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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. NMR temperature measurements using a paramagnetic lanthanide complex.

    PubMed

    Zuo, C S; Metz, K R; Sun, Y; Sherry, A D

    1998-07-01

    NMR thermometry has previously suffered from poor thermal resolution owing to the relatively weak dependence of chemical shift on temperature in diamagnetic molecules. In contrast, the shifts of nuclear spins near a paramagnetic center exhibit strong temperature dependencies. The chemical shifts of the thulium 1,4,7, 10-tetraazacyclododecane-1,4,7,10-tetrakis(methylene phosphonate) complex (TmDOTP5-) have been studied as a function of temperature, pH, and Ca2+ concentration over ranges which may be encountered in vivo. The results demonstrate that the 1H and 31P shifts in TmDOTP5- are highly sensitive to temperature and may be used for NMR thermometry with excellent accuracy and resolution. A new technique is also described which permits simultaneous measurements of temperature and pH changes from the shifts of multiple TmDOTP5- spectral lines. PMID:9654468

  3. Combining NMR of dynamic and paramagnetic molecules: fluxional high-spin nickel(II) complexes bearing bisguanidine ligands.

    PubMed

    Roquette, Pascal; Maronna, Astrid; Reinmuth, Matthias; Kaifer, Elisabeth; Enders, Markus; Himmel, Hans-Jörg

    2011-03-01

    A detailed nuclear magnetic resonance (NMR) study was carried out on a series of paramagnetic, tetrahedrally coordinated nickel(II) dihalide complexes featuring chelating guanidine ligands. A complete assignment of the NMR signals for all complexes was achieved by sophisticated NMR experiments, including correlation spectra. The effects of halide exchange, as well as the variation in the guanidine-metal bite angles on the paramagnetic shifts, were assessed. The paramagnetic shift was derived with the aid of the diamagnetic NMR spectra of the analogous Zn complexes, which were synthesized for this purpose. The experimentally derived paramagnetic shift was then compared with the values obtained from quantum chemical (DFT) calculations. Furthermore, variable-temperature NMR studies were recorded for all complexes. It is demonstrated that NMR spectroscopy can be applied to evaluate the rate constants of fast fluxional processes within paramagnetic and catalytically active metal complexes. PMID:21268654

  4. 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. PMID:26918733

  5. A caged lanthanide complex as a paramagnetic shift agent for protein NMR.

    PubMed

    Prudêncio, Miguel; Rohovec, Jan; Peters, Joop A; Tocheva, Elitza; Boulanger, Martin J; Murphy, Michael E P; Hupkes, Hermen-Jan; Kosters, Walter; Impagliazzo, Antonietta; Ubbink, Marcellus

    2004-07-01

    A lanthanide complex, named CLaNP (caged lanthanide NMR probe) has been developed for the characterisation of proteins by paramagnetic NMR spectroscopy. The probe consists of a lanthanide chelated by a derivative of DTPA (diethylenetriaminepentaacetic acid) with two thiol reactive functional groups. The CLaNP molecule is attached to a protein by two engineered, surface-exposed, Cys residues in a bidentate manner. This drastically limits the dynamics of the metal relative to the protein and enables measurements of pseudocontact shifts. NMR spectroscopy experiments on a diamagnetic control and the crystal structure of the probe-protein complex demonstrate that the protein structure is not affected by probe attachment. The probe is able to induce pseudocontact shifts to at least 40 A from the metal and causes residual dipolar couplings due to alignment at a high magnetic field. The molecule exists in several isomeric forms with different paramagnetic tensors; this provides a fast way to obtain long-range distance restraints. PMID:15224334

  6. The dynamic complex of cytochrome c6 and cytochrome f studied with paramagnetic NMR spectroscopy.

    PubMed

    Díaz-Moreno, Irene; Hulsker, Rinske; Skubak, Pavol; Foerster, Johannes M; Cavazzini, Davide; Finiguerra, Michelina G; Díaz-Quintana, Antonio; Moreno-Beltrán, Blas; Rossi, Gian-Luigi; Ullmann, G Matthias; Pannu, Navraj S; De la Rosa, Miguel A; Ubbink, Marcellus

    2014-08-01

    The rapid transfer of electrons in the photosynthetic redox chain is achieved by the formation of short-lived complexes of cytochrome b6f with the electron transfer proteins plastocyanin and cytochrome c6. A balance must exist between fast intermolecular electron transfer and rapid dissociation, which requires the formation of a complex that has limited specificity. The interaction of the soluble fragment of cytochrome f and cytochrome c6 from the cyanobacterium Nostoc sp. PCC 7119 was studied using NMR spectroscopy and X-ray diffraction. The crystal structures of wild type, M58H and M58C cytochrome c6 were determined. The M58C variant is an excellent low potential mimic of the wild type protein and was used in chemical shift perturbation and paramagnetic relaxation NMR experiments to characterize the complex with cytochrome f. The interaction is highly dynamic and can be described as a pure encounter complex, with no dominant stereospecific complex. Ensemble docking calculations and Monte-Carlo simulations suggest a model in which charge-charge interactions pre-orient cytochrome c6 with its haem edge toward cytochrome f to form an ensemble of orientations with extensive contacts between the hydrophobic patches on both cytochromes, bringing the two haem groups sufficiently close to allow for rapid electron transfer. This model of complex formation allows for a gradual increase and decrease of the hydrophobic interactions during association and dissociation, thus avoiding a high transition state barrier that would slow down the dissociation process. PMID:24685428

  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. PMID:26068746

  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. Effect of chelate dynamics on water exchange reactions of paramagnetic aminopolycarboxylate complexes.

    PubMed

    Maigut, Joachim; Meier, Roland; Zahl, Achim; van Eldik, Rudi

    2008-07-01

    Because of our interest in evaluating a possible relationship between complex dynamics and water exchange reactivity, we performed (1)H NMR studies on the paramagnetic aminopolycarboxylate complexes Fe (II)-TMDTA and Fe (II)-CyDTA and their diamagnetic analogues Zn (II)-TMDTA and Zn (II)-CyDTA. Whereas a fast Delta-Lambda isomerization was observed for the TMDTA species, no acetate scrambling between in-plane and out-of-plane positions is accessible for any of the CyDTA complexes because the rigid ligand backbone prevents any configurational changes in the chelate system. In variable-temperature (1)H NMR studies, no evidence of spectral coalescence due to nitrogen inversion was found for any of the complexes in the available temperature range. The TMDTA complexes exhibit the known solution behavior of EDTA, whereas the CyDTA complexes adopt static solution structures. Comparing the exchange kinetics of flexible EDTA-type complexes and static CyDTA complexes appears to be a suitable method for evaluating the effect of ligand dynamics on the overall reactivity. In order to assess information concerning the rates and mechanism of water exchange, we performed variable-temperature and -pressure (17)O NMR studies of Ni (II)-CyDTA, Fe (II)-CyDTA, and Mn (II)-CyDTA. For Ni (II)-CyDTA, no significant effects on line widths or chemical shifts were apparent, indicating either the absence of any chemical exchange or the existence of a very small amount of the water-coordinated complex in solution. For [Fe (II)(CyDTA)(H 2O)] (2-) and [Mn (II)(CyDTA)(H 2O)] (2-), exchange rate constant values of (1.1 +/- 0.3) x 10 (6) and (1.4 +/- 0.2) x 10 (8) s (-1), respectively, at 298 K were determined from fits to resonance-shift and line-broadening data. A relationship between chelate dynamics and reactivity seems to be operative, since the CyDTA complexes exhibited significantly slower reactions than their EDTA counterparts. The variable-pressure (17)O NMR measurements for [Mn (II

  10. Synthesis and Characterization of Paramagnetic Tungsten Imido Complexes Bearing α-Diimine Ligands.

    PubMed

    Tanahashi, Hiromasa; Ikeda, Hideaki; Tsurugi, Hayato; Mashima, Kazushi

    2016-02-15

    Tungsten imido complexes bearing a redox-active ligand, such as N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-2,3-dimethyl-1,3-butadiene (L1), N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene (L2), and 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (L3), were prepared by salt-free reduction of W(═NC6H3-2,6-(i)Pr2)Cl4 (1) using 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) followed by addition of the corresponding redox-active ligands. In the initial stage, reaction of W(═NC6H3-2,6-(i)Pr2)Cl4 with MBTCD afforded a tetranuclear W(V) imido cluster, [W(═NC6H3-2,6-(i)Pr2)Cl3]4 (2), which served as a unique precursor for introducing redox-active ligands to the tungsten center to give the corresponding mononuclear complexes with a general formula of W(═NC6H3-2,6-(i)Pr2)Cl3(L) (3, L = L1; 4, L = L2; and 6, L = L3). X-ray analyses of complexes 3 and 6 revealed a neutral coordination mode of L1 and L3 to the tungsten in solid state, while the electron paramagnetic resonance (EPR) spectra of 3 and 4 clarified that a radical was predominantly located on the tungsten center supported by neutral L1 or L2, and the EPR spectra of complex 6 indicated that a radical was delocalized over both the tungsten center and the monoanionic redox-active ligand L3. PMID:26841126

  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. NMR paramagnetic relaxation of the spin 2 complex Mn(III)TSPP: a unique mechanism.

    PubMed

    Schaefle, Nathaniel; Sharp, Robert

    2005-04-21

    The S = 2 complex, manganese(III) meso-tetra(4-sulfonatophenyl)porphine chloride (Mn(III)TSPP) is a highly efficient relaxation agent with respect to water protons and has been studied extensively as a possible MRI contrast agent. The NMR relaxation mechanism has several unique aspects, key among which is the unusual role of zero-field splitting (zfs) interactions and the effect of these interactions on the electron spin dynamics. The principal determinant of the shape of the R1 magnetic relaxation dispersion (MRD) profile is the tetragonal 4th-order zfs tensor component, B4(4), which splits the levels of the m(S) = +/-2 non-Kramers doublet. When the splitting due to B4(4) exceeds the Zeeman splitting, the matrix elements of (S(z)) are driven into coherent oscillation, with the result that the NMR paramagnetic relaxation enhancement is suppressed. To confirm the fundamental aspects of this mechanism, proton R1 MRD data have been collected on polyacrylamide gel samples in which Mn(III)TSPP is reorientationally immobilized. Solute immobilization suppresses time-dependence in the electron spin Hamiltonian that is caused by Brownian motion, simplifying the theoretical analysis. Simultaneous fits of both gel and solution data were achieved using a single set of parameters, all of which were known or tightly constrained from prior experiments except the 4th-order zfs parameter, B4(4), and the electron spin relaxation times, which were found to differ in the m(S) = +/-1 and m(S) = +/-2 doublet manifolds. In liquid samples, but not in the gels, the B4(4)-induced splitting of the m(S) = +/-2 non-Kramers doublet is partially collapsed due to Brownian motion. This phenomenon affects the magnitudes of both B4(4) and electron spin relaxation times in the liquid samples. PMID:16833659

  13. Electron paramagnetic resonance (EPR) study of spin-labeled camptothecin derivatives: a different look of the ternary complex.

    PubMed

    Ricci, Antonio; Marinello, Jessica; Bortolus, Marco; Sánchez, Albert; Grandas, Anna; Pedroso, Enrique; Pommier, Yves; Capranico, Giovanni; Maniero, Anna Lisa; Zagotto, Giuseppe

    2011-02-24

    Camptothecin (CPT) derivatives are clinically effective poisons of DNA topoisomerase I (Top1) able to form a ternary complex with the Top1-DNA complex. The aim of this investigation was to examine the dynamic aspects of the ternary complex formation by means of site-directed spin labeling electron paramagnetic resonance (SDSL-EPR). Two semisynthetic CPT derivatives bearing the paramagnetic moiety were synthesized, and their biological activity was tested. A 22-mer DNA oligonucleotide sequence with high affinity cleavage site for Top1 was also synthesized. EPR experiments were carried out on modified CPT in the presence of DNA, of Top1, or of both. In the last case, a slow motion component in the EPR signal appeared, indicating the formation of the ternary complex. Deconvolution of the EPR spectrum allowed to obtain the relative drug amounts in the complex. It was also possible to demonstrate that the residence time of CPT "trapped" in the ternary complex is longer than hundreds of microseconds. PMID:21254781

  14. Integration of Paramagnetic Diruthenium Complexes into an Extended Chain by Heterometallic Metal-Metal Bonds with Diplatinum Complexes.

    PubMed

    Uemura, Kazuhiro; Uesugi, Naoyuki; Matsuyama, Akina; Ebihara, Masahiro; Yoshikawa, Hirofumi; Awaga, Kunio

    2016-07-18

    We successfully obtained a paramagnetic one-dimensional (1D) chain complex [{Ru2(O2CCH3)4}{Pt2(piam)2(NH3)4}2]n(PF6)4n·4nH2O (2; piam = pivalamidate) extended by metal-metal bonds. Compound 2 comprises two types of metal species, ruthenium and platinum, where an acetate-bridged dinuclear ruthenium complex (i.e., [Ru2]) and a pivalamidate-bridged platinum complex (i.e., [Pt2]) are connected by axial metal-metal bonds, forming an attractive quasi-1D infinite chain that can be expressed as -{[Pt2]-[Ru2]-[Pt2]}n-. Such axial metal-metal bonds are attributed to the interaction between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) along the z axis, where both the HOMO in [Pt2(II,II)] and the LUMO in [Ru2(II,II)] are σ* orbitals associated with metal cores. The crystal structure and X-ray photoelectron spectrum for 2 reveal that metal oxidation states are -{[Pt2(II,II)]-[Ru2(II,II)]-[Pt2(II,II)]}n-, where [Ru2(II,II)] can have an electronic configuration of σ(2)π(4)δ(2)δ*(2)π*(2) or σ(2)π(4)δ(2)π*(4). The magnetic susceptibility of 2 has a μeff [∝(χT)(1/2)] value of 2.77 μB per [Pt2(II,II)]-[Ru2(II,II)]-[Pt2(II,II)] unit at 300 K, showing that two unpaired electrons lie on π*(Ru2). Magnetic measurements performed at temperatures of 2-300 K indicate that S = 1 Ru2(II,II) units are weakly antiferromagnetically coupled (zJ = -1.4 cm(-1)) with a large zero-field splitting (D = 221 cm(-1)). PMID:27348516

  15. Binding energies and 19F nuclear magnetic deshielding in paramagnetic halogen-bonded complexes of TEMPO with haloperfluorocarbons.

    PubMed

    Cavallotti, Carlo; Metrangolo, Pierangelo; Meyer, Franck; Recupero, Francesco; Resnati, Giuseppe

    2008-10-01

    19F NMR measurements and theoretical calculations were performed to study paramagnetic complexes of iodoperfluorocarbons with stable nitroxide radicals. Contrary to what is usually measured for diamagnetic halogen-bonded complexes involving iodoperfluorocarbons, it was found that the formation of complexes with the 2,2,6,6-tetramethyl(piperidin-1-yloxyl) (TEMPO) radical determines downfield shifts in the 19F NMR spectra. The experimental finding was confirmed by calculating nuclear shielding using density functional theory and correcting the isotropic diamagnetic (19)F chemical shift with contact interactions evaluated from the hyperfine coupling tensor. The computational analysis of the interaction between CF3I and TEMPO, by using DFT and MP2 theories, showed that the occurrence of the halogen bond between the interacting partners is associated with a significant charge transfer to CF3I and that the measured downfield shift is due to the occurring spin transfer. PMID:18795762

  16. Solvent and metal dependent (1)H NMR hyperfine shifts in paramagnetic pentaamminemetal cyanide-bridged mixed-valence complexes.

    PubMed

    Laidlaw, William Michael; Thompson, Amber L; Denning, Robert Gordon

    2013-04-01

    (1)H NMR resonances, in several aprotic solvents, are reported for axial and equatorial ammonias coordinated to a single spin paramagnetic centre in the Robin-Day Class II cyanide-bridged mixed-valence cations [(OC)(5)Cr(μ-CN)M(NH(3))(5)](2+) (M = Ru, Os) as well as in the complex [(OC)(5)Re(μ-CN)Ru(NH(3))(5)](3+), whose synthesis and properties are reported herein. Using the appropriate isotropic hexaammine complex as a reference, the chemical shift difference between the ammonia protons, δ(ax) - δ(eq), is found to be very sensitive to the paramagnetic metal (M), the remote diamagnetic metal (Cr or Re) and also to the donor properties of the solvent (as well as the counter-ion) as a result of hydrogen bonding interactions. The difference varies linearly with the MMCT energy, and in [(OC)(5)Re(μ-CN)Ru(NH(3))(5)](3+) can be tuned from positive (δ(ax) > δ(eq)) to negative (δ(ax) < δ(eq)) through zero (δ(ax) = δ(eq)) by the choice of solvent. This reflects the sign and magnitude of the axial ligand field parameter which is in turn a result of changes in the π-donor-acceptor interactions between the donor-cyanide bridging group and the pentaammine metal unit. PMID:23361503

  17. The structure of the cytochrome p450cam-putidaredoxin complex determined by paramagnetic NMR spectroscopy and crystallography.

    PubMed

    Hiruma, Yoshitaka; Hass, Mathias A S; Kikui, Yuki; Liu, Wei-Min; Ölmez, Betül; Skinner, Simon P; Blok, Anneloes; Kloosterman, Alexander; Koteishi, Hiroyasu; Löhr, Frank; Schwalbe, Harald; Nojiri, Masaki; Ubbink, Marcellus

    2013-11-15

    Cytochrome P450cam catalyzes the hydroxylation of camphor in a complex process involving two electron transfers (ETs) from the iron-sulfur protein putidaredoxin. The enzymatic control of the successive steps of catalysis is critical for a highly efficient reaction. The injection of the successive electrons is part of the control system. To understand the molecular interactions between putidaredoxin and cytochrome P450cam, we determined the structure of the complex both in solution and in the crystal state. Paramagnetic NMR spectroscopy using lanthanide tags yielded 446 structural restraints that were used to determine the solution structure. An ensemble of 10 structures with an RMSD of 1.3Å was obtained. The crystal structure of the complex was solved, showing a position of putidaredoxin that is identical with the one in the solution structure. The NMR data further demonstrate the presence of a minor state or set of states of the complex in solution, which is attributed to the presence of an encounter complex. The structure of the major state shows a small binding interface and a metal-to-metal distance of 16Å, with two pathways that provide strong electronic coupling of the redox centers. The interpretation of these results is discussed in the context of ET. The structure indicates that the ET rate can be much faster than the reported value, suggesting that the process may be gated. PMID:23856620

  18. Enhanced sensitivity and resolution in (1)H solid-state NMR spectroscopy of paramagnetic complexes under very fast magic angle spinning.

    PubMed

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

    2005-04-27

    High-resolution NMR spectroscopy for paramagnetic complexes in solids has been rarely performed because of its limited sensitivity and resolution due to large paramagnetic shifts and associated technical difficulties. The present study demonstrates that magic angle spinning (MAS) at speeds exceeding 20 kHz provides unusually high sensitivity and excellent resolution in 1H solid-state NMR (SSNMR) for paramagnetic systems. Spinning-speed dependence of 1H MAS spectra showed that very fast MAS (VFMAS) at 24-28 kHz enhanced sensitivity by a factor of 12-18, compared with the sensitivity of 1H SSNMR spectra under moderate MAS at 10 kHz, for Cu(dl-alanine)2.H2O and Mn(acac)3, for which the spectral ranges due to 1H paramagnetic shifts reach 200 and 1000 ppm, respectively. It was theoretically and experimentally confirmed that the absolute sensitivity of 1H VFMAS for small paramagnetic complexes such as Cu(dl-alanine)2 can be an order of magnitude higher than that of equimolar diamagnetic ligands because of short 1H T1 ( approximately 1 ms) of the paramagnetic systems and improved sensitivity under VFMAS. On the basis of this demonstrated high sensitivity, 1H SSNMR micro analysis of paramagnetic systems in a nanomole scale is proposed. Applications were performed on two polymorphs of Cu(II)(8-quinolinol)2, which is a suppressor of human cancer cells. It was demonstrated that 1H VFMAS SSNMR spectra accumulated for 20 nmol of the polycrystalline samples in 10 min enabled one to distinguish alpha- and beta-forms of Cu(II)(8-quinolinol)2 on the basis of shift positions and line widths. PMID:15839671

  19. 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.

  20. Structural switching from paramagnetic to single-molecule magnet behaviour of LnZn2 trinuclear complexes.

    PubMed

    Then, Poh Ling; Takehara, Chika; Kataoka, Yumiko; Nakano, Motohiro; Yamamura, Tomoo; Kajiwara, Takashi

    2015-11-01

    Five LnZn2 trinuclear complexes, [Ln(NO3){Zn(L)(SCN)}2] (H2L is a Schiff base ligand derived from o-vanillin and ethylenediamine; Ln = Tb 1, Dy 2, La 3, Tb0.14La0.864, and Dy0.21La0.795), were synthesised in which the Zn(II)-Ln(III)-Zn(II) array exhibits two slightly different arrangements: 1 and 2 exhibited slightly bent arrangements, whereas 3-5 exhibited more linear arrangements. These differences in the arrangements lead to a slightly different coordination geometry around Ln(III). From the detailed studies of dynamic susceptibility, 1 and 2 were found to be paramagnetic, whereas 4 and 5 were SMMs with barriers for the flipping of magnetisation with a height of 41.2(4) K and 156(4) K, respectively. PMID:26411298

  1. 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). PMID:26123621

  2. 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

  3. 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

  4. 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. PMID:19957934

  5. Early folding events during light harvesting complex II assembly in vitro monitored by pulsed electron paramagnetic resonance.

    PubMed

    Fehr, Niklas; García-Rubio, Inés; Jeschke, Gunnar; Paulsen, Harald

    2016-06-01

    Efficient energy transfer in the major light harvesting complex II (LHCII) of green plants is facilitated by the precise alignment of pigments due to the protein matrix they are bound to. Much is known about the import of the LHCII apoprotein into the chloroplast via the TOC/TIC system and its targeting to the thylakoid membrane but information is sparse about when and where the pigments are bound and how this is coordinated with protein folding. In vitro, the LHCII apoprotein spontaneously folds and binds its pigments if the detergent-solubilized protein is combined with a mixture of chlorophylls a and b and carotenoids. In the present work, we employed this approach to study apoprotein folding and pigment binding in a time-resolved manner by using pulsed electron paramagnetic resonance (EPR). Intra-molecular distances were measured before folding, after 255 ms and 40 s folding time in the absence of cryoprotectant, and in the fully folded and assembled LHCII. In accordance with earlier results, the most of the folding of the three membrane-spanning alpha helices precedes their apposition into the final tertiary structure. However, their formation follows different kinetics, partially extending into the final phase of LHCII formation during which much of the condensation of the pigment-protein structure occurs, presumably governed by the binding of chlorophyll b. A rough timetable is proposed to sort partial events into the LHCII formation process. PMID:27063475

  6. Paramagnetic complexes of 9,10-anthraquinone on zeolite surfaces and their thermal transformations

    NASA Astrophysics Data System (ADS)

    Fionov, A. V.; Nekhaev, A. I.; Shchapin, I. Yu.; Maksimov, A. L.; Lunin, V. V.

    2013-12-01

    The concentration of one-electron transfer sites on the surface of H-ZSM-5, H-Y, H-mordenite, and H-β zeolites was measured by EPR using 9,10-antrhraquinone as a probe. It has been found that the hyperfine structure from four protons typical for one-centered complexes of anthraquinone with one acidic site was observed in the EPR spectra after anthraquinone interaction with a zeolite surface in the temperature range of 373 to 423 K. It has been established that an elevated temperature of 473 K promoted the decomposition of the adsorbed anthraquinone and the disappearance of the hyperfine structure. It has been shown that the thermal instability of anthraquinone adsorbed on zeolites changed in the series H-β > H-Y > H-ZSM-5 ˜ H-mordenite; the coke-forming ability of zeolites with regard to n-decane at 443 K changed in a similar manner. It has been established that the presence of air promoted coke-forming processes upon interaction between n-decane and zeolites.

  7. EPR, ENDOR, and HYSCORE study of the structure and the stability of vanadyl-porphyrin complexes encapsulated in silica: potential paramagnetic biomarkers for the origin of life.

    PubMed

    Gourier, Didier; Delpoux, Olivier; Bonduelle, Audrey; Binet, Laurent; Ciofini, Ilaria; Vezin, Hervé

    2010-03-18

    The possibility of using vanadyl ions as paramagnetic biomarkers for the identification of traces of primitive life fossilized in silica rocks is studied by cw-EPR, ENDOR, HYSCORE, and DFT calculations. It is well-known that porphyrins, which are common to all living organisms, form vanadyl-porphyrin complexes in sediments deposited in oceans. However, the stability of these complexes over a very long time (more than 3 billion years) is not known. By encapsulating vanadyl-porphyrin complexes in silica synthesized by a sol-gel method to mimic SiO(2) sediments, we studied the structure and stability of these complexes upon step heating treatments by monitoring the evolution of the g factor and of the hyperfine interactions with (51)V, (1)H, (14)N, (13)C, and (29)Si nuclei. It is found that vanadyl-porphyrin complexes are progressively transformed into oxygenated vanadyl complexes by transfer of the VO(2+) ion from the porphyrin ring to the mineral matrix. The organic component is transformed into carbonaceous matter which contains paramagnetic centers (IOM(*) centers). To test the validity of this approach, we studied by EPR a 3490 million years old chert (polycrystalline SiO(2) rock) containing some of the oldest putative traces of life. This rock contains oxygenated vanadyl complexes and IOM(*) centers very similar to those found in the synthetic analogues. PMID:20175553

  8. Another challenge to paramagnetic relaxation theory: a study of paramagnetic proton NMR relaxation in closely related series of pyridine-derivatised dysprosium complexes.

    PubMed

    Rogers, Nicola J; Finney, Katie-Louise N A; Senanayake, P Kanthi; Parker, David

    2016-02-14

    Measurements of the relaxation rate behaviour of two series of dysprosium complexes have been performed in solution, over the field range 1.0 to 16.5 Tesla. The field dependence has been modelled using Bloch-Redfield-Wangsness theory, allowing estimates of the electronic relaxation time, T1e, and the size of the magnetic susceptibility, μeff, to be made. Changes in relaxation rate of the order of 50% at higher fields were measured, following variation of the para-substituent in the single pyridine donor. The magnetic susceptibilities deviated unexpectedly from the free-ion values for certain derivatives in each series examined, in a manner that was independent of the electron-releasing/withdrawing ability of the pyridine substituent, suggesting that the polarisability of just one pyridine donor in octadenate ligands can play a significant role in defining the magnetic susceptibility anisotropy. PMID:26792243

  9. 4 f-4 f hypersensitivity in the absorption spectra and NMR studies on paramagnetic lanthanide chloride complexes with 1,10-phenanthroline in non-aqueous solutions

    NASA Astrophysics Data System (ADS)

    Hussain, H. A.; Iftikhar, K.

    2003-03-01

    The optical absorption and NMR studies of trivalent lanthanide chloride complexes with 1,10-phenanthroline (phen) are presented and discussed. The 1H NMR spectra of the complexes of La, Pr, Nd, Eu and Yb have been studied in methanol- d4. The resonances of phen in the NMR spectra of the paramagnetic complexes have been shifted to lower as well as higher fields, which is a manifestation of dipolar interaction. The H (2) protons of the heterocyclic amine display broad resonances. The degree of broadening in Pr, Nd, and Yb complexes follows the order Prparamagnetic shift is predominantly due to dipolar interaction. The electronic spectra of Pr, Nd, Ho and Er complexes have been investigated in methanol, pyridine, DMSO and DMF, which reveal that the hypersensitive transitions exhibit larger variation in oscillator strength values and band shapes. The change in the coordination geometry of the complexes and relative basicity of ligand are found responsible for oscillator strength and band shape variation. The interelectronic repulsion and covalency parameters show covalent nature of bonding between the metal and the ligand.

  10. 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

  11. Paramagnetic intermediates in reactions of the components of catalytic systems of the Ziegler type. Reactions of azo and azomethine complexes of Ni(II) with diethylaluminum chloride

    SciTech Connect

    Abbasov, Ya.A.; Ismailov, E.G.; Medzhidov, A.A.

    1988-04-01

    The intermediate paramagnetic particles, i.e., radical particles, complexes of Ni(I), and Ni/sub n/(O) aggregates, formed as a result of the reaction of azo and azomethine complexes of Ni(II) with Et/sub 2/AlCl in solvent media (toluene, THF, heptane) have been identified with the aid of ESR. The possibility of the stabilization of reactive intermediate complexes of Ni(I) by organophosphorus ligands (DPPE and TPP) has been demonstrated, and the magnetic-resonance parameters of their adducts have been determined. It has been postulated that the formation of radical particles occurs as a result of the coordination of the nitrogen atoms of the azo or azomethine ligands by the organoaluminum compound followed by splitting of the -N=N or -CH=N bonds.

  12. Tuning of the spin distribution between ligand- and metal-based spin: electron paramagnetic resonance of mixed-ligand molybdenum tris(dithiolene) complex anions.

    PubMed

    Fekl, Ulrich; Sarkar, Biprajit; Kaim, Wolfgang; Zimmer-De Iuliis, Marco; Nguyen, Neilson

    2011-09-19

    Electron paramagnetic resonance spectra of homoleptic and mixed-ligand molybdenum tris(dithiolene) complex anions [Mo(tfd)(m)(bdt)(n)](-) (n + m = 3; bdt = S(2)C(6)H(4); tfd = S(2)C(2)(CF(3))(2)) reveal that the spin density has mixed metal-ligand character with more ligand-based spin for [Mo(tfd)(3)](-) and a higher degree of metal-based spin for [Mo(bdt)(3)](-): the magnitude of the isotropic (95,97)Mo hyperfine interaction increases continuously, by a factor of 2.5, on going from the former to the latter. The mixed complexes fall in between, and the metal character of the spin increases with the bdt content. The experiments were corroborated by density functional theory computations, which reproduce this steady increase in metal-based character. PMID:21853970

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

    The observation of a double-quantum filtered signal of quadrupolar nuclei (e.g. 23Na) in solution has been traditionally interpreted as a sign for anisotropic reorientational motion. Ling and Jerschow (2007) [23] have found that a 23Na double-quantum signal is observed also in solutions of TmDOTPNa5. 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.

  14. Cobalt(II) "scorpionate" complexes as models for cobalt-substituted zinc enzymes: electronic structure investigation by high-frequency and -field electron paramagnetic resonance spectroscopy.

    PubMed

    Krzystek, J; Swenson, Dale C; Zvyagin, S A; Smirnov, Dmitry; Ozarowski, Andrew; Telser, Joshua

    2010-04-14

    A series of complexes of formula Tp(R,R')CoL, where Tp(R,R'-) = hydrotris(3-R,5-R'-pyrazol-1-yl)borate ("scorpionate") anion (R = tert-butyl, R' = H, Me, 2'-thienyl (Tn), L = Cl(-), NCS(-), NCO(-), N(3)(-)), has been characterized by electronic absorption spectroscopy in the visible and near-infrared (near-IR) region and by high-frequency and -field electron paramagnetic resonance (HFEPR). Reported here are also crystal structures of seven members of the series that have not been reported previously: R' = H, L = NCO(-), N(3)(-); R' = Me, L = Cl(-), NCS(-), NCO(-), N(3)(-); R' = Tn, L = Cl(-), NCS(-). These include a structure for Tp(t-Bu,Me)CoCl different from that previously reported. All of the investigated complexes contain a four-coordinate cobalt(II) ion (3d(7)) with approximate C(3v) point group symmetry about the metal ion and exhibit an S = (3)/(2) high-spin ground state. The use of HFEPR allows extraction of the full set of intrinsic S = (3)/(2) spin Hamiltonian parameters (D, E, and g values). The axial zero-field splitting parameter, D, for all investigated Tp(R,R')CoL complexes is always positive, a fact not easily determined by other methods. However, the magnitude of this parameter varies widely: 2.4 cm(-1) complexes following the angular overlap model (AOM). This description of electronic structure and bonding in pseudotetrahedral cobalt(II) complexes can enhance the understanding of similar sites in metalloproteins, specifically cobalt-substituted zinc enzymes. PMID:20329727

  15. Strategies to enhance signal intensity with paramagnetic fluorine-labelled lanthanide complexes as probes for 19F magnetic resonance.

    PubMed

    Chalmers, Kirsten H; Botta, Mauro; Parker, David

    2011-01-28

    The synthesis and (19)F NMR spectroscopic properties are reported for three series of CF(3)-labelled lanthanide(III) complexes, based on mono- and diamide cyclen ligands. Analyses of variable temperature, pH and field (19)F, (17)O and (1)H NMR spectroscopic experiments are reported and the merits of a triphosphinate mono-amide complex defined by virtue of its favourable isomer distribution and attractive relaxation properties. These lead to an enhanced sensitivity of detection in (19)F magnetic resonance experiments versus a diamagnetic Y(III) analogue, paving the way for future shift and imaging studies. PMID:21127807

  16. 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

    2010-01-01

    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. PMID:19957317

  17. Electronic structure of four-coordinate C3v nickel(II) scorpionate complexes: investigation by high-frequency and -field electron paramagnetic resonance and electronic absorption spectroscopies.

    PubMed

    Desrochers, Patrick J; Telser, Joshua; Zvyagin, S A; Ozarowski, Andrew; Krzystek, J; Vicic, David A

    2006-10-30

    A series of complexes of formula TpNiX, where Tp*- = hydrotris(3,5-dimethylpyrazole)borate and X = Cl, Br, I, has been characterized by electronic absorption spectroscopy in the visible and near-infrared (NIR) region and by high-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy. The crystal structure of TpNiCl has been previously reported; that for TpNiBr is given here: space group = Pmc2(1), a = 13.209(2) A, b = 8.082(2) A, c = 17.639(4) A, alpha = beta = gamma = 90 degrees , Z = 4. TpNiX contains a four-coordinate nickel(II) ion (3d8) with approximate C3v point group symmetry about the metal and a resulting S = 1 high-spin ground state. As a consequence of sizable zero-field splitting (zfs), TpNiX complexes are "EPR silent" with use of conventional EPR; however, HFEPR allows observation of multiple transitions. Analysis of the resonance field versus the frequency dependence of these transitions allows extraction of the full set of spin Hamiltonian parameters. The axial zfs parameter for TpNiX displays pronounced halogen contributions down the series: D = +3.93(2), -11.43(3), -22.81(1) cm(-1), for X = Cl, Br, I, respectively. The magnitude and change in sign of D observed for TpNiX reflects the increasing bromine and iodine spin-orbit contributions facilitated by strong covalent interactions with nickel(II). These spin Hamiltonian parameters are combined with estimates of 3d energy levels based on the visible-NIR spectra to yield ligand-field parameters for these complexes following the angular overlap model (AOM). This description of electronic structure and bonding in a pseudotetrahedral nickel(II) complex can enhance the understanding of similar sites in metalloproteins, both native nickel enzymes and nickel-substituted zinc enzymes. PMID:17054352

  18. STM Study of Au(111) Surface-Grafted Paramagnetic Macrocyclic Complexes [Ni2L(Hmba)](+) via Ambidentate Coligands.

    PubMed

    Salazar, Christian; Lach, Jochen; Rückerl, Florian; Baumann, Danny; Schimmel, Sebastian; Knupfer, Martin; Kersting, Berthold; Büchner, Bernd; Hess, Christian

    2016-05-10

    Molecular anchoring and electronic properties of macrocyclic complexes fixed on gold surfaces have been investigated mainly by using scanning tunnelling microscopy (STM) and complemented with X-ray photoelectron spectroscopy (XPS). Exchange-coupled macrocyclic complexes [Ni2L(Hmba)](+) were deposited via 4-mercaptobenzoate ligands on the surface of a Au(111) single crystal from a mM solution of the perchlorate salt [Ni2L(Hmba)]ClO4 in dichloromethane. The combined results from STM and XPS show the formation of large monolayers anchored via Au-S bonds with a height of about 1.5 nm. Two apparent granular structures are visible: one related to the dinickel molecular complexes (cationic structures) and a second one related to the counterions ClO4(-) which stabilize the monolayer. No type of short and long-range order is observed. STM tip-interaction with the monolayer reveals higher degradation after 8 h of measurement. Spectroscopy measurements suggest a gap of about 2.5 eV between HOMO and LUMO of the cationic structures and smaller gap in the areas related to the anionic structures. PMID:27093097

  19. Cyclic M2(RL)2 coordination complexes of 5-(3-[N-tert-Butyl-N-aminoxyl]phenyl)pyrimidine with paramagnetic transition metal dications.

    PubMed

    Baskett, Martha; Lahti, Paul M; Paduan-Filho, Armando; Oliveira, Nei F

    2005-09-19

    5-(3-(N-tert-Butyl-N-aminoxyl)phenyl)pyrimidine (RL = 3NITPhPyrim) forms isostructural cyclic M2(RL)2 cyclic dimers with M(hfac)2 (M = Mn, Co, Cu; hfac = hexafluoroacetylacetonate). Mn2(hfac)4(RL)2 exhibits strong antiferromagnetic Mn-RL exchange, with weak ferromagnetic exchange (0.7 cm(-1)) between Mn-RL units that is consistent with a spin polarization exchange mechanism. The magnetic moment of Co2(hfac)4(RL)2 at higher temperatures is consistent with strongly antiferromagnetic exchange within the Co-NIT units and tends toward zero below 50 K at lower magnetic fields. Cu2(hfac)4(RL)2 shows more complex behavior, with no high-temperature plateau in chiT(T) up to 300 K but a monotonic decrease down to about 100 K. The Cu(II)-nitroxide bonds decrease by 0.2-0.3 A over the same temperature range, corresponding to a change of nitroxide coordination from axial to equatorial. This thermally reversible Jahn-Teller distortion leads to a thermally induced spin state conversion from a high-spin, paramagnetic state at higher temperature to a low-spin state at lower temperature. This spin state conversion is accompanied by a reversible solid-state thermochromic change between dull yellow-brown at room temperature and green at 77 K. PMID:16156631

  20. 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.

  1. 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.

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

    PubMed

    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 (14)N 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 (14)N and (1)H 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 (14)N 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 (14)N hyperfine interaction was found to have a very small isotropic hyperfine component of -0.25 to -0.37MHz. Furthermore, the anisotropic hyperfine interactions with the (14)N 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. PMID:26802219

  3. Fluxional processes in diamagnetic and paramagnetic allyl dicarbonyl and 2-methylallyl dicarbonyl molybdenum histidinato complexes as revealed by spectroscopic data and density functional calculations.

    PubMed

    van Staveren, Dave R; Bill, Eckhard; Bothe, Eberhard; Bühl, Michael; Weyhermüller, Thomas; Metzler-Nolte, Nils

    2002-04-01

    This work describes a detailed study on the structure and dynamics of pseudooctahedral low-valent complexes of the type [Mo(His-N(epsilon)-R)(eta-2-R'-allyl)(CO)(2)] (His=N(delta),N,O-L-histidinate; R=H, R'=H (1); R=C(2)H(4)CO(2)Me, R'=H (2); R=H, R'=Me (3); R=C(2)H(4)CO(2)Me, R'=Me (4)). These diamagnetic 18-electron complexes were comprehensively characterized spectroscopically and by X-ray crystallography. In the solid state, the (substituted) allyl ligand is in an endo position in all compounds, but it is trans to the His-N(delta) atom in 1 and 2, whereas it is trans to the carboxylate O atom for the 2-Me-allyl compounds 3 and 4. In solution, both isomers are present in a solvent-dependent equilibrium. The third isomer (allyl trans to His-NH(2)) is not spectroscopically observed in solution. This is in agreement with the results from density functional (DFT) computations (BPW 91 functional) for 1 and 3, which predict a considerably higher energy (+6.3 and +5.9 kJ mol(-1), respectively) for this isomer. A likely path for isomerization is calculated, which is consistent with the activation energy determined by variable temperature NMR measurements. At least for 3, the preferred path involves several intermediates and a rotation of the 2-Me-allyl ligand. For the paramagnetic 17-electron congeners, DFT predicts the exo isomer of 3(+) with the 2-Me-allyl ligand trans to the carboxylate O atom to be by far the most stable isomer. For 1(+), an endo-exo equilibrium between the isomers with the allyl ligand trans to the carboxylate O atom is suggested. These suggestions are confirmed by EPR spectroscopy on the electrochemically generated species, which show signals for one- (4) and two- (2) metal-containing compounds. The appearance of the EPR spectra may be rationalized by inspection of the SOMOs from DFT calculations of the species in question. The notion of a metal-centered oxidation is also substantiated by IR spectroelectrochemistry and by UV/Vis spectra of the 17

  4. Kohn-Sham calculations of NMR shifts for paramagnetic 3d metal complexes: protocols, delocalization error, and the curious amide proton shifts of a high-spin iron(ii) macrocycle complex.

    PubMed

    Martin, Bob; Autschbach, Jochen

    2016-08-01

    A theory for the nuclear chemical shifts of molecules in arbitrary spin states is applied to a set of paramagnetic organometallic complexes of 3d metals. Ligand chemical shifts are calculated and analyzed using Kohn-Sham (KS) density functional theory with and without relativistic corrections. The roles of the KS delocalization error, Gaussian-type versus Slater-type basis sets, relativistic effects (scalar and spin-orbit), and zero field splitting (ZFS) are investigated. A strong functional dependence of the chemical shifts is apparent and correlated with the delocalization error. The functional dependence is between one and two orders of magnitude larger than variations of the NMR shifts due the other influences that are investigated. ZFS effects are negligible in the determination of the NMR chemical shifts of the complexes except at very low temperatures. The DFT calculated shifts agree reasonably well with experiment. A 73 ppm difference in the NMR shifts of the two protons in the amide groups of a high-spin Fe(ii) macrocycle complex arises from selective O → Fe dative bonding that only involves the transfer of β spin density, along with orbital delocalization throughout the ligand bonding framework which electronically couples the coordinating oxygen lone pair orbitals directly to the amide trans proton. PMID:26952694

  5. Paramagnetic spin pumping.

    PubMed

    Shiomi, Y; Saitoh, E

    2014-12-31

    We have demonstrated spin pumping from a paramagnetic state of an insulator La2NiMnO6 into a Pt film. Single-crystalline films of La2NiMnO6 which exhibit a ferromagnetic order at TC≈270  K were grown by pulsed laser deposition. The inverse spin Hall voltage induced by spin-current injection has been observed in the Pt layer not only in the ferromagnetic phase of La2NiMnO6, but also in a wide temperature range above TC. The efficient spin pumping in the paramagnetic phase is ascribable to ferromagnetic correlation, not to ferromagnetic order. PMID:25615367

  6. Mössbauer, electron paramagnetic resonance, and magnetic susceptibility studies on members of a new family of cyano-bridged 3d-4f complexes. Demonstration of anisotropic exchange in a Fe-Gd complex.

    PubMed

    Stoian, Sebastian A; Paraschiv, Carmen; Kiritsakas, Nathalie; Lloret, Francesc; Münck, Eckard; Bominaar, Emile L; Andruh, Marius

    2010-04-01

    The synthesis and crystallographic characterization of a new family of M(mu-CN)Ln complexes are reported. Two structural series have been prepared by reacting in water rare earth nitrates (Ln(III) = La, Pr, Nd, Sm, Eu, Gd, Dy, Ho) with K(3)[M(CN)(6)] (M(III) = Fe, Co) in the presence of hexamethylenetetramine (hmt). The first series consists of six isomorphous heterobinuclear complexes, [(CN)(5)M-CN-Ln(H(2)O)(8)].2hmt ([FeLa] 1, [FePr] 2, [FeNd] 3, [FeSm] 4, [FeEu] 5, [FeGd] 6), while the second series consists of four isostructural ionic complexes, [M(CN)(6)][Ln(H(2)O)(8)].hmt ([FeDy] 7, [FeHo] 8, [CoEu] 9, [CoGd] 10). The hexamethylenetetramine molecules contribute to the stabilization of the crystals by participating in an extended network of hydrogen bond interactions. In both series the aqua ligands are hydrogen bonded to the nitrogen atoms from both the terminal CN(-) groups and the hmt molecules. The [FeGd] complex has been analyzed with (57)Fe Mossbauer spectroscopy and magnetic susceptibility measurements. We have also analyzed the [FeLa] complex, in which the paramagnetic Gd(III) is replaced by diamagnetic La(III), with (57)Fe Mossbauer spectroscopy, electron paramagnetic resonance (EPR), and magnetic susceptibility measurements, to obtain information about the low-spin Fe(III) site that is not accessible in the presence of a paramagnetic ion at the complementary site. For the same reason, the [CoGd] complex, containing diamagnetic Co(III), was studied with EPR and magnetic susceptibility measurements, which confirmed the S = 7/2 spin of Gd(III). Prior knowledge about the paramagnetic sites in [FeGd] allows a detailed analysis of the exchange interactions between them. In particular, the question of whether the exchange interaction in [FeGd] is isotropic or anisotropic has been addressed. Standard variable-temperature magnetic susceptibility measurements provide only the value for a linear combination of J(x), J(y), and J(z) but contain no information

  7. 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…

  8. 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.

  9. 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)

  10. 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.

  11. A paramagnetic molecular voltmeter.

    PubMed

    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 (R(1)) and transverse (R(2)) relaxation rates were separated by applying lineshape analysis to progressive saturation spectra. The ratio of measured R(1) 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

  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. Paramagnetic lanthanide chelates for multicontrast MRI.

    PubMed

    Cakić, Nevenka; Savić, Tanja; Stricker-Shaver, Janice; Truffault, Vincent; Platas-Iglesias, Carlos; Mirkes, Christian; Pohmann, Rolf; Scheffler, Klaus; Angelovski, Goran

    2016-07-28

    The preparation of a paramagnetic chelator that serves as a platform for multicontrast MRI, and can be utilized either as a T1-weighted, paraCEST or (19)F MRI contrast agent is reported. Its europium(iii) complex exhibits an extremely slow water exchange rate which is optimal for the use in CEST MRI. The potential of this platform was demonstrated through a series of MRI studies on tube phantoms and animals. PMID:27291157

  14. Influence of inner-sphere processes on the paramagnetic shifts in the {sup 1}H NMR spectra of some mixed-ligand complexes of rare-earth elements

    SciTech Connect

    Khachatryan, A.S.; Vashchuk, A.V.; Panyushkin, V.T.

    1995-12-20

    Concentration dependences of the observed chemical shifts in the NMR spectra of 1:1:1 and 1:2:1 mixed-ligand complexes of rare-earth elements with acetylacetone and acrylic, methacrylic, maleic, and fumaric acids were analyzed. The complexes undergo inner-sphere structural transformations involving different modes of coordination of the unsaturated acid, which is capable of coordination to the central ion through both the carboxylic group and {pi} electrons of the double bond. The possibility of determining equilibrium constants and limiting chemical shifts of the isomeric forms of the complexes was demonstrated. 9 refs., 4 figs.

  15. Paramagnetic titanium(III) and zirconium(III) metallocene complexes as precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes.

    PubMed

    Helten, Holger; Dutta, Barnali; Vance, James R; Sloan, Matthew E; Haddow, Mairi F; Sproules, Stephen; Collison, David; Whittell, George R; Lloyd-Jones, Guy C; Manners, Ian

    2013-01-01

    Complexes of Group 4 metallocenes in the +3 oxidation state and amidoborane or phosphidoborane function as efficient precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes, such as Me(2) NH⋅BH(3). Such Ti(III) -amidoborane complexes are generated in [Cp(2)Ti]-catalyzed amine-borane dehydrocoupling reactions, for which diamagnetic M(II) and M(IV) species have been previously postulated as precatalysts and intermediates. PMID:23197391

  16. Charge Transfer Salts of BO with Paramagnetic Isothiocyanato Complex Anions: (BO)[ M(isoq) 2(NCS) 4]; M=Cr III or Fe III, isoq=isoquinoline and BO=Bis(ethylenedioxo)tetrathiafulvalene

    NASA Astrophysics Data System (ADS)

    Setifi, Fatima; Ota, Akira; Ouahab, Lahcéne; Golhen, Stèphane; Yamochi, Hideki; Saito, Gunzi

    2002-11-01

    The preparation, X-ray structures and magnetic properties of two isostructural new charge transfer salts: (BO)[ M(isoq) 2(NCS) 4]; M=Cr III(1), Fe III(2) and isoq=isoquinoline are reported. Their structure consists of alternate organic and inorganic layers, each layer being formed by mixed columns of BO radical cations and paramagnetic metal complex anions. There are short intermolecular contacts between donor and anion (S2 anion· · ·S4 BO<3.5 Å) and between adjacent BO molecules (O· · · O1<3.2 Å). The two compounds are insulators. ESR measurements show single signal without separating the donor and anion spins. The magnetic measurements obey the Curie-Weiss law and revealed dominant antiferromagnetic interactions between anion spin and donor spin, but long-range magnetic ordering did not occur down to 2 K. This is directly related to structural reasons which were deduced from a comparison of the title compounds with other 1:1 salts containing same anion complexes and different donors.

  17. Nuclear magnetic resonance characterization of a paramagnetic DNA-drug complex with high spin cobalt; assignment of the 1H and 31P NMR spectra, and determination of electronic, spectroscopic and molecular properties.

    PubMed

    Gochin, M

    1998-08-01

    The proton NMR spectrum of the ternary complex between the octamer duplex d(TTGGCCAA)2, two molecules of the drug chromomycin-A3, and a divalent cobalt ion has been assigned. Assignment procedures used standard two-dimensional techniques and relied upon the expected NOE contacts observed in the equivalent diamagnetic complex containing zinc. The magnetic susceptibility tensor for the cobalt was determined and used to calculate shifts for all nuclei, aiding in the assignment process and verification. Relaxation, susceptibility, temperature and field dependence studies of the paramagnetic spectrum enabled determination of electronic properties of the octahedral cobalt complex. The electronic relaxation tau(s) was determined to be 2.5 +/- 1.5 ps; the effective isotropic g value was found to be 2.6 +/- 0.2, indicating strong spin-orbit coupling. The magnetic susceptibility tensor was determined to be chi(xx) = 8.9 x 10(-3) cm3/mol, chi(yy) = 9.5 x 10(-3) cm3/mol, chi(zz) = 12.8 * 10(-3) cm3/mol. A tentative rotational correlation time of 8 ns was obtained for the complex. Both macroscopic and microscopic susceptibility measurements revealed deviations from Curie behavior over the temperature range accessible in the study. Non-selective relaxation rates were found to be inaccurate for defining distances from the metal center. However, pseudocontact shifts could be calculated with high accuracy using the dipolar shift equation. Isotropic hyperfine shifts were factored into contact and dipolar terms, revealing that the dipolar shift predominates and that contact shifts are relatively small. PMID:9751997

  18. 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

    2016-04-12

    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. PMID:26956368

  19. 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

    2016-04-01

    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

  20. Paramagnetic squeezing of QCD matter.

    PubMed

    Bali, G S; Bruckmann, F; Endrődi, G; Schäfer, A

    2014-01-31

    We determine the magnetization of quantum chromodynamics for several temperatures around and above the transition between the hadronic and the quark-gluon phases of strongly interacting matter. We obtain a paramagnetic response that increases in strength with the temperature. We argue that due to this paramagnetism, chunks of quark-gluon plasma produced in noncentral heavy ion collisions should become squeezed perpendicular to the magnetic field. This anisotropy will then contribute to the elliptic flow v2 observed in such collisions, in addition to the pressure gradient that is usually taken into account. We present a simple estimate for the magnitude of this new effect and a rough comparison to the effect due to the initial collision geometry. We conclude that the paramagnetic effect might have a significant impact on the value of v2. PMID:24580441

  1. Syntheses of Group 4 ansa-trovacene complexes and conversion of [1]silatrovacenophanes into paramagnetic metallopolymers by ring-opening polymerization.

    PubMed

    Adams, Christopher J; Braunschweig, Holger; Fuss, Marco; Kraft, Katharina; Kupfer, Thomas; Manners, Ian; Radacki, Krzysztof; Whittell, George R

    2011-09-01

    An improved protocol for the selective dilithiation of [V(η(5)-C(5)H(5))(η(7)-C(7)H(7))] has been developed, which afforded [V(η(5)-C(5)H(4)Li)(η(7)-C(7)H(6)Li)]·PMDTA (5; PMDTA=N,N,N',N'',N''-pentamethyldiethylenetriamine) in almost quantitative yield (98%). In the solid state, the species features a dimeric structure with two terminal and two bridging lithium atoms, with the latter connecting both sandwich subunits. Reaction with suitable Group 4 dihalide compounds enabled the isolation of highly strained silicon- and germanium-bridged [1]trovacenophanes 6 and 7. Similarly, reaction of 5 with Cl(2)Sn(2)tBu(4) afforded the rather unstrained complex [V(η(5)-C(5)H(4))(η(7)-C(7)H(6))Sn(2)tBu(4)] (8), which together with 7 represent the first trovacenophanes to incorporate heavier analogues of silicon in the ansa-bridge. Ring-opening polymerization reactions of [V(η(5)-C(5)H(4))(η(7)-C(7)H(6))SiRR'] (2a: R=R'=Me; 6: R=Me, R'=iPr) were performed by heating in a solution of toluene in the presence of the Karstedt catalyst, which resulted in the formation of the corresponding soluble poly(trovacenylsilanes) in yields of 41 and 33%, respectively. As estimated by gel permeation chromatography (GPC), the macromolecules possess molecular weights of M(n)=10,010 and 5580 g mol(-1) with polydispersity indices of 2.31 and 1.64 for 9 and 10, respectively. ESR spectroscopic studies on 9 and 10 revealed only a single broad resonance in each case without any identifiable (51)V hyperfine coupling. PMID:21812040

  2. Thermochromism and switchable paramagnetism of cobalt(II) in thiocyanate ionic liquids.

    PubMed

    Osborne, Stephen J; Wellens, Sil; Ward, Chris; Felton, Solveig; Bowman, Robert M; Binnemans, Koen; Swadźba-Kwaśny, Małgorzata; Gunaratne, H Q Nimal; Nockemann, Peter

    2015-07-01

    Temperature-dependent switching of paramagnetism of a cobalt(II) complex is observed in an ionic liquid solution. Paramagnetic and thermochromic switching occur simultaneously due to a reversible change in coordination. This reversible switching is possible in the ionic liquid solution, which enables mobility of thiocyanate anions by remaining mobile at low temperatures and acts as an anion reservoir. PMID:26053484

  3. Solid-State 17O NMR of Paramagnetic Coordination Compounds**

    PubMed Central

    Kong, Xianqi; Terskikh, Victor V.; Khade, Rahul L.; Yang, Liu; Rorick, Amber; Zhang, Yong; He, Peng; Huang, Yining; Wu, Gang

    2015-01-01

    We demonstrate that high-quality solid-state 17O (I = 5/2) NMR spectra can be successfully obtained for paramagnetic coordination compounds in which oxygen atoms are directly bonded to the paramagnetic metal centers. For complexes containing V(III) (S = 1), Cu(II) (S = 1/2), and Mn(III) (S = 2) metal centers, the 17O isotropic paramagnetic shifts were found to span a range of more than 10000 ppm. In several cases, high-resolution 17O NMR spectra were recorded under very fast magic-angle spinning (MAS) conditions at 21.1 T. Quantum chemical computations using density functional theory (DFT) qualitatively reproduced the experimental 17O hyperfine shift tensors. PMID:25694203

  4. Barnett effect in paramagnetic states

    NASA Astrophysics Data System (ADS)

    Ono, Masao; Chudo, Hiroyuki; Harii, Kazuya; Okayasu, Satoru; Matsuo, Mamoru; Ieda, Jun'ichi; Takahashi, Ryo; Maekawa, Sadamichi; Saitoh, Eiji

    2015-11-01

    We report the observation of the Barnett effect in paramagnetic states by mechanically rotating gadolinium (Gd) metal with a rotational frequency of up to 1.5 kHz above the Curie temperature. An in situ magnetic measurement setup comprising a high-speed rotational system and a fluxgate magnetic sensor was developed for the measurement. Temperature dependence of the observed magnetization follows that of paramagnetic susceptibility, indicating that any emergent magnetic field is proportional to the rotational frequency and is independent of temperature. From the proportionality constant of the emergent field, the gyromagnetic ratio of Gd is calculated to be -29 ±5 GHz /T . This study revisits the primordial issue of magnetism with modern technologies to shed new light on the fundamental spin-rotation coupling.

  5. 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.

  6. Paramagnetic Meissner effect in Nb

    SciTech Connect

    Kostic, P.; Veal, B.; Paulikas, A.P.; Welp, U.; Todt, V.R.; Gu, C.; Geiser, U.; Williams, J.M.; Carlson, K.D.; Klemm, R.A.

    1996-01-01

    The paramagnetic Meissner effect (PME), or Wohlleben effect, in which the field-cooled magnetization of superconducting samples is paramagnetic below {ital T}{sub {ital c}}, has been reported to occur in some samples of a variety of high-{ital T}{sub {ital c}} cuprate superconductors. It has been proposed that the effect arose in granular hole-doped cuprates from current loops with {pi} phase shifts of the superconducting order parameter at some grain-boundary junctions. It is argued that such behavior would be expected to occur in a {ital d}-wave superconductor, but not in a conventional {ital s}-wave superconductor. To test this hypothesis, we have searched for the occurrence of the effect in Nb, and have confirmed a recent report by Minhaj {ital et} {ital al}. of its occurrence in some Nb samples. For these studies, the effects of stray fields and field gradients in the measurement volume of the superconducting quantum interference device magnetometer have been carefully considered to rule out the possibility that measurement artifacts might be responsible for the apparent paramagnetic behavior in Nb. The {ital M}({ital T}) and {ital M}({ital H}) curves obtained in Nb samples that show the PME also show remarkably strong resemblance to those curves reported for the cuprate materials exhibiting the PME. Evidence is presented that the effect arises from inhomogeneously trapped flux, and is strongly influenced by sample geometry and surface effects. These results suggest that, for the effect to be observable, {ital T}{sub {ital c}} on the sample surface must be different from the bulk {ital T}{sub {ital c}}. The occurrence of the PME in Nb strongly suggests that the observation of this effect is unrelated to {ital d}-wave superconductivity. {copyright} {ital 1996 The American Physical Society.}

  7. Stable paramagnetic half-sandwich Mo(V) and W(V) polyhydride complexes. Structural, spectroscopic, electrochemical, theoretical, and decomposition mechanism studies of [Cp*MH{sub 3}(dppe)]{sup +} (M = Mo, W)

    SciTech Connect

    Pleune, B.; Morales, D.; Meunier-Prest, R.; Richard, P.; Collange, E.; Fettinger, J.C.; Poli, R.

    1999-03-17

    Compounds Cp*MH{sub 3}(dppe) (M = Mo, 1; W, 2) are oxidized chemically and electrochemically to the corresponding 17-electron cations 1{sup +} and 2{sup +}. Analogous oxidations of 1-d{sub 3} and 2-d{sub 3} provide 1{sup +}-d{sub 3} and 2{sup +}-d{sub 3}, respectively. Complex 2{sup +} is stable in CH{sub 2}Cl{sub 2}, THF and MeCN at room temperature. A single-crystal X-ray analysis of the PF{sub 6}{sup {minus}} salt of 2{sup +} shows a geometry optimization of the [CpWH{sub 3}(PH{sub 2}CH{sub 2}CH{sub 2}PH{sub 2})]{sup +} model at the B3LYP/LANL2DZ level. Identical calculations on the neutral analogue also reproduce the previously reported trigonal prismatic structure for 1. A blue shift in the M-H stretching vibrations upon oxidation for both Mo and W compounds indicates that a M-H bond strengthening accompanies the oxidation process. The DFT calculations (M-H bond lengths, BDE, and stretching frequencies) are in good agreement with the experimental results. Complex 1{sup +} decomposes in solution at room temperature by one or more of three different mechanisms depending on conditions: H{sub 2} reductive elimination, solvent-assisted disproportionation, or deprotonation. In THF or CH{sub 2}Cl{sub 2}, a reductive elimination of H{sub 2} affords the stable paramagnetic monohydride Cp*MoH(dppe)PF{sub 6} (3), which adds a molecule of solvent in CH{sub 2}Cl{sub 2}, THF, and MeCN. EPR studies show that the CH{sub 2}Cl{sub 2} molecule coordinates in a bidentate model to afford a 19-electron configuration. A solvent dependence of the decomposition rate [k(CH{sub 2}Cl{sub 2}) {approx} 7.8k(THF) at 0 C] and an inverse isotope effect [k{sub H}/k{sub d} = 0.50(3) in CH{sub 2}Cl{sub 2} at 0 C] indicate the nature of 1{sup +} as a classical trihydride and suggest a decomposition mechanism which involves equilibrium conversion to a nonclassical intermediate followed by a rate-determining associate exchange of H{sub 2} with a solvent molecule. In MeCN at 20 C, a solvent

  8. 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

  9. 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)

  10. Paramagnetic supercurrent in a mesoscopic superconducting disk

    NASA Astrophysics Data System (ADS)

    Kanda, Akinobu; Ootuka, Youiti

    2003-05-01

    We report an experimental evidence for the paramagnetic supercurrent flowing along the periphery of a mesoscopic superconducting disk in decreasing perpendicular magnetic fields. The sample is an Al superconducting disk with a thin drain lead. Several Cu leads are connected to different parts of the ring periphery through highly resistive tunnel junctions. From voltage drop across a tunnel junction, we study the change in the local superconducting energy gap as a function of perpendicular magnetic field. We find that the energy gap at the ring periphery decreases with decreasing the magnetic field, showing that the circulating supercurrent is in the direction supporting the external magnetic field ( paramagnetic). The condition for the observation is the same as that for the paramagnetic Meissner effect (Geim et al., Nature 390 (1997) 259), implying that the origin of the paramagnetic Meissner effect is the paramagnetic supercurrent.

  11. 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

  12. Giant paramagnetic Meissner effect in multiband superconductors.

    PubMed

    da Silva, R M; Milošević, M V; Shanenko, A A; Peeters, F M; Aguiar, J Albino

    2015-01-01

    Superconductors, ideally diamagnetic when in the Meissner state, can also exhibit paramagnetic behavior due to trapped magnetic flux. In the absence of pinning such paramagnetic response is weak, and ceases with increasing sample thickness. Here we show that in multiband superconductors paramagnetic response can be observed even in slab geometries, and can be far larger than any previous estimate - even multiply larger than the diamagnetic Meissner response for the same applied magnetic field. We link the appearance of this giant paramagnetic response to the broad crossover between conventional Type-I and Type-II superconductors, where Abrikosov vortices interact non-monotonically and multibody effects become important, causing unique flux configurations and their locking in the presence of surfaces. PMID:26244936

  13. Giant paramagnetic Meissner effect in multiband superconductors

    PubMed Central

    da Silva, R. M.; Milošević, M. V.; Shanenko, A. A.; Peeters, F. M.; Aguiar, J. Albino

    2015-01-01

    Superconductors, ideally diamagnetic when in the Meissner state, can also exhibit paramagnetic behavior due to trapped magnetic flux. In the absence of pinning such paramagnetic response is weak, and ceases with increasing sample thickness. Here we show that in multiband superconductors paramagnetic response can be observed even in slab geometries, and can be far larger than any previous estimate - even multiply larger than the diamagnetic Meissner response for the same applied magnetic field. We link the appearance of this giant paramagnetic response to the broad crossover between conventional Type-I and Type-II superconductors, where Abrikosov vortices interact non-monotonically and multibody effects become important, causing unique flux configurations and their locking in the presence of surfaces. PMID:26244936

  14. Giant paramagnetic Meissner effect in multiband superconductors

    NASA Astrophysics Data System (ADS)

    da Silva, R. M.; Milošević, M. V.; Shanenko, A. A.; Peeters, F. M.; Aguiar, J. Albino

    2015-08-01

    Superconductors, ideally diamagnetic when in the Meissner state, can also exhibit paramagnetic behavior due to trapped magnetic flux. In the absence of pinning such paramagnetic response is weak, and ceases with increasing sample thickness. Here we show that in multiband superconductors paramagnetic response can be observed even in slab geometries, and can be far larger than any previous estimate - even multiply larger than the diamagnetic Meissner response for the same applied magnetic field. We link the appearance of this giant paramagnetic response to the broad crossover between conventional Type-I and Type-II superconductors, where Abrikosov vortices interact non-monotonically and multibody effects become important, causing unique flux configurations and their locking in the presence of surfaces.

  15. General magnetic transition dipole moments for electron paramagnetic resonance.

    PubMed

    Nehrkorn, Joscha; Schnegg, Alexander; Holldack, Karsten; Stoll, Stefan

    2015-01-01

    We present general expressions for the magnetic transition rates in electron paramagnetic resonance (EPR) experiments of anisotropic spin systems in the solid state. The expressions apply to general spin centers and arbitrary excitation geometry (Voigt, Faraday, and intermediate). They work for linear and circular polarized as well as unpolarized excitation, and for crystals and powders. The expressions are based on the concept of the (complex) magnetic transition dipole moment vector. Using the new theory, we determine the parities of ground and excited spin states of high-spin (S=5/2) Fe(III) in hemin from the polarization dependence of experimental EPR line intensities. PMID:25615456

  16. End-to-End Thiocyanato-Bridged Helical Chain Polymer and Dichlorido-Bridged Copper(II) Complexes with a Hydrazone Ligand: Synthesis, Characterisation by Electron Paramagnetic Resonance and Variable-Temperature Magnetic Studies, and Inhibitory Effects on Human Colorectal Carcinoma Cells.

    PubMed

    Das, Kuheli; Datta, Amitabha; Sinha, Chittaranjan; Huang, Jui-Hsien; Garribba, Eugenio; Hsiao, Ching-Sheng; Hsu, Chin-Lin

    2012-04-01

    The reactions of the tridentate hydrazone ligand, N'-[1-(pyridin-2-yl)ethylidene]acetohydrazide (HL), obtained by condensation of 2-acetylpyridine with acetic hyadrazide, with copper nitrate trihydrate in the presence of thiocyanate, or with CuCl2 produce two distinct coordination compounds, namely a one-dimensional helical coordination chain of [CuL(NCS)] n (1) units, and a doubly chlorido-bridged dinuclear complex [Cu2L2Cl2] (2) (where L=CH3C(O)=N-N=CCH3C5H4N). Single-crystal X-ray structural determination studies reveal that in complex 1, a deprotonated hydrazone ligand L(-) coordinates a copper(II) ion that is bridged to two neighbouring metal centres by SCN(-) anions, generating a one-dimensional helical coordination chain. In complex 2, two symmetry-related, adjacent copper(II) coordination entities are doubly chlorido-bridged, producing a dicopper entity with a Cu⋅⋅⋅Cu distance of 3.402 (1) Å. The two coordination compounds have been fully characterised by elemental analysis, spectroscopic techniques including IR, UV-vis and electron paramagnetic resonance, and variable-temperature magnetic studies. The biological effects of 1 and 2 on the viability of human colorectal carcinoma cells (COLO-205 and HT-29) were evaluated using an MTT assay, and the results indicate that these complexes induce a decrease in cell-population growth of human colorectal carcinoma cells with apoptosis. PMID:24551495

  17. Elucidating transient macromolecular interactions using paramagnetic relaxation enhancement

    PubMed Central

    Clore, G. Marius; Tang, Chun; Iwahara, Junji

    2007-01-01

    Recent advances in the use of paramagnetic relaxation enhancement (PRE) in structure refinement and in the analysis of transient dynamic processes involved in macromolecular complex formation are presented. In the slow exchange regime, we show, using the SRY/DNA complex as an example, that the PRE provides a powerful tool that can lead to significant increases in the reliability and accuracy of NMR structure determinations. Refinement necessitates the use of an ensemble representation of the paramagnetic center and a model free extension of the Solomon-Bloembergen equations. In the fast exchange regime, the PRE provides insight into dynamic processes and the existence of transient, low population intermediate species. The PRE allows one to characterize dynamic non-specific binding of a protein to DNA; to directly demonstrate that the search process whereby a transcription factor locates its specific DNA target site involves both intramolecular (sliding) and intermolecular (hopping and intersegment transfer) translocation; and to detect and visualize the distribution of an ensemble of transient encounter complexes in protein-protein association. PMID:17913493

  18. Paramagnetic intrinsic Meissner effect in a bulk

    NASA Astrophysics Data System (ADS)

    Lebed, A. G.

    2008-10-01

    We calculate the free energy of a quasi-two-dimensional (Q2D) superconductor with ξ⊥ < d in a parallel magnetic field, where ξ⊥ is a perpendicular to the conducting layer coherence length and d is the interlayer distance. It is shown to be different from that in the famous Lawrence-Doniach model. In particular, at high enough magnetic fields, the Meissner currents are found to create an unexpected paramagnetic moment due to the shrinking of the Cooper pairs “sizes” in a direction perpendicular to the conducting layers. We suggest measuring this paramagnetic intrinsic Meissner effect in Q2D superconductors and superconducting superlattices.

  19. 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.

  20. 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.

  1. Alignment mechanisms of paramagnetic grains revisited

    NASA Technical Reports Server (NTRS)

    Seki, Munezo

    1989-01-01

    Taking into account the tight coupling of grain axis with angular momentum due to effective dissipation of rotation energy, the alignment of spheroidal grains was investigated by paramagnetic relaxation. Alignment degree will be significantly improved in diffuse clouds. The inclusions of superparamagnetic (SPM) substances may play a key role in grain alignment in dark clouds as well as in diffuse clouds.

  2. 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.

  3. 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)

  4. Paramagnetic shimming for high-field MRI

    SciTech Connect

    Tomasi, D.; Tomasi, D.; Wang, R.L.

    2009-01-20

    The diamagnetism of biological tissues reduces the homogeneity of the magnetic field and may limit the number of samples in multi-sample gradient-recalled echo (GRE) experiments. This study aims to (1) evaluate the magnetic field distortions and signal loss artifacts in GRE images of proximal water samples, and (2) develop a passive shimming device to overcome this limitation. The magnetic field distribution produced by a diamagnetic H{sub 2}O sphere and a paramagnetic CuSO{sub 4} disk in a secondary phantom were mapped using GRE experiments and the phase reference method, and compared to the corresponding magnetostatics models. The water sphere produced a pronounced signal loss artifact in amplitude images. This artifact was significantly reduced when the paramagnetic disk was placed symmetrically between the water sphere and the secondary spherical phantom. The present study suggests that the use of paramagnetic shimming devices can help to minimize susceptibility-related MRI signal losses and to increase the number of samples in multi-sample MRI experiments. The volume susceptibility and the shape of paramagnetic shimming devices could be optimized for particular setups and samples accordingly.

  5. Paramagnetic Meissner effect and related dynamical phenomena

    NASA Astrophysics Data System (ADS)

    Li, Mai Suan

    2003-03-01

    The hallmark of superconductivity is the diamagnetic response to external magnetic field. In striking contrast to this behavior, a paramagnetic response or paramagnetic Meissner effect was observed in ceramic high- Tc and in conventional superconductors. The present review is given on this interesting effect and related phenomena. We begin with a detailed discussion of experimental results on the paramagnetic Meissner effect in both granular and conventional superconductors. There are two main mechanisms leading to the paramagnetic response: the so-called d-wave and the flux compression. In the first scenario, the Josephson critical current between two d-wave superconductors becomes negative or equivalently one has a π junction. The paramagnetic signal occurs due to the nonzero spontaneous supercurrent circulating in a loop consisting of odd number of π junctions. In addition to the d-wave mechanism we present the flux compression mechanism for the paramagnetic Meissner effect. The compression may be due to either an inhomogeneous superconducting transition or flux trap inside the giant vortex state. The flux trapping which acts like a total nonzero spontaneous magnetic moment causes the paramagnetic signal. The anisotropic pairing scenario is believed to be valid for granular materials while the flux trap one can be applied to both conventional and high- Tc superconductors. The study of different phenomena by a three-dimensional lattice model of randomly distributed π Josephson junctions with finite self-inductance occupies the main part of our review. By simulations one can show that the chiral glass phase in which chiralities are frozen in time and in space may occur in granular superconductors possessing d-wave pairing symmetry. Experimental attempts on the search for the chiral glass phase are analysed. Experiments on dynamical phenomena such as AC susceptibility, compensation effect, anomalous microwave absorption, aging effect, AC resistivity and

  6. 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.

  7. Paramagnetic Meissner effect in Pb nanowire arrays

    NASA Astrophysics Data System (ADS)

    Yuan, Shijun; Ren, Liyuan; Li, Fashen

    2004-03-01

    The Meissner effect is one of the basic properties of superconductors. Recently, many experiments have shown that small-size superconducting samples may be paramagnetic in a weak magnetic field, the so-called paramagnetic Meissner effect (PME). In this paper, we report the observation of the PME in Pb nanowire arrays. We find that the signal of the PME increases with decreasing diameter of the nanowires. In a lead nanowire array of diameter about 40 nm, the oscillations of the PME are observed in field-cooling temperature-dependent magnetization M(T) curves. Surprisingly, the PME was also observed in zero-field-cooling M(T) curves. We conclude that the PME is in association with the metastable states in superconductors. The PME plays an important role only if the proportion of surface superconductors is sufficiently large.

  8. Spin dynamics in paramagnetic diluted magnetic semiconductors

    NASA Astrophysics Data System (ADS)

    Phan, Van-Nham; Tran, Minh-Tien

    2015-10-01

    Microscopic properties of low-energy spin dynamics in diluted magnetic semiconductor are addressed in a framework of the Kondo lattice model including random distribution of magnetic dopants. Based on the fluctuation-dissipation theorem, we derive an explicit dependence of the spin diffusion coefficient on the single-particle Green function which is directly evaluated by dynamical mean-field theory. In the paramagnetic state, the magnetic scattering has been manifested to suppress spin diffusion. In agreement with other ferromagnet systems, we also point out that the spin diffusion in diluted magnetic semiconductors at small carrier concentration displays a monotonic 1 /T -like temperature dependence. By investigating the spin diffusion coefficient on a wide range of the model parameters, the obtained results have provided a significant scenario to understand the spin dynamics in the paramagnetic diluted magnetic semiconductors.

  9. Electrically Driven Spin Dynamics of Paramagnetic Impurities

    NASA Astrophysics Data System (ADS)

    Saha, D.; Siddiqui, L.; Bhattacharya, P.; Datta, S.; Basu, D.; Holub, M.

    2008-05-01

    The spin dynamics of dilute paramagnetic impurities embedded in a semiconductor GaAs channel of a conventional lateral spin valve has been investigated. It is observed that the electron spin of paramagnetic Mn atoms can be polarized electrically when driven by a spin valve in the antiparallel configuration. The transient current through the MnAs/GaAs/MnAs spin valve bears the signature of the underlying spin dynamics driven by the exchange interaction between the conduction band electrons in GaAs and the localized Mn electron spins. The time constant for this interaction is observed to be dependent on temperature and is estimated to be 80 ns at 15 K.

  10. Electrically driven spin dynamics of paramagnetic impurities.

    PubMed

    Saha, D; Siddiqui, L; Bhattacharya, P; Datta, S; Basu, D; Holub, M

    2008-05-16

    The spin dynamics of dilute paramagnetic impurities embedded in a semiconductor GaAs channel of a conventional lateral spin valve has been investigated. It is observed that the electron spin of paramagnetic Mn atoms can be polarized electrically when driven by a spin valve in the antiparallel configuration. The transient current through the MnAs/GaAs/MnAs spin valve bears the signature of the underlying spin dynamics driven by the exchange interaction between the conduction band electrons in GaAs and the localized Mn electron spins. The time constant for this interaction is observed to be dependent on temperature and is estimated to be 80 ns at 15 K. PMID:18518470

  11. Stoner-enhanced paramagnetism in tungsten tetraboride.

    PubMed

    Shen, Jiaoyan; Zhou, Jingming; Zhao, Meng; Liu, Guozhen; Gao, Ju; Yao, Jinlei

    2016-01-20

    We demonstrate that tungsten tetraboride (WB4), a heavy transition metallic compound without magnetic atoms, is an exchange-enhanced paramagnet revealed by the magnetization and specific heat measurements. WB4 has a small effective magnetic moment of 0.53 μB/fu. The high magnetic susceptibility in the magnitude of 1 memu (mol·Oe)(-1) below 10 K obeys quadratic temperature dependence. The upturn behavior of C(P)/T versus T(2) at low temperatures is attributed to the electron-paramagnon interactions. A high Stoner enhancement parameter, Z  =  0.93, was derived to explain the enhanced paramagnetism based on the Stoner model. PMID:26683343

  12. 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

    2016-09-01

    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. PMID:27525360

  13. The structure of the inhibitory complex of alloxanthine (1H-pyrazolo[3,4-d]pyrimidine-4,6-diol) with the molybdenum centre of xanthine oxidase from electron-paramagnetic-resonance spectroscopy.

    PubMed Central

    Hawkes, T R; George, G N; Bray, R C

    1984-01-01

    Studies were carried out on the inhibitory complex of alloxanthine (1H-pyrazolo[3,4-d]pyrimidine-4,5-diol) with xanthine oxidase, in extension of the work of Williams & Bray [Biochem. J. (1981) 195, 753-760]. By suitable regulation of the reaction conditions, up to 10% of the functional enzyme could be converted into the complex in the Mo(V) oxidation state. The e.p.r. spectrum of the complex was investigated in detail with the help of computer simulation and substitution with stable isotopes. Close structural analogy of the signal-giving species to that of the Very Rapid intermediate in enzyme turnover is shown by g-values (2.0279, 1.9593 and 1.9442) and by coupling to 33S in the cyanide-labile site of the enzyme [A(33S) 0.30, 3.10 and 0.70mT]. However, whereas in the Very Rapid signal there is strong coupling to 17O [Gutteridge & Bray, Biochem. J. (1980) 189, 615-623], instead, in the Alloxanthine signal there is strong coupling to a single nitrogen atom [A(14N) 0.35, 0.35, 0.32 mT]. This is presumed to originate from the 2-position of the heterocyclic ring system. From this work and from earlier kinetic studies it is concluded that alloxanthine, after being bound reversibly at the active centre, reacts slowly with it, in a specific manner, distinct from that in the normal catalytic reaction with substrates. This reaction involves elimination of an oxygen ligand of molybdenum and co-ordination, in this site, of alloxanthine via the N-2 nitrogen atom, to give a complex that is structurally but not chemically closely analogous to that of the Very Rapid species. PMID:6326752

  14. Investigation of paramagnetic response of metallic epoxies

    NASA Technical Reports Server (NTRS)

    Ash, R. L.; Chegini, H.

    1986-01-01

    The paramagnetic properties of epoxies which were impregnated with metal ions were examined as the primary task in this research. A major conclusion was that the quality control of the epoxies was insufficient to permit reliable evaluation. Subsequently, a new set of specimens is being prepared. As an additional task, a new method is investigated for estimating heats of combustion for saturated hydrocarbons. The results of that investigation have shown that the empirical approach is a promising method for on-line measurements.

  15. 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

  16. Unconventional dynamic hysteresis in a periodic assembly of paramagnetic colloids

    NASA Astrophysics Data System (ADS)

    Tierno, Pietro; Johansen, Tom H.; Sancho, J. M.

    2013-06-01

    Dynamic hysteresis phenomena are widespread in physical sciences and describe the complex behavior of systems driven out of equilibrium by a periodic forcing. We use here paramagnetic colloids above a stripe-patterned garnet film as the model system to study dynamic hysteresis, the latter induced when the particles are periodically translated by an oscillating magnetic field. In contrast to the expected behavior for a bistable system, we observe that the area of the hysteresis loop decreases by increasing the driving frequency and reduces to zero for frequencies higher than 5-7s-1. To explain the experimental results, we develop a simple model based on an overdamped Brownian particle driven by a periodic potential with an oscillating amplitude.

  17. 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.

  18. Novel paramagnetic AT1 receptor antagonists.

    PubMed

    Tan, Nichole P H; Taylor, Michelle K; Bottle, Steven E; Wright, Christine E; Ziogas, James; White, Jonathan M; Schiesser, Carl H; Jani, Nitya V

    2011-11-28

    Novel paramagnetic selective angiotensin AT(1) receptor antagonists (sartans) bearing nitroxides (3, 4) have been prepared and their pharmacology evaluated in vitro as well as in vivo. Compounds 3, 4 proved to be effective sartans with pK(B) estimates in the range 6.2-9.1. In addition, the sodium salt (11) of 4 (R = Bu) is able to protect against vascular injury in hypertensive rats as determined by its ability to attenuate the development of intimal thickening caused by balloon injury of the carotid artery. PMID:21963998

  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. Vortex states in superconductors with strong Pauli-paramagnetic effect

    NASA Astrophysics Data System (ADS)

    Ichioka, Masanori; Machida, Kazushige

    2007-08-01

    Using quasiclassical theory, we analyze the vortex structure of strong-paramagnetic superconductors. There, induced paramagnetic moments are accumulated exclusively around the vortex core. We quantitatively evaluate the significant paramagnetic effect in the H dependence of various quantities, such as low temperature specific heat, Knight shift, magnetization, and the flux line lattice (FLL) form factor. The anomalous H dependence of the FLL form factor observed by the small angle neutron scattering in CeCoIn5 is attributable to the large paramagnetic contribution.

  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. 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.

  3. 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

  4. Paramagnetic metal ions in pulsed ESR distance distribution measurements.

    PubMed

    Ji, Ming; Ruthstein, Sharon; Saxena, Sunil

    2014-02-18

    The use of pulsed electron spin resonance (ESR) to measure interspin distance distributions has advanced biophysical research. The three major techniques that use pulsed ESR are relaxation rate based distance measurements, double quantum coherence (DQC), and double electron electron resonance (DEER). Among these methods, the DEER technique has become particularly popular largely because it is easy to implement on commercial instruments and because programs are available to analyze experimental data. Researchers have widely used DEER to measure the structure and conformational dynamics of molecules labeled with the methanethiosulfonate spin label (MTSSL). Recently, researchers have exploited endogenously bound paramagnetic metal ions as spin probes as a way to determine structural constraints in metalloproteins. In this context Cu(2+) has served as a useful paramagnetic metal probe at X-band for DEER based distance measurements. Sample preparation is simple, and a coordinated-Cu(2+) ion offers limited spatial flexibility, making it an attractive probe for DEER experiments. On the other hand, Cu(2+) has a broad absorption ESR spectrum at low temperature, which leads to two potential complications. First, the Cu(2+)-based DEER time domain data has lower signal to noise ratio compared with MTSSL. Second, accurate distance distribution analysis often requires high-quality experimental data at different external magnetic fields or with different frequency offsets. In this Account, we summarize characteristics of Cu(2+)-based DEER distance distribution measurements and data analysis methods. We highlight a novel application of such measurements in a protein-DNA complex to identify the metal ion binding site and to elucidate its chemical mechanism of function. We also survey the progress of research on other metal ions in high frequency DEER experiments. PMID:24289139

  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 at dislocations in germanium

    SciTech Connect

    Pakulis, E.J.

    1982-06-01

    The first observation of the paramagnetic resonance of electrons at dislocations in germanium single crystals is reported. Under subband gap optical excitation, two sets of lines are detected: four lines about the <111> axes with g/sub perpendicular to/ = 0.34 and g/sub parallel/ = 1.94, and 24 lines with g/sub perpendicular to/ = 0.73 and g/sub parallel/ = 1.89 about <111> axes with the six-fold 1.2/sup 0/ distortion. This represents the first measurement of the disortion angle of a dislocation dangling bond. The possibility that the distortion results from a Peierls transition along the dislocation line is discussed.

  7. Paramagnetic Meissner effect in conventional Nb superconductors

    SciTech Connect

    Thompson, D.J.; Wenger, L.E.; Chen, J.T.

    1996-11-01

    The paramagnetic Meissner effect (PME), in which the field-cooled-magnetization (FCM) of superconducting samples is positive below the superconducting transition temperature T{sub c}, has been observed in certain ceramic and single-crystal samples of the high-T{sub c} cuprate superconductors and more recently in disk-shaped Nb samples. Through systematic investigations of the conditions for observing the PME in Nb disks, various surface treatments to the Nb disks were found to change both the zero-field-cooled-magnetization (ZFCM) and the FCM, including the appearance of a positive FCM in samples previously not exhibiting the PME as well as the elimination of the PME through surface abrasion. These results suggest that the PME arises from the field distributions created by the flux pinning associated with microstructural defects on the surface layer of the disk.

  8. Paramagnetic intrinsic Meissner effect in layered superconductors

    NASA Astrophysics Data System (ADS)

    Lebed, A. G.

    2008-07-01

    Free energy of a layered superconductor with ξ⊥paramagnetic intrinsic Meissner effect in a bulk is suggested to detect, by measuring in-plane torque, the upper critical field and magnetization in layered organic and high- Tc superconductors, as well as in superconducting superlattices.

  9. Paramagnetic Intrinsic Meissner Effect in Layered Superconductors

    NASA Astrophysics Data System (ADS)

    Lebed, Andrei

    2008-03-01

    Free energy of a quasi-two-dimensional superconductor with a coherence length perpendicular to the conducting layers being less than an inter-layer distance is calculated. The free energy is shown to differ from that in the textbook Lawerence-Doniach model at high fields, where the Meissner currents are found to create an unexpected positive magnetic moment due to shrinking of the Cooper pairs ``sizes'' by a magnetic field. This unique phenomenon - paramagnetic intrinsic Meissner effect (PIME) in a bulk [1] - is suggested to detect by measuring in-plane magnetization and torque in layered organic and high-Tc superconductors as well as in superconducting superlattices. [1] A.G. Lebed, Physical Review Letters, submitted.

  10. Magneto-Optical Properties of Paramagnetic Superrotors

    NASA Astrophysics Data System (ADS)

    Milner, A. A.; Korobenko, A.; Floß, J.; Averbukh, I. Sh.; Milner, V.

    2015-07-01

    We study the dynamics of paramagnetic molecular superrotors in an external magnetic field. An optical centrifuge is used to create dense ensembles of oxygen molecules in ultrahigh rotational states. In is shown, for the first time, that the gas of rotating molecules becomes optically birefringent in the presence of a magnetic field. The discovered effect of "magneto-rotational birefringence" indicates the preferential alignment of molecular axes along the field direction. We provide an intuitive qualitative model, in which the influence of the applied magnetic field on the molecular orientation is mediated by the spin-rotation coupling. This model is supported by the direct imaging of the distribution of molecular axes, the demonstration of the magnetic reversal of the rotational Raman signal, and by numerical calculations.

  11. Magneto-Optical Properties of Paramagnetic Superrotors.

    PubMed

    Milner, A A; Korobenko, A; Floß, J; Averbukh, I Sh; Milner, V

    2015-07-17

    We study the dynamics of paramagnetic molecular superrotors in an external magnetic field. An optical centrifuge is used to create dense ensembles of oxygen molecules in ultrahigh rotational states. In is shown, for the first time, that the gas of rotating molecules becomes optically birefringent in the presence of a magnetic field. The discovered effect of "magneto-rotational birefringence" indicates the preferential alignment of molecular axes along the field direction. We provide an intuitive qualitative model, in which the influence of the applied magnetic field on the molecular orientation is mediated by the spin-rotation coupling. This model is supported by the direct imaging of the distribution of molecular axes, the demonstration of the magnetic reversal of the rotational Raman signal, and by numerical calculations. PMID:26230789

  12. 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.

  13. Paramagnetic shimming for wide-range variable-field NMR.

    PubMed

    Ichijo, Naoki; Takeda, Kazuyuki; Takegoshi, K

    2014-09-01

    We propose a new passive shimming strategy for variable-field NMR experiments, in which the magnetic field produced by paramagnetic shim pieces placed inside the magnet bore compensates the inhomogeneity of a variable-field magnet for a wide range of magnet currents. Paramagnetic shimming is demonstrated in (7)Li, (87)Rb, and (45)Sc NMR of a liquid solution sample in magnetic fields of 3.4, 4.0, and 5.4T at a fixed carrier frequency of 56.0MHz. Since both the main-field inhomogeneity and the paramagnetic magnetization are proportional to the main-magnet current, the resonance lines are equally narrowed by the improved field homogeneity with an identical configuration of the paramagnetic shim pieces. Paramagnetic shimming presented in this work opens the possibility of high-resolution variable-field NMR experiments. PMID:25080372

  14. Paramagnetic moment in field-cooled superconducting plates: Paramagnetic Meissner effect

    SciTech Connect

    Koshelev, A.E.; Larkin, A.I.

    1995-11-01

    We calculate the magnetic moment for thin superconducting plates after field cooling. We consider the situation when the whole magnetic flux is trapped within the strip and compressed due to inhomogeneous cooling. We demonstrate that the magnetic moment in such a state is paramagnetic. For a thin superconducting strip we found exact solutions for the field and current distributions at any degree of flux compression. The cases of complete and partial Bean states were considered. For a thin superconducting disk we found an approximate solution for the case of weak compression and a complete Bean state. The mechanism considered can explain the paramagnetic Meissner effect observed recently in some high-{ital T}{sub {ital c}} superconductors and in Nb.

  15. Intracellular hypoxia of tumor tissue estimated by noninvasive electron paramagnetic resonance oximetry technique using paramagnetic probes.

    PubMed

    Matsumoto, Atsuko; Matsumoto, Ken-ichiro; Matsumoto, Shingo; Hyodo, Fuminori; Sowers, Anastasia L; Koscielniak, Janusz W; Devasahayam, Nallathamby; Subramanian, Sankaran; Mitchell, James B; Krishna, Murali C

    2011-01-01

    Electron paramagnetic resonance (EPR) oximetry at 700 MHz operating frequency employing a surface coil resonator is used to assess tissue partial pressure of oxygen (pO(2)) using paramagnetic media whose linewidth and decay constant are related to oxygen concentration. Differences in extracellular and intracellular pO(2) in squamous cell carcinoma (SCC) tumor tissue were tested using several types of water-soluble paramagnetic media, which localize extracellularly or permeate through the cell membrane. The nitroxide carboxy-PROXYL (CxP) can only be distributed in blood plasma and extracellular fluids whereas the nitroxides carbamoyl-PROXYL (CmP) and TEMPOL (TPL) can permeate cell membranes and localize intracellularly. EPR signal decay constant and the linewidth of the intravenously administered nitroxides in SCC tumor tissues implanted in mouse thigh and the contralateral normal muscle of healthy mice breathing gases with different pO(2) were compared. The pO(2) in the blood can depend on the oxygen content in the breathing gas while tissue pO(2) was not directly influenced by pO(2) in the breathing gas. The decay constants of CmP and TPL in tumor tissue were significantly larger than in the normal muscles, and lower linewidths of CmP and TPL in tumor tissue was observed. The SCC tumor showed intracellular hypoxia even though the extracellular pO(2) is similar to normal tissue in the peripheral region. PMID:21212532

  16. Seeing the invisible by paramagnetic and diamagnetic NMR

    PubMed Central

    Clore, G. Marius

    2014-01-01

    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 largescale 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. PMID:24256222

  17. Fast structure-based assignment of 15N HSQC spectra of selectively 15N-labeled paramagnetic proteins.

    PubMed

    Pintacuda, Guido; Keniry, Max A; Huber, Thomas; Park, Ah Young; Dixon, Nicholas E; Otting, Gottfried

    2004-03-10

    A novel strategy for fast NMR resonance assignment of (15)N HSQC spectra of proteins is presented. It requires the structure coordinates of the protein, a paramagnetic center, and one or more residue-selectively (15)N-labeled samples. Comparison of sensitive undecoupled (15)N HSQC spectra recorded of paramagnetic and diamagnetic samples yields data for every cross-peak on pseudocontact shift, paramagnetic relaxation enhancement, cross-correlation between Curie-spin and dipole-dipole relaxation, and residual dipolar coupling. Comparison of these four different paramagnetic quantities with predictions from the three-dimensional structure simultaneously yields the resonance assignment and the anisotropy of the susceptibility tensor of the paramagnetic center. The method is demonstrated with the 30 kDa complex between the N-terminal domain of the epsilon subunit and the theta subunit of Escherichia coli DNA polymerase III. The program PLATYPUS was developed to perform the assignment, provide a measure of reliability of the assignment, and determine the susceptibility tensor anisotropy. PMID:14995214

  18. Paramagnetic relaxation of long-lived coherences in solution NMR.

    PubMed

    Singh, Maninder; Srinivas, Chinthalapalli; Deb, Mayukh; Kurur, Narayanan D

    2013-12-01

    Long-lived coherences (LLCs) are known to have lifetimes much longer than transverse magnetization or single quantum coherences (SQCs). The effect of paramagnetic ions on the relaxation of LLCs is not known. This is particularly important, as LLCs have potential applications in various fields like analytical NMR, in vivo NMR and MR imaging methods. We study here the behaviour of LLCs in the presence of paramagnetic relaxation agents. The stepwise increase in the concentration of the metal ion is followed by measuring various relaxation rates. The effect of paramagnetic ions is analysed in terms of the external random field's contribution to the relaxation of two coupled protons in 2,3,6-trichlorobenzaldehyde. The LLCs relax faster than ordinary SQCs in the presence of paramagnetic ions of varying character. This is explained on the basis of an increase in the contribution of the external random field to relaxation due to a paramagnetic relaxation mechanism. Comparison is also made with ordinary Zeeman relaxation rates like R1, R2, R1ρ and also with rate of relaxation of long-lived states RLLS which are known to be less sensitive to paramagnetically induced relaxation. Also, the extent of correlation of random fields at two proton sites is studied and is found to be strongly correlated with each other. The obtained correlation constant is found to be independent of the nature of added paramagnetic impurities. PMID:24151221

  19. Topological paramagnetism in frustrated spin-1 Mott insulators

    NASA Astrophysics Data System (ADS)

    Wang, Chong; Nahum, Adam; Senthil, T.

    2015-05-01

    Time-reversal-protected three-dimensional (3D) topological paramagnets are magnetic analogs of the celebrated 3D topological insulators. Such paramagnets have a bulk gap and no exotic bulk excitations, but have non-trivial surface states protected by symmetry. We propose that frustrated spin-1 quantum magnets are a natural setting for realizing such states in three dimensions. We describe a physical picture of the ground-state wave function for such a spin-1 topological paramagnet in terms of loops of fluctuating Haldane chains with nontrivial linking phases. We illustrate some aspects of such loop gases with simple exactly solvable models. We also show how 3D topological paramagnets can be very naturally accessed within a slave particle description of a spin-1 magnet. Specifically, we construct slave-particle mean-field states which are naturally driven into the topological paramagnet upon including fluctuations. We propose bulk projected wave functions for the topological paramagnet based on this slave-particle description. An alternate slave-particle construction leads to a stable U (1 ) quantum spin liquid from which a topological paramagnet may be accessed by condensing the emergent magnetic monopole excitation of the spin liquid.

  20. Protein docking using an ensemble of spin labels optimized by intra-molecular paramagnetic relaxation enhancement.

    PubMed

    Schilder, Jesika; Liu, Wei-Min; Kumar, Pravin; Overhand, Mark; Huber, Martina; Ubbink, Marcellus

    2016-02-17

    Paramagnetic NMR is a useful technique to study proteins and protein complexes and the use of paramagnetic relaxation enhancement (PRE) for this purpose has become wide-spread. PREs are commonly generated using paramagnetic spin labels (SLs) that contain an unpaired electron in the form of a nitroxide radical, with 1-oxyl-2,2,5,5-tetramethyl-2,5-dihydropyrrol-3-ylmethyl methane thiosulfonate (MTSL) being the most popular tag. The inherent flexibility of the SL causes sampling of several conformations in solution, which can be problematic as over- or underestimation of the spatial distribution of the unpaired electron in structural calculations will lead to errors in the distance restraints. We investigated the effect of this mobility on the accuracy of protein-protein docking calculations using intermolecular PRE data by comparing MTSL and the less mobile 3-methanesulfonilthiomethyl-4-(pyridin-3-yl)-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrol-1-yloxyl (pyMTSL) on the dynamic complex of cytochrome c and cytochrome c peroxidase. No significant differences were found between the two SLs. Docking was performed using either single or multiple conformers and either fixed or flexible SLs. It was found that mobility of the SLs is the limiting factor for obtaining accurate solutions. Optimization of SL conformer orientations using intra-molecular PRE improves the accuracy of docking. PMID:26356049

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

    PubMed

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

    2015-09-01

    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. PMID:26212385

  2. Analysis of paramagnetic centers for threevalent iron in aluminosilicates

    NASA Astrophysics Data System (ADS)

    Apushkinskaya, D.; Apushkinskiy, E.; Popov, B.; Romanov, V. N.; Saveliev, V.; Sobolevskiy, V.

    2015-09-01

    We present the results of investigation of the defects in fluorine aluminosilicates from the Volyn-field Al2 [SiO4][F,OH]2 by the Electron Paramagnetic Resonance (EPR) method. The studies were carried out on the spectrometer Bruker ER 220D. Three types of EPR spectra of single centers were obtained. Their angular dependence was also investigated. The obtained EPR spectra correspond to the paramagnetic ion Fe3+ in the high-spin state S = 5/2. Three types of paramagnetic centers were found: one with cubic-symmetry and two with orthorhombic- symmetries.

  3. Paramagnetism in colour superconductivity and compact stars

    NASA Astrophysics Data System (ADS)

    Ferrer, Efrain J.; de la Incera, Vivian

    2007-06-01

    It is quite plausible that colour superconductivity occurs in the inner regions of neutron stars. At the same time, it is known that strong magnetic fields exist in the interior of these compact objects. In this paper we discuss some important effects that can occur in the colour superconducting core of compact stars due to the presence of the stars' magnetic field. In particular, we consider the modification of the gluon dynamics for a colour superconductor with three massless quark flavours in the presence of an external magnetic field. We show that the long-range component of the external magnetic field that penetrates the colour-flavour locked phase produces an instability for field values larger than the charged gluons' Meissner mass. As a consequence, the ground state is restructured forming a vortex state characterized by the condensation of charged gluons and the creation of magnetic flux tubes. In the vortex state the magnetic field outside the flux tubes is equal to the applied one, while inside the tubes its strength increases by an amount that depends on the amplitude of the gluon condensate. This paramagnetic behaviour of the colour superconductor can be relevant for the physics of compact stars.

  4. In vivo imaging of a stable paramagnetic probe by pulsed-radiofrequency electron paramagnetic resonance spectroscopy.

    PubMed

    Murugesan, R; Cook, J A; Devasahayam, N; Afeworki, M; Subramanian, S; Tschudin, R; Larsen, J A; Mitchell, J B; Russo, A; Krishna, M C

    1997-09-01

    Imaging of free radicals by electron paramagnetic resonance (EPR) spectroscopy using time domain acquisition as in nuclear magnetic resonance (NMR) has not been attempted because of the short spin-spin relaxation times, typically under 1 microsecond, of most biologically relevant paramagnetic species. Recent advances in radiofrequency (RF) electronics have enabled the generation of pulses of the order of 10-50 ns. Such short pulses provide adequate spectral coverage for EPR studies at 300 MHz resonant frequency. Acquisition of free induction decays (FID) of paramagnetic species possessing inhomogenously broadened narrow lines after pulsed excitation is feasible with an appropriate digitizer/averager. This report describes the use of time-domain RF EPR spectrometry and imaging for in vivo applications. FID responses were collected from a water-soluble, narrow line width spin probe within phantom samples in solution and also when infused intravenously in an anesthetized mouse. Using static magnetic field gradients and back-projection methods of image reconstruction, two-dimensional images of the spin-probe distribution were obtained in phantom samples as well as in a mouse. The resolution in the images was better than 0.7 mm and devoid of motional artifacts in the in vivo study. Results from this study suggest a potential use for pulsed RF EPR imaging (EPRI) for three-dimensional spatial and spectral-spatial imaging applications. In particular, pulsed EPRI may find use in vivo studies to minimize motional artifacts from cardiac and lung motion that cause significant problems in frequency-domain spectral acquisition, such as in continuous wave (cw) EPR techniques. PMID:9339442

  5. 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

  6. Paramagnetic Meissner effect in multiply-connected superconductors

    NASA Astrophysics Data System (ADS)

    Nielsen, A. P.; Cawthorne, A. B.; Wellstood, F. C.; Lobb, C. J.; Barbara, P.; Forrester, M. G.; Newrock, R. S.

    2001-03-01

    We have measured a paramagnetic Meissner effect in square Nb-Al_2O_3-Nb Josephson-junction arrays of different sizes (100×150 and 100×30 junctions) using a scanning SQUID microscope. We find that although the array is sometimes diamagnetic, it is preferentially paramagnetic and increasingly paramagnetic with increasing external field, for external fields from zero Φ0 up to 20 Φ0 per unit cell of the array, where Φ0 is the flux quantum. In all cases, we observe diamagnetic screening currents around the edge of the sample. We present a simple model which describes remarkably well the observed paramagnetic phenomena, and is generally applicable to any granular superconducting sample in which the grain size is larger than the penetration depth.

  7. Magnetic control of convection in nonconducting paramagnetic fluids

    NASA Astrophysics Data System (ADS)

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

    1998-01-01

    An inhomogeneous magnetic field exerts a magnetic body force on magnetically permeable fluids. A recent experiment [D. Braithwaite, E. Beaugnon, and R. Tournier, Nature (London) 354, 134 (1991)] demonstrates that this force can be used to compensate for gravity and to control convection in a paramagnetic solution of gadolinium nitrate. We provide the theory of magnetically controlled convection in a horizontal paramagnetic fluid layer heated from either above or below. Our theoretical predictions agree with the experiments.

  8. 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

  9. 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. PMID:24752730

  10. Interpreting the Paramagnetic NMR Spectra of Potential Ru(III) Metallodrugs: Synergy between Experiment and Relativistic DFT Calculations.

    PubMed

    Novotný, Jan; Sojka, Martin; Komorovsky, Stanislav; Nečas, Marek; Marek, Radek

    2016-07-13

    Ruthenium-based compounds are potential candidates for use as anticancer metallodrugs. The central ruthenium atom can be in the oxidation state +2 (e.g., RAPTA, RAED) or +3 (e.g., NAMI, KP). In this study we focus on paramagnetic NAMI analogs of a general structure [4-R-pyH](+)trans-[Ru(III)Cl4(DMSO)(4-R-py)](-), where 4-R-py stands for a 4-substituted pyridine. As paramagnetic systems are generally considered difficult to characterize in detail by NMR spectroscopy, we performed a systematic structural and methodological NMR study of complexes containing variously substituted pyridines. The effect of the paramagnetic nature of these complexes on the (1)H and (13)C NMR chemical shifts was systematically investigated by temperature-dependent NMR experiments and density-functional theory (DFT) calculations. To understand the electronic factors influencing the orbital (δ(orb), temperature-independent) and paramagnetic (δ(para), temperature-dependent) contributions to the total NMR chemical shifts, a relativistic two-component DFT approach was used. The paramagnetic contributions to the (13)C NMR chemical shifts are correlated with the distribution of spin density in the ligand moiety and the (13)C isotropic hyperfine coupling constants, Aiso((13)C), for the individual carbon atoms. To analyze the mechanism of spin distribution in the ligand, the contributions of molecular spin-orbitals (MSOs) to the hyperfine coupling constants and the spatial distribution of the z-component of the spin density in the MSOs calculated at the relativistic four-component DFT level are discussed and rationalized. The significant effects of the substituent and the solvent on δ(para), particularly the contact contribution, are demonstrated. This work should contribute to further understanding of the link between the electronic structure and the NMR chemical shifts in open-shell systems, including the ruthenium-based metallodrugs investigated in this account. PMID:27312929

  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. PMID:26574272

  12. Paramagnetic Meissner effect in MgB 2

    NASA Astrophysics Data System (ADS)

    Sözeri, Hüseyin; Dorosinskii, Lev; Topal, Uǧur; Ercan, İsmail

    2004-08-01

    We observed the paramagnetic Meissner effect (PME) in MgB 2 pellets after cooling in low fields of less than 1 Oe. As external magnetic field increases, the paramagnetic response of the sample decreases and disappears completely at 1 Oe. Effect of gamma irradiation on magnetic properties of MgB 2 has been investigated at low fields. In irradiated samples, the magnitude of the PME was found to be lower. To understand that whether this effect is of geometrical origin (so called flux compression model) or whether it is intrinsic to the material (e.g., π-junctions), measurements were performed with two samples having different geometries. Our results showed that paramagnetic response did not change as the geometry changes.

  13. Pauli paramagnetic gas in the framework of Riemannian geometry.

    PubMed

    Kaviani, K; Dalafi-Rezaie, A

    1999-10-01

    We investigate the thermodynamic curvature resulting from a Riemannian geometry approach to thermodynamics for the Pauli paramagnetic gas which is a system of identical fermions each with spin 1 / 2, and also for classical ideal paramagnetic gas. We find that both the curvature of classical ideal paramagnetic gas and the curvature of the Pauli gas in the classical limit reduce to that of a two-component ideal gas. On the other hand, it is seen straightforwardly that the curvature of classical gas satisfies the geometrical equation exactly. Also a simple relationship between the curvature of Pauli gas and the correlation volume is obtained. We see that it is only in the classical and semiclassical regime that the absolute value of the thermodynamic curvature can be interpreted as a measure of the stability of the system. PMID:11970187

  14. Electron paramagnetic resonance of a donor in aluminum nitride crystals

    NASA Astrophysics Data System (ADS)

    Evans, S. M.; Giles, N. C.; Halliburton, L. E.; Slack, G. A.; Schujman, S. B.; Schowalter, L. J.

    2006-02-01

    Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectra are obtained from a donor in aluminum nitride (AlN) crystals. Although observed in as-grown crystals, exposure to x rays significantly increases the concentration of this center. ENDOR identifies a strong hyperfine interaction with one aluminum neighbor along the c axis and weaker equivalent hyperfine interactions with three additional aluminum neighbors in the basal plane. These aluminum interactions indicate that the responsible center is a deep donor at a nitrogen site. The observed paramagnetic defect is either a neutral oxygen substituting for nitrogen (ON0) or a neutral nitrogen vacancy (VN0).

  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. On Quantum Gravity, Asymptotic Safety and Paramagnetic Dominance

    NASA Astrophysics Data System (ADS)

    Nink, Andreas; Reuter, Martin

    2013-04-01

    We discuss the conceptual ideas underlying the Asymptotic Safety approach to the nonperturbative renormalization of gravity. By now numerous functional renormalization group (RG) studies predict the existence of a suitable nontrivial ultraviolet (UV) 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 (QEG) behave like a polarizable medium with a "paramagnetic" response to external perturbations. Similarities with the vacuum state of Yang-Mills theory are pointed out.

  17. 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.

  18. 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.

  19. Nanostructure of Materials Determined by Relayed Paramagnetic Relaxation Enhancement

    PubMed Central

    2015-01-01

    Particle and domain sizes strongly influence the properties of materials. Here we present an NMR approach based on paramagnetic relaxation enhancement (PRE) relayed by spin diffusion (SD), which allows us to determine lengths in the nm−μm range. We demonstrate the method on multicomponent organic polymer mixtures by selectively doping one component with a paramagnetic center in order to measure the domain size in a second component. Using this approach we determine domain sizes in ethyl cellulose/hydroxypropyl cellulose film coatings in pharmaceutical controlled release formulations. Here we measure particle sizes ranging from around 50 to 200 nm. PMID:26397956

  20. 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

  1. Paramagnetic copper centers in ferroelectric lead germanate with halogens

    NASA Astrophysics Data System (ADS)

    Vazhenin, V. A.; Potapov, A. P.; Artyomov, M. Yu.; Vylkov, A. I.

    2014-08-01

    The electron paramagnetic resonance spectrum of triclinic bivalent copper centers in copper-doped Pb5Ge3O11 single crystals has been investigated. The spectrum intensity increases after thermal treatment in a chlorine- or fluorine-containing atmosphere. The parameters of the electron Zeeman, hyperfine, and nuclear quadrupole interactions have been determined. The model of the observed centers has been proposed.

  2. 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.

  3. Paramagnetic Meissner effect in high-temperature superconductors

    SciTech Connect

    Braunisch, W.; Knauf, N.; Bauer, G.; Kock, A.; Becker, A.; Freitag, B.; Gruetz, A.; Kataev, V.; Neuhausen, S.; Roden, B.; Khomskii, D.; Wohlleben, D. ); Bock, J.; Preisler, E. )

    1993-08-01

    We have studied the low-field Meissner effect of polycrystalline Bi high-temperature superconductors using a special superconducting-quantum-interference-device magnetometer. In certain samples a surprising feature was observed: Instead of the usual diamagnetic moment a paramagnetic moment develops in the field cooling mode below [ital T][sub [ital c

  4. 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…

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  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. Sensitivity enhancement using paramagnetic relaxation in MAS solid-state NMR of perdeuterated proteins

    NASA Astrophysics Data System (ADS)

    Linser, Rasmus; Chevelkov, Veniamin; Diehl, Anne; Reif, Bernd

    2007-12-01

    Previously, Ishii et al., could show that chelated paramagnetic ions can be employed to significantly decrease the recycle delay of a MAS solid-state NMR experiment [N.P. Wickramasinghe, M. Kotecha, A. Samoson, J. Past, Y. Ishii, Sensitivity enhancement in C-13 solid-state NMR of protein microcrystals by use of paramagnetic metal ions for optimizing H-1 T-1 relaxation, J. Magn. Reson. 184 (2007) 350-356]. Application of the method is limited to very robust samples, for which sample stability is not compromised by RF induced heating. In addition, probe integrity might be perturbed in standard MAS PRE experiments due to the use of very short duty cycles. We show that these deleterious effects can be avoided if perdeuterated proteins are employed that have been re-crystallized from D 2O:H 2O = 9:1 containing buffer solutions. The experiments are demonstrated using the SH3 domain of chicken α-spectrin as a model system. The labeling scheme allows to record proton detected 1H, 15N correlation spectra with very high resolution in the absence of heteronuclear dipolar decoupling. Cu-edta as a doping reagent yields a reduction of the recycle delay by up to a factor of 15. In particular, we find that the 1H T1 for the bulk H N magnetization is reduced from 4.4 s to 0.3 s if the Cu-edta concentration is increased from 0 mM to 250 mM. Possible perturbations like chemical shift changes or line broadening due to the paramagnetic chelate complex are minimal. No degradation of our samples was observed in the course of the experiments.

  12. Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via (17)O NMR and DFT Calculations.

    PubMed

    Seymour, Ieuan D; Middlemiss, Derek S; Halat, David M; Trease, Nicole M; Pell, Andrew J; Grey, Clare P

    2016-08-01

    Experimental techniques that probe the local environment around O in paramagnetic Li-ion cathode materials are essential in order to understand the complex phase transformations and O redox processes that can occur during electrochemical delithiation. While Li NMR is a well-established technique for studying the local environment of Li ions in paramagnetic battery materials, the use of (17)O NMR in the same materials has not yet been reported. In this work, we present a combined (17)O NMR and hybrid density functional theory study of the local O environments in Li2MnO3, a model compound for layered Li-ion batteries. After a simple (17)O enrichment procedure, we observed five resonances with large (17)O shifts ascribed to the Fermi contact interaction with directly bonded Mn(4+) ions. The five peaks were separated into two groups with shifts at 1600 to 1950 ppm and 2100 to 2450 ppm, which, with the aid of first-principles calculations, were assigned to the (17)O shifts of environments similar to the 4i and 8j sites in pristine Li2MnO3, respectively. The multiple O environments in each region were ascribed to the presence of stacking faults within the Li2MnO3 structure. From the ratio of the intensities of the different (17)O environments, the percentage of stacking faults was found to be ca. 10%. The methodology for studying (17)O shifts in paramagnetic solids described in this work will be useful for studying the local environments of O in a range of technologically interesting transition metal oxides. PMID:27404908

  13. Application of Paramagnetically Tagged Molecules for Magnetic Resonance Imaging of Biofilm Mass Transport Processes▿

    PubMed Central

    Ramanan, B.; Holmes, W. M.; Sloan, W. T.; Phoenix, V. R.

    2010-01-01

    Molecules become readily visible by magnetic resonance imaging (MRI) when labeled with a paramagnetic tag. Consequently, MRI can be used to image their transport through porous media. In this study, we demonstrated that this method could be applied to image mass transport processes in biofilms. The transport of a complex of gadolinium and diethylenetriamine pentaacetic acid (Gd-DTPA), a commercially available paramagnetic molecule, was imaged both in agar (as a homogeneous test system) and in a phototrophic biofilm. The images collected were T1 weighted, where T1 is an MRI property of the biofilm and is dependent on Gd-DTPA concentration. A calibration protocol was applied to convert T1 parameter maps into concentration maps, thus revealing the spatially resolved concentrations of this tracer at different time intervals. Comparing the data obtained from the agar experiment with data from a one-dimensional diffusion model revealed that transport of Gd-DTPA in agar was purely via diffusion, with a diffusion coefficient of 7.2 × 10−10 m2 s−1. In contrast, comparison of data from the phototrophic biofilm experiment with data from a two-dimensional diffusion model revealed that transport of Gd-DTPA inside the biofilm was by both diffusion and advection, equivalent to a diffusion coefficient of 1.04 × 10−9 m2 s−1. This technology can be used to further explore mass transport processes in biofilms, either by using the wide range of commercially available paramagnetically tagged molecules and nanoparticles or by using bespoke tagged molecules. PMID:20435773

  14. Electron paramagnetic resonance study of paramagnetic centers in carbon-fumed silica adsorbent

    SciTech Connect

    Savchenko, D. V.; Shanina, B. D.; Kalabukhova, E. N.; Sitnikov, A. A.; Lysenko, V. S.; Tertykh, V. A.

    2014-04-07

    Fumed silica A-300 was carbonized by means of pyrolysis of CH{sub 2}Cl{sub 2}. The obtained initial SiO{sub 2}:C nanopowders of black color, with an average diameter of 14–16 nm and carbon (C) concentration 7 wt. %, subjected to the oxidation and passivation treatment were studied by electron paramagnetic resonance (EPR) in the temperature range 4–400 K. Two EPR signals of Lorentzian lineshape with nearly equal g-factors and different linewidth were observed in the initial, oxidized, and passivated SiO{sub 2}:C nanopowders. The two-component EPR spectrum was explained by the presence of C in two electronic states. The intensive narrow EPR signal, which has a temperature-dependent intensity, linewidth, and resonance field position, was attributed to the carbon-related defect with non-localized electron hopping between neighboring C-dangling bonds. The striking effect is that the temperature dependence of the EPR linewidth demonstrates the motional narrowing of the EPR signal at very low temperatures from 4 K to 20 K, which is not typically for nonmetallic materials and was explained by the quantum character of C layer conductivity in the SiO{sub 2}:C. The observed peaks in the temperature dependence of the conduction electron EPR signal integral intensity in the high-temperature range 200–440 K was explained by the presence of the C nanodots at the surface of SiO{sub 2} nanoparticles and the ejection of electrons from the confinement energy levels of C quantum dot when the temperature becomes comparable to the confinement energy.

  15. Electron paramagnetic resonance study of paramagnetic centers in carbon-fumed silica adsorbent

    NASA Astrophysics Data System (ADS)

    Savchenko, D. V.; Shanina, B. D.; Kalabukhova, E. N.; Sitnikov, A. A.; Lysenko, V. S.; Tertykh, V. A.

    2014-04-01

    Fumed silica A-300 was carbonized by means of pyrolysis of CH2Cl2. The obtained initial SiO2:C nanopowders of black color, with an average diameter of 14-16 nm and carbon (C) concentration 7 wt. %, subjected to the oxidation and passivation treatment were studied by electron paramagnetic resonance (EPR) in the temperature range 4-400 K. Two EPR signals of Lorentzian lineshape with nearly equal g-factors and different linewidth were observed in the initial, oxidized, and passivated SiO2:C nanopowders. The two-component EPR spectrum was explained by the presence of C in two electronic states. The intensive narrow EPR signal, which has a temperature-dependent intensity, linewidth, and resonance field position, was attributed to the carbon-related defect with non-localized electron hopping between neighboring C-dangling bonds. The striking effect is that the temperature dependence of the EPR linewidth demonstrates the motional narrowing of the EPR signal at very low temperatures from 4 K to 20 K, which is not typically for nonmetallic materials and was explained by the quantum character of C layer conductivity in the SiO2:C. The observed peaks in the temperature dependence of the conduction electron EPR signal integral intensity in the high-temperature range 200-440 K was explained by the presence of the C nanodots at the surface of SiO2 nanoparticles and the ejection of electrons from the confinement energy levels of C quantum dot when the temperature becomes comparable to the confinement energy.

  16. Light induced particle organization in paramagnetic fluids

    NASA Astrophysics Data System (ADS)

    Bacia, Marcin; Masajada, Jan; Drobczyński, Sławomir; Lamperska, Weronika; Kutrowska, Joanna; Walczak, Katarzyna

    2014-12-01

    Magnetic fluids (ferrofluids) consist of magnetic nanoparticles (diameter ~10nm) which are dispersed in a liquid, often with the use of surfactants. They were first developed by NASA to address the unique requirements of moving liquid fuel in microgravity conditions. With a help of a holographic optical tweezers, interaction of magnetic nanoparticles with strongly focused laser beam was observed. When the light intensity was high enough, magnetic nanoparticles were removed from the beam center and they formed a dark ring. Creation process lasts less than 330μs and cannot be observed precisely even with ultrafast camera. Such rings exist when the laser beam is affecting the sample and disappear (with a lifespan of 10'th second range) after the laser is switched off. Moreover, when several rings are created simultaneously, complex interactions between them can be observed. In this work, the results of our experiments will be presented with hypotheses about the physical background of such a behavior.

  17. Speciation of Iron (III) Oxide Nanoparticles and Other Paramagnetic Intermediates during High-Temperature Oxidative Pyrolysis of 1-Methylnaphthalene

    PubMed Central

    Herring, Michael P.; Khachatryan, Lavrent; Dellinger, Barry

    2015-01-01

    Low Temperature Matrix Isolation - Electron Paramagnetic Resonance (LTMI-EPR) Spectroscopy was utilized to identify the species of iron oxide nanoparticles generated during the oxidative pyrolysis of 1-methylnaphthalene (1-MN). The otherwise gas-phase reactions of 1--MN were impacted by a polypropylenimine tetra-hexacontaamine dendrimer complexed with iron (III) nitrate nonahydrate diluted in air under atmospheric conditions. The EPR fine structure of Fe (III)2O3 nanoparticles clusters, characterized by g-factors of 2.00, 2.28, 3.76 and 4.37 were detected on a cold finger maintained at 77 K after accumulation over a multitude of experiments. Additionally, a high valence Fe (IV) paramagnetic intermediate and superoxide anion-radicals, O2•− adsorbed on nanoparticle surfaces in the form of Fe (IV) --- O2•− were detected from the quenching area of Zone 1 in the gas-phase. PMID:26413257

  18. 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. PMID:27166812

  19. Homogeneity of doping with paramagnetic ions by NMR.

    PubMed

    Li, Wenyu; Celinski, Vinicius R; Weber, Johannes; Kunkel, Nathalie; Kohlmann, Holger; Schmedt auf der Günne, Jörn

    2016-04-14

    In NMR, paramagnetic dopants change the relaxation behavior and the chemical shift of the nuclei in their immediate environment. Based on the concept that the "immediate environment" in a diamagnetic host material can be described as a sphere with radius r0, we developed a function for the fraction of unperturbed nuclei (the fraction of nuclei outside the sphere) which gives a link between the effective radius and the doping concentration. In the case of a homogeneous doping scenario a characteristic dependence is observed in both theory and experiment. We validated the model on a sample series where paramagnetic Eu(II) ions are doped into crystalline SrH2. The fraction of unperturbed nuclei was determined from the (1)H NMR signal and follows the predicted curve for a homogeneous doping scenario where the radius r0 is 17 Å. PMID:27003194

  20. Improved paramagnetic chelate for molecular imaging with MRI

    NASA Astrophysics Data System (ADS)

    Winter, Patrick; Athey, Phillip; Kiefer, Garry; Gulyas, Gyongyi; Frank, Keith; Fuhrhop, Ralph; Robertson, David; Wickline, Samuel; Lanza, Gregory

    2005-05-01

    The relaxivity and transmetallation of two lipophilic paramagnetic chelates incorporated onto perfluorocarbon nanoparticles, i.e., gadolinium-methoxy-tetraazacyclododecane-tetraacetic acid phosphatidylethanolamine (Gd-MeO-DOTA-PE) and gadolinium-methoxy-tetraazacyclododecane-tetraacetic acid triglycine phosphatidylethanolamine (Gd-MeO-DOTA-triglycine-PE (Gd-MeO-DOTA-triglycine-PE)), were compared to a prototypic gadolinium-diethylene-triamine-pentaacetic acid bis-oleate (Gd-DTPA-BOA) paramagnetic formulation. Nanoparticles with MeO-DOTA-based chelates demonstrated higher relaxivity (40% higher for Gd-MeO-DOTA-PE and 55% higher for Gd-MeO-DOTA-triglycine-PE) and less transmetallation than the original Gd-DTPA-BOA-based agent.

  1. Spin injection and spin transport in paramagnetic insulators

    DOE PAGESBeta

    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

  2. Electron paramagnetic resonance and optical absorption spectral studies on chalcocite

    NASA Astrophysics Data System (ADS)

    Reddy, S. Lakshmi; Fayazuddin, Md.; Frost, Ray L.; Endo, Tamio

    2007-11-01

    A chalcocite mineral sample of Shaha, Congo is used in the present study. An electron paramagnetic resonance (EPR) study on powdered sample confirms the presence of Mn(II), Fe(III) and Cu(II). Optical absorption spectrum indicates that Fe(III) impurity is present in octahedral structure whereas Cu(II) is present in rhombically distorted octahedral environment. Mid-infrared results are due to water and sulphate fundamentals.

  3. Electron paramagnetic resonance and optical absorption spectral studies on chalcocite.

    PubMed

    Reddy, S Lakshmi; Fayazuddin, Md; Frost, Ray L; Endo, Tamio

    2007-11-01

    A chalcocite mineral sample of Shaha, Congo is used in the present study. An electron paramagnetic resonance (EPR) study on powdered sample confirms the presence of Mn(II), Fe(III) and Cu(II). Optical absorption spectrum indicates that Fe(III) impurity is present in octahedral structure whereas Cu(II) is present in rhombically distorted octahedral environment. Mid-infrared results are due to water and sulphate fundamentals. PMID:17324611

  4. Investigation of electron paramagnetic resonance in carbon tubes

    NASA Astrophysics Data System (ADS)

    Byszewski, P.; Nabialek, A.

    1996-04-01

    Electron paramagnetic resonance (EPR) on carbon nanotubes was measured in a wide range of temperatures, the resonance disappeared after oxidizing the tubes. The results are discussed in terms of graphite properties and a model introducing a deformation potential to describe tubular structure. It leads to persistent ring currents in the magnetic field due to the carriers circular motion around a tube. A spin angular-momentum interaction is discussed in an attempt to explain the lack of EPR in purified carbon nanotubes.

  5. Electron paramagnetic resonance of material properties and processes

    SciTech Connect

    Brower, K. L.

    1980-01-01

    This paper demonstrates, primarily for the non-specialist and within the context of new and recent achievements, the diagnostic value of electron paramagnetic resonance (EPR) in the study of material properties and processes. I have selected three EPR studies which demonstrate the elegance and uniqueness of EPR in atomic defect studies and exemplify unusual achievements through the use of new techniques for material measurement and preparation. A brief introduction into the origin, interaction, and detection of unpaired electrons is included.

  6. Finite pulse effects in CPMG pulse trains on paramagnetic materials.

    PubMed

    Leskes, Michal; Grey, Clare P

    2015-09-14

    The Carr-Purcell-Meiboom-Gill (CPMG) sequence is commonly used in high resolution NMR spectroscopy and in magnetic resonance imaging for the measurement of transverse relaxation in systems that are subject to diffusion in internal or external gradients and is superior to the Hahn echo measurement, which is more sensitive to diffusion effects. Similarly, it can potentially be used to study dynamic processes in electrode materials for lithium ion batteries. Here we compare the (7)Li signal decay curves obtained with the CPMG and Hahn echo sequences under static conditions (i.e., in the absence of magic angle spinning) in paramagnetic materials with varying transition metal ion concentrations. Our results indicate that under CPMG pulse trains the lifetime of the (7)Li signal is substantially extended and is correlated with the strength of the electron-nuclear interaction. Numerical simulations and analytical calculations using Floquet theory suggest that the combination of large interactions and a train of finite pulses, results in a spin locking effect which significantly slows the signal's decay. While these effects complicate the interpretation of CPMG-based investigations of diffusion and chemical exchange in paramagnetic materials, they may provide a useful approach to extend the signal's lifetime in these often fast relaxing systems, enabling the use of correlation experiments. Furthermore, these results highlight the importance of developing a deeper understanding of the effects of the large paramagnetic interactions during multiple pulse experiments in order to extend the experimental arsenal available for static and in situ NMR investigations of paramagnetic materials. PMID:26246217

  7. 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.

  8. Electron-paramagnetic resonance detection with software time locking

    NASA Astrophysics Data System (ADS)

    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.

  9. Detection of Nitric Oxide by Electron Paramagnetic Resonance Spectroscopy

    PubMed Central

    Hogg, Neil

    2010-01-01

    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 for detecting this species by EPR are somewhat different than those for 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. PMID:20304044

  10. 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.

  11. A Sub-Millimeter Solenoid Device for Trapping Paramagnetic Microbeads

    SciTech Connect

    Garcia, L D; Cheung, L C; Mikkelsen, J C; Santiago, J G; bernhardt, A F; Malba, V

    2001-08-01

    We present the design and preliminary evaluation of a paramagnetic microsphere trapping and separation device consisting of a copper solenoid wrapped around a 1.3 mm diameter glass capillary. The magnetization and subsequent dipole-dipole interaction of paramagnetic spheres under an applied magnetic field results in the formation of bead chains that persist and grow under the applied field, but quickly disperse upon field removal. The chaining of paramagnetic spheres is important to the design of magnetic-based separation devices because the viscous-drag-limited velocities of chains are typically several times larger than that of individual particles. We have performed a set of experiments designed to evaluate the performance of a sub-millimeter solenoid device including measurements of the temperature versus field strength of the device, observations of the controlled chain formation process, and preliminary observations regarding the maximum flow rate over which the bead chains can be held in place by magnetic forces. These results are applicable to the design and characterization of magnetically induced microsphere trapping and separation systems which use pressure driven flow.

  12. 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. PMID:25066905

  13. Imaging of Brain Tumors With Paramagnetic Vesicles Targeted to Phosphatidylserine

    PubMed Central

    Winter, Patrick M.; Pearce, John; Chu, Zhengtao; McPherson, Christopher M.; Takigiku, Ray; Lee, Jing-Huei; Qi, Xiaoyang

    2014-01-01

    Purpose To investigate paramagnetic saposin C and dioleylphosphatidylserine (SapC-DOPS) vesicles as a targeted contrast agent for imaging phosphatidylserine (PS) expressed by glioblastoma multiforme (GBM) tumors. Materials and Methods Gd-DTPA-BSA/SapC-DOPS vesicles were formulated, and the vesicle diameter and relaxivity were measured. Targeting of Gd-DTPA-BSA/ SapC-DOPS vesicles to tumor cells in vitro and in vivo was compared with nontargeted paramagnetic vesicles (lacking SapC). Mice with GBM brain tumors were imaged at 3, 10, 20, and 24 h postinjection to measure the relaxation rate (R1) in the tumor and the normal brain. Results The mean diameter of vesicles was 175 nm, and the relaxivity at 7 Tesla was 3.32 (s*mM)−1 relative to the gadolinium concentration. Gd-DTPA-BSA/SapC-DOPS vesicles targeted cultured cancer cells, leading to an increased R1 and gadolinium level in the cells. In vivo, Gd-DTPA-BSA/SapC-DOPS vesicles produced a 9% increase in the R1 of GBM brain tumors in mice 10 h postinjection, but only minimal changes (1.2% increase) in the normal brain. Nontargeted paramagnetic vesicles yielded minimal change in the tumor R1 at 10 h postinjection (1.3%). Conclusion These experiments demonstrate that Gd-DTPA-BSA/SapC-DOPS vesicles can selectively target implanted brain tumors in vivo, providing noninvasive mapping of the cancer biomarker PS. PMID:24797437

  14. Electron Paramagnetic Resonance of Nitrogenase and Nitrogenase Components from Clostridium pasteurianum W5 and Azotobacter vinelandii OP

    PubMed Central

    Orme-Johnson, W. H.; Hamilton, W. D.; Jones, T. L.; Tso, M.-Y. W.; Burris, R. H.; Shah, V. K.; Brill, W. J.

    1972-01-01

    The electron paramagnetic resonance of nitrogenase components, separately and together with the other reactants in the nitrogenase system (namely, reductant and Mg·ATP), have been examined at low temperatures (<20°K). The MoFe protein, component I or molybdoferredoxin, in the oxidized (but not oxygen-inactivated) state yields signals with g-values of 4.3, 3.7, and 2.01, and when reduced has no observable electron paramagnetic resonance. The Fe protein, component II, or azoferredoxin, yields a signal with g-values of 2.05, 1.94, and 1.89 in the reduced state that is converted by Mg·ATP into an axial signal with g-values near 2.05 and 1.94, and a second split signal near g = 4.3. The Fe protein has no definite electron paramagnetic resonance in the oxidized (not oxygen-denatured) state under these conditions. The Mg·ATP complex of reduced Fe protein reduces the MoFe protein, whereas dithionite alone does not reduce the MoFe protein. Reoxidation of the system by substrate leads to disappearance of the Fe protein signal and the reappearance of the MoFe protein signal. Thus Mg·ATP, which is hydrolyzed during substrate reduction, converts the Fe protein to a reductant capable of transferring electrons to MoFe protein, after which substrate reduction occurs. PMID:4343957

  15. Self-assembly triggered by self-assembly: optically active, paramagnetic micelles encapsulated in protein cage nanoparticles.

    PubMed

    Millán, Jealemy Galindo; Brasch, Melanie; Anaya-Plaza, Eduardo; de la Escosura, Andrés; Velders, Aldrik H; Reinhoudt, David N; Torres, Tomás; Koay, Melissa S T; Cornelissen, Jeroen J L M

    2014-07-01

    In this contribution, optically active and paramagnetic micelles of the ligand 1,4,7,10-tetraaza-1-(1-carboxymethylundecane)-4,7,10-triacetic acid cyclododecane (DOTAC10) have been incorporated inside capsids of the cowpea chlorotic mottle virus (CCMV) protein through a hierarchical process of self-assembly triggered by self-assembly. The DOTAC10 ligand was used to complex Gd(III), in order to form paramagnetic micelles, as well as to encapsulate an amphiphilic Zn(II) phthalocyanine (ZnPc) dye that optically confirmed the encapsulation of the micelles. The incorporation of ZnPc molecules in the paramagnetic micelles led to high capsid loading of both Gd(III) and ZnPc, as the micelles were stabilized by the amphiphilic dye encapsulation. The resulting protein cage nanoparticles (PCNs) show an improved r1 relaxivity, suggesting the possible use of these nanostructures as contrast agents (CAs) for magnetic resonance imaging (MRI). Since the encapsulated ZnPc dye also has a potential therapeutic value, the present results represent a first step towards the consecution of fully self-assembled PCNs for multimodal imaging and therapy. PMID:24513535

  16. Detection of Nitric Oxide by Electron Paramagnetic Resonance Spectroscopy: Spin-Trapping with Iron-Dithiocarbamates.

    PubMed

    Maia, Luisa B; Moura, José J G

    2016-01-01

    Electron paramagnetic resonance (EPR) spectroscopy is the ideal methodology to identify radicals (detection and characterization of molecular structure) and to study their kinetics, in both simple and complex biological systems. The very low concentration and short life-time of NO and of many other radicals do not favor its direct detection and spin-traps are needed to produce a new and persistent radical that can be subsequently detected by EPR spectroscopy.In this chapter, we present the basic concepts of EPR spectroscopy and of some spin-trapping methodologies to study NO. The "strengths and weaknesses" of iron-dithiocarbamates utilization, the NO traps of choice for the authors, are thoroughly discussed and a detailed description of the method to quantify the NO formation by molybdoenzymes is provided. PMID:27094413

  17. Direct electron paramagnetic resonance study of tobacco. 1. Manganese(ii) as a marker.

    PubMed

    Morsy, M A; Khaled, M M

    2001-02-01

    Three categories of tobacco products were studied using electron paramagnetic resonance (EPR) spectroscopy: Cuban cigar brand name Montecristo, four international trademark cigarettes, and three types of Middle Eastern tobacco blends called Al-Moassal or Jurak. The Montecristo Cuban cigar is used as standard of high-quality tobacco. Mainly two EPR signals from all of the studied samples are observed: a very weak sharp EPR signal superimposed on a broad signal. The broad EPR signal is attributed to a manganese(II) complex. The intensity of the manganese(II) EPR signal is found to be related to the quality of the tobacco content. The sharp signal, which is characteristic of semiquinone radicals, is observed at room temperature, and its intensity increases drastically with temperature. PMID:11262012

  18. 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. PMID:19764797

  19. Electron Paramagnetic Resonance -- Nuclear Magnetic Resonance Three Axis Vector Magnetometer

    NASA Astrophysics Data System (ADS)

    Bulatowicz, Michael; Clark, Philip; Griffith, Robert; Larsen, Michael; Mirijanian, James

    2012-06-01

    The Northrop Grumman Corporation is leveraging the technology developed for the Nuclear Magnetic Resonance Gyroscope (NMRG) to build a combined Electron Paramagnetic Resonance -- Nuclear Magnetic Resonance (EPR-NMR) magnetometer. The EPR-NMR approach provides a high bandwidth and high sensitivity simultaneous measurement of all three vector components of the magnetic field averaged over the small volume of the sensor's one vapor cell. This poster will describe the history, operational principles, and design basics of the EPR-NMR magnetometer including an overview of the NSD designs developed and demonstrated to date. General performance results will also be presented.

  20. Synthesis and study of new paramagnetic resveratrol analogues.

    PubMed

    Kálai, Tamás; Borza, Erzsébet; Antus, Csenge; Radnai, Balázs; Gulyás-Fekete, Gergely; Fehér, Andrea; Sümegi, Balázs; Hideg, Kálmán

    2011-12-15

    New resveratrol analogues containing five- and six-membered nitroxides and isoindoline nitroxides were synthesized. These new compounds were compared to resveratrol based on their ABTS radical scavenging ability as well on their capacity to suppress inflammatory process in macrophages induced by lipopolysaccharides. The ABTS and ROS scavenging activities of new molecules were the same or weaker than that of resveratrol, but some of paramagnetic resveratrol derivatives suppressed nitrite and TNFα production more efficiently than resveratrol. Based on these results the new nitroxide and phenol containing hybrid molecules can be considered as new antioxidant and anti-inflammatory agents. PMID:22088309

  1. 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.

  2. 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.

  3. Electron paramagnetic resonance in Zn1-xCoxO

    NASA Astrophysics Data System (ADS)

    Acosta-Humánez, F.; Cogollo Pitalúa, R.; Almanza, O.

    2013-03-01

    In this paper is reported the Electron Paramagnetic Resonance (EPR) studies in Zn1-xCoxO powder, with 0.01≤x≤0.05, at many temperatures (105-250 K). These samples were synthesized by the sol-gel method (citrate route). Results suggest that the ferromagnetism behavior of the materials is governed by ferromagnetic coupling among cobalt ions. For cobalt concentration higher than 3% were obtained mean size particle higher than 25 nm, measured by X-ray diffraction, and for this were also observed shallow free radical.

  4. Electron paramagnetic resonance of nitroxide-doped magnetic fluids

    NASA Astrophysics Data System (ADS)

    Morais, P. C.; Alonso, A.; Silva, O.; Buske, N.

    2002-11-01

    Electron paramagnetic resonance was used to investigate surface-coated magnetite-based magnetic fluids doped with TEMPOL. Two magnetic fluid samples, having magnetite nanoparticles with average diameter of 94 Å and coated with different coating layers (lauric acid plus ethoxylated polyalcohol in one case and oleoylsarcosine in the other case), were doped with TEMPOL (6 mM and pH 7.4) and investigated as a function of the nanoparticle concentration. The resonance field and the resonance linewidth both scale linearly with the nanoparticle concentration.

  5. 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.

  6. Paramagnetic supercurrent and transition points between different vortex states in mesoscopic superconducting disks

    NASA Astrophysics Data System (ADS)

    Kanda, Akinobu; Ootuka, Youiti

    2004-05-01

    We investigated the paramagnetic supercurrent and the transition points between different vortex states in mesoscopic superconducting disks. We observed paramagnetic supercurrent in four disks: two 33 nm thick and two 50 nm thick, all 1.50 μm in diameter. Analyses of the supercurrent symmetry and the intervals between transition points showed that defects did not play a crucial role in our samples or in the samples first reported to show the paramagnetic Meissner effect (PME) [Nature 396 (1998) 144]. This supports our previous conclusion that the origin of the PME is the paramagnetic supercurrent.

  7. A tuneable doubly stacked dielectric resonator housed in an intact TE 102 cavity for electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Mattar, Saba M.; Emwas, Abdul H.

    2003-01-01

    An EPR resonator is constructed by inserting a pair of dielectric ceramic rings in an unmodified rectangular TE 102 cavity. It is tuneable over the range of 8.0-10.0 GHz. Therefore, existing EPR cavities can be easily converted to resonators with superior signal-to-noise ratios that are at least 24 times larger than the original ones in this extended frequency range. The resonator's performance is tested using DPPH, TEMPONE, MnO and Cu 2+ complexes and displays excellent resolution and sensitivity. Thus EPR spectra of small paramagnetic organic and inorganic samples and spin labeled biomolecules may be obtained without resorting to loop gap resonators.

  8. Paramagnetic relaxation enhancements in unfolded proteins: Theory and application to drkN SH3 domain

    PubMed Central

    Xue, Yi; Podkorytov, Ivan S; Rao, D Krishna; Benjamin, Nathan; Sun, Honglei; Skrynnikov, Nikolai R

    2009-01-01

    Site-directed spin labeling in combination with paramagnetic relaxation enhancement (PRE) measurements is one of the most promising techniques for studying unfolded proteins. Since the pioneering work of Gillespie and Shortle (J Mol Biol 1997;268:158), PRE data from unfolded proteins have been interpreted using the theory that was originally developed for rotational spin relaxation. At the same time, it can be readily recognized that the relative motion of the paramagnetic tag attached to the peptide chain and the reporter spin such as 1HN is best described as a translation. With this notion in mind, we developed a number of models for the PRE effect in unfolded proteins: (i) mutual diffusion of the two tethered spheres, (ii) mutual diffusion of the two tethered spheres subject to a harmonic potential, (iii) mutual diffusion of the two tethered spheres subject to a simulated mean-force potential (Smoluchowski equation); (iv) explicit-atom molecular dynamics simulation. The new models were used to predict the dependences of the PRE rates on the 1HN residue number and static magnetic field strength; the results are appreciably different from the Gillespie–Shortle model. At the same time, the Gillespie–Shortle approach is expected to be generally adequate if the goal is to reconstruct the distance distributions between 1HN spins and the paramagnetic center (provided that the characteristic correlation time is known with a reasonable accuracy). The theory has been tested by measuring the PRE rates in three spin-labeled mutants of the drkN SH3 domain in 2M guanidinium chloride. Two modifications introduced into the measurement scheme—using a reference compound to calibrate the signals from the two samples (oxidized and reduced) and using peak volumes instead of intensities to determine the PRE rates—lead to a substantial improvement in the quality of data. The PRE data from the denatured drkN SH3 are mostly consistent with the model of moderately expanded random

  9. Electron paramagnetic resonance of a donor in aluminum nitride crystals.

    NASA Astrophysics Data System (ADS)

    Evans, Sean; Giles, Nancy; Halliburton, Larry; Slack, Glen; Schujman, Sandra; Schowalter, Leo

    2006-03-01

    Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) have been used to characterize a dominant donor in single crystals of aluminum nitride (AlN). A broad EPR signal, with g (parallel) = 2.002 and g (perpendicular) = 2.006, is observed in the as-grown crystals. Exposure to x-rays (i.e., ionizing radiation) increases the concentration of this center by a factor of five to ten (depending on sample), thus indicating that most of these centers are initially present in the crystals in a nonparamagnetic charge state. ENDOR identifies a strong hyperfine interaction with one aluminum neighbor along the c axis (described by A (parallel) = 111.30 MHz, A (perpendicular) = 54.19 MHz, and P = 0.289 MHz) and weaker equivalent hyperfine interactions with three additional aluminum neighbors in the basal plane. These aluminum interactions indicate that the responsible center is a deep donor at a nitrogen site. The observed paramagnetic defect is either a neutral oxygen substituting for nitrogen or a neutral nitrogen vacancy. This work was supported at West Virginia University by the National Science Foundation (Grant DMR-0508140). One of the authors (SME) received support from the WV EPSCoR STEM fellowship program.

  10. Collective spin excitations in 2D paramagnet with dipole interaction

    NASA Astrophysics Data System (ADS)

    Tsiberkin, Kirill

    2016-02-01

    The collective spin excitations in the unbounded 2D paramagnetic system with dipole interactions are studied. The model Hamiltonian includes Zeeman energy and dipole interaction energy, while the exchange vanishes. The system is placed into a constant uniform magnetic field which is orthogonal to the lattice plane. It provides the equilibrium state with spin ordering along the field direction, and the saturation is reached at zero temperature. We consider the deviations of spin magnetic moments from its equilibrium position along the external field. The Holstein-Primakoff representation is applied to spin operators in low-temperature approximation. When the interaction between the spin waves is negligible and only two-magnon terms are taken into account, the Hamiltonian diagonalisation is possible. We obtain the dispersion relation for spin waves in the square and hexagonal honeycomb lattice. Bose-Einstein statistics determine the average number of spin deviations, and total system magnetization. The lattice structure does not influence on magnetization at the long-wavelength limit. The dependencies of the relative magnetization and longitudinal susceptibility on temperature and external field intensity are found. The internal energy and specific heat of the Bose gas of spin waves are calculated. The collective spin excitations play a significant role in the properties of the paramagnetic system at low temperature and strong external magnetic field.

  11. 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

    2013-09-01

    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. PMID:23972068

  12. Electron paramagnetic resonance in positively charged Au25 molecular nanoclusters.

    PubMed

    Akbari-Sharbaf, Arash; Hesari, Mahdi; Workentin, Mark S; Fanchini, Giovanni

    2013-01-14

    In this study, we investigated the unpaired electrons and singly occupied molecular orbitals (SOMO) of positively charged Au(25) molecular clusters using solid-state electron paramagnetic resonance (EPR). The EPR powder spectra of the positively charged (Au(25) (+)) and neutral (Au(25) (0)) species of Au(25) are discussed and compared. Our study demonstrates that Au(25) (+) is paramagnetic with a SOMO that is mostly localized about the central gold atom in the core of the molecule and possesses a strong p-type atomic character. The unpaired electron spin is demonstrated to strongly interact with the nuclear spins from other (197)Au nuclei in the core of Au(25) (+) molecules and the hyperfine tensor describing such interaction was extracted from the comparison of the EPR spectra with quantum mechanical simulations assuming an anisotropic structure of the core. Our simulations suggest that the core of Au(25) (+) molecular clusters is more distorted than in the corresponding neutral counterpart. They also confirm previous hypotheses suggesting that the icosahedral core of Au(25) (+) experiences contraction with decreasing temperature. PMID:23320681

  13. 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.

  14. Grain alignment: Role of radiative torques and paramagnetic relaxation

    NASA Astrophysics Data System (ADS)

    Lazarian, Alexander; Andersson, B.-G.; Hoang, Thiem

    2015-05-01

    Polarization arising from aligned dust grains presents a unique opportunity to study magnetic fields in the diffuse interstellar medium and molecular clouds. Polarization from circumstellar regions, accretion disks and comet atmospheres can also be related to aligned dust.To reliably trace magnetic fields quantitative theory of grain alignment is required. Formulating the theory that would correspond to observations was one of the longstanding problems in astrophysics. Lately this problem has been successfully addressed, and in this review we summarize some of the most important theoretical advances in the theory of grain alignment by radiative torques (RATs) that act on realistic irregular dust grains. We discuss an analytical model of RATs and the ways to make RAT alignment more efficient, e.g. through paramagnetic relaxation when grains have inclusions with strong magnetic response. For very small grains for which RAT alignment is inefficient, we also discuss paramagnetic relaxation and a process termed resonance relaxation. We provide an extensive analysis of the observational tests of grain alignment theory.

  15. 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

  16. High-field paramagnetic Meissner effect up to 14 T in melt-textured YBa2Cu3O7-δ

    NASA Astrophysics Data System (ADS)

    Dias, F. T.; Vieira, V. N.; Wolff-Fabris, F.; Kampert, E.; Gouvêa, C. P.; Campos, A. P. C.; Archanjo, B. S.; Schaf, J.; Obradors, X.; Puig, T.; Roa, J. J.; Sahoo, B. K.

    2016-06-01

    We have performed magnetization experiments in a melt-textured YBa2Cu3O7-δ (Y123) sample with Y2BaCuO5 (Y211) inclusions, under magnetic fields up to 14 T applied parallel or perpendicular to the ab plane. Magnetic anisotropy and paramagnetic moments were observed in both FC (field-cooling) and FCW (field-cooled warming) procedures and these features correspond to the so-called High-Field Paramagnetic Meissner Effect (HFPME). The HFPME effect increases monotonically as the magnetic field rises and a strong paramagnetic relaxation, toward increasing paramagnetic moment was additionally observed as a function of time. Microscopy analysis revealed a complex and correlated microstructure of the Y211 particles. These correlated defects are well known to cause strong flux pinning. Our results suggest a scenario of strong flux compression within weak or non-superconducting regions of the samples, developed as a consequence of the Meissner effect and assisted by strong flux pinning by the Y211 particles. This scenario is observed up to 14 T and clearly persists beyond.

  17. 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. PMID:27171212

  18. Paramagnetic Phospholipid-Based Micelles Targeting VCAM-1 Receptors for MRI Visualization of Inflammation.

    PubMed

    Pagoto, Amerigo; Stefania, Rachele; Garello, Francesca; Arena, Francesca; Digilio, Giuseppe; Aime, Silvio; Terreno, Enzo

    2016-08-17

    Inflammation is signaled by the overexpression of epitopes on the vascular endothelium that primarily aim at recruiting immune cells into the inflamed area. The intravascular localization of these biomarkers makes them suitable targets for the MRI visualization of inflammation. Phospholipid-based nanosystems appear excellent candidates in virtue of their good biocompatibility, ability to deliver a high number of imaging units at the target site, and for the easy functionalization with targeting vectors. In this work, phospholipid-based micelles (hydrodynamic diameter of 20 nm) loaded with the amphiphilic Gd(III)-complex Gd-DOTAMA(C18)2 were vectorized with a small peptide able to specifically bind VCAM-1 receptors. The micelles displayed a high longitudinal relaxivity (36.4 s(-1)mmolGd(-1) at 25 °C and 0.7 T). A (1)H- and (17)O-water relaxometry study indicated that the paramagnetic complex embedded in the nanoparticles adopted two isomeric conformations, likely reflecting the well-known square antiprismatic (SAP) and twisted square antiprismatic (TSAP) configurations typically observed in DOTA-like lanthanide complexes. Interestingly, the TSAP structure, showing a much faster exchange rate for the water molecule coordinated to the metal ion, was the most abundant, thus explaining the high relaxivity of the micellar agent. The systemic administration of the micelles into a lipopolysaccharide-induced murine model of acute inflammation successfully demonstrated the ability of the targeting agents to detect the diseased area by T1 contrast enhanced MRI. PMID:27315634

  19. 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.

  20. Molecular dynamics in paramagnetic materials as studied by magic-angle spinning 2H NMR spectra.

    PubMed

    Mizuno, Motohiro; Suzuki, You; Endo, Kazunaka; Murakami, Miwa; Tansho, Masataka; Shimizu, Tadashi

    2007-12-20

    A magic-angle spinning (MAS) 2H NMR experiment was applied to study the molecular motion in paramagnetic compounds. The temperature dependences of 2H MAS NMR spectra were measured for paramagnetic [M(H2O)6][SiF6] (M=Ni2+, Mn2+, Co2+) and diamagnetic [Zn(H2O)6][SiF6]. The paramagnetic compounds exhibited an asymmetric line shape in 2H MAS NMR spectra because of the electron-nuclear dipolar coupling. The drastic changes in the shape of spinning sideband patterns and in the line width of spinning sidebands due to the 180 degrees flip of water molecules and the reorientation of [M(H2O)6]2+ about its C3 axis were observed. In the paramagnetic compounds, paramagnetic spin-spin relaxation and anisotropic g-factor result in additional linebroadening of each of the spinning sidebands. The spectral simulation of MAS 2H NMR, including the effects of paramagnetic shift and anisotropic spin-spin relaxation due to electron-nuclear dipolar coupling and anisotropic g-factor, was performed for several molecular motions. Information about molecular motions in the dynamic range of 10(2) s(-1)paramagnetic compounds from the analysis of 2H MAS NMR spectra when these paramagnetic effects are taken into account. PMID:18027914

  1. Electron paramagnetic resonance investigation of metalloendofullerene derived carbon nanotube peapods

    NASA Astrophysics Data System (ADS)

    Jakes, P.; Gembus, A.; Dinse, K.-P.; Hata, K.

    2008-02-01

    Single Wall Carbon Nanotubes (SWCNT) prepared by the "super growth" method and arc-grown material were used as templates for peapod preparation with La@C82. A qualitative change of the electron paramagnetic resonance (EPR) properties of La@C82 is observed after incorporation into SWNT. The loss of lanthanum hyperfine interaction in combination with the observed increase of EPR susceptibility by two orders of magnitude after peapod preparation when comparing with signals from "empty" tubes is indicative for the generation of itinerant spins by charge and spin transfer from La@C82 to the tubes. This interpretation is supported by the observation of fast spin dephasing, detected with pulsed EPR techniques.

  2. Electron paramagnetic resonance investigation of metalloendofullerene derived carbon nanotube peapods.

    PubMed

    Jakes, P; Gembus, A; Dinse, K-P; Hata, K

    2008-02-01

    Single Wall Carbon Nanotubes (SWCNT) prepared by the "super growth" method and arc-grown material were used as templates for peapod preparation with La@C(82). A qualitative change of the electron paramagnetic resonance (EPR) properties of La@C(82) is observed after incorporation into SWNT. The loss of lanthanum hyperfine interaction in combination with the observed increase of EPR susceptibility by two orders of magnitude after peapod preparation when comparing with signals from "empty" tubes is indicative for the generation of itinerant spins by charge and spin transfer from La@C(82) to the tubes. This interpretation is supported by the observation of fast spin dephasing, detected with pulsed EPR techniques. PMID:18266423

  3. Wohlleben Effect (paramagnetic Meissner Effect) in high-temperature superconductors

    SciTech Connect

    Khomskii, D. |

    1994-04-01

    Recently a quite unexpected phenomenon was observed during the study of the magnetic properties of High-T{sub c} superconductors: In the field-cooled regime the magnetic response of some HTSC at very low fields ({le} 1 Oe), instead of being diamagnetic, becomes paramagnetic. Such behavior is perfectly reproducible and stable. This effect is now called the Wohlleben Effect. The samples showing the Wohlleben effect also display anomalous behavior in some other properties (microwave absorption, second harmonic of magnetic susceptibility). In this paper a survey is given of the experimental studies of this and related phenomena, carried out in different laboratories. Corresponding theoretical models are also discussed. The effect is attributed to the formation of spontaneous currents (spontaneous orbital magnetic moments) in the ground state of the weak link network in case when Josephson coupling between certain grains is negative ({pi}-contacts). Microscopic mechanisms of inverse Josephson coupling are discussed especially in connection with the possible unconventional pairing in HTSC.

  4. Enhanced Wireless Power Transmission Using Strong Paramagnetic Response

    PubMed Central

    Ahn, Dukju; Kiani, Mehdi; Ghovanloo, Maysam

    2015-01-01

    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. PMID:26120144

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

    PubMed

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

    2015-04-24

    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 (J_{H},J_{K})=(-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. PMID:25955072

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

    DOE PAGESBeta

    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 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

  7. 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.

  8. Horizontal deflection of single particle in a paramagnetic fluid.

    PubMed

    Liu, S; Yi, Xiang; Leaper, M; Miles, N J

    2014-06-01

    This paper describes the horizontal deflection behaviour of a single particle in paramagnetic fluids under a high-gradient superconducting magnetic field. A glass box was designed to carry out experiments and test assumptions. It was found that the particles were deflected away from the magnet bore centre and particles with different density and/or susceptibility settled at a certain position on the container floor due to the combined forces of gravity and magneto-Archimedes as well as lateral buoyant (displacement) force. Matlab was chosen to simulate the movement of the particle in the magnetic fluid, the simulation results were in good accordance with experimental data. The results presented here, though, are still very much in their infancy, which could potentially form the basis of a new approach to separating materials based on a combination of density and susceptibility. PMID:24894886

  9. Electron paramagnetic resonance of individual atoms on a surface.

    PubMed

    Baumann, Susanne; Paul, William; Choi, Taeyoung; Lutz, Christopher P; Ardavan, Arzhang; Heinrich, Andreas J

    2015-10-23

    We combined the high-energy resolution of conventional spin resonance (here ~10 nano-electron volts) with scanning tunneling microscopy to measure electron paramagnetic resonance of individual iron (Fe) atoms placed on a magnesium oxide film. We drove the spin resonance with an oscillating electric field (20 to 30 gigahertz) between tip and sample. The readout of the Fe atom's quantum state was performed by spin-polarized detection of the atomic-scale tunneling magnetoresistance. We determine an energy relaxation time of T1 ≈ 100 microseconds and a phase-coherence time of T2 ≈ 210 nanoseconds. The spin resonance signals of different Fe atoms differ by much more than their resonance linewidth; in a traditional ensemble measurement, this difference would appear as inhomogeneous broadening. PMID:26494753

  10. 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.

  11. 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.

  12. Super-paramagnetic clustering of yeast gene expression profiles

    NASA Astrophysics Data System (ADS)

    Getz, G.; Levine, E.; Domany, E.; Zhang, M. Q.

    2000-04-01

    High-density DNA arrays, used to monitor gene expression at a genomic scale, have produced vast amounts of information which require the development of efficient computational methods to analyze them. The important first step is to extract the fundamental patterns of gene expression inherent in the data. This paper describes the application of a novel clustering algorithm, super-paramagnetic clustering (SPC) to analysis of gene expression profiles that were generated recently during a study of the yeast cell cycle. SPC was used to organize genes into biologically relevant clusters that are suggestive for their co-regulation. Some of the advantages of SPC are its robustness against noise and initialization, a clear signature of cluster formation and splitting, and an unsupervised self-organized determination of the number of clusters at each resolution. Our analysis revealed interesting correlated behavior of several groups of genes which has not been previously identified.

  13. Can Induced Orbital Paramagnetism Be Controlled by Strong Magnetic Fields?

    PubMed

    Pagola, G I; Ferraro, M B; Lazzeretti, P

    2009-11-10

    Magnetic hypersusceptibilities and hypershielding at the nuclei of BH, CH(+), C4H4, and C8H8 molecules in the presence of an external spatially uniform, time-independent magnetic field have been investigated accounting for cubic response contributions via Rayleigh-Schrödinger perturbation theory. Numerical estimates have been obtained at the coupled Hartree-Fock and density-functional levels of theory within the conventional common-origin approach, using extended gaugeless basis sets. The fundamental role of electron correlation effects was assessed. Critical values of the applied magnetic field at which transition from paramagnetic to diamagnetic behavior would occur were estimated. It is shown that perturbative methods may successfully be employed to estimate the interaction energy for big cyclic molecules. PMID:26609984

  14. Use of paramagnetic chelated metal derivatives of polysaccharides and spin-labeled polysaccharides as contrast agents in magnetic resonance imaging

    SciTech Connect

    Bligh, S.W.; Harding, C.T.; Sadler, P.J.; Bulman, R.A.; Bydder, G.M.; Pennock, J.M.; Kelly, J.D.; Latham, I.A.; Marriott, J.A. )

    1991-02-01

    Soluble and insoluble polysaccharides were derivatized with diethylenetriaminepentaacetic acid (DTPA) and/or spin-labeled with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). Polysaccharides derivatized with DTPA were prepared via cyanogen bromide activation, coupling to a diamine linker, and to DTPA anhydride. Spin-labeled polysaccharides were also prepared via cyanogen bromide activation. The extent of derivatization for dextran (18 kDa) was about 120 glucose units per DTPA, and for cellulose and starch about 15-30 units per DTPA. For spin-labeled polysaccharides, the average loading ranged from 1 nitroxide per 16 glucose units for starch to 181 for dextran (82 kDa). These derivatized paramagnetic polysaccharides were shown to be more effective relaxants than the small paramagnetic molecules alone. Both soluble and insoluble polysaccharide-linker-DTPA-Gd(3) complexes were effectively cleared from the body (rats) after oral administration. After intravenous administration, the biodistribution of dextran-linker-DTPA-Gd(3) complexes differed significantly from that of GdDTPA. Reduction of the nitroxide by ascorbic acid was retarded in the polysaccharide derivatives, particularly in starch derivatized with both nitroxide and linker-DTPA-Cu(2). These agents showed contrast enhancement in the gastrointestinal tract of rabbits.

  15. 13C-NMR study of labeled vinyl groups in paramagnetic myoglobin derivatives.

    PubMed

    Sankar, S S; La Mar, G N; Smith, K M; Fujinari, E M

    1987-04-01

    The 13C-NMR spectra of high-spin met-aquo myoglobin, spin-equilibrium met-azido myoglobin, low-spin met-cyano myoglobin, deoxy myoglobin and carbonmonoxy myoglobin from sperm whale reconstituted with hemin 13C enriched at both vinyl alpha or beta positions have been recorded. In all cases the labeled vinyl 13C signals are clearly resolved and useful spectra could be obtained within approx. 15 minutes. The decoupling of multiplet structure due to attached proton(s) has led to the specific assignment of vinyl 13C alpha signals in all paramagnetic derivatives and the 13C beta signals in met-cyano myoglobin. In all other cases, the collapse of the proton multiplet structure as a function of 1H decoupling frequency has located, but not assigned, the attached 1H resonance positions which are obscured by the intense diamagnetic envelope in the 1H-NMR spectrum. The resulting vinyl 13C hyperfine shifts follow Curie behavior, and the patterns closely resemble those in the appropriate model complexes in the same oxidation/spin/ligation state, except that the protein exhibits more in-plane asymmetry. The hyperfine shift patterns are indicative of dominant pi contact shifts for all ferric complexes. Deoxy myoglobin vinyl 13C and 1H contact shifts provide little evidence for pi bonding. PMID:3828362

  16. 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.

  17. Determination of S-nitrosothiols in biological and clinical samples using electron paramagnetic resonance spectrometry with spin trapping.

    PubMed

    Winyard, Paul G; Knight, Iona A; Shaw, Frances L; Rocks, Sophie A; Davies, Claire A; Eggleton, Paul; Haigh, Richard; Whiteman, Matthew; Benjamin, Nigel

    2008-01-01

    S-Nitroso moieties, such as the S-nitroso group within S-nitrosated albumin, constitute a potential endogenous reservoir of nitric oxide (NO.) in human tissues and other biological systems. Moreover, S-nitroso compounds are under investigation as therapeutic agents in humans. Therefore, it is important to be able to detect S-nitrosothiols (RSNOs) in human extracellular fluids, such as plasma and synovial fluid, as well as other biological samples. This chapter describes a method for the determination of S-nitrosothiols in biofluids. The method is based on electron paramagnetic resonance (EPR) spectrometry, in combination with spin trapping using a ferrous ion complex of the iron chelator N-methyl-d-glucamine dithiocarbamate under alkaline conditions. This iron complex mediates the decomposition of RSNO to NO., as well as spin trapping the generated NO.. The resulting spin adduct has a unique EPR signal that can be quantified. PMID:18554533

  18. 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

  19. 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

  20. 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

  1. Comment on {open_quotes}Paramagnetic Meissner effect in Nb{close_quotes}

    SciTech Connect

    Rice, T.M.; Sigrist, M.

    1997-06-01

    The observation of a small paramagnetic signal in a bulk s-wave superconductor Nb does not justify the conclusion drawn by Kosti{hacek c} {ital et al.} that our previous proposal interpreting the paramagnetism of ceramic high-T{sub c} cuprates as arising from the d-wave symmetry of the superconducting state is unlikely to be correct. Several experimental tests are proposed to distinguish between paramagnetism caused by flux compression and that associated with unconventional symmetry. {copyright} {ital 1997} {ital The American Physical Society}

  2. 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.

  3. Paramagnetic materials and practical algorithmic cooling for NMR quantum computing

    NASA Astrophysics Data System (ADS)

    Fernandez, Jose M.; Mor, Tal; Weinstein, Yossi

    2003-08-01

    Algorithmic cooling is a method devised by Boykin, Mor Rowchodhury, Vatan and Vrijen (PNAS Mar '02) for initializing NMR systems in general and NMR quantum computers in particular. The algorithm recursively employs two steps. The first is an adiabatic entropy compression of the computation qubits of the system. The second step is an isothermal heat transfer from the system to the environment through a set of reset qubits that reach thermal relaxation rapidly. To allow experimental algorithmic cooling, the thermalization time of the reset qubits must be much shorter than the thermalization time of the computation qubits. We investigated the effect of the paramagnetic material Chromium Acetylacetonate on the thermalization times of computation qubits (carbons) and reset qubit (hydrogen). We report here the accomplishment of an improved ratio of the thermalization times from T1(H)/T1(C) of approximately 5 to around 15. The magnetic ions from the Chromium Acetylacetonate interact with the reset qubit reducing their thermalization time, while their effect on the less exposed computation qubits is found to be weaker. An experimental demonstrating of non adiabatic cooling by thermalization and magnetic ion is currently performed by our group based on these results.

  4. Electron paramagnetic resonance of Er3+ ions in aluminum nitride

    NASA Astrophysics Data System (ADS)

    Yang, Shan; Evans, S. M.; Halliburton, L. E.; Slack, G. A.; Schujman, S. B.; Morgan, K. E.; Bondokov, R. T.; Mueller, S. G.

    2009-01-01

    An electron paramagnetic resonance (EPR) spectrum from Er3+ ions has been observed in a bulk single crystal of aluminum nitride (AlN). These Er3+ ions were introduced into the crystal during growth and had a concentration of approximately 2×1016 cm-3. The Er3+ EPR signal, monitored at 4.5 K, exhibits axial symmetry (the unique axis is parallel to the c axis in this wurtzite lattice) and shows well-resolved hyperfine splittings due to E167r nuclei. An absence of site splittings in the EPR angular dependence indicates that these erbium ions, replacing aluminum ions in the AlN crystal, have no nearby defects. Principal values for the g and hyperfine matrices are g∥=4.337, g⊥=7.647, |A∥|=454 MHz, and |A⊥|=796 MHz. Forbidden transitions, appearing in the low-field portion of the hyperfine spectrum when the magnetic field is rotated a few degrees away from the c axis, give |P|=7.8 MHz for the nuclear electric quadrupole parameter.

  5. Single Acquisition Quantitative Single Point Electron Paramagnetic Resonance Imaging

    PubMed Central

    Jang, Hyungseok; Subramanian, Sankaran; Devasahayam, Nallathamby; Saito, Keita; Matsumoto, Shingo; Krishna, Murali C; McMillan, Alan B

    2013-01-01

    Purpose Electron paramagnetic resonance imaging (EPRI) has emerged as a promising non-invasive technology to dynamically image tissue oxygenation. Due to its extremely short spin-spin relaxation times, EPRI benefits from a single-point imaging (SPI) scheme where the entire FID signal is captured using pure phase encoding. However, direct T2*/pO2 quantification is inhibited due to constant magnitude gradients which result in time-decreasing FOV. Therefore, conventional acquisition techniques require repeated imaging experiments with differing gradient amplitudes (typically 3), which results in long acquisition time. Methods In this study, gridding was evaluated as a method to reconstruct images with equal FOV to enable direct T2*/pO2 quantification within a single imaging experiment. Additionally, an enhanced reconstruction technique that shares high spatial k-space regions throughout different phase encoding time delays was investigated (k-space extrapolation). Results The combined application of gridding and k-space extrapolation enables pixelwise quantification of T2* from a single acquisition with improved image quality across a wide range of phase encoding delay times. The calculated T2*/pO2 does not vary across this time range. Conclusion By utilizing gridding and k-space extrapolation, accurate T2*/pO2 quantification can be achieved within a single dataset to allow enhanced temporal resolution (by a factor of 3). PMID:23913515

  6. The Contribution of Electron Paramagnetic Resonance to Melanoma Research

    PubMed Central

    Godechal, Quentin; Gallez, Bernard

    2011-01-01

    The incidence of malignant melanoma, the most dangerous form of skin cancer, is rising each year. However, some aspects of the tumor initiation and development are still unclear, and the current method of diagnosis, based on the visual aspect of the tumor, shows limitations. For these reasons, developments of new techniques are ongoing to improve basic knowledge on the disease and diagnosis of tumors in individual patients. This paper shows how electron paramagnetic resonance (EPR), a method able to detect free radicals trapped in melanin pigments, has recently brought its unique value to this specific field. The general principles of the method and the convenience of melanin as an endogenous substrate for EPR measurements are explained. Then, the way by which EPR has recently helped to assess the contribution of ultraviolet rays (UVA and UVB) to the initiation of melanoma is described. Finally, we describe the improvements of EPR spectrometry and imaging in the detection and mapping of melanin pigments inside ex vivo and in vivo melanomas. We discuss how these advances might improve the diagnosis of this skin cancer and point out the present capabilities and limitations of the method. PMID:21941659

  7. 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

  8. 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.

  9. 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. PMID:14511592

  10. 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

  11. Aspects of Quantum Computing with Polar Paramagnetic Molecules

    NASA Astrophysics Data System (ADS)

    Karra, Mallikarjun; Friedrich, Bretislav

    2015-05-01

    Since the original proposal by DeMille, arrays of optically trapped ultracold polar molecules have been considered among the most promising prototype platforms for the implementation of a quantum computer. The qubit of a molecular array is realized by a single dipolar molecule entangled via its dipole-dipole interaction with the rest of the array's molecules. A superimposed inhomogeneous electric field precludes the quenching of the body-fixed dipole moments by rotation and a time dependent external field controls the qubits to perform gate operations. Much like our previous work in which we considered the simplest cases of a polar 1 Σ and a symmetric top molecule, here we consider a X2Π3 / 2 polar molecule (exemplified by the OH radical) which, by virtue of its nonzero electronic spin and orbital angular momenta, is, in addition, paramagnetic. We demonstrate entanglement tuning by evaluating the concurrence (and the requisite frequencies needed for gate operations) between two such molecules in the presence of varying electric and magnetic fields. Finally, we discuss the conditions required for achieving qubit addressability (transition frequency difference, Δω , as compared with the concomitant Stark and Zeeman broadening) and high fidelity. International Max Planck Research School - Functional Interfaces in Physics and Chemistry.

  12. Detection of electron paramagnetic resonance absorption using frequency modulation

    NASA Astrophysics Data System (ADS)

    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 57 μT (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.

  13. Superparamagnetic And Paramagnetic MRI Contrast Agents: Application Of Rapid Magnetic Resonance Imaging To Assess Renal Function

    NASA Astrophysics Data System (ADS)

    Carvlin, Mark J.; Renshaw, Perry F.; Arger, Peter; Kundel, Harold L.; Dougherty, Larry; Axel, Leon; Kassab, Eleanor; Moore, Bethanne

    1988-06-01

    The paramagnetic chelate complex, gadolinium-diethylene-triamine-pentaacetic acid, Gd-DTPA, and superparamagnetic particles, such as those composed of dextran coated magnetite, function as magnetic resonance contrast agents by changing the relaxation rates, 1/T1 and 1/T2. The effects that these agents have upon MR signal intensity are determined by: the inherent biophysical properties of the tissue being imaged, the concentration of the contrast agent and the data acquisition scheme (pulse sequence parameters) employed. Following the time course of MR signal change in the first minutes after the injection of contrast agent(s) allows a dynamic assessment of organ functions in a manner analogous to certain nuclear medicine studies. In order to study renal function, sequential MR fast scan images, gradient echo (TR=35/TE=7 msec, flip angle=25 degrees), were acquired, one every 12 seconds, after intravenous injection of Gd-DTPA and/or dextran-magnetite. Gd-DTPA, which is freely filtered at the glomerulus and is neither secreted nor reabsorbed, provides information concerning renal perfusion, glomerular filtration and tubular concentrating ability. Dextran-magnetite (200 A diameter), which is primarily contained within the intravascular space shortly after injection, provides information on blood flow to and distribution within the kidney. The MR signal change observed after administration of contrast agents varied dramatically depending upon the agents injected and the imaging parameters used. Hence a broad range of physiolgic processes may be described using these techniques, i.e. contrast agent enhanced functional MR examinations.

  14. 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. PMID:20060775

  15. Scalar Relativistic Computations and Localized Orbital Analyses of Nuclear Hyperfine Coupling and Paramagnetic NMR Chemical Shifts

    SciTech Connect

    Aquino, Fredy W.; Pritchard, Ben; Autschbach, Jochen

    2012-02-14

    A method is reported by which calculated hyperfine coupling constants (HFCCs) and paramagnetic NMR (pNMR) chemical shifts can be analyzed in a chemically intuitive way by decomposition into contributions from localized molecular orbitals (LMOs). A new module for density functional calculations with nonhybrid functionals, global hybrids, and range-separated hybrids, utilizing the two-component relativistic zeroth-order regular approximation (ZORA), has been implemented in the parallel open-source NWChem quantum chemistry package. Benchmark results are reported for a test set of few-atom molecules with light and heavy elements. Finite nucleus effects on ¹⁹⁹Hg HFCCs are shown to be on the order of -11 to -15%. A proof of concept for the LMO analysis is provided for the metal and fluorine HFCCs of TiF₃ and NpF₆. Calculated pNMR chemical shifts are reported for the 2-methylphenyl-t-butylnitroxide radical and for five cyclopentadienyl (Cp) sandwich complexes with 3d metals. Nickelocene and vanadocene carbon pNMR shifts are analyzed in detail, demonstrating that the large carbon pNMR shifts calculated as +1540 for Ni (exptl.: +1514) and -443 for V (exptl.: -510) are caused by different spin-polarization mechanisms. For Ni, Cp to Ni π back-donation dominates the result, whereas for vanadocene, V to Cp σ donation with relaxation of the carbon 1s shells can be identified as the dominant mechanism.

  16. 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.

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

    PubMed

    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. PMID:25563439

  18. 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.

  19. Reduction of artifact of metallic implant in magnetic resonance imaging by combining paramagnetic and diamagnetic materials

    NASA Astrophysics Data System (ADS)

    Gao, Yanhui; Muramatsu, Kazuhiro; Kushibe, Atsumichi; Yamazaki, Keita; Chiba, Akihiko; Yamamoto, Toru

    2010-05-01

    The method of coating the metallic implant made of paramagnetic materials with diamagnetic materials has been proposed to reduce the magnetic disturbance of metallic implants which causes artifact in magnetic resonance imaging. The optimal thicknesses of the diamagnetic coatings have been obtained for a straight cylindrical hip joint and an aneurysm clip by using the magnetic field analysis of the finite element method (FEM). Whereas in the manufacturing, with respect to the mechanical force of the diamagnetic material, etc., the new structure of dual-material model with diamagnetic material inside and paramagnetic material outside is considered better. In this paper, first the effectiveness of the structure of the dual-material model with actual diamagnetic material inside and paramagnetic material outside is investigated by using the FEM. Then optimal thicknesses of paramagnetic coating of two models are obtained. Finally the effectiveness of the dual-material model is verified by the experiment.

  20. 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.

  1. Flux line lattice form factor and paramagnetic effects in type II superconductors

    NASA Astrophysics Data System (ADS)

    Ichioka, Masanori; Machida, Kazushige

    2009-03-01

    Based on the quasiclassical Eilenberger theory, we investigate the vortex structure in type II superconductors with strong Pauli-paramagnetic contributions due to the Zeeman effect. We quantitatively study how the paramagnetic effect suppresses the superconductivity, and evaluate the flux line lattice (FLL) form factor from the calculated internal field distribution both in the s-wave and d-wave pairings. When the paramagnetic effects are strong, the intensity of the FLL form factor increases toward Hc2 as a function of an applied field, instead of exponential decay. This anomalous field dependence is due to the induced paramagnetic moments around the vortex core. We discuss the anomalous field-dependence of the FLL form factor observed by the small angle neutron scattering in CeCoIn5.

  2. 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:...

  3. Model-free nuclear magnetic resonance study of intermolecular free energy landscapes in liquids with paramagnetic Ln3+ spotlights: Theory and application to Arg-Gly-Asp

    NASA Astrophysics Data System (ADS)

    Fries, Pascal H.

    2012-01-01

    We propose an easily applicable method for investigating the pair distribution function of a lanthanide Ln3+ complex LnL (L = ligand) with respect to any solvent or solute molecule A carrying observable nuclear spins. Let r be the distance of Ln3+ to the observed nuclear spin I. We derive a simple expression of the experimental value of the configurational average of 1/r6 in terms of longitudinal paramagnetic relaxation (rate) enhancements (PREs) of the spin I measured on a standard high-resolution NMR spectrometer and due to well-chosen concentrations of LnL complexes in which Ln3+ is a fast-relaxing paramagnetic lanthanide or the slowly-relaxing gadolinium Gd3+. The derivation is justified in the general case of a molecule A which is by turns in a bound state where it follows the complex and a free state where it moves independently. It rests on the expression of the underlying PRE theory in terms of the angle-dependent pair distribution function of LnL and A. The simplifications of this theory in the high-field regime and under the condition of fast exchange between bound and free states are carefully discussed. We also show that original information on the angle dependence of the molecular pair distribution function can be gained from the measured paramagnetic dipolar shifts induced by complexed fast-relaxing Ln3+ ions. The method is illustrated by the case study of the anionic Lnttha3- = [Ln3+(ttha)]3- (ttha6- = triethylene tetraamine hexacetate) complex interacting with the biologically important tripeptide Arg-Gly-Asp (RGD) which carries peripheral ionic groups. The usefulness of an auxiliary reference outer sphere probe solute is emphasized.

  4. Model-free nuclear magnetic resonance study of intermolecular free energy landscapes in liquids with paramagnetic Ln3+ spotlights: theory and application to Arg-Gly-Asp.

    PubMed

    Fries, Pascal H

    2012-01-28

    We propose an easily applicable method for investigating the pair distribution function of a lanthanide Ln(3+) complex LnL (L = ligand) with respect to any solvent or solute molecule A carrying observable nuclear spins. Let r be the distance of Ln(3+) to the observed nuclear spin I. We derive a simple expression of the experimental value of the configurational average of 1/r(6) in terms of longitudinal paramagnetic relaxation (rate) enhancements (PREs) of the spin I measured on a standard high-resolution NMR spectrometer and due to well-chosen concentrations of LnL complexes in which Ln(3+) is a fast-relaxing paramagnetic lanthanide or the slowly-relaxing gadolinium Gd(3+). The derivation is justified in the general case of a molecule A which is by turns in a bound state where it follows the complex and a free state where it moves independently. It rests on the expression of the underlying PRE theory in terms of the angle-dependent pair distribution function of LnL and A. The simplifications of this theory in the high-field regime and under the condition of fast exchange between bound and free states are carefully discussed. We also show that original information on the angle dependence of the molecular pair distribution function can be gained from the measured paramagnetic dipolar shifts induced by complexed fast-relaxing Ln(3+) ions. The method is illustrated by the case study of the anionic Lnttha(3-) = [Ln(3+)(ttha)](3-) (ttha(6-) = triethylene tetraamine hexacetate) complex interacting with the biologically important tripeptide Arg-Gly-Asp (RGD) which carries peripheral ionic groups. The usefulness of an auxiliary reference outer sphere probe solute is emphasized. PMID:22299888

  5. 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. PMID:23955558

  6. Me{sup 5}C{sup 5}Ni(acac): A monomeric, paramagnetic, 18-electron, spin-equilibrium molecule

    SciTech Connect

    Smith, M.E.; Anderson, R.A. |

    1996-11-13

    New synthetic procedures have been developed for Me{sup 5}C{sup 5}M(acac), M = Co or Ni. The crystal structures of these 17- or 18-electron monomers show that the compounds are isomorphous and in space group P1{bar O}, with the planes defined by the Me{sup 5}C{sup 5} ring and the M(acac) fragment perpendicular to within 5{degree}. The Me{sup 5}C{sup 5} ring in both molecules has an ene-allyl distortion which is rationalized by the low molecular symmetry (C{sup s}), which removes the degeneracy in the e{sup +} and e{sup -} ring orbitals. The electronic structure of the cobalt compound is {sup 2}A, as deduced from magnetic susceptibility and EPR spectroscopy. The electronic structure of the nickel compound depends upon the temperature. In the solid state, the compound is diamagnetic below 150 K, but it becomes paramagnetic with increasing temperature. The {sup 1}H NMR chemical shift of the compound in solution are nonlinear in temperature, and a plot of {delta} vs T{sup -1} yields an equilibrium constant of 0.47 at 303 K for the low spin high spin equilibrium. The 20-electron phosphine complexes of nickel can be isolated; Me{sup 5}C{sup 5}Ni(acac)(PMe{sup 3}) is a simple paramagnet with two unpaired spins, but the PEt{sup 3} complex exists in equilibrium with its base-free compound in solution. The cobalt compound does not give an isolable phosphine complex. A simple symmetry orbital model is proposed that accounts for the electronic and molecular structures of these organometallic compounds. 34 refs., 7 figs., 5 tabs.

  7. Small-angle neutron scattering of nanocrystalline terbium with random paramagnetic susceptibility.

    PubMed

    Balaji, G; Ghosh, S; Döbrich, F; Eckerlebe, H; Weissmüller, J

    2008-06-01

    We report magnetic small-angle neutron scattering (SANS) data for the nanocrystalline rare earth metal Terbium in its paramagnetic state. Whereas critical scattering dominates at large momentum transfer, q, the (magnetic-) field response of the scattering at small q arises from the spatial nonuniformity of the paramagnetic susceptibility tensor. The finding of an interrelation between SANS and the susceptibility suggests a way for characterizing the nonuniform magnetic interactions in hard magnets by neutron scattering. PMID:18643454

  8. Observation of Paramagnetic Supercurrent in Mesoscopic Superconducting Rings and Disks Using Multiple-Small Method

    NASA Astrophysics Data System (ADS)

    Kanda, A.; Baelus, B. J.; Peeters, F. M.; Kadowaki, K.; Ootuka, Y.

    2005-08-01

    Responses of mesoscopic superconducting rings and disks to perpendicular magnetic fields are studied by using the multiple-small-tunnel-junction method, in which transport properties of several small tunnel junctions attached to the sample are measured simultaneously. This allows us for a direct experimental observation of the paramagnetic supercurrent, which is closely related to the paramagnetic Meissner effect. The results are compared with numerical results based on the nonlinear Ginzburg-Landau theory.

  9. Paramagnetic Meissner Effect in Josephson-Coupled Network of Ybco Ceramics

    NASA Astrophysics Data System (ADS)

    Deguchi, Hiroyuki; Yasunaka, Miyoko; Takagi, Seishi; Koyama, Kuniyuki; Mizuno, Kiyoshi

    2003-03-01

    Magnetic properties of a typical weak-link system, ceramic YBa2Cu3O7-δ, have been investigated in order to clarify the inter-grain superconducting ordering. Paramagnetic Meissner behavior is observed in the field-cooled magnetization of the ceramics below the inter-grain transition temperature. The result suggests that the paramagnetic Meissner effect is one of the inter-grain properties and is due to the spontaneous orbital currents in a Josephson network with π-junctions.

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

    NASA Astrophysics Data System (ADS)

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

    2002-10-01

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