Free radical generation induced by ultrasound in red wine and model wine: An EPR spin-trapping study.

PubMed

Zhang, Qing-An; Shen, Yuan; Fan, Xue-Hui; Martín, Juan Francisco García; Wang, Xi; Song, Yun

2015-11-01

Direct evidence for the formation of 1-hydroxylethyl radicals by ultrasound in red wine and air-saturated model wine is presented in this paper. Free radicals are thought to be the key intermediates in the ultrasound processing of wine, but their nature has not been established yet. Electron paramagnetic resonance (EPR) spin trapping with 5,5-dimethyl-l-pyrrolin N-oxide (DMPO) was used for the detection of hydroxyl free radicals and 1-hydroxylethyl free radicals. Spin adducts of hydroxyl free radicals were detected in DMPO aqueous solution after sonication while 1-hydroxylethyl free radical adducts were observed in ultrasound-processed red wine and model wine. The latter radical arose from ethanol oxidation via the hydroxyl radical generated by ultrasound in water, thus providing the first direct evidence of the formation of 1-hydroxylethyl free radical in red wine exposed to ultrasound. Finally, the effects of ultrasound frequency, ultrasound power, temperature and ultrasound exposure time were assessed on the intensity of 1-hydroxylethyl radical spin adducts in model wine. Copyright © 2015 Elsevier B.V. All rights reserved.

Antioxidant activity of Sempervivum tectorum and its components.

PubMed

Sentjurc, Marjeta; Nemec, Marjana; Connor, Henry D; Abram, Veronika

2003-04-23

The antioxidant properties of components of leaf extracts of the evergreen plant, Sempervivum tectorum (ST), have been evaluated using UV irradiated liposomal systems containing the spin trap 5-(diethoxyphosphoryl)-5-methyl-pyrroline-N-oxide. Decreases in free radical activity in the liposomal systems as measured by electron paramagnetic resonance (EPR) spectroscopy demonstrate that the lipophilic ST juice components, kaempferol (KA) and kaempferol-3-glucoside (KG) contribute significantly to the antioxidant properties of the juice. EPR spectral simulation established the presence of oxygen and carbon centered free radical adducts. The mixtures with low pH, citric and malic acid, and ST juice reveal increased EPR signals from oxygen centered radicals in comparison to the control, pointing to the important role of pH in oxygen radical formation. Parallel assays that measured thiobarbituric acid related substances confirm the antioxidant effects of KA and KG and explain the results of spin trapping experiments complicated by low pH's.

Highly reactive free radicals in electronic cigarette aerosols.

PubMed

Goel, Reema; Durand, Erwann; Trushin, Neil; Prokopczyk, Bogdan; Foulds, Jonathan; Elias, Ryan J; Richie, John P

2015-09-21

Electronic cigarette (EC) usage has increased exponentially, but limited data are available on its potential harmful effects. We tested for the presence of reactive, short-lived free radicals in EC aerosols by electron paramagnetic resonance spectroscopy (EPR) using the spin-trap phenyl-N-tert-butylnitrone (PBN). Radicals were detected in aerosols from all ECs and eliquids tested (2.5 × 10(13) to 10.3 × 10(13) radicals per puff at 3.3 V) and from eliquid solvents propylene glycol and glycerol and from "dry puffing". These results demonstrate, for the first time, the production of highly oxidizing free radicals from ECs which may present a potential toxicological risk to EC users.

Electron Spin Resonance (ESR) Studies of Returned Comet Nucleus Samples

NASA Technical Reports Server (NTRS)

Tsay, Fun-Dow; Kim, Soon Sam; Liang, Ranty H.

1997-01-01

Electron Spin Resonance (ESR) studies have been carried out on organic and inorganic free radicals generated by gamma-ray and/or UV-irradiation and trapped in ice matrices. It is suggested that the concentration of these free radicals together with their thermal stability can be used as an accurate built-in geothermometer and radiation probe for returned comet nucleus sample studies. ESR studies have also been carried out on paramagnetic (Mn(2+), Ti(3+), and Fe(3+)) and ferromagnetic (ferric oxide and metallic iron) centers known to be present in terrestrial and extraterrestrial samples. The presence or absence of these magnetic centers coupled with their characteristic ESR lineshape can be used to investigate the shock effects, quenching/cooling rate and oxidation-reduction conditions in the formation and subsequent evolution of returned comet nucleus samples.

Toward the fourth dimension of membrane protein structure: insight into dynamics from spin-labeling EPR spectroscopy.

PubMed

McHaourab, Hassane S; Steed, P Ryan; Kazmier, Kelli

2011-11-09

Trapping membrane proteins in the confines of a crystal lattice obscures dynamic modes essential for interconversion between multiple conformations in the functional cycle. Moreover, lattice forces could conspire with detergent solubilization to stabilize a minor conformer in an ensemble thus confounding mechanistic interpretation. Spin labeling in conjunction with electron paramagnetic resonance (EPR) spectroscopy offers an exquisite window into membrane protein dynamics in the native-like environment of a lipid bilayer. Systematic application of spin labeling and EPR identifies sequence-specific secondary structures, defines their topology and their packing in the tertiary fold. Long range distance measurements (60 Å-80 Å) between pairs of spin labels enable quantitative analysis of equilibrium dynamics and triggered conformational changes. This review highlights the contribution of spin labeling to bridging structure and mechanism. Efforts to develop methods for determining structures from EPR restraints and to increase sensitivity and throughput promise to expand spin labeling applications in membrane protein structural biology. Copyright © 2011 Elsevier Ltd. All rights reserved.

Feasibility of reading LiF thermoluminescent dosimeters by electron spin resonance

NASA Astrophysics Data System (ADS)

Breen, S. L.; Battista, J. J.

1999-08-01

Lithium fluoride is a commonly used solid state dosimeter. During irradiation, electrons and holes become trapped in crystal imperfections; thermoluminescence dosimetry measures their thermally induced recombination. Electron paramagnetic resonance (EPR) spectroscopy can be used to measure the resonant absorption of microwaves by the unpaired electrons trapped in LiF. In an effort to extend the use of LiF dosimeters to smaller sizes and to the harsh environments encountered in internal dosimetry, EPR was evaluated as an alternative technique to read the radiation dose delivered to TLD-100 dosimeters. TLD-100 rods were irradiated with a 60Co source to doses of 10 Gy to 100 Gy. A radiation-induced signal (with a g-value of 2.002) could be detected only at liquid nitrogen temperatures at doses above 20 Gy. The EPR spectrum of irradiated LiF contains three components, one of which correlates positively with dose. However, the low sensitivity of the technique, and difficulty in interpreting the EPR spectrum from polycrystalline dosimeters, preclude its use as a dosimetry technique.

Feasibility of reading LiF thermoluminescent dosimeters by electron spin resonance.

PubMed

Breen, S L; Battista, J J

1999-08-01

Lithium fluoride is a commonly used solid state dosimeter. During irradiation, electrons and holes become trapped in crystal imperfections; thermoluminescence dosimetry measures their thermally induced recombination. Electron paramagnetic resonance (EPR) spectroscopy can be used to measure the resonant absorption of microwaves by the unpaired electrons trapped in LiF. In an effort to extend the use of LiF dosimeters to smaller sizes and to the harsh environments encountered in internal dosimetry, EPR was evaluated as an alternative technique to read the radiation dose delivered to TLD-100 dosimeters. TLD-100 rods were irradiated with a 60Co source to doses of 10 Gy to 100 Gy. A radiation-induced signal (with a g-value of 2.002) could be detected only at liquid nitrogen temperatures at doses above 20 Gy. The EPR spectrum of irradiated LiF contains three components, one of which correlates positively with dose. However, the low sensitivity of the technique, and difficulty in interpreting the EPR spectrum from polycrystalline dosimeters, preclude its use as a dosimetry technique.

Saturation recovery EPR spin-labeling method for quantification of lipids in biological membrane domains.

PubMed

Mainali, Laxman; Camenisch, Theodore G; Hyde, James S; Subczynski, Witold K

2017-12-01

The presence of integral membrane proteins induces the formation of distinct domains in the lipid bilayer portion of biological membranes. Qualitative application of both continuous wave (CW) and saturation recovery (SR) electron paramagnetic resonance (EPR) spin-labeling methods allowed discrimination of the bulk, boundary, and trapped lipid domains. A recently developed method, which is based on the CW EPR spectra of phospholipid (PL) and cholesterol (Chol) analog spin labels, allows evaluation of the relative amount of PLs (% of total PLs) in the boundary plus trapped lipid domain and the relative amount of Chol (% of total Chol) in the trapped lipid domain [ M. Raguz, L. Mainali, W. J. O'Brien, and W. K. Subczynski (2015), Exp. Eye Res., 140:179-186 ]. Here, a new method is presented that, based on SR EPR spin-labeling, allows quantitative evaluation of the relative amounts of PLs and Chol in the trapped lipid domain of intact membranes. This new method complements the existing one, allowing acquisition of more detailed information about the distribution of lipids between domains in intact membranes. The methodological transition of the SR EPR spin-labeling approach from qualitative to quantitative is demonstrated. The abilities of this method are illustrated for intact cortical and nuclear fiber cell plasma membranes from porcine eye lenses. Statistical analysis (Student's t -test) of the data allowed determination of the separations of mean values above which differences can be treated as statistically significant ( P ≤ 0.05) and can be attributed to sources other than preparation/technique.

Comparison of scavenging capacities of vegetables by ORAC and EPR.

PubMed

Kameya, Hiromi; Watanabe, Jun; Takano-Ishikawa, Yuko; Todoriki, Setsuko

2014-02-15

Reactive oxygen species (ROS) are considered to be causative agents of many health problems. In spite of this, the radical-specific scavenging capacities of food samples have not been well studied. In the present work, we have developed an electron paramagnetic resonance (EPR) spin trapping method for analysis of the scavenging capacities of food samples for multiple ROS, utilising the same photolysis procedure for generating each type of radical. The optimal conditions for effective evaluation of hydroxyl, superoxide, and alkoxyl radical scavenging capacity were determined. Quantification of radical adducts was found to be highly reproducible, with variations of less than 4%. The optimised EPR spin trapping method was used to analyse the scavenging capacities of 54 different vegetable extracts for multiple radicals, and the results were compared with oxygen radical absorption capacity values. Good correlations between the two methods were observed for superoxide and alkoxyl radicals, but not for hydroxyl. Copyright © 2013 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gorai, Prashun; Toberer, Eric S.; Stevanović, Vladan

Here, at room temperature and above, most magnetic materials adopt a spin-disordered (paramagnetic) state whose electronic properties can differ significantly from their low-temperature, spin-ordered counterparts. Yet computational searches for new functional materials usually assume some type of magnetic order. In the present work, we demonstrate a methodology to incorporate spin disorder in computational searches and predict the electronic properties of the paramagnetic phase. We implement this method in a high-throughput framework to assess the potential for thermoelectric performance of 1350 transition-metal sulfides and find that all magnetic systems we identify as promising in the spin-ordered ground state cease to bemore » promising in the paramagnetic phase due to disorder-induced deterioration of the charge carrier transport properties. We also identify promising non-magnetic candidates that do not suffer from these spin disorder effects. In addition to identifying promising materials, our results offer insights into the apparent scarcity of magnetic systems among known thermoelectrics and highlight the importance of including spin disorder in computational searches.« less

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

PubMed

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

2014-05-01

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

Electron Spin Polarization Transfer to ortho-H2 by Interaction of para-H2 with Paramagnetic Species: A Key to a Novel para → ortho Conversion Mechanism.

PubMed

Terenzi, Camilla; Bouguet-Bonnet, Sabine; Canet, Daniel

2015-05-07

We report that at ambient temperature and with 100% enriched para-hydrogen (p-H2) dissolved in organic solvents, paramagnetic spin catalysis of para → ortho hydrogen conversion is accompanied at the onset by a negative ortho-hydrogen (o-H2) proton NMR signal. This novel finding indicates an electron spin polarization transfer, and we show here that this can only occur if the H2 molecule is dissociated upon its transient adsorption by the paramagnetic catalyst. Following desorption, o-H2 is created until the thermodynamic equilibrium is reached. A simple theory confirms that in the presence of a static magnetic field, the hyperfine coupling between unpaired electrons and nuclear spins is responsible for the observed polarization transfer. Owing to the negative electron gyromagnetic ratio, this explains the experimental results and ascertains an as yet unexplored mechanism for para → ortho conversion. Finally, we show that the recovery of o-H2 magnetization toward equilibrium can be simply modeled, leading to the para → ortho conversion rate.

General magnetic transition dipole moments for electron paramagnetic resonance.

PubMed

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

2015-01-09

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.

Thermoelectricity in transition metal compounds: The role of spin disorder

DOE PAGES

Gorai, Prashun; Toberer, Eric S.; Stevanović, Vladan

2016-11-01

Here, at room temperature and above, most magnetic materials adopt a spin-disordered (paramagnetic) state whose electronic properties can differ significantly from their low-temperature, spin-ordered counterparts. Yet computational searches for new functional materials usually assume some type of magnetic order. In the present work, we demonstrate a methodology to incorporate spin disorder in computational searches and predict the electronic properties of the paramagnetic phase. We implement this method in a high-throughput framework to assess the potential for thermoelectric performance of 1350 transition-metal sulfides and find that all magnetic systems we identify as promising in the spin-ordered ground state cease to bemore » promising in the paramagnetic phase due to disorder-induced deterioration of the charge carrier transport properties. We also identify promising non-magnetic candidates that do not suffer from these spin disorder effects. In addition to identifying promising materials, our results offer insights into the apparent scarcity of magnetic systems among known thermoelectrics and highlight the importance of including spin disorder in computational searches.« less

Reactivity of superoxide radical anion and hydroperoxyl radical with alpha-phenyl-N-tert-butylnitrone (PBN) derivatives.

PubMed

Durand, Grégory; Choteau, Fanny; Pucci, Bernard; Villamena, Frederick A

2008-12-04

Nitrones have exhibited pharmacological activity against radical-mediated pathophysiological conditions and as analytical reagents for the identification of transient radical species by electron paramagnetic resonance (EPR) spectroscopy. In this work, competitive spin trapping, stopped-flow kinetics, and density functional theory (DFT) were employed to assess and predict the reactivity of O(2)(*-) and HO(2)(*) with various para-substituted alpha-phenyl-N-tert-butylnitrone (PBN) spin traps. Rate constants of O(2)(*-) trapping by nitrones were determined using competitive UV-vis stopped-flow method with phenol red (PR) as probe, while HO(2)(*) trapping rate constants were calculated using competition kinetics with 5,5-dimethylpyrroline N-oxide (DMPO) by employing EPR spectroscopy. The effects of the para substitution on the charge density of the nitronyl-carbon and on the free energies of nitrone reactivity with O(2)(*-) and HO(2)(*) were computationally rationalized at the PCM/B3LYP/6-31+G(d,p)//B3LYP/6-31G(d) level of theory. Theoretical and experimental data show that the rate of O(2)(*-) addition to PBN derivatives is not affected by the polar effect of the substituents. However, the reactivity of HO(2)(*) follows the Hammett equation and is increased as the substituent becomes more electron withdrawing. This supports the conclusion that the nature of HO(2)(*) addition to PBN derivatives is electrophilic, while the addition of O(2)(*-) to PBN-type compounds is only weakly electrophilic.

Electron spin resonance from NV centers in diamonds levitating in an ion trap

NASA Astrophysics Data System (ADS)

Delord, T.; Nicolas, L.; Schwab, L.; Hétet, G.

2017-03-01

We report observations of the electron spin resonance (ESR) of nitrogen vacancy centers in diamonds that are levitating in an ion trap. Using a needle Paul trap operating under ambient conditions, we demonstrate efficient microwave driving of the electronic spin and show that the spin properties of deposited diamond particles measured by the ESR are retained in the Paul trap. We also exploit the ESR signal to show angle stability of single trapped mono-crystals, a necessary step towards spin-controlled levitating macroscopic objects.

Magnetic-field-induced effects in the electronic structure of itinerant d- and f-metal systems

NASA Astrophysics Data System (ADS)

Grechnev, G. E.

2009-08-01

A paramagnetic response of transition metals and itinerant d- and f-metal compounds in an external magnetic field is studied by employing ab initio full-potential LMTO method in the framework of the local spin density approximation. Within this method the anisotropy of the magnetic susceptibility in hexagonal close-packed transition metals is evaluated for the first time. This anisotropy is owing to the orbital Van Vleck-like paramagnetic susceptibility, which is revealed to be substantial in transition-metal systems due to hybridization effects in the electronic structure. It is demonstrated that compounds TiCo, Ni3Al, YCo2, CeCo2, YNi5, LaNi5, and CeNi5 are strong paramagnets close to the quantum critical point. For these systems the Stoner approximation underestimates the spin susceptibility, whereas the calculated field-induced spin moments provide a good description of the large paramagnetic susceptibilities and magnetovolume effects. It is revealed that an itinerant description of hybridized f electrons produces magnetic properties of the compounds CeCo2, CeNi5, UAl3, UGa3, USi3, and UGe3 in close agreement with experiment. In the uranium compounds UX3 the strong spin-orbit coupling together with hybridization effects give rise to peculiar magnetic states in which the field-induced spin moments are antiparallel to the external field, and the magnetic response is dominated by the orbital contribution.

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.

Free radical generation by non-equilibrium atmospheric pressure plasma in alcohol-water mixtures: an EPR-spin trapping study

NASA Astrophysics Data System (ADS)

Uchiyama, Hidefumi; Ishikawa, Kenji; Zhao, Qing-Li; Andocs, Gabor; Nojima, Nobuyuki; Takeda, Keigo; Krishna, Murali C.; Ishijima, Tatsuo; Matsuya, Yuji; Hori, Masaru; Noguchi, Kyo; Kondo, Takashi

2018-03-01

Free radical species in aqueous solution—various alcohol-water reaction mixtures—by exposure to non-equilibrium cold atmospheric pressure Ar plasma (CAP), were monitored using electron paramagnetic resonance spin-trapping techniques with 3, 5-dibromo-4-nitrosobenzene sulfonate as a water soluble nitroso spin trap. The major radical species were formed by H-abstraction from alcohol molecules due to ·OH radicals. In the ethanol-water mixture ·CH2CH2OH produced by H abstraction from CH3 group of the ethanol and ·CH3 radicals were detected. The latter was due to the decomposition of unstable CH3·CHOH to form the ·CH3 radicals and the stable formaldehyde by C-C bond fission. These intermediates are similar to those observed by reaction with ·OH radicals generation in the H2O2-UV photolysis of the reaction mixtures. The evidence of ·CH3 radical formation in the pyrolytic decomposition of the reaction mixtures by exposure to ultrasound or in methane irradiated with microwave plasma have been reported previously. However, the pyrolytic ·CH3 radicals were not found in both plasma and H2O2-UV photolysis condition. These results suggests that free radicals produced by Ar-CAP are most likely due to the reaction between abundant ·OH radicals and alcohol molecules.

Oxygen radical absorbance capacity (ORAC) of cyclodextrin-solubilized flavonoids, resveratrol and astaxanthin as measured with the ORAC-EPR method

PubMed Central

Sueishi, Yoshimi; Ishikawa, Misa; Yoshioka, Daisuke; Endoh, Nobuyuki; Oowada, Shigeru; Shimmei, Masashi; Fujii, Hirotada; Kotake, Yashige

2012-01-01

Recently, we proposed an oxygen radical absorbance capacity method that directly quantifies the antioxidant’s scavenging capacity against free radicals and evaluated the radical scavenging abilities for water soluble antioxidant compounds. In this study, we determined the radical scavenging abilities of lipophilic antioxidants which were solubilized by cyclodextrin in water. Commonly employed fluorescence-based method measures the antioxidant’s protection capability for the fluorescent probe, while we directly quantify free-radical level using electron paramagnetic resonance spin trapping technique. In addition, the spin trapping-based method adopted controlled UV-photolysis of azo-initiator for free radical generation, but in fluorescence-based method, thermal decomposition of azo-initiator was utilized. We determined the radical scavenging abilities of seven well-known lipophilic antioxidants (five flavonoids, resveratrol and astaxanthin), using methylated β-cyclodextrin as a solubilizer. The results indicated that the agreement between spin trapping-based and fluorescence-based values was only fair partly because of a large variation in the previous fluorescence-based data. Typical radical scavenging abilities in trolox equivalent unit are: catechin 0.96; epicatechin 0.94; epigallocatechin gallate 1.3; kaempferol 0.37; myricetin 3.2; resveratrol 0.64; and astaxanthin 0.28, indicating that myricetin possesses the highest antioxidant capacity among the compounds tested. We sorted out the possible causes of the deviation between the two methods. PMID:22448093

Oxygen radical absorbance capacity (ORAC) of cyclodextrin-solubilized flavonoids, resveratrol and astaxanthin as measured with the ORAC-EPR method.

PubMed

Sueishi, Yoshimi; Ishikawa, Misa; Yoshioka, Daisuke; Endoh, Nobuyuki; Oowada, Shigeru; Shimmei, Masashi; Fujii, Hirotada; Kotake, Yashige

2012-03-01

Recently, we proposed an oxygen radical absorbance capacity method that directly quantifies the antioxidant's scavenging capacity against free radicals and evaluated the radical scavenging abilities for water soluble antioxidant compounds. In this study, we determined the radical scavenging abilities of lipophilic antioxidants which were solubilized by cyclodextrin in water. Commonly employed fluorescence-based method measures the antioxidant's protection capability for the fluorescent probe, while we directly quantify free-radical level using electron paramagnetic resonance spin trapping technique. In addition, the spin trapping-based method adopted controlled UV-photolysis of azo-initiator for free radical generation, but in fluorescence-based method, thermal decomposition of azo-initiator was utilized. We determined the radical scavenging abilities of seven well-known lipophilic antioxidants (five flavonoids, resveratrol and astaxanthin), using methylated β-cyclodextrin as a solubilizer. The results indicated that the agreement between spin trapping-based and fluorescence-based values was only fair partly because of a large variation in the previous fluorescence-based data. Typical radical scavenging abilities in trolox equivalent unit are: catechin 0.96; epicatechin 0.94; epigallocatechin gallate 1.3; kaempferol 0.37; myricetin 3.2; resveratrol 0.64; and astaxanthin 0.28, indicating that myricetin possesses the highest antioxidant capacity among the compounds tested. We sorted out the possible causes of the deviation between the two methods.

Electrical detection of electron-spin-echo envelope modulations in thin-film silicon solar cells

NASA Astrophysics Data System (ADS)

Fehr, M.; Behrends, J.; Haas, S.; Rech, B.; Lips, K.; Schnegg, A.

2011-11-01

Electrically detected electron-spin-echo envelope modulations (ED-ESEEM) were employed to detect hyperfine interactions between nuclear spins and paramagnetic sites, determining spin-dependent transport processes in multilayer thin-film microcrystalline silicon solar cells. Electrical detection in combination with a modified Hahn-echo sequence was used to measure echo modulations induced by 29Si, 31P, and 1H nuclei weakly coupled to electron spins of paramagnetic sites in the amorphous and microcrystalline solar cell layers. In the case of CE centers in the μc-Si:H i-layer, the absence of 1H ESEEM modulations indicates that the adjacencies of CE centers are depleted from hydrogen atoms. On the basis of this result, we discuss several models for the microscopic origin of the CE center and conclusively assign those centers to coherent twin boundaries inside of crystalline grains in μc-Si:H.

300 MHz continuous wave electron paramagnetic resonance spectrometer for small animal in vivo imaging

NASA Astrophysics Data System (ADS)

Koscielniak, J.; Devasahayam, N.; Moni, M. S.; Kuppusamy, P.; Yamada, K.; Mitchell, J. B.; Krishna, M. C.; Subramanian, S.

2000-11-01

Design and construction of an electron paramagnetic resonance (EPR) spectrometer, operating in the continuous wave mode in the radio frequency (rf) region, and capable of performing spectroscopy and in vivo imaging of paramagnetic spin probes is described. A resonant frequency of 300 MHz was chosen to provide the required sensitivity at nontoxic levels of commonly used spin probes and penetration of the rf in small animals. Three major components, the magnet, the radio frequency signal detection bridge, and the data acquisition module are described in this article. Integration of a rapid scan capability to reduce imaging time is also described. Two- and three-dimensional EPR images of the spin probe distribution in phantom objects as well as from in vivo experiments are reported. From the EPR images, morphology of some internal organs could be recognized. EPR images of the spin probe distribution in mice suggest differences in perfusion of the spin probe between normal and tumor regions. Addition of a spectral dimension to spatial images should enable differentiation of oxygen status in normal and pathological conditions.

Ultrafast Magnetization of a Dense Molecular Gas with an Optical Centrifuge.

PubMed

Milner, A A; Korobenko, A; Milner, V

2017-06-16

Strong laser-induced magnetization of oxygen gas at room temperature and atmospheric pressure is achieved experimentally on the subnanosecond time scale. The method is based on controlling the electronic spin of paramagnetic molecules by means of manipulating their rotation with an optical centrifuge. Spin-rotational coupling results in a high degree of spin polarization on the order of one Bohr magneton per centrifuged molecule. Owing to the nonresonant interaction with the laser pulses, the demonstrated technique is applicable to a broad class of paramagnetic rotors. Executed in a high-density gas, it may offer an efficient way of generating macroscopic magnetic fields remotely (as shown in this work) and producing a large amount of spin-polarized electrons.

Ultrafast Magnetization of a Dense Molecular Gas with an Optical Centrifuge

NASA Astrophysics Data System (ADS)

Milner, A. A.; Korobenko, A.; Milner, V.

2017-06-01

Strong laser-induced magnetization of oxygen gas at room temperature and atmospheric pressure is achieved experimentally on the subnanosecond time scale. The method is based on controlling the electronic spin of paramagnetic molecules by means of manipulating their rotation with an optical centrifuge. Spin-rotational coupling results in a high degree of spin polarization on the order of one Bohr magneton per centrifuged molecule. Owing to the nonresonant interaction with the laser pulses, the demonstrated technique is applicable to a broad class of paramagnetic rotors. Executed in a high-density gas, it may offer an efficient way of generating macroscopic magnetic fields remotely (as shown in this work) and producing a large amount of spin-polarized electrons.

Gallium hole traps in irradiated KTiOPO{sub 4}:Ga crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grachev, V.; Meyer, M.; Malovichko, G.

2014-12-07

Nominally pure and gallium doped single crystals of potassium titanyl phosphate (KTiOPO{sub 4}) have been studied by Electron Paramagnetic Resonance at low temperatures before and after irradiation. Irradiation with 20 MeV electrons performed at room temperature and liquid nitrogen temperature caused an appearance of electrons and holes. Gallium impurities act as hole traps in KTiOPO{sub 4} creating Ga{sup 4+} centers. Two different Ga{sup 4+} centers were observed, Ga1 and Ga2. The Ga1 centers are dominant in Ga-doped samples. For the Ga1 center, a superhyperfine structure with one nucleus with nuclear spin ½ was registered and attributed to the interaction of galliummore » electrons with a phosphorus nucleus or proton in its surrounding. In both Ga1 and Ga2 centers, Ga{sup 4+} ions substitute for Ti{sup 4+} ions, but with a preference to one of two electrically distinct crystallographic positions (site selective substitution). The Ga doping eliminates one of the shortcomings of KTP crystals—ionic conductivity of bulk crystals. However, this does not improve significantly the resistance of the crystals to electron and γ-radiation.« less

Copper(II) Thiosemicarbazone Complexes and Their Proligands upon UVA Irradiation: An EPR and Spectrophotometric Steady-State Study.

PubMed

Hricovíni, Michal; Mazúr, Milan; Sîrbu, Angela; Palamarciuc, Oleg; Arion, Vladimir B; Brezová, Vlasta

2018-03-21

X- and Q-band electron paramagnetic resonance (EPR) spectroscopy was used to characterize polycrystalline Cu(II) complexes that contained sodium 5-sulfonate salicylaldehyde thiosemicarbazones possessing a hydrogen, methyl, ethyl, or phenyl substituent at the terminal nitrogen. The ability of thiosemicarbazone proligands to generate superoxide radical anions and hydroxyl radicals upon their exposure to UVA irradiation in aerated aqueous solutions was evidenced by the EPR spin trapping technique. The UVA irradiation of proligands in neutral or alkaline solutions and dimethylsulfoxide (DMSO) caused a significant decrease in the absorption bands of aldimine and phenolic chromophores. Mixing of proligand solutions with the equimolar amount of copper(II) ions resulted in the formation of 1:1 Cu(II)-to-ligand complex, with the EPR and UV-Vis spectra fully compatible with those obtained for the dissolved Cu(II) thiosemicarbazone complexes. The formation of the complexes fully inhibited the photoinduced generation of reactive oxygen species, and only subtle changes were found in the electronic absorption spectra of the complexes in aqueous and DMSO solutions upon UVA steady-state irradiation. The dark redox activity of copper(II) complexes and proligand/Cu(II) aqueous solutions towards hydrogen peroxide which resulted in the generation of hydroxyl radicals, was confirmed by spin trapping experiments.

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…

Radiation-Induced Damage to Nucleic Acid Constituents

NASA Astrophysics Data System (ADS)

Kim, Heasook

The objective of this research was to identify the primary free radical species produced by ionizing radiation in DNA. The ultimate goal would be to use these data obtained from model compounds to analyze radiation-induced damage in DNA itself. The different single crystals were studied in detail. The first was the sodium salt of guanosine-3 ^':5^' -cyclic monophosphate (cyclic GMP). The results of studies on crystals irradiated at 4.2^ circK distinguished two species. One of these species exhibited a non-exchangeable proton coupling that was characterized by ENDOR spectroscopy and shown to be sigma proton. The spin density on C8 was deduced from the ENDOR hyperfine coupling tensor and found to be 0.15. The second species also exhibited a non-exchangeable sigma proton coupling and a beta proton coupling. The spin densities on C8 and N9 were deduced from ENDOR measurements to be 0.09 and 0.36. The former is attributed to the oxidation product and the latter to the primary reduction product. These products are respectively the guanine cation and anion. The second single crystal studied was a sodium salt of 2^'-deoxyguanosine -5^'-monophosphate tetrahydrate. The ESR and ENDOR spectra obtained from this crystal after x-irradiation at 4.2^circK were complex and the paramagnetic species were tentatively identified as ionic species. The third DNA model compound studied was thymidine. Single crystal of thymidine were irradiated at 1.6^ circK and at 4.2^circ K. The lower temperature preserved a more primitive stage of the radiation damage process. ENDOR measurements distinguished three paramagnetic species. The most interesting component of the paramagnetic absorption in crystals irradiated at 1.6^circK is attributed to trapped electron. These electrons are stabilized by the electrostatic fields generated by hydroxy dipoles. The hyperfine couplings between the trapped electron and the proton of these polar groups were deduced from ENDOR measurements. The ESR and ENDOR measurements described in this report were carried out DNA model compounds x-irradiated and measured at lower temperatures than reported previously. The experiments have demonstrated that an earlier stage of radiation damage can sometimes be stabilized and characterized in single crystals by maintaining the sample at 1.4 ^circK. (Abstract shortened with permission of author.).

The electron-spin--nuclear-spin interaction studied by polarized neutron scattering.

PubMed

Stuhrmann, Heinrich B

2007-11-01

Dynamic nuclear spin polarization (DNP) is mediated by the dipolar interaction of paramagnetic centres with nuclear spins. This process is most likely to occur near paramagnetic centres at an angle close to 45 degrees with respect to the direction of the external magnetic field. The resulting distribution of polarized nuclear spins leads to an anisotropy of the polarized neutron scattering pattern, even with randomly oriented radical molecules. The corresponding cross section of polarized coherent neutron scattering in terms of a multipole expansion is derived for radical molecules in solution. An application using data of time-resolved polarized neutron scattering from an organic chromium(V) molecule is tested.

Probing the Dipolar Coupling in a Heterospin Endohedral Fullerene-Phthalocyanine Dyad.

PubMed

Zhou, Shen; Yamamoto, Masanori; Briggs, G Andrew D; Imahori, Hiroshi; Porfyrakis, Kyriakos

2016-02-03

Paramagnetic endohedral fullerenes and phthalocyanine (Pc) complexes are promising building blocks for molecular quantum information processing, for which tunable dipolar coupling is required. We have linked these two spin qubit candidates together and characterized the resulting electron paramagnetic resonance properties, including the spin dipolar coupling between the fullerene spin and the copper spin. Having interpreted the distance-dependent coupling strength quantitatively and further discussed the antiferromagnetic aggregation effect of the CuPc moieties, we demonstrate two ways of tuning the dipolar coupling in such dyad systems: changing the spacer group and adjusting the solution concentration.

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

PubMed

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

2015-07-28

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rocker, J.; Cornu, D.; Kieseritzky, E.

2014-08-01

A new ultrahigh vacuum (UHV) electron paramagnetic resonance (EPR) spectrometer operating at 94 GHz to investigate paramagnetic centers on single crystal surfaces is described. It is particularly designed to study paramagnetic centers on well-defined model catalysts using epitaxial thin oxide films grown on metal single crystals. The EPR setup is based on a commercial Bruker E600 spectrometer, which is adapted to ultrahigh vacuum conditions using a home made Fabry Perot resonator. The key idea of the resonator is to use the planar metal single crystal required to grow the single crystalline oxide films as one of the mirrors of themore » resonator. EPR spectroscopy is solely sensitive to paramagnetic species, which are typically minority species in such a system. Hence, additional experimental characterization tools are required to allow for a comprehensive investigation of the surface. The apparatus includes a preparation chamber hosting equipment, which is required to prepare supported model catalysts. In addition, surface characterization tools such as low energy electron diffraction (LEED)/Auger spectroscopy, temperature programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS) are available to characterize the surfaces. A second chamber used to perform EPR spectroscopy at 94 GHz has a room temperature scanning tunneling microscope attached to it, which allows for real space structural characterization. The heart of the UHV adaptation of the EPR experiment is the sealing of the Fabry-Perot resonator against atmosphere. To this end it is possible to use a thin sapphire window glued to the backside of the coupling orifice of the Fabry Perot resonator. With the help of a variety of stabilization measures reducing vibrations as well as thermal drift it is possible to accumulate data for a time span, which is for low temperature measurements only limited by the amount of liquid helium. Test measurements show that the system can detect paramagnetic species with a density of approximately 5 × 10{sup 11} spins/cm{sup 2}, which is comparable to the limit obtained for the presently available UHV-EPR spectrometer operating at 10 GHz (X-band). Investigation of electron trapped centers in MgO(001) films shows that the increased resolution offered by the experiments at W-band allows to identify new paramagnetic species, that cannot be differentiated with the currently available methodology.« less

Slow spin relaxation induced by magnetic field in [NdCo(bpdo)(H2O)4(CN)6]⋅3H2O.

PubMed

Vrábel, P; Orendáč, M; Orendáčová, A; Čižmár, E; Tarasenko, R; Zvyagin, S; Wosnitza, J; Prokleška, J; Sechovský, V; Pavlík, V; Gao, S

2013-05-08

We report on a comprehensive investigation of the magnetic properties of [NdCo(bpdo)(H2O)4(CN)6]⋅3H2O (bpdo=4, 4'-bipyridine-N,N'-dioxide) by use of electron paramagnetic resonance, magnetization, specific heat and susceptibility measurements. The studied material was identified as a magnet with an effective spin S = 1/2 and a weak exchange interaction J/kB = 25 mK. The ac susceptibility studies conducted at audio frequencies and at temperatures from 1.8 to 9 K revealed that the application of a static magnetic field induces a slow spin relaxation. It is suggested that the relaxation in the magnetic field appears due to an Orbach-like process between the two lowest doublet energy states of the magnetic Nd(3+) ion. The appearance of the slow relaxation in a magnetic field cannot be associated with a resonant phonon trapping. The obtained results suggest that the relaxation is influenced by nuclear spin driven quantum tunnelling which is suppressed by external magnetic field.

Elucidating the design principles of photosynthetic electron-transfer proteins by site-directed spin labeling EPR spectroscopy.

PubMed

Ishara Silva, K; Jagannathan, Bharat; Golbeck, John H; Lakshmi, K V

2016-05-01

Site-directed spin labeling electron paramagnetic resonance (SDSL EPR) spectroscopy is a powerful tool to determine solvent accessibility, side-chain dynamics, and inter-spin distances at specific sites in biological macromolecules. This information provides important insights into the structure and dynamics of both natural and designed proteins and protein complexes. Here, we discuss the application of SDSL EPR spectroscopy in probing the charge-transfer cofactors in photosynthetic reaction centers (RC) such as photosystem I (PSI) and the bacterial reaction center (bRC). Photosynthetic RCs are large multi-subunit proteins (molecular weight≥300 kDa) that perform light-driven charge transfer reactions in photosynthesis. These reactions are carried out by cofactors that are paramagnetic in one of their oxidation states. This renders the RCs unsuitable for conventional nuclear magnetic resonance spectroscopy investigations. However, the presence of native paramagnetic centers and the ability to covalently attach site-directed spin labels in RCs makes them ideally suited for the application of SDSL EPR spectroscopy. The paramagnetic centers serve as probes of conformational changes, dynamics of subunit assembly, and the relative motion of cofactors and peptide subunits. In this review, we describe novel applications of SDSL EPR spectroscopy for elucidating the effects of local structure and dynamics on the electron-transfer cofactors of photosynthetic RCs. Because SDSL EPR Spectroscopy is uniquely suited to provide dynamic information on protein motion, it is a particularly useful method in the engineering and analysis of designed electron transfer proteins and protein networks. This article is part of a Special Issue entitled Biodesign for Bioenergetics--the design and engineering of electronic transfer cofactors, proteins and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson. Copyright © 2016. Published by Elsevier B.V.

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

ERIC Educational Resources Information Center

Eastman, Michael P.

1982-01-01

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

Tea extracts protect normal lymphocytes but not leukemia cells from UV radiation-induced ROS production: An EPR spin trap study.

PubMed

Tepe Çam, Semra; Polat, Mustafa; Esmekaya, Meriç Arda; Canseven, Ayşe G; Seyhan, Nesrin

2015-08-01

An ex vivo method for detection of free radicals and their neutralization by aqueous tea in human normal lymphocytes and MEC-1 leukemia cells under ultraviolet (UV) irradiation was investigated. This method is based on the electron paramagnetic resonance (EPR) spectroscopy spin-trapping technique. 5-tert-butoxycarbonyl 5-methyl-1-pyrroline N-oxide (BMPO) was used as the spin trap. Normal human lymphocytes and leukemia cells were exposed to UVB radiation (290-315 nm) at 47.7 and 159 mJ/cm(2) and to UVA radiation (315-400 nm) at 53.7 J/cm(2). No significant radical production at 47.7 mJ/cm(2) UVB dose in both cell lines was observed. In normal cells, free radical production was observed at 159 mJ/cm(2) UVB and 53.7 J/cm(2) UVA doses. However, both UV sources did not significantly produce free radicals in leukemia cells. A radical scavenging property of tea extracts (black, green, sage, rosehip) was observed in normal lymphocytes after both UVB and UVA exposure. In leukemia cells, the intensities of EPR signals produced in BMPO with tea extracts were found to be increased substantially after UVA exposure. These results showed that UV radiation induced free radical formation in normal human lymphocytes and indicated that tea extracts may be useful as photoprotective agents for them. On the other hand, tea extracts facilitated free radical production in leukemia cells.

Observation of a Discrete Time Crystal

NASA Astrophysics Data System (ADS)

Kyprianidis, A.; Zhang, J.; Hess, P.; Becker, P.; Lee, A.; Smith, J.; Pagano, G.; Potter, A.; Vishwanath, A.; Potirniche, I.-D.; Yao, N.; Monroe, C.

2017-04-01

Spontaneous symmetry breaking is a key concept in the understanding of many physical phenomena, such as the formation of spatial crystals and the phase transition from paramagnetism to magnetic order. While the breaking of time translation symmetry is forbidden in equilibrium systems, it is possible for non-equilibrium Floquet driven systems to break a discrete time translation symmetry, and we present clear signatures of the formation of such a discrete time crystal. We apply a time periodic Hamiltonian to a chain of interacting spins under many-body localization conditions and observe the system's sub-harmonic response at twice that period. This spontaneous doubling of the periodicity is robust to external perturbations. We represent the spins with a linear chain of trapped 171Yb+ ions in an rf Paul trap, generate spin-spin interactions through spin-dependent optical dipole forces, and measure each spin using state-dependent fluorescence. This work is supported by the ARO Atomic Physics Program, the AFOSR MURI on Quantum Measurement and Verification, and the NSF Physics Frontier Center at JQI.

Identification of the substrate radical intermediate derived from ethanolamine during catalysis by ethanolamine ammonia-lyase.

PubMed

Bender, Güneş; Poyner, Russell R; Reed, George H

2008-10-28

Rapid-mix freeze-quench (RMFQ) methods and electron paramagnetic resonance (EPR) spectroscopy have been used to characterize the steady-state radical in the deamination of ethanolamine catalyzed by adenosylcobalamin (AdoCbl)-dependent ethanolamine ammonia-lyase (EAL). EPR spectra of the radical intermediates formed with the substrates, [1-13C]ethanolamine, [2-13C]ethanolamine, and unlabeled ethanolamine were acquired using RMFQ trapping methods from 10 ms to completion of the reaction. Resolved 13C hyperfine splitting in EPR spectra of samples prepared with [1-13C]ethanolamine and the absence of such splitting in spectra of samples prepared with [2-13C]ethanolamine show that the unpaired electron is localized on C1 (the carbinol carbon) of the substrate. The 13C splitting from C1 persists from 10 ms throughout the time course of substrate turnover, and there was no evidence of a detectable amount of a product like radical having unpaired spin on C2. These results correct an earlier assignment for this radical intermediate [Warncke, K., et al. (1999) J. Am. Chem. Soc. 121, 10522-10528]. The EPR signals of the substrate radical intermediate are altered by electron spin coupling to the other paramagnetic species, cob(II)alamin, in the active site. The dipole-dipole and exchange interactions as well as the 1-13C hyperfine splitting tensor were analyzed via spectral simulations. The sign of the isotropic exchange interaction indicates a weak ferromagnetic coupling of the two unpaired electrons. A Co2+-radical distance of 8.7 A was obtained from the magnitude of the dipole-dipole interaction. The orientation of the principal axes of the 13C hyperfine splitting tensor shows that the long axis of the spin-bearing p orbital on C1 of the substrate radical makes an angle of approximately 98 degrees with the unique axis of the d(z2) orbital of Co2+.

High-Yield Spin Labeling of Long RNAs for Electron Paramagnetic Resonance Spectroscopy.

PubMed

Kerzhner, Mark; Matsuoka, Hideto; Wuebben, Christine; Famulok, Michael; Schiemann, Olav

2018-05-10

Site-directed spin labeling is a powerful tool for investigating the conformation and dynamics of biomacromolecules such as RNA. Here we introduce a spin labeling strategy based on click chemistry in solution that, in combination with enzymatic ligation, allows highly efficient labeling of complex and long RNAs with short reaction times and suppressed RNA degradation. With this approach, a 34-nucleotide aptamer domain of the preQ1 riboswitch and an 81-nucleotide TPP riboswitch aptamer could be labeled with two labels in several positions. We then show that conformations of the preQ1 aptamer and its dynamics can be monitored in the absence and presence of Mg 2+ and a preQ1 ligand by continuous wave electron paramagnetic resonance spectroscopy at room temperature and pulsed electron-electron double resonance spectroscopy (PELDOR or DEER) in the frozen state.

A novel microfluidic rapid freeze-quench device for trapping reactions intermediates for high field EPR analysis.

PubMed

Kaufmann, Royi; Yadid, Itamar; Goldfarb, Daniella

2013-05-01

Rapid freeze quench electron paramagnetic resonance (RFQ)-EPR is a method for trapping short lived intermediates in chemical reactions and subjecting them to EPR spectroscopy investigation for their characterization. Two (or more) reacting components are mixed at room temperature and after some delay the mixture is sprayed into a cold trap and transferred into the EPR tube. A major caveat in using commercial RFQ-EPR for high field EPR applications is the relatively large amount of sample needed for each time point, a major part of which is wasted as the dead volume of the instrument. The small sample volume (∼2μl) needed for high field EPR spectrometers, such as W-band (∼3.5T, 95GHz), that use cavities calls for the development of a microfluidic based RFQ-EPR apparatus. This is particularly important for biological applications because of the difficulties often encountered in producing large amounts of intrinsically paramagnetic proteins and spin labeled nucleic acid and proteins. Here we describe a dedicated microfluidic based RFQ-EPR apparatus suitable for small volume samples in the range of a few μl. The device is based on a previously published microfluidic mixer and features a new ejection mechanism and a novel cold trap that allows collection of a series of different time points in one continuous experiment. The reduction of a nitroxide radical with dithionite, employing the signal of Mn(2+) as an internal standard was used to demonstrate the performance of the microfluidic RFQ apparatus. Copyright © 2013 Elsevier Inc. All rights reserved.

Electron paramagnetic resonance g-tensors from state interaction spin-orbit coupling density matrix renormalization group

NASA Astrophysics Data System (ADS)

Sayfutyarova, Elvira R.; Chan, Garnet Kin-Lic

2018-05-01

We present a state interaction spin-orbit coupling method to calculate electron paramagnetic resonance g-tensors from density matrix renormalization group wavefunctions. We apply the technique to compute g-tensors for the TiF3 and CuCl42 - complexes, a [2Fe-2S] model of the active center of ferredoxins, and a Mn4CaO5 model of the S2 state of the oxygen evolving complex. These calculations raise the prospects of determining g-tensors in multireference calculations with a large number of open shells.

Quantum simulations of the Ising model with trapped ions: Devil's staircase and arbitrary lattice proposal

NASA Astrophysics Data System (ADS)

Korenblit, Simcha

A collection of trapped atomic ions represents one of the most attractive platforms for the quantum simulation of interacting spin networks and quantum magnetism. Spin-dependent optical dipole forces applied to an ion crystal create long-range effective spin-spin interactions and allow the simulation of spin Hamiltonians that possess nontrivial phases and dynamics. We trap linear chains of 171Yb+ ions in a Paul trap, and constrain the occupation of energy levels to the ground hyperne clock-states, creating a qubit or pseudo-spin 1/2 system. We proceed to implement spin-spin couplings between two ions using the far detuned Molmer-Sorenson scheme and perform adiabatic quantum simulations of Ising Hamiltonians with long-range couplings. We then demonstrate our ability to control the sign and relative strength of the interaction between three ions. Using this control, we simulate a frustrated triangular lattice, and for the first time establish an experimental connection between frustration and quantum entanglement. We then scale up our simulation to show phase transitions from paramagnetism to ferromagnetism for nine ions, and to anti-ferromagnetism for sixteen ions. The experimental work culminates with our most complicated Hamiltonian---a long range anti-ferromagnetic Ising interaction between 10 ions with a biasing axial field. Theoretical work presented in this thesis shows how the approach to quantum simulation utilized in this thesis can be further extended and improved. It is shown how appropriate design of laser fields can provide for arbitrary multidimensional spin-spin interaction graphs even for the case of a linear spatial array of ions. This scheme uses currently existing trap technology and is scalable to levels where classical methods of simulation are intractable.

Rare earth ions doped ZnO: Synthesis, characterization and preliminary photoactivity assessment

NASA Astrophysics Data System (ADS)

Cerrato, Erik; Gionco, Chiara; Berruti, Ilaria; Sordello, Fabrizio; Calza, Paola; Paganini, Maria Cristina

2018-08-01

This work reports the effect of doping zinc oxide with lanthanide ions on structural, EPR and UV visible properties. Bare and doped samples were synthesized using the simple and green hydrothermal process. Different rare earth ions (RE = La, Ce, Pr, Er and Yb) with 1% molar ratio RE/Zn were used. The samples have been studied using X Ray Diffraction, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and UV visible diffuse reflectance spectroscopy. Finally, electron paramagnetic resonance (EPR) spectroscopy, was used to assess the materials photoactivity under UV irradiation, both in solid state, to see the charge carriers' generation and in solution, evaluating the OH• radical formation using the DMPO (5,5-Dimethyl-1-Pyrroline-N-Oxide) spin trapping technique. The results suggest that the synthesized materials could be interesting systems for the photocatalytic abatement of emerging organic persistent pollutants in wastewater treatment plants.

A portable version of the program of nettar and villafranca for the simulation of electron paramagnetic resonance spectra of powders

NASA Astrophysics Data System (ADS)

Soulié, Edgar; Gaugenot, Jacques

1995-04-01

Nettar and Villafranca wrote in the FORTRAN programming language a computer program which simulates the electron paramagnetic resonance (EPR) spectra of powders (Journal of Magnetic Resonance, vol. 64 (1985) pp. 61-65). The spin Hamiltonian which their program can handle includes the Zeeman electronic interaction, the fine interaction up to the sixth order in the electron spin, a general hyperfine interaction, an isotropic nuclear Zeeman term; anisotropic ligand hyperfine terms are treated to first order in perturbation. The above Hamiltonian, without the ligand hyperfine terms, is treated exactly, i.e. the resonance equation for a transition between states labeled i and j is solved numerically: h.ν=Ei(H)-Ej(H).

Paramagnetic resonance studies of bistrispyrazolylborate cobalt(II) and related derivatives

NASA Astrophysics Data System (ADS)

Myers, William K.

Herein, a systematic frozen solution electron-nuclear double resonance (ENDOR) study of high-spin Co(II) complexes is reported to demonstrate the efficacy of methyl substitutions as a means of separating dipolar and contact coupling, and further, to increase the utility of high-spin Co(II) as a spectroscopic probe for the ubiquitous, but spectroscopically-silent Zn(II) metalloenzymes. High-spin (hs) Co(II) has been subject of paramagnetic resonance studies for over 50 years and has been used as a spectroscopic probe for Zn metalloenzymes for over 35 years. However, as will be seen, the inherent complexity of the electronic properties of the cobaltous ion remains to be exploited to offer a wealth of information on Zn(II) enzymatic environments. Specifically, ENDOR measurements on bistrispyrazolylborate cobalt(II) confirm the utility of the novel method of methyl substitution to differentiate dipolar and Fermi contact couplings. An extensive set of electron paramagnetic resonance (EPR) simulations were performed. Software was developed to implement an ENDOR control interface. Finally, proton relaxation measurements were made in the range of 12-42 MHz, which were accounted for with the large g-value anisotropy of the Co(II) compounds. Taken as a whole, these studies point to the rich complexity of the electronic structure of high-spin cobalt(II) and, when sufficiently well-characterized, the great utility it has as a surrogate of biological Zn(II).

Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves.

PubMed

Thurber, Kent R; Tycko, Robert

2014-05-14

We report solid state (13)C and (1)H nuclear magnetic resonance (NMR) experiments with magic-angle spinning (MAS) on frozen solutions containing nitroxide-based paramagnetic dopants that indicate significant perturbations of nuclear spin polarizations without microwave irradiation. At temperatures near 25 K, (1)H and cross-polarized (13)C NMR signals from (15)N,(13)C-labeled L-alanine in trinitroxide-doped glycerol/water are reduced by factors as large as six compared to signals from samples without nitroxide doping. Without MAS or at temperatures near 100 K, differences between signals with and without nitroxide doping are much smaller. We attribute most of the reduction of NMR signals under MAS near 25 K to nuclear spin depolarization through the cross-effect dynamic nuclear polarization mechanism, in which three-spin flips drive nuclear polarizations toward equilibrium with spin polarization differences between electron pairs. When T1e is sufficiently long relative to the MAS rotation period, the distribution of electron spin polarization across the nitroxide electron paramagnetic resonance lineshape can be very different from the corresponding distribution in a static sample at thermal equilibrium, leading to the observed effects. We describe three-spin and 3000-spin calculations that qualitatively reproduce the experimental observations.

Copper ESEEM and HYSCORE through ultra-wideband chirp EPR spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2015-07-28

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

Benign Synthesis of Black Microspheres of Anatase TiO2 with Paramagnetic Oxygen Vacancies through NH3 Treatment.

PubMed

Maqbool, Qysar; Srivastava, Aasheesh

2017-10-09

Coloured TiO 2 is coveted for its ability to extract energy from the visible region of electromagnetic spectrum. Here a facile synthesis of black anatase titania microspheres (B-TiO 2 ) through a two-step process is reported. In the first step, amorphous white TiO 2 microspheres (W-TiO 2 ) are obtained by hydrolysing titanium tetraisopropoxide by ammonia vapours in ethanol. In the second step, the W-TiO 2 is thermally annealed at 500 °C to obtain B-TiO 2 . The diffuse reflectance analysis showed that B-TiO 2 absorbs across visible spectrum with absorption extending well into NIR region. Raman scattering together with EPR analysis showed compelling evidence of the existence of oxygen deficiency within the crystal in B-TiO 2 that induces black colouration in the sample. The defects present in the black anatase sample were confirmed to be single-electron-trapped (or paramagnetic) oxygen vacancies (V o ⋅) by XPS and EPR studies. The magnetic susceptibility studies showed existence of antiferromagnetic interactions between these unpaired electron spins. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of pH, buffers and role of quinolinic acid, a novel iron chelating agent, in the determination of hydroxyl radical scavenging activity of plant extracts by Electron Paramagnetic Resonance (EPR).

PubMed

Fadda, Angela; Barberis, Antonio; Sanna, Daniele

2018-02-01

The Fenton reaction is used to produce hydroxyl radicals for the evaluation of the antioxidant activity of plant extracts. In this paper the parameters affecting the production of hydroxyl radicals and their spin trapping with DMPO were studied. The use of quinolinic acid (Quin) as an Fe(II) ligand was proposed for antioxidant activity determination of Green tea, orange juice and asparagus extracts. Quin, buffers and pH affect the DMPO-OH signal intensity of the EPR spectra. Quin/Fe(II) and low pH enhance the OH generation. Phosphate and Tris-HCl buffers decrease the signal intensity measured in Fe(II)-sulfate and Fe(II)-Quin systems. The extracts were analyzed with Fenton systems containing Fe(II)-sulfate and Fe(II)-Quin with and without buffer. The highest activity was shown with Fe(II)-Quin without buffer, this system being less influenced by pH and chelating agents present in the extracts. This paper will help researchers to better design spin trapping experiments for food matrices. Copyright © 2017 Elsevier Ltd. All rights reserved.

Direct detection of free radicals and reactive oxygen species in thylakoids.

PubMed

Hideg, Eva; Kálai, Tamás; Hideg, Kálmán

2011-01-01

In plants, reactive oxygen species (ROS), also known as active oxygen species (AOS), are associated with normal, physiologic processes as well as with responses to adverse conditions. ROS are connected to stress in many ways: as primary elicitors, as products and propagators of oxidative damage, or as signal molecules initiating defense or adaptation. The photosynthetic electron transport is a major site of oxidative stress by visible or ultraviolet light, high or low temperature, pollutants or herbicides. ROS production can be presumed from detecting oxidatively damaged lipids, proteins, or pigments as well as from the alleviating effects of added antioxidants. On the contrary, measuring ROS by special sensor molecules provides more direct information. This chapter focuses on the application of spin trapping electron paramagnetic resonance (EPR) spectroscopy for detecting ROS: singlet oxygen and oxygen free radicals in thylakoid membrane preparations.

Hyperoxic sheep pulmonary microvascular endothelial cells generate free radicals via mitochondrial electron transport.

PubMed Central

Sanders, S P; Zweier, J L; Kuppusamy, P; Harrison, S J; Bassett, D J; Gabrielson, E W; Sylvester, J T

1993-01-01

Free radical generation by hyperoxic endothelial cells was studied using electron paramagnetic resonance (EPR) spectroscopy and the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). Studies were performed to determine the radical species produced, whether mitochondrial electron transport was involved, and the effect of the radical generation on cell mortality. Sheep pulmonary microvascular endothelial cell suspensions exposed to 100% O2 for 30 min exhibited prominent DMPO-OH and, occasionally, additional smaller DMPO-R signals thought to arise from the trapping of superoxide anion (O2-.), hydroxyl (.OH), and alkyl (.R) radicals. Superoxide dismutase (SOD) quenched both signals suggesting that the observed radicals were derived from O2-.. Studies with deferoxamine suggested that the generation of .R occurred secondary to the formation of .OH from O2-. via an iron-mediated Fenton reaction. Blocking mitochondrial electron transport with rotenone (20 microM) markedly decreased radical generation. Cell mortality increased slightly in oxygen-exposed cells. This increase was not significantly altered by SOD or deferoxamine, nor was it different from the mortality observed in air-exposed cells. These results suggest that endothelial cells exposed to hyperoxia for 30 min produce free radicals via mitochondrial electron transport, but under the conditions of these experiments, this radical generation did not appear cause cell death. PMID:8380815

Isolation of EPR spectra and estimation of spin-states in two-component mixtures of paramagnets.

PubMed

Chabbra, Sonia; Smith, David M; Bode, Bela E

2018-04-26

The presence of multiple paramagnetic species can lead to overlapping electron paramagnetic resonance (EPR) signals. This complication can be a critical obstacle for the use of EPR to unravel mechanisms and aid the understanding of earth abundant metal catalysis. Furthermore, redox or spin-crossover processes can result in the simultaneous presence of metal centres in different oxidation or spin states. In this contribution, pulse EPR experiments on model systems containing discrete mixtures of Cr(i) and Cr(iii) or Cu(ii) and Mn(ii) complexes demonstrate the feasibility of the separation of the EPR spectra of these species by inversion recovery filters and the identification of the relevant spin states by transient nutation experiments. We demonstrate the isolation of component spectra and identification of spin states in a mixture of catalyst precursors. The usefulness of the approach is emphasised by monitoring the fate of the chromium species upon activation of an industrially used precatalyst system.

Measurement of electron paramagnetic resonance using terahertz time-domain spectroscopy.

PubMed

Kozuki, Kohei; Nagashima, Takeshi; Hangyo, Masanori

2011-12-05

We present a frequency-domain electron spin resonance (ESR) measurement system using terahertz time-domain spectroscopy. A crossed polarizer technique is utilized to increase the sensitivity in detecting weak ESR signals of paramagnets caused by magnetic dipole transitions between magnetic sublevels. We demonstrate the measurements of ESR signal of paramagnetic copper(II) sulfate pentahydrate with uniaxial anisotropy of the g-factor under magnetic fields up to 10 T. The lineshape of the obtained ESR signals agrees well with the theoretical predictions for a powder sample with the uniaxial anisotropy.

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

PubMed Central

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

2016-01-01

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

Carbon-related platinum defects in silicon: An electron paramagnetic resonance study of high spin states

NASA Astrophysics Data System (ADS)

Scheerer, O.; Höhne, M.; Juda, U.; Riemann, H.

1997-10-01

In this article, we report about complexes in silicon investigated by electron paramagnetic resonance (EPR). In silicon doped with C and Pt we detected two different complexes: cr-1Pt (cr: carbon-related, 1Pt: one Pt atom) and cr-3Pt. The complexes have similar EPR properties. They show a trigonal symmetry with effective g-values geff,⊥=2g⊥≈4 and geff,‖=g‖≈2 (g⊥, g‖ true g-values). The g-values can be explained by a spin Hamiltonian with large fine-structure energy (electron spin S=3/2) and smaller Zeeman interaction. The participation of platinum in the complexes is proved by the hyperfine interaction. From experiments with varying carbon concentration we conclude that the complexes contain carbon. Atomistic models based on the Watkins vacancy-model for substitutional Pt were developed.

Rabi oscillation and electron-spin-echo envelope modulation of the photoexcited triplet spin system in silicon

NASA Astrophysics Data System (ADS)

Akhtar, Waseem; Sekiguchi, Takeharu; Itahashi, Tatsumasa; Filidou, Vasileia; Morton, John J. L.; Vlasenko, Leonid; Itoh, Kohei M.

2012-09-01

We report on a pulsed electron paramagnetic resonance (EPR) study of the photoexcited triplet state (S=1) of oxygen-vacancy centers in silicon. Rabi oscillations between the triplet sublevels are observed using coherent manipulation with a resonant microwave pulse. The Hahn echo and stimulated echo decay profiles are superimposed with strong modulations known as electron-spin-echo envelope modulation (ESEEM). The ESEEM spectra reveal a weak but anisotropic hyperfine coupling between the triplet electron spin and a 29Si nuclear spin (I=1/2) residing at a nearby lattice site, that cannot be resolved in conventional field-swept EPR spectra.

Theoretical model of dynamic spin polarization of nuclei coupled to paramagnetic point defects in diamond and silicon carbide

NASA Astrophysics Data System (ADS)

Ivády, Viktor; Szász, Krisztián; Falk, Abram L.; Klimov, Paul V.; Christle, David J.; Janzén, Erik; Abrikosov, Igor A.; Awschalom, David D.; Gali, Adam

2015-09-01

Dynamic nuclear spin polarization (DNP) mediated by paramagnetic point defects in semiconductors is a key resource for both initializing nuclear quantum memories and producing nuclear hyperpolarization. DNP is therefore an important process in the field of quantum-information processing, sensitivity-enhanced nuclear magnetic resonance, and nuclear-spin-based spintronics. DNP based on optical pumping of point defects has been demonstrated by using the electron spin of nitrogen-vacancy (NV) center in diamond, and more recently, by using divacancy and related defect spins in hexagonal silicon carbide (SiC). Here, we describe a general model for these optical DNP processes that allows the effects of many microscopic processes to be integrated. Applying this theory, we gain a deeper insight into dynamic nuclear spin polarization and the physics of diamond and SiC defects. Our results are in good agreement with experimental observations and provide a detailed and unified understanding. In particular, our findings show that the defect electron spin coherence times and excited state lifetimes are crucial factors in the entire DNP process.

Study of the effects of hydroxyapatite nanocrystal codoping by pulsed electron paramagnetic resonance methods

NASA Astrophysics Data System (ADS)

Gafurov, M. R.; Biktagirov, T. B.; Mamin, G. V.; Shurtakova, D. V.; Klimashina, E. S.; Putlyaev, V. I.; Orlinskii, S. B.

2016-03-01

The effect of codoping of hydroxyapatite (HAP) nanocrystals with average sizes of 35 ± 15 nm during "wet" synthesis by CO 3 2- carbonate anions and Mn2+ cations on relaxation characteristics (for the times of electron spin-spin relaxation) of the NO 3 2- nitrate radical anion has been studied. By the example of HAP, it has been demonstrated that the electron paramagnetic resonance (EPR) is an efficient method for studying anion-cation (co)doping of nanoscale particles. It has been shown experimentally and by quantummechanical calculations that simultaneous introduction of several ions can be energetically more favorable than their separate inclusion. Possible codoping models have been proposed, and their energy parameters have been calculated.

Optical manifestation of the Stoner ferromagnetic transition in two-dimensional electron systems

NASA Astrophysics Data System (ADS)

Van'kov, A. B.; Kaysin, B. D.; Kukushkin, I. V.

2017-12-01

We perform a magneto-optical study of a two-dimensional electron systems in the regime of the Stoner ferromagnetic instability for even quantum Hall filling factors on MgxZn1 -xO /ZnO heterostructures. Under conditions of Landau-level crossing, caused by enhanced spin susceptibility in combination with the tilting of the magnetic field, the transition between two rivaling phases, paramagnetic and ferromagnetic, is traced in terms of optical spectra reconstruction. Synchronous sharp transformations are observed both in the photoluminescence structure and parameters of collective excitations upon transition from paramagnetic to ferromagnetic ordering. Based on these measurements, a phase diagram is constructed in terms of the two-dimensional electron density and tilt angle of the magnetic field. Apart from stable paramagnetic and ferromagnetic phases, an instability region is found at intermediate parameters with the Stoner transition occurring at ν ≈2 . The spin configuration in all cases is unambiguously determined by means of inelastic light scattering by spin-sensitive collective excitations. One indicator of the spin ordering is the intra-Landau-level spin exciton, which acquires a large spectral weight in the ferromagnetic phases. The other is an abrupt energy shift of the intersubband charge density excitation due to reconstruction of the many-particle energy contribution. From our analysis of photoluminescence and light scattering data, we estimate the ratio of surface areas occupied by the domains of the two phases in the vicinity of a transition point. In addition, the thermal smearing of a phase transition is characterized.

Investigating electron spin resonance spectroscopy of a spin-½ compound in a home-built spectrometer

NASA Astrophysics Data System (ADS)

Sarkar, Jit; Roy, Subhadip; Singh, Jitendra Kumar; Singh, Sourabh; Chakraborty, Tanmoy; Mitra, Chiranjib

2018-05-01

In this work we report electron spin resonance (ESR) measurements performed on NH4CuPO4.H2O, a Heisenberg spin ½ dimer compound. We carried out the experiments both at room temperature and at 78 K, which are well above the antiferromagnetic ordering temperature of the system where the paramagnetic spins have a dominant role in determining its magnetic behavior. We performed the measurements in a home built custom designed continuous wave electron spin resonance (CW-ESR) spectrometer. By analyzing the experimental data, we were able to quantify the Landé g-factor and the ESR line-width of the sample.

Improved apparatus for trapped radical and other studies down to 1.5 K. [microwave cavity cryogenic equipment for electron paramagnetic resonance experiments

NASA Technical Reports Server (NTRS)

Woollam, J. A.; Sugawara, K.

1978-01-01

A Dewar system and associated equipment for electron paramagnetic resonance (EPR) studies of trapped free radicals and other optical or irradiation experiments are described. The apparatus is capable of reaching a temperature of 1.5 K and transporting on the order of 20 W per K temperature gradient; its principal advantages are for use at pumped cryogen temperatures and for experiments with large heat inputs. Two versions of the apparatus are discussed, one of which is designed for EPR in a rectangular cavity operating in a TE(102) mode and another in which EPR is performed in a cylindrical microwave cavity.

EPR investigation of electronic excitations in rare gas solids (Review Article)

NASA Astrophysics Data System (ADS)

Zhitnikov, R. A.; Dmitriev, Yu. A.

1998-10-01

The methods are described for producing unstable paramagnetic excited states in rare gas cryocrystals Ne, Ar, Kr, and Xe through the trapping, in the cryocrystals growing from the gas phase, the products of the gas discharge taking place in the same or other rare gas. The paper presents a technique and results of an observation and investigation of excited states in rare gas cryocrystals with electron paramagnetic resonance (EPR). The discovered unstable paramagnetic centers are interpreted as being local metastable excited np5(n+1)s atomic-type states in rare gas cryocrystals which are subject to the action of the anisotropic electric field resulted from the crystal surroundings distorted by the center. An account is given of the mechanisms for formation of observed paramagnetic excited states in cryocrystals which arise owing to the excitation energy of the metastable 3P2 atoms of Ne, Ar, Kr, Xe and He 23S1 and 21S0 atoms that form in the discharge in an appropriate gas and trap in the growing cryocrystal.

Dual nature of 3 d electrons in YbT 2 Zn 20 (T = Co; Fe) evidenced by electron spin resonance

DOE PAGES

Ivanshin, V. A.; Litvinova, T. O.; Gimranova, K.; ...

2015-03-18

The electron spin resonance experiments were carried out in the single crystals YbFe 2Zn 20. The observed spin dynamics is compared with that in YbCo 2Zn 20 and Yb 2Co 12P 7 as well as with the data of inelastic neutron scattering and electronic band structure calculations. Our results provide direct evidence that 3d electrons are itinerant in YbFe 2Zn 20 and localized in YbCo 2Zn 20. Possible connection between spin paramagnetism of dense heavy fermion systems, quantum criticality effects, and ESR spectra is discussed.

Development of an electron paramagnetic resonance methodology for studying the photo-generation of reactive species in semiconductor nano-particle assembled films

NASA Astrophysics Data System (ADS)

Twardoch, Marek; Messai, Youcef; Vileno, Bertrand; Hoarau, Yannick; Mekki, Djamel E.; Felix, Olivier; Turek, Philippe; Weiss, Jean; Decher, Gero; Martel, David

2018-06-01

An experimental approach involving electron paramagnetic resonance is proposed for studying photo-generated reactive species in semiconductor nano-particle-based films deposited on the internal wall of glass capillaries. This methodology is applied here to nano-TiO2 and allows a semi-quantitative analysis of the kinetic evolutions of radical production using a spin scavenger probe.

Imaging single spin probes embedded in a conductive diamagnetic layer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Messina, P.; Fradin, F.

2009-01-01

The detection of spin noise by means of scanning tunneling microscopy (STM) has recently been substantially improved by the work presented by Komeda and Manassen (Komeda, T.; Manassen, Y. Appl. Phys. Lett. 2008, 92, 212506). The application of this technique to molecular paramagnets requires the positioning and anchoring of paramagnetic molecules at surfaces. It also requires the possibility of tunneling high current densities into the STM-molecule-substrate tunneling junction. In this letter, we exploit the self-assembly of 1,10-phenantroline on the Au(111) surface to form a diamagnetic matrix that hosts individual molecules and dimers of diphenyl-2-picryl-hydrazyl (DPPH). STM measurements are used tomore » characterize the molecular layer. Electron spin resonance (ESR) measurements elucidate the role of thermal annealing in the preservation of the paramagnetic nature of the DPPH molecules.« less

Electrically Detected Study of Variable Range Hopping in Silicon Nitrides

NASA Astrophysics Data System (ADS)

Waskiewicz, Ryan; Mutch, Michael; Lenahan, Patrick; King, Sean

Electrically detected magnetic resonance (EDMR) offers greatly improved sensitivity over conventional electron paramagnetic resonance (EPR) studies in semiconductor/insulator systems; in EDMR measurements, one observes EPR via changes in device currents which are spin-dependent. In our study, we observe EDMR via spin-dependent trap assisted tunneling (SDTAT) via variable range hopping (VRH) through stoichiometric silicon nitride dielectric films. In these films, leakage current effectively changes at resonance. In our study, we have investigated the EDMR response as a function of dielectric electric field and temperature for films of various thicknesses. We believe that these measurements allow us to identify the defects responsible for transport in such these thin films using EDMR and to some extent measure the distances between the defects. The separation between the defects can, at least in principle, be measured using the recently demonstrated half-field EDMR response and we can also count total number of spins responsible for transport through dielectric films. Although we present results only on silicon nitride thin films, we believe that the approach utilized will be widely applicable to other dielectric films in which electronic transport is of interest. This project is sponsored in part by Intel Corporation and in part by the Department of Defense, Defense Threat Reduction Agency under Grant Number HDTRA1-16-0008.

Dynamical instability of a spin spiral in an interacting Fermi gas as a probe of the Stoner transition

NASA Astrophysics Data System (ADS)

Conduit, G. J.; Altman, E.

2010-10-01

We propose an experiment to probe ferromagnetic phenomena in an ultracold Fermi gas, while alleviating the sensitivity to three-body loss and competing many-body instabilities. The system is initialized in a small pitch spin spiral, which becomes unstable in the presence of repulsive interactions. To linear order the exponentially growing collective modes exhibit critical slowing down close to the Stoner transition point. Also, to this order, the dynamics are identical on the paramagnetic and ferromagnetic sides of the transition. However, we show that scattering off the exponentially growing modes qualitatively alters the collective mode structure. The critical slowing down is eliminated and in its place a new unstable branch develops at large wave vectors. Furthermore, long-wavelength instabilities are quenched on the paramagnetic side of the transition. We study the experimental observation of the instabilities, specifically addressing the trapping geometry and how phase-contrast imaging will reveal the emerging domain structure. These probes of the dynamical phenomena could allow experiments to detect the transition point and distinguish between the paramagnetic and ferromagnetic regimes.

Photoinduced formation of reactive oxygen species and electrons from metal oxide-silica nanocomposite: An EPR spin-trapping study

NASA Astrophysics Data System (ADS)

Zhao, Hongxia; Chen, Xiuying; Li, Xintong; Shen, Chen; Qu, Baocheng; Gao, Jingsuo; Chen, Jingwen; Quan, Xie

2017-09-01

Metal oxide nanocomposites with photocatalytic activity have the potential for many applications in environmental remediation and biomedicine. In this study, we investigated the formation and stabilization of electrons/holes from three metal oxide-silica nanocomposites (CuO-SiO2, Fe2O3-SiO2 and ZnO-SiO2) under irradiation by electron paramagnetic resonance (EPR) technology. The characteristic EPR signals with g = 2.00070-2.00105, ΔHp-p = 2.17-2.37 G were determined, which corresponded to lattice-trapped electrons. Moreover, the generation of active species from CuO-SiO2, Fe2O3-SiO2 and ZnO-SiO2 in aqueous solution under irradiation was also systematically studied. The results showed that all the three nanocomposites could generate hydroxyl radical, singlet oxygen and electron. CuO-SiO2 was more effective than Fe2O3-SiO2 and ZnO-SiO2 in producing hydroxyl radical and electrons, while ZnO-SiO2 was the most efficient in generating singlet oxygen. In addition, CuO-SiO2 exhibited most obviously photocatalytic activity toward degradation of bisphenol A, followed by Fe2O3-SiO2 and ZnO-SiO2. These findings will provide vital insights into photocatalytic mechanisms and potentially photoinduced toxicity of metal oxide-silica nanocomposites.

Effects of the Electronic Spin-Orbit Interaction on the Anomalous Asymmetric Scattering of the Spin-Polarized He+ Beam with Paramagnetic Target Materials II. Partial Wave Representation

NASA Astrophysics Data System (ADS)

Sakai, Osamu; Suzuki, Taku T.

2018-05-01

The scattering of an electron-spin-polarized 4He+ beam on paramagnetic materials has an anomalously large asymmetric scattering component (ASC) around 10%, which is 104 times that expected from the spin-orbit coupling for the potential of the target nucleus. The scattering angle (θ) dependence of the ASC has been measured. It changes sign near 90° for some materials (for example, Au and Pt), while it does not change sign for other materials (for example, Pb and Bi). It has been noted that the spin-orbit interaction of electrons on the target in the electron-transfer intermediate state causes the ASC of He nucleus motion, and it has also been predicted that the sign change in the θ dependence occurs when the d electron transfer is dominant. This seems to correspond to the cases of Au and Pt, but not to the cases of Pb and Bi. The previous approach is refined on the basis of the partial wave representation, which can give a more correct estimation of the ASC. It is shown that the sign change appears in the weak-resonance domain in the case of d electron excitation, whereas the sign change disappears in the strong-resonance domain. Our calculated results qualitatively agree with the material dependence of the ASC observed experimentally.

Magnetic resonance force microscopy of paramagnetic electron spins at millikelvin temperatures.

PubMed

Vinante, A; Wijts, G; Usenko, O; Schinkelshoek, L; Oosterkamp, T H

2011-12-06

Magnetic resonance force microscopy (MRFM) is a powerful technique to detect a small number of spins that relies on force detection by an ultrasoft magnetically tipped cantilever and selective magnetic resonance manipulation of the spins. MRFM would greatly benefit from ultralow temperature operation, because of lower thermomechanical noise and increased thermal spin polarization. Here we demonstrate MRFM operation at temperatures as low as 30 mK, thanks to a recently developed superconducting quantum interference device (SQUID)-based cantilever detection technique, which avoids cantilever overheating. In our experiment, we detect dangling bond paramagnetic centres on a silicon surface down to millikelvin temperatures. Fluctuations of such defects are supposedly linked to 1/f magnetic noise and decoherence in SQUIDs, as well as in several superconducting and single spin qubits. We find evidence that spin diffusion has a key role in the low-temperature spin dynamics.

Point defects in crystalline zircon (zirconium silicate), ZrSiO4: electron paramagnetic resonance studies

NASA Astrophysics Data System (ADS)

Tennant, W. C.; Claridge, R. F. C.; Walsby, C. J.; Lees, N. S.

This article outlines the present state of knowledge of paramagnetic defects in crystalline zircon as obtained mainly, but not exclusively, from electron paramagnetic resonance (EPR) studies in crystalline zircon (zirconium silicate, ZrSiO4). The emphasis is on single-crystal studies where, in principle, unambiguous analysis is possible. Firstly, the crystallography of zircon is presented. Secondly, the relationships between available crystal-site symmetries and the symmetries of observed paramagnetic species in zircon, and how these observations lead to unambiguous assignments of point-group symmetries for particular paramagnetic species are detailed. Next, spin-Hamiltonian (SH) analysis is discussed with emphasis on the symmetry relationships that necessarily exist amongst the Laue classes of the crystal sites in zircon, the paramagnetic species occupying those sites and the SH itself. The final sections of the article then survey the results of EPR studies on zircon over the period 1960-2002.

Oxygen deficiency in Ti O2 : Similarities and differences between the Ti self-interstitial and the O vacancy in bulk rutile and anatase

NASA Astrophysics Data System (ADS)

Deák, Peter; Aradi, Bálint; Frauenheim, Thomas

2015-07-01

Ti O2 is an oxygen-deficient, intrinsically n -type material, but it is often debated whether the electrons are donated by oxygen vacancies (VO) or titanium interstitials (T ii) . Investigating this issue is complicated by the fact that rutile can self-trap electrons in intrinsic small polaron states, while bulk anatase cannot. The screened hybrid functional HSE06 was proven to account for this phenomenon and has provided quantitatively correct results for VO in our earlier study. Here, we use it for T ii in both rutile and anatase, allowing full spin and symmetry freedom, to shed light on the similarities and differences to VO. We find that these two defects give rise to very similar fingerprints in electron paramagnetic resonance, infrared absorption, or photoelectron spectra. In weakly reduced rutile, the ground state of both defects is (2 +) , with two electrons in polaronic traps, bound loosely to the defect. Most of the time, only these latter states (crudely resembling a hydrogenic series, with increasing distance from the defect) are likely to be detected. In anatase, both VO and T ii can be expected to be ionized at room temperature (singly and doubly, respectively), and the next vertical ionization energy is similar in the two defects—and very close to the ionization energy of the bound polarons in rutile. Most signals in paramagnetic resonance experiments on rutile must also be related to the polaron states, and, in general, very special conditions have to be fulfilled to detect electrons localized to VO or T ii itself. We show that, in thermal equilibrium, the dominant defect in intrinsic samples is VO, and T ii can be the majority defect only in strongly reduced anatase, or in case of p -type doping.

OPTESIM, a Versatile Toolbox for Numerical Simulation of Electron Spin Echo Envelope Modulation (ESEEM) that Features Hybrid Optimization and Statistical Assessment of Parameters

PubMed Central

Sun, Li; Hernandez-Guzman, Jessica; Warncke, Kurt

2009-01-01

Electron spin echo envelope modulation (ESEEM) is a technique of pulsed-electron paramagnetic resonance (EPR) spectroscopy. The analyis of ESEEM data to extract information about the nuclear and electronic structure of a disordered (powder) paramagnetic system requires accurate and efficient numerical simulations. A single coupled nucleus of known nuclear g value (gN) and spin I=1 can have up to eight adjustable parameters in the nuclear part of the spin Hamiltonian. We have developed OPTESIM, an ESEEM simulation toolbox, for automated numerical simulation of powder two- and three-pulse one-dimensional ESEEM for arbitrary number (N) and type (I, gN) of coupled nuclei, and arbitrary mutual orientations of the hyperfine tensor principal axis systems for N>1. OPTESIM is based in the Matlab environment, and includes the following features: (1) a fast algorithm for translation of the spin Hamiltonian into simulated ESEEM, (2) different optimization methods that can be hybridized to achieve an efficient coarse-to-fine grained search of the parameter space and convergence to a global minimum, (3) statistical analysis of the simulation parameters, which allows the identification of simultaneous confidence regions at specific confidence levels. OPTESIM also includes a geometry-preserving spherical averaging algorithm as default for N>1, and global optimization over multiple experimental conditions, such as the dephasing time ( ) for three-pulse ESEEM, and external magnetic field values. Application examples for simulation of 14N coupling (N=1, N=2) in biological and chemical model paramagnets are included. Automated, optimized simulations by using OPTESIM lead to a convergence on dramatically shorter time scales, relative to manual simulations. PMID:19553148

Characterization of the Solution Structure of Human Serum Albumin Loaded with a Metal Porphyrin and Fatty Acids

PubMed Central

Junk, Matthias J.N.; Spiess, Hans W.; Hinderberger, Dariush

2011-01-01

The structure of human serum albumin loaded with a metal porphyrin and fatty acids in solution is characterized by orientation-selective double electron-electron resonance (DEER) spectroscopy. Human serum albumin, spin-labeled fatty acids, and Cu(II) protoporphyrin IX—a hemin analog—form a fully self-assembled system that allows obtaining distances and mutual orientations between the paramagnetic guest molecules. We report a simplified analysis for the orientation-selective DEER data which can be applied when the orientation selection of one spin in the spin pair dominates the orientation selection of the other spin. The dipolar spectra reveal a dominant distance of 3.85 nm and a dominant orientation of the spin-spin vectors between Cu(II) protoporphyrin IX and 16-doxyl stearic acid, the electron paramagnetic resonance reporter group of the latter being located near the entry points to the fatty acid binding sites. This observation is in contrast to crystallographic data that suggest an asymmetric distribution of the entry points in the protein and hence the occurrence of various distances. In conjunction with the findings of a recent DEER study, the obtained data are indicative of a symmetric distribution of the binding site entries on the protein's surface. The overall anisotropic shape of the protein is reflected by one spin-spin vector orientation dominating the DEER data. PMID:21539799

Muonium as a model for interstitial hydrogen in the semiconducting and semimetallic elements

NASA Astrophysics Data System (ADS)

Cox, S. F. J.

2009-11-01

Although the interstitial hydrogen atom would seem to be one of the simplest defect centres in any lattice, its solid state chemistry is in fact unknown in many materials, not least amongst the elements. In semiconductors, the realization that hydrogen can profoundly influence electronic properties even as a trace impurity has prompted its study by all available means—but still only in the functionally important or potentially important materials—for the elements, Si, Ge and diamond. Even here, it was not studies of hydrogen itself but of its pseudo-isotope, muonium, that first provided the much needed microscopic pictures of crystallographic site and local electronic structure—now comprehensively confirmed by ab initio computation and such data as exists for monatomic, interstitial hydrogen centres in Si. Muonium can be formed in a variety of neutral paramagnetic states when positive muons are implanted into non-metals. The simple trapped atom is commonly only metastable. It coexists with or reacts to give defect centres with the unpaired electron in somewhat more extended orbitals. Indications of complete delocalization into effective mass states are discussed for B, α-Sn, Bi and even Ge, but otherwise all the muonium centres seen in the elemental semiconductors are deep and relatively compact. These are revealed, distinguished and characterized by μSR spectroscopy—muon spin rotation and resonance informing on sites and spin-density distributions, muon spin relaxation on motional dynamics and charge-state transitions. This Report documents the progress of μSR studies for all the semiconductors and semimetals of the p-block elements, Groups III-VI of the Periodic Table. The striking spectra and originally unanticipated results for Group IV are for the most part well known but deserve summarizing and updating; the sheer diversity of muonium states found is still remarkable, especially in carbon allotropes. The interplay of crystallographic site and charge state in Si and Ge at high temperatures, or under illumination, reflects the capture and loss of charge carriers that should model the electrical activity of monatomic hydrogen but still challenges theoretical descriptions. Spin-flip scattering of conduction electrons by the paramagnetic centres is revealed in heavily doped n-type material, as well as some modification of the local electronic structures. The corresponding spectroscopy for the solid elements of Groups III, V and VI is rather less well known and is reviewed here for the first time; a good deal of previously unpublished data is also included. Theoretical expectations and computational modelling are sparse, here. Recent results for B suggest a relatively shallow centre with molecular character; P and As show deeper quasi-atomic states, but still with substantial overlap of spin density onto surrounding host atoms. Particular attention is paid to the chalcogens. Muonium centres in Te show charge-state transitions already around room temperature; the identification of those in S and Se has been complicated by unusual spin dynamics of a different character, here attributed to spin-orbit coupling and interstitial reorientation. In the metals and semimetals, muonium is not formed as a paramagnetic centre. Here the implanted muons mimic interstital protons and interest shifts to a variety of other topics, including aspects of charge screening (α-Sn, Sb, Bi), site preference and quantum mobility (Al, β-Sn, Pb). The post-transition metals receive only a brief mention, by way of contrast with the nonmetals. Systematic studies of local susceptibility via measurements of muon Knight shifts extends in favourable cases to revealing the elusive high-field Condon domains (Al, Sn, Pb, Bi). Some new information is available on the superconducting phases. Appendices include a derivation of the spin Hamiltonian for paramagnetic muonium centres or molecular radicals having varying admixtures of orbital angular momentum, including the extreme case of orbital degeneracy, and examine the consequences of significant spin-orbit coupling for μSR spectroscopy and muon spin relaxation. This is the framework for the tentative assignments made here for the muonium defect centres formed in sulphur and selenium, namely diatomic species resembling the chalcogen monohydrides. Equally, it provides guidelines for eventual solid-state detection of OMu—the elusive muoniated hydroxyl radical.

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

PubMed

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

2016-08-15

Reactive oxygen and nitrogen species (ROS and RNS) play crucial roles in triggering, mediating and regulating physiological and pathophysiological signal transduction pathways within the cell. Within the cell, ROS efflux is firmly controlled both spatially and temporally, making the study of ROS dynamics a challenging task. Different approaches have been developed for ROS assessment; however, many of these assays are not capable of direct identification or determination of subcellular localization of different ROS. Here we highlight electron paramagnetic resonance (EPR) spectroscopy as a powerful technique that is uniquely capable of addressing questions on ROS dynamics in different biological specimens and cellular compartments. Due to their critical importance in muscle functions and dysfunction, we discuss in some detail spin trapping of various ROS and focus on EPR detection of nitric oxide before highlighting how EPR can be utilized to probe biophysical characteristics of the environment surrounding a given stable radical. Despite the demonstrated ability of EPR spectroscopy to provide unique information on the identity, quantity, dynamics and environment of radical species, its applications in the field of muscle physiology, fatiguing and ageing are disproportionately infrequent. While reviewing the limited examples of successful EPR applications in muscle biology we conclude that the field would greatly benefit from more studies exploring ROS sources and kinetics by spin trapping, protein dynamics by site-directed spin labelling, and membrane dynamics and global redox changes by spin probing EPR approaches. © 2016 The Authors. The Journal of Physiology © 2016 The Physiological Society.

High-frequency EPR of surface impurities on nanodiamond

NASA Astrophysics Data System (ADS)

Peng, Zaili; Stepanov, Viktor; Takahashi, Susumu

Diamond is a fascinating material, hosting nitrogen-vacancy (NV) defect centers with unique magnetic and optical properties. There have been many reports that suggest the existence of paramagnetic impurities near surface of various kinds of diamonds. Electron paramagnetic resonance (EPR) investigation of mechanically crushed nanodiamonds (NDs) as well as detonation NDs revealed g 2 like signals that are attributed to structural defects and dangling bonds near the diamond surface. In this presentation, we investigate paramagnetic impurities in various sizes of NDs using high-frequency (HF) continuous wave (cw) and pulsed EPR spectroscopy. Strong size dependence on the linewidth of HF cw EPR spectra reveals the existence of paramagnetic impurities in the vicinity of the diamond surface. We also study the size dependence of the spin-lattice and spin-spin relaxation times (T1 and T2) of single substitutional nitrogen defects in NDs Significant deviations from the temperature dependence of the phonon-assisted T1 process were observed in the ND samples, and were attributed to the contribution from the surface impurities. This work was supported by the Searle Scholars Program and the National Science Foundation (DMR-1508661 and CHE-1611134).

EPR oximetry in three spatial dimensions using sparse spin distribution

NASA Astrophysics Data System (ADS)

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

2008-08-01

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

Factors Determining the Oxygen Permeability of Biological Membranes: Oxygen Transport Across Eye Lens Fiber-Cell Plasma Membranes.

PubMed

Subczynski, Witold Karol; Widomska, Justyna; Mainali, Laxman

2017-01-01

Electron paramagnetic resonance (EPR) spin-label oximetry allows the oxygen permeability coefficient to be evaluated across homogeneous lipid bilayer membranes and, in some cases, across coexisting membrane domains without their physical separation. The most pronounced effect on oxygen permeability is observed for cholesterol, which additionally induces the formation of membrane domains. In intact biological membranes, integral proteins induce the formation of boundary and trapped lipid domains with a low oxygen permeability. The effective oxygen permeability coefficient across the intact biological membrane is affected not only by the oxygen permeability coefficients evaluated for each lipid domain but also by the surface area occupied by these domains in the membrane. All these factors observed in fiber cell plasma membranes of clear human eye lenses are reviewed here.

Recycling of the High Valence States of Heme Proteins by Cysteine Residues of Thimet-Oligopeptidase

PubMed Central

Ferreira, Juliana C.; Icimoto, Marcelo Y.; Marcondes, Marcelo F.; Oliveira, Vitor; Nascimento, Otaciro R.; Nantes, Iseli L.

2013-01-01

The peptidolytic enzyme THIMET-oligopeptidase (TOP) is able to act as a reducing agent in the peroxidase cycle of myoglobin (Mb) and horseradish peroxidase (HRP). The TOP-promoted recycling of the high valence states of the peroxidases to the respective resting form was accompanied by a significant decrease in the thiol content of the peptidolytic enzyme. EPR (electron paramagnetic resonance) analysis using DBNBS spin trapping revealed that TOP also prevented the formation of tryptophanyl radical in Mb challenged by H2O2. The oxidation of TOP thiol groups by peroxidases did not promote the inactivating oligomerization observed in the oxidation promoted by the enzyme aging. These findings are discussed towards a possible occurrence of these reactions in cells. PMID:24223886

Mechanically detected terahertz electron spin resonance using SOI-based thin piezoresistive microcantilevers

NASA Astrophysics Data System (ADS)

Ohmichi, Eiji; Miki, Toshihiro; Horie, Hidekazu; Okamoto, Tsubasa; Takahashi, Hideyuki; Higashi, Yoshinori; Itoh, Shoichi; Ohta, Hitoshi

2018-02-01

We developed piezoresistive microcantilevers for mechanically detected electron spin resonance (ESR) in the millimeter-wave region. In this article, fabrication process and device characterization of our self-sensing microcantilevers are presented. High-frequency ESR measurements of a microcrystal of paramagnetic sample is also demonstrated at multiple frequencies up to 160 GHz at liquid helium temperature. Our fabrication is based on relatively simplified processes with silicon-on-insulator (SOI) wafers and spin-on diffusion doping, thus enabling cost-effective and time-saving cantilever fabrication.

Electron spin relaxation enhancement measurements of interspin distances in human, porcine, and Rhodobacter electron transfer flavoprotein ubiquinone oxidoreductase (ETF QO)

NASA Astrophysics Data System (ADS)

Fielding, Alistair J.; Usselman, Robert J.; Watmough, Nicholas; Simkovic, Martin; Frerman, Frank E.; Eaton, Gareth R.; Eaton, Sandra S.

2008-02-01

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is a membrane-bound electron transfer protein that links primary flavoprotein dehydrogenases with the main respiratory chain. Human, porcine, and Rhodobacter sphaeroides ETF-QO each contain a single [4Fe-4S] 2+,1+ cluster and one equivalent of FAD, which are diamagnetic in the isolated enzyme and become paramagnetic on reduction with the enzymatic electron donor or with dithionite. The anionic flavin semiquinone can be reduced further to diamagnetic hydroquinone. The redox potentials for the three redox couples are so similar that it is not possible to poise the proteins in a state where both the [4Fe-4S] + cluster and the flavoquinone are fully in the paramagnetic form. Inversion recovery was used to measure the electron spin-lattice relaxation rates for the [4Fe-4S] + between 8 and 18 K and for semiquinone between 25 and 65 K. At higher temperatures the spin-lattice relaxation rates for the [4Fe-4S] + were calculated from the temperature-dependent contributions to the continuous wave linewidths. Although mixtures of the redox states are present, it was possible to analyze the enhancement of the electron spin relaxation of the FAD semiquinone signal due to dipolar interaction with the more rapidly relaxing [4Fe-4S] + and obtain point-dipole interspin distances of 18.6 ± 1 Å for the three proteins. The point-dipole distances are within experimental uncertainty of the value calculated based on the crystal structure of porcine ETF-QO when spin delocalization is taken into account. The results demonstrate that electron spin relaxation enhancement can be used to measure distances in redox poised proteins even when several redox states are present.

Electron Spin Relaxation Enhancement Measurements of Interspin Distances in Human, Porcine, and Rhodobacter Electron Transfer Flavoprotein-ubiquinone Oxidoreductase (ETF-QO)

PubMed Central

Fielding, Alistair J.; Usselman, Robert J.; Watmough, Nicholas; Simkovic, Martin; Frerman, Frank E.; Eaton, Gareth R.; Eaton, Sandra S.

2008-01-01

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is a membrane-bound electron transfer protein that links primary flavoprotein dehydrogenases with the main respiratory chain. Human, porcine, and Rhodobacter sphaeroides ETF-QO each contain a single [4Fe-4S]2+,1+ cluster and one equivalent of FAD, which are diamagnetic in the isolated enzyme and become paramagnetic on reduction with the enzymatic electron donor or with dithionite. The anionic flavin semiquinone can be reduced further to diamagnetic hydroquinone. The redox potentials for the three redox couples are so similar that it is not possible to poise the proteins in a state where both the [4Fe-4S]+ cluster and the flavoquinone are fully in the paramagnetic form. Inversion recovery was used to measure the electron spin-lattice relaxation rates for the [4Fe-4S]+ between 8 and 18 K and for semiquinone between 25 and 65 K. At higher temperatures the spin-lattice relaxation rates for the [4Fe-4S]+ were calculated from the temperature-dependent contributions to the continuous wave linewidths. Although mixtures of the redox states are present, it was possible to analyze the enhancement of the electron spin relaxation of the FAD semiquinone signal due to dipolar interaction with the more rapidly relaxing [4Fe-4S]+ and obtain point dipole interspin distances of 18.6 ± 1 Å for the three proteins. The point-dipole distances are within experimental uncertainty of the value calculated based on the crystal structure of porcine ETF-QO when spin delocalization is taken into account. The results demonstrate that electron spin relaxation enhancement can be used to measure distances in redox poised proteins even when several redox states are present. PMID:18037314

Electron spin relaxation enhancement measurements of interspin distances in human, porcine, and Rhodobacter electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO).

PubMed

Fielding, Alistair J; Usselman, Robert J; Watmough, Nicholas; Simkovic, Martin; Frerman, Frank E; Eaton, Gareth R; Eaton, Sandra S

2008-02-01

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is a membrane-bound electron transfer protein that links primary flavoprotein dehydrogenases with the main respiratory chain. Human, porcine, and Rhodobacter sphaeroides ETF-QO each contain a single [4Fe-4S](2+,1+) cluster and one equivalent of FAD, which are diamagnetic in the isolated enzyme and become paramagnetic on reduction with the enzymatic electron donor or with dithionite. The anionic flavin semiquinone can be reduced further to diamagnetic hydroquinone. The redox potentials for the three redox couples are so similar that it is not possible to poise the proteins in a state where both the [4Fe-4S](+) cluster and the flavoquinone are fully in the paramagnetic form. Inversion recovery was used to measure the electron spin-lattice relaxation rates for the [4Fe-4S](+) between 8 and 18K and for semiquinone between 25 and 65K. At higher temperatures the spin-lattice relaxation rates for the [4Fe-4S](+) were calculated from the temperature-dependent contributions to the continuous wave linewidths. Although mixtures of the redox states are present, it was possible to analyze the enhancement of the electron spin relaxation of the FAD semiquinone signal due to dipolar interaction with the more rapidly relaxing [4Fe-4S](+) and obtain point-dipole interspin distances of 18.6+/-1A for the three proteins. The point-dipole distances are within experimental uncertainty of the value calculated based on the crystal structure of porcine ETF-QO when spin delocalization is taken into account. The results demonstrate that electron spin relaxation enhancement can be used to measure distances in redox poised proteins even when several redox states are present.

Hydride Conformers of the Nitrogenase FeMo-cofactor Two-Electron Reduced State E2(2H), Assigned Using Cryogenic Intra Electron Paramagnetic Resonance Cavity Photolysis.

PubMed

Lukoyanov, Dmitriy A; Khadka, Nimesh; Yang, Zhi-Yong; Dean, Dennis R; Seefeldt, Lance C; Hoffman, Brian M

2018-03-24

Early studies in which nitrogenase was freeze-trapped during enzymatic turnover revealed the presence of high-spin ( S = 3 / 2 ) electron paramagnetic resonance (EPR) signals from the active-site FeMo-cofactor (FeMo-co) in electron-reduced intermediates of the MoFe protein. Historically denoted as 1b and 1c, each of the signals is describable as a fictitious spin system, S' = 1 / 2 , with anisotropic g' tensor, 1b with g' = [4.21, 3.76, ?] and 1c with g' = [4.69, ∼3.20, ?]. A clear discrepancy between the magnetic properties of 1b and 1c and the kinetic analysis of their appearance during pre-steady-state turnover left their identities in doubt, however. We subsequently associated 1b with the state having accumulated 2[e - /H + ], denoted as E 2 (2H), and suggested that the reducing equivalents are stored on the catalytic FeMo-co cluster as an iron hydride, likely an [Fe-H-Fe] hydride bridge. Intra-EPR cavity photolysis (450 nm; temperature-independent from 4 to 12 K) of the E 2 (2H)/1b state now corroborates the identification of this state as storing two reducing equivalents as a hydride. Photolysis converts E 2 (2H)/1b to a state with the same EPR spectrum, and thus the same cofactor structure as pre-steady-state turnover 1c, but with a different active-site environment. Upon annealing of the photogenerated state at temperature T = 145 K, it relaxes back to E 2 (2H)/1b. This implies that the 1c signal comes from an E 2 (2H) hydride isomer of E 2 (2H)/1b that stores its two reducing equivalents either as a hydride bridge between a different pair of iron atoms or an Fe-H terminal hydride.

Direct Identification of Dilute Surface Spins on Al2 O3 : Origin of Flux Noise in Quantum Circuits

NASA Astrophysics Data System (ADS)

de Graaf, S. E.; Adamyan, A. A.; Lindström, T.; Erts, D.; Kubatkin, S. E.; Tzalenchuk, A. Ya.; Danilov, A. V.

2017-02-01

An on-chip electron spin resonance technique is applied to reveal the nature and origin of surface spins on Al2 O3 . We measure a spin density of 2.2 ×1 017 spins/m2 , attributed to physisorbed atomic hydrogen and S =1 /2 electron spin states on the surface. This is direct evidence for the nature of spins responsible for flux noise in quantum circuits, which has been an issue of interest for several decades. Our findings open up a new approach to the identification and controlled reduction of paramagnetic sources of noise and decoherence in superconducting quantum devices.

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

^17O NMR Study of Sr_2CuO_2Cl_2, a Single-Layer Parent Compound of a High Tc Superconductor

NASA Astrophysics Data System (ADS)

Thurber, Kent; Hunt, Allen; Imai, Takashi; Chou, Fang-Cheng; Lee, Young

1997-03-01

We report NMR measurements of the ^17O nuclear spin-lattice relaxation rate 1/T_1, and the ^17O Knight shift of Sr_2CuO_2Cl2 (TN = 257 K) in the paramagnetic state from the Néel temperature up to 700 K. This establishes, for the first time, the temperature and frequency dependence of ^17O NMR in the paramagnetic state of a clean, single-layer, undoped parent compound of a high Tc superconductor. The ^17O NMR results test the nature of elementary spin excitations around q = 0 and give insight into the spin wave damping, Γ. The observation, ^17 1/T1 ~ a T^3 [ 1 + O(T/J) ], agrees semi-quantitatively with theoretical predictions based on spin waves in the spin S=1/2 2D Heisenberg model. electronically.

Superlattice Structures, Electronic Properties, and Spin Dynamics of the Partially Cu-Extracted Phase for the Composite Crystal System CuxV4O11

NASA Astrophysics Data System (ADS)

Onoda, Masashige; Tamura, Asato

2017-02-01

The crystal structures, electronic properties, and spin dynamics of CuxV4O11 with 1.2 ≤ x < 2, classified as the partially Cu-extracted phase for the composite crystal system, are explored through measurements of x-ray four-circle diffraction, electrochemistry, electrical resistivity, thermoelectric power, magnetization, and electron paramagnetic resonance. This system has superlattice structures mainly ascribed to the partial ordering of Cu ions. Cu1.78V4O11 is triclinic with space group Pbar{1} and the double supercell of the V4O11 substructure of the composite crystal. The significantly Cu-extracted crystal Cu1.40V4O11 has a quadruple supercell with space group P1. The electron transport for V ions is nonmetallic owing to the polaronic nature and/or phonon softening and to the random potential of Cu ions. The Curie-Weiss-type paramagnetism basically originates from the Cu2+ chain coordinated octahedrally, and the EPR relaxation at low temperatures is understood through the exchange mechanism for the dipole-dipole and anisotropic exchange interactions. The near absence of paramagnetic behaviors of V4+ ions might be due to the spin-singlet ladder model or alternating-exchange chain model depending on the superlattice structure and valence distribution. The electrochemical performance of Li rechargeable batteries using this superlattice system is about 300 A h kg-1 at voltages above 2 V.

Suppression of Raman electron spin relaxation of radicals in crystals. Comparison of Cu2+ and free radical relaxation in triglycine sulfate and Tutton salt single crystals.

PubMed

Hoffmann, S K; Goslar, J; Lijewski, S

2011-08-31

Electron spin-lattice relaxation was measured by the electron spin echo method in a broad temperature range above 4.2 K for Cu(2+) ions and free radicals produced by ionizing radiation in triglycine sulfate (TGS) and Tutton salt (NH4)(2)Zn(SO4)2 ⋅ 6H2O crystals. Localization of the paramagnetic centres in the crystal unit cells was determined from continuous wave electron paramagnetic resonance spectra. Various spin relaxation processes and mechanisms are outlined. Cu(2+) ions relax fast via two-phonon Raman processes in both crystals involving the whole phonon spectrum of the host lattice. This relaxation is slightly slower for TGS where Cu(2+) ions are in the interstitial position. The ordinary Raman processes do not contribute to the radical relaxation which relaxes via the local phonon mode. The local mode lies within the acoustic phonon band for radicals in TGS but within the optical phonon range in (NH4)(2)Zn(SO4)2 ⋅ 6H2O. In the latter the cross-relaxation was considered. A lack of phonons around the radical molecules suggested a local crystal amorphisation produced by x- or γ-rays.

Nuclear spin cooling by electric dipole spin resonance and coherent population trapping

NASA Astrophysics Data System (ADS)

Li, Ai-Xian; Duan, Su-Qing; Zhang, Wei

2017-09-01

Nuclear spin fluctuation suppression is a key issue in preserving electron coherence for quantum information/computation. We propose an efficient way of nuclear spin cooling in semiconductor quantum dots (QDs) by the coherent population trapping (CPT) and the electric dipole spin resonance (EDSR) induced by optical fields and ac electric fields. The EDSR can enhance the spin flip-flop rate and may bring out bistability under certain conditions. By tuning the optical fields, we can avoid the EDSR induced bistability and obtain highly polarized nuclear spin state, which results in long electron coherence time. With the help of CPT and EDSR, an enhancement of 1500 times of the electron coherence time can been obtained after a 500 ns preparation time.

Inter-spin distance determination using L-band (1-2 GHz) non-adiabatic rapid sweep electron paramagnetic resonance (NARS EPR)

PubMed Central

Kittell, Aaron W.; Hustedt, Eric J.; Hyde, James S.

2014-01-01

Site-directed spin-labeling electron paramagnetic resonance (SDSL EPR) provides insight into the local structure and motion of a spin probe strategically attached to a molecule. When a second spin is introduced to the system, macromolecular information can be obtained through measurement of inter-spin distances either by continuous wave (CW) or pulsed electron double resonance (ELDOR) techniques. If both methodologies are considered, inter-spin distances of 8 to 80 Å can be experimentally determined. However, there exists a region at the upper limit of the conventional X-band (9.5 GHz) CW technique and the lower limit of the four-pulse double electron-electron resonance (DEER) experiment where neither method is particularly reliable. The work presented here utilizes L-band (1.9 GHz) in combination with non-adiabatic rapid sweep (NARS) EPR to address this opportunity by increasing the upper limit of the CW technique. Because L-band linewidths are three to seven times narrower than those at X-band, dipolar broadenings that are small relative to the X-band inhomogeneous linewidth become observable, but the signal loss due to the frequency dependence of the Boltzmann factor, has made L-band especially challenging. NARS has been shown to increase sensitivity by a factor of five, and overcomes much of this loss, making L-band distance determination more feasible [1]. Two different systems are presented and distances of 18–30 Å have been experimentally determined at physiologically relevant temperatures. Measurements are in excellent agreement with a helical model and values determined by DEER. PMID:22750251

EPR-Spin Trapping and Flow Cytometric Studies of Free Radicals Generated Using Cold Atmospheric Argon Plasma and X-Ray Irradiation in Aqueous Solutions and Intracellular Milieu.

PubMed

Uchiyama, Hidefumi; Zhao, Qing-Li; Hassan, Mariame Ali; Andocs, Gabor; Nojima, Nobuyuki; Takeda, Keigo; Ishikawa, Kenji; Hori, Masaru; Kondo, Takashi

2015-01-01

Electron paramagnetic resonance (EPR)-spin trapping and flow cytometry were used to identify free radicals generated using argon-cold atmospheric plasma (Ar-CAP) in aqueous solutions and intracellularly in comparison with those generated by X-irradiation. Ar-CAP was generated using a high-voltage power supply unit with low-frequency excitation. The characteristics of Ar-CAP were estimated by vacuum UV absorption and emission spectra measurements. Hydroxyl (·OH) radicals and hydrogen (H) atoms in aqueous solutions were identified with the spin traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO), 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (M4PO), and phenyl N-t-butylnitrone (PBN). The occurrence of Ar-CAP-induced pyrolysis was evaluated using the spin trap 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS) in aqueous solutions of DNA constituents, sodium acetate, and L-alanine. Human lymphoma U937 cells were used to study intracellular oxidative stress using five fluorescent probes with different affinities to a number of reactive species. The analysis and quantification of EPR spectra revealed the formation of enormous amounts of ·OH radicals using Ar-CAP compared with that by X-irradiation. Very small amounts of H atoms were detected whereas nitric oxide was not found. The formation of ·OH radicals depended on the type of rare gas used and the yield correlated inversely with ionization energy in the order of krypton > argon = neon > helium. No pyrolysis radicals were detected in aqueous solutions exposed to Ar-CAP. Intracellularly, ·OH, H2O2, which is the recombination product of ·OH, and OCl- were the most likely formed reactive oxygen species after exposure to Ar-CAP. Intracellularly, there was no practical evidence for the formation of NO whereas very small amounts of superoxides were formed. Despite the superiority of Ar-CAP in forming ·OH radicals, the exposure to X-rays proved more lethal. The mechanism of free radical formation in aqueous solutions and an intracellular milieu is discussed.

EPR-Spin Trapping and Flow Cytometric Studies of Free Radicals Generated Using Cold Atmospheric Argon Plasma and X-Ray Irradiation in Aqueous Solutions and Intracellular Milieu

PubMed Central

Uchiyama, Hidefumi; Zhao, Qing-Li; Hassan, Mariame Ali; Andocs, Gabor; Nojima, Nobuyuki; Takeda, Keigo; Ishikawa, Kenji; Hori, Masaru; Kondo, Takashi

2015-01-01

Electron paramagnetic resonance (EPR)-spin trapping and flow cytometry were used to identify free radicals generated using argon-cold atmospheric plasma (Ar-CAP) in aqueous solutions and intracellularly in comparison with those generated by X-irradiation. Ar-CAP was generated using a high-voltage power supply unit with low-frequency excitation. The characteristics of Ar-CAP were estimated by vacuum UV absorption and emission spectra measurements. Hydroxyl (·OH) radicals and hydrogen (H) atoms in aqueous solutions were identified with the spin traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO), 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (M4PO), and phenyl N-t-butylnitrone (PBN). The occurrence of Ar-CAP-induced pyrolysis was evaluated using the spin trap 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS) in aqueous solutions of DNA constituents, sodium acetate, and L-alanine. Human lymphoma U937 cells were used to study intracellular oxidative stress using five fluorescent probes with different affinities to a number of reactive species. The analysis and quantification of EPR spectra revealed the formation of enormous amounts of ·OH radicals using Ar-CAP compared with that by X-irradiation. Very small amounts of H atoms were detected whereas nitric oxide was not found. The formation of ·OH radicals depended on the type of rare gas used and the yield correlated inversely with ionization energy in the order of krypton > argon = neon > helium. No pyrolysis radicals were detected in aqueous solutions exposed to Ar-CAP. Intracellularly, ·OH, H2O2, which is the recombination product of ·OH, and OCl- were the most likely formed reactive oxygen species after exposure to Ar-CAP. Intracellularly, there was no practical evidence for the formation of NO whereas very small amounts of superoxides were formed. Despite the superiority of Ar-CAP in forming ·OH radicals, the exposure to X-rays proved more lethal. The mechanism of free radical formation in aqueous solutions and an intracellular milieu is discussed. PMID:26318000

ESR lineshape and {sup 1}H spin-lattice relaxation dispersion in propylene glycol solutions of nitroxide radicals – Joint analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kruk, D., E-mail: danuta.kruk@matman.uwm.edu.pl; Hoffmann, S. K.; Goslar, J.

2013-12-28

Electron Spin Resonance (ESR) spectroscopy and Nuclear Magnetic Relaxation Dispersion (NMRD) experiments are reported for propylene glycol solutions of the nitroxide radical: 4-oxo-TEMPO-d{sub 16} containing {sup 15}N and {sup 14}N isotopes. The NMRD experiments refer to {sup 1}H spin-lattice relaxation measurements in a broad frequency range (10 kHz–20 MHz). A joint analysis of the ESR and NMRD data is performed. The ESR lineshapes give access to the nitrogen hyperfine tensor components and the rotational correlation time of the paramagnetic molecule. The NMRD data are interpreted in terms of the theory of paramagnetic relaxation enhancement in solutions of nitroxide radicals, recentlymore » presented by Kruk et al. [J. Chem. Phys. 138, 124506 (2013)]. The theory includes the effect of the electron spin relaxation on the {sup 1}H relaxation of the solvent. The {sup 1}H relaxation is caused by dipole-dipole interactions between the electron spin of the radical and the proton spins of the solvent molecules. These interactions are modulated by three dynamic processes: relative translational dynamics of the involved molecules, molecular rotation, and electron spin relaxation. The sensitivity to rotation originates from the non-central positions of the interacting spin in the molecules. The electronic relaxation is assumed to stem from the electron spin–nitrogen spin hyperfine coupling, modulated by rotation of the radical molecule. For the interpretation of the NMRD data, we use the nitrogen hyperfine coupling tensor obtained from ESR and fit the other relevant parameters. The consistency of the unified analysis of ESR and NMRD, evaluated by the agreement between the rotational correlation times obtained from ESR and NMRD, respectively, and the agreement of the translation diffusion coefficients with literature values obtained for pure propylene glycol, is demonstrated to be satisfactory.« less

Properties of Fiber Cell Plasma Membranes Isolated from the Cortex and Nucleus of the Porcine Eye Lens

PubMed Central

Mainali, Laxman; Raguz, Marija; O’Brien, William J.; Subczynski, Witold K.

2012-01-01

The organization and physical properties of the lipid bilayer portion of intact cortical and nuclear fiber cell plasma membranes isolated from the eyes lenses of two-year-old pigs were studied using electron paramagnetic resonance (EPR) spin-labeling. Membrane fluidity, hydrophobicity, and the oxygen transport parameter (OTP) were assessed from the EPR spectra of precisely positioned spin labels. Intact cortical and nuclear membranes, which include membrane proteins, were found to contain three distinct lipid environments. These lipid environments were termed the bulk lipid domain, boundary lipid domain, and trapped lipid domain (lipids in protein aggregates). The amount of boundary and trapped lipids was greater in intact nuclear membranes than in cortical membranes. The properties of intact membranes were compared with the organization and properties of lens lipid membranes made of the total lipid extracts from the lens cortex or nucleus. In cortical lens lipid membranes, only one homogenous environment was detected, which was designated as a bulk lipid domain (phospholipid bilayer saturated with cholesterol). Lens lipid membranes prepared from the lens nucleus possessed two domains, assigned as a bulk lipid domain and a cholesterol bilayer domain (CBD). In intact nuclear membranes, it was difficult to discriminate the CBD, which was clearly detected in nuclear lens lipid membranes because the OTP measured in the CBD is the same as in the domain formed by trapped lipids. The two domains unique to intact membranes—namely, the domain formed by boundary lipids and the domain formed by trapped lipids—were most likely formed due to the presence of membrane proteins. It is concluded that formation of rigid and practically impermeable domains is enhanced in the lens nucleus, indicating changes in membrane composition that may help to maintain low oxygen concentration in this lens region. PMID:22326289

Cryogen-free superconducting magnet system for multifrequency electron paramagnetic resonance up to 12.1 T

NASA Astrophysics Data System (ADS)

Smirnov, Alex I.; Smirnova, Tatyana I.; MacArthur, Ryan L.; Good, Jeremy A.; Hall, Renny

2006-03-01

Multifrequency and high field/high frequency (HF) electron paramagnetic resonance (EPR) is a powerful spectroscopy for studying paramagnetic spin systems ranging from organic-free radicals to catalytic paramagnetic metal ion centers in metalloproteins. Typically, HF EPR experiments are carried out at resonant frequencies ν =95-300GHz and this requires magnetic fields of 3.4-10.7T for electronic spins with g ≈2.0. Such fields could be easily achieved with superconducting magnets, but, unlike NMR, these magnets cannot operate in a persistent mode in order to satisfy a wide range of resonant fields required by the experiment. Operating and maintaining conventional passively cooled superconducting magnets in EPR laboratories require frequent transfer of cryogens by trained personnel. Here we describe and characterize a versatile cryogen-free magnet system for HF EPR at magnetic fields up to 12.1T that is suitable for ramping the magnetic field over the entire range, precision scans around the target field, and/or holding the field at the target value. We also demonstrate that in a nonpersistent mode of operation the magnetic field can be stabilized to better than 0.3ppm/h over 15h period by employing a transducer-controlled power supply. Such stability is sufficient for many HF EPR experiments. An important feature of the system is that it is virtually maintenance-free because it is based on a cryogen-free technology and therefore does not require any liquid cryogens (liquid helium or nitrogen) for operation. We believe that actively cooled superconducting magnets are ideally suited for a wide range of HF EPR experiments including studies of spin-labeled nucleic acids and proteins, single-molecule magnets, and metalloproteins.

Computing distance distributions from dipolar evolution data with overtones: RIDME spectroscopy with Gd(iii)-based spin labels.

PubMed

Keller, Katharina; Mertens, Valerie; Qi, Mian; Nalepa, Anna I; Godt, Adelheid; Savitsky, Anton; Jeschke, Gunnar; Yulikov, Maxim

2017-07-21

Extraction of distance distributions between high-spin paramagnetic centers from relaxation induced dipolar modulation enhancement (RIDME) data is affected by the presence of overtones of dipolar frequencies. As previously proposed, we account for these overtones by using a modified kernel function in Tikhonov regularization analysis. This paper analyzes the performance of such an approach on a series of model compounds with the Gd(iii)-PyMTA complex serving as paramagnetic high-spin label. We describe the calibration of the overtone coefficients for the RIDME kernel, demonstrate the accuracy of distance distributions obtained with this approach, and show that for our series of Gd-rulers RIDME technique provides more accurate distance distributions than Gd(iii)-Gd(iii) double electron-electron resonance (DEER). The analysis of RIDME data including harmonic overtones can be performed using the MATLAB-based program OvertoneAnalysis, which is available as open-source software from the web page of ETH Zurich. This approach opens a perspective for the routine use of the RIDME technique with high-spin labels in structural biology and structural studies of other soft matter.

Microstrip resonators for electron paramagnetic resonance experiments

NASA Astrophysics Data System (ADS)

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

2009-07-01

In this article we evaluate the performance of an electron paramagnetic resonance (EPR) setup using a microstrip resonator (MR). The design and characterization of the resonator are described and parameters of importance to EPR and spin manipulation are examined, including cavity quality factor, filling factor, and microwave magnetic field in the sample region. Simulated microwave electric and magnetic field distributions in the resonator are also presented and compared with qualitative measurements of the field distribution obtained by a perturbation technique. Based on EPR experiments carried out with a standard marker at room temperature and a MR resonating at 8.17 GHz, the minimum detectable number of spins was found to be 5×1010 spins/GHz1/2 despite the low MR unloaded quality factor Q0=60. The functionality of the EPR setup was further evaluated at low temperature, where the spin resonance of Cr dopants present in a GaAs wafer was detected at 2.3 K. The design and characterization of a more versatile MR targeting an improved EPR sensitivity and featuring an integrated biasing circuit for the study of samples that require an electrical contact are also discussed.

A Ku band pulsed electron paramagnetic resonance spectrometer using an arbitrary waveform generator for quantum control experiments at millikelvin temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yap, Yung Szen, E-mail: yungszen@utm.my; Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor; Tabuchi, Yutaka

2015-06-15

We present a 17 GHz (Ku band) arbitrary waveform pulsed electron paramagnetic resonance spectrometer for experiments down to millikelvin temperatures. The spectrometer is located at room temperature, while the resonator is placed either in a room temperature magnet or inside a cryogen-free dilution refrigerator; the operating temperature range of the dilution unit is from ca. 10 mK to 8 K. This combination provides the opportunity to perform quantum control experiments on electron spins in the pure-state regime. At 0.6 T, spin echo experiments were carried out using γ-irradiated quartz glass from 1 K to 12.3 mK. With decreasing temperatures, wemore » observed an increase in spin echo signal intensities due to increasing spin polarizations, in accordance with theoretical predictions. Through experimental data fitting, thermal spin polarization at 100 mK was estimated to be at least 99%, which was almost pure state. Next, to demonstrate the ability to create arbitrary waveform pulses, we generate a shaped pulse by superposing three Gaussian pulses of different frequencies. The resulting pulse was able to selectively and coherently excite three different spin packets simultaneously—a useful ability for analyzing multi-spin system and for controlling a multi-qubit quantum computer. By applying this pulse to the inhomogeneously broadened sample, we obtain three well-resolved excitations at 8 K, 1 K, and 14 mK.« less

Origin of the decoherence of the extended electron spin state in Ti-doped β-Ga2O3.

PubMed

Mentink-Vigier, F; Binet, L; Gourier, D; Vezin, H

2013-08-07

The mechanism of decoherence of the electron spin of Ti(3+) in β-Ga2O3 was investigated by pulsed electron paramagnetic resonance. At 4.2 K, both instantaneous and spectral diffusion contribute to the decoherence. For electron spin concentrations ≈10(25) m(-3) in the studied samples, calculations indicate that electron-electron couplings and electron couplings with (69)Ga and (71)Ga nuclei yield similar contributions to the spectral diffusion, but that electron-nuclei interactions could become the dominant cause of spectral diffusion for only slightly lower spin concentrations. Above 20 K, an additional contribution to the decoherence as well as to the spin-lattice relaxation arises from a two-optical-phonon Raman process, which becomes the leading decoherence mechanism for T > 39 K. Rabi oscillations with a damping time of about 79 ns at 4.2 K could also be observed. The damping of the Rabi oscillations, independent of the oscillation frequency, is suspected to arise from electron-nuclei interactions.

Positive Effect of Propolis on Free Radicals in Burn Wounds

PubMed Central

Olczyk, Pawel; Ramos, Pawel; Komosinska-Vassev, Katarzyna; Stojko, Jerzy; Pilawa, Barbara

2013-01-01

Concentration and properties of free radicals in the burn wounds treated with propolis were examined by the use of electron paramagnetic resonance spectroscopy. Magnetic spin-spin interactions and complex free radicals structures in wound beds were studied. The results were compared to those obtained for silver sulphadiazine used as a standard pharmaceutical agent. The changes of free radicals in the matrix of injury with time of exposition on these substances were tested. The aim of this study was to check the hypothesis about the best influence of propolis on the burn wounds healing. It was confirmed that a relatively lower concentration of free radicals exists in the burn wounds treated with propolis. The homogeneously broadened spectra and a complex free radical system characterize the tested tissue samples. The fastening of spin-lattice relaxation processes in the matrix of injury after treatment with propolis and silver sulphadiazine was observed. Practical usefulness of electron paramagnetic resonance spectroscopy in alternative medicine was proved. PMID:23762125

Multi-photon Rabi oscillations in high spin paramagnetic impurity

NASA Astrophysics Data System (ADS)

Bertaina, S.; Groll, N.; Chen, L.; Chiorescu, I.

2011-10-01

We report on multiple photon monochromatic quantum oscillations (Rabi oscillations) observed by pulsed EPR (Electron Paramagnetic Resonance) of Mn2+ (S = 5/2) impurities in MgO. We find that when the microwave magnetic field is similar or large than the anisotropy splitting, the Rabi oscillations have a spectrum made of many frequencies not predicted by the S = l/2 Rabi model. We show that these new frequencies come from multiple photon coherent manipulation of the multi-level spin impurity. We develop a model based on the crystal field theory and the rotating frame approximation, describing the observed phenomenon with a very good agreement.

Hybrid systems based on gold nanostructures and porphyrins as promising photosensitizers for photodynamic therapy.

PubMed

Ferreira, Daniele C; Monteiro, Camila S; Chaves, Claudilene R; Sáfar, Gustavo A M; Moreira, Roberto L; Pinheiro, Maurício V B; Martins, Dayse C S; Ladeira, Luiz Orlando; Krambrock, Klaus

2017-02-01

Gold nanostructures of two different shapes (spheres and rods) were synthesized to form a colloidal hybrid system with 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin tosylate salt (H 2 TM4PyP(OTs) 4 ) (POR) for applications in photodynamic therapy (PDT) using light in the visible spectral range. Electron paramagnetic resonance (EPR) experiments in combination with spin trapping were used for the detection of reactive oxygen species (ROS) and evaluation of the efficiency of these novel hybrid systems as photosensitizers. It is shown that the hybrid system consisting of gold nanorods (AuNR) and porphyrin (POR) is by far more efficient than its isolated components. This enhanced efficiency is explained by a synergetic effect between the AuNR and the porphyrin, wherein a rapid energy transfer from the former to the latter produces a large amount of singlet oxygen followed by its conversion into hydroxyl radicals. The mechanism was investigated using different spin traps and different ROS inhibitors. On the other hand, spherical gold nanoparticles (AuNP) do not show this synergetic effect. The synergetic effect for gold nanorods/POR hybrid is attributed to a larger field enhancement close to the gold nanorod surface in addition to the electrostatic attraction between the components of the hybrid system. Copyright © 2016 Elsevier B.V. All rights reserved.

Degradation and intermediates of diclofenac as instructive example for decomposition of recalcitrant pharmaceuticals by hydroxyl radicals generated with pulsed corona plasma in water.

PubMed

Banaschik, Robert; Jablonowski, Helena; Bednarski, Patrick J; Kolb, Juergen F

2018-01-15

Seven recalcitrant pharmaceutical residues (diclofenac, 17α-ethinylestradiol, carbamazepine, ibuprofen, trimethoprim, diazepam, diatrizoate) were decomposed by pulsed corona plasma generated directly in water. The detailed degradation pathway was investigated for diclofenac and 21 intermediates could be identified in the degradation cascade. Hydroxyl radicals have been found primarily responsible for decomposition steps. By spin trap enhanced electron paramagnetic resonance spectroscopy (EPR), OH-adducts and superoxide anion radical adducts were detected and could be distinguished applying BMPO as a spin trap. The increase of concentrations of adducts follows qualitatively the increase of hydrogen peroxide concentrations. Hydrogen peroxide is eventually consumed in Fenton-like processes but the concentration is continuously increasing to about 2mM for a plasma treatment of 70min. Degradation of diclofenac is inversely following hydrogen peroxide concentrations. No qualitative differences between byproducts formed during plasma treatment or due to degradation via Fenton-induced processes were observed. Findings on degradation kinetics of diclofenac provide an instructive understanding of decomposition rates for recalcitrant pharmaceuticals with respect to their chemical structure. Accordingly, conclusions can be drawn for further development and a first risk assessment of the method which can also be applied towards other AOPs that rely on the generation of hydroxyl radicals. Copyright © 2017 Elsevier B.V. All rights reserved.

Nuclear spin relaxation in ligands outside of the first coordination sphere in a gadolinium (III) complex: Effects of intermolecular forces

NASA Astrophysics Data System (ADS)

Kruk, Danuta; Kowalewski, Jozef

2002-07-01

This article describes paramagnetic relaxation enhancement (PRE) in systems with high electron spin, S, where there is molecular interaction between a paramagnetic ion and a ligand outside of the first coordination sphere. The new feature of our treatment is an improved handling of the electron-spin relaxation, making use of the Redfield theory. Following a common approach, a well-defined second coordination sphere is assumed, and the PRE contribution from these more distant and shorter-lived ligands is treated in a way similar to that used for the first coordination sphere. This model is called "ordered second sphere," OSS. In addition, we develop here a formalism similar to that of Hwang and Freed [J. Chem. Phys. 63, 4017 (1975)], but accounting for the electron-spin relaxation effects. We denote this formalism "diffuse second sphere," DSS. The description of the dynamics of the intermolecular dipole-dipole interaction is based on the Smoluchowski equation, with a potential of mean force related to the radial distribution function. We have used a finite-difference method to calculate numerically a correlation function for translational motion, taking into account the intermolecular forces leading to an arbitrary radial distribution of the ligand protons. The OSS and DSS models, including the Redfield description of the electron-spin relaxation, were used to interpret the PRE in an aqueous solution of a slowly rotating gadolinium (III) complex (S=7/2) bound to a protein.

Ferromagnetism observed in silicon-carbide-derived carbon

NASA Astrophysics Data System (ADS)

Peng, Bo; Zhang, Yuming; Wang, Yutian; Guo, Hui; Yuan, Lei; Jia, Renxu

2018-02-01

Carbide-derived carbon (CDC) is prepared by etching high purity 4H-SiC single crystals in a mixed atmosphere of 5% Cl2 and 95% Ar for 120 min and 240 min. The secondary ion mass spectroscopy (SIMS) bulk analysis technique excludes the possibility of ferromagnetic transition metal (TM) contamination arising during the experimental process. The paramagnetic and ferromagnetic components are separated from the measured magnetization-magnetic field curves of the samples. Through the use of the Brillouin function, paramagnetic centers carrying a magnetic moment of ˜1.3 μB are fitted. A resolvable hysteresis loop in the low magnetic field area is preserved at room temperature. The temperature dependence of the relative intensity of the Lorentzian-like electron spin resonance (ESR) line observed by electron spin spectroscopy reveals the existence of exchange interaction between the localized paramagnetic centers. First-principles calculations show the dominant configuration of defects in the graphitic CDC films. By calculating the energy difference between the antiferromagnetic and ferromagnetic phases, we deduce that the ferromagnetic coupling is sensitive to the concentration of defects.

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

Quantum annealing for the number-partitioning problem using a tunable spin glass of ions

PubMed Central

Graß, Tobias; Raventós, David; Juliá-Díaz, Bruno; Gogolin, Christian; Lewenstein, Maciej

2016-01-01

Exploiting quantum properties to outperform classical ways of information processing is an outstanding goal of modern physics. A promising route is quantum simulation, which aims at implementing relevant and computationally hard problems in controllable quantum systems. Here we demonstrate that in a trapped ion setup, with present day technology, it is possible to realize a spin model of the Mattis-type that exhibits spin glass phases. Our method produces the glassy behaviour without the need for any disorder potential, just by controlling the detuning of the spin-phonon coupling. Applying a transverse field, the system can be used to benchmark quantum annealing strategies which aim at reaching the ground state of the spin glass starting from the paramagnetic phase. In the vicinity of a phonon resonance, the problem maps onto number partitioning, and instances which are difficult to address classically can be implemented. PMID:27230802

Magnetic behavior of the nanophase of YbNi2 alloys

NASA Astrophysics Data System (ADS)

Ivanshin, V. A.; Gataullin, E. M.; Sukhanov, A. A.; Ivanshin, N. A.; Rojas, D. P.; Fernández Barquín, L.

2017-04-01

Variations in magnetic properties of the heavy-fermion YbNi2 alloy when milled in a high energy ball milling system have been investigated. The ferromagnetic transition ( T C = 10.4 K) in the initial sample almost vanishes after milling, which leads to the appearance of a magnetic transition at T* = 3.2 K in nanocrystallites. Before milling, processes of spin-lattice relaxation of the Orbach-Aminov type with the participation of the first excited Stark sublevel of the Yb3+ ion located at 75 K are dominating in the electron spin dynamics in the paramagnetic phase of the alloy. A comparative study of the temperature dependence of the magnetic properties and spectra of electron paramagnetic resonance in poly- and nanocrystalline samples indicates the existence of a magnetic inhomogeneity of the compound arising upon milling.

Electron paramagnetic resonance of a 10B-containing heterocyclic radical

NASA Astrophysics Data System (ADS)

Eaton, Sandra S.; Ngendahimana, Thacien; Eaton, Gareth R.; Jupp, Andrew R.; Stephan, Douglas W.

2018-05-01

Electron paramagnetic resonance measurements for a 10B-containing heterocyclic phenanthrenedione radical, (C6F5)2B(O2C14H8), were made at X-band in 9:1 toluene:dichloromethane from 10 to 293 K and in toluene from 180 to 293 K. In well-deoxygenated 0.1 mM toluene solution at room temperature hyperfine couplings to 10B, four pairs of protons and five pairs of fluorines contribute to a continuous wave spectrum with many resolved lines. Hyperfine couplings were adjusted to provide the best fit for spectra of the radical enriched in 10B and the analogous radical synthesized with 10,11B in natural abundance, resulting in small refinements of the hyperfine coupling constants previously reported for the natural abundance sample. Electron spin relaxation rates at temperatures between 15 and 293 K were similar for samples containing 10B and natural isotope abundance. Analysis of electron spin echo envelope modulation and hyperfine correlation spectroscopy data at 80 K found Axx = -7.5 ± 0.3, Ayy = -8.5 ± 0.3, and Azz = -10.8 ± 0.3 MHz for 11B, which indicates small spin density on the boron. The spin echo and hyperfine spectroscopy data for the 10B -containing radical are consistent with the factor of 2.99 smaller hyperfine values for 10B than for 11B.

A 1-2 GHz pulsed and continuous wave electron paramagnetic resonance spectrometer

NASA Astrophysics Data System (ADS)

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

1996-07-01

A microwave bridge has been constructed that performs three types of electron paramagnetic resonance experiments: continuous wave, pulsed saturation recovery, and pulsed electron spin echo. Switching between experiment types can be accomplished via front-panel switches without moving the sample. Design features and performance of the bridge and of a resonator used in testing the bridge are described. The bridge is constructed of coaxial components connected with semirigid cable. Particular attention has been paid to low-noise design of the preamplifier and stability of automatic frequency control circuits. The bridge incorporates a Smith chart display and phase adjustment meter for ease of tuning.

Influence of Molecular Oxygen on Ortho-Para Conversion of Water Molecules

NASA Astrophysics Data System (ADS)

Valiev, R. R.; Minaev, B. F.

2017-07-01

The mechanism of influence of molecular oxygen on the probability of ortho-para conversion of water molecules and its relation to water magnetization are considered within the framework of the concept of paramagnetic spin catalysis. Matrix elements of the hyperfine ortho-para interaction via the Fermi contact mechanism are calculated, as well as the Maliken spin densities on water protons in H2O and O2 collisional complexes. The mechanism of penetration of the electron spin density into the water molecule due to partial spin transfer from paramagnetic oxygen is considered. The probability of ortho-para conversion of the water molecules is estimated by the quantum chemistry methods. The results obtained show that effective ortho-para conversion of the water molecules is possible during the existence of water-oxygen dimers. An external magnetic field affects the ortho-para conversion rate given that the wave functions of nuclear spin sublevels of the water protons are mixed in the complex with oxygen.

Amplification of Dynamic Nuclear Polarization at 200 GHz by Arbitrary Pulse Shaping of the Electron Spin Saturation Profile.

PubMed

Kaminker, Ilia; Han, Songi

2018-06-07

Dynamic nuclear polarization (DNP) takes center stage in nuclear magnetic resonance (NMR) as a tool to amplify its signal by orders of magnitude through the transfer of polarization from electron to nuclear spins. In contrast to modern NMR and electron paramagnetic resonance (EPR) that extensively rely on pulses for spin manipulation in the time domain, the current mainstream DNP technology exclusively relies on monochromatic continuous wave (CW) irradiation. This study introduces arbitrary phase shaped pulses that constitute a train of coherent chirp pulses in the time domain at 200 GHz (7 T) to dramatically enhance the saturation bandwidth and DNP performance compared to CW DNP, yielding up to 500-fold in NMR signal enhancements. The observed improvement is attributed to the recruitment of additional electron spins contributing to DNP via the cross-effect mechanism, as experimentally confirmed by two-frequency pump-probe electron-electron double resonance (ELDOR).

Electrical detection of nuclear spins in organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Malissa, H.; Kavand, M.; Waters, D. P.; Lupton, J. M.; Vardeny, Z. V.; Saam, B.; Boehme, C.

2014-03-01

We present pulsed combined electrically detected electron paramagnetic and nuclear magnetic resonance experiments on MEH-PPV OLEDs. Spin dynamics in these structures are governed by hyperfine interactions between charge carriers and the surrounding hydrogen nuclei, which are abundant in these materials. Hyperfine coupling has been observed by monitoring the device current during coherent spin excitation. Electron spin echoes (ESEs) are detected by applying one additional readout pulse at the time of echo formation. This allows for the application of high-resolution spectroscopy based on ESE detection, such as electron spin echo envelope modulation (ESEEM) and electron nuclear double resonance (ENDOR) available for electrical detection schemes. We conduct electrically detected ESEEM and ENDOR experiments and show how hyperfine interactions in MEH-PPV with and without deuterated polymer side groups can be observed by device current measurements. We acknowledge support by the Department of Energy, Office of Basic Energy Sciences under Award #DE-SC0000909.

Paramagnetic Ce3 + optical emitters in garnets: Optically detected magnetic resonance study and evidence of Gd-Ce cross-relaxation effects

NASA Astrophysics Data System (ADS)

Tolmachev, D. O.; Gurin, A. S.; Uspenskaya, Yu. A.; Asatryan, G. R.; Badalyan, A. G.; Romanov, N. G.; Petrosyan, A. G.; Baranov, P. G.; Wieczorek, H.; Ronda, C.

2017-06-01

Paramagnetic Ce3 +optical emitters have been studied by means of optically detected magnetic resonance (ODMR) via Ce3 + spin-dependent emission in cerium-doped garnet crystals which were both gadolinium free and contain gadolinium in a concentration from the lowest (0.1%) to 100%, i.e., to the superparamagnetic state. It has been shown that the intensity of photoluminescence excited by circularly polarized light into Ce3 + absorption bands can be used for selective monitoring the population of the Ce3 + ground-state spin sublevels. Direct evidence of the cross-relaxation effects in garnet crystals containing two electron spin systems, i.e., the simplest one of Ce3 + ions with the effective spin S =1/2 and the system of Gd3 + ions with the maximum spin S =7/2 , has been demonstrated. Magnetic resonance of Gd3 + has been found by monitoring Ce3 + emission in cerium-doped garnet crystals with gadolinium concentrations of 0.1 at. %, 4%-8%, and 100%, which implies the impact of the Gd3 + spin polarization on the optical properties of Ce3 +. Strong internal magnetic fields in superparamagnetic crystals were shown to modify the processes of recombination between UV-radiation-induced electron and hole centers that lead to the recombination-induced Ce3 + emission. Observation of spikes and subsequent decay in the cross-relaxation-induced ODMR signals under pulsed microwave excitation is suggested to be an informative method to investigate transient processes in the many-spin system of Ce3 +, Gd3 +, and electron and hole radiation-induced centers.

High resolution in-operando microimaging of solar cells with pulsed electrically-detected magnetic resonance

NASA Astrophysics Data System (ADS)

Katz, Itai; Fehr, Matthias; Schnegg, Alexander; Lips, Klaus; Blank, Aharon

2015-02-01

The in-operando detection and high resolution spatial imaging of paramagnetic defects, impurities, and states becomes increasingly important for understanding loss mechanisms in solid-state electronic devices. Electron spin resonance (ESR), commonly employed for observing these species, cannot meet this challenge since it suffers from limited sensitivity and spatial resolution. An alternative and much more sensitive method, called electrically-detected magnetic resonance (EDMR), detects the species through their magnetic fingerprint, which can be traced in the device's electrical current. However, until now it could not obtain high resolution images in operating electronic devices. In this work, the first spatially-resolved electrically-detected magnetic resonance images (EDMRI) of paramagnetic states in an operating real-world electronic device are provided. The presented method is based on a novel microwave pulse sequence allowing for the coherent electrical detection of spin echoes in combination with powerful pulsed magnetic-field gradients. The applicability of the method is demonstrated on a device-grade 1-μm-thick amorphous silicon (a-Si:H) solar cell and an identical device that was degraded locally by an electron beam. The degraded areas with increased concentrations of paramagnetic defects lead to a local increase in recombination that is mapped by EDMRI with ∼20-μm-scale pixel resolution. The novel approach presented here can be widely used in the nondestructive in-operando three-dimensional characterization of solid-state electronic devices with a resolution potential of less than 100 nm.

IN VIVO EVIDENCE OF FREE RADICAL FORMATION AFTER ASBESTOS INSTILLATION: AN ESR SPIN TRAPPING INVESTIGATION

EPA Science Inventory

It has been postulated that the in vivo toxicity of asbestos results from its catalysis of free radical generation. We examined in vivo radical production using electron spin resonance (ESR) coupled with the spin trap alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone (4-POBN); 180 d...

Back-clocking of Fe2+/Fe1+ spin states in a H2-producing catalyst by advanced EPR

NASA Astrophysics Data System (ADS)

Stathi, Panagiota; Mitrikas, George; Sanakis, Yiannis; Louloudi, Maria; Deligiannakis, Yiannis

2013-10-01

A mononuclear Fe-(P(PPh2)3) ((P(PPh2)3) = tris[2-diphenylphospino)ethyl]phosphine) catalyst was studied in situ under catalytic conditions using advanced electron paramagnetic resonance (EPR) techniques. Fe-(P(PPh2)3) efficiently catalyses H2 production using HCOOH as substrate. Dual-mode continuous-wave (CW) EPR, used to study the initial Fe2+(S = 2) state, shows that the complex is characterised by a - rather small - zero field splitting parameter Δ = 0.45 cm-1 and geff = 8.0. In the presence of HCOOH substrate the complex evolves and a unique Fe1+(S = 1/2) state is trapped. The Fe1+ atom is coordinated by four 31P nuclei in a pseudo-C3 symmetry. Only a small fraction of the Fe1+ spin density is delocalised onto the 31P atoms. Four-pulse electron spin echo envelope modulation (ESEEM) and two-dimensional hyperfine sublevel correlation spectroscopy (2D-HYSCORE) data reveal the existence of two types of 1H couplings. One corresponds to weak, purely dipolar coupling, tentatively assigned to phenyl protons. The most important is a - rather unusual - 1H coupling with negative Aiso (-2.75 MHz) and strong dipolar part (T = 5.5 MHz). This 1H is located on the pseudo-C3 symmetry axis of the Fe1+-(P(PPh2)3-HCOO- complex where one substrate molecule, formate anion, is coordinated on the Fe1+ atom.

Microstrip resonators for electron paramagnetic resonance experiments.

PubMed

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

2009-07-01

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

Electronic state of PuCoGa5 and NpCoGa5 as probed by polarized neutrons.

PubMed

Hiess, A; Stunault, A; Colineau, E; Rebizant, J; Wastin, F; Caciuffo, R; Lander, G H

2008-02-22

By using single crystals and polarized neutrons, we have measured the orbital and spin components of the microscopic magnetization in the paramagnetic state of NpCoGa(5) and PuCoGa(5). The microscopic magnetization of NpCoGa(5) agrees with that observed in bulk susceptibility measurements and the magnetic moment has spin and orbital contributions as expected for intermediate coupling. In contrast, for PuCoGa(5), which is a superconductor with a high transition temperature, the microscopic magnetization in the paramagnetic state is small, temperature-independent, and significantly below the value found with bulk techniques at low temperatures. The orbital moment dominates the magnetization.

Characterisation of β-tricalcium phosphate-based bone substitute materials by electron paramagnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Matković, Ivo; Maltar-Strmečki, Nadica; Babić-Ivančić, Vesna; Dutour Sikirić, Maja; Noethig-Laslo, Vesna

2012-10-01

β-TCP based materials are frequently used as dental implants. Due to their resorption in the body and direct contact with tissues, in order to inactivate bacteria, fungal spores and viruses, they are usually sterilized by γ-irradiation. However, the current literature provides little information about effects of the γ-irradiation on the formation and stability of the free radicals in the bone graft materials during and after sterilization procedure. In this work five different bone graft substitution materials, composed of synthetic beta tricalcium phosphate (β-TCP) and hydroxyapatite (HAP) present in the market were characterized by electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Paramagnetic species Mn2+, Fe3+, trapped H-atoms and CO2- radicals were detected in the biphasic material (60% HAP, 40% β-TCP), while in β-TCP materials only Mn2+ andor trapped hydrogen atoms were detected. EPR analysis revealed the details of the structure of these materials at the atomic level. The results have shown that EPR spectroscopy is a method which can be used to improve the quality control of bone graft materials after syntering, processing and sterilization procedure.

Electron-nuclear coherent spin oscillations probed by spin-dependent recombination

NASA Astrophysics Data System (ADS)

Azaizia, S.; Carrère, H.; Sandoval-Santana, J. C.; Ibarra-Sierra, V. G.; Kalevich, V. K.; Ivchenko, E. L.; Bakaleinikov, L. A.; Marie, X.; Amand, T.; Kunold, A.; Balocchi, A.

2018-04-01

We demonstrate the triggering and detection of coherent electron-nuclear spin oscillations related to the hyperfine interaction in Ga deep paramagnetic centers in GaAsN by band-to-band photoluminescence without an external magnetic field. In contrast to other point defects such as Cr4 + in SiC, Ce3 + in yttrium aluminum garnet crystals, nitrogen-vacancy centers in diamond, and P atoms in silicon, the bound-electron spin in Ga centers is not directly coupled to the electromagnetic field via the spin-orbit interaction. However, this apparent drawback can be turned into an advantage by exploiting the spin-selective capture of conduction band electrons to the Ga centers. On the basis of a pump-probe photoluminescence experiment we measure directly in the temporal domain the hyperfine constant of an electron coupled to a gallium defect in GaAsN by tracing the dynamical behavior of the conduction electron spin-dependent recombination to the defect site. The hyperfine constants and the relative abundance of the nuclei isotopes involved can be determined without the need of an electron spin resonance technique and in the absence of any magnetic field. Information on the nuclear and electron spin relaxation damping parameters can also be estimated from the oscillation amplitude decay and the long-time-delay behavior.

The mechanisms of oxygen reduction and evolution reactions in nonaqueous lithium-oxygen batteries.

PubMed

Cao, Ruiguo; Walter, Eric D; Xu, Wu; Nasybulin, Eduard N; Bhattacharya, Priyanka; Bowden, Mark E; Engelhard, Mark H; Zhang, Ji-Guang

2014-09-01

A fundamental understanding of the mechanisms of both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in nonaqueous lithium-oxygen (Li-O2) batteries is essential for the further development of these batteries. In this work, we systematically investigate the mechanisms of the ORR/OER reactions in nonaqueous Li-O2 batteries by using electron paramagnetic resonance (EPR) spectroscopy, using 5,5-dimethyl-pyrroline N-oxide as a spin trap. The study provides direct verification of the formation of the superoxide radical anion (O2(˙-)) as an intermediate in the ORR during the discharge process, while no O2(˙-) was detected in the OER during the charge process. These findings provide insight into, and an understanding of, the fundamental reaction mechanisms involving oxygen and guide the further development of this field. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Local Nitric Oxide Production in Viral and Autoimmune Diseases of the Central Nervous System

NASA Astrophysics Data System (ADS)

Hooper, D. Craig; Tsuyoshi Ohnishi, S.; Kean, Rhonda; Numagami, Yoshihiro; Dietzschold, Bernhard; Koprowski, Hilary

1995-06-01

Because of the short half-life of NO, previous studies implicating NO in central nervous system pathology during infection had to rely on the demonstration of elevated levels of NO synthase mRNA or enzyme expression or NO metabolites such as nitrate and nitrite in the infected brain. To more definitively investigate the potential causative role of NO in lesions of the central nervous system in animals infected with neurotropic viruses or suffering from experimental allergic encephalitis, we have determined directly the levels of NO present in the central nervous system of such animals. Using spin trapping of NO and electron paramagnetic resonance spectroscopy, we confirm here that copious amounts of NO (up to 30-fold more than control) are elaborated in the brains of rats infected with rabies virus or borna disease virus, as well as in the spinal cords of rats that had received myelin basic protein-specific T cells.

Effect of exogenous hydrogen peroxide on biophoton emission from radish root cells.

PubMed

Rastogi, Anshu; Pospísil, Pavel

2010-01-01

Biophotons spontaneously emitted from radish root cells were detected using highly sensitive photomultiplier tube. Freshly isolated radish root cells exhibited spontaneous photon emission of about 4 counts s(-1). Addition of hydrogen peroxide to the cells caused significant enhancement in biophoton emission to about 500 counts s(-1). Removal of molecular oxygen using glucose/glucose oxidase system and scavengering of reactive oxygen species by reducing agents such are sodium ascorbate and cysteine completely diminished biophoton emission. Spectral analysis of the hydrogen peroxide-induced biophoton emission indicates that biophotons are emitted mainly in green-red region of the spectra. The data provided by electron paramagnetic resonance spin-trapping technique showed that formation of singlet oxygen observed after addition of H2O2 correlates with enhancement in biophoton emission. These observations provide direct evidence that singlet oxygen is involved in biophoton emission from radish root cells. Copyright 2010 Elsevier Masson SAS. All rights reserved.

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

... that is a unique combination of: (1) multi-gradient Single Point Imaging involving global phase...-encoding gradients. The combination approach of single point imaging with the spin-echo signal detection...

First-order melting of a weak spin-orbit mott insulator into a correlated metal

DOE PAGES

Hogan, Tom; Yamani, Z.; Walkup, D.; ...

2015-06-25

Herein, the electronic phase diagram of the weak spin-orbit Mott insulator (Sr 1-xLa x) 3Ir 2O 7 is determined via an exhaustive experimental study. Upon doping electrons via La substitution, an immediate collapse in resistivity occurs along with a narrow regime of nanoscale phase separation comprised of antiferromagnetic, insulating regions and paramagnetic, metallic puddles persisting until x≈0.04. Continued electron doping results in an abrupt, first-order phase boundary where the Néel state is suppressed and a homogenous, correlated, metallic state appears with an enhanced spin susceptibility and local moments. In conclusion, as the metallic state is stabilized, a weak structural distortionmore » develops and suggests a competing instability with the parent spin-orbit Mott state.« less

Photoinduced reactions of dibenzoyl peroxide as studied by EPR and spin-trapping

NASA Astrophysics Data System (ADS)

Rosenthal, Ionel; Mossoba, Magdi M.; Riesz, Peter

The photochemical reactions of dibenzoyl peroxide with some organic compounds were found by EPR and spin-trapping to generate free radicals in dimethyl sulfoxide solutions at room temperature. Two reaction mechanisms occur which determine the structures of the radicals generated. The first involves a one-electron oxidation and the second a hydrogen atom transfer. The prevailing mechanism is primarily dependent on the structure of the substrate. With carboxylic acids the one-electron oxidation occurs exclusively, leading to the loss of the carboxyl group and to formation of the alkyl radical. For alcohols both alkoxy radicals and hydrogen-abstraction α-carbon radicals were spin trapped. The alkoxy radicals were generated by the electron transfer mechanism. Finally pyrimidine bases such as thymine and cytosine yielded C(5)-centered radicals which could also be explained by an electron transfer mechanism. These observations are of interest because of the recently observed skin tumor-promoting activity of dibenzoyl peroxide.

Respiratory chain components involved in the glycerophosphate dehydrogenase-dependent ROS production by brown adipose tissue mitochondria.

PubMed

Vrbacký, Marek; Drahota, Zdenek; Mrácek, Tomás; Vojtísková, Alena; Jesina, Pavel; Stopka, Pavel; Houstek, Josef

2007-07-01

Involvement of mammalian mitochondrial glycerophosphate dehydrogenase (mGPDH, EC 1.1.99.5) in reactive oxygen species (ROS) generation was studied in brown adipose tissue mitochondria by different spectroscopic techniques. Spectrofluorometry using ROS-sensitive probes CM-H2DCFDA and Amplex Red was used to determine the glycerophosphate- or succinate-dependent ROS production in mitochondria supplemented with respiratory chain inhibitors antimycin A and myxothiazol. In case of glycerophosphate oxidation, most of the ROS originated directly from mGPDH and coenzyme Q while complex III was a typical site of ROS production in succinate oxidation. Glycerophosphate-dependent ROS production monitored by KCN-insensitive oxygen consumption was highly activated by one-electron acceptor ferricyanide, whereas succinate-dependent ROS production was unaffected. In addition, superoxide anion radical was detected as a mGPDH-related primary ROS species by fluorescent probe dihydroethidium, as well as by electron paramagnetic resonance (EPR) spectroscopy with DMPO spin trap. Altogether, the data obtained demonstrate pronounced differences in the mechanism of ROS production originating from oxidation of glycerophosphate and succinate indicating that electron transfer from mGPDH to coenzyme Q is highly prone to electron leak and superoxide generation.

Self-Trapped Excitons in Ionic-Covalent Silver Halide Crystals and Nanostructures: High-Frequency EPR, ESE, ENDOR and ODMR Studies

PubMed Central

Baranov, P. G.; Poluektov, O. G.; Schmidt, J.

2010-01-01

Silver halides have unique features in solid state physics because their properties are considered to be of borderline nature between ionic and covalent bonding. In AgCl, the self-trapped hole (STH) is centered and partly trapped in the cationic sublattice, forming an Ag2+ ion inside of a (AgCl6)4− complex as a result of the Jahn–Teller distortion. The STH in AgCl can capture an electron from the conduction band forming the self-trapped exciton (STE). Recent results of a study of STE by means of high-frequency electron paramagnetic resonance, electron spin echo, electron–nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) are reviewed. The properties of the STE in AgCl crystals, such as exchange coupling, the ordering of the triplet and singlet sublevels, the dynamical properties of the singlet and triplet states, and the hyperfine interaction with the Ag and Cl (Br) nuclei are discussed. Direct information about the spatial distribution of the wave function of STE unpaired electrons was obtained by ENDOR. From a comparison with the results of an ENDOR study of the shallow electron center and STH, it is concluded that the electron is mainly contained in a hydrogen-like 1s orbital with a Bohr radius of 15.1 ± 0.6 Å, but near its center the electron density reflects the charge distribution of the hole. The hole of the STE is virtually identical to an isolated STH center. For AgCl nanocrystals embedded into the KCl crystalline matrix, the anisotropy of the g-factor of STE and STH was found to be substantially reduced compared with that of bulk AgCl crystals, which can be explained by a considerable suppression of the Jahn–Teller effect in nanoparticles. A study of ODMR in AgBr nanocrystals in KBr revealed spatial confinement effects and allowed estimating the nanocrystal size from the shape of the ODMR spectra. PMID:21151483

Highly sensitive free radical detection by nitrone-functionalized gold nanoparticles

NASA Astrophysics Data System (ADS)

Du, Libo; Huang, Saipeng; Zhuang, Qianfen; Jia, Hongying; Rockenbauer, Antal; Liu, Yangping; Liu, Ke Jian; Liu, Yang

2014-01-01

The detection of free radicals and related species has attracted significant attention in recent years because of their critical roles in physiological and pathological processes. Among the methods for the detection of free radicals, electron spin resonance (ESR) coupled with the use of the spin trapping technique has been an effective approach for characterization and quantification of these species due to its high specificity. However, its application in biological systems, especially in in vivo systems, has been greatly limited partially due to the low reaction rate between the currently available spin traps with biological radicals. To overcome this drawback, we herein report the first example of nitrone functionalized gold nanoparticles (Au@EMPO) as highly efficient spin traps in which the thiolated EMPO (2-(ethoxycarbonyl)-2-methyl-3,4-dihydro-2H-pyrrole 1-oxide) derivative was self-assembled on gold nanoparticles. Kinetic studies showed that Au@EMPO has a 137-fold higher reaction rate constant with &z.rad;OH than PBN (N-tert-butyl-α-phenylnitrone). Owing to the high rate of trapping &z.rad;OH by Au@EMPO as well as the high stability of the resulting spin adduct (t1/2 ~ 56 min), Au@EMPO affords 124-fold higher sensitivity for &z.rad;OH than EMPO. Thus, this new nanospin trap shows great potential in trapping the important radicals such as &z.rad;OH in various biological systems and provides a novel strategy to design spin traps with much improved properties.The detection of free radicals and related species has attracted significant attention in recent years because of their critical roles in physiological and pathological processes. Among the methods for the detection of free radicals, electron spin resonance (ESR) coupled with the use of the spin trapping technique has been an effective approach for characterization and quantification of these species due to its high specificity. However, its application in biological systems, especially in in vivo systems, has been greatly limited partially due to the low reaction rate between the currently available spin traps with biological radicals. To overcome this drawback, we herein report the first example of nitrone functionalized gold nanoparticles (Au@EMPO) as highly efficient spin traps in which the thiolated EMPO (2-(ethoxycarbonyl)-2-methyl-3,4-dihydro-2H-pyrrole 1-oxide) derivative was self-assembled on gold nanoparticles. Kinetic studies showed that Au@EMPO has a 137-fold higher reaction rate constant with &z.rad;OH than PBN (N-tert-butyl-α-phenylnitrone). Owing to the high rate of trapping &z.rad;OH by Au@EMPO as well as the high stability of the resulting spin adduct (t1/2 ~ 56 min), Au@EMPO affords 124-fold higher sensitivity for &z.rad;OH than EMPO. Thus, this new nanospin trap shows great potential in trapping the important radicals such as &z.rad;OH in various biological systems and provides a novel strategy to design spin traps with much improved properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr04559e

Effect of electron trap states on spin-dependent transport characteristics in CoFe/MgO/n{sup +}-Si junctions investigated by Hanle effect measurements and inelastic electron tunneling spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inokuchi, Tomoaki, E-mail: tomoaki.inokuchi@toshiba.co.jp; Ishikawa, Mizue; Sugiyama, Hideyuki

2014-12-08

Spin-dependent transport properties in CoFe/MgO/n{sup +}-Si junctions were investigated by Hanle effect measurements and inelastic electron tunneling (IET) spectroscopy. The CoFe/MgO/n{sup +}-Si junctions examined in this study exhibited two different Hanle curves. In the low bias region, broad Hanle signals were mainly observed; in the high bias region, narrow Hanle signals were mainly observed. The d{sup 2}I/dV{sup 2}-V curves (which correspond to IET spectra) contain several peaks originating from phonon modes and other peaks originating from electron trap states. At the bias voltage where electron trap states are observed, Δd{sup 2}I/dV{sup 2} depends on the magnetic field and the fullmore » width at half-maximum of the Δd{sup 2}I/dV{sup 2}–H curves corresponds to that of the broad Hanle signals. These results indicate that electron trap states are located in the low energy region and cause a decrease in spin lifetime.« less

Dissociation of O(2-)2 defects into paramagnetic O(-) in wide band-gap insulators - A magnetic susceptibility study of magnesium oxide

NASA Technical Reports Server (NTRS)

Batllo, F.; Leroy, R. C.; Parvin, K.; Freund, F.

1990-01-01

The magnetic susceptibility of single-crystal MgO has been measured in the temperature range 300-1000 K, using a Faraday balance. The high-purity crystal (less than 100 ppm transition metals), grown from the melt in a H2O-containing atmosphere, was found to be paramagnetic due to the presence of defects on the O(2-) sublattice. The defects derive from OH(-) introduced into the MgO matrix by the dissolution of traces of H2O during crystal growth. The OH(-) converts into O(2-)2 and H2. Each O(2-)2 represents two coupled, spin-paired O(-) states. The observed strongly temperature-dependent paramagnetism can be described by three contributions that overlay the intrinsic diamagnetism of MgO and arise from the low level of transition-metal impurities, O(-) generated by 0(2-)2 dissociation, and O(-) states trapped by quenching from high temperatures from previous experiments.

Reaction between peroxynitrite and boronates: EPR spin-trapping, HPLC analyses, and quantum mechanical study of the free radical pathway

PubMed Central

Sikora, Adam; Zielonka, Jacek; Lopez, Marcos; Dybala-Defratyka, Agnieszka; Joseph, Joy; Marcinek, Andrzej; Kalyanaraman, Balaraman

2013-01-01

Recently we showed that peroxynitrite (ONOO−) reacts directly and rapidly with aromatic and aliphatic boronic acids (k ≈ 106 M−1s−1). Product analyses and substrate consumption data indicated that ONOO− reacts stoichiometrically with boronates, yielding the corresponding phenols as the major product (~85–90%), and the remaining products (10–15%) were proposed to originate from free radical intermediates (phenyl and phenoxyl radicals). Here we investigated in detail the minor, free radical pathway of boronate reaction with ONOO−. The electron paramagnetic resonance (EPR) spin-trapping technique was used to characterize the free radical intermediates formed from the reaction between boronates and ONOO−. Using 2-methyl-2-nitrosopropane (MNP) and 5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO) spin traps, phenyl radicals were trapped and detected. Although phenoxyl radicals were not detected, the positive effects of molecular oxygen, and inhibitory effects of hydrogen atom donors (acetonitrile, and 2-propanol) and general radical scavengers (GSH, NADH, ascorbic acid and tyrosine) on the formation of phenoxyl radical-derived nitrated product, suggest that phenoxyl radical was formed as the secondary species. We propose that the initial step of the reaction involves the addition of ONOO− to the boron atom in boronates. The anionic intermediate undergoes both heterolytic (major pathway) and homolytic (minor pathway) cleavage of the peroxy (O-O) bond to form phenol and nitrite as a major product (via a non-radical mechanism), or a radical pair PhB(OH)2O•−…•NO2 as a minor product. It is conceivable that phenyl radicals are formed by the fragmentation of PhB(OH)2O•− radical anion. According to the DFT quantum mechanical calculations, the energy barrier for the dissociation of PhB(OH)2O•− radical anion to form phenyl radicals is only a few kcal/mol, suggesting rapid and spontaneous fragmentation of PhB(OH)2O•− radical anion in aqueous media. Biological implications of the minor free radical pathway are discussed in the context of ONOO− detection, using the boronate probes. PMID:21434648

Spin coherence in a Mn3 single-molecule magnet

NASA Astrophysics Data System (ADS)

Abeywardana, Chathuranga; Mowson, Andrew M.; Christou, George; Takahashi, Susumu

2016-01-01

Spin coherence in single crystals of the spin S = 6 single-molecule magnet (SMM) [Mn3O(O2CEt)3(mpko)3]+ (abbreviated Mn3) has been investigated using 230 GHz electron paramagnetic resonance spectroscopy. Coherence in Mn3 was uncovered by significantly suppressing dipolar contribution to the decoherence with complete spin polarization of Mn3 SMMs. The temperature dependence of spin decoherence time (T2) revealed that the dipolar decoherence is the dominant source of decoherence in Mn3 and T2 can be extended up to 267 ns by quenching the dipolar decoherence.

Key role of persistent free radicals in hydrogen peroxide activation by biochar: implications to organic contaminant degradation.

PubMed

Fang, Guodong; Gao, Juan; Liu, Cun; Dionysiou, Dionysios D; Wang, Yu; Zhou, Dongmei

2014-01-01

We investigated the activation of hydrogen peroxide (H2O2) by biochars (produced from pine needles, wheat, and maize straw) for 2-chlorobiphenyl (2-CB) degradation in the present study. It was found that H2O2 can be effectively activated by biochar, which produces hydroxyl radical ((•)OH) to degrade 2-CB. Furthermore, the activation mechanism was elucidated by electron paramagnetic resonance (EPR) and salicylic acid (SA) trapping techniques. The results showed that biochar contains persistent free radicals (PFRs), typically ∼ 10(18) unpaired spins/gram. Higher trapped [(•)OH] concentrations were observed with larger decreases in PFRs concentration, when H2O2 was added to biochar, indicating that PFRs were the main contributor to the formation of (•)OH. This hypothesis was supported by the linear correlations between PFRs concentration and trapped [(•)OH], as well as kobs of 2-CB degradation. The correlation coefficients (R(2)) were 0.723 and 0.668 for PFRs concentration vs trapped [(•)OH], and PFRs concentration vs kobs, respectively, when all biochars pyrolyzed at different temperatures were included. For the same biochar washed by different organic solvents (methanol, hexane, dichloromethane, and toluene), the correlation coefficients markedly increased to 0.818-0.907. Single-electron transfer from PFRs to H2O2 was a possible mechanism for H2O2 activation by biochars, which was supported by free radical quenching studies. The findings of this study provide a new pathway for biochar implication and insight into the mechanism of H2O2 activation by carbonaceous materials (e.g., activated carbon and graphite).

Measurement of free radicals using electron paramagnetic resonance spectroscopy during open aorto-iliac arterial reconstruction.

PubMed

Majewski, Wacław; Krzyminiewski, Ryszard; Stanisić, Michał; Iskra, Maria; Krasiński, Zbigniew; Nowak, Marek; Dobosz, Bernadeta

2014-11-27

Aortic cross-clamping during abdominal aortic aneurysm (AAA) open repair leads to development of ischemia-reperfusion injury. Electron paramagnetic resonance spectroscopy (EPR) spin-trapping is a valuable method of direct measurement of free radicals. The objective of the study was to evaluate the results of EPR as a direct method of free radical measurement and degree of inflammatory response in open operative treatment of patients with AAA and aorto-iliac occlusive disease (AIOD). The study was performed on a group of 32 patients with AAA and 25 patients with AIOD scheduled for open repair. Peripheral venous blood for EPR spectroscopy and for SOD, GPx, ox-LDL, Il-6, TNF-alfa, CRP, and HO-1 were harvested. Selected parameters were established accordingly to specified EPR and immunohistochemical methods and analyzed between groups by Mann-Whitney U test and Wilcoxon matched-pairs signed-ranks test with Bonferroni correction. Free radicals level was correlated with the time of the aortic cross-clamping after the reperfusion of he first and second leg in AAA (r=0.7; r=0.47). ox-LDL in AAA decreased 5 min after reperfusion of the first leg (32.99 U/L, range: 14.09-77.12) and 5 min after reperfusion of the second leg (26.75 U/L, range: 11.56-82.12) and 24 h after the operation (25.85 U/L, range: 14.29-49.70). HO-1 concentration increased to above the level before intervention 24 h after surgery. The activities of GPx and SOD decreased 5 min after the first-leg reperfusion in AAA. Twenty-four hours after surgery, inflammatory markers increased in AAA to CRP was 14.76 ml/l (0.23-38.55), IL-6 was 141.22 pg/ml (84.3-591.03), TNF-alfa was 6.82 pg/ml (1.76-80.01) and AIOD: CRP was 18.44 mg/l (2.56-33.14), IL-6: 184.1 pg/ml (128.46-448.03), TNF-alfa was 7.74 pg/ml (1.74-74.74). EPR spin-trapping demonstrates temporarily elevated level of free radicals in early phase of reperfusion, leading to decrease antioxidants in AAA. Elevated free radical levels decreased 24 h after surgery due to various endogenous antioxidants and therapies.

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born–Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersionmore » of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.« less

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

DOE PAGES

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert; ...

2017-05-24

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born–Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersionmore » of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.« less

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

NASA Astrophysics Data System (ADS)

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert; van Driel, Tim B.; Chollet, Matthieu; Glownia, James M.; Song, Sanghoon; Zhu, Diling; Pace, Elisabetta; Matar, Samir F.; Nielsen, Martin M.; Benfatto, Maurizio; Gaffney, Kelly J.; Collet, Eric; Cammarata, Marco

2017-05-01

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born-Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersion of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.

Antioxidant and radical-scavenging activities of Slovak honeys - An electron paramagnetic resonance study.

PubMed

Zalibera, Michal; Staško, Andrej; Šlebodová, Anna; Jančovičová, Viera; Čermáková, Tatiana; Brezová, Vlasta

2008-09-15

The antioxidant properties of 15 honey samples from different floral sources and various Slovak regions were investigated by means of electron paramagnetic resonance spectroscopy. Cation radical of ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) diammonium salt), DPPH (1,1-diphenyl-2-picrylhydrazyl) and hydroxyl radicals generated by the photochemical decomposition of hydrogen peroxide were used as oxidants. The antioxidant activities found with ABTS(+), expressed as trolox equivalent antioxidant capacity (TEAC), ranged from 0.15 to 1.14mmolkg(-1), and those determined with DPPH, from 0.04 to 0.32mmolkg(-1). TEAC values correlated well with results found by elimination of DPPH, and both values revealed a linear relationship with the concentration of phenolics obtained with the Folin-Ciocalteu phenol test (expressed as gallic acid equivalents, GAE). The colour coordinates (CIE L(∗)a(∗)b(∗)), as well as reflectance spectra determined for original honeys using a white background, demonstrated that the colour difference (ΔE(∗)) and coordinate b(∗) interrelate with TEAC values. The radical-scavenging capacities (RSC) of the honey samples determined in the experiments with photochemically decomposed hydrogen peroxide, generating reactive OH radicals in the presence of spin trapping agent, differ from those found with ABTS(+) and DPPH. Here, probably, the reactive OH radicals, having higher redox potential, are scavenged by a variety of compounds not effective with ABTS(+) and DPPH (e.g., saccharides, proteins). Copyright © 2008 Elsevier Ltd. All rights reserved.

Evidence on the Formation of Singlet Oxygen in the Donor Side Photoinhibition of Photosystem II: EPR Spin-Trapping Study

PubMed Central

Yadav, Deepak Kumar; Pospíšil, Pavel

2012-01-01

When photosystem II (PSII) is exposed to excess light, singlet oxygen (1O2) formed by the interaction of molecular oxygen with triplet chlorophyll. Triplet chlorophyll is formed by the charge recombination of triplet radical pair 3[P680•+Pheo•−] in the acceptor-side photoinhibition of PSII. Here, we provide evidence on the formation of 1O2 in the donor side photoinhibition of PSII. Light-induced 1O2 production in Tris-treated PSII membranes was studied by electron paramagnetic resonance (EPR) spin-trapping spectroscopy, as monitored by TEMPONE EPR signal. Light-induced formation of carbon-centered radicals (R•) was observed by POBN-R adduct EPR signal. Increased oxidation of organic molecules at high pH enhanced the formation of TEMPONE and POBN-R adduct EPR signals in Tris-treated PSII membranes. Interestingly, the scavenging of R• by propyl gallate significantly suppressed 1O2. Based on our results, it is concluded that 1O2 formation correlates with R• formation on the donor side of PSII due to oxidation of organic molecules (lipids and proteins) by long-lived P680•+/TyrZ•. It is proposed here that the Russell mechanism for the recombination of two peroxyl radicals formed by the interaction of R• with molecular oxygen is a plausible mechanism for 1O2 formation in the donor side photoinhibition of PSII. PMID:23049883

Separated spin-up and spin-down quantum hydrodynamics of degenerated electrons: Spin-electron acoustic wave appearance.

PubMed

Andreev, Pavel A

2015-03-01

The quantum hydrodynamic (QHD) model of charged spin-1/2 particles contains physical quantities defined for all particles of a species including particles with spin-up and with spin-down. Different populations of states with different spin directions are included in the spin density (the magnetization). In this paper I derive a QHD model, which separately describes spin-up electrons and spin-down electrons. Hence electrons with different projections of spins on the preferable direction are considered as two different species of particles. It is shown that the numbers of particles with different spin directions do not conserve. Hence the continuity equations contain sources of particles. These sources are caused by the interactions of the spins with the magnetic field. Terms of similar nature arise in the Euler equation. The z projection of the spin density is no longer an independent variable. It is proportional to the difference between the concentrations of the electrons with spin-up and the electrons with spin-down. The propagation of waves in the magnetized plasmas of degenerate electrons is considered. Two regimes for the ion dynamics, the motionless ions and the motion of the degenerate ions as the single species with no account of the spin dynamics, are considered. It is shown that this form of the QHD equations gives all solutions obtained from the traditional form of QHD equations with no distinction of spin-up and spin-down states. But it also reveals a soundlike solution called the spin-electron acoustic wave. Coincidence of most solutions is expected since this derivation was started with the same basic equation: the Pauli equation. Solutions arise due to the different Fermi pressures for the spin-up electrons and the spin-down electrons in the magnetic field. The results are applied to degenerate electron gas of paramagnetic and ferromagnetic metals in the external magnetic field. The dispersion of the spin-electron acoustic waves in the partially spin-polarized degenerate neutron matter are also considered.

Anisotropic rotational diffusion studied by passage saturation transfer electron paramagnetic resonance

NASA Astrophysics Data System (ADS)

Robinson, Bruce H.; Dalton, Larry R.

1980-01-01

The stochastic Liouville equation for the spin density matrix is modified to consider the effects of Brownian anisotropic rotational diffusion upon electron paramagnetic resonance (EPR) and saturation transfer electron paramagnetic resonance (ST-EPR) spectra. Spectral shapes and the ST-EPR parameters L″/L, C'/C, and H″/H defined by Thomas, Dalton, and Hyde at X-band microwave frequencies [J. Chem. Phys. 65, 3006 (1976)] are examined and discussed in terms of the rotational times τ∥ and τ⊥ and in terms of other defined correlation times for systems characterized by magnetic tensors of axial symmetry and for systems characterized by nonaxially symmetric magnetic tensors. For nearly axially symmetric magnetic tensors, such as nitroxide spin labels studied employing 1-3 GHz microwaves, ST-EPR spectra for systems undergoing anisotropic rotational diffusion are virtually indistinguishable from spectra for systems characterized by isotropic diffusion. For nonaxially symmetric magnetic tensors, such as nitroxide spin labels studied employing 8-35 GHz microwaves, the high field region of the ST-EPR spectra, and hence the H″/H parameter, will be virtually indistinguishable from spectra, and parameter values, obtained for isotropic diffusion. On the other hand, the central spectral region at x-band microwave frequencies, and hence the C'/C parameter, is sensitive to the anisotropic diffusion model provided that a unique and static relationship exists between the magnetic and diffusion tensors. Random labeling or motion of the spin label relative to the biomolecule whose hydrodynamic properties are to be investigated will destroy spectral sensitivity to anisotropic motion. The sensitivity to anisotropic motion is enhanced in proceeding to 35 GHz with the increased sensitivity evident in the low field half of the EPR and ST-EPR spectra. The L″/L parameter is thus a meaningful indicator of anisotropic motion when compared with H″/H parameter analysis. However, consideration of spectral shapes suggests that the C'/C parameter definition is not meaningfully extended from 9.5 to 35 GHz. Alternative definitions of the L″/L and C'/C parameters are proposed for those microwave frequencies for which the electron Zeeman anisotropy is comparable to or greater than the electron-nitrogen nuclear hyperfine anisotropy.

Unconventional spin dynamics in the honeycomb-lattice material α -RuCl3 : High-field electron spin resonance studies

NASA Astrophysics Data System (ADS)

Ponomaryov, A. N.; Schulze, E.; Wosnitza, J.; Lampen-Kelley, P.; Banerjee, A.; Yan, J.-Q.; Bridges, C. A.; Mandrus, D. G.; Nagler, S. E.; Kolezhuk, A. K.; Zvyagin, S. A.

2017-12-01

We present high-field electron spin resonance (ESR) studies of the honeycomb-lattice material α -RuCl3 , a prime candidate to exhibit Kitaev physics. Two modes of antiferromagnetic resonance were detected in the zigzag ordered phase, with magnetic field applied in the a b plane. A very rich excitation spectrum was observed in the field-induced quantum paramagnetic phase. The obtained data are compared with the results of recent numerical calculations, strongly suggesting a very unconventional multiparticle character of the spin dynamics in α -RuCl3 . The frequency-field diagram of the lowest-energy ESR mode is found consistent with the behavior of the field-induced energy gap, revealed by thermodynamic measurements.

Conventional electron paramagnetic resonance of Mn2+ in synthetic hydroxyapatite at different concentrations of the doped manganese

NASA Astrophysics Data System (ADS)

Murzakhanov, F.; Mamin, G.; Voloshin, A.; Klimashina, E.; Putlyaev, V.; Doronin, V.; Bakhteev, S.; Yusupov, R.; Gafurov, M.; Orlinskii, S.

2018-05-01

Powders of synthetic hydroxyapatite doped with Mn2+ ions in concentrations from 0.05 till 5 wt. % were investigated by conventional electron paramagnetic resonance (EPR). The parameters of the spin-Hamiltonian are derived. Partially resolved hyperfine structure in the magnetic fields corresponding to g ≈ 4.3 and g ≈ 9.4 is observed. The narrowing of the central peak with concentration is reported. A possibility to use the linewidth and intensity of the central peak for concentration measurements are discussed. The results could be used for the identification and qualification of Mn2+ in oil, mining and ore formations.

Calculation of spin-spin zero-field splitting within periodic boundary conditions: Towards all-electron accuracy

NASA Astrophysics Data System (ADS)

Biktagirov, Timur; Schmidt, Wolf Gero; Gerstmann, Uwe

2018-03-01

For high-spin centers, one of the key spectroscopic fingerprints is the zero-field splitting (ZFS) addressable by electron paramagnetic resonance. In this paper, an implementation of the spin-spin contribution to the ZFS tensor within the projector augmented-wave (PAW) formalism is reported. We use a single-determinant approach proposed by M. J. Rayson and P. R. Briddon [Phys. Rev. B 77, 035119 (2008), 10.1103/PhysRevB.77.035119], and complete it by adding a PAW reconstruction term which has not been taken into account before. We benchmark the PAW approach against a well-established all-electron method for a series of diatomic radicals and defects in diamond and cubic silicon carbide. While for some of the defect centers the PAW reconstruction is found to be almost negligible, in agreement with the common assumption, we show that in general it significantly improves the calculated ZFS towards the all-electron results.

Physical and chemical interactions at the interface between atmospheric pressure plasmas and aqueous solutions

NASA Astrophysics Data System (ADS)

Lindsay, Alexander; Byrns, Brandon; Knappe, Detlef; Graves, David; Shannon, Steven

2014-10-01

Transport and reactions of charged species, neutrals, and photons at the interface between plasmas and liquids must be better quantified. The work presented here combines theoretical and experimental investigations of conditions in the gas and liquid phases in proximity to the interface for various discharges. OES is used to determine rotational and vibrational temperatures of OH, NO, and N2+; the relationship between these temperatures that characterize the distribution of internal energy states and gas and electron kinetic temperatures is considered. The deviation of OH rotational states from equilibrium under high humidity conditions is also presented. In contradiction with findings of other groups, high energy rotational states appear to become underpopulated with increasing humidity. In the aqueous phase, concentrations of longer-lived species such as nitrate, nitrite, hydrogen peroxide, and ozone are determined using ion chromatography and colorimetric methods. Spin-traps and electron paramagnetic resonance (EPR) are investigated for characterization of short-lived aqueous radicals like OH, O2-, NO, and ONOO-. Finally, experimental results are compared to a numerical model which couples transport and reactions within and between the bulk gas and liquid phases.

Paramagnetic Spin Seebeck Effect

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2015-05-01

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

Excess-Si related defect centers in buried SiO2 thin films

NASA Astrophysics Data System (ADS)

Warren, W. L.; Fleetwood, D. M.; Shaneyfelt, M. R.; Schwank, J. R.; Winokur, P. S.; Devine, R. A. B.

1993-06-01

Using electron paramagnetic resonance (EPR) and capacitance-voltage measurements we have investigated the role of excess-silicon related defect centers as charge traps in separation by the implantation of oxygen materials. Three types of EPR-active centers were investigated: oxygen vacancy Eγ' centers (O3≡Si• +Si≡O3), delocalized Eδ' centers, and D centers (Si3≡Si•). It was found that all of these paramagnetic centers are created by selective hole injection, and are reasonably ascribed as positively charged when paramagnetic. These results provide the first experimental evidence for (1) the charge state of the Eδ' center, and (2) that the D center is an electrically active point defect in these materials.

Concept for room temperature single-spin tunneling force microscopy with atomic spatial resolution

NASA Astrophysics Data System (ADS)

Payne, Adam

A study of a force detected single-spin magnetic resonance measurement concept with atomic spatial resolution is presented. The method is based upon electrostatic force detection of spin-selection rule controlled single electron tunneling between two electrically isolated paramagnetic states. Single-spin magnetic resonance detection is possible by measuring the force detected tunneling charge noise on and off spin resonance. Simulation results of this charge noise, based upon physical models of the tunneling and spin physics, are directly compared to measured atomic force microscopy (AFM) system noise. The results show that the approach could provide single-spin measurement of electrically isolated defect states with atomic spatial resolution at room temperature.

Atomic-resolution single-spin magnetic resonance detection concept based on tunneling force microscopy

NASA Astrophysics Data System (ADS)

Payne, A.; Ambal, K.; Boehme, C.; Williams, C. C.

2015-05-01

A study of a force detected single-spin magnetic resonance measurement concept with atomic spatial resolution is presented. The method is based upon electrostatic force detection of spin-selection rule controlled single-electron tunneling between two electrically isolated paramagnetic states. Single-spin magnetic resonance detection is possible by measuring the force detected tunneling charge noise on and off spin resonance. Simulation results of this charge noise, based upon physical models of the tunneling and spin physics, are directly compared to measured atomic force microscopy system noise. The results show that the approach could provide single-spin measurement of electrically isolated qubit states with atomic spatial resolution at room temperature.

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

PubMed

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

2015-01-01

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

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

PubMed Central

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

2015-01-01

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

Characteristics of the spin-trapping reaction of a free radical derived from AAPH: further development of the ORAC-ESR assay.

PubMed

Nakajima, A; Matsuda, E; Masuda, Y; Sameshima, H; Ikenoue, T

2012-06-01

The characteristics of the spin-trapping reaction in the oxygen radical absorbance capacity (ORAC)-electron spin resonance (ESR) assay were examined, focusing on the kind of spin traps. 2,2-Azobis(2-amidinopropane) dihydrochloride (AAPH) was used as a free radical initiator. The spin adducts of the AAPH-derived free radical were assigned as those of the alkoxyl radical, RO· (R=H(2)N(HN)C-C(CH(3))(2)). Among the spin traps tested, 5,5-dimethyl-1-pyrroline N-oxide (DMPO), 5,5-dimethyl-4-phenyl-1-pyrroline N-oxide (4PDMPO), 5-(2,2-dimethyl-1,3-propoxycyclophosphoryl)-5-methyl-1-pyrroline N-oxide (CYPMPO), and 5-diethoxyphosphoryl-5-methyl-1-pyrroline N-oxide (DEPMPO) were applicable to the ORAC-ESR assay. Optimal formation of spin-trapped radical adduct was observed with 1 mM AAPH, 10 mM spin trap, and 5 s UV irradiation. The calibration curve (the Stern-Volmer's plot) for each spin trap showed good linearity, and their slopes, k (SB)/k (ST), were estimated to be 87.7±2.3, 267±15, 228±9, and 213±16 for DMPO, 4PDMPO, CYPMPO, and DEPMPO, respectively. Though the k (SB)/k (ST) values for selected biosubstances varied with various spin traps, their ratios to Trolox (the relative ORAC values) were almost the same for all spin traps tested. The ORAC-ESR assay also had a very good reproducibility. The ORAC-ESR assay was conducted under stoichiometric experimental conditions. The present results demonstrate the superiority of the ORAC-ESR assay.

Site-specific detection of radicals on α-lactalbumin after a riboflavin-sensitized reaction, detected by immuno-spin trapping, ESR, and MS.

PubMed

Dalsgaard, Trine K; Triquigneaux, Mathilde; Deterding, Leesa; Summers, Fiona; Ranguelova, Kalina; Mortensen, Grith; Mason, Ronald P

2013-01-16

Free radicals and other oxidation products were characterized on α-lactalbumin with electron spin resonance (ESR), immuno-spin trapping, and mass spectrometry (MS) after riboflavin-mediated oxidation. Radicals were detected using the spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in immuno-spin trapping with both enzyme-linked immunosorbent assay (ELISA) and Western blotting and further characterized with mass spectrometry. A DMPO-trapped radical was identified at His68 and another at one of the tyrosine residues, Tyr50 or Tyr36, respectively, generated by a type II or I mechanism. Not all tyrosyl radicals were trapped, as the secondary oxidation product, 3,4-dihydroxyphenylalanine (DOPA), was detected by mass spectrometry at Tyr18 and Tyr50. A further oxidation of DOPA resulted in the DOPA o-semiquinone radical, which was characterized by ESR. Both surface exposure and the neighboring residues in the local environment of the tertiary structure of α-lactalbumin seem to play a role in the generation of DMPO trapped radicals and secondary oxidation products.

Coherent control of a single nitrogen-vacancy center spin in optically levitated nanodiamond

DOE PAGES

Pettit, Robert M.; Neukirch, Levi Patrick; Zhang, Yi; ...

2017-05-12

Here, we report the first observation, to the best of our knowledge, of electron spin transients in single negatively charged nitrogen-vacancy (NV -) centers, contained within optically trapped nanodiamonds, in both atmospheric pressure and low vacuum. It is shown that, after an initial exposure to low vacuum, the trapped nanodiamonds remain at temperatures near room temperature even in low vacuum. Furthermore, the transverse coherence time of the NV - center spin, measured to be T 2=101.4 ns, is robust over the range of trapping powers considered in this study.

Oxidation of spin-traps by chlorine dioxide (ClO2) radical in aqueous solutions: first ESR evidence of formation of new nitroxide radicals.

PubMed

Ozawa, T; Miura, Y; Ueda, J

1996-01-01

The reactivities of the chlorine dioxide (ClO2), which is a stable free radical towards some water-soluble spin-traps were investigated in aqueous solutions by an electron spin resonance (ESR) spectroscopy. The ClO2 radical was generated from the redox reaction of Ti3+ with potassium chlorate (KClO3) in aqueous solutions. When one of the spin-traps, 5,5-dimethyl-1-pyrroline N-oxide (DMPO), was included in the Ti3+-KClO3 reaction system, ESR spectrum due to the ClO2 radical completely disappeared and a new ESR spectrum [aN(1) = 0.72 mT, aH(2) = 0.41 mT], which is different from that of DMPO-ClO2 adduct, was observed. The ESR parameters of this new ESR signal was identical to those of 5,5-dimethylpyrrolidone-(2)-oxyl-(1) (DMPOX), suggesting the radical species giving the new ESR spectrum is assignable to DMPOX. The similar ESR spectrum consisting of a triplet [aN(1) = 0.69 mT] was observed when the derivative of DMPO, 3,3,5,5-tetramethyl-1-pyrroline N-oxide (M4PO) was included in the Ti3+-KClO3 reaction system. This radical species is attributed to the oxidation product of M4PO, 3,3,5,5-tetramethylpyrrolidone-(2)-oxyl-(1) (M4POX). When another nitrone spin-trap, alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN) was used as a spin-trap, the ESR signal intensity due to the ClO2 radical decreased and a new ESR signal consisting of a triplet [aN(1) = 0.76 mT] was observed. The similar ESR spectrum was observed when N-t-butyl-alpha- nitrone (PBN) was used as a spin-trap. This ESR parameter [a(N)(1) = 0.85 mT] was identical to the oxidation product of PBN, PBNX. Thus, the new ESR signal observed from POBN may be assigned to the oxidation product of POBN, POBNX. These results suggest that the ClO2, radical does not form the stable spin adducts with nitrone spin-traps, but oxidizes these spin-traps to give the corresponding nitroxyl radicals. On the other hand, nitroso spin-traps, 5,5-dibromo-4-nitrosobenzenesulfonate (DBNBS), and 2-methyl-2-nitrosopropane (MNP) did not trap the ClO2 radical. This result indicates that an unpaired electron of the ClO2 radical is localized on oxygen atom, because nitroso spin-traps cannot form the stable spin adduct with oxygen-centered radical.

Giant titanium electron wave function in gallium oxide: A potential electron-nuclear spin system for quantum information processing

NASA Astrophysics Data System (ADS)

Mentink-Vigier, Frédéric; Binet, Laurent; Vignoles, Gerard; Gourier, Didier; Vezin, Hervé

2010-11-01

The hyperfine interactions of the unpaired electron with eight surrounding G69a and G71a nuclei in Ti-doped β-Ga2O3 were analyzed by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopies. They are dominated by strong isotropic hyperfine couplings due to a direct Fermi contact interaction with Ga nuclei in octahedral sites of rutile-type chains oriented along b axis, revealing a large anisotropic spatial extension of the electron wave function. Titanium in β-Ga2O3 is thus best described as a diffuse (Ti4+-e-) pair rather than as a localized Ti3+ . Both electron and G69a nuclear spin Rabi oscillations could be observed by pulsed EPR and pulsed ENDOR, respectively. The electron spin decoherence time is about 1μs (at 4 K) and an upper bound of 520μs (at 8 K) is estimated for the nuclear decoherence time. Thus, β-Ga2O3:Ti appears to be a potential spin-bus system for quantum information processing with a large nuclear spin quantum register.

Spin-Orbital Excitation Continuum and Anomalous Electron-Phonon Interaction in the Mott Insulator LaTiO3

NASA Astrophysics Data System (ADS)

Ulrich, C.; Khaliullin, G.; Guennou, M.; Roth, H.; Lorenz, T.; Keimer, B.

2015-10-01

Raman scattering experiments on stoichiometric, Mott-insulating LaTiO3 over a wide range of excitation energies reveal a broad electronic continuum which is featureless in the paramagnetic state, but develops a gap of ˜800 cm-1 upon cooling below the Néel temperature TN=146 K . In the antiferromagnetic state, the spectral weight below the gap is transferred to well-defined spectral features due to spin and orbital excitations. Low-energy phonons exhibit pronounced Fano anomalies indicative of strong interaction with the electron system for T >TN , but become sharp and symmetric for T

Paramagnetic defects and charge trapping behavior of ZrO2 films deposited on germanium by plasma-enhanced CVD

NASA Astrophysics Data System (ADS)

Mahata, C.; Bera, M. K.; Bose, P. K.; Maiti, C. K.

2009-02-01

Internal photoemission and magnetic resonance studies have been performed to investigate the charge trapping behavior and chemical nature of defects in ultrathin (~14 nm) high-k ZrO2 dielectric films deposited on p-Ge (1 0 0) substrates at low temperature (<200 °C) by plasma-enhanced chemical vapor deposition (PECVD) in a microwave (700 W, 2.45 GHz) plasma at a pressure of ~65 Pa. Both the band and defect-related electron states have been characterized using electron paramagnetic resonance, internal photoemission, capacitance-voltage and current-voltage measurements under UV illumination. Capacitance-voltage and photocurrent-voltage measurements were used to determine the centroid of oxide charge within the high-k gate stack. The observed shifts in photocurrent response of the Al/ZrO2/GeO2/p-Ge metal-insulator-semiconductor (MIS) capacitors indicate the location of the centroids to be within the ZrO2 dielectric near to the gate electrode. Moreover, the measured flat band voltage and photocurrent shifts also indicate a large density of traps in the dielectric. The impact of plasma nitridation on the interfacial quality of the oxides has been investigated. Different N sources, such as NO and NH3, have been used for nitrogen engineering. Oxynitride samples show a lower defect density and trapping over the non-nitrided samples. The charge trapping and detrapping properties of MIS capacitors under stressing in constant current and voltage modes have been investigated in detail.

Zero Quantum Coherence in a Series of Covalent Spin-Correlated Radical Pairs.

PubMed

Nelson, Jordan N; Krzyaniak, Matthew D; Horwitz, Noah E; Rugg, Brandon K; Phelan, Brian T; Wasielewski, Michael R

2017-03-23

Photoinitiated subnanosecond electron transfer within covalently linked electron donor-acceptor molecules can result in the formation of a spin-correlated radical pair (SCRP) with a well-defined initial singlet spin configuration. Subsequent coherent mixing between the SCRP singlet and triplet m s = 0 spin states, the so-called zero quantum coherence (ZQC), is of potential interest in quantum information processing applications because the ZQC can be probed using pulse electron paramagnetic resonance (pulse-EPR) techniques. Here, pulse-EPR spectroscopy is utilized to examine the ZQC oscillation frequencies and ZQC dephasing in three structurally well-defined D-A systems. While transitions between the singlet and triplet m s = 0 spin states are formally forbidden (Δm s = 0), they can be addressed using specific microwave pulse turning angles to map information from the ZQC onto observable single quantum coherences. In addition, by using structural variations to tune the singlet-triplet energy gap, the ZQC frequencies determined for this series of molecules indicate a stronger dependence on the electronic g-factor than on electron-nuclear hyperfine interactions.

Single crystal EPR and optical studies of paramagnetic ions doped zinc potassium phosphate hexahydrate—Part I: Cu(II)—a case of orthorhombic symmetry

NASA Astrophysics Data System (ADS)

Sambasiva Rao, P.; Rajendiran, T. M.; Venkatesan, R.; Madhu, N.; Chandrasekhar, A. V.; Reddy, B. J.; Reddy, Y. P.; Ravikumar, R. V. S. S. N.

2001-12-01

Single crystal electron paramagnetic resonance (EPR) studies on Cu(II) doped zinc potassium phosphate hexahydrate (ZPPH) were carried out at room temperature. The angular variation spectra in the three orthogonal planes indicate that the paramagnetic impurity has entered the lattice substitutionally in place of Zn(II) and the spin Hamiltonian parameters calculated from these spectra are gxx=2.188, gyy=2.032, gzz=2.373, Axx=50 G, Ayy=65.0 G and Azz=80 G. The g and A tensors were coincident and these values matched fairly well with the values obtained from powder spectrum. The bonding parameters have also been calculated.

Time-dependent broken-symmetry density functional theory simulation of the optical response of entangled paramagnetic defects: Color centers in lithium fluoride

NASA Astrophysics Data System (ADS)

Janesko, Benjamin G.

2018-02-01

Parameter-free atomistic simulations of entangled solid-state paramagnetic defects may aid in the rational design of devices for quantum information science. This work applies time-dependent density functional theory (TDDFT) embedded-cluster simulations to a prototype entangled-defect system, namely two adjacent singlet-coupled F color centers in lithium fluoride. TDDFT calculations accurately reproduce the experimental visible absorption of both isolated and coupled F centers. The most accurate results are obtained by combining spin symmetry breaking to simulate strong correlation, a large fraction of exact (Hartree-Fock-like) exchange to minimize the defect electrons' self-interaction error, and a standard semilocal approximation for dynamical correlations between the defect electrons and the surrounding ionic lattice. These results motivate application of two-reference correlated ab initio approximations to the M-center, and application of TDDFT in parameter-free simulations of more complex entangled paramagnetic defect architectures.

TRIAGE of Irradiated Personnel

DTIC Science & Technology

1996-09-25

Vivo Electron Paramagnetic Resonance, Electron Spin Resonance (EPR, ESR) for In Vivo Dosimetry Under Field Conditions Dr. Harold M. Swartz Dartmouth...Force Medical Center Andrews Air Force Base, MD • Status and Limitations of Physical Dosimetry in the Field Environment David A. Schauer, LCDR, MSC...USN Naval Dosimetry Center Navy Environmental Health Center Detachment Bethesda, MD • NATO Policy and Guidance on Antiemetic Usage Robert Kehlet

Electron spin resonance (ESR) dose measurement in bone of Hiroshima A-bomb victim.

PubMed

Kinoshita, Angela; Baffa, Oswaldo; Mascarenhas, Sérgio

2018-01-01

Explosion of the bombs in Hiroshima and Nagasaki corresponds to the only historical moment when atomic bombs were used against civilians. This event triggered countless investigations into the effects and dosimetry of ionizing radiation. However, none of the investigations has used the victims' bones as dosimeter. Here, we assess samples of bones obtained from fatal victims of the explosion by Electron Spin Resonance (ESR). In 1973, one of the authors of the present study (SM) traveled to Japan and conducted a preliminary experiment on the victims' bone samples. The idea was to use the paramagnetism induced in bone after irradiation to measure the radiation dose. Technological advances involved in the construction of spectrometers, better knowledge of the paramagnetic center, and improvement in signal processing techniques have allowed us to resume the investigation. We obtained a reconstructed dose of 9.46 ± 3.4 Gy from the jawbone, which was compatible with the dose distribution in different locations as measured in non-biological materials such as wall bricks and roof tiles.

Comparison of pulse sequences for R1-based electron paramagnetic resonance oxygen imaging.

PubMed

Epel, Boris; Halpern, Howard J

2015-05-01

Electron paramagnetic resonance (EPR) spin-lattice relaxation (SLR) oxygen imaging has proven to be an indispensable tool for assessing oxygen partial pressure in live animals. EPR oxygen images show remarkable oxygen accuracy when combined with high precision and spatial resolution. Developing more effective means for obtaining SLR rates is of great practical, biological and medical importance. In this work we compared different pulse EPR imaging protocols and pulse sequences to establish advantages and areas of applicability for each method. Tests were performed using phantoms containing spin probes with oxygen concentrations relevant to in vivo oxymetry. We have found that for small animal size objects the inversion recovery sequence combined with the filtered backprojection reconstruction method delivers the best accuracy and precision. For large animals, in which large radio frequency energy deposition might be critical, free induction decay and three pulse stimulated echo sequences might find better practical usage. Copyright © 2015 Elsevier Inc. All rights reserved.

The impact of adsorption on the localization of spins in graphene oxide and reduced graphene oxide, observed with electron paramagnetic resonance

NASA Astrophysics Data System (ADS)

Kempiński, Mateusz; Florczak, Patryk; Jurga, Stefan; Śliwińska-Bartkowiak, Małgorzata; Kempiński, Wojciech

2017-08-01

We report the observations of electronic properties of graphene oxide and reduced graphene oxide, performed with electron paramagnetic resonance technique in a broad temperature range. Both materials were examined in pure form and saturated with air, helium, and heavy water molecules. We show that spin localization strongly depends on the type and amount of molecules adsorbed at the graphene layer edges (and possible in-plane defects). Physical and chemical states of edges play crucial role in electrical transport within graphene-based materials, with hopping as the leading mechanism of charge carrier transport. Presented results are a good basis to understand the electronic properties of other carbon structures made of graphene-like building blocks. Most active carbons show some degree of functionalization and are known of having good adsorptive properties; thus, controlling both phenomena is important for many applications. Sample treatment with temperature, vacuum, and various adsorbents allowed for the observation of a possible metal-insulator transition and sorption pumping effects. The influence of adsorption on the localization phenomena in graphene would be very important if to consider the graphene-based material as possible candidates for the future spintronics that works in ambient conditions.

Developing Density of Laser-Cooled Neutral Atoms and Molecules in a Linear Magnetic Trap

NASA Astrophysics Data System (ADS)

Velasquez, Joe, III; Walstrom, Peter; di Rosa, Michael

2013-05-01

In this poster we show that neutral particle injection and accumulation using laser-induced spin flips may be used to form dense ensembles of ultracold magnetic particles, i.e., laser-cooled paramagnetic atoms and molecules. Particles are injected in a field-seeking state, are switched by optical pumping to a field-repelled state, and are stored in the minimum-B trap. The analogous process in high-energy charged-particle accumulator rings is charge-exchange injection using stripper foils. The trap is a linear array of sextupoles capped by solenoids. Particle-tracking calculations and design of our linear accumulator along with related experiments involving 7Li will be presented. We test these concepts first with atoms in preparation for later work with selected molecules. Finally, we present our preliminary results with CaH, our candidate molecule for laser cooling. This project is funded by the LDRD program of Los Alamos National Laboratory.

Direct measurement of ferromagnetic ordering in biaxially strained LaCoO3 thin films

NASA Astrophysics Data System (ADS)

Klie, R. F.; Yuan, T.; Tanase, M.; Yang, G.; Ramasse, Q.

2010-02-01

LaCoO3 undergoes a transition from a nonmagnetic to a paramagnetic semiconductor at 80 K, associated with a spin-state transition of the Co3+ ions. It was proposed that the temperature of the spin-state transition depends strongly on the LaCoO3 lattice parameter, suggesting that strain can stabilize different spin states at different temperatures. By combining atomic-resolution Z-contrast imaging, electron diffraction, and angular-resolved electron energy-loss spectroscopy (EELS) with in situ cooling experiments, we show that epitaxially strained LaCoO3 (001) thin films grown on LaAlO3 (001) do not undergo a low temperature spin-state transition. Our EELS study explores the origins of the ferromagnetic ordering in strained LaCoO3 films.

Unconventional spin dynamics in the honeycomb-lattice material α - RuCl 3 : High-field electron spin resonance studies

DOE PAGES

Ponomaryov, A. N.; Schulze, E.; Wosnitza, J.; ...

2017-12-19

Here, we present high-field electron spin resonance (ESR) studies of the honeycomb-lattice material α-RuCl 3, a prime candidate to exhibit Kitaev physics. Two modes of antiferromagnetic resonance were detected in the zigzag ordered phase, with magnetic field applied in the a b plane. A very rich excitation spectrum was observed in the field-induced quantum paramagnetic phase. We compare the data obtained with the results of recent numerical calculations, strongly suggesting a very unconventional multiparticle character of the spin dynamics in α-RuCl 3. Finally, the frequency-field diagram of the lowest-energy ESR mode is found consistent with the behavior of the field-inducedmore » energy gap, revealed by thermodynamic measurements.« less

Unconventional spin dynamics in the honeycomb-lattice material α - RuCl 3 : High-field electron spin resonance studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ponomaryov, A. N.; Schulze, E.; Wosnitza, J.

Here, we present high-field electron spin resonance (ESR) studies of the honeycomb-lattice material α-RuCl 3, a prime candidate to exhibit Kitaev physics. Two modes of antiferromagnetic resonance were detected in the zigzag ordered phase, with magnetic field applied in the a b plane. A very rich excitation spectrum was observed in the field-induced quantum paramagnetic phase. We compare the data obtained with the results of recent numerical calculations, strongly suggesting a very unconventional multiparticle character of the spin dynamics in α-RuCl 3. Finally, the frequency-field diagram of the lowest-energy ESR mode is found consistent with the behavior of the field-inducedmore » energy gap, revealed by thermodynamic measurements.« less

The local magnetic properties of [MnIII6 CrIII]3+ and [FeIII6 CrIII]3+ single-molecule magnets deposited on surfaces studied by spin-polarized photoemission and XMCD with circularly polarized synchrotron radiation

NASA Astrophysics Data System (ADS)

Heinzmann, U.; Helmstedt, A.; Dohmeier, N.; Müller, N.; Gryzia, A.; Brechling, A.; Hoeke, V.; Krickemeyer, E.; Glaser, T.; Fonin, M.; Bouvron, S.; Leicht, P.; Tietze, T.; Goering, E.; Kuepper, K.

2014-04-01

It is demonstrated that local magnetic moments of single molecule magnets (SMM) normally studied by XMCD at very low temperatures and high magnetic fields can be measured by means of spin-resolved electron emission in the paramagnetic phase at room temperature by use of circularly polarized radiation.

Binding of manganese(II) to a tertiary stabilized hammerhead ribozyme as studied by electron paramagnetic resonance spectroscopy

PubMed Central

KISSELEVA, NATALIA; KHVOROVA, ANASTASIA; WESTHOF, ERIC; SCHIEMANN, OLAV

2005-01-01

Electron paramagnetic resonance (EPR) spectroscopy is used to study the binding of MnII ions to a tertiary stabilized hammer-head ribozyme (tsHHRz) and to compare it with the binding to the minimal hammerhead ribozyme (mHHRz). Continuous wave EPR measurements show that the tsHHRz possesses a single high-affinity MnII binding site with a KD of ≤10 nM at an NaCl concentration of 0.1 M. This dissociation constant is at least two orders of magnitude smaller than the KD determined previously for the single high-affinity MnII site in the mHHRz. In addition, whereas the high-affinity MnII is displaced from the mHHRz upon binding of the aminoglycoside antibiotic neomycin B, it is not from the tsHHRz. Despite these pronounced differences in binding, a comparison between the electron spin echo envelope modulation and hyperfine sublevel correlation spectra of the minimal and tertiary stabilized HHRz demonstrates that the structure of both binding sites is very similar. This suggests that the MnII is located in both ribozymes between the bases A9 and G10.1 of the sheared G · A tandem base pair, as shown previously and in detail for the mHHRz. Thus, the much stronger MnII binding in the tsHHRz is attributed to the interaction between the two external loops, which locks in the RNA fold, trapping the MnII in the tightly bound conformation, whereas the absence of long-range loop–loop interactions in the mHHRz leads to more dynamical and open conformations, decreasing MnII binding. PMID:15611296

Acetate in mixotrophic growth medium affects photosystem II in Chlamydomonas reinhardtii and protects against photoinhibition.

PubMed

Roach, Thomas; Sedoud, Arezki; Krieger-Liszkay, Anja

2013-10-01

Chlamydomonas reinhardtii is a photoautotrophic green alga, which can be grown mixotrophically in acetate-supplemented media (Tris-acetate-phosphate). We show that acetate has a direct effect on photosystem II (PSII). As a consequence, Tris-acetate-phosphate-grown mixotrophic C. reinhardtii cultures are less susceptible to photoinhibition than photoautotrophic cultures when subjected to high light. Spin-trapping electron paramagnetic resonance spectroscopy showed that thylakoids from mixotrophic C. reinhardtii produced less (1)O2 than those from photoautotrophic cultures. The same was observed in vivo by measuring DanePy oxalate fluorescence quenching. Photoinhibition can be induced by the production of (1)O2 originating from charge recombination events in photosystem II, which are governed by the midpoint potentials (Em) of the quinone electron acceptors. Thermoluminescence indicated that the Em of the primary quinone acceptor (QA/QA(-)) of mixotrophic cells was stabilised while the Em of the secondary quinone acceptor (QB/QB(-)) was destabilised, therefore favouring direct non-radiative charge recombination events that do not lead to (1)O2 production. Acetate treatment of photosystem II-enriched membrane fragments from spinach led to the same thermoluminescence shifts as observed in C. reinhardtii, showing that acetate exhibits a direct effect on photosystem II independent from the metabolic state of a cell. A change in the environment of the non-heme iron of acetate-treated photosystem II particles was detected by low temperature electron paramagnetic resonance spectroscopy. We hypothesise that acetate replaces the bicarbonate associated to the non-heme iron and changes the environment of QA and QB affecting photosystem II charge recombination events and photoinhibition. Copyright © 2013 Elsevier B.V. All rights reserved.

Theory for electron transfer from a mixed-valence dimer with paramagnetic sites to a mononuclear acceptor

NASA Astrophysics Data System (ADS)

Bominaar, E. L.; Achim, C.; Borshch, S. A.

1999-06-01

Polynuclear transition-metal complexes, such as Fe-S clusters, are the prosthetic groups in a large number of metalloproteins and serve as temporary electron storage units in a number of important redox-based biological processes. Polynuclearity distinguishes clusters from mononuclear centers and confers upon them unique properties, such as spin ordering and the presence of thermally accessible excited spin states in clusters with paramagnetic sites, and fractional valencies in clusters of the mixed-valence type. In an earlier study we presented an effective-mode (EM) analysis of electron transfer from a binuclear mixed-valence donor with paramagnetic sites to a mononuclear acceptor which revealed that the cluster-specific attributes have an important impact on the kinetics of long-range electron transfer. In the present study, the validity of these results is tested in the framework of more detailed theories which we have termed the multimode semiclassical (SC) model and the quantum-mechanical (QM) model. It is found that the qualitative trends in the rate constant are the same in all treatments and that the semiclassical models provide a good approximation of the more rigorous quantum-mechanical description of electron transfer under physiologically relevant conditions. In particular, the present results corroborate the importance of electron transfer via excited spin states in reactions with a low driving force and justify the use of semiclassical theory in cases in which the QM model is computationally too demanding. We consider cases in which either one or two donor sites of a dimer are electronically coupled to the acceptor. In the case of multiconnectivity, the rate constant for electron transfer from a valence-delocalized (class-III) donor is nonadditive with respect to transfer from individual metal sites of the donor and undergoes an order-of-magnitude change by reversing the sign of the intradimer metal-metal resonance parameter (β). In the case of single connectivity, the rate constant for electron transfer from a valence-localized (class-II) donor can readily be tuned over several orders of magnitude by introducing differences in the electronic potentials at the two metal sites of the donor. These results indicate that theories of cluster-based electron transfer, in order to be realistic, need to consider both intrinsic electronic structure and extrinsic interactions of the cluster with the protein environment.

Unravelling electronic and structural requisites of triplet-triplet energy transfer by advanced electron paramagnetic resonance and density functional theory

NASA Astrophysics Data System (ADS)

Di Valentin, M.; Salvadori, E.; Barone, V.; Carbonera, D.

2013-10-01

Advanced electron paramagnetic resonance (EPR) techniques, in combination with Density Functional theory (DFT), have been applied to the comparative study of carotenoid triplet states in two major photosynthetic antenna complexes, the Peridinin-chlorophyll a-protein of dinoflagellates and the light-harvesting complex II of higher plants. Carotenoid triplet states are populated by triplet-triplet energy transfer (TTET) from chlorophyll molecules to photoprotect the system from singlet oxygen formation under light-stress conditions. The TTET process is strongly dependent on the relative arrangement and on the electronic properties of the triplet states involved. The proposed spectroscopic approach exploits the concept of spin conservation during TTET, which leads to recognisable spin polarisation effects in the time-resolved and field-swept echo-detected EPR spectra. The electron spin polarisation produced at the carotenoid acceptor site depends on the initial polarisation of the chlorophyll donor and on the relative geometrical arrangement of the donor-acceptor zero-field splitting axes. We have demonstrated that a proper analysis of the spectra in the framework of spin angular momentum conservation allows to derive the pathways of TTET and to gain insight into the structural requirements of this mechanism for those antenna complexes, whose X-ray structure is available. We have further proved that this method, developed for natural antenna complexes of known X-ray structure, can be extended to systems lacking structural information in order to derive the relative arrangement of the partners in the energy transfer process. The structural requirements for efficient TTET, obtained from time-resolved and pulse EPR, have been complemented by a detailed description of the electronic structure of the carotenoid triplet state, provided by pulse Electron-Nuclear DOuble Resonance (ENDOR) experiments. Triplet-state hyperfine couplings of the α- and β-protons of the carotenoid conjugated chain have been assigned with the aid of quantum chemical calculation. DFT predictions of the electronic structure of the carotenoid triplet state, in terms of spin density distribution, frontier orbital description and orbital excitation represent suitable building blocks toward a deeper understanding of electronic requirements for efficient TTET.

Strongly driven electron spins using a Ku band stripline electron paramagnetic resonance resonator

NASA Astrophysics Data System (ADS)

Yap, Yung Szen; Yamamoto, Hiroshi; Tabuchi, Yutaka; Negoro, Makoto; Kagawa, Akinori; Kitagawa, Masahiro

2013-07-01

This article details our work to obtain strong excitation for electron paramagnetic resonance (EPR) experiments by improving the resonator's efficiency. The advantages and application of strong excitation are discussed. Two 17 GHz transmission-type, stripline resonators were designed, simulated and fabricated. Scattering parameter measurements were carried out and quality factor were measured to be around 160 and 85. Simulation results of the microwave's magnetic field distribution are also presented. To determine the excitation field at the sample, nutation experiments were carried out and power dependence were measured using two organic samples at room temperature. The highest recorded Rabi frequency was rated at 210 MHz with an input power of about 1 W, which corresponds to a π/2 pulse of about 1.2 ns.

Engineered spin-spin interactions on a 2D array of trapped ions

NASA Astrophysics Data System (ADS)

Britton, Joe; Sawyer, Brian; Bollinger, John

2013-05-01

We work with laser cooled 9Be+ ions confined in a Penning trap to simulate quantum magnetic interactions. The valence electron of each ion behaves as an ideal spin- 1 / 2 particle. We recently demonstrated a uniform anti-ferromagnetic Ising interaction on a naturally occurring two-dimensional (2D) triangular crystal of 100 < N < 350 ions. The Ising interaction is generated by a spin-dependent optical dipole force (ODF). For spins separated by distance d, we show that the range can be tuned according to (d / d 0)-a, for 0 < a < 3 . For different operating parameters we can also generate an infinite range ferromagnetic Ising interaction. We also use the ODF for spectroscopy and thermometry of the normal modes of the trapped ion array. A detailed understanding of the modes is important because they mediate the spin-spin interactions. This work is supported by NIST and the DARPA OLE program.

Electron spin resonance microscopic imaging of oxygen concentration in cancer spheroids

NASA Astrophysics Data System (ADS)

Hashem, Mada; Weiler-Sagie, Michal; Kuppusamy, Periannan; Neufeld, Gera; Neeman, Michal; Blank, Aharon

2015-07-01

Oxygen (O2) plays a central role in most living organisms. The concentration of O2 is important in physiology and pathology. Despite the importance of accurate knowledge of the O2 levels, there is very limited capability to measure with high spatial resolution its distribution in millimeter-scale live biological samples. Many of the current oximetric methods, such as oxygen microelectrodes and fluorescence lifetime imaging, are compromised by O2 consumption, sample destruction, invasiveness, and difficulty to calibrate. Here, we present a new method, based on the use of the pulsed electron spin resonance (ESR) microimaging technique to obtain a 3D mapping of oxygen concentration in millimeter-scale biological samples. ESR imaging requires the incorporation of a suitable stable and inert paramagnetic spin probe into the desirable object. In this work, we use microcrystals of a paramagnetic spin probe in a new crystallographic packing form (denoted tg-LiNc-BuO). These paramagnetic species interact with paramagnetic oxygen molecules, causing a spectral line broadening that is linearly proportional to the oxygen concentration. Typical ESR results include 4D spatial-spectral images that give an indication about the oxygen concentration in different regions of the sample. This new oximetry microimaging method addresses all the problems mentioned above. It is noninvasive, sensitive to physiological oxygen levels, and easy to calibrate. Furthermore, in principle, it can be used for repetitive measurements without causing cell damage. The tissue model used in this research is spheroids of Human Colorectal carcinoma cell line (HCT-116) with a typical diameter of ∼600 μm. Most studies of the microenvironmental O2 conditions inside such viable spheroids carried out in the past used microelectrodes, which require an invasive puncturing of the spheroid and are also not applicable to 3D O2 imaging. High resolution 3D oxygen maps could make it possible to evaluate the relationship between morphological and physiological alterations in the spheroids, which would help understand the oxygen metabolism in solid tumors and its correlation with the susceptibility of tumors to various oncologic treatments.

Electron spin resonance microscopic imaging of oxygen concentration in cancer spheroids.

PubMed

Hashem, Mada; Weiler-Sagie, Michal; Kuppusamy, Periannan; Neufeld, Gera; Neeman, Michal; Blank, Aharon

2015-07-01

Oxygen (O2) plays a central role in most living organisms. The concentration of O2 is important in physiology and pathology. Despite the importance of accurate knowledge of the O2 levels, there is very limited capability to measure with high spatial resolution its distribution in millimeter-scale live biological samples. Many of the current oximetric methods, such as oxygen microelectrodes and fluorescence lifetime imaging, are compromised by O2 consumption, sample destruction, invasiveness, and difficulty to calibrate. Here, we present a new method, based on the use of the pulsed electron spin resonance (ESR) microimaging technique to obtain a 3D mapping of oxygen concentration in millimeter-scale biological samples. ESR imaging requires the incorporation of a suitable stable and inert paramagnetic spin probe into the desirable object. In this work, we use microcrystals of a paramagnetic spin probe in a new crystallographic packing form (denoted tg-LiNc-BuO). These paramagnetic species interact with paramagnetic oxygen molecules, causing a spectral line broadening that is linearly proportional to the oxygen concentration. Typical ESR results include 4D spatial-spectral images that give an indication about the oxygen concentration in different regions of the sample. This new oximetry microimaging method addresses all the problems mentioned above. It is noninvasive, sensitive to physiological oxygen levels, and easy to calibrate. Furthermore, in principle, it can be used for repetitive measurements without causing cell damage. The tissue model used in this research is spheroids of Human Colorectal carcinoma cell line (HCT-116) with a typical diameter of ∼600μm. Most studies of the microenvironmental O2 conditions inside such viable spheroids carried out in the past used microelectrodes, which require an invasive puncturing of the spheroid and are also not applicable to 3D O2 imaging. High resolution 3D oxygen maps could make it possible to evaluate the relationship between morphological and physiological alterations in the spheroids, which would help understand the oxygen metabolism in solid tumors and its correlation with the susceptibility of tumors to various oncologic treatments. Copyright © 2015 Elsevier Inc. All rights reserved.

Computer simulation of magnetic resonance spectra employing homotopy.

PubMed

Gates, K E; Griffin, M; Hanson, G R; Burrage, K

1998-11-01

Multidimensional homotopy provides an efficient method for accurately tracing energy levels and hence transitions in the presence of energy level anticrossings and looping transitions. Herein we describe the application and implementation of homotopy to the analysis of continuous wave electron paramagnetic resonance spectra. The method can also be applied to electron nuclear double resonance, electron spin echo envelope modulation, solid-state nuclear magnetic resonance, and nuclear quadrupole resonance spectra. Copyright 1998 Academic Press.

Metastable Defect Formation at Microvoids Identified as a Source of Light-Induced Degradation in a-Si :H

NASA Astrophysics Data System (ADS)

Fehr, M.; Schnegg, A.; Rech, B.; Astakhov, O.; Finger, F.; Bittl, R.; Teutloff, C.; Lips, K.

2014-02-01

Light-induced degradation of hydrogenated amorphous silicon (a-Si :H), known as the Staebler-Wronski effect, has been studied by time-domain pulsed electron-paramagnetic resonance. Electron-spin echo relaxation measurements in the annealed and light-soaked state revealed two types of defects (termed type I and II), which can be discerned by their electron-spin echo relaxation. Type I exhibits a monoexponential decay related to indirect flip-flop processes between dipolar coupled electron spins in defect clusters, while the phase relaxation of type II is dominated by H1 nuclear spin dynamics and is indicative for isolated spins. We propose that defects are either located at internal surfaces of microvoids (type I) or are isolated and uniformly distributed in the bulk (type II). The concentration of both defect type I and II is significantly higher in the light-soaked state compared to the annealed state. Our results indicate that in addition to isolated defects, defects on internal surfaces of microvoids play a role in light-induced degradation of device-quality a-Si :H.

The spatial effect of protein deuteration on nitroxide spin-label relaxation: Implications for EPR distance measurement

PubMed Central

El Mkami, Hassane; Ward, Richard; Bowman, Andrew; Owen-Hughes, Tom; Norman, David G.

2014-01-01

Pulsed electron–electron double resonance (PELDOR) coupled with site-directed spin labeling is a powerful technique for the elucidation of protein or nucleic acid, macromolecular structure and interactions. The intrinsic high sensitivity of electron paramagnetic resonance enables measurement on small quantities of bio-macromolecules, however short relaxation times impose a limit on the sensitivity and size of distances that can be measured using this technique. The persistence of the electron spin-echo, in the PELDOR experiment, is one of the most crucial limitations to distance measurement. At a temperature of around 50 K one of the predominant factors affecting persistence of an echo, and as such, the sensitivity and measurable distance between spin labels, is the electron spin echo dephasing time (Tm). It has become normal practice to use deuterated solvents to extend Tm and recently it has been demonstrated that deuteration of the underlying protein significantly extends Tm. Here we examine the spatial effect of segmental deuteration of the underlying protein, and also explore the concentration and temperature dependence of highly deuterated systems. PMID:25310878

Peptide-membrane Interactions by Spin-labeling EPR

PubMed Central

Smirnova, Tatyana I.; Smirnov, Alex I.

2016-01-01

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

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

PubMed

Petasis, Doros T; Hendrich, Michael P

2015-01-01

Electron paramagnetic resonance (EPR) spectroscopy has long been a primary method for characterization of paramagnetic centers in materials and biological complexes. Transition metals in biological complexes have valence d-orbitals that largely define the chemistry of the metal centers. EPR spectra are distinctive for metal type, oxidation state, protein environment, substrates, and inhibitors. The study of many metal centers in proteins, enzymes, and biomimetic complexes has led to the development of a systematic methodology for quantitative interpretation of EPR spectra from a wide array of metal containing complexes. The methodology is now contained in the computer program SpinCount. SpinCount allows simulation of EPR spectra from any sample containing multiple species composed of one or two metals in any spin state. The simulations are quantitative, thus allowing determination of all species concentrations in a sample directly from spectra. This chapter will focus on applications to transition metals in biological systems using EPR spectra from multiple microwave frequencies and modes. © 2015 Elsevier Inc. All rights reserved.

Spin-dependent analysis of two-dimensional electron liquids

NASA Astrophysics Data System (ADS)

Bulutay, C.; Tanatar, B.

2002-05-01

Two-dimensional electron liquid (2D EL) at full Fermi degeneracy is revisited, giving special attention to the spin-polarization effects. First, we extend the recently proposed classical-map hypernetted-chain (CHNC) technique to the 2D EL, while preserving the simplicity of the original proposal. An efficient implementation of CHNC is given utilizing Lado's quadrature expressions for the isotropic Fourier transforms. Our results indicate that the paramagnetic phase stays to be the ground state until the Wigner crystallization density, even though the energy separation with the ferromagnetic and other partially polarized states become minute. We analyze compressibility and spin stiffness variations with respect to density and spin polarization, the latter being overlooked until now. Spin-dependent static structure factor and pair-distribution functions are computed; agreement with the available quantum Monte Carlo data persists even in the strong-coupling regime of the 2D EL.

Electron Paramagnetic Resonance Measurements of Reactive Oxygen Species by Cyclic Hydroxylamine Spin Probes.

PubMed

Dikalov, Sergey I; Polienko, Yuliya F; Kirilyuk, Igor

2018-05-20

Oxidative stress contributes to numerous pathophysiological conditions such as development of cancer, neurodegenerative, and cardiovascular diseases. A variety of measurements of oxidative stress markers in biological systems have been developed; however, many of these methods are not specific, can produce artifacts, and do not directly detect the free radicals and reactive oxygen species (ROS) that cause oxidative stress. Electron paramagnetic resonance (EPR) is a unique tool that allows direct measurements of free radical species. Cyclic hydroxylamines are useful and convenient molecular probes that readily react with ROS to produce stable nitroxide radicals, which can be quantitatively measured by EPR. In this work, we critically review recent applications of various cyclic hydroxylamine spin probes in biology to study oxidative stress, their advantages, and the shortcomings. Recent Advances: In the past decade, a number of new cyclic hydroxylamine spin probes have been developed and their successful application for ROS measurement using EPR has been published. These new state-of-the-art methods provide improved selectivity and sensitivity for in vitro and in vivo studies. Although cyclic hydroxylamine spin probes EPR application has been previously described, there has been lack of translation of these new methods into biomedical research, limiting their widespread use. This work summarizes "best practice" in applications of cyclic hydroxylamine spin probes to assist with EPR studies of oxidative stress. Additional studies to advance hydroxylamine spin probes from the "basic science" to biomedical applications are needed and could lead to better understanding of pathological conditions associated with oxidative stress. Antioxid. Redox Signal. 28, 1433-1443.

Dynamic nuclear polarisation via the integrated solid effect II: experiments on naphthalene-h8 doped with pentacene-d14

NASA Astrophysics Data System (ADS)

Eichhorn, T. R.; van den Brandt, B.; Hautle, P.; Henstra, A.; Wenckebach, W. Th.

2014-07-01

In dynamic nuclear polarisation (DNP), also called hyperpolarisation, a small amount of unpaired electron spins is added to the sample containing the nuclear spins, and the polarisation of these unpaired electron spins is transferred to the nuclear spins by means of a microwave field. Traditional DNP polarises the electron spin of stable paramagnetic centres by cooling down to low temperature and applying a strong magnetic field. Then weak continuous wave microwave fields are used to induce the polarisation transfer. Complicated cryogenic equipment and strong magnets can be avoided using short-lived photo-excited triplet states that are strongly aligned in the optical excitation process. However, a much faster transfer of the electron spin polarisation is needed and pulsed DNP methods like nuclear orientation via electron spin locking (NOVEL) and the integrated solid effect (ISE) are used. To describe the polarisation transfer with the strong microwave fields in NOVEL and ISE, the usual perturbation methods cannot be used anymore. In the previous paper, we presented a theoretical approach to calculate the polarisation transfer in ISE. In the present paper, the theory is applied to the system naphthalene-h8 doped with pentacene-d14 yielding the photo-excited triplet states and compared with experimental results.

Enhanced hydroxyl radical production by dihydroxybenzene-driven Fenton reactions: implications for wood biodegradation.

PubMed

Contreras, David; Rodríguez, Jaime; Freer, Juanita; Schwederski, Brigitte; Kaim, Wolfgang

2007-09-01

Brown rot fungi degrade wood, in initial stages, mainly through hydroxyl radicals (.OH) produced by Fenton reactions. These Fenton reactions can be promoted by dihydroxybenzenes (DHBs), which can chelate and reduce Fe(III), increasing the reactivity for different substrates. This mechanism allows the extensive degradation of carbohydrates and the oxidation of lignin during wood biodegradation by brown rot fungi. To understand the enhanced reactivity in these systems, kinetics experiments were carried out, measuring .OH formation by the spin-trapping technique of electron paramagnetic resonance spectroscopy. As models of the fungal DHBs, 1,2-dihydroxybenzene (catechol), 2,3-dihydroxybenzoic acid and 3,4-dihydroxybenzoic acid were utilized as well as 1,2-dihydroxy-3,5-benzenedisulfonate as a non-Fe(III)-reducing substance for comparison. Higher amounts and maintained concentrations of .OH were observed in the driven Fenton reactions versus the unmodified Fenton process. A linear correlation between the logarithms of complex stability constants and the .OH production was observed, suggesting participation of such complexes in the radical production.

Comparison of free radicals formation induced by cold atmospheric plasma, ultrasound, and ionizing radiation.

PubMed

Rehman, Mati Ur; Jawaid, Paras; Uchiyama, Hidefumi; Kondo, Takashi

2016-09-01

Plasma medicine is increasingly recognized interdisciplinary field combining engineering, physics, biochemistry and life sciences. Plasma is classified into two categories based on the temperature applied, namely "thermal" and "non-thermal" (i.e., cold atmospheric plasma). Non-thermal or cold atmospheric plasma (CAP) is produced by applying high voltage electric field at low pressures and power. The chemical effects of cold atmospheric plasma in aqueous solution are attributed to high voltage discharge and gas flow, which is transported rapidly on the liquid surface. The argon-cold atmospheric plasma (Ar-CAP) induces efficient reactive oxygen species (ROS) in aqueous solutions without thermal decomposition. Their formation has been confirmed by electron paramagnetic resonance (EPR) spin trapping, which is reviewed here. The similarities and differences between the plasma chemistry, sonochemistry, and radiation chemistry are explained. Further, the evidence for free radical formation in the liquid phase and their role in the biological effects induced by cold atmospheric plasma, ultrasound and ionizing radiation are discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

Photosensitization of InP/ZnS quantum dots for anti-cancer and anti-microbial applications

NASA Astrophysics Data System (ADS)

Nadeau, Jay; Chibli, Hicham; Carlini, Lina

2012-03-01

Cadmium-free quantum dots (QDs), such as those made from InP, show similar optical properties to those containing toxic heavy metals and thus provide a promising alternative for imaging and therapeutics. The band gap of InP is similar to that of CdTe, so photosensitization of InP QDs with porphyrins or other dyes should lead to generation of reactive oxygen species, useful for targeted destruction of malignant cells or pathogenic bacteria. Here we show the results of measurements of singlet oxygen and superoxide generation from InP QDs with single and double ZnS shells compared with CdTe and CdSe/ZnS. Reactive oxygen species are measured using colorimetric or fluorescent reporter assays and spin-trap electron paramagnetic resonance (EPR) spectroscopy. We find that the size of the InP QDs and the thickness of the ZnS shell both strongly influence ROS generation. These results suggest future approaches to the design of therapeutic nanoparticles.

Quantum decoherence dynamics of divacancy spins in silicon carbide

DOE PAGES

Seo, Hosung; Falk, Abram L.; Klimov, Paul V.; ...

2016-09-29

Long coherence times are key to the performance of quantum bits (qubits). Here, we experimentally and theoretically show that the Hahn-echo coherence time of electron spins associated with divacancy defects in 4H-SiC reaches 1.3 ms, one of the longest Hahn-echo coherence times of an electron spin in a naturally isotopic crystal. Using a first-principles microscopic quantum-bath model, we find that two factors determine the unusually robust coherence. First, in the presence of moderate magnetic fields (30mT and above), the 29Si and 13C paramagnetic nuclear spin baths are decoupled. In addition, because SiC is a binary crystal, homo-nuclear spin pairs aremore » both diluted and forbidden from forming strongly coupled, nearest-neighbour spin pairs. Longer neighbour distances result in fewer nuclear spin flip-flops, a less fluctuating intra-crystalline magnetic environment, and thus a longer coherence time. Lastly, our results point to polyatomic crystals as promising hosts for coherent qubits in the solid state.« less

Quantum decoherence dynamics of divacancy spins in silicon carbide.

PubMed

Seo, Hosung; Falk, Abram L; Klimov, Paul V; Miao, Kevin C; Galli, Giulia; Awschalom, David D

2016-09-29

Long coherence times are key to the performance of quantum bits (qubits). Here, we experimentally and theoretically show that the Hahn-echo coherence time of electron spins associated with divacancy defects in 4H-SiC reaches 1.3 ms, one of the longest Hahn-echo coherence times of an electron spin in a naturally isotopic crystal. Using a first-principles microscopic quantum-bath model, we find that two factors determine the unusually robust coherence. First, in the presence of moderate magnetic fields (30 mT and above), the 29 Si and 13 C paramagnetic nuclear spin baths are decoupled. In addition, because SiC is a binary crystal, homo-nuclear spin pairs are both diluted and forbidden from forming strongly coupled, nearest-neighbour spin pairs. Longer neighbour distances result in fewer nuclear spin flip-flops, a less fluctuating intra-crystalline magnetic environment, and thus a longer coherence time. Our results point to polyatomic crystals as promising hosts for coherent qubits in the solid state.

Spin injection and spin transport in paramagnetic insulators

DOE PAGES

Okamoto, Satoshi

2016-02-22

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

Engineered long-range interactions on a 2D array of trapped ions

NASA Astrophysics Data System (ADS)

Britton, Joseph W.; Sawyer, Brian C.; Bollinger, John J.; Freericks, James K.

2014-03-01

Ising interactions are one paradigm used to model quantum magnetism in condensed matter systems. At NIST Boulder we confine and Doppler laser cool hundreds of 9Be+ ions in a Penning trap. The valence electron of each ion behaves as an ideal spin-1/2 particle and, in the limit of weak radial confinement relative to axial confinement, the ions naturally form a two-dimensional triangular lattice. A variable-range anti-ferromagnetic Ising interaction is engineered with a spin-dependent optical dipole force (ODF) through spin-dependent excitation of collective modes of ion motion. We have also exploited this spin-dependent force to perform spectroscopy and thermometry of the normal modes of the trapped ion crystal. The high spin-count and long-range spin-spin couplings achievable in the NIST Penning trap brings within reach simulation of computationally intractable problems in quantum magnetism. Examples include modeling quantum magnetic phase transitions and propagation of spin correlations resulting from a quantum quench. The Penning system may also be amenable to observation of spin-liquid behavior thought to arise in systems where the underlying lattice structure can frustrate long-range ordering. Supported by DARPA OLE and NIST.

Single crystal EPR and optical studies of paramagnetic ions doped zinc potassium phosphate hexahydrate--part I: Cu(II)--a case of orthorhombic symmetry.

PubMed

Sambasiva Rao, P; Rajendiran, T M; Venkatesan, R; Madhu, N; Chandrasekhar, A V; Reddy, B J; Reddy, Y P; Ravikumar, R V

2001-12-01

Single crystal electron paramagnetic resonance (EPR) studies on Cu(II) doped zinc potassium phosphate hexahydrate (ZPPH) were carried out at room temperature. The angular variation spectra in the three orthogonal planes indicate that the paramagnetic impurity has entered the lattice substitutionally in place of Zn(II) and the spin Hamiltonian parameters calculated from these spectra are g(xx) = 2.188, g(yy) = 2.032, g(zz) = 2.373, Axx = 50 G, Ayy = 65.0 G and Azz = 80 G. The g and A tensors were coincident and these values matched fairly well with the values obtained from powder spectrum. The bonding parameters have also been calculated.

Energy dependence of the spin excitation anisotropy in uniaxial-strained BaFe 1.9Ni 0.1As 2

DOE PAGES

Song, Yu; Lu, Xingye; Abernathy, Douglas L.; ...

2015-11-06

In this study, we use inelastic neutron scattering to study the temperature and energy dependence of the spin excitation anisotropy in uniaxial-strained electron-doped iron pnictide BaFe 1.9Ni 0.1As 2 near optimal superconductivity (T c = 20K). Our work has been motivated by the observation of in-plane resistivity anisotropy in the paramagnetic tetragonal phase of electron-underdoped iron pnictides under uniaxial pressure, which has been attributed to a spin-driven Ising-nematic state or orbital ordering. Here we show that the spin excitation anisotropy, a signature of the spin-driven Ising-nematic phase, exists for energies below 60 meV in uniaxial-strained BaFe 1.9Ni 0.1As 2. Sincemore » this energy scale is considerably larger than the energy splitting of the d xz and d yz bands of uniaxial-strained Ba(Fe 1–xCox) 2As 2 near optimal superconductivity, spin Ising-nematic correlations are likely the driving force for the resistivity anisotropy and associated electronic nematic correlations.« less

Anisotropy reversal of the upper critical field at low temperatures and spin-locked superconductivity in K 2 Cr 3 As 3

DOE PAGES

Balakirev, F. F.; Kong, T.; Jaime, M.; ...

2015-06-23

We report measurements of the anisotropic upper critical field H c2(T) for K 2Cr 3As 3 single crystals up to 60 T and T>0.6K. Our results show that the upper critical field parallel to the Cr chains, H ∥ c2(T), exhibits a paramagnetically limited behavior, whereas the shape of the H ⊥ c2(T) curve (perpendicular to the Cr chains) has no evidence of paramagnetic effects. As a result, the curves H ⊥ c2(T) and H ∥ c2(T) cross at T≈4K, so that the anisotropy parameter γ H(T)=H ⊥ c2/H ∥ c2(T) increases from γ H(T c)≈0.35 near T c tomore » γ H(0)≈1.7 at 0.6 K. The paramagnetically limited behavior of H ∥ c2(T) is inconsistent with triplet superconductivity but suggests a form of singlet superconductivity with the electron spins locked onto the direction of Cr chains.« less

Electron spin control of optically levitated nanodiamonds in vacuum

NASA Astrophysics Data System (ADS)

Hoang, Thai; Ahn, Jonghoon; Bang, Jaehoon; Li, Tongcang

2016-05-01

Electron spins of diamond nitrogen-vacancy (NV) centers are important quantum resources for nanoscale sensing and quantum information. Combining such NV spin systems with levitated optomechanical resonators will provide a hybrid quantum system for many novel applications. Here we optically levitate a nanodiamond and demonstrate electron spin control of its built-in NV centers in low vacuum. We observe that the strength of electron spin resonance (ESR) is enhanced when the air pressure is reduced. To better understand this novel system, we also investigate the effects of trap power and measure the absolute internal temperature of levitated nanodiamonds with ESR after calibration of the strain effect.

Electronic interaction in an outer-sphere mixed-valence double salt: a polarized neutron diffraction study of K(3)(MnO(4))(2).

PubMed

Cannon, Roderick D; Jayasooriya, Upali A; Tilford, Claire; Anson, Christopher E; Sowrey, Frank E; Rosseinsky, David R; Stride, John A; Tasset, Francis; Ressouche, Eric; White, Ross P; Ballou, Rafik

2004-11-01

The mixed-valence double salt K(3)(MnO(4))(2) crystallizes in space group P2(1)/m with Z = 2. The manganese centers Mn1 and Mn2 constitute discrete "permanganate", [Mn(VII)O(4)](-), and "manganate", [Mn(VI)O(4)](2-), ions, respectively. There is a spin-ordering transition to an antiferromagnetic state at ca. T = 5 K. The spin-density distribution in the paramagnetic phase at T = 10 K has been determined by polarized neutron diffraction, confirming that unpaired spin is largely confined to the nominal manganate ion Mn2. Through use of both Fourier refinement and maximum entropy methods, the spin on Mn1 is estimated as 1.75 +/- 1% of one unpaired electron with an upper limit of 2.5%.

Infrared, Raman and Magnetic Resonance Spectroscopic Study of SiO2:C Nanopowders.

PubMed

Savchenko, Dariya; Vorliček, Vladimir; Kalabukhova, Ekaterina; Sitnikov, Aleksandr; Vasin, Andrii; Kysil, Dmytro; Sevostianov, Stanislav; Tertykh, Valentyn; Nazarov, Alexei

2017-12-01

Optical and magnetic properties of SiO 2 :C nanopowders obtained by chemical and thermal modification of fumed silica were studied by Fourier transform infrared spectroscopy, Raman, continuous wave (CW) electron paramagnetic resonance (EPR), echo-detected EPR and pulsed electron nuclear double resonance (ENDOR) spectroscopy. Two overlapping signals of Lorentzian lineshape were detected in CW EPR spectra of the initial SiO 2 :C. The EPR signal at g = 2.0055(3) is due to the silicon dangling bonds, which vanishes after thermal annealing, and the second EPR signal at g = 2.0033(3) was attributed to the carbon-related defect (CRD). The annealing of the SiO 2 :C samples gives rise to the increase of the CRD spin density and shift to the higher g-values due to the appearance of the oxygen in the vicinity of the CRD. Based on the temperature-dependent behavior of the CRD EPR signal intensity, linewidth and resonance field position we have attributed it to the spin system with non-localized electrons hopping between neighboring carbon dangling bonds, which undergo a strong exchange interaction with a localized spin system of carbon nanodots. The observed motional narrowing of the CRD EPR signal in the temperature interval from 4 to 20 K indicates that electrons are mobile at 4 K which can be explained by a quantum character of the conductivity in the vicinity of the carbon layer. The electrons trapped in quantum wells move from one carbon nanodot to another by hopping process through the energy barrier. The fact that echo-detected EPR signal at g = 2.0035(3) was observed in SiO 2 :C sample annealed at T ann  ≥ 700 °C serves as evidence that non-localized electrons coexist with localized electrons that have the superhyperfine interaction with surrounding 13 C and 29 Si nuclei located at the SiO 2 :C interface. The presence of the superhyperfine interaction of CRD with 1 H nuclei indicates the existence of hydrogenated regions in SiO 2 :C sample.

Magnetic properties of graphene quantum dots

NASA Astrophysics Data System (ADS)

Espinosa-Ortega, T.; Luk'yanchuk, I. A.; Rubo, Y. G.

2013-05-01

Using the tight-binding approximation we calculated the diamagnetic susceptibility of graphene quantum dots (GQDs) of different geometrical shapes and characteristic sizes of 2-10 nm, when the magnetic properties are governed by the electron edge states. Two types of edge states can be discerned: the zero-energy states (ZESs), located exactly at the zero-energy Dirac point, and the dispersed edge states (DESs), with the energy close but not exactly equal to zero. DESs are responsible for a temperature-independent diamagnetic response, while ZESs provide a temperature-dependent spin paramagnetism. Hexagonal, circular, and randomly shaped GQDs contain mainly DESs, and, as a result, they are diamagnetic. The edge states of the triangular GQDs are of ZES type. These dots reveal the crossover between spin paramagnetism, dominating for small dots and at low temperatures, and orbital diamagnetism, dominating for large dots and at high temperatures.

Melanin in Fonsecaea pedrosoi: a trap for oxidative radicals

PubMed Central

2010-01-01

Background The pathogenic fungus Fonsecaea pedrosoi constitutively produces the pigment melanin, an important virulence factor in fungi. Melanin is incorporated in the cell wall structure and provides chemical and physical protection for the fungus. We evaluated the production of nitric oxide (NO) in macrophages, the oxidative burst and the inducible nitric oxide synthase (i-NOS) activity in interactions between activated murine macrophages and F. pedrosoi. Experiments were carried out with or without tricyclazole (TC) treatment, a selective inhibitor of the dihydroxynaphthalene (DHN)-melanin biosynthesis pathway in F. pedrosoi. The paramagnetisms of melanin and the TC-melanin were analysed by electron spin resonance. The fungal growth responses to H2O2 and to S-nitroso-N-acetylpenicillamine (SNAP), a nitric oxide donor, were also evaluated. Results Melanised F. pedrosoi cells were more resistant to both H2O2 and NO. Nitrite was not detected in the supernatant of macrophages incubated with melanised fungal cells. However, i-NOS expression was unaffected by the presence of either untreated control F. pedrosoi or TC-treated F. pedrosoi. In addition, the inhibition of the DHN-melanin pathway by TC improved the oxidative burst capability of the macrophages. Conclusion The NO-trapping ability of F. pedrosoi melanin is an important mechanism to escape the oxidative burst of macrophages. PMID:20233438

Ageing and thermal recovery of paramagnetic centers induced by electron irradiation in yttria-stabilized zirconia

NASA Astrophysics Data System (ADS)

Costantini, J. M.; Beuneu, F.

We have used electron spin resonance spectroscopy to study the defects induced in yttria-stabilized zirconia (YSZ) single crystals by 2.5-MeV electron irradiations. Two paramagnetic centers are produced: the first one with an axial <111> symmetry is similar to the trigonal Zr3+ electron center (T center) found after X-ray irradiation or thermo-chemical reduction, whereas the second one is a new oxygen hole center with an axial <100> symmetry different from the orthorhombic O- center induced by X-ray irradiation. At a fluence around 10(18) e/cm(2) , both centers are bleached out near 600 K, like the corresponding X-ray induced defects. At a fluence around 10(19) e/cm(2) , defects are much more stable, since complete thermal bleaching occurs near 1000 K. Accordingly, ageing of as-irradiated samples shows that high-dose defects at more stable than the low-dose ones.

Calculation of nuclear spin-spin coupling constants using frozen density embedding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Götz, Andreas W., E-mail: agoetz@sdsc.edu; Autschbach, Jochen; Visscher, Lucas, E-mail: visscher@chem.vu.nl

2014-03-14

We present a method for a subsystem-based calculation of indirect nuclear spin-spin coupling tensors within the framework of current-spin-density-functional theory. Our approach is based on the frozen-density embedding scheme within density-functional theory and extends a previously reported subsystem-based approach for the calculation of nuclear magnetic resonance shielding tensors to magnetic fields which couple not only to orbital but also spin degrees of freedom. This leads to a formulation in which the electron density, the induced paramagnetic current, and the induced spin-magnetization density are calculated separately for the individual subsystems. This is particularly useful for the inclusion of environmental effects inmore » the calculation of nuclear spin-spin coupling constants. Neglecting the induced paramagnetic current and spin-magnetization density in the environment due to the magnetic moments of the coupled nuclei leads to a very efficient method in which the computationally expensive response calculation has to be performed only for the subsystem of interest. We show that this approach leads to very good results for the calculation of solvent-induced shifts of nuclear spin-spin coupling constants in hydrogen-bonded systems. Also for systems with stronger interactions, frozen-density embedding performs remarkably well, given the approximate nature of currently available functionals for the non-additive kinetic energy. As an example we show results for methylmercury halides which exhibit an exceptionally large shift of the one-bond coupling constants between {sup 199}Hg and {sup 13}C upon coordination of dimethylsulfoxide solvent molecules.« less

Measurement of the magnetic interaction between two bound electrons of two separate ions.

PubMed

Kotler, Shlomi; Akerman, Nitzan; Navon, Nir; Glickman, Yinnon; Ozeri, Roee

2014-06-19

Electrons have an intrinsic, indivisible, magnetic dipole aligned with their internal angular momentum (spin). The magnetic interaction between two electronic spins can therefore impose a change in their orientation. Similar dipolar magnetic interactions exist between other spin systems and have been studied experimentally. Examples include the interaction between an electron and its nucleus and the interaction between several multi-electron spin complexes. The challenge in observing such interactions for two electrons is twofold. First, at the atomic scale, where the coupling is relatively large, it is often dominated by the much larger Coulomb exchange counterpart. Second, on scales that are substantially larger than the atomic, the magnetic coupling is very weak and can be well below the ambient magnetic noise. Here we report the measurement of the magnetic interaction between the two ground-state spin-1/2 valence electrons of two (88)Sr(+) ions, co-trapped in an electric Paul trap. We varied the ion separation, d, between 2.18 and 2.76 micrometres and measured the electrons' weak, millihertz-scale, magnetic interaction as a function of distance, in the presence of magnetic noise that was six orders of magnitude larger than the magnetic fields the electrons apply on each other. The cooperative spin dynamics was kept coherent for 15 seconds, during which spin entanglement was generated, as verified by a negative measured value of -0.16 for the swap entanglement witness. The sensitivity necessary for this measurement was provided by restricting the spin evolution to a decoherence-free subspace that is immune to collective magnetic field noise. Our measurements show a d(-3.0(4)) distance dependence for the coupling, consistent with the inverse-cube law.

Role of crystal field in mixed alkali metal effect: electron paramagnetic resonance study of mixed alkali metal oxyfluoro vanadate glasses.

PubMed

Honnavar, Gajanan V; Ramesh, K P; Bhat, S V

2014-01-23

The mixed alkali metal effect is a long-standing problem in glasses. Electron paramagnetic resonance (EPR) is used by several researchers to study the mixed alkali metal effect, but a detailed analysis of the nearest neighbor environment of the glass former using spin-Hamiltonian parameters was elusive. In this study we have prepared a series of vanadate glasses having general formula (mol %) 40 V2O5-30BaF2-(30 - x)LiF-xRbF with x = 5, 10, 15, 20, 25, and 30. Spin-Hamiltonian parameters of V(4+) ions were extracted by simulating and fitting to the experimental spectra using EasySpin. From the analysis of these parameters it is observed that the replacement of lithium ions by rubidium ions follows a "preferential substitution model". Using this proposed model, we were able to account for the observed variation in the ratio of the g parameter, which goes through a maximum. This reflects an asymmetric to symmetric changeover of the alkali metal ion environment around the vanadium site. Further, this model also accounts for the variation in oxidation state of vanadium ion, which was confirmed from the variation in signal intensity of EPR spectra.

Singlet oxygen production in Chlamydomonas reinhardtii under heat stress.

PubMed

Prasad, Ankush; Ferretti, Ursula; Sedlářová, Michaela; Pospíšil, Pavel

2016-02-01

In the current study, singlet oxygen formation by lipid peroxidation induced by heat stress (40 °C) was studied in vivo in unicellular green alga Chlamydomonas reinhardtii. Primary and secondary oxidation products of lipid peroxidation, hydroperoxide and malondialdehyde, were generated under heat stress as detected using swallow-tailed perylene derivative fluorescence monitored by confocal laser scanning microscopy and high performance liquid chromatography, respectively. Lipid peroxidation was initiated by enzymatic reaction as inhibition of lipoxygenase by catechol and caffeic acid prevented hydroperoxide formation. Ultra-weak photon emission showed formation of electronically excited species such as triplet excited carbonyl, which, upon transfer of excitation energy, leads to the formation of either singlet excited chlorophyll or singlet oxygen. Alternatively, singlet oxygen is formed by direct decomposition of hydroperoxide via Russell mechanisms. Formation of singlet oxygen was evidenced by the nitroxyl radical 2,2,6,6-tetramethylpiperidine-1-oxyl detected by electron paramagnetic resonance spin-trapping spectroscopy and the imaging of green fluorescence of singlet oxygen sensor green detected by confocal laser scanning microscopy. Suppression of singlet oxygen formation by lipoxygenase inhibitors indicates that singlet oxygen may be formed via enzymatic lipid peroxidation initiated by lipoxygenase.

Spin Coherence in Silicon-based Quantum Structures and Devices

DTIC Science & Technology

2017-08-31

Using electron spin resonance (ESR) to measure the den- sity of shallow traps, we find that the two sets of devices are nearly identical , indicating...experiments which cannot utilize a clock transition or a field-cancelling decoherence-free subspace. Our approach was to lock the microwave source driving...the electron spins to a strong nuclear spin signal. In our initial experiments we locked to the proton signal in a water cell. However, the noise in

Cytotoxicity of InP/ZnS quantum dots related to reactive oxygen species generation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chibli, H.; Carlini, L.; Park, S.

Indium phosphide (InP) quantum dots (QDs) have emerged as a presumably less hazardous alternative to cadmium-based particles, but their cytotoxicity has not been well examined. Although their constituent elements are of very low toxicity to cells in culture, they nonetheless exhibit phototoxicity related to generation of reactive oxygen species by excited electrons and/or holes interacting with water and molecular oxygen. Using spin-trap electron paramagnetic resonance (EPR) spectroscopy and reporter assays, we find a considerable amount of superoxide and a small amount of hydroxyl radical formed under visible illumination of biocompatible InP QDs with a single ZnS shell, comparable to whatmore » is seen with CdTe. A double thickness shell reduces the reactive oxygen species concentration approximately two-fold. Survival assays in five cell lines correspondingly indicate a distinct reduction in toxicity with the double-shell InP QDs. Toxicity varies significantly across cell lines according to the efficiency of uptake, being overall significantly less than what is seen with CdTe or CdSe/ZnS. This indicates that InP QDs are a useful alternative to cadmium-containing QDs, while remaining capable of electron-transfer processes that may be undesirable or which may be exploited for photosensitization applications.« less

Cytotoxicity of InP/ZnS quantum dots related to reactive oxygen species generation.

PubMed

Chibli, Hicham; Carlini, Lina; Park, Soonhyang; Dimitrijevic, Nada M; Nadeau, Jay L

2011-06-01

Indium phosphide (InP) quantum dots (QDs) have emerged as a presumably less hazardous alternative to cadmium-based particles, but their cytotoxicity has not been well examined. Although their constituent elements are of very low toxicity to cells in culture, they nonetheless exhibit phototoxicity related to generation of reactive oxygen species by excited electrons and/or holes interacting with water and molecular oxygen. Using spin-trap electron paramagnetic resonance (EPR) spectroscopy and reporter assays, we find a considerable amount of superoxide and a small amount of hydroxyl radical formed under visible illumination of biocompatible InP QDs with a single ZnS shell, comparable to what is seen with CdTe. A double thickness shell reduces the reactive oxygen species concentration approximately two-fold. Survival assays in five cell lines correspondingly indicate a distinct reduction in toxicity with the double-shell InP QDs. Toxicity varies significantly across cell lines according to the efficiency of uptake, being overall significantly less than what is seen with CdTe or CdSe/ZnS. This indicates that InP QDs are a useful alternative to cadmium-containing QDs, while remaining capable of electron-transfer processes that may be undesirable or which may be exploited for photosensitization applications.

Cytotoxicity of InP/ZnS quantum dots related to reactive oxygen species generation

NASA Astrophysics Data System (ADS)

Chibli, Hicham; Carlini, Lina; Park, Soonhyang; Dimitrijevic, Nada M.; Nadeau, Jay L.

2011-06-01

Indium phosphide (InP) quantum dots (QDs) have emerged as a presumably less hazardous alternative to cadmium-based particles, but their cytotoxicity has not been well examined. Although their constituent elements are of very low toxicity to cells in culture, they nonetheless exhibit phototoxicity related to generation of reactive oxygen species by excited electrons and/or holes interacting with water and molecular oxygen. Using spin-trap electron paramagnetic resonance (EPR) spectroscopy and reporter assays, we find a considerable amount of superoxide and a small amount of hydroxyl radical formed under visible illumination of biocompatible InP QDs with a single ZnS shell, comparable to what is seen with CdTe. A double thickness shell reduces the reactive oxygen species concentration approximately two-fold. Survival assays in five cell lines correspondingly indicate a distinct reduction in toxicity with the double-shell InP QDs. Toxicity varies significantly across cell lines according to the efficiency of uptake, being overall significantly less than what is seen with CdTe or CdSe/ZnS. This indicates that InP QDs are a useful alternative to cadmium-containing QDs, while remaining capable of electron-transfer processes that may be undesirable or which may be exploited for photosensitization applications.

Revealing giant internal magnetic fields due to spin fluctuations in magnetically doped colloidal nanocrystals

DOE PAGES

Rice, William D.; Liu, Wenyong; Baker, Thomas A.; ...

2015-11-23

Strong quantum confinement in semiconductors can compress the wavefunctions of band electrons and holes to nanometre-scale volumes, significantly enhancing interactions between themselves and individual dopants. In magnetically doped semiconductors, where paramagnetic dopants (such as Mn 2+, Co 2+ and so on) couple to band carriers via strong sp–d spin exchange, giant magneto-optical effects can therefore be realized in confined geometries using few or even single impurity spins. Importantly, however, thermodynamic spin fluctuations become increasingly relevant in this few-spin limit. In nanoscale volumes, the statistical √N fluctuations of N spins are expected to generate giant effective magnetic fields B eff, whichmore » should dramatically impact carrier spin dynamics, even in the absence of any applied field. In this paper, we directly and unambiguously reveal the large B eff that exist in Mn 2+-doped CdSe colloidal nanocrystals using ultrafast optical spectroscopy. At zero applied magnetic field, extremely rapid (300–600 GHz) spin precession of photoinjected electrons is observed, indicating B eff ~ 15-30 T for electrons. Precession frequencies exceed 2 THz in applied magnetic fields. Finally, these signals arise from electron precession about the random fields due to statistically incomplete cancellation of the embedded Mn 2+ moments, thereby revealing the initial coherent dynamics of magnetic polaron formation, and highlighting the importance of magnetization fluctuations on carrier spin dynamics in nanomaterials.« less

Electron spin resonance (ESR) dose measurement in bone of Hiroshima A-bomb victim

PubMed Central

2018-01-01

Explosion of the bombs in Hiroshima and Nagasaki corresponds to the only historical moment when atomic bombs were used against civilians. This event triggered countless investigations into the effects and dosimetry of ionizing radiation. However, none of the investigations has used the victims’ bones as dosimeter. Here, we assess samples of bones obtained from fatal victims of the explosion by Electron Spin Resonance (ESR). In 1973, one of the authors of the present study (SM) traveled to Japan and conducted a preliminary experiment on the victims’ bone samples. The idea was to use the paramagnetism induced in bone after irradiation to measure the radiation dose. Technological advances involved in the construction of spectrometers, better knowledge of the paramagnetic center, and improvement in signal processing techniques have allowed us to resume the investigation. We obtained a reconstructed dose of 9.46 ± 3.4 Gy from the jawbone, which was compatible with the dose distribution in different locations as measured in non-biological materials such as wall bricks and roof tiles. PMID:29408890

Application of electron paramagnetic resonance imaging to the characterization of the Ultem(R) exposed to 1 MeV electrons. Correlation of radical density data to tiger code calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suleman, N.K.

1994-12-01

A major long-term goal of the Materials Division at the NASA Langley Research Center is the characterization of new high-performance materials that have potential applications in the aircraft industry, and in space. The materials used for space applications are often subjected to a harsh and potentially damaging radiation environment. The present study constitutes the application of a novel technique to obtain reliable data for ascertaining the molecular basis for the resilience and durability of materials that have been exposed to simulated space radiations. The radiations of greatest concern are energetic electrons and protons, as well as galactic cosmic rays. Presently,more » the effects of such radiation on matter are not understood in their entirety. It is clear however, that electron radiation causes ionization and homolytic bond rupture, resulting in the formation of paramagnetic spin centers in the polymer matrices of the structural materials. Since the detection and structure elucidation of paramagnetic species are most readily accomplished using Electron Paramagnetic Resonance (EPR) Spectroscopy, the NASA LaRC EPR system was brought back on-line during the 1991 ASEE term. The subsequent 1992 ASEE term was devoted to the adaptation of the EPR core system to meet the requirements for EPR Imaging (EPRI), which provides detailed information on the spatial distribution of paramagnetic species in bulk media. The present (1994) ASEE term was devoted to the calibration of this EPR Imaging system, as well as to the application of this technology to study the effects of electron irradiation on Ultem(exp R), a high performance polymer which is a candidate for applications in aerospace. The Ultem was exposed to a dose of 2.4 x 10(exp 9) Rads (1-MeV energy/electron) at the LaRC electron accelerator facility. Subsequently, the exposed specimens were stored in liquid nitrogen, until immediately prior to analyses by EPRI.« less

Strong spin-photon coupling in silicon

NASA Astrophysics Data System (ADS)

Samkharadze, N.; Zheng, G.; Kalhor, N.; Brousse, D.; Sammak, A.; Mendes, U. C.; Blais, A.; Scappucci, G.; Vandersypen, L. M. K.

2018-03-01

Long coherence times of single spins in silicon quantum dots make these systems highly attractive for quantum computation, but how to scale up spin qubit systems remains an open question. As a first step to address this issue, we demonstrate the strong coupling of a single electron spin and a single microwave photon. The electron spin is trapped in a silicon double quantum dot, and the microwave photon is stored in an on-chip high-impedance superconducting resonator. The electric field component of the cavity photon couples directly to the charge dipole of the electron in the double dot, and indirectly to the electron spin, through a strong local magnetic field gradient from a nearby micromagnet. Our results provide a route to realizing large networks of quantum dot–based spin qubit registers.

Preserving electron spin coherence in solids by optimal dynamical decoupling.

PubMed

Du, Jiangfeng; Rong, Xing; Zhao, Nan; Wang, Ya; Yang, Jiahui; Liu, R B

2009-10-29

To exploit the quantum coherence of electron spins in solids in future technologies such as quantum computing, it is first vital to overcome the problem of spin decoherence due to their coupling to the noisy environment. Dynamical decoupling, which uses stroboscopic spin flips to give an average coupling to the environment that is effectively zero, is a particularly promising strategy for combating decoherence because it can be naturally integrated with other desired functionalities, such as quantum gates. Errors are inevitably introduced in each spin flip, so it is desirable to minimize the number of control pulses used to realize dynamical decoupling having a given level of precision. Such optimal dynamical decoupling sequences have recently been explored. The experimental realization of optimal dynamical decoupling in solid-state systems, however, remains elusive. Here we use pulsed electron paramagnetic resonance to demonstrate experimentally optimal dynamical decoupling for preserving electron spin coherence in irradiated malonic acid crystals at temperatures from 50 K to room temperature. Using a seven-pulse optimal dynamical decoupling sequence, we prolonged the spin coherence time to about 30 mus; it would otherwise be about 0.04 mus without control or 6.2 mus under one-pulse control. By comparing experiments with microscopic theories, we have identified the relevant electron spin decoherence mechanisms in the solid. Optimal dynamical decoupling may be applied to other solid-state systems, such as diamonds with nitrogen-vacancy centres, and so lay the foundation for quantum coherence control of spins in solids at room temperature.

Selective electron spin resonance measurements of micrometer-scale thin samples on a substrate

NASA Astrophysics Data System (ADS)

Dikarov, Ekaterina; Fehr, Matthias; Schnegg, Alexander; Lips, Klaus; Blank, Aharon

2013-11-01

An approach to the selective observation of paramagnetic centers in thin samples or surfaces with electron spin resonance (ESR) is presented. The methodology is based on the use of a surface microresonator that enables the selective obtention of ESR data from thin layers with minimal background signals from the supporting substrate. An experimental example is provided, which measures the ESR signal from a 1.2 µm polycrystalline silicon layer on a glass substrate used in modern solar-cell technology. The ESR results obtained with the surface microresonator show the effective elimination of background signals, especially at low cryogenic temperatures, compared to the use of a conventional resonator. The surface microresonator also facilitates much higher absolute spin sensitivity, requiring much smaller surfaces for the measurement.

Polarized Neutron Diffraction to Probe Local Magnetic Anisotropy of a Low-Spin Fe(III) Complex.

PubMed

Ridier, Karl; Mondal, Abhishake; Boilleau, Corentin; Cador, Olivier; Gillon, Béatrice; Chaboussant, Grégory; Le Guennic, Boris; Costuas, Karine; Lescouëzec, Rodrigue

2016-03-14

We have determined by polarized neutron diffraction (PND) the low-temperature molecular magnetic susceptibility tensor of the anisotropic low-spin complex PPh4 [Fe(III) (Tp)(CN)3]⋅H2O. We found the existence of a pronounced molecular easy magnetization axis, almost parallel to the C3 pseudo-axis of the molecule, which also corresponds to a trigonal elongation direction of the octahedral coordination sphere of the Fe(III) ion. The PND results are coherent with electron paramagnetic resonance (EPR) spectroscopy, magnetometry, and ab initio investigations. Through this particular example, we demonstrate the capabilities of PND to provide a unique, direct, and straightforward picture of the magnetic anisotropy and susceptibility tensors, offering a clear-cut way to establish magneto-structural correlations in paramagnetic molecular complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis Properties and Electron Spin Resonance Properties of Titanic Materials (abstract)

NASA Astrophysics Data System (ADS)

Cho, Jung Min; Lee, Jun; Kim, Tak Hee; Sun, Min Ho; Jang, Young Bae; Cho, Sung June

2009-04-01

Titanic materials were synthesized by hydrothermal method of TiO2 anatase in 10M LiOH, 10M NaOH, and 14M KOH at 130° C for 30 hours. Alkaline media were removed from the synthesized products using 0.1N HCl aqueous solution. The as-prepared samples were characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, Brunauer-Emmett-Teller isotherm, and electron spin resonance. Different shapes of synthesized products were observed through the typical electron microscope and indicated that the formation of the different morphologies depends on the treatment conditions of highly alkaline media. Many micropores were observed in the cubic or octahedral type of TiO2 samples through the typical electron microscope and Langmuir adsorption-desorption isotherm of liquid nitrogen at 77° K. Electron spin resonance studies have also been carried out to verify the existence of paramagnetic sites such as oxygen vacancies on the titania samples. The effect of alkali metal ions on the morphologies and physicochemical properties of nanoscale titania are discussed.

Dynamics of paramagnetic agents by off-resonance rotating frame technique in the presence of magnetization transfer effect

NASA Astrophysics Data System (ADS)

Zhang, Huiming; Xie, Yang

2007-02-01

The simple method for measuring the rotational correlation time of paramagnetic ion chelates via off-resonance rotating frame technique is challenged in vivo by the magnetization transfer effect. A theoretical model for the spin relaxation of water protons in the presence of paramagnetic ion chelates and magnetization transfer effect is described. This model considers the competitive relaxations of water protons by the paramagnetic relaxation pathway and the magnetization transfer pathway. The influence of magnetization transfer on the total residual z-magnetization has been quantitatively evaluated in the context of the magnetization map and various difference magnetization profiles for the macromolecule conjugated Gd-DTPA in cross-linked protein gels. The numerical simulations and experimental validations confirm that the rotational correlation time for the paramagnetic ion chelates can be measured even in the presence of strong magnetization transfer. This spin relaxation model also provides novel approaches to enhance the detection sensitivity for paramagnetic labeling by suppressing the spin relaxations caused by the magnetization transfer. The inclusion of the magnetization transfer effect allows us to use the magnetization map as a simulation tool to design efficient paramagnetic labeling targeting at specific tissues, to design experiments running at low RF power depositions, and to optimize the sensitivity for detecting paramagnetic labeling. Thus, the presented method will be a very useful tool for the in vivo applications such as molecular imaging via paramagnetic labeling.

Electron paramagnetic resonance spectra of CdO-Al2O3-Bi2O3-B2O3 quaternary glasses containing VO2+ ions

NASA Astrophysics Data System (ADS)

Lalithaphani, A. V.; Srinivas, B.; Hameed, Abdul; Chary, M. Narasimha; Shareefuddin, Md.

2018-04-01

Borate glasses containing different concentrations of heavy metal oxide (CdO) with 2mol% of V2O5 as the paramagnetic probe were prepared by the conventional melt quenching technique. The prepared glasses were characterized by XRD to confirm the amorphous nature. EPR and Optical absorption studies were carried out at room temperature. EPR spectra of these glass samples were recorded at X-band frequency with 100 kHz field modulation at room temperature. From the EPR spectra the spin-Hamiltonian parameters were evaluated. The spin-Hamiltonian parameter values indicated that g|| < g┴ < ge [=2.0023] and A∥︀ > A┴. This suggests that VO2+ ions are present in octahedral sites with tetragonal compression and belong to C4v symmetry with dxy being the ground state. The measure of tetragonal distortion (Δg∥︀/Δg┴)varies non-linearly with glass composition indicating change in tetragonal distortion. The covalency rates were estimated. The number of spins participating in the resonance [N] and susceptibility (χ) values were also evaluated.

Synthesis and characterization of gadolinium nanosheets with bound rose bengal: potential use in photodynamic therapy and MRI

NASA Astrophysics Data System (ADS)

Stefanakis, Dimitrios; Seimenis, Ioannis; Ghanotakis, Demetrios

2014-11-01

Gadolinium (Gd) is a trivalent paramagnetic element, making it useful as a contrast agent for magnetic resonance imaging (MRI). Gd2(OH)5NO3· xH2O belongs to a new family of nanosheets. The advantages of these materials are their relatively small size, paramagnetic behavior, stability, lack of toxicity and highly ordered structure. In the present study, Gd2(OH)5NO3 nanosheets were functionalized with amino groups and modified with the photosensitiser rose bengal (RB). This surface modification makes possible the use of the nanosheets in photodynamic therapy. The coated nanosheets were characterized with X-ray diffraction, fourier transform infrared spectroscopy and UV-Vis spectroscopy, as well as transmission electron microscopy. The possibility of using these nanosheets as potential spin-lattice ( T 1) and spin-spin relaxation ( T 2) contrast agents in MRI was evaluated at 1.5 T. Finally, the ability of Gd2(OH)5NO3-RB to catalyze photooxidization reactions was examined using nuclear magnetic resonance (1H NMR) and gas chromatography-mass spectrometry (GC/MS).

Pulse Double-Resonance EPR Techniques for the Study of Metallobiomolecules.

PubMed

Cox, Nicholas; Nalepa, Anna; Pandelia, Maria-Eirini; Lubitz, Wolfgang; Savitsky, Anton

2015-01-01

Electron paramagnetic resonance (EPR) spectroscopy exploits an intrinsic property of matter, namely the electron spin and its related magnetic moment. This can be oriented in a magnetic field and thus, in the classical limit, acts like a little bar magnet. Its moment will align either parallel or antiparallel to the field, giving rise to different energies (termed Zeeman splitting). Transitions between these two quantized states can be driven by incident microwave frequency radiation, analogous to NMR experiments, where radiofrequency radiation is used. However, the electron Zeeman interaction alone provides only limited information. Instead, much of the usefulness of EPR is derived from the fact that the electron spin also interacts with its local magnetic environment and thus can be used to probe structure via detection of nearby spins, e.g., NMR-active magnetic nuclei and/or other electron spin(s). The latter is exploited in spin labeling techniques, an exciting new area in the development of noncrystallographic protein structure determination. Although these interactions are often smaller than the linewidth of the EPR experiment, sophisticated pulse EPR methods allow their detection. A number of such techniques are well established today and can be broadly described as double-resonance methods, in which the electron spin is used as a reporter. Below we give a brief description of pulse EPR methods, particularly their implementation at higher magnetic fields, and how to best exploit them for studying metallobiomolecules. © 2015 Elsevier Inc. All rights reserved.

Spatially resolved nuclear spin relaxation, electron spin relaxation and light absorption in swift heavy ion irradiated LiF crystals.

PubMed

Stork, H; Dinse, K-P; Ditter, M; Fujara, F; Masierak, W; Neumann, R; Schuster, B; Schwartz, K; Trautmann, C

2010-05-12

Spatially resolved (19)F and (7)Li spin-lattice relaxation rates are measured for LiF single crystals after irradiation with two kinds of swift heavy ions ((12)C of 133 MeV and (208)Pb of 1.78 GeV incident energy). Like in earlier studies on (130)Xe and (238)U irradiated LiF crystals, we found a strong enhancement of the nuclear spin-lattice relaxation rate within the ion penetration depth and a slight--but still significant--enhancement beyond. By evaluating the nuclear relaxation rate enhancement within the ion range after irradiation with different projectiles, a universal relationship between the spin-lattice relaxation rate and the dose is deduced. The results of accompanying X-band electron paramagnetic resonance relaxation measurements and optical absorption spectroscopy are included in a physical interpretation of this relationship. Also the reason for the enhanced relaxation rate beyond the ion range is further discussed.

Free-radical probes for functional in vivo EPR imaging

NASA Astrophysics Data System (ADS)

Subramanian, S.; Krishna, M. C.

2007-02-01

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

Free-radical chemistry as a means to evaluate lunar dust health hazard in view of future missions to the moon.

PubMed

Turci, Francesco; Corazzari, Ingrid; Alberto, Gabriele; Martra, Gianmario; Fubini, Bice

2015-05-01

Lunar dust toxicity has to be evaluated in view of future manned missions to the Moon. Previous studies on lunar specimens and simulated dusts have revealed an oxidant activity assigned to HO· release. However, the mechanisms behind the reactivity of lunar dust are still quite unclear at the molecular level. In the present study, a complementary set of tests--including terephthalate (TA) hydroxylation, free radical release as measured by means of the spin-trapping/electron paramagnetic resonance (EPR) technique, and cell-free lipoperoxidation--is proposed to investigate the reactions induced by the fine fraction of a lunar dust analogue (JSC-1A-vf) in biologically relevant experimental environments. Our study proved that JSC-1A-vf is able to hydroxylate TA also in anaerobic conditions, which indicates that molecular oxygen is not involved in such a reaction. Spin-trapping/EPR measures showed that the HO· radical is not the reactive intermediate involved in the oxidative potential of JSC-1A-vf. A surface reactivity implying a redox cycle of phosphate-complexed iron via a Fe(IV) state is proposed. The role of this iron species was investigated by assessing the reactivity of JSC-1A-vf toward hydrogen peroxide (Fenton-like activity), formate ions (homolytic rupture of C-H bond), and linoleic acid (cell-free lipoperoxidation). JSC-1A-vf was active in all tests, confirming that redox centers of transition metal ions on the surface of the dust may be responsible for dust reactivity and that the TA assay may be a useful field probe to monitor the surface oxidative potential of lunar dust.

Search for exotic short-range interactions using paramagnetic insulators

DOE PAGES

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

2015-05-26

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

Electron Spin Relaxation Rates for High-Spin Fe(III) in Iron Transferrin Carbonate and Iron Transferrin Oxalate

PubMed Central

Gaffney, Betty Jean; Eaton, Gareth R.; Eaton*, Sandra S.

2005-01-01

To optimize simulations of CW EPR spectra for high-spin Fe(III) with zero-field splitting comparable to the EPR quantum, information is needed on the factors that contribute to the line shapes and line widths. Continuous wave electron paramagnetic resonance (EPR) spectra obtained for iron transferrin carbonate from 4 to 150 K and for iron transferrin oxalate from 4 to 100 K did not exhibit significant temperature dependence of the line shape, which suggested that the line shapes were not relaxation determined. To obtain direct information concerning the electron spin relaxation rates, electron spin echo and inversion recovery EPR were used to measure T1 and Tm for the high-spin Fe(III) in iron transferrin carbonate and iron transferrin oxalate between 5 and 20–30 K. For comparison with the data for the transferrin complexes, relaxation times were obtained for tris(oxalato)ferrate(III). The relaxation rates are similar for the three complexes and do not exhibit a strong dependence on position in the spectrum. Extrapolation of the observed temperature dependence of the relaxation rates to higher temperatures gives values consistent with the conclusion that the CW line shapes are not relaxation determined up to 150 K. PMID:16429607

Single-shot quantum nondemolition measurement of a quantum-dot electron spin using cavity exciton-polaritons

NASA Astrophysics Data System (ADS)

Puri, Shruti; McMahon, Peter L.; Yamamoto, Yoshihisa

2014-10-01

We propose a scheme to perform single-shot quantum nondemolition (QND) readout of the spin of an electron trapped in a semiconductor quantum dot (QD). Our proposal relies on the interaction of the QD electron spin with optically excited, quantum well (QW) microcavity exciton-polaritons. The spin-dependent Coulomb exchange interaction between the QD electron and cavity polaritons causes the phase and intensity response of left circularly polarized light to be different than that of right circularly polarized light, in such a way that the QD electron's spin can be inferred from the response to a linearly polarized probe reflected or transmitted from the cavity. We show that with careful device design it is possible to essentially eliminate spin-flip Raman transitions. Thus a QND measurement of the QD electron spin can be performed within a few tens of nanoseconds with fidelity ˜99.95%. This improves upon current optical QD spin readout techniques across multiple metrics, including speed and scalability.

Paramagnetic species on catalytic surfaces--DFT investigations into structure sensitivity of the hyperfine coupling constants.

PubMed

Sojka, Zbigniew; Pietrzyk, Piotr

2004-05-01

Structure sensitivity of the hyperfine coupling constants was investigated by means of DFT calculations for selected surface paramagnetic species. A *CH2OH radical trapped on silica and intrazeolite copper nitrosyl adducts encaged in ZSM-5 were taken as the examples. The surface of amorphous silica was modeled with a [Si5O8H10] cluster, whereas the zeolite hosting sites were epitomized by [Si4AlO5(OH)10]- cluster. Three different coordination modes of the *CH2OH radical were considered and the isotropic 13C and 1H hyperfine constants of the resultant van der Waals complexes, calculated with B3LYP/6-311G(d), were discussed in terms of the angular deformations caused by hydrogen bonds with the cluster. The magnetic parameters of the eta1-N[CuNO]11 and eta1-O[CuNO]11 linkage isomers were calculated at the BPW91/LanL2DZ and 6-311G(df) level. For the most stable eta1-N adduct a clear dependence of the spin density distribution within the Cu-NO moiety on changes in the Cu-N-O angle and the Cu-N bond distance was observed and accounted for by varying spin polarization and delocalization contributions.

A magnetic trap for living cells suspended in a paramagnetic buffer

NASA Astrophysics Data System (ADS)

Winkleman, Adam; Gudiksen, Katherine L.; Ryan, Declan; Whitesides, George M.; Greenfield, Derek; Prentiss, Mara

2004-09-01

This manuscript describes the fabrication and use of a three-dimensional magnetic trap for diamagnetic objects in an aqueous solution of paramagnetic ions; this trap uses permanent magnets. It demonstrates trapping of polystyrene spheres, and of various types of living cells: mouse fibroblast (NIH-3T3), yeast (Saccharomyces cerevisiae), and algae (Chlamydomonas reinhardtii). For a 40mM solution of gadolinium (III) diethylenetriaminepentaacetic acid (Gd .DTPA) in aqueous buffer, the smallest cell (particle) that could be trapped had a radius of ˜2.5μm. The trapped particle and location of the magnetic trap can be translated in three dimensions by independent manipulation of the permanent magnets. This letter a1so characterizes the biocompatibility of the trapping solution.

Tipping the magnetic instability in paramagnetic S r 3 R u 2 O 7 by Fe impurities [Tipping the magnetic instability in paramagnetic S r 3 R u 2 O 7 by modest Fe substitution

DOE PAGES

Zhu, M.; Wang, Y.; Li, P. G.; ...

2017-05-19

We report the magnetic and electronic properties of the bilayer ruthenate Sr 3Ru 2O 7 upon Fe substitution for Ru. We find that Sr 3(Ru 1-xFe x) 2O 7 shows spin-glass-like phase below 4 K for x = 0.01 and commensurate E-type antiferromagnetically ordered insulating ground state characterized by the propagation vector q c = (0.25 0.25 0) for x ≥ 0.03, in contrast to the paramagnetic metallic state in the parent compound with strong spin fluctuations occurring at wave vectors q = (0.09 0 0) and (0.25 0 0). The observed antiferromagnetic ordering is quasitwo-dimensional with very short correlationmore » length along the c axis, a feature similar to the Mndoped Sr 3Ru 2O 7. Lastly, our results suggest that this ordered ground state is associated with the intrinsic magnetic instability in the pristine compound, which can be readily tipped by the local magnetic coupling between the 3d orbitals of the magnetic dopants and Ru 4d orbitals.« less

Electron interactions, spin-orbit coupling, intersite correlations in pyrochlore iridates: a comparison of single-site and cluster calculations

NASA Astrophysics Data System (ADS)

Wang, Runzhi; Go, Ara; Millis, Andrew

Pyrochlore iridates (R2 Ir2O7) are studied using density functional theory plus single-site and cluster dynamical mean-field theory (DFT+DMFT). The calculations include spin-orbit coupling. Significant differences between the single-site and cluster calculations are found. The single-site approximation fails to account for the properties of the paramagnetic insulator phase, in particular predicting a larger gap than found in experiments, while cluster calculations yield gaps consistent with transport data. A ground-state phase diagram is computed. Paramagnetic metal, metallic all-in/all-out (AIAO) and insulating AIAO phases are found. Tilted Weyl cones are observed in the AIAO metallic phase for a relatively wide range of interaction strength. Our paramagnetic calculations predict almost identical behaviors for the Y and Eu compound, conflicting with the strong material dependence reported in experiments. Inclusion of magnetic order restores the material difference. The physical origin of the difference is discussed. The results indicate that intersite effects, most likely of antiferromagnetic origin, play an important role in studying the physics of pyrochlore iridates. This work is supported by DOE-ER046169.

Tipping the magnetic instability in paramagnetic S r 3 R u 2 O 7 by Fe impurities [Tipping the magnetic instability in paramagnetic S r 3 R u 2 O 7 by modest Fe substitution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, M.; Wang, Y.; Li, P. G.

We report the magnetic and electronic properties of the bilayer ruthenate Sr 3Ru 2O 7 upon Fe substitution for Ru. We find that Sr 3(Ru 1-xFe x) 2O 7 shows spin-glass-like phase below 4 K for x = 0.01 and commensurate E-type antiferromagnetically ordered insulating ground state characterized by the propagation vector q c = (0.25 0.25 0) for x ≥ 0.03, in contrast to the paramagnetic metallic state in the parent compound with strong spin fluctuations occurring at wave vectors q = (0.09 0 0) and (0.25 0 0). The observed antiferromagnetic ordering is quasitwo-dimensional with very short correlationmore » length along the c axis, a feature similar to the Mndoped Sr 3Ru 2O 7. Lastly, our results suggest that this ordered ground state is associated with the intrinsic magnetic instability in the pristine compound, which can be readily tipped by the local magnetic coupling between the 3d orbitals of the magnetic dopants and Ru 4d orbitals.« less

Charge ordering transition in GdBaCo2O5: Evidence of reentrant behavior

NASA Astrophysics Data System (ADS)

Allieta, M.; Scavini, M.; Lo Presti, L.; Coduri, M.; Loconte, L.; Cappelli, S.; Oliva, C.; Ghigna, P.; Pattison, P.; Scagnoli, V.

2013-12-01

We present a detailed study on the charge ordering transition in a GdBaCo2O5.0 system by combining high-resolution synchrotron powder/single-crystal diffraction with electron paramagnetic resonance experiments as a function of temperature. We found a second-order structural phase transition at TCO = 247 K (Pmmm to Pmma) associated with the onset of long-range charge ordering. At Tmin ≈ 1.2TCO, the electron paramagnetic resonance linewidth rapidly broadens, providing evidence of antiferromagnetic spin fluctuations. This likely indicates that, analogously to manganites, the long-range antiferromagnetic order in GdBaCo2O5.0 sets in at ≈TCO. Pair distribution function analysis of diffraction data revealed signatures of structural inhomogeneities at low temperature. By comparing the average and local bond valences, we found that above TCO the local structure is consistent with a fully random occupation of Co2+ and Co3+ in a 1:1 ratio and with a complete charge ordering below TCO. Below T ≈ 100 K the charge localization is partially melted at the local scale, suggesting a reentrant behavior of charge ordering. This result is supported by the weakening of superstructure reflections and the temperature evolution of electron paramagnetic resonance linewidth that is consistent with paramagnetic reentrant behavior reported in the GdBaCo2O5.5 parent compound.

Distance measurements across randomly distributed nitroxide probes from the temperature dependence of the electron spin phase memory time at 240 GHz

NASA Astrophysics Data System (ADS)

Edwards, Devin T.; Takahashi, Susumu; Sherwin, Mark S.; Han, Songi

2012-10-01

At 8.5 T, the polarization of an ensemble of electron spins is essentially 100% at 2 K, and decreases to 30% at 20 K. The strong temperature dependence of the electron spin polarization between 2 and 20 K leads to the phenomenon of spin bath quenching: temporal fluctuations of the dipolar magnetic fields associated with the energy-conserving spin "flip-flop" process are quenched as the temperature of the spin bath is lowered to the point of nearly complete spin polarization. This work uses pulsed electron paramagnetic resonance (EPR) at 240 GHz to investigate the effects of spin bath quenching on the phase memory times (TM) of randomly-distributed ensembles of nitroxide molecules below 20 K at 8.5 T. For a given electron spin concentration, a characteristic, dipolar flip-flop rate (W) is extracted by fitting the temperature dependence of TM to a simple model of decoherence driven by the spin flip-flop process. In frozen solutions of 4-Amino-TEMPO, a stable nitroxide radical in a deuterated water-glass, a calibration is used to quantify average spin-spin distances as large as r¯=6.6 nm from the dipolar flip-flop rate. For longer distances, nuclear spin fluctuations, which are not frozen out, begin to dominate over the electron spin flip-flop processes, placing an effective ceiling on this method for nitroxide molecules. For a bulk solution with a three-dimensional distribution of nitroxide molecules at concentration n, we find W∝n∝1/r, which is consistent with magnetic dipolar spin interactions. Alternatively, we observe W∝n for nitroxides tethered to a quasi two-dimensional surface of large (Ø ˜ 200 nm), unilamellar, lipid vesicles, demonstrating that the quantification of spin bath quenching can also be used to discern the geometry of molecular assembly or organization.

Characterization of radiation-induced damage in high performance polymers by electron paramagnetic resonance imaging spectroscopy

NASA Technical Reports Server (NTRS)

Suleman, Naushadalli K.

1992-01-01

The potential for long-term human activity beyond the Earth's protective magnetosphere is limited in part by the lack of detailed information on the effectiveness and performance of existing structural materials to shield the crew and spacecraft from highly penetrating space radiations. The two radiations of greatest concern are high energy protons emitted during solar flares and galactic cosmic rays which are energetic ions ranging from protons to highly oxidized iron. Although the interactions of such high-energy radiations with matter are not completely understood at this time, the effects of the incident radiation are clearly expected to include the formation of paramagnetic spin centers via ionization and bond-scission reactions in the molecular matrices of structural materials. Since this type of radiation damage is readily characterized by Electron Paramagnetic Resonance (EPR) spectroscopy, the NASA Langley Research Center EPR system was repaired and brought on-line during the 1991 ASEE term. A major goal of the 1992 ASEE term was to adapt the existing core of the LaRC EPR system to meet the requirements for EPR Imaging--a powerful new technique which provides detailed information on the internal structure of materials by mapping the spatial distribution of unpaired spin density in bulk media. Major impetus for this adaptation arises from the fact that information derived from EPRI complements other methods such as scanning electron microscopy which primarily characterize surface phenomena. The modification of the EPR system has been initiated by the construction of specially designed, counterwound Helmholtz coils which will be mounted on the main EPR electromagnet. The specifications of the coils have been set to achieve a static linear magnetic field gradient of 10 gauss/mm/amp along the principal (Z) axis of the Zeeman field. Construction is also in progress of a paramagnetic standard in which the spin distribution is known in all three dimensions. This sample will be used to assess the linearity of the magnetic field gradient and to ensure authentic image reconstruction. A second major task was to secure the computer capability to enable image reconstruction from projection data generated by the magnetic field gradients. To this end, commercially available and public domain software packages which perform inverse Fourier Transform and convoluted (filtered) back projection functions are being integrated into the existing EPR data processing system.

EPR and Ferromagnetism in Diluted Magnetic Semiconductor Quantum Wells

NASA Astrophysics Data System (ADS)

König, Jürgen; MacDonald, Allan H.

2003-08-01

Motivated by recent measurements of electron paramagnetic resonance spectra in modulation-doped CdMnTe quantum wells [

Pentacene appended to a TEMPO stable free radical: the effect of magnetic exchange coupling on photoexcited pentacene.

PubMed

Chernick, Erin T; Casillas, Rubén; Zirzlmeier, Johannes; Gardner, Daniel M; Gruber, Marco; Kropp, Henning; Meyer, Karsten; Wasielewski, Michael R; Guldi, Dirk M; Tykwinski, Rik R

2015-01-21

Understanding the fundamental spin dynamics of photoexcited pentacene derivatives is important in order to maximize their potential for optoelectronic applications. Herein, we report on the synthesis of two pentacene derivatives that are functionalized with the [(2,2,6,6-tetramethylpiperidin-1-yl)oxy] (TEMPO) stable free radical. The presence of TEMPO does not quench the pentacene singlet excited state, but does quench the photoexcited triplet excited state as a function of TEMPO-to-pentacene distance. Time-resolved electron paramagnetic resonance experiments confirm that triplet quenching is accompanied by electron spin polarization transfer from the pentacene excited state to the TEMPO doublet state in the weak coupling regime.

Magnetic Ordering in Gold Nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Agrachev, Mikhail; Antonello, Sabrina; Dainese, Tiziano

Here, several research groups have observed magnetism in monolayer-protected gold-cluster samples, but the results were often contradictory and thus a clear understanding of this phenomenon is still missing. We used Au 25(SCH 2CH 2Ph) 18 0, which is a paramagnetic cluster that can be prepared with atomic precision and whose structure is known precisely. Previous magnetometry studies only detected paramagnetism. We used samples representing a range of crystallographic orders and studied their magnetic behaviors by electron paramagnetic resonance (EPR). As a film, Au 25(SCH 2CH 2Ph) 18 0 displays paramagnetic behavior but, at low temperature, ferromagnetic interactions are detectable. Onemore » or few single crystals undergo physical reorientation with the applied field and display ferromagnetism, as detected through hysteresis experiments. A large collection of microcrystals is magnetic even at room temperature and shows distinct paramagnetic, superparamagnetic, and ferromagnetic behaviors. Simulation of the EPR spectra shows that both spin-orbit coupling and crystal distortion are important to determine the observed magnetic behaviors. DFT calculations carried out on single cluster and periodic models predict values of spin6orbit coupling and crystal6splitting effects in agreement with the EPR derived quantities. Magnetism in gold nanoclusters is thus demonstrated to be the outcome of a very delicate balance of factors. To obtain reproducible results, the samples must be (i) controlled for composition and thus be monodispersed with atomic precision, (ii) of known charge state, and (iii) well defined also in terms of crystallinity and experimental conditions. This study highlights the efficacy of EPR spectroscopy to provide a molecular understanding of these phenomena« less

Magnetic Ordering in Gold Nanoclusters

DOE PAGES

Agrachev, Mikhail; Antonello, Sabrina; Dainese, Tiziano; ...

2017-06-12

Here, several research groups have observed magnetism in monolayer-protected gold-cluster samples, but the results were often contradictory and thus a clear understanding of this phenomenon is still missing. We used Au 25(SCH 2CH 2Ph) 18 0, which is a paramagnetic cluster that can be prepared with atomic precision and whose structure is known precisely. Previous magnetometry studies only detected paramagnetism. We used samples representing a range of crystallographic orders and studied their magnetic behaviors by electron paramagnetic resonance (EPR). As a film, Au 25(SCH 2CH 2Ph) 18 0 displays paramagnetic behavior but, at low temperature, ferromagnetic interactions are detectable. Onemore » or few single crystals undergo physical reorientation with the applied field and display ferromagnetism, as detected through hysteresis experiments. A large collection of microcrystals is magnetic even at room temperature and shows distinct paramagnetic, superparamagnetic, and ferromagnetic behaviors. Simulation of the EPR spectra shows that both spin-orbit coupling and crystal distortion are important to determine the observed magnetic behaviors. DFT calculations carried out on single cluster and periodic models predict values of spin6orbit coupling and crystal6splitting effects in agreement with the EPR derived quantities. Magnetism in gold nanoclusters is thus demonstrated to be the outcome of a very delicate balance of factors. To obtain reproducible results, the samples must be (i) controlled for composition and thus be monodispersed with atomic precision, (ii) of known charge state, and (iii) well defined also in terms of crystallinity and experimental conditions. This study highlights the efficacy of EPR spectroscopy to provide a molecular understanding of these phenomena« less

Kondo necklace model in approximants of Fibonacci chains

NASA Astrophysics Data System (ADS)

Reyes, Daniel; Tarazona, H.; Cuba-Supanta, G.; Landauro, C. V.; Espinoza, R.; Quispe-Marcatoma, J.

2017-11-01

The low energy behavior of the one dimensional Kondo necklace model with structural aperiodicity is studied using a representation for the localized and conduction electron spins, in terms of local Kondo singlet and triplet operators at zero temperature. A decoupling scheme on the double time Green's functions is used to find the dispersion relation for the excitations of the system. We determine the dependence between the structural aperiodicity modulation and the spin gap in a Fibonacci approximant chain at zero temperature and in the paramagnetic side of the phase diagram.

Multi-level modeling of total ionizing dose in a-silicon dioxide: First principles to circuits

NASA Astrophysics Data System (ADS)

Nicklaw, Christopher J.

Oxygen vacancies have long been known to be the dominant intrinsic defect in amorphous SiO2. They exist, in concentrations dependent on processing conditions, as neutral defects in thermal oxides without usually causing any significant deleterious effects, with some spatial and energy distribution. During irradiation they can capture holes and become positively charged E '-centers, contributing to device degradation. Over the years, a considerable database has been amassed on the dynamics of E' -centers in bulk SiO2 films, and near the interface under different irradiation and annealing conditions. Theoretical calculations so far have revealed the basic properties of prototype oxygen vacancies, primarily as they behave in either a crystalline quartz environment, or in small clusters that serve as a substitute for a real amorphous structure. To date at least three categories of E'-centers, existing at or above room temperature, have been observed in SiO2. The unifying feature is an unpaired electron on a threefold coordinated silicon atom, having the form O3 ≡ Si·. Feigl et al. identified the E'1 -center in crystalline quartz as a trapped hole on an oxygen vacancy, which causes an asymmetrical relaxation, resulting in a paramagnetic center. The unpaired electron in the E'1 -center is localized on the three-fold coordinated Si atoms, while the hole is localized on the other Si atom. Results from an ab initio statistical simulation examination of the behaviors of oxygen vacancies, within amorphous structures, identify a new form of the E'-center, the E'g5 and help in the understanding of the underlying physical mechanisms involved in switched-bias annealing, and electron paramagnetic resonance (EPR) studies. The results also suggest a common border trap, induced by trapped holes in SiO2, is a hole trapped at an oxygen vacancy defect, which can be compensated by an electron, as originally proposed by Lelis and co-workers at Harry Diamond Laboratories. This dissertation provides new insights into the basic mechanisms of a-SiO2 defects, and provides a link between basic mechanisms and Electronic Design Automation (EDA) tools, providing an enhanced design flow for radiation-resistant electronics.

Membrane Structure: Spin Labeling and Freeze Etching of Mycoplasma laidlawii*

PubMed Central

Tourtellotte, Mark E.; Branton, Daniel; Keith, Alec

1970-01-01

A spin-labeled fatty acid was incorporated in vivo into the polar lipids of Mycoplasma laidlawii membranes. The electron paramagnetic resonance signal from either intact cells or their extracted lipids reflected the fatty acid composition of the Mycoplasma membranes. Comparison of signals from intact cells, gramicidin-treated cells, heat-treated cells, and extracted lipids indicates that a major portion of the membrane lipids is in a semiviscous hydrocarbon environment. The results also show that the spin label in the intact membrane is slightly but significantly less mobile than it is in protein-free lipid extracts made from these membranes. Correlated electron microscope examinations using the freeze-etch technique reveal particulate components in the hydrophobic region of the membrane. The mobility of the lipids in the intact cell membrane may be influenced by their association with these particles. Images PMID:4316683

Chemical disorder influence on magnetic state of optimally-doped La0.7Ca0.3MnO3

NASA Astrophysics Data System (ADS)

Rozenberg, E.; Auslender, M.; Shames, A. I.; Jung, G.; Felner, I.; Tsindlekht, M. I.; Mogilyansky, D.; Sominski, E.; Gedanken, A.; Mukovskii, Ya. M.; Gorodetsky, G.

2011-10-01

X-band electron magnetic resonance and dc/ac magnetic measurements have been employed to study the effects of chemical disorder on magnetic ordering in bulk and nanometer-sized single crystals and bulk ceramics of optimally-doped La0.7Ca0.3MnO3 manganite. The magnetic ground state of bulk samples appeared to be ferromagnetic with the lower Curie temperature and higher magnetic homogeneity in the vicinity of the ferromagnetic-paramagnetic phase transition in the crystal, as compared with those characteristics in the ceramics. The influence of technological driven "macroscopic" fluctuations of Ca-dopant level in crystal and "mesoscopic" disorder within grain boundary regions in ceramics was proposed to be responsible for these effects. Surface spin disorder together with pronounced inter-particle interactions within agglomerated nano-sample results in well defined core/shell spin configuration in La0.7Ca0.3MnO3 nano-crystals. The analysis of the electron paramagnetic resonance data enlightened the reasons for the observed difference in the magnetic order. Lattice effects dominate the first-order nature of magnetic phase transition in bulk samples. However, mesoscale chemical disorder seems to be responsible for the appearance of small ferromagnetic polarons in the paramagnetic state of bulk ceramics. The experimental results and their analysis indicate that a chemical/magnetic disorder has a strong impact on the magnetic state even in the case of mostly stable optimally hole-doped manganites.

Characterization of Point Defects in Lithium Aluminate (LiAlO2) Single Crystals

DTIC Science & Technology

2015-09-17

high-quality neutron detectors since 235U and 239Pu, the two isotopes used to fuel nuclear weapons , both emit neu- trons through spontaneous fission of...dissertation has iden- tified and characterized the major point defects created and induced through x ray and neutron radiation using electron paramagnetic... neutron irradiation is an F+ center; an oxygen vacancy with one trapped electron. This defect has two states, a stable state that survives up to 500 ◦C and

The structural and magnetic phase transitions in Ca 0.73La 0.27FeAs 2 with electron overdoped FeAs layers.

DOE PAGES

Jiang, Shan; Liu, Chang; Cao, H.; ...

2016-02-26

Here we report a study of the Ca 0.73La 0.27FeAs 2 single crystals. We unravel a monoclinic to triclinic phase transition at 58 K, and a paramagnetic to stripe antiferromagnetic (AFM) phase transition at 54 K, below which spins order 45° away from the stripe direction. Furthermore, we demonstrate this material is substantially structurally untwinned at ambient pressure with the formation of spin rotation walls (S-walls). Finally, in addition to the central-hole and corner-electron Fermi pockets usually appearing in FPS, angle-resolved photoemission (ARPES) measurements resolve a Fermiology where an extra electron pocket of mainly As chain character exists at themore » Brillouin zone edge.« less

Low-temperature electron-spin relaxation in the crystalline and glassy states of solid ethanol

NASA Astrophysics Data System (ADS)

Kveder, Marina; Merunka, Dalibor; Jokić, Milan; Rakvin, Boris

2008-03-01

X -band electron paramagnetic resonance spectroscopy was used to study the spectral properties of a nitroxide spin probe in ethanol glass and crystalline ethanol, at 5-11.5K . The different anisotropy of molecular packing in the two host matrices was evidenced by different rigid limit values for maximal hyperfine splitting in the signal of the spin probe. The significantly shorter phase memory time Tm for the spin probe dissolved in crystalline ethanol, as compared to ethanol glass, was discussed in terms of contribution from spectral diffusion. The effect of low-frequency dynamics was manifested in the temperature dependence of Tm and in the difference between the data measured at different spectral positions. This phenomenon was addressed within the framework of the slow-motional isotropic diffusion model [S. Lee and S. Z. Tang, Phys. Rev. B 31, 1308 (1985)] predicting the spin probe dynamics within the millisecond range, at very low temperatures. The shorter spin-lattice relaxation time of the spin probe in ethanol glass was interpreted in terms of enhanced energy exchange between the spin system and the lattice in the glass matrix due to boson peak excitations.

Influence of the electron intrinsic magnetic moment on the transverse dielectric permittivity of degenerate electron gas

NASA Astrophysics Data System (ADS)

Maslov, S. A.; Bobrov, V. B.; Kirillin, A. V.; Trigger, S. A.

2018-01-01

Using the linear response theory, the transverse dielectric permittivity of a homogeneous and isotropic system of charged particles is considered. In the ideal gas approximation for the polarization function, an explicit analytical expression for the transverse permittivity of a degenerate electron plasma, which takes into account electron spin, is found. This result describes both the Landau diamagnetism and Pauli paramagnetism in electron plasma. The influence of the electron intrinsic magnetic moment on the spatial and frequency dispersion of the transverse dielectric permittivity of degenerate electron plasma is numerically studied, that is crucial for determining the optical characteristics of plasma.

Electric Field Generation and Control of Bipartite Quantum Entanglement between Electronic Spins in Mixed Valence Polyoxovanadate [GeV14O40]8.

PubMed

Palii, Andrew; Aldoshin, Sergey; Tsukerblat, Boris; Borràs-Almenar, Juan José; Clemente-Juan, Juan Modesto; Cardona-Serra, Salvador; Coronado, Eugenio

2017-08-21

As part of the search for systems in which control of quantum entanglement can be achieved, here we consider the paramagnetic mixed valence polyoxometalate K 2 Na 6 [GeV 14 O 40 ]·10H 2 O in which two electrons are delocalized over the 14 vanadium ions. Applying a homogeneous electric field can induce an antiferromagnetic coupling between the two delocalized electronic spins that behave independently in the absence of the field. On the basis of the proposed theoretical model, we show that the external field can be used to generate controllable quantum entanglement between the two electronic spins traveling over a vanadium network of mixed valence polyoxoanion [GeV 14 O 40 ] 8- . Within a simplified two-level picture of the energy pattern of the electronic pair based on the previous ab initio analysis, we evaluate the temperature and field dependencies of concurrence and thus indicate that the entanglement can be controlled via the temperature, magnitude, and orientation of the electric field with respect to molecular axes of [GeV 14 O 40 ] 8- .

Aerobic photoreactivity of synthetic eumelanins and pheomelanins: generation of singlet oxygen and superoxide anion.

PubMed

Szewczyk, Grzegorz; Zadlo, Andrzej; Sarna, Michal; Ito, Shosuke; Wakamatsu, Kazumasa; Sarna, Tadeusz

2016-11-01

In this work, we examined photoreactivity of synthetic eumelanins, formed by autooxidation of DOPA, or enzymatic oxidation of 5,6-dihydroxyindole-2-carboxylic acid and synthetic pheomelanins obtained by enzymatic oxidation of 5-S-cysteinyldopa or 1:1 mixture of DOPA and cysteine. Electron paramagnetic resonance oximetry and spin trapping were used to measure oxygen consumption and formation of superoxide anion induced by irradiation of melanin with blue light, and time-resolved near-infrared luminescence was employed to determine the photoformation of singlet oxygen between 300 and 600 nm. Both superoxide anion and singlet oxygen were photogenerated by the synthetic melanins albeit with different efficiency. At 450-nm, quantum yield of singlet oxygen was very low (~10 -4 ) but it strongly increased in the UV region. The melanins quenched singlet oxygen efficiently, indicating that photogeneration and quenching of singlet oxygen may play an important role in aerobic photochemistry of melanin pigments and could contribute to their photodegradation and photoaging. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Radical scavenging ability of some compounds isolated from Piper cubeba towards free radicals.

PubMed

Aboul-Enein, Hassan Y; Kładna, Aleksandra; Kruk, Irena

2011-01-01

The purpose of this study was to identify the antioxidant activity of 16 compounds isolated from Piper cubeba (CNCs) through the extent of their capacities to scavenge free radicals, hydroxyl radical (HO(•)), superoxide anion radical O•(2)(-) and 2,2-diphenyl-1-picrylhydrazyl radical (DPPH(•)), in different systems. Electron paramagnetic resonance (EPR) and 5,5-dimethyl-1-pyrroline-N-oxide, DMPO, as the spin trap, and chemiluminescence techniques were applied. Using the Fenton-like reaction [Fe(II) + H(2)O(2)], CNCs were found to inhibit DMPO-OH radical formation ranging from 5 to 57% at 1.25 mmol L(-1) concentration. The examined CNCs also showed a high DPPH antiradical activity (ranging from 15 to 99% at 5 mmol L(-1) concentration). Furthermore, the results indicated that seven of the 16 tested compounds may catalyse the conversion of superoxide radicals generated in the potassium superoxide/18-crown-6 ether system, thus showing superoxide dismutase-like activity. The data obtained suggest that radical scavenging properties of CNCs might have potential application in many plant medicines. Copyright © 2010 John Wiley & Sons, Ltd.

New method to measure the carbamoylating activity of nitrosoureas by electron paramagnetic resonance spectroscopy.

PubMed

Gadzheva, V; Ichimori, K; Raikov, Z; Nakazawa, H

1997-08-01

A new method for measuring the carbamoylating activity of nitrosoureas and isocyanates using electron paramagnetic resonance (EPR) spectroscopy is described. The extent and time course of carbamoylation reaction of chloroethyl isocyanate and a series of 9 nitrosoureas toward amino group of 4-amino-2,2,6,6-tetramethyl-piperidine-1-oxyl were examined with both the EPR method and the HPLC method which has been proposed by Brubaker et al. [Biochem. Pharmacol. 35:2359 (1986)]. Spin-labeled nitrosoureas we synthesized are included in this study since they have less toxicity or more efficiency than commercially available drug in some cases. The concentration of carbamoylated product was easily determined with the EPR spectra. There is a very high correlation (r = 0.982, t = 2.58, N = 10, p < 0.001) between the EPR and HPLC methods. Spin-labeled nitrosoureas showed lower carbamoylating activity than non-labeled analogues. The carbamoylating activity for these nitrosourea depended on the reactivity of isocyanate intermediate and almost independent of their half life. This rapid and simple EPR method is suitable for the detailed investigation of the rate and extent of carbamoylation reaction.

Nitrogen-vacancy-assisted magnetometry of paramagnetic centers in an individual diamond nanocrystal.

PubMed

Laraoui, Abdelghani; Hodges, Jonathan S; Meriles, Carlos A

2012-07-11

Semiconductor nanoparticles host a number of paramagnetic point defects and impurities, many of them adjacent to the surface, whose response to external stimuli could help probe the complex dynamics of the particle and its local, nanoscale environment. Here, we use optically detected magnetic resonance in a nitrogen-vacancy (NV) center within an individual diamond nanocrystal to investigate the composition and spin dynamics of the particle-hosted spin bath. For the present sample, a ∼45 nm diamond crystal, NV-assisted dark-spin spectroscopy reveals the presence of nitrogen donors and a second, yet-unidentified class of paramagnetic centers. Both groups share a common spin lifetime considerably shorter than that observed for the NV spin, suggesting some form of spatial clustering, possibly on the nanoparticle surface. Using double spin resonance and dynamical decoupling, we also demonstrate control of the combined NV center-spin bath dynamics and attain NV coherence lifetimes comparable to those reported for bulk, Type Ib samples. Extensions based on the experiments presented herein hold promise for applications in nanoscale magnetic sensing, biomedical labeling, and imaging.

A new pulse width reduction technique for pulsed electron paramagnetic resonance spectroscopy.

PubMed

Ohba, Yasunori; Nakazawa, Shigeaki; Kazama, Shunji; Mizuta, Yukio

2008-03-01

We present a new technique for a microwave pulse modulator that generates a short microwave pulse of approximately 1ns for use in an electron paramagnetic resonance (EPR) spectrometer. A quadruple-frequency multiplier that generates a signal of 16-20GHz from an input of 4-5GHz was employed to reduce the rise and fall times of the pulse prepared by a PIN diode switch. We examined the transient response characteristics of a commercial frequency multiplier and found that the device can function as a multiplier for pulsed signal even though it was designed for continuous wave operation. We applied the technique to a Ku band pulsed EPR spectrometer and successfully observed a spin echo signal with a broad excitation bandwidth of approximately 1.6mT using 80 degrees pulses of 1.5ns.

Identical spin rotation effect and electron spin waves in quantum gas of atomic hydrogen

NASA Astrophysics Data System (ADS)

Lehtonen, L.; Vainio, O.; Ahokas, J.; Järvinen, J.; Novotny, S.; Sheludyakov, S.; Suominen, K.-A.; Vasiliev, S.; Khmelenko, V. V.; Lee, D. M.

2018-05-01

We present an experimental study of electron spin waves in atomic hydrogen gas compressed to high densities of ∼5 × 1018 cm‑3 at temperatures ranging from 0.26 to 0.6 K in the strong magnetic field of 4.6 T. Hydrogen gas is in a quantum regime when the thermal de-Broglie wavelength is much larger than the s-wave scattering length. In this regime the identical particle effects play a major role in atomic collisions and lead to the identical spin rotation effect (ISR). We observed a variety of spin wave modes caused by this effect with strong dependence on the magnetic potential caused by variations of the polarizing magnetic field. We demonstrate confinement of the ISR modes in the magnetic potential and manipulate their properties by changing the spatial profile of the magnetic field. We have found that at a high enough density of H gas the magnons accumulate in their ground state in the magnetic trap and exhibit long coherence, which has a profound effect on the electron spin resonance spectra. Such macroscopic accumulation of the ground state occurs at a certain critical density of hydrogen gas, where the chemical potential of the magnons becomes equal to the energy of their ground state in the trapping potential.

A 2D Array of 100's of Ions for Quantum Simulation and Many-Body Physics in a Penning Trap

NASA Astrophysics Data System (ADS)

Bohnet, Justin; Sawyer, Brian; Britton, Joseph; Bollinger, John

2015-05-01

Quantum simulations promise to reveal new materials and phenomena for experimental study, but few systems have demonstrated the capability to control ensembles in which quantum effects cannot be directly computed. One possible platform for intractable quantum simulations may be a system of 100's of 9Be+ ions in a Penning trap, where the valence electron spins are coupled with an effective Ising interaction in a 2D geometry. Here we report on results from a new Penning trap designed for 2D quantum simulations. We characterize the ion crystal stability and describe progress towards bench-marking quantum effects of the spin-spin coupling using a spin-squeezing witness. We also report on the successful photodissociation of BeH+ contaminant molecular ions that impede the use of such crystals for quantum simulation. This work lays the foundation for future experiments such as the observation of spin dynamics under the quantum Ising Hamiltonian with a transverse field. Supported by a NIST-NRC Research Associateship.

Induction-detection electron spin resonance with spin sensitivity of a few tens of spins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Artzi, Yaron; Twig, Ygal; Blank, Aharon

2015-02-23

Electron spin resonance (ESR) is a spectroscopic method that addresses electrons in paramagnetic materials directly through their spin properties. ESR has many applications, ranging from semiconductor characterization to structural biology and even quantum computing. Although it is very powerful and informative, ESR traditionally suffers from low sensitivity, requiring many millions of spins to get a measureable signal with commercial systems using the Faraday induction-detection principle. In view of this disadvantage, significant efforts were made recently to develop alternative detection schemes based, for example, on force, optical, or electrical detection of spins, all of which can reach single electron spin sensitivity.more » This sensitivity, however, comes at the price of limited applicability and usefulness with regard to real scientific and technological issues facing modern ESR which are currently dealt with conventional induction-detection ESR on a daily basis. Here, we present the most sensitive experimental induction-detection ESR setup and results ever recorded that can detect the signal from just a few tens of spins. They were achieved thanks to the development of an ultra-miniature micrometer-sized microwave resonator that was operated at ∼34 GHz at cryogenic temperatures in conjunction with a unique cryogenically cooled low noise amplifier. The test sample used was isotopically enriched phosphorus-doped silicon, which is of significant relevance to spin-based quantum computing. The sensitivity was experimentally verified with the aid of a unique high-resolution ESR imaging approach. These results represent a paradigm shift with respect to the capabilities and possible applications of induction-detection-based ESR spectroscopy and imaging.« less

Structural Refinement of Membrane Proteins by Restrained Molecular Dynamics and Solvent Accessibility Data

PubMed Central

Sompornpisut, Pornthep; Roux, Benoît; Perozo, Eduardo

2008-01-01

We present an approach for incorporating solvent accessibility data from electron paramagnetic resonance experiments in the structural refinement of membrane proteins through restrained molecular dynamics simulations. The restraints have been parameterized from oxygen (ΠO2) and nickel-ethylenediaminediacetic acid (ΠNiEdda) collision frequencies, as indicators of lipid or aqueous exposed spin-label sites. These are enforced through interactions between a pseudoatom representation of the covalently attached Nitroxide spin-label and virtual “solvent” particles corresponding to O2 and NiEdda in the surrounding environment. Interactions were computed using an empirical potential function, where the parameters have been optimized to account for the different accessibilities of the spin-label pseudoatoms to the surrounding environment. This approach, “pseudoatom-driven solvent accessibility refinement”, was validated by refolding distorted conformations of the Streptomyces lividans potassium channel (KcsA), corresponding to a range of 2–30 Å root mean-square deviations away from the native structure. Molecular dynamics simulations based on up to 58 electron paramagnetic resonance restraints derived from spin-label mutants were able to converge toward the native structure within 1–3 Å root mean-square deviations with minimal computational cost. The use of energy-based ranking and structure similarity clustering as selection criteria helped in the convergence and identification of correctly folded structures from a large number of simulations. This approach can be applied to a variety of integral membrane protein systems, regardless of oligomeric state, and should be particularly useful in calculating conformational changes from a known reference crystal structure. PMID:18676641

Ligand protons in a frozen solution of copper histidine relax via a T1e-driven three-spin mechanism

NASA Astrophysics Data System (ADS)

Stoll, S.; Epel, B.; Vega, S.; Goldfarb, D.

2007-10-01

Davies electron-nuclear double resonance spectra can exhibit strong asymmetries for long mixing times, short repetition times, and large thermal polarizations. These asymmetries can be used to determine nuclear relaxation rates in paramagnetic systems. Measurements of frozen solutions of copper(L-histidine)2 reveal a strong field dependence of the relaxation rates of the protons in the histidine ligand, increasing from low (g‖) to high (g⊥) field. It is shown that this can be attributed to a concentration-dependent T1e-driven relaxation process involving strongly mixed states of three spins: the histidine proton, the Cu(II) electron spin of the same complex, and another distant electron spin with a resonance frequency differing from the spectrometer frequency approximately by the proton Larmor frequency. The protons relax more efficiently in the g⊥ region, since the number of distant electrons able to participate in this relaxation mechanism is higher than in the g‖ region. Analytical expressions for the associated nuclear polarization decay rate Teen-1 are developed and Monte Carlo simulations are carried out, reproducing both the field and the concentration dependences of the nuclear relaxation.

Pulse EPR distance measurements to study multimers and multimerisation

NASA Astrophysics Data System (ADS)

Ackermann, Katrin; Bode, Bela E.

2018-06-01

Pulse dipolar electron paramagnetic resonance (PD-EPR) has become a powerful tool for structural biology determining distances on the nanometre scale. Recent advances in hardware, methodology, and data analysis have widened the scope to complex biological systems. PD-EPR can be applied to systems containing lowly populated conformers or displaying large intrinsic flexibility, making them all but intractable for cryo-electron microscopy and crystallography. Membrane protein applications are of particular interest due to the intrinsic difficulties for obtaining high-resolution structures of all relevant conformations. Many drug targets involved in critical cell functions are multimeric channels or transporters. Here, common approaches for introducing spin labels for PD-EPR cause the presence of more than two electron spins per multimeric complex. This requires careful experimental design to overcome detrimental multi-spin effects and to secure sufficient distance resolution in presence of multiple distances. In addition to obtaining mere distances, PD-EPR can also provide information on multimerisation degrees allowing to study binding equilibria and to determine dissociation constants.

Structure and dynamics of spin-labeled insulin entrapped in a silica matrix by the sol-gel method.

PubMed

Vanea, E; Gruian, C; Rickert, C; Steinhoff, H-J; Simon, V

2013-08-12

The structure and conformational dynamics of insulin entrapped into a silica matrix was monitored during the sol to maturated-gel transition by electron paramagnetic resonance (EPR) spectroscopy. Insulin was successfully spin-labeled with iodoacetamide and the bifunctional nitroxide reagent HO-1944. Room temperature continuous wave (cw) EPR spectra of insulin were recorded to assess the mobility of the attached spin labels. Insulin conformation and its distribution within the silica matrix were studied using double electron-electron resonance (DEER) and low-temperature cw-EPR. A porous oxide matrix seems to form around insulin molecules with pore diameters in the order of a few nanometers. Secondary structure of the encapsulated insulin investigated by Fourier transform infrared spectroscopy proved a high structural integrity of insulin even in the dried silica matrix. The results show that silica encapsulation can be used as a powerful tool to effectively isolate and functionally preserve biomolecules during preparation, storage, and release.

Magnetic Control of the Charge-Separated State Lifetime Realized by Covalent Attachment of a Platinum Complex.

PubMed

Miura, Tomoaki; Fujiwara, Dai; Akiyama, Kimio; Horikoshi, Takafumi; Suzuki, Shuichi; Kozaki, Masatoshi; Okada, Keiji; Ikoma, Tadaaki

2017-02-02

Dynamics of the photogenerated charge-separated (CS) state is studied for a newly synthesized molecular triad, in which the donor (D) dimethoxytriphenylamine, 1,3-bis(2-pyridylimino)isoindolate platinum (BPIPt), and the acceptor (A) naphthaldiimide are linked with a triethynylbenzene unit (BPIPt-DA). Photoexcitation of BPIPt gives rise to generation of a long-lived (∼4 μs) CS state BPIPt-D + A - , of which the lifetime is considerably increased by an applied magnetic field of 270 mT. The positive magnetic field effect (MFE) is in contrast to the negative MFE for the reference DA molecule, which indicates successful switching of the initial spin state of the CS state from singlet to triplet. Simulations of the MFE and time-resolved electron paramagnetic resonance show that spin-selective charge recombination and spin relaxation are unaffected by attachment of BPIPt. The minimum impact of heavy atom substitution on the electronic and magnetic properties has been realized by the small electronic coupling mediated by the rigid meta-triethynylbenzene.

Electron paramagnetic resonance study of neutral Mg acceptors in β-Ga2O3 crystals

NASA Astrophysics Data System (ADS)

Kananen, B. E.; Halliburton, L. E.; Scherrer, E. M.; Stevens, K. T.; Foundos, G. K.; Chang, K. B.; Giles, N. C.

2017-08-01

Electron paramagnetic resonance (EPR) is used to directly observe and characterize neutral Mg acceptors ( M gGa0 ) in a β-Ga2O3 crystal. These acceptors, best considered as small polarons, are produced when the Mg-doped crystal is irradiated at or near 77 K with x rays. During the irradiation, neutral acceptors are formed when holes are trapped at singly ionized Mg acceptors ( M gGa- ). Unintentionally present Fe3+ (3d5) and Cr3+ (3d3) transition-metal ions serve as the corresponding electron traps. The hole is localized in a nonbonding p orbital on a threefold-coordinated oxygen ion adjacent to an Mg ion at a sixfold-coordinated Ga site. These M gGa0 acceptors (S = 1/2) have a slightly anisotropic g matrix (principal values are 2.0038, 2.0153, and 2.0371). There is also partially resolved 69Ga and 71Ga hyperfine structure resulting from unequal interactions with the two Ga ions adjacent to the hole. With the magnetic field along the a direction, hyperfine parameters are 2.61 and 1.18 mT for the 69Ga nuclei at the two inequivalent neighboring Ga sites. The M gGa0 acceptors thermally convert back to their nonparamagnetic M gGa- charge state when the temperature of the crystal is raised above approximately 250 K.

Theoretical study of the density of states and magnetic properties of LaCoO3

NASA Astrophysics Data System (ADS)

Zhuang, Min; Zhang, Weiyi; Hu, Cheng; Ming, Naiben

1998-05-01

The density of states and magnetic properties of low-spin, high-spin, and mixing states of LaCoO3 have been studied within the unrestricted Hartree-Fock approximation. The real-space recursion method is adopted for computing the electronic structure of the disordered system. The paramagnetic high-spin state is dealt with using the usual binary alloy coherent potential approximation (CPA); an extended trinary alloy CPA approximation is developed to describe the mixing state. In agreement with experiments, our results show that the main features of the quasiparticle spectra in the mixing state are not a sensitive function of the high-spin component, but the spectrum does get broadened due to spin scattering. The increasing of the high-spin component also results in a pileup of the density of states at the Fermi energy which indicates an insulator to metal phase transition. Some limitations of the present approach are also discussed.

Imaging free radicals in organelles, cells, tissue, and in vivo with immuno-spin trapping.

PubMed

Mason, Ronald Paul

2016-08-01

The accurate and sensitive detection of biological free radicals in a reliable manner is required to define the mechanistic roles of such species in biochemistry, medicine and toxicology. Most of the techniques currently available are either not appropriate to detect free radicals in cells and tissues due to sensitivity limitations (electron spin resonance, ESR) or subject to artifacts that make the validity of the results questionable (fluorescent probe-based analysis). The development of the immuno-spin trapping technique overcomes all these difficulties. This technique is based on the reaction of amino acid- and DNA base-derived radicals with the spin trap 5, 5-dimethyl-1-pyrroline N-oxide (DMPO) to form protein- and DNA-DMPO nitroxide radical adducts, respectively. These adducts have limited stability and decay to produce the very stable macromolecule-DMPO-nitrone product. This stable product can be detected by mass spectrometry, NMR or immunochemistry by the use of anti-DMPO nitrone antibodies. The formation of macromolecule-DMPO-nitrone adducts is based on the selective reaction of free radical addition to the spin trap and is thus not subject to artifacts frequently encountered with other methods for free radical detection. The selectivity of spin trapping for free radicals in biological systems has been proven by ESR. Immuno-spin trapping is proving to be a potent, sensitive (a million times higher sensitivity than ESR), and easy (not quantum mechanical) method to detect low levels of macromolecule-derived radicals produced in vitro and in vivo. Anti-DMPO antibodies have been used to determine the distribution of free radicals in cells and tissues and even in living animals. In summary, the invention of the immuno-spin trapping technique has had a major impact on the ability to accurately and sensitively detect biological free radicals and, subsequently, on our understanding of the role of free radicals in biochemistry, medicine and toxicology. Published by Elsevier B.V.

Electron spin resonance of nitrogen-vacancy centers in optically trapped nanodiamonds

PubMed Central

Horowitz, Viva R.; Alemán, Benjamín J.; Christle, David J.; Cleland, Andrew N.; Awschalom, David D.

2012-01-01

Using an optical tweezers apparatus, we demonstrate three-dimensional control of nanodiamonds in solution with simultaneous readout of ground-state electron-spin resonance (ESR) transitions in an ensemble of diamond nitrogen-vacancy color centers. Despite the motion and random orientation of nitrogen-vacancy centers suspended in the optical trap, we observe distinct peaks in the measured ESR spectra qualitatively similar to the same measurement in bulk. Accounting for the random dynamics, we model the ESR spectra observed in an externally applied magnetic field to enable dc magnetometry in solution. We estimate the dc magnetic field sensitivity based on variations in ESR line shapes to be approximately . This technique may provide a pathway for spin-based magnetic, electric, and thermal sensing in fluidic environments and biophysical systems inaccessible to existing scanning probe techniques. PMID:22869706

Precision Measurement of the Electron's Electric Dipole Moment Using Trapped Molecular Ions

NASA Astrophysics Data System (ADS)

Cairncross, William B.; Gresh, Daniel N.; Grau, Matt; Cossel, Kevin C.; Roussy, Tanya S.; Ni, Yiqi; Zhou, Yan; Ye, Jun; Cornell, Eric A.

2017-10-01

We describe the first precision measurement of the electron's electric dipole moment (de) using trapped molecular ions, demonstrating the application of spin interrogation times over 700 ms to achieve high sensitivity and stringent rejection of systematic errors. Through electron spin resonance spectroscopy on 180Hf 19F+ in its metastable 3Δ1 electronic state, we obtain de=(0.9 ±7. 7stat±1. 7syst)×10-29 e cm , resulting in an upper bound of |de|<1.3 ×10-28 e cm (90% confidence). Our result provides independent confirmation of the current upper bound of |de|<9.4 ×10-29 e cm [J. Baron et al., New J. Phys. 19, 073029 (2017), 10.1088/1367-2630/aa708e], and offers the potential to improve on this limit in the near future.

Electron spin control of optically levitated nanodiamonds in vacuum.

PubMed

Hoang, Thai M; Ahn, Jonghoon; Bang, Jaehoon; Li, Tongcang

2016-07-19

Electron spins of diamond nitrogen-vacancy (NV) centres are important quantum resources for nanoscale sensing and quantum information. Combining NV spins with levitated optomechanical resonators will provide a hybrid quantum system for novel applications. Here we optically levitate a nanodiamond and demonstrate electron spin control of its built-in NV centres in low vacuum. We observe that the strength of electron spin resonance (ESR) is enhanced when the air pressure is reduced. To better understand this system, we investigate the effects of trap power and measure the absolute internal temperature of levitated nanodiamonds with ESR after calibration of the strain effect. We also observe that oxygen and helium gases have different effects on both the photoluminescence and the ESR contrast of nanodiamond NV centres, indicating potential applications of NV centres in oxygen gas sensing. Our results pave the way towards a levitated spin-optomechanical system for studying macroscopic quantum mechanics.

Electron spin control of optically levitated nanodiamonds in vacuum

NASA Astrophysics Data System (ADS)

Hoang, Thai M.; Ahn, Jonghoon; Bang, Jaehoon; Li, Tongcang

2016-07-01

Electron spins of diamond nitrogen-vacancy (NV) centres are important quantum resources for nanoscale sensing and quantum information. Combining NV spins with levitated optomechanical resonators will provide a hybrid quantum system for novel applications. Here we optically levitate a nanodiamond and demonstrate electron spin control of its built-in NV centres in low vacuum. We observe that the strength of electron spin resonance (ESR) is enhanced when the air pressure is reduced. To better understand this system, we investigate the effects of trap power and measure the absolute internal temperature of levitated nanodiamonds with ESR after calibration of the strain effect. We also observe that oxygen and helium gases have different effects on both the photoluminescence and the ESR contrast of nanodiamond NV centres, indicating potential applications of NV centres in oxygen gas sensing. Our results pave the way towards a levitated spin-optomechanical system for studying macroscopic quantum mechanics.

Measurement of myocardial free radical production during exercise using EPR spectroscopy.

PubMed

Traverse, Jay H; Nesmelov, Yuri E; Crampton, Melanie; Lindstrom, Paul; Thomas, David D; Bache, Robert J

2006-06-01

Exercise is associated with an increase in oxygen flux through the mitochondrial electron transport chain that has recently been demonstrated to increase the production of reactive oxygen species (ROS) in skeletal muscle. This study examined whether exercise also causes free radical production in the heart. We measured ROS production in seven chronically instrumented dogs during rest and treadmill exercise (6.4 km/h at 10 degrees grade; and heart rate, 204 +/- 3 beats/min) using electron paramagnetic resonance spectroscopy in conjunction with the spin trap alpha-phenyl-tert-butylnitrone (PBN) (0.14 mol/l) in blood collected from the aorta and coronary sinus (CS). To improve signal detection, the free radical adducts were deoxygenated over a nitrogen stream for 15 min and extracted with toluene. The hyperfine splitting constants of the radicals were alpha(N) = 13.7 G and alpha(H) = 1.0 G, consistent with an alkoxyl or carbon-centered radical. Resting aortic and CS PBN adduct concentrations were 6.7 and 6.3 x 10(8) arbitrary units (P = not significant). Both aortic and CS adduct concentrations increased during exercise, but there was no significant difference between the aortic and CS concentrations. Thus, in contrast to skeletal muscle, submaximal treadmill exercise did not result in detectable free radical production by the heart.

The effect of band Jahn-Teller distortion on the magnetoresistivity of manganites: a model study.

PubMed

Rout, G C; Panda, Saswati; Behera, S N

2011-10-05

We present a model study of magnetoresistance through the interplay of magnetisation, structural distortion and external magnetic field for the manganite systems. The manganite system is described by the Hamiltonian which consists of the s-d type double exchange interaction, Heisenberg spin-spin interaction among the core electrons, and the static and dynamic band Jahn-Teller (JT) interaction in the e(g) band. The relaxation time of the e(g) electron is found from the imaginary part of the Green's function using the total Hamiltonian consisting of the interactions due to the electron and phonon. The calculated resistivity exhibits a peak in the pure JT distorted insulating phase separating the low temperature metallic ferromagnetic phase and the high temperature paramagnetic phase. The resistivity is suppressed with the increase of the external magnetic field. The e(g) electron band splitting and its effect on magnetoresistivity is reported here. © 2011 IOP Publishing Ltd

Room temperature ferromagnetism in Fe-doped semiconductor ZrS2 single crystals

NASA Astrophysics Data System (ADS)

Muhammad, Zahir; Lv, Haifeng; Wu, Chuanqiang; Habib, Muhammad; Rehman, Zia ur; Khan, Rashid; Chen, Shuangming; Wu, Xiaojun; Song, Li

2018-04-01

Two dimensional (2D) layered magnetic materials have obtained much attention due to their intriguing properties with a potential application in the field of spintronics. Herein, room-temperature ferromagnetism with 0.2 emu g‑1 magnetic moment is realized in Fe-doped ZrS2 single crystals of millimeter size, in comparison with diamagnetic behaviour in ZrS2. The electron paramagnetic resonance spectroscopy reveals that 5.2wt% Fe-doping ZrS2 crystal exhibit high spin value of g-factor about 3.57 at room temperature also confirmed this evidence, due to the unpaired electrons created by doped Fe atoms. First principle static electronic and magnetic calculations further confirm the increased stability of long range ferromagnetic ordering and enhanced magnetic moment in Fe-doped ZrS2, originating from the Fe spin polarized electron near the Fermi level.

Hyperpolarization of Frozen Hydrocarbon Gases by Dynamic Nuclear Polarization at 1.2 K.

PubMed

Vuichoud, Basile; Canet, Estel; Milani, Jonas; Bornet, Aurélien; Baudouin, David; Veyre, Laurent; Gajan, David; Emsley, Lyndon; Lesage, Anne; Copéret, Christophe; Thieuleux, Chloé; Bodenhausen, Geoffrey; Koptyug, Igor; Jannin, Sami

2016-08-18

We report a simple and general method for the hyperpolarization of condensed gases by dynamic nuclear polarization (DNP). The gases are adsorbed in the pores of structured mesoporous silica matrices known as HYPSOs (HYper Polarizing SOlids) that have paramagnetic polarizing agents covalently bound to the surface of the mesopores. DNP is performed at low temperatures and moderate magnetic fields (T = 1.2 K and B0 = 6.7 T). Frequency-modulated microwave irradiation is applied close to the electron spin resonance frequency (f = 188.3 GHz), and the electron spin polarization of the polarizing agents of HYPSO is transferred to the nuclear spins of the frozen gas. A proton polarization as high as P((1)H) = 70% can be obtained, which can be subsequently transferred to (13)C in natural abundance by cross-polarization, yielding up to P((13)C) = 27% for ethylene.

Delocalization of Coherent Triplet Excitons in Linear Rigid Rod Conjugated Oligomers.

PubMed

Hintze, Christian; Korf, Patrick; Degen, Frank; Schütze, Friederike; Mecking, Stefan; Steiner, Ulrich E; Drescher, Malte

2017-02-02

In this work, the triplet state delocalization in a series of monodisperse oligo(p-phenyleneethynylene)s (OPEs) is studied by pulsed electron paramagnetic resonance (EPR) and pulsed electron nuclear double resonance (ENDOR) determining zero-field splitting, optical spin polarization, and proton hyperfine couplings. Neither the zero-field splitting parameters nor the optical spin polarization change significantly with OPE chain length, in contrast to the hyperfine coupling constants, which showed a systematic decrease with chain length n according to a 2/(1 + n) decay law. The results provide striking evidence for the Frenkel-type nature of the triplet excitons exhibiting full coherent delocalization in the OPEs under investigation with up to five OPE repeat units and with a spin density distribution described by a nodeless particle in the box wave function. The same model is successfully applied to recently published data on π-conjugated porphyrin oligomers.

Electron spin resonance study of CuGa1-xMnxSe2 magnetic semiconducting compounds

NASA Astrophysics Data System (ADS)

Fermin, José R.; Nava, Alexander; Durante-Rincón, C. A.; Castro, Jaime; Silva, Pedro J.

2013-02-01

We report on the magnetic properties of the diluted magnetic semiconductor CuGa1-xMnxSe2. For this, Electron spin resonance (ESR) experiments in the temperature range 70 K

Zero-field splitting in the isoelectronic aqueous Gd(III) and Eu(II) complexes from a first principles analysis

NASA Astrophysics Data System (ADS)

Khan, S.; Peters, V.; Kowalewski, J.; Odelius, M.

2018-03-01

The zero-field splitting (ZFS) of the ground state octet in aqueous Eu(II) and Gd(III) solutions was investigated through multi- configurational quantum chemical calculations and ab initio molecular dynamics (AIMD) simulations. Investigation of the ZFS of the lanthanide ions is essential to understand the electron spin dynamics and nuclear spin relaxation around paramagnetic ions and consequently the mechanisms underlying applications like magnetic resonance imaging. We found by comparing clusters at identical geometries but different metallic centres that there is not a simple relationship for their ZFS, in spite of the complexes being isoelectronic - each containing 7 unpaired f electrons. Through sampling it was established that inclusion of the first hydration shell has a dominant (over 90 %) influence on the ZFS. Extended sampling of aqueous Gd(III) showed that the 2 nd order spin Hamiltonian formalism is valid and that the rhombic ZFS component is decisive.

On the temperature-dependent exchange splitting in the quasiparticle bandstructure of Ni

NASA Astrophysics Data System (ADS)

Borgiel, W.; Nolting, W.; Donath, M.

1989-11-01

A theoretical model for the bandferromagnet Ni is proposed, which takes into account the intraatomic electron interactions within the d band complex. After introducing effective spin operators the model-Hamiltonian consists of a one-particle part, an intraband interaction of Hubbard-type, and an interband exchange, formally describing electron magnon scattering (s-f model). The one particle energies are taken from a realistic bandstructure calculation for paramagnetic Ni. We use a many body procedure for a detailed inspection of the quasiparticle bandstructure in KX and XW directions, present the corresponding spectral densities, and compare the temperature dependent exchange splittings near the X and W point with recent results from spin resolved photoemission (PE) - and inverse photoemission (IPE) - experiments.

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

PubMed Central

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

2011-01-01

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

Spin-labeled 1-alkyl-1-nitrosourea synergists of antitumor antibiotics.

PubMed

Gadjeva, V; Koldamova, R

2001-01-01

A new method for synthesis of four spin-labeled structural analogues of the antitumor drug 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea (CCNU), using ethyl nitrite for nitrosation of the intermediate spin-labeled ureas has been described. In vitro synergistic effects of 1-ethyl-3-[4-(2,2,6,6-tetramethylpiperidine-1-oxyl)]-1-nitrosourea (3b) on the cytotoxicity of bleomycin and farmorubicin were found in human lymphoid leukemia tumor cells. We measured the tissue distribution of 3b in organ homogenates of C57BL mice by an electron paramagnetic resonance method. The spin-labeled nitrosourea was mainly localized in the lungs. Our results strongly support the development and validation of a new approach for synthesis of less toxic nitrosourea derivatives as potential synergists of antitumor drugs.

A spin labelling study of immunomodulating peptidoglycan monomer and adamantyltripeptides entrapped into liposomes.

PubMed

Frkanec, Ruza; Noethig-Laslo, Vesna; Vranesić, Branka; Mirosavljević, Krunoslav; Tomasić, Jelka

2003-04-01

The interaction of immunostimulating compounds, the peptidoglycan monomer (PGM) and structurally related adamantyltripeptides (AdTP1 and AdTP2), respectively, with phospholipids in liposomal bilayers were investigated by electron paramagnetic resonance spectroscopy. (1). The fatty acids bearing the nitroxide spin label at different positions along the acyl chain were used to investigate the interaction of tested compounds with negatively charged multilamellar liposomes. Electron spin resonance (ESR) spectra were studied at 290 and 310 K. The entrapment of the adamantyltripeptides affected the motional properties of all spin labelled lipids, while the entrapment of PGM had no effect. (2). Spin labelled PGM was prepared and the novel compound bearing the spin label attached via the amino group of diaminopimelic acid was chromatographically purified and chemically characterized. The rotational correlation time of the spin labelled molecule dissolved in buffer at pH 7.4 was studied as a function of temperature. The conformational change was observed above 300 K. The same effect was observed with the spin labelled PGM incorporated into liposomes. Such effect was not observed when the spin labelled PGM was studied at alkaline pH, probably due to the hydrolysis of PGM molecule. The study of possible interaction with liposomal membrane is relevant to the use of tested compounds incorporated into liposomes, as adjuvants in vivo.

Quantitative electron spin resonance (ESR) analysis of antioxidative properties using the acetaldehyde/xanthine oxidase system

NASA Astrophysics Data System (ADS)

Souchard, J.-P.; Nepveu, F.

1998-05-01

We present a method for the quantitative ESR analysis of the antioxidant properties of drugs using the acetaldhehyde/xanthine oxidase (AC/XOD) superoxide generating system and 5,5-dimethyl-l-pyrroline-N-oxide (DMPO) as spin trap. In stoichiometric conditions (AC/XOD, 60 mM/0.018 U), the resulting paramagnetic DMPO adduct disappeared with superoxide dismutase and remained when catalase or DMSO were used. That adduct was dependent only on superoxide and resulted from the trapping of a carboxyl radical by DMPO (aN = 15.2 G, aH = 18.9 G). Similar results were obtained using 4-pyridyl-l-oxide-N-t-butyl nitrone (POBN) as spin trap. The ESR signal of the DMPO-CO2- adduct was very stable and allowed quantitative analysis of the antioxidative activity of redox molecules from an IC{50} value representing the concentration causing 50% inhibition of its intensity. Among the tested compounds, manganese(II), complexes were the most effective, 25 times as active as ascorbic acid or (+)catechin and 500-fold more antioxidative than Trolox^R. Nous présentons une méthode d'analyse quantitative de l'activité antioxydante de composés d'intérêt pharmaceutique basée sur le système acétaldéhyde/xanthine oxydase (AC/XOD), l'utilisation de la RPE et du piégeage de spin avec le 5,5-diméthyl-l-pyrroline-N-oxyde (DMPO). Dans les conditions stoechiométriques {AC/XOD, 60 mM/0,018 U/ml}, l'adduit radicalaire résultant de ce système disparaît en présence de superoxyde dismutase et persiste en présence de catalase ou de DMSO. Cet adduit ne dépend que de la présence de l'anion superoxyde et provient du piégeage d'un radical carboxyle CO2- sur le DMPO (aN = 15.2 G, aH = 18.9 G). Des résultats similaires ont été obtenus avec le piégeur de spin 4-pyridyl-l-oxyde-N-t-butyl nitrone (POBN). Le signal RPE de l'adduit DMPO-CO2- est très stable et permet la quantification de l'activité antioxydante de pharmacophores redox par la détermination de la CI{50}, concentration qui diminue de 50 % son intensité. Parmi les composés testés, les complexes du manganèse sont les plus antioxydants, 25 fois plus actifs que la vitamine C ou la catéchine(+), 500 fois plus antioxydants que le Trolox^R.

Magnon Spin Hall Magnetoresistance of a Gapped Quantum Paramagnet.

PubMed

Ulloa, Camilo; Duine, R A

2018-04-27

Motivated by recent experimental work, we consider spin transport between a normal metal and a gapped quantum paramagnet. We model the latter as the magnonic Mott-insulating phase of an easy-plane ferromagnetic insulator. We evaluate the spin current mediated by the interface exchange coupling between the ferromagnet and the adjacent normal metal. For the strongly interacting magnons that we consider, this spin current gives rise to a spin Hall magnetoresistance that strongly depends on the magnitude of the magnetic field, rather than its direction. This Letter may motivate electrical detection of the phases of quantum magnets and the incorporation of such materials into spintronic devices.

Magnon Spin Hall Magnetoresistance of a Gapped Quantum Paramagnet

NASA Astrophysics Data System (ADS)

Ulloa, Camilo; Duine, R. A.

2018-04-01

Motivated by recent experimental work, we consider spin transport between a normal metal and a gapped quantum paramagnet. We model the latter as the magnonic Mott-insulating phase of an easy-plane ferromagnetic insulator. We evaluate the spin current mediated by the interface exchange coupling between the ferromagnet and the adjacent normal metal. For the strongly interacting magnons that we consider, this spin current gives rise to a spin Hall magnetoresistance that strongly depends on the magnitude of the magnetic field, rather than its direction. This Letter may motivate electrical detection of the phases of quantum magnets and the incorporation of such materials into spintronic devices.

Electronic Structure of Fullerene Acceptors in Organic Bulk-Heterojunctions. A Combined EPR and DFT Study

DOE PAGES

Mardis, Kristy L.; Webb, J.; Holloway, Tarita; ...

2015-12-03

Organic photovoltaic (OPV) devices are a promising alternative energy source. Attempts to improve their performance have focused on the optimization of electron-donating polymers, while electron-accepting fullerenes have received less attention. Here, we report an electronic structure study of the widely used soluble fullerene derivatives PC61BM and PC71BM in their singly reduced state, that are generated in the polymer:fullerene blends upon light-induced charge separation. Density functional theory (DFT) calculations characterize the electronic structures of the fullerene radical anions through spin density distributions and magnetic resonance parameters. The good agreement of the calculated magnetic resonance parameters with those determined experimentally by advancedmore » electron paramagnetic resonance (EPR) allows the validation of the DFT calculations. Thus, for the first time, the complete set of magnetic resonance parameters including directions of the principal g-tensor axes were determined. For both molecules, no spin density is present on the PCBM side chain, and the axis of the largest g-value lies along the PCBM molecular axis. While the spin density distribution is largely uniform for PC61BM, it is not evenly distributed for PC71BM.« less

Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes

DOE PAGES

Bucinsky, Lukas; Breza, Martin; Lee, Wei-Tsung; ...

2017-04-05

High-oxidation state metal complexes with multiply bonded ligands are of great interest for both their reactivity as well as their fundamental bonding properties. This paper reports a combined spectroscopic and theoretical investigation into the effect of the apical multiply bonded ligand on the spin state preferences of three-fold symmetric iron(IV) complexes with tris(carbene) donor ligands. Specifically, singlet (S = 0) nitrido [{PhB(Im R) 3}FeN], R = tBu (1), Mes (mesityl, 2) and the related triplet (S = 1) imido complexes, [{PhB(Im R) 3}Fe(NR')] +, R = Mes, R' = Ad (1- adamantyl, 3), tBu (4), have been investigated by electronicmore » absorption and Mössbauer effect spectroscopies. For comparison, two other Fe(IV) nitrido complexes, [(TIMEN Ar)FeN] +, (TIMEN Ar = tris[2-(3-aryl-imidazol-2-ylidene)ethyl]amine; Ar = Xyl (xylyl), Mes), have been investigated by 57Fe Mössbauer spectroscopy, including applied-field measurements. The paramagnetic imido complexes 3 and 4 were also studied by magnetic susceptibility measurements (for 3) and paramagnetic resonance spectroscopy: high-frequency and -field electron paramagnetic resonance (HFEPR) (for 3 and 4) and frequency-domain Fouriertransform (FD-FT) THz EPR (for 3), which reveal their zero-field splitting (zfs) parameters. Experimentally correlated theoretical studies comprising ligand-field theory (LFT) and quantum chemical theory (QCT), the latter including both density functional theory (DFT) and ab initio methods reveal the key role played by the Fe3 d z2 (a1) orbital in these systems: the nature of its interaction with the nitrido or imido ligand dictates the spin state preference of the complex. Lastly, the ability to tune the spin state through the energy and nature of a single orbital has general relevance to the factors controlling spin states in complexes with applicability as single molecule devices.« less

Physico-Chemical Evaluation of Rationally Designed Melanins as Novel Nature-Inspired Radioprotectors

PubMed Central

Schweitzer, Andrew D.; Howell, Robertha C.; Jiang, Zewei; Bryan, Ruth A.; Gerfen, Gary; Chen, Chin-Cheng; Mah, Dennis; Cahill, Sean

2009-01-01

Background Melanin, a high-molecular weight pigment that is ubiquitous in nature, protects melanized microorganisms against high doses of ionizing radiation. However, the physics of melanin interaction with ionizing radiation is unknown. Methodology/Principal Findings We rationally designed melanins from either 5-S-cysteinyl-DOPA, L-cysteine/L-DOPA, or L-DOPA with diverse structures as shown by elemental analysis and HPLC. Sulfur-containing melanins had higher predicted attenuation coefficients than non-sulfur-containing melanins. All synthetic melanins displayed strong electron paramagnetic resonance (2.14·1018, 7.09·1018, and 9.05·1017 spins/g, respectively), with sulfur-containing melanins demonstrating more complex spectra and higher numbers of stable free radicals. There was no change in the quality or quantity of the stable free radicals after high-dose (30,000 cGy), high-energy (137Cs, 661.6 keV) irradiation, indicating a high degree of radical stability as well as a robust resistance to the ionizing effects of gamma irradiation. The rationally designed melanins protected mammalian cells against ionizing radiation of different energies. Conclusions/Significance We propose that due to melanin's numerous aromatic oligomers containing multiple π-electron system, a generated Compton recoil electron gradually loses energy while passing through the pigment, until its energy is sufficiently low that it can be trapped by stable free radicals present in the pigment. Controlled dissipation of high-energy recoil electrons by melanin prevents secondary ionizations and the generation of damaging free radical species. PMID:19789711

Physico-chemical evaluation of rationally designed melanins as novel nature-inspired radioprotectors.

PubMed

Schweitzer, Andrew D; Howell, Robertha C; Jiang, Zewei; Bryan, Ruth A; Gerfen, Gary; Chen, Chin-Cheng; Mah, Dennis; Cahill, Sean; Casadevall, Arturo; Dadachova, Ekaterina

2009-09-30

Melanin, a high-molecular weight pigment that is ubiquitous in nature, protects melanized microorganisms against high doses of ionizing radiation. However, the physics of melanin interaction with ionizing radiation is unknown. We rationally designed melanins from either 5-S-cysteinyl-DOPA, L-cysteine/L-DOPA, or L-DOPA with diverse structures as shown by elemental analysis and HPLC. Sulfur-containing melanins had higher predicted attenuation coefficients than non-sulfur-containing melanins. All synthetic melanins displayed strong electron paramagnetic resonance (2.14.10(18), 7.09.10(18), and 9.05.10(17) spins/g, respectively), with sulfur-containing melanins demonstrating more complex spectra and higher numbers of stable free radicals. There was no change in the quality or quantity of the stable free radicals after high-dose (30,000 cGy), high-energy ((137)Cs, 661.6 keV) irradiation, indicating a high degree of radical stability as well as a robust resistance to the ionizing effects of gamma irradiation. The rationally designed melanins protected mammalian cells against ionizing radiation of different energies. We propose that due to melanin's numerous aromatic oligomers containing multiple pi-electron system, a generated Compton recoil electron gradually loses energy while passing through the pigment, until its energy is sufficiently low that it can be trapped by stable free radicals present in the pigment. Controlled dissipation of high-energy recoil electrons by melanin prevents secondary ionizations and the generation of damaging free radical species.

Distribution of Localized States from Fine Analysis of Electron Spin Resonance Spectra in Organic Transistors

NASA Astrophysics Data System (ADS)

Matsui, Hiroyuki; Mishchenko, Andrei S.; Hasegawa, Tatsuo

2010-02-01

We developed a novel method for obtaining the distribution of trapped carriers over their degree of localization in organic transistors, based on the fine analysis of electron spin resonance spectra at low enough temperatures where all carriers are localized. To apply the method to pentacene thin-film transistors, we proved through continuous wave saturation experiments that all carriers are localized at below 50 K. We analyzed the spectra at 20 K and found that the major groups of traps comprise localized states having wave functions spanning around 1.5 and 5 molecules and a continuous distribution of states with spatial extent in the range between 6 and 20 molecules.

Distribution of localized states from fine analysis of electron spin resonance spectra in organic transistors.

PubMed

Matsui, Hiroyuki; Mishchenko, Andrei S; Hasegawa, Tatsuo

2010-02-05

We developed a novel method for obtaining the distribution of trapped carriers over their degree of localization in organic transistors, based on the fine analysis of electron spin resonance spectra at low enough temperatures where all carriers are localized. To apply the method to pentacene thin-film transistors, we proved through continuous wave saturation experiments that all carriers are localized at below 50 K. We analyzed the spectra at 20 K and found that the major groups of traps comprise localized states having wave functions spanning around 1.5 and 5 molecules and a continuous distribution of states with spatial extent in the range between 6 and 20 molecules.

Electrochemistry and electron paramagnetic resonance spectroscopy of cytochrome c and its heme-disrupted analogs.

PubMed

Novak, David; Mojovic, Milos; Pavicevic, Aleksandra; Zatloukalova, Martina; Hernychova, Lenka; Bartosik, Martin; Vacek, Jan

2018-02-01

Cytochrome c (cyt c) is one of the most studied conjugated proteins due to its electron-transfer properties and ability to regulate the processes involved in homeostasis or apoptosis. Here we report an electrochemical strategy for investigating the electroactivity of cyt c and its analogs with a disrupted heme moiety, i.e. apocytochrome c (acyt c) and porphyrin cytochrome c (pcyt c). The electrochemical data are supplemented with low-temperature and spin-probe electron paramagnetic resonance (EPR) spectroscopy. The main contribution of this report is a complex evaluation of cyt c reduction and oxidation at the level of surface-localized amino acid residues and the heme moiety in a single electrochemical scan. The electrochemical pattern of cyt c is substantially different to both analogs acyt c and pcyt c, which could be applicable in further studies on the redox properties and structural stability of cytochromes and other hemeproteins. Copyright © 2017 Elsevier B.V. All rights reserved.

Electron spin control and spin-libration coupling of a levitated nanodiamond

NASA Astrophysics Data System (ADS)

Hoang, Thai; Ma, Yue; Ahn, Jonghoon; Bang, Jaehoon; Robicheaux, Francis; Gong, Ming; Yin, Zhang-Qi; Li, Tongcang

2017-04-01

Hybrid spin-mechanical systems have great potentials in sensing, macroscopic quantum mechanics, and quantum information science. Recently, we optically levitated a nanodiamond and demonstrated electron spin control of its built-in nitrogen-vacancy (NV) centers in vacuum. We also observed the libration (torsional vibration) of a nanodiamond trapped by a linearly polarized laser beam in vacuum. We propose to achieve strong coupling between the electron spin of a NV center and the libration of a levitated nanodiamond with a uniform magnetic field. With a uniform magnetic field, multiple spins can couple to the torsional vibration at the same time. We propose to use this strong coupling to realize the Lipkin-Meshkov-Glick (LMG) model and generate rotational superposition states. This work is supported by the National Science Foundation under Grant No. 1555035-PHY.

Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc00830a Click here for additional data file.

PubMed Central

Lu, Jian; Ozel, I. Ozge; Belvin, Carina A.; Li, Xian; Skorupskii, Grigorii; Sun, Lei; Ofori-Okai, Benjamin K.; Dincă, Mircea; Gedik, Nuh

2017-01-01

Zero-field splitting (ZFS) parameters are fundamentally tied to the geometries of metal ion complexes. Despite their critical importance for understanding the magnetism and spectroscopy of metal complexes, they are not routinely available through general laboratory-based techniques, and are often inferred from magnetism data. Here we demonstrate a simple tabletop experimental approach that enables direct and reliable determination of ZFS parameters in the terahertz (THz) regime. We report time-domain measurements of electron paramagnetic resonance (EPR) signals associated with THz-frequency ZFSs in molecular complexes containing high-spin transition-metal ions. We measure the temporal profiles of the free-induction decays of spin resonances in the complexes at zero and nonzero external magnetic fields, and we derive the EPR spectra via numerical Fourier transformation of the time-domain signals. In most cases, absolute values of the ZFS parameters are extracted from the measured zero-field EPR frequencies, and the signs can be determined by zero-field measurements at two different temperatures. Field-dependent EPR measurements further allow refined determination of the ZFS parameters and access to the g-factor. The results show good agreement with those obtained by other methods. The simplicity of the method portends wide applicability in chemistry, biology and material science. PMID:29163882

Selective photoswitching of the binuclear spin crossover compound {[Fe(bt)(NCS)2]2(bpm)} into two distinct macroscopic phases.

PubMed

Moussa, N Ould; Molnár, G; Bonhommeau, S; Zwick, A; Mouri, S; Tanaka, K; Real, J A; Bousseksou, A

2005-03-18

The low-spin (LS-LS, S = 0) diamagnetic form of the binuclear spin crossover complex {[Fe(bt)(NCS)(2)](2)(bpm)} was selectively photoconverted into two distinct macroscopic phases at different excitation wavelengths (1342 or 647.1 nm). These long-lived metastable phases have been identified, respectively, as the symmetry-broken paramagnetic form (HS-LS, S = 2) and the antiferromagnetically coupled (HS-HS, S = 0) high-spin form of the compound. The selectivity may be explained by the strong coupling of the primary excited states to the paramagnetic state.

EPR investigations of silicon carbide nanoparticles functionalized by acid doped polyaniline

NASA Astrophysics Data System (ADS)

Karray, Fekri; Kassiba, Abdelhadi

2012-06-01

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

Imaging thiol redox status in murine tumors in vivo with rapid-scan electron paramagnetic resonance

NASA Astrophysics Data System (ADS)

Epel, Boris; Sundramoorthy, Subramanian V.; Krzykawska-Serda, Martyna; Maggio, Matthew C.; Tseytlin, Mark; Eaton, Gareth R.; Eaton, Sandra S.; Rosen, Gerald M.; Kao, Joseph P. Y.; Halpern, Howard J.

2017-03-01

Thiol redox status is an important physiologic parameter that affects the success or failure of cancer treatment. Rapid scan electron paramagnetic resonance (RS EPR) is a novel technique that has shown higher signal-to-noise ratio than conventional continuous-wave EPR in in vitro studies. Here we used RS EPR to acquire rapid three-dimensional images of the thiol redox status of tumors in living mice. This work presents, for the first time, in vivo RS EPR images of the kinetics of the reaction of 2H,15N-substituted disulfide-linked dinitroxide (PxSSPx) spin probe with intracellular glutathione. The cleavage rate is proportional to the intracellular glutathione concentration. Feasibility was demonstrated in a FSa fibrosarcoma tumor model in C3H mice. Similar to other in vivo and cell model studies, decreasing intracellular glutathione concentration by treating mice with L-buthionine sulfoximine (BSO) markedly altered the kinetic images.

The “Beta-Clasp” model of apolipoprotein A-I - a lipid-free solution structure determined by electron paramagnetic resonance spectroscopy

PubMed Central

Lagerstedt, Jens O.; Budamagunta, Madhu S.; Liu, Grace S.; DeValle, Nicole C.; Voss, John C.; Oda, Michael N.

2012-01-01

Apolipoprotein A-I (apoA-I) is the major protein component of high density lipoproteins (HDL) and plays a central role in cholesterol metabolism. The lipid-free / lipid-poor form of apoA-I is the preferred substrate for the ATP-binding cassette transporter A1 (ABCA1). The interaction of apoA-I with ABCA1 leads to the formation of cholesterol laden high density lipoprotein (HDL) particles, a key step in reverse cholesterol transport and the maintenance of cholesterol homeostasis. Knowledge of the structure of lipid-free apoA-I is essential to understanding its critical interaction with ABCA1 and the molecular mechanisms underlying HDL biogenesis. We therefore examined the structure of lipid-free apoA-I by electron paramagnetic resonance spectroscopy (EPR). Through site directed spin label EPR, we mapped the secondary structure of apoA-I and identified sites of spin coupling as residues 26, 44, 64, 167, 217 and 226. We capitalize on the fact that lipid-free apoA-I self-associates in an anti-parallel manner in solution. We employed these sites of spin coupling to define the central plane in the dimeric apoA-I complex. Applying both the constraints of dipolar coupling with the EPR-derived pattern of solvent accessibility, we assembled the secondary structure into a tertiary context, providing a solution structure for lipid-free apoA-I. PMID:22245143

Syntheses, X-ray structures, solid state high-field electron paramagnetic resonance, and density-functional theory investigations on chloro and aqua Mn(II) mononuclear complexes with amino-pyridine pentadentate ligands.

PubMed

Hureau, Christelle; Groni, Sihem; Guillot, Régis; Blondin, Geneviève; Duboc, Carole; Anxolabéhère-Mallart, Elodie

2008-10-20

The two pentadentate amino-pyridine ligands L5(2) and L5(3) (L5(2) and L5(3) stand for the N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine and the N-methyl-N,N',N'-tris(2-pyridylmethyl)propane-1,3-diamine, respectively) were used to synthesize four mononuclear Mn(II) complexes, namely [(L5(2))MnCl](PF6) (1(PF6)), [(L5(3))MnCl](PF6) (2(PF6)), [(L5(2))Mn(OH2)](BPh4)2 (3(BPh4)2), and [(L5(3))Mn(OH2)](BPh4)2 (4(BPh4)2). The X-ray diffraction studies revealed different configurations for the ligand L5(n) (n = 2, 3) depending on the sixth exogenous ligand and/or the counterion. Solid state high-field electron paramagnetic resonance spectra were recorded on complexes 1-4 as on previously described mononuclear Mn(II) systems with tetra- or hexadentate amino-pyridine ligands. Positive and negative axial zero-field splitting (ZFS) parameters D were determined whose absolute values ranged from 0.090 to 0.180 cm(-1). Density-functional theory calculations were performed unraveling that, in contrast with chloro systems, the spin-spin and spin-orbit coupling contributions to the D-parameter are comparable for mixed N,O-coordination sphere complexes.

The effect of lipophilicity of spin-labeled compounds on their distribution in solid lipid nanoparticle dispersions studied by electron paramagnetic resonance.

PubMed

Pegi, Ahlin; Julijana, Kristl; Slavko, Pecar; Janez, Strancar; Marjeta, Sentjurc

2003-01-01

Solid lipid nanoparticles (SLN) constitute an attractive drug carrier system. The aim of this study was to investigate the influence of lipophilicity and structure of different model molecules on their distribution in SLN dispersions. SLN composed of glyceryl tripalmitate as lipid and soybean lecithin and poloxamer 188 as stabilizers were prepared by a melt-emulsification process. PC(10,3), MeFASL(10,3), C(14)-Tempo, and Tempol were incorporated into SLN as spin-labeled compounds. The partition of SP between triglyceride and water was determined experimentally by electron paramagnetic resonance (EPR) and compared with calculated partition coefficients. The distribution of molecules in SLN dispersions was determined from the parameters of EPR spectra, from the reduction kinetics of the spin-labeled compounds with sodium ascorbate, and by computer simulation of EPR spectral line shapes. The experimentally obtained partition coefficients increase in the order Tempol < MeFASL(10,3) < C(14)-Tempo, showing the same trend as the partition coefficients calculated according to Rekker. In SLN dispersions, it was estimated that the ratio of SP between solid lipid core, phospholipid layers (deeper in SLN layer or in liposomes and closer to the surface of SLN), and water is for Tempol 0:0:100, for C(14)-Tempo 46:54(20:34):0, for MeFASL(10,3) 34:65(38:27):1, and for PC(10,3) 10:89(26:3:60):1. Copyright 2002 Wiley-Liss, Inc. and the American Pharmaceutical Association

Effect of storage conditions on carbon-centered radicals in soy protein products.

PubMed

Boatright, William L; Lei, Qingxin; Shah Jahan, M

2009-09-09

Using electron paramagnetic resonance (EPR) spectroscopy, the levels of carbon-centered radicals in retail samples of isolated soy protein (ISP), soy protein concentrate (SPC), and powdered soy milk were estimated to contain from 6.12 x 10(14) to 1.98 x 10(15) spins/g of soy product. Roasted soy nuts contained about 5.70 x 10(15) spins/g. The peak to peak line width of the carbon-centered radicals from soy nuts was about 10 gauss, whereas ISP samples with a similar peak height had a peak to peak line width of about 8 gauss. Retail snack bars containing ISP, SPC, and/or roasted soy nuts with a total protein content of either 13, 21, or 29% contained 5.32 x 10(14), 6.67 x 10(14), and 5.74 x 10(14) spins/g of snack bar, respectively. Levels of carbon-centered radicals in newly prepared samples of ISP were much lower than levels in the retail soy protein products and levels previously reported for commercial ISP and laboratory ISP samples. The levels of radicals in ISP samples increased over a 12-25 week period of storage in the dark at 22 degrees C and exposed to air from about 8.00 x 10(13) spins/g immediately after preparation to 9.95 x 10(14) spins/g of ISP. Storing the ISP samples under nitrogen at 22 degrees C greatly reduced the increase in radical content, whereas storing the ISP in 99.9% oxygen at 40 degrees C accelerated the formation of stable carbon-centered radicals. ISP samples hydrated at either 22 or 92 degrees C, rapidly frozen, and dried lost about 92% of the trapped radicals. The level of carbon-centered radicals in these same ISP samples immediately began to increase during subsequent storage exposed to the air and gradually returned to similar levels obtained before they were hydrated.

Effects of structural spin-orbit coupling in two dimensional electron and hole liquids

NASA Astrophysics Data System (ADS)

Chesi, Stefano

The recent interest in spin-dependent phenomena in semiconductor heterostructures motivates our detailed study of the structural spin-orbit coupling present in clean two-dimensional electron and hole liquids. Interesting polarization effects are produced in a system out of equilibrium, as when a finite current flows in the sample. In particular, the consequences of a lateral confinement creating a quasi one-dimensional wire are studied in detail, partially motivated by a recent experimental investigation of the point-contact transmission for two-dimensional holes. We also address the role of the electron-electron interaction in the presence of spin-orbit coupling, which has received little attention in the literature. We discuss the formulation of the Hartree-Fock approximation in the particular case of linear Rashba spin-orbit. We establish the form of the mean-field phase diagram in the homogeneous case, which shows a complex interplay between paramagnetic and ferromagnetic states. The latter can be polarized in the plane or in a transverse direction, and are characterized by a complex spin structure and nontrivial occupation. The generality of the Hartree-Fock method allows a simple treatment of the Pauli spin susceptibility, and the application to different forms of spin-orbit coupling. Correlation corrections can be obtained in an analytic form for particular asymptotic regimes. For linear Rashba spin-orbit we identified the relevance of the large spin-orbit limit, dominated by many-body effects, and explicitly treated the high density limit, in which the system is asymptotically noninteracting. As a special case, we derive a new exact formula for the polarization dependence of the ring-diagram correlation energy.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Segawa, Takuya F., E-mail: takuya.segawa@alumni.ethz.ch; Doppelbauer, Maximilian; Garbuio, Luca

2016-05-21

Water accessibility is a key parameter for the understanding of the structure of biomolecules, especially membrane proteins. Several experimental techniques based on the combination of electron paramagnetic resonance (EPR) spectroscopy with site-directed spin labeling are currently available. Among those, we compare relaxation time measurements and electron spin echo envelope modulation (ESEEM) experiments using pulse EPR with Overhauser dynamic nuclear polarization (DNP) at X-band frequency and a magnetic field of 0.33 T. Overhauser DNP transfers the electron spin polarization to nuclear spins via cross-relaxation. The change in the intensity of the {sup 1}H NMR spectrum of H{sub 2}O at a Larmormore » frequency of 14 MHz under a continuous-wave microwave irradiation of the nitroxide spin label contains information on the water accessibility of the labeled site. As a model system for a membrane protein, we use the hydrophobic α-helical peptide WALP23 in unilamellar liposomes of DOPC. Water accessibility measurements with all techniques are conducted for eight peptides with different spin label positions and low radical concentrations (10–20 μM). Consistently in all experiments, the water accessibility appears to be very low, even for labels positioned near the end of the helix. The best profile is obtained by Overhauser DNP, which is the only technique that succeeds in discriminating neighboring positions in WALP23. Since the concentration of the spin-labeled peptides varied, we normalized the DNP parameter ϵ, being the relative change of the NMR intensity, by the electron spin concentration, which was determined from a continuous-wave EPR spectrum.« less

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

PubMed

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

2016-05-21

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

Mechanisms of relaxation and spin decoherence in nanomagnets

NASA Astrophysics Data System (ADS)

van Tol, Johan

Relaxation in spin systems is of great interest with respect to various possible applications like quantum information processing and storage, spintronics, and dynamic nuclear polarization (DNP). The implementation of high frequencies and fields is crucial in the study of systems with large zero-field splitting or large interactions, as for example molecular magnets and low dimensional magnetic materials. Here we will focus on the implementation of pulsed Electron Paramagnetic Resonance (ERP) at multiple frequencies of 10, 95, 120, 240, and 336 GHz, and the relaxation and decoherence processes as a function of magnetic field and temperature. Firstly, at higher frequencies the direct single-phonon spin-lattice relaxation (SLR) is considerably enhanced, and will more often than not be the dominant relaxation mechanism at low temperatures, and can be much faster than at lower fields and frequencies. In principle the measurement of the SLR rates as a function of the frequency provides a means to map the phonon density of states. Secondly, the high electron spin polarization at high fields has a strong influence on the spin fluctuations in relatively concentrated spin systems, and the contribution of the electron-electron dipolar interactions to the coherence rate can be partially quenched at low temperatures. This not only allows the study of relatively concentrated spin systems by pulsed EPR (as for example magnetic nanoparticles and molecular magnets), it enables the separation of the contribution of the fluctuations of the electron spin system from other decoherence mechanisms. Besides choice of temperature and field, several strategies in sample design, pulse sequences, or clock transitions can be employed to extend the coherence time in nanomagnets. A review will be given of the decoherence mechanisms with an attempt at a quantitative comparison of experimental rates with theory.

Studying lipid-protein interactions with electron paramagnetic resonance spectroscopy of spin-labeled lipids.

PubMed

Páli, Tibor; Kóta, Zoltán

2013-01-01

Spin label electron paramagnetic resonance (EPR) of lipid-protein interactions reveals crucial features of the structure and assembly of integral membrane proteins. Spin label EPR spectroscopy is the technique of choice to characterize the protein-solvating lipid shell in its highly dynamic nature, because the EPR spectra of lipids that are spin labeled close to the terminal methyl end of their acyl chains display two spectral components, those corresponding to lipids directly contacting the protein and those corresponding to lipids in the bulk fluid bilayer regions of the membrane. In this chapter, typical spin label EPR procedures are presented that allow determination of the stoichiometry of interaction of spin-labeled lipids with the intra-membranous region of membrane proteins or polypeptides, as well as the association constant of the spin-labeled lipid with respect to the host lipid. The lipids giving rise to the so-called immobile spectral component in the EPR spectrum of such samples are identified as the motionally restricted first-shell lipids solvating membrane proteins in biomembranes. Stoichiometry and selectivity are directly related to the structure of the intra-membranous sections of membrane-associated proteins or polypeptides and can be used to study the state of assembly of such proteins in the membrane. Since these characteristics of lipid-protein interactions are discussed in detail in the literature [see Marsh (Eur Biophys J 39:513-525, 2010) for a most recent review], here we focus more on how to spin label model and biomembranes and how to measure and analyze the two-component EPR spectra of spin-labeled lipids in phospholipid bilayers that contain proteins or polypeptides. After a description of how to prepare spin-labeled model and native biological membranes, we present the reader with computational procedures for determining the molar fraction of motionally restricted lipids when both, one, or none of the pure isolated-mobile or immobile-spectral components are available. With these topics, this chapter complements a recent methodological paper [Marsh (Methods 46:83-96, 2008)]. The interpretation of the data is discussed briefly, as well as other relevant and recent spin label EPR techniques for studying lipid-protein interactions, not only from the point of view of lipid chain dynamics.

Precision Measurement of the Electron's Electric Dipole Moment Using Trapped Molecular Ions.

PubMed

Cairncross, William B; Gresh, Daniel N; Grau, Matt; Cossel, Kevin C; Roussy, Tanya S; Ni, Yiqi; Zhou, Yan; Ye, Jun; Cornell, Eric A

2017-10-13

We describe the first precision measurement of the electron's electric dipole moment (d_{e}) using trapped molecular ions, demonstrating the application of spin interrogation times over 700 ms to achieve high sensitivity and stringent rejection of systematic errors. Through electron spin resonance spectroscopy on ^{180}Hf^{19}F^{+} in its metastable ^{3}Δ_{1} electronic state, we obtain d_{e}=(0.9±7.7_{stat}±1.7_{syst})×10^{-29}  e cm, resulting in an upper bound of |d_{e}|<1.3×10^{-28}  e cm (90% confidence). Our result provides independent confirmation of the current upper bound of |d_{e}|<9.4×10^{-29}  e cm [J. Baron et al., New J. Phys. 19, 073029 (2017)NJOPFM1367-263010.1088/1367-2630/aa708e], and offers the potential to improve on this limit in the near future.

Stripe Antiferromagnetic Spin Fluctuations in SrCo 2As 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jayasekara, Wageesha; Lee, Young-Jin; Pandey, Abhishek

Inelastic neutron scattering measurements of paramagnetic SrCo 2As 2 at T = 5 K reveal antiferromagnetic (AFM) spin fluctuations that are peaked at a wave vector of Q AFM = (1/2, 1/2, 1) and possess a large energy scale. These stripe spin fluctuations are similar to those found in AFe 2As 2 compounds, where spin-density wave AFM is driven by Fermi surface nesting between electron and hole pockets separated by Q AFM. SrCo 2As 2 has a more complex Fermi surface and band-structure calculations indicate a potential instability toward either a ferromagnetic or stripe AFM ground state. The results suggestmore » that stripe AFM magnetism is a general feature of both iron and cobalt-based arsenides and the search for spin fluctuation-induced unconventional superconductivity should be expanded to include cobalt-based compounds.« less

Electron paramagnetic resonance, scanning electron microscopy with energy dispersion X-ray spectrometry, X-ray powder diffraction, and NMR characterization of iron-rich fired clays.

PubMed

Presciutti, Federica; Capitani, Donatella; Sgamellotti, Antonio; Brunetti, Brunetto Giovanni; Costantino, Ferdinando; Viel, Stéphane; Segre, Annalaura

2005-12-01

The aim of this study is to clarify the structure of an iron-rich clay and the structural changes involved in the firing process as a preliminary step to get information on ancient ceramic technology. To this purpose, illite-rich clay samples fired at different temperatures were characterized using a multitechnique approach, i.e., by electron paramagnetic resonance, scanning electron microscopy with electron dispersion X-ray spectrometry, X-ray powder diffraction, magic angle spinning and multiple quantum magic angle spinning NMR. During firing, four main reaction processes occur: dehydration, dehydroxylation, structural breakdown, and recrystallization. When the results are combined from all characterization methods, the following conclusions could be obtained. Interlayer H2O is located close to aluminum in octahedral sites and is driven off at temperatures lower than 600 degrees C. Between 600 and 700 degrees C dehydroxylation occurs whereas, between 800 and 900 degrees C, the aluminum in octahedral sites disappears, due to the breakdown of the illite structure, and all iron present is oxidized to Fe3+. In samples fired at 1000 and 1100 degrees C iron clustering was observed as well as large single crystals of iron with the occurrence of ferro- or ferrimagnetic effects. Below 900 degrees C the aluminum in octahedral sites presents a continuous distribution of chemical shift, suggesting the presence of slightly distorted sites. Finally, over the whole temperature range, the presence of at least two tetrahedral aluminum sites was revealed, characterized by different values of the quadrupolar coupling constant.

Non-thermalization in trapped atomic ion spin chains

NASA Astrophysics Data System (ADS)

Hess, P. W.; Becker, P.; Kaplan, H. B.; Kyprianidis, A.; Lee, A. C.; Neyenhuis, B.; Pagano, G.; Richerme, P.; Senko, C.; Smith, J.; Tan, W. L.; Zhang, J.; Monroe, C.

2017-10-01

Linear arrays of trapped and laser-cooled atomic ions are a versatile platform for studying strongly interacting many-body quantum systems. Effective spins are encoded in long-lived electronic levels of each ion and made to interact through laser-mediated optical dipole forces. The advantages of experiments with cold trapped ions, including high spatio-temporal resolution, decoupling from the external environment and control over the system Hamiltonian, are used to measure quantum effects not always accessible in natural condensed matter samples. In this review, we highlight recent work using trapped ions to explore a variety of non-ergodic phenomena in long-range interacting spin models, effects that are heralded by the memory of out-of-equilibrium initial conditions. We observe long-lived memory in static magnetizations for quenched many-body localization and prethermalization, while memory is preserved in the periodic oscillations of a driven discrete time crystal state. This article is part of the themed issue 'Breakdown of ergodicity in quantum systems: from solids to synthetic matter'.

Non-thermalization in trapped atomic ion spin chains.

PubMed

Hess, P W; Becker, P; Kaplan, H B; Kyprianidis, A; Lee, A C; Neyenhuis, B; Pagano, G; Richerme, P; Senko, C; Smith, J; Tan, W L; Zhang, J; Monroe, C

2017-12-13

Linear arrays of trapped and laser-cooled atomic ions are a versatile platform for studying strongly interacting many-body quantum systems. Effective spins are encoded in long-lived electronic levels of each ion and made to interact through laser-mediated optical dipole forces. The advantages of experiments with cold trapped ions, including high spatio-temporal resolution, decoupling from the external environment and control over the system Hamiltonian, are used to measure quantum effects not always accessible in natural condensed matter samples. In this review, we highlight recent work using trapped ions to explore a variety of non-ergodic phenomena in long-range interacting spin models, effects that are heralded by the memory of out-of-equilibrium initial conditions. We observe long-lived memory in static magnetizations for quenched many-body localization and prethermalization, while memory is preserved in the periodic oscillations of a driven discrete time crystal state.This article is part of the themed issue 'Breakdown of ergodicity in quantum systems: from solids to synthetic matter'. © 2017 The Author(s).

Magnetic characterization of mixed phases in FeVO4sbnd Co3V2O8 system

NASA Astrophysics Data System (ADS)

Guskos, N.; Zolnierkiewicz, G.; Pilarska, M.; Typek, J.; Berczynski, P.; Blonska-Tabero, A.; Aidinis, K.

2018-04-01

Dynamic and static magnetic properties of four nFeVO4/(1-n)Co3V2O8 composites obtained in reactions between nFeVO4 and (1-n)Co3V2O8 (n = 0.82, 0.80, 0.78 and 0.76) have been investigated by dc magnetometry and electron paramagnetic resonance (EPR). All samples were diphase containing both the howardevansite-type and the lyonsite-type phases in different proportions. Dc magnetic susceptibility study showed the Curie-Weiss paramagnetic behavior with strong antiferromagnetic (AFM) interaction in the high-temperature range and the phase transition to the AFM state at low temperatures. The calculated effective magnetic moment could be justified by the presence of high spin Fe3+ and Co2+ ions. The appearance of hysteresis loop in isothermal magnetisation at low temperature indicates the existence of the ferromagnetic component in all four samples, but only 0.5% of all magnetic ions are involved in this phase. EPR spectra recorded in high-temperature range (T > 90 K) consisted of a single broad line centred at ∼3.2 kG. The fitting of observed spectra with two Gaussian lineshape functions allowed to study the temperature dependence of EPR parameters (resonance field, linewidth, integrated intensity). This analysis suggests that EPR signal arises from two spin subsystems: paramagnetic Fe3+ ions subjected to AFM interaction and AFM spin pairs/clusters of iron/cobalt visible only at high temperatures. At low temperatures two transitions to AFM states, due to the mixture of two structural phases, are registered in magnetic susceptibility measurements.

Nuclear Spin Locking and Extended Two-Electron Spin Decoherence Time in an InAs Quantum Dot Molecule

NASA Astrophysics Data System (ADS)

Chow, Colin; Ross, Aaron; Steel, Duncan; Sham, L. J.; Bracker, Allan; Gammon, Daniel

2015-03-01

The spin eigenstates for two electrons confined in a self-assembled InAs quantum dot molecule (QDM) consist of the spin singlet state, S, with J = 0 and the triplet states T-, T0 and T+, with J = 1. When a transverse magnetic field (Voigt geometry) is applied, the two-electron system can be initialized to the different states with appropriate laser excitation. Under the excitation of a weak probe laser, non-Lorentzian lineshapes are obtained when the system is initialized to either T- or T+, where T- results in a ``resonance locking'' lineshape while T+ gives a ``resonance avoiding '' lineshape: two different manifestations of hysteresis showing the importance of memory in the system. These observations signify dynamic nuclear spin polarization (DNSP) arising from a feedback mechanism involving hyperfine interaction between lattice nuclei and delocalized electron spins, and Overhauser shift due to nuclear spin polarization. Using pump configurations that generate coherent population trapping, the isolation of the electron spin from the optical excitation shows the stabilization of the nuclear spin ensemble. The dark-state lineshape measures the lengthened electron spin decoherence time, from 1 ns to 1 μs. Our detailed spectra highlight the potential of QDM for realizing a two-qubit gate. This work is supported by NSF, ARO, AFOSR, DARPA, and ONR.

Electron spin control of optically levitated nanodiamonds in vacuum

PubMed Central

Hoang, Thai M.; Ahn, Jonghoon; Bang, Jaehoon; Li, Tongcang

2016-01-01

Electron spins of diamond nitrogen-vacancy (NV) centres are important quantum resources for nanoscale sensing and quantum information. Combining NV spins with levitated optomechanical resonators will provide a hybrid quantum system for novel applications. Here we optically levitate a nanodiamond and demonstrate electron spin control of its built-in NV centres in low vacuum. We observe that the strength of electron spin resonance (ESR) is enhanced when the air pressure is reduced. To better understand this system, we investigate the effects of trap power and measure the absolute internal temperature of levitated nanodiamonds with ESR after calibration of the strain effect. We also observe that oxygen and helium gases have different effects on both the photoluminescence and the ESR contrast of nanodiamond NV centres, indicating potential applications of NV centres in oxygen gas sensing. Our results pave the way towards a levitated spin–optomechanical system for studying macroscopic quantum mechanics. PMID:27432560

Electron Paramagnetic Resonance Studies of Spin-Labeled Hemoglobins and Their Implications to the Nature of Cooperative Oxygen Binding to Hemoglobin*

PubMed Central

Ho, Chien; Baldassare, Joseph J.; Charache, Samuel

1970-01-01

The spin label technique has been used to study human hemoglobins A, F, Zürich, and Chesapeake as a function of carbon monoxide saturation. The experimental results suggest that the changes in the electron paramagnetic resonance spectra of hemoglobin labeled with N-(1-oxyl-2,2,6,6-tetramethyl-4-piperidinyl)iodoacetamide depend on the state of ligation of more than one heme group. For those hemoglobins with full or large cooperative ligand binding (such as A, F, and Zürich), there is a lack of isosbestic points in the spectra as a function of CO saturation. However, for those hemoglobins with little or no cooperative ligand binding (such as Chesapeake and methemoglobins), there is a sharp set of isosbestic points. These findings confirm and extend the early work of McConnell and co-workers. The absence of a set of isosbestic points in those hemoglobins with full cooperative ligand binding is consistent with the sequential model of Koshland, Némethy, and Filmer for cooperative oxygen binding to hemoglobin. The present results, with hemoglobin variants having known amino acid substitutions, also focus on the importance of the interactions among the amino acid residues located at α1-β2 or α2-β1 subunit contacts for the functioning of hemoglobin as an oxygen carrier. In addition, the resonance spectra of the spin label are very sensitive to small structural variations around the heme groups in the β- or γ-chains where the labels are attached. The results of the spin label experiment are discussed in relation to recent findings on the mechanism of oxygenation of hemoglobin from the nuclear magnetic resonance studies of this laboratory and the x-ray crystallographic analysis of Perutz and co-workers. PMID:4316679

Slater Insulator in Iridate Perovskites with Strong Spin-Orbit Coupling.

PubMed

Cui, Q; Cheng, J-G; Fan, W; Taylor, A E; Calder, S; McGuire, M A; Yan, J-Q; Meyers, D; Li, X; Cai, Y Q; Jiao, Y Y; Choi, Y; Haskel, D; Gotou, H; Uwatoko, Y; Chakhalian, J; Christianson, A D; Yunoki, S; Goodenough, J B; Zhou, J-S

2016-10-21

The perovskite SrIrO_{3} is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn^{4+} for Ir^{4+} in the SrIr_{1-x}Sn_{x}O_{3} perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at T_{N}≥225  K. The continuous change of the cell volume as detected by x-ray diffraction and the λ-shape transition of the specific heat on cooling through T_{N} demonstrate that the metal-insulator transition is of second order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type-G AF spin ordering below T_{N}. Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. A reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below T_{N} in the same way as proposed by Slater.

Radiation-induced defects in manganese-doped lithium tetraborate phosphor.

PubMed

Annalakshmi, O; Jose, M T; Madhusoodanan, U; Sridevi, J; Venkatraman, B; Amarendra, G; Mandal, A B

2015-01-01

Lithium tetraborate doped with manganese synthesised by solid-state sintering technique exhibits a dosimetric peak at 280°C. The high-temperature glow curve results in no fading for three months. The sensitivity of Li2B4O7:Mn is determined to be 0.9 times that of TLD-100. The infrared spectrum of this phosphor indicates the presence of bond vibrations corresponding to BO4 tetrahedral and BO3 triangles. The mechanism for thermoluminescence in this phosphor was proposed based on the thermoluminescence (TL) emission spectra, kinetic analysis of TL glow curves and electron paramagnetic resonance (EPR) measurements on non-irradiated and gamma-irradiated phosphors. It was identified that oxygen vacancies and Boron oxygen hole centre (BOHC) are the electron and hole trap centres for TL in this phosphor. When the phosphor is heated, the electrons are released from the electron trap and recombine with the trapped holes. The excitation energy during the recombination is transferred to the nearby Mn(2+) ions, which emit light at 580 nm. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Electrically detected crystal orientation dependent spin-Rabi beat oscillation of c-Si(111)/SiO2 interface states

NASA Astrophysics Data System (ADS)

Paik, Seoyoung; Lee, Sang-Yun; McCamey, Dane R.; Boehme, Christoph

2011-12-01

Electrically detected spin-Rabi beat oscillation of pairs of paramagnetic near interface states at the phosphorous doped (1016 cm-3) Si(111)/SiO2 interface is reported. Due to the g-factor anisotropy of the Pb center (a silicon surface dangling bond), one can tune intrapair Larmor frequency differences (Larmor separations) by orientation of the crystal with regard to an external magnetic field. Since Larmor separation governs the number of beating spin pairs, crystal orientation can control the beat current. This is used to identify spin states that are paired by mutual electronic transitions. The experiments confirm the presence of the previously reported 31P-Pb transition and provide direct experimental evidence of the previously hypothesized Pb-E' center (a near interface SiO2 bulk state) transition.

Modeling the active site of [NiFe] hydrogenases and the [NiFeu] subsite of the C-cluster of carbon monoxide dehydrogenases: low-spin iron(II) versus high-spin iron(II).

PubMed

Weber, Katharina; Erdem, Özlen F; Bill, Eckhard; Weyhermüller, Thomas; Lubitz, Wolfgang

2014-06-16

A series of four [S2Ni(μ-S)2FeCp*Cl] compounds with different tetradentate thiolate/thioether ligands bound to the Ni(II) ion is reported (Cp* = C5Me5). The {S2Ni(μ-S)2Fe} core of these compounds resembles structural features of the active site of [NiFe] hydrogenases. Detailed analyses of the electronic structures of these compounds by Mössbauer and electron paramagnetic resonance spectroscopy, magnetic measurements, and density functional theory calculations reveal the oxidation states Ni(II) low spin and Fe(II) high spin for the metal ions. The same electronic configurations have been suggested for the Cred1 state of the C-cluster [NiFeu] subsite in carbon monoxide dehydrogenases (CODH). The Ni-Fe distance of ∼3 Å excludes a metal-metal bond between nickel and iron, which is in agreement with the computational results. Electrochemical experiments show that iron is the redox active site in these complexes, performing a reversible one-electron oxidation. The four complexes are discussed with regard to their similarities and differences both to the [NiFe] hydrogenases and the C-cluster of Ni-containing CODH.

A Versatile High Speed 250 MHz Pulse Imager for Biomedical Applications

PubMed Central

Epel, Boris; Sundramoorthy, Subramanian V.; Mailer, Colin; Halpern, Howard J.

2009-01-01

A versatile 250 MHz pulse electron paramagnetic resonance (EPR) instrument for imaging of small animals is presented. Flexible design of the imager hardware and software makes it possible to use virtually any pulse EPR imaging modality. A fast pulse generation and data acquisition system based on general purpose PCI boards performs measurements with minimal additional delays. Careful design of receiver protection circuitry allowed us to achieve very high sensitivity of the instrument. In this article we demonstrate the ability of the instrument to obtain three dimensional images using the electron spin echo (ESE) and single point imaging (SPI) methods. In a phantom that contains a 1 mM solution of narrow line (16 μT, peak-to-peak) paramagnetic spin probe we achieved an acquisition time of 32 seconds per image with a fast 3D ESE imaging protocol. Using an 18 minute 3D phase relaxation (T2e) ESE imaging protocol in a homogeneous sample a spatial resolution of 1.4 mm and a standard deviation of T2e of 8.5% were achieved. When applied to in vivo imaging this precision of T2e determination would be equivalent to 2 torr resolution of oxygen partial pressure in animal tissues. PMID:19924261

Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy.

PubMed

Lu, Jian; Ozel, I Ozge; Belvin, Carina A; Li, Xian; Skorupskii, Grigorii; Sun, Lei; Ofori-Okai, Benjamin K; Dincă, Mircea; Gedik, Nuh; Nelson, Keith A

2017-11-01

Zero-field splitting (ZFS) parameters are fundamentally tied to the geometries of metal ion complexes. Despite their critical importance for understanding the magnetism and spectroscopy of metal complexes, they are not routinely available through general laboratory-based techniques, and are often inferred from magnetism data. Here we demonstrate a simple tabletop experimental approach that enables direct and reliable determination of ZFS parameters in the terahertz (THz) regime. We report time-domain measurements of electron paramagnetic resonance (EPR) signals associated with THz-frequency ZFSs in molecular complexes containing high-spin transition-metal ions. We measure the temporal profiles of the free-induction decays of spin resonances in the complexes at zero and nonzero external magnetic fields, and we derive the EPR spectra via numerical Fourier transformation of the time-domain signals. In most cases, absolute values of the ZFS parameters are extracted from the measured zero-field EPR frequencies, and the signs can be determined by zero-field measurements at two different temperatures. Field-dependent EPR measurements further allow refined determination of the ZFS parameters and access to the g -factor. The results show good agreement with those obtained by other methods. The simplicity of the method portends wide applicability in chemistry, biology and material science.

REVIEW ARTICLE: Unconventional isotope effects in the high-temperature cuprate superconductors

NASA Astrophysics Data System (ADS)

Zhao, Guo-meng; Keller, H.; Conder, K.

2001-07-01

We review various isotope effects in the high-Tc cuprate superconductors to assess the role of the electron-phonon interaction in the basic physics of these materials. Of particular interest are the unconventional isotope effects on the supercarrier mass, on the charge-stripe formation temperature, on the pseudogap formation temperature, on the electron paramagnetic resonance (EPR) linewidth, on the spin-glass freezing temperature and on the antiferromagnetic ordering temperature. The observed unconventional isotope effects strongly suggest that lattice vibrations play an important role in the microscopic pairing mechanism of high-temperature superconductivity.

Phospholipid bilayer relaxation dynamics as revealed by the pulsed electron-electron double resonance of spin labels

NASA Astrophysics Data System (ADS)

Syryamina, V. N.; Dzuba, S. A.

2012-10-01

Electron paramagnetic resonance (EPR) spectroscopy in the form of pulsed electron-electron double resonance (ELDOR) was applied to 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) phospholipid bilayers containing lipids that were spin-labeled at different carbon positions along the lipid acyl chain. Pulsed ELDOR detects motionally induced spin flips of nitrogen nuclei in the nitroxide spin labels, which manifests itself as magnetization transfer (MT) in the nitroxide EPR spectrum. The MT effect was observed over a wide temperature range (100-225 K) on a microsecond time scale. In line with a previous study on molecular glasses [N. P. Isaev and S. A. Dzuba, J. Chem. Phys. 135, 094508 (2011), 10.1063/1.3633241], the motions that induce MT effect were suggested to have the same nature as those in dielectric secondary (β) Johari-Goldstein fast relaxation. The results were compared with literature dielectric relaxation data for POPC bilayers, revealing some common features. Molecular motions resulting in MT are faster for deeper spin labels in the membrane interior. The addition of cholesterol to the bilayer suppresses the lipid motions near the steroid nucleus and accelerates the lipid motions beyond the steroid nucleus, in the bilayer interior. This finding was attributed to the lipid acyl chains being more ordered near the steroid nucleus and less ordered in the bilayer interior. The motions are absent in dry lipids, indicating that the motions are determined by intermolecular interactions in the bilayer.

Gate control of spin-polarized conductance in alloyed transitional metal nanocontacts

NASA Astrophysics Data System (ADS)

Sivkov, Ilia N.; Brovko, Oleg O.; Rungger, Ivan; Stepanyuk, Valeri S.

2017-03-01

To date, endeavors in nanoscale spintronics are dominated by the use of single-electron or single-spin transistors having at their heart a semiconductor, metallic, or molecular quantum dot whose localized states are non-spin-degenerate and can be controlled by an external bias applied via a gate electrode. Adjusting the bias of the gate one can realign those states with respect to the chemical potentials of the leads and thus tailor the spin-polarized transmission properties of the device. Here we show that similar functionality can be achieved in a purely metallic junction comprised of a metallic magnetic chain attached to metallic paramagnetic leads and biased by a gate electrode. Our ab initio calculations of electron transport through mixed Pt-Fe (Fe-Pd and Fe-Rh) atomic chains suspended between Pt (Pd and Rh) electrodes show that spin-polarized confined states of the chain can be shifted by the gate bias causing a change in the relative contributions of majority and minority channels to the nanocontact's conductance. As a result, we observe strong dependence of conductance spin polarization on the applied gate potential. In some cases the spin polarization of conductance can even be reversed in sign upon gate potential application, which is a remarkable and promising trait for spintronic applications.

Observation of vacuum-enhanced electron spin resonance of optically levitated nanodiamonds

NASA Astrophysics Data System (ADS)

Li, Tongcang; Hoang, Thai; Ahn, Jonghoon; Bang, Jaehoon

Electron spins of diamond nitrogen-vacancy (NV) centers are important quantum resources for nanoscale sensing and quantum information. Combining such NV spin systems with levitated optomechanical resonators will provide a hybrid quantum system for many novel applications. Here we optically levitate a nanodiamond and demonstrate electron spin control of its built-in NV centers in low vacuum. We observe that the strength of electron spin resonance (ESR) is enhanced when the air pressure is reduced. To better understand this novel system, we also investigate the effects of trap power and measure the absolute internal temperature of levitated nanodiamonds with ESR after calibration of the strain effect. Our results show that optical levitation of nanodiamonds in vacuum not only can improve the mechanical quality of its oscillation, but also enhance the ESR contrast, which pave the way towards a novel levitated spin-optomechanical system for studying macroscopic quantum mechanics. The results also indicate potential applications of NV centers in gas sensing.

Electron spin control and torsional optomechanics of an optically levitated nanodiamond in vacuum

NASA Astrophysics Data System (ADS)

Li, Tongcang; Hoang, Thai; Ahn, Jonghoon; Bang, Jaehoon

Electron spins of diamond nitrogen-vacancy (NV) centers are important quantum resources for nanoscale sensing and quantum information. Combining such NV spin systems with levitated optomechanical resonators will provide a hybrid quantum system for many novel applications. Here we optically levitate a nanodiamond and demonstrate electron spin control of its built-in NV centers in vacuum. We observe that the strength of electron spin resonance (ESR) is enhanced when the air pressure is reduced. We also observe that oxygen and helium gases have different effects on both the photoluminescence and the ESR contrast of nanodiamond NV centers, indicating potential applications of NV centers in oxygen gas sensing. For spin-optomechanics, it is important to control the orientation of the nanodiamond and NV centers in a magnetic field. Recently, we have observed the angular trapping and torsional vibration of a levitated nanodiamond, which paves the way towards levitated torsional optomechanics in the quantum regime. NSF 1555035-PHY.

Fermionic spin liquid analysis of the paramagnetic state in volborthite

NASA Astrophysics Data System (ADS)

Chern, Li Ern; Schaffer, Robert; Sorn, Sopheak; Kim, Yong Baek

2017-10-01

Recently, thermal Hall effect has been observed in the paramagnetic state of volborthite, which consists of distorted kagome layers with S =1 /2 local moments. Despite the appearance of magnetic order below 1 K , the response to external magnetic field and unusual properties of the paramagnetic state above 1 K suggest possible realization of exotic quantum phases. Motivated by these discoveries, we investigate possible spin liquid phases with fermionic spinon excitations in a nonsymmorphic version of the kagome lattice, which belongs to the two-dimensional crystallographic group p 2 g g . This nonsymmorphic structure is consistent with the spin model obtained in the density functional theory calculation. Using projective symmetry group analysis and fermionic parton mean field theory, we identify twelve distinct Z2 spin liquid states, four of which are found to have correspondence in the eight Schwinger boson spin liquid states we classified earlier. We focus on the four fermionic states with bosonic counterpart and find that the spectrum of their corresponding root U (1 ) states features spinon Fermi surface. The existence of spinon Fermi surface in candidate spin liquid states may offer a possible explanation of the finite thermal Hall conductivity observed in volborthite.

Consensus structures of the Mo(v) sites of sulfite-oxidizing enzymes derived from variable frequency pulsed EPR spectroscopy, isotopic labelling and DFT calculations.

PubMed

Enemark, John H

2017-10-10

Sulfite-oxidizing enzymes from eukaryotes and prokaryotes have five-coordinate distorted square-pyramidal coordination about the molybdenum atom. The paramagnetic Mo(v) state is easily generated, and over the years four distinct CW EPR spectra have been identified, depending upon enzyme source and the reaction conditions, namely high and low pH (hpH and lpH), phosphate inhibited (P i ) and sulfite (or blocked). Extensive studies of these paramagnetic forms of sulfite-oxidizing enzymes using variable frequency pulsed electron spin echo (ESE) spectroscopy, isotopic labeling and density functional theory (DFT) calculations have led to the consensus structures that are described here. Errors in some of the previously proposed structures are corrected.

The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2

NASA Astrophysics Data System (ADS)

Zhang, Xin; Mu, Sai; Liu, Yang; Luo, Jian; Zhang, Jian; N'Diaye, Alpha T.; Enders, Axel; Dowben, Peter A.

2018-05-01

The unoccupied electronic structure of the spin crossover molecule cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, [Co(dpzca)2] was investigated, using X-ray absorption spectroscopy (XAS) and compared with magnetometry (SQUID) measurements. The temperature dependence of the XAS and molecular magnetic susceptibility χmT are in general agreement for [Co(dpzca)2], and consistent with density functional theory (DFT). This agreement of magnetic susceptibility and X-ray absorption spectroscopy provides strong evidence that the changes in magnetic moment can be ascribed to changes in electronic structure. Calculations show the choice of Coulomb correlation energy U has a profound effect on the electronic structure of the low spin state, but has little influence on the electronic structure of the high spin state. In the temperature dependence of the XAS, there is also evidence of an X-ray induced excited state trapping for [Co(dpzca)2] at 15 K.

Magnetic properties and electronic structure of manganese-based blue pigments: a high-frequency and -field EPR study.

PubMed

Krzystek, J; Telser, Joshua; Li, Jun; Subramanian, M A

2015-09-21

A variety of new oxide-based materials based on hexagonal phase of YInO3 have been recently described. In some of these materials, the In(III) ions are substituted by Mn(III), which finds itself in a trigonal-bipyramidal (TBP) coordination environment. While YInO3 is colorless and YMnO3 is black, mixed systems YIn1-xMnxO3 (0.02 < x < 0.25) display intense blue color and have been proposed as novel blue pigments. Since the Mn(III) ion is paramagnetic, its presence imparts distinct magnetic properties to the whole class of materials. These properties were investigated by electron paramagnetic resonance (EPR) in its high-frequency and -field version (HFEPR), a technique ideally suited for transition metal ions such as Mn(III) that, in contrast to, for example, Mn(II), are difficult to study by EPR at (conventional) low frequency and field. YIn1-xMnxO3 with 0.02 < x < 0.2 exhibited high-quality HFEPR spectra up to room temperature that could be interpreted as arising from isolated S = 2 paramagnets. A simple ligand-field model, based on the structure and optical spectra, explains the spin Hamiltonian parameters provided by HFEPR, which were D = +3.0 cm(-1), E = 0; g⊥ = 1.99, g∥ = 2.0. This study demonstrates the general applicability of a combined spectroscopic and classical theoretical approach to understanding the electronic structure of novel materials containing paramagnetic dopants. Moreover, HFEPR complements optical and other experimental methods as being a sensitive probe of dopant level.

Coherent manipulation of three-qubit states in a molecular single-ion magnet

NASA Astrophysics Data System (ADS)

Jenkins, M. D.; Duan, Y.; Diosdado, B.; García-Ripoll, J. J.; Gaita-Ariño, A.; Giménez-Saiz, C.; Alonso, P. J.; Coronado, E.; Luis, F.

2017-02-01

We study the quantum spin dynamics of nearly isotropic Gd3 + ions entrapped in polyoxometalate molecules and diluted in crystals of a diamagnetic Y3 + derivative. The full energy-level spectrum and the orientations of the magnetic anisotropy axes have been determined by means of continuous-wave electron paramagnetic resonance experiments, using X-band (9-10 GHz) cavities and on-chip superconducting waveguides and 1.5-GHz resonators. The results show that seven allowed transitions between the 2 S +1 spin states can be separately addressed. Spin coherence T2 and spin-lattice relaxation T1 rates have been measured for each of these transitions in properly oriented single crystals. The results suggest that quantum spin coherence is limited by residual dipolar interactions with neighbor electronic spins. Coherent Rabi oscillations have been observed for all transitions. The Rabi frequencies increase with microwave power and agree quantitatively with predictions based on the spin Hamiltonian of the molecular spin. We argue that the spin states of each Gd3 + ion can be mapped onto the states of three addressable qubits (or, alternatively, of a d =8 -level "qudit"), for which the seven allowed transitions form a universal set of operations. Within this scheme, one of the coherent oscillations observed experimentally provides an implementation of a controlled-controlled-NOT (or Toffoli) three-qubit gate.

Self-trapped holes in β-Ga2O3 crystals

NASA Astrophysics Data System (ADS)

Kananen, B. E.; Giles, N. C.; Halliburton, L. E.; Foundos, G. K.; Chang, K. B.; Stevens, K. T.

2017-12-01

We have experimentally observed self-trapped holes (STHs) in a β-Ga2O3 crystal using electron paramagnetic resonance (EPR). These STHs are an intrinsic defect in this wide-band-gap semiconductor and may serve as a significant deterrent to producing usable p-type material. In our study, an as-grown undoped n-type β-Ga2O3 crystal was initially irradiated near room temperature with high-energy neutrons. This produced gallium vacancies (acceptors) and lowered the Fermi level. The STHs (i.e., small polarons) were then formed during a subsequent irradiation at 77 K with x rays. Warming the crystal above 90 K destroyed the STHs. This low thermal stability is a strong indicator that the STH is the correct assignment for these new defects. The S = 1/2 EPR spectrum from the STHs is easily observed near 30 K. A holelike angular dependence of the g matrix (the principal values are 2.0026, 2.0072, and 2.0461) suggests that the defect's unpaired spin is localized on one oxygen ion in a nonbonding p orbital aligned near the a direction in the crystal. The EPR spectrum also has resolved hyperfine structure due to equal and nearly isotropic interactions with 69,71Ga nuclei at two neighboring Ga sites. With the magnetic field along the a direction, the hyperfine parameters are 0.92 mT for the 69Ga nuclei and 1.16 mT for the 71Ga nuclei.

Electron paramagnetic resonance of Cr{sup 3+} ions in ABO{sub 3} (A = Sc, Lu, In) diamagnetic crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vorotynov, A. M., E-mail: sasa@iph.krasn.ru; Ovchinnikov, S. G.; Rudenko, V. V.

2016-04-15

A magnetic resonance method is applied to the investigation of a number of isostructural diamagnetic compounds ABO{sub 3} (A = Sc, Lu, In) with small additions of Cr{sup 3+} ions (S = 3/2) sufficient to observe single-ion spectra. It is shown that the resonance spectra for isolated Cr{sup 3+} ions can be described to a good accuracy by the ordinary axial spin Hamiltonian for 3d ions in octahedral oxygen environment. The parameters of the spin Hamiltonian are determined. It is established that Cr{sup 3+} ions in these crystals are characterized by easy-axis-type anisotropy.

Distribution of localized states from fine analysis of electron spin resonance spectra of organic semiconductors: Physical meaning and methodology

NASA Astrophysics Data System (ADS)

Mishchenko, Andrey S.; Matsui, Hiroyuki; Hasegawa, Tatsuo

2012-02-01

We develop an analytical method for the processing of electron spin resonance (ESR) spectra. The goal is to obtain the distributions of trapped carriers over both their degree of localization and their binding energy in semiconductor crystals or films composed of regularly aligned organic molecules [Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.104.056602 104, 056602 (2010)]. Our method has two steps. We first carry out a fine analysis of the shape of the ESR spectra due to the trapped carriers; this reveals the distribution of the trap density of the states over the degree of localization. This analysis is based on the reasonable assumption that the linewidth of the trapped carriers is predetermined by their degree of localization because of the hyperfine mechanism. We then transform the distribution over the degree of localization into a distribution over the binding energies. The transformation uses the relationships between the binding energies and the localization parameters of the trapped carriers. The particular relation for the system under study is obtained by the Holstein model for trapped polarons using a diagrammatic Monte Carlo analysis. We illustrate the application of the method to pentacene organic thin-film transistors.

Nitroxide paramagnet-induced para-ortho conversion and nuclear spin relaxation of H2 in organic solvents.

PubMed

Sartori, Elena; Ruzzi, Marco; Lawler, Ronald G; Turro, Nicholas J

2008-09-24

The kinetics of para-ortho conversion and nuclear spin relaxation of H 2 in chloroform- d 1 were investigated in the presence of nitroxides as paramagnetic catalysts. The back conversion from para-hydrogen ( p-H 2) to ortho-hydrogen ( o-H 2) was followed by NMR by recording the increase in the intensity of the signal of o-H 2 at regular intervals of time. The nitroxides proved to be hundreds of times more effective at inducing relaxation among the spin levels of o-H 2 than they are in bringing about transitions between p-H 2 and the levels of o-H 2. The value of the encounter distance d between H 2 and the paramagnetic molecule, calculated from the experimental bimolecular conversion rate constant k 0, using the Wigner theory of para-ortho conversion, agrees perfectly with that calculated from the experimental relaxivity R 1 using the force free diffusion theory of spin-lattice relaxation.

Cu doped diamond: Effect of charge state and defect aggregation on spin interactions in a 3d transition metal doped wide band-gap semiconductor

NASA Astrophysics Data System (ADS)

Benecha, E. M.; Lombardi, E. B.

2018-05-01

We present a first principles study of Cu in diamond using DFT+U electronic structure methods, by carefully considering the impact of co-doping, charge state, and Fermi level position on its stability, lattice location, spin states, and electronic properties. We show that the energetic stability and spin states of Cu are strongly dependent on the Fermi level position and the type of diamond co-doping, with Cu being energetically more favorable in n-type or p-type co-doped diamond compared to intrinsic diamond. Since Cu has been predicted to order magnetically in a number of other wide band-gap semiconductors, we have also evaluated this possibility for Cu doped diamond. We show that while Cu exhibits strong spin interactions at specific interatomic separations in diamond, a detailed consideration of the impact of Fermi level position and Cu aggregation precludes magnetic ordering, with Cu forming non-magnetic, antiferromagnetic, or paramagnetic clusters. These results have important implications in the understanding of the properties of transition metal dopants in diamond for device applications.

Radiation effects in x-irradiated hydroxy compounds

NASA Astrophysics Data System (ADS)

Budzinski, Edwin E.; Potter, William R.; Box, Harold C.

1980-01-01

Radiation effects are compared in single crystals of xylitol, sorbitol, and dulcitol x-irradiated at 4.2 °K. In xylitol and dulcitol, but not in sorbitol, a primary oxidation product is identified as an alkoxy radical. ENDOR measurements detected three proton hyperfine couplings associated with the alkoxy ESR absorption, one of which is attributed to a proton three bond lengths removed from the seat of unpaired spin density. Intermolecular trapping of electrons is observed in all three crystals. ENDOR measurements were made of the hyperfine couplings between the trapped electron and the hydroxy protons forming the trap.

Radical production from the interaction of ozone and PUFA as demonstrated by electron spin resonance spin-trapping techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pryor, W.A.; Prier, D.G.; Church, D.F.

1981-02-01

There is considerable evidence that indicates that a fraction of the damage caused by ozone to cellular systems involves radical-mediated reactions. The most direct method for probing the mechanism by which ozone reacts with target molecules such as polyunsaturated fatty acids involves the use of electron spin resonance. In 1968, Goldstein et al. reported that ESR signals were observed when 40 ppM ozone in air is bubbled through linoleic acid. We have repeated this experiment and have performed several experiments modified from this design; in none of these do we observe ESR signals. We have studied the reaction of ozonemore » with PUFA at -78/sup 0/C using spin traps. Spin traps themselves react with ozone, but the following protocol avoids that reaction. (1) Ozone in air or oxygen-free ozone is allowed to bubble through the sample in Freon-11 in an ESR tube at -78/sup 0/C; no ESR absorption is observed. (2) Unreacted ozone is flushed out with argon or nitrogen. (3) The spin trap in Freon-11 is added to give a 0.1 M solution, still at -78/sup 0/C; no ESR signal is observed. (4) The tube is allowed to warm slowly. At about -45/sup 0/C, the ESR spectra of spin adducts appear. Using this method with methyl linoleate we observe spin adducts of alkoxy radicals and also a signal that is consistent with a carbon radical with one ..cap alpha..-H. We hypothesize that an intermediate is formed from the reaction of ozone with PUFA that is stable at -78/sup 0/Cbut decomposes to form radicals at about -45/sup 0/C. We tentatively identify the intermediate as a trioxide on the basis of analogies and its temperature profile for decomposition to radicals. It appears reasonable to suggest that the reaction(s) responsible for the production of radicals under these low-temperature conditions also occurs at room temperature. Although the low-temperature intermediate cannot be observed at ambient temperatures, radicals from it could be responsible for the effects on autoxidation that are induced by ozone.« less

Muon-spin-relaxation and inelastic neutron scattering investigations of the caged-type Kondo semimetals: CeT2Al10 (T = Fe, Ru and Os)

NASA Astrophysics Data System (ADS)

Adroja, D. T.; Hillier, A. D.; Muro, Y.; Takabatake, T.; Strydom, A. M.; Bhattacharyya, A.; Daoud-Aladin, A.; Taylor, J. W.

2013-12-01

Recently, Ce-based caged-type compounds with the general formula CeT2Al10 (T = Fe, Ru and Os) have generated considerable interest due to the Kondo semiconducting paramagnetic ground state (down to 40 mK) observed in CeFe2Al10 and anomalously high magnetic ordering temperature with spin gap formation at low temperatures in Kondo semimetals CeRu2Al10 and CeOs2Al10. The formation of long-range magnetic ordering out of the Kondo semiconducting/semimetallic state itself is extraordinary and these are the first examples of this enigmatic coexistence of electronic ground states. These compounds also exhibit strong anisotropy in magnetic and transport properties, which has been explained on the basis of single-ion crystal electric field anisotropy in the presence of strongly anisotropic hybridization between localized 4f-electron and conduction electrons. Furthermore, they also exhibit a remarkable modification of magnetic and transport properties with doping on Ce, or T or Al sites. In this article, we briefly discuss the bulk properties of these compounds, giving a detailed discussion on our muon-spin-relaxation (μSR) investigations and inelastic neutron scattering (INS) results. We present the μSR and the INS results of Ce(Ru1-xFex)2Al10 and CeOs2Al10 as well as the μSR results of NdFe2Al10, NdOs2Al10 and YFe2Al10 for comparison. The zero-field μSR spectra clearly reveal coherent two-frequency oscillations at low temperatures in CeT2Al10 (T = Ru and Os) and Ce(Ru1-xFex)2Al10 (x = 0.3-0.5), which confirms the long-range magnetic ordering with a reduced moment of the Ce. On the other hand, the μSR spectra of Ce(Ru1-xFex)2Al10 (x = 0.8 and 1) down to 1.2 and 0.04 K, respectively, exhibit a temperature independent Kubo-Toyabe (KT) term confirming a paramagnetic ground state. INS measurements on CeT2Al10 (T = Ru and Os) exhibit sharp inelastic excitations at 8 and 11 meV at 5 K due to an opening of a gap in the spin excitation spectrum. A spin gap of 8-12 meV at 7 K, with a strong Q-dependent intensity, is observed in the magnetic ordered state of Ce(Ru1-xFex)2Al10 with x = 0.3 and 0.5 which remarkably extends into the paramagnetic state of x = 0.8 and 1. The observation of a spin gap in the paramagnetic samples (x = 0.8 and 1) is an interesting finding in this study and it challenges our understanding of the origin of the semiconducting energy gap in CeT2Al10 (T = Ru and Os) in terms of a hybridization gap opening only a small part of the Fermi surface, gapped spin waves or a spin-dimer gap. Furthermore, the μSR study of NdFe2Al10 below TN exhibits a clear sign of two frequency oscillations, which are absent in NdOs2Al10. Moreover, the μSR study of YFe2Al10, which has been proposed as a compound exhibiting ferromagnetic critical fluctuations did not reveal any clear sign of critical magnetic fluctuations down to 60 mK, within the ISIS μSR time window, which is unexpected for a T → 0 quantum phase transition (QPT).

SimLabel: a graphical user interface to simulate continuous wave EPR spectra from site-directed spin labeling experiments.

PubMed

Etienne, E; Le Breton, N; Martinho, M; Mileo, E; Belle, V

2017-08-01

Site-directed spin labeling (SDSL) combined with continuous wave electron paramagnetic resonance (cw EPR) spectroscopy is a powerful technique to reveal, at the residue level, structural transitions in proteins. SDSL-EPR is based on the selective grafting of a paramagnetic label on the protein under study, followed by cw EPR analysis. To extract valuable quantitative information from SDSL-EPR spectra and thus give reliable interpretation on biological system dynamics, numerical simulations of the spectra are required. Such spectral simulations can be carried out by coding in MATLAB using functions from the EasySpin toolbox. For non-expert users of MATLAB, this could be a complex task or even impede the use of such simulation tool. We developed a graphical user interface called SimLabel dedicated to run cw EPR spectra simulations particularly coming from SDSL-EPR experiments. Simlabel provides an intuitive way to visualize, simulate, and fit such cw EPR spectra. An example of SDSL-EPR spectra simulation concerning the study of an intrinsically disordered region undergoing a local induced folding is described and discussed. We believe that this new tool will help the users to rapidly obtain reliable simulated spectra and hence facilitate the interpretation of their results. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Interactions of the GM2 activator protein with phosphatidylcholine bilayers: a site-directed spin-labeling power saturation study.

PubMed

Mathias, Jordan D; Ran, Yong; Carter, Jeffery D; Fanucci, Gail E

2009-09-02

The GM2 activator protein (GM2AP) is an accessory protein that is an essential component in the catabolism of the ganglioside GM2. A function of GM2AP is to bind and extract GM2 from intralysosomal vesicles, forming a soluble protein-lipid complex, which interacts with the hydrolase Hexosaminidase A, the enzyme that cleaves the terminal sugar group of GM2. Here, we used site-directed spin labeling with power saturation electron paramagnetic resonance to determine the surface-bound orientation of GM2AP upon phosphatidylcholine vesicles. Because GM2AP extracts lipid ligands from the vesicle and is undergoing exchange on and off the vesicle surface, we utilized a nickel-chelating lipid to localize the paramagnetic metal collider to the lipid bilayer-aqueous interface. Spin-labeled sites that collide with the lipid-bound metal relaxing agent provide a means for mapping sites of the protein that interact with the lipid bilayer interface. Results show that GM2AP binds to lipid bilayers such that the residues lining the lipid-binding cavity lie on the vesicle surface. This orientation creates a favorable microenvironment that can allow for the lipid tails to flip out of the bilayer directly into the hydrophobic pocket of GM2AP.

Anti-HER2 immunoliposomes for selective delivery of electron paramagnetic resonance imaging probes to HER2-overexpressing breast tumor cells

PubMed Central

Burks, Scott R.; Macedo, Luciana F.; Barth, Eugene D.; Tkaczuk, Katherine H.; Martin, Stuart S.; Rosen, Gerald M.; Halpern, Howard J.; Brodie, Angela M.

2014-01-01

Electron paramagnetic resonance (EPR) imaging is an emerging modality that can detect and localize paramagnetic molecular probes (so-called spin probes) in vivo. We previously demonstrated that nitroxide spin probes can be encapsulated in liposomes at concentrations exceeding 100 mM, at which nitroxides exhibit a concentration-dependent quenching of their EPR signal that is analogous to the self-quenching of fluorescent molecules. Therefore, intact liposomes encapsulating high concentrations of nitroxides exhibit greatly attenuated EPR spectral signals, and endocytosis of such liposomes represents a cell-activated contrast-generating mechanism. After endocytosis, the encapsulated nitroxide is liberated and becomes greatly diluted in the intracellular milieu. This dequenches the nitroxides to generate a robust intracellular EPR signal. It is therefore possible to deliver a high concentration of nitroxides to cells while minimizing background signal from unendocytosed liposomes. We report here that intracellular EPR signal can be selectively generated in a specific cell type by exploiting its expression of Human Epidermal Growth Factor Receptor 2 (HER2). When targeted by anti-HER2 immunoliposomes encapsulating quenched nitroxides, Hc7 cells, which are novel HER2-overexpressing cells derived from the MCF7 breast tumor cell line, endocytose the liposomes copiously, in contrast to the parent MCF7 cells or control CV1 cells, which do not express HER2. HER2-dependent liposomal delivery enables Hc7 cells to accumulate 750 μM nitroxide intracellularly. Through the use of phantom models, we verify that this concentration of nitroxides is more than sufficient for EPR imaging, thus laying the foundation for using EPR imaging to visualize HER2-overexpressing Hc7 tumors in animals. PMID:20066490

Spontaneous magnetic order in complex materials: Role of longitudinal spin-orbit interactions

NASA Astrophysics Data System (ADS)

Chakraborty, Subrata; Vijay, Amrendra

2017-06-01

We show that the longitudinal spin-orbit interactions (SOI) critically determine the fate of spontaneous magnetic order (SMO) in complex materials. To study the magnetic response of interacting electrons constituting the material, we implement an extension of the Hubbard model that faithfully accounts for the SOI. Next, we use the double-time Green functions of quantum statistical mechanics to obtain the spontaneous magnetization, Msp , and thence ascertain the possibility of SMO. For materials with quenched SOI, in an arbitrary dimension, Msp vanishes at finite temperatures, implying the presence of the disordered (paramagnetic) phase. This is consistent with and goes beyond the Bogolyubov's inequality based analysis in one and two dimensions. In the presence of longitudinal SOI, Msp , for materials in an arbitrary dimension, remains non-zero at finite temperatures, which indicates the existence of the ordered (ferromagnetic) phase. As a plausible experimental evidence of the present SOI-based phenomenology, we discuss, inter alia, a recent experimental study on Y4Mn1-xGa12-yGey, an intermetallic compound, which exhibits a magnetic phase transition (paramagnetic to ferromagnetic) upon tuning the fraction of Ge atoms and thence the vacancies of the magnetic centers in this system. The availability of Ge atoms to form a direct chemical bond with octahedral Mn in this material appears to quench the SOI and, as a consequence, favours the formation of the disordered (paramagnetic) phase.

Peculiarities of magnetic and spin effects in a biradical/stable radical complex (three-spin system). Theory and comparison with experiment.

PubMed

Magin, Ilya M; Purtov, Petr A; Kruppa, Alexander I; Leshina, Tatiana V

2005-08-25

The field dependencies of biradical recombination probability in the presence of paramagnetic species with spins S(3) = 1 and S(3) = (1)/(2) have been calculated in the framework of the density matrix formalism. To describe the effect of the "third" spin on the spin evolution in biradical, we have also considered the spin exchange interaction between the added spin and one of the paramagnetic biradical centers. A characteristic feature of the calculated field dependencies is the existence of several extrema with positions and magnitudes depending on the signs and values of the exchange integrals in the system. The method proposed can be used to describe the effect of spin catalysis. It is shown that for the system with the third spin S(3) = 1 spin catalysis manifests itself stronger than in the case of spin S(3) = (1)/(2). The dependence of spin catalysis efficiency on the exchange interaction with the third spin has an extremum with position independent of the value of the spin added.

Towards Simulating the Transverse Ising Model in a 2D Array of Trapped Ions

NASA Astrophysics Data System (ADS)

Sawyer, Brian

2013-05-01

Two-dimensional Coulomb crystals provide a useful platform for large-scale quantum simulation. Penning traps enable confinement of large numbers of ions (>100) and allow for the tunable-range spin-spin interactions demonstrated in linear ion strings, facilitating simulation of quantum magnetism at a scale that is currently intractable on classical computers. We readily confine hundreds of Doppler laser-cooled 9Be+ within a Penning trap, producing a planar array of ions with self-assembled triangular order. The transverse ``drumhead'' modes of our 2D crystal along with the valence electron spin of Be+ serve as a resource for generating spin-motion and spin-spin entanglement. Applying a spin-dependent optical dipole force (ODF) to the ion array, we perform spectroscopy and thermometry of individual drumhead modes. This ODF also allows us to engineer long-range Ising spin couplings of either ferromagnetic or anti-ferromagnetic character whose approximate power-law scaling with inter-ion distance, d, may be varied continuously from 1 /d0 to 1 /d3. An effective transverse magnetic field is applied via microwave radiation at the ~124-GHz spin-flip frequency, and ground states of the effective Ising Hamiltonian may in principle be prepared adiabatically by slowly decreasing this transverse field in the presence of the induced Ising coupling. Long-range anti-ferromagnetic interactions are of particular interest due to their inherent spin frustration and resulting large, near-degenerate manifold of ground states. We acknowledge support from NIST and the DARPA-OLE program.

Generation of hydroxyl radicals by urban suspended particulate air matter. The role of iron ions

NASA Astrophysics Data System (ADS)

Valavanidis, Athanasios; Salika, Anastasia; Theodoropoulou, Anna

Recent epidemiologic studies showed statistical associations between particulate air pollution in urban areas and increased morbidity and mortality, even at levels well within current national air quality standards. Inhalable particulate matter (PM 10) can penetrate into the lower airways where they can cause acute and chronic lung injury by generating toxic oxygen free radicals. We tested inhalable total suspended particulates (TSP) from the Athens area, diesel and gasoline exhaust particles (DEP and GED), and urban street dusts, by Electron Paramagnetic Resonance (EPR). All particulates can generate hydroxyl radicals (HO ṡ), in aqueous buffered solutions, in the presence of hydrogen peroxide. Results showed that oxidant generating activity is related with soluble iron ions. Leaching studies showed that urban particulate matter can release large amounts of Fe 3+ and lesser amounts of Fe 2+, as it was shown from other studies. Direct evidence of HO ṡ was confirmed by spin trapping with DMPO and measurement of DMPO-OH adduct by EPR. Evidence was supported with the use of chelator (EDTA), which increases the EPR signal, and the inhibition of the radical generating activity by desferrioxamine or/and antioxidants ( D-mannitol, sodium benzoate).

Non-Thermal Plasma in Contact with Water: The Origin of Species.

PubMed

Gorbanev, Yury; O'Connell, Deborah; Chechik, Victor

2016-03-01

Non-thermal atmospheric pressure plasma has attracted considerable attention in recent years due to its potential for biomedical applications. Determining the mechanism of the formation of reactive species in liquid treated with plasma is thus of paramount importance for both fundamental and applied research. In this work, the origin of reactive species in plasma-treated aqueous solutions was investigated by using spin-trapping, hydrogen and oxygen isotopic labelling and electron paramagnetic resonance (EPR) spectroscopy. The species originating from molecules in the liquid phase and those introduced with the feed gas were differentiated by EPR and 1 H NMR analysis of liquid samples. The effects of water vapour and oxygen admixtures in the feed gas were investigated. All the reactive species detected in the liquid samples were shown to be formed largely in the plasma gas phase. It is suggested that hydrogen peroxide (determined by UV/Vis analysis) is formed primarily in the plasma tube, whereas the radical species ⋅OOH, ⋅OH and ⋅H are proposed to originate from the region between the plasma nozzle and the liquid sample. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Quenching of Superoxide Radicals by Green Fluorescent Protein

PubMed Central

Bou-Abdallah, Fadi; Chasteen, N. Dennis; Lesser, Michael P.

2006-01-01

Green fluorescent protein (GFP) is a widely used in vivo molecular marker. These proteins are particularly resistant, and maintain function, under a variety of cellular conditions such as pH extremes and elevated temperatures. Green fluorescent proteins are also abundant in several groups of marine invertebrates including reef-forming corals. While molecular oxygen is required for the post-translational maturation of the protein, mature GFPs are found in corals where hyperoxia and reactive oxygen species (ROS) occur due to the photosynthetic activity of algal symbionts. In vitro spin trapping electron paramagnetic resonance and spectrophotometric assays of superoxide dismutase (SOD)-like enzyme activity show that wild type GFP from the hydromedusa, Aequorea victoria, quenches superoxide radicals (O2•−) and exhibits SOD-like activity by competing with cytochrome c for reaction with O2•−. When exposed to high amounts of O2•− the SOD-like activity and protein structure of GFP are altered without significant changes to the fluorescent properties of the protein. Because of the distribution of fluorescent proteins in both the epithelial and gastrodermal cells of reef-forming corals we propose that GFP, and possibly other fluorescent proteins, can provide supplementary antioxidant protection. PMID:17023114

Role of ascorbic acid in stratum corneum lipid models exposed to UV irradiation.

PubMed

Trommer, Hagen; Böttcher, Roif; Pöppl, Andreas; Hoentsch, Joachim; Wartewig, Siegfried; Neubert, Reinhard H H

2002-07-01

The effects of ascorbic acid on Stratum corneum lipid models following ultraviolet irradiation were studied adding iron ions as transition metal catalysts. Lipid peroxidation was quantified by the thiobarbituric acid assay. The qualitative changes were studied on a molecular level by mass spectrometry. To elucidate the nature of free radical involvement we carried out electron paramagnetic resonance studies. The influence of ascorbic acid on the concentration of hydroxyl radicals was examined using the spin trapping technique. Moreover, we checked the vitamin's ability to react with stable radicals. Ascorbic acid was found to have prooxidative effects in all lipid systems in a concentration dependent manner. The degradation products of ascorbic acid after its prooxidative action were detected. The concentration of the hydroxyl radicals in the Fenton assay was decreased by ascorbic acid. The quantification assay of 2,2-diphenyl-1-picrylhydrazyl hydrate showed reduced concentration levels of the stable radical caused by ascorbic acid. Considering human skin and its constant exposure to UV light and oxygen, an increased pool of iron ions in irradiated skin and the depletion of co-antioxidants, the administration of ascorbic acid in cosmetic formulations or in sunscreens could unfold adverse effects among the Stratum corneum lipids.

Antiparallel Triple-strand Architecture for Prefibrillar Aβ42 Oligomers*

PubMed Central

Gu, Lei; Liu, Cong; Stroud, James C.; Ngo, Sam; Jiang, Lin; Guo, Zhefeng

2014-01-01

Aβ42 oligomers play key roles in the pathogenesis of Alzheimer disease, but their structures remain elusive partly due to their transient nature. Here, we show that Aβ42 in a fusion construct can be trapped in a stable oligomer state, which recapitulates characteristics of prefibrillar Aβ42 oligomers and enables us to establish their detailed structures. Site-directed spin labeling and electron paramagnetic resonance studies provide structural restraints in terms of side chain mobility and intermolecular distances at all 42 residue positions. Using these restraints and other biophysical data, we present a novel atomic-level oligomer model. In our model, each Aβ42 protein forms a single β-sheet with three β-strands in an antiparallel arrangement. Each β-sheet consists of four Aβ42 molecules in a head-to-tail arrangement. Four β-sheets are packed together in a face-to-back fashion. The stacking of identical segments between different β-sheets within an oligomer suggests that prefibrillar oligomers may interconvert with fibrils via strand rotation, wherein β-strands undergo an ∼90° rotation along the strand direction. This work provides insights into rational design of therapeutics targeting the process of interconversion between toxic oligomers and non-toxic fibrils. PMID:25118290

Spin dynamics of light-induced charge separation in composites of semiconducting polymers and PC60BM revealed using Q-band pulse EPR.

PubMed

Lukina, E A; Suturina, E; Reijerse, E; Lubitz, W; Kulik, L V

2017-08-23

Light-induced processes in composites of semiconducting polymers and fullerene derivatives have been widely studied due to their usage as active layers of organic solar cells. However the process of charge separation under light illumination - the key process of an organic solar cell is not well understood yet. Here we report a Q-band pulse electron paramagnetic resonance study of composites of the fullerene derivative PC 60 BM ([6,6]-phenyl-C 61 -butyric acid methyl ester) with different p-type semiconducting polymers regioregular and regiorandom P3HT (poly(3-hexylthiophene-2,5-diyl), MEH-PPV (poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]), PCDTBT (poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]), PTB7 (poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}))), resulting in a detailed description of the in-phase laser flash-induced electron spin echo (ESE) signal. We found that in organic donor-acceptor composites the laser flash simultaneously induces species of two types: a polymer˙ + /fullerene˙ - spin-correlated polaron pair (SCPP) with an initial singlet spin state and (nearly) free polymer˙ + and fullerene˙ - species with non-equilibrium spin polarization. Species of the first type (SCPP) are well-known for polymer/fullerene blends and are usually associated with a charge-separated state. Also, spin polarization of long-living free species (polarons in deep traps) is affected by the laser flash, which is the third contribution to the flash-induced ESE signal. A protocol for extracting the in-phase ESE signal of the SCPP based on the dependence of the microwave nutation frequency on the strength of the spin coupling within the polaron pair was developed. Nutation experiments revealed an unusual pattern of the SCPP in RR-P3HT/PC 60 BM composites, from which the strength of the exchange interaction between the polymer˙ + and fullerene˙ - was extracted. In composites with low-efficient polymers the contribution of the SCPP to the in-phase ESE signal is high, while in composites with high-efficient polymers it is low. This finding can be used as a selection criterion of charge separation efficiency in the polymer/fullerene composites.

Fabrication and physical evaluation of a polymer-encapsulated paramagnetic probe for biomedical oximetry

PubMed Central

Meenakshisundaram, Guruguhan; Eteshola, Edward; Pandian, Ramasamy P.; Bratasz, Anna; Kuppusamy, Periannan

2009-01-01

Lithium octa-n-butoxynaphthalocyanine (LiNc-BuO) is a promising probe for biological electron paramagnetic resonance (EPR) oximetry and is being developed for clinical use. However, clinical applicability of LiNc-BuO may be hindered by potential limitations associated with biocompatibility, biodegradation, and migration of individual crystals in tissue. To overcome these limitations, we have encapsulated LiNc-BuO crystals in polydimethyl siloxane (PDMS), an oxygen-permeable and bioinert polymer, to fabricate conveniently implantable and retrievable oxygen-sensing chips. Encapsulation was performed by a simple cast-molding process, giving appreciable control over size, shape, thickness and spin density of chips. The in vitro oxygen response of the chip was linear, reproducible, and not significantly different from that of unencapsulated crystals. Cast-molding of the structurally-flexible PDMS enabled the fabrication of chips with tailored spin densities, and ensured non-exposure of embedded LiNc-BuO, mitigating potential biocompatibility/toxicological concerns. Our results establish PDMS-encapsulated LiNc-BuO as a promising candidate for further biological evaluation and potential clinical application. PMID:19291409

Analysis of spin-Hamiltonian and molecular orbital coefficients of Cu2+ doped C8H11KO8 single crystal through EPR technique

NASA Astrophysics Data System (ADS)

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

2018-04-01

Electron paramagnetic resonance (EPR) studies have been investigated at X-band microwave frequency on Cu2+ ion incorporated into the single crystal of potassium succinate-succinic acid (KSSA) at room temperature. The angular variation of the EPR spectra has shown two magnetically in-equivalent Cu2+ sites in the KSSA single crystal system. The spin Hamiltonian parameters g and A are determined which reveals that the site I and site II occupied in rhombic and axial local field symmetry around the impurity ion. Among the two paramagnetic impurity ions, sites one occupies at substituitional position in the place of monovalent cation (K+) in the crystal whereas the other enters in its lattice interstitially by the correlation of EPR and crystal structure data. From the calculated principle values gxx, gyy, gzz and Axx, Ayy, Azz of both the sites, the admixture coefficients and molecular orbital coefficients were evaluated which gives the information of ground state wave function and types of bonding of impurity ions with the ligands.

Decoherence mechanisms in Mn3 single-molecule magnet

NASA Astrophysics Data System (ADS)

Abeywardana, C.; Mowson, A. M.; Christou, G.; Takahashi, S.

In spite of wide interest in the quantum nature of SMMs, decoherence effects that ultimately limit such behavior have yet to be fully understood. Recent investigations have shown that there are three main decoherence mechanisms present in SMMs: spins can couple locally (i) to phonons (phonon decoherence); (ii) to many nuclear spins (nuclear decoherence); and (iii) to each other via dipolar interactions (dipolar decoherence). We have recently uncovered quantum coherence in a Mn3 SMM by quenching decoherence due to dipole interaction between SMMs using a high frequency electron paramagnetic resonance and low temperature. In this presentation, we will discuss temperature dependence of spin relaxation times and the decoherence mechanisms in the Mn3 SMM. This work is supported by the National Science Foundation (DMR-1508661) and the Searle scholars program.

Electron paramagnetic resonance study of lipid and protein membrane components of erythrocytes oxidized with hydrogen peroxide

PubMed Central

Mendanha, S.A.; Anjos, J.L.V.; Silva, A.H.M.; Alonso, A.

2012-01-01

Electron paramagnetic resonance (EPR) spectroscopy of spin labels was used to monitor membrane dynamic changes in erythrocytes subjected to oxidative stress with hydrogen peroxide (H2O2). The lipid spin label, 5-doxyl stearic acid, responded to dramatic reductions in membrane fluidity, which was correlated with increases in the protein content of the membrane. Membrane rigidity, associated with the binding of hemoglobin (Hb) to the erythrocyte membrane, was also indicated by a spin-labeled maleimide, 5-MSL, covalently bound to the sulfhydryl groups of membrane proteins. At 2% hematocrit, these alterations in membrane occurred at very low concentrations of H2O2 (50 µM) after only 5 min of incubation at 37°C in azide phosphate buffer, pH 7.4. Lipid peroxidation, suggested by oxidative hemolysis and malondialdehyde formation, started at 300 µM H2O2 (for incubation of 3 h), which is a concentration about six times higher than those detected with the probes. Ascorbic acid and α-tocopherol protected the membrane against lipoperoxidation, but did not prevent the binding of proteins to the erythrocyte membrane. Moreover, the antioxidant (+)-catechin, which also failed to prevent the cross-linking of cytoskeletal proteins with Hb, was very effective in protecting erythrocyte ghosts from lipid peroxidation induced by the Fenton reaction. This study also showed that EPR spectroscopy can be useful to assess the molecular dynamics of red blood cell membranes in both the lipid and protein domains and examine oxidation processes in a system that is so vulnerable to oxidation. PMID:22473321

All-optical coherent population trapping with defect spin ensembles in silicon carbide.

PubMed

Zwier, Olger V; O'Shea, Danny; Onur, Alexander R; van der Wal, Caspar H

2015-06-05

Divacancy defects in silicon carbide have long-lived electronic spin states and sharp optical transitions. Because of the various polytypes of SiC, hundreds of unique divacancies exist, many with spin properties comparable to the nitrogen-vacancy center in diamond. If ensembles of such spins can be all-optically manipulated, they make compelling candidate systems for quantum-enhanced memory, communication, and sensing applications. We report here direct all-optical addressing of basal plane-oriented divacancy spins in 4H-SiC. By means of magneto-spectroscopy, we fully identify the spin triplet structure of both the ground and the excited state, and use this for tuning of transition dipole moments between particular spin levels. We also identify a role for relaxation via intersystem crossing. Building on these results, we demonstrate coherent population trapping -a key effect for quantum state transfer between spins and photons- for divacancy sub-ensembles along particular crystal axes. These results, combined with the flexibility of SiC polytypes and device processing, put SiC at the forefront of quantum information science in the solid state.

Microfluidic ultralow interfacial tensiometry with magnetic particles.

PubMed

Tsai, Scott S H; Wexler, Jason S; Wan, Jiandi; Stone, Howard A

2013-01-07

We describe a technique that measures ultralow interfacial tensions using paramagnetic spheres in a co-flow microfluidic device designed with a magnetic section. Our method involves tuning the distance between the co-flowing interface and the magnet's center, and observing the behavior of the spheres as they approach the liquid-liquid interface-the particles either pass through or are trapped by the interface. Using threshold values of the magnet-to-interface distance, we make estimates of the two-fluid interfacial tension. We demonstrate the effectiveness of this technique for measuring very low interfacial tensions, O(10(-6)-10(-5)) N m(-1), by testing solutions of different surfactant concentrations, and we show that our results are comparable with measurements made using a spinning drop tensiometer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, J.; Roy, B.; Tanatar, M. A.

We report 75As nuclear magnetic resonance (NMR) measurements of single-crystalline Ca(Fe 1–xCo x) 2As 2 (x=0.023, 0.028, 0.033, and 0.059) annealed at 350°C for 7 days. From the observation of a characteristic shape of 75As NMR spectra in the stripe-type antiferromagnetic (AFM) state, as in the case of x=0 (T N=170 K), clear evidence for the commensurate AFM phase transition with the concomitant structural phase transition is observed in x=0.023 (T N=106 K) and x=0.028 (T N=53 K). Through the temperature dependence of the Knight shifts and the nuclear spin lattice relaxation rates (1/T 1), although stripe-type AFM spin fluctuationsmore » are realized in the paramagnetic state as in the case of other iron pnictide superconductors, we found a gradual decrease of the AFM spin fluctuations below a crossover temperature T* that was nearly independent of Co-substitution concentration, and it is attributed to a pseudogaplike behavior in the spin excitation spectra of these systems. The T* feature finds correlation with features in the temperature-dependent interplane resistivity, ρc(T), but not with the in-plane resistivity ρa(T). The temperature evolution of anisotropic stripe-type AFM spin fluctuations is tracked in the paramagnetic and pseudogap phases by the 1/T 1 data measured under magnetic fields parallel and perpendicular to the c axis. As a result, based on our NMR data, we have added a pseudogaplike phase to the magnetic and electronic phase diagram of Ca(Fe 1–xCo x) 2As 2.« less

Antiferromagnetic spin correlations and pseudogaplike behavior in Ca(Fe 1-xCo x) 2As 2 studied by 75As nuclear magnetic resonance and anisotropic resistivity

DOE PAGES

Cui, J.; Roy, B.; Tanatar, M. A.; ...

2015-11-06

We report 75As nuclear magnetic resonance (NMR) measurements of single-crystalline Ca(Fe 1–xCo x) 2As 2 (x=0.023, 0.028, 0.033, and 0.059) annealed at 350°C for 7 days. From the observation of a characteristic shape of 75As NMR spectra in the stripe-type antiferromagnetic (AFM) state, as in the case of x=0 (T N=170 K), clear evidence for the commensurate AFM phase transition with the concomitant structural phase transition is observed in x=0.023 (T N=106 K) and x=0.028 (T N=53 K). Through the temperature dependence of the Knight shifts and the nuclear spin lattice relaxation rates (1/T 1), although stripe-type AFM spin fluctuationsmore » are realized in the paramagnetic state as in the case of other iron pnictide superconductors, we found a gradual decrease of the AFM spin fluctuations below a crossover temperature T* that was nearly independent of Co-substitution concentration, and it is attributed to a pseudogaplike behavior in the spin excitation spectra of these systems. The T* feature finds correlation with features in the temperature-dependent interplane resistivity, ρc(T), but not with the in-plane resistivity ρa(T). The temperature evolution of anisotropic stripe-type AFM spin fluctuations is tracked in the paramagnetic and pseudogap phases by the 1/T 1 data measured under magnetic fields parallel and perpendicular to the c axis. As a result, based on our NMR data, we have added a pseudogaplike phase to the magnetic and electronic phase diagram of Ca(Fe 1–xCo x) 2As 2.« less

Direct access to dithiobenzoate RAFT agent fragmentation rate coefficients by ESR spin-trapping.

PubMed

Ranieri, Kayte; Delaittre, Guillaume; Barner-Kowollik, Christopher; Junkers, Thomas

2014-12-01

The β-scission rate coefficient of tert-butyl radicals fragmenting off the intermediate resulting from their addition to tert-butyl dithiobenzoate-a reversible addition-fragmentation chain transfer (RAFT) agent-is estimated via the recently introduced electron spin resonance (ESR)-trapping methodology as a function of temperature. The newly introduced ESR-trapping methodology is critically evaluated and found to be reliable. At 20 °C, a fragmentation rate coefficient of close to 0.042 s(-1) is observed, whereas the activation parameters for the fragmentation reaction-determined for the first time-read EA = 82 ± 13.3 kJ mol(-1) and A = (1.4 ± 0.25) × 10(13) s(-1) . The ESR spin-trapping methodology thus efficiently probes the stability of the RAFT adduct radical under conditions relevant for the pre-equilibrium of the RAFT process. It particularly indicates that stable RAFT adduct radicals are indeed formed in early stages of the RAFT poly-merization, at least when dithiobenzoates are employed as controlling agents as stipulated by the so-called slow fragmentation theory. By design of the methodology, the obtained fragmentation rate coefficients represent an upper limit. The ESR spin-trapping methodology is thus seen as a suitable tool for evaluating the fragmentation rate coefficients of a wide range of RAFT adduct radicals. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cavity-Enhanced Optical Readout of a Single Solid-State Spin

NASA Astrophysics Data System (ADS)

Sun, Shuo; Kim, Hyochul; Solomon, Glenn S.; Waks, Edo

2018-05-01

We demonstrate optical readout of a single spin using cavity quantum electrodynamics. The spin is based on a single trapped electron in a quantum dot that has a poor branching ratio of 0.43. Selectively coupling one of the optical transitions of the quantum dot to the cavity mode results in a spin-dependent cavity reflectivity that enables spin readout by monitoring the reflected intensity of an incident optical field. Using this approach, we demonstrate spin-readout fidelity of 0.61. Achieving this fidelity using resonance fluorescence from a bare dot would require 43 times improvement in photon collection efficiency.

EPR investigation of the trivalent chromium complexes in SrTiO3

NASA Astrophysics Data System (ADS)

Azamat, D. V.; Dejneka, A.; Lančok, J.; Jastrabik, L.; Trepakov, V. A.; Bryknar, Z.; Neverova, E. V.; Badalyan, A. G.

2014-02-01

The trivalent chromium centers were investigated by means of electron paramagnetic resonance (EPR) in SrTiO3 single crystals grown using the Verneuil technique. It was shown that the charge compensation of the Cr3+-VO dominant centers in octahedral environment is due to the remote oxygen vacancy located on the axial axis of the center. In order to provide insight into spin-phonon relaxation processes the studies of axial distortion of Cr3+-VO centers have been performed as function of temperature. The analysis of the trigonal Cr3+ centers found in SrTiO3 indicates the presence of the nearest-neighbor strontium vacancy. The next-nearest-neighbor exchange-coupled pairs of Cr3+ in SrTiO3 has been analyzed from the angular variation of the total electron spin of S=2 resonance lines.

New developments in high field electron paramagnetic resonance with applications in structural biology

NASA Astrophysics Data System (ADS)

Bennati, Marina; Prisner, Thomas F.

2005-02-01

Recent developments in microwave technologies have led to a renaissance of electron paramagnetic resonance (EPR) due to the implementation of new spectrometers operating at frequencies >=90 GHz. EPR at high fields and high frequencies (HF-EPR) has been established up to THz (very high frequency (VHF) EPR) in continuous wave (cw) operation and up to about 300 GHz in pulsed operation. To date, its most prominent application field is structural biology. This review article first gives an overview of the theoretical basics and the technical aspects of HF-EPR methodologies, such as cw and pulsed HF-EPR, as well as electron nuclear double resonance at high fields (HF-ENDOR). In the second part, the article illustrates different application areas of HF-EPR in studies of protein structure and function. In particular, HF-EPR has delivered essential contributions to disentangling complex spectra of radical cofactors or reaction intermediates in photosynthetic reaction centres, radical enzymes (such as ribonucleotide reductase) and in metalloproteins. Furthermore, HF-EPR combined with site-directed spin labelling in membranes and soluble proteins provides new methods of investigating complex molecular dynamics and intermolecular distances.

Slater insulator in iridate perovskites with strong spin-orbit coupling

DOE PAGES

Cui, Q.; Cheng, J. -G.; Fan, W.; ...

2016-10-20

The perovskite SrIrO 3 is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn 4+ for Ir 4+ in the SrIr 1–xSn xO 3 perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at T N ≥ 225 K. The continuous change of the cell volume as detected by x-ray diffractionmore » and the λ-shape transition of the specific heat on cooling through T N demonstrate that the metal-insulator transition is of second order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type- G AF spin ordering below T N. Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. Furthermore, a reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below T N in the same way as proposed by Slater.« less

Tuning Magnetic Order in Transition Metal Oxide Thin Films

NASA Astrophysics Data System (ADS)

Grutter, Alexander John

In recent decades, one of the most active and promising areas of condensed matter research has been that of complex oxides. With the advent of new growth techniques such as pulsed laser deposition and molecular beam epitaxy, a wealth of new magnetic and electronic ground states have emerged in complex oxide heterostructures. The wide variety of ground states in complex oxides is well known and generally attributed to the unprecedented variety of valence, structure, and bonding available in these systems. The tunability of this already diverse playground of states and interactions is greatly multiplied in thin films and heterostructures by the addition of parameters such as substrate induced strain and interfacial electronic reconstruction. Thus, recent studies have shown emergent properties such as the stabilization of ferromagnetism in a paramagnetic system, conductivity at the interface of two insulators, and even exchange bias at the interface between a paramagnet and a ferromagnet. Despite these steps forward, there remains remarkable disagreement on the mechanisms by which these emergent phenomena are stabilized. The contributions of strain, stoichiometry, defects, intermixing, and electronic reconstruction are often very difficult to isolate in thin films and superlattices. This thesis will present model systems for isolating the effects of strain and interfacial electronic interactions on the magnetic state of complex oxides from alternative contributions. We will focus first on SrRuO3, an ideal system in which to isolate substrate induced strain effects. We explore the effects of structural distortions in the simplest case of growth on (100) oriented substrates. We find that parameters including saturated magnetic moment and Curie temperature are all highly tunable through substrate induced lattice distortions. We also report the stabilization of a nonmagnetic spin-zero configuration of Ru4+ in tetragonally distorted films under tensile strain. Through growth on (110) and (111) oriented substrates we explore the effects of different distortion symmetries on SrRuO3 and demonstrate the first reported strain induced transition to a high-spin state of Ru 4+. Finally, we examine the effects of strain on SrRuO3 thin films and demonstrate a completely reversible universal out-of-plane magnetic easy axis on films grown on different substrate orientations. Having demonstrated the ability to tune nearly every magnetic parameter of SrRuO 3 through strain, we turn to magnetic properties at interfaces. We study the emergent interfacial ferromagnetism in superlattices of the paramagnetic metal CaRuO3 and the antiferromagnetic insulator CaMnO3 and demonstrate that the interfacial ferromagnetic layer in this system is confined to a single unit cell of CaMnO3 at the interface. We discuss the remarkable oscillatory dependence of the saturated magnetic moment on the thickness of the CaMnO3 layers and explore mechanisms by which this oscillation may be stabilized. We find long range coherence of the antiferromagnetism of the CaMnO3 layers across intervening layers of paramagnetic CaRuO3. Finally, we utilize the system of LaNiO3/CaMnO3 to separate the effects of intermixing and interfacial electronic reconstruction and conclusively demonstrate intrinsic interfacial ferromagnetism at the interface between a paramagnetic metal and an antiferromagnetic insulator. We find that the emergent ferromagnetism is stabilized through interfacial double exchange and that the leakage of conduction electrons from the paramagnetic metal to the antiferromagnetic insulator is critical to establishing the ferromagnetic ground state.

Electron Tunneling in Lithium Ammonia Solutions Probed by Frequency-Dependent Electron-Spin Relaxation Studies

PubMed Central

Maeda, Kiminori; Lodge, Matthew T.J.; Harmer, Jeffrey; Freed, Jack H.; Edwards, Peter P.

2012-01-01

Electron transfer or quantum tunneling dynamics for excess or solvated electrons in dilute lithium-ammonia solutions have been studied by pulse electron paramagnetic resonance (EPR) spectroscopy at both X- (9.7 GHz) and W-band (94 GHz) frequencies. The electron spin-lattice (T1) and spin-spin (T2) relaxation data indicate an extremely fast transfer or quantum tunneling rate of the solvated electron in these solutions which serves to modulate the hyperfine (Fermi-contact) interaction with nitrogen nuclei in the solvation shells of ammonia molecules surrounding the localized, solvated electron. The donor and acceptor states of the solvated electron in these solutions are the initial and final electron solvation sites found before, and after, the transfer or tunneling process. To interpret and model our electron spin relaxation data from the two observation EPR frequencies requires a consideration of a multi-exponential correlation function. The electron transfer or tunneling process that we monitor through the correlation time of the nitrogen Fermi-contact interaction has a time scale of (1–10)×10−12 s over a temperature range 230–290K in our most dilute solution of lithium in ammonia. Two types of electron-solvent interaction mechanisms are proposed to account for our experimental findings. The dominant electron spin relaxation mechanism results from an electron tunneling process characterized by a variable donor-acceptor distance or range (consistent with such a rapidly fluctuating liquid structure) in which the solvent shell that ultimately accepts the transferring electron is formed from random, thermal fluctuations of the liquid structure in, and around, a natural hole or Bjerrum-like defect vacancy in the liquid. Following transfer and capture of the tunneling electron, further solvent-cage relaxation with a timescale of ca. 10−13 s results in a minor contribution to the electron spin relaxation times. This investigation illustrates the great potential of multi-frequency EPR measurements to interrogate the microscopic nature and dynamics of ultra fast electron transfer or quantum-tunneling processes in liquids. Our results also impact on the universal issue of the role of a host solvent (or host matrix, e.g. a semiconductor) in mediating long-range electron transfer processes and we discuss the implications of our results with a range of other materials and systems exhibiting the phenomenon of electron transfer. PMID:22568866

Application of electron paramagnetic resonance imaging to the characterization of the Ultem(R) exposed to 1 MeV electrons. Correlation of radical density data to tiger code calculations

NASA Technical Reports Server (NTRS)

Suleman, Naushadalli K.

1994-01-01

A major long-term goal of the Materials Division at the NASA Langley Research Center is the characterization of new high-performance materials that have potential applications in the aircraft industry, and in space. The materials used for space applications are often subjected to a harsh and potentially damaging radiation environment. The present study constitutes the application of a novel technique to obtain reliable data for ascertaining the molecular basis for the resilience and durability of materials that have been exposed to simulated space radiations. The radiations of greatest concern are energetic electrons and protons, as well as galactic cosmic rays. Presently, the effects of such radiation on matter are not understood in their entirety. It is clear however, that electron radiation causes ionization and homolytic bond rupture, resulting in the formation of paramagnetic spin centers in the polymer matrices of the structural materials. Since the detection and structure elucidation of paramagnetic species are most readily accomplished using Electron Paramagnetic Resonance (EPR) Spectroscopy, the NASA LaRC EPR system was brought back on-line during the 1991 ASEE term. The subsequent 1992 ASEE term was devoted to the adaptation of the EPR core system to meet the requirements for EPR Imaging (EPRI), which provides detailed information on the spatial distribution of paramagnetic species in bulk media. The present (1994) ASEE term was devoted to the calibration of this EPR Imaging system, as well as to the application of this technology to study the effects of electron irradiation on Ultem(exp R), a high performance polymer which is a candidate for applications in aerospace. The Ultem was exposed to a dose of 2.4 x 10(exp 9) Rads (1-MeV energy/electron) at the LaRC electron accelerator facility. Subsequently, the exposed specimens were stored in liquid nitrogen, until immediately prior to analyses by EPRI. The intensity and dimensions of the EPR Images that were generated for the irradiated specimens showed that the electrons penetrated the material to a depth of approximately 0.125 inch. These data show a very high degree of correlation to the energy deposition profile as predicted by the Tiger Code, a Monte Carlo code that provides guidelines for the transport of electrons in matter. Subsequent efforts will focus on delineating the transport properties of energetic protons in Ultem(R).

Paramagnetic resonance of Mn4+ and Mn2+ centers in lanthanum gallate single crystals

NASA Astrophysics Data System (ADS)

Vazhenin, V. A.; Potapov, A. P.; Guseva, V. B.; Artyomov, M. Yu.

2010-03-01

An increase in the manganese concentration in lanthanum gallate in the range 0.5-5.0% has been found to result in a complete replacement of individual Mn4+ ions by Mn2+ ions. The relative concentrations and binding energies of individual Mn4+, Mn3+, and Mn2+ ions have been determined. The spin Hamiltonians of the Mn2+ and Mn4+ centers in the rhombohedral and orthorhombic phases, respectively, have been constructed and the orientation of the principal axes of the fine-structure tensor of Mn4+ at room temperature has been found. The possibility of using electron paramagnetic resonance for determining the rotation angles of oxygen octahedra of lanthanum gallate with respect to the perovskite structure has been discussed.

Theoretical and experimental studies of the molecular orbital bonding coefficients for Cu{sup 2+} ion in cesium hydrogen oxalate single crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalfaoğlu, Emel, E-mail: emelkalfaoglu@mynet.com; Karabulut, Bünyamin

2016-03-25

Electron paramagnetic resonance (EPR) and optical absorption spectra of Cu{sup 2+} ions in cesium hydrogen oxalate single crystals have been investigated at room temperature. The spin-Hamiltonian parameters (g and A), have been determined. Crystalline field around the Cu{sup 2+} ion is almost axially symmetric. The results show a single paramagnetic site which confirms the triclinic crystal symmetry. Molecular orbital bonding coefficients are studied from the EPR and optical data. Theoretical octahedral field parameter and the tetragonal field parameters have been evaluated from the superposition model. Using these parameters, various bonding parameters are analyzed and the nature of bonding in themore » complex is discussed. The theoretical results are supported by experimental results.« less

Crystal orientation induced spin Rabi beat oscillations of point defects at the c-Si(111)/ SiO 2 interface

NASA Astrophysics Data System (ADS)

Paik, Seoyoung; Lee, Sang-Yun; Boehme, Christoph

2011-03-01

Spin-dependent electronic transitions such as certain charge carrier recombination and transport processes in semiconductors are usually governed by the Pauli blockade within pairs of two paramagnetic centers. One implication of this is that the manipulation of spin states, e.g. by magnetic resonant excitation, can produce changes to electric currents of the given semiconductor material. If both spins are changed at the same time, quantum beat effects such as beat oscillation between resonantly induced spin Rabi nutation becomes detectable through current measurements. Here, we report on electrically detected spin Rabi beat oscillation caused by pairs of 31 P donor states and Pb interface defects at the phosphorous doped Si(111)/ Si O2 interface. Due to the g-factor anisotropy of the Pb center we can tune the intra pair Larmor frequency difference (so called Larmor separation) through orientation of the sample with regard to the external magnetic field. As the Larmor separation governs the spin Rabi beat oscillation, we show experimentally how the crystal orientation can influence the beat effect.

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

PubMed

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

2016-10-01

The present study describes a new approach for direct imaging of redox status in live cells using paramagnetic spin-probes, which allows evaluation of the level of oxidative stress due to overproduction of superoxide. The method is based on redox cycling of cell/mitochondria-penetrating nitroxide radicals (e.g. mito-TEMPO) and their electron-paramagnetic resonance (EPR) contrast, which makes them useful molecular sensors for analysis of redox status and oxidative stress in cells and tissues. Oxidative stress was induced in normal human lymphocytes by treatment with 2-methoxyestradiol and rotenone (ME/Rot) at different concentrations. This combination provokes mitochondrial dysfunction, which is accompanied by overproduction of superoxide. The EPR measurements were performed in dynamics on X-Band spectrometer after addition of mito-TEMPO to cell suspensions. The intensity of the EPR signal in untreated cells decreased significantly, which indicates a conversion of paramagnetic mito-TEMPO to its non-contrast diamagnetic form (hydroxylamine - mito-TEMPOH) due to reduction. In ME/Rot-treated cells, the signal decreased more slowly and to a lower level with increasing the concentration of ME/Rot. These data indicate an induction of oxidative stress in the cells in a concentration-dependent manner. A very good positive correlation between the intensity of EPR signal of mito-TEMPO and the intracellular level of superoxide was found, analyzed by conventional dihydroethidium test (R=0.9143, p<0.001). In conclusion, our study demonstrated that cell-penetrating paramagnetic spin-probes, such as mito-TEMPO, are valuable tools for EPR imaging of the superoxide level in live cells, as well as for EPR imaging of mitochondrial dysfunction and metabolic activity, accompanied by superoxide imbalance. Copyright© 2016 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

High-Frequency Electron Paramagnetic Resonance Spectroscopy of Nitroxide-Functionalized Nanodiamonds in Aqueous Solution.

PubMed

Akiel, R D; Stepanov, V; Takahashi, S

2017-06-01

Nanodiamond (ND) is an attractive class of nanomaterial for fluorescent labeling, magnetic sensing of biological molecules, and targeted drug delivery. Many of those applications require tethering of target biological molecules on the ND surface. Even though many approaches have been developed to attach macromolecules to the ND surface, it remains challenging to characterize dynamics of tethered molecule. Here, we show high-frequency electron paramagnetic resonance (HF EPR) spectroscopy of nitroxide-functionalized NDs. Nitroxide radical is a commonly used spin label to investigate dynamics of biological molecules. In the investigation, we developed a sample holder to overcome water absorption of HF microwave. Then, we demonstrated HF EPR spectroscopy of nitroxide-functionalized NDs in aqueous solution and showed clear spectral distinction of ND and nitroxide EPR signals. Moreover, through EPR spectral analysis, we investigate dynamics of nitroxide radicals on the ND surface. The demonstration sheds light on the use of HF EPR spectroscopy to investigate biological molecule-functionalized nanoparticles.

Electron spin resonance of (CO 2 H)CH 2 CH 2 CH(CO 2 H) in irradiated glutaric acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horsfield, A.; Morton, J. R.; Whiffen, D. H.

It is concluded from electron spin resonance spectra that the radical (CO 2 H)CH 2 CH 2 CH(CO 2 H) remains trapped in a glutaric acid crystal after gamma -irradiation. This radical is found in two different conformations. Approximate hyperfine coupling constants are given for each, although exact interpretation is hindered by the overlapping of spectra. Reasons for the formation of the two forms of the radical are discussed.

The 13C nuclear magnetic resonance in graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Resing, H. A.

1985-01-01

The (13)C NMR chemical shifts of graphite intercalation compounds were calculated. For acceptor types, the shifts come mainly from the paramagnetic (Ramsey) intra-atomic terms. They are related to the gross features of the two-dimensional band structures. The calculated anisotropy is about -140 ppm and is independent of the finer details such as charge transfer. For donor types, the carbon 2p pi orbitals are spin-polarized because of mixing with metal conduction electrons, thus there is an additional dipolar contribution which may be correlated with the electronic specific heat. The general agreement with experimental data is satisfactory.

C-13 nuclear magnetic resonance in graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Resing, H. A.

1985-01-01

The C-13 NMR chemical shifts of graphite intercalation compounds have been calculated. For acceptor types, the shifts come mainly from the paramagnetic (Ramsey) intra-atomic terms. They are related to the gross features of the two-dimensional band structures. The calculated anisotropy is about - 140 ppm and is independent of the finer details such as charge transfer. For donor types, the carbon 2p pi orbitals are spin-polarized because of mixing with metal-conduction electrons, thus there is an additional dipolar contribution which may be correlated with the electronic specific heat. The general agreement with experimental data is satisfactory.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, Q.; Cheng, J. -G.; Fan, W.

The perovskite (Pv) SrIrO 3 is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn 4+ for Ir 4+ in the SrIr 1-xSn xO 3 perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic phase at TN ≥ 225 K. The continuous change of the cell volume as detected by X-ray diffraction andmore » the l-shape transition of the specific heat on cooling through TN demonstrate that the metal-insulator transition is of second-order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type-G AF spin ordering below TN. Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. A reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below TN in the same way as proposed by Slater.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, Q.; Cheng, J. -G.; Fan, W.

The perovskite SrIrO 3 is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn 4+ for Ir 4+ in the SrIr 1–xSn xO 3 perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at T N ≥ 225 K. The continuous change of the cell volume as detected by x-ray diffractionmore » and the λ-shape transition of the specific heat on cooling through T N demonstrate that the metal-insulator transition is of second order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type- G AF spin ordering below T N. Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. Furthermore, a reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below T N in the same way as proposed by Slater.« less

Spectroscopic studies on the active site of hydroperoxide lyase; the influence of detergents on its conformation.

PubMed

Noordermeer, M A; Veldink, G A; Vliegenthart, J F

2001-02-02

Expression of high quantities of alfalfa hydroperoxide lyase in Escherichia coli made it possible to study its active site and structure in more detail. Circular dichroism (CD) spectra showed that hydroperoxide lyase consists for about 75% of alpha-helices. Electron paramagnetic resonance (EPR) spectra confirmed its classification as a cytochrome P450 enzyme. The positive influence of detergents on the enzyme activity is paralleled by a spin state transition of the heme Fe(III) from low to high spin. EPR and CD spectra showed that detergents induce a subtle conformational change, which might result in improved substrate binding. Because hydroperoxide lyase is thought to be a membrane bound protein and detergents mimic a membrane environment, the more active, high spin form likely represents the in vivo conformation. Furthermore, the spin state appeared to be temperature-dependent, with the low spin state favored at low temperature. Point mutants of the highly conserved cysteine in domain D indicated that this residue might be involved in heme binding.

Paramagnet induced signal quenching in MAS-DNP experiments in frozen homogeneous solutions

NASA Astrophysics Data System (ADS)

Corzilius, Björn; Andreas, Loren B.; Smith, Albert A.; Ni, Qing Zhe; Griffin, Robert G.

2014-03-01

The effects of nuclear signal quenching induced by the presence of a paramagnetic polarizing agent are documented for conditions used in magic angle spinning (MAS)-dynamic nuclear polarization (DNP) experiments on homogeneous solutions. In particular, we present a detailed analysis of three time constants: (1) the longitudinal build-up time constant TB for 1H; (2) the rotating frame relaxation time constant T1ρ for 1H and 13C and (3) T2 of 13C, the transverse relaxation time constant in the laboratory frame. These relaxation times were measured during microwave irradiation at a magnetic field of 5 T (140 GHz) as a function of the concentration of four polarizing agents: TOTAPOL, 4-amino-TEMPO, trityl (OX063), and Gd-DOTA and are compared to those obtained for a sample lacking paramagnetic doping. We also report the EPR relaxation time constants T1S and T2S, the DNP enhancements, ε, and the parameter E, defined below, which measures the sensitivity enhancement for the four polarizing agents as a function of the electron concentration. We observe substantial intensity losses (paramagnetic quenching) with all of the polarizing agents due to broadening mechanisms and cross relaxation during MAS. In particular, the monoradical trityl and biradical TOTAPOL induce ∼40% and 50% loss of signal intensity. In contrast there is little suppression of signal intensity in static samples containing these paramagnetic species. Despite the losses due to quenching, we find that all of the polarizing agents provide substantial gains in signal intensity with DNP, and in particular that the net enhancement is optimal for biradicals that operate with the cross effect. We discuss the possibility that much of this polarization loss can be regained with the development of instrumentation and methods to perform electron decoupling.

Frustrated Magnetism of Dipolar Molecules on a Square Optical Lattice: Prediction of a Quantum Paramagnetic Ground State

NASA Astrophysics Data System (ADS)

Zou, Haiyuan; Zhao, Erhai; Liu, W. Vincent

2017-08-01

Motivated by the experimental realization of quantum spin models of polar molecule KRb in optical lattices, we analyze the spin 1 /2 dipolar Heisenberg model with competing anisotropic, long-range exchange interactions. We show that, by tilting the orientation of dipoles using an external electric field, the dipolar spin system on square lattice comes close to a maximally frustrated region similar, but not identical, to that of the J1-J2 model. This provides a simple yet powerful route to potentially realize a quantum spin liquid without the need for a triangular or kagome lattice. The ground state phase diagrams obtained from Schwinger-boson and spin-wave theories consistently show a spin disordered region between the Néel, stripe, and spiral phase. The existence of a finite quantum paramagnetic region is further confirmed by an unbiased variational ansatz based on tensor network states and a tensor renormalization group.

Identification of mitochondrial electron transport chain-mediated NADH radical formation by EPR spin-trapping techniques.

PubMed

Matsuzaki, Satoshi; Kotake, Yashige; Humphries, Kenneth M

2011-12-20

The mitochondrial electron transport chain (ETC) is a major source of free radical production. However, due to the highly reactive nature of radical species and their short lifetimes, accurate detection and identification of these molecules in biological systems is challenging. The aim of this investigation was to determine the free radical species produced from the mitochondrial ETC by utilizing EPR spin-trapping techniques and the recently commercialized spin-trap, 5-(2,2-dimethyl-1,3-propoxycyclophosphoryl)-5-methyl-1-pyrroline N-oxide (CYPMPO). We demonstrate that this spin-trap has the preferential quality of having minimal mitochondrial toxicity at concentrations required for radical detection. In rat heart mitochondria and submitochondrial particles supplied with NADH, the major species detected under physiological pH was a carbon-centered radical adduct, indicated by markedly large hyperfine coupling constant with hydrogen (a(H) > 2.0 mT). In the presence of the ETC inhibitors, the carbon-centered radical formation was increased and exhibited NADH concentration dependency. The same carbon-centered radical could also be produced with the NAD biosynthesis precursor, nicotinamide mononucleotide, in the presence of a catalytic amount of NADH. The results support the conclusion that the observed species is a complex I derived NADH radical. The formation of the NADH radical could be blocked by hydroxyl radical scavengers but not SOD. In vitro experiments confirmed that an NADH-radical is readily formed by hydroxyl radical but not superoxide anion, further implicating hydroxyl radical as an upstream mediator of NADH radical production. These findings demonstrate the identification of a novel mitochondrial radical species with potential physiological significance and highlight the diverse mechanisms and sites of production within the ETC.

The Effect of Neighboring Methionine Residue on Tyrosine Nitration & Oxidation in Peptides Treated with MPO, H2O2, & NO2- or Peroxynitrite and Bicarbonate: Role of Intramolecular Electron-Transfer Mechanism?

PubMed Central

Zhang, Hao; Zielonka, Jacek; Sikora, Adam; Joseph, Joy; Xu, Yingkai; Kalyanaraman, B.

2009-01-01

Recent reports suggest that intramolecular electron-transfer reactions can profoundly affect the site and specificity of tyrosyl nitration and oxidation in peptides and proteins. Here we investigated the effects of methionine on tyrosyl nitration and oxidation induced by myeloperoxidase (MPO), H2O2 and NO2- and peroxynitrite (ONOO-) or ONOO- and bicarbonate (HCO3-) in model peptides, tyrosylmethionine (YM), tyrosylphenylalanine (YF) and tyrosine. Nitration and oxidation products of these peptides were analysed by HPLC with UV/Vis and fluorescence detection, and mass spectrometry; radical intermediates were identified by electron paramagnetic resonance (EPR)-spin-trapping. We have previously shown (Zhang et al., J. Biol. Chem. (2005) 280, 40684-40698) that oxidation and nitration of tyrosyl residue was inhibited in tyrosylcysteine(YC)-type peptides as compared to free tyrosine. Here we show that methionine, another sulfur-containing amino acid, does not inhibit nitration and oxidation of a neighboring tyrosine residue in the presence of ONOO- (or ONOOCO2-) or MPO/H2O2/NO2- system. Nitration of tyrosyl residue in YM was actually stimulated under the conditions of in situ generation of ONOO- (formed by reaction of superoxide with nitric oxide during SIN-1 decomposition), as compared to YF, YC and tyrosine. The dramatic variations in tyrosyl nitration profiles caused by methionine and cysteine residues have been attributed to differences in the direction of intramolecular electron transfer mechanism in these peptides. Further confirmation of HPLC data analysis was obtained by steady-state radiolysis and photolysis experiments. Potential implications of the intramolecular electron-transfer mechanism in mediating selective nitration of protein tyrosyl groups are discussed. PMID:19056332

Spin trapping combined with quantitative mass spectrometry defines free radical redistribution within the oxidized hemoglobin:haptoglobin complex.

PubMed

Vallelian, Florence; Garcia-Rubio, Ines; Puglia, Michele; Kahraman, Abdullah; Deuel, Jeremy W; Engelsberger, Wolfgang R; Mason, Ronald P; Buehler, Paul W; Schaer, Dominik J

2015-08-01

Extracellular or free hemoglobin (Hb) accumulates during hemolysis, tissue damage, and inflammation. Heme-triggered oxidative reactions can lead to diverse structural modifications of lipids and proteins, which contribute to the propagation of tissue damage. One important target of Hb׳s peroxidase reactivity is its own globin structure. Amino acid oxidation and crosslinking events destabilize the protein and ultimately cause accumulation of proinflammatory and cytotoxic Hb degradation products. The Hb scavenger haptoglobin (Hp) attenuates oxidation-induced Hb degradation. In this study we show that in the presence of hydrogen peroxide (H2O2), Hb and the Hb:Hp complex share comparable peroxidative reactivity and free radical generation. While oxidation of both free Hb and Hb:Hp complex generates a common tyrosine-based free radical, the spin-trapping reaction with 5,5-dimethyl-1-pyrroline N-oxide (DMPO) yields dissimilar paramagnetic products in Hb and Hb:Hp, suggesting that radicals are differently redistributed within the complex before reacting with the spin trap. With LC-MS(2) mass spectrometry we assigned multiple known and novel DMPO adduct sites. Quantification of these adducts suggested that the Hb:Hp complex formation causes extensive delocalization of accessible free radicals with drastic reduction of the major tryptophan and cysteine modifications in the β-globin chain of the Hb:Hp complex, including decreased βCys93 DMPO adduction. In contrast, the quantitative changes in DMPO adduct formation on Hb:Hp complex formation were less pronounced in the Hb α-globin chain. In contrast to earlier speculations, we found no evidence that free Hb radicals are delocalized to the Hp chain of the complex. The observation that Hb:Hp complex formation alters free radical distribution in Hb may help to better understand the structural basis for Hp as an antioxidant protein. Copyright © 2015 Elsevier Inc. All rights reserved.

Effect of analytical proton beam irradiation on lead-white pigments, characterized by EPR spectroscopy

NASA Astrophysics Data System (ADS)

Gourier, Didier; Binet, Laurent; Gonzalez, Victor; Vezin, Hervé; Touati, Nadia; Calligaro, Thomas

2018-01-01

Analytical techniques using proton beams with energy in the MeV range are commonly used to study archeological artefact and artistic objects. However ion beams can induce alteration of fragile materials, which is notably the case of easel paintings, limiting the use of these techniques. We used continuous wave EPR and pulse EPR spectroscopy to reveal the effect of 3 MeV proton irradiation on lead carbonates, which were extensively employed as white pigments from the antiquity to the 20th century. Two kinds of paramagnetic centers were identified in cerussite (PbCO3): the first one is CO3- radicals formed by hole trapping by CO32- ions, and the second one is NO32- radical resulting from electron trapping by NO3- impurities. Hydrocerussite (2PbCO3·Pb(OH)2) is the most darkened material under proton beam, however it exhibits no NO32- radicals and 20 times less CO3- radicals than cerussite. Consequently these paramagnetic centers are not directly responsible for the darkening of lead-white pigments. We proposed that their higher instability in hydrocerussite might be at the origin of the formation of color centers in this material.

Low-dimensional quantum magnetism in Cu (NCS) 2: A molecular framework material

NASA Astrophysics Data System (ADS)

Cliffe, Matthew J.; Lee, Jeongjae; Paddison, Joseph A. M.; Schott, Sam; Mukherjee, Paromita; Gaultois, Michael W.; Manuel, Pascal; Sirringhaus, Henning; Dutton, Siân E.; Grey, Clare P.

2018-04-01

Low-dimensional magnetic materials with spin-1/2 moments can host a range of exotic magnetic phenomena due to the intrinsic importance of quantum fluctuations to their behavior. Here, we report the structure, magnetic structure, and magnetic properties of copper ii thiocyanate, Cu(NCS ) 2, a one-dimensional coordination polymer which displays low-dimensional quantum magnetism. Magnetic susceptibility, electron paramagnetic resonance spectroscopy, 13C magic-angle spinning nuclear magnetic resonance spectroscopy, and density functional theory investigations indicate that Cu(NCS ) 2 behaves as a two-dimensional array of weakly coupled antiferromagnetic spin chains [J2=133 (1 ) K , α =J1/J2=0.08 ] . Powder neutron-diffraction measurements confirm that Cu(NCS ) 2 orders as a commensurate antiferromagnet below TN=12 K , with a strongly reduced ordered moment (0.3 μB ) due to quantum fluctuations.

Chiral Spin Texture in the Charge-Density-Wave Phase of the Correlated Metallic Pb /Si (111 ) Monolayer

NASA Astrophysics Data System (ADS)

Tresca, C.; Brun, C.; Bilgeri, T.; Menard, G.; Cherkez, V.; Federicci, R.; Longo, D.; Debontridder, F.; D'angelo, M.; Roditchev, D.; Profeta, G.; Calandra, M.; Cren, T.

2018-05-01

We investigate the 1 /3 monolayer α -Pb /Si (111 ) surface by scanning tunneling spectroscopy (STS) and fully relativistic first-principles calculations. We study both the high-temperature √{3 }×√{3 } and low-temperature 3 ×3 reconstructions and show that, in both phases, the spin-orbit interaction leads to an energy splitting as large as 25% of the valence-band bandwidth. Relativistic effects, electronic correlations, and Pb-substrate interaction cooperate to stabilize a correlated low-temperature paramagnetic phase with well-developed lower and upper Hubbard bands coexisting with 3 ×3 periodicity. By comparing the Fourier transform of STS conductance maps at the Fermi level with calculated quasiparticle interference from nonmagnetic impurities, we demonstrate the occurrence of two large hexagonal Fermi sheets with in-plane spin polarizations and opposite helicities.

Lipid Domains in Intact Fiber-Cell Plasma Membranes Isolated from Cortical and Nuclear Regions of Human Eye Lenses of Donors from Different Age Groups

PubMed Central

Raguz, Marija; Mainali, Laxman; O’Brien, William J.; Subczynski, Witold K.

2015-01-01

The results reported here clearly document changes in the properties and the organization of fiber-cell membrane lipids that occur with age, based on electron paramagnetic resonance (EPR) analysis of lens membranes of clear lenses from donors of age groups from 0 to 20, 21 to 40, and 61 to 80 years. The physical properties, including profiles of the alkyl chain order, fluidity, hydrophobicity, and oxygen transport parameter, were investigated using EPR spin-labeling methods, which also provide an opportunity to discriminate coexisting lipid domains and to evaluate the relative amounts of lipids in these domains. Fiber-cell membranes were found to contain three distinct lipid environments: bulk lipid domain, which appears minimally affected by membrane proteins, and two domains that appear due to the presence of membrane proteins, namely boundary and trapped lipid domains. In nuclear membranes the amount of boundary and trapped phospholipids as well as the amount of cholesterol in trapped lipid domains increased with the donors’ age and was greater than that in cortical membranes. The difference between the amounts of lipids in domains uniquely formed due to the presence of membrane proteins in nuclear and cortical membranes increased with the donors’ age. It was also shown that cholesterol was to a large degree excluded from trapped lipid domains in cortical membranes. It is evident that the rigidity of nuclear membranes was greater than that of cortical membranes for all age groups. The amount of lipids in domains of low oxygen permeability, mainly in trapped lipid domains, were greater in nuclear than cortical membranes and increased with the age of donors. These results indicate that the nuclear fiber cell plasma membranes were less permeable to oxygen than cortical membranes and become less permeable to oxygen with age. In clear lenses, age-related changes in the lens lipid and protein composition and organization appear to occur in ways that increase fiber cell plasma membrane resistance to oxygen permeation. PMID:25617680

Lipid domains in intact fiber-cell plasma membranes isolated from cortical and nuclear regions of human eye lenses of donors from different age groups.

PubMed

Raguz, Marija; Mainali, Laxman; O'Brien, William J; Subczynski, Witold K

2015-03-01

The results reported here clearly document changes in the properties and the organization of fiber-cell membrane lipids that occur with age, based on electron paramagnetic resonance (EPR) analysis of lens membranes of clear lenses from donors of age groups from 0 to 20, 21 to 40, and 61 to 80 years. The physical properties, including profiles of the alkyl chain order, fluidity, hydrophobicity, and oxygen transport parameter, were investigated using EPR spin-labeling methods, which also provide an opportunity to discriminate coexisting lipid domains and to evaluate the relative amounts of lipids in these domains. Fiber-cell membranes were found to contain three distinct lipid environments: bulk lipid domain, which appears minimally affected by membrane proteins, and two domains that appear due to the presence of membrane proteins, namely boundary and trapped lipid domains. In nuclear membranes the amount of boundary and trapped phospholipids as well as the amount of cholesterol in trapped lipid domains increased with the donors' age and was greater than that in cortical membranes. The difference between the amounts of lipids in domains uniquely formed due to the presence of membrane proteins in nuclear and cortical membranes increased with the donors' age. It was also shown that cholesterol was to a large degree excluded from trapped lipid domains in cortical membranes. It is evident that the rigidity of nuclear membranes was greater than that of cortical membranes for all age groups. The amount of lipids in domains of low oxygen permeability, mainly in trapped lipid domains, were greater in nuclear than cortical membranes and increased with the age of donors. These results indicate that the nuclear fiber cell plasma membranes were less permeable to oxygen than cortical membranes and become less permeable to oxygen with age. In clear lenses, age-related changes in the lens lipid and protein composition and organization appear to occur in ways that increase fiber cell plasma membrane resistance to oxygen permeation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Disordered Quantum Gases and Spin-Dependent Lattices

DTIC Science & Technology

2013-07-07

regarding the role of disorder in many-particle quantum systems, such as superconductors and electronic solids. These issues are of great technological...REPORT Disordered Quantum Gases and Spin-Dependent Lattices 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: This grant supported the first realization of...the disordered Bose-Hubbard models using ultra-cold atoms trapped in a disordered optical lattice. Several critical questions regarding this crucial

Spectroscopy of a Synthetic Trapped Ion Qubit

NASA Astrophysics Data System (ADS)

Hucul, David; Christensen, Justin E.; Hudson, Eric R.; Campbell, Wesley C.

2017-09-01

133Ba+ has been identified as an attractive ion for quantum information processing due to the unique combination of its spin-1 /2 nucleus and visible wavelength electronic transitions. Using a microgram source of radioactive material, we trap and laser cool the synthetic A =133 radioisotope of barium II in a radio-frequency ion trap. Using the same, single trapped atom, we measure the isotope shifts and hyperfine structure of the 62P1 /2↔62S1 /2 and 62P1 /2↔52D3 /2 electronic transitions that are needed for laser cooling, state preparation, and state detection of the clock-state hyperfine and optical qubits. We also report the 62P1 /2↔52D3 /2 electronic transition isotope shift for the rare A =130 and 132 barium nuclides, completing the spectroscopic characterization necessary for laser cooling all long-lived barium II isotopes.

Nonlocal magnon spin transport in yttrium iron garnet with tantalum and platinum spin injection/detection electrodes

NASA Astrophysics Data System (ADS)

Liu, J.; Cornelissen, L. J.; Shan, J.; van Wees, B. J.; Kuschel, T.

2018-06-01

We study the magnon spin transport in the magnetic insulator yttrium iron garnet (YIG) in a nonlocal experiment and compare the magnon spin excitation and detection for the heavy metal paramagnetic electrodes platinum (Pt|YIG|Pt) and tantalum (Ta|YIG|Ta). The electrical injection and detection processes rely on the (inverse) spin Hall effect in the heavy metals and the conversion between the electron spin and magnon spin at the heavy metal|YIG interface. Pt and Ta possess opposite signs of the spin Hall angle. Furthermore, their heterostructures with YIG have different interface properties, i.e. spin mixing conductances. By varying the distance between injector and detector, the magnon spin transport is studied. Using a circuit model based on the diffusion-relaxation transport theory, a similar magnon relaxation length of  ∼10 μm was extracted from both Pt and Ta devices. By changing the injector and detector material from Pt to Ta, the influence of interface properties on the magnon spin transport has been observed. For Ta devices on YIG the spin mixing conductance is reduced compared with Pt devices, which is quantitatively consistent when comparing the dependence of the nonlocal signal on the injector-detector distance with the prediction from the circuit model.

Polar-Core Spin Vortex of Quasi-2D Spin-2 Condensate in a Flat-Bottomed Optical Trap

NASA Astrophysics Data System (ADS)

Zheng, Gong-Ping; Chang, Gao-Zhan; Li, Pin; Li, Ting

2017-10-01

Motivated by the recent experiments realized in a flat-bottomed optical trap [Science 347 (2015) 167; Nat. Commun. 6 (2015) 6162], we study the ground state of polar-core spin vortex of quasi-2D spin-2 condensate in a homogeneous trap plus a weak magnetic field. The exact spatial distribution of local spin is obtained and the vortex core are observed to decrease with the growth of the effective spin-spin interaction. For the larger effective spin-spin interaction, the spatial distribution of spin magnitude in spin-2 condensate we obtained agrees well with that of spin-1 condensate in a homogeneous trap, where a polar-core spin vortex was schematically demonstrated as a fully-magnetized planar spin texture with a zero-spin core. The effective spin-spin interaction is proportional to both the bare spin-spin interaction and the radius of the homogeneous trap, simultaneously. Thus the polar-core spin vortex we obtained can be easily controlled by the radius of the trap. Supported by the National Natural Science Foundation of China under Grant No. 11274095, the Key Scientific Research Project of Henan Province of China under Grant No. 16A140011, and the High Performance Computing Center of Henan Normal University

Multifrequency electron paramagnetic resonance and electron-nuclear double-resonance studies of photo-hole processes in AgBr and AgCl emulsion grains

NASA Astrophysics Data System (ADS)

Eachus, R. S.; Pawlik, Th D.; Baetzold, R. C.

2000-10-01

By using a combination of multifrequency EPR spectroscopy, ENDOR spectroscopy and calculations of structure and energy, the reactivities of photo-generated holes in microcrystalline AgBr and AgCl dispersions (photographic emulsions) have been followed in detail. Progress has been facilitated by the use of both gelatin and polyvinyl alcohol (PVA) as peptizers. The initial trapped hole centres produced by band-gap excitation have been identified. In AgBr, this species is [(Br4)3-.V], a neutral complex formed from hole trapping by the four nearest neighbours of a surface Ag+ vacancy (=V). [(Br4)3-.V] reacts with gelatin to produce a transient organic radical at the grain's surface. It does not, however, react with PVA. The formation of the oxidized gelatin radical might involve atomic bromine as an intermediate. In AgCl, the well-known self-trapped hole centre (AgCl6)4- is the initial hole species. The hole diffuses by an electron exchange process until it is trapped by a silver ion on the grain's surface or within its penultimate layer of lattice ions. It is subsequently released from this Ag2+ site to be retrapped at a centre containing four equivalent Cl- ions. The precise identity of this defect has yet to be determined, but its decay also results in the oxidation of gelatin.

Comparison of 250 MHz electron spin echo and continuous wave oxygen EPR imaging methods for in vivo applications

PubMed Central

Epel, Boris; Sundramoorthy, Subramanian V.; Barth, Eugene D.; Mailer, Colin; Halpern, Howard J.

2011-01-01

Purpose: The authors compare two electron paramagnetic resonance imaging modalities at 250 MHz to determine advantages and disadvantages of those modalities for in vivo oxygen imaging. Methods: Electron spin echo (ESE) and continuous wave (CW) methodologies were used to obtain three-dimensional images of a narrow linewidth, water soluble, nontoxic oxygen-sensitive trityl molecule OX063 in vitro and in vivo. The authors also examined sequential images obtained from the same animal injected intravenously with trityl spin probe to determine temporal stability of methodologies. Results: A study of phantoms with different oxygen concentrations revealed a threefold advantage of the ESE methodology in terms of reduced imaging time and more precise oxygen resolution for samples with less than 70 torr oxygen partial pressure. Above∼100 torr, CW performed better. The images produced by both methodologies showed pO2 distributions with similar mean values. However, ESE images demonstrated superior performance in low pO2 regions while missing voxels in high pO2 regions. Conclusions: ESE and CW have different areas of applicability. ESE is superior for hypoxia studies in tumors. PMID:21626937

Investigation of strain effect on electronic, chemical bonding, magnetic and phonon properties of ScNiBi: a DFT study

NASA Astrophysics Data System (ADS)

Bano, Amreen; Gaur, N. K.

2018-04-01

In this paper, we have investigated the electronic band structure, magnetic state, chemical bonding and phonon properties of intermetallic compound ScNiBi (SNB) under the effect of strain using first-principles calculations. Our results showed that at 0% strain, SNB appears to be semiconducting with 0.22 eV energy gap. As the amount of strain increases over the system, the energy gap disappears and metallic character with ionic bonding appears. Covalent bonding at 0% lattice strain is observed between Bi-6p and Ni-3{d}{z2} orbitals with small contribution of Sc-3d states, with increasing strain, this bonding becomes ionic as SNB becomes a metal. From density of states (DoS), similar occupancy of energy states in the same energy range is observed in both spin channels, i.e. spin up and spin down. Hence, no spin polarization is found. From magnetic susceptibility as a function of temperature, we conclude that magnetic state of SNB is paramagnetic. Also, from phonon dispersion curves, we find that with increasing lattice strain, the frequency gap between acoustic phonon branches and optical phonon branches reduced and instability with negative frequencies at Γ are observed.

EPR, optical and modeling of Mn(2+) doped sarcosinium oxalate monohydrate.

PubMed

Kripal, Ram; Singh, Manju

2015-01-25

Electron paramagnetic resonance (EPR) study of Mn(2+) ions doped in sarcosinium oxalate monohydrate (SOM) single crystal is done at liquid nitrogen temperature (LNT). EPR spectrum shows a bunch of five fine structure lines and further they split into six hyperfine components. Only one interstitial site was observed. With the help of EPR spectra the spin Hamiltonian parameters including zero field splitting (ZFS) parameters are evaluated. The optical absorption study at room temperature is also done in the wavelength range 195-1100 nm. From this study cubic crystal field splitting parameter, Dq=730 cm(-1) and Racah inter-electronic repulsion parameters B=792 cm(-1), C=2278 cm(-1) are determined. ZFS parameters D and E are also calculated using crystal field parameters from superposition model and microscopic spin Hamiltonian theory. The calculated ZFS parameter values are in good match with the experimental values obtained by EPR. Copyright © 2014 Elsevier B.V. All rights reserved.

Communication: Alamethicin can capture lipid-like molecules in the membrane

NASA Astrophysics Data System (ADS)

Afanasyeva, Ekaterina F.; Syryamina, Victoria N.; Dzuba, Sergei A.

2017-01-01

Alamethicin (Alm) is a 19-mer antimicrobial peptide produced by fungus Trichoderma viride. Above a threshold concentration, Alm forms pores across the membrane, providing a mechanism of its antimicrobial action. Here we show that at a small concentration which is below the threshold value, Alm participates in formation of nanoscale lipid-mediated clusters of guest lipid-like molecules in the membrane. These results are obtained by electron spin echo (ESE) technique—a pulsed version of electron paramagnetic resonance—on spin-labeled stearic acid in a 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine bilayer with Alm added at 1/200 peptide-to-lipid ratio. ESE decay measurements are interpreted assuming that stearic acid molecules in the membrane are assembling around the Alm molecule. One may suggest that this Alm capturing effect on the guest lipid-like molecules could be important for the peptide antimicrobial action.

Enhancement of room temperature ferromagnetism in tin oxide nanocrystal using organic solvents

NASA Astrophysics Data System (ADS)

Sakthiraj, K.; Hema, M.; Balachandra Kumar, K.

2017-10-01

The effect of organic solvents (ethanol & ethylene glycol) on the room temperature ferromagnetism in nanocrystalline tin oxide has been studied. The samples were synthesized using sol-gel method with the mixture of water & organic liquid as solvent. It is found that pristine SnO2 nanocrystal contain two different types of paramagnetic centres over their surface:(i) surface chemisorbed oxygen species and (ii) Sn interstitial & oxygen vacancy defect pair. The magnetic moment induced in the as-prepared samples is mainly contributed by the alignment of local spin moments resulting from these defects. These surface defect states are highly activated by the usage of ethylene glycol solvent rather than ethylene in tin oxide nanostructure synthesis. Powder X-ray diffraction, transmission electron microscope imaging, energy dispersive spectrometry, Fourier transformed infrared spectroscopy, UV-vis absorption spectroscopy, photoluminescence spectroscopy, vibrating sample magnetometer measurement and electron spin resonance spectroscopy were employed to characterize the nanostructured tin oxide materials.

Coulomb correlations in 4d and 5d oxides from first principles—or how spin-orbit materials choose their effective orbital degeneracies

NASA Astrophysics Data System (ADS)

Martins, C.; Aichhorn, M.; Biermann, S.

2017-07-01

The interplay of spin-orbit coupling and Coulomb correlations has become a hot topic in condensed matter theory and is especially important in 4d and 5d transition metal oxides, like iridates or rhodates. Here, we review recent advances in dynamical mean-field theory (DMFT)-based electronic structure calculations for treating such compounds, introducing all necessary implementation details. We also discuss the evaluation of Hubbard interactions in spin-orbit materials. As an example, we perform DMFT calculations on insulating strontium iridate (Sr2IrO4) and its 4d metallic counterpart, strontium rhodate (Sr2RhO4). While a Mott-insulating state is obtained for Sr2IrO4 in its paramagnetic phase, the spectral properties and Fermi surfaces obtained for Sr2RhO4 show excellent agreement with available experimental data. Finally, we discuss the electronic structure of these two compounds by introducing the notion of effective spin-orbital degeneracy as the key quantity that determines the correlation strength. We stress that effective spin-orbital degeneracy introduces an additional axis into the conventional picture of a phase diagram based on filling and on the ratio of interactions to bandwidth, analogous to the degeneracy-controlled Mott transition in d1 perovskites.

Coulomb correlations in 4d and 5d oxides from first principles-or how spin-orbit materials choose their effective orbital degeneracies.

PubMed

Martins, C; Aichhorn, M; Biermann, S

2017-07-05

The interplay of spin-orbit coupling and Coulomb correlations has become a hot topic in condensed matter theory and is especially important in 4d and 5d transition metal oxides, like iridates or rhodates. Here, we review recent advances in dynamical mean-field theory (DMFT)-based electronic structure calculations for treating such compounds, introducing all necessary implementation details. We also discuss the evaluation of Hubbard interactions in spin-orbit materials. As an example, we perform DMFT calculations on insulating strontium iridate (Sr 2 IrO 4 ) and its 4d metallic counterpart, strontium rhodate (Sr 2 RhO 4 ). While a Mott-insulating state is obtained for Sr 2 IrO 4 in its paramagnetic phase, the spectral properties and Fermi surfaces obtained for Sr 2 RhO 4 show excellent agreement with available experimental data. Finally, we discuss the electronic structure of these two compounds by introducing the notion of effective spin-orbital degeneracy as the key quantity that determines the correlation strength. We stress that effective spin-orbital degeneracy introduces an additional axis into the conventional picture of a phase diagram based on filling and on the ratio of interactions to bandwidth, analogous to the degeneracy-controlled Mott transition in d 1 perovskites.

Spin excitations in optimally P-doped BaFe 2 ( As 0.7 P 0.3 ) 2 superconductor

DOE PAGES

Hu, Ding; Yin, Zhiping; Zhang, Wenliang; ...

2016-09-02

We use inelastic neutron scattering to study temperature and energy dependence of spin excitations in optimally P-doped BaFe 2(As 0:7P 0:3) 2 superconductor (T c = 30 K) throughout the Brillouin zone. In the undoped state, spin waves and paramagnetic spin excitations of BaFe 2As 2 stem from antiferromagnetic (AF) ordering wave vector QAF = ( 1; 0) and peaks near zone boundary at ( 1; 1) around 180 meV. Replacing 30% As by smaller P to induce superconductivity, low-energy spin excitations of BaFe 2(As 0:7P 0:3) 2 form a resonance in the superconducting state and high-energy spin excitations nowmore » peaks around 220 meV near ( 1; 1). These results are consistent with calculations from a combined density functional theory and dynamical mean field theory, and suggest that the decreased average pnictogen height in BaFe 2(As 0:7P 0:3) 2 reduces the strength of electron correlations and increases the effective bandwidth of magnetic excitations.« less

Isolated Spin Qubits in SiC with a High-Fidelity Infrared Spin-to-Photon Interface

NASA Astrophysics Data System (ADS)

Christle, David J.; Klimov, Paul V.; de las Casas, Charles F.; Szász, Krisztián; Ivády, Viktor; Jokubavicius, Valdas; Ul Hassan, Jawad; Syväjärvi, Mikael; Koehl, William F.; Ohshima, Takeshi; Son, Nguyen T.; Janzén, Erik; Gali, Ádám; Awschalom, David D.

2017-04-01

The divacancies in SiC are a family of paramagnetic defects that show promise for quantum communication technologies due to their long-lived electron spin coherence and their optical addressability at near-telecom wavelengths. Nonetheless, a high-fidelity spin-photon interface, which is a crucial prerequisite for such technologies, has not yet been demonstrated. Here, we demonstrate that such an interface exists in isolated divacancies in epitaxial films of 3C-SiC and 4H-SiC. Our data show that divacancies in 4H-SiC have minimal undesirable spin mixing, and that the optical linewidths in our current sample are already similar to those of recent remote entanglement demonstrations in other systems. Moreover, we find that 3C-SiC divacancies have a millisecond Hahn-echo spin coherence time, which is among the longest measured in a naturally isotopic solid. The presence of defects with these properties in a commercial semiconductor that can be heteroepitaxially grown as a thin film on Si shows promise for future quantum networks based on SiC defects.

La 139 NMR investigation of the charge and spin order in a La 1.885 Sr 0.115 CuO 4 single crystal

DOE PAGES

Arsenault, A.; Takahashi, S. K.; Imai, T.; ...

2018-02-14

139La NMR is suited for investigations into magnetic properties of La 2CuO 4 -based cuprates in the vicinity of their magnetic instabilities, owing to the modest hyperfine interactions between 139La nuclear spins and Cu electron spins. We report comprehensive 139La NMR measurements on a single-crystal sample of high-T c superconductor La 1.885 Sr 0.115 CuO 4 in a broad temperature range across the charge and spin order transitions (T charge ≃ 80 K, T neutron spin ≃ T c = 30 K). From the high-precision measurements of the linewidth for the nuclear spin I z = + 1 / 2 to -1/2 central transition, we show that paramagnetic line broadening sets in precisely at T charge due to enhanced spin correlations within the CuO 2 planes. Additional paramagnetic line broadening ensues below ~35 K, signaling that Cu spins in some segments of CuO 2 planes are on the verge of three-dimensional magnetic order. A static hyperfine magnetic field arising from ordered Cu moments along the ab plane, however, begins to develop only below Tmore » $$μSR\\atop{spin}$$ = 15 – 20 K, where earlier muon spin rotation measurements detected Larmor precession for a small volume fraction (~20 % ) of the sample. Based on the measurement of 139 La nuclear-spin-lattice relaxation rate 1/T 1, we also show that charge order triggers enhancement of low-frequency Cu spin fluctuations inhomogeneously; a growing fraction of 139 La sites is affected by enhanced low-frequency spin fluctuations toward the eventual magnetic order, whereas a diminishing fraction continues to exhibit a behavior analogous to the optimally superconducting phase even below T charge. In conclusion, these 139La NMR results corroborate our recent 63Cu NMR observation that a very broad, anomalous winglike signal gradually emerges below T charge, whereas the normally behaving, narrower main peak is gradually wiped out [T. Imai et al., Phys. Rev. B 96, 224508 (2017)]. Furthermore, we show that the enhancement of low-energy spin excitations in the low-temperature regime below Tneutron spin (≃ Tc) depends strongly on the magnitude and orientation of the applied magnetic field.« less

La 139 NMR investigation of the charge and spin order in a La 1.885 Sr 0.115 CuO 4 single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arsenault, A.; Takahashi, S. K.; Imai, T.

139La NMR is suited for investigations into magnetic properties of La 2CuO 4 -based cuprates in the vicinity of their magnetic instabilities, owing to the modest hyperfine interactions between 139La nuclear spins and Cu electron spins. We report comprehensive 139La NMR measurements on a single-crystal sample of high-T c superconductor La 1.885 Sr 0.115 CuO 4 in a broad temperature range across the charge and spin order transitions (T charge ≃ 80 K, T neutron spin ≃ T c = 30 K). From the high-precision measurements of the linewidth for the nuclear spin I z = + 1 / 2 to -1/2 central transition, we show that paramagnetic line broadening sets in precisely at T charge due to enhanced spin correlations within the CuO 2 planes. Additional paramagnetic line broadening ensues below ~35 K, signaling that Cu spins in some segments of CuO 2 planes are on the verge of three-dimensional magnetic order. A static hyperfine magnetic field arising from ordered Cu moments along the ab plane, however, begins to develop only below Tmore » $$μSR\\atop{spin}$$ = 15 – 20 K, where earlier muon spin rotation measurements detected Larmor precession for a small volume fraction (~20 % ) of the sample. Based on the measurement of 139 La nuclear-spin-lattice relaxation rate 1/T 1, we also show that charge order triggers enhancement of low-frequency Cu spin fluctuations inhomogeneously; a growing fraction of 139 La sites is affected by enhanced low-frequency spin fluctuations toward the eventual magnetic order, whereas a diminishing fraction continues to exhibit a behavior analogous to the optimally superconducting phase even below T charge. In conclusion, these 139La NMR results corroborate our recent 63Cu NMR observation that a very broad, anomalous winglike signal gradually emerges below T charge, whereas the normally behaving, narrower main peak is gradually wiped out [T. Imai et al., Phys. Rev. B 96, 224508 (2017)]. Furthermore, we show that the enhancement of low-energy spin excitations in the low-temperature regime below Tneutron spin (≃ Tc) depends strongly on the magnitude and orientation of the applied magnetic field.« less

Thermodynamic properties of paramagnetic α - and β -Mn from first principles: The effect of transverse spin fluctuations

NASA Astrophysics Data System (ADS)

Ehteshami, Hossein; Korzhavyi, Pavel A.

2017-12-01

First-principles-based thermodynamic modeling of cubic α and β phases of Mn represent a challenge due to their structural complexity and the necessity of simultaneous treatment of several types of disorder (electronic, magnetic, and vibrational) that have very different characteristic time scales. Here we employ mean-field theoretical models to describe the different types of disorder and then we connect each layer of theory to the others using the adiabatic principle of separating faster and slower degrees of freedom. The slowest (vibrational) degrees of freedom are treated using the Moruzzi, Janak, and Schwarz formalism [Phys. Rev. B 37, 790 (1988), 10.1103/PhysRevB.37.790] of the Debye-Grüneisen model parametrized based on the first-principles calculated equation of state which includes the free-energy contributions due to the fast (electronic and magnetic) degrees of freedom via the Fermi-Dirac distribution function and a mean-field theory of transverse spin fluctuations. The magnetic contribution due to transverse spin fluctuations has been computed self-consistently within the disordered local moment picture of the paramagnetic state. The obtained results for thermodynamic properties such as lattice parameter, linear thermal expansion coefficient, and heat capacity of both phases show a good agreement with available experimental data. We also tested the assumption about the nature (localized versus delocalized) of magnetic moment on site IV in α -Mn and site I in β -Mn on the thermodynamic properties of these two phases. Similar to the findings of experimental studies, we conclude that magnetic moment on site IV in α -Mn is not of a localized character. However, a similar analysis suggests that the magnetic moment of site I in β -Mn should be treated as localized.

Free Radical Production from the Interaction of 2-Chloroethyl Vesicants (Mustard Gas) with Pyridine Nucleotide-Driven Flavoprotein Electron Transport Systems

DTIC Science & Technology

2009-01-01

or HN2 at desired mM levels and 2.4 mM NADPH were introduced with 40 µM cytochrome c in 0.1 M KPO4 buffer pH 7.5 made 0.25 M with respect to NaCl. The...because 4-POBN is a nitrone , the adduct formed occurred at the carbon adjacent to the imino nitrogen of the spin trap, too many bonds distant from...EPR spectrometry with spin trapping. Inclusion of the nitrone 4-POBN in our incubation mixture at the molar level enabled us to observe a six-line 4

Crystal-field, exchange interactions and magnetism in pyrochlore ferromagnet R2V2O7 (R3+=Y, Lu)

NASA Astrophysics Data System (ADS)

Ali Biswas, A.; Jana, Y. M.

2013-03-01

The temperature dependence of the observed bulk magnetic susceptibility, magnetization, paramagnetic Curie temperature θCW, magnetic specific heat of ferromagnetic semi-conducting pyrochlore-based vanadate compounds Y2V2O7 and Lu2V2O7, which are the simplest of R2M2O7 pyrochlore series of oxides, are simulated and analyzed, simultaneously and consistently, within the frame work of the appropriate crystal-field (CF) theory and a mean-field approximation by introducing effective anisotropic molecular-field tensors and also taking account of appreciable spin-orbit coupling. The electronic and magnetic properties are correlated to the structural parameters. Ten-fold degenerate 2D term of 3d1 V4+-ions is split into five Kramers doublets with overall CF splitting Δ1≈2 eV and the total splitting of the 2T2g state Δ0≈0.4 eV under combined actions of octahedral CF, trigonal (D3d) distortion at V-site and spin-orbit coupling. The ground doublet is a well-isolated effectively spin s=1/2 state, characterized by the anisotropic g-tensors and directional magnetic moments. The degeneracy of the ground state is lifted by the spin-spin correlations among V4-tetrahedra at T∼170 K, which causes the formation of ferromagnetic clusters in these pyrochlores. The temperature dependence of the calculated directional site-susceptibilities shows that the V4+ ions have a substantial easy-axis single-ion anisotropy along local <111> axis of a given V4-tetrahedron in the magnetic phase where ferromagnetic clusters coexist with paramagnetic phase.

Ag/Bi2MoO6-x with enhanced visible-light-responsive photocatalytic activities via the synergistic effect of surface oxygen vacancies and surface plasmon

NASA Astrophysics Data System (ADS)

Wang, Danjun; Shen, Huidong; Guo, Li; Wang, Chan; Fu, Feng; Liang, Yucang

2018-04-01

In this study, a heterostructured Ag/Bi2MoO6-x photocatalyst was rationally designed and successfully fabricated via the deposition of plasmonic silver nanoparticles onto the surface of Bi2MoO6 with surface oxygen vacancy (denoted as Bi2MoO6-x). Bi2MoO6-x (Abbr. BMO6-x was first synthesized via a solvothermal synthesis and calcination process. The plasmonic silver nanoparticles were then loaded onto the surface of BMO6-x using a simple photoreduction process to form Ag/BMO6-x composite. Surface oxygen vacancies (SOVs) in BMO6-x were confirmed by electron paramagnetic resonance (EPR) spectrum. The structures of BMO6-xand Ag/BiMoO6-x) were characterized using high-resolution transmission electron microscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy. Under visible light irradiation, sample Ag/BMO6-x exhibits a highest visible-light-responsive photocatalytic performance compared to those of pure-Bi2MoO6 (BMO), BMO6-x and Ag/BMO for the degradation of rhodamine B (RhB), which is attributed predominantly to the synergistic effect of SOVs and Ag surface plasmonic resonance (SPR) on the surface of Bi2MoO6-x leading to the efficient separation and migration of photogenerated electrons/holes and hence broadening light responsive region. The significant improvement of the migration and separation of photogenerated electrons/holes in the Ag/BMO6-x was evidenced by photoluminescence spectra, time-resolved fluorescence decay, photocurrent, and electrochemical impedance spectrum. The ESR with spin-trap technique and reactive species trapping experiments confirm that the mainly active species O2- and h+ are playing key roles in the RhB photodegradation process over Ag/BMO6-x. This study not only provides an understandable synergistic effect of SOVs and SPR Ag but also pioneers a new approach for fabricating a series of highly catalytically active metal-semiconductor photocatalysts with surface atom defects.

Optical spectroscopy of magnetoelectric and frustrated spin-dimer systems

NASA Astrophysics Data System (ADS)

Cherian, Judy George

This dissertation encompasses an optical spectroscopic study of the temperature and magnetic field dependence of two magnetic materials with significant electron-electron correlation: antiferromagnetic MnTiO3 and frustrated spin-dimer SrCu2(BO3)2 having a low-dimensional quantum spin structure. The first part deals with the nonlinear optical analysis of MnTiO3 using second harmonic generation (SHG) technique to understand its electronic structure and magnetic symmetry in the paramagnetic, antiferromagnetic and spin-flop phases. Ilmenite MnTiO3 is an antiferromagnetic oxide (T N=64 K) which possesses a spin-flop phase above the critical magnetic field of 6.4 T. It is thought to be ferrotoroidic and might have potential technological applications. We measured the second harmonic generation and linear absorbance spectra of MnTiO3 and the 1.88, 2.41, 2.63, and 3.06 eV SHG features were identified as d-d optical transitions from the 6A1g ground state to excited states namely, 4T 1g(4G), 4T2g(4 G), {4Eg,4A 1g(4G)}, and 4Eg(4D), respectively. These narrow SHG peaks, which are red-shifted from the broad linear absorption peaks, can be ascribed to the zero-phonon lines (ZPL) in MnTiO3. We also estimated the crystal field splitting energy (Delta0) and the Racah parameters B and C. The SHG circular intensity difference (CID) we report, shows a significant distinction between the antiferromagnetic phase and the paramagnetic or spin-flop phase. SHG spectra in the paramagnetic phase, created by magnetic dipole transitions, showed a non-negligible CID due to the interference between the two i-type components of the nonlinear optical susceptibility. Inversion symmetry breaking in the antiferromagnetic phase allows c-type tensors, which when coupled to the existing i-type tensors, create a significantly strong CID in the low temperature phase of MnTiO3. The CID in AFM phase remains the same through out the spectral region, compared to the CID in the paramagnetic phase which becomes negligible at the resonance frequency. The polarization dependence of the SHG in the spin-flop phase provided optical evidence that the spins canted from the c-axis toward the alpha-axis. These distinctions between the three magnetic phases could be useful for mapping 180° antiferromagnetic domains in MnTiO3. Temperature and magnetic field dependence of the optical reflectivity in SrCu2(BO3)2 was measured from 1.4 eV to 2.17 eV. Optical reflectivity spectra of SrCu2(BO3) 2 revealed a feature at 1.5 eV assigned as the energy gap for the charge-transfer excitation. With increasing temperature, the reflectivity edge became steep and shifted by 160 meV to the higher energy side. Strong spin-charge correlation in SrCu2(BO3)2 contributed to this significant shift since thermal lattice expansion alone cannot account for this anomalous behavior. Changes in optical reflectivity due to temperature (4-215 K) and applied magnetic field (0-35 T) were analyzed using a Curie-like model and it demonstrated that comparison between magnetic susceptibility and reflectivity changes at the band-edge was possible. The analysis also extracted the Weiss constant and spin-gap energy which matched up with those obtained from other prior measurements. We also observed a significant difference between temperature and magnetic field induced changes to the optical reflectivity and it was indicative of a multi-triplet excitation or cooperative interaction between dimer spin-excitations and band-edge charge carriers. Raman spectroscopy of under ultra-high magnetic field (45 T) demonstrated the significant spin-lattice coupling in SrCu2(BO 3)2. Magnetic field dependence of the frequency of Raman modes demonstrated hardening of 203 and 458 cm-1 which was due to the modulation of intradimer superexchange interaction due to lattice distortion when the Cu-Cu near-neighbor distance and the corresponding bond angle are reduced when triplet states are formed with applied field. The frequency change also displayed plateaus similar to those in magnetization, thereby demonstrating a strong magnetoelastic interaction which facilitated the field-induced lattice distortion to probe the magnetic excitations in this low-dimensional frustrated quantum magnet. In addition, the significant difference between the Raman data and magnetization with respect to the early onset of critical field in vibrational measurement is also discussed.

1,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled β-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexes.

PubMed

Ansari, Mohd Asif; Mandal, Abhishek; Paretzki, Alexa; Beyer, Katharina; Fiedler, Jan; Kaim, Wolfgang; Lahiri, Goutam Kumar

2016-06-06

The dinuclear complexes {(μ-H2L)[Ru(bpy)2]2}(ClO4)2 ([3](ClO4)2), {(μ-H2L)[Ru(pap)2]2}(ClO4)2 ([4](ClO4)2), and the asymmetric [(bpy)2Ru(μ-H2L)Ru(pap)2](ClO4)2 ([5](ClO4)2) were synthesized via the mononuclear species [Ru(H3L)(bpy)2]ClO4 ([1]ClO4) and [Ru(H3L)(pap)2]ClO4 ([2]ClO4), where H4L is the centrosymmetric 1,5-diamino-9,10-anthraquinone, bpy is 2,2'-bipyridine, and pap is 2-phenylazopyridine. Electrochemistry of the structurally characterized [1]ClO4, [2]ClO4, [3](ClO4)2, [4](ClO4)2, and [5](ClO4)2 reveals multistep oxidation and reduction processes, which were analyzed by electron paramagnetic resonance (EPR) of paramagnetic intermediates and by UV-vis-NIR spectro-electrochemistry. With support by time-dependent density functional theory (DFT) calculations the redox processes could be assigned. Significant results include the dimetal/bridging ligand mixed spin distribution in 3(3+) versus largely bridge-centered spin in 4(3+)-a result of the presence of Ru(II)-stabilizig pap coligands. In addition to the metal/ligand alternative for electron transfer and spin location, the dinuclear systems allow for the observation of ligand/ligand and metal/metal site differentiation within the multistep redox series. DFT-supported EPR and NIR absorption spectroscopy of the latter case revealed class II mixed-valence behavior of the oxidized asymmetric system 5(3+) with about equal contributions from a radical bridge formulation. In comparison to the analogues with the deprotonated 1,4-diaminoanthraquinone isomer the centrosymmetric H2L(2-) bridge shows anodically shifted redox potentials and weaker electronic coupling between the chelate sites.

Reaching the quantum limit of sensitivity in electron spin resonance

DOE PAGES

Bienfait, A.; Pla, J. J.; Kubo, Y.; ...

2015-12-14

The detection and characterization of paramagnetic species by electron spin resonance (ESR) spectroscopy is widely used throughout chemistry, biology and materials science, from in vivo imaging to distance measurements in spin-labelled proteins. ESR relies on the inductive detection of microwave signals emitted by the spins into a coupled microwave resonator during their Larmor precession. However, such signals can be very small, prohibiting the application of ESR at the nanoscale (for example, at the single-cell level or on individual nanoparticles). Here in this work, using a Josephson parametric microwave amplifier combined with high-quality-factor superconducting microresonators cooled at millikelvin temperatures, we improvemore » the state-of-the-art sensitivity of inductive ESR detection by nearly four orders of magnitude. We demonstrate the detection of 1,700 bismuth donor spins in silicon within a single Hahn echo with unit signal-to-noise ratio, reduced to 150 spins by averaging a single Carr-Purcell-Meiboom-Gill sequence. This unprecedented sensitivity reaches the limit set by quantum fluctuations of the electromagnetic field instead of thermal or technical noise, which constitutes a novel regime for magnetic resonance. In conclusion, the detection volume of our resonator is ~0.02nl, and our approach can be readily scaled down further to improve sensitivity, providing a new versatile toolbox for ESR at the nanoscale.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maryasov, Alexander G.; Bowman, Michael K.

2004-07-08

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolff-Fabris, F.; Lei, Hechang; Wosnitza, J.

We have studied the temperature dependence of the upper critical fields μ 0 H c 2 of K x Fe 2 - y Se 2 - z S z single crystals up to 60 T. The μ 0 H c 2 for H ∥ a b and H ∥ c decrease with increasing sulfur content. The detailed analysis using Werthamer-Helfand-Hohenberg theory including the Pauli spin-paramagnetic effect shows that μ 0 H c 2 for H ∥ a b is dominated by the spin-paramagnetic effect, which diminishes with higher S content, whereas μ 0 H c 2 for H ∥ cmore » shows a linear temperature dependence with an upturn at high fields. The latter observation can be ascribed to multiband effects that become weaker for higher S content. This results in an enhanced anisotropy of μ 0 H c 2 for high S content due to the different trends of the spin-paramagnetic and multiband effect for H ∥ a b and H ∥ c , respectively.« less

Quantum phases in circuit QED with a superconducting qubit array

PubMed Central

Zhang, Yuanwei; Yu, Lixian; Liang, J. -Q; Chen, Gang; Jia, Suotang; Nori, Franco

2014-01-01

Circuit QED on a chip has become a powerful platform for simulating complex many-body physics. In this report, we realize a Dicke-Ising model with an antiferromagnetic nearest-neighbor spin-spin interaction in circuit QED with a superconducting qubit array. We show that this system exhibits a competition between the collective spin-photon interaction and the antiferromagnetic nearest-neighbor spin-spin interaction, and then predict four quantum phases, including: a paramagnetic normal phase, an antiferromagnetic normal phase, a paramagnetic superradiant phase, and an antiferromagnetic superradiant phase. The antiferromagnetic normal phase and the antiferromagnetic superradiant phase are new phases in many-body quantum optics. In the antiferromagnetic superradiant phase, both the antiferromagnetic and superradiant orders can coexist, and thus the system possesses symmetry. Moreover, we find an unconventional photon signature in this phase. In future experiments, these predicted quantum phases could be distinguished by detecting both the mean-photon number and the magnetization. PMID:24522250

Electrical transport properties and giant baroresistance effect at martensitic transformation of Ni43.7Fe5.3Mn35.4In15.6 Heusler alloy

NASA Astrophysics Data System (ADS)

Zhang, Yuanlei; He, Xijia; Li, Zhe; Xu, Kun; Liu, Changqin; Huang, Yinsheng; Jing, Chao

2018-04-01

The electrical transport properties at martensitic transformation (MT) in polycrystalline Ni43.7Fe5.3Mn35.4In15.6 have been intensively investigated under different hydrostatic pressures. For this alloy, the experimental results show that applying a higher hydrostatic pressure can convert its MT from the metamagnetic type into the paramagnetic type. It provides a unique opportunity to separate the relative contributions of electron-spin and electron-lattice scatterings across the metamagnetic MT based on the dynamical Clausius-Clapeyron equation, which delivers a deeper insight into the resistivity change of metamagnetic MT for the Mn-rich Ni-Mn based Heusler alloys. In addition, the studied alloy also reveals a giant positive baroresistance (BR) effect with a saturated value of 115% at 242 K. This performance originates from the combined effect of electron-spin and electron-lattice scatterings associated with a prominent hydrostatic pressure-induced MT, which contribute 46% and 69% to the overall BR ratio, respectively.

Evolution of Triplet Paramagnetic Centers in Diamonds Obtained by Sintering of Detonation Nanodiamonds at High Pressure and Temperature

NASA Astrophysics Data System (ADS)

Osipov, V. Yu.; Shames, A. I.; Efimov, N. N.; Shakhov, F. M.; Kidalov, S. V.; Minin, V. V.; Vul', A. Ya.

2018-04-01

The electron paramagnetic resonance (EPR) spectra of triplet centers in detonation nanodiamonds (DNDs) and diamond single crystals of submicrometer size, synthesized from those DNDs at high pressures and temperatures, are studied. In the EPR spectra of DNDs, signals from negatively charged nitrogen- vacancy centers (NV)/sup(-) with a g factor of g 1 = 4.24 and multivacancies with g 2 = 4.00 are observed. The signals from (NV)/sup(-) centers disappear in the spectra of diamond single crystals, and a quintet signal with g = 4.00 is detected at the position of the signal from multivacancies. Analysis of the shape and position of the quintet' lines showed that this ESR signal is due to the pairs of nitrogen substitution centers in diamond, separated from each other by distances not exceeding 0.7 nm, between which a strong exchange interaction takes place. A comparison of the experimental data and the simulation results allows determining the spin-Hamiltonian parameters of the exchange-coupled pairs of paramagnetic impurity nitrogen atoms.

Specific features of the EPR spectra of KTaO3: Mn nanopowders

NASA Astrophysics Data System (ADS)

Golovina, I. S.; Shanina, B. D.; Geifman, I. N.; Andriiko, A. A.; Chernenko, L. V.

2012-03-01

The electron paramagnetic resonance spectra of KTaO3: Mn nanocrystalline powders in the temperature range from 77 to 620 K have been measured and studied for the first time. The change observed in the spectra has been investigated as a function of the doping level. The doping regions in which Mn2+ ions are individual paramagnetic impurities have been established, as well as the regions where the dipole-dipole and exchange interactions of these ions begin to occur. The spin-Hamiltonian constants for the spectrum of non-interacting individual Mn2+ ions have been determined as follows: g = 2.0022, D = 0.0170 cm-1, and A = 85 × 10-4 cm-1. A significant decrease in the axial constant D in the KTaO3: Mn nanopowder, as compared to the single crystal, has been explained by the remoteness of the charge compensator from the paramagnetic ion and by the influence of the surface of the nanoparticle. It has been assumed that the Mn2+ ions are located near the surface and do not penetrate deep into the crystallites.

Local electronic structure and ferromagnetic interaction in La(Co,Ni)O3

NASA Astrophysics Data System (ADS)

Schuppler, S.; Nagel, P.; Fuchs, D.; Löhneysen, H. V.; Merz, M.; Huang, M.-J.

Perovskite-related transition-metal oxides exhibit properties ranging from insulating to superconducting as well as unusual magnetic phases, and cobaltates, in particular, have been known for their propensity for spin-state transitions. Nonmagnetic LaCoO3 and paramagnetic LaNiO3 are parent compounds for the La(Co1-xNix) O3 (LCNO) family, which, for intermediate Ni content x, exhibits ferromagnetism. The local electronic structure and the ferromagnetic interaction in LCNO have been studied by x-ray absorption (XAS) and x-ray magnetic circular dichroism (XMCD). XAS indicates a mixed-valence state for both Co and Ni, with both valences changing systematically with increasing x. Simultaneously, a spin-state redistribution towards HS (Co site) and LS (Ni site) occurs, and temperature-dependent spin-state transitions are increasingly suppressed. XMCD identifies the element-specific contributions to the magnetic moment and interactions. A simple model based on a double-exchange-like mechanism between Co3+ HS and Ni3+HS can qualitatively account for the evolution of ferromagnetism in the LCNO series.

Electron spin-echo envelope modulation (ESEEM) reveals water and phosphate interactions with the KcsA potassium channel.

PubMed

Cieslak, John A; Focia, Pamela J; Gross, Adrian

2010-02-23

Electron spin-echo envelope modulation (ESEEM) spectroscopy is a well-established technique for the study of naturally occurring paramagnetic metal centers. The technique has been used to study copper complexes, hemes, enzyme mechanisms, micellar water content, and water permeation profiles in membranes, among other applications. In the present study, we combine ESEEM spectroscopy with site-directed spin labeling (SDSL) and X-ray crystallography in order to evaluate the technique's potential as a structural tool to describe the native environment of membrane proteins. Using the KcsA potassium channel as a model system, we demonstrate that deuterium ESEEM can detect water permeation along the lipid-exposed surface of the KcsA outer helix. We further demonstrate that (31)P ESEEM is able to identify channel residues that interact with the phosphate headgroup of the lipid bilayer. In combination with X-ray crystallography, the (31)P data may be used to define the phosphate interaction surface of the protein. The results presented here establish ESEEM as a highly informative technique for SDSL studies of membrane proteins.

First iron and cobalt(II) hexabromoclathrochelates: structural, magnetic, redox, and electrocatalytic behavior.

PubMed

Dolganov, Alexander V; Belov, Alexander S; Novikov, Valentin V; Vologzhanina, Anna V; Romanenko, Galina V; Budnikova, Yulia G; Zelinskii, Genrikh E; Buzin, Michail I; Voloshin, Yan Z

2015-02-07

Template condensation of dibromoglyoxime with n-butylboronic acid on the corresponding metal ion as a matrix under vigorous reaction conditions afforded iron and cobalt(ii) hexabromoclathrochelates. The paramagnetic cobalt clathrochelate was found to be a low-spin complex at temperatures below 100 K, with a gradual increase in the effective magnetic moment at higher temperatures due to the temperature 1/2↔3/2 spin crossover and a gap caused by the structure phase transition. The multitemperature X-ray and DSC studies of this complex and its iron(ii)-containing analog also showed temperature structural transitions. The variation of an encapsulated metal ion's radius, electronic structure and spin state caused substantial differences in the geometry of its coordination polyhedron; these differences increase with the decrease in temperature due to Jahn-Teller distortion of the encapsulated cobalt(ii) ion with an electronic configuration d(7). As follows from CV and GC data, these cage iron and cobalt complexes undergo both oxidation and reduction quasireversibly, and showed an electrocatalytic activity for hydrogen production in different producing systems.

Electron spin-echo techniques for the study of protein motion

NASA Astrophysics Data System (ADS)

Kar, Leela; Johnson, Michael E.; Bowman, Michael K.

Electron spin-echo (ESE) spectroscopy has been used to make the first direct measurements of spin-spin relaxation times of a spin-labeled protein at physiological temperatures. Results from experiments using maleimide-labeled deoxygenated hemoglobin (dHb) from individuals homozygous for sickle cell anemia (dHbS) have been compared with those from control experiments using dHb from normal adults (dHbA). Hb "immobilized" by ammonium sulfate precipitation and by siloxane polymer entrapment have been studied for a suitable "rigid" reference. Two-dimensional ESE (2D-ESE) experiments have been performed using all of these systems. The 2D contour plots show that 2D-ESE is sensitive to the slow motion of dHbS polymers and can differentiate it from both that of immobilized Hb and of HbA molecules in solution at the same temperature and concentration. More importantly, the 2D-ESE technique enables one to select for slower motion and thereby extract the dHbS polymer signal from the total signal generated by the heterogeneous system containing dHbS molecules in solution as well as in the polymer. Computer simulations using current slow motional theories show that detailed motional and structural information may be obtained by such studies. The considerable potential of 2D-ESE spectroscopy in the study of macromolecular motion is illustrated by comparing 2D-ESE with the nonlinear technique of saturation transfer electron paramagnetic resonance.

Paramagnetic defects in KH{sub 2}PO{sub 4} crystals with high concentration of embedded TiO{sub 2} nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grachev, Valentin G., E-mail: grachev@physics.montana.edu; Tse, Romand; Malovichko, Galina I.

2016-01-21

Qualitative transformations of spectra of Electron Paramagnetic Resonance, EPR, were found in KH{sub 2}PO{sub 4} crystals grown from liquor with 10{sup −5}–10{sup −1 }wt. % of anatase TiO{sub 2} nanoparticles in comparison with nominally pure KH{sub 2}PO{sub 4}. The nanoparticles have larger segregation coefficient for prismatic parts of the crystals than for pyramidal ones. Significant decrease in resonance absorption, complete disappearance of EPR lines of Fe{sup 3+} and Cr{sup 3+} centers, and appearance of four weak lines of equal intensities together with broad asymmetric lines with g-factors about 2.07–2.5 was observed in pyramidal parts grown with concentration of TiO{sub 2} nanoparticlesmore » larger than the threshold value 10{sup −2 }wt. %. The four lines were attributed to non-controlled impurity As substituted for P. In the presence of TiO{sub 2} nanoparticles, non-paramagnetic AsO{sub 4}{sup 3−} clusters trap electrons becoming AsO{sub 4}{sup 4−}. Disappearance of Fe{sup 3+} and Cr{sup 3+} centers was explained by their recharge to “EPR-silent” states and/or pairing at the surface of TiO{sub 2} nanoparticles.« less

Spin correlations and spin-wave excitations in Dirac-Weyl semimetals

NASA Astrophysics Data System (ADS)

Araki, Yasufumi; Nomura, Kentaro

We study correlations among magnetic dopants in three-dimensional Dirac and Weyl semimetals. Effective field theory for localized magnetic moments is derived by integrating out the itinerant electron degrees of freedom. We find that spin correlation in the spatial direction parallel to local magnetization is more rigid than that in the perpendicular direction, reflecting spin-momentum locking nature of the Dirac Hamiltonian. Such an anisotropy becomes stronger for Fermi level close to the Dirac points, due to Van Vleck paramagnetism triggered by spin-orbit coupling. One can expect topologically nontrivial spin textures under this anisotropy, such as a hedgehog around a single point, or a radial vortex around an axis, as well as a uniform ferromagnetic order. We further investigate the characteristics of spin waves in the ferromagnetic state. Spin-wave dispersion also shows a spatial anisotropy, which is less dispersed in the direction transverse to the magnetization than that in the longitudinal direction. The spin-wave dispersion anisotropy can be traced back to the rigidity and flexibility of spin correlations discussed above. This work was supported by Grant-in-Aid for Scientific Research (Grants No.15H05854, No.26107505, and No.26400308) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.

ESR evidence for radical production from the reaction of ozone with unsaturated lipids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Church, D.F.; McAdams, M.L..; Pryor, W.A.

1991-03-15

The authors report electron spin resonance (ESR) spin trapping evidence for radical production by the reaction of ozone with unsaturated compounds. Soy and egg phosphatidylcholine liposomes, fatty acid emulsions, and homogeneous aqueous solutions of 3-hexenoic acid were treated with ozone in the presence of the spin trap {alpha}-phenyl-N-tert-butyl nitrone (PBN). Under these conditions, they observe spin adducts resulting from the trapping of both organic carbon- and oxygen-centered radicals. When the lipid-soluble antioxidant alpha-tocopherol is included in the liposomal systems, the formation of spin adducts is completely inhibited. The authors suggest that radicals giving rise to these spin adducts arise formmore » the rapid decomposition of the 1,2,3-trioxolane intermediate that is initially formed when ozone reacts with the carbon-carbon double bonds of the substrates. These free radicals are not formed by the decomposition of the Criegee ozonide, since little of the ozonide is formed in the presence of water. Although hydrogen peroxide is the predominate peroxidic product of the ozone/alkene reaction, its decomposition is not responsible for the observed radical production since neither catalase nor iron chelators significantly affect the spin adduct yield. The radical yield is approximately 1%. Since a polyunsaturated fatty acid (PUFA) such as linoleic acid produces much higher concentrations of spin trappable radicals than does the monounsaturated fatty oleic acid, the results also suggest that sites in the lung containing higher levels of PUFA may be an important target for radical formation.« less

Upper critical fields in Ba2Ti2Fe2As4O single crystals: Evidence for dominant Pauli paramagnetic effect

NASA Astrophysics Data System (ADS)

Abdel-Hafiez, M.; Brisbois, J.; Zhu, Z.; Adamski, A.; Hassen, A.; Vasiliev, A. N.; Silhanek, A. V.; Krellner, C.

2018-03-01

We report on magneto-optical imaging and the temperature dependency of the upper critical fields Hc2 c(T ) parallel to the c axis and Hc2 a b(T ) parallel to the a b plane in Ba2Ti2Fe2As4O single crystals. These data were inferred from the measurements of the temperature-dependent resistance in static magnetic fields up to 14 T and magnetoresistance in pulsed fields up to 60 T. Hc 2 values are found to be 52 and 50 T for H ∥a b and H ∥c , respectively. These values are 1.2-1.35 times larger than the weak-coupling Pauli paramagnetic limit (Hp˜1.84 Tc ), indicating that enhanced paramagnetic limiting is essential and this superconductor is unconventional. Our observations of strong bending in the Hc2 a b(T ) curves and a nearly isotropic maximum upper critical field Hc2 a b(0 ) ≈Hc2 c(0 ) support the presence of a strong Pauli paramagnetic effect. We show that the Werthamer-Helfand-Hohenberg (WHH) formula that includes the spin-orbit scattering can effectively describe the Hc2 a b(T ) curve, whereas Hc 2 deviates from the conventional WHH theoretical model without considering the spin paramagnetic effect for the H ∥c and H ∥a b directions. For H ∥c , a two-band model is required to fully reproduce the behavior of Hc 2, while for H ∥a b the spin paramagnetic effect is responsible for the behavior of Hc 2. The anisotropy of Hc 2 is close to 3 near Tc and decreases rapidly at lower temperatures.

Interaction of Spin-Labeled Lipid Membranes with Transition Metal Ions

PubMed Central

2015-01-01

The large values of spin relaxation enhancement (RE) for PC spin-labels in the phospholipid membrane induced by paramagnetic metal salts dissolved in the aqueous phase can be explained by Heisenberg spin exchange due to conformational fluctuations of the nitroxide group as a result of membrane fluidity, flexibility of lipid chains, and, possibly, amphiphilic nature of the nitroxide label. Whether the magnetic interaction occurs predominantly via Heisenberg spin exchange (Ni) or by the dipole–dipole (Gd) mechanism, it is essential for the paramagnetic ion to get into close proximity to the nitroxide moiety for efficient RE. For different salts of Ni the RE in phosphatidylcholine membranes follows the anionic Hofmeister series and reflects anion adsorption followed by anion-driven attraction of paramagnetic cations on the choline groups. This adsorption is higher for chaotropic ions, e.g., perchlorate. (A chaotropic agent is a molecule in water solution that can disrupt the hydrogen bonding network between water molecules.) However, there is no anionic dependence of RE for model membranes made from negatively charged lipids devoid of choline groups. We used Ni-induced RE to study the thermodynamics and electrostatics of ion/membrane interactions. We also studied the effect of membrane composition and the phase state on the RE values. In membranes with cholesterol a significant difference is observed between PC labels with nitroxide tethers long enough vs not long enough to reach deep into the membrane hydrophobic core behind the area of fused cholesterol rings. This study indicates one must be cautious in interpreting data obtained by PC labels in fluid membranes in terms of probing membrane properties at different immersion depths when it can be affected by paramagnetic species at the membrane surface. PMID:26490692

Optically controlled locking of the nuclear field via coherent dark-state spectroscopy.

PubMed

Xu, Xiaodong; Yao, Wang; Sun, Bo; Steel, Duncan G; Bracker, Allan S; Gammon, Daniel; Sham, L J

2009-06-25

A single electron or hole spin trapped inside a semiconductor quantum dot forms the foundation for many proposed quantum logic devices. In group III-V materials, the resonance and coherence between two ground states of the single spin are inevitably affected by the lattice nuclear spins through the hyperfine interaction, while the dynamics of the single spin also influence the nuclear environment. Recent efforts have been made to protect the coherence of spins in quantum dots by suppressing the nuclear spin fluctuations. However, coherent control of a single spin in a single dot with simultaneous suppression of the nuclear fluctuations has yet to be achieved. Here we report the suppression of nuclear field fluctuations in a singly charged quantum dot to well below the thermal value, as shown by an enhancement of the single electron spin dephasing time T(2)*, which we measure using coherent dark-state spectroscopy. The suppression of nuclear fluctuations is found to result from a hole-spin assisted dynamic nuclear spin polarization feedback process, where the stable value of the nuclear field is determined only by the laser frequencies at fixed laser powers. This nuclear field locking is further demonstrated in a three-laser measurement, indicating a possible enhancement of the electron spin T(2)* by a factor of several hundred. This is a simple and powerful method of enhancing the electron spin coherence time without use of 'spin echo'-type techniques. We expect that our results will enable the reproducible preparation of the nuclear spin environment for repetitive control and measurement of a single spin with minimal statistical broadening.

EPR spin trapping of oxygen radicals in plants: a methodological overview.

PubMed

Bacić, Goran; Mojović, Milos

2005-06-01

We present a brief account of the difficulties involved in detection of oxygen free radicals in plants and give a rationale for using the EPR spin trapping technique in such studies. Comparative analysis of characteristics of different spin traps is given, having in mind their suitability in trapping oxygen-centered free radicals. Certain technical aspects of EPR experiments related to successful trapping of free radicals are discussed. Previous studies of trapping of oxygen radicals in plants are reviewed in terms of how efficient the experimental approach employed has been in their detection and how this influences conclusions about the mechanisms of their production. In addition, we analyze the potential of spin labels in the analysis of free radical production in plants and demonstrate that the combination of EPR spin traps and spin labels is extremely efficient for this purpose.

Spin-Transfer Studies in Magnetic Multilayer Nanostructures

NASA Astrophysics Data System (ADS)

Emley, N. C.; Albert, F. J.; Ryan, E. M.; Krivorotov, I. N.; Ralph, D. C.; Buhrman, R. A.

2003-03-01

Numerous experiments have demonstrated current-induced magnetization reversal in ferromagnet/paramagnet/ferromagnet nanostructures with the current in the CPP geometry. The primary mechanism for this reversal is the transfer of angular momentum from the spin-polarized conduction electrons to the nanomagnet moment the spin transfer effect. This phenomenon has potential application in nanoscale, current-controlled non-volatile memory elements, but several challenges must be overcome for realistic device implementation. Typical Co/Cu/Co nanopillar devices, although effective for fundamental studies, are not advantageous for technological applications because of their large switching currents Ic ( 3-10 mA) and small R·A (< 1 mΩ·µm^2). Here we report initial results testing some possible approaches for enhancing spin-transfer device performance which involve the addition of more layers, and hence, more complexity, to the simple Co/Cu/Co trilayer structure. These additions include synthetic antiferromagnet layers (SAF), exchange biased layers, nano-oxide layers (NOL), and additional magnetic layers. Research supported by NSF and DARPA

Strong-coupling phases of the spin-orbit-coupled spin-1 Bose-Hubbard chain: Odd-integer Mott lobes and helical magnetic phases

NASA Astrophysics Data System (ADS)

Pixley, J. H.; Cole, William S.; Spielman, I. B.; Rizzi, Matteo; Das Sarma, S.

2017-10-01

We study the odd-integer filled Mott phases of a spin-1 Bose-Hubbard chain and determine their fate in the presence of a Raman induced spin-orbit coupling which has been achieved in ultracold atomic gases; this system is described by a quantum spin-1 chain with a spiral magnetic field. The spiral magnetic field initially induces helical order with either ferromagnetic or dimer order parameters, giving rise to a spiral paramagnet at large field. The spiral ferromagnet-to-paramagnet phase transition is in a universality class with critical exponents associated with the divergence of the correlation length ν ≈2 /3 and the order-parameter susceptibility γ ≈1 /2 . We solve the effective spin model exactly using the density-matrix renormalization group, and compare with both a large-S classical solution and a phenomenological Landau theory. We discuss how these exotic bosonic magnetic phases can be produced and probed in ultracold atomic experiments in optical lattices.

The O-(Al2) centre in topaz and its relation to the blue colour

NASA Astrophysics Data System (ADS)

da Silva, D. N.; Guedes, K. J.; Pinheiro, M. V. B.; Schweizer, S.; Spaeth, J.-M.; Krambrock, K.

2005-01-01

Colour-enhanced blue topaz is one of the most traded gemstones. Naturally very rare, mostly topaz is irradiated by neutrons, electrons, gamma radiation and combinations of them. The colour centre is still not identified. It was speculated that it is related to a Si dangling bond defect occupied by two electrons with spin S = 0. We investigated natural blue as well as colourless topaz from different regions in Brazil by electron paramagnetic resonance (EPR), optical absorption and Raman spectroscopy. The results are compared with neutron and gamma-irradiated blue topaz. By EPR two paramagnetic defects are identified in all samples: (i) the peroxy radical (O2-) measured at room temperature and (ii) an (O-) hole centre interacting with two equivalent Al neighbours measured at low temperature. Blue samples show an absorption band centred at 620 nm which is responsible for the blue colour. From our investigation we find that the O-(Al2) hole centre has nearly the same thermal stability as the optical absorption band. However, we cannot say whether it is responsible for the absorption band and the blue colour. We suggest that at least it plays a dominant role in the stabilization of the blue colour.

Gate-Sensing the Potential Landscape of a GaAs Two-Dimensional Electron Gas

NASA Astrophysics Data System (ADS)

Croot, Xanthe; Mahoney, Alice; Pauka, Sebastian; Colless, James; Reilly, David; Watson, John; Fallahi, Saeed; Gardner, Geoff; Manfra, Michael; Lu, Hong; Gossard, Arthur

In situ dispersive gate sensors hold potential as a means of enabling the scalable readout of quantum dot arrays. Sensitive to quantum capacitance, dispersive sensors have been used to detect inter- and intra-dot transitions in GaAs double quantum dots, and can distinguish the spin states of singlet triplet qubits. In addition, the gate-sensing technique is likely of value in probing the physics of Majorana zero modes in nanowire devices. Beyond the readout signatures associated with charge and spin configurations of qubits, gate-sensing is sensitive to trapped charge in the potential landscape. Here, we report gate-sensing signals arising from tunnelling of electrons between puddles of trapped charge in a GaAs 2DEG. We examine these signals in a family of different devices with varying mobilities, and as a function of temperature and bias. Implications for qubit readout using the gate-sensing technique are discussed.

Heisenberg necklace model in a magnetic field

DOE PAGES

Tsvelik, A. M.; Zaliznyak, I. A.

2016-08-26

Here, we study the low-energy sector of the Heisenberg necklace model. Using the field-theory methods, we estimate how the coupling of the electronic spins with the paramagnetic Kondo spins affects the overall spin dynamics and evaluate its dependence on a magnetic field. We are motivated by the experimental realizations of the spin-1/2 Heisenberg chains in SrCuO 2 and Sr 2CuO 3 cuprates, which remain one-dimensional Luttinger liquids down to temperatures much lower than the in-chain exchange coupling J. We also consider the perturbation of the energy spectrum caused by the interaction γ with nuclear spins (I=3/2) present on the samemore » sites. We find that the resulting necklace model has a characteristic energy scale, Λ~J 1/3(γI) 2/3, at which the coupling between (nuclear) spins of the necklace and the spins of the Heisenberg chain becomes strong. Furthermore, this energy scale is insensitive to a magnetic field B. For μBB>Λ we find two gapless bosonic modes that have different velocities, whose ratio at strong fields approaches a universal number, 2√+1.« less

Coupled Electronic and Magnetic Phase Transition in the Infinite-Layer Phase LaSrNiRuO4.

PubMed

Patino, Midori Amano; Zeng, Dihao; Bower, Ryan; McGrady, John E; Hayward, Michael A

2016-09-06

Topochemical reduction of the ordered double perovskite LaSrNiRuO6 with CaH2 yields LaSrNiRuO4, an extended oxide phase containing infinite sheets of apex-linked, square-planar Ni(1+)O4 and Ru(2+)O4 units ordered in a checkerboard arrangement. At room temperature the localized Ni(1+) (d(9), S = (1)/2) and Ru(2+) (d(6), S = 1) centers behave paramagnetically. However, on cooling below 250 K the system undergoes a cooperative phase transition in which the nickel spins align ferromagnetically, while the ruthenium cations appear to undergo a change in spin configuration to a diamagnetic spin state. Features of the low-temperature crystal structure suggest a symmetry lowering Jahn-Teller distortion could be responsible for the observed diamagnetism of the ruthenium centers.

The Development of Spectroscopic Techniques to Study Defects in Thin Film Silicon-Dioxide

NASA Astrophysics Data System (ADS)

Zvanut, Mary Ellen

This dissertation research concerns the study of defects in thin film sputtered SiO_2 which is used as an optical coating material. The capacitance-voltage and current-voltage techniques typically used in microelectronics investigations were used to examine the concentration, location, and kinetics of charge in an aluminum-sputtered oxide-native oxide-silicon capacitor. The response of the capacitor to low field bias stress reveals a hysteretic trapping behavior similar to that observed in microelectronic grade oxide films. In an effort to understand this phenomenon, a band-to-trap tunneling model was developed based on the assumption that the defect involved exhibits a delta function spatial distribution and an extended energy distribution. The central feature of this model, defect relaxation, provides a physical explanation for the hysteretic trapping behavior. Analysis yields that the trap is located spatially within 2 nm of the Si/SiO _2 interface and energetically less than 5 eV from the SiO_2 conduction band edge. The relaxation energy associated with the capture of an electron at the trap is 0.1-2.2 eV. Correlation of the electrical measurements executed for this investigation with electron paramagnetic resonance (EPR) data obtained by Dr. P. Caplan provides structural information about the defect involved with the hysteretic trapping phenomenon. EPR results obtained before and after subjecting an oxide-silicon structure to corona discharge suggest that the trapping center is an E^ ' defect. The technique of band-to-trap tunneling spectroscopy combined with the EPR experiments provides the first reported trap depth associated with the capture of a hole at an E^' center located near the silicon surface of an oxide/silicon system.

Electron paramagnetic resonance of Nb-doped BaTiO3 ceramics with positive temperature coefficient of resistivity

NASA Astrophysics Data System (ADS)

Jida, Shin'suke; Miki, Toshikatsu

1996-11-01

Paramagnetic centers in Nb-doped BaTiO3 ceramics are measured at 77-500 K by electron paramagnetic resonance (EPR) for investigating the role of the centers on the well-known positive temperature coefficient of resistivity (PTCR) effect (PTCR at the Curie temperature). EPR detects four signals; an anisotropically broad singlet signal at g=2.005, a sextet signal due to Mn2+, a Cr3+ signal, and a Ti3+ signal. The former two signals arise in the rhombohedral and cubic phases, but disappear in the tetragonal and orthorhombic phases. The Cr3+ signal appears in all of the phases, while the Ti3+ signal is detected only at low temperatures. The singlet signal also arises in undoped, barium-deficient BaTiO3 ceramics, therefore the signal is attributable to barium-vacancy-associated centers rather than Nb4+ ions or Fe3+ ions proposed by several authors. In this article, we propose that the singlet signal is due to vacancy-pairs of VBa-F+ type, i.e., the vacancy pair of VBa-VO capturing one electron. The electrical resistivity data show a polaronic character of low-temperature conduction and a high resistivity jump around the Curie temperature. The low-temperature polaronic conduction is explained in terms of electron-hopping between Ti4+ and Ti3+ ions. The resistivity jump at the Curie temperature occurs along with the EPR intensity increase of the singlet signal, the Mn2+ signal and the Cr3+ signal. We conclude that the PTCR of Nb-doped BaTiO3 ceramics is strongly associated with the trap activation of the VBa-VO vacancy-pairs and manganese centers at the tetragonal-to-cubic transition.

Hydroxyl radical production by a heterogeneous Fenton reaction supported in insoluble tannin from bark of Pinus radiata.

PubMed

Romero, Romina; Contreras, David; Segura, Cristina; Schwederski, Brigitte; Kaim, Wolfgang

2017-03-01

Fenton reactions driven by dihydroxybenzenes (DHBs) have been used for pollutant removal via advanced oxidation processes (AOPs), but such systems have the disadvantage of DHB release into the aqueous phase. In this work, insoluble tannins from bark can be used to drive Fenton reactions and as a heterogeneous support. This avoids the release of DHBs into the aqueous phase and can be used for AOPs. The production of ·OH was investigated using a spin-trapping electron paramagnetic resonance technique (5-dimethyl-1-pyrroline-N-oxide/·OH) in the first minute of the reaction and a high-performance liquid chromatography-fluorescence technique (coumarin/7-hydroxycoumarin) for 20 min. The ·OH yield achieved using insoluble tannins from Pinus radiata bark was higher than that achieved using catechin to drive the Fenton reaction. The Fenton-like system driven by insoluble tannins achieved 92.6 ± 0.3 % degradation of atrazine in 30 min. The degradation kinetics of atrazine was linearly correlated with ·OH production. The increased reactivity in ·OH production and insolubility of the ligand are promising for the development of a new technique for degradation of pollutants in wastewater using heterogeneous Fenton systems.

Genotoxicity of tungsten carbide-cobalt (WC-Co) nanoparticles in vitro: mechanisms-of-action studies.

PubMed

Moche, Hélène; Chevalier, Dany; Vezin, Hervé; Claude, Nancy; Lorge, Elisabeth; Nesslany, Fabrice

2015-02-01

We showed previously that tungsten carbide-cobalt (WC-Co) nanoparticles (NP) can be used as a nanoparticulate positive control in some in vitro mammalian genotoxicity assays. Here, we investigate the mechanisms of action involved in WC-Co NP genotoxicity in L5178Y mouse lymphoma cells and primary human lymphocytes, in vitro. Data from the micronucleus assay coupled with centromere staining and from the chromosome-aberration assay show the involvement of both clastogenic and aneugenic events. Experiments with the formamidopyrimidine DNA glycosylase (FPG)-modified comet assay showed a slight (non-significant) increase in FPG-sensitive sites in the L5178Y mouse lymphoma cells but not in the human lymphocytes. Electron paramagnetic resonance spin-trapping results showed the presence of hydroxyl radicals (•OH) in WC-Co NP suspensions, with or without cells, but with time-dependent production in the presence of cells. However, a significant difference in •OH production was observed between human lymphocytes from two different donors. Using H2O2, we showed that WC-Co NP can participate in Fenton-like reactions. Thus, •OH might be produced either via intrinsic generation by WC-Co NP or through a Fenton-like reaction in the presence of cells. Copyright © 2015 Elsevier B.V. All rights reserved.

The effects of hyaluronan and its fragments on lipid models exposed to UV irradiation.

PubMed

Trommer, Hagen; Wartewig, Siegfried; Böttcher, Rolf; Pöppl, Andreas; Hoentsch, Joachim; Ozegowski, Jörg H; Neubert, Reinhard H H

2003-03-26

The effects of hyaluronan and its degradation products on irradiation-induced lipid peroxidation were investigated. Liposomal skin lipid models with increasing complexity were used. Hyaluronan and its fragments were able to reduce the amount of lipid peroxidation secondary products quantified by the thiobarbituric acid (TBA) assay. The qualitative changes were studied by mass spectrometry. To elucidate the nature of free radical involvement electron paramagnetic resonance (EPR) studies were carried out. The influence of hyaluronan and its fragments on the concentration of hydroxyl radicals generated by the Fenton system was examined using the spin trapping technique. Moreover, the mucopolysaccharide's ability to react with stable radicals was checked. The quantification assay of 2,2-diphenyl-1-picrylhydrazyl hydrate (DPPH) showed no concentration changes of the stable radical caused by hyaluronan. Hyaluronan was found to exhibit prooxidative effects in the Fenton assay in a concentration dependent manner. A transition metal chelation was proposed as a mechanism of this behavior. Considering human skin and its constant exposure to UV light and oxygen and an increased pool of iron in irradiated skin the administration of hyaluronan or its fragments in cosmetic formulations or sunscreens could be helpful for the protection of the human skin. Copyright 2003 Elsevier Science B.V.

Bioactive glass coupling with natural polyphenols: Surface modification, bioactivity and anti-oxidant ability

NASA Astrophysics Data System (ADS)

Cazzola, Martina; Corazzari, Ingrid; Prenesti, Enrico; Bertone, Elisa; Vernè, Enrica; Ferraris, Sara

2016-03-01

Polyphenols are actually achieving an increasing interest due to their potential health benefits, such as antioxidant, anticancer, antibacterial and bone stimulation abilities. However their poor bioavailability and stability hamper an effective clinical application as therapeutic principles. The opportunity to couple these biomolecules with synthetic biomaterials, in order to obtain local delivery at the site of interest, improve their bioavailability and stability and combine their properties with the ones of the substrate, is a challenging opportunity for the biomedical research. A silica based bioactive glass, CEL2, has been successfully coupled with gallic acid and natural polyphenols extracted from red grape skins and green tea leaves. The effectiveness of grafting has been verified by means of XPS analyses and the Folin&Ciocalteu tests. In vitro bioactivity has been investigated by soaking in simulated body fluid (SBF). Surface modification after functionalization and early stage reactivity in SBF have been studied by means of zeta potential electrokinetic measurements in KCl and SBF. Finally the antioxidant properties of bare and modified bioactive glasses has been investigated by means of the evaluation of free radical scavenging activity by Electron Paramagnetic Resonance (EPR)/spin trapping technique after UV photolysis of H2O2 highlighting scavenging activity of the bioactive glass.

An oxygen radical absorbance capacity-like assay that directly quantifies the antioxidant's scavenging capacity against AAPH-derived free radicals.

PubMed

Kohri, Shunji; Fujii, Hirotada; Oowada, Shigeru; Endoh, Nobuyuki; Sueishi, Yoshimi; Kusakabe, Miku; Shimmei, Masashi; Kotake, Yashige

2009-03-15

A new method is proposed for the evaluation of oxygen radical absorbance capacity (ORAC). The current fluorescence-based ORAC assay (ORAC-FL) is an indirect method that monitors the antioxidant's ability to protect the fluorescent probe from free radical-mediated damage, and an azo-radical initiator, AAPH (2,2-azobis(2-amidinopropane) dihydrochloride), has been used as a thermal free radical source. The new ORAC assay employs a short in situ photolysis of AAPH to generate free radicals. The electron paramagnetic resonance (EPR) spin trapping method was employed to identify and quantify AAPH radicals. In the presence of antioxidant, the level of AAPH radicals was decreased, and ORAC-EPR values were calculated following a simple kinetic formulation. Alkyl-oxy radical was identified as the sole decomposition product from AAPH; therefore, we concluded that ORAC-FL is the assay equivalent to alkyl-oxy radical scavenging capacity measurement. ORAC-EPR results for several antioxidants and human serum indicated that the overall tendency is in agreement with ORAC-FL, but absolute values showed significant discrepancies. ORAC-EPR is a rapid and simple method that is especially suitable for thermally labile biological specimens because the sample heating is not required for free radical production.

The enhancement of oxidative DNA damage by anti-diabetic metformin, buformin, and phenformin, via nitrogen-centered radicals.

PubMed

Ohnishi, Shiho; Mizutani, Hideki; Kawanishi, Shosuke

2016-08-01

Metformin (N,N-dimethylbiguanide), buformin (1-butylbiguanide), and phenformin (1-phenethylbiguanide) are anti-diabetic biguanide drugs, expected to having anti-cancer effect. The mechanism of anti-cancer effect by these drugs is not completely understood. In this study, we demonstrated that these drugs dramatically enhanced oxidative DNA damage under oxidative condition. Metformin, buformin, and phenformin enhanced generation of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) in isolated DNA reacted with hydrogen peroxide (H2O2) and Cu(II), although these drugs did not form 8-oxodG in the absence of H2O2 or Cu(II). An electron paramagnetic resonance (EPR) study, utilizing alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone and 3,3,5,5-tetramethyl-1-pyrroline-N-oxide as spin trapping agents, showed that nitrogen-centered radicals were generated from biguanides in the presence of Cu(II) and H2O2, and that these radicals were decreased by the addition of DNA. These results suggest that biguanides enhance Cu(II)/H2O2-mediated 8-oxodG generation via nitrogen-centered radical formation. The enhancing effect on oxidative DNA damage may play a role on anti-cancer activity.

Mn Impurity in Bulk GaAs Crystals

NASA Astrophysics Data System (ADS)

Pawłowski, M.; Piersa, M.; Wołoś, A.; Palczewska, M.; Strzelecka, G.; Hruban, A.; Gosk, J.; Kamińska, M.; Twardowski, A.

2006-11-01

Magnetic and electron transport properties of GaAs:Mn crystals grown by Czochralski method were studied. Electron spin resonance showed the presence of Mn acceptor A in two charge states: singly ionized A- in the form of Mn2+(d5), and neutral A0 in the form of Mn2+(d5) plus a bound hole (h). It was possible to determine the relative concentration of both types of centers from intensity of the corresponding electron spin resonance lines. Magnetization measured as a function of magnetic field (up to 6 T) in the temperature range of 2-300 K revealed overall paramagnetic behavior of the samples. Effective spin was found to be about 1.5 value, which was consistent with the presence of two types of Mn configurations. In most of the studied samples the dominance of Mn2+(d5)+h configuration was established and it increased after annealing of native donors. The total value of Mn content was obtained from fitting of magnetization curves with the use of parameters obtained from electron spin resonance. In electron transport, two mechanisms of conductivity were observed: valence band transport dominated above 70 K, and hopping conductivity within Mn impurity band at lower temperatures. From the analysis of the hopping conductivity and using the obtained values of the total Mn content, the effective radius of Mn acceptor in GaAs was estimated as a = 11 ± 3 Å.