of 1.0, 1.5, 2.0 and 2.5 MeV. The paramagnetic centre production was studied by X-band EPR spectroscopy. The same paramagnetic centres were identified for both chemical compositions, namely two electron centres, i.e. i) F+-type centres (involving singly ionized oxygen vacancies), and ii) so-called T centres (Zr3+ in a trigonal symmetry site), and hole-centres. A strong effect is observed on the production of hole-centres which are strongly enhanced when doubling the yttria content. However, no striking effect is found on the electron centres (except the enhancement of an extra line associated to the F+-type centres). It is concluded that hole-centres are produced by inelastic interactions, whereas F+-type centres are produced by elastic collisions with no effect of the yttria content on the defect production rate. In the latter case, the threshold displacement energy (Ed) of oxygen is estimated from the electron-energy dependence of the F+-type centre production rate, with no significant effect of the yttria content on Ed. An Ed value larger than 120 eV is found. Accordingly, classical molecular dynamics (MD) simulations with a Buckingham-type potential show that Ed values for Y and O are likely to be in excess of 200 eV. Due to the difficulty in displacing O or Y atoms, the radiation-induced defects may alternatively be a result of Zr atom displacements for Ed = 80 1 eV with subsequent defect re-arrangement.

  11. Curie-type paramagnetic NMR relaxation in the aqueous solution of Ni(II).

    PubMed

    Mareš, Jiří; Hanni, Matti; Lantto, Perttu; Lounila, Juhani; Vaara, Juha

    2014-04-21

    Ni(2+)(aq) has been used for many decades as a model system for paramagnetic nuclear magnetic resonance (pNMR) relaxation studies. More recently, its magnetic properties and also nuclear magnetic relaxation rates have been studied computationally. We have calculated electron paramagnetic resonance and NMR parameters using quantum-mechanical (QM) computation of molecular dynamics snapshots, obtained using a polarizable empirical force field. Statistical averages of hyperfine coupling, g- and zero-field splitting tensors, as well as the pNMR shielding terms, are compared to the available experimental and computational data. In accordance with our previous work, the isotropic hyperfine coupling as well as nuclear shielding values agree well with experimental measurements for the (17)O nuclei of water molecules in the first solvation shell of the nickel ion, whereas larger deviations are found for (1)H centers. We report, for the first time, the Curie-type contribution to the pNMR relaxation rate using QM calculations together with Redfield relaxation theory. The Curie relaxation mechanism is analogous to chemical shift anisotropy relaxation, well-known in diamagnetic NMR. Due to the predominance of other types of paramagnetic relaxation mechanisms for this system, it is possible to extract the Curie term only computationally. The Curie mechanism alone would result in around 16 and 20 s(-1) of relaxation rates (R1 and R2 respectively) for the (1)H nuclei of water molecules bonded to the Ni(2+) center, in a magnetic field of 11.7 T. The corresponding (17)O relaxation rates are around 33 and 38 s(-1). We also report the Curie contribution to the relaxation rate for molecules beyond the first solvation shell in a 1 M solution of Ni(2+) in water.

  12. Electron paramagnetic resonance study of ZnAl(2)S(4) spinel.

    PubMed

    Güner, S; Yıldız, F; Rameev, B; Aktaş, B

    2005-06-29

    Single crystals of ZnAl(2)S(4) spinel doped by paramagnetic Cr(3+) and Mn(2+) ions have been studied by the electron paramagnetic resonance (EPR) technique. The crystal field symmetry around the impurity ions has been determined from the angular behaviour of X-band EPR spectra. The anisotropic EPR signal of the Cr(3+) ions shows splitting into 31 narrow lines due to the super-hyperfine interaction between unpaired electron spins of the chromium centres and nuclear spins of six neighbouring Al(27) (I = 5/2) ions. It has been established that the Cr(3+) ions are located at the octahedral sites in the spinel structure, and the super-hyperfine interaction results from a weak covalent bounding with the Al atoms. The EPR signals of the Cr(3+) paramagnetic centres show no fine-structure splitting due to a perfectly cubic symmetry of the local crystal field in the octahedral sites of the ZnAl(2)S(4) spinel structure. A weak EPR signal consisting of six components has been ascribed to the transitions between hyperfine levels of the Mn(2+) (I = 5/2,S = 5/2) ions located at tetrahedral sites, while the fine-structure splitting of each component could be resolved only for special orientations of the sample in the external magnetic field. The parameters of the EPR signal of both chromium and manganese centres indicate that there is an essential covalence in the ZnAl(2)S(4) spinel crystal. Very narrow linewidths (∼2 Oe) of the Cr(3+) EPR signal components point to very high homogeneity and quality of the ZnAl(2)S(4) crystals.

  13. Paramagnetic defects in electron-irradiated yttria-stabilized zirconia: Effect of yttria content

    SciTech Connect

    Costantini, Jean-Marc; Beuneu, Francois; Morrison-Smith, Sarah E.; Devanathan, Ramaswami; Weber, William J.

    2011-12-20

    We have studied the effect of the yttria content on the paramagnetic centres in electron-irradiated yttria-stabilized zirconia (ZrO2: Y3+) or YSZ. Single crystals with 9.5 mol% or 18 mol% Y2O3 were irradiated with electrons of 1.0, 1.5, 2.0 and 2.5 MeV. The paramagnetic centre production was studied by X-band EPR spectroscopy. The same paramagnetic centres were identified for both chemical compositions, namely two electron centres, i.e. i) F+-type centres (involving singly ionized oxygen vacancies), and ii) so-called T centres (Zr3+ in a trigonal symmetry site), and hole-centres. A strong effect is observed on the production of hole-centres which are strongly enhanced when doubling the yttria content. However, no striking effect is found on the electron centres (except the enhancement of an extra line associated to the F+-type centres). It is concluded that hole-centres are produced by inelastic interactions, whereas F+-type centres are produced by elastic collisions with no effect of the yttria content on the defect production rate. In the latter case, the threshold displacement energy (Ed) of oxygen is estimated from the electron-energy dependence of the F+-type centre production rate, with no significant effect of the yttria content on Ed. An Ed value larger than 120 eV is found. Accordingly, classical molecular dynamics (MD) simulations with a Buckingham-type potential show that Ed values for Y and O are likely to be in excess of 200 eV. It is concluded that F+-type centres might be actually oxygen divacancies (F2+-type centres). Due to the difficulty in displacing O or Y atoms, the radiation-induced defects may alternatively be a result of Zr atom displacements for Ed = 80 ± 1 eV with subsequent defect re-arrangement.

  14. Sorption selectivity in natural organic matter studied with nitroxyl paramagnetic relaxation probes.

    PubMed

    Lattao, Charisma; Cao, Xiaoyan; Li, Yuan; Mao, Jingdong; Schmidt-Rohr, Klaus; Chappell, Mark A; Miller, Lesley F; dela Cruz, Albert Leo; Pignatello, Joseph J

    2012-12-04

    Sorption site selectivity and mechanism in natural organic matter (NOM) were addressed spectroscopically by the sorption of paramagnetic nitroxyl compounds (spin probes) of different polarity, TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) and HTEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl). The sorbents were Pahokee peat, Beulah-Zap lignite, and a polystyrene-poly(vinyl methyl ether) (PS-PVME) polymer blend representing the mixed aliphatic-aromatic, polar-nonpolar character of NOM. Nuclear-electron spin interaction serves as an efficient relaxation pathway, resulting in attenuation of the (13)C-CP/TOSS NMR signal for (13)C nuclei in proximity to the N-O· group (r(-6) dependence). In the natural solids the spin probes sorbed more specifically (greater isotherm nonlinearity) and had lower rotational mobility (broader electron paramagnetic resonance signals) than in PS-PVME. Titration with spin probe indicated almost no selectivity for the different carbon functional groups of PS-PVME, and little to no selectivity for the different carbon moieties of Pahokee and Beulah, including aromatic, alkyl, O-alkyl, di-O-alkyl, and O-methyl. In any case, sorption site selectivity of spin probes to NOM was always weaker than partition selectivity found in model solvent-water (toluene, hexadecane, anisole, octanol) and cellulose-water systems. The results indicate little or no preferential sorption in NOM based on functional group chemistry or putative microdomain character, but rather are consistent with the filling of pores whose walls have an average chemical environment reflecting the bulk chemical composition of the solid. This work demonstrates for the first time the use of paramagnetic probes to study sorption specificity.

  15. Saturation-recovery electron paramagnetic resonance discrimination by oxygen transport (DOT) method for characterizing membrane domains.

    PubMed

    Subczynski, Witold K; Widomska, Justyna; Wisniewska, Anna; Kusumi, Akihiro

    2007-01-01

    The discrimination by oxygen transport (DOT) method is a dual-probe saturation-recovery electron paramagnetic resonance approach in which the observable parameter is the spin-lattice relaxation time (T1) of lipid spin labels, and the measured value is the bimolecular collision rate between molecular oxygen and the nitroxide moiety of spin labels. This method has proven to be extremely sensitive to changes in the local oxygen diffusion-concentration product (around the nitroxide moiety) because of the long T1 of lipid spin labels (1-10 micros) and also because molecular oxygen is a unique probe molecule. Molecular oxygen is paramagnetic, small, and has the appropriate level of hydrophobicity that allows it to partition into various supramolecular structures such as different membrane domains. When located in two different membrane domains, the spin label alone most often cannot differentiate between these domains, giving very similar (indistinguishable) conventional electron paramagnetic resonance spectra and similar T1 values. However, even small differences in lipid packing in these domains will affect oxygen partitioning and oxygen diffusion, which can be easily detected by observing the different T1s from spin labels in these two locations in the presence of molecular oxygen. The DOT method allows one not only to distinguish between the different domains, but also to obtain the value of the oxygen diffusion-concentration product in these domains, which is a useful physical characteristic of the organization of lipids in domains. Profiles of the oxygen diffusion-concentration product (the oxygen transport parameter) in coexisting domains can be obtained in situ without the need for the physical separation of the two domains. Furthermore, under optimal conditions, the exchange rate of spin-labeled molecules between the two domains could be measured.

  16. Temperature dependence of contact and dipolar NMR chemical shifts in paramagnetic molecules.

    PubMed

    Martin, Bob; Autschbach, Jochen

    2015-02-07

    Using a recently proposed equation for NMR nuclear magnetic shielding for molecules with unpaired electrons [A. Soncini and W. Van den Heuvel, J. Chem. Phys. 138, 021103 (2013)], equations for the temperature (T) dependent isotropic shielding for multiplets with an effective spin S equal to 1/2, 1, 3/2, 2, and 5/2 in terms of electron paramagnetic resonance spin Hamiltonian parameters are derived and then expanded in powers of 1/T. One simplifying assumption used is that a matrix derived from the zero-field splitting (ZFS) tensor and the Zeeman coupling matrix (g-tensor) share the same principal axis system. The influence of the rhombic ZFS parameter E is only investigated for S = 1. Expressions for paramagnetic contact shielding (from the isotropic part of the hyperfine coupling matrix) and pseudo-contact or dipolar shielding (from the anisotropic part of the hyperfine coupling matrix) are considered separately. The leading order is always 1/T. A temperature dependence of the contact shielding as 1/T and of the dipolar shielding as 1/T(2), which is sometimes assumed in the assignment of paramagnetic chemical shifts, is shown to arise only if S ≥ 1 and zero-field splitting is appreciable, and only if the Zeeman coupling matrix is nearly isotropic (Δg = 0). In such situations, an assignment of contact versus dipolar shifts may be possible based only on linear and quadratic fits of measured variable-temperature chemical shifts versus 1/T. Numerical data are provided for nickelocene (S = 1). Even under the assumption of Δg = 0, a different leading order of contact and dipolar shifts in powers of 1/T is not obtained for S = 3/2. When Δg is not very small, dipolar and contact shifts both depend in leading order in 1/T in all cases, with sizable contributions in order 1/T(n) with n = 2 and higher.

  17. Stopping paramagnetic supersonic beams: the advantage of a co-moving magnetic trap decelerator.

    PubMed

    Lavert-Ofir, Etay; David, Liron; Henson, Alon B; Gersten, Sasha; Narevicius, Julia; Narevicius, Edvardas

    2011-11-14

    The long standing goal of chemical physics is finding a convenient method to create slow and cold beams intense enough to observe chemical reactions in the temperature range of a few Kelvin. We present an extensive numerical analysis of our moving magnetic trap decelerator showing that a 3D confinement throughout the deceleration process enables deceleration of almost all paramagnetic particles within the original supersonic expansion to stopping velocities. We show that the phase space region containing the decelerating species is larger by two orders of magnitude as compared to other available deceleration methods.

  18. 3D Computational Modeling of Proteins Using Sparse Paramagnetic NMR Data.

    PubMed

    Pilla, Kala Bharath; Otting, Gottfried; Huber, Thomas

    2017-01-01

    Computational modeling of proteins using evolutionary or de novo approaches offers rapid structural characterization, but often suffers from low success rates in generating high quality models comparable to the accuracy of structures observed in X-ray crystallography or nuclear magnetic resonance (NMR) spectroscopy. A computational/experimental hybrid approach incorporating sparse experimental restraints in computational modeling algorithms drastically improves reliability and accuracy of 3D models. This chapter discusses the use of structural information obtained from various paramagnetic NMR measurements and demonstrates computational algorithms implementing pseudocontact shifts as restraints to determine the structure of proteins at atomic resolution.

  19. Condition for the appearance of a live magnetic layer on paramagnetic pure transition metals

    NASA Astrophysics Data System (ADS)

    Mokrani, A.; Demangeat, C.; Dreyssé, H.

    1990-12-01

    Self-consistent real-space calculations in the unrestricted Hartree-Fock approximation of the Hubbard Hamiltonian are performed for slabs of metallic systems with unfilled d shells in order to investigate a possible appearance of a live magnetic surface plane on paramagnetic bulk. These results can also be obtained qualitatively within a flat-band model, which gives a simple relation between the appearance of magnetism and the coordination number. Within this model, vanadium is shown to have a ferromagnetic surface plane, as observed experimentally.

  20. Macroscopic T nonconservation - Prospects for a new experiment. [magnetizing paramagnet by electric field

    NASA Technical Reports Server (NTRS)

    Bialek, W.; Moody, J.; Wilczek, F.

    1986-01-01

    Breakdown of time-reversal invariance can be detected in macroscopic samples as a magnetic alignment along an electric field. It is shown that both fundamental and practical limits to the detection of this effect in paramagnets correspond to measurement of electron electric dipole moments down to d(e) of about 10 to the -28th e cm on 50-g quantities of EuS near its Curie point; this compares to the current limit of d(e) not greater than 10 to the -24th e cm. Strategies for still greater sensitivity are outlined.

  1. Strong Paramagnetism of Gold Nanoparticles Deposited on a Sulfolobus acidocaldarius S Layer

    NASA Astrophysics Data System (ADS)

    Bartolomé, J.; Bartolomé, F.; García, L. M.; Figueroa, A. I.; Repollés, A.; Martínez-Pérez, M. J.; Luis, F.; Magén, C.; Selenska-Pobell, S.; Pobell, F.; Reitz, T.; Schönemann, R.; Herrmannsdörfer, T.; Merroun, M.; Geissler, A.; Wilhelm, F.; Rogalev, A.

    2012-12-01

    Magnetic properties of Au nanoparticles deposited on an archaeal S layer are reported. X-ray magnetic circular dichroism and superconducting quantum interference device magnetometries demonstrate that the particles are strongly paramagnetic, without any indication of magnetic blocking down to 16 mK. The average magnetic moment per particle is Mpart=2.36(7) μB. This contribution originates at the particle’s Au 5d band, in which an increased number of holes with respect to the bulk value is observed. The magnetic moment per Au atom is 25 times larger than any measured in other Au nanoparticles or any other configurations up to date.

  2. Strong paramagnetism of gold nanoparticles deposited on a Sulfolobus acidocaldarius S layer.

    PubMed

    Bartolomé, J; Bartolomé, F; García, L M; Figueroa, A I; Repollés, A; Martínez-Pérez, M J; Luis, F; Magén, C; Selenska-Pobell, S; Pobell, F; Reitz, T; Schönemann, R; Herrmannsdörfer, T; Merroun, M; Geissler, A; Wilhelm, F; Rogalev, A

    2012-12-14

    Magnetic properties of Au nanoparticles deposited on an archaeal S layer are reported. X-ray magnetic circular dichroism and superconducting quantum interference device magnetometries demonstrate that the particles are strongly paramagnetic, without any indication of magnetic blocking down to 16 mK. The average magnetic moment per particle is M(part)=2.36(7) μ(B). This contribution originates at the particle's Au 5d band, in which an increased number of holes with respect to the bulk value is observed. The magnetic moment per Au atom is 25 times larger than any measured in other Au nanoparticles or any other configurations up to date.

  3. Al-doped MgB2 materials studied using electron paramagnetic resonance and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Bateni, Ali; Erdem, Emre; Repp, Sergej; Weber, Stefan; Somer, Mehmet

    2016-05-01

    Undoped and aluminum (Al) doped magnesium diboride (MgB2) samples were synthesized using a high-temperature solid-state synthesis method. The microscopic defect structures of Al-doped MgB2 samples were systematically investigated using X-ray powder diffraction, Raman spectroscopy, and electron paramagnetic resonance. It was found that Mg-vacancies are responsible for defect-induced peculiarities in MgB2. Above a certain level of Al doping, enhanced conductive properties of MgB2 disappear due to filling of vacancies or trapping of Al in Mg-related vacancy sites.

  4. Low temperature electron paramagnetic resonance anomalies in Fe-based nanoparticles

    NASA Astrophysics Data System (ADS)

    Koksharov, Yu. A.; Gubin, S. P.; Kosobudsky, I. D.; Beltran, M.; Khodorkovsky, Y.; Tishin, A. M.

    2000-08-01

    A study of the electron paramagnetic resonance of Fe-based nanoparticles embedded in polyethylene matrix was performed as a function of temperature ranging from 3.5 to 500 K. Nanoparticles with a narrow size distribution were prepared by the high-velocity thermodestruction of iron-containing compounds. A temperature-driven transition from superparamagnetic to ferromagnetic resonance was observed for samples with different Fe content. The unusual behavior of the spectra at about 25 K is considered evidence of a spin-glass state in iron oxide nanoparticles.

  5. Search for an Axionlike Spin Coupling Using a Paramagnetic Salt with a dc SQUID

    NASA Astrophysics Data System (ADS)

    Ni, Wei-Tou; Pan, Sheau-Shi; Yeh, Hsien-Chi; Hou, Li-Shing; Wan, Juling

    1999-03-01

    We use a paramagnetic salt TbF3 with a dc SQUID to search for a possible axionlike σ˙r interaction of a rotating copper mass with the salt. We set new limits on the axion coupling constant gsgp/ħc and the finite-range Leitner-Okubo-Hari Dass coupling constant A. Our limit for range λ at 30 mm is 2 orders of magnitude better than previous results. For λ>30 mm, gsgp/ħc is \\(0.14+/-0.67\\)×10-28, and A is less than 10. The outlook for further improvement is discussed.

  6. Paramagnetic to antiferromagnetic transition in epitaxial tetragonal CuMnAs (invited)

    SciTech Connect

    Hills, V.; Wadley, P. Campion, R. P.; Beardsley, R.; Edmonds, K. W.; Gallagher, B. L.; Novak, V.; Ouladdiaf, B.; Jungwirth, T.

    2015-05-07

    In this paper, we use neutron scattering and electrical transport to investigate the paramagnetic to antiferromagnetic phase transition in tetragonal CuMnAs films on GaP(001). X-ray diffraction and cross-sectional transmission electron microscopy measurements show that the films are chemically ordered with high structural quality. The temperature dependence of the structurally forbidden (100) neutron scattering peak is used to determine the Néel temperature, T{sub N}. We then demonstrate the presence of a clear peak in the temperature derivative of the resistivity around T{sub N}. The effect of disorder-induced broadening on the shape of the peak is discussed.

  7. High-energy spin-density-wave correlated fluctuations in paramagnetic Cr + 5 at. % V

    SciTech Connect

    Werner, S.A.; Fawcett, E.; Elmiger, M.W.; Shirane, G.

    1992-11-01

    Measurements of the magnetic fluctuations, termed spin-density-wave (SDW) paramagnons, in the nearly antiferromagnetic alloy Cr + 5 at.%V are extended up in energy to about 80 MeV. These fluctuating spin-spin correlations occur at incommensurate positions, corresponding to the SDW wavevector Q. Their characteristic energy is at least an order of magnitude larger than that of the magnetic fluctuations seen in the paramagnetic phase of pure Cr, but their intensity is more than two orders of magnitude smaller. We find that the dynamic susceptibility decreases by about 50% between temperature T = 10K and 300K.

  8. High-energy spin-density-wave correlated fluctuations in paramagnetic Cr + 5 at. % V

    SciTech Connect

    Werner, S.A. . Dept. of Physics); Fawcett, E. . Dept. of Physics); Elmiger, M.W.; Shirane, G. )

    1992-01-01

    Measurements of the magnetic fluctuations, termed spin-density-wave (SDW) paramagnons, in the nearly antiferromagnetic alloy Cr + 5 at.%V are extended up in energy to about 80 MeV. These fluctuating spin-spin correlations occur at incommensurate positions, corresponding to the SDW wavevector Q. Their characteristic energy is at least an order of magnitude larger than that of the magnetic fluctuations seen in the paramagnetic phase of pure Cr, but their intensity is more than two orders of magnitude smaller. We find that the dynamic susceptibility decreases by about 50% between temperature T = 10K and 300K.

  9. Family of exactly solvable models with an ultimate quantum paramagnetic ground state.

    PubMed

    Schmidt, Kai Phillip; Laad, Mukul

    2010-06-11

    We present a family of two-dimensional frustrated quantum magnets solely based on pure nearest-neighbor Heisenberg interactions which can be solved quasiexactly. All lattices are constructed in terms of frustrated quantum cages containing a chiral degree of freedom protected by frustration. The ground states of these models are dubbed ultimate quantum paramagnets and exhibit an extensive entropy at zero temperature. We discuss the unusual and extensively degenerate excitations in such phases. Implications for thermodynamic properties as well as for decoherence free quantum computation are discussed.

  10. Thermally modulated photoacoustic imaging with super-paramagnetic iron oxide nanoparticles.

    PubMed

    Feng, Xiaohua; Gao, Fei; Zheng, Yuanjin

    2014-06-15

    Thermally modulated photoacoustic imaging (TMPI) is reported here for contrast enhancement when using nanoparticles as contrast agents. Exploiting the excellent sensitivity of the photoacoustic (PA) process on temperature and the highly selective heating capability of nanoparticles under electromagnetic field, the PA signals stemming from the nanoparticles labeled region can be efficiently modulated whereas those from highly light absorptive backgrounds are minimally affected. A coherent difference imaging procedure reduces the background signal and thus improves the imaging contrast. Phantom experiments with super-paramagnetic iron oxide nanoparticles (SPIONs) as contrast agents and alternating magnetic fields for heating are demonstrated. Further improvements toward clinical applications are also discussed.

  11. Nondestructive measurement of large objects with electron paramagnetic resonance: Pottery, sculpture, and jewel ornament

    NASA Astrophysics Data System (ADS)

    Ikeya, Motoji; Yamamoto, Masahiro; Ishii, Hiroshi

    1994-12-01

    A cylindicral cavity of TE111 mode with an aperture of 3 mm in diameter has been used to measure the electron paramagnetic resonance (EPR) spectrum of a large object placed over the aperture. EPR spectra of a precious fossil of a dinosaur tooth piece and a fossil bone of the Machikane Alligator were measured nondestructively in addition to a jadeite sculpture, a pearl and turquoise necklace, a large turmaline, a star ruby, and ceramic pottery. Thus, EPR can be a nondestructive tool to detect forgery and to test the authenticity in art as well as to allocate ancient objects in archaeological provenance study.

  12. Ordering of PCDTBT revealed by time-resolved electron paramagnetic resonance spectroscopy of its triplet excitons.

    PubMed

    Biskup, Till; Sommer, Michael; Rein, Stephan; Meyer, Deborah L; Kohlstädt, Markus; Würfel, Uli; Weber, Stefan

    2015-06-22

    Time-resolved electron paramagnetic resonance (TREPR) spectroscopy is shown to be a powerful tool to characterize triplet excitons of conjugated polymers. The resulting spectra are highly sensitive to the orientation of the molecule. In thin films cast on PET film, the molecules' orientation with respect to the surface plane can be determined, providing access to sample morphology on a microscopic scale. Surprisingly, the conjugated polymer investigated here, a promising material for organic photovoltaics, exhibits ordering even in bulk samples. Orientation effects may significantly influence the efficiency of solar cells, thus rendering proper control of sample morphology highly important.

  13. Electron paramagnetic resonance of Fe3+ in near-stoichiometric LiTaO3

    NASA Astrophysics Data System (ADS)

    Loyo-Menoyo, M.; Keeble, D. J.; Furukawa, Y.; Kitamura, K.

    2004-12-01

    Electron paramagnetic resonance (EPR) experiments on the dominant Fe3+ centre in near-stoichiometric LiTaO3 crystals grown by the double crucible Czochralski method are reported. A near complete roadmap of EPR positions was obtained, and transitions from two magnetically non-equivalent sites clearly resolved in the zx plane, perpendicular to the glide plane. This allowed accurate determination of C3 symmetry spin Hamiltonian parameters. Newman superposition model analyses of second and fourth order zero field splitting term parameters were performed to give further insight into the site of incorporation. The second order calculations provide evidence for Fe3+ substitution within the Li octahedron.

  14. Spin-transfer pathways in paramagnetic lithium transition-metal phosphates from combined broadband isotropic solid-state MAS NMR spectroscopy and DFT calculations.

    PubMed

    Clément, Raphaële J; Pell, Andrew J; Middlemiss, Derek S; Strobridge, Fiona C; Miller, Joel K; Whittingham, M Stanley; Emsley, Lyndon; Grey, Clare P; Pintacuda, Guido

    2012-10-17

    Substituted lithium transition-metal (TM) phosphate LiFe(x)Mn(1-x)PO(4) materials with olivine-type structures are among the most promising next generation lithium ion battery cathodes. However, a complete atomic-level description of the structure of such phases is not yet available. Here, a combined experimental and theoretical approach to the detailed assignment of the (31)P NMR spectra of the LiFe(x)Mn(1-x)PO(4) (x = 0, 0.25, 0.5, 0.75, 1) pure and mixed TM phosphates is developed and applied. Key to the present work is the development of a new NMR experiment enabling the characterization of complex paramagnetic materials via the complete separation of the individual isotropic chemical shifts, along with solid-state hybrid DFT calculations providing the separate hyperfine contributions of all distinct Mn-O-P and Fe-O-P bond pathways. The NMR experiment, referred to as aMAT, makes use of short high-powered adiabatic pulses (SHAPs), which can achieve 100% inversion over a range of isotropic shifts on the order of 1 MHz and with anisotropies greater than 100 kHz. In addition to complete spectral assignments of the mixed phases, the present study provides a detailed insight into the differences in electronic structure driving the variations in hyperfine parameters across the range of materials. A simple model delimiting the effects of distortions due to Mn/Fe substitution is also proposed and applied. The combined approach has clear future applications to TM-bearing battery cathode phases in particular and for the understanding of complex paramagnetic phases in general.

  15. Magnetism and electronic structure of triplet binuclear niobium complexes in inorganic glasses, organic ligand environment, and polymers

    NASA Astrophysics Data System (ADS)

    Rakhimov, R. R.; Arrington, S. A.; Jackson, E. M.; Hwang, J. S.; Prokof'ev, A. I.; Alexandrov, I. A.; Aleksandrov, A. I.

    2005-05-01

    We investigated paramagnetic properties of binuclear niobium complexes Nb-O-Nb with two nonequivalent Nb4+ ions in lithium-niobium phosphate glasses (LNPG), in the environment of catechol/ortho-quinone ligands and in polyethylene. Experimental electron paramagnetic resonance spectrum analysis revealed nonequivalent distribution of the charge and electron spin density between two Nb atoms. Mechanochemical interaction of LNPG with an organic donor-acceptor mixture catechol/ortho-quinone followed by organic solvent extraction leads to the formation of a new binuclear complex with catechol/ortho-quinone ligands. This complex can be further incorporated into polyethylene matrix to form the complex with properties close to the complex in LNPG.

  16. Protein structure refinement based on paramagnetic NMR shifts: applications to wild-type and mutant forms of cytochrome c.

    PubMed Central

    Gochin, M.; Roder, H.

    1995-01-01

    A new approach to NMR solution structure refinement is introduced that uses paramagnetic effects on nuclear chemical shifts as constraints in energy minimization or molecular dynamics calculations. Chemical shift differences between oxidized and reduced forms of horse cytochrome c for more than 300 protons were used as constraints to refine the structure of the wild-type protein in solution and to define the structural changes induced by a Leu 94 to Val mutation. A single round of constrained minimization, using the crystal structure as the starting point, converged to a low-energy structure with an RMS deviation between calculated and observed pseudo-contact shifts of 0.045 ppm, 7.5-fold lower than the starting structure. At the same time, the procedure provided stereospecific assignments for more than 45 pairs of methylene protons and methyl groups. Structural changes caused by the mutation were determined to a precision of better than 0.3 A. Structure determination based on dipolar paramagnetic (pseudocontact) shifts is applicable to molecules containing anisotropic paramagnetic centers with short electronic relaxation times, including numerous naturally occurring metalloproteins, as well as proteins or nucleic acids to which a paramagnetic metal ion or ligand may be attached. The long range of paramagnetic shift effects (up to 20 A from the iron in the case of cytochrome c) provides global structural constraints, which, in conjunction with conventional NMR distance and dihedral angle constraints, will enhance the precision of NMR solution structure determination. PMID:7757018

  17. Field-theory calculation of the electric dipole moment of the neutron and paramagnetic atoms

    NASA Astrophysics Data System (ADS)

    Griffith, Joel; Blundell, Steven; Sapirstein, Jonathan

    2013-04-01

    Electric dipole moments (edms) of bound states that arise from the constituents having edms are studied with field-theoretic techniques. The systems treated are the neutron and a set of paramagnetic atoms. In the latter case it is well known that the atomic edm differs greatly from the electron edm when the internal electric fields of the atom are taken into account. In the nonrelativistic limit these fields lead to a complete suppression, but for heavy atoms large enhancement factors are present. A general bound-state field theory approach applicable to both the neutron and paramagnetic atoms is set up. It is applied first to the neutron, treating the quarks as moving freely in a confining spherical well. It is shown that the effect of internal electric fields is small in this case. The atomic problem is then revisited using field-theory techniques in place of the usual Hamiltonian methods, and the atomic enhancement factor is shown to be consistent with previous calculations. Possible application of bound-state techniques to other sources of the neutron edm is discussed.

  18. Distance information for disordered proteins from NMR and ESR measurements using paramagnetic spin labels.

    PubMed

    Eliezer, David

    2012-01-01

    The growing recognition of the many roles that disordered protein states play in biology places an increasing importance on developing approaches to characterize the structural properties of this class of proteins and to clarify the links between these properties and the associated biological functions. Disordered proteins, when isolated in solution, do not adopt a fixed structure, but can and often do contain detectable and significant residual or transient structure, including both secondary and long-range structure. Such residual structure can play a role in nucleating local structural transitions as well as modulating intramolecular or intermolecular tertiary interactions, including those involved in ordered protein aggregation. An increasing array of tools has been recruited to help characterize the structural properties of disordered proteins. While a number of methods can report on residual secondary structure, detecting and quantifying transient long-range structure has proven to be more difficult. This chapter describes the use of paramagnetic spin labeling in combination with paramagnetic relaxation enhancement (PRE) in NMR spectroscopy and pulsed dipolar ESR spectroscopy (PDS) for this purpose.

  19. Ferromagnetic and paramagnetic magnetization of implanted GaN:Ho,Tb,Sm,Tm films

    SciTech Connect

    Maryško, M. Hejtmánek, J.; Laguta, V.; Sofer, Z.; Sedmidubský, D.; Šimek, P.; Veselý, M.; Mikulics, M.; Buchal, C.; Macková, A.; Malínský, P.; Wilhelm, R. A.

    2015-05-07

    The SQUID magnetic measurements were performed on the GaN films prepared by metal-organic vapour phase epitaxy and implanted by Tb{sup 3+}, Tm{sup 3+}, Sm{sup 3+}, and Ho{sup 3+} ions. The sapphire substrate was checked by the electron paramagnetic resonance method which showed a content of Cr{sup 3+} and Fe{sup 3+} impurities. The samples 5 × 5 mm{sup 2} were positioned in the classical straws and within an estimated accuracy of 10{sup −6 }emu, no ferromagnetic moment was detected in the temperature region of 2–300 K. The paramagnetic magnetization was studied for parallel and perpendicular orientation. In the case of GaN:Tb sample, at T = 2 K, a pronounced anisotropy with the easy axis perpendicular to the film was observed which can be explained by the lowest quasi-doublet state of the non-Kramers Tb{sup 3+} ion. The Weiss temperature deduced from the susceptibility data using the Curie-Weiss (C-W) law was found to depend substantially on the magnetic field.

  20. Electron Paramagnetic Resonance of Rhyolite and γ-Irradiated Trona Minerals

    NASA Astrophysics Data System (ADS)

    Köksal, F.; Köseoğlu, R.; Bașaran, E.

    2003-06-01

    Rhyolite from the "Yellow Stone of Nevșehir" and γ-irradiated trona from the Ankara Mine have been investigated by electron paramagnetic resonance at ambient temperature and at 113 K. Rhyolite was examined by X-ray powder diffraction and found to consist mainly of SiO2. Before γ-irradiation, the existing paramagnetic species in rhyolite were identified as ṖO42-, ĊH2OH, ĊO3-, ṠO2-, ĊO33-, and ĊO2- free radicals and Fe3+ at ambient temperature. At 113 K ṠO2- , ĊO33- , and ĊO2- radicals and Fe3+ were observed. The γ-irradiation produced neither new species nor detectable effects on these free radicals. The disappearance of some of the radicals at 113 K is attributed to the freezing of their motions. Before γ-irradiation, the trona mineral shows only Mn2+ lines, but after γ-irradiation it indicated the inducement of ĊO33- and ĊO2- radicals at ambient temperature, 113 K, in addition to the Mn2+ lines. The g and a values of the species were determined.

  1. Optical properties of a paramagnetic metalloporphyrin hematoporphyrin monomethyl ether coordinated to divalent manganese metal ion

    NASA Astrophysics Data System (ADS)

    Zhao, Huimin; Zang, Lixin; Hu, Guixiang; Guo, Chenshan

    2017-02-01

    Metalloporphyrins with paramagnetism are becoming research focus because their potential use in biomedical field as fluorescence probes and the magnetic resonance imaging (MRI) contrast agents. Divalent manganese metal ion (Mn2+) has a half-filled 3d shell with a strong paramagnetic effect. To investigate whether porphyrins coordinated to Mn2+ can serve as multiple functional probes, hematoporphyrin monomethyl ether coordinated to Mn2+ (Mn-HMME) was synthesized and its characterization, MRI enhancement property, luminescence property and photosensitivity were studied. Mn-HMME was characterized by UV-visible spectrum and Fourier transform infrared spectrum. It was found that the number of Q bands in the absorption spectrum of Mn-HMME reduced to two compared to free HMME. From the Fourier transform infrared spectrum of Mn-HMME, the characteristic infrared absorption peak of N-H bond in HMME at 970 cm-1 disappears, but the nitrogen-metal characteristic absorption peaks (1114 cm-1 and 1093 cm-1) were observed. The MRI of Mn-HMME indicates that Mn-HMME has relatively strong MRI enhancement effect. From luminescence spectroscopic analysis, the fluorescence emission of Mn-HMME was weaker than that of free HMME but still detectable. This may be caused by the energy transfer from free HMME to Mn2+. The test of photosensitivity of Mn- HMME denotes that the photosensitivity of Mn-HMME disappears. Our results indicate that Mn-HMME has the potential as a multiple functional probe in both fluorescence imaging and MRI.

  2. Investigating lanthanide dopant distributions in Yttrium Aluminum Garnet (YAG) using solid state paramagnetic NMR.

    PubMed

    McCarty, Ryan J; Stebbins, Jonathan F

    2016-10-01

    This paper demonstrates the approach of using paramagnetic effects observed in NMR spectra to investigate the distribution of lanthanide dopant cations in YAG (yttrium aluminum garnet, Y3Al5O12) optical materials, as a complimentary technique to optical spectroscopy and other standard methods of characterization. We investigate the effects of Ce(3+), Nd(3+), Yb(3+), Tm(3+), and Tm(3+)-Cr(3+) on (27)Al and (89)Y NMR spectra. We note shifted resonances for both AlO4 and AlO6 sites. In some cases, multiple shifted peaks are observable, and some of these can be empirically assigned to dopant cations in known configurations to the observed nuclides. In many cases, AlO6 peaks shifted by more than one magnetic neighbor can be detected. In general, we observe that the measured intensities of shifted resonances, when spinning sidebands are included, are consistent with predictions from models with dopant cations that are randomly distributed throughout the lattice. In at least one set of (27)Al spectra, we identify two sub-peaks possibly resulting from two paramagnetic cations with magnetically coupled spin states neighboring the observed nucleus. We identify systematic changes in the spectra related to known parameters describing the magnetic effects of lanthanide cations, such as larger shift distances when the expectation value of electron spins is greater. We lastly comment on the promise of this technique in future analyses of laser and other crystalline oxide materials. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Paramagnetic behavior of Co doped TiO2 nanocrystals controlled by self-purification mechanism

    NASA Astrophysics Data System (ADS)

    Anitha, B.; Khadar, M. Abdul; Banerjee, Alok

    2016-07-01

    Doping in nanocrystals is a challenging process because of the self- purification mechanism which tends to segregate out the dopants resulting in a greater dopant concentration near the surface than at the interior of nanocrystals. In the present work nanocrystals of TiO2 doped with different atom % of Co were synthesized by peroxide gel method. XRD analysis confirmed the tetragonal anatase structure and HRTEM images showed the rod-like morphology of the samples. Raman modes of anatase phase of TiO2 along with weak intensity peaks of Co3O4 for higher Co dopant concentrations were observed for the samples. EPR measurements revealed the presence of cobalt in +2 oxidation state in the TiO2 matrix. SQUID measurements indicated paramagnetic behavior of the Co doped TiO2 nanocrystals. The paramagnetic behavior is attributed to an increased concentration of Co2+ ions and an increased presence of Co3O4 phase near the surface of the TiO2 nanocrystals due to self-purification mechanism.

  4. How Ions Arrange in Solution: Detailed Insight from NMR Spectroscopy of Paramagnetic Ion Pairs.

    PubMed

    Damjanović, Marko; Morita, Takaumi; Horii, Yoji; Katoh, Keiichi; Yamashita, Masahiro; Enders, Markus

    2016-11-04

    Ion pairing between the paramagnetic anion [Tb(obPc)2 ](-) (obPc=2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato), which has a very large magnetic anisotropy, with various diamagnetic counterions [P(Ph)4 ](+) (1 a), [As(Ph)4 ](+) (1 b), bis(triphenylphosphine)iminium ([PPN](+) , 1 c) and tetra-n-butylammonium ([TBA](+) , 1 d) was studied by means of (1) H, (13) C, (14) N, and (31) P NMR spectroscopy in solution at various temperatures. The influence of the paramagnetic anion on the NMR spectroscopy properties of the diamagnetic cations allowed a detailed insight into the distances and relative orientations of the paired ions. Isotropic tumbling models for the description of the quaternary cations are inaccurate, particularly for [TBA](+) with its flexible butyl chains. The effects of temperature and concentration were also assessed. The advantage of this technique is that relatively large distances and the orientation between molecules or ions in solution can be studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Calorimetric Measurements of Magnetic-Field-Induced Inhomogeneous Superconductivity Above the Paramagnetic Limit

    NASA Astrophysics Data System (ADS)

    Agosta, Charles C.; Fortune, Nathanael A.; Hannahs, Scott T.; Gu, Shuyao; Liang, Lucy; Park, Ju-Hyun; Schleuter, John A.

    2017-06-01

    We report the first magnetocaloric and calorimetric observations of a magnetic-field-induced phase transition within a superconducting state to the long-sought exotic Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) superconducting state, first predicted over 50 years ago. Through the combination of bulk thermodynamic calorimetric and magnetocaloric measurements in the organic superconductor κ -(BEDT -TTF )2Cu (NCS )2 as a function of temperature, magnetic field strength, and magnetic field orientation, we establish for the first time that this field-induced first-order phase transition at the paramagnetic limit Hp is a transition to a higher-entropy superconducting phase, uniquely characteristic of the FFLO state. We also establish that this high-field superconducting state displays the bulk paramagnetic ordering of spin domains required of the FFLO state. These results rule out the alternate possibility of spin-density wave ordering in the high-field superconducting phase. The phase diagram determined from our measurements—including the observation of a phase transition into the FFLO phase at Hp—is in good agreement with recent NMR results and our own earlier tunnel-diode magnetic penetration depth experiments but is in disagreement with the only previous calorimetric report.

  6. Calorimetric Measurements of Magnetic-Field-Induced Inhomogeneous Superconductivity Above the Paramagnetic Limit.

    PubMed

    Agosta, Charles C; Fortune, Nathanael A; Hannahs, Scott T; Gu, Shuyao; Liang, Lucy; Park, Ju-Hyun; Schleuter, John A

    2017-06-30

    We report the first magnetocaloric and calorimetric observations of a magnetic-field-induced phase transition within a superconducting state to the long-sought exotic Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) superconducting state, first predicted over 50 years ago. Through the combination of bulk thermodynamic calorimetric and magnetocaloric measurements in the organic superconductor κ-(BEDT-TTF)_{2}Cu(NCS)_{2} as a function of temperature, magnetic field strength, and magnetic field orientation, we establish for the first time that this field-induced first-order phase transition at the paramagnetic limit H_{p} is a transition to a higher-entropy superconducting phase, uniquely characteristic of the FFLO state. We also establish that this high-field superconducting state displays the bulk paramagnetic ordering of spin domains required of the FFLO state. These results rule out the alternate possibility of spin-density wave ordering in the high-field superconducting phase. The phase diagram determined from our measurements-including the observation of a phase transition into the FFLO phase at H_{p}-is in good agreement with recent NMR results and our own earlier tunnel-diode magnetic penetration depth experiments but is in disagreement with the only previous calorimetric report.

  7. Protein fold determined by paramagnetic magic-angle spinning solid-state NMR spectroscopy

    PubMed Central

    Sengupta, Ishita; Nadaud, Philippe S.; Helmus, Jonathan J.; Schwieters, Charles D.; Jaroniec, Christopher P.

    2012-01-01

    Biomacromolecules that are challenging for the usual structural techniques can be studied with atomic resolution by solid-state nuclear magnetic resonance. However, the paucity of >5 Å distance restraints, traditionally derived from measurements of magnetic dipole-dipole couplings between protein nuclei, is a major bottleneck that hampers such structure elucidation efforts. Here we describe a general approach that enables the rapid determination of global protein fold in the solid phase via measurements of nuclear paramagnetic relaxation enhancements (PREs) in several analogs of the protein of interest containing covalently-attached paramagnetic tags, without the use of conventional internuclear distance restraints. The method is demonstrated using six cysteine-EDTA-Cu2+ mutants of the 56-residue B1 immunoglobulin-binding domain of protein G, for which ~230 longitudinal backbone 15N PREs corresponding to ~10-20 Å distances were obtained. The mean protein fold determined in this manner agrees with the X-ray structure with a backbone atom root-mean-square deviation of 1.8 Å. PMID:22522262

  8. Magnetometry and electron paramagnetic resonance studies of phosphine- and thiol-capped gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Guerrero, E.; Muñoz-Márquez, M. A.; Fernández, A.; Crespo, P.; Hernando, A.; Lucena, R.; Conesa, J. C.

    2010-03-01

    In the last years, the number of studies performed by wholly independent research groups that confirm the permanent magnetism, first observed in our research lab, for thiol-capped Au nanoparticles (NPs) has rapidly increased. Throughout the years, the initial magnetometry studies have been completed with element-specific magnetization measurements based on, for example, the x-ray magnetic circular dichroism technique that have allowed the identification of gold as the magnetic moment carrier. In the research work here presented, we have focused our efforts in the evaluation of the magnetic behavior and iron impurities content in the synthesized samples by means of superconducting quantum interference device magnetometry and electron paramagnetic resonance spectrometry, respectively. As a result, hysteresis cycles typical of a ferromagnetic material have been measured from nominally iron-free gold NPs protected with thiol, phosphine, and chlorine ligands. It is also observed that for samples containing both, capped gold NPs and highly diluted iron concentrations, the magnetic behavior of the NPs is not affected by the presence of paramagnetic iron impurities. The hysteresis cycles reported for phosphine-chlorine-capped gold NPs confirm that the magnetic behavior is not exclusively for the metal-thiol system.

  9. Paramagnetic relaxation in anisotropic materials in zero and weak constant fields

    SciTech Connect

    Fokina, N. P.; Khalvashi, E. Kh.; Khutsishvili, K. O.

    2014-12-21

    Paramagnetic relaxation in strongly anisotropic materials is analytically investigated in zero and weak constant magnetic fields. The objectives of the microscopic analytical investigation are (i) the weak-field electron paramagnetic resonance (EPR) linewidth and (ii) the electron spin relaxation rates given by a calorimetric Gorter type experiment in the zero constant field at the arbitrary low-frequency field directions, respectively, to the sample crystallographic axes. The EPR linewidth is calculated under the suggestion of its spin-phonon nature at the one-phonon mechanism of the spin-lattice relaxation in the case of the strong isotropic exchange interaction for the arbitrary direction Z of the constant magnetic field. The EPR linewidth is presented as the half sum of the zero-field relaxation rates, measured by the Gorter experiment with the low-frequency field oriented along the X, Y axes. With the help of the macroscopic consideration, it is shown that the zero-field relaxation rates describe the relaxation of the X and Y magnetization components in a zero or weak constant magnetic field. The relaxation rates of the magnetizations created along a,b,c crystallographic axes by a low-frequency field in a Gorter type experiment follow the obtained expressions in the particular cases and are in the experimentally confirmed relations with the EPR linewidth.

  10. Local structure and paramagnetic properties of the nanostructured carbonaceous material shungite.

    PubMed

    Krasnovyd, Serhii Volodymyrovich; Konchits, Andriy Andriyovich; Shanina, Bela Dmytrivna; Valakh, Mykhaylo Yakovych; Yanchuk, Igor Bogdanovich; Yukhymchuk, Volodymyr Olexsandrovych; Yefanov, Andriy Volodymyrovich; Skoryk, Mykola Andriyovich

    2015-01-01

    Using a scanning electron microscopy, elemental analysis, electron paramagnetic resonance, and Raman scattering methods, two types of the shungite materials (Sh-II from Zazhogino deposit and shungite from a commercial filter (ShF)), with different carbon content and porosity, are studied in this work. It was established by scanning electron microscopy data that the structure of the shungite samples is formed by a micron-size agglomeration of carbon and silicon dioxide clusters. It is found from the Raman data that carbon fraction is formed from sp(2)-hybridized clusters, size of which increases from 9 up to 12 nm after annealing of the samples. High conductivity of shungite is found to belong to the carbon nanoclusters of different sizes. Big clusters give the conduction electron spin resonance signal with a Dysonian line shape with variable g-factor and line width. The careful search of the nature of two other narrow electron paramagnetic resonance signals in shungite, which used to be prescribed to fullerene-like molecules, is fulfilled. Here, it is shown that the oxygen-deficient E'γ centers are responsible for these signals. A strong correlation is revealed between the concentration of Е'γ centers and the line width of conduction electron spin resonance signal, which occurs under annealing process of the samples at T = 570 K. The correlation reasons are a spin-spin coupling between two spin subsystems and time dependent of the Е'γ concentration during annealing process.

  11. Direct observation of electrically induced Pauli paramagnetism in single-layer graphene using ESR spectroscopy

    PubMed Central

    Fujita, Naohiro; Matsumoto, Daisuke; Sakurai, Yuki; Kawahara, Kenji; Ago, Hiroki; Takenobu, Taishi; Marumoto, Kazuhiro

    2016-01-01

    Graphene has been actively investigated as an electronic material owing to many excellent physical properties, such as high charge mobility and quantum Hall effect, due to the characteristics of a linear band structure and an ideal two-dimensional electron system. However, the correlations between the transport characteristics and the spin states of charge carriers or atomic vacancies in graphene have not yet been fully elucidated. Here, we show the spin states of single-layer graphene to clarify the correlations using electron spin resonance (ESR) spectroscopy as a function of accumulated charge density using transistor structures. Two different electrically induced ESR signals were observed. One is originated from a Fermi-degenerate two-dimensional electron system, demonstrating the first observation of electrically induced Pauli paramagnetism from a microscopic viewpoint, showing a clear contrast to no ESR observation of Pauli paramagnetism in carbon nanotubes (CNTs) due to a one-dimensional electron system. The other is originated from the electrically induced ambipolar spin vanishments due to atomic vacancies in graphene, showing a universal phenomenon for carbon materials including CNTs. The degenerate electron system with the ambipolar spin vanishments would contribute to high charge mobility due to the decrease in spin scatterings in graphene. PMID:27731338

  12. (89)Zr-labeled paramagnetic octreotide-liposomes for PET-MR imaging of cancer.

    PubMed

    Abou, Diane S; Thorek, Daniel L J; Ramos, Nicholas N; Pinkse, Martijn W H; Wolterbeek, Hubert T; Carlin, Sean D; Beattie, Bradley J; Lewis, Jason S

    2013-03-01

    Dual-modality PET/MR platforms add a new dimension to patient diagnosis with high resolution, functional, and anatomical imaging. The full potential of this emerging hybrid modality could be realized by using a corresponding dual-modality probe. Here, we report pegylated liposome (LP) formulations, housing a MR T(1) contrast agent (Gd) and the positron-emitting (89)Zr (half-life: 3.27 days), for simultaneous PET and MR tumor imaging capabilities. (89)Zr oxophilicity was unexpectedly found advantageous for direct radiolabeling of preformed paramagnetic LPs. LPs were conjugated with octreotide to selectively target neuroendocrine tumors via human somatostatin receptor subtype 2 (SSTr2). (89)Zr-Gd-LPs and octreotide-conjugated homolog were physically, chemically and biologically characterized. (89)Zr-LPs showed reasonable stability over serum proteins and chelator challenges for proof-of-concept in vitro and in vivo investigations. Nuclear and paramagnetic tracking quantified superior SSTr2-recognition of octreotide-LP compared to controls. This study demonstrated SSTr2-targeting specificity along with direct chelator-free (89)Zr-labeling of LPs and dual PET/MR imaging properties.

  13. Characterisation of β-tricalcium phosphate-based bone substitute materials by electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Matković, Ivo; Maltar-Strmečki, Nadica; Babić-Ivančić, Vesna; Dutour Sikirić, Maja; Noethig-Laslo, Vesna

    2012-10-01

    β-TCP based materials are frequently used as dental implants. Due to their resorption in the body and direct contact with tissues, in order to inactivate bacteria, fungal spores and viruses, they are usually sterilized by γ-irradiation. However, the current literature provides little information about effects of the γ-irradiation on the formation and stability of the free radicals in the bone graft materials during and after sterilization procedure. In this work five different bone graft substitution materials, composed of synthetic beta tricalcium phosphate (β-TCP) and hydroxyapatite (HAP) present in the market were characterized by electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Paramagnetic species Mn2+, Fe3+, trapped H-atoms and CO2- radicals were detected in the biphasic material (60% HAP, 40% β-TCP), while in β-TCP materials only Mn2+ andor trapped hydrogen atoms were detected. EPR analysis revealed the details of the structure of these materials at the atomic level. The results have shown that EPR spectroscopy is a method which can be used to improve the quality control of bone graft materials after syntering, processing and sterilization procedure.

  14. Paramagnetic decoration of DNA origami nanostructures by Eu³⁺ coordination.

    PubMed

    Opherden, Lars; Oertel, Jana; Barkleit, Astrid; Fahmy, Karim; Keller, Adrian

    2014-07-15

    The folding of DNA into arbitrary two- and three-dimensional shapes, called DNA origami, represents a powerful tool for the synthesis of functional nanostructures. Here, we present the first approach toward the paramagnetic functionalization of DNA origami nanostructures by utilizing postassembly coordination with Eu(3+) ions. In contrast to the usual formation of toroidal dsDNA condensates in the presence of trivalent cations, planar as well as rod-like DNA origami maintain their shape and monomeric state even under high loading with the trivalent lanthanide. Europium coordination was demonstrated by the change in Eu(3+) luminescence upon binding to the two DNA origami. Their natural circular dichroism in the Mg(2+)- and Eu(3+)-bound state was found to be very similar to that of genomic DNA, evidencing little influence of the DNA origami superstructure on the local chirality of the stacked base pairs. In contrast, the magnetic circular dichroism of the Mg(2+)-bound DNA origami deviates from that of genomic DNA. Furthermore, the lanthanide affects the magnetic properties of DNA in a superstructure-dependent fashion, indicative of the existence of superstructure-specific geometry of Eu(3+) binding sites in the DNA origami that are not formed in genomic DNA. This simple approach lays the foundation for the generation of magneto-responsive DNA origami nanostructures. Such systems do not require covalent modifications and can be used for the magnetic manipulation of DNA nanostructures or for the paramagnetic alignment of molecules in NMR spectroscopy.

  15. Band structure evolution during the ultrafast ferromagnetic-paramagnetic phase transition in cobalt

    PubMed Central

    Eich, Steffen; Plötzing, Moritz; Rollinger, Markus; Emmerich, Sebastian; Adam, Roman; Chen, Cong; Kapteyn, Henry Cornelius; Murnane, Margaret M.; Plucinski, Lukasz; Steil, Daniel; Stadtmüller, Benjamin; Cinchetti, Mirko; Aeschlimann, Martin; Schneider, Claus M.; Mathias, Stefan

    2017-01-01

    The evolution of the electronic band structure of the simple ferromagnets Fe, Co, and Ni during their well-known ferromagnetic-paramagnetic phase transition has been under debate for decades, with no clear and even contradicting experimental observations so far. Using time- and spin-resolved photoelectron spectroscopy, we can make a movie on how the electronic properties change in real time after excitation with an ultrashort laser pulse. This allows us to monitor large transient changes in the spin-resolved electronic band structure of cobalt for the first time. We show that the loss of magnetization is not only found around the Fermi level, where the states are affected by the laser excitation, but also reaches much deeper into the electronic bands. We find that the ferromagnetic-paramagnetic phase transition cannot be explained by a loss of the exchange splitting of the spin-polarized bands but instead shows rapid band mirroring after the excitation, which is a clear signature of extremely efficient ultrafast magnon generation. Our result helps to understand band structure formation in these seemingly simple ferromagnetic systems and gives first clear evidence of the transient processes relevant to femtosecond demagnetization. PMID:28378016

  16. Protein fold determined by paramagnetic magic-angle spinning solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Sengupta, Ishita; Nadaud, Philippe S.; Helmus, Jonathan J.; Schwieters, Charles D.; Jaroniec, Christopher P.

    2012-05-01

    Biomacromolecules that are challenging for the usual structural techniques can be studied with atomic resolution by solid-state NMR spectroscopy. However, the paucity of distance restraints >5 Å, traditionally derived from measurements of magnetic dipole-dipole couplings between protein nuclei, is a major bottleneck that hampers such structure elucidation efforts. Here, we describe a general approach that enables the rapid determination of global protein fold in the solid phase via measurements of nuclear paramagnetic relaxation enhancements (PREs) in several analogues of the protein of interest containing covalently attached paramagnetic tags, without the use of conventional internuclear distance restraints. The method is demonstrated using six cysteine-EDTA-Cu2+ mutants of the 56-residue B1 immunoglobulin-binding domain of protein G, for which ~230 longitudinal backbone 15N PREs corresponding to distances of ~10-20 Å were obtained. The mean protein fold determined in this manner agrees with the X-ray structure with a backbone atom root-mean-square deviation of 1.8 Å.

  17. Paramagnetic defects induced by electron irradiation in barium hollandite ceramics for caesium storage.

    PubMed

    Aubin-Chevaldonnet, V; Gourier, D; Caurant, D; Esnouf, S; Charpentier, T; Costantini, J M

    2006-04-26

    We have studied by electron paramagnetic resonance the mechanism of defect production by electron irradiation in barium hollandite, a material used for immobilization of radioactive caesium. The irradiation conditions were the closest possible to those occurring in Cs storage waste forms. Three paramagnetic defects were observed, independently of the irradiation conditions. A hole centre (H centre) is attributed to a superoxide ion O(2)(-) originating from hole trapping by interstitial oxygen produced by electron irradiation. An electron centre (E(1) centre) is attributed to a Ti(3+) ion adjacent to the resulting oxygen vacancy. Another electron centre (E(2) centre) is attributed to a Ti(3+) ion in a cation site adjacent to an extra Ba(2+) ion in a neighbouring tunnel, originating from barium displacement by elastic collisions. Comparison of the effects of external irradiations by electrons with the β-decay of Cs in storage waste forms is discussed. It is concluded that the latter would be dominated by E(1) and H centres rather than E(2) centres.

  18. Electron paramagnetic resonance oxygen imaging of a rabbit tumor using localized spin probe delivery.

    PubMed

    Epel, Boris; Haney, Chad R; Hleihel, Danielle; Wardrip, Craig; Barth, Eugene D; Halpern, Howard J

    2010-06-01

    Application of in vivo electron paramagnetic resonance (EPR) oxygen imaging (EPROI) to tumors larger than those of mice requires development of both instrumental and medical aspects of imaging. 250 MHz EPR oxygen imaging was performed using a loop-gap resonator with a volume exceeding 100 cm3. The paramagnetic spin probe was injected directly into the femoral artery feeding the rabbit leg/tumor. The authors present continuous wave and electron spin echo EPR oxygen images of a large size (4 cm) VX-2 tumor located on the leg of a New Zealand white rabbit. This study demonstrates the feasibility of continuous wave and electron spin echo oxygen imaging modalities for investigation of volumes of tumor and normal tissue relevant to large animals. The injection of the spin probe directly into the artery feeding a rabbit leg will allow one to reduce, by over one order of magnitude, the amount of spin probe used as compared to whole animal i.v. injection.

  19. On the propagation of hypersonic solitons in a strained paramagnetic crystal

    SciTech Connect

    Sazonov, S. V.

    2013-11-15

    Nonlinear dynamics of a subnanosecond transverse elastic pulse in a low-temperature paramagnetic crystal placed into a magnetic field and statically strained in the same direction is investigated. Paramagnetic impurities implanted into the crystal have an effective spin of 3/2, and the pulse propagates at right angles to the magnetic field. In the general case, the structure of the pulse is such that the approximation of slowly varying envelopes, which is standard for quasi-monochromatic signals, is inapplicable. Under certain conditions, the pulse propagation in the 1D case is described by the Konno-Kameyama-Sanuki integrable wave equation for strain, which is transformed into the Hirota equation for the envelope of the given strain in the quasi-monochromatic limit. The effect of transverse perturbations on extremely short and quasi-monochromatic solitons is studied in detail. The conditions and features of self-focusing and defocusing of acoustic solitons in the form of extremely short pulses and envelope solitons are revealed. The propagation of an extremely short “half-wave” hypersonic pulse in the “acoustic bullet” regime in the medium with a quasiequilibrium population of quantum sublevels of effective spins is predicted.

  20. Redox-dependent conformational changes in eukaryotic cytochromes revealed by paramagnetic NMR spectroscopy.

    PubMed

    Volkov, Alexander N; Vanwetswinkel, Sophie; Van de Water, Karen; van Nuland, Nico A J

    2012-03-01

    Cytochrome c (Cc) is a soluble electron carrier protein, transferring reducing equivalents between Cc reductase and Cc oxidase in eukaryotes. In this work, we assessed the structural differences between reduced and oxidized Cc in solution by paramagnetic NMR spectroscopy. First, we have obtained nearly-complete backbone NMR resonance assignments for iso-1-yeast Cc and horse Cc in both oxidation states. These were further used to derive pseudocontact shifts (PCSs) arising from the paramagnetic haem group. Then, an extensive dataset comprising over 450 measured PCSs and high-resolution X-ray and solution NMR structures of both proteins were used to define the anisotropic magnetic susceptibility tensor, Δχ. For most nuclei, the PCSs back-calculated from the Δχ tensor are in excellent agreement with the experimental PCS values. However, several contiguous stretches-clustered around G41, N52, and A81-exhibit large deviations both in yeast and horse Cc. This behaviour is indicative of redox-dependent structural changes, the extent of which is likely conserved in the protein family. We propose that the observed discrepancies arise from the changes in protein dynamics and discuss possible functional implications.

  1. Electron paramagnetic resonance studies of copper ion-exchanged ZSM-5

    SciTech Connect

    Larsen, S.C.; Aylor, A.; Bell, A.T.; Reimer, J.A. )

    1994-11-03

    Electron paramagnetic resonance (EPR) spectroscopy was utilized to probe the oxidation state and coordination environment of copper in ion-exchanged CuZSM-5. EPR spectra of hydrated samples were consistent with octahedral coordination. Square pyramidal and square-planar sites were identified in pretreated CuZSM-5 samples, and the relative concentration of square-pyramidal sites in these samples was linearly correlated with the copper-exchange level. The extent of autoreduction was monitored by EPR and it was determined that a substantial fraction (approximately 40-60%) of the copper was reduced and the reduction process was reversible in the presence of water. A mechanism for the autoreduction of copper is proposed that is consistent with the EPR results. Further, the reactivity of the proposed copper species was probed in reducing and oxidizing environments and in the presence of nitric oxide. The increase in EPR signal intensity that was observed after room-temperature NO exposure of pretreated and oxidized CuZSM-5 is attributed to the formation of copper nitrite and nitrate species. High-temperature in situ EPR experiments revealed that on the time scale of the EPR experiment, the paramagnetic copper environment did not change at elevated temperatures in the presence of nitric oxide. 39 refs., 13 figs., 3 tabs.

  2. A new ion-exchange adsorbent with paramagnetic properties for the separation of genomic DNA.

    PubMed

    Feng, Guodong; Jiang, Luan; Wen, Puhong; Cui, Yali; Li, Hong; Hu, Daodao

    2011-11-21

    A new ion-exchange adsorbent (IEA) derived from Fe(3)O(4)/SiO(2)-GPTMS-DEAE with paramagnetic properties was prepared. Fe(3)O(4) nanoparticles were firstly prepared in water-in-oil microemulsion. The magnetic Fe(3)O(4) particles were modified in situ by hydrolysis and condensation reactions with tetraethoxysilane (TEOS) to form the core-shell Fe(3)O(4)/SiO(2). The modified particles were further treated by 3-glycidoxypropyltrimethoxysilane (GPTMS) to form Fe(3)O(4)/SiO(2)-GPTMS nanoparticles. Fe(3)O(4)/SiO(2)-GPTMS-DEAE nanoparticles (IEA) were finally obtained through the condensation reaction between the Cl of diethylaminoethyl chloride-HCl (DEAE) and the epoxy groups of GPTMS in the Fe(3)O(4)/SiO(2)-GPTMS. The obtained IEA has features of paramagnetic and ion exchange properties because of the Fe(3)O(4) nanoparticles and protonated organic amine in the sample. The intermediates and final product obtained in the synthesis process were characterized. The separation result of genomic DNA from blood indicated that Fe(3)O(4)/SiO(2)-GPTMS-DEAE nanoparticles have outstanding advantages in operation, selectivity, and capacity.

  3. Magnetization at the interface of Cr2O3 and paramagnets with large stoner susceptibility.

    PubMed

    Cao, Shi; Street, M; Wang, Junlei; Wang, Jian; Zhang, Xiaozhe; Binek, Ch; Dowben, P A

    2017-03-15

    From the Cr 2p3/2 x-ray magnetic circular dichroism signal, there is clear evidence of interface polarization with overlayers of both Pd and Pt on chromia (Cr2O3). The residual boundary polarization of chomia is stronger for a Pt overlayer than in the case of a Pd overlayer. The reduction of chromia boundary magnetization with a paramagnetic metal overlayer, compared to the free surface, is interpreted as a response to the induced spin polarization in Pt and Pd. Magnetization induced in a Pt overlayer, via proximity to the chromia boundary magnetization, is evident in the polar magneto-optical Kerr measurements. These results are essential to explainations why Pt and Pd are excellent spacer layers for voltage controlled exchange bias, in the [Pd/Co] n /Pd/Cr2O3 and [Pt/Co] n /Pt/Cr2O3 perpendicular magneto-electric exchange bias systems. The findings pave the way to realize ultra-fast reversal of induced magnetization in a free moment paramagnetic layer, with possible application in voltage-controlled magnetic random access memory.

  4. Magnetization at the interface of Cr2O3 and paramagnets with large stoner susceptibility

    NASA Astrophysics Data System (ADS)

    Cao, Shi; Street, M.; Wang, Junlei; Wang, Jian; Zhang, Xiaozhe; Binek, Ch; Dowben, P. A.

    2017-03-01

    From the Cr 2p3/2 x-ray magnetic circular dichroism signal, there is clear evidence of interface polarization with overlayers of both Pd and Pt on chromia (Cr2O3). The residual boundary polarization of chomia is stronger for a Pt overlayer than in the case of a Pd overlayer. The reduction of chromia boundary magnetization with a paramagnetic metal overlayer, compared to the free surface, is interpreted as a response to the induced spin polarization in Pt and Pd. Magnetization induced in a Pt overlayer, via proximity to the chromia boundary magnetization, is evident in the polar magneto-optical Kerr measurements. These results are essential to explainations why Pt and Pd are excellent spacer layers for voltage controlled exchange bias, in the [Pd/Co] n /Pd/Cr2O3 and [Pt/Co] n /Pt/Cr2O3 perpendicular magneto-electric exchange bias systems. The findings pave the way to realize ultra-fast reversal of induced magnetization in a free moment paramagnetic layer, with possible application in voltage-controlled magnetic random access memory.

  5. Synthesis and characterization of surface-modified Fe3O4 super-paramagnetic nanoparticles.

    PubMed

    Zhang, Zhan-jie; Ma, Jia; Xu, Shuang-bing; Ren, Jing-hua; Qin, You; Huang, Jing; Yang, Kun-yu; Zhang, Zhi-ping; Wu, Gang

    2014-04-01

    Aqueous dispersion and stability of Fe3O4 nanoparticles remain an issue unresolved since aggregation of naked iron nanoparticles in water. In this study, we successfully synthesized different Fe3O4 super-paramagnetic nanoparticles which were modified by three kinds of materials [DSPE-MPEG2000, TiO2 and poly acrylic acid (PAA)] and further detected their characteristics. Transmission electron microscopy (TEM) clearly showed sizes and morphology of the four kinds of nanoparticles. X-ray diffraction (XRD) proved successfully coating of the three kinds of nanoparticles and their structures were maintained. Vibrating sample magnetometer (VSM) verified that their magnetic properties fitted for the super-paramagnetic function. More importantly, the particle size analysis indicated that Fe3O4@PAA had a better size distribution, biocompatibility, stability and dispersion than the other two kinds of nanoparticles. In addition, using CNE2 cells as a model, we found that all nanoparticles were nontoxic. Taken together, our data suggest that Fe3O4@PAA nanoaparticles are superior in the application of biomedical field among the four kinds of Fe3O4 nanoparticles in the future.

  6. Chondroitin sulfate-capped super-paramagnetic iron oxide nanoparticles as potential carriers of doxorubicin hydrochloride.

    PubMed

    Mallick, Neha; Anwar, Mohammed; Asfer, Mohammed; Mehdi, Syed Hassan; Rizvi, Mohammed Moshahid Alam; Panda, Amulya Kumar; Talegaonkar, Sushama; Ahmad, Farhan Jalees

    2016-10-20

    Chondroitin-4-sulfate (CS), a glycosaminoglycan, was used to prepare CS-capped super-paramagnetic iron oxide nanoparticles, which were further employed for loading a water-soluble chemotherapeutic agent (doxorubicin hydrochloride, DOX). CS-capped SPIONs have potential biomedical application in cancer targeting. The optimized formulation had a hydrodynamic size of 91.2±0.8nm (PDI; 0.228±0.004) and zeta potential of -49.1±1.66mV. DOX was loaded onto the formulation up to 2% (w/w) by physical interaction with CS. TEM showed nano-sized particles having a core-shell structure. XRD confirmed crystal phase of iron oxide. FT-IR conceived the interaction of iron oxide with CS as bidentate chelation and also confirmed DOX loading. Vibration sample magnetometry confirmed super-paramagnetic nature of nanoparticles, with saturation magnetization of 0.238emug(-1). In vitro release profile at pH 7.4 showed that 96.67% of DOX was released within 24h (first order kinetics). MTT assay in MCF7 cells showed significantly higher (p<0.0001) cytotoxicity for DOX in SPIONs than DOX solution (IC50 values 6.294±0.4169 and 11.316±0.1102μgmL(-1), respectively).

  7. Super-paramagnetic nanoparticles synthesis in a thermal plasma reactor assisted by magnetic bottle

    NASA Astrophysics Data System (ADS)

    Cartaya, R.; Puerta, J.; Martín, P.

    2015-03-01

    The present work is a study of the synthesis of super-paramagnetic particles. A preliminary study based on thermodynamic diagrams of Gibbs free energy minimization, was performed with the CSIRO Thermochemical System. In this way, the synthesis of magnetite nanoparticles from precursor powder of ore iron in a thermal reactor, was performed. Then the process was simulated mathematically using magnetohydrodynamic and kinetic equations, in order to predict the synthesis process. A cylindrical reactor assisted by magnetic mirrors was used. The peak intensity of 0.1 tesla (1000 Gauss) was measured at the end of the solenoid. A PlazjetTM 105/15 thermal plasma torch was used. The precursor powder was iron oxide and the plasma gas, nitrogen. The magnetite powder was magnetized whit rare-earth super-magnets, alloy of neodymium-iron boron (NdFeB) grade N-42. The synthesized nanoparticles diameters was measured with a scanning electron microscope LECO and the permanent magnetization with a YOKOGAWA gauss meter, model 325i. Our experimental results show that it is possible the synthesis of super-paramagnetic nanoparticles in thermal plasma reactors.

  8. 89Zr-Labeled Paramagnetic Octreotide-Liposomes for PET-MR Imaging of Cancer

    PubMed Central

    Abou, Diane S.; Thorek, Daniel L. J.; Ramos, Nicholas N.; Pinkse, Martijn W. H.; Wolterbeek, Hubert T.; Carlin, Sean D.; Beattie, Bradley J.

    2013-01-01

    Purpose Dual-modality PET/MR platforms add a new dimension to patient diagnosis with high resolution, functional, and anatomical imaging. The full potential of this emerging hybrid modality could be realized by using a corresponding dual-modality probe. Here, we report pegylated liposome (LP) formulations, housing a MR T1 contrast agent (Gd) and the positron-emitting 89Zr (half-life: 3.27 days), for simultaneous PET and MR tumor imaging capabilities. Methods 89Zr oxophilicity was unexpectedly found advantageous for direct radiolabeling of preformed paramagnetic LPs. LPs were conjugated with octreotide to selectively target neuroendocrine tumors via human somatostatin receptor subtype 2 (SSTr2). 89Zr-Gd-LPs and octreotide-conjugated homolog were physically, chemically and biologically characterized. Results 89Zr-LPs showed reasonable stability over serum proteins and chelator challenges for proof-of-concept in vitro and in vivo investigations. Nuclear and paramagnetic tracking quantified superior SSTr2-recognition of octreotide-LP compared to controls. Conclusions This study demonstrated SSTr2-targeting specificity along with direct chelator-free 89Zr-labeling of LPs and dual PET/MR imaging properties. PMID:23224977

  9. Magneto-vibratory separation of glass and bronze granular mixtures immersed in a paramagnetic liquid.

    PubMed

    López-Alcaraz, P; Catherall, A T; Hill, R J A; Leaper, M C; Swift, Michael R; King, P J

    2007-10-01

    A fluid-immersed granular mixture may spontaneously separate when subjected to vertical vibration, separation occurring when the ratio of particle inertia to fluid drag is sufficiently different between the component species of the mixture. Here, we describe how fluid-driven separation is influenced by magneto-Archimedes buoyancy, the additional buoyancy force experienced by a body immersed in a paramagnetic fluid when a strong inhomogeneous magnetic field is applied. In our experiments glass and bronze mixtures immersed in paramagnetic aqueous solutions of MnCl2 have been subjected to sinusoidal vertical vibration. In the absence of a magnetic field the separation is similar to that observed when the interstitial fluid is water. However, at modest applied magnetic fields, magneto-Archimedes buoyancy may balance the inertia/fluid-drag separation mechanism, or it may dominate the separation process. We identify the vibratory and magnetic conditions for four granular configurations, each having distinctive granular convection. Abrupt transitions between these states occur at well-defined values of the magnetic and vibrational parameters. In order to gain insight into the dynamics of the separation process we use computer simulations based on solutions of the Navier-Stokes' equations. The simulations reproduce the experimental results revealing the important role of convection and gap formation in the stability of the different states.

  10. Pulling on super paramagnetic beads with micro cantilevers: single molecule mechanical assay application.

    PubMed

    Muñoz, Romina; Aguilar Sandoval, Felipe; Wilson, Christian A M; Melo, Francisco

    2015-07-22

    This paper demonstrates that it is possible to trap and release a super paramagnetic micro bead by fixing three super paramagnetic micro beads in a triangular array at the sensitive end of a micro cantilever, and by simply switching on/off an external magnetic field. To provide evidence of this principle we trap a micro bead that is attached to the free end of single DNA molecule and that has been previously fixed at the other end to a glass surface, using the standard sample preparation protocol of magnetic tweezers assays. The switching process is reversible which preserves the integrity of the tethered molecule, and a local force applied over the tethered bead excludes the neighbouring beads from the magnetic trap. We have developed a quadrature phase interferometer which is able to perform under fluid environments to accurately measure small deflections, which permits the exploration of DNA elasticity. Our results agree with measurements from magnetic tweezer assays performed under similar conditions. Furthermore, compared to the magnetic tweezer methodology, the combination of the magnetic trap with a suitable measurement system for cantilever deflection, allows for the exploration of a wide range of forces using a local method that has an improved temporal resolution.

  11. Thin chitosan films containing super-paramagnetic nanoparticles with contrasting capability in magnetic resonance imaging.

    PubMed

    Farjadian, Fatemeh; Moradi, Sahar; Hosseini, Majid

    2017-03-01

    Magnetic nanoparticles have found application as MRI contrasting agents. Herein, chitosan thin films containing super-paramagnetic iron oxide nanoparticles (SPIONs) are evaluated in magnetic resonance imaging (MRI). To determine their contrasting capability, super-paramagnetic nanoparticles coated with citrate (SPIONs-cit) were synthesized. Then, chitosan thin films with different concentrations of SPIONs-cit were prepared and their MRI data (i.e., r 2 and r 2*) was evaluated in an aqueous medium. The synthesized SPIONs-cit and chitosan/SPIONs-cit films were characterized by FTIR, EDX, XRD as well as VSM with the morphology evaluated by SEM and AFM. The nanoparticle sizes and distribution confirmed well-defined nanoparticles and thin films formation along with high contrasting capability in MRI. Images revealed well-dispersed uniform nanoparticles, averaging 10 nm in size. SPIONs-cit's hydrodynamic size averaged 23 nm in diameter. The crystallinity obeyed a chitosan and SPIONs pattern. The in vitro cellular assay of thin films with a novel route was performed within Hek293 cell lines showing that thin films can be biocompatible.

  12. Pulsed Electron Paramagnetic Resonance Study of Domain Docking in Neuronal Nitric Oxide Synthase: The Calmodulin and Output State Perspective

    PubMed Central

    2015-01-01

    The binding of calmodulin (CaM) to neuronal nitric oxide synthase (nNOS) enables formation of the output state of nNOS for nitric oxide production. Essential to NOS function is the geometry and dynamics of CaM docking to the NOS oxygenase domain, but little is known about these details. In the present work, the domain docking in a CaM-bound oxygenase/FMN (oxyFMN) construct of nNOS was investigated using the relaxation-induced dipolar modulation enhancement (RIDME) technique, which is a pulsed electron paramagnetic resonance technique sensitive to the magnetic dipole interaction between the electron spins. A cysteine was introduced at position 110 of CaM, after which a nitroxide spin label was attached at the position. The RIDME study of the magnetic dipole interaction between the spin label and the ferric heme centers in the oxygenase domain of nNOS revealed that, with increasing [Ca2+], the concentration of nNOS·CaM complexes increases and reaches a maximum at [Ca2+]/[CaM] ≥ 4. The RIDME kinetics of CaM-bound nNOS represented monotonous decays without well-defined oscillations. The analysis of these kinetics based on the structural models for the open and docked states has shown that only about 15 ± 3% of the CaM-bound nNOS is in the docked state at any given time, while the remaining 85 ± 3% of the protein is in the open conformations characterized by a wide distribution of distances between the bound CaM and the oxygenase domain. The results of this investigation are consistent with a model that the Ca2+–CaM interaction causes CaM docking with the oxygenase domain. The low population of the docked state indicates that the CaM-controlled docking between the FMN and heme domains is highly dynamic. PMID:25046446

  13. The Characterization and Imaging Behavior of a New Developed Paramagnetic Contrast Agent NMG2[Gd(TTDA-BOM)].

    PubMed

    Jao, Jo-Chi; Wang, Yun-Ming; Ou, Ming-Hung; Hsie Chen, Shih; Chen, Yen-Ku; Jaw, Twei-Shiun; Liu, Gin-Chung; Chen, Po-Chou

    2005-01-01

    [Gd(TTDA-BOM)]2-is a newly developed paramagnetic contrast agent.The ligand,TTDA-BOM,bears a benzyloxymethyl group so that the lipophilicity is increased. The water exchange rate for [Gd(TTDA-BOM)]2-is significantly higher than that of [Gd(DTPA)]2-and [Gd(BOPTA)]2-.In addition, the bound relaxivity of this Gd (III) complex has a remarkably high value with HSA. Therefore,it has potential to be used as a blood pool contrast agent for MRI. The aim of this study is to investigate the characterization and imaging behavior of NMG2[Gd(TTDA-BOM)] in normal rat livers and hearts using a 3T high field whole-body MR scanner.The high field MR scanner is expected to have a higher signal to noise ratio. The relaxivities r1and r2for [Gd(TTDA-BOM)]2-at 3T are 5.97 mM-1s-1and 7.99 mM-1s-1respectively, which are higher than those for [Gd(DTPA)]2(r1=4.64 mM-1s-1and r2= 5.08 mM-1s-1). The dynamic MRI studies show that there is marked enhancement in livers and hearts right after the bolus injection and the enhancement ratios keep high until two hours. In conclusion, [Gd(TTDA-BOM)]2-might have a good potential in both cardiovascular and hepatobiliary applications.

  14. Electron Paramagnetic Resonance and Electron-Nuclear Double Resonance Studies of the Reactions of Cryogenerated Hydroperoxoferric–Hemoprotein Intermediates

    PubMed Central

    2015-01-01

    The fleeting ferric peroxo and hydroperoxo intermediates of dioxygen activation by hemoproteins can be readily trapped and characterized during cryoradiolytic reduction of ferrous hemoprotein–O2 complexes at 77 K. Previous cryoannealing studies suggested that the relaxation of cryogenerated hydroperoxoferric intermediates of myoglobin (Mb), hemoglobin, and horseradish peroxidase (HRP), either trapped directly at 77 K or generated by cryoannealing of a trapped peroxo-ferric state, proceeds through dissociation of bound H2O2 and formation of the ferric heme without formation of the ferryl porphyrin π-cation radical intermediate, compound I (Cpd I). Herein we have reinvestigated the mechanism of decays of the cryogenerated hydroperoxyferric intermediates of α- and β-chains of human hemoglobin, HRP, and chloroperoxidase (CPO). The latter two proteins are well-known to form spectroscopically detectable quasistable Cpds I. Peroxoferric intermediates are trapped during 77 K cryoreduction of oxy Mb, α-chains, and β-chains of human hemoglobin and CPO. They convert into hydroperoxoferric intermediates during annealing at temperatures above 160 K. The hydroperoxoferric intermediate of HRP is trapped directly at 77 K. All studied hydroperoxoferric intermediates decay with measurable rates at temperatures above 170 K with appreciable solvent kinetic isotope effects. The hydroperoxoferric intermediate of β-chains converts to the S = 3/2 Cpd I, which in turn decays to an electron paramagnetic resonance (EPR)-silent product at temperature above 220 K. For all the other hemoproteins studied, cryoannealing of the hydroperoxo intermediate directly yields an EPR-silent majority product. In each case, a second follow-up 77 K γ-irradiation of the annealed samples yields low-spin EPR signals characteristic of cryoreduced ferrylheme (compound II, Cpd II). This indicates that in general the hydroperoxoferric intermediates relax to Cpd I during cryoanealing at low temperatures, but

  15. Emission Mössbauer spectroscopy study of fluence dependence of paramagnetic relaxation in Mn/Fe implanted ZnO

    NASA Astrophysics Data System (ADS)

    Masenda, H.; Geburt, S.; Bharuth-Ram, K.; Naidoo, D.; Gunnlaugsson, H. P.; Johnston, K.; Mantovan, R.; Mølholt, T. E.; Ncube, M.; Shayestehaminzadeh, S.; Gislason, H. P.; Langouche, G.; Ólafsson, S.; Ronning, C.

    2016-12-01

    Emission Mössbauer Spectroscopy following the implantation of radioactive precursor isotope 57Mn+ ( T 1/2= 1.5 min) into ZnO single crystals at ISOLDE/CERN shows that a large fraction of 57Fe atoms produced in the 57Mn beta decay is created as paramagnetic Fe3+ with relatively long spin-lattice relaxation times. Here we report on ZnO pre-implanted with 56Fe to fluences of 2×1013, 5×10 13 and 8 × 1013 ions/cm2 in order to investigate the dependence of the paramagnetic relaxation rate of Fe3+ on fluence. The spectra are dominated by magnetic features displaying paramagnetic relaxation effects. The extracted spin-lattice relaxation rates show a slight increase with increasing ion fluence at corresponding temperatures and the area fraction of Fe3+ at room temperature reaches a maximum contribution of 80(3)% in the studied fluence range.

  16. Short-range magnetic correlations and spin dynamics in the paramagnetic regime of (Mn,Fe)2(P,Si)

    NASA Astrophysics Data System (ADS)

    Miao, X. F.; Caron, L.; Cedervall, J.; Gubbens, P. C. M.; Dalmas de Réotier, P.; Yaouanc, A.; Qian, F.; Wildes, A. R.; Luetkens, H.; Amato, A.; van Dijk, N. H.; Brück, E.

    2016-07-01

    The spatial and temporal correlations of magnetic moments in the paramagnetic regime of (Mn,Fe ) 2(P ,Si ) have been investigated by means of polarized neutron diffraction and muon-spin relaxation techniques. Short-range magnetic correlations are present at temperatures far above the ferromagnetic transition temperature (TC). This leads to deviations of paramagnetic susceptibility from Curie-Weiss behavior. These short-range magnetic correlations extend in space, slow down with decreasing temperature, and finally develop into long-range magnetic order at TC.

  17. Application of electron paramagnetic resonance spectroscopy for validation of the novel (AN+DN) solvent polarity scale.

    PubMed

    Malavolta, Luciana; Poletti, Erick F; Silva, Elias H; Schreier, Shirley; Nakaie, Clovis R

    2008-06-01

    Based on solvation studies of polymers, the sum (1:1) of the electron acceptor (AN) and electron donor (DN) values of solvents has been proposed as an alternative polarity scale. To test this, the electron paramagnetic resonance isotropic hyperfine splitting constant, a parameter known to be dependent on the polarity/proticity of the medium, was correlated with the (AN+DN) term using three paramagnetic probes. The linear regression coefficient calculated for 15 different solvents was approximately 0.9, quite similar to those of other well-known polarity parameters, attesting to the validity of the (AN+DN) term as a novel "two-parameter" solvent polarity scale.

  18. The mechanism of paramagnetic NMR relaxation produced by Mn(II): role of orthorhombic and fourth-order zero field splitting terms.

    PubMed

    Sharp, Robert

    2008-10-14

    Mn(II) is a spin-5/2 paramagnetic ion that mediates a characteristically large NMR paramagnetic relaxation enhancement (NMR-PRE) of nuclear spins in solution. In the range of high magnetic field strengths (above about 0.3 T), where the electronic Zeeman interaction provides the largest term of the electron spin Hamiltonian, NMR relaxation mechanism is well understood. In the lower field range, the physical picture is more complex because of the presence in the spin Hamiltonian of zero field splitting (ZFS) terms that are comparable to or greater than the Zeeman term. This work describes a systematic study of the relaxation mechanism in the low field range, particularly aspects involving the dependence of NMR-PRE on the orthorhombic (E) and fourth-order (a(q)(4), q=0,2,4) ZFS tensor components. It is shown that the fourfold (a(4)(4)) and twofold (a(2)(4)) fourth-order components exert large orientation-dependent influences on the NMR-PRE. Thus, fourth-order terms with magnitudes equal to only a few percent of the quadratic ZFS terms (D,E) produce large changes in the shape of the magnetic field profile of the PRE. Effects arising from the orthorhombic quadratic ZFS term (E) are much smaller than those of the fourth-order terms and can in most cases be neglected. However, effects due to a(4)(4) and a(2)(4) need to be included in simulations of low field data.

  19. Characterization of radiation-induced damage in high performance polymers by electron paramagnetic resonance imaging spectroscopy

    NASA Technical Reports Server (NTRS)

    Suleman, Naushadalli K.

    1992-01-01

    The potential for long-term human activity beyond the Earth's protective magnetosphere is limited in part by the lack of detailed information on the effectiveness and performance of existing structural materials to shield the crew and spacecraft from highly penetrating space radiations. The two radiations of greatest concern are high energy protons emitted during solar flares and galactic cosmic rays which are energetic ions ranging from protons to highly oxidized iron. Although the interactions of such high-energy radiations with matter are not completely understood at this time, the effects of the incident radiation are clearly expected to include the formation of paramagnetic spin centers via ionization and bond-scission reactions in the molecular matrices of structural materials. Since this type of radiation damage is readily characterized by Electron Paramagnetic Resonance (EPR) spectroscopy, the NASA Langley Research Center EPR system was repaired and brought on-line during the 1991 ASEE term. A major goal of the 1992 ASEE term was to adapt the existing core of the LaRC EPR system to meet the requirements for EPR Imaging--a powerful new technique which provides detailed information on the internal structure of materials by mapping the spatial distribution of unpaired spin density in bulk media. Major impetus for this adaptation arises from the fact that information derived from EPRI complements other methods such as scanning electron microscopy which primarily characterize surface phenomena. The modification of the EPR system has been initiated by the construction of specially designed, counterwound Helmholtz coils which will be mounted on the main EPR electromagnet. The specifications of the coils have been set to achieve a static linear magnetic field gradient of 10 gauss/mm/amp along the principal (Z) axis of the Zeeman field. Construction is also in progress of a paramagnetic standard in which the spin distribution is known in all three dimensions. This

  20. Compensation of magnetic field distortions from paramagnetic instruments by added diamagnetic material: measurements and numerical simulations.

    PubMed

    Müller-Bierl, Bernd; Graf, Hansjörg; Steidle, Günter; Schick, Fritz

    2005-01-01

    In minimally invasive procedures guided by magnetic resonance (MR) imaging instruments usually are made of titanium or titanium alloys (e.g., nitinol), because other more MR-compatible materials often cannot provide sufficient mechanical properties. Artifacts depending on susceptibility arise in MR images due to incorrect spatial encoding and intravoxel dephasing and thereby hamper the surgeon's view onto the region of interest. To overcome the artifact problem, compensation of the paramagnetic properties by diamagnetic coating or filling of the instruments has been proposed in the literature. We used a numerical modeling procedure to estimate the effect of compensation. Modeling of the perturbation of the static magnetic field close to the instruments reflects the underlying problem and is much faster and cost efficient than manufacturing prototypes and measuring artifact behavior of these prototypes in the MR scanner. A numerical model based on the decomposition of the susceptibility distribution in elementary dipoles was developed by us. The program code was written object oriented to allow for both maximum computational speed and minimum random access memory. We used System International units throughout the modeling for the magnetic field, allowing absolute quantification of the magnetic field disturbance. The field outside a simulated needlelike instrument, modeled by a paramagnetic cylinder (out of titan, chi =181.1) of length 8.0 mm and of diameter 1.0 mm, coated with a diamagnetic layer (out of bismuth, chi=-165.0) of thickness 0, 0.1, 0.2, 0.3, and 0.4 mm, was found to be best compensated if the cross-sectional area of the cylinder, multiplied by the absolute susceptibility value of the cylinder material, is equal to the cross-sectional area of the coating, multiplied by the absolute susceptibility value of the coating material. At the extremity of the coated cylinder an uncompensated field distortion was found to remain. We studied various tip shapes and

  1. Analysis of paramagnetic point defects in potassium dihydrogen phosphate and potassium titanyl phosphate crystals

    NASA Astrophysics Data System (ADS)

    Garces, Nelson Yovanny

    A series of paramagnetic defects have been characterized in KH2 PO4 (KDP) and KTiOPO4 (KTP) using optical absorption, electron paramagnetic resonance (EPR), and electron- nuclear double resonance (ENDOR) techniques. In KDP, one hole-like center and five electronlike centers were investigated. Spin-Hamiltonian parameters were obtained for the holelike center and two electronlike centers. The hole center consists of a hole trapped on an oxygen ion adjacent to a silicon impurity substituting for a phosphorus ion. The electron centers are oxygen vacancies with one trapped electron, i.e., they are (PO3)2- molecular units. Both the hole center and the electron centers can be formed at room temperature (or at 77 K) with x-rays or the fourth harmonic output (266 nm) of a Nd:YAG laser. Their EPR spectra are best observed at room temperature. These defects are stable for several weeks at room temperature. Also, in KDP, an Fe3+ paramagnetic defect characterized in an earlier work was revisited and a complete set of spin-Hamiltonian parameters, including fourth order, were determined. In KTP crystals, three platinum centers and two silver centers were identified. The platinum centers were produced by exposure to 355 nm laser light or by irradiation with x-rays, while the silver centers were produced with x-rays only. Spin-Hamiltonian parameters were determined for the three platinum centers. One of these defects is assigned to a Pt3+ ion (3d7 ) substituting for a Ti4+; it is formed when a Pt 4+ ion traps an electron. The other two platinum centers are suggested to be hole traps, and are formed when a hole is trapped at a Pt0 atom substituting for a K+ ion, which results in a Pt + ion (3d9). A silver center was characterized in KTP using ENDOR. Silver was diffused into the crystal during a post-growth anneal. It is suggested that Ag+ ions occupy K+ sites and upon irradiation with x-rays trap a hole, thus becoming Ag2+ ions. The various Pt and Ag centers characterized in the

  2. New Magnetic confirguration in paramagnetic phase of HoCo2

    SciTech Connect

    Bonilla, C.M.; Calvo, I.; Herrero-Albillos, J.; Figueroa, A.I.; Castan-Guerrero, C.; Bertolome, J.; Rodriguez-Velamazan, J.A.; Schmitz, D.; Weschke, E.; Paudyal, Durga; Pecharsky, Vitalij; Gschneidner Jr, Karl; Bartolome, F.; Garcia, D.

    2012-02-23

    X-ray magnetic circular dichroism (XMCD) measurements on HoCo2 reveal the inversion of Co moment at temperatures higher than the critical temperature, Tc, showing that the net magnetization under a field of the Ho and Co sublattices remain antiparallel even above Tc. The Ho moment also changes its orientation to align antiparallel to the applied field at high temperature giving rise to a new magnetic configuration in the paramagnetic regime. Transverse susceptibility (TS) and small angle neutron scattering (SANS) measurements performed above Tc indicate the existence of sizable magnetic short-range correlated regions in HoCo2. First principles calculations based on spin polarized local-density approximation, LSDA+U havebeen performed to obtain insights on the origin of the short-range correlated volume.

  3. Ion exchange in alginate gels--dynamic behaviour revealed by electron paramagnetic resonance.

    PubMed

    Ionita, Gabriela; Ariciu, Ana Maria; Smith, David K; Chechik, Victor

    2015-12-14

    The formation of alginate gel from low molecular weight alginate and very low molecular weight alginate in the presence of divalent cations was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. The transition from sol to gel in the presence of divalent cations was monitored by the changes in the dynamics of spin labelled alginate. The immobilisation of the spin labelled alginate in the gel reflects the strength of interaction between the cation and alginate chain. Diffusion experiments showed that both the cation and alginate polyanion in the gel fibres can exchange with molecules in solution. In particular, we showed that dissolved alginate polyanions can replace alginates in the gel fibres, which can hence diffuse through the bulk of the gel. This illustrates the surprisingly highly dynamic nature of these gels and opens up the possibility of preparing multicomponent alginate gels via polyanion exchange process.

  4. Bulk Quantum Computation with Pulsed Electron Paramagnetic Resonance: Simulations of Single-Qubit Error Correction Schemes

    NASA Astrophysics Data System (ADS)

    Ishmuratov, I. K.; Baibekov, E. I.

    2016-12-01

    We investigate the possibility to restore transient nutations of electron spin centers embedded in the solid using specific composite pulse sequences developed previously for the application in nuclear magnetic resonance spectroscopy. We treat two types of systematic errors simultaneously: (i) rotation angle errors related to the spatial distribution of microwave field amplitude in the sample volume, and (ii) off-resonance errors related to the spectral distribution of Larmor precession frequencies of the electron spin centers. Our direct simulations of the transient signal in erbium- and chromium-doped CaWO4 crystal samples with and without error corrections show that the application of the selected composite pulse sequences can substantially increase the lifetime of Rabi oscillations. Finally, we discuss the applicability limitations of the studied pulse sequences for the use in solid-state electron paramagnetic resonance spectroscopy.

  5. Electron paramagnetic resonance spectroscopy in radiation research: Current status and perspectives

    PubMed Central

    Rana, Sudha; Chawla, Raman; Kumar, Raj; Singh, Shefali; Zheleva, Antoaneta; Dimitrova, Yanka; Gadjeva, Veselina; Arora, Rajesh; Sultana, Sarwat; Sharma, Rakesh Kumar

    2010-01-01

    Exposure to radiation leads to a number of health-related malfunctions. Ionizing radiation is more harmful than non-ionizing radiation, as it causes both direct and indirect effects. Irradiation with ionizing radiation results in free radical-induced oxidative stress. Free radical-mediated oxidative stress has been implicated in a plethora of diseased states, including cancer, arthritis, aging, Parkinson's disease, and so on. Electron Paramagnetic Resonance (EPR) spectroscopy has various applications to measure free radicals, in radiation research. Free radicals disintegrate immediately in aqueous environment. Free radicals can be detected indirectly by the EPR spin trapping technique in which these forms stabilize the radical adduct and produce characteristic EPR spectra for specific radicals. Ionizing radiation-induced free radicals in calcified tissues, for example, teeth, bone, and fingernail, can be detected directly by EPR spectroscopy, due to their extended stability. Various applications of EPR in radiation research studies are discussed in this review. PMID:21814437

  6. Absence of the Pauli-Paramagnetic Limit in a Superconducting U6Co

    NASA Astrophysics Data System (ADS)

    Manago, Masahiro; Ishida, Kenji; Aoki, Dai

    2017-07-01

    We performed 59Co nuclear magnetic resonance (NMR) measurements of single-crystalline U6Co. There is a small decrease in the Knight shift in the superconducting (SC) state, but this change mainly arises from the SC diamagnetic effect. The negligible change of the spin part of the Knight shift, together with the absence of the Pauli-paramagnetic effect in the SC U6Co, is understood as a consequence of the small spin susceptibility. The nuclear spin-lattice relaxation rate 1/T1 is also measured in the SC state under the magnetic field, and exhibits a tiny Hebel-Slichter peak just below the SC transition temperature and exponential behavior at lower temperatures. These behaviors are in agreement with the full-gap s-wave pairing in U6Co.

  7. Exactly solvable models of spin liquids with spinons, and of three-dimensional topological paramagnets

    NASA Astrophysics Data System (ADS)

    Ben-Zion, Daniel; Das, Diptarka; McGreevy, John

    2016-04-01

    We develop a scheme to make exactly solvable gauge theories whose electric flux lines host (1+1)-dimensional topological phases. We use this exact "decorated-string-net" framework to construct several classes of interesting models. In particular, we construct an exactly solvable model of a quantum spin liquid whose (gapped) elementary excitations form doublets under an internal symmetry, and hence may be regarded as spin-carrying spinons. The model may be formulated, and is solvable, in any number of dimensions on any bipartite graph. Another example, in any dimension, has Z2 topological order and anyons which are Kramers' doublets of time-reversal symmetry. Further, we make exactly solvable models of three-dimensional topological paramagnets.

  8. Dosimetric evaluation of sodium carbonate (Na2CO3) by electronic paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Ureña-Núñez, F.; Dávila Ballesteros, M. R.

    This work presents the possibility to use the electron paramagnetic resonance (EPR) signal of gamma-irradiated sodium carbonate for dosimetric purposes. The dosimeters were irradiated in a 60Co source. The process induced in sodium carbonate by gamma rays results in the formation of carboxil radical anions ./GRAD_A_327316_O_XML_IMAGES/GRAD_A_327316_O_ILM0001.gif . This way, the method is based on the evaluation of the EPR signal of these radical anions in the material. The aspects studied were peak-to-peak signal amplitude as a function of received dose, signal fading, signal repeatability, sample homogeneity, zero response and environmental effects. It has been concluded that sodium carbonate can be used as a sensitive material to gamma radiation.

  9. Strength and scales of itinerant spin fluctuations in 3 d paramagnetic metals

    NASA Astrophysics Data System (ADS)

    Wysocki, Aleksander L.; Kutepov, Andrey; Antropov, Vladimir P.

    2016-10-01

    The full spin density fluctuations (SDF) spectra in 3 d paramagnetic metals are analyzed from first principles using the linear response technique. Using the calculated complete wave vector and energy dependence of the dynamic spin susceptibility, we obtain the most important, but elusive, characteristic of SDF in solids: on-site spin correlator (SC). We demonstrate that the SDF have a mixed character consisting of interacting collective and single-particle excitations of similar strength spreading continuously over the entire Brillouin zone and a wide energy range up to femtosecond time scales. These excitations cannot be adiabatically separated and their intrinsically multiscale nature should always be taken into account for a proper description of metallic systems. Overall, in all studied systems, despite the lack of local moment, we found a very large SC resulting in an effective fluctuating moment of the order of several Bohr magnetons.

  10. Age of an Indonesian Fossil Tooth Determined by Electron Paramagnetic Resonance

    SciTech Connect

    Bogard, JS

    2004-04-07

    The first fossil hominid tooth recovered during 1999 excavations from the Cisanca River region in West Java, Indonesia, was associated with a series of bovid teeth from a single individual that was recovered 190 cm beneath the hominid tooth. The age of the fossil bovid teeth was determined using electron paramagnetic resonance (EPR) analysis as part of an effort to bracket the age of the hominid tooth. The EPR-derived age of the bovid teeth is (5.16 {+-} 2.01) x 10{sup 5} years. However, the age estimate reported here is likely an underestimate of the actual age of deposition since evidence of heating was detected in the EPR spectra of the bovid teeth, and the heating may have caused a decrease in the intensity of EPR components on which the age calculation is based.

  11. 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.

  12. Imaging of Nitroxides at 250 MHz using Rapid-Scan Electron Paramagnetic Resonance

    PubMed Central

    Biller, Joshua R.; Tseitlin, Mark; Quine, Richard W.; Rinard, George A.; Weismiller, Hilary A.; Elajaili, Hanan; Rosen, Gerald M.; Kao, Joseph P. Y.; Eaton, Sandra S.; Eaton, Gareth R.

    2014-01-01

    Projections for 2D spectral-spatial images were obtained by continuous wave and rapid-scan electron paramagnetic resonance using a bimodal cross-loop resonator at 251 MHz. The phantom consisted of three 4 mm tubes containing different 15N,2H-substituted nitroxides. Rapid-scan and continuous wave images were obtained with 5 min total acquisition times. For comparison, images also were obtained with 29 s acquisition time for rapid scan and 15 min for continuous wave. Relative to continuous wave projections obtained for the same data acquisition time, rapid-scan projections had significantly less low-frequency noise and substantially higher signal-to-noise at higher gradients. Because of the improved image quality for the same data acquisition time, linewidths could be determined more accurately from the rapid-scan images than from the continuous wave images. PMID:24650729

  13. Imaging of nitroxides at 250MHz using rapid-scan electron paramagnetic resonance.

    PubMed

    Biller, Joshua R; Tseitlin, Mark; Quine, Richard W; Rinard, George A; Weismiller, Hilary A; Elajaili, Hanan; Rosen, Gerald M; Kao, Joseph P Y; Eaton, Sandra S; Eaton, Gareth R

    2014-05-01

    Projections for 2D spectral-spatial images were obtained by continuous wave and rapid-scan electron paramagnetic resonance using a bimodal cross-loop resonator at 251MHz. The phantom consisted of three 4mm tubes containing different (15)N,(2)H-substituted nitroxides. Rapid-scan and continuous wave images were obtained with 5min total acquisition times. For comparison, images also were obtained with 29s acquisition time for rapid scan and 15min for continuous wave. Relative to continuous wave projections obtained for the same data acquisition time, rapid-scan projections had significantly less low-frequency noise and substantially higher signal-to-noise at higher gradients. Because of the improved image quality for the same data acquisition time, linewidths could be determined more accurately from the rapid-scan images than from the continuous wave images.

  14. Electron paramagnetic resonance dose response studies for neutron irradiated human teeth

    NASA Astrophysics Data System (ADS)

    Khan, Rao F. H.; Aslam; Rink, W. J.; Boreham, D. R.

    2004-10-01

    The dosimetric response of neutron irradiated human tooth enamel has been investigated using electron paramagnetic resonance (EPR) dosimetry. Continuous energy fast neutrons of mean energy less than 450 keV were produced from the McMaster University 3 MV K.N. Van de Graaff accelerator employing a thick lithium target via 7Li(p,n) 7Be interaction. Prior to its use for various experiments, the gamma dose contamination of the neutron beams was determined at the selected proton beam energies using the tissue-equivalent proportional counter (TEPC). The neutron sensitivity (/Gy-100 mg) of human tooth enamel remained constant for various mean neutron energies ranging from 167 to 450 keV. Similarly, the EPR signal intensity remained independent of the neutron dose rate variation from 0.5 to 2.4 Gy/h.

  15. Paramagnetic nanoparticle-based detection of hepatitis B virus using cathodic stripping voltammetry.

    PubMed

    Fatemi, Kamal; Ghourchian, Hedayatollah; Ziaee, Abed-Ali; Samiei, Shahram; Hanaee, Hana

    2009-03-01

    A nanoparticle-based electrochemical method for detection of hepatitis B virus DNA sequences has been developed. This method relies on the adsorption of amplified hepatitis B virus DNA strands on to probe-coated paramagnetic particles and electrochemical detection of hybridized strands using a hanging mercury drop electrode. For hepatitis B virus detection, a combination of dynamic DNA hybridization on transportable reactive surfaces and label-free detection of DNA based on the electrochemical determination of adenines was used. Separation of the hybridization area from the detection electrode eliminates non-specific adsorption of long DNAs, and combining this method with dynamic synthesis of probe may result in new flexible approaches for detection of other infectious agents by lab-on-a-chip technology.

  16. 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.

  17. Simultaneous electrochemical and electron paramagnetic resonance studies of carotenoids. Effect of electron donating and accepting substituents

    SciTech Connect

    Jeevarajan, A.S.; Khaled, M.; Kispert, L.D. )

    1994-08-11

    A series of substituted phenyl-7[prime]-apocarotenoids with varying electron donating and accepting substituents was examined by cyclic voltammogram (CV) and simultaneous electrochemical electron paramagnetic resonance (SEEPR). Carotenoids substituted with electron donating groups are more easily oxidized than those with electron accepting substituents. Comproportionation constants for the dication and the neutral species were measured by SEEPR techniques and by simulation of the CVs. The [Delta]H[sub pp] of the SEEPR spectrum of the cation radicals varies from 13.2 to 15.6 G, and the g factors are 2.0027 [+-] 0.0002. These EPR parameters suggest a polyene [pi]-cation radical structure. The CVs are calculated using DigiSim, a CV simulation program, and the proposed mechanism involves three electrode reactions and two homogeneous reactions. 24 refs., 3 figs., 2 tabs.

  18. Observation of Classical-Quantum Crossover of 1 /f Flux Noise and Its Paramagnetic Temperature Dependence

    NASA Astrophysics Data System (ADS)

    Quintana, C. M.; Chen, Yu; Sank, D.; Petukhov, A. G.; White, T. C.; Kafri, Dvir; Chiaro, B.; Megrant, A.; Barends, R.; Campbell, B.; Chen, Z.; Dunsworth, A.; Fowler, A. G.; Graff, R.; Jeffrey, E.; Kelly, J.; Lucero, E.; Mutus, J. Y.; Neeley, M.; Neill, C.; O'Malley, P. J. J.; Roushan, P.; Shabani, A.; Smelyanskiy, V. N.; Vainsencher, A.; Wenner, J.; Neven, H.; Martinis, John M.

    2017-02-01

    By analyzing the dissipative dynamics of a tunable gap flux qubit, we extract both sides of its two-sided environmental flux noise spectral density over a range of frequencies around 2 kBT /h ≈1 GHz , allowing for the observation of a classical-quantum crossover. Below the crossover point, the symmetric noise component follows a 1 /f power law that matches the magnitude of the 1 /f noise near 1 Hz. The antisymmetric component displays a 1 /T dependence below 100 mK, providing dynamical evidence for a paramagnetic environment. Extrapolating the two-sided spectrum predicts the linewidth and reorganization energy of incoherent resonant tunneling between flux qubit wells.

  19. High-Frequency Electron Paramagnetic Resonance Spectroscopy of Nitroxide-Functionalized Nanodiamonds in Aqueous Solution.

    PubMed

    Akiel, R D; Stepanov, V; Takahashi, S

    2016-06-21

    Nanodiamond (ND) is an attractive class of nanomaterial for fluorescent labeling, magnetic sensing of biological molecules, and targeted drug delivery. Many of those applications require tethering of target biological molecules on the ND surface. Even though many approaches have been developed to attach macromolecules to the ND surface, it remains challenging to characterize dynamics of tethered molecule. Here, we show high-frequency electron paramagnetic resonance (HF EPR) spectroscopy of nitroxide-functionalized NDs. Nitroxide radical is a commonly used spin label to investigate dynamics of biological molecules. In the investigation, we developed a sample holder to overcome water absorption of HF microwave. Then, we demonstrated HF EPR spectroscopy of nitroxide-functionalized NDs in aqueous solution and showed clear spectral distinction of ND and nitroxide EPR signals. Moreover, through EPR spectral analysis, we investigate dynamics of nitroxide radicals on the ND surface. The demonstration sheds light on the use of HF EPR spectroscopy to investigate biological molecule-functionalized nanoparticles.

  20. Local structure and paramagnetic properties of the nanostructured carbonaceous material shungite

    NASA Astrophysics Data System (ADS)

    Krasnovyd, Serhii Volodymyrovich; Konchits, Andriy Andriyovich; Shanina, Bela Dmytrivna; Valakh, Mykhaylo Yakovych; Yanchuk, Igor Bogdanovich; Yukhymchuk, Volodymyr Olexsandrovych; Yefanov, Andriy Volodymyrovich; Skoryk, Mykola Andriyovich

    2015-02-01

    Using a scanning electron microscopy, elemental analysis, electron paramagnetic resonance, and Raman scattering methods, two types of the shungite materials (Sh-II from Zazhogino deposit and shungite from a commercial filter (ShF)), with different carbon content and porosity, are studied in this work. It was established by scanning electron microscopy data that the structure of the shungite samples is formed by a micron-size agglomeration of carbon and silicon dioxide clusters. It is found from the Raman data that carbon fraction is formed from sp2-hybridized clusters, size of which increases from 9 up to 12 nm after annealing of the samples. High conductivity of shungite is found to belong to the carbon nanoclusters of different sizes. Big clusters give the conduction electron spin resonance signal with a Dysonian line shape with variable g-factor and line width.