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Sample records for pulsed epr spectroscopy

  1. Metallomic EPR spectroscopy.

    Science.gov (United States)

    Hagen, Wilfred R

    2009-09-01

    Based on explicit definitions of biomolecular EPR spectroscopy and of the metallome, this tutorial review positions EPR in the field of metallomics as a unique method to study native, integrated systems of metallobiomolecular coordination complexes subject to external stimuli. The specific techniques of whole-system bioEPR spectroscopy are described and their historic, recent, and anticipated applications are discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-01-01

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

  3. Broadband Transmission EPR Spectroscopy

    NARCIS (Netherlands)

    Hagen, W.R.

    2013-01-01

    EPR spectroscopy employs a resonator operating at a single microwave frequency and phase-sensitive detection using modulation of the magnetic field. The X-band spectrometer is the general standard with a frequency in the 9–10 GHz range. Most (bio)molecular EPR spectra are determined by a combination

  4. Biomolecular EPR spectroscopy

    CERN Document Server

    Hagen, Wilfred Raymond

    2008-01-01

    Comprehensive, Up-to-Date Coverage of Spectroscopy Theory and its Applications to Biological SystemsAlthough a multitude of books have been published about spectroscopy, most of them only occasionally refer to biological systems and the specific problems of biomolecular EPR (bioEPR). Biomolecular EPR Spectroscopy provides a practical introduction to bioEPR and demonstrates how this remarkable tool allows researchers to delve into the structural, functional, and analytical analysis of paramagnetic molecules found in the biochemistry of all species on the planet. A Must-Have Reference in an Intrinsically Multidisciplinary FieldThis authoritative reference seamlessly covers all important bioEPR applications, including low-spin and high-spin metalloproteins, spin traps and spin lables, interaction between active sites, and redox systems. It is loaded with practical tricks as well as do's and don'ts that are based on the author's 30 years of experience in the field. The book also comes with an unprecedented set of...

  5. Pulsed electron-electron double resonance (PELDOR) as EPR spectroscopy in nanometre range

    Energy Technology Data Exchange (ETDEWEB)

    Tsvetkov, Yu D; Milov, A D; Maryasov, A G [Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation)

    2008-06-30

    The results of development of pulsed electron-electron double resonance (PELDOR) method and its applications in structural studies are generalised and described systematically. The foundations of the theory of the method are outlined, some methodological features and applications are considered, in particular, determination of the distances between spin labels in the nanometre range for iminoxyl biradicals, spin-labelled biomacromolecules, radical ion pairs and peptide-membrane complexes. The attention is focussed on radical systems that form upon self-assembly of nanosized complexes (in particular, peptide complexes), spatial effects, and radical pairs in photolysis and photosynthesis. The position of PELDOR among other structural EPR techniques is analysed.

  6. Broadband transmission EPR spectroscopy.

    Directory of Open Access Journals (Sweden)

    Wilfred R Hagen

    Full Text Available EPR spectroscopy employs a resonator operating at a single microwave frequency and phase-sensitive detection using modulation of the magnetic field. The X-band spectrometer is the general standard with a frequency in the 9-10 GHz range. Most (biomolecular EPR spectra are determined by a combination of the frequency-dependent electronic Zeeman interaction and a number of frequency-independent interactions, notably, electron spin - nuclear spin interactions and electron spin - electron spin interactions, and unambiguous analysis requires data collection at different frequencies. Extant and long-standing practice is to use a different spectrometer for each frequency. We explore the alternative of replacing the narrow-band source plus single-mode resonator with a continuously tunable microwave source plus a non-resonant coaxial transmission cell in an unmodulated external field. Our source is an arbitrary wave digital signal generator producing an amplitude-modulated sinusoidal microwave in combination with a broadband amplifier for 0.8-2.7 GHz. Theory is developed for coaxial transmission with EPR detection as a function of cell dimensions and materials. We explore examples of a doublet system, a high-spin system, and an integer-spin system. Long, straigth, helical, and helico-toroidal cells are developed and tested with dilute aqueous solutions of spin label hydroxy-tempo. A detection limit of circa 5 µM HO-tempo in water at 800 MHz is obtained for the present setup, and possibilities for future improvement are discussed.

  7. Use of the Frank sequence in pulsed EPR

    DEFF Research Database (Denmark)

    Tseitlin, Mark; Quine, Richard W.; Eaton, Sandra S.;

    2011-01-01

    The Frank polyphase sequence has been applied to pulsed EPR of triarylmethyl radicals at 256MHz (9.1mT magnetic field), using 256 phase pulses. In EPR, as in NMR, use of a Frank sequence of phase steps permits pulsed FID signal acquisition with very low power microwave/RF pulses (ca. 1.5m......W in the application reported here) relative to standard pulsed EPR. A 0.2mM aqueous solution of a triarylmethyl radical was studied using a 16mm diameter cross-loop resonator to isolate the EPR signal detection system from the incident pulses. Keyword: Correlation spectroscopy,Multi-pulse EPR,Low power pulses...

  8. Pulsed EPR in the method of spin labels and probes

    Energy Technology Data Exchange (ETDEWEB)

    Dzuba, Sergei A [Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation)

    2007-08-31

    Various pulsed EPR in the method of spin labels and probes based on electron spin echo spectroscopy (spin echo envelope modulation through electron-nuclear interactions, electron-electron double resonance, echo detected EPR, etc.) are considered. These methods provide information on the conformations of complex biomolecules, nanostructure of matter, depth of water penetration into biological membranes, supramolecular structure of multicomponent systems (membrane-peptide, etc.), co-operative orientational dynamics of molecules and dynamic low-temperature transitions in disordered molecular media and biosystems.

  9. Pulsed EPR in the method of spin labels and probes

    Science.gov (United States)

    Dzuba, Sergei A.

    2007-08-01

    Various pulsed EPR in the method of spin labels and probes based on electron spin echo spectroscopy (spin echo envelope modulation through electron-nuclear interactions, electron-electron double resonance, echo detected EPR, etc.) are considered. These methods provide information on the conformations of complex biomolecules, nanostructure of matter, depth of water penetration into biological membranes, supramolecular structure of multicomponent systems (membrane-peptide, etc.), co-operative orientational dynamics of molecules and dynamic low-temperature transitions in disordered molecular media and biosystems.

  10. Spin signatures of photogenerated radical anions in polymer-[70]fullerene bulk-heterojunctions : high-frequency pulsed EPR spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Poluektov, O. G.; Filippone, S.; Martin, N.; Sperlich, A.; Deibel, C.; Dyakonov, V. (Chemical Sciences and Engineering Division); (Univ. Complutense de Madrid); (Univ. of Wurzburg)

    2010-04-14

    Charged polarons in thin films of polymer-fullerene composites are investigated by light-induced electron paramagnetic resonance (EPR) at 9.5 GHz (X-band) and 130 GHz (D-band). The materials studied were poly(3-hexylthiophene) (PHT), [6,6]-phenyl-C61-butyric acid methyl ester (C{sub 60}-PCBM), and two different soluble C{sub 70}-derivates: C{sub 70}-PCBM and diphenylmethano[70]fullerene oligoether (C{sub 70}-DPM-OE). The first experimental identification of the negative polaron localized on the C{sub 70}-cage in polymer-fullerene bulk heterojunctions has been obtained. When recorded at conventional X-band EPR, this signal is overlapping with the signal of the positive polaron, which does not allow for its direct experimental identification. Owing to the superior spectral resolution of the high frequency D-band EPR, we were able to separate light-induced signals from P{sup +} and P{sup -} in PHT-C{sub 70} bulk heterojunctions. Comparing signals from C{sub 70}-derivatives with different side-chains, we have obtained experimental proof that the polaron is localized on the cage of the C{sub 70} molecule.

  11. Spin Signatures of Photogenerated Radical Anions in Polymer-[70]Fullerene Bulk Heterojunctions: High Frequency Pulsed EPR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Poluektov, Oleg G. [Argonne National Lab. (ANL), Argonne, IL (United States); Filippone, Salvatore [Universidad Complutense de Madrid (Spain); Martin, C. R. [Universidad Complutense de Madrid (Spain); Sperlich, Andreas [Julius-Maximilians Univ. of Wurzburg (Germany); Deibel, Carsten [Julius-Maximilians Univ. of Wurzburg (Germany); Dyakonov, Vladimir [Julius-Maximilians Univ. of Wurzburg (Germany)

    2010-11-18

    Charged polarons in thin films of polymer-fullerene composites are investigated by light-induced electron paramagnetic resonance (EPR) at 9.5 GHz (X-band) and 130 GHz (D-band). The materials studied were poly(3-hexylthiophene) (PHT), [6,6]-phenyl-C61-butyric acid methyl ester (C60-PCBM), and two different soluble C70-derivates: C70-PCBM and diphenylmethano[70]fullerene oligoether (C70-DPM-OE). The first experimental identification of the negative polaron localized on the C70-cage in polymer-fullerene bulk heterojunctions has been obtained. When recorded at conventional X-band EPR, this signal is overlapping with the signal of the positive polaron, which does not allow for its direct experimental identification. Owing to the superior spectral resolution of the high frequency D-band EPR, we were able to separate light-induced signals from P+ and P- in PHT-C70 bulk heterojunctions. Comparing signals from C70-derivatives with different side-chains, we have obtained experimental proof that the polaron is localized on the cage of the C70 molecule.

  12. Spin signatures of photogenerated radical anions in polymer-[70]fullerene bulk heterojunctions: high frequency pulsed EPR spectroscopy.

    Science.gov (United States)

    Poluektov, Oleg G; Filippone, Salvatore; Martín, Nazario; Sperlich, Andreas; Deibel, Carsten; Dyakonov, Vladimir

    2010-11-18

    Charged polarons in thin films of polymer-fullerene composites are investigated by light-induced electron paramagnetic resonance (EPR) at 9.5 GHz (X-band) and 130 GHz (D-band). The materials studied were poly(3-hexylthiophene) (PHT), [6,6]-phenyl-C61-butyric acid methyl ester (C(60)-PCBM), and two different soluble C(70)-derivates: C(70)-PCBM and diphenylmethano[70]fullerene oligoether (C(70)-DPM-OE). The first experimental identification of the negative polaron localized on the C(70)-cage in polymer-fullerene bulk heterojunctions has been obtained. When recorded at conventional X-band EPR, this signal is overlapping with the signal of the positive polaron, which does not allow for its direct experimental identification. Owing to the superior spectral resolution of the high frequency D-band EPR, we were able to separate light-induced signals from P(+) and P(-) in PHT-C(70) bulk heterojunctions. Comparing signals from C(70)-derivatives with different side-chains, we have obtained experimental proof that the polaron is localized on the cage of the C(70) molecule.

  13. Spin signatures of photogenerated radical anions in polymer-[70] fullerene bulk-heterojunctions : high-frequency pulsed EPR spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Poluektov, O. G.; Filippone, S.; Martin, N.; Sperlich, A.; Deibel, C.; Dyakonov, V. (Chemical Sciences and Engineering Division); (Univ. Complutense de Madrid); (Univ. of Wurzburg)

    2010-01-01

    Charged polarons in thin films of polymer-fullerene composites are investigated by light-induced electron paramagnetic resonance (EPR) at 9.5 GHz (X-band) and 130 GHz (D-band). The materials studied were poly(3-hexylthiophene) (PHT), [6,6]-phenyl-C61-butyric acid methyl ester (C{sub 60}-PCBM), and two different soluble C{sub 70}-derivates: C{sub 70}-PCBM and diphenylmethano[70]fullerene oligoether (C{sub 70}-DPM-OE). The first experimental identification of the negative polaron localized on the C{sub 70}-cage in polymer-fullerene bulk heterojunctions has been obtained. When recorded at conventional X-band EPR, this signal is overlapping with the signal of the positive polaron, which does not allow for its direct experimental identification. Owing to the superior spectral resolution of the high frequency D-band EPR, we were able to separate light-induced signals from P{sup +} and P{sup -} in PHT-C{sub 70} bulk heterojunctions. Comparing signals from C{sub 70}-derivatives with different side-chains, we have obtained experimental proof that the polaron is localized on the cage of the C{sub 70} molecule.

  14. Monitoring enzymatic ATP hydrolysis by EPR spectroscopy.

    Science.gov (United States)

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

    2014-07-14

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

  15. Pulsed EPR and NMR spectroscopy of paramagnetic iron porphyrinates and related iron macrocycles: how to understand patterns of spin delocalization and recognize macrocycle radicals.

    Science.gov (United States)

    Walker, F Ann

    2003-07-28

    Pulsed EPR spectroscopic techniques, including ESEEM (electron spin echo envelope modulation) and pulsed ENDOR (electron-nuclear double resonance), are extremely useful for determining the magnitudes of the hyperfine couplings of macrocycle and axial ligand nuclei to the unpaired electron(s) on the metal as a function of magnetic field orientation relative to the complex. These data can frequently be used to determine the orientation of the g-tensor and the distribution of spin density over the macrocycle, and to determine the metal orbital(s) containing unpaired electrons and the macrocycle orbital(s) involved in spin delocalization. However, these studies cannot be carried out on metal complexes that do not have resolved EPR signals, as in the case of paramagnetic even-electron metal complexes. In addition, the signs of the hyperfine couplings, which are not determined directly in either ESEEM or pulsed ENDOR experiments, are often needed in order to translate hyperfine couplings into spin densities. In these cases, NMR isotropic (hyperfine) shifts are extremely useful in determining the amount and sign of the spin density at each nucleus probed. For metal complexes of aromatic macrocycles such as porphyrins, chlorins, or corroles, simple rules allow prediction of whether spin delocalization occurs through sigma or pi bonds, and whether spin density on the ligands is of the same or opposite sign as that on the metal. In cases where the amount of spin density on the macrocycle and axial ligands is found to be too large for simple metal-ligand spin delocalization, a macrocycle radical may be suspected. Large spin density on the macrocycle that is of the same sign as that on the metal provides clear evidence of either no coupling or weak ferromagnetic coupling of a macrocycle radical to the unpaired electron(s) on the metal, while large spin density on the macrocycle that is of opposite sign to that on the metal provides clear evidence of antiferromagnetic coupling

  16. Simultaneous acquisition of pulse EPR orientation selective spectra

    Science.gov (United States)

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

    2011-01-01

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

  17. Accurate Extraction of Nanometer Distances in Multimers by Pulse EPR

    Science.gov (United States)

    Valera, Silvia; Ackermann, Katrin; Pliotas, Christos; Huang, Hexian; Naismith, James H.

    2016-01-01

    Abstract Pulse electron paramagnetic resonance (EPR) is gaining increasing importance in structural biology. The PELDOR (pulsed electron–electron double resonance) method allows extracting distance information on the nanometer scale. Here, we demonstrate the efficient extraction of distances from multimeric systems such as membrane‐embedded ion channels where data analysis is commonly hindered by multi‐spin effects. PMID:26865468

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

    Science.gov (United States)

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

    2014-08-21

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

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

    Science.gov (United States)

    2017-07-01

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

  20. Identification of slow relaxing spin components by pulse EPR techniques in graphene-related materials

    Directory of Open Access Journals (Sweden)

    Antonio Barbon

    2017-01-01

    Full Text Available Electron Paramagnetic Resonance (EPR is a powerful technique that is suitable to study graphene-related materials. The challenging ability requested to the spectroscopy is its capability to resolve the variety of structures, relatively similar, that are obtained in materials produced through different methods, but that also coexist inside a single sample. In general, because of the intrinsic inhomogeneity of the samples, the EPR spectra are therefore a superposition of spectra coming from different structures. We show that by pulse EPR techniques (echo-detected EPR, ESEEM and Mims ENDOR we can identify and characterize species with slow spin relaxing properties. These species are generally called molecular states, and are likely small pieces of graphenic structures of limited dimensions, thus conveniently described by a molecular approach. We have studied commercial reduced graphene oxide and chemically exfoliated graphite, which are characterized by different EPR spectra. Hyperfine spectroscopies enabled us to characterize the molecular components of the different materials, especially in terms of the interaction of the unpaired electrons with protons (number of protons and hyperfine coupling constants. We also obtained useful precious information about extent of delocalization of the molecular states.

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

    Science.gov (United States)

    Delpoux, Olivier; Gourier, Didier; Binet, Laurent; Vezin, Hervé; Derenne, Sylvie; Robert, François

    2008-05-01

    Insoluble organic matter (IOM) of Orgueil and Tagish Lake meteorites are studied by CW-EPR and pulsed-EPR spectroscopies. The EPR line is due to polycyclic paramagnetic moieties concentrated in defect-rich regions of the IOM, with concentrations of the order of 4x10(19) spin/g. CW-EPR reveals two types of paramagnetic defects: centres with S=1/2, and centres with S=0 ground state and thermally accessible triple state S=1. In spite of the Lorentzian shape of the EPR and its narrowing upon increasing the spin concentration, the EPR line is not in the exchange narrowing regime as previously deduced from multi-frequency CW-EPR [L. Binet, D. Gourier, Appl. Magn. Reson. 30 (2006) 207-231]. It is inhomogeneously broadened as demonstrated by the presence of nuclear modulations in the spin-echo decay. The line narrowing, similar to an exchange narrowing effect, is the result of an increasing contribution of the narrow line of the triplet state centres in addition to the broader line of doublet states. Hyperfine sublevel correlation spectroscopy (HYSCORE) of hydrogen and (13)C nuclei indicates that IOM* centres are small polycyclic moieties that are moderately branched with aliphatic chains, as shown by the presence of aromatic hydrogen atoms. On the contrary the lack of such aromatic hydrogen in triplet states suggests that these radicals are most probably highly branched. Paramagnetic centres are considerably enriched in deuterium, with D/H approximately 1.5+/-0.5x10(-2) of the order of values existing in interstellar medium.

  2. EPR spectroscopy of nitrite complexes of methemoglobin.

    Science.gov (United States)

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

    2010-07-19

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

  3. Pulsed electron-nuclear-electron triple resonance spectroscopy

    Science.gov (United States)

    Thomann, Hans; Bernardo, Marcelino

    1990-05-01

    A new experimental technique, pulsed electron-nuclear-electron triple resonance spectroscopy, is demonstrated. It is based on a modification of the pulse sequence for electron-nuclear double resonance (ENDOR) in which two EPR and one NMR transition are irradiated. The irradiation of one EPR transition is detected via a second EPR transition. The nuclear hyperfine coupling, which separates these EPR transition frequencies, is the irradiated NMR transition. The major advantages of triple resonance spectroscopy include the ability to resolve overlapping nuclear resonances in the ENDOR spectrum and a more direct quantitative assignment of nuclear hyperfine and quadrupole couplings. The triple resonance experiment is an alternative to the recently proposed method of employing rapid magnetic field jumps between microwave pulses for generating hyperfine selective ENDOR spectra.

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

    Science.gov (United States)

    Spasojević, Ivan

    2011-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Daniel eNohr

    2015-09-01

    Full Text Available 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.

  6. New Developments in Spin Labels for Pulsed Dipolar EPR

    Directory of Open Access Journals (Sweden)

    Alistair J. Fielding

    2014-10-01

    Full Text Available Spin labelling is a chemical technique that enables the integration of a molecule containing an unpaired electron into another framework for study. Given the need to understand the structure, dynamics, and conformational changes of biomacromolecules, spin labelling provides a relatively non-intrusive technique and has certain advantages over X-ray crystallography; which requires high quality crystals. The technique relies on the design of binding probes that target a functional group, for example, the thiol group of a cysteine residue within a protein. The unpaired electron is typically supplied through a nitroxide radical and sterically shielded to preserve stability. Pulsed electron paramagnetic resonance (EPR techniques allow small magnetic couplings to be measured (e.g., <50 MHz providing information on single label probes or the dipolar coupling between multiple labels. In particular, distances between spin labels pairs can be derived which has led to many protein/enzymes and nucleotides being studied. Here, we summarise recent examples of spin labels used for pulse EPR that serve to illustrate the contribution of chemistry to advancing discoveries in this field.

  7. Active cancellation - A means to zero dead-time pulse EPR

    Science.gov (United States)

    Franck, John M.; Barnes, Ryan P.; Keller, Timothy J.; Kaufmann, Thomas; Han, Songi

    2015-12-01

    The necessary resonator employed in pulse electron paramagnetic resonance (EPR) rings after the excitation pulse and creates a finite detector dead-time that ultimately prevents the detection of signal from fast relaxing spin systems, hindering the application of pulse EPR to room temperature measurements of interesting chemical or biological systems. We employ a recently available high bandwidth arbitrary waveform generator (AWG) to produce a cancellation pulse that precisely destructively interferes with the resonant cavity ring-down. We find that we can faithfully detect EPR signal at all times immediately after, as well as during, the excitation pulse. This is a proof of concept study showcasing the capability of AWG pulses to precisely cancel out the resonator ring-down, and allow for the detection of EPR signal during the pulse itself, as well as the dead-time of the resonator. However, the applicability of this approach to conventional EPR experiments is not immediate, as it hinges on either (1) the availability of low-noise microwave sources and amplifiers to produce the necessary power for pulse EPR experiment or (2) the availability of very high conversion factor micro coil resonators that allow for pulse EPR experiments at modest microwave power.

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

    Directory of Open Access Journals (Sweden)

    Peter Strauch

    2012-02-01

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

  9. Arbitrary waveform modulated pulse EPR at 200 GHz

    Science.gov (United States)

    Kaminker, Ilia; Barnes, Ryan; Han, Songi

    2017-06-01

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

  10. The possible use of EPR spectroscopy for paint pigment identification

    Energy Technology Data Exchange (ETDEWEB)

    Troup, G.J.; Hutton, D.R. [Monash Univ., Clayton, VIC (Australia). Dept. of Physics; Bacci, M.; Lotti, F.; Casini, A.; Picollo, M. [Istituto di Ricerca sulle Onde Elettromagnetiche, Florence, Italy (Italy)

    1996-12-31

    Full text: Visible and near-infra-red reflectance spectroscopy are now routinely used for the identification of paint pigments in Renaissance painting, thus playing a part in authentication and restoration. Since most of the pigments are minerals, and many minerals either contain traces of paramagnetic ions, or have paramagnetic ions in their main components (e.g., chromic oxide, haematite), it seemed logical to determine whether EPR could distinguish between different pigments. 14 pigments of different colours were tested in a Varian E-12 EPR spectrometer, at a frequency of {approx} 9.1 GHz. Measurements were made at room ({approx} 20 deg C) and liquid N{sub 2} temperatures, in the standard special quartz sample tubes. The active volume is 0. 15 ml, but at most, a volume of sample (powder) one tenth of this was used. The spectra (to be shown) clearly demonstrate that EPR can distinguish between different pigments. The power was 1 milliwatt, the modulation amplitude 4 gauss, the total field sweep 10,000 gauss, centred 5000 gauss and the amplification between 10{sup 2} and 10{sup 4}, as indicated on the charts. The signal to noise ratio is excellent, and sensitivity could be increased (if necessary) by a factor of {approx} 10{sup 3}, thus allowing much smaller samples to be tested. Because the signals are so strong it should be possible to scan at least small painted canvases by the following non-destructive technique, using existing equipment. All that is required is a modified resonant cavity; it must have a high Q, and a slot where the magnetic field is maximum, and the electric field zero. The canvas can thus be placed flush with the waveguide, to interact with the microwave magnetic field emanating from the slot

  11. Multi-frequency, multi-technique pulsed EPR investigation of the copper binding site of murine amyloid β peptide.

    Science.gov (United States)

    Kim, Donghun; Bang, Jeong Kyu; Kim, Sun Hee

    2015-01-26

    Copper-amyloid peptides are proposed to be the cause of Alzheimer's disease, presumably by oxidative stress. However, mice do not produce amyloid plaques and thus do not suffer from Alzheimer's disease. Although much effort has been focused on the structural characterization of the copper- human amyloid peptides, little is known regarding the copper-binding mode in murine amyloid peptides. Thus, we investigated the structure of copper-murine amyloid peptides through multi-frequency, multi-technique pulsed EPR spectroscopy in conjunction with specific isotope labeling. Based on our pulsed EPR results, we found that Ala2, Glu3, His6, and His14 are directly coordinated with the copper ion in murine amyloid β peptides at pH 8.5. This is the first detailed structural characterization of the copper-binding mode in murine amyloid β peptides. This work may advance the knowledge required for developing inhibitors of Alzheimer's disease.

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

    Science.gov (United States)

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

    2016-05-01

    Water accessibility is a key parameter for the understanding of the structure of biomolecules, especially membrane proteins. Several experimental techniques based on the combination of electron paramagnetic resonance (EPR) spectroscopy with site-directed spin labeling are currently available. Among those, we compare relaxation time measurements and electron spin echo envelope modulation (ESEEM) experiments using pulse EPR with Overhauser dynamic nuclear polarization (DNP) at X-band frequency and a magnetic field of 0.33 T. Overhauser DNP transfers the electron spin polarization to nuclear spins via cross-relaxation. The change in the intensity of the 1H NMR spectrum of H2O at a Larmor frequency of 14 MHz under a continuous-wave microwave irradiation of the nitroxide spin label contains information on the water accessibility of the labeled site. As a model system for a membrane protein, we use the hydrophobic α-helical peptide WALP23 in unilamellar liposomes of DOPC. Water accessibility measurements with all techniques are conducted for eight peptides with different spin label positions and low radical concentrations (10-20 μM). Consistently in all experiments, the water accessibility appears to be very low, even for labels positioned near the end of the helix. The best profile is obtained by Overhauser DNP, which is the only technique that succeeds in discriminating neighboring positions in WALP23. Since the concentration of the spin-labeled peptides varied, we normalized the DNP parameter ɛ, being the relative change of the NMR intensity, by the electron spin concentration, which was determined from a continuous-wave EPR spectrum.

  13. FID detection of EPR and ENDOR spectra at high microwave frequencies.

    Science.gov (United States)

    Blok, H; Akimoto, I; Milikisyants, S; Gast, P; Groenen, E J J; Schmidt, J

    2009-11-01

    High-frequency pulsed EPR spectroscopy allows FID detection of EPR spectra owing to the short dead time that can be achieved. This FID detection is particularly attractive for EPR and ENDOR spectroscopy of paramagnetic species that exhibit inhomogeneously broadened EPR lines and short dephasing times. Experiments are reported for the metalloprotein azurin at 275 GHz.

  14. FID detection of EPR and ENDOR spectra at high microwave frequencies

    Science.gov (United States)

    Blok, H.; Akimoto, I.; Milikisyants, S.; Gast, P.; Groenen, E. J. J.; Schmidt, J.

    2009-11-01

    High-frequency pulsed EPR spectroscopy allows FID detection of EPR spectra owing to the short dead time that can be achieved. This FID detection is particularly attractive for EPR and ENDOR spectroscopy of paramagnetic species that exhibit inhomogeneously broadened EPR lines and short dephasing times. Experiments are reported for the metalloprotein azurin at 275 GHz.

  15. EPR and NMR spectroscopy on spin-labeled proteins

    NARCIS (Netherlands)

    Finiguerra, Michelina Giuseppina

    2011-01-01

    Spin labeling and electron paramagnetic resonance (EPR) have been employed to study structure and dynamics of proteins. The surface polarity of four single cysteine mutants of the Zn-azurin in frozen solution were studied using 275 GHz EPR (J-band), with the advantage compared to 9 GHz (X-band) and

  16. Identification of gamma-irradiated fruit juices by EPR spectroscopy

    Science.gov (United States)

    Aleksieva, K. I.; Dimov, K. G.; Yordanov, N. D.

    2014-10-01

    The results of electron paramagnetic resonance (EPR) study on commercially available juices from various fruits and different fruit contents: 25%, 40%, 50%, and 100%, homemade juices, nectars and concentrated fruit syrups, before and after gamma-irradiation are reported. In order to remove water from non- and irradiated samples all juices and nectars were filtered; the solid residue was washed with alcohol and dried at room temperature. Only concentrated fruit syrups were dried for 60 min at 40 °C in a standard laboratory oven. All samples under study show a singlet EPR line with g=2.0025 before irradiation with exception of concentrated fruit syrups, which are EPR silent. Irradiation of juice samples gives rise to complex EPR spectra which gradually transferred to "cellulose-like" EPR spectrum from 25% to 100% fruit content. Concentrated fruit syrups show typical "sugar-like" spectra due to added saccharides. All EPR spectra are characteristic and can prove radiation treatment. The fading kinetics of radiation-induced EPR signals were studied for a period of 60 days after irradiation.

  17. Cd 2+ effect on free radicals in Cladosporium cladosporioides-melanin tested by EPR spectroscopy

    Science.gov (United States)

    Matuszczyk, Magdalena; Buszman, Ewa; Pilawa, Barbara; Witoszyńska, Teresa; Wilczok, Tadeusz

    2004-08-01

    Changes in free radicals system of Cladosporium cladosporioides-melanin and model DOPA-melanin caused by diamagnetic Cd 2+ ions were studied by electron paramagnetic resonance (EPR) spectroscopy. EPR line of eumelanin was mainly found in the spectrum of Cl.cl.-melanin. Cd 2+ ions increased o-semiquinone free radicals concentration in both natural and synthetic melanins. Cd 2+ broadened EPR lines of Cl.cl.-melanin in mycelium and the ions fastened spin-lattice relaxation processes. The narrower EPR lines and slower spin-lattice relaxation were obtained for DOPA-melanin-Cd 2+ complexes than for DOPA-melanin. Pheomelanin additionally existing in Cl.cl. samples was responsible for differences between the EPR data for Cl.cl. melanin and DOPA-melanin.

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

    Science.gov (United States)

    Mentink-Vigier, F.; Collauto, A.; Feintuch, A.; Kaminker, I.; Tarle, V.; Goldfarb, D.

    2013-11-01

    Modern pulse EPR experiments are routinely used to study the structural features of paramagnetic centers. They are usually performed at low temperatures, where relaxation times are long and polarization is high, to achieve a sufficient Signal/Noise Ratio (SNR). However, when working with samples whose amount and/or concentration are limited, sensitivity becomes an issue and therefore measurements may require a significant accumulation time, up to 12 h or more. As the detection scheme of practically all pulse EPR sequences is based on the integration of a spin echo - either primary, stimulated or refocused - a considerable increase in SNR can be obtained by replacing the single echo detection scheme by a train of echoes. All these echoes, generated by Carr-Purcell type sequences, are integrated and summed together to improve the SNR. This scheme is commonly used in NMR and here we demonstrate its applicability to a number of frequently used pulse EPR experiments: Echo-Detected EPR, Davies and Mims ENDOR (Electron-Nuclear Double Resonance), DEER (Electron-Electron Double Resonance|) and EDNMR (Electron-Electron Double Resonance (ELDOR)-Detected NMR), which were combined with a Carr-Purcell-Meiboom-Gill (CPMG) type detection scheme at W-band. By collecting the transient signal and integrating a number of refocused echoes, this detection scheme yielded a 1.6-5 folds SNR improvement, depending on the paramagnetic center and the pulse sequence applied. This improvement is achieved while keeping the experimental time constant and it does not introduce signal distortion.

  19. Application of electron paramagnetic resonance (EPR) spectroscopy and imaging in drug delivery research - chances and challenges.

    Science.gov (United States)

    Kempe, Sabine; Metz, Hendrik; Mäder, Karsten

    2010-01-01

    Electron Paramagnetic Resonance (EPR) spectroscopy is a powerful technique to study chemical species with unpaired electrons. Since its discovery in 1944, it has been widely used in a number of research fields such as physics, chemistry, biology and material and food science. This review is focused on its application in drug delivery research. EPR permits the direct measurement of microviscosity and micropolarity inside drug delivery systems (DDS), the detection of microacidity, phase transitions and the characterization of colloidal drug carriers. Additional information about the spatial distribution can be obtained by EPR imaging. The chances and also the challenges of in vitro and in vivo EPR spectroscopy and imaging in the field of drug delivery are discussed.

  20. Evaluation of the original dose in irradiated dried fruit by EPR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    D' Oca, Maria Cristina, E-mail: mcristina.doca@unipa.it [Dipartimento Farmacochimico, Tossicologico e Biologico, Universita di Palermo, via Archirafi 32, 90123 Palermo (Italy); Bartolotta, Antonio [Dipartimento Farmacochimico, Tossicologico e Biologico, Universita di Palermo, via Archirafi 32, 90123 Palermo (Italy)

    2011-09-15

    The electron paramagnetic resonance spectroscopy (EPR) is one of the physical methods, recommended by the European Committee for Standardization, for the identification of irradiated food containing cellulose, such as dried fruit. In this work the applicability of EPR as identification method of irradiated pistachios, hazelnuts, peanuts, chestnuts, pumpkin seeds is evaluated; the time stability of the radiation induced signal is studied and the single aliquot additive dose method is used to evaluate the dose in the product.

  1. High Fidelity Single Qubit Operations using Pulsed EPR

    CERN Document Server

    Morton, J J L; Ardavan, A; Porfyrakis, K; Lyon, S A; Briggs, G A D; Morton, John J. L.; Tyryshkin, Alexei M.; Ardavan, Arzhang; Porfyrakis, Kyriakos

    2005-01-01

    The fidelity of quantum logic operations performed on electron spin qubits using simple RF pulses falls well below the threshold for the application of quantum algorithms. Using three independent techniques, we demonstrate the use of composite pulses to improve this fidelity by several orders of magnitude. The observed high-fidelity operations are limited by pulse phase errors, but nevertheless fall within the limits required for the application of quantum error correction algorithms.

  2. EPR spectroscopy of protein microcrystals oriented in a liquid crystalline polymer medium

    Science.gov (United States)

    Caldeira, Jorge; Figueirinhas, João Luis; Santos, Celina; Godinho, Maria Helena

    2004-10-01

    Correlation of the g-tensor of a paramagnetic active center of a protein with its structure provides a unique experimental information on the electronic structure of the metal site. To address this problem, we made solid films containing metalloprotein ( Desulfovibrio gigas cytochrome c3) microcrystals. The microcrystals in a liquid crystalline polymer medium (water/hydroxypropylcellulose) were partially aligned by a shear flow. A strong orientation effect of the metalloprotein was observed by EPR spectroscopy and polarizing optical microscopy. The EPR spectra of partially oriented samples were simulated, allowing for molecular orientation distribution function determination. The observed effect results in enhanced sensitivity and resolution of the EPR spectra and provides a new approach towards the correlation of spectroscopic data, obtained by EPR or some other technique, with the three-dimensional structure of a protein or a model compound.

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

    Science.gov (United States)

    Sütçü, Kerem; Osmanoǧlu, Yunus Emre

    2017-02-01

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

  4. SPIDYAN, a MATLAB library for simulating pulse EPR experiments with arbitrary waveform excitation.

    Science.gov (United States)

    Pribitzer, Stephan; Doll, Andrin; Jeschke, Gunnar

    2016-02-01

    Frequency-swept chirp pulses, created with arbitrary waveform generators (AWGs), can achieve inversion over a range of several hundreds of MHz. Such passage pulses provide defined flip angles and increase sensitivity. The fact that spectra are not excited at once, but single transitions are passed one after another, can cause new effects in established pulse EPR sequences. We developed a MATLAB library for simulation of pulse EPR, which is especially suited for modeling spin dynamics in ultra-wideband (UWB) EPR experiments, but can also be used for other experiments and NMR. At present the command line controlled SPin DYnamics ANalysis (SPIDYAN) package supports one-spin and two-spin systems with arbitrary spin quantum numbers. By providing the program with appropriate spin operators and Hamiltonian matrices any spin system is accessible, with limits set only by available memory and computation time. Any pulse sequence using rectangular and linearly or variable-rate frequency-swept chirp pulses, including phase cycling can be quickly created. To keep track of spin evolution the user can choose from a vast variety of detection operators, including transition selective operators. If relaxation effects can be neglected, the program solves the Liouville-von Neumann equation and propagates spin density matrices. In the other cases SPIDYAN uses the quantum mechanical master equation and Liouvillians for propagation. In order to consider the resonator response function, which on the scale of UWB excitation limits bandwidth, the program includes a simple RLC circuit model. Another subroutine can compute waveforms that, for a given resonator, maintain a constant critical adiabaticity factor over the excitation band. Computational efficiency is enhanced by precomputing propagator lookup tables for the whole set of AWG output levels. The features of the software library are discussed and demonstrated with spin-echo and population transfer simulations.

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

    Energy Technology Data Exchange (ETDEWEB)

    Alberti, Angelo, E-mail: aalberti@isof.cnr.it [CNR-ISOF, Area della Ricerca di Bologna, Via P. Gobetti 101, Bologna I-40129 (Italy); Chiaravalle, Eugenio [Istituto Zooprofilattico Sperimentale della Puglia e Basilicata, Via Manfredonia 20, Foggia I-71100 (Italy); Fuochi, Piergiorgio; Macciantelli, Dante [CNR-ISOF, Area della Ricerca di Bologna, Via P. Gobetti 101, Bologna I-40129 (Italy); Mangiacotti, Michele, E-mail: michelemangiacotti@libero.it [Istituto Zooprofilattico Sperimentale della Puglia e Basilicata, Via Manfredonia 20, Foggia I-71100 (Italy); Marchesani, Giuliana [Istituto Zooprofilattico Sperimentale della Puglia e Basilicata, Via Manfredonia 20, Foggia I-71100 (Italy); Plescia, Elena [CNR-ISOF, Area della Ricerca di Bologna, Via P. Gobetti 101, Bologna I-40129 (Italy)

    2011-12-15

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

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

    Science.gov (United States)

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

    2012-06-01

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

  7. Application of EPR spectroscopy to the examination of pro-oxidant activity of coffee.

    Science.gov (United States)

    Krakowian, Daniel; Skiba, Dominik; Kudelski, Adam; Pilawa, Barbara; Ramos, Paweł; Adamczyk, Jakub; Pawłowska-Góral, Katarzyna

    2014-05-15

    Free radicals present in coffee may be responsible for exerting toxic effects on an organism. The objectives of this work were to compare free radicals properties and concentrations in different commercially available coffees, in solid and liquid states, and to determine the effect of roasting on the formation of free radicals in coffee beans of various origins. The free radicals content of 15 commercially available coffees (solid and liquid) was compared and the impact of processing examined using electron paramagnetic resonance (EPR) spectroscopy at X-band (9.3 GHz). First derivative EPR spectra were measured at microwave power in the range of 0.7-70 mW. The following parameters were calculated for EPR spectra: amplitude (A), integral intensity (I), and line-width (ΔBpp); g-Factor was obtained from resonance condition. Our study showed that free radicals exist in green coffee beans (10(16) spin/g), roasted coffee beans (10(18) spin/g), and in commercially available coffee (10(17)-10(18) spin/g). Free radical concentrations were higher in solid ground coffee than in instant or lyophilised coffee. Continuous microwave saturation indicated homogeneous broadening of EPR lines from solid and liquid commercial coffee samples as well as green and roasted coffee beans. Slow spin-lattice relaxation processes were found to be present in all coffee samples tested, solid and liquid commercial coffees as well as green and roasted coffee beans. Higher free radicals concentrations were obtained for both the green and roasted at 240 °C coffee beans from Peru compared with those originating from Ethiopia, Brazil, India, or Colombia. Moreover, more free radicals occurred in Arabica coffee beans roasted at 240 °C than Robusta. EPR spectroscopy is a useful method of examining free radicals in different types of coffee. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. EPR spectroscopy as a tool in homogeneous catalysis research

    NARCIS (Netherlands)

    Goswami, M.; Chirila, A.; Rebreyend, C.; de Bruin, B.

    2015-01-01

    In the context of homogeneous catalysis, open-shell systems are often quite challenging to characterize. Nuclear magnetic resonance (NMR) spectroscopy is the most frequently applied tool to characterize organometallic compounds, but NMR spectra are usually broad, difficult to interpret and often fut

  9. High-field EPR spectroscopy of thermal donors in silicon

    DEFF Research Database (Denmark)

    Dirksen, R.; Rasmussen, F.B.; Gregorkiewicz, T.

    1997-01-01

    Thermal donors generated in p-type boron-doped Czochralski-grown silicon by a 450 degrees C heat treatment have been studied by high-field magnetic resonance spectroscopy. In the experiments conducted at a microwave frequency of 140 GHz and in a magnetic field of approximately 5 T four individual...

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

    Science.gov (United States)

    Zdybel, Magdalena; Pilawa, Barbara; Chodurek, Ewa

    2015-01-01

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

  11. Model compounds of humic acid and oxovanadium cations. Potentiometric titration and EPR spectroscopy studies

    Directory of Open Access Journals (Sweden)

    Mercê Ana Lucia Ramalho

    1999-01-01

    Full Text Available The stability constants and the isotropic EPR parameters Ao (hyperfine splitting constant and g o (g value were obtained by potentiometric titrations and EPR spectroscopy, respectively, of 85%v/v aqueous solutions of model compounds of humic acids - salicylic acid (SALA - and both nitrohumic acids, a laboratory artifact - nitrosalicylic acids, 3-nitrosalicylic acid (3-NSA, 5-nitrosalicylic acid (5-NSA and 3,5-dinitrosalicylic acid (3,5-DNSA and oxovanadium cations. It was possible to record EPR spectra of those model compounds and the ion VO2+ (V(IV, and the stability constants were obtained from a solution of VO3+ (V(V, the values for the logarithms of the stability constants ranging from 12.77 ± 0.04 to 7.06 ± 0.05 for the species ML, and from 9.90 ±0.04 to 4.06 ± 0.05 for the species ML2 according to the decrease in the acidity of the carboxylic and the hydroxyl groups in the aromatic ring of the model compounds studied as the -NO2 substituents were added. Species distribution diagrams were also obtained for the equilibria studied. The EPR parameters showed that as the logarithm of the overall stability constants increase, g o values also increase, while Ao values show a tendency to decrease.

  12. A 140 GHz pulsed EPR/212 MHz NMR spectrometer for DNP studies

    Science.gov (United States)

    Smith, Albert A.; Corzilius, Björn; Bryant, Jeffrey A.; DeRocher, Ronald; Woskov, Paul P.; Temkin, Richard J.; Griffin, Robert G.

    2012-10-01

    We described a versatile spectrometer designed for the study of dynamic nuclear polarization (DNP) at low temperatures and high fields. The instrument functions both as an NMR spectrometer operating at 212 MHz (1H frequency) with DNP capabilities, and as a pulsed-EPR operating at 140 GHz. A coiled TE011 resonator acts as both an NMR coil and microwave resonator, and a double balanced (1H, 13C) radio frequency circuit greatly stabilizes the NMR performance. A new 140 GHz microwave bridge has also been developed, which utilizes a four-phase network and ELDOR channel at 8.75 GHz, that is then multiplied and mixed to obtain 140 GHz microwave pulses with an output power of 120 mW. Nutation frequencies obtained are as follows: 6 MHz on S = 1/2 electron spins, 100 kHz on 1H, and 50 kHz on 13C. We demonstrate basic EPR, ELDOR, ENDOR, and DNP experiments here. Our solid effect DNP results demonstrate an enhancement of 144 and sensitivity gain of 310 using OX063 trityl at 80 K and an enhancement of 157 and maximum sensitivity gain of 234 using Gd-DOTA at 20 K, which is significantly better performance than previously reported at high fields (⩾3 T).

  13. A 140 GHz pulsed EPR/212 MHz NMR spectrometer for DNP studies.

    Science.gov (United States)

    Smith, Albert A; Corzilius, Björn; Bryant, Jeffrey A; DeRocher, Ronald; Woskov, Paul P; Temkin, Richard J; Griffin, Robert G

    2012-10-01

    We described a versatile spectrometer designed for the study of dynamic nuclear polarization (DNP) at low temperatures and high fields. The instrument functions both as an NMR spectrometer operating at 212 MHz ((1)H frequency) with DNP capabilities, and as a pulsed-EPR operating at 140 GHz. A coiled TE(011) resonator acts as both an NMR coil and microwave resonator, and a double balanced ((1)H, (13)C) radio frequency circuit greatly stabilizes the NMR performance. A new 140 GHz microwave bridge has also been developed, which utilizes a four-phase network and ELDOR channel at 8.75 GHz, that is then multiplied and mixed to obtain 140 GHz microwave pulses with an output power of 120 mW. Nutation frequencies obtained are as follows: 6 MHz on S=1/2 electron spins, 100 kHz on (1)H, and 50 kHz on (13)C. We demonstrate basic EPR, ELDOR, ENDOR, and DNP experiments here. Our solid effect DNP results demonstrate an enhancement of 144 and sensitivity gain of 310 using OX063 trityl at 80 K and an enhancement of 157 and maximum sensitivity gain of 234 using Gd-DOTA at 20 K, which is significantly better performance than previously reported at high fields (≥3 T).

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

    Science.gov (United States)

    Pawłowska-Góral, Katarzyna; Pilawa, Barbara

    2011-10-01

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

  15. Can copper(II) mediate Hoogsteen base-pairing in a left-handed DNA duplex? A pulse EPR study.

    Science.gov (United States)

    Santangelo, Maria Grazia; Antoni, Philipp M; Spingler, Bernhard; Jeschke, Gunnar

    2010-02-22

    Pulse EPR spectroscopy is used to investigate possible structural features of the copper(II) ion coordinated to poly(dG-dC).poly(dG-dC) in a frozen aqueous solution, and the structural changes of the polynucleotide induced by the presence of the metal ion. Two different copper species were identified and their geometry explained by a molecular model. According to this model, one species is exclusively coordinated to a single guanine with the N7 nitrogen atom forming a coordinative bond with the copper. In the other species, a guanine and a cytosine form a ternary complex together with the copper ion. A copper crosslink between the N7 of guanine and N3 of cytosine is proposed as the most probable coordination site. Moreover, no evidence was found for an interaction of either copper species with a phosphate group or equatorial water molecules. In addition, circular dichroism (CD) spectroscopy showed that the DNA of the Cu(II)-poly(dG-dC).poly(dG-dC) adducts resembles the left-handed Z-form. These results suggest that metal-mediated Hoogsteen base pairing, as previously proposed for a right-handed DNA duplex, can also occur in a double-stranded left-handed DNA.

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

    Science.gov (United States)

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

    2017-07-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Andrews, J.C. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley Lab., CA (United States). Structural Biology Div.

    1995-08-01

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

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

    Science.gov (United States)

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

    2011-12-01

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

  19. An improved approach to identify irradiated spices using electronic nose, FTIR, and EPR spectroscopy.

    Science.gov (United States)

    Sanyal, Bhaskar; Ahn, Jae-Jun; Maeng, Jeong-Hwan; Kyung, Hyun-Kyu; Lim, Ha-Kyeong; Sharma, Arun; Kwon, Joong-Ho

    2014-09-01

    Changes in cumin and chili powder from India resulting from electron-beam irradiation were investigated using 3 analytical methods: electronic nose (E-nose), Fourier transform infrared (FTIR) spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy. The spices had been exposed to 6 to 14 kGy doses recommended for microbial decontamination. E-nose measured a clear difference in flavor patterns of the irradiated spices in comparison with the nonirradiated samples. Principal component analysis further showed a dose-dependent variation. FTIR spectra of the samples showed strong absorption bands at 3425, 3007 to 2854, and 1746 cm(-1). However, both nonirradiated and irradiated spice samples had comparable patterns without any noteworthy changes in functional groups. EPR spectroscopy of the irradiated samples showed a radiation-specific triplet signal at g = 2.006 with a hyper-fine coupling constant of 3 mT confirming the results obtained with the E-nose technique. Thus, E-nose was found to be a potential tool to identify irradiated spices.

  20. 2'-Alkynylnucleotides: A Sequence- and Spin Label-Flexible Strategy for EPR Spectroscopy in DNA.

    Science.gov (United States)

    Haugland, Marius M; El-Sagheer, Afaf H; Porter, Rachel J; Peña, Javier; Brown, Tom; Anderson, Edward A; Lovett, Janet E

    2016-07-27

    Electron paramagnetic resonance (EPR) spectroscopy is a powerful method to elucidate molecular structure through the measurement of distances between conformationally well-defined spin labels. Here we report a sequence-flexible approach to the synthesis of double spin-labeled DNA duplexes, where 2'-alkynylnucleosides are incorporated at terminal and internal positions on complementary strands. Post-DNA synthesis copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions with a variety of spin labels enable the use of double electron-electron resonance experiments to measure a number of distances on the duplex, affording a high level of detailed structural information.

  1. Thermodynamic basis of electron transfer in dihydroorotate dehydrogenase B from Lactococcus lactis: analysis by potentiometry, EPR spectroscopy, and ENDOR spectroscopy.

    Science.gov (United States)

    Mohsen, Al-Walid A; Rigby, Stephen E J; Jensen, Kaj Frank; Munro, Andrew W; Scrutton, Nigel S

    2004-06-01

    Dihydroorotate dehydrogenase B (DHODB) is a complex iron-sulfur flavoprotein that catalyzes the conversion of dihydroorotate to orotate and the reduction of NAD(+). The enzyme is a dimer of heterodimers containing an FMN, an FAD, and a 2Fe-2S center. UV-visible, EPR, and ENDOR spectroscopies have been used to determine the reduction potentials of the flavins and the 2Fe-2S center and to characterize radicals and their interactions. Reductive titration using dithionite indicates a five-electron capacity for DHODB. The midpoint reduction potential of the 2Fe-2S center (-212 +/- 3 mV) was determined from analysis of absorption data at 540 nm, where absorption contributions from the two flavins are small. The midpoint reduction potentials of the oxidized/semiquinone (E(1)) and semiquinone/hydroquinone (E(2)) couples for the FMN (E(1) = -301 +/- 6 mV; E(2) = -252 +/- 8 mV) and FAD (E(1) = -312 +/- 6 mV; E(2) = -297 +/- 5 mV) were determined from analysis of spectral changes at 630 nm. Corresponding values for the midpoint reduction potentials for FMN (E(1) = -298 +/- 4 mV; E(2) = -259 +/- 5 mV) in the isolated catalytic subunit (subunit D, which lacks the 2Fe-2S center and FAD) are consistent with the values determined for the FMN couples in DHODB. During reductive titration of DHODB, small amounts of the neutral blue semiquinone are observed at approximately 630 nm, consistent with the measured midpoint reduction potentials of the flavins. An ENDOR spectrum of substrate-reduced DHODB identifies hyperfine couplings to proton nuclei similar to those recorded for the blue semiquinone of free flavins in aqueous solution, thus confirming the presence of this species in DHODB. Spectral features observed during EPR spectroscopy of dithionite-reduced DHODB are consistent with the midpoint reduction potentials determined using UV-visible spectroscopy and further identify an unusual EPR signal with very small rhombic anisotropy and g values of 2.02, 1.99, and 1.96. This unusual

  2. High-Field EPR Spectroscopy on Transfer Proteins in Biological Action

    Science.gov (United States)

    Möbius, K.; Schnegg, A.; Plato, M.; Fuchs, M. R.; Savitsky, A.

    2006-08-01

    In the last decade joint efforts of biologists, chemists, and physicists were made to understand the dominant factors determining specificity and directionality of transmembrane transfer processes in proteins. Characteristic examples of such factors are time varying specific H-bonding patterns and/or polarity effects of the microenvironment. In this overview, a few large paradigm biosystems are surveyed which have been explored lately in our laboratory. Taking advantage of the improved spectral and temporal resolution of high-frequency/high-field EPR at 95 GHz/3.4 T and 360 GHz/12.9 T, as compared to conventional X-band EPR (9.5 GHz/0.34 T), three transfer proteins in action are characterized with respect to structure and dynamics: (1) light-induced electron-transfer intermediates in wild-type and mutant reaction-centre proteins from photosynthetic bacteria Rhodobacter sphaeroides, (2) light-driven proton-transfer intermediates of site-specifically nitroxide spin-labelled mutants of bacteriorhodopsin proteins from Halobacterium salinarium, (3) refolding intermediates of site-specifically nitroxide spin-labelled mutants of the channel-forming protein domain of Colicin A bacterial toxin produced in Escherichia coli. The information obtained is complementary to that of protein crystallography, solid-state NMR, infrared and optical spectroscopy techniques. A unique strength of high-field EPR is particularly noteworthy: it can provide detailed information on transient intermediates of proteins in biological action. They can be observed and characterized while staying in their working states on biologically relevant time scales.

  3. DETECTION OF NITRIC OXIDE REDUCTION DURING ISCHAEMIA-REPERFUSION BY EPR SPECTROSCOPY

    Directory of Open Access Journals (Sweden)

    KADKHODAEE M

    2001-01-01

    Full Text Available Introduction: Acute renal failure is a common consequence of sepisis due to concurrent renal ischaemia. The role of nitric oxide (NO in endotoxaemia and in ischaemic injury in the kidney is not well defined. Material and Methods: In this study we have used an animal model of sepsis induced by injection of bacterial lipopolysaccharide (LPS in the rat and measured renal nitric oxide by X-band electron paramagnetic resonance (EPR spectroscopy using the spin trap Fe2+-N-methyl-D-glucamine dithiocarbamate [Fe(MGD2] given by intravenous injection 6 minutes before sacrifice. Results: The characteristic EPR spectrum of [Fe(NO(MGD2] was observed in kidneys of rats treated with LPS for 5h. Rat kidneys subjected to 20 min ischaemia and 5 min reperfusion had lower concentrations of [Fe(NO(MGD2] (1.0 ± 0.6 (M compared to the contralateral nonischaemic kidneys (1.5 ± 0.9 (M, P<0.05. Conclusion: This study shows reduced levels of NO after renal ischaemia in vivo.

  4. Matrix isolation and EPR spectroscopy of septet 3,5-difluoropyridyl-2,4,6-trinitrene.

    Science.gov (United States)

    Chapyshev, Sergei V; Grote, Dirk; Finke, Christopher; Sander, Wolfram

    2008-09-19

    Septet 3,5-difluoropyridyl-2,4,6-trinitrene along with quintet 2-azido-3,5-difluoropyridyl-4,6-dinitrene, quintet 4-azido-3,5-difluoropyridyl-2,6-dinitrene, triplet 2,6-diazido-3,5-difluoropyridyl-4-nitrene, and triplet 2,4-diazido-3,5-difluoropyridyl-6-nitrene have been obtained by photolysis of 2,4,6-triazido-3,5-difluoropyridine in solid argon at 4 K. The electronic and magnetic properties of the matrix-isolated nitrenes were studied using electron paramagnetic resonance (EPR) spectroscopy in combination with density functional theory (DFT) calculations. The fine-structure parameters of the nitrenes were determined with high accuracy from computer spectral simulations. All signals in the EPR spectra of the nitrenes randomly oriented in the solid phase were unambiguously assigned on the basis of eigenfield calculations of the Zeeman energy levels and angular dependencies of resonance fields from the direction of the applied magnetic field.

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

    Science.gov (United States)

    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.

  6. The influence of additives on beer stability investigated by EPR spectroscopy

    Science.gov (United States)

    Brezová, Vlasta; Polovka, Martin; Staško, Andrej

    2002-04-01

    In thermally-accelerated aging followed by EPR spectroscopy of beer samples of various stabilities, free radical 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPOL) was shown to be an effective indicator of the breakdown of a sample's stability, comparable to the commonly used spin trapping agent α-phenyl- N- tert-butylnitrone (PBN). Both indicators were then employed to investigate the influence of additives on beer stability. The addition of L-ascorbic acid (ASC) to the beer samples accelerated the radical processes and a lower stability was found. DL-α-tocopherol (α-TOC) did not influence beer stability significantly (probably due to its limited solubility). Na 2SO 3, described as a very effective stabilizer in experiments with the PBN spin trap, was found not to be effective using the TEMPOL indicator. This is probably due to inhibition in the formation of spin adducts or their degradation by Na 2SO 3.

  7. Thermodynamic Basis of Electron Transfer in Dihydroorotate Dehydrogenase B from Lactococcus lactis:  Analysis by Potentiometry, EPR Spectroscopy, and ENDOR Spectroscopy

    DEFF Research Database (Denmark)

    Mohnsen, Al-Walid A.; Rigby, Stephen E. J.; Jensen, Kaj Frank

    2004-01-01

    Dihydroorotate dehydrogenase B (DHODB) is a complex iron-sulfur flavoprotein that catalyzes the conversion of dihydroorotate to orotate and the reduction of NAD+. The enzyme is a dimer of heterodimers containing an FMN, an FAD, and a 2Fe-2S center. UV-visible, EPR, and ENDOR spectroscopies have...... similar to those recorded for the blue semiquinone of free flavins in aqueous solution, thus confirming the presence of this species in DHODB. Spectral features observed during EPR spectroscopy of dithionite-reduced DHODB are consistent with the midpoint reduction potentials determined using UV-visible...

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

    Science.gov (United States)

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

    2012-01-01

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

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

    Science.gov (United States)

    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.

  10. Adsorption-desorption induced structural changes of Cu-MOF evidenced by solid state NMR and EPR spectroscopy.

    Science.gov (United States)

    Jiang, Yijiao; Huang, Jun; Kasumaj, Besnik; Jeschke, Gunnar; Hunger, Michael; Mallat, Tamas; Baiker, Alfons

    2009-02-18

    Adsorption-desorption induced structural changes of Cu(bpy)(H(2)O)(2)(BF(4)),(bpy) (bpy = 4,4'-bipyridine) [Cu-MOF] have been evidenced by combined NMR and EPR spectroscopy. Upon adsorption of probe molecules even at a few mbar, EPR spectra show that they are activated to form complexes at Cu(II) sites, which results in a change of the Cu-MOF's structure as indicated by a high-field shift of the (11)B MAS NMR. After desorption, both EPR and (11)B MAS NMR spectra evidenced that the structure of the Cu-MOF reversibly shifted to the original state. This observation indicates that MOFs can undergo structural changes during processes where adsorption-desorption steps are involved such as gas storage, separation, and catalysis.

  11. A comparison of antioxidative capacities of fruit juices, drinks and nectars, as determined by EPR and UV-vis spectroscopies.

    Science.gov (United States)

    Bartoszek, Mariola; Polak, Justyna

    2016-01-15

    The differences in the Trolox Equivalent Antioxidant Capacity (TEAC) values at the same incubation time obtained by two different techniques: electron paramagnetic resonance (EPR) spectroscopy and ultraviolet visible (UV-vis) spectroscopy, which use the same antioxidant-free radical reaction mechanism, were determined for fruit juices, nectars and drinks. For this study, the stable free radical 1,1-Diphenyl-2-picryl-hydrazyl (DPPH(•)) was used. The antioxidant capacity was presented in Trolox Equivalents, e.g., μM trolox per 100 ml of sample. All of the studied fruit juices, drinks and nectars showed antioxidative properties. Dependencies between TEAC values and the percent fruit content and sample color were observed for the studied beverages. It was found that EPR spectroscopy is the more adequate method for determining TEAC values for these kinds of samples.

  12. The structure and function of quinones in biological solar energy transduction: a cyclic voltammetry, EPR, and hyperfine sub-level correlation (HYSCORE) spectroscopy study of model naphthoquinones.

    Science.gov (United States)

    Coates, Christopher S; Ziegler, Jessica; Manz, Katherine; Good, Jacob; Kang, Bernard; Milikisiyants, Sergey; Chatterjee, Ruchira; Hao, Sijie; Golbeck, John H; Lakshmi, K V

    2013-06-20

    Quinones function as electron transport cofactors in photosynthesis and cellular respiration. The versatility and functional diversity of quinones is primarily due to the diverse midpoint potentials that are tuned by the substituent effects and interactions with surrounding amino acid residues in the binding site in the protein. In the present study, a library of substituted 1,4-naphthoquinones are analyzed by cyclic voltammetry in both protic and aprotic solvents to determine effects of substituent groups and hydrogen bonds on the midpoint potential. We use continuous-wave electron paramagnetic resonance (EPR) spectroscopy to determine the influence of substituent groups on the electronic properties of the 1,4-naphthoquinone models in an aprotic solvent. The results establish a correlation between the presence of substituent group(s) and the modification of electronic properties and a corresponding shift in the midpoint potential of the naphthoquinone models. Further, we use pulsed EPR spectroscopy to determine the effect of substituent groups on the strength and planarity of the hydrogen bonds of naphthoquinone models in a protic solvent. This study provides support for the tuning of the electronic properties of quinone cofactors by the influence of substituent groups and hydrogen bonding interactions.

  13. Conformational Analysis of the Partially Disordered Measles Virus NTAIL-XD Complex by SDSL EPR Spectroscopy

    Science.gov (United States)

    Kavalenka, Aleh; Urbančič, Iztok; Belle, Valérie; Rouger, Sabrina; Costanzo, Stéphanie; Kure, Sandra; Fournel, André; Longhi, Sonia; Guigliarelli, Bruno; Strancar, Janez

    2010-01-01

    To characterize the structure of dynamic protein systems, such as partly disordered protein complexes, we propose a novel approach that relies on a combination of site-directed spin-labeled electron paramagnetic resonance spectroscopy and modeling of local rotation conformational spaces. We applied this approach to the intrinsically disordered C-terminal domain of the measles virus nucleoprotein (NTAIL) both free and in complex with the X domain (XD, aa 459–507) of the viral phosphoprotein. By comparing measured and modeled temperature-dependent restrictions of the side-chain conformational spaces of 12 SL cysteine-substituted NTAIL variants, we showed that the 490–500 region of NTAIL is prestructured in the absence of the partner, and were able to quantitatively estimate, for the first time to our knowledge, the extent of the α-helical sampling of the free form. In addition, we showed that the 505–525 region of NTAIL conserves a significant degree of freedom even in the bound form. The latter two findings provide a mechanistic explanation for the reported rather high affinity of the NTAIL-XD binding reaction. Due to the nanosecond timescale of X-band EPR spectroscopy, we were also able to monitor the disordering in the 488–525 region of NTAIL, in particular the unfolding of the α-helical region when the temperature was increased from 281 K to 310 K. PMID:20303863

  14. Application of EPR spectroscopy to examine free radicals evolution during storage of the thermally sterilized Ungentum ophthalmicum.

    Science.gov (United States)

    Ramos, Paweł; Pilawa, Barbara

    2016-06-24

    Free radicals formed during thermal sterilization of the Ungentum ophthalmicum were examined by an X-band EPR spectroscopy. The influence of storage time (15 min; 1, 2 and 3 days after heating) on free radical properties and concentrations in this sample was determined. Thermal sterilization was done according to the pharmaceutical norms. The first-derivative EPR spectra with g-values about 2 were measured with magnetic modulation of 100 kHz in the range of microwave power 2.2-70 mW. The changes of amplitudes (A) and linewidths (ΔBpp) with microwave powers were evaluated. Free radicals in concentration ∼10(17) spin/g were formed during heating of the tested Ungentum. Free radical concentration decreased with increase in storage time, and reached values ∼10(17) spin/g after 3 days from sterilization. The tested U. ophthalmicum should not be sterilized at a temperature of 160 °C because of the free radicals formation, or it should be used 3 days after heating, when free radicals were considerably quenched. Free radical properties remain unchanged during storage of the Ungentum. The EPR lines of the U. ophthalmicum were homogeneously broadened and their linewidths (ΔBpp) increased with increase in microwave power. EPR spectroscopy is useful to examine free radicals to optimize sterilization process and storage conditions of ophthalmologic samples.

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

    Energy Technology Data Exchange (ETDEWEB)

    Bahar, N; Roberts, K; Stabile, F; Mongillo, N; Decker, RD; Wilson, LD; Husain, Z; Contessa, J; Carlson, DJ [Yale University School of Medicine, New Haven, Connecticut (United States); Williams, BB; Flood, AB; Swartz, HM [Geisel Medical School at Dartmouth University, Hanover, New Hampshire (United States)

    2015-06-15

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

  16. In Vivo Imaging of Tissue Physiological Function using EPR Spectroscopy | NCI Technology Transfer Center | TTC

    Science.gov (United States)

    Electron paramagnetic resonance (EPR) is a technique for studying chemical species that have one or more unpaired electrons.  The current invention describes Echo-based Single Point Imaging (ESPI), a novel EPR image formation strategy that allows in vivo imaging of physiological function.  The National Cancer Institute's Radiation Biology Branch is seeking statements of capability or interest from parties interested in in-licensing an in vivo imaging using Electron paramagnetic resonance (EPR) to measure active oxygen species.

  17. Pulsed EPR/ENDOR characterization of perturbations of the Cu(A) center ground state by axial methionine ligand mutations.

    Science.gov (United States)

    Slutter, C E; Gromov, I; Epel, B; Pecht, I; Richards, J H; Goldfarb, D

    2001-06-01

    The effect of axial ligand mutation on the Cu(A) site in the recombinant water soluble fragment of subunit II of Thermus thermophilus cytochrome c oxidase ba(3) has been investigated. The weak methionine ligand was replaced by glutamate and glutamine which are stronger ligands. Two constructs, M160T0 and M160T9, that differ in the length of the peptide were prepared. M160T0 is the original soluble fragment construct of cytochrome ba(3) that encodes 135 amino acids of subunit II, omitting the transmembrane helix that anchors the domain in the membrane. In M160T9 nine C-terminal amino acids are missing, including one histidine. The latter has been used to reduce the amount of a secondary T2 copper which is most probably coordinated to a surface histidine in M160T0. The changes in the spin density in the Cu(A) site, as manifested by the hyperfine couplings of the weakly and strongly coupled nitrogens, and of the cysteine beta-protons, were followed using a combination of advanced EPR techniques. X-band ( approximately 9 GHz) electron-spin-echo envelope modulation (ESEEM) and two-dimensional (2D) hyperfine sublevel correlation (HYSCORE) spectroscopy were employed to measure the weakly coupled (14)N nuclei, and X- and W-band (95 GHz) pulsed electron-nuclear double resonance (ENDOR) spectroscopy for probing the strongly coupled (14)N nuclei and the beta-protons. The high field measurements were extremely useful as they allowed us to resolve the T2 and Cu(A) signals in the g( perpendicular) region and gave (1)H ENDOR spectra free of overlapping (14)N signals. The effects of the M160Q and M160E mutations were: (i) increase in A( parallel)((63,65)Cu), (ii) larger hyperfine coupling of the weakly coupled backbone nitrogen of C153, (iii) reduction in the isotropic hyperfine interaction, a(iso), of some of the beta-protons making them more similar, (iv) the a(iso) value of one of the remote nitrogens of the histidine residues is decreased, thus distinguishing the two

  18. Utilizing NMR and EPR spectroscopy to probe the role of copper in prion diseases

    KAUST Repository

    Emwas, Abdul-Hamid M.

    2013-02-24

    Copper is an essential nutrient for the normal development of the brain and nervous system, although the hallmark of several neurological diseases is a change in copper concentrations in the brain and central nervous system. Prion protein (PrP) is a copper-binding, cell-surface glycoprotein that exists in two alternatively folded conformations: a normal isoform (PrPC) and a disease-associated isoform (PrPSc). Prion diseases are a group of lethal neurodegenerative disorders that develop as a result of conformational conversion of PrPC into PrPSc. The pathogenic mechanism that triggers this conformational transformation with the subsequent development of prion diseases remains unclear. It has, however, been shown repeatedly that copper plays a significant functional role in the conformational conversion of prion proteins. In this review, we focus on current research that seeks to clarify the conformational changes associated with prion diseases and the role of copper in this mechanism, with emphasis on the latest applications of NMR and EPR spectroscopy to probe the interactions of copper with prion proteins. Copyright © 2013 John Wiley & Sons, Ltd.

  19. Fe (III - Galactomannan Solid and Aqueous Complexes: Potentiometric, EPR Spectroscopy and Thermal Data

    Directory of Open Access Journals (Sweden)

    Mercê Ana L. R.

    2001-01-01

    Full Text Available Galactomannans can be employed in food industries to modify the final rheological properties of the products. Since they are not absorbed by the living organisms they can also be used in dietary foods. The equilibria involving the interactions of Fe(III and galactomannans and arabinogalactan of several leguminous plants were characterized by potentiometric titrations and EPR spectroscopy. The log of the equilibrium constants for the formation of ML species, where M is the metal ion and L is the monomeric unit of the biopolymers, were 15.4, 14.1 and 18.5, for the galactomannans of C. fastuosa, L. leucocephala and S. macranthera, respectively. Log K values for protonated species (MHL were 3.1, 3.3, and were not detected for the galactomannan of S. macranthera. The log K values for the formation of ML2 were 14.1, 13.3 and 15.2, respectively. Early formation of insoluble products in the equilibrium with arabinogalactan and Fe(III prevented acquisition of reliable data. The solid complexes assays showed a great dipolar interaction between two Fe(III ions in the inner structure of the biopolymer which increased as the degree of substitution of the galactomannan decreased, and also showed the resulting thermal stability. The complexes impart a new possibility of providing essential metal ions in dietary foods since decomplexation of the complexes can occur at different pH values existing in the human body.

  20. Application of EPR Spectroscopy to Examination of the Effect of Sterilization Process on Free Radicals in Different Herbs.

    Science.gov (United States)

    Pawłowska-Góral, Katarzyna; Ramos, Paweł; Pilawa, Barbara; Kurzeja, Ewa

    2013-03-01

    Free radicals in the original and sterilized caraway, curry, curcuma and cardamom were studied. An X-band (9.3 GHz) electron paramagnetic resonance (EPR) spectroscopy was the experimental technique. Effect of microwave power in the range of 2.2-70 mW on amplitudes, linewidths, and lineshape parameters of the EPR spectra was tested. Free radicals concentrations in the non- and sterilized herb samples were compared. The aim of this work was to determine properties and concentration of free radicals in steam sterilized caraway, curry, curcuma and cardamom. It was pointed out that free radicals (~10(18) spin/g) exist in both the original and sterilized herbs. Complex free radical system with oxygen and carbon paramagnetic centers characterizes the examined herbs. Homogeneously dipolar broadened EPR spectra were measured for all the tested herbs. Slow spin-lattice relaxation processes exist in the examined samples. Practical usefulness of EPR method in food technology was discussed.

  1. Pulsed EPR Spin-probe study of intracellular glasses in seed and pollen

    NARCIS (Netherlands)

    Buitink, J.; Dzuba, S.A.; Hoekstra, F.A.; Tsvetkov, Y.D.

    2000-01-01

    EPR spectra of 3-carboxy-proxyl (CP) in dry biological tissues exhibited a temperature-dependent change in the principal value A′zz of the hyperfine interaction tensor. The A′zz value changed sharply at a particular temperature that was dependent on water content. At elevated water contents, the bre

  2. Arsenic speciation in synthetic gypsum (CaSO4·2H2O): A synchrotron XAS, single-crystal EPR, and pulsed ENDOR study

    Science.gov (United States)

    Lin, Jinru; Chen, Ning; Nilges, Mark J.; Pan, Yuanming

    2013-04-01

    Gypsum (CaSO4·2H2O) is a major by-product of mining and milling processes of borate, phosphate and uranium deposits worldwide and, therefore, potentially plays an important role in the stability and bioavailability of heavy metalloids, including As, in tailings and surrounding areas. Gypsum containing 1900 and 185 ppm As, synthesized with Na2HAsO4·7H2O and NaAsO2 in the starting materials, respectively, have been investigated by synchrotron X-ray absorption spectroscopy (XAS), single-crystal electron paramagnetic resonance spectroscopy (EPR), and pulsed electron nuclear double resonance spectroscopy (ENDOR). Quantitative analyses of As K edge XANES and EXAFS spectra show that arsenic occurs in both +3 and +5 oxidation states and the As3+/As5+ value varies from 0.35 to 0.79. Single-crystal EPR spectra of gamma-ray-irradiated gypsum reveal two types of arsenic-associated oxyradicals: [AsO3]2- and an [AsO2]2-. The [AsO3]2- center is characterized by principal 75As hyperfine coupling constants of A1 = 1952.0(2) MHz, A2 = 1492.6(2) MHz and A3 = 1488.7(2) MHz, with the unique A axis along the S-O1 bond direction, and contains complex 1H superhyperfine structures that have been determined by pulsed ENDOR. These results suggest that the [AsO3]2- center formed from electron trapping on the central As5+ ion of a substitutional (AsO4)3- group after removal of an O1 atom. The [AsO2]2- center is characterized by its unique A(75As) axis approximately perpendicular to the O1-S-O2 plane and the A2 axis along the S-O2 bond direction, consistent with electron trapping on the central As3+ ion of a substitutional (AsO3)3- group after removal of an O2 atom. These results confirm lattice-bound As5+ and As3+ in gypsum and point to potential application of this mineral for immobilization and removal of arsenic pollution.

  3. Investigating fatty acids inserted into magnetically aligned phospholipid bilayers using EPR and solid-state NMR spectroscopy

    Science.gov (United States)

    Nusair, Nisreen A.; Tiburu, Elvis K.; Dave, Paresh C.; Lorigan, Gary A.

    2004-06-01

    This is the first time 2H solid-state NMR spectroscopy and spin-labeled EPR spectroscopy have been utilized to probe the structural orientation and dynamics of a stearic acid incorporated into magnetically aligned phospholipid bilayers or bicelles. The data gleaned from the two different techniques provide a more complete description of the bilayer membrane system. Both methods provided similar qualitative information on the phospholipid bilayer, high order, and low motion for the hydrocarbon segment close to the carboxyl groups of the stearic acid and less order and more rapid motion at the end towards the terminal methyl groups. However, the segmental order parameters differed markedly due to the different orientations that the nitroxide and C-D bond axes transform with the various stearic acid acyl chain conformations, and because of the difference in dynamic sensitivity between NMR and EPR over the timescales examined. 5-, 7-, 12-, and 16-doxylstearic acids spin-labels were used in the EPR experiments and stearic acid-d 35 was used in the solid-state NMR experiments. The influence of the addition of cholesterol and the variation of temperature on the fatty acid hydrocarbon chain ordering in the DMPC/DHPC phospholipid bilayers was also studied. Cholesterol increased the degree of ordering of the hydrocarbon chains. Conversely, as the temperature of the magnetically aligned phospholipid bilayers increased, the order parameters decreased due to the higher random motion of the acyl chain of the stearic acid. The results indicate that magnetically aligned phospholipid bilayers are an excellent model membrane system and can be used for both NMR and EPR studies.

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

    Science.gov (United States)

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

    2017-07-01

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

  5. Chirped Pulse Microwave Spectroscopy in Pulsed Uniform Supersonic Flows

    Science.gov (United States)

    Abeysekera, Chamara; Oldham, James; Prozument, Kirill; Joalland, Baptiste; Park, Barratt; Field, Robert W.; Sims, Ian; Suits, Arthur; Zack, Lindsay

    2014-06-01

    We present preliminary results describing the development of a new instrument that combines two powerful techniques: Chirped Pulse-Fourier Transform MicroWave (CP-FTMW) spectroscopy and pulsed uniform supersonic flows. It promises a nearly universal detection method that can deliver quantitative isomer, conformer, and vibrational level specific detection, characterization of unstable reaction products and intermediates and perform unique spectroscopic, kinetics and dynamics measurements. We have constructed a new high-power K_a-band, 26-40 GHz, chirped pulse spectrometer with sub-MHz resolution, analogous to the revolutionary CP-FTMW spectroscopic technique developed in the Pate group at University of Virginia. In order to study smaller molecules, the E-band, 60-90 GHz, CP capability was added to our spectrometer. A novel strategy for generating uniform supersonic flow through a Laval nozzle is introduced. High throughput pulsed piezo-valve is used to produce cold (30 K) uniform flow with large volumes of 150 cm^3 and densities of 1014 molecules/cm3 with modest pumping facilities. The uniform flow conditions for a variety of noble gases extend as far as 20 cm from the Laval nozzle and a single compound turbo-molecular pump maintains the operating pressure. Two competing design considerations are critical to the performance of the system: a low temperature flow is needed to maximize the population difference between rotational levels, and high gas number densities are needed to ensure rapid cooling to achieve the uniform flow conditions. At the same time, collision times shorter than the chirp duration will give inaccurate intensities and reduced signal levels due to collisional dephasing of free induction decay. Details of the instrument and future directions and challenges will be discussed.

  6. EPR-based distance measurements at ambient temperature

    Science.gov (United States)

    Krumkacheva, Olesya; Bagryanskaya, Elena

    2017-07-01

    Pulsed dipolar (PD) EPR spectroscopy is a powerful technique allowing for distance measurements between spin labels in the range of 2.5-10.0 nm. It was proposed more than 30 years ago, and nowadays is widely used in biophysics and materials science. Until recently, PD EPR experiments were limited to cryogenic temperatures (T relaxation enhancement; RE). In this paper, we review the features of PD EPR and RE at ambient temperatures, in particular, requirements on electron spin phase memory time, ways of immobilization of biomolecules, the influence of a linker between the spin probe and biomolecule, and future opportunities.

  7. EPR Spectroscopy of Different Sol Concentration Synthesized Nanocrystalline-ZnO Thin Films

    Directory of Open Access Journals (Sweden)

    Manju Arora

    2015-01-01

    Full Text Available Nanocrystalline zinc oxide (nc-ZnO thin films were grown on p-type silicon substrate through spin coating by sol-gel process using different sol concentrations (10 wt.%, 15 wt.%, and 25 wt.%. These films were characterized by high resolution nondestructive X-ray diffraction (XRD, scanning electron microscopy (SEM with energy dispersive X-ray analysis (EDS attachment, and electron paramagnetic resonance (EPR techniques to understand variations in structural, morphological, and oxygen vacancy with respect to sol concentration. The film surface morphology changes from nanowall to nanorods on increasing sol concentration. EPR spectra revealed the systematic variation from ferromagnetic to paramagnetic nature in these nc-ZnO films. The broad EPR resonance signal arising from the strong dipolar-dipolar interactions among impurity defects present in nc-ZnO film deposited from 10 wt.% sol has been observed and a single strong narrow resonance signal pertaining to oxygen vacancies is obtained in 25 wt.% sol derived nc-ZnO film. The concentrations of impurity defects and oxygen vacancies are evaluated from EPR spectra, necessary for efficient optoelectronic devices development.

  8. EPR spectroscopy and its use in planta - a promising technique to disentangle the origin of specific ROS

    Directory of Open Access Journals (Sweden)

    Anja eSteffen-Heins

    2015-03-01

    Full Text Available While it is widely accepted that reactive oxygen species (ROS are common players in developmental processes and a large number of adaptations to abiotic and biotic stresses in plants, we still do not know a lot about ROS level control at cellular or organelle level. One major problem that makes ROS hard to quantify and even to identify is their short lifetime. A promising technique that helps to understand ROS level control in planta is the electron paramagnetic resonance (EPR spectroscopy. Application of the spin trapping method and the spin probe technique by this advanced method enables the quantification and identification of specific ROS in different plant tissues, cells or organelles or under different conditions. This mini review summarizes the knowledge using EPR spectroscopy as a method for ROS detection in plants under different stress conditions or during development. This technique allows disentangling the origin of specific ROS and transient alteration in ROS levels that occur by changes in ROS production and scavenging.

  9. Nickelacyclic-cobaltocene vs. nickelacyclic-nickelocene. Synthesis, X-ray structures, electron transfer activity, EPR spectroscopy, and theoretical calculations.

    Science.gov (United States)

    Buchalski, Piotr; Kamińska, Elzbieta; Piwowar, Katarzyna; Suwińska, Kinga; Jerzykiewicz, Lucjan; Rossi, Fulvio; Laschi, Franco; de Biani, Fabrizia Fabrizi; Zanello, Piero

    2009-06-01

    Reactions of 9-nickelafluorenyllithium with cobalt and nickel pentamethylcyclopentadienyl-acetylacetonates resulted in the formation of the novel nickelacyclic-cobaltocene 2 and nickelacyclic-nickelocene 3, respectively, in which the central metal atom is bonded to the nickelafluorenyl ring. On the basis of their redox propensity, compounds 2 and 3 were oxidized to the corresponding monocations [2](+) and [3](+). The crystal and molecular structures of both the redox couples were determined by single-crystal X-ray analysis. In spite of their structural similarity, they display a rather different electron transfer ability. To throw light on such an aspect, the pertinent redox couples have been examined by EPR spectroscopy and the nature of the frontier orbitals involved in the redox activity of the neutral precursors has been supported by extended Huckel theoretical calculations.

  10. Protonated paramagnetic redox forms of di-o-quinone bridged with p-phenylene-extended TTF: A EPR spectroscopy study

    Directory of Open Access Journals (Sweden)

    Nikolay O. Chalkov

    2016-11-01

    Full Text Available The chemical oxidation and reduction processes of deprotonated, direduced o-quinone-exTTF-o-quinone in protic solvents were studied by EPR spectroscopy. The formation of relatively stable paramagnetic protonated redox forms of the parent triad was very surprising. The character of spin-density distribution in the semiquinone–quinone and semiquinone–catechol redox forms indicates that the p-phenylene-extended tetrathiafulvalene connector provides a quite effective electronic communication channel between dioxolene coordination sites. It was found that the deprotonated, direduced o-quinone-exTTF-o-quinone is capable to reduction of the metal copper in solution. The radical anion species formed in this reaction exists in solution as a solvent-separated ion pair with a copper cation. A character of spin-density distribution in a radical anion species leads to the conclusion that the ligand corresponds to type III of the Robin–Day classification.

  11. Heavy-ion-induced sucrose radicals investigated using EPR and UV spectroscopy.

    Science.gov (United States)

    Nakagawa, Kouichi; Karakirova, Yordanka; Yordanov, Nicola D

    2015-05-01

    The potential use of a sucrose dosimeter for estimating both linear energy transfer (LET) and the absorbed dose of heavy ion and X-ray radiation was investigated. The stable free radicals were produced when sucrose was irradiated with heavy ions, such as helium, carbon, silicon and neon ions, and when the X-ray radiation was similar to the obtained electron paramagnetic resonance (EPR) spectra, which were ∼7 mT wide and composed of several hyperfine structures. In addition, the total spin concentration resulting from heavy-ion irradiation increased linearly as the absorbed dose increased, and decreased logarithmically as the LET increased. These empirical relations imply that the LET at a certain dose can be determined from the spin concentration. For sucrose and alanine, both cross-sections following C-ion irradiation with a 50 Gy dose were ∼1.3 × 10(-12) [μm(2)], taking into account the molecular size of the samples. The values of these cross-sections imply that multiple ionizing particles were involved in the production of stable radicals. Furthermore, UV absorbance at 267 nm of an aqueous solution of irradiated sucrose was found to linearly increase with increasing absorbed dose. Therefore, the EPR and UV results suggest that sucrose can be a useful dosimeter for heavy-ion irradiation.

  12. Temporal resolution beyond the average pulse duration in shaped noisy-pulse transient absorption spectroscopy.

    Science.gov (United States)

    Meyer, Kristina; Müller, Niklas; Liu, Zuoye; Pfeifer, Thomas

    2016-12-20

    In time-resolved spectroscopy, it is a widespread belief that the temporal resolution is determined by the laser pulse duration. Recently, it was observed and shown that partially coherent laser pulses as they are provided by free-electron-laser (FEL) sources offer an alternative route to reach a temporal resolution below the average pulse duration. Here, we demonstrate the generation of partially coherent light in the laboratory like we observe it at FELs. We present the successful implementation of such statistically fluctuating pulses by using the pulse-shaping technique. These pulses exhibit an average pulse duration about 10 times larger than their bandwidth limit. The shaped pulses are then applied to transient-absorption measurements in the dye IR144. Despite the noisy characteristics of the laser pulses, features in the measured absorption spectra occurring on time scales much faster than the average pulse duration are resolved, thus proving the universality of the described noisy-pulse concept.

  13. Comparison of parabolic filtration methods for 3D filtered back projection in pulsed EPR imaging.

    Science.gov (United States)

    Qiao, Zhiwei; Redler, Gage; Epel, Boris; Halpern, Howard J

    2014-11-01

    Pulse electron paramagnetic resonance imaging (Pulse EPRI) is a robust method for noninvasively measuring local oxygen concentrations in vivo. For 3D tomographic EPRI, the most commonly used reconstruction algorithm is filtered back projection (FBP), in which the parabolic filtration process strongly influences image quality. In this work, we designed and compared 7 parabolic filtration methods to reconstruct both simulated and real phantoms. To evaluate these methods, we designed 3 error criteria and 1 spatial resolution criterion. It was determined that the 2 point derivative filtration method and the two-ramp-filter method have unavoidable negative effects resulting in diminished spatial resolution and increased artifacts respectively. For the noiseless phantom the rectangular-window parabolic filtration method and sinc-window parabolic filtration method were found to be optimal, providing high spatial resolution and small errors. In the presence of noise, the 3 point derivative method and Hamming-window parabolic filtration method resulted in the best compromise between low image noise and high spatial resolution. The 3 point derivative method is faster than Hamming-window parabolic filtration method, so we conclude that the 3 point derivative method is optimal for 3D FBP. Copyright © 2014. Published by Elsevier Inc.

  14. EPR spectrum of the Y@C82 metallofullerene isolated in solid argon matrix: hyperfine structure from EPR spectroscopy and relativistic DFT calculations.

    Science.gov (United States)

    Misochko, Eugenii Ya; Akimov, Alexander V; Belov, Vasilii A; Tyurin, Daniil A; Bubnov, Vyacheslav P; Kareev, Ivan E; Yagubskii, Eduard B

    2010-08-21

    The EPR spectrum of the Y@C(82) molecules isolated in solid argon matrix was recorded for the first time at a temperature of 5 K. The isotropic hyperfine coupling constant (hfcc) A(iso) = 0.12 +/- 0.02 mT on the nucleus (89)Y as derived from the EPR spectrum is found in more than two times greater than that obtained in previous EPR measurements in liquid solutions. Comparison of the measured hfcc on a metal atom with that predicted by density-functional theory calculations (PBE/L22) indicate that relativistic method provides good agreement between experiment in solid argon and theory. Analysis of the DFT calculated dipole-dipole hf-interaction tensor and electron spin distribution in the endometallofullerenes with encaged group 3 metal atoms Sc, Y and La has been performed. It shows that spin density on the scandium atom represents the Sc d(yz) orbital lying in the symmetry plane of the C(2v) fullerene isomer and interacting with two carbon atoms located in the para-position on the fullerene hexagon. In contrast, the configuration of electron spin density on the heavier atoms, Y and La, is associated with the hybridized orbital formed by interaction of the metal d(yz) and p(y) electronic orbitals.

  15. EPR and Mössbauer spectroscopy of intact mitochondria isolated from Yah1p-depleted Saccharomyces cerevisiae.

    Science.gov (United States)

    Miao, Ren; Martinho, Marlène; Morales, Jessica Garber; Kim, Hansoo; Ellis, E Ann; Lill, Roland; Hendrich, Michael P; Münck, Eckard; Lindahl, Paul A

    2008-09-16

    Yah1p, an [Fe 2S 2]-containing ferredoxin located in the matrix of Saccharomyces cerevisiae mitochondria, functions in the synthesis of Fe/S clusters and heme a prosthetic groups. EPR, Mossbauer spectroscopy, and electron microscopy were used to characterize the Fe that accumulates in Yah1p-depleted isolated intact mitochondria. Gal- YAH1 cells were grown in standard rich media (YPD and YPGal) under O 2 or argon atmospheres. Mitochondria were isolated anaerobically, then prepared in the as-isolated redox state, the dithionite-treated state, and the O 2-treated state. The absence of strong EPR signals from Fe/S clusters when Yah1p was depleted confirms that Yah1p is required in Fe/S cluster assembly. Yah1p-depleted mitochondria, grown with O 2 bubbling through the media, accumulated excess Fe (up to 10 mM) that was present as 2-4 nm diameter ferric nanoparticles, similar to those observed in mitochondria from yfh1Delta cells. These particles yielded a broad isotropic EPR signal centered around g = 2, characteristic of superparamagnetic relaxation. Treatment with dithionite caused Fe (3+) ions of the nanoparticles to become reduced and largely exported from the mitochondria. Fe did not accumulate in mitochondria isolated from cells grown under Ar; a significant portion of the Fe in these organelles was in the high-spin Fe (2+) state. This suggests that the O 2 used during growth of Gal- YAH1 cells is responsible, either directly or indirectly, for Fe accumulation and for oxidizing Fe (2+) --> Fe (3+) prior to aggregation. Models are proposed in which the accumulation of ferric nanoparticles is caused either by the absence of a ligand that prevents such precipitation in wild-type mitochondria or by a more oxidizing environment within the mitochondria of Yah1p-depleted cells exposed to O 2. The efficacy of reducing accumulated Fe along with chelating it should be considered as a strategy for its removal in diseases involving such accumulations.

  16. Irradiation free radicals in freshwater crayfish Astacus leptodactylus Esch investigated by EPR spectroscopy

    Science.gov (United States)

    Bercu, V.; Negut, C. D.; Duliu, O. G.

    2017-04-01

    The free radicals of irradiated crayfish Astaculs leptodactylus cuticle were studied by X-band electron paramagnetic resonance. The kinetic behaviour as well as the thermal stability of the radiation-induced free radicals in crayfish cuticle were investigated by means of both isothermal and isochronal annealing. Both short, presumable juvenile and long, mature exemplars of freshwater crayfish were investigated. Only the long exemplars cuticle displayed the presence of Mn2+ ions, very similar to those reported for Mn2+ ions in calcite. The 200 °C isothermal annealing studies attested the existence of a multitude of radical species, some of them being generated during the first minutes of thermal treatment and then partially of totally vanishing. Regardless these peculiarities, the EPR spectrum of 15 kGy irradiated cuticle showed remarkable time stability, its amplitude decreasing with about 18% after more than 16 months of storage at room temperature. The implications of these observations regarding the diversity of irradiation free radicals as well as their suitability to identify gamma radiation decontamination treatment are discussed.

  17. High-Precision Spectroscopy with Counter-Propagating Femtosecond Pulses

    CERN Document Server

    Barmes, Itan; Eikema, Kjeld S E

    2013-01-01

    An experimental realization of high-precision direct frequency comb spectroscopy using counter-propagating femtosecond pulses on two-photon atomic transitions is presented. Doppler broadened background signal, hampering precision spectroscopy with ultrashort pulses, is effectively eliminated with a simple pulse shaping method. As a result, all four 5S-7S two-photon transitions in a rubidium vapor are determined with both statistical and systematic uncertainties below 10$^{-11}$, which is an order of magnitude better than previous experiments on these transitions.

  18. Photoinduced electron transfer between 2-methylanthraquinone and triethylamine in an ionic liquid: Time-resolved EPR and transient absorption spectroscopy study

    Science.gov (United States)

    Zhu, Guanglai; Wang, Yu; Fu, Haiying; Xu, Xinsheng; Cui, Zhifeng; Ji, Xuehan; Wu, Guozhong

    2015-02-01

    Photoinduced electron transfer between 2-methylanthraquinone (MeAQ) and triethylamine (TEA) in a room-temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), was investigated by comparing the time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy and the transient absorption spectroscopy. The results of TR-EPR spectroscopy, in which MeAQ was 8 mmol L-1 and TEA was 150 mmol L-1, indicated that the transient radical would exist longer time in [bmim][PF6] than in acetonitrile. At the delay time of 8 μs after laser excitation, the TR-EPR signal transformed from an emissive peak into an absorptive peak when the experiment was performed in [bmim][PF6]. The results of the transient absorption spectroscopy, in which MeAQ was 0.1 mmol L-1 and TEA was 2.2 mmol L-1, showed that the efficiency and the rate of the photoinduced electron transfer reaction in [bmim][PF6] were obviously lower than that in acetonitrile. It was concluded that various factors, such as concentration, viscosity and local structural transformation of the solution, have an influence on the process of photoinduced electron transfer in [bmim][PF6].

  19. Photoinduced electron transfer between 2-methylanthraquinone and triethylamine in an ionic liquid: time-resolved EPR and transient absorption spectroscopy study.

    Science.gov (United States)

    Zhu, Guanglai; Wang, Yu; Fu, Haiying; Xu, Xinsheng; Cui, Zhifeng; Ji, Xuehan; Wu, Guozhong

    2015-02-25

    Photoinduced electron transfer between 2-methylanthraquinone (MeAQ) and triethylamine (TEA) in a room-temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), was investigated by comparing the time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy and the transient absorption spectroscopy. The results of TR-EPR spectroscopy, in which MeAQ was 8 mmol L(-1) and TEA was 150 mmol L(-1), indicated that the transient radical would exist longer time in [bmim][PF6] than in acetonitrile. At the delay time of 8 μs after laser excitation, the TR-EPR signal transformed from an emissive peak into an absorptive peak when the experiment was performed in [bmim][PF6]. The results of the transient absorption spectroscopy, in which MeAQ was 0.1 mmol L(-1) and TEA was 2.2 mmol L(-1), showed that the efficiency and the rate of the photoinduced electron transfer reaction in [bmim][PF6] were obviously lower than that in acetonitrile. It was concluded that various factors, such as concentration, viscosity and local structural transformation of the solution, have an influence on the process of photoinduced electron transfer in [bmim][PF6].

  20. Ramsey-comb spectroscopy with intense ultrashort laser pulses

    CERN Document Server

    Morgenweg, Jonas; Eikema, Kjeld S E

    2014-01-01

    Optical frequency combs based on mode-locked lasers have revolutionised the field of metrology and precision spectroscopy by providing precisely calibrated optical frequencies and coherent pulse trains. Amplification of the pulsed output from these lasers is very desirable, as nonlinear processes can then be employed to cover a much wider range of transitions and wavelengths for ultra-high precision, direct frequency comb spectroscopy. Therefore full repetition rate laser amplifiers and enhancement resonators have been employed to produce up to microjoule-level pulse energies. Here we show that the full frequency comb accuracy and resolution can be obtained by using only two frequency comb pulses amplified to the millijoule pulse energy level, orders of magnitude more energetic than what has previously been possible. The novel properties of this approach, such as cancellation of optical light-shift effects, is demonstrated on weak two-photon transitions in atomic rubidium and caesium, thereby improving the fr...

  1. Single-pulse stimulated Raman scattering spectroscopy

    CERN Document Server

    Frostig, Hadas; Natan, Adi; Silberberg, Yaron

    2010-01-01

    We demonstrate the acquisition of stimulated Raman scattering spectra with the use of a single femtosecond pulse. High resolution vibrational spectra are obtained by shifting the phase of a narrow band of frequencies in the broadband input pulse spectrum, using spectral shaping. The vibrational spectrum is resolved by examining the amplitude features formed in the spectrum after interaction with the sample. Using this technique, low frequency Raman lines (<100cm^-1) are resolved in a straightforward manner.

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

    DEFF Research Database (Denmark)

    Murugesan; Cook; Devasahayam

    1997-01-01

    Imaging of free radicals by electron paramagnetic resonance (EPR) spectroscopy using time domain acquisition as in nuclear magnetic resonance (NMR) has not been attempted because of the short spin-spin relaxation times, typically under 1 μs, of most biologically relevant paramagnetic species...... to minimize motional artifacts from cardiac and lung motion that cause significant problems in frequency-domain spectral acquisition, such as in continuous wave (cw) EPR techniques...

  3. Identification of Fe3+-Li+ complexes in ZnO by means of high-frequency EPR/ENDOR spectroscopy

    Science.gov (United States)

    Kutin, Yu. S.; Mamin, G. V.; Orlinskii, S. B.

    2013-12-01

    Theoretical prediction of a high Curie temperature in ZnO doped with Mn, Fe, and other transition metals has stimulated the investigation of these materials by many research groups. Although charge-compensated Fe3+ centers in ZnO:Fe have been observed by means of EPR and have been known for decades, conclusions on the chemical nature of these defects are still contradictory. Originally, these centers were treated as Fe3+-Li+ complexes with both ions occupying adjacent cationic sites. Recently, however, the centers were interpreted as a substitutional Fe3+ ion with a vacancy at an adjacent zinc or oxygen site (Fe-VZn or Fe-VO). In order to determine the chemical nature of the impurity associated with Fe3+, electron-nuclear double resonance (ENDOR) spectroscopy was used. ENDOR measurements reveal NMR transitions corresponding to nuclei with g-factor gN = 2.171 and spin I = 3/2. This unambiguously shows presence of Li as a charge compensator and also resolves contradictions with the theoretical prediction of the Fe-VO formation energy. The electric field gradients at the 7Li nuclei (within the Fe3+-Li+ complexes) were estimated to be significantly lower than the gradient at undistorted Zn sites.

  4. Conformational analysis of the partially disordered measles virus N(TAIL)-XD complex by SDSL EPR spectroscopy.

    Science.gov (United States)

    Kavalenka, Aleh; Urbancic, Iztok; Belle, Valérie; Rouger, Sabrina; Costanzo, Stéphanie; Kure, Sandra; Fournel, André; Longhi, Sonia; Guigliarelli, Bruno; Strancar, Janez

    2010-03-17

    To characterize the structure of dynamic protein systems, such as partly disordered protein complexes, we propose a novel approach that relies on a combination of site-directed spin-labeled electron paramagnetic resonance spectroscopy and modeling of local rotation conformational spaces. We applied this approach to the intrinsically disordered C-terminal domain of the measles virus nucleoprotein (N(TAIL)) both free and in complex with the X domain (XD, aa 459-507) of the viral phosphoprotein. By comparing measured and modeled temperature-dependent restrictions of the side-chain conformational spaces of 12 SL cysteine-substituted N(TAIL) variants, we showed that the 490-500 region of N(TAIL) is prestructured in the absence of the partner, and were able to quantitatively estimate, for the first time to our knowledge, the extent of the alpha-helical sampling of the free form. In addition, we showed that the 505-525 region of N(TAIL) conserves a significant degree of freedom even in the bound form. The latter two findings provide a mechanistic explanation for the reported rather high affinity of the N(TAIL)-XD binding reaction. Due to the nanosecond timescale of X-band EPR spectroscopy, we were also able to monitor the disordering in the 488-525 region of N(TAIL), in particular the unfolding of the alpha-helical region when the temperature was increased from 281 K to 310 K. Copyright 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  5. The EPR reactor; Le reacteur EPR

    Energy Technology Data Exchange (ETDEWEB)

    Lacoste, A.C.; Dupuy, Ph.; Gupta, O.; Perez, J.R.; Emond, D. [Direction Generale de la Surete Nucleaire et de la Radioprotection, 75 - Paris (France); Cererino, G.; Rousseau, J.M.; Jeffroy, F.; Evrard, J.M. [Institut de Radioprotection et de Surete Nucleaire (IRSN), Dir. de la Surete des Reacteurs, 92 - Clamart (France); Seiler, J.M. [CEA Cadarache (DEN/DTN), 13 - Saint-Paul-lez-Durance (France); Azarian, G. [FRAMATOME ANP, 92 - Paris-La-Defence (France); Chaumont, B. [Institut de Radioprotection et de Surete Nucleaire (IRSN/DSR), 92 - Fontenay-aux-Roses (France); Dubail, A. [Electricite de France (EDF), 78 - Chatou (France); Fischer, M. [Framatome ANP GmbH, Erlangen (Germany); Tiippana, P.; Hyvarinen, J. [Stuk, Autorite de Surete Nucleaire et de Radioprotection (Finland); Zaleski, C.P.; Meritet, S. [Paris-9 Univ. Dauphine, Centre de Geopolitique de l' Energie et des Matieres Premieres, 75 (France); Iglesias, F.; Vincent, C. [Direction Generale de l' Energie et des Matieres Premieres, 75 - Paris (France); Massart, S.; Graillat, G. [Electricite de France (EDF), 75 - Paris (France); Esteve, B. [AREVA/Framatome, 75 - Paris (France); Mansillon, Y. [Commission Nationale de Debat Public, 75 - Paris (France); Gatinol, C. [Assemblee Nationale, 75 - Paris (France); Carre, F. [CEA, Dir. de Programme Systemes du Futur, France (France)

    2005-05-01

    This document reviews economical and environmental aspects of the EPR project. The following topics are discussed: role and point of view of the French Nuclear Safety Authority on EPR, control of design and manufacturing of EPR by the French Nuclear Safety Authority, assessment by IRSN of EPR safety, research and development in support of EPR, STUK safety review of EPR design, standpoint on EPR, the place of EPR in the French energy policy, the place of EPR in EDF strategy, EPR spearhead of nuclear rebirth, the public debate, the local stakes concerning the building of EPR in France at Flamanville (Manche) and the research on fourth generation reactors. (A.L.B.)

  6. Multifrequency EPR Spectroscopy: A Toolkit for the Characterization of Mono- and Di-nuclear Metal Ion Centers in Complex Biological Systems

    Science.gov (United States)

    Hanson, Graeme R.

    Metalloenzymes are ubiquitous in nature containing complex metal ion cofactors intimately involved in the enzymes' biological function. The application of multifrequency continuous wave and orientation selective pulsed EPR in conjunction with computer simulation and density functional theory calculations has proven to be a powerful toolkit for the geometric and electronic structural characterization of these metal ion cofactors in the resting enzyme, enzyme-substrate and -product complexes, which in turn provides a detailed understanding of the enzymes' catalytic mechanism. In this chapter, a brief description of the multifrequency EPR toolkit used to structurally (geometric and electronic) characterize metal ion binding sites in complex biological systems and its application in the structural characterization of (i) molybdenum containing enzymes and model complexes, (ii) mono- and di-nuclear copper(II) cyclic peptide complexes (marine and synthetic analogues) and (iii) dinuclear metal ion centers in purple acid phosphatases will be presented.

  7. COMPLIS: COllinear spectroscopy Measurements using a Pulsed Laser Ion Source

    CERN Multimedia

    2002-01-01

    A Pulsed Laser spectroscopy experiment has been installed for the study of hyperfine structure and isotope shift of refractory and daughter elements from ISOLDE beams. It includes decelerated ion-implantation, element-selective laser ionization, magnetic and time-of-flight mass separation. The laser spectroscopy has been performed on the desorbed atoms in a set-up at ISOLDE-3 but later on high resolution laser collinear spectroscopy with the secondary pulsed ion beam is planned for the Booster ISOLDE set-up. During the first operation time of ISOLDE-3 we restricted our experiments to Doppler-limited resonant ionization laser and $\\gamma$-$\\gamma$ nuclear spectroscopy on neutron deficient platinum isotopes of even mass number down to A~=~186 and A~=~179 respectively. These isotopes have been produced by implantation of radioactive Hg and their subsequent $\\beta$-decay.

  8. Physical characterization of the state of motion of the phenalenyl spin probe in cation-exchanged faujasite zeolite supercages with pulsed EPR

    Science.gov (United States)

    Doetschman, D. C.; Dwyer, D. W.; Fox, J. D.; Frederick, C. K.; Scull, S.; Thomas, G. D.; Utterback, S. G.; Wei, J.

    1994-08-01

    The molecular motion of the phenalenyl (PNL) spin probe in the supercages of cation-exchanged X and Y zeolites (faujasites) has been physically characterized by pulsed and continuous wave (CW) electron paramagnetic resonance (EPR). Both X and Y zeolites, whose cation sites were exchanged with the alkali metal ions, Li +, Na +, K +, Rb + and Cs + were examined. There is a good correspondence between the temperature dependences of the PNL electron spin phase memory time and the CW EPR spectra. Both display evidence of a thermal activation from a stationary, non-rotating molecular state to a low-temperature state of in-plane rotation (Das et al., Chem Phys. 143 (1990) 253). The rate of in-plane rotation is an activated process, with E* | / R=1289 |+- 35 K and 1462 ± 47 K in NaX and KX zeolites, respectively. The rotation appears to be about an axis along which the half-filled, non-bonding π orbital interacts with the exchanged cation in the supercage. Both CW and pulsed EPR also show a higher temperature activation from the in-plane rotating state to an effectively isoptropic state of rotation of PNL in which the PNL-cation bond is thought to be broken, with E* ⊥ / R=2050 ± 110 K, 1956 ± 46K, 1335 ± 97 K in LiX, NaX and KX zeolites, respectively. The strength of the PNL-cation bonding decreases with increasing cation atomic number as indicated by E* ⊥ and the peripheral repulsion (crowding) of PNL increases with cation size as indicated E* |. There are qualitative indications that the binding of PNL to the cations in the Y zeolite is stronger than in the X zeolite.

  9. Laser induced breakdown spectroscopy with picosecond pulse train

    Science.gov (United States)

    Lednev, Vasily N.; Pershin, Sergey M.; Sdvizhenskii, Pavel A.; Grishin, Mikhail Ya; Davydov, Mikhail A.; Stavertiy, Anton Ya; Tretyakov, Roman S.

    2017-02-01

    Picosecond pulse train and nanosecond pulse were compared for laser ablation and laser induced breakdown spectroscopy (LIBS) measurements. A detailed study revealed that the picosecond pulse train ablation improved the quality of laser craters (symmetric crater walls and the absence of large redeposited droplets), which was explained by a smaller heat affected zone and suppression of melt splash. Greater plasma dimensions and brighter plasma emission were observed by gated imaging for picosecond pulse train compared to nanosecond pulse ablation. Increased intensity of atomic and ionic lines in gated and time integrated spectra provided better signal-to-noise ratio for picosecond pulse train sampling. Higher temperature and electron density were detected during first microsecond for the plasma induced by the picosecond pulse train. Improved shot-to-shot reproducibility for atomic/ionic line intensity in the case of picosecond pulse train LIBS was explained by more effective atomization of target material in plasma and better quality of laser craters. Improved precision and limits of detections were determined for picosecond pulse train LIBS due to better reproducibility of laser sampling and increased signal-to-noise ratio.

  10. Electron paramagnetic resonance (EPR) spectroscopy characterization of wheat grains from plants of different water stress tolerance.

    Science.gov (United States)

    Łabanowska, Maria; Filek, Maria; Kurdziel, Magdalena; Bednarska, Elżbieta; Dłubacz, Aleksandra; Hartikainen, Helina

    2012-09-01

    Grains of five genotypes of wheat (four Polish and one Finnish), differing in their tolerance to drought stress were chosen for this investigation. Electron paramagnetic resonance spectroscopy allowed observation of transition metal ions (Mn, Fe, Cu) and different types of stable radicals, including semiquinone centers, present in seed coats, as well as several types of carbohydrate radicals found mainly in the inner parts of grains. The content of paramagnetic metal centers was higher in sensitive genotypes (Radunia, Raweta) than in tolerant ones (Parabola, Nawra), whereas the Finnish genotype (Manu) exhibited intermediate amounts. Similarly, the concentrations of both types of radicals, carbohydrates and semiquinone were significantly higher in the grains originating from more sensitive wheat genotypes. The nature of carbohydrate radicals and their concentrations were confronted with the kinds and amounts of sugars found by the biochemical analyses and microscopy observations. It is suggested that some long lived radicals (semiquinone and starch radicals) occurring in grains could be indicators of stress resistance of wheat plants.

  11. Pulsed cavity ring-down spectroscopy in combustion environments

    NARCIS (Netherlands)

    Evertsen, Rogier

    2002-01-01

    This thesis gives an introduction to pulsed cavity ring-down absorption spectroscopy (CRDS) and its application in combustion research. Experimental results have been compared to numerical simulations, providing a means to validate reaction mechanisms and numerical approaches. Up to now, the

  12. Detection of diamond in ore using pulsed laser Raman spectroscopy

    CSIR Research Space (South Africa)

    Lamprecht, GH

    2007-10-01

    Full Text Available The viability of using pulsed laser excited Raman spectroscopy as a method for diamond detection from ore, has been investigated. In this method the spontaneous Stokes Raman signal is used as indicator of diamond, and a dual channel system...

  13. Localization of dexamethasone within dendritic core-multishell (CMS) nanoparticles and skin penetration properties studied by multi-frequency electron paramagnetic resonance (EPR) spectroscopy.

    Science.gov (United States)

    Saeidpour, S; Lohan, S B; Anske, M; Unbehauen, M; Fleige, E; Haag, R; Meinke, M C; Bittl, R; Teutloff, C

    2016-10-15

    The skin and especially the stratum corneum (SC) act as a barrier and protect epidermal cells and thus the whole body against xenobiotica of the external environment. Topical skin treatment requires an efficient drug delivery system (DDS). Polymer-based nanocarriers represent novel transport vehicles for dermal application of drugs. In this study dendritic core-multishell (CMS) nanoparticles were investigated as promising candidates. CMS nanoparticles were loaded with a drug (analogue) and were applied to penetration studies of skin. We determined by dual-frequency electron paramagnetic resonance (EPR) how dexamethasone (Dx) labelled with 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (PCA) is associated with the CMS. The micro-environment of the drug loaded to CMS nanoparticles was investigated by pulsed high-field EPR at cryogenic temperature, making use of the fact that magnetic parameters (g-, A-matrices, and spin-lattice relaxation time) represent specific probes for the micro-environment. Additionally, the rotational correlation time of spin-labelled Dx was probed by continuous wave EPR at ambient temperature, which provides independent information on the drug environment. Furthermore, the penetration depth of Dx into the stratum corneum of porcine skin after different topical applications was investigated. The location of Dx in the CMS nanoparticles is revealed and the function of CMS as penetration enhancers for topical application is shown.

  14. Photodissociation of Isoxazole and Pyridine Studied Using Chirped Pulse Microwave Spectroscopy in Pulsed Uniform Supersonic Flows

    Science.gov (United States)

    Ariyasingha, Nuwandi M.; Joalland, Baptiste; Mebel, Alexander M.; Suits, Arthur

    2016-06-01

    Chirped - Pulse Fourier-transform microwave spectroscopy in uniform supersonic flows (Chirped- Pulse/Uniform Flow: CPUF) has been applied to study the photodissociation of two atmospherically relevant N containing heterocyclic compounds; pyridine and isoxazole. Products were detected using rotational spectroscopy. HC3N, HCN were observed for pyridine and CH3CN, HCO and HCN were observed for isoxazole and we report the first detection of HNC for both of the systems. Key points in potential energy surface were explored and compared with the experimental observations. Branching ratios were calculated for all the possible channels and will be presented.

  15. Optimally shaped narrowband picosecond pulses for femtosecond stimulated Raman spectroscopy.

    Science.gov (United States)

    Hoffman, David P; Valley, David; Ellis, Scott R; Creelman, Mark; Mathies, Richard A

    2013-09-09

    A comparison between a Fabry-Pérot etalon filter and a conventional grating filter for producing the picosecond (ps) Raman pump pulses for femtosecond stimulated Raman spectroscopy (FSRS) is presented. It is shown that for pulses of equal energy the etalon filter produces Raman signals twice as large as that of the grating filter while suppressing the electronically resonant background signal. The time asymmetric profile of the etalon-generated pulse is shown to be responsible for both of these observations. A theoretical discussion is presented which quantitatively supports this hypothesis. It is concluded that etalons are the ideal method for the generation of narrowband ps pulses for FSRS because of the optical simplicity, efficiency, improved FSRS intensity and reduced backgrounds.

  16. EPR spectroscopy of a clinically active (1:2) copper(II)-histidine complex used in the treatment of Menkes disease: a Fourier transform analysis of a fluid CW-EPR spectrum.

    Science.gov (United States)

    Gala, Lukas; Lawson, Michael; Jomova, Klaudia; Zelenicky, Lubomir; Congradyova, Andrea; Mazur, Milan; Valko, Marian

    2014-01-15

    Redox active transition metal ions (e.g., iron and copper) have been implicated in the etiology of many oxidative stress-related diseases including also neurodegenerative disorders. Unbound copper can catalyze formation of reactive oxygen species (hydroxyl radicals) via Fenton reaction/Haber-Weiss chemistry and therefore, under physiological conditions, free copper is potentially toxic and very rarely exists inside cells. Copper(II) bound to the aminoacid L-histidine represents a species discovered in blood in the mid 60s and since then extensive research on this complex was carried out. Copper bound to L-histidine represents an exchangeable pool of copper(II) in equilibrium with the most abundant blood plasma protein, human serum albumin. The structure of this complex, in aqueous solution, has been a subject of many studies and reviews, however without convincing success. The significance of the (1:2) copper(II)-L-histidine complex at physiological pH documents its therapeutic applications in the treatment of Menkes disease and more recently in the treatment of infantile hypertrophic cardioencephalomyopathy. While recently the (1:2) Cu(II)-L-His complex has been successfully crystallized and the crystal structure was solved by X-ray diffraction, the structure of the complex in fluid solution at physiological pH is not satisfactorily known. The aim of this paper is to study the (1:2) Cu(II)-L-histidine complex at low temperatures by X-band and S-band EPR spectroscopy and at physiological pH at room temperature by Fourier transform CW-EPR spectroscopy.

  17. EPR Spectroscopy of a Clinically Active (1:2 Copper(II-Histidine Complex Used in the Treatment of Menkes Disease: A Fourier Transform Analysis of a Fluid CW-EPR Spectrum

    Directory of Open Access Journals (Sweden)

    Lukas Gala

    2014-01-01

    Full Text Available Redox active transition metal ions (e.g., iron and copper have been implicated in the etiology of many oxidative stress-related diseases including also neurodegenerative disorders. Unbound copper can catalyze formation of reactive oxygen species (hydroxyl radicals via Fenton reaction/Haber–Weiss chemistry and therefore, under physiological conditions, free copper is potentially toxic and very rarely exists inside cells. Copper(II bound to the aminoacid L-histidine represents a species discovered in blood in the mid 60s and since then extensive research on this complex was carried out. Copper bound to L-histidine represents an exchangeable pool of copper(II in equilibrium with the most abundant blood plasma protein, human serum albumin. The structure of this complex, in aqueous solution, has been a subject of many studies and reviews, however without convincing success. The significance of the (1:2 copper(II-L-histidine complex at physiological pH documents its therapeutic applications in the treatment of Menkes disease and more recently in the treatment of infantile hypertrophic cardioencephalomyopathy. While recently the (1:2 Cu(II-L-His complex has been successfully crystallized and the crystal structure was solved by X-ray diffraction, the structure of the complex in fluid solution at physiological pH is not satisfactorily known. The aim of this paper is to study the (1:2 Cu(II-L-histidine complex at low temperatures by X-band and S-band EPR spectroscopy and at physiological pH at room temperature by Fourier transform CW-EPR spectroscopy.

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

    DEFF Research Database (Denmark)

    Marsh, Derek

    2016-01-01

    Nuclear relaxation is a sensitive monitor of rotational dynamics in spin-label EPR. It also contributes competing saturation transfer pathways in T1-exchange spectroscopy, and the determination of paramagnetic relaxation enhancement in site-directed spin labelling. A survey shows that the definit......Nuclear relaxation is a sensitive monitor of rotational dynamics in spin-label EPR. It also contributes competing saturation transfer pathways in T1-exchange spectroscopy, and the determination of paramagnetic relaxation enhancement in site-directed spin labelling. A survey shows...... that the definition of nitrogen nuclear relaxation rate Wn commonly used in the CW-EPR literature for 14N-nitroxyl spin labels is inconsistent with that currently adopted in time-resolved EPR measurements of saturation recovery. Redefinition of the normalised 14N spin-lattice relaxation rate, b = Wn/(2We), preserves...... the expressions used for CW-EPR, whilst rendering them consistent with expressions for saturation recovery rates in pulsed EPR. Furthermore, values routinely quoted for nuclear relaxation times that are deduced from EPR spectral diffusion rates in 14N-nitroxyl spin labels do not accord with conventional analysis...

  19. Encoded loop-lanthanide-binding tags for long-range distance measurements in proteins by NMR and EPR spectroscopy.

    Science.gov (United States)

    Barthelmes, Dominic; Gränz, Markus; Barthelmes, Katja; Allen, Karen N; Imperiali, Barbara; Prisner, Thomas; Schwalbe, Harald

    2015-11-01

    We recently engineered encodable lanthanide binding tags (LBTs) into proteins and demonstrated their applicability in Nuclear Magnetic Resonance (NMR) spectroscopy, X-ray crystallography and luminescence studies. Here, we engineered two-loop-LBTs into the model protein interleukin-1β (IL1β) and measured (1)H, (15)N-pseudocontact shifts (PCSs) by NMR spectroscopy. We determined the Δχ-tensors associated with each Tm(3+)-loaded loop-LBT and show that the experimental PCSs yield structural information at the interface between the two metal ion centers at atomic resolution. Such information is very valuable for the determination of the sites of interfaces in protein-protein-complexes. Combining the experimental PCSs of the two-loop-LBT construct IL1β-S2R2 and the respective single-loop-LBT constructs IL1β-S2, IL1β-R2 we additionally determined the distance between the metal ion centers. Further, we explore the use of two-loop LBTs loaded with Gd(3+) as a novel tool for distance determination by Electron Paramagnetic Resonance spectroscopy and show the NMR-derived distances to be remarkably consistent with distances derived from Pulsed Electron-Electron Dipolar Resonance.

  20. A tunable general purpose Q-band resonator for CW and pulse EPR/ENDOR experiments with large sample access and optical excitation

    Science.gov (United States)

    Reijerse, Edward; Lendzian, Friedhelm; Isaacson, Roger; Lubitz, Wolfgang

    2012-01-01

    We describe a frequency tunable Q-band cavity (34 GHz) designed for CW and pulse Electron Paramagnetic Resonance (EPR) as well as Electron Nuclear Double Resonance (ENDOR) and Electron Electron Double Resonance (ELDOR) experiments. The TE 011 cylindrical resonator is machined either from brass or from graphite (which is subsequently gold plated), to improve the penetration of the 100 kHz field modulation signal. The (self-supporting) ENDOR coil consists of four 0.8 mm silver posts at 2.67 mm distance from the cavity center axis, penetrating through the plunger heads. It is very robust and immune to mechanical vibrations. The coil is electrically shielded to enable CW ENDOR experiments with high RF power (500 W). The top plunger of the cavity is movable and allows a frequency tuning of ±2 GHz. In our setup the standard operation frequency is 34.0 GHz. The microwaves are coupled into the resonator through an iris in the cylinder wall and matching is accomplished by a sliding short in the coupling waveguide. Optical excitation of the sample is enabled through slits in the cavity wall (transmission ˜60%). The resonator accepts 3 mm o.d. sample tubes. This leads to a favorable sensitivity especially for pulse EPR experiments of low concentration biological samples. The probehead dimensions are compatible with that of Bruker flexline Q-band resonators and it fits perfectly into an Oxford CF935 Helium flow cryostat (4-300 K). It is demonstrated that, due to the relatively large active sample volume (20-30 μl), the described resonator has superior concentration sensitivity as compared to commercial pulse Q-band resonators. The quality factor ( Q L) of the resonator can be varied between 2600 (critical coupling) and 1300 (over-coupling). The shortest achieved π/2-pulse durations are 20 ns using a 3 W microwave amplifier. ENDOR (RF) π-pulses of 20 μs ( 1H @ 51 MHz) were obtained for a 300 W amplifier and 7 μs using a 2500 W amplifier. Selected applications of the

  1. Electronic Structure of ZnO Quantum Dots studied by High-frequency EPR, ESE, ENDOR and ODMR Spectroscopy

    NARCIS (Netherlands)

    Baranov, P.G.; Romanov, N.G.; Bundakova, A.P.; de Mello-Donega, Celso; Schmidt, J.

    2016-01-01

    High-frequency electron paramagnetic resonance (EPR), electron spin echo (ESE), electron-nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) were applied for the investigation of the electronic properties of ZnO colloidal quantum dots (QDs) which consist of a ZnO

  2. Electronic Structure of ZnO Quantum Dots studied by High-frequency EPR, ESE, ENDOR and ODMR Spectroscopy

    NARCIS (Netherlands)

    Baranov, P.G.; Romanov, N.G.; Bundakova, A.P.; de Mello-Donega, Celso; Schmidt, J.

    2016-01-01

    High-frequency electron paramagnetic resonance (EPR), electron spin echo (ESE), electron-nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) were applied for the investigation of the electronic properties of ZnO colloidal quantum dots (QDs) which consist of a ZnO nanocr

  3. 3D printed sample holder for in-operando EPR spectroscopy on high temperature polymer electrolyte fuel cells.

    Science.gov (United States)

    Niemöller, Arvid; Jakes, Peter; Kayser, Steffen; Lin, Yu; Lehnert, Werner; Granwehr, Josef

    2016-08-01

    Electrochemical cells contain electrically conductive components, which causes various problems if such a cell is analyzed during operation in an EPR resonator. The optimum cell design strongly depends on the application and it is necessary to make certain compromises that need to be individually arranged. Rapid prototyping presents a straightforward option to implement a variable cell design that can be easily adapted to changing requirements. In this communication, it is demonstrated that sample containers produced by 3D printing are suitable for EPR applications, with a particular emphasis on electrochemical applications. The housing of a high temperature polymer electrolyte fuel cell (HT-PEFC) with a phosphoric acid doped polybenzimidazole membrane was prepared from polycarbonate by 3D printing. Using a custom glass Dewar, this fuel cell could be operated at temperatures up to 140°C in a standard EPR cavity. The carbon-based gas diffusion layer showed an EPR signal with a characteristic Dysonian line shape, whose evolution could be monitored in-operando in a non-invasive manner.

  4. 3D printed sample holder for in-operando EPR spectroscopy on high temperature polymer electrolyte fuel cells

    Science.gov (United States)

    Niemöller, Arvid; Jakes, Peter; Kayser, Steffen; Lin, Yu; Lehnert, Werner; Granwehr, Josef

    2016-08-01

    Electrochemical cells contain electrically conductive components, which causes various problems if such a cell is analyzed during operation in an EPR resonator. The optimum cell design strongly depends on the application and it is necessary to make certain compromises that need to be individually arranged. Rapid prototyping presents a straightforward option to implement a variable cell design that can be easily adapted to changing requirements. In this communication, it is demonstrated that sample containers produced by 3D printing are suitable for EPR applications, with a particular emphasis on electrochemical applications. The housing of a high temperature polymer electrolyte fuel cell (HT-PEFC) with a phosphoric acid doped polybenzimidazole membrane was prepared from polycarbonate by 3D printing. Using a custom glass Dewar, this fuel cell could be operated at temperatures up to 140 °C in a standard EPR cavity. The carbon-based gas diffusion layer showed an EPR signal with a characteristic Dysonian line shape, whose evolution could be monitored in-operando in a non-invasive manner.

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

    Science.gov (United States)

    Marsh, Derek

    2016-11-01

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

  6. Cysteine, thiourea and thiocyanate interactions with clays: FT-IR, Mössbauer and EPR spectroscopy and X-ray diffractometry studies.

    Science.gov (United States)

    de Santana, Henrique; Paesano, Andrea; da Costa, Antonio C S; di Mauro, Eduardo; de Souza, Ivan G; Ivashita, Flávio F; de Souza, Cláudio M D; Zaia, Cássia T B V; Zaia, Dimas A M

    2010-04-01

    The present study examined the adsorption of cysteine, thiourea and thiocyanate on bentonite and montmorillonite at two different pHs (3.00, 8.00). The conditions used here are closer to those of prebiotic earth. As shown by FT-IR, Mössbauer and EPR spectroscopy and X-ray diffractometry, the most important finding of this work is that cysteine and thiourea penetrate into the interlayer of the clays and reduce Fe(3+) to Fe(2+), and as consequence, cystine and c,c'-dithiodiformamidinium ion are formed. This mechanism resembles that which occurs with aconitase. This is a very important result for prebiotic chemistry; we should think about clays not just sink of molecules, but as primitive vessels of production of biomolecules. At pH 8.00, an increasing expansion was observed in the following order for both minerals: thiourea > thiocyanate > cysteine. At pH 3.00, the same order was not observed and thiourea had an opposite behavior, being the compound producing the lowest expansion. Mössbauer spectroscopy showed that at pH 8.00, the proportion of Fe(2+) ions in bentonite increased, doubling for thiourea, or more than doubling for cysteine, in both clays. However, at pH 3.00, cysteine and thiourea did not change significantly the relative amount of Fe(2+) and Fe(3+) ions, when compared to clays without adsorption. For thiocyanate, the amount of Fe(2+) produced was independent of the pH or clay used, probably because the interlayers of clays are very acidic and HSCN formed does not reduce Fe(3+) to Fe(2+). For the interaction of thiocyanate with the clays, it was not possible to identify any potential compound formed. For the samples of bentonite and montmorillonite at pH 8.00 with cysteine, EPR spectroscopy showed that intensity of the lines due to Fe(3+) decreased because the reaction of Fe(3+)/cysteine. Intensity of EPR lines did not change when the samples of bentonite at pH 3.00 with and without cysteine were compared. These results are in accordance with those

  7. Cpuf: Chirped-Pulse Microwave Spectroscopy in Pulsed Uniform Supersonic Flows

    Science.gov (United States)

    Suits, Arthur; Abeysekera, Chamara; Zack, Lindsay N.; Joalland, Baptiste; Ariyasingha, Nuwandi M.; Park, Barratt; Field, Robert W.; Sims, Ian

    2015-06-01

    Chirped-pulse Fourier-transform microwave spectroscopy has stimulated a resurgence of interest in rotational spectroscopy owing to the dramatic reduction in spectral acquisition time it enjoys when compared to cavity-based instruments. This suggests that it might be possible to adapt the method to study chemical reaction dynamics and even chemical kinetics using rotational spectroscopy. The great advantage of this would be clear, quantifiable spectroscopic signatures for polyatomic products as well as the possibility to identify and characterize new radical reaction products and transient intermediates. To achieve this, however, several conditions must be met: 1) products must be thermalized at low temperature to maximize the population difference needed to achieve adequate signal levels and to permit product quantification based on the rotational line strength; 2) a large density and volume of reaction products is also needed to achieve adequate signal levels; and 3) for kinetics studies, a uniform density and temperature is needed throughout the course of the reaction. These conditions are all happily met by the uniform supersonic flow produced from a Laval nozzle expansion. In collaboration with the Field group at MIT we have developed a new instrument we term a CPUF (Chirped-pulse/Uniform Flow) spectrometer in which we can study reaction dynamics, photochemistry and kinetics using broadband microwave and millimeter wave spectroscopy as a product probe. We will illustrate the performance of the system with a few examples of photodissociation and reaction dynamics, and also discuss a number of challenges unique to the application of chirped-pulse microwave spectroscopy in the collisional environment of the flow. Future directions and opportunities for application of CPUF will also be explored.

  8. Applications of digital pulse processing in nuclear spectroscopy

    CERN Document Server

    Grzywacz, R

    2003-01-01

    Data acquisition systems for nuclear spectroscopy have traditionally been based on hybrid systems with analog shaping amplifiers followed by analog-to-digital converters. Recently, however, new systems based on digital signal processing concepts have been developed. For example, one specific design, the Digital Gamma Finder (DGF-4C), has been used extensively for particle- and gamma-spectroscopy of nuclei far from stability. Using the DGF-4C, a variety of data acquisition systems have been implemented and used for measurements with semiconductor and scintillator detectors at recoil separators like the RMS at ORNL, the FRS at GSI and LISE at GANIL. Some novel features and unique advantages, such as trigger-less operation and pulse shape recording, are discussed in the context of selected studies.

  9. Ferric haem forms of Mycobacterium tuberculosis catalase-peroxidase probed by EPR spectroscopy: Their stability and interplay with pH.

    Science.gov (United States)

    Svistunenko, Dimitri A; Worrall, Jonathan A R; Chugh, Snehpriya B; Haigh, Sarah C; Ghiladi, Reza A; Nicholls, Peter

    2012-06-01

    Low temperature EPR spectroscopy was used to characterise Mycobacterium tuberculosis catalase-peroxidase in its resting ferric haem state. Several high spin ferric haem forms and no low spin forms were found in the enzyme samples frozen in methanol on dry ice. The EPR spectra depended not only on the pH but also on the buffer type. As a general trend, the higher the pH, the greater the 'rhombic' fraction of the high spin ferric haem that was observed. The rhombic form was characterised by well separated two lines in the g = 6 region whereas in the 'axial' form the two lines overlap. This pH dependence of the equilibrium of axial and rhombic ferric haem forms is also seen in rapidly freeze-quenched samples. Different high spin ferric haem forms were monitored during a 3 week storage of the enzyme at 4 °C. For some forms, extremal dependences, i.e. those progressing via maxima or minima over storage time, were found. This indicates that the mechanism of the time-dependent transition from one high spin ferric haem form to another must be more complex than a simple single site oxidation.

  10. Continuous wave W- and D-Band EPR spectroscopy offer “sweet-spots” for characterizing conformational changes and dynamics in intrinsically disordered proteins

    Energy Technology Data Exchange (ETDEWEB)

    Casey, Thomas M.; Liu, Zhanglong; Esquiaqui, Jackie M.; Pirman, Natasha L.; Milshteyn, Eugene; Fanucci, Gail E., E-mail: fanucci@chem.ufl.edu

    2014-07-18

    Highlights: • W- and D-Band line shapes are sensitive to motions in the 0.1–2 ns time regime. • These frequencies effectively report on conformational dynamics of IDPs. • W-band spectra reflecting helical formation in IA{sub 3} is experimentally demonstrated. - Abstract: Site-directed spin labeling (SDSL) electron paramagnetic resonance (EPR) spectroscopy is a powerful tool for characterizing conformational sampling and dynamics in biological macromolecules. Here we demonstrate that nitroxide spectra collected at frequencies higher than X-band (∼9.5 GHz) have sensitivity to the timescale of motion sampled by highly dynamic intrinsically disordered proteins (IDPs). The 68 amino acid protein IA{sub 3}, was spin-labeled at two distinct sites and a comparison of X-band, Q-band (35 GHz) and W-band (95 GHz) spectra are shown for this protein as it undergoes the helical transition chemically induced by tri-fluoroethanol. Experimental spectra at W-band showed pronounced line shape dispersion corresponding to a change in correlation time from ∼0.3 ns (unstructured) to ∼0.6 ns (α-helical) as indicated by comparison with simulations. Experimental and simulated spectra at X- and Q-bands showed minimal dispersion over this range, illustrating the utility of SDSL EPR at higher frequencies for characterizing structural transitions and dynamics in IDPs.

  11. Redox reactions and the influence of natural Mn oxides on Cr oxidation in a contaminated site in northern Italy: evidence from Cr stable-isotopes and EPR spectroscopy

    Directory of Open Access Journals (Sweden)

    Marafatto F. F.

    2013-04-01

    Full Text Available Hexavalent chromium-contaminated groundwaters and sediments in northern Italy have been studied using the Cr stable-isotope systematics and electron spin resonance spectroscopy (ESR, in order to explore redox changes and soil-groundwater interactions. The isotopic data indicate a possible Cr(VI source released into the environment from an industrial plant. EPR spectra on the sediments which constitute the aquifers show a broad asymmetric absorption due to coupled Fe(III and coupled Cr(III ions and a well resolved hyperfine structure due to manganese ions, resulting from Mn(IV and Mn(II. The isotopic and EPR data support the hypothesis of Cr(III being oxidized by Mn oxides which are widespread in the aquifer, possibly related to the oscillation of the phreatic level. The obtained results highlight the usefulness of chromium stable isotopes as environmental tracers and support the observations that naturally occurring Mn oxides in soils may catalize Cr oxidation from the stable Cr(III form to the toxic Cr(VI soluble form, yielding valuable information in planning remediation interventions.

  12. Identification of the sites of chlorophyll triplet quenching in relation to the structure of LHC-II from higher plants. Evidence from EPR spectroscopy.

    Science.gov (United States)

    Di Valentin, Marilena; Biasibetti, Federico; Ceola, Stefano; Carbonera, Donatella

    2009-10-01

    The Chlorophyll a (Chl a) molecules involved in the triplet-triplet energy transfer to the central luteins in trimeric LHC-II are identified by time-resolved and pulse EPR techniques. The concept of spin angular momentum conservation during triplet-triplet energy transfer is exploited for the calculation of the spin polarization of the carotenoid triplet states. The sites with the highest probability of forming triplet states, which are quenched by the central luteins, result to be Chl603 and Chl612. "Unquenched" Chl triplet states are produced by photoexcitation in the LHC-II complex. Putative sites of these triplet states are Chl614, Chl611, Chl604, and Chl613 since they do not contribute to the formation of the observed carotenoid triplet states.

  13. Modelling multi-pulse population dynamics from ultrafast spectroscopy.

    Directory of Open Access Journals (Sweden)

    Luuk J G W van Wilderen

    Full Text Available Current advanced laser, optics and electronics technology allows sensitive recording of molecular dynamics, from single resonance to multi-colour and multi-pulse experiments. Extracting the occurring (bio- physical relevant pathways via global analysis of experimental data requires a systematic investigation of connectivity schemes. Here we present a Matlab-based toolbox for this purpose. The toolbox has a graphical user interface which facilitates the application of different reaction models to the data to generate the coupled differential equations. Any time-dependent dataset can be analysed to extract time-independent correlations of the observables by using gradient or direct search methods. Specific capabilities (i.e. chirp and instrument response function for the analysis of ultrafast pump-probe spectroscopic data are included. The inclusion of an extra pulse that interacts with a transient phase can help to disentangle complex interdependent pathways. The modelling of pathways is therefore extended by new theory (which is included in the toolbox that describes the finite bleach (orientation effect of single and multiple intense polarised femtosecond pulses on an ensemble of randomly oriented particles in the presence of population decay. For instance, the generally assumed flat-top multimode beam profile is adapted to a more realistic Gaussian shape, exposing the need for several corrections for accurate anisotropy measurements. In addition, the (selective excitation (photoselection and anisotropy of populations that interact with single or multiple intense polarised laser pulses is demonstrated as function of power density and beam profile. Using example values of real world experiments it is calculated to what extent this effectively orients the ensemble of particles. Finally, the implementation includes the interaction with multiple pulses in addition to depth averaging in optically dense samples. In summary, we show that mathematical

  14. Noisy pulses enhance temporal resolution in pump-probe spectroscopy

    CERN Document Server

    Meyer, Kristina; Raith, Philipp; Kaldun, Andreas; Jiang, Yuhai; Senftleben, Arne; Kurka, Moritz; Moshammer, Robert; Ullrich, Joachim; Pfeifer, Thomas

    2011-01-01

    Time-resolved measurements of quantum dynamics are based on the availability of controlled events (e.g. pump and probe pulses) that are shorter in duration than the typical evolution time scale of the dynamical processes to be observed. Here we introduce the concept of noise-enhanced pump-probe spectroscopy, allowing the measurement of dynamics significantly shorter than the average pulse duration by exploiting randomly varying, partially coherent light fields consisting of bunched colored noise. It is shown that statistically fluctuating fields can be superior by more than a factor of 10 to frequency-stabilized fields, with important implications for time-resolved pump-probe experiments at x-ray free-electron lasers (FELs) and, in general, for measurements at the frontiers of temporal resolution (e.g. attosecond spectroscopy). As an example application, the concept is used to explain the recent experimental observation of vibrational wave packet motion in a deuterium molecular ion on time scales shorter than...

  15. Selective Alcohol Oxidation by a Copper TEMPO Catalyst: Mechanistic Insights by Simultaneously Coupled Operando EPR/UV-Vis/ATR-IR Spectroscopy.

    Science.gov (United States)

    Rabeah, Jabor; Bentrup, Ursula; Stößer, Reinhard; Brückner, Angelika

    2015-09-28

    The first coupled operando EPR/UV-Vis/ATR-IR spectroscopy setup for mechanistic studies of gas-liquid phase reactions is presented and exemplarily applied to the well-known copper/TEMPO-catalyzed (TEMPO=(2,2,6,6-tetramethylpiperidin-1-yl)oxyl) oxidation of benzyl alcohol. In contrast to previous proposals, no direct redox reaction between TEMPO and Cu(I) /Cu(II) has been detected. Instead, the role of TEMPO is postulated to be the stabilization of a (bpy)(NMI)Cu(II) -O2 (⋅-) -TEMPO (bpy=2,2'-bipyridine, NMI=N-methylimidazole) intermediate formed by electron transfer from Cu(I) to molecular O2 .

  16. Applying the conventional moving average filter for estimation of low radiation doses using EPR spectroscopy: Benefits and drawbacks

    Energy Technology Data Exchange (ETDEWEB)

    Maghraby, Ahmed M., E-mail: maghrabism@yahoo.com [National Institute of Standards (NIS), Radiation Dosimetry Department, Ministry of Scientific Research, Tersa Street, P.O. Box 136, Giza, Haram 12211 (Egypt); Physics Department, Faculty of Science and Humanities, Salman Bin AbdulAziz University, Alkharj (Saudi Arabia)

    2014-02-11

    Alanine/EPR is the most common dosimetry system for high radiation doses because of its high stability and wide linear response, however, use of alanine in most of medical applications still require special sophisticated methodologies and techniques in order to extend alanine detection limit to low levels of radiation doses. One of these techniques is the use of digital processing of acquired alanine spectra for enhancing useful components in spectra while useless features are suppressed. Simple moving average filter (MA) impacts on alanine EPR spectra have been studied in terms of peak-to-peak height, peak-to-peak line width, and associated uncertainty. Three types of the used filter were investigated: upward MA, central MA, and downward MA filters, effects of each on the peak position for different values of filter width were studied. It was found that MA filter always lead to the reduction in signal intensity and the increase of line width of the central peak of alanine spectrum. Peak position also changes in cases of the upward MA and downward MA filters while no significant changes were observed in the case of central MA. Uncertainties associated to the averaging process were evaluated and plotted versus the filter width resulting in a linear relationship. Filter width value should be carefully selected in order to avoid probable distortion in processed spectra while gaining less noisy spectra with less associated uncertainties.

  17. Pulse EPR, 55Mn-ENDOR and ELDOR-detected NMR of the S2-state of the oxygen evolving complex in photosystem II.

    Science.gov (United States)

    Kulik, Leonid; Epel, Boris; Messinger, Johannes; Lubitz, Wolfgang

    2005-06-01

    Pulse EPR, 55Mn-ENDOR and ELDOR-detected NMR experiments were performed on the S2-state of the oxygen-evolving complex from spinach Photosystem II. The novel technique of random acquisition in ENDOR was used to suppress heating artefacts. Our data unambiguously shows that four Mn ions have significant hyperfine coupling constants. Numerical simulation of the 55Mn-ENDOR spectrum allowed the determination of the principal values of the hyperfine interaction tensors for all four Mn ions of the oxygen-evolving complex. The results of our 55Mn-ENDOR experiments are in good agreement with previously published data [Peloquin JM et al. (2000) J Am Chem Soc 122: 10926-10942]. For the first time ELDOR-detected NMR was applied to the S2-state and revealed a broad peak that can be simulated numerically with the same parameters that were used for the simulation of the 55Mn-ENDOR spectrum. This provides strong independent support for the assigned hyperfine parameters.

  18. Experimental study of the structure of chalcogenide glassy semiconductors in three-component systems of Ge-As-Se and As-Sb-Se by means of NQR and EPR spectroscopy

    Science.gov (United States)

    Bolebrukh, Olga; Sinyavsky, Nikolay; Korneva, Irina; Dobosz, Bernadeta; Ostafin, Michal; Nogaj, Boleslaw; Krzyminiewski, Ryszard

    2013-12-01

    The structure of chalcogenide glassy semiconductors in three-component systems of Ge-As-Se and As-Sb-Se has been studied by means of both NQR (nuclear quadrupole resonance) and EPR (electron paramagnetic resonance) spectroscopy. It is investigated that in the glasses of both systems the value of the electric field gradient at the resonating nuclei grows with increasing concentration of the clusters As2Se3 and Sb2Se3, thereby increasing the NQR resonance frequencies. It appears that for the Ge-As-Se system the structural transition from a two-dimensional to three-dimensional structure occurs at average coordination number bar r = 2.45. The EPR spectral parameters of glasses depend on the composition, the average coordination number and the temperature, and these are discussed. The effect of "ageing" for CGS (chalcogenide glassy semiconductors) of As-Sb-Se system due to partial crystallization of the sample is observed from the EPR spectra.

  19. Instrumental correction of counting losses in nuclear pulse spectroscopy

    Science.gov (United States)

    Westphal, G. P.

    1985-05-01

    The virtual pulse generator (VPG) method of counting loss correction [1-3] is the first truly quantitative instrumental correction procedure taking into account both dead-time and pileup losses of a spectroscopy system over its full operative range of counting rates without the need for fast signal detection channels [4-6] or ambiguous post-processing of data [7,8], or the necessity to process artificial test pulses in addition to the detector signals [9]. Consequently, the VPG method is not limited in test frequency thus enabling the on-line generation of loss correction factors of sufficient statistical accuracy within extremely short periods of time. By adding weighting factors to the channels addressed by the analog-to-digital converter during the course of the measurement (instead of one as in conventional pulse height analysis) real-time correction of counting losses is made possible with millisecond time of response. Increased statistical accuracy may be achieved when using the VPG principle for loss-dependent prolonging of the measuring time similar to the live-time clock method. Both real-time and live-time modes of operation are provided for in a commercially available VPG correction module [10]. After a description of the set-up procedure of the module in connection with a likewise commercial semi-Gaussian shaping amplifier the performance of the VPG correction is exemplified to a level of 0.2% with the aid of repetitive two-source measurements in both the real-time and the live-time mode of operation.

  20. Investigation of the cutaneous penetration behavior of dexamethasone loaded to nano-sized lipid particles by EPR spectroscopy, and confocal Raman and laser scanning microscopy.

    Science.gov (United States)

    Lohan, Silke B; Saeidpour, Siavash; Solik, Agnieszka; Schanzer, Sabine; Richter, Heike; Dong, Pin; Darvin, Maxim E; Bodmeier, Roland; Patzelt, Alexa; Zoubari, Gaith; Unbehauen, Michael; Haag, Rainer; Lademann, Jürgen; Teutloff, Christian; Bittl, Robert; Meinke, Martina C

    2017-07-01

    An improvement of the penetration efficiency combined with the controlled release of actives in the skin can facilitate the medical treatment of skin diseases immensely. Dexamethasone (Dx), a synthetic glucocorticoid, is frequently used for the treatment of inflammatory skin diseases. To investigate the penetration of nano-sized lipid particles (NLP) loaded with Dx in comparison to a commercially available base cream, different techniques were applied. Electron paramagnetic resonance (EPR) spectroscopy was used to monitor the penetration of Dx, which was covalently labeled with the spin probe 3-(Carboxy)-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (PCA). The penetration into hair follicles was studied using confocal laser scanning microscopy (CLSM) with curcumin-loaded NLP. The penetration of the vehicle was followed by confocal Raman microscopy (CRM). Penetration studies using excised porcine skin revealed a more than twofold higher penetration efficiency for DxPCA into the stratum corneum (SC) after 24h incubation compared to 4h incubation when loaded to the NLP, whereas when applied in the base cream, almost no further penetration was observed beyond 4h. The distribution of DxPCA within the SC was investigated by consecutive tape stripping. The release of DxPCA from the base cream after 24h in deeper SC layers and the viable epidermis was shown by EPR. For NLP, no release from the carrier was observed, although DxPCA was detectable in the skin after the complete SC was removed. This phenomenon can be explained by the penetration of the NLP into the hair follicles. However, penetration profiles measured by CRM indicate that NLP did not penetrate as deeply into the SC as the base cream formulation. In conclusion, NLP can improve the accumulation of Dx in the skin and provide a reservoir within the SC and in the follicular infundibula. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Mapping alpha-helical induced folding within the intrinsically disordered C-terminal domain of the measles virus nucleoprotein by site-directed spin-labeling EPR spectroscopy.

    Science.gov (United States)

    Belle, Valérie; Rouger, Sabrina; Costanzo, Stéphanie; Liquière, Elodie; Strancar, Janez; Guigliarelli, Bruno; Fournel, André; Longhi, Sonia

    2008-12-01

    Using site-directed spin-labeling EPR spectroscopy, we mapped the region of the intrinsically disordered C-terminal domain of measles virus nucleoprotein (N(TAIL)) that undergoes induced folding. In addition to four spin-labeled N(TAIL) variants (S407C, S488C, L496C, and V517C) (Morin et al. (2006), J Phys Chem 110: 20596-20608), 10 new single-site cysteine variants were designed, purified from E. coli, and spin-labeled. These 14 spin-labeled variants enabled us to map in detail the gain of rigidity of N(TAIL) in the presence of either the secondary structure stabilizer 2,2,2-trifluoroethanol or the C-terminal domain X (XD) of the viral phosphoprotein. Different regions of N(TAIL) were shown to contribute to a different extent to the binding to XD, while the mobility of the spin labels grafted at positions 407 and 460 was unaffected upon addition of XD; that of the spin labels grafted within the 488-502 and the 505-522 regions was severely and moderately reduced, respectively. Furthermore, EPR experiments in the presence of 30% sucrose allowed us to precisely map to residues 488-502, the N(TAIL) region undergoing alpha-helical folding. The mobility of the 488-502 region was found to be restrained even in the absence of the partner, a behavior that could be accounted for by the existence of a transiently populated folded state. Finally, we show that the restrained motion of the 505-522 region upon binding to XD is due to the alpha-helical transition occurring within the 488-502 region and not to a direct interaction with XD.

  2. EPR/PTFE dosimetry for test reactor environments

    Energy Technology Data Exchange (ETDEWEB)

    Vehar, D.W.; Griffin, P.J.; Quirk, T.J. [Sandia National Laboratories, Albuquerque, NM 87185-1146 (United States)

    2011-07-01

    The use of Electron Paramagnetic Resonance (EPR) spectroscopy with materials such as alanine is well established as a technique for measurement of ionizing radiation absorbed dose in photon and electron fields such as Co-60, high-energy bremsstrahlung and electron-beam fields [1]. In fact, EPR/Alanine dosimetry has become a routine transfer standard for national standards bodies such as NIST and NPL. In 1992 the Radiation Metrology Laboratory (RML) at Sandia National Laboratories implemented EPR/Alanine capabilities for use in routine and calibration activities at its Co-60 and pulsed-power facilities. At that time it also investigated the usefulness of the system for measurement of absorbed dose in the mixed neutron/photon environments of reactors such as the Sandia Pulsed Reactor and the Annular Core Research Reactor used for hardness testing of electronics. The RML concluded that the neutron response of alanine was a sufficiently high fraction of the overall dosimeter response that the resulting uncertainties in the photon dose would be unacceptably large for silicon-device testing. However, it also suggested that non-hydrogenous materials such as polytetrafluoroethylene (PTFE) would exhibit smaller neutron response and might be useful in mixed environments. Preliminary research with PTFE in photon environments indicated considerable promise, but further development was not pursued at that time. Because of renewed interest in absorbed dose measurements that could better define the individual contributions of photon and neutron components to the overall dose delivered to a test object, the RML has re-initiated the development of an EPR/PTFE dosimetry system. This effort consists of three stages: 1) Identification of PTFE materials that may be suitable for dosimetry applications. It was speculated that the inconsistency of EPR signatures in the earlier samples may have been due to variability in PTFE manufacturing processes. 2) Characterization of dosimetry in

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

    Science.gov (United States)

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

    2017-08-01

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

  4. Reactive oxygen species generation by copper(II) oxide nanoparticles determined by DNA damage assays and EPR spectroscopy.

    Science.gov (United States)

    Angelé-Martínez, Carlos; Nguyen, Khanh Van T; Ameer, Fathima S; Anker, Jeffrey N; Brumaghim, Julia L

    2017-03-01

    Copper(II) oxide nanoparticles ((NP)CuO) have many industrial applications, but are highly cytotoxic because they generate reactive oxygen species (ROS). It is unknown whether the damaging ROS are generated primarily from copper leached from the nanoparticles, or whether the nanoparticle surface plays a significant role. To address this question, we separated nanoparticles from the supernatant containing dissolved copper, and measured their ability to damage plasmid DNA with addition of hydrogen peroxide, ascorbate, or both. While DNA damage from the supernatant (measured using an electrophoresis assay) can be explained solely by dissolved copper ions, damage by the nanoparticles in the presence of ascorbate is an order of magnitude higher than can be explained by dissolved copper and must, therefore, depend primarily upon the nanoparticle surface. DNA damage is time-dependent, with shorter incubation times resulting in higher EC50 values. Hydroxyl radical ((•)OH) is the main ROS generated by (NP)CuO/hydrogen peroxide as determined by EPR measurements; (NP)CuO/hydrogen peroxide/ascorbate conditions generate ascorbyl, hydroxyl, and superoxide radicals. Thus, (NP)CuO generate ROS through several mechanisms, likely including Fenton-like and Haber-Weiss reactions from the surface or dissolved copper ions. The same radical species were observed when (NP)CuO suspensions were replaced with the supernatant containing leached copper, washed (NP)CuO, or dissolved copper solutions. Overall, (NP)CuO generate significantly more ROS and DNA damage in the presence of ascorbate than can be explained simply from dissolved copper, and the (NP)CuO surface must play a large role.

  5. Phase-locked pulses for two-dimensional spectroscopy by a birefringent delay line.

    Science.gov (United States)

    Brida, Daniele; Manzoni, Cristian; Cerullo, Giulio

    2012-08-01

    We introduce the translating wedge-based identical pulses encoding system, a novel device for the generation of collinear, interferometrically locked ultrashort pulse pairs. By means of birefringent wedges, we are able to control the pulse delay with attosecond precision and stability better that λ/360, without affecting the pulse duration and in a spectral range that spans from UV to mid-IR. This device is expected to dramatically simplify two-dimensional spectroscopy experiments.

  6. Kissing G domains of MnmE monitored by X-ray crystallography and pulse electron paramagnetic resonance spectroscopy.

    Science.gov (United States)

    Meyer, Simon; Böhme, Sabine; Krüger, André; Steinhoff, Heinz-Jürgen; Klare, Johann P; Wittinghofer, Alfred

    2009-10-01

    MnmE, which is involved in the modification of the wobble position of certain tRNAs, belongs to the expanding class of G proteins activated by nucleotide-dependent dimerization (GADs). Previous models suggested the protein to be a multidomain protein whose G domains contact each other in a nucleotide dependent manner. Here we employ a combined approach of X-ray crystallography and pulse electron paramagnetic resonance (EPR) spectroscopy to show that large domain movements are coupled to the G protein cycle of MnmE. The X-ray structures show MnmE to be a constitutive homodimer where the highly mobile G domains face each other in various orientations but are not in close contact as suggested by the GDP-AlF(x) structure of the isolated domains. Distance measurements by pulse double electron-electron resonance (DEER) spectroscopy show that the G domains adopt an open conformation in the nucleotide free/GDP-bound and an open/closed two-state equilibrium in the GTP-bound state, with maximal distance variations of 18 A. With GDP and AlF(x), which mimic the transition state of the phosphoryl transfer reaction, only the closed conformation is observed. Dimerization of the active sites with GDP-AlF(x) requires the presence of specific monovalent cations, thus reflecting the requirements for the GTPase reaction of MnmE. Our results directly demonstrate the nature of the conformational changes MnmE was previously suggested to undergo during its GTPase cycle. They show the nucleotide-dependent dynamic movements of the G domains around two swivel positions relative to the rest of the protein, and they are of crucial importance for understanding the mechanistic principles of this GAD.

  7. Kissing G domains of MnmE monitored by X-ray crystallography and pulse electron paramagnetic resonance spectroscopy.

    Directory of Open Access Journals (Sweden)

    Simon Meyer

    2009-10-01

    Full Text Available MnmE, which is involved in the modification of the wobble position of certain tRNAs, belongs to the expanding class of G proteins activated by nucleotide-dependent dimerization (GADs. Previous models suggested the protein to be a multidomain protein whose G domains contact each other in a nucleotide dependent manner. Here we employ a combined approach of X-ray crystallography and pulse electron paramagnetic resonance (EPR spectroscopy to show that large domain movements are coupled to the G protein cycle of MnmE. The X-ray structures show MnmE to be a constitutive homodimer where the highly mobile G domains face each other in various orientations but are not in close contact as suggested by the GDP-AlF(x structure of the isolated domains. Distance measurements by pulse double electron-electron resonance (DEER spectroscopy show that the G domains adopt an open conformation in the nucleotide free/GDP-bound and an open/closed two-state equilibrium in the GTP-bound state, with maximal distance variations of 18 A. With GDP and AlF(x, which mimic the transition state of the phosphoryl transfer reaction, only the closed conformation is observed. Dimerization of the active sites with GDP-AlF(x requires the presence of specific monovalent cations, thus reflecting the requirements for the GTPase reaction of MnmE. Our results directly demonstrate the nature of the conformational changes MnmE was previously suggested to undergo during its GTPase cycle. They show the nucleotide-dependent dynamic movements of the G domains around two swivel positions relative to the rest of the protein, and they are of crucial importance for understanding the mechanistic principles of this GAD.

  8. Visible-light spectroscopy of pulsed-power plasmas (invited)

    Science.gov (United States)

    Arad, R.; Clark, R. E. H.; Dadusc, G.; Davara, G.; Duvall, R. E.; Fisher, A.; Fisher, V.; Foord, M. E.; Fruchtman, A.; Gregorian, L.; Krasik, Ya.; Litwin, C.; Maron, Y.; Perelmutter, L.; Sarfaty, M.; Sarid, E.; Shkolnikova, S.; Shpitalnik, R.; Troyansky, L.; Weingarten, A.

    1992-10-01

    We describe the investigations of the plasma behavior in three pulsed-power systems: a magnetically insulated ion diode, and plasma opening switch, and a gas-puffed Z pinch. Recently developed spectroscopic diagnostic techniques allow for measurements with relatively high spectral, temporal, and spatial resolutions. The particle velocity and density distributions within a few tens of microns from the dielectric-anode surface are observed using laser spectroscopy. Fluctuating electric fields in the plasma are inferred from anisotropic Stark broadening. For the plasma opening switch experiment, a novel gaseous plasma source was developed which is mounted inside the high-voltage inner conductor. The properties of this source, together with spectroscopic observations of the electron density and particle velocities of the injected plasma, are described. Emission line intensities during the switch operation are discussed. In the Z-pinch experiment, spectral emission-line profiles of various charge-state ions are studied during the implosion phase. Radial velocity distributions are observed from the line Doppler shifts and widths.

  9. Suppression mechanism of radiation-induced darkening by Ce doping in Al/Yb/Ce-doped silica glasses: Evidence from optical spectroscopy, EPR and XPS analyses

    Science.gov (United States)

    Shao, Chongyun; Xu, Wenbin; Ollier, Nadege; Guzik, Malgorzata; Boulon, Georges; Yu, Lu; Zhang, Lei; Yu, Chunlei; Wang, Shikai; Hu, Lili

    2016-10-01

    Yb3+/Al3+ co-doped silica glasses with different Ce2O3 contents were prepared using the sol-gel method combined with high-temperature sintering. Changes in refractive index, absorption, emission and fluorescence lifetime of these glasses caused by X-ray irradiation were recorded and analyzed systematically. It is found that co-doping with certain amount of Ce could greatly improve the radiation resistance without evident negative effects on the basic optical properties of the Yb3+ ions in the near-infrared region. The nature of the radiation-induced color centres and the mechanism by which Ce prevented the formation of these centres were studied using optical absorption, electron paramagnetic resonance (EPR), and X-ray photoelectron spectroscopy (XPS) methods. Direct evidence confirmed that trapped electron centres (Yb2+/Si-E'/Al-E') and trapped hole centres (Al-OHCs) were effectively inhibited by Ce doping, which was correlated to the coexistence of the redox couple Ce3+/Ce4+ in the glasses. These results are helpful to understand the micro-structural origin and the suppression mechanism by Ce co-doping of the photodarkening effect in Yb3+-doped silica fibers.

  10. An Advantage of the Equivalent Velocity Spectroscopy for Femtsecond Pulse Radiolysis

    CERN Document Server

    Kondoh, Takafumi; Tagawa, Seiichi; Tomosada, Hiroshi; Yang Jin Feng; Yoshida, Yoichi

    2005-01-01

    For studies of electron beam induced ultra-fast reaction process, femtosecond(fs) pulse radiolysis is under construction. To realize fs time resolution, fs electron and analyzing light pulses and their jitter compensation system are needed. About a 100fs electron pulse was generated by a photocathode RF gun linac and a magnetic pulse compressor. Synchronized Ti: Sapphire laser have a puleswidth about 160fs. And, it is significant to avoid degradation of time resolution caused by velocity difference between electron and analyzing light in a sample. In the 'Equivalent velocity spectroscopy' method, incident analyzing light is slant toward electron beam with an angle associated with refractive index of sample. Then, to overlap light wave front and electron pulse shape, electron pulse shape is slanted toward the direction of travel. As a result of the equivalent velocity spectroscopy for hydrated electrons, using slanted electron pulse shape, optical absorption rise time was about 1.4ps faster than normal electro...

  11. Responsive metal complexes: a click-based "allosteric scorpionate" complex permits the detection of a biological recognition event by EPR/ENDOR spectroscopy.

    Science.gov (United States)

    Tamanini, Emiliano; Rigby, Stephen E J; Motevalli, Majid; Todd, Matthew H; Watkinson, Michael

    2009-01-01

    Chemical sensing is a mature field, and many effective sensors for small anions and cations have been devised. Metal complexes have been used widely for this purpose, but there are fewer reports of their use in the detection of organic and biological analytes. To date metal complexes have been used in sensing via the direct displacement of a pre-existing ligand by an analyte, or by an adventitious complementarity between the complex and analyte. These strategies do not permit a general approach to the sensing of biological molecules with metal complexes because of the demands to engineer molecular recognition into the complex architecture. We describe a fundamentally new approach to this field-the "allosteric scorpionate" metal complex. The binding partner of a biological analyte is attached to a scorpionate ligand on a metal complex, remote from the metal centre. Binding of the analyte causes a change in the primary coordination sphere at the metal, thereby revealing the presence of the biological molecule. We show that azamacrocyclic complexes with a triazole scorpion ligand may be easily assembled with the [3+2] Huisgens 'click' cycloaddition. We demonstrate the synthesis of a biotin-functionalised cyclam derivative using this methodology. This, and our previously communicated zinc sensor, are to the best of our knowledge the first examples of a triazole being employed as a scorpion ligand on an azamacrocycle. Coordination by the triazole to the metal is perturbed by the binding of avidin to the pendant ligand. This event can be sensitively detected with EPR spectroscopy, and the details of the coordination change probed with ENDOR spectroscopy, confirming the loss of the axial triazole nitrogen donor upon binding to avidin. This represents the first metal complex where remote, 'allosteric' coordination of an analyte has been shown to cause a change in the primary coordination sphere of the metal. Since the synthesis is modular and straightforward, other

  12. Aggregation behavior of amphiphilic p(HPMA)-co-p(LMA) copolymers studied by FCS and EPR spectroscopy.

    Science.gov (United States)

    Hemmelmann, Mirjam; Kurzbach, Dennis; Koynov, Kaloian; Hinderberger, Dariush; Zentel, Rudolf

    2012-12-10

    A combined study of fluorescence correlation spectroscopy and electron paramagnetic resonance spectroscopy gave a unique picture of p(HPMA)-co-p(LMA) copolymers in aqueous solutions, ranging from the size of micelles and aggregates to the composition of the interior of these self-assembled systems. P(HPMA)-co-p(LMA) copolymers have shown high potential as brain drug delivery systems, and a detailed study of their physicochemical properties can help to elucidate their mechanism of action. Applying two complementary techniques, we found that the self-assembly behavior as well as the strength of hydrophobic attraction of the amphiphilic copolymers can be tuned by the hydrophobic LMA content or the presence of hydrophobic molecules or domains. Studies on the dependence of the hydrophobic lauryl side chain content on the aggregation behavior revealed that above 5 mol % laury side-chain copolymers self-assemble into intrachain micelles and larger aggregates. Above this critical alkyl chain content, p(HPMA)-co-p(LMA) copolymers can solubilize the model drug domperidone and exhibit the tendency to interact with model cell membranes.

  13. The role of EPR spectroscopy in studies of the oxidative status of biological systems and the antioxidative properties of various compounds - REVIEW

    Directory of Open Access Journals (Sweden)

    IVAN SPASOJEVIĆ

    2011-05-01

    Full Text Available In this era of intense study of free radicals and antioxidants, electron paramagnetic resonance (EPR is arguably the best-suited technique for such research, particularly when considering biochemical and biological systems. No attempt was made to cover all the topics of EPR application but instead attention was restricted to two areas that are both novel and received less attention in previous reviews. In the first section, the application of EPR in assessing the oxidative status of various biological systems, using endogenous stabile paramagnetic species, such as the ascorbyl radical, semiquinone, melanin, and oxidized pigments, is addressed. The second section covers the use of EPR in the emerging field of antioxidant development, using EPR spin-trapping and spin-probing techniques. In both sections, in addition to giving an overview of the available literature, examples (mostly from the authors’ recent work are also presented in sufficient detail to illustrate how to explore the full potential of EPR. This review aims at encouraging biologists, chemists and pharmacologists interested in the redox metabolism of living systems, free radical chemistry or antioxidative properties of new drugs and natural products to take advantage of this technique for their investigations.

  14. The secondary structure of apolipoprotein A-I on 9.6-nm reconstituted high-density lipoprotein determined by EPR spectroscopy

    Science.gov (United States)

    Oda, Michael N; Budamagunta, Madhu S; Borja, Mark S; Petrlova, Jitka; Voss, John C; Lagerstedt, Jens O

    2013-01-01

    Apolipoprotein A-I (ApoA-I) is the major protein component of high-density lipoprotein (HDL), and is critical for maintenance of cholesterol homeostasis. During reverse cholesterol transport, HDL transitions between an array of subclasses, differing in size and composition. This process requires ApoA-I to adapt to changes in the shape of the HDL particle, transiting from an apolipoprotein to a myriad of HDL subclass-specific conformations. Changes in ApoA-I structure cause alterations in HDL-specific enzyme and receptor-binding properties, and thereby direct the HDL particle through the reverse cholesterol transport pathway. In this study, we used site-directed spin label spectroscopy to examine the conformational details of the ApoA-I central domain on HDL. The motional dynamics and accessibility to hydrophobic/hydrophilic relaxation agents of ApoA-I residues 99–163 on 9.6-nm reconstituted HDL was analyzed by EPR. In previous analyses, we examined residues 6–98 and 164–238 (of ApoA-I's 243 residues), and combining these findings with the current results, we have generated a full-length map of the backbone structure of reconstituted HDL-associated ApoA-I. Remarkably, given that the majority of ApoA-I's length is composed of amphipathic helices, we have identified nonhelical residues, specifically the presence of a β-strand (residues 149–157). The significance of these nonhelical residues is discussed, along with the other features, in the context of ApoA-I function in contrast to recent models derived by other methods. PMID:23668303

  15. EPR Spectroscopy of catalytic systems based on nickel complexes of 1,4-diaza-1,3-butadiene (α-diimine) ligands in hydrogenation and polymerization reactions

    Science.gov (United States)

    Titova, Yu. Yu.; Belykh, L. B.; Schmidt, F. K.

    2015-01-01

    EPR spectroscopy is used to study catalytic hydration and polymerization reaction systems based on α-diimine complexes of Ni(0) and Ni(II) with the general formula NiBr2(DAD-R) (R = -C3H7 or -CH3) or Ni(DAD-CH3)2 (DAD(-C3H7) = 1,4-bis(2,6-diiso-propylphenyl)-2,3-(dimethyl-1,4-diazabuta-1,3-diene, DAD(-CH3) = 1,4-bis(2,6-dimethylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene)), in combination with Lewis acids (AlEt3, AlEt2Cl, AlEtCl2, B(F5C6)3, BF3.OEt2). Ni(I) complexes of the form (DAD-R)NiX2AlX'y(C2H5)3-y composition (an aluminum atom can be replaced by a boron atom) were identified, where R = -CH3 or -C3H7, X = Br, and X' = Cl or -C2H5 and α-diimine anion radicals are included in derivatives of aluminum or boron. Oxidation reactions of the Ni(DAD-CH3)2 complex with aluminum alkyl halides and boron derivatives with formation of paramagnetic nickel complexes are observed. It is found that there is no direct relationship between the polymerization activity of ethylene or hydration of the alkenes and the concentration of paramagnetic particles.

  16. EPR spectroscopy of MolB2C2-a reveals mechanism of transport for a bacterial type II molybdate importer.

    Science.gov (United States)

    Rice, Austin J; Alvarez, Frances J D; Schultz, Kathryn M; Klug, Candice S; Davidson, Amy L; Pinkett, Heather W

    2013-07-19

    In bacteria, ATP-binding cassette (ABC) transporters are vital for the uptake of nutrients and cofactors. Based on differences in structure and activity, ABC importers are divided into two types. Type I transporters have been well studied and employ a tightly regulated alternating access mechanism. Less is known about Type II importers, but much of what we do know has been observed in studies of the vitamin B12 importer BtuC2D2. MolB2C2 (formally known as HI1470/71) is also a Type II importer, but its substrate, molybdate, is ∼10-fold smaller than vitamin B12. To understand mechanistic differences among Type II importers, we focused our studies on MolBC, for which alternative conformations may be required to transport its relatively small substrate. To investigate the mechanism of MolBC, we employed disulfide cross-linking and EPR spectroscopy. From these studies, we found that nucleotide binding is coupled to a conformational shift at the periplasmic gate. Unlike the larger conformational changes in BtuCD-F, this shift in MolBC-A is akin to unlocking a swinging door: allowing just enough space for molybdate to slip into the cell. The lower cytoplasmic gate, identified in BtuCD-F as "gate I," remains open throughout the MolBC-A mechanism, and cytoplasmic gate II closes in the presence of nucleotide. Combining our results, we propose a peristaltic mechanism for MolBC-A, which gives new insight in the transport of small substrates by a Type II importer.

  17. Pulsed Green Laser for Time Resolved Raman Spectroscopy Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR Phase I effort will demonstrate the feasibility of developing a fully packaged, efficient, short pulse, high repetition rate frequency doubled micro-chip...

  18. Two attosecond pulse transient absorption spectroscopy and extraction of the instantaneous AC Stark shift in helium

    Science.gov (United States)

    Bækhøj, Jens E.; Bojer Madsen, Lars

    2016-07-01

    In two attosecond pulse absorption spectroscopy (TAPAS) the use of two attosecond XUV pulses allows the extraction of atomic and molecular quantum mechanical dipole phases from spectroscopic measurements. TAPAS relies on interference between processes that individually only include a single XUV photon, and therefore does not rely on high intensity attosecond pulses. To show the usefulness and limitations of the TAPAS method we investigate its capability of capturing the instantaneous AC Stark shift induced by a midinfrared 3200 nm pulse in the | 1{{s}}2{{p}}> state of helium.

  19. Pulsed Electron Beam Spectroscopy for Temperature Measurements in Hypersonic Flows

    Science.gov (United States)

    2010-01-01

    as rotational-level dependent, so the proper modeling of k i can be important as temperature changes and if tem perature measurements based on the...through a hy drogen thyratron switch into the primary of a step-up transformer. A limited number of off-th e-shelf prod ucts perfor ming the function...of a thyratron drive for pulse switching were identifie d, but none met the specialize d power a nd switchin g wavefor m requirements of the pulsed

  20. Hydration structure of the Ti(III) cation as revealed by pulse EPR and DFT studies: new insights into a textbook case.

    Science.gov (United States)

    Maurelli, Sara; Livraghi, Stefano; Chiesa, Mario; Giamello, Elio; Van Doorslaer, Sabine; Di Valentin, Cristiana; Pacchioni, Gianfranco

    2011-03-21

    The (17)O and (1)H hyperfine interactions of water ligands in the Ti(III) aquo complex in a frozen solution were determined using Hyperfine Sublevel Correlation (HYSCORE) and Pulse Electron Nuclear Double Resonance (ENDOR) spectroscopies at 9.5 GHz. The isotropic hyperfine interaction (hfi) constant of the water ligand (17)O was found to be about 7.5 MHz. (1)H Single Matched Resonance Transfer (SMART) HYSCORE spectra allowed resolution of the hfi interactions of the two inequivalent water ligand protons and the relative orientations of their hfi tensors. The magnetic and geometrical parameters extracted from the experiments were compared with the results of DFT computations for different geometrical arrangements of the water ligands around the cation. The theoretical observable properties (g tensor (1)H and (17)O hfi tensors and their orientations) of the [Ti(H(2)O)(6)](3+) complex are in quantitative agreement with the experiments for two slightly different geometrical arrangements associated with D(3d) and C(i) symmetries.

  1. In situ characterization of few-cycle laser pulses in transient absorption spectroscopy

    CERN Document Server

    Blättermann, Alexander; Kaldun, Andreas; Ding, Thomas; Stooß, Veit; Laux, Martin; Rebholz, Marc; Pfeifer, Thomas

    2016-01-01

    Attosecond transient absorption spectroscopy has thus far been lacking the capability to simultaneously characterize the intense laser pulses at work within a time-resolved quantum-dynamics experiment. However, precise knowledge of these pulses is key to extracting quantitative information in strong-field highly nonlinear light-matter interactions. Here, we introduce and experimentally demonstrate an ultrafast metrology tool based on the time-delay-dependent phase shift imprinted on a strong-field driven resonance. Since we analyze the signature of the laser pulse interacting with the absorbing spectroscopy target, the laser pulse duration and intensity are determined in situ. As we also show, this approach allows for the quantification of time-dependent bound-state dynamics in one and the same experiment. In the future, such experimental data will facilitate more precise tests of strong-field dynamics theories.

  2. In situ characterization of few-cycle laser pulses in transient absorption spectroscopy.

    Science.gov (United States)

    Blättermann, Alexander; Ott, Christian; Kaldun, Andreas; Ding, Thomas; Stooß, Veit; Laux, Martin; Rebholz, Marc; Pfeifer, Thomas

    2015-08-01

    Attosecond transient absorption spectroscopy has thus far been lacking the capability to simultaneously characterize the intense laser pulses at work within a time-resolved quantum-dynamics experiment. However, precise knowledge of these pulses is key to extracting quantitative information in strong-field highly nonlinear light-matter interactions. Here, we introduce and experimentally demonstrate an ultrafast metrology tool based on the time-delay-dependent phase shift imprinted on a strong-field-driven resonance. Since we analyze the signature of the laser pulse interacting with the absorbing spectroscopy target, the laser pulse duration and intensity are determined in situ. As we also show, this approach allows for the quantification of time-dependent bound-state dynamics in one and the same experiment. In the future, such experimental data will facilitate more precise tests of strong-field dynamics theories.

  3. Pulsed-laser Pumped Photothermal Deflection Spectroscopy for Liquid Thermal Diffusivity Measurement

    Institute of Scientific and Technical Information of China (English)

    XIAO Liantuan; LI Changyong; ZHANG Linjie; ZHAO Yanting; JIA Suotang; ZHOU Guosheng

    2000-01-01

    The pulsed-laser pumped photothermal deflection spectroscopy (PPDS) is applied to measure liquid thermal diffusivity in a modified collinear configuration. Here the pulsed beam is regarded as in the form of a Dirac delta function. The experiment setup used is described. Measurement result for the thermal diffusivity of a liquid sample(magnta/ethanol saturated solution) is reported. The measurement error is less than 3%.

  4. The Marriage of Spectroscopy and Dynamics: Chirped-Pulse Fourier-Transform Mm-Wave Cp-Ft Spectroscopy in Pulsed Uniform Supersonic Flows

    Science.gov (United States)

    Abeysekera, Chamara; Oldham, James M.; Suits, Arthur G.; Park, G. Barratt; Field, Robert W.

    2012-06-01

    A new experimental scheme is presented that combines two powerful emerging technologies: chirped-pulse Fourier-transform mm-Wave spectroscopy and pulsed uniform supersonic flows. It promises a nearly universal detection method that can deliver quantitative isomer, conformer, and vibrational level specific detection, characterization of unstable reaction products and intermediates, and perform unique spectroscopic, kinetics, and dynamics measurements. Chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy, pioneered by Pate and coworkers, allows rapid acquisition of broadband microwave spectrum through advancements in waveform generation and oscilloscope technology. This revolutionary approach has successfully been adapted to higher frequencies by the Field group at MIT. Our new apparatus will exploit amplified chirped pulses in the range of 26-40 GHz, in combination with a pulsed uniform supersonic flow from a Laval nozzle. This nozzle source, pioneered by Rowe, Sims, and Smith for low temperature kinetics studies, produces thermalized reactants at high densities and low temperatures perfectly suitable for reaction dynamics experiments studied using the CP-mmW approach. This combination of techniques shall enhance the thousand-fold improvement in data acquisition rate achieved in the CP method by a further 2-3 orders of magnitude. A pulsed flow alleviates the challenges of continuous uniform flow, e.g. large gas loads and reactant consumption rates. In contrast to other pulsed Laval systems currently in use, we will use a fast piezo valve and small chambers to achieve the desired pressures while minimizing the gas load, so that a 10 Hz repetition rate can be achieved with one turbomolecular pump. The proposed technique will be suitable for many diverse fields, including fundamental studies in spectroscopy and reaction dynamics, reaction kinetics, combustion, atmospheric chemistry, and astrochemistry. We expect a significant advancement in the ability to

  5. Double pulse laser-induced breakdown spectroscopy with femtosecond laser pulses

    Energy Technology Data Exchange (ETDEWEB)

    Pinon, V. [Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL-FORTH), P.O. Box 1385, GR 71110 Heraklion, Crete (Greece); Universidad de A Coruna, Departamento de Ingenieria Industrial II, E-15403 Ferrol, A Coruna (Spain); Fotakis, C. [Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL-FORTH), P.O. Box 1385, GR 71110 Heraklion, Crete (Greece); Nicolas, G. [Universidad de A Coruna, Departamento de Ingenieria Industrial II, E-15403 Ferrol, A Coruna (Spain); Anglos, D. [Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL-FORTH), P.O. Box 1385, GR 71110 Heraklion, Crete (Greece)], E-mail: anglos@iesl.forth.gr

    2008-10-15

    This paper presents results obtained in a study of collinear geometry double pulse femtosecond LIBS analysis of solids in ambient environment. LIBS signal enhancement of 3-10 fold, accompanied by significant improvement of signal reproducibility, in comparison with the single pulse case, has been found in different samples such as brass, iron, silicon, barium sulfate and aluminum when an optimum temporal separation between the two ablating pulses is used. The influence of the delay between pulses in the LIBS signal intensity was investigated and two intervals of interaction were established. A first transient regime from 0 to 50 ps, in which the LIBS signal increases until reaching a maximum, and a second regime that ranges from 50 to 1000 ps (maximum inter-pulse delay investigated) in which the signal enhancement remains constant. Emissions from both ionized and neutral atoms show the same pattern of enhancement with a clear tendency of lines arising from higher energy emissive states to exhibit higher enhancement factors.

  6. EPR spectroscopy of a family of Cr(III) 7M(II) (M = Cd, Zn, Mn, Ni) "wheels": studies of isostructural compounds with different spin ground states

    DEFF Research Database (Denmark)

    Piligkos, Stergios; Weihe, Høgni; Bill, Eckhard

    2009-01-01

    Spinning wheels: The presented highly resolved multifrequency continuous wave EPR spectra (e.g., see figure) of the heterooctametalic "wheels" Cr(7)M provide rare examples of high nuclearity polymetallic systems where detailed information on the spin-Hamiltonian parameters of the ground and excited...... examples of high nuclearity polymetallic systems where detailed information on the spin-Hamiltonian parameters of the ground and excited spin states is observed. We interpret the EPR spectra by use of restricted size effective subspaces obtained by the rigorous solution of spin-Hamiltonians of dimension up...... to 10(5) by use of the Davidson algorithm. We show that transferability of spin-Hamiltonian parameters across complexes of the Cr(7)M family is possible and that the spin-Hamiltonian parameters of Cr(7)M do not have sharply defined values, but are rather distributed around a mean value....

  7. Relaxation and crystallization of amorphous carbamazepine studied by terahertz pulsed spectroscopy

    DEFF Research Database (Denmark)

    Zeitler, J Axel; Taday, Philip F; Pepper, Michael;

    2007-01-01

    At the example of carbamazepine the crystallization of a small organic molecule from its amorphous phase was studied using in situ variable temperature terahertz pulsed spectroscopy (TPS). Even though terahertz spectra of disordered materials in the glassy state exhibit no distinct spectral featu...

  8. Pulsed terahertz spectroscopy and imaging applied to inspection of explosives and inflammable liquids

    Science.gov (United States)

    Yamamoto, Kohji; Yamaguchi, Mariko; Miyamaru, Fumiaki; Tani, Masahiko; Hangyo, Masanori; Ikeda, Takeshi; Matsushita, Akira; Koide, Kenji; Tatsuno, Michiaki; Manami, Yukio

    We carried out applied researches on the pulsed terahertz spectroscopy and the terahertz imaging to detect the C-4 explosive hidden in a mail and inflammable liquids stored in plastic bottles. We confirm that THz techniques are quite efficient at contactless and nondestructive inspection of hazardous materials used in terrorist activities.

  9. Magnetic properties of weakly exchange-coupled high spin Co(II) ions in pseudooctahedral coordination evaluated by single crystal X-band EPR spectroscopy and magnetic measurements.

    Science.gov (United States)

    Neuman, Nicolás I; Winkler, Elín; Peña, Octavio; Passeggi, Mario C G; Rizzi, Alberto C; Brondino, Carlos D

    2014-03-01

    We report single-crystal X-band EPR and magnetic measurements of the coordination polymer catena-(trans-(μ2-fumarato)tetraaquacobalt(II)), 1, and the Co(II)-doped Zn(II) analogue, 2, in different Zn:Co ratios. 1 presents two magnetically inequivalent high spin S = 3/2 Co(II) ions per unit cell, named A and B, in a distorted octahedral environment coordinated to four water oxygen atoms and trans coordinated to two carboxylic oxygen atoms from the fumarate anions, in which the Co(II) ions are linked by hydrogen bonds and fumarate molecules. Magnetic susceptibility and magnetization measurements of 1 indicate weak antiferromagnetic exchange interactions between the S = 3/2 spins of the Co(II) ions in the crystal lattice. Oriented single crystal EPR experiments of 1 and 2 were used to evaluate the molecular g-tensor and the different exchange coupling constants between the Co(II) ions, assuming an effective spin S′= 1/2. Unexpectedly, the eigenvectors of the molecular g-tensor were not lying along any preferential bond direction, indicating that, in high spin Co(II) ions in roughly octahedral geometry with approximately axial EPR signals, the presence of molecular pseudo axes in the metal site does not determine preferential directions for the molecular g-tensor. The EPR experiment and magnetic measurements, together with a theoretical analysis relating the coupling constants obtained from both techniques, allowed us to evaluate selectively the exchange coupling constant associated with hydrogen bonds that connect magnetically inequivalent Co(II) ions (|JAB(1/2)| = 0.055(2) cm(–1)) and the exchange coupling constant associated with a fumarate bridge connecting equivalent Co(II) ions (|JAA(1/2)| ≈ 0.25 (1) cm(–1)), in good agreement with the average J(3/2) value determined from magnetic measurements.

  10. Sensitive detection of chlorine in iron oxide by single pulse and dual pulse laser-induced breakdown spectroscopy

    Science.gov (United States)

    Pedarnig, J. D.; Haslinger, M. J.; Bodea, M. A.; Huber, N.; Wolfmeir, H.; Heitz, J.

    2014-11-01

    The halogen chlorine is hard to detect in laser-induced breakdown spectroscopy (LIBS) mainly due to its high excited state energies of 9.2 and 10.4 eV for the most intense emission lines at 134.72 nm and 837.59 nm, respectively. We report on sensitive detection of Cl in industrial iron oxide Fe2O3 powder by single-pulse (SP) and dual-pulse (DP) LIBS measurements in the near infrared range in air. In compacted powder measured by SP excitation (Nd:YAG laser, 532 nm) Cl was detected with limit of detection LOD = 440 ppm and limit of quantitation LOQ = 720 ppm. Orthogonal DP LIBS was studied on pressed Fe2O3 pellets and Fe3O4 ceramics. The transmission of laser-induced plasma for orthogonal Nd:YAG 1064 nm and ArF 193 nm laser pulses showed a significant dependence on interpulse delay time (ipd) and laser wavelength (λL). The UV pulses (λL = 193 nm) were moderately absorbed in the plasma and the Cl I emission line intensity was enhanced while IR pulses (λL = 1064 nm) were not absorbed and Cl signals were not enhanced at ipd = 3 μs. The UV laser enhancement of Cl signals is attributed to the much higher signal/background ratio for orthogonal DP excitation compared to SP excitation and to the increased plasma temperature and electron number density. This enabled measurement at a very short delay time of td ≥ 0.1 μs with respect to the re-excitation pulse and detection of the very rapidly decaying Cl emission with higher efficiency.

  11. Perspective: The first ten years of broadband chirped pulse Fourier transform microwave spectroscopy

    Science.gov (United States)

    Park, G. Barratt; Field, Robert W.

    2016-05-01

    Since its invention in 2006, the broadband chirped pulse Fourier transform spectrometer has transformed the field of microwave spectroscopy. The technique enables the collection of a ≥10 GHz bandwidth spectrum in a single shot of the spectrometer, which allows broadband, high-resolution microwave spectra to be acquired several orders of magnitude faster than what was previously possible. We discuss the advantages and challenges associated with the technique and look back on the first ten years of chirped pulse Fourier transform spectroscopy. In addition to enabling faster-than-ever structure determination of increasingly complex species, the technique has given rise to an assortment of entirely new classes of experiments, ranging from chiral sensing by three-wave mixing to microwave detection of multichannel reaction kinetics. However, this is only the beginning. Future generations of microwave experiments will make increasingly creative use of frequency-agile pulse sequences for the coherent manipulation and interrogation of molecular dynamics.

  12. Perspective: The first ten years of broadband chirped pulse Fourier transform microwave spectroscopy.

    Science.gov (United States)

    Park, G Barratt; Field, Robert W

    2016-05-28

    Since its invention in 2006, the broadband chirped pulse Fourier transform spectrometer has transformed the field of microwave spectroscopy. The technique enables the collection of a ≥10 GHz bandwidth spectrum in a single shot of the spectrometer, which allows broadband, high-resolution microwave spectra to be acquired several orders of magnitude faster than what was previously possible. We discuss the advantages and challenges associated with the technique and look back on the first ten years of chirped pulse Fourier transform spectroscopy. In addition to enabling faster-than-ever structure determination of increasingly complex species, the technique has given rise to an assortment of entirely new classes of experiments, ranging from chiral sensing by three-wave mixing to microwave detection of multichannel reaction kinetics. However, this is only the beginning. Future generations of microwave experiments will make increasingly creative use of frequency-agile pulse sequences for the coherent manipulation and interrogation of molecular dynamics.

  13. Chirped Pulse Microwave Spectroscopy in Pulsed Uniform Supersonic Flows: Observation of K-Dependent Rates in the CL + Propyne Reaction

    Science.gov (United States)

    Ariyasingha, Nuwandi M.; Broderick, Bernadette M.; Thompson, James O. F.; Suits, Arthur

    2016-06-01

    Chirped-Pulse Fourier-transform microwave spectroscopy in uniform supersonic flows (CPUF) has been applied to study the reaction of Cl atoms with propyne. The approach utilizes broad-band microwave spectroscopy to extract structural information with MHz resolution and near universal detection, in conjunction with a Laval flow system, which offers thermalized conditions at low temperatures and high number densities. Our previous studies have exploited this approach to obtain multichannel product branching fractions in a number of polyatomic systems, with isomer and often vibrational level specificity. This report highlights an additional capability of the CPUF technique: here, the state-specific reactant depletion is directly monitored on a microsecond timescale. In doing so, a clear dependence on the rotational quantum number K in the rate of the reaction between Cl atoms and propyne is revealed. Future prospects for the technique will be discussed.

  14. Double pulse laser-induced breakdown spectroscopy of explosives: Initial study towards improved discrimination

    Energy Technology Data Exchange (ETDEWEB)

    De Lucia, Frank C. [U.S. Army Research Laboratory, AMSRD-ARL-WM-BD, Aberdeen Proving Ground, MD, 21005-5069 (United States)], E-mail: fdelucia@arl.army.mil; Gottfried, Jennifer L.; Munson, Chase A.; Miziolek, Andrzej W. [U.S. Army Research Laboratory, AMSRD-ARL-WM-BD, Aberdeen Proving Ground, MD, 21005-5069 (United States)

    2007-12-15

    Detecting trace explosive residues at standoff distances in real-time is a difficult problem. One method ideally suited for real-time standoff detection is laser-induced breakdown spectroscopy (LIBS). However, atmospheric oxygen and nitrogen contributes to the LIBS signal from the oxygen- and nitrogen-containing explosive compounds, complicating the discrimination of explosives from other organic materials. While bathing the sample in an inert gas will remove atmospheric oxygen and nitrogen interference, it cannot practically be applied for standoff LIBS. Alternatively, we have investigated the potential of double pulse LIBS to improve the discrimination of explosives by diminishing the contribution of atmospheric oxygen and nitrogen to the LIBS signal. These initial studies compare the close-contact (< 1 m) LIBS spectra of explosives using single pulse LIBS in argon with double pulse LIBS in atmosphere. We have demonstrated improved discrimination of an explosive and an organic interferent using double pulse LIBS to reduce the air entrained in the analytical plasma.

  15. Identification of irradiated crab using EPR

    Energy Technology Data Exchange (ETDEWEB)

    Maghraby, A. [Radiation Dosimetry Department, National Institute for Standards (NIS), Ministry of Scientific Research, Haram, 12211- Giza, P.O. Box: 136 (Egypt)]. E-mail: maghrabism@yahoo.com

    2007-02-15

    EPR spectroscopy is a fast and powerful technique for the identification of irradiated food. Crab exoskeleton was divided into six parts: dactyl, cheliped, carapace, apron, swimming legs, and walking legs. Samples of the exoskeleton were prepared and irradiated to Cs-137 gamma radiation in the range (1.156-5.365 kGy). EPR spectra of unirradiated as well as irradiated samples were recorded and analyzed. Response to gamma radiation was plotted for each part of the exoskeleton, dactyl was found to be the most sensitive part, followed by the apron (38%), cheliped (37%), walking legs (30%), swimming legs (24%), and carapace (21%) relative to the dactyl response.

  16. Pulsed ELDOR spectroscopy of the Mo(V)/Fe(III) state of sulfite oxidase prepared by one-electron reduction with Ti(III) citrate.

    Science.gov (United States)

    Codd, Rachel; Astashkin, Andrei V; Pacheco, Andrew; Raitsimring, Arnold M; Enemark, John H

    2002-03-01

    The titration of chicken liver sulfite oxidase (SO) with the one-electron reductant Ti(III) citrate, at pH 7.0, results in nearly quantitative selective reduction of the Mo(VI) center to Mo(V), while the b-type heme center remains in the fully oxidized Fe(III) state. The selective reduction of the Mo(VI/V) couple has been established from electronic and EPR spectra. The electronic spectrum of the Fe(III) heme center is essentially unchanged during the titration, and the continuous wave (CW)-EPR spectrum shows the appearance of the well-known Mo(V) signal due to the low pH ( lpH) form of SO. Further confirmation of the selective formation of the Mo(V)/Fe(III) form of SO is provided by the approximately 1:1 ratio of the integrated intensities of the Mo(V) and low-spin Fe(III) EPR signals after addition of one equivalent of Ti(III). The selective generation of the Mo(V)/Fe(III) form of SO is unexpected, considering that previous microcoulometry and flash photolysis investigations have indicated that the Mo(VI/V) and Fe(III/II) couples of SO have similar reduction potentials at pH 7. The nearly quantitative preparation of the one-electron reduced Mo(V)/Fe(III) form of SO by reduction with Ti(III) has enabled the interaction between these two paramagnetic metal centers, which are linked by a flexible loop with no secondary structure, to be investigated for the first time by variable-frequency pulsed electron-electron double resonance (ELDOR) spectroscopy. The ELDOR kinetics were obtained from frozen solutions at 4.2 K at several microwave frequencies by pumping on the narrow Mo(V) signal and observing the effect on the Fe(III) primary echo at both higher and lower frequencies within the microwave C-band region. The ELDOR data indicate that freezing the solution of one-electron reduced SO produces localized regions where the concentration of SO approaches that in the crystal structure, which results in the interpair interactions being the dominant dipolar interaction

  17. Ultrafast Internal Conversion of Aromatic Molecules Studied by Photoelectron Spectroscopy using Sub-20 fs Laser Pulses

    Directory of Open Access Journals (Sweden)

    Toshinori Suzuki

    2014-02-01

    Full Text Available This article describes our recent experimental studies on internal conversion via a conical intersection using photoelectron spectroscopy. Ultrafast S2(ππ*–S1(nπ* internal conversion in pyrazine is observed in real time using sub-20 fs deep ultraviolet pulses (264 and 198 nm. While the photoelectron kinetic energy distribution does not exhibit a clear signature of internal conversion, the photoelectron angular anisotropy unambiguously reveals the sudden change of electron configuration upon internal conversion. An explanation is presented as to why these two observables have different sensitivities to internal conversion. The 198 nm probe photon energy is insufficient for covering the entire Franck-Condon envelopes upon photoionization from S2/S1 to D1/D0. A vacuum ultraviolet free electron laser (SCSS producing 161 nm radiation is employed to solve this problem, while its pulse-to-pulse timing jitter limits the time resolution to about 1 ps. The S2–S1 internal conversion is revisited using the sub-20 fs 159 nm pulse created by filamentation four-wave mixing. Conical intersections between D1(π−1 and D0(n−1 and also between the Rydberg state with a D1 ion core and that with a D0 ion core of pyrazine are studied by He(I photoelectron spectroscopy, pulsed field ionization photoelectron spectroscopy and one-color resonance-enhanced multiphoton ionization spectroscopy. Finally, ultrafast S2(ππ*–S1(ππ* internal conversion in benzene and toluene are compared with pyrazine.

  18. Single-pulse coherent anti-Stokes Raman spectroscopy via fiber Bragg grating

    Science.gov (United States)

    Oh, Seung Ryeol; Park, Joo Hyun; Kwon, Won Sik; Kim, Jin Hwan; Kim, Kyung-Soo; Lee, Jae Yong; Kim, Soohyun

    2016-03-01

    Fiber Bragg grating is used in a variety of applications. In this study, we suggest compact, cost-effective coherent anti- Stokes Raman spectroscopy which is based on the pulse shaping methods via commercialized fiber Bragg grating. The experiment is performed incorporating a commercialized femtosecond pulse laser system (MICRA, Coherent) with a 100 mm length of 780-HP fiber which is inscribed 50 mm of Bragg grating. The pump laser for coherent anti-Stokes Raman spectroscopy has a bandwidth of 90 nm and central wavelength of 815 nm with a notch shaped at 785 nm. The positive chirped pulse is compensated by chirped mirror set. We compensate almost 14000 fs2 of positive group delay dispersion for the transform-limited pulse at the sample position. The pulse duration was 15 fs with average power of 50 mW, and showed an adequate notch shape. Finally, coherent anti-Stokes Raman signals are observed using a spectrometer (Jobin Yvon Triax320 and TE-cooled Andor Newton EMCCD). We obtained coherent anti-Stokes Raman signal of acetone sample which have Raman peak at the spectral finger-print region. In conclusion, the proposed method is more simple and cost-effective than the methods of previous research which use grating pairs and resonant photonic crystal slab. Furthermore, the proposed method can be used as endoscope application.

  19. A comparative study of the effect of cholesterol on bicelle model membranes using X-band and Q-band EPR spectroscopy.

    Science.gov (United States)

    Ghimire, Harishchandra; Inbaraj, Johnson J; Lorigan, Gary A

    2009-08-01

    X-band and Q-band electron paramagnetic resonance (EPR) spectroscopic techniques were used to investigate the structure and dynamics of cholesterol containing phospholipid bicelles based upon molecular order parameters (S(mol)), orientational dependent hyperfine splittings and line shape analysis of the corresponding EPR spectra. The nitroxide spin-label 3-beta-doxyl-5-alpha-cholestane (cholestane) was incorporated into DMPC/DHPC bicelles to report the alignment of bicelles in the static magnetic field. The influence of cholesterol on aligned phospholipid bicelles in terms of ordering, the ease of alignment, phase transition temperature have been studied comparatively at X-band and Q-band. At a magnetic field of 1.25 T (Q-band), bicelles with 20 mol% cholesterol aligned at a much lower temperature (313 K), when compared to 318 K at a 0.35 T field strength for X-band, showed better hyperfine splitting values (18.29 G at X-band vs. 18.55 G at Q-band for perpendicular alignment and 8.25 G at X-band vs. 7.83 G at Q-band for the parallel alignment at 318 K) and have greater molecular order parameters (0.76 at X-band vs. 0.86 at Q-band at 318 K). Increasing cholesterol content increased the bicelle ordering, the bicelle-alignment temperature and the gel to liquid crystalline phase transition temperature. We observed that Q-band is more effective than X-band for studying aligned bicelles, because it yielded a higher ordered bicelle system for EPR spectroscopic studies.

  20. Pulsed photothermal radiometry for noncontact spectroscopy, material testing and inspection measurement

    Science.gov (United States)

    Tam, A. C.

    1984-08-01

    Photothermal Radiometry (PTR) is a sensitive technique for noncontact spectroscopy and inspection. Its principle is the following: a modulated beam of photons (or other particles) produces temperature transients in a sample; the corresponding transients in the infrared thermal radiation emitted from the sample are analyzed. This can provide absolute absorption coefficients, as well as information on thermal diffusivity, layered structure, and dimensions. Variations of PTR are possible with continuously-modulated or pulsed excitation, and with transmission or back-scattering detection. These variations are reviewed. The recent technique of pulsed PTR with backscattering detection is described in more detail, and some important single-ended remote sensing applications are discussed.

  1. 2D IR spectroscopy with phase-locked pulse pairs from a birefringent delay line.

    Science.gov (United States)

    Réhault, Julien; Maiuri, Margherita; Manzoni, Cristian; Brida, Daniele; Helbing, Jan; Cerullo, Giulio

    2014-04-21

    We introduce a new scheme for two-dimensional IR spectroscopy in the partially collinear pump-probe geometry. Translating birefringent wedges allow generating phase-locked pump pulses with exceptional phase stability, in a simple and compact setup. A He-Ne tracking scheme permits to scan continuously the acquisition time. For a proof-of-principle demonstration we use lithium niobate, which allows operation up to 5 μm. Exploiting the inherent perpendicular polarizations of the two pump pulses, we also demonstrate signal enhancement and scattering suppression.

  2. Double-pulse standoff laser-induced breakdown spectroscopy for versatile hazardous materials detection

    Energy Technology Data Exchange (ETDEWEB)

    Gottfried, Jennifer L. [U.S. Army Research Laboratory, AMSRD-ARL-WM-BD, Aberdeen Proving Ground, MD, 21005-5069 (United States)], E-mail: jennifer.gottfried@arl.army.mil; De Lucia, Frank C.; Munson, Chase A.; Miziolek, Andrzej W. [U.S. Army Research Laboratory, AMSRD-ARL-WM-BD, Aberdeen Proving Ground, MD, 21005-5069 (United States)

    2007-12-15

    We have developed a double-pulse standoff laser-induced breakdown spectroscopy (ST-LIBS) system capable of detecting a variety of hazardous materials at tens of meters. The use of a double-pulse laser improves the sensitivity and selectivity of ST-LIBS, especially for the detection of energetic materials. In addition to various metallic and plastic materials, the system has been used to detect bulk explosives RDX and Composition-B, explosive residues, biological species such as the anthrax surrogate Bacillus subtilis, and chemical warfare simulants at 20 m. We have also demonstrated the discrimination of explosive residues from various interferents on an aluminum substrate.

  3. Resonant femtosecond stimulated Raman spectroscopy with an intense actinic pump pulse: Application to conical intersections

    Science.gov (United States)

    Rao, B. Jayachander; Gelin, Maxim F.; Domcke, Wolfgang

    2017-02-01

    We theoretically investigate the feasibility of characterizing conical intersections with time-resolved resonant femtosecond stimulated Raman spectroscopy (FSRS) using an intense actinic pump pulse. We perform nonperturbative numerical simulations of FSRS signals for a three-electronic-state two-vibrational-mode model, which is inspired by the S 2 ( π π * )- S 1 ( n π * ) conical intersection in pyrazine. Our results show that moderately strong actinic pulses increase the intensity of vibrational fingerprint lines in FSRS transients. They facilitate the extraction of useful spectroscopic information by enhancing peaks revealing the coupling and tuning modes of the conical intersection.

  4. Spectroscopy of the hydrogen 1 S -3 S transition with chirped laser pulses

    Science.gov (United States)

    Yost, D. C.; Matveev, A.; Grinin, A.; Peters, E.; Maisenbacher, L.; Beyer, A.; Pohl, R.; Kolachevsky, N.; Khabarova, K.; Hänsch, T. W.; Udem, Th.

    2016-04-01

    We identify a systematic present in two-photon direct frequency comb spectroscopy (DFCS) which is a result of chirped laser pulses and is a manifestation of the first-order Doppler effect. We carefully analyze this systematic and propose methods for its mitigation within the context of our measurement of the hydrogen 1 S -3 S transition. We also report on our determination of the absolute frequency of this transition, which is comparable to a previous measurement using continuous-wave spectroscopy [O. Arnoult et al., Eur. Phys. J. D 60, 243 (2010), 10.1140/epjd/e2010-00249-6], but was obtained with a different experimental method.

  5. Application of spectroscopic methods for identification (FT-IR, Raman spectroscopy) and determination (UV, EPR) of quercetin-3-O-rutinoside. Experimental and DFT based approach.

    Science.gov (United States)

    Paczkowska, Magdalena; Lewandowska, Kornelia; Bednarski, Waldemar; Mizera, Mikołaj; Podborska, Agnieszka; Krause, Anna; Cielecka-Piontek, Judyta

    2015-04-05

    Vibrational (FT-IR, Raman) and electronic (UV, EPR) spectral measurements were performed for an analysis of rutin (quercetin-3-O-rutinoside) obtained from Rutaofficinalis. The identification of rutin was done with the use of FT-IR and Raman spectra. Those experimental spectra were determined with the support of theoretical calculations based on a DFT method with the B3LYP hybrid functional and 6-31G(d,p) basis set. The application of UV and EPR spectra was found to be a suitable analytical approach to the evaluation of changes in rutin exposed to certain physicochemical factors. Differences in absorbance observed in direct UV spectra were used to monitor changes in the concentration of rutin in degraded samples. Spectra of electron paramagnetic resonance allowed studying the process of free-radical quenching in rutin following its exposure to light. The molecular electrostatic potential (MEP) and frontier molecular orbitals (LUMO-HOMO) were also determined in order to predict structural changes and reactive sites in rutin.

  6. Application of spectroscopic methods for identification (FT-IR, Raman spectroscopy) and determination (UV, EPR) of quercetin-3-O-rutinoside. Experimental and DFT based approach

    Science.gov (United States)

    Paczkowska, Magdalena; Lewandowska, Kornelia; Bednarski, Waldemar; Mizera, Mikołaj; Podborska, Agnieszka; Krause, Anna; Cielecka-Piontek, Judyta

    2015-04-01

    Vibrational (FT-IR, Raman) and electronic (UV, EPR) spectral measurements were performed for an analysis of rutin (quercetin-3-O-rutinoside) obtained from Rutaofficinalis. The identification of rutin was done with the use of FT-IR and Raman spectra. Those experimental spectra were determined with the support of theoretical calculations based on a DFT method with the B3LYP hybrid functional and 6-31G(d,p) basis set. The application of UV and EPR spectra was found to be a suitable analytical approach to the evaluation of changes in rutin exposed to certain physicochemical factors. Differences in absorbance observed in direct UV spectra were used to monitor changes in the concentration of rutin in degraded samples. Spectra of electron paramagnetic resonance allowed studying the process of free-radical quenching in rutin following its exposure to light. The molecular electrostatic potential (MEP) and frontier molecular orbitals (LUMO-HOMO) were also determined in order to predict structural changes and reactive sites in rutin.

  7. Improved Sensing Pulses for Increased Human Head Depth Measurement Sensitivity With Electrical Impedance Spectroscopy

    Science.gov (United States)

    Lev, Michael H.

    2017-01-01

    This paper describes an improved electrical impedance spectroscopy (EIS) stimulus paradigm, based on dual-energy pulses using the stochastic Gabor function (SGF) that may more sensitively assess deep brain tissue impedance than current single-pulse paradigms. The SGF is a uniformly distributed noise, modulated by a Gaussian envelope, with a wide-frequency spectrum representation regardless of the stimuli energy, and is least compact in the sample frequency phase plane. Numerical results obtained using a realistic human head model confirm that two sequential SGF pulses at different energies can improve EIS depth sensitivity when used in a dual-energy subtraction scheme. Specifically, although the two SGF pulses exhibit different tissue current distributions, they maintain the broadband sensing pulse characteristics needed to generate all the frequencies of interest. Moreover, finite-difference time domain simulations show that this dual-energy excitation scheme is capable of reducing the amplitude of weighted current densities surface directly underneath the electrodes by approximately 3 million times versus single stimulation pulses, while maintaining an acceptable tissue conductivity distribution at depth. This increased sensitivity for the detection of small, deep impedance changes might be of value in potential future EIS applications, such as the portable, point-of-care detection of deep brain hemorrhage or infarction. PMID:24043365

  8. A compact field-portable double-pulse laser system to enhance laser induced breakdown spectroscopy

    Science.gov (United States)

    Li, Shuo; Liu, Lei; Yan, Aidong; Huang, Sheng; Huang, Xi; Chen, Rongzhang; Lu, Yongfeng; Chen, Kevin

    2017-02-01

    This paper reports the development of a compact double-pulse laser system to enhance laser induced breakdown spectroscopy (LIBS) for field applications. Pumped by high-power vertical-surface emitting lasers, the laser system that produces 16 ns pulse at 12 mJ/pulse with total weight less than 10 kg is developed. The inter-pulse delay can be adjusted from 0 μ s with 0.5 μ s increment. Several LIBS experiments were carried out on NIST standard aluminum alloy samples. Comparing with the single-pulse LIBS, up to 9 times enhancement in atomic emission line was achieved with continuum background emission reduced by 70%. This has led to up to 10 times improvement in the limit of detection. Signal stability was also improved by 128% indicating that a more robust and accurate LIBS measurement can be achieved using a compact double-pulse laser system. This paper presents a viable and field deployable laser tool to dramatically improve the sensitivity and applicability of LIBS for a wide array of applications.

  9. Multidimensional resonant nonlinear spectroscopy with coherent broadband x-ray pulses

    Science.gov (United States)

    Bennett, Kochise; Zhang, Yu; Kowalewski, Markus; Hua, Weijie; Mukamel, Shaul

    2016-12-01

    New x-ray free electron laser (XFEL) and high harmonic generation (HHG) light sources are capable of generating short and intense pulses that make x-ray nonlinear spectroscopy possible. Multidimensional spectroscopic techniques, which have long been used in the nuclear magnetic resonance, infrared, and optical regimes to probe the electronic structure and nuclear dynamics of molecules by sequences of short pulses with variable delays, can thus be extended to the attosecond x-ray regime. This opens up the possibility of probing core-electronic structure and couplings, the real-time tracking of impulsively created valence-electronic wavepackets and electronic coherences, and monitoring ultrafast processes such as nonadiabatic electron-nuclear dynamics near conical-intersection crossings. We survey various possible types of multidimensional x-ray spectroscopy techniques and demonstrate the novel information they can provide about molecules.

  10. Glass transition temperatures of epoxy resins by pulsed nuclear magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rutenberg, A.C.; Dorsey, G.F.; Peck, C.G.

    1976-04-21

    Pulsed nuclear magnetic resonance spectroscopy has been used to measure the glass transition temperatures of cured epoxy resins. These measurements make it possible to monitor the cure and determine the glass transition temperature as a function of the curing conditions and the concentration of the components. Knowledge of the glass transition temperature of the cured epoxies allows screening of them for a number of uses, including adhesives and coatings operations.

  11. A trap-based pulsed positron beam optimised for positronium laser spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, B. S., E-mail: ben.cooper.13@ucl.ac.uk; Alonso, A. M.; Deller, A.; Wall, T. E.; Cassidy, D. B. [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom)

    2015-10-15

    We describe a pulsed positron beam that is optimised for positronium (Ps) laser-spectroscopy experiments. The system is based on a two-stage Surko-type buffer gas trap that produces 4 ns wide pulses containing up to 5 × 10{sup 5} positrons at a rate of 0.5-10 Hz. By implanting positrons from the trap into a suitable target material, a dilute positronium gas with an initial density of the order of 10{sup 7} cm{sup −3} is created in vacuum. This is then probed with pulsed (ns) laser systems, where various Ps-laser interactions have been observed via changes in Ps annihilation rates using a fast gamma ray detector. We demonstrate the capabilities of the apparatus and detection methodology via the observation of Rydberg positronium atoms with principal quantum numbers ranging from 11 to 22 and the Stark broadening of the n = 2 → 11 transition in electric fields.

  12. Applications of ultra-short pulsed laser ablation: thin films deposition and fs/ns dual-pulse laser-induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Teghil, R; De Bonis, A; Galasso, A [Dipartimento di Chimica, Universita della Basilicata, Via N. Sauro 85, 85100 Potenza (Italy); Santagata, A; Albano, G; Villani, P; Spera, D; Parisi, G P [CNR-IMIP, Unita di Potenza, Via S. Loja, 85050 Tito Scalo (Italy)], E-mail: roberto.teghil@unibas.it

    2008-10-15

    In this paper, we report a survey of two of the large number of possible practical applications of the laser ablation performed by an ultra-short pulse laser, namely pulsed laser deposition (PLD) and fs/ns dual-pulse laser-induced breakdown spectroscopy (DP-LIBS). These applications differ from those using just longer pulsed lasers as a consequence of the distinctive characteristics of the plasma produced by ultra-short laser beams. The most important feature of this plasma is the large presence of particles with nanometric size which plays a fundamental role in both applications.

  13. Pulse Phase-coherent Timing and Spectroscopy of CXOU J164710.2-45521 Outbursts

    CERN Document Server

    Castillo, Guillermo A Rodríguez; Esposito, Paolo; Pons, José A; Rea, Nanda; Turolla, Roberto; Viganò, Daniele; Zane, Silvia

    2014-01-01

    We present a long-term phase-coherent timing analysis and pulse-phase resolved spectroscopy for the two outbursts observed from the transient anomalous X-ray pulsar CXOU J164710.2-45521. For the first outburst we used 11 Chandra and XMM-Newton observations between September 2006 to August 2009, the longest baseline yet for this source. We obtain a coherent timing solution with $P=10.61065583(4)$ s, $\\dot{P} = 9.72(1) \\times 10^{-13}\\;$s s$^{-1}$ and $\\ddot{P} = -1.05(5)\\times10^{-20}\\; $s s$^{-2}$. Under the standard assumptions this implies a surface dipolar magnetic field of $\\sim 10^{14}$ G, confirming this source as a standard-$B$ magnetar. We also study the evolution of the pulse profile (shape, intensity and pulsed fraction) as a function of time and energy. Using the phase-coherent timing solution we perform a phase-resolved spectroscopy analysis, following the spectral evolution of pulse-phase features, which hints at the physical processes taking place on the star. The results are discussed from the ...

  14. Electron Paramagnetic Resonance Imaging: 1. CW-EPR Imaging

    Indian Academy of Sciences (India)

    2016-07-01

    Twentieth century bore witness to remarkable scientists whohave advanced our understanding of the brain. Among them,EPR (Electron Paramagnetic Resonance) imaging is particularlyuseful in monitoring hypoxic zones in tumors which arehighly resistant to radiation and chemotherapeutic treatment.This first part of the article covers aspects of CW(continuous wave) imaging with details of FT (pulsed FourierTransform)-EPR imaging covered in Part 2, to be publishedin the next issue of Resonance.

  15. Synthesis, characterization, EPR spectroscopy and catalytic activity of a new oxidovanadium(IV) complex with N2O2-donor ligand

    Science.gov (United States)

    Mahboubi-Anarjan, Parisa; Bikas, Rahman; Hosseini-Monfared, Hassan; Aleshkevych, Pavlo; Mayer, Peter

    2017-03-01

    A new oxidovanadium(IV) complex, 2[VOL(OH2)] CH3OH (1), was synthesized from the reaction of VO(acac)2 with a symmetric N,O-donor Schiff base ligand (H2L), in which H2L is 6,6'-((1E,1‧E)-((2-hydroxypropane-1,3-diyl)bis(azanylylidene))bis(methanylylidene))bis(2-methoxyphenol). The compounds were characterized by elemental analysis and spectroscopic methods. The molecular structure of complex was determined by single-crystal X-ray analysis which indicated that the crystal packing of complex contains two independent mononuclear vanadium complexes connected together by several strong hydrogen bonding interactions. The EPR spectrum of powdered complex 1 at liquid helium temperature showed two intensive octets which proved to be associated with V4+ ions with 3d1 electronic configuration. From EPR spectrum the values of the parameters: g|| = 1.9454 ± 0.0004, g⊥ = 1.9491 ± 0.0004, A|| = 0.0084 ± 0.0008 cm-1 and A⊥ = 0.0033 ± 0.0006 cm-1 were calculated for this complex. Complex 1 was employed as catalyst for oxidation of cyclooctene in the presence of H2O2 as oxidant. In order to obtain the suitable condition of catalytic oxidation, the effect of various parameters including the amount of the catalyst, temperature and solvent was studied. The results of catalytic studies showed that complex 1 can provide an effective and selective catalytic system for epoxidation of cyclooctene.

  16. Quantitative analysis of arsenic in mine tailing soils using double pulse-laser induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Ji-hyun [Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 500-712 (Korea, Republic of); Lenth, Christoph; Salb, Christian [Photonic Sensor Technology, Laser-Laboratorium Goettingen e.V., Hans-Adolf-Krebs-Weg 1 D-37077 Goettingen (Germany); Ko, Eun-Joung; Kim, Kyoung-Woong [Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 500-712 (Korea, Republic of); Park, Kihong, E-mail: kpark@gist.ac.k [Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 500-712 (Korea, Republic of)

    2009-10-15

    A double pulse-laser induced breakdown spectroscopy (DP-LIBS) was used to determine arsenic (As) concentration in 16 soil samples collected from 5 different mine tailing sites in Korea. We showed that the use of double pulse laser led to enhancements of signal intensity (by 13% on average) and signal-to-noise ratio of As emission lines (by 165% on average) with smaller relative standard deviation compared to single pulse laser approach. We believe this occurred because the second laser pulse in the rarefied atmosphere produced by the first pulse led to the increase of plasma temperature and populations of exited levels. An internal standardization method using a Fe emission line provided a better correlation and sensitivity between As concentration and the DP-LIBS signal than any other elements used. The Fe was known as one of the major components in current soil samples, and its concentration varied not substantially. The As concentration determined by the DP-LIBS was compared with that obtained by atomic absorption spectrometry (AAS) to evaluate the current LIBS system. They are correlated with a correlation coefficient of 0.94. The As concentration by the DP-LIBS was underestimated in the high concentration range (>1000 mg-As/kg). The loss of sensitivity that occurred at high concentrations could be explained by self-absorption in the generated plasma.

  17. Double-pulse laser ablation coupled to laser-induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Glaus, Reto, E-mail: reglaus@ufl.edu; Hahn, David W.

    2014-08-01

    Laser ablation coupled to laser-induced breakdown spectroscopy (LA-LIBS) is an analytical method, which minimizes sample matrix effects typically found in quantitative LIBS-based direct solid analyses. This paper reports the application of double-pulse laser ablation (DP-LA) to improve the analyte response and the achievable precisions of LA-LIBS. Two coaxial laser beams were applied at the ablation site and the analytical signals were then collected from a second free-standing LIBS plasma downstream of the ablation site. Signal improvements of up to one order of magnitude were observed compared to single-pulse LA-LIBS. The effect of the interpulse delay on the observed signal-to-noise ratios was studied and the quantification capabilities of the optimized DP-LA-LIBS setup were investigated for manganese and iron in a broad range of different alloy types. A linear response was observed for manganese across the different matrices, allowing for nonmatrix-matched calibrations. Matrix effects were observed when analyzing aluminum samples, which, however, could be compensated for by applying iron as internal standard. Size distributions of the ablated material and electron density measurements provide additional insight into the double-pulse process, with additional future work suggested. - Highlights: • Double-pulse laser ablation was coupled to laser-induced breakdown spectroscopy. • Nonmatrix-matched calibration of manganese in various alloys was performed. • Improved sensitivities and precisions compared to single-pulse LA were demonstrated. • Remaining matrix effects and internal standardization are discussed.

  18. Development of Sub 10 fs Visible-NIR, UV, and DUV Pulses and Their Applications to Ultrafast Spectroscopy

    OpenAIRE

    Takayoshi Kobayashi; Atsushi Yabushita; Yuichiro Kida

    2016-01-01

    In the first section of this Chapter, the basics of nonlinear optical (NLO) processes are systematically described. Then the generation of the visible pulse utilizing the NLO processes is described and ultrafast spectroscopy using the visible pulse is discussed. By using such short pulse, fast chemical reactions, which cannot be identified by utilizing strobe light or flash lamp, can be studied. After the development of femtosecond lasers, they have been widely applied to observe the transiti...

  19. Unprecedented access of phenolic substrates to the heme active site of a catalase: substrate binding and peroxidase-like reactivity of Bacillus pumilus catalase monitored by X-ray crystallography and EPR spectroscopy.

    Science.gov (United States)

    Loewen, Peter C; Villanueva, Jacylyn; Switala, Jacek; Donald, Lynda J; Ivancich, Anabella

    2015-05-01

    Heme-containing catalases and catalase-peroxidases catalyze the dismutation of hydrogen peroxide as their predominant catalytic activity, but in addition, individual enzymes support low levels of peroxidase and oxidase activities, produce superoxide, and activate isoniazid as an antitubercular drug. The recent report of a heme enzyme with catalase, peroxidase and penicillin oxidase activities in Bacillus pumilus and its categorization as an unusual catalase-peroxidase led us to investigate the enzyme for comparison with other catalase-peroxidases, catalases, and peroxidases. Characterization revealed a typical homotetrameric catalase with one pentacoordinated heme b per subunit (Tyr340 being the axial ligand), albeit in two orientations, and a very fast catalatic turnover rate (kcat  = 339,000 s(-1) ). In addition, the enzyme supported a much slower (kcat  = 20 s(-1) ) peroxidatic activity utilizing substrates as diverse as ABTS and polyphenols, but no oxidase activity. Two binding sites, one in the main access channel and the other on the protein surface, accommodating pyrogallol, catechol, resorcinol, guaiacol, hydroquinone, and 2-chlorophenol were identified in crystal structures at 1.65-1.95 Å. A third site, in the heme distal side, accommodating only pyrogallol and catechol, interacting with the heme iron and the catalytic His and Arg residues, was also identified. This site was confirmed in solution by EPR spectroscopy characterization, which also showed that the phenolic oxygen was not directly coordinated to the heme iron (no low-spin conversion of the Fe(III) high-spin EPR signal upon substrate binding). This is the first demonstration of phenolic substrates directly accessing the heme distal side of a catalase.

  20. Double-pulse laser-induced breakdown spectroscopy analysis of scales from petroleum pipelines

    Energy Technology Data Exchange (ETDEWEB)

    Cavalcanti, G.H. [Physics Department of University Federal Fluminense, Av. Gal. Milton Tavares de Souza, s/n" o – CEP 24210-346 – Niterói, Rio de Janeiro (Brazil); Rocha, A.A. [Department of Analytical Chemistry of the Fluminense Federal University (UFF), Niterói, Rio de Janeiro CEP: 24020-141 (Brazil); Damasceno, R.N. [Biomass and Water Research Center of the Fluminense Federal University (NAB/UFF), Niterói, Rio de Janeiro (Brazil); Legnaioli, S.; Lorenzetti, G.; Pardini, L. [Institute of Chemistry of Organometallic Compounds Of CNR, Research Area of National Research Council, Via G. Moruzzi, 1 — 56124 Pisa (Italy); Palleschi, V., E-mail: vincenzo.palleschi@cnr.it [Institute of Chemistry of Organometallic Compounds Of CNR, Research Area of National Research Council, Via G. Moruzzi, 1 — 56124 Pisa (Italy)

    2013-09-01

    Pipeline scales from the Campos Bay Petroleum Field near Rio de Janeiro, Brazil have been analyzed by both Raman spectroscopy and by laser-induced breakdown spectroscopy (LIBS) using a double-pulse, calibration-free approach. Elements that are characteristic of petroleum (e.g. C, H, N, O, Mg, Na, Fe and V) were detected, in addition to the Ca, Al, and Si which form the matrix of the scale. The LIBS results were compared with the results of micro-Raman spectroscopy, which confirmed the nature of the incrustations inferred by the LIBS analysis. Results of this preliminary study suggest that diffusion of pipe material into the pipeline intake column plays an important role in the growth of scale. Thanks to the simplicity and relative low cost of equipment and to the fact that no special chemical pre-treatment of the samples is needed, LIBS can offer very fast acquisition of data and the possibility of in situ measurements. LIBS could thus represent an alternative or complementary method for the chemical characterization of the scales by comparison to conventional analytical techniques, such as X-ray diffraction or X-ray fluorescence. - Highlights: • Samples of scales from petroleum pipelines were analyzed using double pulse LIBS. • LIBS is proposed as an alternative method to conventional analytical techniques. • The scale growth is influenced by the product of corrosion in the column of production. • The diffusion of pipe material into the inlay is important for the growth of scale.

  1. Electron spin dynamics of Ce3 + ions in YAG crystals studied by pulse-EPR and pump-probe Faraday rotation

    Science.gov (United States)

    Azamat, D. V.; Belykh, V. V.; Yakovlev, D. R.; Fobbe, F.; Feng, D. H.; Evers, E.; Jastrabik, L.; Dejneka, A.; Bayer, M.

    2017-08-01

    The spin relaxation dynamics of Ce3 + ions in heavily cerium-doped YAG crystals is studied using pulse-electron paramagnetic resonance and time-resolved pump-probe Faraday rotation. Both techniques address the 4 f ground state, while pump-probe Faraday rotation also provides access to the excited 5 d state. We measure a millisecond spin-lattice relaxation time T1, a microsecond spin coherence time T2, and a ˜10 ns inhomogeneous spin dephasing time T2* for the Ce3 + ground state at low temperatures. The spin-lattice relaxation of Ce3 + ions is due to modified Raman processes involving the optical phonon mode at ˜125 cm-1 . The relaxation at higher temperature goes through a first excited level of the 5/2 2F term at about ℏ ω ≈228 cm-1 . Effects provided by the hyperfine interaction of the Ce3 + with the 27Al nuclei are observed.

  2. Synthesis, structure, magnetic properties and EPR spectroscopy of a copper(II) coordination polymer with a ditopic hydrazone ligand and acetate bridges.

    Science.gov (United States)

    Bikas, Rahman; Aleshkevych, Pavlo; Hosseini-Monfared, Hassan; Sanchiz, Joaquín; Szymczak, Ritta; Lis, Tadeusz

    2015-01-28

    A new one dimensional coordination polymer of copper(II), [Cu4(L)2(μ2-1,1-OAc)2(μ2-1,3-OAc)4]n (1), has been synthesized and characterized by spectroscopic methods and single crystal X-ray analysis [HL = (E)-N'-(phenyl(pyridin-2-yl)methylene)isonicotinhydrazide, OAc = acetate anion]. The coordination polymer contains two kinds of Cu(II) dimers which are connected by two types of acetate (μ2-1,1- and μ2-1,3-) bridging groups. The ditopic isonicotinhydrazone ligand coordinates to the Cu1 center through the N2O-donor set and connects to the Cu2 center by a pyridine group of the isonicotine part. The EPR and magnetic susceptibility measurements confirm the existence of two kinds of Cu(II) dimers. The intradimer isotropic exchange was estimated to be +0.80(1) cm(-1) for the ferromagnetic Cu1···Cu1 dimeric unit and -315 (1) cm(-1) for the antiferromagnetic Cu2···Cu2 dimeric unit.

  3. Pulsed photothermal radiometry for noncontact spectroscopy, material testing and inspection measurements

    Science.gov (United States)

    Tam, A. C.

    1985-02-01

    Photothermal radiometry (PTR) is a sensitive technique for noncontact spectroscopy and inspection. Its principle is the following: a modulated beam of photons (or other particles) produces temperature transients in a sample; the corresponding transients in the IR thermal radiation emitted from the sample are analyzed. This can provide absolute absorption coefficients, as well as information on thermal diffusivity, layered structure and dimensions. Variations of PTR are possible with continuously-modulated or pulsed excitation, and with transmission or back-scattering detection. These variations are reviewed. The recent technique of pulsed PTR with back-scattering detection is described in more detail, and some important single-ended remote-sensing applications are discussed.

  4. Sensitive and ultra-fast species detection using pulsed cavity ringdown spectroscopy

    KAUST Repository

    Alquaity, Awad

    2015-01-01

    Pulsed cavity ringdown spectroscopy (CRDS) is used to develop a novel, ultra-fast, high-sensitivity diagnostic for measuring species concentrations in shock tube experiments. The diagnostic is demonstrated by monitoring trace concentrations of ethylene in the mid-IR region near 949.47 cm-1. Each ringdown measurement is completed in less than 1 μs and the time period between successive pulses is 10 μs. The high sensitivity diagnostic has a noise-equivalent detection limit of 1.08 x 10-5 cm-1 which enables detection of 15 ppm ethylene at fuel pyrolysis conditions (1845 K and 2 bar) and 294 ppb ethylene under ambient conditions (297 K and 1 bar). To our knowledge, this is the first successful application of the cavity ringdown method to the measurement of species time-histories in a shock tube. © 2015 OSA.

  5. Quantitative interpretation of time-resolved coherent anti-Stokes Raman spectroscopy with all Gaussian pulses

    CERN Document Server

    Ariunbold, Gombojav O

    2016-01-01

    Coherent Raman scattering spectroscopy is studied purposely, with the Gaussian ultrashort pulses as a hands-on elucidatory extraction tool of the clean coherent Raman resonant spectra from the overall measured data contaminated with the non-resonant four wave mixing background. The integral formulae for both the coherent anti-Stokes and Stokes Raman scattering are given in the semiclassical picture, and the closed-form solutions in terms of a complex error function are obtained. An analytic form of maximum enhancement of pure coherent Raman spectra at threshold time delay depending on bandwidth of probe pulse is also obtained. The observed experimental data for pyridine in liquid-phase are quantitatively elucidated and the inferred time-resolved coherent Raman resonant results are reconstructed with a new insight.

  6. Composite pulses in Hyper-Ramsey spectroscopy for the next generation of atomic clocks

    Science.gov (United States)

    Zanon-Willette, T.; Minissale, M.; Yudin, V. I.; Taichenachev, A. V.

    2016-06-01

    The next generation of atomic frequency standards based on an ensemble of neutral atoms or a single-ion will provide very stringent tests in metrology, applied and fundamental physics requiring a new step in very precise control of external systematic corrections. In the proceedings of the 8th Symposium on Frequency Standards and Metrology, we present a generalization of the recent Hyper-Ramsey spectroscopy with separated oscillating fields using composites pulses in order to suppress field frequency shifts induced by the interrogation laser itself. Sequences of laser pulses including specific selection of phases, frequency detunings and durations are elaborated to generate spectroscopic signals with a strong reduction of the light-shift perturbation by off resonant states. New optical clocks based on weakly allowed or completely forbidden transitions in atoms, ions, molecules and nuclei will benefit from these generalized Ramsey schemes to reach relative accuracies well below the 10-18 level.

  7. Femtosecond time-resolved impulsive stimulated Raman spectroscopy using sub-7-fs pulses: Apparatus and applications

    Science.gov (United States)

    Kuramochi, Hikaru; Takeuchi, Satoshi; Tahara, Tahei

    2016-04-01

    We describe details of the setup for time-resolved impulsive stimulated Raman spectroscopy (TR-ISRS). In this method, snapshot molecular vibrational spectra of the photoreaction transients are captured via time-domain Raman probing using ultrashort pulses. Our instrument features transform-limited sub-7-fs pulses to impulsively excite and probe coherent nuclear wavepacket motions, allowing us to observe vibrational fingerprints of transient species from the terahertz to 3000-cm-1 region with high sensitivity. Key optical components for the best spectroscopic performance are discussed. The TR-ISRS measurements for the excited states of diphenylacetylene in cyclohexane are demonstrated, highlighting the capability of our setup to track femtosecond dynamics of all the Raman-active fundamental molecular vibrations.

  8. Composite pulses in Hyper-Ramsey spectroscopy for the next generation of atomic clocks

    CERN Document Server

    Zanon-Willette, T; Yudin, V I; Taichenachev, A V

    2016-01-01

    The next generation of atomic frequency standards based on an ensemble of neutral atoms or a single-ion will provide very stringent tests in metrology, applied and fundamental physics requiring a new step in very precise control of external systematic corrections. In the proceedings of the 8th Symposium on Frequency Standards and Metrology, we present a generalization of the recent Hyper-Ramsey spectroscopy with separated oscillating fields using composites pulses in order to suppress field frequency shifts induced by the interrogation laser itself. Sequences of laser pulses including specific selection of phases, frequency detunings and durations are elaborated to generate spectroscopic signals with a strong reduction of the light-shift perturbation by off resonant states. New optical clocks based on weakly allowed or completely forbidden transitions in atoms, ions, molecules and nuclei will benefit from these generalized Ramsey schemes to reach relative accuracies well below the 10$^{-18}$ level.

  9. Light Dependent Resistance as a Sensor in Spectroscopy Setups Using Pulsed Light and Compared with Electret Microphones

    Directory of Open Access Journals (Sweden)

    Daniel Acosta-Avalos

    2006-05-01

    Full Text Available Light-dependent resistances (LDR are cheap light sensors. A less known lightdetector is the electret microphone, whose electret membrane functions as a perfectabsorber, but only detects pulsed light. The aim of this study was to analyze the use of aLDR and an electret microphone as a light sensor in an optical spectroscopy system usingpulsed light. A photoacoustic spectroscopy setup was used, substituting the photoacousticchamber by the light sensor proposed. The absorption spectra of two different liquids wereanalyzed. The results obtained allow the recommendation of the LDR as the first choice inthe construction of cheap homemade pulsed light spectroscopy systems.

  10. Regional spectroscopy of paraffin-embedded breast cancer tissue using pulsed terahertz transmission imaging

    Science.gov (United States)

    Bowman, Tyler; El-Shenawee, Magda; Campbell, Lucas

    2016-03-01

    This work seeks to obtain the properties of paraffin-embedded breast cancer tumor tissues using transmission imaging and spectroscopy. Formalin-fixed and paraffin-embedded breast tumors are first sectioned into slices of 20 μm and 30 μm and placed between two tsurupica slides. The slides are then scanned in a pulsed terahertz system using transmission imaging. The tissue regions in adjacent pathology section are compared to the transmission imaging scan in order to define a region of points over which to average the electrical properties results from the scan.

  11. Dual-Comb Coherent Raman Spectroscopy with Lasers of 1-GHz Pulse Repetition Frequency

    CERN Document Server

    Mohler, Kathrin J; Yan, Ming; Hänsch, Theodor W; Picqué, Nathalie

    2016-01-01

    We extend the technique of multiplex coherent Raman spectroscopy with two femtosecond mode-locked lasers to oscillators of a pulse repetition frequency of 1 GHz. We demonstrate spectra of liquids, which span 1100 cm$^{-1}$ of Raman shifts. At a resolution of 6 cm$^{-1}$, their measurement time may be as short as 5 microseconds for a refresh rate of 2 kHz. The waiting period between acquisitions is improved ten-fold compared to previous experiments with two lasers of 100-MHz repetition frequencies.

  12. Characterization of Temperature Induced Phase Transitions in the Five Polymorphic Forms of Sulfathia-zole by Terahertz Pulsed Spectroscopy and Differential Scanning Calorimetry

    DEFF Research Database (Denmark)

    Zeitler, J. Axel; Newnham, David A.; Taday, Philip F.;

    2006-01-01

    The far-infrared properties of all five described polymorphic forms of the drug sulfathiazole have been studied by terahertz pulsed spectroscopy and low frequency Raman spectroscopy. The spectra of the different polymorphs are distinctly different. Terahertz pulsed spectroscopy proves to be a rapid...

  13. Effect of atmosphere on collinear double-pulse laser-induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Andrew J. Effenberger, Jr.; Jill R. Scott

    2010-09-01

    Double pulse laser induced breakdown spectroscopy (DP-LIBS) has been shown to enhance LIBS spectra. Several researches have reported significant increases in signal-to-noise and or spectral intensity [1-4]. In addition to DP-LIBS, atmospheric conditions can also increase spectra intensity. For example, Iida [5] found that He and Ar both increase LIBS intensity compared to air at one 1 atm. It was also found that as the pressure was decreased to 100 Torr, LIBS intensity increased in Ar and air for single pulse (SP) LIBS. In this study, a collinear DP-LIBS scheme is used along with manipulation of the atmospheric conditions. The DP-LIBS scheme consists of a 355 nm ablative pulse fired into a sample contained in a vacuum chamber. A second analytical 1064 nm pulse is then fired 100 ns to 10 µs after and along the same path of the first pulse. Ar, He and air at pressures ranging from atmospheric pressure (630 Torr at elevation) to 10-5 Torr are introduced during DP-LIBS and SP-LIBS experiments. For a brass sample, a significant increase in spectral intensity of Cu and Zn lines were observed in DP-LIBS under Ar compared to DP-LIBS in air (Figure 1). It was also found that Cu and Zn lines acquired with SP-LIBS in Ar are nearly as intense as DP-LIBS in air. Signal-to-noise for lines from various samples will be reported for both DP-LIBS and SP-LIBS in Ar, He, and air at pressures ranging from 630 Torr to 10-5 Torr.

  14. Signal enhancement in collinear double-pulse laser-induced breakdown spectroscopy applied to different soils

    Energy Technology Data Exchange (ETDEWEB)

    Nicolodelli, Gustavo, E-mail: gunicolodelli@hotmail.com [Embrapa Instrumentation, Rua XV de Novembro, 1452, CEP 13560-970 São Carlos, SP (Brazil); Senesi, Giorgio Saverio, E-mail: giorgio.senesi@imip.cnr.it [Institute of Inorganic Methodologies and Plasmas, CNR, Bari, 70126 Bari (Italy); Romano, Renan Arnon, E-mail: renan.romano@gmail.com [Embrapa Instrumentation, Rua XV de Novembro, 1452, CEP 13560-970 São Carlos, SP (Brazil); Physics Institute of São Carlos, University of São Paulo, IFSC-USP, Av. Trabalhador são-carlense, 400 Pq. Arnold Schimid, 13566-590 São Carlos, SP (Brazil); Oliveira Perazzoli, Ivan Luiz de, E-mail: ivanperazzoli@hotmail.com [Embrapa Instrumentation, Rua XV de Novembro, 1452, CEP 13560-970 São Carlos, SP (Brazil); Milori, Débora Marcondes Bastos Pereira, E-mail: debora.milori@embrapa.br [Embrapa Instrumentation, Rua XV de Novembro, 1452, CEP 13560-970 São Carlos, SP (Brazil)

    2015-09-01

    Laser-induced breakdown spectroscopy (LIBS) is a well-known consolidated analytical technique employed successfully for the qualitative and quantitative analysis of solid, liquid, gaseous and aerosol samples of very different nature and origin. Several techniques, such as dual-pulse excitation setup, have been used in order to improve LIBS's sensitivity. The purpose of this paper was to optimize the key parameters as excitation wavelength, delay time and interpulse, that influence the double pulse (DP) LIBS technique in the collinear beam geometry when applied to the analysis at atmospheric air pressure of soil samples of different origin and texture from extreme regions of Brazil. Additionally, a comparative study between conventional single pulse (SP) LIBS and DP LIBS was performed. An optimization of DP LIBS system, choosing the correct delay time between the two pulses, was performed allowing its use for different soil types and the use of different emission lines. In general, the collinear DP LIBS system improved the analytical performances of the technique by enhancing the intensity of emission lines of some elements up to about 5 times, when compared with conventional SP-LIBS, and reduced the continuum emission. Further, the IR laser provided the best performance in re-heating the plasma. - Highlights: • The correct choice of the delay time between the two pulses is crucial for the DP system. • An optimization of DP LIBS system was performed allowing its use for different soil and the use of different emission lines. • The DP LIBS system improved the analytical performances of the technique up to about 5 times, when compared with SP LIBS. • The IR laser provided the best performance in re-heating the plasma.

  15. A novel non-linear recursive filter design for extracting high rate pulse features in nuclear medicine imaging and spectroscopy.

    Science.gov (United States)

    Sajedi, Salar; Kamal Asl, Alireza; Ay, Mohammad R; Farahani, Mohammad H; Rahmim, Arman

    2013-06-01

    Applications in imaging and spectroscopy rely on pulse processing methods for appropriate data generation. Often, the particular method utilized does not highly impact data quality, whereas in some scenarios, such as in the presence of high count rates or high frequency pulses, this issue merits extra consideration. In the present study, a new approach for pulse processing in nuclear medicine imaging and spectroscopy is introduced and evaluated. The new non-linear recursive filter (NLRF) performs nonlinear processing of the input signal and extracts the main pulse characteristics, having the powerful ability to recover pulses that would ordinarily result in pulse pile-up. The filter design defines sampling frequencies lower than the Nyquist frequency. In the literature, for systems involving NaI(Tl) detectors and photomultiplier tubes (PMTs), with a signal bandwidth considered as 15 MHz, the sampling frequency should be at least 30 MHz (the Nyquist rate), whereas in the present work, a sampling rate of 3.3 MHz was shown to yield very promising results. This was obtained by exploiting the known shape feature instead of utilizing a general sampling algorithm. The simulation and experimental results show that the proposed filter enhances count rates in spectroscopy. With this filter, the system behaves almost identically as a general pulse detection system with a dead time considerably reduced to the new sampling time (300 ns). Furthermore, because of its unique feature for determining exact event times, the method could prove very useful in time-of-flight PET imaging.

  16. Signal enhancement in laser-induced breakdown spectroscopy using fast square-pulse discharges

    Science.gov (United States)

    Sobral, H.; Robledo-Martinez, A.

    2016-10-01

    A fast, high voltage square-shaped electrical pulse initiated by laser ablation was investigated as a means to enhance the analytical capabilities of laser Induced breakdown spectroscopy (LIBS). The electrical pulse is generated by the discharge of a charged coaxial cable into a matching impedance. The pulse duration and the stored charge are determined by the length of the cable. The ablation plasma was produced by hitting an aluminum target with a nanosecond 532-nm Nd:YAG laser beam under variable fluence 1.8-900 J cm- 2. An enhancement of up to one order of magnitude on the emission signal-to-noise ratio can be achieved with the spark discharge assisted laser ablation. Besides, this increment is larger for ionized species than for neutrals. LIBS signal is also increased with the discharge voltage with a tendency to saturate for high laser fluences. Electron density and temperature evolutions were determined from time delays of 100 ns after laser ablation plasma onset. Results suggest that the spark discharge mainly re-excites the laser produced plume.

  17. Time-resolved tunable diode laser absorption spectroscopy of pulsed plasma.

    Science.gov (United States)

    Adámek, P; Olejníček, J; Čada, M; Kment, Š; Hubička, Z

    2013-07-15

    A method for time-resolved tunable diode laser absorption spectroscopy (LAS) has been developed. In this Letter, we describe in detail a developed electronic module that controls the time resolution of the LAS system. The transistor-transistor logic signal triggering the plasma pulse is used for generation of two signals: the first one triggers fine tuning of the laser wavelength and the second one controls time-defined signal sampling from the absorption detector. The described method and electronic system enable investigation of the temporal evolution of the density and temperature of selected particles in technological plasma systems. The high-power impulse magnetron sputtering system with a period of 10 ms and a duty cycle of 1% has been used to verify this method. The temporal evolution of argon metastable density was measured in the active part of the pulse and in the afterglow. The resulting density of Ar* displays a double-peak structure with a first peak in the plasma "ON" phase and a second peak in the afterglow approximately 1 ms after the end of the pulse.

  18. Optimal emission enhancement in orthogonal double-pulse laser-induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sanginés, R. [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México (CCADET-UNAM), Apartado Postal 70-186, México, DF 04510 (Mexico); Cátedra CONACyT, Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Apartado Postal 14, Ensenada, BC 22800 (Mexico); Contreras, V. [Department of Physics, Tampere University of Technology, P.O. Box 692, FI-33101 Tampere (Finland); Sobral, H., E-mail: martin.sobral@ccadet.unam.mx [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México (CCADET-UNAM), Apartado Postal 70-186, México, DF 04510 (Mexico); Robledo-Martinez, A. [Universidad Autónoma Metropolitana-Unidad Azcapotzalco, Av. San Pablo 180, Azcapotzalco, México, DF 02200 (Mexico)

    2015-08-01

    Orthogonal double-pulse (DP) laser-induced breakdown spectroscopy (LIBS) was performed using reheating and pre-ablative configurations. The ablation pulse power density was varied by two orders of magnitude and the DP experiments were carried out for a wide range of interpulse delays. For both DP-LIBS schemes, the signal enhancement was evaluated with respect to the corresponding single-pulse (SP) LIBS as a function of the interpulse delay. The reheating scheme shows a sharp maximum signal enhancement of up to 200-fold for low ablative power densities (0.4 GW cm{sup −2}); however, for power densities larger than 10 GW cm{sup −2} this configuration did not improve the SP outcome. On the other hand, a more uniform signal enhancement of about 4–6 was obtained for the pre-ablative scheme nearly independently of the used ablative power density. In terms of the signal-to-noise ratio (SNR) the pre-ablative scheme shows a monotonic increment with the ablative power density. Whereas the reheating configuration reaches a maximum at 2.2 GW cm{sup −2}, its enhancement effect collapses markedly for fluencies above 10 GW cm{sup −2}. - Highlights: • Comparison of reheating and pre-ablative double-pulse LIBS was done using a wide range of ablation power densities. • Experimental parameters that could achieve optimal signal-to-noise ratio were investigated. • A reheating scheme is better for low-ablation power densities. • A pre-ablative configuration is better for high-ablation power densities.

  19. Development of Sub 10 fs Visible-NIR, UV, and DUV Pulses and Their Applications to Ultrafast Spectroscopy

    Directory of Open Access Journals (Sweden)

    Takayoshi Kobayashi

    2016-12-01

    Full Text Available In the first section of this Chapter, the basics of nonlinear optical (NLO processes are systematically described. Then the generation of the visible pulse utilizing the NLO processes is described and ultrafast spectroscopy using the visible pulse is discussed. By using such short pulse, fast chemical reactions, which cannot be identified by utilizing strobe light or flash lamp, can be studied. After the development of femtosecond lasers, they have been widely applied to observe the transition state of various chemical reactions. In the near infrared (NIR region, a commercial light source of Ti:sapphire laser is available as a femtosecond light source, but not available in the visible and ultraviolet (UV regions. In this article, we report our development of sub 10 fs visible-NIR, UV, and deep-ultraviolet (DUV pulses and their applications to ultrafast spectroscopy.

  20. Pulse

    Science.gov (United States)

    ... resting for at least 10 minutes. Take the exercise heart rate while you are exercising. ... pulse rate can help determine if the person's heart is pumping. Pulse ... rate gives information about your fitness level and health.

  1. Vanadium(IV/V) speciation of pyridine-2,6-dicarboxylic acid and 4-hydroxy-pyridine-2,6-dicarboxylic acid complexes: potentiometry, EPR spectroscopy and comparison across oxidation states.

    Science.gov (United States)

    Jakusch, Tamás; Jin, Wenzheng; Yang, Luqin; Kiss, Tamás; Crans, Debbie C

    2003-05-01

    Evaluation of stability of vanadium(IV) and (V) complexes under similar conditions is critical for the interpretation and assessment of bioactivity of various vanadium species. Detailed understanding of the chemical properties of these complexes is necessary to explain differences observed their activity in biological systems. These studies are carried out to link the chemistry of both vanadium(IV) and (V) complexes of two ligands, 2,6-pyridinedicarboxylic acid (dipicolinic acid, H(2)dipic) and 4-hydroxy-2,6-pyridinedicarboxylic acid (H(2)dipic-OH). Solution speciation of the two 2,6-pyridinedicarboxylic acids with vanadium(IV) and vanadium(V) ions was determined by pH-potentiometry at I=0.2 M (KCl) ionic strength and at T=298 K. The stability and the metal affinities of the ligands were compared. Vanadium(V) complexes were found to form only tridentate coordinated 1:1 complexes, while vanadium(IV) formed complexes with both 1:1 and 1:2 stoichiometries. The formation constant reflects hindered coordination of a second ligand molecule, presumably because of the relatively small size of the metal ion. The most probable binding mode of the complexes was further explored using ambient and low temperature EPR spectroscopy for vanadium(IV) and 51V NMR spectroscopy for vanadium(V) systems. Upon complex formation the pyridinol-OH in position 4 deprotonates with pK approximately 3.7-4.1, which is approximately 6 orders of magnitude lower than that of the free ligand. The deprotonation enhances the ligand metal ion affinity compared to the parent ligand dipicolinic acid. In the light of the speciation and stability data of the metal complexes, the efficiency of the two ligands in transporting the metal ion in the two different oxidation states are assessed and discussed.

  2. Ultra-short laser pulse ablation using shear-force feedback: Femtosecond laser induced breakdown spectroscopy feasibility study

    Energy Technology Data Exchange (ETDEWEB)

    Samek, Ota [ISAS-Institute for Analytical Sciences, Bunsen-Kirchhoff Str.11, 44139 Dortmund (Germany)]. E-mail: samek@ansci.de; Kurowski, Andre [ISAS-Institute for Analytical Sciences, Bunsen-Kirchhoff Str.11, 44139 Dortmund (Germany); Kittel, Silke [ISAS-Institute for Analytical Sciences, Bunsen-Kirchhoff Str.11, 44139 Dortmund (Germany); Kukhlevsky, Sergei [Institute of Physics, University of Pecs, Ifjusag u. 6, Pecs 7624 (Hungary); Hergenroeder, Roland [ISAS-Institute for Analytical Sciences, Bunsen-Kirchhoff Str.11, 44139 Dortmund (Germany)

    2005-08-31

    This work reports on a feasibility study of proximity ablation using femtosecond pulses. Ultra-short pulses were launched to a bare tapered optical fiber and delivered to the sample. The tip-sample distance was controlled by means of shear-force feedback. Consequently, ablation craters with submicrometer dimensions were obtained. Potential analytical applications for Laser Induced Breakdown Spectroscopy (LIBS) technique, such as e.g. inclusions in steel or bio cells, are suggested.

  3. A Comparative Study of Single-pulse and Double-pulse Laser-Induced Breakdown Spectroscopy with Uranium-containing Samples.

    Science.gov (United States)

    Skrodzki, Patrick J; Becker, Jason R; Diwakar, Prasoon K; Harilal, Sivanandan S; Hassanein, Ahmed

    2016-03-01

    Laser-induced breakdown spectroscopy (LIBS) holds potential advantages in special nuclear material (SNM) sensing and nuclear forensics, which require rapid analysis, minimal sample preparation, and stand-off distance capability. SNM, such as U, however, result in crowded emission spectra with LIBS, and characteristic emission lines are challenging to discern. It is well-known that double-pulse LIBS (DPLIBS) improves the signal intensity for analytes over conventional single-pulse LIBS (SPLIBS). This study investigates the U signal in a glass matrix using DPLIBS and compares it to signal obtained using SPLIBS. Double-pulse LIBS involves sequential firing of a 1.06 µm Nd:YAG pre-pulse and 10.6 µm TEA CO2 heating pulse in a near collinear geometry. Optimization of experimental parameters including inter-pulse delay and energy follows identification of characteristic lines for the bulk analyte Ca and the minor constituent analyte U for both DPLIBS and SPLIBS. Spatial and temporal coupling of the two pulses in the proposed DPLIBS technique yields improvements in analytical merits with a negligible increase in damage to the sample compared to SPLIBS. Subsequently, the study discusses optimum plasma emission conditions of U lines and relative figures of merit in both SPLIBS and DPLIBS. Investigation into plasma characteristics also addresses plausible mechanisms related to the observed U analyte signal variation between SPLIBS and DPLIBS.

  4. Quantitative EPR A Practitioners Guide

    CERN Document Server

    Eaton, Gareth R; Barr, David P; Weber, Ralph T

    2010-01-01

    This is the first comprehensive yet practical guide for people who perform quantitative EPR measurements. No existing book provides this level of practical guidance to ensure the successful use of EPR. There is a growing need in both industrial and academic research to provide meaningful and accurate quantitative EPR results. This text discusses the various sample, instrument and software related aspects required for EPR quantitation. Specific topics include: choosing a reference standard, resonator considerations (Q, B1, Bm), power saturation characteristics, sample positioning, and finally, putting all the factors together to obtain an accurate spin concentration of a sample.

  5. Molecular Structure and Chirality Determination from Pulsed-Jet Fourier Transform Microwave Spectroscopy

    Science.gov (United States)

    Lobsiger, Simon; Perez, Cristobal; Evangelisti, Luca; Seifert, Nathan A.; Pate, Brooks; Lehmann, Kevin

    2014-06-01

    Fourier transform microwave (FTMW) spectroscopy has been used for many years as one of the most accurate methods to determine gas-phase structures of molecules and small molecular clusters. In the last years two pioneering works ushered in a new era applications. First, by exploiting the reduced measurement time and the high sensitivity, the development of chirped-pulse CP-FTMW spectrometers enabled the full structural determination of molecules of increasing size as well as molecular clusters. Second, and more recently, Patterson et al. showed that rotational spectroscopy can also be used for enantiomer-specific detection. Here we present an experimental approach that combines both in a single spectrometer. This set-up is capable to rapidly obtain the full heavy-atom substitution structure using the CP-FTMW features. The inclusion of an extra set of broadband horns allows for a chirality-sensitive measurement of the sample. The measurement we implement is a three-wave mixing experiment that uses time-separated pulses to optimally create the chiral coherence - an approach that was proposed recently. Using samples of R-, S- and racemic Solketal, the physical properties of the three-wave mixing experiment were studied. This involved the measurement of the corresponding nutation curves (molecular signal intensity vs excitation pulse duration) to demonstrate the optimal pulse sequence. The phase stability of the chiral signal, required to assign the absolute stereochemistry, has been studied as a function of the measurement signal-to-noise ratio using a "phasogram" method. G. G. Brown, B. C. Dian, K. O. Douglass, S. M. Geyer, S. T. Shipman, B. H. Pate, Rev. Sci. Instrum. 2008, 79, 053103. D. Patterson, M. Schnell, J. M. Doyle, Nature 2013, 497, 475-477. D. Patterson, J. M. Doyle, Phys. Rev. Lett. 2013, 111, 023008. V. A. Shubert, D. Schmitz, D. Patterson, J. M. Doyle, M. Schnell, Angew. Chem. Int. Ed. 2014, 53, 1152-1155. J.-U. Grabow, Angew. Chem. 2013, 125, 11914

  6. Multifrequency pulsed electron paramagnetic resonance on metalloproteins.

    Science.gov (United States)

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

    2010-02-16

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

  7. Investigation of fiber Bragg grating as a spectral notch shaper for single-pulse coherent anti-Stokes Raman spectroscopy

    Science.gov (United States)

    Oh, Seung Ryeol; Park, Joo Hyun; Kim, Kyung-Soo; Lee, Eun Seong; Lee, Jae Yong; Kim, Soohyun

    2017-01-01

    We experimentally demonstrate compact and efficient single-pulse coherent anti-Stokes Raman spectroscopy (CARS) via spectral notch shaping implemented with a fiber Bragg grating. We show that a fiber Bragg grating can serve as a narrowband notch filtering component on a 90 nm broadband femtosecond pulsed laser without spectral distortion. Finally, we obtain CARS spectra of various samples in the fingerprint region of molecular vibrations. This scheme has potential for compact implementations of all-fiber single-pulse multiplex CARS due to its compatibility with fiber optics.

  8. Inter-pulse delay optimization in dual-pulse laser induced breakdown vacuum ultraviolet spectroscopy of a steel sample in ambient gases at low pressure

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, X., E-mail: xi.jiang2@mail.dcu.ie [School of Physical Sciences, Dublin City University, Dublin (Ireland); National Centre for Plasma Science and Technology, Dublin City University, Dublin (Ireland); Hayden, P. [School of Physical Sciences, Dublin City University, Dublin (Ireland); National Centre for Plasma Science and Technology, Dublin City University, Dublin (Ireland); Laasch, R. [Institut fuer Experimentalphysik, Universitat Hamburg, Luruper Chaussee 149, 22761 Hamburg (Germany); Costello, J.T.; Kennedy, E.T. [School of Physical Sciences, Dublin City University, Dublin (Ireland); National Centre for Plasma Science and Technology, Dublin City University, Dublin (Ireland)

    2013-08-01

    Time-integrated spatially-resolved Laser Induced Breakdown Spectroscopy (LIBS) has been used to investigate spectral emissions from laser-induced plasmas generated on steel targets. Instead of detecting spectral lines in the visible/near ultraviolet (UV), as investigated in conventional LIBS, this work explored the use of spectral lines emitted by ions in the shorter wavelength vacuum ultraviolet (VUV) spectral region. Single-pulse (SP) and dual-pulse LIBS (DP-LIBS) experiments were performed on standardized steel samples. In the case of the double-pulse scheme, two synchronized lasers were used, an ablation laser (200 mJ/15 ns), and a reheating laser (665 mJ/6 ns) in a collinear beam geometry. Spatially resolved and temporally integrated laser induced plasma VUV emission in the DP scheme and its dependence on inter-pulse delay time were studied. The VUV spectral line intensities were found to be enhanced in the DP mode and were significantly affected by the inter-pulse delay time. Additionally, the influence of ambient conditions was investigated by employing low pressure nitrogen, argon or helium as buffer gases in the ablation chamber. The results clearly demonstrate the existence of a sharp ubiquitous emission intensity peak at 100 ns and a wider peak, in the multi-microsecond range of inter-pulse time delay, dependent on the ambient gas conditions. - Highlights: • First dual-pulse and ambient gas deep VUV LIBS plasma emission study • Optimization of inter-pulse delay time for vacuum and ambient gas environments • A sharp intensity peak implies optimal inter-pulse delay of 100 ns for all conditions. • A broad peak appears in the microsecond delay range, but only in ambient gases. • Pressure dependence implies a different enhancement process.

  9. Dose reconstruction by EPR spectroscopy of tooth enamel: application to the population of Zaborie village exposed to high radioactive contamination after the Chernobyl accident.

    Science.gov (United States)

    Ivannikov, A I; Gaillard-Lecanu, E; Trompier, F; Stepanenko, V F; Skvortsov, V G; Borysheva, N B; Tikunov, D D; Petin, D V

    2004-02-01

    Individual irradiation doses were determined by electron paramagnetic resonance spectroscopy of the tooth enamel of the inhabitants of Zaborie, the most contaminated inhabited settlement not evacuated after the Chernobyl accident. Dose determination was performed using a specially developed automatic spectrum processing procedure. Spectrum processing was carried out in different operating modes, and average results were taken in order to reduce the contribution of uncertainty in dose determination caused by spectrum processing. The absorbed doses determined in enamel were corrected to take into account the contribution of natural background radiation and to determine the individual excess dose due to radioactive contamination of the territory. Individual excess doses are compared to calculated individualized doses to teeth, estimated using the local radioactive contamination levels, dose rates, and information concerning individual behavior. The individual excess doses measured by electron paramagnetic resonance spectroscopy and the calculated individualized doses are fully independent. Mean square variation between results of two methods was found to be 34 mGy, which is consistent with error estimation for both methods. This result can validate both the methodology of signal processing presented here when using electron paramagnetic resonance dosimetry of tooth enamel for low doses and the methodology of individualized dose calculation.

  10. A high-frequency electron paramagnetic resonance spectrometer for multi-dimensional, multi-frequency, and multi-phase pulsed measurements

    Energy Technology Data Exchange (ETDEWEB)

    Cho, F. H. [Department of Physics, University of Southern California, Los Angeles, California 90089 (United States); Stepanov, V. [Department of Chemistry, University of Southern California, Los Angeles, California 90089 (United States); Takahashi, S., E-mail: susumu.takahashi@usc.edu [Department of Chemistry, University of Southern California, Los Angeles, California 90089 (United States); Department of Physics, University of Southern California, Los Angeles, California 90089 (United States)

    2014-07-15

    We describe instrumentation for a high-frequency electron paramagnetic resonance (EPR) and pulsed electron-electron double resonance (PELDOR) spectroscopy. The instrumentation is operated in the frequency range of 107−120 GHz and 215−240 GHz and in the magnetic field range of 0−12.1 T. The spectrometer consisting of a high-frequency high-power solid-state source, a quasioptical system, a phase-sensitive detection system, a cryogenic-free superconducting magnet, and a {sup 4}He cryostat enables multi-frequency continuous-wave EPR spectroscopy as well as pulsed EPR measurements with a few hundred nanosecond pulses. Here we discuss the details of the design and the pulsed EPR sensitivity of the instrumentation. We also present performance of the instrumentation in unique experiments including PELDOR spectroscopy to probe correlations in an insulating electronic spin system and application of dynamical decoupling techniques to extend spin coherence of electron spins in an insulating solid-state system.

  11. Characterisation of historic plastics using terahertz time-domain spectroscopy and pulsed imaging.

    Science.gov (United States)

    Pastorelli, Gianluca; Trafela, Tanja; Taday, Phillip F; Portieri, Alessia; Lowe, David; Fukunaga, Kaori; Strlič, Matija

    2012-05-01

    Terahertz (THz) time-domain spectroscopy and 3D THz pulsed imaging have been explored with regard to polymer materials, both commodity and historic polymers. A systematic spectroscopic study of a wide range of different polymer materials showed significant differences in their spectra. Polyolefins and polystyrenes generally exhibit lower absorption than other examined polymers, various cellulose derivates, poly(vinyl chloride), poly(methyl methacrylate), polyamide, hard rubber and phenol formaldehyde resin, the last of these exhibiting the most intense absorption over the entire range, 0.15-4.2 THz. It was also examined how the presence of plasticisers in poly(vinyl chloride), the presence of fillers in polypropylene, and the degree of branching in polyethylene and polystyrene affect the spectra; inorganic fillers in polypropylene affected the absorption most. With 3D THz pulsed imaging, features in polymer objects were explored, appearing either as integral parts of the material (coatings and pores in foams) or as a consequence of physical deterioration (cracks, delamination). All of these features of various complexities can be successfully imaged in 3D. Terahertz technology is thus shown to have significant potential for both chemical and structural characterisation of polymers, which will be of interest to heritage science, but also to the polymer industry and development of analytical technologies in general.

  12. Isotopologue-Sensitive Detection Using Chirped-Pulse Ft-Mw Spectroscopy: Minor Species of Propofol

    Science.gov (United States)

    Lesarri, Alberto; Neill, Justin; Muckle, Matt; Shipman, Steven T.; Pate, Brooks H.; Suenram, Richard D.; Caminati, Walther

    2009-06-01

    The capabilities of chirped-pulse FT-microwave spectroscopy to achieve full-bandwidth (11 GHz) isotopologue-sensitive detection have been tested on the 13-heavy atoms molecule of propofol (2,6-diisopropylphenol). The analysis of the rotational spectrum using moderate signal averaging (10 k FIDs) had previously detected the presence of two conformers arising from the combined internal rotations of the hydroxyl and the two isopropyl groups. In the new experiment reported here 600 k FID's were coherently averaged, using three pulsed nozzle sources and reading multiple FIDs per sample injection cycle to reduce the total acquisition time and sample consumption. The new spectrum revealed a very large number of weak transitions, suggesting that full-band ^{13}C sensitivity had been surpassed. The new data have resulted in the assignment of a third conformer of propofol, followed by all twelve ^{13}C-monosubstituted species in natural abundance for the most stable conformer. The isotopic information confirmed the molecular structure for the preferred conformation of propofol, validating the ab initio predictions for this compound. The potential function for the OH internal rotation has been determined using a flexible model. A. Lesarri, S. T. Shipman, G. G. Brown, L. Alvarez-Valtierra, R. D. Suenram and B. H. Pate, 63^rd OSU Int. Symp. On Mol. Spectrosc., Columbus, OH, 2008, RH07 In the

  13. Concentration measurements in molecular gas mixtures with a two-pump pulse femtosecond polarization spectroscopy technique

    Science.gov (United States)

    Hertz, E.; Chaux, R.; Faucher, O.; Lavorel, B.

    2001-08-01

    Recently, we have demonstrated the ability of the Raman-induced polarization spectroscopy (RIPS) technique to accurately determine concentration or polarizability anisotropy ratio in low-pressure binary molecular mixtures [E. Hertz, B. Lavorel, O. Faucher, and R. Chaux, J. Chem. Phys. 113, 6629 (2000)]. It has been also pointed out that macroscopic interference, occurring when two revivals associated to different molecules time overlap, can be used to achieve measurements with picosecond time resolution. The applicability of the technique is intrinsically limited to a concentration range where the signals of both molecules are of the same magnitude. In this paper, a two-pump pulse sequence with different intensities is used to overcome this limitation. The relative molecular responses are weighted by the relative laser pump intensities to give comparable signals. Furthermore, by tuning the time delay between the two-pump pulses, macroscopic interference can be produced regardless of the accidental coincidences between the two molecular temporal responses. The study is performed in a CO2-N2O gas mixture and the concentration is measured with and without macroscopic interference. Applications of the method in the field of noninvasive diagnostics of combustion media are envisaged.

  14. Optical absorbance measurements of opaque liquids by pulsed laser photoacoustic spectroscopy.

    Science.gov (United States)

    Schmid, Thomas; Panne, Ulrich; Niessner, Reinhard; Haisch, Christoph

    2009-03-15

    In many relevant industrial applications, UV-vis online process monitoring is hampered by light scattering and opacity of the samples, whereas diluted and filtered samples are rarely available. Pulsed laser photoacoustic (PA) spectroscopy allows the measurement of both high and low absorptions without any need for sample preparation. An optimized detection geometry for absorption measurements in opaque liquids is described. The proposed PA sensor was realized by using two orthogonal detectors based on piezoelectric poly(vinylidene fluoride) (PVDF). Laser-induced pressure waves were sensed perpendicularly to (side-on mode) and along the axis of the laser beam (forward mode). Pressure waves generated by a single laser pulse, optical transmission and absorption, as well as the speed of sound in liquid samples were determined simultaneously using time-resolved detection. Evaluation of the PA signal permits the determination of absorption coefficients ranging from 0.1 to 1000 cm(-1). The influence of absorbing or scattering compounds on the signal was investigated in dye solutions and suspensions of TiO(2) particles.

  15. Assessment of an alanine EPR dosimetry technique with enhanced precision and accuracy

    CERN Document Server

    Hayes, R B; Wieser, A; Romanyukha, A A; Hardy, B L; Barrus, J K

    2000-01-01

    Dose reconstruction in the course of a series of blind tests demonstrated that an accuracy of 10 mGy for low doses and 1% for high doses can be achieved using EPR spectroscopy. This was accomplished using a combination of methodologies including polynomial filtration of the EPR spectrum, dosimeter rotation during scanning, use of an EPR standard fixed into the resonator and subtraction of all nonradiogenic signals. Doses were reconstructed over the range of 0.01-1000 Gy using this compound spectral EPR analysis. This EPR technique, being equally applicable to fractionated doses (such as those delivered during multiple radiotherapy treatments), was verified to exhibit dose reciprocity. Irradiated alanine dosimeters which were stored exhibited compound spectral EPR signal fading of ca 3% over 9 months. All error estimates given in this paper are given at the 1 standard deviation level and unless otherwise specified do not account for uncertainties in source calibration.

  16. A Comparative Study of Single-pulse and Double-pulse Laser-Induced Breakdown Spectroscopy with Uranium-containing Samples

    Energy Technology Data Exchange (ETDEWEB)

    Skrodzki, P. J.; Becker, J. R.; Diwakar, P. K.; Harilal, S. S.; Hassanein, A.

    2016-01-25

    Laser-induced breakdown spectroscopy (LIBS) holds potential advantages in special nuclear material (SNM) sensing and nuclear forensics which require rapid analysis, minimal sample preparation and stand-off distance capability. SNM, such as U, however, result in crowded emission spectra with LIBS, and characteristic emission lines are challenging to discern. It is well-known that double-pulse LIBS (DPLIBS) improves the signal intensity for analytes over conventional single-pulse LIBS (SPLIBS). This study investigates U signal in a glass matrix using DPLIBS and compares to signal features obtained using SPLIBS. DPLIBS involves sequential firing of 1.06 µm Nd:YAG pre-pulse and 10.6 µm TEA CO2 heating pulse in near collinear geometry. Optimization of experimental parameters including inter-pulse delay and energy follows identification of characteristic lines and signals for bulk analyte Ca and minor constituent analyte U for both DPLIBS and SPLIBS. Spatial and temporal coupling of the two pulses in the proposed DPLIBS technique yields improvements in analytical merits with negligible further damage to the sample compared to SPLIBS. Subsequently, the study discusses optimum plasma emission conditions of U lines and relative figures of merit in both SPLIBS and DPLIBS. Investigation into plasma characteristics also addresses plausible mechanisms related to observed U analyte signal variation between SPLIBS and DPLIBS.

  17. Inter-pulse delay optimization in dual-pulse laser induced breakdown vacuum ultraviolet spectroscopy of a steel sample in ambient gases at low pressure

    Science.gov (United States)

    Jiang, X.; Hayden, P.; Laasch, R.; Costello, J. T.; Kennedy, E. T.

    2013-08-01

    Time-integrated spatially-resolved Laser Induced Breakdown Spectroscopy (LIBS) has been used to investigate spectral emissions from laser-induced plasmas generated on steel targets. Instead of detecting spectral lines in the visible/near ultraviolet (UV), as investigated in conventional LIBS, this work explored the use of spectral lines emitted by ions in the shorter wavelength vacuum ultraviolet (VUV) spectral region. Single-pulse (SP) and dual-pulse LIBS (DP-LIBS) experiments were performed on standardized steel samples. In the case of the double-pulse scheme, two synchronized lasers were used, an ablation laser (200 mJ/15 ns), and a reheating laser (665 mJ/6 ns) in a collinear beam geometry. Spatially resolved and temporally integrated laser induced plasma VUV emission in the DP scheme and its dependence on inter-pulse delay time were studied. The VUV spectral line intensities were found to be enhanced in the DP mode and were significantly affected by the inter-pulse delay time. Additionally, the influence of ambient conditions was investigated by employing low pressure nitrogen, argon or helium as buffer gases in the ablation chamber. The results clearly demonstrate the existence of a sharp ubiquitous emission intensity peak at 100 ns and a wider peak, in the multi-microsecond range of inter-pulse time delay, dependent on the ambient gas conditions.

  18. Chirped Pulse-Fourier Transform Microwave Spectroscopy of Ethyl 3-METHYL-3-PHENYLGLYCIDATE (strawberry Aldehyde)

    Science.gov (United States)

    Shipman, Steven T.; Neill, Justin L.; Muckle, Matt T.; Suenram, Richard D.; Pate, Brooks H.

    2009-06-01

    Strawberry aldehyde (C_{12} O_3 H_{14}), a common artificial flavoring compound, has two non-interconvertible conformational families defined by the relative stereochemistry around its epoxide carbons. In one family, referred to as the trans because the two large substituents (a phenyl ring and an ethyl ester) are on opposite sides of the epoxide ring, these two substituents are unable to interact with each other. However, in the cis family, there is a long-range interaction that is difficult to accurately capture in electronic structure calculations. Three trans and two cis conformations have been assigned by broadband chirped pulse Fourier transform microwave spectroscopy, along with the C-13 isotopomers in natural abundance for one conformer from each of the families. The agreement of the rotational constants, relative dipole moments, and relative energies between theory and experiment is excellent, even at relatively crude levels of theory, for the trans family, but is quite poor for the cis conformers. In addition, due to the reactivity of strawberry aldehyde and the high temperature to which it must be heated to yield a suitable vapor pressure, several decomposition products have been assigned, and more, as of yet unassigned, are likely to be present. This project demonstrates some of the challenges in performing large-molecule rotational spectroscopy.

  19. Emission enhancement using two orthogonal targets in double pulse laser-induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez-Ake, C. [Laboratorio de Fotofisica, Centro de Ciencias Aplicadas y Desarrollo Tecnologico, Universidad Nacional Autonoma de Mexico, Apartado Postal 70-186, Mexico D.F., C.P. 04510 (Mexico)], E-mail: citlali.sanchez@ccadet.unam.mx; Bolanos, Marduk [Laboratorio de Fotofisica, Centro de Ciencias Aplicadas y Desarrollo Tecnologico, Universidad Nacional Autonoma de Mexico, Apartado Postal 70-186, Mexico D.F., C.P. 04510 (Mexico); Ramirez, C.Z. [Colegio de Ciencias y Humanidades Plantel Sur, Universidad Nacional Autonoma de Mexico (Mexico)

    2009-09-15

    The enhancement of emission intensity resulting from the interaction between two laser-induced plasmas on two orthogonal targets was investigated using double pulse laser-induced breakdown spectroscopy (LIBS) at 0.7 Pa, by means of time-resolved spectroscopy and fast photography. The results showed that the interaction between both plasmas improved carbon emission intensity in comparison to a single laser-induced plasma. For all the carbon lines of interest 477.2 nm (CI), 426.7 nm (CII), and 473.4 nm (C{sub 2} Swan band head), the intensity enhancement showed a maximum at a delay between lasers in the range from 2 to 5 {mu}s; moreover it increased with the fluence of the first laser. On the other hand, in the case of C{sub 2} the intensity enhancement reached a maximum at 5 mm from the target; however it decreased with increasing fluence of the second laser. The largest intensity enhancement found was twofold for atomic species and sixfold for molecular species.

  20. Dynamical theory of spectroscopy with femtosecond pulse excitation(Ⅲ)——Transient rate equation in Liouville space

    Institute of Scientific and Technical Information of China (English)

    陆靖; 范康年

    1999-01-01

    A dynamical theory of spectroscopy with femtosecond pulse excitation is developed in Liouville space. By using density matrix formalism, the transient rate equation that can be reduced to the classical KHD expression in CW case is obtained. This theory is applied to the Raman excitation profile of IBr and the results are in agreement with the experiments.

  1. Chirped Pulse Rotational Spectroscopy of a Single THUJONE+WATER Sample

    Science.gov (United States)

    Kisiel, Zbigniew; Perez, Cristobal; Schnell, Melanie

    2016-06-01

    Rotational spectroscopy of natural products dates over 35 years when six different species including thujone were investigated. Nevertheless, the technique of low-resolution microwave spectroscopy employed therein allowed determination of only a single conformational parameter. Advances in sensitivity and resolution possible with supersonic expansion techniques of rotational spectroscopy made possible much more detailed studies such that, for example, the structures of first camphor, and then of multiple clusters of camphor with water were determined. We revisited the rotational spectrum of the well known thujone molecule by using the chirped pulse spectrometer in Hamburg. The spectrum of a single thujone sample was recorded with an admixture of 18O enriched water and was successively analysed using an array of techniques, including the AUTOFIT program, the AABS package and the STRFIT program. We have, so far, been able to assign rotational transitions of α-thujone, β-thujone, another thujone isomer, fenchone, and several thujone-water clusters in the spectrum of this single sample. Natural abundance molecular populations were sufficient to determine precise heavy atom backbones of thujone and fenchone, and H_218O enrichment delivered water molecule orientations in the hydrated clusters. An overview of these results will be presented. Z.Kisiel, A.C.Legon, JACS 100, 8166 (1978) Z.Kisiel, O.Desyatnyk, E.Białkowska-Jaworska, L.Pszczółkowski, PCCP 5 820 (2003) C.Pérez, A.Krin, A.L.Steber, J.C.López, Z.Kisiel, M.Schnell, J.Phys.Chem.Lett. 7 154 (2016) N.A.Seifert, I.A.Finneran, C.Perez, et al. J.Mol.Spectrosc. 312, 12 (2015) Z.Kisiel, L.Pszczółkowski, B.J.Drouin, et al. J.Mol.Spectrosc. 280, 134 (2012). Z.Kisiel, J.Mol.Spectrosc. 218, 58 (2003)

  2. Background-free coherent anti-stokes Raman spectroscopy and microscopy by dual-soliton pulse generation

    CERN Document Server

    Chen, Kun; Wei, Haoyun; Li, Yan

    2016-01-01

    We propose an all-fiber-generated dual-soliton pulses based scheme for the background-free detection of coherent anti-Stokes Raman spectroscopy under the spectral focusing mechanism. Due to the strong birefringence and high nonlinearity of a polarization-maintaining photonic crystal fiber (PM-PCF), two redshifted soliton pulses can be simultaneously generated relying on high-order dispersion and nonlinear effects along two eigenpolarization axes in the anomalous dispersion regime, while allowing feasible tunability of the frequency distance and temporal interval between them. This proposed scheme, termed as DS-CARS, exploits a unique combination of slight frequency-shift and advisable temporal walk-off of this two soliton pulses to achieve robust and efficient suppression of nonresonant background with compact all-fiber coherent excitation source. Capability of the DS-CARS is experimentally demonstrated by the background-free CARS spectroscopy and unambiguous CARS microscopy of polymer beads in the fingerprin...

  3. Continuous-Wave Cavity Ring-Down Spectroscopy in a Pulsed Uniform Supersonic Flow

    Science.gov (United States)

    Thawoos, Shameemah; Suas-David, Nicolas; Suits, Arthur

    2017-06-01

    We introduce a new approach that couples a pulsed uniform supersonic flow with high sensitivity continuous wave cavity ringdown spectroscopy (UF-CRDS) operated in the near infrared (NIR). This combination is related to the CRESU technique developed in France and used for many years to study reaction kinetics at low temperature, and to the microwave based chirped-pulse uniform supersonic flow spectrometer (CPUF) developed in our group which has successfully demonstrated the use of pulsed uniform supersonic flow to probe reaction dynamics at temperatures as low as 22 K. CRDS operated with NIR permits access to the first overtones of C-H and O-H stretching/bending which, in combination with its extraordinary sensitivity opens new experiments complementary to the CPUF technique. The UF-CRDS apparatus (Figure) utilizes the pulsed uniform flow produced by means of a piezo-electric stack valve in combination with a Laval nozzle. At present, two machined aluminum Laval nozzles designed for carrier gases Ar and He generate flows with a temperature of approximately 25 K and pressure around 0.15 mbar. This flow is probed by an external cavity diode laser in the NIR (1280-1380 nm). Laval nozzles designed using a newly developed MATLAB-based program will be used in the future. A detailed illustration of the novel UF-CRDS instrumentation and its performance will be presented along with future directions and applications. I. Sims, J. L. Queffelec, A. Defrance, C. Rebrion-Rowe, D. Travers, P. Bocherel, B. Rowe, I. W. Smith, J. Chem. Phys. 100, 4229-4241, (1994). C. Abeysekera, B. Joalland, N. Ariyasingha, L. N. Zack, I. R. Sims, R. W. Field, A. G. Suits, J. Phys. Chem. Lett. 6, 1599-1604, (2015). N. Suas-David, T. Vanfleteren, T. Foldes, S. Kassi, R. Georges, M. Herman, J. Phys. Chem.A, 119, 10022-10034, (2015). C. Abeysekera, B. Joalland, Y. Shi, A. Kamasah, J. M. Oldham, A. G. Suits, Rev. Sci. Instrum. 85, 116107, (2014).

  4. Study on the influence of laser pulse duration in the long nanosecond regime on the laser induced plasma spectroscopy

    Science.gov (United States)

    Elnasharty, I. Y.

    2016-10-01

    By using a high power pulsed fiber laser, this study reports the experimental investigation of the laser-induced plasma characteristics for the laser pulse duration range extended from 40 ns to 200 ns. The experiments were performed with keeping the laser fluence constant at 64 J/cm2. The measurements show that, for the early phase of plasma formation, the spectral line intensities and the continuum emissions as well as the plasma characteristics decay to a certain extent with the increase of the pulse duration. On the other hand, as the plasma evolves in post laser pulse regime, the electron density and the degree of ionization increase slightly for the longer pulses, while the plume temperature is more or less independent from the pulse duration. Furthermore, the ablation characteristics, such as the ablation rate, coincide with the results of plasma characteristics for the different pulse durations. Eventually, with keeping the laser fluence constant at 64 J/cm2, the analytical performance of Laser-Induced Plasma Spectroscopy (LIPS) for the corresponding pulse duration range is examined by using a temporal gating and non-gating analyses. The measurements show that, in the case of gating analysis, all pulse durations yield almost the same range of limits of detections LODs. On the other hand, for non-gating analysis, the longer pulse durations provide lower LODs (better) than the shorter ones by orders of magnitude. Moreover, the calculated absolute limit of detection (LODAbs) for the longest pulse duration (i.e. 200 ns) is lower by approximately factor 2 than that of the shortest one (i.e. 40 ns).

  5. Full cycle rapid scan EPR deconvolution algorithm

    Science.gov (United States)

    Tseytlin, Mark

    2017-08-01

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

  6. Two-Pulse Atomic Coherent Control (2PACC) Spectroscopy of Eley-Rideal Reactions. An Application of an Atom Laser

    CERN Document Server

    Jorgensen, S F; Jorgensen, Solvejg; Kosloff, Ronnie

    2003-01-01

    A spectroscopic application of the atom laser is suggested. The spectroscopy termed 2PACC employs the coherent properties of matter-waves from a two pulse atom laser. These waves are employed to control a gas-surface chemical recombination reaction. The method is demonstrated for an Eley-Rideal reaction of a hydrogen or alkali atom-laser pulse where the surface target is an adsorbed hydrogen atom. The reaction yields either a hydrogen or alkali hydride molecule. The desorbed gas phase molecular yield and its internal state is shown to be controlled by the time and phase delay between two atom-laser pulses. The calculation is based on solving the time-dependent Schrodinger equation in a diabatic framework. The probability of desorption which is the predicted 2PACC signal has been calculated as a function of the pulse parameters.

  7. High-resolution three-dimensional compositional imaging by double-pulse laser-induced breakdown spectroscopy

    Science.gov (United States)

    Schiavo, C.; Menichetti, L.; Grifoni, E.; Legnaioli, S.; Lorenzetti, G.; Poggialini, F.; Pagnotta, S.; Palleschi, V.

    2016-08-01

    In this paper we present a new instrument specifically realized for high-resolution three-dimensional compositional analysis and mapping of materials. The instrument is based on the coupling of a Double-Pulse Laser-Induced Breakdown Spectroscopy (LIBS) instrument with an optical microscope. The compositional mapping of the samples is obtained by scanning the laser beam across the surface of the sample, while the in depth analysis is performed by sending multiple laser pulses on the same point. Depths of analysis of several tens of microns can be obtained. The instrument presented has definite advantages with respect to Laser Ablation-ICP Mass Spectrometry in many applications related to material analysis, biomedicine and environmental diagnostics. An application to the diagnostics of industrial ceramics is presented, demonstrating the feasibility of Double-Pulse LIBS Imaging and its advantages with respect to conventional single-pulse LIBS imaging.

  8. Pulse-echo ultrasound transit time spectroscopy: A comparison of experimental measurement and simulation prediction.

    Science.gov (United States)

    Wille, Marie-Luise; Almualimi, Majdi A; Langton, Christian M

    2016-01-01

    Considering ultrasound propagation through complex composite media as an array of parallel sonic rays, a comparison of computer-simulated prediction with experimental data has previously been reported for transmission mode (where one transducer serves as transmitter, the other as receiver) in a series of 10 acrylic step-wedge samples, immersed in water, exhibiting varying degrees of transit time inhomogeneity. In this study, the same samples were used but in pulse-echo mode, where the same ultrasound transducer served as both transmitter and receiver, detecting both 'primary' (internal sample interface) and 'secondary' (external sample interface) echoes. A transit time spectrum was derived, describing the proportion of sonic rays with a particular transit time. A computer simulation was performed to predict the transit time and amplitude of various echoes created, and compared with experimental data. Applying an amplitude-tolerance analysis, 91.7% ± 3.7% of the simulated data were within ±1 standard deviation of the experimentally measured amplitude-time data. Correlation of predicted and experimental transit time spectra provided coefficients of determination (R(2)%) ranging from 100.0% to 96.8% for the various samples tested. The results acquired from this study provide good evidence for the concept of parallel sonic rays. Furthermore, deconvolution of experimental input and output signals has been shown to provide an effective method to identify echoes otherwise lost due to phase cancellation. Potential applications of pulse-echo ultrasound transit time spectroscopy include improvement of ultrasound image fidelity by improving spatial resolution and reducing phase interference artefacts.

  9. Hydrogen isotope detection in metal matrix using double-pulse laser-induced breakdown-spectroscopy

    Science.gov (United States)

    Fantoni, Roberta; Almaviva, Salvatore; Caneve, Luisa; Colao, Francesco; Maddaluno, Giorgio; Gasior, Pawel; Kubkowska, Monika

    2017-03-01

    The amount of hydrogen isotopes retained in plasma facing components (PFCs) and the determination of their surface layer composition are among the most critical issues for the next generation fusion device, ITER, under construction in Cadarache (France). Laser Induced Breakdown Spectroscopy (LIBS) is currently under evaluation as a technique suitable for quantitative, in situ, non-invasive measurements of these quantities. In order to detect traces of contaminant in metallic samples and improve its limit of detection (LOD), the Double Pulse LIBS (DP-LIBS) variant can be used instead of the standard Single Pulse LIBS (SP-LIBS), as it has been proven by several authors that DP-LIBS can considerably raise the analytical performances of the technique. In this work Mo samples coated with a 1.5-1.8 μm thick W-Al mixed layer, contaminated with co-deposited deuterium (D) were measured by SP- and DP-LIBS under vacuum (p 5 × 10- 5 mbar), with an experimental set-up simulating conditions that can be found in a real fusion device between plasma discharges. A partial Calibration Free procedure (pCF) was applied to the LIBS data in order to retrieve the relative concentration of W and Al in the mixed layer. The amount of deuterium was then inferred by using tungsten as internal standard, accounting for the intensity ratio between the Dα line and nearby W I lines. The results are in satisfactory agreement with those obtained from preliminary Ion Beam Analysis measurements performed immediately after the specimen's realization.

  10. Effect of pulse repetition rate and number of pulses in the analysis of polypropylene and high density polyethylene by nanosecond infrared laser induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Leme, Flavio O. [Laboratorio de Quimica Analitica ' Henrique Bergamin Filho' , Centro de Energia Nuclear na Agricultura, Universidade de Sao Paulo, Av. Centenario 303, 13416-000 Piracicaba, SP (Brazil); Godoi, Quienly [Laboratorio de Quimica Analitica ' Henrique Bergamin Filho' , Centro de Energia Nuclear na Agricultura, Universidade de Sao Paulo, Av. Centenario 303, 13416-000 Piracicaba, SP (Brazil); Departamento de Quimica, Universidade Federal de Sao Carlos, Rod. Washington Luis, km 235, 13565-905 Sao Carlos, SP (Brazil); Kiyataka, Paulo H.M. [Centro de Tecnologia de Embalagens, Instituto de Tecnologia de Alimentos, Av. Brasil 2880, 13070-178 Campinas, SP (Brazil); Santos, Dario [Departamento de Ciencias Exatas e da Terra, Universidade Federal de Sao Paulo, Rua Prof. Artur Riedel 275, 09972-270 Diadema, SP (Brazil); Agnelli, Jose A.M. [Departamento de Engenharia de Materiais, Universidade Federal de Sao Carlos, Rod. Washington Luis, km 235, 13565-905 Sao Carlos, SP (Brazil); and others

    2012-02-01

    Pulse repetition rates and the number of laser pulses are among the most important parameters that do affect the analysis of solid materials by laser induced breakdown spectroscopy, and the knowledge of their effects is of fundamental importance for suggesting analytical strategies when dealing with laser ablation processes of polymers. In this contribution, the influence of these parameters in the ablated mass and in the features of craters was evaluated in polypropylene and high density polyethylene plates containing pigment-based PbCrO{sub 4}. Surface characterization and craters profile were carried out by perfilometry and scanning electron microscopy. Area, volume and profile of craters were obtained using Taylor Map software. A laser induced breakdown spectroscopy system consisted of a Q-Switched Nd:YAG laser (1064 nm, 5 ns) and an Echelle spectrometer equipped with ICCD detector were used. The evaluated operating conditions consisted of 10, 25 and 50 laser pulses at 1, 5 and 10 Hz, 250 mJ/pulse (85 J cm{sup -2}), 2 {mu}s delay time and 6 {mu}s integration time gate. Differences in the topographical features among craters of both polymers were observed. The decrease in the repetition rate resulted in irregular craters and formation of edges, especially in polypropylene sample. The differences in the topographical features and ablated masses were attributed to the influence of the degree of crystallinity, crystalline melting temperature and glass transition temperature in the ablation process of the high density polyethylene and polypropylene. It was also observed that the intensities of chromium and lead emission signals obtained at 10 Hz were two times higher than at 5 Hz by keeping the number of laser pulses constant.

  11. Study of deep level characteristics in the neutrons irradiated Si structures by combining pulsed and steady-state spectroscopy techniques

    Science.gov (United States)

    Gaubas, E.; Kalendra, V.; Ceponis, T.; Uleckas, A.; Tekorius, A.; Vaitkus, J.; Velicka, A.

    2012-11-01

    The standard methods, such as capacitance deep level transient spectroscopy (C-DLTS) and thermally stimulated current (TSC) techniques are unsuitable for the analysis of heavily irradiated devices. In this work, therefore, several steady-state and pulsed techniques have been combined to comprehensively evaluate parameters of radiation defects and functional characteristics of the irradiated Si pin detectors. In order to understand defects created by radiation and evaluate their evolution with fluence, C-DLTS and TSC techniques have been employed to make a baseline identification of the radiation induced traps after irradiation with a rather small neutron fluence of 1012 cm-2. The steady-state photo-ionization spectroscopy (PIS) technique has been involved to correlate thermal- and photo- activation energies for definite radiation defects. A contactless technique for simultaneous measurements of the carrier lifetime and the parameters of deep levels based on microwave probed pulsed photo-conductivity (MW-PC) spectroscopy has been applied to correlate carrier capture cross-sections and densities of the identified different radiation defects. A technique for spectroscopy of deep levels in junction structures (BELIV) based on measurements of barrier capacitance charging current transient changes due to additional spectrally resolved pulsed illumination has been applied to evaluate the functional characteristics of the irradiated diodes. Pulsed spectroscopic measurements were implemented by combining the analysis of generation current and of barrier capacitance charging transients modified by a single fs pulse of illumination generated by an optical parametric oscillator of varied wavelength in the range from 0.5 to 10 μm. Several deep levels with activation energy in the range of 0.18-0.8 eV have been resolved from spectral analysis in the samples of Si grown by magnetic field applied Czochralski (MCz) technology.

  12. Dynamics of double-pulse laser produced titanium plasma inferred from thin film morphology and optical emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Krstulović, N., E-mail: niksak@ifs.hr [Institute of Physics, Bijenička 46, HR-10000 Zagreb (Croatia); Salamon, K., E-mail: ksalamon@ifs.hr [Institute of Physics, Bijenička 46, HR-10000 Zagreb (Croatia); Modic, M., E-mail: martina.modic@ijs.si [Jožef Stefan Institute, Jamova 39, 1001 Ljubljana (Slovenia); Bišćan, M., E-mail: mbiscan@ifs.hr [Institute of Physics, Bijenička 46, HR-10000 Zagreb (Croatia); Milat, O., E-mail: milat@ifs.hr [Institute of Physics, Bijenička 46, HR-10000 Zagreb (Croatia); Milošević, S., E-mail: slobodan@ifs.hr [Institute of Physics, Bijenička 46, HR-10000 Zagreb (Croatia)

    2015-05-01

    In this paper, dynamics of double-pulse laser produced titanium plasma was studied both directly using optical emission spectroscopy (OES) and indirectly from morphological properties of deposited thin films. Both approaches yield consistent results. Ablated material was deposited in a form of thin film on the Si substrate. During deposition, plasma dynamics was monitored using optical emission spectroscopy with spatial and temporal resolutions. The influence of ablation mode (single and double) and delay time τ (delay between first and second pulses in double-pulse mode) on plasma dynamics and consequently on morphology of deposited Ti-films was studied using X-ray reflectivity and atomic force microscopy. Delay time τ was varied from 170 ns to 4 μs. The results show strong dependence of both emission signal and Ti-film properties, such as thickness, density and roughness, on τ. In addition, correlation of average density and thickness of film is observed. These results are discussed in terms of dependency of angular distribution and kinetic energy of plasma plume particles on τ. Advantages of using double-pulse laser deposition for possible application in thin film production are shown. - Highlights: • Ti-thin films produced by single and double pulse laser ablation mode. • Ablation mode and delay time influenced plasma plume and film characteristics. • Films are most compact for optimized delay time (thinnest, smoothest and most dense). • Plasma dynamics can be inferred from film characteristics.

  13. Development and application of resistive pulse spectroscopy: studies on the size, form and deformability of red blood cells

    Energy Technology Data Exchange (ETDEWEB)

    Yee, J.P.

    1979-01-01

    The following studies were conducted using the resistive pulse spectroscopy (RPS) technique: cumulative spectra and individual pulse forms for rigid latex polymer spheres; acquisition and analysis of RPS spectral data by means of special computer program; interaction of red blood cells with glutaraldehyde; membrane properties of erythrocytes undergoing abrupt osmotic hemolysis; reversible effects of the binding of chlorpromazine HCl at the red cell membrane surface; effects of high cholesterol diet on erythrocytes of guinea pigs; and multi-population analysis for a mixture of fetal and maternal red cells. (HLW)

  14. Fast analysis of complex metallic alloys by double-pulse time-integrated Laser-Induced Breakdown Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sorrentino, F., E-mail: marwan@df.unipi.i [Marwan Technology s.r.l., Spin-off University of Pisa Largo Pontecorvo 3, 56127 Pisa (Italy); Carelli, G.; Francesconi, F.; Francesconi, M.; Marsili, P. [Marwan Technology s.r.l., Spin-off University of Pisa Largo Pontecorvo 3, 56127 Pisa (Italy); Cristoforetti, G.; Legnaioli, S.; Palleschi, V.; Tognoni, E. [Applied Laser Spectroscopy Laboratory, IPCF/CNR - Via G.Moruzzi 1, 56124 Pisa (Italy)

    2009-10-15

    Results are reported on the application of double-pulse Laser-Induced Breakdown Spectroscopy (LIBS) for fast analysis of complex metallic alloys. The approach followed for the determination of the composition of the alloys is based on the time-integrated acquisition of LIBS spectra emitted by plasmas induced by collinear double-pulse laser excitation. The spectra are analysed using the Partial Least Squares method, which allows the determination of sample composition even in the presence of strong spectral interferences. The results shown indicate the possibility of measuring the composition of complex metallic alloys in very short times and using relatively cheap LIBS instrumentation.

  15. Design and application of robust rf pulses for toroid cavity NMR spectroscopy

    CERN Document Server

    Skinner, Thomas E; Woelk, Klaus; Gershenzon, Naum I; Glaser, Steffen J

    2010-01-01

    We present robust radio frequency (rf) pulses that tolerate a factor of six inhomogeneity in the B1 field, significantly enhancing the potential of toroid cavity resonators for NMR spectroscopic applications. Both point-to-point (PP) and unitary rotation (UR) pulses were optimized for excitation, inversion, and refocusing using the gradient ascent pulse engineering (GRAPE) algorithm based on optimal control theory. In addition, the optimized parameterization (OP) algorithm applied to the adiabatic BIR-4 UR pulse scheme enabled ultra-short (50 microsec) pulses with acceptable performance compared to standard implementations. OP also discovered a new class of non-adiabatic pulse shapes with improved performance within the BIR-4 framework. However, none of the OP-BIR4 pulses are competitive with the more generally optimized UR pulses. The advantages of the new pulses are demonstrated in simulations and experiments. In particular, the DQF COSY result presented here represents the first implementation of 2D NMR sp...

  16. Raman spectroscopy of organic dyes adsorbed on pulsed laser deposited silver thin films

    Energy Technology Data Exchange (ETDEWEB)

    Fazio, E.; Neri, F. [Dipartimento di Fisica della Materia e Ingegneria Elettronica, Universitá di Messina, V.le F. Stagno d’Alcontres 31, I-98166, Messina, Italy. (Italy); Valenti, A. [Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Universitá di Messina, V.le F. Stagno d’Alcontres 31, I-98166, Messina, Italy. (Italy); Ossi, P.M., E-mail: paolo.ossi@polimi.it [Dipartimento di Energia, Politecnico di Milano, via Ponzio 34-3, 20133 Milano, Italy. (Italy); Trusso, S.; Ponterio, R.C. [CNR-Istituto per i Processi Chimico-Fisici Sede di Messina, V.le F. Stagno d’Alcontres 37, I-98158 Messina, Italy. (Italy)

    2013-08-01

    The results of a surface-enhanced Raman scattering (SERS) study performed on representative organic and inorganic dyes adsorbed on silver nanostructured thin films are presented and discussed. Silver thin films were deposited on glass slides by focusing the beam from a KrF excimer laser (wavelength 248 nm, pulse duration 25 ns) on a silver target and performing the deposition in a controlled Ar atmosphere. Clear Raman spectra were acquired for dyes such as carmine lake, garanza lake and brazilwood overcoming their fluorescence and weak Raman scattering drawbacks. UV–visible absorption spectroscopy measurements were not able to discriminate among the different chromophores usually referred as carmine lake (carminic, kermesic and laccaic acid), as brazilwood (brazilin and brazilein) and as garanza lake (alizarin and purpurin). SERS measurements showed that the analyzed samples are composed of a mixture of different chromophores: brazilin and brazilein in brazilwood, kermesic and carminic acid in carmine lake, alizarin and purpurin in garanza lake. Detection at concentration level as low as 10{sup −7} M in aqueous solutions was achieved. Higher Raman intensities were observed using the excitation line of 632.8 nm wavelength with respect to the 785 nm, probably due to a pre-resonant effect with the molecular electronic transitions of the dyes.

  17. Raman Spectroscopy of DLC/a-Si Bilayer Film Prepared by Pulsed Filtered Cathodic Arc

    Directory of Open Access Journals (Sweden)

    C. Srisang

    2012-01-01

    Full Text Available DLC/a-Si bilayer film was deposited on germanium substrate. The a-Si layer, a seed layer, was firstly deposited on the substrate using DC magnetron sputtering and DLC layer was then deposited on the a-Si layer using pulsed filtered cathodic arc method. The bilayer films were deposited with different DLC/a-Si thickness ratios, including 2/2, 2/6, 4/4, 6/2, and 9/6. The effect of DLC/a-Si thickness ratios on the sp3 content of DLC was analyzed by Raman spectroscopy. The results show that a-Si layer has no effect on the structure of DLC film. Furthermore, the upper shift in G wavenumber and the decrease in ID/IG inform that sp3 content of the film is directly proportional to DLC thickness. The plot modified from the three-stage model informed that the structural characteristics of DLC/a-Si bilayer films are located close to the tetrahedral amorphous carbon. This information may be important for analyzing and developing bilayer protective films for future hard disk drive.

  18. Librational motion of spin-labeled lipids in high-cholesterol containing membranes from echo-detected EPR spectra.

    Science.gov (United States)

    Erilov, Denis A; Bartucci, Rosa; Guzzi, Rita; Marsh, Derek; Dzuba, Sergei A; Sportelli, Luigi

    2004-12-01

    Two-pulse, echo-detected (ED) electron paramagnetic resonance (EPR) spectroscopy was used to study the librational motions of spin-labeled lipids in membranes of dipalmitoylphosphatidylcholine + 50 mol % cholesterol. The temperature dependence, over the range 77-240 K, and the dependence on position of spin-labeling in the sn-2 chain (n=5, 7, 10, 12, and 14) of the phospholipid, were characterized in detail. The experimental ED-spectra were corrected for instantaneous spin diffusion arising from static spin-spin interactions, by using spectra recorded at 77 K, where motional contributions are negligible. Simulations according to a model of rapid, small-amplitude librations about an axis whose direction is randomly distributed are able to describe the experimental spectra. Calibrations, in terms of the amplitude-correlation time product, alpha2tauc, were constructed for diagnostic spectral line-height ratios at different echo delay times, and for relaxation spectra obtained from the ratio of ED-spectra recorded at two different echo delays. The librational amplitude, alpha2, was determined for a spin label at the 14-C position of the lipid chain from the partially motionally averaged hyperfine splitting in the conventional EPR spectra. The librational correlation time, tauc, which is deduced from combination of the conventional and ED-EPR results, lies in the subnanosecond regime and depends only weakly on temperature. The temperature dependence of the ED-EPR spectra arises mainly from an increase in librational amplitude with increasing temperature, and position down the lipid chain. A gradual transition takes place at higher temperatures, from a situation in which segmental torsional librations are cumulative, i.e., the contributions of the individual segments add up progressively upon going down the chain, to one of concerted motion only weakly dependent on chain position. Such librational motions are important for glass-like states and are generally relevant to

  19. Electrochemical and EPR characterization of 1,4-dihydropyridines. Reactivity towards alkyl radicals.

    Science.gov (United States)

    Núñez-Vergara, Luis J; López-Alarcón, C; Navarrete-Encina, P A; Atria, A M; Camargo, C; Squella, J A

    2003-01-01

    This work reports the electrochemical oxidation of a series of three synthesized 4-substituted-1,4-dihydropyridine derivatives in different electrolytic media. Also, an EPR characterization of intermediates and the reactivity of derivatives towards ABAP-derived alkyl radicals are reported. Dynamic, differential pulse and cyclic voltammetry studies on a glassy carbon electrode showed an irreversible single-peak due to the oxidation of the 1,4-dihydropyridine (1,4-DHP) ring via 2-electrons to the corresponding pyridine derivative. Levich plots were linear in different media, indicating that the oxidation process is diffusion-controlled. Calculated diffusion coefficients did not exhibit significant differences between the derivatives in the same medium. The oxidation mechanism follows the general pathway (electron, H+, electron, H+) with formation of an unstable pyridinium radical. One-electron oxidation intermediate was confirmed with controlled potential electrolysis (CPE) and EPR experiments. On applying N-tert-butyl-alpha-phenylnitrone (PBN) and 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as the spin trap, these unstable radical intermediates from the oxidation of 1,4-DHP derivatives were intercepted. The final product of the CPE, i.e. pyridine derivative, was identified by GC-MS technique. Direct reactivity of the synthesized compounds towards alkyl radicals was demonstrated by UV-Vis. spectroscopy and GC-MS technique. Results indicate that these derivatives significantly react with the radicals, even compared with a well-known antioxidant drug such as nisoldipine.

  20. Ultrashort Generation Regimes in the All-Fiber Kerr Mode-Locked Erbium-Doped Fiber Ring Laser for Terahertz Pulsed Spectroscopy

    Directory of Open Access Journals (Sweden)

    V. S. Voropaev

    2015-01-01

    Full Text Available Many femtosecond engineering applications require for a stable generation of ultrashort pulses. Thus, in the terahertz pulsed spectroscopy a measurement error in the refractive index is strongly dependent on the pulse duration stability with allowable variation of few femtoseconds. The aim of this work is to study the ultrashort pulses (USP regimes stability in the all – fiber erbium doped ring laser with Kerr mode-locking. The study was conducted at several different values of the total resonator intra-cavity dispersion. Three laser schemes with the intra-cavity dispersion values from -1.232 ps2 to +0.008 ps2 have been studied. In the experiment there were two regimes of generation observed: the stretched pulse generation and ordinary soliton generation. Main attention is focused on the stability of regimes under study. The most stable regime was that of the stretched pulse generation with a spectrum form of sech2 , possible pulse duration of 490 fs at least, repetition rate of 2.9 MHz, and average output power of 17 mW. It is worth noting, that obtained regimes had characteristics suitable for the successful use in the terahertz pulsed spectroscopy. The results may be useful in the following areas of science and technology: a high-precision spectroscopy, optical frequency standards, super-continuum generation, and terahertz pulsed spectroscopy. The future system development is expected to stabilize duration and repetition rate of the obtained regime of ultra-short pulse generation.

  1. Retrospective dosimetry using EPR and TL techniques: a status report

    Energy Technology Data Exchange (ETDEWEB)

    Haskell, E.H.

    1996-12-31

    Methods of retrospective dosimetry, including luminescence and electron paramagnetic resonance spectroscopy (EPR), rely on measurement of accident dose absorbed by naturally occurring materials - ceramics in the case of both thermoluminescence (TL) and optically stimulated luminescence (OSL) and organic materials and bio- minerals in the case of EPR. Each of these methods relies on measurement of radiation defects resulting from accidental exposure. Since defects also result from natural sources of radiation over the lifetime of a sample, analysis is usually restricted to materials for which the natural dose may be determined and subtracted from the measured cumulative dose. Luminescence dating techniques rely heavily on an accurate assessment of cumulative dose from natural radiation sources, and dating research has provided us with the bulk of our knowledge in this area. Virtually all of the work on natural dose determination can be directly applied to retrospective techniques. With EPR techniques the cumulative dose from diagnostic x- rays is also of importance.

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

    Energy Technology Data Exchange (ETDEWEB)

    Maghraby, A., E-mail: maghrabism@yahoo.com [National Institute of Standards (NIS) - Radiation Dosimetry Department - Tersa st. 12211 Giza, P.O. Box 136 (Egypt); Salama, E. [Physics Department, Faculty of Science, Ain Shams University, 11566 Cairo (Egypt); Mansour, A. [National Center for Radiation Research and Technology, Atomic Energy Authority, Nasr City, Cairo (Egypt)

    2011-12-11

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

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

    Science.gov (United States)

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

    2011-12-01

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

  4. Detection of cerebral ischemia using the power spectrum of the pulse wave measured by near-infrared spectroscopy.

    Science.gov (United States)

    Ebihara, Akira; Tanaka, Yuichi; Konno, Takehiko; Kawasaki, Shingo; Fujiwara, Michiyuki; Watanabe, Eiju

    2013-10-01

    The diagnosis and medical treatment of cerebral ischemia are becoming more important due to the increase in the prevalence of cerebrovascular disease. However, conventional methods of evaluating cerebral perfusion have several drawbacks: they are invasive, require physical restraint, and the equipment is not portable, which makes repeated measurements at the bedside difficult. An alternative method is developed using near-infrared spectroscopy (NIRS). NIRS signals are measured at 44 positions (22 on each side) on the fronto-temporal areas in 20 patients with cerebral ischemia. In order to extract the pulse-wave component, the raw total hemoglobin data recorded from each position are band-pass filtered (0.8 to 2.0 Hz) and subjected to a fast Fourier transform to obtain the power spectrum of the pulse wave. The ischemic region is determined by single-photon emission computed tomography. The pulse-wave power in the ischemic region is compared with that in the symmetrical region on the contralateral side. In 17 cases (85%), the pulse-wave power on the ischemic side is significantly lower than that on the contralateral side, which indicates that the transmission of the pulse wave is attenuated in the region with reduced blood flow. Pulse-wave power might be useful as a noninvasive marker of cerebral ischemia.

  5. Time domain dielectric spectroscopy of nanosecond pulsed electric field induced changes in dielectric properties of pig whole blood.

    Science.gov (United States)

    Zhuang, Jie; Kolb, Juergen F

    2015-06-01

    The dielectric spectra of fresh pig whole blood in the β-dispersion range after exposure to 300-nanosecond pulsed electric fields (nsPEFs) with amplitude higher than the supra-electroporation threshold for erythrocytes were recorded by time domain reflectometry dielectric spectroscopy. The implications of the dielectric parameters on the dynamics of post-pulse pore development were discussed in light of the Cole-Cole relaxation model. The temporal development of the Cole-Cole parameters indicates that nsPEFs induced significant poration and swelling of erythrocytes within the first 5 min. The results also show that the majority of erythrocytes could not fully recover from supra-electroporation up to 30 min. The findings of this study suggest that time domain dielectric spectroscopy is a promising label-free and real-time physiological measuring technique for nsPEF-blood related biomedical applications, capable of following the conformational and morphological changes of cells.

  6. Recent development of double pulse laser induced breakdown spectroscopy (DP-LIBS setup

    Directory of Open Access Journals (Sweden)

    David Prochazka

    2010-12-01

    Full Text Available Single pulse (SP LIBS setup was modified to DP setup to achievemore accurate analytical sensitivity and spatial resolution. Allparameters, like interpulse delay, acquisition delay or energy ofablation and excitation laser pulses were optimized.

  7. Transient X-ray pulsar V0332+53: pulse phase-resolved spectroscopy and the reflection model

    CERN Document Server

    Lutovinov, A A; Suleimanov, V F; Mushtukov, A A; Doroshenko, V; Nagirner, D I; Poutanen, J

    2015-01-01

    We present the results of the pulse phase- and luminosity-resolved spectroscopy of the transient X-ray pulsar V0332+53, performed for the first time in a wide luminosity range (1-40)x10^{37} erg/s during a giant outburst observed by the RXTE observatory in Dec 2004 - Feb 2005. We characterize the spectra quantitatively and built the detailed "three-dimensional" picture of spectral variations with pulse phase and throughout the outburst. We show that all spectral parameters are strongly variable with the pulse phase, and the pattern of this variability significantly changes with luminosity directly reflecting the associated changes in the structure of emission regions and their beam patterns. Obtained results are qualitatively discussed in terms of the recently developed reflection model for the formation of cyclotron lines in the spectra of X-ray pulsars.

  8. A Chemical Detector for Gas Chromatography Using Pulsed Discharge Emission Spectroscopy on a Microchip

    Science.gov (United States)

    Luo, X.; Zhu, W.; Mitra, B.; Liu, J.; Liu, T.; Fan, X.; Gianchandani, Y.

    2011-12-01

    There is increasing interest in miniaturized systems for chemical analysis in harsh environments. Chemical detection by emission spectroscopy of on-chip microdischarges [1-3] can be performed at >200°C [4], suggesting utility inspace exploration, volcanic monitoring, and oil well monitoring. This abstract describes the first use of pulsed microdischarge spectroscopy for gas chromatography (GC).This effort supports NASA interests in monitoring closed-loop life support systems for spacecraft. The microdischarge occurs on a 1cm2 glass chip (Fig. 1a), with thin-film Ni electrodes separated by 160μm. A glass lid with a grooved gas-flow channel, and inlet/outlet capillary tubes are epoxy-sealed to the chip. Located downstream of the 1.7m-long, RTX-1-coated, GC separation column, the microdischarge chip is read by a spectrometer. In a typical experiment (Fig. 1b), a mixture of acetone 3.6μg, 1-hexanol 2.8μg and nitrobenzene 3.0μg, is injected, with He carrier gas at 1.56sccm, through the GC. Acetone elutes quickly while nitrobenzene is slower. Microdischarges are triggered at 0.5Hz for 6 min., and 0.04Hz thereafter. Each microdischarge consumes ≈8mJ; the average power is ≈1.14mW. The spectrum (Fig. 1b, inset) shows that the 388nm peak, representing CN/CH fragments [5], is enhanced by carbon compounds. Its strength relative to the 588nm peak of He provides a chromatogram. Fig. 1b also shows a benchmark result from a commercial flame ionization detector (FID). The differences in elution time are attributed to differences in the gas flow paths for the two detectors [1]. REFERENCES [1] Eijkel et al, Anal. Chem, 2000 [2] Mitra et al, IEEE Trans Plasma Sci, 2008 [3] Mitra et al, IEEE Sensors, 2008 [4] Wright et al, APL, 2009 [5] Pearse et al, The Identification of Molecular Spectra, 1963

  9. Alcoholic extraction enables EPR analysis to characterize radiation-induced cellulosic signals in spices.

    Science.gov (United States)

    Ahn, Jae-Jun; Sanyal, Bhaskar; Akram, Kashif; Kwon, Joong-Ho

    2014-11-19

    Different spices such as turmeric, oregano, and cinnamon were γ-irradiated at 1 and 10 kGy. The electron paramagnetic resonance (EPR) spectra of the nonirradiated samples were characterized by a single central signal (g = 2.006), the intensity of which was significantly enhanced upon irradiation. The EPR spectra of the irradiated spice samples were characterized by an additional triplet signal at g = 2.006 with a hyperfine coupling constant of 3 mT, associated with the cellulose radical. EPR analysis on various sample pretreatments in the irradiated spice samples demonstrated that the spectral features of the cellulose radical varied on the basis of the pretreatment protocol. Alcoholic extraction pretreatment produced considerable improvements of the EPR signals of the irradiated spice samples relative to the conventional oven and freeze-drying techniques. The alcoholic extraction process is therefore proposed as the most suitable sample pretreatment for unambiguous detection of irradiated spices by EPR spectroscopy.

  10. Radiation chemistry of L-Alanine: application to EPR dosimetry (1)

    Energy Technology Data Exchange (ETDEWEB)

    Kim, M. J.; Jeo, Y. H.; Ha, Y. K.; Park, Y. S.; Choi, I. G. [KAERI, Taejon (Korea, Republic of)

    2003-10-01

    High energy ionizing radiation leaves stable radicals to certain organic materials, such as alanine and tartrate. Electron Paramagnetic Resonance (EPR) spectroscopy is a powerful tool for the identification and quantification of these radiation-induced radicals. An EPR method has been applied to study the radical characteristics of L-alanine after gamma radiation dose in the range of {approx}mGy to 60 kGy. The free radicals induced by gamma radiation were fairly stable, and EPR intensity, radical concentration, was proportional to the absorbed dose up to 60 kGy. From the results of our EPR measurements, it can be concluded that an alanine/EPR method is a useful technique for gamma radiation dosimetry from very low to high dose range.

  11. Characterization of a high current pulsed arc using optical emission spectroscopy

    Science.gov (United States)

    Sousa Martins, R.; Zaepffel, C.; Chemartin, L.; Lalande, Ph; Soufiani, A.

    2016-10-01

    In this paper, we present the investigation realized on an experimental setup that simulates an arc column subjected to the transient phase of a lightning current waveform in laboratory conditions. Optical emission spectroscopy is employed to assess space- and time-resolved properties of this high current pulsed arc. Different current peak levels are utilised in this work, ranging from 10 kA to 100 kA, with a peak time around 15 µs. Ionic lines of nitrogen and oxygen are used to determine the radial profiles of temperature and electron density of the arc channel over time from 2 µs to 36 µs. A combination of 192 N II and O II lines is considered in the calculation of the bound-bound contribution of the absorption coefficient of the plasma channel. Calculations of the optical thickness showed that self-absorption of these ionic lines in the arc column is important. To obtain temperature and electron density profiles in the arc, we solved the radiative transfer equation across the channel under an axisymmetric assumption and considering the channel formed by uniform concentric layers. For the 100 kA current peak level, the temperature reaches more than 38 000 K and the electron density reaches 5  ×  1018 cm-3. The pressure inside the channel is calculated using the air plasma composition at local thermodynamic equilibrium, and reaches 45 bar. The results are discussed and utilised to estimate the electrical conductivity of the arc channel.

  12. The Fantastic Four: A plug 'n' play set of optimal control pulses for enhancing nmr spectroscopy

    CERN Document Server

    Nimbalkar, Manoj; Skinner, Thomas E; Neves, Jorge L; Gershenzon, Naum I; Kobzar, Kyryl; Bermel, Wolfgang; Glaser, Steffen J

    2012-01-01

    We present highly robust, optimal control-based shaped pulses designed to replace all 90{\\deg} and 180{\\deg} hard pulses in a given pulse sequence for improved performance. Special attention was devoted to ensuring that the pulses can be simply substituted in a one-to-one fashion for the original hard pulses without any additional modification of the existing sequence. The set of four pulses for each nucleus therefore consists of 90{\\deg} and 180{\\deg} point-to-point (PP) and universal rotation (UR) pulses of identical duration. These 1 ms pulses provide uniform performance over resonance offsets of 20 kHz (1H) and 35 kHz (13C) and tolerate reasonably large radio frequency (RF) inhomogeneity/miscalibration of (+/-)15% (1H) and (+/-)10% (13C), making them especially suitable for NMR of small-to-medium-sized molecules (for which relaxation effects during the pulse are negligible) at an accessible and widely utilized spectrometer field strength of 600 MHz. The experimental performance of conventional hard-pulse ...

  13. Optimally enhanced optical emission in laser-induced breakdown spectroscopy by combining spatial confinement and dual-pulse irradiation.

    Science.gov (United States)

    Guo, L B; Zhang, B Y; He, X N; Li, C M; Zhou, Y S; Wu, T; Park, J B; Zeng, X Y; Lu, Y F

    2012-01-16

    In laser-induced breakdown spectroscopy (LIBS), a pair of aluminum-plate walls were used to spatially confine the plasmas produced in air by a first laser pulse (KrF excimer laser) from chromium (Cr) targets with a second laser pulse (Nd:YAG laser at 532 nm, 360 mJ/pulse) introduced parallel to the sample surface to re-excite the plasmas. Optical emission enhancement was achieved by combing the spatial confinement and dual-pulse LIBS (DP-LIBS), and then optimized by adjusting the distance between the two walls and the interpulse delay time between both laser pulses. A significant enhancement factor of 168.6 for the emission intensity of the Cr lines was obtained at an excimer laser fluence of 5.6 J/cm(2) using the combined spatial confinement and DP-LIBS, as compared with an enhancement factor of 106.1 was obtained with DP-LIBS only. The enhancement mechanisms based on shock wave theory and reheating in DP-LIBS are discussed.

  14. Photon-induced positron annihilation lifetime spectroscopy using ultrashort laser-Compton-scattered gamma-ray pulses.

    Science.gov (United States)

    Taira, Y; Toyokawa, H; Kuroda, R; Yamamoto, N; Adachi, M; Tanaka, S; Katoh, M

    2013-05-01

    High-energy ultrashort gamma-ray pulses can be generated via laser Compton scattering with 90° collisions at the UVSOR-II electron storage ring. As an applied study of ultrashort gamma-ray pulses, a new photon-induced positron annihilation lifetime spectroscopy approach has been developed. Ultrashort gamma-ray pulses with a maximum energy of 6.6 MeV and pulse width of 2.2 ps created positrons throughout bulk lead via pair production. Annihilation gamma rays were detected by a BaF2 scintillator mounted on a photomultiplier tube. A positron lifetime spectrum was obtained by measuring the time difference between the RF frequency of the electron storage ring and the detection time of the annihilation gamma rays. We calculated the response of the BaF2 scintillator and the time jitter caused by the variation in the total path length of the ultrashort gamma-ray pulses, annihilation gamma rays, and scintillation light using a Monte Carlo simulation code. The positron lifetime for bulk lead was successfully measured.

  15. Issues in deep ocean collinear double-pulse laser induced breakdown spectroscopy: Dependence of emission intensity and inter-pulse delay on solution pressure

    Energy Technology Data Exchange (ETDEWEB)

    Lawrence-Snyder, Marion; Scaffidi, Jonathan P.; Pearman, William F.; Gordon, Christopher M.; Angel, S. Michael

    2014-09-01

    Double-pulse laser-induced breakdown spectroscopy (DP-LIBS) with a collinear laser beam orientation is shown for high-pressure bulk aqueous solutions (up to 50 bar) along with bubble and plasma images. These investigations reveal that the emission plasma is quenched much more rapidly in solution requiring much shorter detector gate delays than for typical LIBS measurements in air. Also, the emission is inversely proportional to solution pressure, and the most intense emission at all pressures occurs when the laser-induced vapor bubble is at a maximum diameter. It is also shown that the laser-induced bubble grows initially at the same rate for all solution pressures, collapsing more quickly as the pressure is increased. Intense emission is best obtained for conditions where the laser-induced bubble formed by the first laser pulse is small and spherically shaped. - Highlights: • Collinear double-pulse LIBS is shown for 50 bar bulk aqueous solutions. • LIBS plasma in solution is much more rapidly quenched than a LIBS plasma in air. • For DP LIBS, the emission is inversely proportional to solution pressure. • Laser-induced bubble growth rate is the same at all solution pressures. • Large spherical laser-induced bubbles produce the strongest DP LIBS emission.

  16. The Role of Plasma Shielding in Double-Pulse Femtosecond Laser-Induced Breakdown Spectroscopy

    CERN Document Server

    Penczak, John S; Bar, Ilana; Gordon, Robert J

    2013-01-01

    It is well known that optical emission produced by femtosecond laser-induced breakdown on a surface may be enhanced by using a pair of laser pulses separated by a suitable delay. Here we elucidate the mechanism for this effect both experimentally and theoretically. Using a bilayer sample consisting of a thin film of Ag deposited on an Al substrate as the ablation target and measuring the breakdown spectrum as a function of fluence and pulse delay, it is shown experimentally that the enhanced signal is not caused by additional ablation initiated by the second pulse. Rather, particle-in-cell calculations show that the plasma produced by the first pulse shields the surface from the second pulse for delays up to 100 ps. These results indicate that the enhancement is the result of excitement of particles entrained in the plasma produced by the first pulse.

  17. A conceptual design of the set-up for solid state spectroscopy with free electron laser and insertion device radiation

    CERN Document Server

    Makhov, V N

    2001-01-01

    The set-up for complex solid state spectroscopy with the use of enhanced properties of radiation from insertion devices and free electron lasers is proposed. Very high flux and pulsed properties of radiation from insertion devices and free electron lasers offer the possibility for the use of such powerful techniques as electron paramagnetic resonance (EPR) and optically detected magnetic resonance (ODMR) for the studies of excited states of electronic excitations or defects in solids. The power density of radiation can become high enough for one more method of exited-state spectroscopy: transient optical absorption spectroscopy. The set-up is supposed to combine the EPR/ODMR spectrometer, i.e. cryostat supplied with superconducting magnet and microwave system, and the optical channels for excitation (by radiation from insertion devices or free electron laser) and detection of luminescence (i.e. primary and secondary monochromators). The set-up can be used both for 'conventional' spectroscopy of solids (reflec...

  18. Effect of microwave power on EPR spectra of natural and synthetic dental biocompatible materials

    Directory of Open Access Journals (Sweden)

    Adamczyk Jakub

    2015-07-01

    Full Text Available Paramagnetic centers in the two exemplary synthetic and natural dental biocompatible materials applied in implantology were examined by the use of an X-band (9.3 GHz electron paramagnetic resonance (EPR spectroscopy. The EPR spectra were measured in the range of microwave power 2.2–70 mW. The aims of this work were to compare paramagnetic centers concentrations in different dental biocompatible materials and to determine the effect of microwave power on parameters of their EPR spectra. It is the very first and innovatory examination of paramagnetic centers in these materials. It was pointed out that paramagnetic centers existed in both natural (~1018 spin/g and synthetic (~1019 spin/g dental biocompatible materials, but the lower free radical concentration characterized the natural sample. Continuous microwave saturation of EPR spectra indicated that faster spin-lattice relaxation processes existed in synthetic dental biocompatible materials than in natural material. Linewidths (ΔBpp of the EPR spectra of the natural dental material slightly increased for the higher microwave powers. Such effect was not observed for the synthetic material. The broad EPR lines (ΔBpp: 2.4 mT, 3.9 mT, were measured for the natural and synthetic dental materials, respectively. Probably strong dipolar interactions between paramagnetic centers in the studied samples may be responsible for their line broadening. EPR spectroscopy is the useful experimental method in the examination of paramagnetic centers in dental biocompatible materials.

  19. Copper-phthalocyanine encapsulated into zeolite-Y with high Si/Al: An EPR study

    Science.gov (United States)

    Yahiro, Hidenori; Kimoto, Kunihiro; Yamaura, Hiroyuki; Komaguchi, Kenji; Lund, Anders

    2005-10-01

    Copper (II) phthalocyanine (CuPc) molecules encapsulated into zeolite-Y with Si/Al ratios of 2.7 and 410 were prepared by an in situ synthesis and characterized by UV-Vis and electron paramagnetic resonance (EPR) spectroscopies. Resolved Cu-hyperfine and N-superhyperfine structures were observed in the EPR spectrum of CuPc encapsulated into zeolite-Y with a high Si/Al ratio. UV-Vis and EPR studies as well as theoretical calculations suggest that the encapsulated CuPc molecule was distorted in zeolite-Y with keeping of the square-planar symmetry around the center copper (II) ion.

  20. EPR investigation of some desiccated Ascomycota and Basidiomycota gamma-irradiated mushrooms

    Energy Technology Data Exchange (ETDEWEB)

    Bercu, V., E-mail: vbercu@gmail.co [University of Bucharest, Department of Atomic and Nuclear Physics, P.O. Box MG-11, 077125 Magurele (Ilfov) (Romania); Negut, C.D., E-mail: dnegut@nipne.r [University of Bucharest, Department of Atomic and Nuclear Physics, P.O. Box MG-11, 077125 Magurele (Ilfov) (Romania); Horia Hulubei National Institute for Physics and Nuclear Engineering, P.O. Box MG-6, 077125 Magurele (Ilfov) (Romania); Duliu, O.G., E-mail: duliu@b.astral.r [University of Bucharest, Department of Atomic and Nuclear Physics, P.O. Box MG-11, 077125 Magurele (Ilfov) (Romania)

    2010-12-15

    The suitability of the EPR spectroscopy for detection of {gamma}-irradiation in five species of dried mushroom, currently used in gastronomy: yellow morel-Morchella esculenta, (L.) Pers. (Phylum Ascomycota), button mushroom-Agaricus bisporus (J.E.Lange), Agaricus haemorrhoidarius Fr., golden chantarelle-Cantharellus cibarius Fr., as well as oyster mushroom-Pleurotus ostreatus (Jacq. ex Fr.) (Phylum Basidiomycota) is presented and discussed. Although after irradiation at doses up to 11 kGy, all specimens presented well defined EPR spectra, only A. bisporus EPR signal was enough stable to make detection possible after 18 months.

  1. EPR investigation of some desiccated Ascomycota and Basidiomycota gamma-irradiated mushrooms

    Science.gov (United States)

    Bercu, V.; Negut, C. D.; Duliu, O. G.

    2010-12-01

    The suitability of the EPR spectroscopy for detection of γ-irradiation in five species of dried mushroom, currently used in gastronomy: yellow morel— Morchella esculenta, (L.) Pers. (Phylum Ascomycota), button mushroom— Agaricus bisporus (J.E.Lange), Agaricus haemorrhoidarius Fr., golden chantarelle— Cantharellus cibarius Fr., as well as oyster mushroom— Pleurotus ostreatus (Jacq. ex Fr.) (Phylum Basidiomycota) is presented and discussed. Although after irradiation at doses up to 11 kGy, all specimens presented well defined EPR spectra, only A. bisporus EPR signal was enough stable to make detection possible after 18 months.

  2. Double core-hole spectroscopy of transient plasmas produced in the interaction of ultraintense x-ray pulses with neon

    CERN Document Server

    Gao, Cheng; Yuan, Jianmin

    2015-01-01

    Double core-hole (DCH) spectroscopy is investigated systematically for neon atomic system in the interaction with ultraintense x-ray pulses with photon energy from 937 eV to 2000 eV. A time-dependent rate equation, implemented in the detailed level accounting approximation, is utilized to study the dynamical evolution of the level population and emission properties of the highly transient plasmas. For x-ray pulses with photon energy in the range of 937-1030 eV, where $1s\\rightarrow 2p$ resonance absorption from single core-hole (SCH) states of neon charge states exist, inner-shell resonant absorption (IRA) effects play important roles in the time evolution of population and DCH spectroscopy. Such IRA physical effects are illustrated in detail by investigating the interaction of x-ray pulses at a photon energy of 944 eV, which corresponds to the $1s\\rightarrow 2p$ resonant absorption from the SCH states ($1s2s^22p^4$, $1s2s2p^5$ and $1s2p^6$) of Ne$^{3+}$. After averaging over the space and time distribution o...

  3. Visible and ultraviolet photoelectron spectroscopy of fullerenes using femtosecond laser pulses

    OpenAIRE

    Campbell E. E. B.; Henderson G. G.; Johansson J. O.

    2013-01-01

    Photoelectron spectra are presented for C60 excited with fs pulses of wavelengths 532 and 267 nm. The spectra indicate a quick redistribution of the excitation energy. Excitation of SAMO states is observed with 532 nm excitation, but due to the relatively large photon energy of the 267 nm pulses, these orbitals are not populated for this wavelength.

  4. The role of plasma shielding in collinear double-pulse femtosecond laser-induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Penczak, John [Department of Chemistry (m/c 111), University of Illinois at Chicago, Chicago, IL 60680-7061 (United States); Kupfer, Rotem; Bar, Ilana [Department of Physics, Ben-Gurion University of the Negev, Beer-Sheva 84105 (Israel); Gordon, Robert J. [Department of Chemistry (m/c 111), University of Illinois at Chicago, Chicago, IL 60680-7061 (United States)

    2014-07-01

    We report an experimental and theoretical study of the mechanism for the enhancement of the laser-induced breakdown signal produced by two collinear femtosecond pulses separated by a suitable delay. A bilayer sample consisting of a 500 nm thick film of Ag deposited on Al was used in the experiments, and a particle-in-cell (PIC) simulation was implemented in the theoretical part of the study. Experiments on the effect of laser polarization, performed at a 30° angle of incidence over a wide range of fluences, together with the PIC results, showed that the plasma produced by the first pulse was further excited by the second pulse. Experiments at normal incidence and a fluence of 200 J/cm{sup 2} showed that the second pulse did not penetrate the Ag layer. In addition, measurements of the effect of pulse delay on the signal supported the conclusion that double pulse enhancement is produced by plasma heating rather than by increased surface ablation. - Highlights: • We study the mechanism for collinear double-pulse enhancement of LIBS produced by a fs laser. • We use a bilayer of Ag on Al to determine which region is reached by the 2nd pulse. • Signal enhancement is produced by plasma heating rather than by increased surface ablation. • Particle-in-cell calculations show that plasma shielding plays a key role.

  5. Investigation of the nitrogen hyperfine coupling of the second stable radical in γ-irradiated L-alanine crystals by 2D-HYSCORE spectroscopy

    Science.gov (United States)

    Maltar-Strmečki, Nadica; Rakvin, Boris

    2012-09-01

    The second stable radical, NH3+C(CH3)COO, R2, in the γ-irradiated single crystal of L-alanine and its fully 15N-enriched analogue were studied by an advanced pulsed EPR technique, 2D-HYSCORE (two-dimensional hyperfine sublevel correlation) spectroscopy at 200 K. The nitrogen hyperfine coupling tensor of the R2 radical was determined from the HYSCORE data and provides new experimental data for improved characterization of the R2 radical in the crystal lattice. The results obtained complement the experimental proton data available for the R2 radical and could lead to increased accuracy and reliability of EPR spectrum simulations.

  6. Mid-Infrared Pulse Shaping and Two-Dimensional Spectroscopy of Open Quantum Systems in Liquid Solution

    Science.gov (United States)

    Ross, Matthew R.

    The primary focus of this work is the development of a mid-infrared pulse shaping system. The primary motivation for this system is for two-dimensional infrared (2DIR) spectroscopy, however, the mid-infrared pulse shaper also allows for more sophisticated spectroscopic experiments not previously attempted in the mid-infrared. Moreover, many can be implemented without changes or realignment of the optical setup. Example spectra are presented along with a discussion of capabilities and diagnostics. A second major project presented is 2DIR spectroscopy of iron pentacarbonyl, Fe(CO)5, a small metal carbonyl. This molecule undergoes Berry pseudorotation, a form of fluxtionality. This fast exchange of ligands mixes axial and equatorial modes and occurs on a timescale of picoseconds, too fast for NMR and other methods of measuring chemical structure and isomerization. Ultrafast chemical exchange spectroscopy, a measurement within 2DIR spectroscopy, is capable of resolving the time scales of this motion. We found that this process is affected by the solvent environment, specifically the solvent viscosity in alkanes and hydrogen bonding environments in alcohols. Lastly, a study is presented in which a series of synthetic metalloenzymes with a metal active site are studied by 2DIR spectroscopy. In this case a carbonyl is ligated to a copper-I atom in the active site, which then serves as our spectroscopic probe. We find, unexpectedly, that the shape of the carbonyl vibrational potential, as measured by the anharmonicity, is time-dependent. We attribute this to a geometrical rearrangement and are able to suggest that this effect is dependent on local site structure and dynamics and not significantly affected by electric potential near the peptide.

  7. Kinetics of the reaction F+NO+M->FNO+M studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.

    1996-01-01

    The title reaction was initiated by pulse radiolysis of SF6/NO gas mixtures, and the formation of FNO was studied by time-resolved IR and UV spectroscopy. At SF6 pressures of 10-320 mbar at 298 K, the formation of FNO was studied by infrared diode laser spectroscopy at 1857.324 cm(-1). Comparative...

  8. EPR: the nuclear impasse; EPR: l'impasse nucleaire

    Energy Technology Data Exchange (ETDEWEB)

    Marillier, F. [Association Ecologiste Greenpeace (France)

    2008-07-01

    The questions relative to the climatic change constitute crucial challenges for the next ten years. In this context the author aims to show how the EPR project illustrates the nuclear french ''autism''. He presents and analyzes the international and environmental impacts of this obsolete technology, as a project useless and dangerous. (A.L.B.)

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

    Science.gov (United States)

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

    1995-02-01

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

  10. Development of Ultrashort Pulse Lasers and Their Applications to Ultrafast Spectroscopy in the Visible and NIR Ranges

    Science.gov (United States)

    Kobayashi, Takayoshi

    2016-07-01

    The use of ultrafast spectroscopy to gain detailed information about nonlinear processes can disclose the key physical mechanisms in the processes. The information promises to be a useful means to enhance the necessary nonlinearity for optical devices such as optical switches and optical manipulations of quantum states. Our group has generated stable visible to near-infrared laser pulses with a sub-5-fs duration using a non-collinear optical parametric amplifier. We also developed a detection system composed of 128 lock-in detectors, which provides an indispensable means of obtaining ultrafast nonlinear responses simultaneously in a very broad spectral range. The developed ultrashort pulse laser is used to study the electronic relaxation and molecular vibration dynamics in molecular systems through the interaction of the ultrashort pulses with the systems. Ultrashort pulses can stimulate Raman scattering in a molecular system. Observed time-resolved spectrum was analyzed to separate the electronic and vibrational contributions to the transient difference absorbance. The probe wavelength dependence of the vibrational amplitude is explained in terms of the coupling between the two pairing components among the pump field, Stokes field, anti-Stokes field, and coherent vibrational coordinates.

  11. Ultraviolet absorption spectroscopy in optically dense fireballs using broadband second-harmonic generation of a pulsed modeless dye laser.

    Science.gov (United States)

    Soo, Michael; Glumac, Nick

    2014-01-01

    Broadband frequency doubling of a modeless dye laser pulse is used to enable single-shot absorption spectroscopy in the ultraviolet for optically dense, energetic-materials fireball applications. Band widths of approximately 1-3 nm are generated in the 226 and 268 nm regions using a doubling crystal. Strong focusing of the fundamental beam onto the crystal is found to be sufficient to achieve 1-5% conversion efficiency with a pulse intensity sufficient to saturate the array detector even after 75% attenuation through the fireball. The technique is demonstrated with nitric oxide (NO) absorption in a gas cell and is then used to perform the first detection and temperature fitting of aluminum monofluoride (AlF) and magnesium monofluoride (MgF) in a fireball environment.

  12. Generation of 8.5-fs pulses at 1.3 microm for ultrabroadband pump-probe spectroscopy.

    Science.gov (United States)

    Brida, Daniele; Bonora, Stefano; Manzoni, Cristian; Marangoni, Marco; Villoresi, Paolo; De Silvestri, Sandro; Cerullo, Giulio

    2009-07-20

    We report on a near-infrared non-collinear optical parametric amplifier (NOPA) based on periodically poled stoichiometric lithium tantalate. The NOPA generates muJ-energy pulses with spectrum spanning the 1-1.7 microm wavelength range, which are compressed to nearly transformlimited 8.5 fs duration by a deformable mirror. By synchronizing this source with a sub-10-fs visible NOPA, we demonstrate an unprecedented combination of temporal resolution and spectral coverage in two-colour pump-probe spectroscopy.

  13. Investigation of the osteitis deformans phases in snake vertebrae by double-pulse laser-induced breakdown spectroscopy.

    Science.gov (United States)

    Galiová, M; Kaiser, J; Novotný, K; Ivanov, M; Nývltová Fisáková, M; Mancini, L; Tromba, G; Vaculovic, T; Liska, M; Kanický, V

    2010-09-01

    Double-pulse laser-induced breakdown spectroscopy (DP-LIBS) was optimized for microspatial analyses of fossil and recent snake vertebrae. As complimentary techniques, solution analysis by inductively coupled plasma mass spectrometry and synchrotron radiation X-ray microtomography was utilized in order to determine the overall concentration of the selected elements in the samples and to visualize nondestructively the fossil sample microstructure, respectively. Elemental mapping of pathological bony tissue by DP-LIBS has been proven as a powerful tool for considering the osteitis deformans phases in fossil vertebrae.

  14. A Direct Method to Extract Transient Sub-Gap Density of State (DOS) Based on Dual Gate Pulse Spectroscopy

    Science.gov (United States)

    Dai, Mingzhi; Khan, Karim; Zhang, Shengnan; Jiang, Kemin; Zhang, Xingye; Wang, Weiliang; Liang, Lingyan; Cao, Hongtao; Wang, Pengjun; Wang, Peng; Miao, Lijing; Qin, Haiming; Jiang, Jun; Xue, Lixin; Chu, Junhao

    2016-06-01

    Sub-gap density of states (DOS) is a key parameter to impact the electrical characteristics of semiconductor materials-based transistors in integrated circuits. Previously, spectroscopy methodologies for DOS extractions include the static methods, temperature dependent spectroscopy and photonic spectroscopy. However, they might involve lots of assumptions, calculations, temperature or optical impacts into the intrinsic distribution of DOS along the bandgap of the materials. A direct and simpler method is developed to extract the DOS distribution from amorphous oxide-based thin-film transistors (TFTs) based on Dual gate pulse spectroscopy (GPS), introducing less extrinsic factors such as temperature and laborious numerical mathematical analysis than conventional methods. From this direct measurement, the sub-gap DOS distribution shows a peak value on the band-gap edge and in the order of 1017-1021/(cm3·eV), which is consistent with the previous results. The results could be described with the model involving both Gaussian and exponential components. This tool is useful as a diagnostics for the electrical properties of oxide materials and this study will benefit their modeling and improvement of the electrical properties and thus broaden their applications.

  15. A Direct Method to Extract Transient Sub-Gap Density of State (DOS) Based on Dual Gate Pulse Spectroscopy.

    Science.gov (United States)

    Dai, Mingzhi; Khan, Karim; Zhang, Shengnan; Jiang, Kemin; Zhang, Xingye; Wang, Weiliang; Liang, Lingyan; Cao, Hongtao; Wang, Pengjun; Wang, Peng; Miao, Lijing; Qin, Haiming; Jiang, Jun; Xue, Lixin; Chu, Junhao

    2016-06-14

    Sub-gap density of states (DOS) is a key parameter to impact the electrical characteristics of semiconductor materials-based transistors in integrated circuits. Previously, spectroscopy methodologies for DOS extractions include the static methods, temperature dependent spectroscopy and photonic spectroscopy. However, they might involve lots of assumptions, calculations, temperature or optical impacts into the intrinsic distribution of DOS along the bandgap of the materials. A direct and simpler method is developed to extract the DOS distribution from amorphous oxide-based thin-film transistors (TFTs) based on Dual gate pulse spectroscopy (GPS), introducing less extrinsic factors such as temperature and laborious numerical mathematical analysis than conventional methods. From this direct measurement, the sub-gap DOS distribution shows a peak value on the band-gap edge and in the order of 10(17)-10(21)/(cm(3)·eV), which is consistent with the previous results. The results could be described with the model involving both Gaussian and exponential components. This tool is useful as a diagnostics for the electrical properties of oxide materials and this study will benefit their modeling and improvement of the electrical properties and thus broaden their applications.

  16. Neutron resonance transmission spectroscopy with high spatial and energy resolution at the J-PARC pulsed neutron source

    Energy Technology Data Exchange (ETDEWEB)

    Tremsin, A.S., E-mail: ast@ssl.berkeley.edu [University of California at Berkeley, 7 Gauss Way, Berkeley, CA 94720 (United States); Shinohara, T.; Kai, T.; Ooi, M. [Japan Atomic Energy Agency, 2–4 Shirakata-shirane, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan); Kamiyama, T.; Kiyanagi, Y.; Shiota, Y. [Hokkaido University, Kita 13 Nishi 8 Kita-ku, Sapporo-shi, Hokkaido 060-8628 (Japan); McPhate, J.B.; Vallerga, J.V.; Siegmund, O.H.W. [University of California at Berkeley, 7 Gauss Way, Berkeley, CA 94720 (United States); Feller, W.B. [NOVA Scientific, Inc., 10 Picker Rd., Sturbridge, MA 01566 (United States)

    2014-05-11

    The sharp variation of neutron attenuation at certain energies specific to particular nuclides (the lower range being from ∼1 eV up to ∼1 keV), can be exploited for the remote mapping of element and/or isotope distributions, as well as temperature probing, within relatively thick samples. Intense pulsed neutron beam-lines at spallation sources combined with a high spatial, high-timing resolution neutron counting detector, provide a unique opportunity to measure neutron transmission spectra through the time-of-flight technique. We present the results of experiments where spatially resolved neutron resonances were measured, at energies up to 50 keV. These experiments were performed with the intense flux low background NOBORU neutron beamline at the J-PARC neutron source and the high timing resolution (∼20 ns at epithermal neutron energies) and spatial resolution (∼55 µm) neutron counting detector using microchannel plates coupled to a Timepix electronic readout. Simultaneous element-specific imaging was carried out for several materials, at a spatial resolution of ∼150 µm. The high timing resolution of our detector combined with the low background beamline, also enabled characterization of the neutron pulse itself – specifically its pulse width, which varies with neutron energy. The results of our measurements are in good agreement with the predicted results for the double pulse structure of the J-PARC facility, which provides two 100 ns-wide proton pulses separated by 600 ns, broadened by the neutron energy moderation process. Thermal neutron radiography can be conducted simultaneously with resonance transmission spectroscopy, and can reveal the internal structure of the samples. The transmission spectra measured in our experiments demonstrate the feasibility of mapping elemental distributions using this non-destructive technique, for those elements (and in certain cases, specific isotopes), which have resonance energies below a few keV, and with lower

  17. Spin system trajectory analysis under optimal control pulses

    Science.gov (United States)

    Kuprov, Ilya

    2013-08-01

    Several methods are proposed for the analysis, visualization and interpretation of high-dimensional spin system trajectories produced by quantum mechanical simulations. It is noted that expectation values of specific observables in large spin systems often feature fast, complicated and hard-to-interpret time dynamics and suggested that populations of carefully selected subspaces of states are much easier to analyze and interpret. As an illustration of the utility of the proposed methods, it is demonstrated that the apparent "noisy" appearance of many optimal control pulses in NMR and EPR spectroscopy is an illusion - the underlying spin dynamics is shown to be smooth, orderly and very tightly controlled.

  18. Highly-Efficient Charge Separation and Polaron Delocalization in Polymer-Fullerene Bulk-Heterojunctions: A Comparative Multi-Frequency EPR & DFT Study

    Science.gov (United States)

    Niklas, Jens; Mardis, Kristy L.; Banks, Brian P.; Grooms, Gregory M.; Sperlich, Andreas; Dyakonov, Vladimir; Beaupré, Serge; Leclerc, Mario; Xu, Tao; Yu, Luping; Poluektov, Oleg G.

    2016-01-01

    The ongoing depletion of fossil fuels has led to an intensive search for additional renewable energy sources. Solar-based technologies could provide sufficient energy to satisfy the global economic demands in the near future. Photovoltaic (PV) cells are the most promising man-made devices for direct solar energy utilization. Understanding the charge separation and charge transport in PV materials at a molecular level is crucial for improving the efficiency of the solar cells. Here, we use light-induced EPR spectroscopy combined with DFT calculations to study the electronic structure of charge separated states in blends of polymers (P3HT, PCDTBT, and PTB7) and fullerene derivatives (C60-PCBM and C70-PCBM). Solar cells made with the same composites as active layers show power conversion efficiencies of 3.3% (P3HT), 6.1% (PCDTBT), and 7.3% (PTB7), respectively. Under illumination of these composites, two paramagnetic species are formed due to photo-induced electron transfer between the conjugated polymer and the fullerene. They are the positive, P+, and negative, P-, polarons on the polymer backbone and fullerene cage, respectively, and correspond to radical cations and radical anions. Using the high spectral resolution of high-frequency EPR (130 GHz), the EPR spectra of these species were resolved and principal components of the g-tensors were assigned. Light-induced pulsed ENDOR spectroscopy allowed the determination of 1H hyperfine coupling constants of photogenerated positive and negative polarons. The experimental results obtained for the different polymer-fullerene composites have been compared with DFT calculations, revealing that in all three systems the positive polaron is distributed over distances of 40 - 60 Å on the polymer chain. This corresponds to about 15 thiophene units for P3HT, approximately three units PCDTBT, and about three to four units for PTB7. No spin density delocalization between neighboring fullerene molecules was detected by EPR. Strong

  19. Highly-efficient charge separation and polaron delocalization in polymer-fullerene bulk-heterojunctions: a comparative multi-frequency EPR and DFT study.

    Science.gov (United States)

    Niklas, Jens; Mardis, Kristy L; Banks, Brian P; Grooms, Gregory M; Sperlich, Andreas; Dyakonov, Vladimir; Beaupré, Serge; Leclerc, Mario; Xu, Tao; Yu, Luping; Poluektov, Oleg G

    2013-06-28

    The ongoing depletion of fossil fuels has led to an intensive search for additional renewable energy sources. Solar-based technologies could provide sufficient energy to satisfy the global economic demands in the near future. Photovoltaic (PV) cells are the most promising man-made devices for direct solar energy utilization. Understanding the charge separation and charge transport in PV materials at a molecular level is crucial for improving the efficiency of the solar cells. Here, we use light-induced EPR spectroscopy combined with DFT calculations to study the electronic structure of charge separated states in blends of polymers (P3HT, PCDTBT, and PTB7) and fullerene derivatives (C60-PCBM and C70-PCBM). Solar cells made with the same composites as active layers show power conversion efficiencies of 3.3% (P3HT), 6.1% (PCDTBT), and 7.3% (PTB7), respectively. Upon illumination of these composites, two paramagnetic species are formed due to photo-induced electron transfer between the conjugated polymer and the fullerene. They are the positive, P(+), and negative, P(-), polarons on the polymer backbone and fullerene cage, respectively, and correspond to radical cations and radical anions. Using the high spectral resolution of high-frequency EPR (130 GHz), the EPR spectra of these species were resolved and principal components of the g-tensors were assigned. Light-induced pulsed ENDOR spectroscopy allowed the determination of (1)H hyperfine coupling constants of photogenerated positive and negative polarons. The experimental results obtained for the different polymer-fullerene composites have been compared with DFT calculations, revealing that in all three systems the positive polaron is distributed over distances of 40-60 Å on the polymer chain. This corresponds to about 15 thiophene units for P3HT, approximately three units for PCDTBT, and about three to four units for PTB7. No spin density delocalization between neighboring fullerene molecules was detected by EPR

  20. The strength of EPR and ENDOR techniques in revealing structure-function relationships in metalloproteins.

    Science.gov (United States)

    Van Doorslaer, Sabine; Vinck, Evi

    2007-09-01

    Recent technological and methodological advances have strongly increased the potential of electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) techniques to characterize the structure and dynamics of metalloproteins. These developments include the introduction of powerful pulsed EPR/ENDOR methodologies and the development of spectrometers operating at very high microwave frequencies and high magnetic fields. This overview focuses on how valuable information about metalloprotein structure-function relations can be obtained using a combination of EPR and ENDOR techniques. After an overview of the historical development and a limited theoretical description of some of the key EPR and ENDOR techniques, their potential will be highlighted using selected examples of applications to iron-, nickel-, cobalt-, and copper-containing proteins. We will end with an outlook of future developments.

  1. The Flamanville 3 EPR reactor; Le reacteur EPR Flamanville 3

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2007-07-01

    On April 10. 2007, the french government authorized EDF to create on the site of Flamanville ( La Manche) a nuclear base installation containing a pressurized water EPR type reactor. This nuclear reactor, conceived by AREVA NP and EDF, is the first copy of a generation susceptible to replace later, at least partly, the French nuclear reactors at present in operation.Within the framework of its mission of technical support of the Authority of Nuclear Safety ( A.S.N.), the I.R.S.N. widely contributed successively: to define the general objectives of safety assigned to this new generation of pressurized water nuclear reactors; to analyze the options of safety proposed by EDF for the EPR project; To deepen, upstream to the authorization of creation, the evaluation of the step of safety and the measures of conception retained by EDF that have to allow to respect the objectives of safety which were notified to it. (N.C.)

  2. 25 Tesla pulsed-high-magnetic-field system for soft X-ray spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hayashi, M., E-mail: mhaya@imr.tohoku.ac.jp [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Narumi, Y.; Nojiri, H. [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Nakamura, T.; Hirono, T.; Kinoshita, T. [JASRI/SPring-8, Sayo, Hyogo 679-5198 (Japan); Kodama, K. [Department of Mechanical Engineering, Nara National College of Technology, Nara 639-1080 (Japan); Kindo, K. [Institute for Solid State Physics, University of Tokyo, Kashiwa 277-8581 (Japan)

    2011-04-15

    Research highlights: {yields} We have developed a 25 T pulsed magnetic field system for soft X-ray MCD. {yields} The new capacitor bank can generate a field in the bipolar mode. {yields} We measured the Soft X-ray MCD of paramagnetic Gd{sub 2}O{sub 3} up to 25 T. - Abstract: We have developed a 25 T pulsed high magnetic field system for soft X-ray Magnetic Circular Dichroism: XMCD. The ultra-high vacuum chamber with a pulse magnet coil is installed. By using a newly developed bipolar capacitor bank, the XMCD of paramagnetic Gd{sub 2}O{sub 3} at the M{sub 5} and the M{sub 4} edges was clearly observed at low temperatures. The present system is capable of measuring XMCD of field induced moments in various compounds including paramagnets and antiferromagnets.

  3. Ultrafast spectroscopy of coherent phonon in carbon nanotubes using sub-5-fs visible pulses

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Takayoshi [Advanced Ultrafast Laser Research Center, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo, 182-8585 (Japan); JST, CREST, 5 Sanbancho, Chiyoda-ku, Tokyo 102-0075 Japan (Japan); Department of Electrophysics, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Institute of Laser Engineering, Osaka University, 2-6 Yamada-oka, Suita, Osaka 565-0871, Japan kobayashi@ils.uec.ac.jp (Japan)

    2016-02-01

    In the last two decades, nano materials are attracting many scientists’ interest for both basic and application viewpoints. In order to understand the properties of nano systems it is needed to understand the dynamic properties which control the specific properties of the systems. All the primary processes in nano systems are taking place in femtosecond regime. Our group has been able to stably generate visible to near-infrared sub-5-fs laser pulses using a noncollinear optical parametric amplifier (NOPA) by the combination of various novel techniques including non-collinear optical parametric amplifier, pulse compression by a prism pair and grating pair. We apply the sub-5-fs pulses to study real-time coherent phonon in a one-dimensional system of carbon nanotubes. We determine exciton-phonon coupling mechanisms by observing the breathing mode in semiconducting carbon nanotubes and show the effect of electronic transition affected by the vibrational mode.

  4. Direct spectral analysis and determination of high content of carcinogenic bromine in bread using UV pulsed laser induced breakdown spectroscopy.

    Science.gov (United States)

    Mehder, A O; Gondal, Mohammed A; Dastageer, Mohamed A; Habibullah, Yusuf B; Iqbal, Mohammed A; Oloore, Luqman E; Gondal, Bilal

    2016-01-01

    Laser induced breakdown spectroscopy (LIBS) was applied for the detection of carcinogenic elements like bromine in four representative brands of loaf bread samples and the measured bromine concentrations were 352, 157, 451, and 311 ppm, using Br I (827.2 nm) atomic transition line as the finger print atomic transition. Our LIBS system is equipped with a pulsed laser of wavelength 266 nm with energy 25 mJ pulse(-1), 8 ns pulse duration, 20 Hz repetition rate, and a gated ICCD camera. The LIBS system was calibrated with the standards of known concentrations in the sample (bread) matrix and such plot is linear in 20-500 ppm range. The capability of our system in terms of limit of detection and relative accuracy with respect to the standard inductively coupled plasma mass spectrometry (ICPMS) technique was evaluated and these values were 5.09 ppm and 0.01-0.05, respectively, which ensures the applicability of our system for Br trace level detection, and LIBS results are in excellent agreement with that of ICPMS results.

  5. Effects of finite laser pulse width on two-dimensional electronic spectroscopy

    Science.gov (United States)

    Leng, Xuan; Yue, Shuai; Weng, Yu-Xiang; Song, Kai; Shi, Qiang

    2017-01-01

    We combine the hierarchical equations of motion method and the equation-of-motion phase-matching approach to calculate two-dimensional electronic spectra of model systems. When the laser pulse is short enough, the current method reproduces the results based on third-order response function calculations in the impulsive limit. Finite laser pulse width is found to affect both the peak positions and shapes, as well as the time evolution of diagonal and cross peaks. Simulations of the two-color two-dimensional electronic spectra also show that, to observe quantum beats in the diagonal and cross peaks, it is necessary to excite the related excitonic states simultaneously.

  6. A simple pulsed drain feedback preamplifier for high resolution high rate nuclear spectroscopy

    Science.gov (United States)

    Lakatos, Tamás; Hegyesi, Gyula; Kalinka, Gábor

    1996-02-01

    A non-optical, pulsed reset technique for use in charge sensitive preamplifiers with Si(Li) X-ray semiconductor detectors of conventional polarity is described. The phenomenon of impact ionization in the field effect transistor is used for charge restoration. The process is controlled via the detector capacitance. The method needs no extra components in the input circuitry. No significant resolution degradation can be detected up to 600 kcps Mn K intensity if following the 5 μs resetting pulse the signal processor is inhibited for 50 μs.

  7. A simple pulsed drain feedback preamplifier for high resolution high rate nuclear spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lakatos, T. [Magyar Tudomanyos Akademia, Debrecen (Hungary). Atommag Kutato Intezete; Hegyesi, G. [Magyar Tudomanyos Akademia, Debrecen (Hungary). Atommag Kutato Intezete; Kalinka, G. [Magyar Tudomanyos Akademia, Debrecen (Hungary). Atommag Kutato Intezete

    1996-08-21

    A non-optical, pulsed reset technique for use in charge sensitive preamplifiers with Si(Li) X-ray semiconductor detectors of conventional polarity is described. The phenomenon of impact ionization in the field effect transistor is used for charge restoration. The process is controlled via the detector capacitance. The method needs no extra components in the input circuitry. No significant resolution degradation can be detected up to 600 kcps Mn K intensity if following the 5 {mu}s resetting pulse the signal processor is inhibited for 50 {mu}s. (orig.).

  8. Picosecond Transient Photoconductivity in Functionalized Pentacene Molecular Crystals Probed by Terahertz Pulse Spectroscopy

    Science.gov (United States)

    Hegmann, F. A.; Tykwinski, R. R.; Lui, K. P.; Bullock, J. E.; Anthony, J. E.

    2002-11-01

    We have measured transient photoconductivity in functionalized pentacene molecular crystals using ultrafast optical pump-terahertz probe techniques. The single crystal samples were excited using 800nm, 100fs pulses, and the change in transmission of time-delayed, subpicosecond terahertz pulses was used to probe the photoconducting state over a temperature range from 10 to 300K. A subpicosecond rise in photoconductivity is observed, suggesting that mobile carriers are a primary photoexcitation. At times longer than 4ps, a power-law decay is observed consistent with dispersive transport.

  9. A cryogenic receiver for EPR.

    Science.gov (United States)

    Narkowicz, R; Ogata, H; Reijerse, E; Suter, D

    2013-12-01

    Cryogenic probes have significantly increased the sensitivity of NMR. Here, we present a compact EPR receiver design capable of cryogenic operation. Compared to room temperature operation, it reduces the noise by a factor of ≈2.5. We discuss in detail the design and analyze the resulting noise performance. At low microwave power, the input noise density closely follows the emission of a cooled 50Ω resistor over the whole measurement range from 20K up to room temperature. To minimize the influence of the microwave source noise, we use high microwave efficiency (≈1.1-1.7mTW(-1/2)) planar microresonators. Their efficient conversion of microwave power to magnetic field permits EPR measurements with very low power levels, typically ranging from a few μW down to fractions of nW. Copyright © 2013 Elsevier Inc. All rights reserved.

  10. Hydrogen Analyses in the EPR

    Energy Technology Data Exchange (ETDEWEB)

    Worapittayaporn, S.; Eyink, J.; Movahed, M. [AREVA NP GmbH, P.O. Box 3220, D-91050 Erlangen (Germany)

    2008-07-01

    In severe accidents with core melting large amounts of hydrogen may be released into the containment. The EPR provides a combustible gas control system to prevent hydrogen combustion modes with the potential to challenge the containment integrity due to excessive pressure and temperature loads. This paper outlines the approach for the verification of the effectiveness and efficiency of this system. Specifically, the justification is a multi-step approach. It involves the deployment of integral codes, lumped parameter containment codes and CFD codes and the use of the sigma criterion, which provides the link to the broad experimental data base for flame acceleration (FA) and deflagration to detonation transition (DDT). The procedure is illustrated with an example. The performed analyses show that hydrogen combustion at any time does not lead to pressure or temperature loads that threaten the containment integrity of the EPR. (authors)

  11. Optimizing pulse-pileup detection for soft-x-ray spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Greenberger, A.J.

    1981-04-01

    The problem of optimizing detection of the pileup of randomly occurring exponential tail pulses in white noise is considered. An attempt is made to reduce the process to an algorithm that could practically be performed in real time. Quantitative estimates are made for the performance of such an optimum detector. The relation to a more general pattern recognition problem is mentioned.

  12. Photon-echo spectroscopy of the hydrated electron with 5-fs pulses

    NARCIS (Netherlands)

    Pshenichnikov, MS; Baltuska, A; Emde, MF; Wiersma, DA; Elsaesser, T; Mukamel, S; Murnane, MM; Scherer, NF

    2001-01-01

    Employing photon-echo techniques with extremely short laser pulses that consist of only few optical cycles, we investigate the dynamics of the equilibrated hydrated electron. The pure dephasing time of the hydrated electron deduced from the measurements is similar to1.6 fs. The shape of the absorpti

  13. Design and implementation of an FPGA-based timing pulse programmer for pulsed-electron paramagnetic resonance applications.

    Science.gov (United States)

    Sun, Li; Savory, Joshua J; Warncke, Kurt

    2013-08-01

    The design, construction and implementation of a field-programmable gate array (FPGA) -based pulse programmer for pulsed-electron paramagnetic resonance (EPR) experiments is described. The FPGA pulse programmer offers advantages in design flexibility and cost over previous pulse programmers, that are based on commercial digital delay generators, logic pattern generators, and application-specific integrated circuit (ASIC) designs. The FPGA pulse progammer features a novel transition-based algorithm and command protocol, that is optimized for the timing structure required for most pulsed magnetic resonance experiments. The algorithm was implemented by using a Spartan-6 FPGA (Xilinx), which provides an easily accessible and cost effective solution for FPGA interfacing. An auxiliary board was designed for the FPGA-instrument interface, which buffers the FPGA outputs for increased power consumption and capacitive load requirements. Device specifications include: Nanosecond pulse formation (transition edge rise/fall times, ≤3 ns), low jitter (≤150 ps), large number of channels (16 implemented; 48 available), and long pulse duration (no limit). The hardware and software for the device were designed for facile reconfiguration to match user experimental requirements and constraints. Operation of the device is demonstrated and benchmarked by applications to 1-D electron spin echo envelope modulation (ESEEM) and 2-D hyperfine sublevel correlation (HYSCORE) experiments. The FPGA approach is transferrable to applications in nuclear magnetic resonance (NMR; magnetic resonance imaging, MRI), and to pulse perturbation and detection bandwidths in spectroscopies up through the optical range.

  14. Peptide-membrane Interactions by Spin-labeling EPR

    Science.gov (United States)

    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

  15. Microwave spectral taxonomy: A semi-automated combination of chirped-pulse and cavity Fourier-transform microwave spectroscopy

    Science.gov (United States)

    Crabtree, Kyle N.; Martin-Drumel, Marie-Aline; Brown, Gordon G.; Gaster, Sydney A.; Hall, Taylor M.; McCarthy, Michael C.

    2016-03-01

    Because of its structural specificity, rotational spectroscopy has great potential as an analytical tool for characterizing the chemical composition of complex gas mixtures. However, disentangling the individual molecular constituents of a rotational spectrum, especially if many of the lines are entirely new or unknown, remains challenging. In this paper, we describe an empirical approach that combines the complementary strengths of two techniques, broadband chirped-pulse Fourier transform microwave spectroscopy and narrowband cavity Fourier transform microwave spectroscopy, to characterize and assign lines. This procedure, called microwave spectral taxonomy, involves acquiring a broadband rotational spectrum of a rich mixture, categorizing individual lines based on their relative intensities under series of assays, and finally, linking rotational transitions of individual chemical compounds within each category using double resonance techniques. The power of this procedure is demonstrated for two test cases: a stable molecule with a rich spectrum, 3,4-difluorobenzaldehyde, and products formed in an electrical discharge through a dilute mixture of C2H2 and CS2, in which spectral taxonomy has enabled the identification of propynethial, HC(S)CCH.

  16. "Pulse pair technique in high resolution NMR" a reprint of the historical 1971 lecture notes on two-dimensional spectroscopy.

    Science.gov (United States)

    Jeener, Jean; Alewaeters, Gerrit

    2016-05-01

    The review articles published in "Progress in NMR Spectroscopy" are usually invited treatments of topics of current interest, but occasionally the Editorial Board may take an initiative to publish important historical material that is not widely available. The present article represents just such a case. Jean Jeener gave a lecture in 1971 at a summer school in Basko Polje, in what was then called Yugoslavia. As is now widely known, Jean Jeener laid down the foundations in that lecture of two - and higher - dimensional NMR spectroscopy by proposing the homonuclear COSY experiment. Jeener realized that the new proposal would open the door towards protein NMR and molecular structure determinations, but he felt that useful versions of such experiments could not be achieved with the NMR, computer and electronics technology available at that time, so that copies of the lecture notes were circulated (the Basko Polje lecture notes by J. Jeener and G. Alewaeters), but no formal publication followed. Fortunately, Ernst, Freeman, Griffin, and many others were more far-sighted and optimistic. An early useful extension was Ernst's proposal to replace the original projection/reconstruction technique of MRI by the widely adopted Fourier transform method inspired by the Basko Polje lecture. Later, the pulse method spread over many fields of spectroscopy as soon as the required technology became available. Jean Jeener, Emeritus professor, Université Libre de Bruxelles. Geoffrey Bodenhausen, Ecole Normale Supérieure, Paris.

  17. COMPLIS experiments: COllaboration for spectroscopy Measurements using a Pulsed Laser Ion Source

    Energy Technology Data Exchange (ETDEWEB)

    Sauvage, J. [IN2P3-CNRS, Institut de Physique Nucleaire (France); Boos, N. [Universitaet Mainz, Institut fuer Physik (Germany); Cabaret, L. [Laboratoire AimeCotton (France); Crawford, J.E. [McGill University, Physics Department (Canada); Duong, H.T. [Laboratoire AimeCotton (France); Genevey, J. [IN2P3-CNRS, Institut des Sciences Nucleaires (France); Girod, M. [Commissariat al' Energie Atomique, Service de Physique Nucleaire (France); Huber, G. [Universitaet Mainz, Institut fuer Physik (Germany); Ibrahim, F. [IN2P3-CNRS, Institut de Physique Nucleaire (France); Krieg, M. [Universitaet Mainz, Institut fuer Physik (Germany); Le Blanc, F. [IN2P3-CNRS, Institut de Physique Nucleaire (France); Lee, J.K.P. [McGill University, Physics Department (Canada); Libert, J. [Centre d' Etudes Nucleaires de Bordeaux Gradignan (France); Lunney, D.; Obert, J.; Oms, J. [IN2P3-CNRS, Institut de Physique Nucleaire (France); Peru, S. [Commissariat al' Energie Atomique, Service de Physique Nucleaire (France); Pinard, J. [Laboratoire AimeCotton (France); Putaux, J.C.; Roussiere, B. [IN2P3-CNRS, Institut de Physique Nucleaire (France)] (and others)

    2000-12-15

    Laser spectroscopy measurements have been carried out on very neutron-deficient isotopes of Au, Pt and Ir, produced as daughter elements from a Hg ISOLDE beam. For these transitional region nuclides, the hyperfine structure (HFS) and isotope shift (IS) were measured by Resonance Ionization Spectroscopy (RIS). Magnetic moments {mu}, spectroscopic quadrupole moments Q{sub s} and changes of the nuclear mean square charge radius {delta}along isotopic series have been extracted. For some results, a detailed comparison with theoretical predictions is presented.

  18. A sensitive EPR dosimetry system based on sulfamic acid

    Science.gov (United States)

    Maghraby, A.

    2007-08-01

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

  19. A pulsed supersonic gas jet target for precision spectroscopy at the HITRAP facility at GSI

    Energy Technology Data Exchange (ETDEWEB)

    Tiedemann, D. [Institut für Kernphysik der Goethe Universität, Max von Laue Straße 1, D-60438, Frankfurt am Main (Germany); Stiebing, K.E., E-mail: stiebing@em.uni-frankfurt.de [Institut für Kernphysik der Goethe Universität, Max von Laue Straße 1, D-60438, Frankfurt am Main (Germany); Winters, D.F.A. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, Planckstraße 1, D-64291, Darmstadt (Germany); Quint, W. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, Planckstraße 1, D-64291, Darmstadt (Germany); Physikalisches Institut der Universität Heidelberg, Im Neuenheimer Feld 226, D-69120, Heidelberg (Germany); Varentsov, V. [Institute for Theoretical and Experimental Physics, Moscow (Russian Federation); Facility for Antiproton and Ion Research in Europe (FAIR), Darmstadt (Germany); Warczak, A.; Malarz, A. [Institute of Physics, Jagiellonian University, Krakow (Poland); Stöhlker, Th. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, Planckstraße 1, D-64291, Darmstadt (Germany); Physikalisch-Astronomische Fakultät der Friedrich-Schiller-Universität Jena, Helmholtz-Institut Jena, Fröbelstieg 3, D-07743, Jena (Germany)

    2014-11-11

    A pulsed supersonic gas jet target for experiments at the HITRAP facility at the GSI Helmholtzzentrum für Schwerionenforschung in Darmstadt has been designed and built as a multi-purpose installation for key experiments on fundamental atomic physics in strong fields. This setup is currently installed at the Institut für Kernphysik of Goethe-University, Frankfurt am Main (IKF), in order to explore its operation prior to its installation at the HITRAP facility. Design and performance of the target are described. The measured target densities of 5.9×10{sup 12} atoms/cm{sup 3} for helium and 8.1×10{sup 12} atoms/cm³ for argon at the stagnation pressure of 30 bar match the required values. The target-beam diameter of 0.9 mm and the pulsed operation mode (jet built-up-time ≤15 ms) are well suited for the use at HITRAP.

  20. Biophysical Characterisation of Globins and Multi-Heme Cytochromes Using Electron Paramagnetic Resonance and Optical Spectroscopy

    Science.gov (United States)

    Desmet, Filip

    Heme proteins of different families were investigated in this work, using a combination of pulsed and continuous-wave electron paramagnetic resonance (EPR) spectroscopy, optical absorption spectroscopy, resonance Raman spectroscopy and laser flash photolysis. The first class of proteins that were investigated, were the globins. The globin-domain of the globin-coupled sensor of the bacterium Geobacter sulfurreducens was studied in detail using different pulsed EPR techniques (HYSCORE and Mims ENDOR). The results of this pulsed EPR study are compared with the results of the optical investigation and the crystal structure of the protein. The second globin, which was studied, is the Protoglobin of Methanosarcina acetivorans, various mutants of this protein were studied using laser flash photolysis and Raman spectroscopy to unravel the link between this protein's unusual structure and its ligand-binding kinetics. In addition to this, the CN -bound form of this protein was investigated using EPR and the influence of the strong deformation of the heme on the unusual low gz values is discussed. Finally, the neuroglobins of three species of fishes, Danio rerio, Dissostichus mawsoni and Chaenocephalus aceratus are studied. The influence of the presence or absence of two cysteine residues in the C-D and D-region of the protein on the EPR spectrum, and the possible formation of a disulfide bond is studied. The second group of proteins that were studied in this thesis belong to the family of the cytochromes. First the Mouse tumor suppressor cytochrome b561 was studied, the results of a Raman and EPR investigation are compared to the Human orthologue of the protein. Secondly, the tonoplast cytochrome b561 of Arabidopsis was investigated in its natural form and in two double-mutant forms, in which the heme at the extravesicular side was removed. The results of this investigation are then compared with two models in literature that predict the localisation of the hemes in this

  1. Using Terahertz pulse spectroscopy to study the crystalline structure of a drug: a case study of the polymorphs of ranitidine hydrochloride.

    Science.gov (United States)

    Taday, P F; Bradley, I V; Arnone, D D; Pepper, M

    2003-04-01

    We describe the application of Terahertz pulse spectroscopy to polymorph identification. The particular compounds investigated were the different crystalline Forms 1 and 2 of ranitidine hydrochloride, both in the pure form and also obtained as a marketed pharmaceutical product. Identification was clear. The technique has advantages that excitation is not via a powerful laser source, as used in Raman spectroscopy, so phase changes or photochemical reactions in polymorphs do not occur. Terahertz absorption spectral interpretation and instrumentation are similar to basic Fourier transform infrared (FTIR) spectroscopy and therefore easy to understand. The sample preparation techniques used are the same as those used in FTIR and Raman spectroscopies. The data obtained is complementary to Raman Spectroscopy. As the selection rules are different between the two techniques, we are able to obtain new data set directly related to crystalline structure adding to that obtained by Raman spectroscopy. Terahertz pulse spectroscopy provides information on low-frequency intermolecular vibrational modes; these are difficult to assess in Raman spectroscopy due to the proximity of the laser exciting line. It is concluded that the method has a wide range of applications in pharmaceutical science including formulation, high throughput screening, and inspection in storage.

  2. Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hellman, Hal

    1968-01-01

    This booklet discusses spectroscopy, the study of absorption of radiation by matter, including X-ray, gamma-ray, microwave, mass spectroscopy, as well as others. Spectroscopy has produced more fundamental information to the study of the detailed structure of matter than any other tools.

  3. Studies of growth, microstructure, Raman spectroscopy and annealing effect of pulsed laser deposited Ca-doped NBCO thin films

    Energy Technology Data Exchange (ETDEWEB)

    Palai, R [Department of Physics, University of Strathclyde, Glasgow, G4 0NG (United Kingdom); Romans, E J [Department of Physics, University of Strathclyde, Glasgow, G4 0NG (United Kingdom); Martin, R W [Department of Physics, University of Strathclyde, Glasgow, G4 0NG (United Kingdom); Docherty, F T [Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL (United Kingdom); Maas, P [Department of Physics, University of Strathclyde, Glasgow, G4 0NG (United Kingdom); Pegrum, C M [Department of Physics, University of Strathclyde, Glasgow, G4 0NG (United Kingdom)

    2005-01-07

    Superconducting thin films of Nd{sub 1-x}Ca{sub x}Ba{sub 2}Cu{sub 3}O{sub 7-{delta}} (x = 0.03 and 0.08) have been grown on single crystal SrTiO{sub 3} substrates by pulsed laser deposition. The statistical methods of Experimental Design and regression analysis were used to optimize the film properties and to understand the correlation between the growth parameters and film properties. The orientation of the films was investigated by x-ray diffraction. The surface morphology of the films was examined by atomic force microscopy and scanning tunnelling microscopy. Qualitative and quantitative elemental analyses of the films were carried out using electron probe microanalysis. Micro-Raman spectroscopy was used to study the oxygen sublattice vibrations of the films. The effect of annealing on the superconducting transition temperature of the patterned films was also studied.

  4. Syntheses, spectroscopy, cyclic voltammetry, thermal analyses, EPR, and DFT/TDDFT on bis[N-2-(R-pyridyl)salicylaldiminato-κ2NˆO]copper(II) (R = H, 4/6-CH3)

    Science.gov (United States)

    Enamullah, Mohammed; Quddus, Mohammad Abdul; Rahman, Mohammad Mostafizur; Burrow, Timothy Edward

    2017-02-01

    Bis[N-2-(R-pyridyl)salicylaldiminato-κ2NˆO]copper(II) (R = H: 1, 4/6-CH3: 2/3) are synthesized and characterized by UV-Vis., IR, mass, cyclic voltammetry, magnetic moment, DSC, EPR and DFT/TDDFT, respectively. Mass spectra show parent ion peaks at m/z 458 (1) and 486 (2 or 3). Electronic spectra feature different bands for intra-ligand (<350 nm), metal-ligand (350-540 nm) and metal-metal (540-940 nm) transitions, respectively. Spectra in different solvents show a blue shift of absorption maxima with increasing polarity, dielectric constants and donor/acceptor number of solvent, respectively. DSC analyses show an irreversible phase transformation from crystalline to isotropic liquid phase. CV studies demonstrate a quasi-reversible two electrons charge transfer processes for [Cu(L)2]0/[Cu(L)2]- and [Cu(L)2]-/[Cu(L)2]2- (L = deprotonated Schiff base ligand) couples, respectively in acetonitrile. EPR spectrum in chloroform shows an isotropic pattern with four lines due to nuclear hyperfine splitting from copper(II) with spin 3/2, and giso value of 2.1244, indicating considerable covalent character in M-L bonds. Magnetic moment values (μ = 1.49-1.61 μB) in methanol indicate the formation of copper(II)-NˆO-chelate complexes with one unpaired electron. The optimized structures and excitation properties studied by DFT/TDDFT are comparable to the experimental results.

  5. Pulsed laser deposited Ag nanoparticles on nickel hydroxide nanosheet arrays for highly sensitive surface-enhanced Raman scattering spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Jing, Yuting; Wang, Huanwen; Chen, Xiao [Department of Chemistry, Tongji University, Shanghai 200092 (China); Wang, Xuefeng, E-mail: xfwang@tongji.edu.cn [Department of Chemistry, Tongji University, Shanghai 200092 (China); Wei, Huige [Integrated Composites Laboratory (ICL), Dan F. Smith Department of Chemical Engineering, Lamar University, Beaumont, Texas 77710 (United States); Guo, Zhanhu, E-mail: zhanhu.guo@lamar.edu [Integrated Composites Laboratory (ICL), Dan F. Smith Department of Chemical Engineering, Lamar University, Beaumont, Texas 77710 (United States)

    2014-10-15

    Highlights: • Silver nanoparticles (NPs) were deposited on nickel hydroxide nanosheet (NS) arrays by pulsed laser deposition (PLD) for surface-enhanced Raman scattering (SERS) spectroscopy. • The Ag/Ni(OH){sub 2} composite film exhibits very high Raman scattering enhancement ability, possessing an enhancement factor as high as 5 × 10{sup 6}. • The enhancement ability of the substrate was strongly dependent on the size and interparticle gap of Ag NPs. • The 3D structure of Ni(OH){sub 2} NS arrays and the charge transfer of Ag NPs may be responsible for this high sensitivity Raman phenomenon. - Abstract: In the present work, silver nanoparticles (NPs) were deposited on nickel hydroxide nanosheet (NS) arrays by pulsed laser deposition (PLD) for surface-enhanced Raman scattering (SERS) spectroscopy. The effective high specific surface area with silver NPs decorated on the NS arrays was revealed by field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The microstructure and optical property of this three-dimensional (3D) substrate were investigated by X-ray diffraction (XRD) and UV–vis spectra, respectively. Using rhodamine 6G (R6G) as probe molecules with the concentration down to 10{sup −5} M, the Ag/Ni(OH){sub 2} composite film exhibits very high Raman scattering enhancement ability, possessing an enhancement factor as high as 5 × 10{sup 6}. It has been found that the enhancement ability of the substrate was strongly dependent on the size and interparticle gap of Ag NPs rather than the testing position on the film surface. In addition, the 3D structure of Ni(OH){sub 2} NS arrays and the charge transfer of Ag NPs may be responsible for this high sensitivity Raman phenomenon.

  6. Spectroscopy

    CERN Document Server

    Walker, S

    1976-01-01

    The three volumes of Spectroscopy constitute the one comprehensive text available on the principles, practice and applications of spectroscopy. By giving full accounts of those spectroscopic techniques only recently introduced into student courses - such as Mössbauer spectroscopy and photoelectron spectroscopy - in addition to those techniques long recognised as being essential in chemistry teaching - sucha as e.s.r. and infrared spectroscopy - the book caters for the complete requirements of undergraduate students and at the same time provides a sound introduction to special topics for graduate students.

  7. Time resolved ESR spectroscopy. ESR pulse radiolysis equipment with microsecond time resolution

    Energy Technology Data Exchange (ETDEWEB)

    Beckert, D.; Mehler, K. (Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung)

    1983-01-01

    Time resolved ESR experiments allow the study of the chemical kinetics as well as spin dynamics of free radicals in the liquid phase. Starting from the physical and chemical requirements the experimental parameters of a universal time resolved ESR spectrometer are derived. The main components of the ESR pulse radiolysis equipment are described and their technical parameters are discussed. By two experimental examples it is shown that at a time resolution of 0.3 ..mu..s a sensitivity of c/sub min/ = 10/sup -6/ mol dm/sup -3/ for simple radical spectra can be achieved.

  8. Electron-volt spectroscopy at a pulsed neutron source using a resonance detector technique

    CERN Document Server

    Andreani, C; Senesi, R; Gorini, G; Tardocchi, M; Bracco, A; Rhodes, N; Schooneveld, E M

    2002-01-01

    The effectiveness of the neutron resonance detector spectrometer for deep inelastic neutron scattering measurements has been assessed by measuring the Pb scattering on the eVS spectrometer at ISIS pulsed neutron source and natural U foils as (n,gamma) resonance converters. A conventional NaI scintillator with massive shielding has been used as gamma detector. A neutron energy window up to 90 eV, including four distinct resonance peaks, has been assessed. A net decrease of the intrinsic width of the 6.6 eV resonance peak has also been demonstrated employing the double difference spectrum technique, with two uranium foils of different thickness.

  9. Interference spectroscopy with coherent anti-Stokes Raman scattering of noisy broadband pulses

    CERN Document Server

    Shapiro, Evgeny A; Milner, Valery

    2011-01-01

    We propose a new technique for comparing two Raman active samples. The method employs optical interference of the signals generated via coherent anti-Stokes Raman scattering (CARS) of broadband laser pulses with noisy spectra. It does not require spectrally resolved detection, and no prior knowledge about either the Raman spectrum of the samples, or the spectrum of the incident light is needed. We study the proposed method theoretically, and demonstrate it in a proof-of-principle experiment on Toluene and ortho-Xylene samples.

  10. Pulsed-field ionization electron spectroscopy and binding energies of alkali metal-dimethyl ether and -dimethoxyethane complexes.

    Science.gov (United States)

    Sohnlein, Bradford R; Li, Shenggang; Fuller, Jason F; Yang, Dong-Sheng

    2005-07-01

    Lithium and sodium complexes of dimethyl ether (DME) and dimethoxyethane (DXE) were produced by reactions of laser-vaporized metal atoms with organic vapors in a pulsed nozzle cluster source. The mono-ligand complexes were studied by photoionization and pulsed field ionization zero electron kinetic energy (ZEKE) spectroscopy. Vibrationally resolved ZEKE spectra were obtained for Li(DME), Na(DME) and Li(DXE) and a photoionization efficiency spectrum for Na(DXE). The ZEKE spectra were analyzed by comparing with the spectra of other metal-ether complexes and with electronic structure calculations and spectral simulations. Major vibrations measured for the M(DME) (M=Li,Na) ions were M-O and C-O stretches and M-O-C and C-O-C bends. These vibrations and additional O-Li-O and O-C-C-O bends were observed for the Li(DXE) ion. The M(DME) complexes were in C2v symmetry with the metal atom binding to oxygen, whereas Li(DXE) was in a C2 ring configuration with the Li atom attaching to both oxygen atoms. Moreover, the ionization energies of these complexes were measured from the ZEKE or photoionization spectra and bond dissociation energies were derived from a thermodynamic cycle.

  11. Ultrafast time-resolved pump-probe spectroscopy of PYP by a sub-8 fs pulse laser at 400 nm.

    Science.gov (United States)

    Liu, Jun; Yabushita, Atsushi; Taniguchi, Seiji; Chosrowjan, Haik; Imamoto, Yasushi; Sueda, Keiichi; Miyanaga, Noriaki; Kobayashi, Takayoshi

    2013-05-01

    Impulsive excitation of molecular vibration is known to induce wave packets in both the ground state and excited state. Here, the ultrafast dynamics of PYP was studied by pump-probe spectroscopy using a sub-8 fs pulse laser at 400 nm. The broadband spectrum of the UV pulse allowed us to detect the pump-probe signal covering 360-440 nm. The dependence of the vibrational phase of the vibrational mode around 1155 cm(-1) on the probe photon energy was observed for the first time to our knowledge. The vibrational mode coupled to the electronic transition observed in the probe spectral ranges of 2.95-3.05 and 3.15-3.35 eV was attributed to the wave packets in the ground state and the excited state, respectively. The frequencies in the ground state and excited state were determined to be 1155 ± 1 and 1149 ± 1 cm(-1), respectively. The frequency difference is due to change after photoexcitation. This means a reduction of the bond strength associated with π-π* excitation, which is related to the molecular structure change associated with the primary isomerization process in the photocycle in PYP. Real-time vibrational modes at low frequency around 138, 179, 203, 260, and 317 cm(-1) were also observed and compared with the Raman spectrum for the assignment of the vibrational wave packet.

  12. EPR Studies of DOPA–Melanin Complexes with Netilmicin and Cu(II) at Temperatures in the Range of 105–300 K

    OpenAIRE

    Zdybel, Magdalena; Pilawa, Barbara; Buszman, Ewa; Wrześniok, Dorota; Krzyminiewski, Ryszard; Kruczyński, Zdzisław

    2012-01-01

    The application of electron paramagnetic resonance (EPR) spectroscopy in pharmacy of melanin complexes with netilmicin and Cu(II) was presented. The continuous microwave saturation of EPR spectra of DOPA–melanin and the complexes was performed. EPR spectra were measured on an X-band (9.3 GHz) spectrometer at temperatures in the range of 105–300 K. Paramagnetic copper ions decrease the intensity of the EPR lines of melanin’s free radicals. It was found that fast spin–lattice relaxation charact...

  13. Three-dimensional compositional mapping using double-pulse micro-laser-induced breakdown spectroscopy technique

    Science.gov (United States)

    Grassi, R.; Grifoni, E.; Gufoni, S.; Legnaioli, S.; Lorenzetti, G.; Macro, N.; Menichetti, L.; Pagnotta, S.; Poggialini, F.; Schiavo, C.; Palleschi, V.

    2017-01-01

    In this communication, we present the development of the first double-pulse micro-LIBS (DP-μLIBS) instrument for three-dimensional compositional mapping of materials. The system allows for high-resolution three-dimensional scanning of materials; its advantages with respect to conventional single-pulse micro-LIBS systems are described and discussed. As a test example, we analyzed three Euro coins to show the performances of the system on homogeneous samples (20 Eurocents), heterogeneous samples (1 Euro) and layered samples (5 Eurocents). DP-μLIBS cannot provide isotopic information and has, typically, limits of detection for the elements of interest much higher with respect to Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). However, when the isotopic information and the extreme sensitivity to trace elements is not be necessary, the results obtained show that DP-μLIBS can be a viable alternative to LA-ICP-MS for the acquisition of high resolution three-dimensional compositional maps.

  14. EPR of exchange coupled systems

    CERN Document Server

    Bencini, Alessandro

    2012-01-01

    From chemistry to solid state physics to biology, the applications of Electron Paramagnetic Resonance (EPR) are relevant to many areas. This unified treatment is based on the spin Hamiltonian approach and makes extensive use of irreducible tensor techniques to analyze systems in which two or more spins are magnetically coupled. This edition contains a new Introduction by coauthor Dante Gatteschi, a pioneer and scholar of molecular magnetism.The first two chapters review the foundations of exchange interactions, followed by examinations of the spectra of pairs and clusters, relaxation in oligon

  15. EPR techniques for space biodosimetry

    Energy Technology Data Exchange (ETDEWEB)

    Haskell, E.; Hayes, R.; Kenner, G.; Sholom, S.; Chumak, V.

    1996-12-31

    Retrospective dosimetry of tooth enamel has become an increasingly complex and difficult discipline to undertake while still attaining accuracy. The paper provides a review of the major obstacles, advances and pertinent phenomenon associated with low level retrospective dosimetry of human tooth enamel. Also covered is the many sources of error in EPR dosimetry, their potential solutions, as well as the different analysis and scanning techniques in use with their prospective pros and cons. Prospective directions for new approaches, methods, and instruments are also reviewed.

  16. Dynamic Time-Resolved Chirped-Pulse Rotational Spectroscopy of Vinyl Cyanide Photoproducts in a Room Temperature Flow Reactor

    Science.gov (United States)

    Zaleski, Daniel P.; Prozument, Kirill

    2017-06-01

    Chirped-pulsed (CP) Fourier transform rotational spectroscopy invented by Brooks Pate and coworkers a decade ago is an attractive tool for gas phase chemical dynamics and kinetics studies. A good reactor for such a purpose would have well-defined (and variable) temperature and pressure conditions to be amenable to accurate kinetic modeling. Furthermore, in low pressure samples with large enough number of molecular emitters, reaction dynamics can be observable directly, rather than mediated by supersonic expansion. In the present work, we are evaluating feasibility of in situ time-resolved CP spectroscopy in a room temperature flow tube reactor. Vinyl cyanide (CH_2CHCN), neat or mixed with inert gasses, flows through the reactor at pressures 1-50 μbar (0.76-38 mTorr) where it is photodissociated by a 193 nm laser. Millimeter-wave beam of the CP spectrometer co-propagates with the laser beam along the reactor tube and interacts with nascent photoproducts. Rotational transitions of HCN, HNC, and HCCCN are detected, with ≥10 μs time-steps for 500 ms following photolysis of CH_2CHCN. The post-photolysis evolution of the photoproducts' rotational line intensities is investigated for the effects of rotational and vibrational thermalization of energized photoproducts. Possible contributions from bimolecular and wall-mediated chemistry are evaluated as well.

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

    CERN Document Server

    Fischer, Axel Walter; Woetzel, Nils; Karakas, Mert; Weiner, Brian; Meiler, Jens

    2015-01-01

    For many membrane proteins the determination of their topology remains a challenge for methods like X-ray crystallography and nuclear magnetic resonance (NMR) spectroscopy. Electron paramagnetic resonance (EPR) spectroscopy has evolved as an alternative technique to study structure and dynamics of membrane proteins. The present study demonstrates the feasibility of membrane protein topology determination using limited EPR distance and accessibility measurements. The BCL::MP-Fold (BioChemical Library membrane protein fold) algorithm assembles secondary structure elements (SSEs) in the membrane using a Monte Carlo Metropolis (MCM) approach. Sampled models are evaluated using knowledge-based potential functions and agreement with the EPR data and a knowledge-based energy function. Twenty-nine membrane proteins of up to 696 residues are used to test the algorithm. The RMSD100 value of the most accurate model is better than 8{\\AA} for twenty-seven, better than 6{\\AA} for twenty-two and better than 4{\\AA} for fifte...

  18. Kinetics of the F+NO2+M->FNO2+M reaction studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.

    1996-01-01

    The title reaction was initiated by the pulse radiolysis of SF6/NO2 gas mixtures, and the formation of FNO2 was studied by time-resolved infrared spectroscopy employing strong rotational transitions within the nu(1) and nu(4) bands of FNO2. The pressure dependence of the formation kinetics...

  19. [Study of a wire-to-plate positive pulsed corona discharge reactor by emission spectroscopy].

    Science.gov (United States)

    Wang, Shen-Bing; Luo, Zhong-Yang; Zhao, Lei; Xuan, Jian-Yong; Jiang, Jian-Ping; Cen, Ke-Fa

    2011-11-01

    In order to get extensive knowledge of wire-to-plate pulsed corona discharge reactor, the influences of different diameters of wire electrode, different wire-to-plate and wire-to-wire spacing on OH radical generation were experimentally investigated under atmospheric pressure based on emission spectrum, and the spatial distribution of OH radicals in the electric field was also discussed in detail The results showed that OH radicals decrease along the X-axis, and the activation radius is approximately 20 mm; showing a trend of first increase and then decrease along the Y-axis, with the activation radius being more than 30 mm. OH radical has small change as the diameter of wire electrode changes below 2 mm, with a sharp decline as the diameter continues to increase. OH radical emission intensity increases as wire-to-wire spacing increases and decrease as wire-to-plate spacing increases.

  20. The Determination of Deuterium and Tritium in Effluent Wastewater by Pulsed Nuclear Magnetic Resonance Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Attalla, A.; Birkbeck, J. C.

    1985-04-01

    A pulsed nuclear magnetic resonance (NMR) procedure was developed for the quantitative determination of deuterium and tritium in radioactive, effluent, wastewater to aid in the design of an efficient combined electrolytic/catalytic exchange system for the recovery of these hydrogen isotopes. The deuterium and tritium NMR signals were observed at 9.210 and 45.7 MHz, respectively. Ten different effluent water samples were analyzed for deuterium and tritium to establish base-line data for the preparation of standard reference samples. The hydrogen isotope concentrations ranged from 0.11 to 2.40 g deuterium and from 2.0 to 21.0 mg tritium per liter of processed sample. The standard deviation of the hydrogen isotope determinations is +- 0.017 g deuterium and +- 0.06 mg tritium per liter of processed effluent water. In the future, the effectiveness of specially prepared and analyzed (calorimetry) effluent samples as tritium standards will be investigated.

  1. Single-Shot Terahertz Time-Domain Spectroscopy in Pulsed High Magnetic Fields

    CERN Document Server

    Noe, G Timothy; Katsutani, Fumiya; Allred, James J; Horowitz, Jeffrey A; Zhang, Qi; Sekiguch, Fumiya; Woods, Gary L; Sullivan, David M; Hoffmann, Matthias C; Nojiri, Hiroyuki; Kono, Junichiro

    2016-01-01

    We have developed a single-shot terahertz time-domain spectrometer to perform optical pump/terahertz probe experiments in pulsed, high magnetic fields up to 30 T. The single-shot detection scheme for measuring a terahertz waveform incorporates a reflective echelon to create time-delayed beamlets across the intensity profile of the gate beam before it spatially and temporally overlaps with the terahertz radiation in a ZnTe detection crystal. After imaging the gate beam onto a camera, the terahertz time-domain waveform can be retrieved by analyzing the resulting image. Here, we have measured cyclotron resonance absorption of optically excited carriers in the terahertz frequency range in bulk, intrinsic silicon at high magnetic fields.

  2. Use of ns and fs pulse excitation in laser-induced breakdown spectroscopy to improve its analytical performances: A case study on quaternary bronze alloys

    Energy Technology Data Exchange (ETDEWEB)

    Almaviva, Salvatore [ENEA, UTAPRAD, V. E. Fermi 45, 00044 Frascati (Italy); Fantoni, Roberta, E-mail: roberta.fantoni@enea.it [ENEA, UTAPRAD, V. E. Fermi 45, 00044 Frascati (Italy); Caneve, Luisa; Colao, Francesco [ENEA, UTAPRAD, V. E. Fermi 45, 00044 Frascati (Italy); Fornarini, Lucilla [ENEA,UTTAMB, SP Anguillarese 301, Roma (Italy); Santagata, Antonio [CNR-IMIP, UOS Potenza, Zona Industriale, 85050 Tito Scalo (PZ) (Italy); Teghil, Roberto [Università degli Studi della Basilicata, Dipartimento di Scienze, Via dell' Ateneo Lucano 10, 85100 Potenza (Italy)

    2014-09-01

    Analytical performances of Laser Induced Breakdown Spectroscopy (LIBS) resulted not fully satisfactory in some cases such as historical bronzes, therefore, efforts should be focussed on improving ablation efficiency and on better understanding the plasma parameter evolution. To this aim a set of double pulse experiments have been carried out in almost collinear geometry at about 530 nm laser excitation. The first emitting source was either a ns or a fs laser the second a ns one. Data were collected as a function of the interpulse delay, in order to determine the ablation efficiency increase, to study the kinetics of plasma parameters (temperature, electron density) and the decay of atomic and ionic intensities with respect to the optical background. In parallel a previously developed model for laser ablation, ionization and following plasma decay, was implemented, adding a second laser pulse, to analyse the double pulse excitation in the considered geometry, and the time evolution of the same variables was investigated. Model results are able to reproduce the observed experimental trends and support the possibility of improving analytical performances by using the double pulse technique with inter-pulse delays in the entire investigated range. - Highlights: • The Double Pulse LIBS technique is applied to a quaternary metal alloy sample. • Two different Double Pulse LIBS configurations are investigated. • Signal enhancement was experimentally verified in the Double Pulse technique. • Comparison of the experimental results with the proposed theoretical model • Dependence of the LIBS signal by some experimental parameters.

  3. Overview of LBB implementation for the EPR

    Energy Technology Data Exchange (ETDEWEB)

    Cauquelin, C.

    1997-04-01

    This paper presents an overview of the use of leak-before-break (LBB) analysis for EPR reactors. EPR is an evolutionary Nuclear Island of the 4 loop x 1500 Mwe class currently in the design phase. Application of LBB to the main coolant lines and resulting design impacts are summarized. Background information on LBB analysis in France and Germany is also presented.

  4. EPR Dosimetry - Present and Future

    Energy Technology Data Exchange (ETDEWEB)

    Regulla, D.F. [GSF - National Research Centre for Environment and Health, Institute of Radiation Protection, 85764 Neuherberg (Germany)

    1999-07-01

    In the past, IAEA has played a central role in stipulating research and development in EPR high-dose standardisation as well as in coordinating and organising international dose intercomparison programs, within the Member States of the United Nations from the mid-seventies till today. The future tasks of EPR dosimetry seem to tend towards different subjects such as bio markers, biological radiation effects, post-accident dose reconstruction in the environment, and retrospective human dosimetry. The latter may be considered a promising tool for epidemiology on the way to re-define radiation risk of man for chronicle radiation exposures, based on e.g. South Ural civil population and radiation workers. There are on-going international activities in the field of standardising high-level dosimetry by the American Standards on Testing and Materials (Astm), and by the International Organisation of Standards (ISO). The International Commission on Radiation Units and Measurements (ICRU) is considering the establishment of relevant recommendations concerning industrial radiation processing, but also human dose reconstruction. (Author)

  5. Preparation and applicability of fresh fruit samples for the identification of radiation treatment by EPR

    Energy Technology Data Exchange (ETDEWEB)

    Yordanov, Nicola D. [Laboratory EPR, Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)], E-mail: ndyepr@bas.bg; Aleksieva, Katerina [Laboratory EPR, Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)

    2009-03-15

    The results of electron paramagnetic resonance (EPR) study on fresh fruits (whole pulp of pears, apples, peaches, apricots, avocado, kiwi and mango) before and after gamma-irradiation are reported using two drying procedures before EPR investigation. In order to remove water from non-irradiated and irradiated samples of the first batch, the pulp of fresh fruits is pressed, and the solid residue is washed with alcohol and dried at room temperature. The fruits of the second batch are pressed and dried in a standard laboratory oven at 40 deg. C. The results obtained with both drying procedures are compared. All samples under study show a singlet EPR line with g=2.0048{+-}0.0005 before irradiation. Irradiation gives rise to typical 'cellulose-like' EPR spectrum featuring one intensive line with g=2.0048{+-}0.0005 and two very weak satellite lines situated 3 mT at left and right of the central line. Only mango samples show a singlet line after irradiation. The fading kinetics of radiation-induced EPR signal is studied for a period of 50 days after irradiation. When the irradiated fruit samples are stored in their natural state and dried just before each EPR measurement, the satellite lines are measurable for less than 17 days of storage. Irradiated fruit samples, when stored dried, lose for 50 days ca. 40% of their radiation-induced radicals if treated with alcohol or ca. 70% if dried in an oven. The reported results unambiguously show that the presence of the satellite lines in the EPR spectra could be used for identification of radiation processing of fresh fruits, thus extending the validity of European Protocol EN 1787 (2000). Foodstuffs-Detection of Irradiated Food Containing Cellulose by EPR Spectroscopy. European Committee for Standardisation. Brussels for dry herbs.

  6. Preparation and applicability of fresh fruit samples for the identification of radiation treatment by EPR

    Science.gov (United States)

    Yordanov, Nicola D.; Aleksieva, Katerina

    2009-03-01

    The results of electron paramagnetic resonance (EPR) study on fresh fruits (whole pulp of pears, apples, peaches, apricots, avocado, kiwi and mango) before and after gamma-irradiation are reported using two drying procedures before EPR investigation. In order to remove water from non-irradiated and irradiated samples of the first batch, the pulp of fresh fruits is pressed, and the solid residue is washed with alcohol and dried at room temperature. The fruits of the second batch are pressed and dried in a standard laboratory oven at 40 °C. The results obtained with both drying procedures are compared. All samples under study show a singlet EPR line with g=2.0048±0.0005 before irradiation. Irradiation gives rise to typical "cellulose-like" EPR spectrum featuring one intensive line with g=2.0048±0.0005 and two very weak satellite lines situated 3 mT at left and right of the central line. Only mango samples show a singlet line after irradiation. The fading kinetics of radiation-induced EPR signal is studied for a period of 50 days after irradiation. When the irradiated fruit samples are stored in their natural state and dried just before each EPR measurement, the satellite lines are measurable for less than 17 days of storage. Irradiated fruit samples, when stored dried, lose for 50 days ca. 40% of their radiation-induced radicals if treated with alcohol or ca. 70% if dried in an oven. The reported results unambiguously show that the presence of the satellite lines in the EPR spectra could be used for identification of radiation processing of fresh fruits, thus extending the validity of European Protocol EN 1787 (2000). Foodstuffs—Detection of Irradiated Food Containing Cellulose by EPR Spectroscopy. European Committee for Standardisation. Brussels for dry herbs.

  7. Effects of temporal laser profile on the emission spectra for underwater laser-induced breakdown spectroscopy: Study by short-interval double pulses with different pulse durations

    Energy Technology Data Exchange (ETDEWEB)

    Tamura, Ayaka, E-mail: tamura.ayaka.88m@st.kyoto-u.ac.jp; Matsumoto, Ayumu; Nishi, Naoya; Sakka, Tetsuo, E-mail: sakka.tetsuo.2a@kyoto-u.ac.jp [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510 (Japan); Nakajima, Takashi; Ogata, Yukio H. [Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011 (Japan); Fukami, Kazuhiro [Department of Materials Science and Engineering, Graduate School of Engineering, Kyoto University, Kyoto 606-8501 (Japan)

    2015-01-14

    We investigate the effects of temporal laser profile on the emission spectra of laser ablation plasma in water. We use short-interval (76 ns) double pulses with different pulse durations of the composing two pulses for the irradiation of underwater target. Narrow atomic spectral lines in emission spectra are obtained by the irradiation, where the two pulses are wide enough to be merged into a single-pulse-like temporal profile, while deformed spectra are obtained when the two pulses are fully separated. The behavior of the atomic spectral lines for the different pulse durations is consistent with that of the temporal profiles of the optical emission intensities of the plasma. All these results suggest that continuous excitation of the plasma during the laser irradiation for ∼100 ns is a key to obtain narrow emission spectral lines.

  8. Note: High sensitivity pulsed electron spin resonance spectroscopy with induction detection.

    Science.gov (United States)

    Twig, Ygal; Dikarov, Ekaterina; Hutchison, Wayne D; Blank, Aharon

    2011-07-01

    Commercial electron spin resonance spectroscopy and imaging systems make use of the so-called "induction" or "Faraday" detection, which is based on a radio frequency coil or a microwave resonator. The sensitivity of induction detection does not exceed ~3 × 10(8) spins/√Hz. Here we show that through the use of a new type of surface loop-gap microresonators (inner size of 20 μm), operating at cryogenic temperatures at a field of 0.5 T, one can improve upon this sensitivity barrier by more than 2 orders of magnitude and reach spin sensitivities of ~1.5 × 10(6) spins/√Hz or ~2.5 × 10(4) spins for 1 h.

  9. EPR spectroscopy as a tool for investigation of differences in radical status in wheat plants of various tolerances to osmotic stress induced by NaCl and PEG-treatment.

    Science.gov (United States)

    Labanowska, Maria; Filek, Maria; Kurdziel, Magdalena; Bidzińska, Ewa; Miszalski, Zbigniew; Hartikainen, Hélina

    2013-01-15

    Two kinds of wheat genotypes with different tolerance to osmotic stress (NaCl and PEG-treatment) were investigated with biochemical analyses, including the measurements of total antioxidant capacity, 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging activity, reducing power and starch content. The results were compared with electron paramagnetic resonance (EPR) data concerning the nature and amounts of stable long lived radicals present in the control and stressed plants. In addition, the changes in manganese content upon stress conditions were monitored. Different mechanisms of protection against PEG stress in sensitive and tolerant wheat genotypes were postulated. In sensitive genotypes, electrons were created in excess in stress conditions, and were stabilized by polysaccharide molecules, whereas in tolerant genotypes, protection by antioxidants dominated. Moreover, the quinone-semiquinone balance shifted towards semiquinone, which became the place of electron trapping. NaCl-treatment yielded significant effects mainly in sensitive genotypes and was connected with the changes of water structure, leading to inactivation of reactive oxygen species by water molecules.

  10. New developed cylindrical TM010 mode EPR cavity for X-band in vivo tooth dosimetry.

    Directory of Open Access Journals (Sweden)

    Guo Junwang

    Full Text Available EPR tooth in vivo dosimetry is an attractive approach for initial triage after unexpected nuclear events. An X-band cylindrical TM010 mode resonant cavity was developed for in vivo tooth dosimetry and used in EPR applications for the first time. The cavity had a trapezoidal measuring aperture at the exact position of the cavity's cylindrical wall where strong microwave magnetic field H1 concentrated and weak microwave electric field E1 distributed. Theoretical calculations and simulations were used to design and optimize the cavity parameters. The cavity features were evaluated by measuring DPPH sample, intact incisor samples embed in a gum model and the rhesus monkey teeth. The results showed that the cavity worked at designed frequency and had the ability to make EPR spectroscopy in relative high sensitivity. Sufficient modulation amplitude and microwave power could be applied into the aperture. Radiation induced EPR signal could be observed remarkably from 1 Gy irradiated intact incisor within only 30 seconds, which was among the best in scan time and detection limit. The in vivo spectroscopy was also realized by acquiring the radiation induced EPR signal from teeth of rhesus monkey whose teeth was irradiated by dose of 2 Gy. The results suggested that the cavity was sensitive to meet the demand to assess doses of significant level in short time. This cavity provided a very potential option for the development of X-band in vivo dosimetry.

  11. Time-resolved soft X-ray core-level photoemission spectroscopy at 880 °C using the pulsed laser and synchrotron radiation and the pulse heating current

    Science.gov (United States)

    Abukawa, T.; Yamamoto, S.; Yukawa, R.; Kanzaki, S.; Mukojima, K.; Matsuda, I.

    2017-02-01

    We developed a time-resolved photoemission spectroscopy system for tracking the temporal variation in an electronic state of a heated sample. Our pump-probe method used laser and synchrotron radiation pulses on a silicon surface that was heated by a synchronized pulse current that did not interfere with the measurements. The transient surface photovoltage effect on the Si 2p core spectra was measured from room temperature to 880 °C and was found to be consistent with the thermal carrier distributions in silicon crystals at the corresponding temperatures. This versatile technique may have applications studying molecular dynamics on high temperature surfaces such as in catalytic reactions.

  12. Spectroscopy of the tungsten plasma produced by pulsed plasma-ion streams or laser beams

    Science.gov (United States)

    Skladnik-Sadowska, E.; Malinowski, K.; Sadowski, M. J.; Wolowski, J.; Gasior, P.; Kubkowska, M.; Rosinski, M.; Marchenko, A. K.; Sartowska, B.

    2009-06-01

    The paper reports on experiments, which concerned studies of plasma produced from a tungsten (W) target bombarded by powerful (ca. 5 μs, 1-5 MW/cm 2) plasma-ion streams in RPI-IBIS plasma accelerator, and a similar target irradiated with intense Nd:YAG laser pulses (0.5 J, 3 ns, ca. 5.3 × 10 9 W/cm 2) in another vacuum chamber. In both experiments optical measurements were performed with a Mechelle ®900 spectrometer, which enabled the spectrum from 300 nm to 1100 nm to be recorded, and different WI- and WII-lines to be identified. From space- and time-resolved measurements of those lines, basic W-plasma parameters were estimated. During W-plasma expansion the electron temperature was found to be 0.8-1 eV and electron concentration (2-8) × 10 16 cm -3. The emission of higher-ionized W-ions (up to W +6) was confirmed by measurements with an ion-energy analyzer. Structural changes in the irradiated targets were investigated with an optical microscope and SEM.

  13. Spectroscopy of the tungsten plasma produced by pulsed plasma-ion streams or laser beams

    Energy Technology Data Exchange (ETDEWEB)

    Skladnik-Sadowska, E.; Malinowski, K. [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland); Sadowski, M.J., E-mail: msadowski@ipj.gov.p [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland); Institute of Plasma Physics and Laser Microfusion (IPPLM), 01-497 Warsaw (Poland); Wolowski, J.; Gasior, P.; Kubkowska, M.; Rosinski, M. [Institute of Plasma Physics and Laser Microfusion (IPPLM), 01-497 Warsaw (Poland); Marchenko, A.K. [Institute of Plasma Physics, NSC KIPT, 61-108 Kharkov (Ukraine); Sartowska, B. [Institute of Nuclear Chemistry and Technology, 03-195 Warsaw (Poland)

    2009-06-15

    The paper reports on experiments, which concerned studies of plasma produced from a tungsten (W) target bombarded by powerful (ca. 5 mus, 1-5 MW/cm{sup 2}) plasma-ion streams in RPI-IBIS plasma accelerator, and a similar target irradiated with intense Nd:YAG laser pulses (0.5 J, 3 ns, ca. 5.3 x 10{sup 9} W/cm{sup 2}) in another vacuum chamber. In both experiments optical measurements were performed with a Mechelle 900 spectrometer, which enabled the spectrum from 300 nm to 1100 nm to be recorded, and different WI- and WII-lines to be identified. From space- and time-resolved measurements of those lines, basic W-plasma parameters were estimated. During W-plasma expansion the electron temperature was found to be 0.8-1 eV and electron concentration (2-8) x 10{sup 16} cm{sup -3}. The emission of higher-ionized W-ions (up to W{sup +6}) was confirmed by measurements with an ion-energy analyzer. Structural changes in the irradiated targets were investigated with an optical microscope and SEM.

  14. Pulsed Bromine-81 Nuclear Quadrupole Resonance Spectroscopy of Brominated Flame Retardants and Associated Polymer Blends.

    Science.gov (United States)

    Mrse, Anthony A.; Lee, Youngil; Bryant, Pamela L.; Fronczek, Frank R.; Butler, Leslie G.; Simeral, Larry S.

    1998-03-01

    The dispersion of brominated flame retardants in polymers is monitored with bromine-81 NQR using a pulse NQR spectrometer. The NQR spectrometer consists of a homemade 10-300 MHz single-channel NMR console coupled to a broadly tunable probe. The probe is a loop-gap resonator usable from 220 to 300 MHz, and automatically tuned over any 5 MHz region with a stepping motor and an RF bidirectional coupler. Bromine-81 NQR spectra of several brominated aromatic flame retardants, as pure materials and in polymers, were recorded in the range of 227 to 256 MHz in zero applied magnetic field. Two factors affect the bromine-79/81 NQR transition frequencies in brominated aromatics: electron withdrawing substituents on the ring and intermolecular contacts with other bromine atoms in the crystal structure. An existing model for substituents is updated and a point charge model for the intermolecular contacts is developed. In this study, we exploit the bromine-81 NQR transition frequency dependence on intermolecular contacts to learn how a flame retardant is dispersed in a polymer matrix.

  15. Pulse laser photolysis of aqueous ozone in the microsecond range studied by time-resolved far-ultraviolet absorption spectroscopy.

    Science.gov (United States)

    Goto, Takeyoshi; Morisawa, Yusuke; Higashi, Noboru; Ikehata, Akifumi; Ozaki, Yukihiro

    2013-05-01

    Chemical dynamics of an ozone (O3) pulse-photolytic reaction in aqueous solutions were studied with pump-probe transient far-ultraviolet (FUV) absorption spectroscopy. With a nanosecond pulse laser of 266 nm as pump light, transient spectra of O3 aqueous solutions (78-480 μM, pH 2.5-11.3) were acquired in the time range from -50 to 50 μs in the wavelength region from 190 to 225 nm. The measured transient spectra were linearly decomposed into the molar absorption coefficients and the concentration-time profiles of constituted chemical components with a multivariate curve resolution method. From the dependences of the time-averaged concentrations for 20 μs of the constituted chemicals on the initial concentration of O3, it was found that the transient spectra involve the decomposition of O3 and the formation of hydrogen peroxide (H2O2) and a third component that is assigned to hydroxyl radical (OH) or perhydroxyl radical (HO2). Furthermore, the pH dependence of the time-averaged concentration of the third components indicates that HO2 is more probable than OH as the third component. The time-averaged concentration ratio of each chemical component to the initial O3 concentration depends on the pH conditions from -0.95 to -0.60 for O3, 0.98 to 1.2 for H2O2, 0.002 to 0.29 for OH, and 0.012 to 0.069 for HO2.

  16. Emission Characteristics of Laser-Induced Plasma Using Collinear Long and Short Dual-Pulse Laser-Induced Breakdown Spectroscopy (LIBS).

    Science.gov (United States)

    Wang, Zhenzhen; Deguchi, Yoshihiro; Liu, Renwei; Ikutomo, Akihiro; Zhang, Zhenzhen; Chong, Daotong; Yan, Junjie; Liu, Jiping; Shiou, Fang-Jung

    2017-09-01

    Collinear long and short dual-pulse laser-induced breakdown spectroscopy (DP-LIBS) was employed to clarify the emission characteristics from laser-induced plasma. The plasma was sustained and became stable by the long pulse-width laser with the pulse width of 60 μs under free running (FR) conditions as an external energy source. Comparing the measurement results of stainless steel in air using single-pulse LIBS (SP-LIBS) and DP-LIBS, the emission intensity was markedly enhanced using DP-LIBS. The temperature of plasma induced by DP-LIBS was maintained at a higher temperature under different gate delay time and short pulse-width laser power conditions compared with those measured using short SP-LIBS. Moreover, the variation rates of plasma temperatures measured using DP-LIBS were also lower. The superior detection ability was verified by the measurement of aluminum sample in water. The spectra were clearly detected using DP-LIBS, whereas it cannot be identified using SP-LIBS of short and long pulse widths. The effects of gate delay time and short pulse-width laser power were also discussed. These results demonstrate the feasibility and enhanced detection ability of the proposed collinear long and short DP-LIBS method.

  17. High Frequency Sampling of TTL Pulses on a Raspberry Pi for Diffuse Correlation Spectroscopy Applications.

    Science.gov (United States)

    Tivnan, Matthew; Gurjar, Rajan; Wolf, David E; Vishwanath, Karthik

    2015-08-12

    Diffuse Correlation Spectroscopy (DCS) is a well-established optical technique that has been used for non-invasive measurement of blood flow in tissues. Instrumentation for DCS includes a correlation device that computes the temporal intensity autocorrelation of a coherent laser source after it has undergone diffuse scattering through a turbid medium. Typically, the signal acquisition and its autocorrelation are performed by a correlation board. These boards have dedicated hardware to acquire and compute intensity autocorrelations of rapidly varying input signal and usually are quite expensive. Here we show that a Raspberry Pi minicomputer can acquire and store a rapidly varying time-signal with high fidelity. We show that this signal collected by a Raspberry Pi device can be processed numerically to yield intensity autocorrelations well suited for DCS applications. DCS measurements made using the Raspberry Pi device were compared to those acquired using a commercial hardware autocorrelation board to investigate the stability, performance, and accuracy of the data acquired in controlled experiments. This paper represents a first step toward lowering the instrumentation cost of a DCS system and may offer the potential to make DCS become more widely used in biomedical applications.

  18. High Frequency Sampling of TTL Pulses on a Raspberry Pi for Diffuse Correlation Spectroscopy Applications

    Directory of Open Access Journals (Sweden)

    Matthew Tivnan

    2015-08-01

    Full Text Available Diffuse Correlation Spectroscopy (DCS is a well-established optical technique that has been used for non-invasive measurement of blood flow in tissues. Instrumentation for DCS includes a correlation device that computes the temporal intensity autocorrelation of a coherent laser source after it has undergone diffuse scattering through a turbid medium. Typically, the signal acquisition and its autocorrelation are performed by a correlation board. These boards have dedicated hardware to acquire and compute intensity autocorrelations of rapidly varying input signal and usually are quite expensive. Here we show that a Raspberry Pi minicomputer can acquire and store a rapidly varying time-signal with high fidelity. We show that this signal collected by a Raspberry Pi device can be processed numerically to yield intensity autocorrelations well suited for DCS applications. DCS measurements made using the Raspberry Pi device were compared to those acquired using a commercial hardware autocorrelation board to investigate the stability, performance, and accuracy of the data acquired in controlled experiments. This paper represents a first step toward lowering the instrumentation cost of a DCS system and may offer the potential to make DCS become more widely used in biomedical applications.

  19. Wide-bandgap nonlinear crystal LiGaSsub>2sub> for femtosecond mid-infrared spectroscopy with chirped-pulse upconversion.

    Science.gov (United States)

    Nakamura, Ryosuke; Inagaki, Yoshizumi; Hata, Hidefumi; Hamada, Norio; Umemura, Nobuhiro; Kamimura, Tomosumi

    2016-11-20

    Femtosecond time-resolved mid-infrared (MIR) spectroscopy based on chirped-pulse upconversion is a promising method for observing molecular vibrational dynamics. A quantitative study on nonlinear media for upconversion is still essential for wide applications, particularly at the frequencies below 2000  cm-1. We evaluate wide-bandgap nonlinear crystals of Li-containing ternary chalcogenides based on their performance as the upconversion medium for femtosecond MIR spectroscopy. The upconversion efficiency is measured as a function of the MIR pulse frequency and the chirped pulse energy. LiGaSsub>2sub> is found to be an efficient crystal for the upconversion of MIR pulses in a wide frequency range of 1100-2700  cm-1, especially below 2000  cm-1. By using LiGaSsub>2sub> as an efficient upconversion crystal, we develop a MIR pump-probe spectroscopy system with a spectral resolution of 2.5  cm-1, a time resolution of 0.2 ps, and a probe window of 120  cm-1. Vibrational relaxation dynamics of CO stretching modes of Mnsub>2sub>(CO)sub>10sub> in cyclohexane and bovine serum albumin in Dsub>2sub>O are demonstrated with a high signal-to-noise ratio.

  20. Pulsed ELDOR detected NMR

    Science.gov (United States)

    Schosseler, P.; Wacker, Th.; Schweiger, A.

    1994-07-01

    A pulsed EPR method for the determination of small hyperfine interactions in disordered systems is described. A selective preparation pulse of frequency ω mw(1) excites allowed and forbidden transitions, thereby burning spectral holes into the EPR line. The positions of the holes caused by the excitation of forbidden transitions correspond to the nuclear transition frequencies of the spin system. A selective detection pulse of frequency ω mw(2) creates an FID with integrated intensity proportional to the magnetization at frequency ω mw(2). The entire hole pattern is obtained by recording the integrated intensity of the FID while varying the frequency difference Δω mw=ω mw(1)-ω mw(2) step by step.

  1. Spectroscopy

    DEFF Research Database (Denmark)

    Berg, Rolf W.

    This introductory booklet covers the basics of molecular spectroscopy, infrared and Raman methods, instrumental considerations, symmetry analysis of molecules, group theory and selection rules, as well as assignments of fundamental vibrational modes in molecules.......This introductory booklet covers the basics of molecular spectroscopy, infrared and Raman methods, instrumental considerations, symmetry analysis of molecules, group theory and selection rules, as well as assignments of fundamental vibrational modes in molecules....

  2. Nitrosyl hemoglobins: EPR above 80 K

    Energy Technology Data Exchange (ETDEWEB)

    Wajnberg, E.; Bemski, G.; El-Jaick, L.J.; Alves, O.C.

    1995-03-01

    The EPR spectra of nitrosyl hemoglobin and myoglobin in different conditions (native, denatured and lyophilized), as well as of hematin-NO were obtained in the temperature range of 80 K-280 K. There is a substantial and reversible.decrease of the areas of the EPR spectra of all the hemoglobin samples above 150 K. The interpretation of the results implies the existence of two conformational states in thermal equilibrium only one of which is EPR detectable. Thermodynamical parameters are determined for the hexa and penta-coordinated cases. (author). 25 refs, 3 figs.

  3. Absolute quantitative proton NMR spectroscopy based on the amplitude of the local water suppression pulse. Quantification of brain water and metabolites

    DEFF Research Database (Denmark)

    Danielsen, E R; Henriksen, O

    1994-01-01

    Quantification in localized proton NMR spectroscopy has been achieved by various methods in recent years. A new method for absolute quantification is described in this paper. The method simultaneously rules out problems with B1 field inhomogeneity and coil loading, utilizing a relation between...... the locally optimized amplitude of a chemical shift selective water suppression pulse and the acquired signal. Validity and feasibility of quantification using the method of the water suppression pulse is demonstrated. Brain water and cerebral metabolites have been quantified in a study of 12 healthy...

  4. EPR dosimetry of teeth in past and future accidents: a prospective look at a retrospective method

    Energy Technology Data Exchange (ETDEWEB)

    Haskell, E.H.; Kenner, G.H.; Hayes, R.B. [Utah Univ., Salt Lake City, UT (United States). Center for Applied Dosimetry; Chumak, V.; Shalom, S. [All-Union Scientific Centre of Radiation Medicine, Kiev (Ukraine)

    1996-01-01

    Electron paramagnetic resonance spectroscopy (EPR) of tooth enamel is a relatively new technique for retrospective dosimetry that in the past two years has seen increasing effort towards its development and evaluation. Efforts have centered on determining the accuracy which may be achieved with current measurement techniques as well as the minimum doses detectable. The study was focused on evaluating some factors which influence the accuracy of EPR dosimetry of enamel. Reported are studies on sample intercomparisions, instrumental considerations, and effects of dental x-rays, environmental sunlight and ultraviolet radiation.

  5. EPR, UV-Visible, and Near-Infrared Spectroscopic Characterization of Dolomite

    OpenAIRE

    S. Lakshmi Reddy; Frost, R. L.; G. Sowjanya; Reddy, N. C. G.; G. Siva Reddy; Reddy, B. J.

    2008-01-01

    Dolomite mineral samples having white and light green colors of Indian origin have been characterized by EPR, optical, and NIR spectroscopy. The optical spectrum exhibits a number of electronic bands due to presence of Fe(III) ions in the mineral. From EPR studies, the parameters of g for Fe(III) and g,A, and D for Mn(II) are evaluated and the data confirm that the ions are in distorted octahedron. Optical absorption studies reveal that Fe(III) is in distorted octahedron. The bands in NIR spe...

  6. Finite-Difference Time-Domain Modeling of Free Induction Decay Signal in Chirped Pulse Millimeter Wave Spectroscopy

    Science.gov (United States)

    Heifetz, Alexander; Bakhtiari, Sasan; Chien, Hual-Teh; Prozument, Kirill; Gray, Stephen K.; Williams, Richard M.

    2016-06-01

    We have developed computational electrodynamics model of free induction decay (FID) signal in chirped pulse millimeter wave (CPMMW) spectroscopy. The computational model is based on finite-difference time-domain (FDTD) solution of Maxwell's equations in 1-D. Molecular medium is represented by two-level system derived using density matrix (DM) formulation. Each cell in the grid is assigned an independent set of DM equations, and thus acts as an independent source of induced polarization. Computer simulations with our 1-D model have shown that FID signal is propagating entirely in the forward direction. Intensity of FID radiation increases linearly along the cell length. These results can be explained analytically by considering phases of electromagnetic field radiated by each independent region of induced polarization. We show that there is constructive interference in the forward in forward direction, and destructive interference in backscattering direction. Results in this study are consistent with experimental observations that FID has been measured in the forward scattering direction, but not in backscattering direction.

  7. Short-term pulse rate variability is better characterized by functional near-infrared spectroscopy than by photoplethysmography

    Science.gov (United States)

    Holper, Lisa; Seifritz, Erich; Scholkmann, Felix

    2016-09-01

    Pulse rate variability (PRV) can be extracted from functional near-infrared spectroscopy (fNIRS) (PRVNIRS) and photoplethysmography (PPG) (PRVPPG) signals. The present study compared the accuracy of simultaneously acquired PRVNIRS and PRVPPG, and evaluated their different characterizations of the sympathetic (SNS) and parasympathetic (PSNS) autonomous nervous system activity. Ten healthy subjects were recorded during resting-state (RS) and respiratory challenges in two temperature conditions, i.e., room temperature (23°C) and cold temperature (4°C). PRVNIRS was recorded based on fNIRS measurement on the head, whereas PRVPPG was determined based on PPG measured at the finger. Accuracy between PRVNIRS and PRVPPG, as assessed by cross-covariance and cross-sample entropy, demonstrated a high degree of correlation (r>0.9), which was significantly reduced by respiration and cold temperature. Characterization of SNS and PSNS using frequency-domain, time-domain, and nonlinear methods showed that PRVNIRS provided significantly better information on increasing PSNS activity in response to respiration and cold temperature than PRVPPG. The findings show that PRVNIRS may outperform PRVPPG under conditions in which respiration and temperature changes are present, and may, therefore, be advantageous in research and clinical settings, especially if characterization of the autonomous nervous system is desired.

  8. Detection of calculus by laser-induced breakdown spectroscopy (LIBS) using an ultra-short pulse laser system (USPL)

    Science.gov (United States)

    Schelle, F.; Brede, O.; Krueger, S.; Oehme, B.; Dehn, C.; Frentzen, M.; Braun, A.

    2011-03-01

    The aim of this study was to assess the detection of calculus by Laser Induced Breakdown Spectroscopy (LIBS). The study was performed with an Nd:YVO4 laser, emitting pulses with a duration of 8 ps at a wavelength of 1064 nm. A repetition rate of 500 kHz at an average power of 5 W was used. Employing a focusing lense, intensities of the order of 1011 W/cm2 were reached on the tooth surface. These high intensities led to the generation of a plasma. The light emitted by the plasma was collimated into a fibre and then analyzed by an echelle spectroscope in the wavelength region from 220 nm - 900 nm. A total number of 15 freshly extracted teeth was used for this study. For each tooth the spectra of calculus and cementum were assessed separately. Comprising all single measurements median values were calculated for the whole spectrum, leading to two specific spectra, one for calculus and one for cementum. For further statistical analysis 28 areas of interest were defined as wavelength regions, in which the signal strength differed regarding the material. In 7 areas the intensity of the calculus spectrum differed statistically significant from the intensity of the cementum spectrum (p minimally invasive method allowing a safe application in laser-guided dentistry.

  9. Monitoring of atmospheric nitrogen dioxide by long-path pulsed differential optical absorption spectroscopy using two different light paths.

    Science.gov (United States)

    Kambe, Yasuaki; Yoshii, Yotsumi; Takahashi, Kenshi; Tonokura, Kenichi

    2012-03-01

    Measurements of the local distribution of atmospheric nitrogen dioxide (NO(2)) by long-path pulsed differential optical absorption spectroscopy (LP-PDOAS) in Tokyo during August 2008 are presented. Two LP-PDOAS systems simultaneously measured average NO(2) temporal mixing ratios along two different paths from a single observation point. Two flashing aviation obstruction lights, located 7.0 km north and 6.3 km east from the observation point, were used as light sources, allowing spatiotemporal variations of NO(2) in Tokyo to be inferred. The LP-PDOAS data were compared with ground-based data measured using chemiluminescence. Surface wind data indicated that large inhomogeneities were present in the spatial NO(2) distributions under southerly wind conditions, while northerly wind conditions displayed greater homogeneity between the two systems. The higher correlation in the NO(2) mixing ratio between the two LP-PDOAS systems was observed under northerly wind conditions with a correlation factor R(2) = 0.88. We demonstrated that the combined deployment of two LP-PDOAS systems oriented in different directions provides detailed information on the spatial distribution of NO(2).

  10. UV/Vis, MCD and EPR Spectra of Mononuclear Manganese and Molybdenum Complexes

    OpenAIRE

    Westphal, Anne

    2012-01-01

    This PhD thesis deals with the spectroscopic characterization of the electronic structures of mononuclear manganese and molybdenum complexes. At this, in addition to UV/Vis absorption spectroscopy, electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectroscopy were applied in this work. Additionally, new procedures for the general analysis of MCD C-term intensities were developed within the scope of this thesis. It is divided into four parts. Following a general p...

  11. Solvent effect on librational dynamics of spin-labelled haemoglobin by ED- and CW-EPR.

    Science.gov (United States)

    Scarpelli, Francesco; Bartucci, Rosa; Sportelli, Luigi; Guzzi, Rita

    2011-03-01

    Two-pulse, echo-detected electron paramagnetic resonance (ED-EPR) spectra and continuous-wave EPR (CW-EPR) spectra were used to investigate the solvent effect on the librational motion of human haemoglobin spin-labelled on cysteine β93 with the nitroxide derivative of maleimide, 6-MSL. Protein samples fully hydrated in phosphate buffer solution (PBS), in a 60% v/v glycerol/water mixture and in the lyophilized form were measured at cryogenic temperature in the frozen state. The protein librational motion was characterized by the amplitude-correlation time product, τ(c), deduced from the ED-EPR spectra. The librational amplitude, τ(c), was determined independently, from the motionally averaged hyperfine splitting in the CW-EPR spectra, and the librational correlation time, τ(c), was derived from the combination of the pulsed and conventional EPR data. Rapid librational motion of small amplitude was detected in all samples. In each case, the librational dynamics was restricted up to 180 K, beyond which it increased steeply for the hydrated protein in PBS and in the presence of glycerol. In contrast, in the dehydrated protein, the librational dynamics was hindered and less dependent on temperature up to ~240 K. In all samples, deviated from small values only for T > 200 K, where a rapid increase of was evident for the hydrated samples, whereas limited temperature variation was shown in the lyophilized samples. The librational correlation time was in the sub-nanosecond regime and weakly dependent on temperature. The results evidence that solvent favours protein dynamics.

  12. The EPR in a few words: all you need to know about the EPR nuclear reactor; L'EPR en bref: ce qu'il faut savoir sur le reacteur nucleaire EPR

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2009-07-01

    After a brief presentation of the EPR (European - or Evolutionary - Pressurized Reactor) type nuclear reactor, this paper, proposed by the collective group 'Stop EPR', develops the following points: EPR is as dangerous as other reactors; EPR flouts democracy; France's energy demand do not need the construction of EPRs; the construction of EPRs is not a factor of economical and social development; EPR should not be constructed neither in France nor elsewhere and the present building sites should be cancelled; the EPR will not help France to increase its energy independence and protect itself from oil price increases; choosing the EPR is incompatible with the large investments to be made in energy conservation and renewable energies; the EPR is not a solution to climate change; the VHV line corridor that will starts at Flamanville is not justified and poses risks to the environment and public health

  13. In vivo EPR: an effective new tool for studying pathophysiology, physiology and pharmacology

    Energy Technology Data Exchange (ETDEWEB)

    Maeder, K.; Swartz, H.M. [Dartmouth Univ., Hanover, NH (United States). Dept. of Radiology; Gallez, B. [Louvain Univ., Brussels (Belgium). Dept. of Medicinal Chemistry

    1996-11-01

    The development of spectrometers working at lower frequencies with improved resonators now permits the routine use of non-invasive EPR spectroscopy in vivo. The capabilities of EPR spectra to reflect environmental conditions, combined with the use of paramagnetic materials as selective non-toxic labels, has led to increasingly widespread and productive applications of the technique to complex problems involving physiology, pharmacology and pathophysiology. Some of the especially promising applications in which EPR techniques uniquely appear to provide valuable information are illustrated, including the measurement of oxygen and oxygen gradients, monitoring of the metabolism of xenobiotics, monitoring pharmacokinetics of drugs, measurement of perfusion, measurement of pH, recognition and labeling of receptors, and characterization of drug releasing systems. (author).

  14. EPR, UV-Visible, and Near-Infrared Spectroscopic Characterization of Dolomite

    Directory of Open Access Journals (Sweden)

    S. Lakshmi Reddy

    2008-01-01

    Full Text Available Dolomite mineral samples having white and light green colors of Indian origin have been characterized by EPR, optical, and NIR spectroscopy. The optical spectrum exhibits a number of electronic bands due to presence of Fe(III ions in the mineral. From EPR studies, the parameters of g for Fe(III and g,A, and D for Mn(II are evaluated and the data confirm that the ions are in distorted octahedron. Optical absorption studies reveal that Fe(III is in distorted octahedron. The bands in NIR spectra are due to the overtones and combinations of water molecules. Thus EPR and optical absorption spectral studies have proven useful for the study of the solid state chemistry of dolomite.

  15. Applications of EPR in radiation research

    CERN Document Server

    Lund, Anders

    2014-01-01

    Applications of EPR in Radiation Research is a multi-author contributed volume presented in eight themes: I. Elementary radiation processes (in situ and low temperature radiolysis, quantum solids); II: Solid state radiation chemistry (crystalline, amorphous and heterogeneous systems); III: Biochemistry, biophysics and biology applications (radicals in biomaterials, spin trapping, free-radical-induced DNA damage); IV: Materials science (polymeric and electronic materials, materials for treatment of nuclear waste, irradiated food); V: Radiation metrology (EPR-dosimetry, retrospective and medical

  16. Protocol for emergency EPR dosimetry in fingernails

    OpenAIRE

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

    2007-01-01

    There is an increased need for after-the-fact dosimetry because of the high risk of radiation exposures due to terrorism or accidents. In case of such an event, a method is needed to make measurements of dose in a large number of individuals rapidly and with sufficient accuracy to facilitate effective medical triage. Dosimetry based on EPR measurements of fingernails potentially could be an effective tool for this purpose. This paper presents the first operational protocols for EPR fingernail...

  17. Accurate quantitative analysis of gold alloys using multi-pulse laser induced breakdown spectroscopy and a correlation-based calibration method

    Energy Technology Data Exchange (ETDEWEB)

    Galbacs, Gabor [Department of Inorganic and Analytical Chemistry, University of Szeged, 6720 Szeged, Dom ter 7. (Hungary)], E-mail: galbx@chem.u-szeged.hu; Jedlinszki, Nikoletta; Cseh, Gabor; Galbacs, Zoltan; Turi, Laszlo [Department of Inorganic and Analytical Chemistry, University of Szeged, 6720 Szeged, Dom ter 7. (Hungary)

    2008-05-15

    Multi-pulse laser induced breakdown spectroscopy (LIBS), in combination with the generalized linear correlation calibration method (GLCM), was applied to the quantitative analysis (fineness determination) of quaternary gold alloys. Accuracy and precision on the order of a few thousandths ( per mille ) was achieved. The analytical performance is directly comparable to that of the standard cupellation method (fire assay), but provides results within minutes and is virtually non-destructive, as it consumes only a few micrograms of the sample.

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

    Energy Technology Data Exchange (ETDEWEB)

    Miksic, V.; Pivac, B. E-mail: pivac@rudjer.irb.hr; Rakvin, B.; Zorc, H.; Corni, F.; Tonini, R.; Ottaviani, G

    2002-01-01

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

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

    Science.gov (United States)

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

    2015-02-01

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

  20. Taurine-EVA copolymer-paraffin rods dosimeters for EPR high-dose radiation dosimetry

    Directory of Open Access Journals (Sweden)

    Maghraby Ahmed M.

    2014-03-01

    Full Text Available Taurine/EPR rods (3 × 10 mm have been prepared by a simple technique in the laboratory where taurine powder was mixed with a molten mixture of paraffin wax and an ethylene vinyl acetate (EVA copolymer. The binding mixture EVA/Paraffin does not present interference or noise in the EPR signal before or after irradiation. The rods show good mechanical properties for safe and multi-use handling. An EPR investigation of radiation induced radicals in taurine rods revealed that there are two types of radicals produced after exposure to gamma radiation (60Co. EPR spectra were recorded and analyzed - also the microwave power saturation and modulation amplitude were studied and optimized. Response of taurine to different radiation doses (1.5-100 kGy was studied and found to follow a linear relationship up to 100 kGy. Radiation induced radicals in taurine persists and showed a noticeable stability over 94 days following irradiation. Uncertainities associated with the evaluation of radiation doses using taurine dosimeters were discussed and tabulated. It was found that taurine possesses good dosimetric properties using EPR spectroscopy in high doses in addition to its simple spectrum.

  1. Noncollinear wave mixing of attosecond XUV and few-cycle optical laser pulses in gas-phase atoms: Toward multidimensional spectroscopy involving XUV excitations

    Science.gov (United States)

    Cao, Wei; Warrick, Erika R.; Fidler, Ashley; Neumark, Daniel M.; Leone, Stephen R.

    2016-11-01

    Ultrafast nonlinear spectroscopy, which records transient wave-mixing signals in a medium, is a powerful tool to access microscopic information using light sources in the radio-frequency and optical regimes. The extension of this technique towards the extreme ultraviolet (XUV) or even x-ray regimes holds the promise to uncover rich structural or dynamical information with even higher spatial or temporal resolution. Here, we demonstrate noncollinear wave mixing between weak XUV attosecond pulses and a strong near-infrared (NIR) few-cycle laser pulse in gas phase atoms (one photon of XUV and two photons of NIR). In the noncollinear geometry the attosecond and either one or two NIR pulses interact with argon atoms. Nonlinear XUV signals are generated in a spatially resolved fashion as required by phase matching. Different transition pathways can be identified from these background-free nonlinear signals according to the specific phase-matching conditions. Time-resolved measurements of the spatially gated XUV signals reveal electronic coherences of Rydberg wave packets prepared by a single XUV photon or XUV-NIR two-photon excitation, depending on the applied pulse sequences. These measurements open possible applications of tabletop multidimensional spectroscopy to the study of dynamics associated with valence or core excitation with XUV photons.

  2. Collinear double-pulse laser-induced breakdown spectroscopy as an in-situ diagnostic tool for wall composition in fusion devices

    Energy Technology Data Exchange (ETDEWEB)

    Hai, Ran; Liu, Ping; Wu, Ding [Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Chinese Ministry of Education, School of Physics and Optical Electronic Technology, Dalian University of Technology, Dalian 116024 (China); Ding, Hongbin, E-mail: hding@dlut.edu.cn [Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Chinese Ministry of Education, School of Physics and Optical Electronic Technology, Dalian University of Technology, Dalian 116024 (China); Wu, Jing; Luo, Guang-Nan [Institute of Plasma Physics, Chinese Academy of Sciences, PO Box 1126, Hefei 230031, Anhui (China)

    2014-10-15

    Highlights: • DP-LIBS is proposed as an in-situ diagnostic method for characterizing PFCs of EAST in vacuum. • The collinear DP-LIBS configuration overcame the sensitivity shortcomings of the conventional SP-LIBS. • Plasma emission signals are dependent on the inter-pulse delay in 3.5 × 10{sup −3} Pa. • Exposed divertor tiles were tested by DP-LIBS at low pressure and remotely. - Abstract: Our recent investigations have indicated the potential of double-pulse laser-induced breakdown spectroscopy (DP-LIBS) for analysis of the deposited impurity on divertor tiles in the experimental advanced superconducting tokamak (EAST). The collinear DP-LIBS configuration was suggested with the aim of overcoming the sensitivity shortcomings of the conventional single pulse laser-induced breakdown spectroscopy (SP-LIBS) technique in vacuum conditions. A systematic study of plasma emission signal dependence on the inter-pulse delay at 3.5 × 10{sup −3} Pa was performed, and the results were compared with the ones obtained with a single laser pulse of energy corresponding to the sum of the two pulses. For a molybdenum tile, it was found that the atomic spectral lines of Mo were enhanced by a factor of 6.5 when an inter-delay time of 1.5 μs was installed. For an exposed divertor tile, significant increases in the emission line intensities of various minor elements (such as Mo, Si, Fe, Cr, Ti, Ni and Ca) were observed in DP-LIBS, while no spectra signal was achieved in SP-LIBS. This collinear DP-LIBS technique would help us to develop a more promising system to monitor the fuel retention and impurity deposition on plasma facing components of EAST.

  3. Characterization of nosocomial Serratia marcescens isolates: comparison of Fourier-transform infrared spectroscopy with pulsed-field gel electrophoresis of genomic DNA fragments and multilocus enzyme electrophoresis.

    Science.gov (United States)

    Irmscher, H M; Fischer, R; Beer, W; Seltmann, G

    1999-07-01

    A total of 66 Serratia marcescens isolates from 46 patients was investigated by macrorestriction using XbaI followed by pulsed-field gel electrophoresis. 7 restriction fragment patterns attributable to more than one patient and 9 individual patterns were identified. The isolates were additionally characterized by multilocus enzyme electrophoresis and Fourier-transform infrared spectroscopy. The macrorestriction patterns and the multilocus enzyme electrophoresis patterns corresponded fairly well while the classifications derived from these methods were not completely congruent. The grouping achieved by Fourier-transform infrared spectroscopy on the basis of high (> 1000) and moderately high heterogeneity values (300) was consistent with the macrorestriction results. Grouping on a lower heterogeneity level did not contribute to further discrimination. In general, Fourier-transform infrared spectroscopy was less discriminatory than the two other methods, but easier to perform. Therefore, laboratories equipped with the necessary devices may use it to rapidly select bacterial isolates for macrorestriction or other well established characterization procedures.

  4. Single and double core-hole ion emission spectroscopy of transient neon plasmas produced by ultraintense x-ray laser pulses

    Science.gov (United States)

    Gao, Cheng; Zeng, Jiaolong; Yuan, Jianmin

    2016-05-01

    Single core-hole (SCH) and double core-hole (DCH) spectroscopy is investigated systematically for neon gas in the interaction with ultraintense x-ray pulses with photon energy from 937 eV to 2000 eV. A time-dependent rate equation, implemented in the detailed level accounting approximation, is utilized to study the dynamical evolution of the level population and emission properties of the laser-produced highly transient plasmas. The plasma density effects on level populations are demonstrated with an x-ray photon energy of 2000 eV. For laser photon energy in the range of 937 - 1360 eV, resonant absorptions (RA) of 1s-np (n> = 2) transitions play important roles in time evolution of the population and DCH emission spectroscopy. For x-ray photon energy larger than 1360 eV, no RA exist and transient plasmas show different features in the DCH spectroscopy.

  5. Pulse saturation recovery, pulse ELDOR, and free induction decay electron paramagnetic resonance detection using time-locked subsampling

    Science.gov (United States)

    Froncisz, W.; Camenisch, Theodore G.; Ratke, Joseph J.; Hyde, James S.

    2001-03-01

    Time locked subsampling (TLSS) in electron paramagnetic resonance (EPR) involves the steps of (i) translation of the signal from a microwave carrier to an intermediate frequency (IF) carrier where the (IF) offset between the signal oscillator and local oscillator frequencies is synthesized, (ii) sampling the IF carrier four times in an odd number of cycles, say 4 in 3, where the analog-to-digital (A/D) converter is driven by a frequency synthesizer that has the same clock input as the IF synthesizer, (iii) signal averaging as required for adequate signal to noise, (iv) separating the even and odd digitized words into two separate signal channels, which correspond to signals in phase and in quadrature with respect to the IF carrier, i.e., I and Q, and (v) detecting the envelope of I and also of Q by changing the signs of alternate words in each of the two channels. TLSS detection has been demonstrated in three forms of pulse EPR spectroscopy at X band: saturation recovery, pulse electron-electron double resonance, and free induction decay. The IF was 187.5 MHz, the A/D converter frequency was 250 MHz, the overall bandwidth was 125 MHz, and the bandwidths for the separate I and Q channels were each 62.5 MHz. Experiments were conducted on nitroxide radical spin labels. The work was directed towards development of methodology to monitor bimolecular collisions of oxygen with spin labels in a context of site-directed spin labeling.

  6. Criterions preparation and characterization of earthworm-composts in view of animal waste recycling: Part II. A synergistic utilization of EPR and {sup 1}H NMR spectroscopies on the characterization of humic acids from vermi composts

    Energy Technology Data Exchange (ETDEWEB)

    Guimaraes, Elisete [Centro Federal de Educacao Tecnologica, Pato Branco, PR (Brazil); Mangrich, Antonio S.; Machado, Vanderlei G. [Parana Univ., Curitiba, PR (Brazil). Dept. de Quimica]. E-mail: mangrich@quimica.ufpr.br; Traghetta, Dinis G.; Lobo, Maria A. [Centro Universitario Positivo, Curitiba, PR (Brazil)

    2001-12-01

    Humic acids (HA) extracted from sheep (SHHA), cow (COHA), goat (GOHA) and rabbit (RAHA) vermi composted manure were analyzed by electron paramagnetic resonance and hydrogen nuclear magnetic resonance spectroscopies. Carboxylic acids, amine, amide, ester, ether and phenol functions bonded to saturated aliphatic, unsaturated aliphatic conjugated double and single bonds, and aromatic chains constitute the backbone structure of these fresh humic substances (H S). Mn {sup 2+} outer sphere complexes (SHHA, COHA), Fe{sup 3+} axial (COHA, RAHA) or rhombic (SHAHA, COHA, GOHA, RAHA) complexes and Cu{sup 2+} as weak field (COHA, GOHA, RAHA) and strong field (SHAHA, COHA, GOHA, RAHA) complexes were characterized. (author)

  7. Criterious Preparation and Characterization of Earthworm-composts in View of Animal Waste Recycling: Part II. A Synergistic Utilization of EPR and 1H NMR Spectroscopies on the Characterization of Humic Acids from Vermicomposts

    Directory of Open Access Journals (Sweden)

    Guimarães Elisete

    2001-01-01

    Full Text Available Humic acids (HA extracted from sheep (SHHA, cow (COHA, goat (GOHA and rabbit (RAHA vermicomposted manure were analyzed by electron paramagnetic resonance and hydrogen nuclear magnetic resonance spectroscopies. Carboxylic acids, amine, amide, ester, ether and phenol functions bonded to saturated aliphatic, unsaturated aliphatic conjugated double and single bonds, and aromatic chains constitute the backbone structure of these fresh humic substances (HS. Mn2+ outer sphere complexes (SHHA, COHA, Fe3+ axial (COHA, RAHA or rhombic (SHAHA, COHA, GOHA, RAHA complexes and Cu2+ as weak field (COHA, GOHA, RAHA and strong field (SHAHA, COHA, GOHA, RAHA complexes were characterized.

  8. Time-resolved measurement of emission profiles in pulsed radiofrequency glow discharge optical emission spectroscopy: Investigation of the pre-peak

    Energy Technology Data Exchange (ETDEWEB)

    Alberts, D. [Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julian Claveria 8, 33006 Oviedo (Spain); Horvath, P. [Swiss Federal Laboratories for Materials Testing and Research (EMPA), Feuerwerkerstrasse 39, 3602 Thun (Switzerland); Nelis, Th. [LAPLACE, Universite Paul Sabatier, 118 rte de Narbonne, Bat3R2, 31062 Toulouse Cedex (France); CU Jean Francois Champollion, Place de Verdun 81012 Albi Cedex 9 (France); Pereiro, R. [Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julian Claveria 8, 33006 Oviedo (Spain); Bordel, N. [Department of Physics, Faculty of Science, University of Oviedo, Calvo Sotelo, 33007 Oviedo (Spain); Michler, J. [Swiss Federal Laboratories for Materials Testing and Research (EMPA), Feuerwerkerstrasse 39, 3602 Thun (Switzerland); Sanz-Medel, A., E-mail: asm@uniovi.e [Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julian Claveria 8, 33006 Oviedo (Spain)

    2010-07-15

    Radiofrequency glow discharge coupled to optical emission spectroscopy has been used in pulsed mode in order to perform a detailed study of the measured temporal emission profiles for a wide range of copper transitions. Special attention has been paid to the early emission peak (or so-called pre-peak), observed at the beginning of the emission pulse profile. The effects of the important pulse parameters such as frequency, duty cycle, pulse width and power-off time, have been studied upon the Cu pulse emission profiles. The influence of discharge parameters, such as pressure and power, was studied as well. Results have shown that the intensity observed in the pre-peak can be 10 times as large as the plateau value for resonant lines and up to 5 times in case of transitions to the metastable levels. Increasing pressure or power increased the pre-peak intensity while its appearance in time changed. The pre-peak decreased when the discharge off-time was shorter than 100 {mu}s. According to such results, the presence of the pre-peak could be probably due to the lack of self-absorption during the first 50 {mu}s, and not to the ignition of the plasma. Under the selected operation conditions, the use of the pre-peak emission as analytical signals increases the linearity of calibration curves for resonant lines subjected to self-absorption at high concentrations.

  9. Absolute atomic oxygen density measurements for nanosecond-pulsed atmospheric-pressure plasma jets using two-photon absorption laser-induced fluorescence spectroscopy

    Science.gov (United States)

    Jiang, C.; Carter, C.

    2014-12-01

    Nanosecond-pulsed plasma jets that are generated under ambient air conditions and free from confinement of electrodes have become of great interest in recent years due to their promising applications in medicine and dentistry. Reactive oxygen species that are generated by nanosecond-pulsed, room-temperature non-equilibrium He-O2 plasma jets among others are believed to play an important role during the bactericidal or sterilization processes. We report here absolute measurements of atomic oxygen density in a 1 mm-diameter He/(1%)O2 plasma jet at atmospheric pressure using two-photon absorption laser-induced fluorescence spectroscopy. Oxygen number density on the order of 1013 cm-3 was obtained in a 150 ns, 6 kV single-pulsed plasma jet for an axial distance up to 5 mm above the device nozzle. Temporally resolved O density measurements showed that there are two maxima, separated in time by 60-70 µs, and a total pulse duration of 260-300 µs. Electrostatic modeling indicated that there are high-electric-field regions near the nozzle exit that may be responsible for the observed temporal behavior of the O production. Both the field-distribution-based estimation of the time interval for the O number density profile and a pulse-energy-dependence study confirmed that electric-field-dependent, direct and indirect electron-induced processes play important roles for O production.

  10. Nitric oxide adsorbed on zeolites: EPR studies.

    Science.gov (United States)

    Yahiro, Hidenori; Lund, Anders; Shiotani, Masaru

    2004-05-01

    CW-EPR studies of NO adsorbed on sodium ion-exchanged zeolites were focused on the geometrical structure of NO monoradical and (NO)2 biradical formed on zeolites. The EPR spectrum of NO monoradical adsorbed on zeolite can be characterized by the three different g-tensor components and the resolved y-component hyperfine coupling with the 14N nucleus. Among the g-tensor components, the value of g(zz) is very sensitive to the local environment of zeolite and becomes a measure of the electrostatic field in zeolite. The temperature dependence of the g-tensor demonstrated the presence of two states of the Na-NO adduct, in rigid and rotational states. The EPR spectra of NO adsorbed on alkaline metal ion-exchanged zeolite and their temperature dependency are essentially the same as that on sodium ion-exchanged zeolite. On the other hand, for NO adsorbed on copper ion-exchanged zeolite it is known that the magnetic interaction between NO molecule and paramagnetic copper ion are observable in the spectra recorded at low temperature. The signals assigned to (NO)2 biradical were detected for EPR spectrum of NO adsorbed on Na-LTA. CW-EPR spectra as well as their theoretical calculation suggested that the two NO molecules are aligned along their N-O bond axes. A new procedure for automatical EPR simulation is described which makes it possible to analyze EPR spectrum easily. In the last part of this paper, some instances when other nitrogen oxides were used as a probe molecule to characterize the zeolite structure, chemical properties of zeolites, and dynamics of small molecules were described on the basis of selected literature data reported recently.

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

    Science.gov (United States)

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

    2015-11-01

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

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

    Science.gov (United States)

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

    2000-05-01

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

  13. Observation of Atomic Emission Enhancement by fs-ns Dual-Pulse Laser-Induced Breakdown Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    YAN Li-Xin; ZHANG Yong-Sheng; ZHANG Li-Rong; LIU Jing-Ru; CHENG Jian-Ping; L(U) Min

    2006-01-01

    An experiment of a 500-fs KrF laser pulse incident upon a high density supersonic O2 gas jet synchronously with an ns frequency-doubled Nd:YAG laser pulse is performed in orthogonal configuration.Significant atomic emission enhancement of over forty-fold is observed with an optical multi-channel analyser.The enhancement effect is probably attributed to the different ionization mechanisms between fs and ns laser pulses.

  14. Time-resolved measurement of atomic emission enhancement by fs-ns dual-pulsed laser-induced breakdown spectroscopy

    Institute of Scientific and Technical Information of China (English)

    Yan Li-Xin; Zhang Yong-Sheng; Zheng Guo-Xin; Liu Jing-Ru; Cheng Jian-Ping; Lü Min

    2006-01-01

    Time-resolved measurement of atomic emission enhancement is performed by using a 500-fs KrF laser pulse incident upon a high density supersonic O2 gas jet, synchronized with an orthogonal ns frequency-doubled Nd:YAG laser pulse. The ultra-short pulse serves as an igniter of the gas jet, and the subsequent ns-laser pulse significantly enhances the atomic emission. Analysis shows that the contributions to the enhancement effect are made mainly by the bremsstrahlung radiation and cascade ionization.

  15. Time-resolved OES of nanosecond pulsed discharges in N$_{2}$ and N$_{2}$/H$_{2}$O mixtures]{Time-resolved optical emission spectroscopy of nanosecond pulsed discharges in atmospheric pressure N$_{2}$ and N$_{2}$/H$_{2}$O mixtures

    CERN Document Server

    van der Horst, R M; van Veldhuizen, E M; Bruggeman, P J

    2014-01-01

    In this contribution, nanosecond pulsed discharges in N$_{2}$ and N$_{2}$/0.9% H$_{2}$O at atmospheric pressure (at 300 K) are studied with time-resolved imaging, optical emission spectroscopy and Rayleigh scattering. A 170 ns high voltage pulse is applied across two pin-shaped electrodes at a frequency of 1 kHz. The discharge consists of three phases: an ignition phase, a spark phase and a recombination phase. During the ignition phase the emission is mainly caused by molecular nitrogen (N$_{2}$(C-B)). In the spark and recombination phase mainly atomic nitrogen emission is observed. The emission when H$_{2}$O is added is very similar, except the small contribution of H$_{\\alpha}$ and the intensity of the molecular N$_{2}$(C-B) emission is less.

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

    Science.gov (United States)

    Nakagawa, K; Hara, H

    2015-01-01

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

  17. Computational and instrumental methods in EPR

    CERN Document Server

    Bender, Christopher J

    2006-01-01

    Computational and Instrumental Methods in EPR Prof. Bender, Fordham University Prof. Lawrence J. Berliner, University of Denver Electron magnetic resonance has been greatly facilitated by the introduction of advances in instrumentation and better computational tools, such as the increasingly widespread use of the density matrix formalism. This volume is devoted to both instrumentation and computation aspects of EPR, while addressing applications such as spin relaxation time measurements, the measurement of hyperfine interaction parameters, and the recovery of Mn(II) spin Hamiltonian parameters via spectral simulation. Key features: Microwave Amplitude Modulation Technique to Measure Spin-Lattice (T1) and Spin-Spin (T2) Relaxation Times Improvement in the Measurement of Spin-Lattice Relaxation Time in Electron Paramagnetic Resonance Quantitative Measurement of Magnetic Hyperfine Parameters and the Physical Organic Chemistry of Supramolecular Systems New Methods of Simulation of Mn(II) EPR Spectra: Single Cryst...

  18. Protocol for emergency EPR dosimetry in fingernails.

    Science.gov (United States)

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

    2007-08-01

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

  19. Can EPR non-locality be geometrical?

    Energy Technology Data Exchange (ETDEWEB)

    Ne`eman, Y. [Tel-Aviv Univ. (Israel). Raymond and Beverly Sackler Faculty of Exact Sciences]|[Univ. of Texas, Austin, TX (United States). Center for Particle Physics; Botero, A. [Texas Univ., Austin, TX (United States)

    1995-10-01

    The presence in Quantum Mechanics of non-local correlations is one of the two fundamentally non-intuitive features of that theory. The non-local correlations themselves fall into two classes: EPR and Geometrical. The non-local characteristics of the geometrical type are well-understood and are not suspected of possibly generating acausal features, such as faster-than-light propagation of information. This has especially become true since the emergence of a geometrical treatment for the relevant gauge theories, i.e. Fiber Bundle geometry, in which the quantum non-localities are seen to correspond to pure homotopy considerations. This aspect is reviewed in section 2. Contrary-wise, from its very conception, the EPR situation was felt to be paradoxical. It has been suggested that the non-local features of EPR might also derive from geometrical considerations, like all other non-local characteristics of QM. In[7], one of the authors was able to point out several plausibility arguments for this thesis, emphasizing in particular similarities between the non-local correlations provided by any gauge field theory and those required by the preservation of the quantum numbers of the original EPR state-vector, throughout its spatially-extended mode. The derivation was, however, somewhat incomplete, especially because of the apparent difference between, on the one hand, the closed spatial loops arising in the analysis of the geometrical non-localities, from Aharonov-Bohm and Berry phases to magnetic monopoles and instantons, and on the other hand, in the EPR case, the open line drawn by the positions of the two moving decay products of the disintegrating particle. In what follows, the authors endeavor to remove this obstacle and show that as in all other QM non-localities, EPR is somehow related to closed loops, almost involving homotopy considerations. They develop this view in section 3.

  20. Monte Carlo simulation algorithm for pileup effect of pulses in gamma spectroscopy and pileup distortion calculation on 137Cs pulse height spectrum in NaI(Tl detector

    Directory of Open Access Journals (Sweden)

    AA Mowlavi

    2011-12-01

    Full Text Available  In this paper, an algorithm base on Monte Carlo simulation for pileup effect in gamma spectrum of a detection system is presented whose its code was written in FORTRAN language. The code can be run in paralayzable and nonparalazable mode to obtain the pileup distortion and value of pulses pileup for any detection system. The result show, that the computed spectrum of 137Cs is in good agreement with the experimental spectrum in NaI(Tl detector. The free of pileup free spectrum and sub-spectra with different degrees of pulses of pileup are calculated. Also, we can apply it to different sources and detectors for pileup correction.

  1. Depth-resolved measurements with elliptically polarized reflectance spectroscopy.

    Science.gov (United States)

    Bailey, Maria J; Sokolov, Konstantin

    2016-07-01

    The ability of elliptical polarized reflectance spectroscopy (EPRS) to detect spectroscopic alterations in tissue mimicking phantoms and in biological tissue in situ is demonstrated. It is shown that there is a linear relationship between light penetration depth and ellipticity. This dependence is used to demonstrate the feasibility of a depth-resolved spectroscopic imaging using EPRS. The advantages and drawbacks of EPRS in evaluation of biological tissue are analyzed and discussed.

  2. TL and EPR dating: some applications

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, S. [Institute of Physics, University of Sao Paulo, Sao Paulo (Brazil)

    2006-07-01

    The intensity of thermoluminescence light emitted by a crystal is a function of radiation dose. The number of defects or of radicals in a crystal or organic substances is also a function of radiation dose. Since such defects or radicals present EPR signals, the EPR intensity is also a function of radiation dose. These facts are basis for radiation dosimetry and can be applied in dating of archaeological potteries or other materials, as well as in dating geological substances such as sediments, caves speleothemes, animal teeth and bones. Recent investigation on sensitized quartz based dosimeters and dating calcite covering ancient wall painting to find early settlers in Brazil will be presented. (Author)

  3. RosettaTMH: a method for membrane protein structure elucidation combining EPR distance restraints with assembly of transmembrane helices

    Directory of Open Access Journals (Sweden)

    Andrew Leaver-Fay

    2015-12-01

    Full Text Available Membrane proteins make up approximately one third of all proteins, and they play key roles in a plethora of physiological processes. However, membrane proteins make up less than 2% of experimentally determined structures, despite significant advances in structure determination methods, such as X-ray crystallography, nuclear magnetic resonance spectroscopy, and cryo-electron microscopy. One potential alternative means of structure elucidation is to combine computational methods with experimental EPR data. In 2011, Hirst and others introduced RosettaEPR and demonstrated that this approach could be successfully applied to fold soluble proteins. Furthermore, few computational methods for de novo folding of integral membrane proteins have been presented. In this work, we present RosettaTMH, a novel algorithm for structure prediction of helical membrane proteins. A benchmark set of 34 proteins, in which the proteins ranged in size from 91 to 565 residues, was used to compare RosettaTMH to Rosetta’s two existing membrane protein folding protocols: the published RosettaMembrane folding protocol (“MembraneAbinitio” and folding from an extended chain (“ExtendedChain”. When EPR distance restraints are used, RosettaTMH+EPR outperforms ExtendedChain+EPR for 11 proteins, including the largest six proteins tested. RosettaTMH+EPR is capable of achieving native-like folds for 30 of 34 proteins tested, including receptors and transporters. For example, the average RMSD100SSE relative to the crystal structure for rhodopsin was 6.1 ± 0.4 Å and 6.5 ± 0.6 Å for the 449-residue nitric oxide reductase subunit B, where the standard deviation reflects variance in RMSD100SSE values across ten different EPR distance restraint sets. The addition of RosettaTMH and RosettaTMH+EPR to the Rosetta family of de novo folding methods broadens the scope of helical membrane proteins that can be accurately modeled with this software suite.

  4. Laser-induced breakdown spectroscopy for on-line control of selective removal of cobalt binder from tungsten carbide hardmetal by pulsed UV laser surface ablation

    Science.gov (United States)

    Li, Tiejun; Lou, Qihong; Wei, Yunrong; Huang, Feng; Dong, Jingxing; Liu, Jingru

    2001-09-01

    Laser-induced breakdown spectroscopy (LIBS) was successfully used in on-line control of selective removal of cobalt from tungsten carbide hardmetal by pulsed UV laser surface ablation. The dependence of LIBS on number of laser shots was investigated at different laser fluences. The optimal laser fluence of 2.5 J/cm 2 suited for selective removal of cobalt from surface layer of hardmetal was confirmed. The result sample was also subject to different post-examinations to evaluate the feasibility of the application of LIBS in this laser ablation process. It was demonstrated that, monitoring of the emission intensity of cobalt lines could be used as a control parameter for selective removal of cobalt from surface layer of hardmetal by pulsed UV laser. The on-line implementation of the spectroscopic technique LIBS to the surface-ablation process provided important information about the optimal-ablation parameters.

  5. Angle-resolved photoemission spectroscopy with 9-eV photon-energy pulses generated in a gas-filled hollow-core photonic crystal fiber

    Energy Technology Data Exchange (ETDEWEB)

    Bromberger, H., E-mail: Hubertus.Bromberger@mpsd.mpg.de; Liu, H.; Chávez-Cervantes, M.; Gierz, I. [Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg (Germany); Ermolov, A.; Belli, F.; Abdolvand, A.; Russell, P. St. J.; Travers, J. C. [Max Planck Institute for the Science of Light, Günther-Scharowsky-Str. 1, 91058 Erlangen (Germany); Calegari, F. [Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg (Germany); Institute for Photonics and Nanotechnologies, IFN-CNR, Piazza Leonardo da Vinci 32, I-20133 Milano (Italy); Li, M. T.; Lin, C. T. [Max Planck Institute for Solid State Research, Heisenbergstr. 1, 70569 Stuttgart (Germany); Cavalleri, A. [Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg (Germany); Clarendon Laboratory, Department of Physics, University of Oxford, Parks Rd. Oxford OX1 3PU (United Kingdom)

    2015-08-31

    A recently developed source of ultraviolet radiation, based on optical soliton propagation in a gas-filled hollow-core photonic crystal fiber, is applied here to angle-resolved photoemission spectroscopy (ARPES). Near-infrared femtosecond pulses of only few μJ energy generate vacuum ultraviolet radiation between 5.5 and 9 eV inside the gas-filled fiber. These pulses are used to measure the band structure of the topological insulator Bi{sub 2}Se{sub 3} with a signal to noise ratio comparable to that obtained with high order harmonics from a gas jet. The two-order-of-magnitude gain in efficiency promises time-resolved ARPES measurements at repetition rates of hundreds of kHz or even MHz, with photon energies that cover the first Brillouin zone of most materials.

  6. Angle-resolved photoemission spectroscopy with 9-eV photon-energy pulses generated in a gas-filled hollow-core photonic crystal fiber

    CERN Document Server

    Bromberger, H; Belli, F; Liu, H; Calegari, F; Chavez-Cervantes, M; Li, M T; Lin, C T; Abdolvand, A; Russell, P St J; Cavalleri, A; Travers, J C; Gierz, I

    2015-01-01

    A recently developed source of ultraviolet radiation, based on optical soliton propagation in a gas-filled hollow-core photonic crystal fiber, is applied here to angle-resolved photoemission spectroscopy (ARPES). Near-infrared femtosecond pulses of only few {\\mu}J energy generate vacuum ultraviolet (VUV) radiation between 5.5 and 9 eV inside the gas-filled fiber. These pulses are used to measure the band structure of the topological insulator Bi2Se3 with a signal to noise ratio comparable to that obtained with high order harmonics from a gas jet. The two-order-of-magnitude gain in efficiency promises time-resolved ARPES measurements at repetition rates of hundreds of kHz or even MHz, with photon energies that cover the first Brillouin zone of most materials.

  7. Terahertz cyclotron resonance spectroscopy of an AlGaN/GaN heterostructure using a high-field pulsed magnet and an asynchronous optical sampling technique

    Science.gov (United States)

    Spencer, B. F.; Smith, W. F.; Hibberd, M. T.; Dawson, P.; Beck, M.; Bartels, A.; Guiney, I.; Humphreys, C. J.; Graham, D. M.

    2016-05-01

    The effective mass, sheet carrier concentration, and mobility of electrons within a two-dimensional electron gas in an AlGaN/GaN heterostructure were determined using a laboratory-based terahertz cyclotron resonance spectrometer. The ability to perform terahertz cyclotron resonance spectroscopy with magnetic fields of up to 31 T was enabled by combining a high-field pulsed magnet with a modified asynchronous optical sampling terahertz detection scheme. This scheme allowed around 100 transmitted terahertz waveforms to be recorded over the 14 ms magnetic field pulse duration. The sheet density and mobility were measured to be 8.0 × 1012 cm-2 and 9000 cm2 V-1 s-1 at 77 K. The in-plane electron effective mass at the band edge was determined to be 0.228 ± 0.002m0.

  8. Probing Pulsar Emission on Short Timescales: Rotating Radio Transients, Cyclic Spectroscopy, and Single-Pulse Studies of Millisecond Pulsars

    Science.gov (United States)

    Palliyaguru, Nipuni Tharaka

    Rotating radio transients (RRATs) are neutron stars are that characterized by the emission of strong sporadic bursts. We have analysed the long- and short-term time dependence of the pulse arrival times and the pulse detection rates for eight RRAT sources from the Parkes Multi-beam Pulsar Survey (PMPS). We find significant periodicities in the individual pulse arrival times from six RRATs. These periodicities range from ˜30 minutes to 2100 days and from one to 16 independent (i.e. non-harmonically related) periodicities are detected for each RRAT. In addition, we find that pulse emission is a random process on short (hour-long) time scales but that most of the objects exhibit longer term (months-years) non-random behaviour. We find that PSRs J1819--1458 and J1317--5759 emit more doublets (two consecutive pulses) and triplets (three consecutive pulses) than is expected in random pulse distributions. No evidence for such an excess is found for the other RRATs. There are several different models for RRAT emission depending on both extrinsic and intrinsic factors which are consistent with these properties. Light travel time changes due to gravitational waves may be detected within the next decade through precision timing of an array of millisecond pulsars. Removal of frequency-dependent interstellar medium (ISM) delays due to dispersion and scattering is a key issue in the detection process. Current timing algorithms routinely correct pulse times of arrival (TOAs) for time-variable delays due to cold plasma dispersion. However, none of the major pulsar timing groups routinely correct for delays due to scattering from multi-path propagation in the ISM. Scattering introduces a phase change in the signal that results in pulse broadening and arrival time delays. As a step toward a more comprehensive ISM propagation delay correction, we demonstrate through a simulation that we can accurately recover pulse broadening functions (PBFs), such as those that would be introduced

  9. Electron Paramagnetic Resonance Imaging: 2. Radiofrequency FT-EPR Imaging

    Indian Academy of Sciences (India)

    2016-08-01

    In this part we shall outline the challenges one faces whiledeveloping time-domain radiofrequency (RF) EPR imagingspectrometer for in vivo studies. Time-domain or FT-EPR isquite a different animal compared to the CW modality. Theevolution of FT-EPR instrumentation at the National CancerInstitute, NIH, USA and representative examples of applicationin cancer research are outlined in this article.

  10. SAX J1808.4-3658: high resolution spectroscopy and decrease of pulsed fraction at low energies

    CERN Document Server

    Patruno, Alessandro; Altamirano, Diego; Linares, Manuel; Wijnands, R; Van der Klis, M

    2009-01-01

    XMM-Newton observed the accreting millisecond pulsar SAX J1808.4-3658 during its 2008 outburst. We present timing and spectral analyses of this observation, in particular the first pulse profile study below 2 keV, and the high-resolution spectral analysis of this source during the outburst. Combined spectral and pulse profile analyses suggest the presence of a strong unpulsed source below 2 keV that strongly reduces the pulsed fraction and a hard pulsed component that generates markedly double peaked profiles at higher energies. We also studied the high-resolution grating spectrum of SAX J1808.4-3658, and found several absorption edges and Oxygen absorption lines with whom we infer, in a model independent way, the interstellar column densities of several elements in the direction of SAX J1808.4-3658.

  11. NMR and EPR Studies of Free-Radical Intermediates from Experiments Mimicking the Winds on Mars

    DEFF Research Database (Denmark)

    Jakobsen, Hans J.; Song, Likai; Gan, Zhehong

    2016-01-01

    A new kind of solid gas chemical reactions has been investigated using solid-state powder H-2, C-13, and Si-29 NMR and EPR spectroscopies. These studies involve reactions between a silicate-created Si free-radical intermediate and a few ordinary gases such as isotopically H-2-, C-13-, and O-17......)-C-13, (encapsulation of the gas) and the indication of a congested methyl group in the product from reaction with methane....

  12. Free Radical Scavenging Activity of Drops and Spray Containing Propolis—An EPR Examination

    OpenAIRE

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

    2017-01-01

    The influence of heating at a temperature of 50 °C and UV-irradiation of propolis drops and spray on their free radical scavenging activity was determined. The kinetics of interactions of the propolis samples with DPPH free radicals was analyzed. Interactions of propolis drops and propolis spray with free radicals were examined by electron paramagnetic resonance spectroscopy. A spectrometer generating microwaves of 9.3 GHz frequency was used. The EPR spectra of the model DPPH free radicals we...

  13. EPR and Magnetic Susceptibility Investigation of Fe Ions in B2O3-SrF2 Glass Matrix

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The structural and magnetic properties of an oxide-fluoride mixed vitreous matrix 2B2O3@SrF2, were explored by using Fe impurities as probes. Information about the structural units involving iron ions, their valence state, the strengths and type of interactions involving them was obtained using EPR spectroscopy and magnetic susceptibility measurements.

  14. Analysis of natural and artificial ultramarine blue pigments using laser induced breakdown and pulsed Raman spectroscopy, statistical analysis and light microscopy

    Science.gov (United States)

    Osticioli, I.; Mendes, N. F. C.; Nevin, A.; Gil, Francisco P. S. C.; Becucci, M.; Castellucci, E.

    2009-08-01

    Pulsed laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy were performed using a novel laboratory setup employing the same Nd:YAG laser emission at 532 nm for the analysis of five commercially available pigments collectively known as "ultramarine blue", a sodium silicate material of either mineral origin or an artificially produced glass. LIBS and Raman spectroscopy have provided information regarding the elemental and molecular composition of the samples; additionally, an analytical protocol for the differentiation between natural (lapis lazuli) and artificial ultramarine blue pigments is proposed. In particular LIBS analysis has allowed the discrimination between pigments on the basis of peaks ascribed to calcium. The presence of calcite in the natural blue pigments has been confirmed following Raman spectroscopy in specific areas of the samples, and micro-Raman and optical microscopy have further corroborated the presence of calcite inclusions in the samples of natural origin. Finally multivariate analysis of Laser induced breakdown spectra using principal component analysis (PCA) further enhanced the differentiation between natural and artificial ultramarine blue pigments.

  15. Analysis of natural and artificial ultramarine blue pigments using laser induced breakdown and pulsed Raman spectroscopy, statistical analysis and light microscopy.

    Science.gov (United States)

    Osticioli, I; Mendes, N F C; Nevin, A; Gil, Francisco P S C; Becucci, M; Castellucci, E

    2009-08-01

    Pulsed laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy were performed using a novel laboratory setup employing the same Nd:YAG laser emission at 532 nm for the analysis of five commercially available pigments collectively known as "ultramarine blue", a sodium silicate material of either mineral origin or an artificially produced glass. LIBS and Raman spectroscopy have provided information regarding the elemental and molecular composition of the samples; additionally, an analytical protocol for the differentiation between natural (lapis lazuli) and artificial ultramarine blue pigments is proposed. In particular LIBS analysis has allowed the discrimination between pigments on the basis of peaks ascribed to calcium. The presence of calcite in the natural blue pigments has been confirmed following Raman spectroscopy in specific areas of the samples, and micro-Raman and optical microscopy have further corroborated the presence of calcite inclusions in the samples of natural origin. Finally multivariate analysis of Laser induced breakdown spectra using principal component analysis (PCA) further enhanced the differentiation between natural and artificial ultramarine blue pigments.

  16. EPR spin trapping of protein radicals

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan; Hawkins, Clare Louise

    2004-01-01

    Electron paramagnetic resonance (EPR) spin trapping was originally developed to aid the detection of low-molecular-mass radicals formed in chemical systems. It has subsequently found widespread use in biology and medicine for the direct detection of radical species formed during oxidative stress ...... examples of radical formation on proteins....

  17. Dependence of laser-induced breakdown spectroscopy results on pulse energies and timing parameters using soil simulants.

    Science.gov (United States)

    Kurek, Lauren; Najarian, Maya L; Cremers, David A; Chinni, Rosemarie C

    2013-09-23

    The dependence of some LIBS detection capabilities on lower pulse energies (<100 mJ) and timing parameters were examined using synthetic silicate samples. These samples were used as simulants for soil and contained minor and trace elements commonly found in soil at a wide range of concentrations. For this study, over 100 calibration curves were prepared using different pulse energies and timing parameters; detection limits and sensitivities were determined from the calibration curves. Plasma temperatures were also measured using Boltzmann plots for the various energies and the timing parameters tested. The electron density of the plasma was calculated using the full-width half maximum (FWHM) of the hydrogen line at 656.5 nm over the energies tested. Overall, the results indicate that the use of lower pulse energies and non-gated detection do not seriously compromise the analytical results. These results are very relevant to the design of field- and person-portable LIBS instruments.

  18. Microstructure variation in fused silica irradiated by different fluence of UV laser pulses with positron annihilation lifetime and Raman scattering spectroscopy

    Science.gov (United States)

    Li, Chunhong; Zheng, Wanguo; Zhu, Qihua; Chen, Jun; Wang, B. Y.; Ju, Xin

    2016-10-01

    We present an original study on the non-destructive evaluation of the microstructure evolution of fused silica induced by pulsed UV laser irradiation at low fluence (less than 50% Fth). Positron annihilation spectroscopy discloses that the spatial size of the vacancy cluster is increased exponentially with the linearly elevated laser fluence. Particularly, the vacancy cluster size in bulk silica is significantly increased by 14.5% after irradiated by pulsed 355 nm laser at F = 14 J/cm2 (50% Fth), while the void size varies only ∼2%. UV laser-excited Raman results suggest that the bond length and average bond angle of Sisbnd Osbnd Si bridging bond are both slightly reduced. Results reveals that the rearrangement process of (Sisbnd O)n fold rings and breakage of the Sisbnd O bridging bond in bulk silica occurred during pulsed UV laser irradiation. The micro-structural changes were taken together to clarify the effect of sub-threshold laser fluence on material stability of silica glass. The obtained data provide important information for studying material stability and controlling the lifetime of fused silica optics for high power laser system.

  19. In situ diagnosis of pulsed UV laser surface ablation of tungsten carbide hardmetal by using laser-induced optical emission spectroscopy

    Science.gov (United States)

    Li, Tiejun; Lou, Qihong; Wei, Yunrong; Huang, Feng; Dong, Jingxing; Liu, Jingru

    2001-12-01

    Surface ablation of cobalt cemented tungsten carbide hardmetal with pulsed UV laser has been in situ diagnosed by using the technique of laser-induced optical emission spectroscopy. The dependence of emission intensity of cobalt lines on number of laser shots was investigated at laser fluence of 2.5 J/cm 2. As a comparison, the reliance of emission intensity of cobalt lines as a function of laser pulse number by using pure cobalt as ablation sample was also studied at the same laser condition. It was found that for surface ablation of tungsten carbide hardmetal at laser fluence of 2.5 J/cm 2, the intensities of cobalt lines fell off dramatically in the first 300 consecutive laser shots and then slowed down to a low stable level with even more shots. For surface ablation of pure cobalt at the same laser condition, the intensities of cobalt lines remained constant more or less even after 500 laser shots and then reduced very slowly with even more shots. It was concluded that selective evaporation of cobalt at this laser fluence should be responsible for the dramatic fall-off of cobalt lines with laser shots accumulation for surface ablation of tungsten carbide hardmetal. In contrast, for surface ablation of pure cobalt, the slow reduction of cobalt lines with pulse number accumulation should be due to the formation of laser-induced crater effect.

  20. Time-resolved thermal lens spectroscopy with a single-pulsed laser excitation beam: an analytical model for dual-beam mode-mismatched experiments.

    Science.gov (United States)

    Sabaeian, Mohammad; Rezaei, Hamidreza; Ghalambor-Dezfouli, Abdolmohammad

    2017-02-01

    Pulsed laser beam excitations are more commonly used in thermal lens spectroscopy (TLS) than continuous-wave (CW) ones, because CW excitations limit the measurement to linear absorption processes [J. Opt. A5, 256 (2003)]. In this work, we present a new and full analytical model for a single-pulsed laser excitation dual-beam mode-mismatched TLS for low absorption solid-state and liquid samples. Our model has been based on a new solution of time-dependent heat equation for a finite-radius cylindrical sample exposed to a single-pulsed excitation laser beam. For low absorbent samples, unlike previous models, all aberration terms associated in the thermal lens were taken into account in Fresnel integration. Besides, the model provides a full analytical mathematical expression for the temperature rise, normalized signal intensity, and Z-scan photothermal lens signal. The model was confirmed with experimental data of distilled deionized water with excellent agreement. Therefore, the model allows us to extract thermo-optical properties of samples in an analytical and more accurate way.

  1. Synergistic effect of nanoclay and EPR-g-MA on the properties of nylon6/EPR blends.

    Science.gov (United States)

    Mallick, Sumana; Das, Tanya; Das, C K; Khatua, B B

    2009-05-01

    The effect of EPR-g-MA, nanoclay and a combination of the two on phase morphology and properties of (70/30 w/w) nylon6/EPR blends prepared by melt processing technique has been studied. We found that the number average domain diameter (D(n)) of the dispersed EPR phase in the blend decreased in presence of EPR-g-MA, and clay. This observation indicated that nanoclay could be used as an effective compatibilizer in nylon6/EPR blend. X-ray diffraction study and TEM analysis of the blend/clay nanocomposites revealed the delaminated clay morphology and preferential location of the exfoliated clay platelets in nylon6 phase. Thus, selective dispersion of the clay platelets with delaminated morphology in the matrix phase acted as the barrier and thereby prevented the coalescence of dispersed EPR domains during melt processing. However, addition of nanoclay in the blend did not improve the impact property of the blend. Interestingly, the impact strength of the nylon6/EPR/EPR-g-MA/clay blend was much higher than the nylon6/EPR/EPR-g-MA and nylon6/EPR/clay blends at certain compositions with comparable D(n) values. This could be explained by assuming the presence of delaminated clay platelets at the interface, which were stiffer than the polymers. Hence, the bending energy of the interfaces was high.

  2. EPR in characterization of seeds paramagnetic species

    Energy Technology Data Exchange (ETDEWEB)

    Luiz, A.P.C.; Mauro, M.F.F.L.; Portugal, K.O.; Barbana, V.M.; Guedes, C.L.B.; Mauro, E. di; Carneiro, C.E.A.; Zaia, D.A.M.; Prete, C.E.C. [Universidade Estadual de Londrina (UEL), PR (Brazil)

    2011-07-01

    Full text. In Brazil, since 1970s, renewable fuel programs has been developed in order to replace petroleum. Today a program that has been discussed is the bio diesel, which intend to replace diesel fuel, fossil oil, to bio diesel, renewal fuel. As seeds are the basis for production of oil and consequently processed into bio diesel, the goal of this work is to characterize and compare paramagnetic species present in the seeds by Electron Paramagnetic Resonance (EPR). Samples used in this study were seeds of sorghum, barley, corn, peanuts, soy beans, cotton, wheat, oats, mustard, rice, sunflower and turnip. Some paramagnetic species present in soil was also investigated as goethite (FeOOH), hematite (Fe{sub 2}O{sub 3}), magnetite (Fe{sub 3}O{sub 4}), and ferrihydrite (Fe{sub 5}HO{sub 8} {center_dot} 4H{sub 2}O), since, these species present in appreciable quantities in the soil can be present in the seeds and analyzed for comparison. The characterization of these species is essential to understand the EPR seeds spectra. Each sample is placed in a thin quartz tube 4 mm in diameter, and it is inserted into the cavity of the spectrometer at room temperature, at low temperature (77 K) and variable temperature using liquid nitrogen flow and hot flow through a compressor air. It was used as standard Mg O:Mn{sup 2+}, which is also inserted into the cavity. Shortly after the potency is regulated, frequency, amplitude and sweep the field. The spectroscopic analysis by EPR X-band ({approx} 9:5GHz), were performed at the Fluorescence and Electron Paramagnetic Resonance Laboratory, Exact Sciences Center, State University of Londrina, Parana state, Brazil, through an EPR spectrometer JEOL brand (JES-PE-3X). In the EPR spectra, spectroscopic factor or g factor and line width were determined in paramagnetic species. Studies from several seeds with EPR technique detected in all of them presence of same complex of Fe{sup 3+} present in the goethite at g {approx} 2, and in the seeds

  3. Effect of a C298D Mutation in CaHydA [FeFe]-Hydrogenase: Insights into the Protein-Metal Cluster Interaction by EPR and FTIR Spectroscopic Investigation

    Energy Technology Data Exchange (ETDEWEB)

    Morra, Simone; Maurelli, Sara; Chiesa, Mario; Mulder, David W.; Ratzloff, Michael W.; Giamello, Elio; King, Paul W.; Gilardi, Gianfranco; Valettia, Francesca

    2016-01-01

    A conserved cysteine located in the signature motif of the catalytic center (H-cluster) of [FeFe]-hydrogenases functions in proton transfer. This residue corresponds to C298 in Clostridium acetobutylicum CaHydA. Despite the chemical and structural difference, the mutant C298D retains fast catalytic activity, while replacement with any other amino acid caused significant activity loss. Given the proximity of C298 to the H-cluster, the effect of the C298D mutation on the catalytic center was studied by continuous wave (CW) and pulse electron paramagnetic resonance (EPR) and by Fourier transform infrared (FTIR) spectroscopies. Comparison of the C298D mutant with the wild type CaHydA by CW and pulse EPR showed that the electronic structure of the center is not altered. FTIR spectroscopy confirmed that absorption peak values observed in the mutant are virtually identical to those observed in the wild type, indicating that the H-cluster is not generally affected by the mutation. Significant differences were observed only in the inhibited state Hox-CO: the vibrational modes assigned to the COexo and Fed-CO in this state are shifted to lower values in C298D, suggesting different interaction of these ligands with the protein moiety when C298 is changed to D298. More relevant to the catalytic cycle, the redox equilibrium between the Hox and Hred states is modified by the mutation, causing a prevalence of the oxidized state. This work highlights how the interactions between the protein environment and the H-cluster, a dynamic closely interconnected system, can be engineered and studied in the perspective of designing bio-inspired catalysts and mimics.

  4. (55)Mn pulsed ENDOR spectroscopy of Mn(2+) ions in ZnO thin films and single crystal.

    Science.gov (United States)

    Böttcher, Rolf; Pöppl, Andreas; Lorenz, Michael; Friedländer, Stefan; Spemann, Daniel; Grundmann, Marius

    2014-08-01

    (55)Mn pulsed electron nuclear double resonance (ENDOR) experiments were performed at X-band on high spin S=5/2 Mn(2+) ions incorporated at zinc lattice sites in heteroepitaxial ZnO thin films. The films have been prepared by pulsed laser deposition and the manganese ions were doped during the growth process. We examine how the c/a lattice axes ratio of the ZnO films influences the (55)Mn hyperfine (hf) and nuclear quadrupole (nq) coupling parameters of the Mn(2+) probe ions. The results are compared with those obtained for Mn(2+) ions present as impurities in ZnO single crystals and revealed that the (55)Mn nq coupling monitors sensitively the structural distortions in the bonding environment of the Mn(2+) ions. The experiments provided the full axially symmetric (55)Mn hf and nq interaction tensors. The latter is found to be very sensitive to small axial distortions of the MnO4 tetrahedrons. In particular, the (55)Mn pulsed ENDOR spectra of the ZnO:Mn thin films are strongly subjected to strain effects in the nq coupling parameter indicating a variation of the local structural parameters for the heteroepitaxial films. In the analysis of the (55)Mn pulsed ENDOR spectra the axial and cubic zero field splitting of the Mn(2+) ions was taken into account and intensity effects in the ENDOR spectra due to the zero field splitting effects were discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

  5. Bulk measurement of copper and sodium content in CuIn(0.7)Ga(0.3)Se(2) (CIGS) solar cells with nanosecond pulse length laser induced breakdown spectroscopy (LIBS)

    CERN Document Server

    Kowalczyk, Jeremy M D; DeAngelis, Alexander; Kaneshiro, Jess; Mallory, Stewart A; Chang, Yuancheng; Gaillard, Nicolas

    2013-01-01

    In this work, we show that laser induced breakdown spectroscopy (LIBS) with a nanosecond pulse laser can be used to measure the copper and sodium content of CuIn(0.7)Ga(0.3)Se(2) (CIGS) thin film solar cells on molybdenum. This method has four significant advantages over methods currently being employed: the method is inexpensive, measurements can be taken in times on the order of one second, without high vacuum, and at distances up to 5 meters or more. The final two points allow for in-line monitoring of device fabrication in laboratory or industrial environments. Specifically, we report a linear relationship between the copper and sodium spectral lines from LIBS and the atomic fraction of copper and sodium measured via secondary ion mass spectroscopy (SIMS), discuss the ablation process of this material with a nanosecond pulse laser compared to shorter pulse duration lasers, and examine the depth resolution of nanosecond pulse LIBS.

  6. Holographic EPR Pairs, Wormholes and Radiation

    CERN Document Server

    Chernicoff, Mariano; Pedraza, Juan F

    2013-01-01

    As evidence for the ER=EPR conjecture, it has recently been observed that the string that is holographically dual to an entangled quark-antiquark pair separating with (asymptotically) uniform acceleration has a wormhole on its worldsheet. We point out that a two-sided horizon and a wormhole actually appear for much more generic quark-antiquark trajectories, which is consistent with the fact that the members of an EPR pair need not be permanently out of causal contact. The feature that determines whether the causal structure of the string worldsheet is trivial or not turns out to be the emission of gluonic radiation by the dual quark and antiquark. In the strongly-coupled gauge theory, it is only when radiation is emitted that one obtains an unambiguous separation of the pair into entangled subsystems, and this is what is reflected on the gravity side by the existence of the worldsheet horizon.

  7. EPR-dosimetry with carious teeth

    Energy Technology Data Exchange (ETDEWEB)

    Sholom, S.V. E-mail: sholom@leed1.kiev.ua; Haskell, E.H.; Hayes, R.B.; Chumak, V.V.; Kenner, G.H

    2000-12-15

    The effect of caries in EPR dosimetry of tooth enamel (in the dose range of 0-1 Gy) was investigated. The enamel of each tooth was divided into carious, non-carious and intermediate portions. The EPR signals of enamel at g=2.0018 (dosimetric) and g=2.0045 (native) were examined. The intensity of the dosimetric signal was the same for all three portions, while that of the native signal was higher for carious portions than for non-carious and intermediate portions. Reconstruction of the laboratory applied doses was done using all portions. Reasonable correlation between nominal and reconstructed doses was found in most cases. The effect of alkali treatment on the native and dosimetric signals of enamel was also tested. Reduction of the native signal intensity, particularly in the carious portions, was found to be the only significant effect. This resulted in a slight improvement in the accuracy of the reconstructed doses.

  8. Self-testing through EPR-steering

    Science.gov (United States)

    Šupić, Ivan; Hoban, Matty J.

    2016-07-01

    The verification of quantum devices is an important aspect of quantum information, especially with the emergence of more advanced experimental implementations of quantum computation and secure communication. Within this, the theory of device-independent robust self-testing via Bell tests has reached a level of maturity now that many quantum states and measurements can be verified without direct access to the quantum systems: interaction with the devices is solely classical. However, the requirements for this robust level of verification are daunting and require high levels of experimental accuracy. In this paper we discuss the possibility of self-testing where we only have direct access to one part of the quantum device. This motivates the study of self-testing via EPR-steering, an intermediate form of entanglement verification between full state tomography and Bell tests. Quantum non-locality implies EPR-steering so results in the former can apply in the latter, but we ask what advantages may be gleaned from the latter over the former given that one can do partial state tomography? We show that in the case of self-testing a maximally entangled two-qubit state, or ebit, EPR-steering allows for simpler analysis and better error tolerance than in the case of full device-independence. On the other hand, this improvement is only a constant improvement and (up to constants) is the best one can hope for. Finally, we indicate that the main advantage in self-testing based on EPR-steering could be in the case of self-testing multi-partite quantum states and measurements. For example, it may be easier to establish a tensor product structure for a particular party’s Hilbert space even if we do not have access to their part of the global quantum system.

  9. Cytochrome c-554 from Methylosinus trichosporium OB3b; a protein that belongs to the cytochrome c2 family and exhibits a HALS-Type EPR signal.

    Directory of Open Access Journals (Sweden)

    Espen Harbitz

    Full Text Available A small soluble cytochrome c-554 purified from Methylosinus trichosporium OB3b has been purified and analyzed by amino acid sequencing, mass spectrometry, visible, CD and EPR spectroscopies. It is found to be a mono heme protein with a characteristic cytochrome c fold, thus fitting into the class of cytochrome c(2, which is the bacterial homologue of mitochondrial cytochrome c. The heme iron has a Histidine/Methionine axial ligation and exhibits a highly anisotropic/axial low spin (HALS EPR signal, with a g(max at 3.40, and ligand field parameters V/ξ = 0.99, Δ/ξ = 4.57. This gives the rhombicity V/Δ = 0.22. The structural basis for this HALS EPR signal in Histidine/Methionine ligated hemes is not resolved. The ligand field parameters observed for cytochrome c-554 fits the observed pattern for other cytochromes with similar ligation and EPR behaviour.

  10. EPR studies of free radicals decay and survival in gamma irradiated aminoglycoside antibiotics: sisomicin, tobramycin and paromomycin.

    Science.gov (United States)

    Wilczyński, Sławomir; Pilawa, Barbara; Koprowski, Robert; Wróbel, Zygmunt; Ptaszkiewicz, Marta; Swakoń, Jan; Olko, Paweł

    2012-02-14

    Radiation sterilization technology is more actively used now that any time because of its many advantages. Gamma radiation has high penetrating power, relatively low chemical reactivity and causes small temperature rise. But on the other hand radiosterilization can lead to radiolytic products appearing, in example free radicals. Free radicals in radiative sterilized sisomicin, tobramycin and paromomycin were studied by electron paramagnetic resonance (EPR) spectroscopy. Dose of gamma irradiation of 25kGy was used. Concentrations and properties of free radicals in irradiated antibiotics were studied. EPR spectra were recorded for samples stored in air and argon. For gamma irradiated antibiotics strong EPR lines were recorded. One- and two-exponential functions were fitted to experimental points during testing and researching of time influence of the antibiotics storage to studied parameters of EPR lines. Our study of free radicals in radiosterilized antibiotics indicates the need for characterization of medicinal substances prior to sterilization process using EPR values. We propose the concentration of free radicals and other spectroscopic parameters as useful factors to select the optimal type of sterilization for the individual drug. The important parameters are i.a. the τ time constants and K constants of exponential functions. Time constants τ give us information about the speed of free radicals concentration decrease in radiated medicinal substances. The constant K(0) shows the free radicals concentration in irradiated medicament after long time of storage.

  11. Time resolved study of the emission enhancement mechanisms in orthogonal double-pulse laser-induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sanginés, R., E-mail: roberto.sangines@ccadet.unam.mx; Sobral, H.

    2013-10-01

    The evolution of laser induced ablation plume on aluminum targets has been investigated in orthogonal pre-ablation double pulse scheme at atmospheric pressure from the earliest stages of plasma evolution. Time-resolved emission spectra from neutrals, singly- and doubly-ionized species obtained with the double pulse experiment have been compared with those from the single pulse configuration. Signal-to-noise enhancement reaches values of up to 15 depending on the analyzed species; and the lower the charge state the later its maximum signal-to-noise ratio is reached. Ablation plume dynamics was monitored from 10 ns after the plasma onset via shadowgraphy and fast-photography with narrow interference filters to follow the evolution of individual species. Results show that ionic species from the target are located at the plasma core while nitrogen from the background air is found at the plume peripheral. Initially both configurations exhibit similar ablation plume sizes and their expansions were successfully fitted with the strong explosion model for the first 500 ns. At later times a good agreement was obtained by using the drag model, which predicts that the plume expansion eventually stops due to interaction with the background gas particles. The emission enhancement measured in the double pulse scheme is discussed in terms of the models describing the plume dynamics. - Highlights: • Production of 2 + ions at the earliest stages of plasma evolution • The higher the charge state the inner the location within the ablation plume. • The expansion rate of the second (ablation) plume was measured. • Shock and drag models successfully fit the ablation shock front expansion.

  12. Spin-resolved photoelectron spectroscopy using femtosecond extreme ultraviolet light pulses from high-order harmonic generation

    Science.gov (United States)

    Plötzing, M.; Adam, R.; Weier, C.; Plucinski, L.; Eich, S.; Emmerich, S.; Rollinger, M.; Aeschlimann, M.; Mathias, S.; Schneider, C. M.

    2016-04-01

    The fundamental mechanism responsible for optically induced magnetization dynamics in ferromagnetic thin films has been under intense debate since almost two decades. Currently, numerous competing theoretical models are in strong need for a decisive experimental confirmation such as monitoring the triggered changes in the spin-dependent band structure on ultrashort time scales. Our approach explores the possibility of observing femtosecond band structure dynamics by giving access to extended parts of the Brillouin zone in a simultaneously time-, energy- and spin-resolved photoemission experiment. For this purpose, our setup uses a state-of-the-art, highly efficient spin detector and ultrashort, extreme ultraviolet light pulses created by laser-based high-order harmonic generation. In this paper, we present the setup and first spin-resolved spectra obtained with our experiment within an acquisition time short enough to allow pump-probe studies. Further, we characterize the influence of the excitation with femtosecond extreme ultraviolet pulses by comparing the results with data acquired using a continuous wave light source with similar photon energy. In addition, changes in the spectra induced by vacuum space-charge effects due to both the extreme ultraviolet probe- and near-infrared pump-pulses are studied by analyzing the resulting spectral distortions. The combination of energy resolution and electron count rate achieved in our setup confirms its suitability for spin-resolved studies of the band structure on ultrashort time scales.

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

    Science.gov (United States)

    Panagiota, Stathi; Louloudi, Maria; Deligiannakis, Yiannis

    2009-04-01

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

  14. Crystal Structure and EPR Spectra of cis-Dioxo-molybdenum(Ⅴ) Complex with o-Aminophenol

    Institute of Scientific and Technical Information of China (English)

    LU,Xiao-Ming(鲁晓明); LU,Jing-Fen(卢景芬); MAO,Xi-An(毛希安)

    2002-01-01

    The paramagnetic cis-dioxo-molybdenum(V) complex,[NH2CH2CH2NH3]3[HNC6H4O)2] was obtained by the reaction of tetra-butyl ammonium β-octamolybdate with oaminophenol and ethylenediamine in the mixed solvent of CH3OH and CH3CN, and characterized by IR,NMR,EPR spectroscopy and X-ray diffraction analysis .The determination of single crystal X-ray analysis revealed octahedral coordination withcis-dioxo o-aminophenol.The EPR spectra of both the complex and flavoenzyme show similarly.Thus it suggests that the complex anion[MovO2(HNC6H49)2]3-and flavoenzyme have related structure feature.

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

    Science.gov (United States)

    Beshir, W. B.

    2014-03-01

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

  16. DAC-board based X-band EPR spectrometer with arbitrary waveform control.

    Science.gov (United States)

    Kaufmann, Thomas; Keller, Timothy J; Franck, John M; Barnes, Ryan P; Glaser, Steffen J; Martinis, John M; Han, Songi

    2013-10-01

    We present arbitrary control over a homogenous spin system, demonstrated on a simple, home-built, electron paramagnetic resonance (EPR) spectrometer operating at 8-10 GHz (X-band) and controlled by a 1 GHz arbitrary waveform generator (AWG) with 42 dB (i.e. 14-bit) of dynamic range. Such a spectrometer can be relatively easily built from a single DAC (digital to analog converter) board with a modest number of stock components and offers powerful capabilities for automated digital calibration and correction routines that allow it to generate shaped X-band pulses with precise amplitude and phase control. It can precisely tailor the excitation profiles "seen" by the spins in the microwave resonator, based on feedback calibration with experimental input. We demonstrate the capability to generate a variety of pulse shapes, including rectangular, triangular, Gaussian, sinc, and adiabatic rapid passage waveforms. We then show how one can precisely compensate for the distortion and broadening caused by transmission into the microwave cavity in order to optimize corrected waveforms that are distinctly different from the initial, uncorrected waveforms. Specifically, we exploit a narrow EPR signal whose width is finer than the features of any distortions in order to map out the response to a short pulse, which, in turn, yields the precise transfer function of the spectrometer system. This transfer function is found to be consistent for all pulse shapes in the linear response regime. In addition to allowing precise waveform shaping capabilities, the spectrometer presented here offers complete digital control and calibration of the spectrometer that allows one to phase cycle the pulse phase with 0.007° resolution and to specify the inter-pulse delays and pulse durations to ≤ 250 ps resolution. The implications and potential applications of these capabilities will be discussed.

  17. Kinetics of the addition reaction of methyl radicals with nitric oxide studied by pulse radiolysis combined with infrared diode laser spectroscopy

    DEFF Research Database (Denmark)

    Jodkowski, J.T.; Ratajczak, E.; Sillesen, A.

    1993-01-01

    The reaction CH3 + NO (+ M) --> CH3NO ( + M) was initiated by pulse radiolysis of acetone/nitric oxide mixtures and the kinetics of methyl radicals was studied by time-resolved infrared absorption spectroscopy. The rate constant was found to be strongly pressure dependent in the range of p (M) = 6.......5-150 mbar at 298 K with M = acetone as the third body. The experimental results are represented in terms of a fall-off curve centered at 37 mbar with limiting high- and low-pressure rate constants of k(rec,infinity) = (6.6 +/- 0.9) x 10(9) x (T/300)0.6 M-1 s-1 and k(rec,0)/[M] = (4.4 +/- 0.4) x 10(12) x (T...

  18. Determination of chlorine, sulfur and carbon in reinforced concrete structures by double-pulse laser-induced breakdown spectroscopy

    Science.gov (United States)

    Labutin, Timur A.; Popov, Andrey M.; Zaytsev, Sergey M.; Zorov, Nikita B.; Belkov, Mikhail V.; Kiris, Vasilii V.; Raikov, Sergey N.

    2014-09-01

    Accurate and reliable quantitative determination of non-metal corrosion agents in concrete is still an actual task of analytical use of LIBS. Two double-pulse LIBS systems were tested as a tool for the determination of chlorine, sulfur and carbon in concretes. Both systems had collinear configuration; a laboratory setup was equipped with an ICCD and two lasers (355/532 nm + 540 nm), but a CCD was a detector for a mobile system with one laser (1064 nm). Analytical lines of Cl I at 837.59 nm, S I at 921 nm and C I at 247.86 nm were used to plot calibration curves. Optimal interpulse delays for the laboratory setup were 4 μs for chlorine and 2.8 μs for carbon, while an interpulse delay of 2 μs was optimal for chlorine and sulfur determination with the mobile system. We suggested the normalization of the Cl I line at 837.59 nm to the Mg II line at 279.08 nm (visible at 837.23 nm in the third order) to compensate for pulse-to-pulse fluctuations of chlorine lines. It provided the decrease of the detection limit of chlorine from 400 ppm to 50 ppm. Therefore, we reported that LIBS can be used to determine main corrosive active substances under ambient conditions in concrete below critical threshold values. Moreover, the application of the mobile system for in-situ qualitative assessment of corrosion way of a steel cage of a swimming pool dome was also demonstrated. It was found that chloride corrosion due to the disinfection of water was the main way for corrosion of the open part steel and the steel rebar inside the concrete.

  19. Determination of chlorine, sulfur and carbon in reinforced concrete structures by double-pulse laser-induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Labutin, Timur A., E-mail: timurla@laser.chem.msu.ru [Lomonosov Moscow State University, Department of Chemistry, Leninskie Gory 1-3, Moscow 119991 (Russian Federation); Popov, Andrey M.; Zaytsev, Sergey M.; Zorov, Nikita B. [Lomonosov Moscow State University, Department of Chemistry, Leninskie Gory 1-3, Moscow 119991 (Russian Federation); Belkov, Mikhail V.; Kiris, Vasilii V.; Raikov, Sergey N. [B.I. Stepanov Institute of Physics, Nezavisimosti Ave. 68, Minsk 220072 (Belarus)

    2014-09-01

    Accurate and reliable quantitative determination of non-metal corrosion agents in concrete is still an actual task of analytical use of LIBS. Two double-pulse LIBS systems were tested as a tool for the determination of chlorine, sulfur and carbon in concretes. Both systems had collinear configuration; a laboratory setup was equipped with an ICCD and two lasers (355/532 nm + 540 nm), but a CCD was a detector for a mobile system with one laser (1064 nm). Analytical lines of Cl I at 837.59 nm, S I at 921 nm and C I at 247.86 nm were used to plot calibration curves. Optimal interpulse delays for the laboratory setup were 4 μs for chlorine and 2.8 μs for carbon, while an interpulse delay of 2 μs was optimal for chlorine and sulfur determination with the mobile system. We suggested the normalization of the Cl I line at 837.59 nm to the Mg II line at 279.08 nm (visible at 837.23 nm in the third order) to compensate for pulse-to-pulse fluctuations of chlorine lines. It provided the decrease of the detection limit of chlorine from 400 ppm to 50 ppm. Therefore, we reported that LIBS can be used to determine main corrosive active substances under ambient conditions in concrete below critical threshold values. Moreover, the application of the mobile system for in-situ qualitative assessment of corrosion way of a steel cage of a swimming pool dome was also demonstrated. It was found that chloride corrosion due to the disinfection of water was the main way for corrosion of the open part steel and the steel rebar inside the concrete. - Highlights: • Determination of chlorine, sulfur and carbon in concrete in the air. • Comparison of mobile and laboratory LIBS systems. • LOD by double-pulse LIBS under ambient conditions: for sulfur 1500 ppm, for chlorine — 50 ppm. • Background level of carbon content in concrete is about 0.27% wt.

  20. Cavity-enhanced absorption spectroscopy with a ps-pulsed UV laser for sensitive, high-speed measurements in a shock tube.

    Science.gov (United States)

    Wang, Shengkai; Sun, Kai; Davidson, David F; Jeffries, Jay B; Hanson, Ronald K

    2016-01-11

    We report the first application of cavity-enhanced absorption spectroscopy (CEAS) with a ps-pulsed UV laser for sensitive and rapid gaseous species time-history measurements in a transient environment (in this study, a shock tube). The broadband nature of the ps pulses enabled instantaneous coupling of the laser beam into roughly a thousand cavity modes, which grants excellent immunity to laser-cavity coupling noise in environments with heavy vibrations, even with an on-axis alignment. In this proof-of-concept experiment, we demonstrated an absorption gain of 49, which improved the minimum detectable absorbance by ~20 compared to the conventional single-pass strategy at similar experimental conditions. For absorption measurements behind reflected shock waves, an effective time-resolution of ~2 μs was achieved, which enabled time-resolved observations of transient phenomena, such as the vibrational relaxation of O(2) demonstrated here. The substantial improvement in detection sensitivity, together with microsecond measurement resolution implies excellent potential for studies of transient physical and chemical processes in nonequilibrium situations, particularly via measurements of weak absorptions of trace species in dilute reactive systems.

  1. Double pulse laser induced breakdown spectroscopy: A potential tool for the analysis of contaminants and macro/micronutrients in organic mineral fertilizers.

    Science.gov (United States)

    Nicolodelli, Gustavo; Senesi, Giorgio Saverio; de Oliveira Perazzoli, Ivan Luiz; Marangoni, Bruno Spolon; De Melo Benites, Vinícius; Milori, Débora Marcondes Bastos Pereira

    2016-09-15

    Organic fertilizers are obtained from waste of plant or animal origin. One of the advantages of organic fertilizers is that, from the composting, it recycles waste-organic of urban and agriculture origin, whose disposal would cause environmental impacts. Fast and accurate analysis of both major and minor/trace elements contained in organic mineral and inorganic fertilizers of new generation have promoted the application of modern analytical techniques. In particular, laser induced breakdown spectroscopy (LIBS) is showing to be a very promising, quick and practical technique to detect and measure contaminants and nutrients in fertilizers. Although, this technique presents some limitations, such as a low sensitivity, if compared to other spectroscopic techniques, the use of double pulse (DP) LIBS is an alternative to the conventional LIBS in single pulse (SP). The macronutrients (Ca, Mg, K, P), micronutrients (Cu, Fe, Na, Mn, Zn) and contaminant (Cr) in fertilizer using LIBS in SP and DP configurations were evaluated. A comparative study for both configurations was performed using optimized key parameters for improving LIBS performance. The limit of detection (LOD) values obtained by DP LIBS increased up to seven times as compared to SP LIBS. In general, the marked improvement obtained when using DP system in the simultaneous LIBS quantitative determination for fertilizers analysis could be ascribed to the larger ablated mass of the sample. The results presented in this study show the promising potential of the DP LIBS technique for a qualitative analysis in fertilizers, without requiring sample preparation with chemical reagents.

  2. Laser-induced breakdown spectroscopy analysis of solids using a long-pulse (150 ns) Q-switched Nd:YAG laser.

    Science.gov (United States)

    Yamamoto, Karen Y; Cremers, David A; Foster, Leeann E; Davies, Mathew P; Harris, Ronny D

    2005-09-01

    Laser-induced breakdown spectroscopy (LIBS) measurements are typically carried out using pulses (50 mJ) from a flashlamp-pumped electro-optically Q-switched Nd:YAG laser (EO-laser) or excimer laser. Here we report LIBS analyses of solids using an acousto-optically Q-switched Nd:YAG laser (AO-laser) producing 150 ns pulses of lower energy (10 mJ) at repetition rates up to 6 kHz. The high repetition rate allows increased spatial or depth sampling over a given time period compared to the EO-laser. Results of AO-laser based LIBS analysis of (1) steels, (2) soils, and (3) surface stains and dusts are described. Detection limits for Cr, Cu, Mn, Ni, and Si in steel ranged from 0.11 to 0.24% using a commercial polychromator-based detection system with limits 4--30 times lower achieved using a laboratory-based detection system. The minimum detectable masses of Ba, Cr, Mn, and Sr on a metal surface were estimated with 1.2 pg/shot achieved for Sr. Detection limits for Ba and Sr in soil were 296 and 52 ppm, respectively. The temperatures, spectra, and emission decay curves from plasmas generated by the AO- and EO-lasers are compared and some characteristics of particles ablated by the AO-laser are described.

  3. Double-pulse laser induced breakdown spectroscopy with ambient gas in the vacuum ultraviolet: Optimization of parameters for detection of carbon and sulfur in steel

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, X., E-mail: xi.jiang2@mail.dcu.ie [School of Physical Sciences, Dublin City University, Dublin (Ireland); National Centre for Plasma Science and Technology, Dublin City University, Dublin (Ireland); Hayden, P. [School of Physics, Atomic, Molecular and Plasma Spectroscopy Group, University College Dublin, Dublin (Ireland); Costello, J.T.; Kennedy, E.T. [School of Physical Sciences, Dublin City University, Dublin (Ireland); National Centre for Plasma Science and Technology, Dublin City University, Dublin (Ireland)

    2014-11-01

    Laser induced breakdown spectroscopy (LIBS) in the vacuum ultraviolet (VUV) has been applied to calibrated steel samples for the low concentration level detection of the light elements, carbon and sulfur in steel. Experimental optimization parameters, aimed at enhancing the sensitivity of the technique, included short wavelength spectral detection, double-pulse (DP) operation, variable focusing conditions and different ambient environments in terms of gas type and pressure. Two lasers were employed respectively as an ablation laser (Spectron: 1.06 μm/200 mJ/15 ns) and a reheating laser (Surelite: 1.06 μm/665 mJ/6 ns) in a collinear geometry. The results include insight into the most salient experimental variables and limits of detection in the parts per million range. - Highlights: • First overall optimization of TISR-LIBS in the deep VUV • First combination of double pulse VUV emission with low pressure ambient gas • The influence of each parameter on the plasm emission • Improvement of LOD for C and S in steel with optimized parameters.

  4. EPR study on gamma-irradiated fruits dehydrated via osmosis

    Energy Technology Data Exchange (ETDEWEB)

    Yordanov, N.D. [Laboratory EPR, Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)]. E-mail: ndyepr@bas.bg; Aleksieva, K. [Laboratory EPR, Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)

    2007-06-15

    The shape and time stability of the electron paramagnetic resonance (EPR) spectra of non- and {gamma}-irradiated papaya, melon, cherry and fig samples dehydrated via osmosis are reported. It is shown that non-irradiated samples are generally EPR silent whereas {gamma}-irradiated exhibit 'sugar-like' EPR spectra. The recorded EPR spectra are monitored for a period of 7 months after irradiation (stored at low humidity and in the dark). The results suggest longer period of unambiguous identification of the radiation processing of osmose dehydrated fruits. Therefore, the Protocol EN 13708,2001 issued by CEN is fully applicable for the studied fruit samples.

  5. Fs–ns double-pulse Laser Induced Breakdown Spectroscopy of copper-based-alloys: Generation and elemental analysis of nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Guarnaccio, A.; Parisi, G.P.; Mollica, D. [CNR-ISM, U.O.S. Tito Scalo, Zona Industriale, 85050 Tito Scalo, PZ (Italy); De Bonis, A. [CNR-ISM, U.O.S. Tito Scalo, Zona Industriale, 85050 Tito Scalo, PZ (Italy); Dipartimento di Scienze, Università degli Studi della Basilicata, Via dell' Ateneo Lucano 10, 85100 Potenza (Italy); Teghil, R. [Dipartimento di Scienze, Università degli Studi della Basilicata, Via dell' Ateneo Lucano 10, 85100 Potenza (Italy); Santagata, A. [CNR-ISM, U.O.S. Tito Scalo, Zona Industriale, 85050 Tito Scalo, PZ (Italy)

    2014-11-01

    Evolution of nanoparticles ejected during ultra-short (250 fs) laser ablation of certified copper alloys and relative calibration plots of a fs–ns double-pulse Laser Induced Breakdown Spectroscopy orthogonal configuration is presented. All work was performed in air at atmospheric pressure using certified copper-based-alloy samples irradiated by a fs laser beam and followed by a delayed perpendicular ns laser pulse. In order to evaluate possible compositional changes of the fs induced nanoparticles, it was necessary to consider, for all samples used, comparable features of the detected species. With this purpose the induced nanoparticles black-body-like emission evolution and their relative temperature decay have been studied. These data were exploited for defining the distance between the target surface and the successive ns laser beam to be used. The consequent calibration plots of minor constituents (i.e. Sn, Pb and Zn) of the certified copper-based-alloy samples have been reported by taking into account self-absorption effects. The resulting linear regression coefficients suggest that the method used, for monitoring and ruling the fs laser induced nanoparticles, could provide a valuable approach for establishing the occurrence of potential compositional changes of the detected species. All experimental data reveal that the fs laser induced nanoparticles can be used for providing a coherent composition of the starting target. In the meantime, the fs–ns double-pulse Laser Induced Breakdown Spectroscopy orthogonal configuration here used can be considered as an efficient technique for compositional determination of the nanoparticles ejected during ultra-short laser ablation processes. - Highlights: • Laser induced NP continuum black-body-like emission was used for T determination. • Invariable composition of generated NPs was assumed in the range of 20 μs. • Fs-ns DP-LIBS was employed for the compositional characterization of NPs. • NPs obtained by fs

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

    Science.gov (United States)

    Nakagawa, Kouichi; Epel, Boris

    2014-10-01

    In this study, noninvasive 9 GHz electron paramagnetic resonance (EPR)-imaging and continuous wave (CW) EPR were used to investigate the locations of paramagnetic species in black pepper seeds without further irradiation. First, lithium phthalocyanine (LiPC) phantom was used to examine 9 GHz EPR imaging capabilities. The 9 GHz EPR-imager easily resolved the LiPC samples at a distance of ∼2 mm. Then, commercially available black pepper seeds were measured. We observed signatures from three different radical species, which were assigned to stable organic radicals, Fe3+, and Mn2+ complexes. In addition, no EPR spectral change in the seed was observed after it was submerged in distilled H2O for 1 h. The EPR and spectral-spatial EPR imaging results suggested that the three paramagnetic species were mostly located at the seed surface. Fewer radicals were found inside the seed. We demonstrated that the CW EPR and 9 GHz EPR imaging were useful for the determination of the spatial distribution of paramagnetic species in various seeds.

  7. Two-photon excited spectroscopies of ex vivo human skin endogenous species irradiated by femtosecond laser pulses

    Institute of Scientific and Technical Information of China (English)

    Jianxin Chen; Shuangmu Zhuo; Tianshu Luo; Jingjun Zhao

    2006-01-01

    Two-photon excited spectroscopies from ex vivo human skin are investigated by using a femtosecond laser and a confocal microscope (Zeiss LSM 510 META). In the dermis, collagen is responsible for second harmonic generation (SHG); elastin, nicotinamide adenine dinucleotide (NADH), melanin and porphyrin are the primary endogenous sources of two-photon excited autofluorescence. In the epidermis, keratin,NADH, melanin and porphyrins contribute to autofluorescence signals. The results also show that the SHG spectra have the ability to shift with the excitation wavelength and the autofluorescence spectra display a red shift of the spectral peaks when increasing the excitation wavelength. These results may have practical implications for diagnosis of skin diseases.

  8. Two-photon excited spectroscopies of ex vivo human skin endogenous species irradiated by femtosecond laser pulses

    Science.gov (United States)

    Chen, Jianxin; Zhuo, Shuangmu; Luo, Tianshu; Zhao, Jingjun

    2006-10-01

    Two-photon excited spectroscopies from ex vivo human skin are investigated by using a femtosecond laser and a confocal microscope (Zeiss LSM 510 META). In the dermis, collagen is responsible for second harmonic generation (SHG); elastin, nicotinamide adenine dinucleotide (NADH), melanin and porphyrin are the primary endogenous sources of two-photon excited autofluorescence. In the epidermis, keratin, NADH, melanin and porphyrins contribute to autofluorescence signals. The results also show that the SHG spectra have the ability to shift with the excitation wavelength and the autofluorescence spectra display a red shift of the spectral peaks when increasing the excitation wavelength. These results may have practical implications for diagnosis of skin diseases.

  9. Public debate on the EPR reactor; Debat public sur le reacteur EPR

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2005-10-15

    In the framework of the new EPR European Pressurized Reactor implementation in France, the public asked the first Ministry on the protection of nuclear matters, transports and installations against the terrorism and the spiteful actions. This document provides information on the subject and shows the safety of the new reactor. (A.L.B.)

  10. Sistemas de salvaguardia en reactores EPR

    OpenAIRE

    2015-01-01

    En este documento se describe brevemente el funcionamiento de los diversos sistemas de una planta nuclear operada con un reactor de tipo PWR. Más concretamente, el proyecto se centra en una descripción exhaustiva de los sistemas de salvaguardia y seguridad que regulan el funcionamiento de un reactor de tipo EPR, así como la central nuclear que contiene a dicho reactor. El proceso ha consistido en clasificar y resumir los distintos sistemas que operan en dicha planta, estudiando sus caracterís...

  11. Choosing the best pulse sequences, acquisition parameters, postacquisition processing strategies, and probes for natural product structure elucidation by NMR spectroscopy.

    Science.gov (United States)

    Reynolds, William F; Enríquez, Raúl G

    2002-02-01

    The relative merits of different pairs of two-dimensional NMR pulse sequences (COSY-90 vs COSY-45, NOESY vs T-ROESY, HSQC vs HMQC, HMBC vs CIGAR, etc.) are compared and recommendations are made for the preferred choice of sequences for natural product structure elucidation. Similar comparisons are made between different selective 1D sequences and the corresponding 2D sequences. Many users of 2D NMR use longer than necessary relaxation delays and neglect to use forward linear prediction processing. It is shown that using shorter relaxation delays in combination with forward linear prediction allows one to get better resolved spectra in less time. The relative merits of different probes and likely future probe developments are also discussed.

  12. Electronic Properties of Layered Oxides:. Pulsed Laser Deposition of YBCO Films for In-Situ Studies by Photoemission Spectroscopy

    Science.gov (United States)

    Pavuna, D.; Ariosa, D.; Berger, H.; Christensen, S.; Frazer, B.; Gatt, R.; Grioni, M.; Margaritondo, G.; Misra, S.; Onellion, M.; Schmauder, T.; Vobornik, I.; Xi, X.; Zacchigna, M.; Zwick, F.

    Due to imperfect surfaces of most cuprate samples, almost all Photoemission studies in the past decade were performed on Bi2Sr2CaCu2O8+x, even though a large fraction of other studies and electronic applications was reported for YBa2Cu3O7-δ (YBCO) family of superconducting compounds. In order to systematically study the gap parameter and the Fermi surface variation in high symmetry directions of YBCO and related oxide films we have constructed a new facility at the Wisconsin Synchrotron Radiation Center. We use the pulsed laser ablation (PLD) system that is directly linked to the photoemission chamber. In our unique approach, the samples never leave the controlled ambient and we oxidize our films, either by molecular oxygen or by ozone. In this paper, we, summarize some of the most relevant recent results on electronic properties of layered oxides and describe our new facility for the study of YBCO and related oxide films.

  13. EPR identification of intrinsic defects in SiC

    Energy Technology Data Exchange (ETDEWEB)

    Umeda, T.; Mizuochi, N. [University of Tsukuba, Tsukuba 305-8550 (Japan); Son, N.T.; Janzen, E. [Department of Physics, Chemistry and Biology, Linkoeping University, Linkoeping (Sweden); Ohshima, T. [Japan Atomic Energy Agency, Takasaki 370-1292 (Japan); Isoya, J.

    2008-07-15

    The structure determination of intrinsic defects in 4H-SiC, 6H-SiC, and 3C-SiC by means of EPR is based on measuring the angular dependence of the {sup 29}Si/{sup 13}C hyperfine (HF) satellite lines, from which spin densities, sp-hybrid ratio, and p-orbital direction can be determined over major atoms comprising a defect. In most cases, not only the assignment of the variety due to the inequivalent sites (h- and k-sites in 4H-SiC) but also the identification of the defect species is accomplished through the comparison of the obtained HF parameters with those obtained from first principles calculations. Our works of identifying vacancy-related defects such as the monovacancies, divacancies, and antisite-vacancy pairs in 4H-SiC are reviewed. In addition, it is demonstrated that the observation of the central line of the T{sub V2a} center of S=3/2 has been achieved by pulsed-ELDOR. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

    Science.gov (United States)

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

    2015-01-01

    Electron paramagnetic resonance (EPR) Imaging (EPRI) is a robust method for measuring in vivo oxygen concentration (pO2). For 3D pulse EPRI, a commonly used reconstruction algorithm is the filtered backprojection (FBP) algorithm, in which the backprojection process is computationally intensive and may be time consuming when implemented on a CPU. A multistage implementation of the backprojection can be used for acceleration, however it is not flexible (requires equal linear angle projection distribution) and may still be time consuming. In this work, single-stage backprojection is implemented on a GPU (Graphics Processing Units) having 1152 cores to accelerate the process. The GPU implementation results in acceleration by over a factor of 200 overall and by over a factor of 3500 if only the computing time is considered. Some important experiences regarding the implementation of GPU-accelerated backprojection for EPRI are summarized. The resulting accelerated image reconstruction is useful for real-time image reconstruction monitoring and other time sensitive applications.

  15. Determining the Secondary Structure of Membrane Proteins and Peptides Via Electron Spin Echo Envelope Modulation (ESEEM) Spectroscopy

    Science.gov (United States)

    Liu, Lishan; Mayo, Daniel J.; Sahu, Indra D.; Zhou, Andy; Zhang, Rongfu; McCarrick, Robert M.; Lorigan, Gary A.

    2016-01-01

    Revealing detailed structural and dynamic information of membrane embedded or associated proteins is challenging due to their hydrophobic nature which makes NMR and X-ray crystallographic studies challenging or impossible. Electron paramagnetic resonance (EPR) has emerged as a powerful technique to provide essential structural and dynamic information for membrane proteins with no size limitations in membrane systems which mimic their natural lipid bilayer environment. Therefore, tremendous efforts have been devoted toward the development and application of EPR spectroscopic techniques to study the structure of biological systems such as membrane proteins and peptides. This chapter introduces a novel approach established and developed in the Lorigan lab to investigate membrane protein and peptide local secondary structures utilizing the pulsed EPR technique electron spin echo envelope modulation (ESEEM) spectroscopy. Detailed sample preparation strategies in model membrane protein systems and the experimental setup are described. Also, the ability of this approach to identify local secondary structure of membrane proteins and peptides with unprecedented efficiency is demonstrated in model systems. Finally, applications and further developments of this ESEEM approach for probing larger size membrane proteins produced by over-expression systems are discussed. PMID:26477255

  16. Nonselective excitation of pulsed ELDOR using multi-frequency microwaves

    Science.gov (United States)

    Asada, Yuki; Mutoh, Risa; Ishiura, Masahiro; Mino, Hiroyuki

    2011-12-01

    The use of a polychromatic microwave pulse to expand the pumping bandwidth in pulsed electron-electron double resonance (PELDOR) was investigated. The pumping pulse was applied in resonance with the broad (˜100 mT) electron paramagnetic resonance (EPR) signal of the manganese cluster of photosystem II in the S 2 state. The observation pulses were in resonance with the narrow EPR signal of the tyrosine radical, YDrad . It was found that in the case of the polychromatic pumping pulse containing five harmonics with the microwave frequencies between 8.5 and 10.5 GHz the PELDOR effect corresponding to the dipole interaction between the Mn cluster and YDrad was about 2.9 times larger than that achieved with a monochromatic pulse. In addition to the dipolar modulation, the nuclear modulation effects were observed. The effects could be suppressed by averaging the PELDOR trace over the time interval between the observation microwave pulses. The polychromatic excitation technique described will be useful for improving the PELDOR sensitivity in the measurements of long distances in biological samples, where the pair consists of a radical with a narrow EPR spectrum and slow phase relaxation, and a metal center that has a broad EPR spectrum and a short phase relaxation time.

  17. THE RADIATION CROSSLINKING OF EPR/SBR BLEND

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wanxi; L(U) Yingtao; SUN Jiazhen

    1990-01-01

    The radiation crosslinking of EPR/SBR blend has been studied. A relationship between sol fraction and radiation dose for the different weight ratio polymer blends and the method to calculate βb value of EPR/SBR blend system have been established.

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

    Energy Technology Data Exchange (ETDEWEB)

    Aleksieva, K. [Laboratory EPR, Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Georgieva, L.; Tzvetkova, E. [Institute of Cryobiology and Food Technology, 1162 Sofia (Bulgaria); Yordanov, N.D. [Laboratory EPR, Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)], E-mail: ndyepr@bas.bg

    2009-09-15

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

  19. Quantum Encryption Protocol Based on Continuous Variable EPR Correlations

    Institute of Scientific and Technical Information of China (English)

    HE Guang-Qiang; ZENG Gui-Hua

    2006-01-01

    A quantum encryption protocol based on Gaussian-modulated continuous variable EPR correlations is proposed. The security is guaranteed by continuous variable EPR entanglement correlations produced by nondegenerate optical parametric amplifier (NOPA). For general beam splitter eavesdropping strategy, the mutual information Ⅰ(α, ε)between Alice and Eve is calculated by employing Shannon information theory. Finally the security analysis is presented.

  20. Which Parts of a Clinical Process EPR Needs Special Configuration

    DEFF Research Database (Denmark)

    Barlach, Anders; Simonsen, Jesper

    2007-01-01

    Subject: Which parts of an electronic patient record (EPR) can initially form a stable standard solution to be used by all clinicians? And which parts of an EPR can we predict needs initial as well as on-going re-configuration to meet the needs from diverse medical specialties. Purpose: To analyz...

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

    Directory of Open Access Journals (Sweden)

    Udo Kielmann

    2014-02-01

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

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

    Science.gov (United States)

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

    2016-04-01

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

  3. An EPR spin probe study of liposomes from sunflower and soybean phospholipids.

    Science.gov (United States)

    Melnyk, Andrii K; Sukhoveev, Olexandr V; Kononets, Lyudmyla A; Khilchevsky, Olexandr M; Shulga, Serhiy M; Kukhar, Valery P; Vovk, Andriy I

    2016-01-01

    Comparative properties of lecithin-based liposomes prepared from the mixed phospholipids of sunflower seeds, soybean and egg yolk were investigated by electron paramagnetic resonance (EPR) spectroscopy. For these investigations, stable nitroxide radicals, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 5,7-dimethyladamantane-1-carboxylate (DMAC-TEMPO), 5-doxylstearic acid (5-DSA) and 16-doxylstearic acid (16-DSA) were used as spin probes. Binding of the spin probes to the liposome membranes resulted in a substantial increase of the apparent rotational diffusion correlation times. The EPR spectra of the incorporated nitroxides underwent temperature-dependent changes. For every spin probe, values of apparent enthalpy and entropy of activation were calculated from the temperature dependence of rotational diffusion correlation times via Arrhenius equation. In case of DMAC-TEMPO, the data point to differences between the phospholipid bilayer of liposomes derived from sunflower and soy lecithin, and some similarity between the sunflower and egg yolk liposomes. Anisotropic hyperfine interaction constants of DMAC-TEMPO and 16-DSA included in the liposomes have been analyzed and attributed to different micropolarity of the surroundings of the spin probes. The kinetics of EPR signal decay of DMAC-TEMPO in the presence of 2,2'-azobis(2-amidinopropane) suggest the better stability of the sunflower liposomes to lipid peroxidation as compared to the liposomes prepared from soy lecithin.

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

    Science.gov (United States)

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

    2017-01-13

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

  5. Temperature dependent electron paramagnetic resonance (EPR) of SrZrO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Santosh K., E-mail: santufrnd@gmail.com [Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai (India); Pathak, Nimai [Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai (India); Ghosh, P.S. [Materials Science Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Rajeshwari, B. [Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai (India); Materials Science Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Natarajan, V. [Materials Science Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Kadam, R.M. [Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai (India)

    2015-10-01

    SrZrO{sub 3} (SZO), a distorted perovskite was synthesized using gel-combustion route employing citric acid as a fuel and ammonium nitrate as oxidizer followed by characterization using X-ray diffraction (XRD) and electron paramagnetic resonance (EPR). Purity of the sample is confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis. Broadening and shift of the resonance field position in EPR spectrum to the lower field was observed as the temperature is lowered; which is the characteristic of ferromagnetic resonance spectra. The value of Curie–Weiss temperature obtained for SZO particles is 8.7 K. The positive sign of the Curie–Weiss temperature indicates that some of the spins are ferromagnetically coupled in this sample. Theoretical investigation using density functional theory (DFT) calculation revealed that Vacancy at zirconium site contribute maximum to the magnetic moment. - Highlights: • Gel-combustion synthesis of SrZrO{sub 3} perovskite at relatively low temperature. • EPR evidence for ferromagnetic resonance. • Positive sign of the Curie–Weiss temperature ~8.7 K. • Defect induced magnetism- Zirconium vacancy induces maximum magnetic moment.

  6. High resolution pulsed field ionization photoelectron spectroscopy using multibunch synchrotron radiation: Time-of-flight selection scheme

    Energy Technology Data Exchange (ETDEWEB)

    Jarvis, G.K. [Chemical Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Song, Y.; Ng, C.Y. [Ames Laboratory, United States Department of Energy and Department of Chemistry, Iowa State University, Ames, Iowa 50011 (United States)

    1999-06-01

    We have developed an efficient electron time-of-flight (TOF) selection scheme for high resolution pulsed field ionization (PFI) photoelectron (PFI-PE) measurements using monochromatized multibunch undulator synchrotron radiation at the Advanced Light Source. By employing a simple electron TOF spectrometer, we show that PFI-PEs produced by the PFI in the dark gap of a synchrotron ring period can be cleanly separated from prompt background photoelectrons. A near complete suppression of prompt electrons was achieved in PFI-PE measurements by gating the PFI-PE TOF peak, as indicated by monitoring background electron counts at the Ar(11s{sup {prime}}) autoionizing Rydberg peak, which is adjacent to the Ar{sup +}({sup 2}P{sub 3/2}) PFI-PE band. The rotational-resolved PFI-PE band for H{sub 2}{sup +} (X {sup 2}{Sigma}{sub g}{sup +},v{sup +}=0) measured using this electron TOF selection scheme is nearly free from residues of nearby autoionizing features, which were observed in the previous measurement by employing an electron spectrometer equipped with a hemispherical energy analyzer. This comparison indicates that the TOF PFI-PE scheme is significantly more effective in suppressing the hot-electron background. In addition to attaining a high PFI-PE transmission, a major advantage of the electron TOF scheme is that it allows the use of a smaller pulsed electric field and thus results in a higher instrumental PFI-PE resolution. We have demonstrated instrumental resolutions of 1.0 cm{sup {minus}1} full width at half maximum (FWHM) and 1.9 cm{sup {minus}1} FWHM in the PFI-PE bands for Xe{sup +}({sup 2}P{sub 3/2}) and Ar{sup +}({sup 2}P{sub 3/2}) at 12.123 and 15.760 eV, respectively. These resolutions are more than a factor 2 better than those achieved in previous synchrotron based PFI-PE studies. {copyright} {ital 1999 American Institute of Physics.}

  7. Enhancement of laser-induced breakdown spectroscopy (LIBS) Detection limit using a low-pressure and short-pulse laser-induced plasma process.

    Science.gov (United States)

    Wang, Zhen Zhen; Deguchi, Yoshihiro; Kuwahara, Masakazu; Yan, Jun Jie; Liu, Ji Ping

    2013-11-01

    Laser-induced breakdown spectroscopy (LIBS) technology is an appealing technique compared with many other types of elemental analysis because of the fast response, high sensitivity, real-time, and noncontact features. One of the challenging targets of LIBS is the enhancement of the detection limit. In this study, the detection limit of gas-phase LIBS analysis has been improved by controlling the pressure and laser pulse width. In order to verify this method, low-pressure gas plasma was induced using nanosecond and picosecond lasers. The method was applied to the detection of Hg. The emission intensity ratio of the Hg atom to NO (IHg/INO) was analyzed to evaluate the LIBS detection limit because the NO emission (interference signal) was formed during the plasma generation and cooling process of N2 and O2 in the air. It was demonstrated that the enhancement of IHg/INO arose by decreasing the pressure to a few kilopascals, and the IHg/INO of the picosecond breakdown was always much higher than that of the nanosecond breakdown at low buffer gas pressure. Enhancement of IHg/INO increased more than 10 times at 700 Pa using picosecond laser with 35 ps pulse width. The detection limit was enhanced to 0.03 ppm (parts per million). We also saw that the spectra from the center and edge parts of plasma showed different features. Comparing the central spectra with the edge spectra, IHg/INO of the edge spectra was higher than that of the central spectra using the picosecond laser breakdown process.

  8. Double pulse laser induced breakdown spectroscopy of a solid in water: Effect of hydrostatic pressure on laser induced plasma, cavitation bubble and emission spectra

    Science.gov (United States)

    López-Claros, M.; Dell'Aglio, M.; Gaudiuso, R.; Santagata, A.; De Giacomo, A.; Fortes, F. J.; Laserna, J. J.

    2017-07-01

    There is a growing interest in the development of sensors use in exploration of the deep ocean. Techniques for the chemical analysis of submerged solids are of special interest, as they show promise for subsea mining applications where a rapid sorting of materials found in the sea bottom would improve efficiency. Laser-Induced Breakdown Spectroscopy (LIBS) has demonstrated potential for this application thanks to its unique capability of providing the atomic composition of submerged solids. Here we present a study on the parameters that affect the spectral response of metallic targets in an oceanic pressure environment. Following laser excitation of the solid, the plasma persistence and the cavitation bubble size are considerably reduced as the hydrostatic pressure increases. These effects are of particular concern in dual pulse excitation as reported here, where a careful choice of the interpulse timing is required. Shadowgraphic images of the plasma demonstrate that cavitation bubbles are formed early after the plasma onset and that the effect of hydrostatic pressure is negligible during the early stage of plasma expansion. Contrarily to what is observed at atmospheric pressure, emission spectra observed at high pressures are characterized by self-absorbed atomic lines on continuum radiation resulting from strong radiative recombination in the electron-rich confined environment. This effect is much less evident with ionic lines due to the much higher energy of the levels involved and ionization energy of ions, as well as to the lower extent of absorption effects occurring in the inner part of the plasma, where ionized species are more abundant. As a result of the smaller shorter-lived cavitation bubble, the LIBS intensity enhancement resulting from dual pulse excitation is reduced when the applied pressure increases.

  9. High-Frequency Electron Paramagnetic Resonance Spectroscopy of Nitroxide-Functionalized Nanodiamonds in Aqueous Solution.

    Science.gov (United States)

    Akiel, R D; Stepanov, V; Takahashi, S

    2016-06-21

    Nanodiamond (ND) is an attractive class of nanomaterial for fluorescent labeling, magnetic sensing of biological molecules, and targeted drug delivery. Many of those applications require tethering of target biological molecules on the ND surface. Even though many approaches have been developed to attach macromolecules to the ND surface, it remains challenging to characterize dynamics of tethered molecule. Here, we show high-frequency electron paramagnetic resonance (HF EPR) spectroscopy of nitroxide-functionalized NDs. Nitroxide radical is a commonly used spin label to investigate dynamics of biological molecules. In the investigation, we developed a sample holder to overcome water absorption of HF microwave. Then, we demonstrated HF EPR spectroscopy of nitroxide-functionalized NDs in aqueous solution and showed clear spectral distinction of ND and nitroxide EPR signals. Moreover, through EPR spectral analysis, we investigate dynamics of nitroxide radicals on the ND surface. The demonstration sheds light on the use of HF EPR spectroscopy to investigate biological molecule-functionalized nanoparticles.

  10. Effect of UV irradiation on free radicals in synthetic melanin and melanin biopolymer from Sepia officinalis – EPR examination

    Directory of Open Access Journals (Sweden)

    Zdybel Magdalena

    2015-07-01

    Full Text Available Free radicals in synthetic melanin and melanin from Sepia officinalis were studied by electron paramagnetic resonance (EPR spectroscopy. The effect of time of ultraviolet (UV irradiation on free radicals in these melanins was tested. The samples were exposed to UV during 15, 30, and 60 minutes. EPR spectra were measured with microwaves from an X-band (9.3 GHz in the range of microwave power of 2.2–70 mW. The performed EPR examinations indicate that high concentrations (~1021–1022 spin/g of o-semiquinone free radicals with g factors of 2.0039–2.0045 exist in all the tested samples. For nonirradiated samples, free radical concentration was higher in natural melanin than in synthetic melanin. UV irradiation caused the increase of free radical concentrations in synthetic melanin samples and this effect depends on the time of irradiation. The largest free radical formation in the both melanins was obtained for 60 min of UV irradiation. Free radical concentrations after the UV irradiation of melanins during 30 min were lower than during irradiation by 15 min, and probably this effect was the result of recombination of the radiatively formed free radicals. EPR lines of the tested samples broadened with increasing microwave power, so these lines were homogeneously broadened. The two types of melanins differed in the time of spin-lattice relaxation processes. Slower spin-lattice relaxation processes exist in melanin from Sepia officinalis than in synthetic melanin. UV irradiation did not change the time of spin-lattice relaxation processes in the tested melanins. The performed studies confirmed the usefulness of EPR spectroscopy in cosmetology and medicine.

  11. Optical (DRUV-VIS and magnetic (EPR behavior of synthetic melanins

    Directory of Open Access Journals (Sweden)

    Júlio César Pereira dos Santos

    2012-04-01

    Full Text Available The properties of melanins prepared from L-dopa oxidation by both chemical and electrochemical methods are reported, searching for a material with more intense optical absorption in the visible region. The characterization of the samples have been done by cyclic voltammetry (CV, cronoamperometry (CA, Fourier transformed infrared spectroscopy (FTIR, electron paramagnetic resonance spectroscopy (EPR and diffuse reflectance ultraviolet-visible spectroscopy (DRUV-VIS techniques. The electrochemical method enhanced the organic free radical (spin concentration and the absorption intensity in the visible region of the spectrum. The DRUV-VIS technique along with mathematical tools, such as the Kubelka-Munk remission function, were good options for the characterization of the final products.

  12. EPR dating CO2- sites in tooth enamel apatites by ENDOR and triple resonance.

    Science.gov (United States)

    Vugman, N V; Rossi, A M; Rigby, S E

    1995-05-01

    In this work we combine electron paramagnetic resonance (EPR), high-resolution electron nucleus double resonance (ENDOR) and general triple resonance (GTR) spectroscopies, to study the local environment of the CO2- groups created by ionizing radiation in fossil tooth enamel. We demonstrate that the CO2- groups occupy slightly modified phosphate sites in the hydroxyapatite lattice. In quaternary shark enamel we found these groups to be interacting with water molecules in the apatite channels. The absence of water molecules as first neighbors in mammalian samples indicate, however, that these molecules are not significantly responsible for the stabilization of CO2- dating centers in enamel.

  13. Phospholipid bilayer relaxation dynamics as revealed by the pulsed electron-electron double resonance of spin labels

    Science.gov (United States)

    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.

  14. EPR tooth dosimetry of SNTS area inhabitants

    Energy Technology Data Exchange (ETDEWEB)

    Sholom, Sergey [Scientific Center for Radiation Medicine, Melnikova str., 53, Kiev (Ukraine); Desrosiers, Marc [Ionizing Radiation Division, National Institute of Standards and Technology, Gaithersburg, MD (United States); Bouville, Andre; Luckyanov, Nicholas [Division of Cancer Epidemiology and Genetics, National Cancer Institute, National Institutes of Health, 6120 Executive Boulevard, Bethesda, MD (United States); Chumak, Vadim [Scientific Center for Radiation Medicine, Melnikova str., 53, Kiev (Ukraine); Simon, Steven L. [Division of Cancer Epidemiology and Genetics, National Cancer Institute, National Institutes of Health, 6120 Executive Boulevard, Bethesda, MD (United States)], E-mail: ssimon@mail.nih.gov

    2007-07-15

    The determination of external dose to teeth of inhabitants of settlements near the Semipalatinsk Nuclear Test Site (SNTS) was conducted using the EPR dosimetry technique to assess radiation doses associated with exposure to radioactive fallout from the test site. In this study, tooth doses have been reconstructed for 103 persons with all studied teeth having been formed before the first nuclear test in 1949. Doses above those received from natural background radiation, termed 'accident doses', were found to lie in the range from zero to approximately 2 Gy, with one exception, a dose for one person from Semipalatinsk city was approximately 9 Gy. The variability of reconstructed doses within each of the settlements demonstrated heterogeneity of the deposited fallout as well as variations in lifestyle. The village mean external gamma doses for residents of nine settlements were in the range from a few tens of mGy to approximately 100 mGy.

  15. Asymmetric EPR entanglement in continuous variable systems

    CERN Document Server

    Wagner, Katherine; Armstrong, Seiji; Morizur, Jean-Francois; Lam, Ping Koy; Bachor, Hans-Albert

    2012-01-01

    Continuous variable entanglement can be produced in nonlinear systems or via interference of squeezed states. In many of optical systems, such as parametric down conversion or interference of optical squeezed states, production of two perfectly symmetric subsystems is usually used for demonstrating the existence of entanglement. This symmetry simplifies the description of the concept of entanglement. However, asymmetry in entanglement may arise naturally in a real experiment, or be intentionally introduced in a given quantum information protocol. These asymmetries can emerge from having the output beams experience different losses and environmental contamination, or from the availability of non-identical input quantum states in quantum communication protocols. In this paper, we present a visualisation of entanglement using quadrature amplitude plots of the twin beams. We quantitatively discuss the strength of asymmetric entanglement using EPR and inseparability criteria and theoretically show that the optimal...

  16. Multivariate approach to the chemical mapping of uranium in sandstone-hosted uranium ores analyzed using double pulse Laser-Induced Breakdown Spectroscopy

    Science.gov (United States)

    Klus, Jakub; Mikysek, Petr; Prochazka, David; Pořízka, Pavel; Prochazková, Petra; Novotný, Jan; Trojek, Tomáš; Novotný, Karel; Slobodník, Marek; Kaiser, Jozef

    2016-09-01

    The goal of this work is to provide high resolution mapping of uranium in sandstone-hosted uranium ores using Laser-Induced Breakdown Spectroscopy (LIBS) technique. In order to obtain chemical image with highest possible spatial resolution, LIBS system in orthogonal double pulse (DP LIBS) arrangement was employed. Owing to this experimental arrangement the spot size of 50 μm in diameter resulting in lateral resolution of 100 μm was reached. Despite the increase in signal intensity in DP LIBS modification, the detection of uranium is challenging. The main cause is the high density of uranium spectral lines, which together with broadening of LIBS spectral lines overreaches the resolution of commonly used spectrometers. It results in increased overall background radiation with only few distinguishable uranium lines. Three different approaches in the LIBS data treatment for the uranium detection were utilized: i) spectral line intensity, ii) region of apparent background and iii) multivariate data analysis. By utilizing multivariate statistical methods, a specific specimen features (in our case uranium content) were revealed by processing complete spectral information obtained from broadband echelle spectrograph. Our results are in a good agreement with conventional approaches such as line fitting and show new possibilities of processing spectral data in mapping. As a reference technique to LIBS was employed X-ray Fluorescence (XRF). The XRF chemical images used in this paper have lower resolution (approximately 1-2 mm per image point), nevertheless the elemental distribution is apparent and corresponds to presented LIBS experiments.

  17. Transport-related triplet states and hyperfine couplings in organic tandem solar cells probed by pulsed electrically detected magnetic resonance spectroscopy.

    Science.gov (United States)

    Kraffert, Felix; Bahro, Daniel; Meier, Christoph; Denne, Maximilian; Colsmann, Alexander; Behrends, Jan

    2017-09-01

    Tandem solar cells constitute the most successful organic photovoltaic devices with power conversion efficiencies comparable to thin-film silicon solar cells. Especially their high open-circuit voltage - only achievable by a well-adjusted layer stacking - leads to their high efficiencies. Nevertheless, the microscopic processes causing the lossless recombination of charge carriers within the recombination zone are not well understood yet. We show that advanced pulsed electrically detected magnetic resonance techniques such as electrically detected (ED)-Rabi nutation measurements and electrically detected hyperfine sublevel correlation (ED-HYSCORE) spectroscopy help to understand the role of triplet excitons in these microscopic processes. We investigate fully working miniaturised organic tandem solar cells and detect current-influencing doublet states in different layers as well as triplet excitons located on the fullerene-based acceptor. We apply ED-HYSCORE in order to study the nuclear spin environment of the relevant electron/hole spins and detect a significant amount of the low abundant (13)C nuclei coupled to the observer spins. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Transport-related triplet states and hyperfine couplings in organic tandem solar cells probed by pulsed electrically detected magnetic resonance spectroscopy

    Science.gov (United States)

    Kraffert, Felix; Bahro, Daniel; Meier, Christoph; Denne, Maximilian; Colsmann, Alexander; Behrends, Jan

    2017-09-01

    Tandem solar cells constitute the most successful organic photovoltaic devices with power conversion efficiencies comparable to thin-film silicon solar cells. Especially their high open-circuit voltage - only achievable by a well-adjusted layer stacking - leads to their high efficiencies. Nevertheless, the microscopic processes causing the lossless recombination of charge carriers within the recombination zone are not well understood yet. We show that advanced pulsed electrically detected magnetic resonance techniques such as electrically detected (ED)-Rabi nutation measurements and electrically detected hyperfine sublevel correlation (ED-HYSCORE) spectroscopy help to understand the role of triplet excitons in these microscopic processes. We investigate fully working miniaturised organic tandem solar cells and detect current-influencing doublet states in different layers as well as triplet excitons located on the fullerene-based acceptor. We apply ED-HYSCORE in order to study the nuclear spin environment of the relevant electron/hole spins and detect a significant amount of the low abundant 13C nuclei coupled to the observer spins.

  19. Pulse on Pulse

    DEFF Research Database (Denmark)

    Schmidt, Ulrik; Carlson, Merete

    2012-01-01

    Pulse on Pulse” investigates the relation between signifying processes and non-signifying material dynamism in the installation Pulse Room (2006-) by Mexican Canadian artist Rafael Lozano-Hemmer. In Pulse Room the sense of pulse is ambiguous. Biorhythms are transmitted from the pulsing energy...... and pulsating ‘room’. Hence, the visitors in Pulse Room are invited into a complex scenario that continuously oscillates between various aspects of signification (the light bulbs representing individual lives; the pulse itself as the symbolic ‘rhythm of life’) and instants of pure material processuality...... a multilayered sense of time and space that is central to the sensory experience of Pulse Room as a whole. Pulse Room is, at the very same time, an anthropomorfized archive of a past intimacy and an all-encompassing immersive environment modulating continuously in real space-time....

  20. Identification and Quantification of Copper Sites in Zeolites by Electron Paramagnetic Resonance Spectroscopy

    DEFF Research Database (Denmark)

    Godiksen, Anita; Vennestrøm, Peter N. R.; Rasmussen, Søren Birk

    2016-01-01

    Recent quantitative electron paramagnetic resonance spectroscopy (EPR) data on different copper species present in copper exchanged CHA zeolites are presented and put into context with the literature on other copper zeolites. Results presented herein were obtained using ex situ and in situ EPR...... on copper ion exchanged into a CHA zeolite with Si/Al = 14 ± 1 to obtain Cu/Al = 0.46 ± 0.02. The results shed light on the identity of different copper species present after activation in air. Since the EPR signal is quantifiable, the content of the different EPR active species has been elucidated and Cu2...... information about the reactivity and the quantity of some of the otherwise EPR silent species. In this way the [Cu–OH]+ species in copper substituted low-Al zeolites has been indirectly observed and quantified. EPR active Cu2+ species have been followed under reduction and oxidation with gas mixtures relevant...

  1. Hyperfine-structure study of the 3d10 5p 2P3/2 level of neutral copper using pulsed level-crossing spectroscopy at short laser wavelengths

    Science.gov (United States)

    Bengtsson, J.; Larsson, J.; Svanberg, S.; Wahlstrom, C.-G.

    1990-01-01

    A hyperfine-structure study of the strongly perturbed 3d10 5p 2P3/2 state of neutral copper was performed using pulsed level-crossing spectroscopy. Excitation was accomplished at the short wavelength of 202 nm, where intense laser pulses were obtained using frequency tripling of dye laser radiation. For Cu-63, a = 61.7(9) MHz, b = 4.9(7) MHz, and tau = 25,5(10) ns were obtained for the magnetic dipole and the electric quadrupoles interaction constants and the lifetime, respectively. A comparison with theoretical calculations based on the multiconfiguration Hartree-Fock method is made. A discussion of the usefulness of level-crossing, quantum-beat, and radio-frequency techniques for high-resolution spectroscopy at wavelengths in the UV and vacuum-UV region is presented.

  2. Comparing continuous wave progressive saturation EPR and time domain saturation recovery EPR over the entire motional range of nitroxide spin labels.

    Science.gov (United States)

    Nielsen, Robert D; Canaan, Stephane; Gladden, James A; Gelb, Michael H; Mailer, Colin; Robinson, Bruce H

    2004-07-01

    The measurement of spin-lattice relaxation rates from spin labels, such as nitroxides, in the presence and absence of spin relaxants provides information that is useful for determining biomolecular properties such as nucleic acid dynamics and the interaction of proteins with membranes. We compare X-band continuous wave (CW) and pulsed or time domain (TD) EPR methods for obtaining spin-lattice relaxation rates of spin labels across the entire range of rotational motion to which relaxation rates are sensitive. Model nitroxides and spin-labeled biological species are used to illustrate the potential complications that arise in extracting relaxation data under conditions typical to biological experiments. The effect of super hyperfine (SHF) structure is investigated for both CW and TD spectra. First and second harmonic absorption and dispersion CW spectra of the nitroxide spin label, TEMPOL, are all fit simultaneously to a model of SHF structure over a range of microwave amplitudes. The CW spectra are novel because all harmonics and microwave phases were acquired simultaneously using our homebuilt CW/TD spectrometer. The effect of the SHF structure on the pulsed free induction decay (FID) and pulsed saturation recovery spectrum is shown for both protonated and deuterated TEMPOL. We present novel pulsed saturation recovery measurements on biological molecules, including spin-lattice relaxation rates of spin-labeled proteins and spin-labeled double-stranded DNA. The impact of structure and dynamics on relaxation rates are discussed in the context of each of these examples. Collisional relaxation rates with oxygen and transition metal paramagnetic relaxants are extracted using both continuous wave and time domain methods. The extent of the errors inherent in the CW method and the advantages of pulsed methods for unambiguously measuring collisional relaxation rates are discussed. Spin-lattice relaxation rates, determined by both CW and pulsed methods, are used to determine

  3. EPR and optical study of Yb3+-doped β-PbF2 single crystals and nanocrystals of glass-ceramics

    Science.gov (United States)

    Dantelle, G.; Mortier, M.; Goldner, Ph; Vivien, D.

    2006-08-01

    β-PbF2 single crystals doped with YbF3 (0.2% and 2%) were studied by x-ray diffraction (XRD), electron paramagnetic resonance (EPR) and optical spectroscopy. EPR revealed the presence of only one kind of paramagnetic ion Yb3+, in a cubic symmetry site. The optical absorption, emission and excitation spectra enabled us to identify the transitions attributed to Yb3+ in the cubic site and to determine its energy level diagram. Site-selective laser spectroscopy also evidenced the presence of another type of Yb3+ ions, undetectable by classical EPR. This second type, which dominates in the 2%-doped crystal and exhibits cooperative luminescence, was attributed to Yb3+ ions forming clusters. Transparent oxyfluoride glass-ceramics, containing β-Pb1-yYbyF2+y nanocrystallites, were also synthesized and studied by XRD, EPR and optical spectroscopy. Two types of Yb3+ ions were found, as in β-PbF2 single crystals. The optical properties of the oxyfluoride glass-ceramics turn out to be similar to those of ytterbium activated β-PbF2 single crystals. Moreover, the Yb environments found in PbF2 single crystals seem to already occur in the parent glass. Therefore, these materials are expected to be good laser media, like the rare-earth doped fluorite crystals, either in bulk or fibre form.

  4. Sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy setup for pulsed and constant wave X-ray light sources.

    Science.gov (United States)

    Shavorskiy, Andrey; Neppl, Stefan; Slaughter, Daniel S; Cryan, James P; Siefermann, Katrin R; Weise, Fabian; Lin, Ming-Fu; Bacellar, Camila; Ziemkiewicz, Michael P; Zegkinoglou, Ioannis; Fraund, Matthew W; Khurmi, Champak; Hertlein, Marcus P; Wright, Travis W; Huse, Nils; Schoenlein, Robert W; Tyliszczak, Tolek; Coslovich, Giacomo; Robinson, Joseph; Kaindl, Robert A; Rude, Bruce S; Ölsner, Andreas; Mähl, Sven; Bluhm, Hendrik; Gessner, Oliver

    2014-09-01

    An apparatus for sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy studies with pulsed and constant wave X-ray light sources is presented. A differentially pumped hemispherical electron analyzer is equipped with a delay-line detector that simultaneously records the position and arrival time of every single electron at the exit aperture of the hemisphere with ~0.1 mm spatial resolution and ~150 ps temporal accuracy. The kinetic energies of the photoelectrons are encoded in the hit positions along the dispersive axis of the two-dimensional detector. Pump-probe time-delays are provided by the electron arrival times relative to the pump pulse timing. An average time-resolution of (780 ± 20) ps (FWHM) is demonstrated for a hemisphere pass energy E(p) = 150 eV and an electron kinetic energy range KE = 503-508 eV. The time-resolution of the setup is limited by the electron time-of-flight (TOF) spread related to the electron trajectory distribution within the analyzer hemisphere and within the electrostatic lens system that images the interaction volume onto the hemisphere entrance slit. The TOF spread for electrons with KE = 430 eV varies between ~9 ns at a pass energy of 50 eV and ~1 ns at pass energies between 200 eV and 400 eV. The correlation between the retarding ratio and the TOF spread is evaluated by means of both analytical descriptions of the electron trajectories within the analyzer hemisphere and computer simulations of the entire trajectories including the electrostatic lens system. In agreement with previous studies, we find that the by far dominant contribution to the TOF spread is acquired within the hemisphere. However, both experiment and computer simulations show that the lens system indirectly affects the time resolution of the setup to a significant extent by inducing a strong dependence of the angular spread of electron trajectories entering the hemisphere on the retarding ratio. The scaling of the angular spread with

  5. Software for evaluation of EPR-dosimetry performance.

    Science.gov (United States)

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

    2014-06-01

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

  6. EPR detection of foods preserved with ionizing radiation

    Science.gov (United States)

    Stachowicz, W.; Burlinska, G.; Michalik, J.

    1998-06-01

    The applicability of the epr technique for the detection of dried vegetables, mushrooms, some spices, flavour additives and some condiments preserved with ionizing radiation is discussed. The epr signals recorded after exposure to gamma rays and to beams of 10 MeV electrons from linac are stable, intense and specific enough as compared with those observed with nonirradiated samples and could be used for the detection of irradiation. However, stability of radiation induced epr signals produced in these foods depends on storage condition. No differences in shapes (spectral parameters) and intensities of the epr spectra recorded with samples exposed to the same doses of gamma rays ( 60Co) and 10 MeV electrons were observed

  7. Investigation of the calcium-binding site of the oxygen evolving complex of photosystem II using 87Sr ESEEM spectroscopy.

    Science.gov (United States)

    Kim, Sun Hee; Gregor, Wolfgang; Peloquin, Jeffrey M; Brynda, Marcin; Britt, R David

    2004-06-16

    The proximity of the calcium/strontium binding site of the oxygen evolving complex (OEC) of photosystem II (PSII) to the paramagnetic Mn cluster is explored with (87)Sr three-pulse electron spin-echo envelope modulation (ESEEM) spectroscopy. CW-EPR spectra of Sr(2+)-substituted Ca(2+)-depleted PSII membranes show the modified g = 2 multiline EPR signal as previously reported. We performed three-pulse ESEEM on this modified multiline signal of the Mn cluster using natural abundance Sr and (87)Sr, respectively. Three-pulse ESEEM of the natural abundance Sr sample exhibits no detectable modulation by the 7% abundance (87)Sr. On the other hand, that of the (87)Sr enriched (93%) sample clearly reveals modulation arising from the I = (9)/(2) (87)Sr nucleus weakly magnetically coupled to the Mn cluster. Using a simple point dipole approximation for the electron spin, analysis of the (87)Sr ESEEM modulation depth via an analytic expression suggests a Mn-Ca (Sr) distance of 4.5 A. Simulation of three-pulse ESEEM with a numerical matrix diagonalization procedure gave good agreement with this analytical result. A more appropriate tetranuclear magnetic/structural model for the Mn cluster converts the 4.5 A point dipole distance to a 3.8-5.0 A range of distances. DFT calculations of (43)Ca and (87)Sr quadrupolar interactions on Ca (and Sr substituted) binding sites in various proteins suggest that the lack of the nuclear quadrupole induced splitting in the ESEEM spectrum of (87)Sr enriched PSII samples is related to a very high degree of symmetry of the ligands surrounding the Sr(2+) ion in the substituted Ca site. Numerical simulations show that moderate (87)Sr quadrupolar couplings decrease the envelope modulation relative to the zero quadrupole case, and therefore we consider that the 3.8-5.0 A range obtained without quadrupolar coupling included in the simulation represents an upper limit to the actual manganese-calcium distance. This (87)Sr pulsed EPR spectroscopy provides

  8. Use of the EPR technique to determine thermal stability of some humified organic substances found in soil organic-mineral fractions

    Directory of Open Access Journals (Sweden)

    Sérgio da Costa Saab

    2003-08-01

    Full Text Available In this work, using the EPR spectroscopy, we analysed the thermal stability of some organic-mineral compounds found in a Gleysoil from Rio Janeiro. It was observed a complete disappearance of the EPR signal around 600 °C for the < 2 µm fraction and a residual EPR signal of semiquinone free radical for the 2-20 µm and 20-53 µm fractions at the same temperature. Also, the experiments showed that the 2-20 µm fraction had a larger concentration of semiquinone free radical per g of carbon and a smaller line width indicated a larger humification of this fraction. This is an evidence that the soil organic matter of this fraction (2-20 µm is more stable than the other ones.

  9. Most advanced HTP fuel assembly design for EPR

    Energy Technology Data Exchange (ETDEWEB)

    Francillon, Eric [AREVA - Framatome ANP, 10 rue Juliette Recamier - 69456 Lyon Cedex 06 (France); Kiehlmann, Horst-Dieter [AREVA - Framatome ANP GmbH, P.O. Box 3220, 91050 Erlangen (Germany)

    2006-07-01

    End 2003, the Finnish electricity utility Teollisuuden Voima Oy (TVO) signed the contract for building an EPR in Olkiluoto (Finland). Mid 2004, the French electricity utility EDF selected an EPR to be built in France. In 2005, Framatome ANP, an AREVA and Siemens company, announced that they will be pursuing a design certification in the U.S. The EPR development is based on the latest PWR product lines of former Framatome (N4) and Siemens Nuklear (Konvoi). As an introductory part, different aspects of the EPR core characteristics connected to fuel assembly design are presented. It includes means of ensuring reactivity control like hybrid AIC/B4C control rod absorbers and gadolinium as burnable absorber integrated in fuel rods, and specific options for in-core instrumentation, such as Aeroball type instrumentation. Then the design requirements for the EPR fuel assembly are presented in term of very high burnup capacity, rod cladding and fuel assembly reliability. Framatome ANP fuel assembly product characteristics meeting these requirements are then described. EPR fuel assembly design characteristics benefit from the experience feedback of the latest fuel assembly products designed within Framatome ANP, leading to resistance to assembly deformation, high fuel rod restraint and prevention of handling hazards. EPR fuel assembly design features the best components composing the cornerstones of the upgraded family of fuel assemblies that FRAMATOME ANP proposes today. This family is based on a set of common characteristics and associated features, which include the HMP grid as bottom end spacer, the MONOBLOC guide tube and the Robust FUELGUARD as lower tie plate, the use of the M5 Alloy, as cladding and structure material. This fully re-crystallized, ternary Zr-Nb-O alloy produces radically improved in-reactor corrosion, very low hydrogen uptake and growth and an excellent creep behavior, which are described there. EPR fuel assembly description also includes fuel rod

  10. EPR and NMR studies of amorphous aluminum borates

    NARCIS (Netherlands)

    Simon, S.; Pol, A. van der; Reijerse, E.J.; Kentgens, A.P.M.; Moorsel, G.J.M.P. van; Boer, E. de

    1994-01-01

    Amorphous aluminium borates, Al2(1–x)B2xO3 with O [less-than-or-eq]x[less-than-or-eq] 0.5, prepared from mixtures of aluminium nitrate, boric acid and glycerol, have been studied by EPR and 27Al MASNMR as a function of composition and heat-treatment temperature (Tt[less-than-or-eq] 860 °C). EPR stud

  11. EPR and NMR studies of amorphous aluminum borates

    NARCIS (Netherlands)

    Simon, S.; Pol, A. van der; Reijerse, E.J.; Kentgens, A.P.M.; Moorsel, G.J.M.P. van; Boer, E. de

    1994-01-01

    Amorphous aluminium borates, Al2(1–x)B2xO3 with O [less-than-or-eq]x[less-than-or-eq] 0.5, prepared from mixtures of aluminium nitrate, boric acid and glycerol, have been studied by EPR and 27Al MASNMR as a function of composition and heat-treatment temperature (Tt[less-than-or-eq] 860 °C). EPR stud

  12. Study of metalloproteins using continuous wave electron paramagnetic resonance (EPR).

    Science.gov (United States)

    Gambarelli, Serge; Maurel, Vincent

    2014-01-01

    Electron paramagnetic resonance (EPR) is an invaluable tool when studying systems with paramagnetic centers. It is a sensitive spectroscopic method, which can be used with dilute samples in aqueous buffer solutions. Here, we describe the basic procedure for recording an X-band EPR spectrum of a metalloprotein sample at low temperature. We also discuss basic optimization techniques to provide spectra with a high signal to noise ratio and minimum distortion.

  13. Lorentz symmetry breaking effects on relativistic EPR correlations

    Energy Technology Data Exchange (ETDEWEB)

    Belich, H. [Universidade Federal do Espirito Santo, Departamento de Fisica e Quimica, Vitoria, ES (Brazil); Furtado, C.; Bakke, K. [Universidade Federal da Paraiba, Departamento de Fisica, Caixa Postal 5008, Joao Pessoa, PB (Brazil)

    2015-09-15

    Lorentz symmetry breaking effects on relativistic EPR (Einstein-Podolsky-Rosen) correlations are discussed. From the modified Maxwell theory coupled to gravity, we establish a possible scenario of the Lorentz symmetry violation and write an effective metric for the Minkowski spacetime. Then we obtain the Wigner rotation angle via the Fermi-Walker transport of spinors and consider the WKB (Wentzel-Kramers-Brillouin) approximation in order to study the influence of Lorentz symmetry breaking effects on the relativistic EPR correlations. (orig.)

  14. Field-swept pulsed electron paramagnetic resonance of Cr{sup 3+}-doped ZBLAN fluoride glass

    Energy Technology Data Exchange (ETDEWEB)

    Drew, S.C. [School of Physics and Materials Engineering, Monash University, VIC (Australia)]. E-mail: simon.drew@spme.monash.edu.au; Pilbrow, J.R. [School of Physics and Materials Engineering, Monash University, VIC (Australia); Newman, P.J.; MacFarlane, D.R. [Department of Chemistry, Monash University, VIC (Australia)

    2001-10-07

    Field-swept pulsed electron paramagnetic resonance (EPR) spectra of a ZBLAN fluoride glass doped with a low concentration of Cr{sup 3+} are obtained using echo-detected EPR and hole-burning free induction decay detection. We review the utility of the pulsed EPR technique in generating field-swept EPR spectra, as well as some of the distorting effects that are peculiar to the pulsed detection method. The application of this technique to Cr{sup 3+}-doped ZBLAN reveals that much of the broad resonance extending from g{sup eff}=5.1 to g{sup eff}=1.97, characteristic of X-band continuous wave EPR of Cr{sup 3+} in glasses, is absent. We attribute this largely to the variation in nutation frequencies across the spectrum that result from sites possessing large fine structure interactions. The description of the spin dynamics of such sites is complicated and we discuss some possible approaches to the simulation of the pulsed EPR spectra. (author)

  15. EPC projects for EPR Flamanville 3 NPP

    Energy Technology Data Exchange (ETDEWEB)

    Diaz, J.I.; Polo, J.; Aymerich, E.; Cubian, B. [Nuclear Generation Department, Iberdrola Ingenieria y Construccion, Avda. Manoteras 20, 28050 Madrid (Spain)

    2010-07-01

    IBERDROLA Ingenieria y Construccion is carrying out a handful of activities in the EPR Flamanville 3 -FA3 NPP- context since 2007 matching oriented to position the company in the emerging marketplace of new nuclear power plants Generation III+, whose expectation for the next years is highly promising. IBERDROLA Ingenieria y Construccion leads 5 EPC -Engineering, Procurement and Commissioning- projects for FA3 NPP from the Nuclear Island till Sea Water Pumping Station as follows: - Design, procurement. fabrication, installation and testing of 21 shell and tubes heat-exchangers for the nuclear island. 12 out of these 17 HXs are conventional and will be designed according to ASME BPV code Section VIII and have to comply with PED 97/23/CE and ESPN. The remaining 5 HXs are nuclear and will be designed according to ASME BPV code Section III and have also to comply with PED and ESPN. - Design, procurement, fabrication and assembly of 9 demineralizers for different plant systems. Three of these Important To Safety (IPS) equipments have been manufactured according with ASME VIII codes and six of them with EN 13445 code plus additional requirements to comply with PED and final client requirements for nuclear island. - Design, fabrication and installation of qualified travelling water screening filters. The equipments furnished will be two nuclear safety qualified filters and associated equipment (cleaning water system and control system). Additionally some auxiliary devices such as grids, automatic trash rakes and stop gates are included in the contract. - Engineering, procurement, fabrication, erection and commissioning for the condensate treatment plant. This system includes a demineralizer tank, 5 filters, reactive injection mixer, pneumatic and manual valves, piping and instrumentation and control systems. - Engineering, procurement erection and commissioning for the electro-chlorination plant to protect the IPS piping for Condensate Water System for FA3. This system

  16. Electron paramagnetic resonance spectroscopy in radiation research: Current status and perspectives

    Directory of Open Access Journals (Sweden)

    Sudha Rana

    2010-01-01

    Full Text Available Exposure to radiation leads to a number of health-related malfunctions. Ionizing radiation is more harmful than non-ionizing radiation, as it causes both direct and indirect effects. Irradiation with ionizing radiation results in free radical-induced oxidative stress. Free radical-mediated oxidative stress has been implicated in a plethora of diseased states, including cancer, arthritis, aging, Parkinson′s disease, and so on. Electron Paramagnetic Resonance (EPR spectroscopy has various applications to measure free radicals, in radiation research. Free radicals disintegrate immediately in aqueous environment. Free radicals can be detected indirectly by the EPR spin trapping technique in which these forms stabilize the radical adduct and produce characteristic EPR spectra for specific radicals. Ionizing radiation-induced free radicals in calcified tissues, for example, teeth, bone, and fingernail, can be detected directly by EPR spectroscopy, due to their extended stability. Various applications of EPR in radiation research studies are discussed in this review.

  17. EPR study on non- and gamma-irradiated herbal pills

    Energy Technology Data Exchange (ETDEWEB)

    Aleksieva, K., E-mail: katerina_bas@abv.b [Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Lagunov, O. [Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Dimov, K. [Institute of Cryobiology and Food Technologies, 1162 Sofia (Bulgaria); Yordanov, N.D. [Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)

    2011-06-15

    The results of EPR studies on herbal pills of marigold, hawthorn, yarrow, common balm, tutsan, nettle and thyme before and after gamma-irradiation are reported. Before irradiation all samples exhibit one weak singlet EPR line with a g-factor of 2.0048{+-}0.0005. After irradiation herbal pills could be separated in two groups according to their EPR spectra. Radiation-induced free radicals in pills of marigold, yarrow, nettle, tutsan and thyme could be attributed mainly to saccharide excipients. Tablets of hawthorn and common balm show 'cellulose-like' EPR spectrum, superimposed on partly resolved carbohydrate spectrum, due to the active part (herb) and inulin, which is present in the pills as an excipient. Fading study of the radiation-induced EPR signals confirms that sugar radicals are more stable than cellulose species. The reported results show that the presence of characteristic EPR spectra of herbal pills due to excipients or active part can be used as unambiguous proof of radiation processing within 35 or more days after irradiation.

  18. EPR study on non- and gamma-irradiated herbal pills

    Science.gov (United States)

    Aleksieva, K.; Lagunov, O.; Dimov, K.; Yordanov, N. D.

    2011-06-01

    The results of EPR studies on herbal pills of marigold, hawthorn, yarrow, common balm, tutsan, nettle and thyme before and after gamma-irradiation are reported. Before irradiation all samples exhibit one weak singlet EPR line with a g-factor of 2.0048±0.0005. After irradiation herbal pills could be separated in two groups according to their EPR spectra. Radiation-induced free radicals in pills of marigold, yarrow, nettle, tutsan and thyme could be attributed mainly to saccharide excipients. Tablets of hawthorn and common balm show "cellulose-like" EPR spectrum, superimposed on partly resolved carbohydrate spectrum, due to the active part (herb) and inulin, which is present in the pills as an excipient. Fading study of the radiation-induced EPR signals confirms that sugar radicals are more stable than cellulose species. The reported results show that the presence of characteristic EPR spectra of herbal pills due to excipients or active part can be used as unambiguous proof of radiation processing within 35 or more days after irradiation.

  19. Assessing Guest-Molecule Diffusion in Heterogeneous Powder Samples of Metal-Organic Frameworks through Pulsed-Field-Gradient (PFG) NMR Spectroscopy.

    Science.gov (United States)

    Thoma, Roland; Kärger, Jörg; de Sousa Amadeu, Nader; Nießing, Sandra; Janiak, Christoph

    2017-07-19

    Investigation of guest diffusion in porous metal-organic frameworks (MOFs) is of major importance, because many porosity-related properties of MOFs are influenced by diffusion effects. The diffusion of dimethyl sulfoxide (DMSO) in the MOF MIL-53-NH2 (Al) was investigated through pulsed-field-gradient (PFG) NMR spectroscopy. The microporous material was synthesized in small crystallites (under 500 nm), which agglomerated in a large range of particle sizes (from hundreds of nanometers to tens of micrometers), giving a morphologically very heterogeneous sample. No special agglomeration pattern could be observed, which makes a PFG NMR investigation very challenging, yet it represents a realistic situation for the diffusion of guest molecules in porous materials. We were able to distinguish between two diffusion regimes existing in parallel with each other over the total range from 15 to 200 ms of observation times as accessible in the experiments: In the large crystal agglomerates (diameters above 20 μm), guest movement was found to be subdiffusive, with a time exponent κ =0.8 (rather than one as for normal diffusion). Guest diffusion in the remaining, smaller host particles followed the pattern of normal diffusion within a bed of spheres of impenetrable external surfaces, with a size distribution in good agreement with that of the material under study. Diffusion in a rather complex system could thus be referred to a two-region model with new potentials for application to systems of intricate topology. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Qualitative and quantitative spectro-chemical analysis of dates using UV-pulsed laser induced breakdown spectroscopy and inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Mehder, A O; Habibullah, Y B; Gondal, M A; Baig, Umair

    2016-08-01

    Laser Induced Breakdown Spectroscopy (LIBS) is demonstrated for the spectral analysis of nutritional and toxic elements present in several varieties of date fruit samples available in the Saudi Arabia market. The method analyzes the optical emission of a test sample when subjected to pulsed laser ablation. In this demonstration, our primary focus is on calcium (Ca) and magnesium (Mg), as nutritional elements, and on chromium (Cr), as a toxic element. The local thermodynamic equilibrium (LTE) condition was confirmed prior to the elemental characterization of date samples to ensure accuracy of the LIBS analysis. This was achieved by measuring parameters associated with the plasma, such as the electron temperature and the electron number density. These plasma parameters aid interpretation of processes such as ionization, dissociation, and excitation occurring in the plasma plume formed by ablating the date palm sample. The minimum detection limit was established from calibration curves that involved plotting the LIBS signal intensity as a function of standard date samples with known concentrations. The concentration of Ca and Mg detected in different varieties of date samples was between 187 and 515 and 35-196mgL(-1) respectively, while Cr concentration measured between 1.72 and 7.76mgL(-1). In order to optimize our LIBS system, we have studied how the LIBS signal intensity depends on the incident laser energy and the delay time. In order to validate our LIBS analysis results, standard techniques such as inductively coupled plasma mass spectrometry (ICP-MS) were also applied on an identical (duplicate) date samples as those used for the LIBS analysis. The LIBS results exhibit remarkable agreement with those obtained from the ICP-MS analysis. In addition, the finger print wavelengths of other elements present in date samples were also identified and are reported here, which has not been previously reported, to the best of our knowledge. Copyright © 2016 Elsevier B