WorldWideScience

Sample records for homonuclear dipolar recoupling

  1. Improved Narrowband Dipolar Recoupling for Homonuclear Distance Measurements in Rotating Solids

    Science.gov (United States)

    Goobes, G.; Vega, S.

    2002-02-01

    Recovery of the magnetic dipolar interaction between nuclei bearing the same gyromagnetic ratio in rotating solids can be promoted by synchronous rf irradiation. Determination of the dipolar interaction strength can serve as a tool for structural elucidation in polycrystalline powders. Spinning frequency dependent narrow-band (nb) RFDR and SEDRA experiments are utilized as simple techniques for the determination of dipolar interactions between the nuclei in coupled homonuclear spin pairs. The magnetization exchange and coherence dephasing due to a fixed number of rotor-synchronously applied π-pulses is monitored at spinning frequencies in the vicinity of the rotational resonance (R2) conditions. The powder nbRFDR and nbSEDRA decay curves of spin magnetizations and coherences, respectively, as a function of the spinning frequency can be measured and analyzed using simple rate equations providing a quantitative measure of the dipolar coupling. The effects of the phenomenological relaxation parameters in these rate equations are discussed and an improved methodology is suggested for analyzing nbRFDR data for small dipolar couplings. The distance between the labeled nuclei in the 1,3-13C2-hydroxybutyric acid molecule is rederived using existing nbRFDR results and the new simulation procedure. A nbSEDRA experiment has been performed successfully on a powder sample of singly labeled 1-13C-L-leucine measuring the dipolar interaction between the labeled carboxyl carbon and the natural abundant β-carbon. Both narrowband techniques are employed for the determination of the nuclear distances between the side-chain carbons of leucine and its carbonyl carbon in a tripeptide Leu-Gly-Phe that is singly 13C-labeled at the leucine carbonyl carbon position.

  2. Combined zero-quantum and spin-diffusion mixing for efficient homonuclear correlation spectroscopy under fast MAS: broadband recoupling and detection of long-range correlations.

    Science.gov (United States)

    Lu, Xingyu; Guo, Changmiao; Hou, Guangjin; Polenova, Tatyana

    2015-01-01

    Fast magic angle spinning (MAS) NMR spectroscopy is emerging as an essential analytical and structural biology technique. Large resolution and sensitivity enhancements observed under fast MAS conditions enable structural and dynamics analysis of challenging systems, such as large macromolecular assemblies and isotopically dilute samples, using only a fraction of material required for conventional experiments. Homonuclear dipolar-based correlation spectroscopy constitutes a centerpiece in the MAS NMR methodological toolbox, and is used essentially in every biological and organic system for deriving resonance assignments and distance restraints information necessary for structural analysis. Under fast MAS conditions (rotation frequencies above 35-40 kHz), dipolar-based techniques that yield multi-bond correlations and non-trivial distance information are ineffective and suffer from low polarization transfer efficiency. To overcome this limitation, we have developed a family of experiments, CORD-RFDR. These experiments exploit the advantages of both zero-quantum RFDR and spin-diffusion based CORD methods, and exhibit highly efficient and broadband dipolar recoupling across the entire spectrum, for both short-range and long-range correlations. We have verified the performance of the CORD-RFDR sequences experimentally on a U-(13)C,(15)N-MLF tripeptide and by numerical simulations. We demonstrate applications of 2D CORD-RFDR correlation spectroscopy in dynein light chain LC8 and HIV-1 CA tubular assemblies. In the CORD-RFDR spectra of LC8 acquired at the MAS frequency of 40 kHz, many new intra- and inter-residue correlations are detected, which were not observed with conventional dipolar recoupling sequences. At a moderate MAS frequency of 14 kHz, the CORD-RFDR experiment exhibits excellent performance as well, as demonstrated in the HIV-1 CA tubular assemblies. Taken together, the results indicate that CORD-RFDR experiment is beneficial in a broad range of conditions

  3. Coherence Transfer in Dipolar-Coupled Homonuclear Spin Systems in Solids Rotating at the Magic Angle

    Science.gov (United States)

    Weintraub, O.; Vega, S.; Hoelger, C.; Limbach, H. H.

    Two routes for the exploitation of the t-SEDRA pulse scheme, which induces coherence transfer in dipolar-coupled homonuclear spin systems in rotating samples, are demonstrated and discussed. This sequence is utilized to deduce intramolecular connectivities by creating an initial coherence of one spin only, applying the t-SEDRA sequence, and monitoring the signal enhancement of the coupled spin. Probing the signal amplitude variations of the two spins and comparing them to simulations can also yield molecular distances. Using 2D spectroscopy, t-SEDRA can also be utilized to establish spin correlations. In this case, the t-SEDRA sequence is applied during the mixing time of a 2D dipolar-correlation experiment. These two approaches are demonstrated by performing 15N CPMAS NMR experiments on a 15N-doubly labeled sample of 3(5)-methyl-5(3)-phenylpyrazole.

  4. An explanation for the high stability of polycarboxythiophenes in photovoltaic devices—A solid-state NMR dipolar recoupling study

    DEFF Research Database (Denmark)

    Bierring, M.; Nielsen, J.S.; Siu, Ana

    2008-01-01

    acid carbon atoms were measured by C-13 solid-state magic-angle-spinning (MAS) NMR using symmetry-based double-quantum (2Q) dipolar recoupling. This revealed the presence of C-13-C-13 distances of 3.85 angstrom, which correspond to the C-C distance in hydrogen-bonded carboxylic acid dimers. In spite...... of the presence of carboxylic groups in the polymer as demonstrated by C-13 CP/MAS NMR and IR spectroscopy, the absence of carboxylic protons in solid state H-1 NMR spectra indicate that they are mobile. We link the extraordinary stability of this system to the rigid nature, cross-linking through a hydrogen...

  5. Two pulse recoupling

    Science.gov (United States)

    Khaneja, Navin; Kumar, Ashutosh

    2017-08-01

    The paper describes a family of novel recoupling pulse sequences in magic angle spinning (MAS) solid state NMR, called two pulse recoupling. These pulse sequences can be employed for both homonuclear and heteronuclear recoupling experiments and are robust to dispersion in chemical shifts and rf-inhomogeneity. The homonuclear pulse sequence consists of a building block (π)ϕ(π) - ϕ where ϕ =π/4n, and n is number of blocks in a rotor period. The recoupling block is made robust to rf-inhomogeneity by extending it to (π)ϕ(π) - ϕ(π) π + ϕ(π) π - ϕ . The heteronuclear recoupling pulse sequence consists of a building block (π)ϕ1(π)-ϕ1 and (π)ϕ2(π)-ϕ2 on channel I and S, where ϕ1 = 3π/8n, ϕ2 = π/8n and n is number of blocks in a rotor period. The recoupling block is made robust to rf-inhomogeneity by extending it to (π)ϕ1(π)-ϕ1(π) π +ϕ1(π) π -ϕ1 and (π)ϕ2(π)-ϕ2(π) π +ϕ2(π) π -ϕ2 on two channels respectively. The recoupling pulse sequences mix the z magnetization. Experimental quantification of this method is shown for 13Cα-13CO homonuclear recoupling in a sample of Glycine and 15N-13Cα heteronuclear recoupling in Alanine. Application of this method is demonstrated on a sample of tripeptide N-formyl-[U-13C,15N]-Met-Leu-Phe-OH (MLF). Compared to R-sequences (Levitt, 2002), these sequences are more robust to rf-inhomogeneity and give better sensitivity, as shown in Fig. 3.

  6. Recoupling of chemical shift anisotropy by R-symmetry sequences in magic angle spinning NMR spectroscopy

    Science.gov (United States)

    Hou, Guangjin; Byeon, In-Ja L.; Ahn, Jinwoo; Gronenborn, Angela M.; Polenova, Tatyana

    2012-10-01

    13C and 15N chemical shift (CS) interaction is a sensitive probe of structure and dynamics in a wide variety of biological and inorganic systems, and in the recent years several magic angle spinning NMR approaches have emerged for residue-specific measurements of chemical shift anisotropy (CSA) tensors in uniformly and sparsely enriched proteins. All of the currently existing methods are applicable to slow and moderate magic angle spinning (MAS) regime, i.e., MAS frequencies below 20 kHz. With the advent of fast and ultrafast MAS probes capable of spinning frequencies of 40-100 kHz, and with the superior resolution and sensitivity attained at such high frequencies, development of CSA recoupling techniques working under such conditions is necessary. In this work, we present a family of R-symmetry based pulse sequences for recoupling of 13C/15N CSA interactions that work well in both natural abundance and isotopically enriched systems. We demonstrate that efficient recoupling of either first-rank (σ1) or second-rank (σ2) spatial components of CSA interaction is attained with appropriately chosen γ-encoded RNnv symmetry sequences. The advantage of these γ-encoded RNnv-symmetry based CSA (RNCSA) recoupling schemes is that they are suitable for CSA recoupling under a wide range of MAS frequencies, including fast MAS regime. Comprehensive analysis of the recoupling properties of these RNnv symmetry sequences reveals that the σ1-CSA recoupling symmetry sequences exhibit large scaling factors; however, the partial homonuclear dipolar Hamiltonian components are symmetry allowed, which makes this family of sequences suitable for CSA measurements in systems with weak homonuclear dipolar interactions. On the other hand, the γ-encoded symmetry sequences for σ2-CSA recoupling have smaller scaling factors but they efficiently suppress the homonuclear dipole-dipole interactions. Therefore, the latter family of sequences is applicable for measurements of CSA parameters in

  7. A new NMR method for determining the particle thickness in nanocomposites, using T2,H-selective X{1H} recoupling.

    Science.gov (United States)

    Schmidt-Rohr, K; Rawal, A; Fang, X-W

    2007-02-07

    A new nuclear magnetic resonance approach for characterizing the thickness of phosphate, silicate, carbonate, and other nanoparticles in organic-inorganic nanocomposites is presented. The particle thickness is probed using the strongly distant-dependent dipolar couplings between the abundant protons in the organic phase and X nuclei (31P, 29Si, 13C, 27Al, 23Na, etc.) in the inorganic phase. This approach requires pulse sequences with heteronuclear dephasing only by the polymer or surface protons that experience strong homonuclear interactions, but not by dispersed OH or water protons in the inorganic phase, which have long transverse relaxation times T2,H. This goal is achieved by heteronuclear recoupling with dephasing by strong homonuclear interactions of protons (HARDSHIP). The pulse sequence alternates heteronuclear recoupling for approximately 0.15 ms with periods of homonuclear dipolar dephasing that are flanked by canceling 90 degrees pulses. The heteronuclear evolution of the long-T2,H protons is refocused within two recoupling periods, so that 1H spin diffusion cannot significantly dephase these coherences. For the short-T2,H protons of a relatively immobile organic matrix, the heteronuclear dephasing rate depends simply on the heteronuclear second moment. Homonuclear interactions do not affect the dephasing, even though no homonuclear decoupling is applied, because long-range 1H-X dipolar couplings approximately commute with short-range 1H-1H couplings, and heteronuclear recoupling periods are relatively short. This is shown in a detailed analysis based on interaction representations. The algorithm for simulating the dephasing data is described. The new method is demonstrated on a clay-polymer nanocomposite, diamond nanocrystals with protonated surfaces, and the bioapatite-collagen nanocomposite in bone, as well as pure clay and hydroxyapatite. The diameters of the nanoparticles in these materials range between 1 and 5 nm. Simulations show that spherical

  8. Second order average Hamiltonian theory of symmetry-based pulse schemes in the nuclear magnetic resonance of rotating solids: application to triple-quantum dipolar recoupling.

    NARCIS (Netherlands)

    Brinkmann, A.; Eden, M.

    2004-01-01

    The average Hamiltonian theory (AHT) of several classes of symmetry-based radio-frequency pulse sequences is developed to second order, allowing quantitative analyses of a wide range of recoupling and decoupling applications in magic-angle-spinning solid state nuclear magnetic resonance. General

  9. MAS solid state NMR of proteins: simultaneous {sup 15}N–{sup 13}CA and {sup 15}N–{sup 13}CO dipolar recoupling via low-power symmetry-based RF pulse schemes

    Energy Technology Data Exchange (ETDEWEB)

    Herbst, Christian [Ubon Ratchathani University, Department of Physics, Faculty of Science (Thailand); Bellstedt, Peter; Görlach, Matthias; Ramachandran, Ramadurai, E-mail: raman@fli-leibniz.de [Leibniz Institute for Age Research, Fritz Lipmann Institute, Research group Biomolecular NMR Spectroscopy (Germany)

    2015-05-15

    The generation of efficient RN{sub n}{sup ν}s,{sup ν}k symmetry-based low-power RF pulse schemes for simultaneous {sup 15}N–{sup 13}CA and {sup 15}N–{sup 13}CO dipolar recoupling is demonstrated. The method involves mixing schemes employing phase and amplitude-modulated dual band-selective 180° pulses as basic “R” element and tailoring of the RF field-modulation profile of the 180° pulses so as to obtain efficient magnetisation transfer characteristics over the resonance offset range of the nuclei involved. Mixing schemes leading to simultaneous {sup 15}N–{sup 13}CA and {sup 15}N–{sup 13}CO dipolar recoupling would permit the one-shot acquisition of different chemical shift correlation spectra that are typically utilized for protein backbone resonance assignments and thereby save data acquisition time. At representative MAS frequencies the efficacies of the mixing schemes presented here have been experimentally demonstrated via the simultaneous acquisition of {3D CONH and 3D CANH}, {3D CONH and 3D CO(CA)NH} and {3D CONH, 3D CANH, 3D CO(CA)NH and 3D CA(CO)NH} spectra generated via the magnetisation transfer pathways {sup 1}H → {sup 13}CO → {sup 15}N → {sup 1}H (CONH), {sup 1}H → {sup 13}CA → {sup 15}N → {sup 1}H (CANH) and {sup 1}H → {sup 13}CO → {sup 13}CA → {sup 15}N → {sup 1}H (CO(CA)NH) and {sup 1}H → {sup 13}CA → {sup 13}CO → {sup 15}N → {sup 1}H (CA(CO)NH)

  10. Distance Measurements between Homonuclear Spins in Rotating Solids

    Science.gov (United States)

    Weintraub, O.; Vega, S.; Hoelger, C.; Limbach, H. H.

    The effective Hamiltonian of the "simple excitation for the dephasing of the rotational-echo amplitudes" (SEDRA) experiment has been derived. This experiment enables the determination of the strength of the dipolar interaction of a homonuclear spin pair in a solid, rotating at the magic angle, and thus provides a way to measure internuclear distances. The dipolar decay of the rotational-echo amplitudes of powder samples, generated by a set of π pulses, is measured together with the echo decay that is not influenced by the dipolar interaction. The latter is measured by the transverse-echo SEDRA experiment that refocuses the SEDRA decay. The Floquet theory approach is utilized to evaluate the effective Hamiltonians that describe the behavior of the spin systems. The influence of the chemical-shift anisotropy parameters of the interacting spins on the effective SEDRA Hamiltonian is also discussed. Results of Δ S/ S0 SEDRA experiments on the 15N spin pair in solid 3(5)-methyl-5(3) -phenylpyrazole- 15N 2 are shown and compared with exact calculations. The data suggest a nuclear distance between the nitrogen atoms of 1.385 ± 0.025 Å.

  11. Recoupling: Development and Establishment of the Spousal Subsystem in Remarriage.

    Science.gov (United States)

    Kvanli, Judith A.; Jennings, Glen

    1986-01-01

    Discusses study investigating the development and establishment of the spousal subsystem in remarriage following divorce. Analyzed interviews of 10 remarried couples. As the tasks of the early period of remarriage were completed, each spousal subsystem gradually experienced a recoupling process, that is, perceived the occurrence of an emotional…

  12. A new method for the simultaneous measurement of magnitude and sign of 1DCH and 1DHH dipolar couplings in methylene groups

    Energy Technology Data Exchange (ETDEWEB)

    Carlomagno, Teresa; Peti, Wolfgang; Griesinger, Christian [Universitaet Frankfurt, Institut fuer Organische Chemie (Germany)

    2000-06-15

    Heteronuclear dipolar couplings of the protein backbone have proven to have a big impact on the accuracy of protein NMR structures. H,H dipolar couplings might have the same impact on side chains. Here we present a method that combines both heteronuclear and homonuclear dipolar couplings to investigate the local conformation of methylene groups. A new pulse sequence (SPITZE-HSQC) is presented, that allows to measure the two C,H and the H,H dipolar couplings at the same time, using spin state selective transfers. The new method has been applied to the methylene groups of glycines in the protein ubiquitin. The C,H and the H,H dipolar couplings might have a key role in fast stereospecific assignment of protons in CH{sub 2} groups.

  13. Optimizing symmetry-based recoupling sequences in solid-state NMR by pulse-transient compensation and asynchronous implementation.

    Science.gov (United States)

    Hellwagner, Johannes; Sharma, Kshama; Tan, Kong Ooi; Wittmann, Johannes J; Meier, Beat H; Madhu, P K; Ernst, Matthias

    2017-06-28

    Pulse imperfections like pulse transients and radio-frequency field maladjustment or inhomogeneity are the main sources of performance degradation and limited reproducibility in solid-state nuclear magnetic resonance experiments. We quantitatively analyze the influence of such imperfections on the performance of symmetry-based pulse sequences and describe how they can be compensated. Based on a triple-mode Floquet analysis, we develop a theoretical description of symmetry-based dipolar recoupling sequences, in particular, R26411, calculating first- and second-order effective Hamiltonians using real pulse shapes. We discuss the various origins of effective fields, namely, pulse transients, deviation from the ideal flip angle, and fictitious fields, and develop strategies to counteract them for the restoration of full transfer efficiency. We compare experimental applications of transient-compensated pulses and an asynchronous implementation of the sequence to a supercycle, SR26, which is known to be efficient in compensating higher-order error terms. We are able to show the superiority of R26 compared to the supercycle, SR26, given the ability to reduce experimental error on the pulse sequence by pulse-transient compensation and a complete theoretical understanding of the sequence.

  14. GYutsis: heuristic based calculation of general recoupling coefficients

    Science.gov (United States)

    Van Dyck, D.; Fack, V.

    2003-08-01

    General angular momentum recoupling coefficients can be expressed as a summation formula over products of 6- j coefficients. Yutsis, Levinson and Vanagas developed graphical techniques for representing the general recoupling coefficient as a cubic graph and they describe a set of reduction rules allowing a stepwise generation of the corresponding summation formula. This paper is a follow up to [Van Dyck and Fack, Comput. Phys. Comm. 151 (2003) 353-368] where we described a heuristic algorithm based on these techniques. In this article we separate the heuristic from the algorithm and describe some new heuristic approaches which can be plugged into the generic algorithm. We show that these new heuristics lead to good results: in many cases we get a more efficient summation formula than our previous approach, in particular for problems of higher order. In addition the new features and the use of our program GYutsis, which implements these techniques, is described both for end users and application programmers. Program summaryTitle of program: CycleCostAlgorithm, GYutsis Catalogue number: ADSA Program Summary URL:http://cpc.cs.qub.ac.uk/summaries/ADSA Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland. Users may obtain the program also by downloading either the compressed tar file gyutsis.tgz (for Unix and Linux) or the zip file gyutsis.zip (for Windows) from our website ( http://caagt.rug.ac.be/yutsis/). An applet version of the program is also available on our website and can be run in a web browser from the URL http://caagt.rug.ac.be/yutsis/GYutsisApplet.html. Licensing provisions: none Computers for which the program is designed: any computer with Sun's Java Runtime Environment 1.4 or higher installed. Programming language used: Java 1.2 (Compiler: Sun's SDK 1.4.0) No. of lines in program: approximately 9400 No. of bytes in distributed program, including test data, etc.: 544 117 Distribution format: tar gzip file Nature of

  15. The first row anomaly and recoupled pair bonding in the halides of the late p-block elements.

    Science.gov (United States)

    Dunning, Thom H; Woon, David E; Leiding, Jeff; Chen, Lina

    2013-02-19

    The dramatic differences between the properties of molecules formed from the late p-block elements of the first row of the periodic table (N-F) and those of the corresponding elements in subsequent rows is well recognized as the first row anomaly. Certain properties of the atoms, such as the relative energies and spatial extents of the ns and np orbitals, can explain some of these differences, but not others. In this Account, we summarize the results of our recent computational studies of the halides of the late p-block elements. Our studies point to a single underlying cause for many of these differences: the ability of the late p-block elements in the second and subsequent rows of the periodic table to form recoupled pair bonds and recoupled pair bond dyads with very electronegative ligands. Recoupled pair bonds form when an electron in a singly occupied ligand orbital recouples the pair of electrons in a doubly occupied lone pair orbital on the central atom, leading to a central atom-ligand bond. Recoupled pair bond dyads occur when a second ligand forms a bond with the orbital left over from the initial recoupled pair bond. Recoupled pair bonds and recoupled pair bond dyads enable the late p-block elements to form remarkably stable hypervalent compounds such as PF(5) and SF(6) and lead to unexpected excited states in smaller halides of the late p-block elements such as SF and SF(2). Recoupled pair bonding also causes the F(n-1)X-F bond energies to oscillate dramatically once the normal valences of the central atoms have been satisfied. In addition, recoupled pair bonding provides a lower-energy pathway for inversion in heavily fluorinated compounds (PF(3) and PF(2)H, but not PH(2)F and PH(3)) and leads to unusual intermediates and products in reactions involving halogens and late p-block element compounds, such as (CH(3))(2)S + F(2). Although this Account focuses on the halides of the second row, late p-block elements, recoupled pair bonds and recoupled pair

  16. Even harmonic generation in isotropic media of dissociating homonuclear molecules

    CERN Document Server

    Silva, R E F; Morales, F; Smirnova, O; Ivanov, M; Martín, F

    2016-01-01

    Isotropic gases irradiated by long pulses of intense IR light can generate very high harmonics of the incident field. It is generally accepted that, due to the symmetry of the generating medium, be it an atomic or an isotropic molecular gas, only odd harmonics of the driving field can be produced. Here we show how the interplay of electronic and nuclear dynamics can lead to a marked breakdown of this standard picture: a substantial part of the harmonic spectrum can consist of even rather than odd harmonics. We demonstrate the effect using ab-initio solutions of the time-dependent Schr\\"odinger equation for $H$$_2$$^+$ and its isotopes in full dimensionality. By means of a simple analytical model, we identify its physical origin, which is the appearance of a permanent dipole moment in dissociating homonuclear molecules, caused by light-induced localization of the electric charge during dissociation. The effect arises for sufficiently long laser pulses and the region of the spectrum where even harmonics are pro...

  17. Tilted fiber grating accelerometer incorporating an abrupt biconical taper for cladding to core recoupling

    National Research Council Canada - National Science Library

    Tuan Guo; Liyang Shao; Hwa-Yaw Tam; Peter A. Krug; Jacques Albert

    2009-01-01

    ...) combined with an abrupt biconical taper. The electric-arc-heating induced taper is located a short distance upstream from the TFBG and functions as a bridge to recouple the TFBG-excited lower-order cladding modes back into the fiber core...

  18. Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

    Science.gov (United States)

    Hou, Guangjin; Lu, Xingyu; Vega, Alexander J.; Polenova, Tatyana

    2014-09-01

    We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear 1H-X (X = 13C, 15N, 31P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the 1H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the 1H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from 1H chemical shift anisotropy, while keeping the 1H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [15N]-N-acetyl-valine and [U-13C,15N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate 1H-15N dipolar couplings in the context of 3D experiments is presented on U-13C,15N-enriched dynein light chain protein LC8.

  19. Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy.

    Science.gov (United States)

    Hou, Guangjin; Lu, Xingyu; Vega, Alexander J; Polenova, Tatyana

    2014-09-14

    We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear (1)H-X (X = (13)C, (15)N, (31)P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the (1)H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the (1)H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from (1)H chemical shift anisotropy, while keeping the (1)H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [(15)N]-N-acetyl-valine and [U-(13)C,(15)N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate (1)H-(15)N dipolar couplings in the context of 3D experiments is presented on U-(13)C,(15)N-enriched dynein light chain protein LC8.

  20. Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Guangjin, E-mail: hou@udel.edu, E-mail: tpolenov@udel.edu; Lu, Xingyu, E-mail: luxingyu@udel.edu, E-mail: lexvega@comcast.net; Vega, Alexander J., E-mail: luxingyu@udel.edu, E-mail: lexvega@comcast.net; Polenova, Tatyana, E-mail: hou@udel.edu, E-mail: tpolenov@udel.edu [Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA and Pittsburgh Center for HIV Protein Interactions, University of Pittsburgh School of Medicine, 1051 Biomedical Science Tower 3, 3501 Fifth Ave., Pittsburgh, Pennsylvania 15261 (United States)

    2014-09-14

    We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear {sup 1}H-X (X = {sup 13}C, {sup 15}N, {sup 31}P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the {sup 1}H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the {sup 1}H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from {sup 1}H chemical shift anisotropy, while keeping the {sup 1}H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [{sup 15}N]-N-acetyl-valine and [U-{sup 13}C,{sup 15}N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate {sup 1}H-{sup 15}N dipolar couplings in the context of 3D experiments is presented on U-{sup 13}C,{sup 15}N-enriched dynein light chain protein LC8.

  1. Dipolar response of hydrated proteins

    OpenAIRE

    Matyushov, Dmitry V.

    2011-01-01

    The paper presents an analytical theory and numerical simulations of the dipolar response of hydrated proteins. The effective dielectric constant of the solvated protein, representing the average dipole moment induced at the protein by a uniform external field, shows a remarkable variation among the proteins studied by numerical simulations. It changes from 0.5 for ubiquitin to 640 for cytochrome c. The former value implies a negative dipolar susceptibility of ubiquitin, that is a dia-electri...

  2. Dipolar quantum gases and liquids

    Science.gov (United States)

    Pfau, Tilman

    2017-04-01

    Dipolar interactions are fundamentally different from the usual van der Waals forces in real gases. Besides the anisotropy the dipolar interaction is nonlocal and as such allows for self organized structure formation. Candidates for dipolar species are polar molecules, Rydberg atoms and magnetic atoms. More than ten years ago the first dipolar effects in a quantum gas were observed in an ultracold Chromium gas. By the use of a Feshbach resonance a purely dipolar quantum gas was observed three years after. By now dipolar interaction effects have been observed in lattices and also for polar molecules. Recently it became possible to study degenerate gases of lanthanide atoms among which one finds the most magnetic atoms. Similar to the Rosensweig instability in classical magnetic ferrofluids self-organized structure formation was expected. In our experiments with quantum gases of Dysprosium atoms we could recently observe the formation of a droplet crystal. In contrast to theoretical mean field based predictions the superfluid droplets did not collapse. We find that this unexpected stability is due to beyond meanfield quantum corrections of the Lee-Huang-Yang type. We observe and study self-bound droplets which can interfere with each other. These droplets are 100 million times less dense than liquid helium droplets and open new perspectives as a truly isolated quantum system.

  3. Recoupling in Mid-Life and Beyond: From Love at Last to Not So Fast.

    Science.gov (United States)

    Papernow, Patricia L

    2017-09-09

    Divorce rates have dropped in the United States, except for couples over 50 where they are rising steeply, along with rates of late-life recoupling. Both stepcouples and their young adult and adult children in new older stepfamilies are often surprised to find themselves facing many of the same challenges that younger stepfamilies do. Some challenges are even intensified by the decades-long relationships and additional layers of extended family that come with recoupling after mid-life. Stepfamilies formed in later life must also negotiate decisions about estate planning and elder care among stakeholders who often have sharply divergent agendas before there is time to establish trusting relationships. This article describes the "normal" challenges facing stepcouples who come together over age 50. It provides evidence-informed guidance for therapists in meeting these challenges on three levels of clinical work: Psychoeducational, Interpersonal, and Intrapsychic/Intergenerational. As in younger stepfamilies, "family therapy" must usually begin in subsystems-often the adult stepcouple and parent-adult child. The article then describes a particularly fraught subgroup of recouplers: over-50 fathers and their new partners, where the dad's young adult or adult daughter is very unhappy with his new relationship. In these latter stepfamilies, father-daughter repair must precede stepfamily bonding. Stepfamilies that are preceded by a partner's death and those that begin with affairs are also discussed. Finally, some "easy wrong turns" for therapists are described. © 2017 Family Process Institute.

  4. Dipolar response of hydrated proteins.

    Science.gov (United States)

    Matyushov, Dmitry V

    2012-02-28

    The paper presents an analytical theory and numerical simulations of the dipolar response of hydrated proteins in solution. We calculate the effective dielectric constant representing the average dipole moment induced at the protein by a uniform external field. The dielectric constant shows a remarkable variation among the proteins, changing from 0.5 for ubiquitin to 640 for cytochrome c. The former value implies a negative dipolar susceptibility, that is a dia-electric dipolar response and negative dielectrophoresis. It means that ubiquitin, carrying an average dipole of ≃240 D, is expected to repel from the region of a stronger electric field. This outcome is the result of a negative cross-correlation between the protein and water dipoles, compensating for the positive variance of the intrinsic protein dipole in the overall dipolar susceptibility. In contrast to the neutral ubiquitin, charged proteins studied here show para-electric dipolar response and positive dielectrophoresis. The study suggests that the dipolar response of proteins in solution is strongly affected by the coupling of the protein surface charge to the hydration water. The protein-water dipolar cross-correlations are long-ranged, extending ~2 nm from the protein surface into the bulk. A similar correlation length of about 1 nm is seen for the electrostatic potential produced by the hydration water inside the protein. The analysis of numerical simulations suggests that the polarization of the protein-water interface is highly heterogeneous and does not follow the standard dielectric results for cavities carved in dielectrics. The polarization of the water shell gains in importance, relative to the intrinsic protein dipole, at high frequencies, above the protein Debye peak. The induced interfacial dipole can be either parallel or antiparallel to the protein dipole, depending on the distribution of the protein surface charge. As a result, the high-frequency absorption of the protein solution can

  5. A discrete Fourier-encoded, diagonal-free experiment to simplify homonuclear 2D NMR correlations

    Science.gov (United States)

    Huang, Zebin; Guan, Quanshuai; Chen, Zhong; Frydman, Lucio; Lin, Yulan

    2017-07-01

    Nuclear magnetic resonance (NMR) spectroscopy has long served as an irreplaceable, versatile tool in physics, chemistry, biology, and materials sciences, owing to its ability to study molecular structure and dynamics in detail. In particular, the connectivity of chemical sites within molecules, and thereby molecular structure, becomes visible by multi-dimensional NMR. Homonuclear correlation experiments are a powerful tool for identifying coupled spins. Generally, diagonal peaks in these correlation spectra display the strongest intensities and do not offer any new information beyond the standard one-dimensional spectrum, whereas weaker, symmetrically placed cross peaks contain most of the coupling information. The cross peaks near the diagonal are often affected by the tails of strong diagonal peaks or even obscured entirely by the diagonal. In this paper, we demonstrate a homonuclear encoding approach based on imparting a discrete phase modulation of the targeted cross peaks and combine it with a site-selective sculpting scheme, capable of simplifying the patterns arising in these 2D correlation spectra. The theoretical principles of the new methods are laid out, and experimental observations are rationalized on the basis of theoretical analyses. The ensuing techniques provide a new way to retrieve 2D coupling information within homonuclear spin systems, with enhanced sensitivity, speed, and clarity.

  6. Tilted fiber grating accelerometer incorporating an abrupt biconical taper for cladding to core recoupling.

    Science.gov (United States)

    Guo, Tuan; Shao, Liyang; Tam, Hwa-Yaw; Krug, Peter A; Albert, Jacques

    2009-11-09

    We demonstrate a compact power-referenced fiber-optic accelerometer using a weakly tilted fiber Bragg grating (TFBG) combined with an abrupt biconical taper. The electric-arc-heating induced taper is located a short distance upstream from the TFBG and functions as a bridge to recouple the TFBG-excited lower-order cladding modes back into the fiber core. This recoupling is extremely sensitive to microbending. We avoid complex wavelength interrogation by simply monitoring power change in reflection, which we show to be proportional to acceleration. In addition, the Bragg resonance is virtually unaffected by fiber bending and can be used as a power reference to cancel out any light source fluctuations. The proposed sensing configuration provides a constant linear response (nonlinearity < 1%) over a vibration frequency range from DC to 250 Hz. The upper vibration frequency limit of measurement is determined by mechanical resonance, and can be tuned by varying the sensor length. The tip-reflection sensing feature enables the sensor head to be made small enough (20~100 mm in length and 2 mm in diameter) for embedded detection. The polymer-tube-package makes the sensor sufficiently stiff for in-field acceleration measurement.

  7. Orientation-dependent (19)F dipolar couplings within a trifluoromethyl group are revealed by static multipulse NMR in the solid state.

    Science.gov (United States)

    Grage, S L; Ulrich, A S

    2000-09-01

    The homonuclear dipolar coupling between the three equivalent (19)F-spins of a trifluoromethyl group, rotating about its threefold symmetry axis, was studied by multipulse solid-state NMR. A modified CPMG sequence was used first to resolve the dipolar splitting of a powder sample, and then to follow its orientation-dependence in uniaxially aligned samples. Our aim is to employ the CF(3)-group as a highly sensitive reporter to describe the mobility and spacial alignment of (19)F-labeled molecules in biomembranes. As an example, the fluorinated anti-inflammatory drug, flufenamic acid, was embedded as a guest compound in lipid bilayers. Undistorted (19)F dipolar spectra of its CF(3)-group were obtained without (1)H-decoupling, revealing a sharp triplet lineshape. When an oriented membrane sample was tilted in the magnetic field, the change in dipolar splittings confirmed that the guest molecule is motionally averaged about the membrane normal, as expected. A different behavior of flufenamic acid, however, was observed under conditions of low bilayer hydration. From this set of orientation-dependent lineshapes we conclude that the axis of motional averaging becomes aligned perpendicular to the sample normal. It thus appears that flufenamic acid induces a hexagonal phase in the membrane at low hydration. Finally, the dipolar (19)F NMR experiments were extended to frozen samples, where no molecular diffusion occurs besides the fast rotation about the CF(3)-axis. Also under these conditions, the CPMG experiment with composite pulses could successfully resolve the dipolar coupling between the three (19)F-nuclei. Copyright 2000 Academic Press.

  8. Second virial coefficients of dipolar hard spheres

    NARCIS (Netherlands)

    Philipse, A.P.; Kuipers, B.W.M.

    2010-01-01

    An asymptotic formula is reported for the second virial coefficient B2 of a dipolar hard-sphere (DHS) fluid, in zero external field, for strongly coupled dipolar interactions. This simple formula, together with the one for the weak-coupling B2, provides an accurate prediction of the second virial

  9. Overall structure and sugar dynamics of a DNA dodecamer from homo- and heteronuclear dipolar couplings and {sup 31}P chemical shift anisotropy

    Energy Technology Data Exchange (ETDEWEB)

    Wu Zhengrong; Delaglio, Frank [National Institute of Diabetes and Digestive and Kidney Diseases, Laboratory of Chemical Physics (United States); Tjandra, Nico [National Heart, Lung and Blood Institute, National Cancer Institute, National Institutes of Health, Laboratory of Biophysical Chemistry (United States); Zhurkin, Victor B. [National Cancer Institute, National Institutes of Health, Laboratory of Experimental and Computational Biology (United States); Bax, Ad [National Institute of Diabetes and Digestive and Kidney Diseases, Laboratory of Chemical Physics (United States)

    2003-08-15

    The solution structure of d(CGCGAATTCGCG){sub 2} has been determined on the basis of an exceptionally large set of residual dipolar couplings. In addition to the heteronuclear {sup 13}C-{sup 1}H and {sup 15}N-{sup 1}H and qualitative homonuclear {sup 1}H-{sup 1}H dipolar couplings, previously measured in bicelle medium, more than 300 quantitative {sup 1}H-{sup 1}H and 22 {sup 31}P-{sup 1}H dipolar restraints were obtained in liquid crystalline Pf1 medium, and 22 {sup 31}P chemical shift anisotropy restraints. High quality DNA structures can be obtained solely on the basis of these new restraints, and these structures are in close agreement with those calculated previously on the basis of {sup 13}C-{sup 1}H and {sup 15}N-{sup 1}H dipolar couplings. In the newly calculated structures, {sup 31}P-{sup 1}H dipolar and {sup 3}JsubH3{sup '}Psub couplings and {sup 31}P CSA data restrain the phosphodiester backbone torsion angles. The final structure represents a quite regular B-form helix with a modest bending of {approx}10 deg., which is essentially independent of whether or not electrostatic terms are used in the calculation. Combined, the number of homo- and heteronuclear dipolar couplings significantly exceeds the number of degrees of freedom in the system. Results indicate that the dipolar coupling data cannot be fit by a single structure, but are compatible with the presence of rapid equilibria between C2{sup '}-endo and C3{sup '}-endo deoxyribose puckers (sugar switching). The C2{sup '}-H2{sup '}/H2{sup ''} dipolar couplings in B-form DNA are particularly sensitive to sugar pucker and yield the largest discrepancies when fit to a single structure. To resolve these discrepancies, we suggest a simplified dipolar coupling analysis that yields N/S equilibria for the ribose sugar puckers, which are in good agreement with previous analyses of NMR J{sub HH} couplings, with a population of the minor C3{sup '}-endo form higher for

  10. Phase cycling schemes for finite-pulse-RFDR MAS solid state NMR experiments.

    Science.gov (United States)

    Zhang, Rongchun; Nishiyama, Yusuke; Sun, Pingchuan; Ramamoorthy, Ayyalusamy

    2015-03-01

    The finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used in 2D homonuclear chemical shift correlation experiments under magic angle spinning (MAS). A recent study demonstrated the advantages of using a short phase cycle, XY4, and its super-cycle, XY4(1)4, for the fp-RFDR pulse sequence employed in 2D (1)H/(1)H single-quantum/single-quantum correlation experiments under ultrafast MAS conditions. In this study, we report a comprehensive analysis on the dipolar recoupling efficiencies of XY4, XY4(1)2, XY4(1)3, XY4(1)4, and XY8(1)4 phase cycles under different spinning speeds ranging from 10 to 100 kHz. The theoretical calculations reveal the presence of second-order terms (T(10)T(2,±2), T(1,±1)T(2,±1), etc.) in the recoupled homonuclear dipolar coupling Hamiltonian only when the basic XY4 phase cycle is utilized, making it advantageous for proton-proton magnetization transfer under ultrafast MAS conditions. It is also found that the recoupling efficiency of fp-RFDR is quite dependent on the duty factor (τ180/τR) as well as on the strength of homonuclear dipolar couplings. The rate of longitudinal magnetization transfer increases linearly with the duty factor of fp-RFDR for all the XY-based phase cycles investigated in this study. Examination of the performances of different phase cycles against chemical shift offset and RF field inhomogeneity effects revealed that XY4(1)4 is the most tolerant phase cycle, while the shortest phase cycle XY4 suppressed the RF field inhomogeneity effects most efficiently under slow spinning speeds. Our results suggest that the difference in the fp-RFDR recoupling efficiencies decreases with the increasing MAS speed, while ultrafast (>60 kHz) spinning speed is advantageous as it recouples a large amount of homonuclear dipolar couplings and therefore enable fast magnetization exchange. The effects of higher-order terms and cross terms between various interactions in the effective Hamiltonian of fp

  11. Dipolar correlations in liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Cui [Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States); Galli, Giulia, E-mail: gagalli@uchicago.edu [Institute for Molecular Engineering, The University of Chicago, Chicago, Illinois 60637 (United States)

    2014-08-28

    We present an analysis of the dipolar correlations in water as a function of temperature and density and in the presence of simple ionic solutes, carried out using molecular dynamics simulations and empirical potentials. We show that the dipole-dipole correlation function of the liquid exhibits sizable oscillations over nanodomains of about 1.5 nm radius, with several isosbestic points as a function of temperature; the size of the nanodomains is nearly independent on temperature and density, between 240 and 400 K and 0.9 and 1.3 g/cm{sup 3}, but it is substantially affected by the presence of solvated ions. In the same range of thermodynamic conditions, the decay time (τ) of the system dipole moment varies by a factor of about 30 and 1.5, as a function of temperature and density, respectively. At 300 K, we observed a maximum in τ as a function of density, and a corresponding shallow maximum in the tetrahedral order parameter, in a range where the diffusion coefficient, the pressure and the dielectric constant increase monotonically.

  12. Dipolar correlations in liquid water.

    Science.gov (United States)

    Zhang, Cui; Galli, Giulia

    2014-08-28

    We present an analysis of the dipolar correlations in water as a function of temperature and density and in the presence of simple ionic solutes, carried out using molecular dynamics simulations and empirical potentials. We show that the dipole-dipole correlation function of the liquid exhibits sizable oscillations over nanodomains of about 1.5 nm radius, with several isosbestic points as a function of temperature; the size of the nanodomains is nearly independent on temperature and density, between 240 and 400 K and 0.9 and 1.3 g/cm(3), but it is substantially affected by the presence of solvated ions. In the same range of thermodynamic conditions, the decay time (τ) of the system dipole moment varies by a factor of about 30 and 1.5, as a function of temperature and density, respectively. At 300 K, we observed a maximum in τ as a function of density, and a corresponding shallow maximum in the tetrahedral order parameter, in a range where the diffusion coefficient, the pressure and the dielectric constant increase monotonically.

  13. Dielectric relaxation in dipolar mixtures

    Science.gov (United States)

    Sharma, Ashok K.; Agarwal, Vinod K.; Mansingh, Abhai

    1981-08-01

    Dielectric constants and losses have been measured at several microwave frequencies in the range 2.4-25 GHz for two binary mixtures: bromoform +1-bromonaphthalene (dipole moment ratio is about 1:1), and nitrobenzene +1-bromonaphthalene (dipole moment ratio is about 4:1). The dielectric data of each binary system have been analyzed in terms of two superimposed Debye regions. This analysis has been carried out to study the effect of internal field on the numerical values of the relative weights or amplitudes C1 and C2 in the dipolar mixtures. It is observed that the discrepancy between the numerical values of weight factors obtained from relaxation data and dipole moment and mole fractions of the binary mixture cannot be attributed to the internal field. For the bromoform +1-bromonaphthalene system, it has been found that both the Budo and Cole-Cole equation represent the system equally well, but for nitrobenzene +1-bromonaphthalene system the Cole distribution fits better than Budo's equation.

  14. Longitudinal expansion of field line dipolarization

    Science.gov (United States)

    Saka, O.; Hayashi, K.

    2017-11-01

    We examine the substorm expansions that started at 1155 UT 10 August 1994 in the midnight sector focusing on the longitudinal (eastward) expansion of field line dipolarization in the auroral zone. Eastward expansion of the dipolarization region was observed in all of the H, D, and Z components. The dipolarization that started at 1155 UT (0027 MLT) from 260° of geomagnetic longitude (CMO) expanded to 351°(PBQ) in about 48 min. The expansion velocity was 0.03-0.04°/s, or 1.9 km/s at 62°N of geomagnetic latitude. The dipolarization region expanding to the east was accompanied by a bipolar event at the leading edge of the expansion in latitudes equatorward of the westward electrojet (WEJ). In the midnight sector at the onset meridian, the Magnetospheric Plasma Analyzer (MAP) on board geosynchronous satellite L9 measured electrons and ions between 10 eV and 40 keV. We conclude from the satellite observations that this dipolarization was characterized by the evolution of temperature anisotropies, an increase of the electron and ion temperatures, and a rapid change in the symmetry axis of the temperature tensor. The field line dipolarization and its longitudinal expansion were interpreted in terms of the slow MHD mode triggered by the current disruption. We propose a new magnetosphere-ionosphere coupling (MI-coupling) mechanism based on the scenario that transmitted westward electric fields from the magnetosphere in association with expanding dipolarization produced electrostatic potential (negative) in the ionosphere through differences in the mobility of collisional ions and collisionless electrons. The field-aligned currents that emerged from the negative potential region are arranged in a concentric pattern around the negative potential region, upward toward the center and downward on the peripheral.

  15. Folic Acid Promotes Recycling of Tetrahydrobiopterin and Protects Against Hypoxia-Induced Pulmonary Hypertension by Recoupling Endothelial Nitric Oxide Synthase

    Science.gov (United States)

    Chalupsky, Karel; Kračun, Damir; Kanchev, Ivan; Bertram, Katharina

    2015-01-01

    Abstract Aims: Nitric oxide (NO) derived from endothelial NO synthase (eNOS) has been implicated in the adaptive response to hypoxia. An imbalance between 5,6,7,8-tetrahydrobiopterin (BH4) and 7,8-dihydrobiopterin (BH2) can result in eNOS uncoupling and the generation of superoxide instead of NO. Dihydrofolate reductase (DHFR) can recycle BH2 to BH4, leading to eNOS recoupling. However, the role of DHFR and eNOS recoupling in the response to hypoxia is not well understood. We hypothesized that increasing the capacity to recycle BH4 from BH2 would improve NO bioavailability as well as pulmonary vascular remodeling (PVR) and right ventricular hypertrophy (RVH) as indicators of pulmonary hypertension (PH) under hypoxic conditions. Results: In human pulmonary artery endothelial cells and murine pulmonary arteries exposed to hypoxia, eNOS was uncoupled as indicated by reduced superoxide production in the presence of the nitric oxide synthase inhibitor, L-(G)-nitro-L-arginine methyl ester (L-NAME). Concomitantly, NO levels, BH4 availability, and expression of DHFR were diminished under hypoxia. Application of folic acid (FA) restored DHFR levels, NO bioavailability, and BH4 levels under hypoxia. Importantly, FA prevented the development of hypoxia-induced PVR, right ventricular pressure increase, and RVH. Innovation: FA-induced upregulation of DHFR recouples eNOS under hypoxia by improving BH4 recycling, thus preventing hypoxia-induced PH. Conclusion: FA might serve as a novel therapeutic option combating PH. Antioxid. Redox Signal. 23, 1076–1091. PMID:26414244

  16. Homonuclear 1H NMR and circular dichroism study of the HIV-1 Tat Eli variant

    Science.gov (United States)

    Watkins, Jennifer D; Campbell, Grant R; Halimi, Hubert; Loret, Erwann P

    2008-01-01

    Background The HIV-1 Tat protein is a promising target to develop AIDS therapies, particularly vaccines, due to its extracellular role that protects HIV-1-infected cells from the immune system. Tat exists in two different lengths, 86 or 87 residues and 99 or 101 residues, with the long form being predominant in clinical isolates. We report here a structural study of the 99 residue Tat Eli variant using 2D liquid-state NMR, molecular modeling and circular dichroism. Results Tat Eli was obtained from solid-phase peptide synthesis and the purified protein was proven biologically active in a trans-activation assay. Circular dichroism spectra at different temperatures up to 70°C showed that Tat Eli is not a random coil at 20°C. Homonuclear 1H NMR spectra allowed us to identify 1639 NMR distance constraints out of which 264 were interresidual. Molecular modeling satisfying at least 1474 NMR constraints revealed the same folding for different model structures. The Tat Eli model has a core region composed of a part of the N-terminus including the highly conserved Trp 11. The extra residues in the Tat Eli C-terminus protrude from a groove between the basic region and the cysteine-rich region and are well exposed to the solvent. Conclusion We show that active Tat variants share a similar folding pattern whatever their size, but mutations induce local structural changes. PMID:18808674

  17. Determination of proton transverse relaxation times in homonuclear-coupled Spin Systems

    Science.gov (United States)

    Gochin, Miriam

    A new method is described for obtaining proton transverse relaxation times in homonuclear-coupled systems. The oscillatory effect of the coupling on the T2 decay was removed by using the attached heteronucleus as a filter. A BIRD pulse (J. R. Garbow, D. P. Weitekamp, and A. Pines, Chem. Phys. Lett.93, 504, 1982) was applied in the center of the T2 decay period, causing protons directly and remotely connected to the heteronucleus to be decoupled from each other. Protons directly bound to the heteronucleus were inverted, leaving remote protons unaffected. Thus the method works well in natural-abundance 13C and 15N systems or for 15N-enriched biological materials, where no NN connectivities exist. The importance of obtaining proton T2 values pertains to their usefulness and sensitivity in quantitating structure and mobility in molecules. Sequences for obtaining proton T2 values were described and demonstrated on formate, alcohol, and gramicidin S. The accuracy of the measured T2 as a function of X-nucleus offset and heteronuclear coupling constant was assessed.

  18. Dipolar structures in colloidal magnetite dispersions

    NARCIS (Netherlands)

    Klokkenburg, Mark

    2007-01-01

    Dipolar structures in liquid colloidal dispersions comprising well-defined magnetite (Fe3O4) nanoparticles with a permanent magnetic dipole moment are analyzed on a single-particle level by in situ cryogenic transmission electron microscopy (2D). Compared to conventional ferrofluids, these

  19. Heteronuclear dipolar couplings, total spin coherence, and bilinear rotations in NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Garbow, J.R.

    1983-07-01

    In Chapter 1 a variety of different introductory topics are presented. The potential complexity of the nuclear magnetic resonsnace (NMR) spectra of molecules dissolved in liquid crystal solvents serves to motivate the development of multiple quantum (MQ) spectroscopy. The basics of MQ NMR are reviewed in Chapter 2. An experimental search procedure for the optimization of MQ pulse sequences is introduced. Chapter 3 discusses the application of MQ NMR techniques to the measurement of dipolar couplings in heteronuclear spin systems. The advantages of MQ methods in such systems are developed and experimental results for partially oriented (1-/sup 13/C) benzene are presented. Several pulse sequences are introduced which employ a two-step excitation of heteronuclear MQ coherence. A new multiple pulse method, involving the simultaneous irradiation of both rare and abundant spin species, is described. The problem of the broadening of MQ transitions due to magnetic field inhomogeneity is considered in Chapter 4. The method of total spin coherence transfer echo spectroscopy (TSCTES) is presented, with experimets on partially oriented acetaldehyde serving to demonstrate this new technique. TSCTES results in MQ spectra which are sensitive to all chemical shifts and spin-spin couplings and which are free of inhomogeneous broadening. In Chapter 5 the spectroscopy of spin systems of several protons and a /sup 13/C nucleus in the isotropic phase is discussed. The usefulness of the heteronuclear bilinear rotation as a calculational tool is illustrated. Compensated bilinear ..pi.. rotations, which are relatively insensitive to timing parameter missets, are presented. A new technique for homonuclear proton decoupling, Bilinear Rotation Decoupling, is described and its success in weakly coupled systems is demonstrated.

  20. Dark High Density Dipolar Liquid of Excitons.

    Science.gov (United States)

    Cohen, Kobi; Shilo, Yehiel; West, Ken; Pfeiffer, Loren; Rapaport, Ronen

    2016-06-08

    The possible phases and the nanoscale particle correlations of two-dimensional interacting dipolar particles is a long-sought problem in many-body physics. Here we observe a spontaneous condensation of trapped two-dimensional dipolar excitons with internal spin degrees of freedom from an interacting gas into a high density, closely packed liquid state made mostly of dark dipoles. Another phase transition, into a bright, highly repulsive plasma, is observed at even higher excitation powers. The dark liquid state is formed below a critical temperature Tc ≈ 4.8 K, and it is manifested by a clear spontaneous spatial condensation to a smaller and denser cloud, suggesting an attractive part to the interaction which goes beyond the purely repulsive dipole-dipole forces. Contributions from quantum mechanical fluctuations are expected to be significant in this strongly correlated, long living dark liquid. This is a new example of a two-dimensional atomic-like interacting dipolar liquid, but where the coupling of light to its internal spin degrees of freedom plays a crucial role in the dynamical formation and the nature of resulting condensed dark ground state.

  1. Existence of solitary waves in dipolar quantum gases

    KAUST Repository

    Antonelli, Paolo

    2011-02-01

    We study a nonlinear Schrdinger equation arising in the mean field description of dipolar quantum gases. Under the assumption of sufficiently strong dipolar interactions, the existence of standing waves, and hence solitons, is proved together with some of their properties. This gives a rigorous argument for the possible existence of solitary waves in BoseEinstein condensates, which originate solely due to the dipolar interaction between the particles. © 2010 Elsevier B.V. All rights reserved.

  2. S(3) HMBC: Spin-State-Selective HMBC for accurate measurement of homonuclear coupling constants. Application to strychnine yielding thirteen hitherto unreported J(HH).

    Science.gov (United States)

    Kjaerulff, Louise; Benie, Andrew J; Hoeck, Casper; Gotfredsen, Charlotte H; Sørensen, Ole W

    2016-02-01

    A novel method, Spin-State-Selective (S(3)) HMBC, for accurate measurement of homonuclear coupling constants is introduced. As characteristic for S(3) techniques, S(3) HMBC yields independent subspectra corresponding to particular passive spin states and thus allows determination of coupling constants between detected spins and homonuclear coupling partners along with relative signs. In the presented S(3) HMBC experiment, spin-state selection occurs via large one-bond coupling constants ensuring high editing accuracy and unequivocal sign determination of the homonuclear long-range relative to the associated one-bond coupling constant. The sensitivity of the new experiment is comparable to that of regular edited HMBC and the accuracy of the J/RDC measurement is as usual for E.COSY and S(3)-type experiments independent of the size of the homonuclear coupling constant of interest. The merits of the method are demonstrated by an application to strychnine where thirteen J(HH) coupling constants not previously reported could be measured. Copyright © 2015 Elsevier Inc. All rights reserved.

  3. Magnetization behavior of ferrofluids with cryogenically imaged dipolar chains

    NARCIS (Netherlands)

    Klokkenburg, M.; Erne, B.H.; Mendelev, V.; Ivanov, A.O.

    2008-01-01

    Theories and simulations have demonstrated that field-induced dipolar chains affect the static magnetic properties of ferrofluids. Experimental verification, however, has been complicated by the high polydispersity of the available ferrofluids, and the morphology of the dipolar chains was left to

  4. Cluster and Double Star observations of dipolarization

    Directory of Open Access Journals (Sweden)

    R. Nakamura

    2005-11-01

    Full Text Available We studied two types of dipolarization events with different IMF conditions when Cluster and Double Star (TC-1 were located in the same local time sector: 7 August 2004, 18:00-24:00 UT, during a disturbed southward/northward IMF interval, and 14 August 2004, 21:00-24:00 UT, when the IMF was stably northward. Cluster observed dipolarization as well as fast flows during both intervals, but this was not the case for TC-1. For both events the satellites crossed near the conjugate location of the MIRACLE stations. By using multi-point analysis techniques, the direction/speed of the propagation is determined using Cluster and is then compared with the disturbances at TC-1 to discuss its spatial/temporal scale. The propagation direction of the BZ disturbance at Cluster was mainly dawnward with a tailward component for 7 August and with a significant Earthward component for 14 August associated with fast flows. We suggest that the role of the midtail fast flows can be quite different in the dissipation process depending on the condition of the IMF and resultant configuration of the tail.

  5. Cluster and Double Star observations of dipolarization

    Directory of Open Access Journals (Sweden)

    R. Nakamura

    2005-11-01

    Full Text Available We studied two types of dipolarization events with different IMF conditions when Cluster and Double Star (TC-1 were located in the same local time sector: 7 August 2004, 18:00-24:00 UT, during a disturbed southward/northward IMF interval, and 14 August 2004, 21:00-24:00 UT, when the IMF was stably northward. Cluster observed dipolarization as well as fast flows during both intervals, but this was not the case for TC-1. For both events the satellites crossed near the conjugate location of the MIRACLE stations. By using multi-point analysis techniques, the direction/speed of the propagation is determined using Cluster and is then compared with the disturbances at TC-1 to discuss its spatial/temporal scale. The propagation direction of the BZ disturbance at Cluster was mainly dawnward with a tailward component for 7 August and with a significant Earthward component for 14 August associated with fast flows. We suggest that the role of the midtail fast flows can be quite different in the dissipation process depending on the condition of the IMF and resultant configuration of the tail.

  6. Imaging using long range dipolar field effects Nuclear magnetic resonance

    CERN Document Server

    Gutteridge, S

    2002-01-01

    The work in this thesis has been undertaken by the except where indicated in reference, within the Magnetic Resonance Centre, at the University of Nottingham during the period from October 1998 to March 2001. This thesis details the different characteristics of the long range dipolar field and its application to magnetic resonance imaging. The long range dipolar field is usually neglected in nuclear magnetic resonance experiments, as molecular tumbling decouples its effect at short distances. However, in highly polarised samples residual long range components have a significant effect on the evolution of the magnetisation, giving rise to multiple spin echoes and unexpected quantum coherences. Three applications utilising these dipolar field effects are documented in this thesis. The first demonstrates the spatial sensitivity of the signal generated via dipolar field effects in structured liquid state samples. The second utilises the signal produced by the dipolar field to create proton spin density maps. Thes...

  7. Assessment of zinc finger orientations by residual dipolar coupling constants

    Energy Technology Data Exchange (ETDEWEB)

    Tsui, Vickie; Zhu Leiming; Huang, T.-H.; Wright, Peter E.; Case, David A. [Scripps Research Institute, Department of Molecular Biology (United States)

    2000-01-15

    Residual dipolar coupling constants measured in anisotropic solution contain information on orientations between internuclear vectors and the magnetic field, providing long-range information that may help determine the relative orientations of distinct domains in biomolecules. Here we describe the measurement and use of residual dipolar coupling restraints in the refinement of the structure of the complex of DNA with three zinc fingers of transcription factor IIIA (TFIIIA), measured in a DMPC/DHPC bicelle solution. These dipolar restraints were applied on a variety of orientations of the zinc finger domains (derived from crystallography, previous NMR studies, and systematic modeling) in order to examine the validity and sensitivity of using residual dipolar splittings to study interdomain orientations. The spread in interdomain angles between zinc fingers is reduced from 24 deg. to 9 deg. upon incorporation of dipolar restraints. However, the results also show that the ability to determine relative orientations is strongly dependent on the structural accuracy of the local domain structures.

  8. Calculation of Ground State Rotational Populations for Kinetic Gas Homonuclear Diatomic Molecules including Electron-Impact Excitation and Wall Collisions

    Energy Technology Data Exchange (ETDEWEB)

    David R. Farley

    2010-08-19

    A model has been developed to calculate the ground-state rotational populations of homonuclear diatomic molecules in kinetic gases, including the effects of electron-impact excitation, wall collisions, and gas feed rate. The equations are exact within the accuracy of the cross sections used and of the assumed equilibrating effect of wall collisions. It is found that the inflow of feed gas and equilibrating wall collisions can significantly affect the rotational distribution in competition with non-equilibrating electron-impact effects. The resulting steady-state rotational distributions are generally Boltzmann for N≥3, with a rotational temperature between the wall and feed gas temperatures. The N=0,1,2 rotational level populations depend sensitively on the relative rates of electron-impact excitation versus wall collision and gas feed rates.

  9. Universal Behavior of Spin Dipolar Relaxation in Atomic Condensates

    Science.gov (United States)

    Deng, Yuangang; Zhou, Yiquan; Deng, Min; Liu, Qi; Tey, Mengkhoon; Gao, Bo; You, Li

    2017-04-01

    The dipolar relaxation of atomic spinor condensates is studied in terms of the semi-analytical scattering wave functions by utilizing the quantum-defect theory. At nonzero magnetic fields, inelastic dipolar relaxation of exothermic reaction leads to loss of the atomic population. By tuning the bias field, we find that the dipolar relaxation rate exhibits a universal behavior involving a unique dip and peak structure, different from the commonly referenced result based on the Born or the distortedwave Born approximations. The positions for the dip and the peak are shown to be determined dominantly by the short-range s-wave scattering length and the Van der Waals radius, independent of the dipolar interaction strength of ultracold atoms. This is confirmed by the precision measured dipolar relaxation decay rate for both spin-polarized atomic coherent spin states and twin-Fock states of F = 1 87 Rb BoseEinstein condensates. We observe the dipolar relaxation suppression as predicted by our theory for the large bias field, a feature not previously studied experimentally. Our results implicate the possibility of extracting the short-range scattering length and the Van der Waals dispersion coefficient from spin dipolar decay measurements.

  10. Non-adiabatic rotational excitation of dipolar molecule under the ...

    Indian Academy of Sciences (India)

    adiabatically by half cycle pulse. (HCP) is controlled using the second ultrashort HCP. ... excited to create a rotational quantum wave packet, a .... Non-adiabatic rotational excitation of dipolar molecule under the influence of delayed pulses. 1215.

  11. Dipolar Interaction in a One-Dimensional Ising Ring

    Directory of Open Access Journals (Sweden)

    Gina Rose Tongco

    2004-12-01

    Full Text Available As synthesis of low-dimensional magnetic systems become possible, the need for theoretical understanding of their behavior arises. In this work, the authors explore a one-dimensional magnetic structure with the spins having dipolar interaction.

  12. Isospin equilibration processes and dipolar signals: Coherent cluster production

    Science.gov (United States)

    Papa, M.; Berceanu, I.; Acosta, L.; Agodi, C.; Auditore, L.; Cardella, G.; Chatterjee, M. B.; Dell'Aquila, D.; De Filippo, E.; Francalanza, L.; Lanzalone, G.; Lombardo, I.; Maiolino, C.; Martorana, N.; Pagano, A.; Pagano, E. V.; Pirrone, S.; Politi, G.; Quattrocchi, L.; Rizzo, F.; Russotto, P.; Trifiró, A.; Trimarchi, M.; Verde, G.; Vigilante, M.

    2017-11-01

    The total dipolar signal related to multi-break-up processes induced on the system ^{48}Ca +{^{27}Al} at 40MeV/nucleon has been investigated with the CHIMERA multi-detector. Experimental data related to semi-peripheral collisions are shown and compared with CoMD-III calculations. The strong connection between the dipolar signal as obtained from the detected fragments and the dynamics of the isospin equilibration processes is also shortly discussed.

  13. Expanding the 2, 2’-bipyrimidine bridged 1D homonuclear coordination polymers family: [MIIbpymCl2] (M=Fe, Co) magnetic and structural characterization

    OpenAIRE

    Alborés, Pablo; Rentschler, Eva

    2015-01-01

    One pot reaction of hydrated chloride salts of Fe(II) and Co(II) with stoichiometric amounts of 2, 2’-bipyrimidine (bpym) in a methanol/ acetonitrile mixture afforded the corresponding 1D homonuclear coordination polymers, [μ-(bpym)MCl2]n. Crystal structures of both complexes are isomorphous in the highly symmetric orthorhombic space group Fddd. The 1D coordination polymers are composed of almost orthogonal alternating bipyrimidine bridges linking the {MCl2} units. The magnetic behaviour of t...

  14. Asymptotic behavior of local dipolar fields in thin films

    Energy Technology Data Exchange (ETDEWEB)

    Bowden, G.J., E-mail: gjb@phys.soton.ac.uk [School of Physics and Astronomy, University of Southampton, SO17 1BJ (United Kingdom); Stenning, G.B.G., E-mail: Gerrit.vanderlaan@diamond.ac.uk [Magnetic Spectroscopy Group, Diamond Light Source, Didcot OX11 0DE (United Kingdom); Laan, G. van der, E-mail: gavin.stenning@stfc.ac.uk [ISIS Neutron and Muon Source, Rutherford Appleton Laboratory, Didcot OX11 0QX (United Kingdom)

    2016-10-15

    A simple method, based on layer by layer direct summation, is used to determine the local dipolar fields in uniformly magnetized thin films. The results show that the dipolar constants converge ~1/m where the number of spins in a square film is given by (2m+1){sup 2}. Dipolar field results for sc, bcc, fcc, and hexagonal lattices are presented and discussed. The results can be used to calculate local dipolar fields in films with either ferromagnetic, antiferromagnetic, spiral, exponential decay behavior, provided the magnetic order only changes normal to the film. Differences between the atomistic (local fields) and macroscopic fields (Maxwellian) are also examined. For the latter, the macro B-field inside the film is uniform and falls to zero sharply outside, in accord with Maxwell boundary conditions. In contrast, the local field for the atomistic point dipole model is highly non-linear inside and falls to zero at about three lattice spacing outside the film. Finally, it is argued that the continuum field B (used by the micromagnetic community) and the local field B{sub loc}(r) (used by the FMR community) will lead to differing values for the overall demagnetization energy. - Highlights: • Point-dipolar fields in uniformly magnetized thin films are characterized by just three numbers. • Maxwell's boundary condition is partially violated in the point-dipole approximation. • Asymptotic values of point dipolar fields in circular monolayers scale as π/r.

  15. Dipolar dark matter with massive bigravity

    Energy Technology Data Exchange (ETDEWEB)

    Blanchet, Luc [GRECO Institut d’Astrophysique de Paris - UMR 7095 du CNRS,Université Pierre & Marie Curie,98" b" i" s boulevard Arago, 75014 Paris (France); Heisenberg, Lavinia [Nordita, KTH Royal Institute of Technology and Stockholm University,Roslagstullsbacken 23, 10691 Stockholm (Sweden); Department of Physics & The Oskar Klein Centre, AlbaNova University Centre,Roslagstullsbacken 21, 10691 Stockholm (Sweden)

    2015-12-14

    Massive gravity theories have been developed as viable IR modifications of gravity motivated by dark energy and the problem of the cosmological constant. On the other hand, modified gravity and modified dark matter theories were developed with the aim of solving the problems of standard cold dark matter at galactic scales. Here we propose to adapt the framework of ghost-free massive bigravity theories to reformulate the problem of dark matter at galactic scales. We investigate a promising alternative to dark matter called dipolar dark matter (DDM) in which two different species of dark matter are separately coupled to the two metrics of bigravity and are linked together by an internal vector field. We show that this model successfully reproduces the phenomenology of dark matter at galactic scales (i.e. MOND) as a result of a mechanism of gravitational polarisation. The model is safe in the gravitational sector, but because of the particular couplings of the matter fields and vector field to the metrics, a ghost in the decoupling limit is present in the dark matter sector. However, it might be possible to push the mass of the ghost beyond the strong coupling scale by an appropriate choice of the parameters of the model. Crucial questions to address in future work are the exact mass of the ghost, and the cosmological implications of the model.

  16. Dipolar droplets in bosonic erbium quantum fluids

    Science.gov (United States)

    Chomaz, Lauriane; Baier, Simon; Petter, Daniel; Faraoni, Giulia; Becher, Jan-Hendrik; van Bijnen, Rick; Mark, Manfred J.; Ferlaino, Francesca

    2017-04-01

    Due to their large magnetic moment and exotic electronic configuration, atoms of the lanthanide family, such as dysprosium (Dy) and erbium (Er), are an ideal platform for exploring the competition between inter-particle interactions of different origins and behaviors. Recently, a novel phase of dilute droplet has been observed in an ultracold gas of bosonic Dy when changing the ratio of the contact and dipole-dipole interactions and setting the mean-field interactions to slightly attractive. This has been attributed to the distinct, non-vanishing, beyond-mean-field effects in dipolar gases when the mean interaction cancels. Here we report on the investigation of droplet physics in fluids of bosonic Er. By precise control of the scattering length a, we quantitatively probe the Bose-Einstein condensate (BEC)-to-droplet phase diagram and the rich underlying dynamics. In a prolate geometry, we observe a crossover from a BEC to a single macro-droplet, prove the stabilizing role of quantum fluctuations and characterize the special dynamical properties of the droplet. In an oblate geometry, we observe the formation of assemblies of tinier droplets arranged in a chain and explore the special state dynamics following a quench of a, marked by successive merging and reformation events. L.C. is supported within the Marie Curie Individual Fellowship DIPPHASE No. 706809 of the European Commission.

  17. Self-replication with magnetic dipolar colloids

    Science.gov (United States)

    Dempster, Joshua M.; Zhang, Rui; Olvera de la Cruz, Monica

    2015-10-01

    Colloidal self-replication represents an exciting research frontier in soft matter physics. Currently, all reported self-replication schemes involve coating colloidal particles with stimuli-responsive molecules to allow switchable interactions. In this paper, we introduce a scheme using ferromagnetic dipolar colloids and preprogrammed external magnetic fields to create an autonomous self-replication system. Interparticle dipole-dipole forces and periodically varying weak-strong magnetic fields cooperate to drive colloid monomers from the solute onto templates, bind them into replicas, and dissolve template complexes. We present three general design principles for autonomous linear replicators, derived from a focused study of a minimalist sphere-dimer magnetic system in which single binding sites allow formation of dimeric templates. We show via statistical models and computer simulations that our system exhibits nonlinear growth of templates and produces nearly exponential growth (low error rate) upon adding an optimized competing electrostatic potential. We devise experimental strategies for constructing the required magnetic colloids based on documented laboratory techniques. We also present qualitative ideas about building more complex self-replicating structures utilizing magnetic colloids.

  18. Self-replication with magnetic dipolar colloids.

    Science.gov (United States)

    Dempster, Joshua M; Zhang, Rui; Olvera de la Cruz, Monica

    2015-10-01

    Colloidal self-replication represents an exciting research frontier in soft matter physics. Currently, all reported self-replication schemes involve coating colloidal particles with stimuli-responsive molecules to allow switchable interactions. In this paper, we introduce a scheme using ferromagnetic dipolar colloids and preprogrammed external magnetic fields to create an autonomous self-replication system. Interparticle dipole-dipole forces and periodically varying weak-strong magnetic fields cooperate to drive colloid monomers from the solute onto templates, bind them into replicas, and dissolve template complexes. We present three general design principles for autonomous linear replicators, derived from a focused study of a minimalist sphere-dimer magnetic system in which single binding sites allow formation of dimeric templates. We show via statistical models and computer simulations that our system exhibits nonlinear growth of templates and produces nearly exponential growth (low error rate) upon adding an optimized competing electrostatic potential. We devise experimental strategies for constructing the required magnetic colloids based on documented laboratory techniques. We also present qualitative ideas about building more complex self-replicating structures utilizing magnetic colloids.

  19. Mass effects in the photodissociation of homonuclear diatomic molecules in helium nanodroplets: inelastic collision and viscous flow energy exchange regimes.

    Science.gov (United States)

    Vilà, Arnau; González, Miguel

    2016-10-05

    The influence of the mass in the photodissociation dynamics of a homonuclear diatomic molecule (X2), embedded in a superfluid helium nanodroplet (T = 0.37 K) of 300 atoms, has been investigated using a hybrid quantum dynamics method recently proposed by us. Several hypothetical isotopic variants of Cl2 have been examined in order to make possible the analysis of a wide diversity of masses (mX: 0.25mCl-1.50mCl). This is probably the first time that this problem has been considered theoretically. The photodissociation mechanism of X2(B) is very similar to that of Cl2(B) and the efficiency of the X2-helium energy exchange mechanism can be so great that it leads to the full and partial (≈86%) geminate recombination for the lower masses explored (mX = 0.25mCl and 0.50mCl, respectively). From the energy exchange perspective two dynamic regimes have been identified. The first regime occurs at the initial times of the photodissociation and corresponds to a perfectly inelastic collision (IC) between the atomic fragments (X) and some helium atoms of the solvation shell. The second regime occurs when the atomic fragments are moving through the nanodroplet, which behaves as a viscous fluid (VF). The ICVF mechanism has probably general character in the photodissociation of molecules embedded in superfluid helium nanodroplets.

  20. Dipolar magnetism in ordered and disordered low-dimensional nanoparticle assemblies

    DEFF Research Database (Denmark)

    Varón, M.; Beleggia, M; Kasama, T

    2013-01-01

    Magnetostatic (dipolar) interactions between nanoparticles promise to open new ways to design nanocrystalline magnetic materials and devices if the collective magnetic properties can be controlled at the nanoparticle level. Magnetic dipolar interactions are sufficiently strong to sustain magnetic...

  1. Quantum states with topological properties via dipolar interactions

    Energy Technology Data Exchange (ETDEWEB)

    Peter, David

    2015-06-25

    This thesis proposes conceptually new ways to realize materials with topological properties by using dipole-dipole interactions. First, we study a system of ultracold dipolar fermions, where the relaxation mechanism of dipolar spins can be used to reach the quantum Hall regime. Second, in a system of polar molecules in an optical lattice, dipole-dipole interactions induce spin-orbit coupling terms for the rotational excitations. In combination with time-reversal symmetry breaking this leads to topological bands with Chern numbers greater than one.

  2. Nonlocal and nonlinear electrostatics of a dipolar Coulomb fluid.

    Science.gov (United States)

    Sahin, Buyukdagli; Ralf, Blossey

    2014-07-16

    We study a model Coulomb fluid consisting of dipolar solvent molecules of finite extent which generalizes the point-like dipolar Poisson-Boltzmann model (DPB) previously introduced by Coalson and Duncan (1996 J. Phys. Chem. 100 2612) and Abrashkin et al (2007 Phys. Rev. Lett. 99 077801). We formulate a nonlocal Poisson-Boltzmann equation (NLPB) and study both linear and nonlinear dielectric response in this model for the case of a single plane geometry. Our results shed light on the relevance of nonlocal versus nonlinear effects in continuum models of material electrostatics.

  3. Electron dynamics during substorm dipolarization in Mercury's magnetosphere

    Directory of Open Access Journals (Sweden)

    D. C. Delcourt

    2005-11-01

    Full Text Available We examine the nonlinear dynamics of electrons during the expansion phase of substorms at Mercury using test particle simulations. A simple model of magnetic field line dipolarization is designed by rescaling a magnetic field model of the Earth's magnetosphere. The results of the simulations demonstrate that electrons may be subjected to significant energization on the time scale (several seconds of the magnetic field reconfiguration. In a similar manner to ions in the near-Earth's magnetosphere, it is shown that low-energy (up to several tens of eV electrons may not conserve the second adiabatic invariant during dipolarization, which leads to clusters of bouncing particles in the innermost magnetotail. On the other hand, it is found that, because of the stretching of the magnetic field lines, high-energy electrons (several keVs and above do not behave adiabatically and possibly experience meandering (Speiser-type motion around the midplane. We show that dipolarization of the magnetic field lines may be responsible for significant, though transient, (a few seconds precipitation of energetic (several keVs electrons onto the planet's surface. Prominent injections of energetic trapped electrons toward the planet are also obtained as a result of dipolarization. These injections, however, do not exhibit short-lived temporal modulations, as observed by Mariner-10, which thus appear to follow from a different mechanism than a simple convection surge.

  4. Electron heating and Tp/Te variations during magnetic dipolarizations

    Science.gov (United States)

    Grigorenko, Elena; Kronberg, Elena; Daly, Patrick; Ganushkina, Natalia; Lavraud, Benoit; Sauvaud, Jean-Andre; Zelenyi, Lev

    2017-04-01

    The proton-to-electron temperature ratio (Tp/Te) in the plasma sheet (PS) of the Earth's magnetotail is studied by using 5 years of Cluster observations (2001-2005). The PS intervals are searched within a region defined with -19GSM) under the condition |Bx|≤10nT and 160 intervals were selected. In many PS intervals from our data base Tp/Te varies over a wide range from a few units to several tens of units. In 86 PS intervals the Tp/Te decreases below 3.5. In the majority of these intervals the Tp/Te drops are observed during magnetotail dipolarizations. A superposed epoch analysis applied to these events shows that the minimum value of Tp/Te is observed after the dipolarization onset during the "turbulent phase" of dipolarization, when a number of transient Bz pulses are reduced, but the value of Bz field is still large and an intensification of wave activity is observed. The Tp/Te drops and associated increases of Te often coincide either with bursts of broadband electrostatic emissions, which may include electron cyclotron harmonics, or with broadband electromagnetic emission in a frequency range from proton plasma frequency (fpp) up to the electron gyrofrequency (fce). These findings show that the wave activity developing in the current sheet after dipolarization onset may play a role in the additional electron heating and the associated Tp/Te decrease. This work was supported by the Volskwagen Foundation (grant Az 90 312).

  5. Functionalization of Graphene via 1,3-Dipolar Cycloaddition

    NARCIS (Netherlands)

    Quintana, Mildred; Spyrou, Konstantinos; Grzelczak, Marek; Browne, Wesley R.; Rudolf, Petra; Prato, Maurizio

    Few-layer graphenes (FLG) produced by dispersion and exfoliation of graphite in N-methylpyrrolidone were successfully functionalized using the 1,3-dipolar cycloaddition of azomethine ylides. The amino functional groups attached to graphene sheets were quantified by the Kaiser test. These amino

  6. Dipolar collisions of polar molecules in the quantum regime.

    Science.gov (United States)

    Ni, K-K; Ospelkaus, S; Wang, D; Quéméner, G; Neyenhuis, B; de Miranda, M H G; Bohn, J L; Ye, J; Jin, D S

    2010-04-29

    Ultracold polar molecules offer the possibility of exploring quantum gases with interparticle interactions that are strong, long-range and spatially anisotropic. This is in stark contrast to the much studied dilute gases of ultracold atoms, which have isotropic and extremely short-range (or 'contact') interactions. Furthermore, the large electric dipole moment of polar molecules can be tuned using an external electric field; this has a range of applications such as the control of ultracold chemical reactions, the design of a platform for quantum information processing and the realization of novel quantum many-body systems. Despite intense experimental efforts aimed at observing the influence of dipoles on ultracold molecules, only recently have sufficiently high densities been achieved. Here we report the experimental observation of dipolar collisions in an ultracold molecular gas prepared close to quantum degeneracy. For modest values of an applied electric field, we observe a pronounced increase in the loss rate of fermionic potassium-rubidium molecules due to ultracold chemical reactions. We find that the loss rate has a steep power-law dependence on the induced electric dipole moment, and we show that this dependence can be understood in a relatively simple model based on quantum threshold laws for the scattering of fermionic polar molecules. In addition, we directly observe the spatial anisotropy of the dipolar interaction through measurements of the thermodynamics of the dipolar gas. These results demonstrate how the long-range dipolar interaction can be used for electric-field control of chemical reaction rates in an ultracold gas of polar molecules. Furthermore, the large loss rates in an applied electric field suggest that creating a long-lived ensemble of ultracold polar molecules may require confinement in a two-dimensional trap geometry to suppress the influence of the attractive, 'head-to-tail', dipolar interactions.

  7. Internal dipolar field and soft magnons in periodic nanocomposite magnets

    Science.gov (United States)

    Belemuk, A. M.; Chui, S. T.

    2017-07-01

    We study spin wave excitations in a three-dimensional nanocomposite magnet of exchange coupled hard (SmCo5) and soft (FeCo) phases. The dipolar interaction splits the spin wave energies into the upper and lower branches of the spin wave manifold. When the amount of the soft phase is increased the energy of low-lying spin excitations is considerably softened due to two reasons: (i) the low- lying mode locked into the soft phase region with a spin wave gap at k = 0 which scales approximately proportional to the anisotropy constant of the soft phase and (ii) the internal dipolar field which comes from magnetic charges forming at hard-soft boundaries with normals parallel to the magnetization displaces the spin wave manifold toward the lower energies. With adding more soft phase the spin wave gap closes and the system moves to another ground state characterized by the magnetization mismatch between spins of the hard and soft phases.

  8. A Thorough Dynamic Interpretation of Residual Dipolar Couplings in Ubiquitin

    Energy Technology Data Exchange (ETDEWEB)

    Lakomek, Nils A.; Carlomagno, Teresa; Becker, Stefan; Griesinger, Christian [Max Planck Institute for Biophysical Chemistry, NMR based structural biology (Germany)], E-mail: cigr@nmr.mpibpc.mpg.de; Meiler, Jens [Vanderbilt University, Center of Structural Biology, Department of Chemistry (United States)

    2006-02-15

    The presence of slow motions with large amplitudes, as detected by measurements based on residual dipolar couplings [Peti, W., Meiler, J., Brueschweiler, R. and Griesinger, C. (2002) J. Am. Chem. Soc., 124, 5822-5833], has stirred up much discussion in recent years. Based on ubiquitin NH residual dipolar couplings (rdcs) measured in 31 different alignment conditions, a model-free analysis of structure and dynamics [Meiler, J., Peti, W., Prompers, J., Griesinger, C. and Brueschweiler, R. (2001) J. Am. Chem. Soc., 123, 6098-6107] is presented. Starting from this broad experimental basis, rdc-based order parameters with so far unattained accuracy were determined. These rdc-based order parameters underpin the presence of new modes of motion slower than the inverse overall tumbling correlation time. Amplitudes and anisotropies of the motion were derived. The effect of structural noise on the results was proven to be negligible.

  9. Dipolar atomic spin ensembles in a double-well potential

    Science.gov (United States)

    de Paz, A.; Naylor, B.; Huckans, J.; Carrance, A.; Gorceix, O.; Maréchal, E.; Pedri, P.; Laburthe-Tolra, B.; Vernac, L.

    2014-10-01

    We experimentally study the spin dynamics of mesoscopic ensembles of ultracold magnetic spin-3 atoms located in two separated wells of an optical dipole trap. We use a radio-frequency sweep to selectively flip the spin of the atoms in one of the wells, which produces two separated spin domains of opposite polarization. We observe that these engineered spin domains are metastable with respect to the long-range magnetic dipolar interactions between the two ensembles. The absence of intercloud dipolar spin-exchange processes reveals a classical behavior, in contrast to previous results with atoms loaded in an optical lattice. When we merge the two subsystems, we observe spin-exchange dynamics due to contact interactions which enable the determination of the s-wave scattering length of Cr52 atoms in the S =0 molecular channel a0=13.5-10.5+11aB (where aB is the Bohr radius).

  10. Unconventional States of Matter with Cold Atoms and Dipolar Molecules

    Science.gov (United States)

    2014-08-20

    levels. Just like the 2D quantum Hall effect can be viewed as chiral anomaly on two spatially separated 1D edges, the 4D counterpart is the spatially...separated chiral anomaly on the 3D boundaries. 1.4 Many-body physics with dipolar interactions We have investigated the many-body physics with both...where + and − represent even and odd parities , respectively. An exotic propagating collective mode is identified as spin-orbit coupled Fermi surface

  11. Minor magnetization loops in two-dimensional dipolar Ising model

    Energy Technology Data Exchange (ETDEWEB)

    Sarjala, M. [Aalto University, Department of Applied Physics, P.O. Box 14100, FI-00076 Aalto (Finland); Seppaelae, E.T., E-mail: eira.seppala@nokia.co [Nokia Research Center, Itaemerenkatu 11-13, FI-00180 Helsinki (Finland); Alava, M.J., E-mail: mikko.alava@tkk.f [Aalto University, Department of Applied Physics, P.O. Box 14100, FI-00076 Aalto (Finland)

    2011-05-15

    The two-dimensional dipolar Ising model is investigated for the relaxation and dynamics of minor magnetization loops. Monte Carlo simulations show that in a stripe phase an exponential decrease can be found for the magnetization maxima of the loops, M{approx}exp(-{alpha}N{sub l}) where N{sub l} is the number of loops. We discuss the limits of this behavior and its relation to the equilibrium phase diagram of the model.

  12. Dipolar atomic spin ensembles in a double-well potential

    OpenAIRE

    de Paz, A.; Naylor, B.; Carrance, J. Huckans A.; Gorceix, O.; Marechal, E.; Pedri, P.; Laburthe-Tolra, B.; Vernac, L.

    2014-01-01

    We experimentally study the spin dynamics of mesoscopic ensembles of ultracold magnetic spin-3 atoms located in two separated wells of an optical dipole trap. We use a radio-frequency sweep to selectively flip the spin of the atoms in one of the wells, which produces two separated spin domains of opposite polarization. We observe that these engineered spin domains are metastable with respect to the long-range magnetic dipolar interactions between the two ensembles. The absence of inter-cloud ...

  13. Cross-tail current evolution during substorm dipolarization

    Directory of Open Access Journals (Sweden)

    A. T. Y. Lui

    2013-06-01

    Full Text Available We examine evolution of the cross-tail current during substorm current disruption/dipolarization using observations from two satellites in the near-Earth magnetotail at the downtail distances of 8–9 RE. By choosing times when these two satellites are separated, mainly in the north–south distance in the tail current sheet, precise determination of current density in the layer embedded between these satellites can be obtained with Ampère's law. Two such events are examined and several common features are found. The current densities in the layer embedded by the two satellites were reduced by ~ 40–70% during substorm dipolarization. The changes in current densities have the fast kinetic timescale, i.e., in seconds, implying a kinetic process for current disruption/dipolarization. The estimated power within the current layer was mainly dissipative in the dawn–dusk direction and mainly dynamo in the Sun–tail direction that is needed to drive the north–south substorm current system in the ionosphere. Remote sensing of the energization site with the ion sounding technique shows that the energization site was initially earthward of the satellite and moved down the tail at later times. Breakdown of the frozen-in condition occurred intermittently during the disturbance interval. These features provide important clues to the substorm onset process.

  14. Calculations of NMR dipolar coupling strengths in model peptides

    Energy Technology Data Exchange (ETDEWEB)

    Case, David A. [Scripps Research Institute, Department of Molecular Biology (United States)], E-mail: case@scripps.edu

    1999-10-15

    Ab initio MP2 and density functional quantum chemistry calculations are used to explore geometries and vibrational properties of N-methylacetamide and of the alanine dipeptide with backbone angles characteristic of helix and sheet regions in proteins. The results are used to explore one-bond direct dipolar couplings for the N-H, C{alpha}-H{alpha}, C'-N, and C{alpha}-C' bonds, as well as for the two-bond C'-H interaction. Vibrational averaging affects these dipolar couplings, and these effects can be expressed as effective bond lengths that are 0.5-3% larger than the true bond lengths; bending and torsion vibrations have a bigger influence on the effective coupling than do stretching vibrations. Because of zero-point motion, these effects are important even at low temperature. Hydrogen bonding interactions at the amide group also increase the N-H effective bond length. Although vibrational contributions to effective bond lengths are small, they can have a significant influence on the extraction of order parameters from relaxation data, and a knowledge of relative bond lengths is needed when several types of dipolar couplings are to be simultaneously used for refinement. The present computational results are compared to both solid- and liquid-state NMR experiments. The analysis suggests that secondary structural elements in many proteins may be more rigid than is commonly thought.

  15. Near-Earth plasma sheet boundary dynamics during substorm dipolarization

    Science.gov (United States)

    Nakamura, Rumi; Nagai, Tsugunobu; Birn, Joachim; Sergeev, Victor A.; Le Contel, Olivier; Varsani, Ali; Baumjohann, Wolfgang; Nakamura, Takuma; Apatenkov, Sergey; Artemyev, Anton; Ergun, Robert E.; Fuselier, Stephen A.; Gershman, Daniel J.; Giles, Barbara J.; Khotyaintsev, Yuri V.; Lindqvist, Per-Arne; Magnes, Werner; Mauk, Barry; Russell, Christopher T.; Singer, Howard J.; Stawarz, Julia; Strangeway, Robert J.; Anderson, Brian; Bromund, Ken R.; Fischer, David; Kepko, Laurence; Le, Guan; Plaschke, Ferdinand; Slavin, James A.; Cohen, Ian; Jaynes, Allison; Turner, Drew L.

    2017-09-01

    We report on the large-scale evolution of dipolarization in the near-Earth plasma sheet during an intense (AL -1000 nT) substorm on August 10, 2016, when multiple spacecraft at radial distances between 4 and 15 R E were present in the night-side magnetosphere. This global dipolarization consisted of multiple short-timescale (a couple of minutes) B z disturbances detected by spacecraft distributed over 9 MLT, consistent with the large-scale substorm current wedge observed by ground-based magnetometers. The four spacecraft of the Magnetospheric Multiscale were located in the southern hemisphere plasma sheet and observed fast flow disturbances associated with this dipolarization. The high-time-resolution measurements from MMS enable us to detect the rapid motion of the field structures and flow disturbances separately. A distinct pattern of the flow and field disturbance near the plasma boundaries was found. We suggest that a vortex motion created around the localized flows resulted in another field-aligned current system at the off-equatorial side of the BBF-associated R1/R2 systems, as was predicted by the MHD simulation of a localized reconnection jet. The observations by GOES and Geotail, which were located in the opposite hemisphere and local time, support this view. We demonstrate that the processes of both Earthward flow braking and of accumulated magnetic flux evolving tailward also control the dynamics in the boundary region of the near-Earth plasma sheet.[Figure not available: see fulltext.

  16. Ground state configurations in antiferromagnetic ultrathin films with dipolar anisotropy

    Energy Technology Data Exchange (ETDEWEB)

    Leon, H., E-mail: hleon@imre.oc.uh.cu [Instituto de Ciencia y Tecnologia de Materiales, Universidad de La Habana, Zapata e/ Mazon y G. Vedado, 10400 La Habana (Cuba)

    2013-02-15

    The formalism developed in a previous work to calculate the dipolar energy in quasi-two-dimensional crystals with ferromagnetic order is now extended to collinear antiferromagnetic order. Numerical calculations of the dipolar energy are carried out for systems with tetragonally distorted fcc [001] structures, the case of NiO and MnO ultrathin film grown in non-magnetic substrates, where the magnetic phase is a consequence of superexchange and dipolar interactions. The employed approximation allows to demonstrate that dipolar coupling between atomic layers is responsible for the orientation of the magnetization when it differs from the one in a single layer. The ground state energy of a given NiO or MnO film is found to depend not only on the strain, but also on how much the interlayer separation and the 2D lattice constant are changed with respect to the ideal values corresponding to the non-distorted cubic structure. Nevertheless, it is shown that the orientation of the magnetization in the magnetic phase of any of these films is determined by the strain exclusively. A striped phase with the magnetization along the [112{sup Macron }] direction appears as the ground state configuration of NiO and MnO ultrathin films. In films with equally oriented stripes along the layers this magnetic phase is twofold degenerate, while in films with multidomain layers it is eightfold degenerate. These results are not in contradiction with experimentally observed out-of-plane or in-plane magnetization of striped phases in NiO and MnO ultrathin films. - Highlights: Black-Right-Pointing-Pointer Dipolar energy in collinear antiferromagnetic ultrathin films is calculated. Black-Right-Pointing-Pointer Numerical results are presented for distorted fcc [001] structures. Black-Right-Pointing-Pointer The lowest energy of a system depends on how the tetragonal distortion is achieved. Black-Right-Pointing-Pointer A striped phase with magnetization in the [112{sup Macron }] direction is the

  17. Study of the vibrational characteristics of the homonuclear diatomic nuclear schrödinger equation with a numerov method using a number of empirical potential functions

    Science.gov (United States)

    Heidari, Alireza; Anwar Bég, O.; Ghorbani, Mohammadali

    2013-02-01

    Many empirical potential energy functions have been modeled to represent the potential energy function of a diatomic molecule along whole range of internuclear distance coordinate, whereby one can determine certain molecular constants. Here we employ various potential functions such as Morse, Rydberg, Varshni(II), Varshni(III), Varshni(VI), Pöschl-Teller, Hulburt-Hirschfelder, Lippincott, Frost-Musulin, Linnet, and Rosen-Morse, and the Numerov method to solve the nuclear Schrödinger equation for F2, as an example of a homonuclear diatomic molecule. Herewith, the vibrational and vibration-rotation energy levels are obtained and excellent accuracy is achieved. The potential of employing the Numerov method in engineering physics computations is emphasized.

  18. Study of the interaction between graphene and planar terahertz metamaterial with toroidal dipolar resonance.

    Science.gov (United States)

    Chen, Xu; Fan, Wenhui

    2017-05-15

    A planar terahertz metamaterial consisting of square split ring resonators is proposed, and the excitation of toroidal dipolar resonance is demonstrated. Moreover, we theoretically investigate the strong interaction between graphene and toroidal dipolar resonance of the metamaterial. By varying its Fermi energy, the simulations show that graphene can actively modulate the transmission amplitude of toroidal dipolar resonance and even switch it off. The interaction of the toroidal dipolar resonance with monolayer graphene further highlights the ultrasensitive sensing characteristic of the planar metamaterial, which can be utilized for other graphene-like two-dimensional materials. These intriguing properties of the proposed metamaterial may have potential applications in terahertz modulators and ultrasensitive sensors.

  19. Netrin-1 abrogates ischemia/reperfusion-induced cardiac mitochondrial dysfunction via nitric oxide-dependent attenuation of NOX4 activation and recoupling of NOS.

    Science.gov (United States)

    Siu, Kin Lung; Lotz, Christopher; Ping, Peipei; Cai, Hua

    2015-01-01

    Despite an established role of mitochondrial dysfunction in cardiac ischemia/reperfusion (I/R) injury, the upstream activators have remained incompletely defined. We have recently identified an innovative role of exogenously applied netrin-1 in cardioprotection, which is mediated by increased nitric oxide (NO) bioavailability. Here, we tested the hypothesis that this "pharmacological" treatment of netrin-1 preserves mitochondrial function via novel mechanisms that are NO dependent. Freshly isolated C57BL6 mouse hearts were perfused using a Langendorff system, and subjected to a 20min global ischemia/60min reperfusion, in the presence or absence of netrin-1. I/R induced marked increases in infarct size, total superoxide and hydrogen peroxide production, activity and protein abundance of NADPH oxidase (NOX) isoform 4 (NOX4), as well as impaired mitochondrial integrity and function, all of which were attenuated by netrin-1. This protective effect of netrin-1 is attributed to cGMP, a downstream effector of NO. The protein levels of NOX1 and NOX2 were however unaffected, and infarct size from NOX1 and NOX2 knockouts was not different from wild type animals. Scavenging of NO with PTIO reversed inhibitory effects of netrin-1 on NOX4, while NO donor attenuated NOX4 protein abundance. In vivo NOX4 RNAi, or sepiapterin perfusion, resulted in recoupling of NOS, decreased infarct size, and blockade of dysfunctional mitochondrial swelling and mitochondrial superoxide production. These data demonstrate that netrin-1 induces cardioprotection through inhibition of NOX4 activity, which leads to recoupling of NOS, augmented NO bioavailability, reduction in oxidative stress, and ultimately preservation of mitochondrial function. The NO-dependent NOX4 inhibition connects with our previously established pathway of DCC/ERK1/2/eNOS/NO/DCC feed-forward mechanism, to maintain NOS in the coupling state to attenuate oxidative stress to preserve mitochondrial function. These findings may

  20. Pitfalls in the dipolar model for the neocortical EEG sources.

    Science.gov (United States)

    Riera, Jorge J; Ogawa, Takeshi; Goto, Takakuni; Sumiyoshi, Akira; Nonaka, Hiroi; Evans, Alan; Miyakawa, Hiroyoshi; Kawashima, Ryuta

    2012-08-01

    For about six decades, primary current sources of the electroencephalogram (EEG) have been assumed dipolar in nature. In this study, we used electrophysiological recordings from anesthetized Wistar rats undergoing repeated whisker deflections to revise the biophysical foundations of the EEG dipolar model. In a first experiment, we performed three-dimensional recordings of extracellular potentials from a large portion of the barrel field to estimate intracortical multipolar moments generated either by single spiking neurons (i.e., pyramidal cells, PC; spiny stellate cells, SS) or by populations of them while experiencing synchronized postsynaptic potentials. As expected, backpropagating spikes along PC dendrites caused dipolar field components larger in the direction perpendicular to the cortical surface (49.7 ± 22.0 nA·mm). In agreement with the fact that SS cells have "close-field" configurations, their dipolar moment at any direction was negligible. Surprisingly, monopolar field components were detectable both at the level of single units (i.e., -11.7 ± 3.4 nA for PC) and at the mesoscopic level of mixed neuronal populations receiving extended synaptic inputs within either a cortical column (-0.44 ± 0.20 μA) or a 2.5-m(3)-voxel volume (-3.32 ± 1.20 μA). To evaluate the relationship between the macroscopically defined EEG equivalent dipole and the mesoscopic intracortical multipolar moments, we performed concurrent recordings of high-resolution skull EEG and laminar local field potentials. From this second experiment, we estimated the time-varying EEG equivalent dipole for the entire barrel field using either a multiple dipole fitting or a distributed type of EEG inverse solution. We demonstrated that mesoscopic multipolar components are altogether absorbed by any equivalent dipole in both types of inverse solutions. We conclude that the primary current sources of the EEG in the neocortex of rodents are not precisely represented by a single equivalent

  1. Time of Flight Transients in the Dipolar Glass Model

    OpenAIRE

    Novikov, S. V.; Tyutnev, A. P.; Schein, L. B.

    2013-01-01

    Using Monte Carlo simulation we investigated time of flight current transients predicted by the dipolar glass model for a random spatial distribution of hopping centers. Behavior of the carrier drift mobility was studied at room temperature over a broad range of electric field and sample thickness. A flat plateau followed by $j\\propto t^{-2}$ current decay is the most common feature of the simulated transients. Poole-Frenkel mobility field dependence was confirmed over 5 to 200 V/$\\mu$m as we...

  2. The effect of dipolar interaction on the magnetic isotope effect

    DEFF Research Database (Denmark)

    Mojaza, Matin; Pedersen, Jørgen Boiden; Lukzen, Nikita

    2010-01-01

    A multi-channel kinetic description is used to study the magnetic isotope effect (MIE) in zero magnetic field. The maximal isotope effect is equal to the number of channels, two for the hyperfine interaction but four for the electron spin dipole–dipole interaction of the intermediate radical pair....... Quantum mechanical calculations agree with these conclusion and show that large MIE may be obtained even in the presence of a strong exchange interaction. The observed magnesium isotope effect on the rate of enzymatic synthesis of adenosine triphosphate (ATP) is approximately 3 implying that the dipolar...... interaction is responsible for the effect. Our calculations provide support for the proposed mechanism....

  3. Zero field entanglement in dipolar coupling spin system at negative temperatures

    OpenAIRE

    Furman, Gregory B.; Meerovich, Victor M.; Sokolovsky, Vladimir L.

    2013-01-01

    A dipolar coupled spin system can achieve internal thermodynamic equilibrium states at negative absolute temperature. We study analytically and numerically the temperature dependence of the concurrence in a dipolar coupled spin-1/2 system in both non-zero and zero fields and show that, at negative temperatures, entangled states can exist even in zero magnetic field.

  4. Colloidal polymers via dipolar assembly of magnetic nanoparticle monomers.

    Science.gov (United States)

    Hill, Lawrence J; Pyun, Jeffrey

    2014-05-14

    In this Spotlight on Applications, we describe our recent progress in the preparation of hierarchical one-dimensional (1-D) materials constructed from polymer-coated ferromagnetic cobalt nanoparticles. We begin with a general discussion of nanoparticles capable of 1-D self-organization to form 1-D assemblies, which we term colloidal polymers. The need for efficient, highly directional interactions prompted our investigation with polymer-coated ferromagnetic nanoparticles, which spontaneously form linear assemblies through coupling of north and south magnetic poles present in these single-domain ferromagnetic nanoparticles. These highly directional N-S interactions and the resulting formation of 1-D assemblies can be understood in the context of traditional polymer-forming reactions. The dipolar assembly of these ferromagnetic nanoparticles into chains and binary assemblies while dispersed in organic media has been investigated as a key foundation to form novel magnetic materials and heterostructured nanocomposites. These studies enabled the fabrication of magnetic nanoactuating systems resembling "artificial cilia and flagella". We then discuss our recent efforts to prepare cobalt oxide nanowires using various nanoparticle conversion reactions through a process termed colloidal polymerization. A series of novel functional "colloidal monomers" based on dipolar cobalt nanoparticles were also prepared, incorporating noble metal or semiconductor nanoinclusions to form heterostructured cobalt oxide nanocomposites.

  5. Quantum Fluctuations in Quasi-One-Dimensional Dipolar Bose-Einstein Condensates

    Science.gov (United States)

    Edler, D.; Mishra, C.; Wächtler, F.; Nath, R.; Sinha, S.; Santos, L.

    2017-08-01

    Recent experiments have revealed that beyond-mean-field corrections are much more relevant in weakly interacting dipolar condensates than in their nondipolar counterparts. We show that in quasi-one-dimensional geometries quantum corrections in dipolar and nondipolar condensates are strikingly different due to the peculiar momentum dependence of the dipolar interactions. The energy correction of the condensate presents not only a modified density dependence, but it may even change from attractive to repulsive at a critical density due to the surprising role played by the transversal directions. The anomalous quantum correction translates into a strongly modified physics for quantum-stabilized droplets and dipolar solitons. Moreover, and for similar reasons, quantum corrections of three-body correlations, and hence of three-body losses, are strongly modified by the dipolar interactions. This intriguing physics can be readily probed in current experiments with magnetic atoms.

  6. Sign determination of dipolar couplings in field-oriented bicelles by variable angle sample spinning (VASS)

    Energy Technology Data Exchange (ETDEWEB)

    Tian, F.; Losonczi, J.A.; Fischer, M.W.F.; Prestegard, J.H. [University of Georgia, Complex Carbohydrate Research Center (United States)

    1999-10-15

    Residual dipolar couplings are being increasingly used as structural constraints for NMR studies of biomolecules. A problem arises when dipolar coupling contributions are larger than scalar contributions for a given spin pair, as is commonly observed in solid state NMR studies, in that signs of dipolar couplings cannot easily be determined. Here the sign ambiguities of dipolar couplings in field-oriented bicelles are resolved by variable angle sample spinning (VASS) techniques. The director behavior of field-oriented bicelles (DMPC/DHPC, DMPC/CHAPSO) in VASS is studied by {sup 31}P NMR. A stable configuration occurs when the spinning angle is smaller than the magic angle, 54.7 deg., and the director (or bicelle normal) of the disks is mainly distributed in a plane perpendicular to the rotation axis. Since the dipolar couplings depend on how the bicelles are oriented with respect to the magnetic field, it is shown that the dipolar interaction can be scaled to the same order as the J-coupling by moving the spinning axis from 0 deg. toward 54.7 deg. Thus the relative sign of dipolar and scalar couplings can be determined.

  7. Axial dipolar dynamo action in the Taylor-Green vortex.

    Science.gov (United States)

    Krstulovic, Giorgio; Thorner, Gentien; Vest, Julien-Piera; Fauve, Stephan; Brachet, Marc

    2011-12-01

    We present a numerical study of the magnetic field generated by the Taylor-Green vortex. We show that periodic boundary conditions can be used to mimic realistic boundary conditions by prescribing the symmetries of the velocity and magnetic fields. This gives insight into some problems of central interest for dynamos: the possible effect of velocity fluctuations on the dynamo threshold, and the role of boundary conditions on the threshold and on the geometry of the magnetic field generated by dynamo action. In particular, we show that an axial dipolar dynamo similar to the one observed in a recent experiment can be obtained with an appropriate choice of the symmetries of the magnetic field. The nonlinear saturation is studied and a simple model explaining the magnetic Prandtl number dependence of the super- and subcritical nature of the dynamo transition is given.

  8. Rapid Pitch Angle Evolution of Suprathermal Electrons Behind Dipolarization Fronts

    Science.gov (United States)

    Liu, C. M.; Fu, H. S.; Cao, J. B.; Xu, Y.; Yu, Y. Q.; Kronberg, E. A.; Daly, P. W.

    2017-10-01

    The pitch angle distribution (PAD) of suprathermal electrons can have both spatial and temporal evolution in the magnetotail and theoretically can be an indication of electron energization/cooling processes there. So far, the spatial evolution of PAD has been well studied, leaving the temporal evolution as an open question. To reveal the temporal evolution of electron PAD, spacecraft should monitor the same flux tube for a relatively long period, which is not easy in the dynamic magnetotail. In this study, we present such an observation by Cluster spacecraft in the magnetotail behind a dipolarization front (DF). We find that the PAD of suprathermal electrons can evolve from pancake type to butterfly type during effect, which possibly exists behind the DF as well.

  9. Fragmentation of magnetism in artificial kagome dipolar spin ice

    Science.gov (United States)

    Canals, Benjamin; Chioar, Ioan-Augustin; Nguyen, Van-Dai; Hehn, Michel; Lacour, Daniel; Montaigne, François; Locatelli, Andrea; Menteş, Tevfik Onur; Burgos, Benito Santos; Rougemaille, Nicolas

    2016-01-01

    Geometrical frustration in magnetic materials often gives rise to exotic, low-temperature states of matter, such as the ones observed in spin ices. Here we report the imaging of the magnetic states of a thermally active artificial magnetic ice that reveal the fingerprints of a spin fragmentation process. This fragmentation corresponds to a splitting of the magnetic degree of freedom into two channels and is evidenced in both real and reciprocal space. Furthermore, the internal organization of both channels is interpreted within the framework of a hybrid spin–charge model that directly emerges from the parent spin model of the kagome dipolar spin ice. Our experimental and theoretical results provide insights into the physics of frustrated magnets and deepen our understanding of emergent fields through the use of tailor-made magnetism. PMID:27173154

  10. Optical Force and Torque on Dipolar Dual Chiral Particles

    CERN Document Server

    Rahimzadegan, Aso; Alaee, Rasoul; Fernandez-Corbaton, Ivan; Rockstuhl, Carsten

    2016-01-01

    On the one hand, electromagnetic dual particles preserve the helicity of light upon interaction. On the other hand, chiral particles respond differently to light of opposite helicity. These two properties on their own constitute a source of fascination. Their combined action, however, is less explored. Here, we study on analytical grounds the force and torque as well as the optical cross sections of dual chiral particles in dipolar approximation exerted by a wave of well-defined helicity, i.e. a circularly polarized plane wave. We put emphasis on particles that possess a maximally electromagnetic chiral and hence dual response. Besides the analytical insights, we also investigate the exerted optical force and torque on a real particle at the example of a metallic helix that is designed to approach the maximal electromagnetic chirality condition. Various applications in the context of optical sorting but also nanorobotics can be perceived considering the particles studied in this contribution.

  11. Hidden magnetism in periodically modulated one dimensional dipolar fermions

    Science.gov (United States)

    Fazzini, S.; Montorsi, A.; Roncaglia, M.; Barbiero, L.

    2017-12-01

    The experimental realization of time-dependent ultracold lattice systems has paved the way towards the implementation of new Hubbard-like Hamiltonians. We show that in a one-dimensional two-components lattice dipolar Fermi gas the competition between long range repulsion and correlated hopping induced by periodically modulated on-site interaction allows for the formation of hidden magnetic phases, with degenerate protected edge modes. The magnetism, characterized solely by string-like nonlocal order parameters, manifests in the charge and/or in the spin degrees of freedom. Such behavior is enlighten by employing Luttinger liquid theory and numerical methods. The range of parameters for which hidden magnetism is present can be reached by means of the currently available experimental setups and probes.

  12. Evolution of multiple quantum coherences with scaled dipolar Hamiltonian

    Science.gov (United States)

    Sánchez, Claudia M.; Buljubasich, Lisandro; Pastawski, Horacio M.; Chattah, Ana K.

    2017-08-01

    In this article, we introduce a pulse sequence which allows the monitoring of multiple quantum coherences distribution of correlated spin states developed with scaled dipolar Hamiltonian. The pulse sequence is a modification of our previous Proportionally Refocused Loschmidt echo (PRL echo) with phase increment, in order to verify the accuracy of the weighted coherent quantum dynamics. The experiments were carried out with different scaling factors to analyze the evolution of the total magnetization, the time dependence of the multiple quantum coherence orders, and the development of correlated spins clusters. In all cases, a strong dependence between the evolution rate and the weighting factor is observed. Remarkably, all the curves appeared overlapped in a single trend when plotted against the self-time, a new time scale that includes the scaling factor into the evolution time. In other words, the spin system displayed always the same quantum evolution, slowed down as the scaling factor decreases, confirming the high performance of the new pulse sequence.

  13. Energetic Electron Acceleration and Injection During Dipolarization Events in Mercury's Magnetotail

    Science.gov (United States)

    Dewey, Ryan M.; Slavin, James A.; Raines, Jim M.; Baker, Daniel N.; Lawrence, David J.

    2017-12-01

    Energetic particle bursts associated with dipolarization events within Mercury's magnetosphere were first observed by Mariner 10. The events appear analogous to particle injections accompanying dipolarization events at Earth. The Energetic Particle Spectrometer (3 s resolution) aboard MESSENGER determined the particle bursts are composed entirely of electrons with energies ≳ 300 keV. Here we use the Gamma-Ray Spectrometer high-time-resolution (10 ms) energetic electron measurements to examine the relationship between energetic electron injections and magnetic field dipolarization in Mercury's magnetotail. Between March 2013 and April 2015, we identify 2,976 electron burst events within Mercury's magnetotail, 538 of which are closely associated with dipolarization events. These dipolarizations are detected on the basis of their rapid ( 2 s) increase in the northward component of the tail magnetic field (ΔBz 30 nT), which typically persists for 10 s. Similar to those at Earth, we find that these dipolarizations appear to be low-entropy, depleted flux tubes convecting planetward following the collapse of the inner magnetotail. We find that electrons experience brief, yet intense, betatron and Fermi acceleration during these dipolarizations, reaching energies 130 keV and contributing to nightside precipitation. Thermal protons experience only modest betatron acceleration. While only 25% of energetic electron events in Mercury's magnetotail are directly associated with dipolarization, the remaining events are consistent with the Near-Mercury Neutral Line model of magnetotail injection and eastward drift about Mercury, finding that electrons may participate in Shabansky-like closed drifts about the planet. Magnetotail dipolarization may be the dominant source of energetic electron acceleration in Mercury's magnetosphere.

  14. The soluble guanylate cyclase activator BAY 58-2667 protects against morbidity and mortality in endotoxic shock by recoupling organ systems.

    Directory of Open Access Journals (Sweden)

    Benjamin Vandendriessche

    Full Text Available Sepsis and septic shock are associated with high mortality rates and the majority of sepsis patients die due to complications of multiple organ failure (MOF. The cyclic GMP (cGMP producing enzyme soluble guanylate cyclase (sGC is crucially involved in the regulation of (microvascular homeostasis, cardiac function and, consequently, organ function. However, it can become inactivated when exposed to reactive oxygen species (ROS. The resulting heme-free sGC can be reactivated by the heme- and nitric oxide (NO-independent sGC activator BAY 58-2667 (Cinaciguat. We report that late (+8 h post-treatment with BAY 58-2667 in a mouse model can protect against lethal endotoxic shock. Protection was associated with reduced hypothermia, circulating IL-6 levels, cardiomyocyte apoptosis, and mortality. In contrast to BAY 58-2667, the sGC stimulator BAY 41-2272 and the phosphodiesterase 5 inhibitor Sildenafil did not have any beneficial effect on survival, emphasizing the importance of the selectivity of BAY 58-2667 for diseased vessels and tissues. Hemodynamic parameters (blood pressure and heart rate were decreased, and linear and nonlinear indices of blood pressure variability, reflective for (uncoupling of the communication between the autonomic nervous system and the heart, were improved after late protective treatment with BAY 58-2667. In conclusion, our results demonstrate the pivotal role of the NO/sGC axis in endotoxic shock. Stabilization of sGC function with BAY 58-2667 can prevent mortality when given in the correct treatment window, which probably depends on the dynamics of the heme-free sGC pool, in turn influenced by oxidative stress. We speculate that, considering the central role of sGC signaling in many pathways required for maintenance of (microcirculatory homeostasis, BAY 58-2667 supports organ function by recoupling inter-organ communication pathways.

  15. Do independent-particle-model broken-symmetry solutions contain more physics than the symmetry-adapted ones? The case of homonuclear diatomics.

    Science.gov (United States)

    Li, Xiangzhu; Paldus, Josef

    2009-02-28

    We explore spin-preserving, singlet stability of restricted Hartree-Fock (RHF) solutions for a number of closed-shell, homonuclear diatomics in the entire relevant range of internuclear separations. In the presence of such instabilities we explore the implied broken-symmetry (bs) solutions and check their stability. We also address the occurrence of vanishing roots rendered by the stability problem in the case of bs solutions. The RHF bs solutions arise primarily due to the symmetry breaking of the relevant, mostly frontier, molecular orbitals, which approach atomic-type orbitals in the dissociation limit. The resulting bs RHF solutions yield more realistic potential energy curves (PECs) than do the symmetry adapted (sa) solutions. These PECs are shown to be very similar to those rendered by the density functional theory (DFT). Moreover, the sa DFT solutions are found to be stable in a much wider range of internuclear separations than are the RHF solutions, and their bs analogs differ very little from the sa ones. Finally, we examine a possible usefulness of bs RHF solutions in post-HF correlated approaches to the many-electron problem, specifically in the limited configuration interaction and coupled-cluster methods.

  16. 1, 3-Dipolar cycloaddition reactions: Synthesis of 5-benzyl-1-(2 ,4 ...

    Indian Academy of Sciences (India)

    yielding, efficient, regio and stereo- controlled method for the synthesis of many heterocyclic compounds.1–4 1,3-Dipolar cycloaddition reaction has been described as 'the single most important method for the construction of heterocyclic five- ...

  17. Near-Heisenberg-limited parameter estimation precision by a dipolar-Bose-gas reservoir engineering

    Science.gov (United States)

    Tan, Qing-Shou; Yuan, Ji-Bing; Jin, Guang-Ri; Kuang, Le-Man

    2017-12-01

    We propose a scheme to obtain the Heisenberg-limited parameter estimation precision by immersing atoms in a thermally equilibrated quasi-one-dimensional dipolar Bose-Einstein condensate reservoir. We show that the collisions between the dipolar atoms and the immersed atoms can result in a controllable nonlinear interaction through tuning the relative strength and the sign of the dipolar and contact interaction. We find that the repulsive dipolar interaction reservoir is preferential for the spin squeezing and the appearance of an entangled non-Gaussian state. As a useful resource for quantum metrology, we also show that the non-Gaussian state results in the phase estimation precision in the Heisenberg scaling, outperforming that of the spin-squeezed state.

  18. Role of dipolar interaction in the mesoscopic domains of phospholipid monolayers: dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylethanolamine.

    Science.gov (United States)

    Thirumoorthy, K; Nandi, N; Vollhardt, D

    2007-06-19

    The role of dipolar interactions in determining the lipid domain shapes at the air-water interface with a change in the chemical structure of the head groups of lipids is theoretically studied. The phospholipids considered are dipalmitoylphosphatidylcholine (D,L-DPPC) and dipalmitoylphosphatidylethanolamine (DPPE). Despite closely similar chemical structures, the domains of the two lipids are strikingly different. The DPPC domains exhibit elongated arms, while the DPPE domains are nearly round-shaped. To compare the dipolar repulsions in the domains of the two phospholipids, different energy-minimized conformers of DPPC and DPPE are studied using the semiempirical quantum chemical method (PM3). It is found that the dipole moment of DPPC is significantly larger than that of DPPE. The in-plane and out-of-plane components of the dipole moments are calculated using grazing incidence X-ray diffraction data at different surface pressure values, as used in the experiment. The result indicates that the magnitude of the dipolar interaction is significantly larger in DPPC than that in DPPE over the surface pressure range considered. The enhanced dipolar repulsion corroborates well with the difference in the domain shapes in the two phospholipid monolayers. The larger dipolar repulsion in DPPC leads to development of elongated domain arms, while relatively less dipolar repulsion allows a closed shape of the condensed-phase DPPE domains.

  19. Bose-Einstein condensation and superfluidity of dipolar excitons in a phosphorene double layer

    Science.gov (United States)

    Berman, Oleg L.; Gumbs, Godfrey; Kezerashvili, Roman Ya.

    2017-07-01

    We study the formation of dipolar excitons and their superfluidity in a phosphorene double layer. The analytical expressions for the single dipolar exciton energy spectrum and wave function are obtained. It is predicted that a weakly interacting gas of dipolar excitons in a double layer of black phosphorus exhibits superfluidity due to the dipole-dipole repulsion between the dipolar excitons. In calculations are employed the Keldysh and Coulomb potentials for the interaction between the charge carriers to analyze the influence of the screening effects on the studied phenomena. It is shown that the critical velocity of superfluidity, the spectrum of collective excitations, concentrations of the superfluid and normal component, and mean-field critical temperature for superfluidity are anisotropic and demonstrate the dependence on the direction of motion of dipolar excitons. The critical temperature for superfluidity increases if the exciton concentration and the interlayer separation increase. It is shown that the dipolar exciton binding energy and mean-field critical temperature for superfluidity are sensitive to the electron and hole effective masses. The proposed experiment to observe a directional superfluidity of excitons is addressed.

  20. AC susceptibility as a tool to probe the dipolar interaction in magnetic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Landi, Gabriel T., E-mail: gtlandi@gmail.com [Universidade Federal do ABC, 09210-580 Santo André (Brazil); Arantes, Fabiana R. [Universidade Federal do ABC, 09210-580 Santo André (Brazil); Cornejo, Daniel R. [Instituto de Física da Universidade de São Paulo, São Paulo 05508-090 (Brazil); Bakuzis, Andris F. [Instituto de Física, Universidade Federal de Goiás, 74690-900 Goiânia-GO (Brazil); Andreu, Irene; Natividad, Eva [Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC-Universidad de Zaragoza, Zaragoza 50018 (Spain)

    2017-01-01

    The dipolar interaction is known to substantially affect the properties of magnetic nanoparticles. This is particularly important when the particles are kept in a fluid suspension or packed within nano-carriers. In addition to its usual long-range nature, in these cases the dipolar interaction may also induce the formation of clusters of particles, thereby strongly modifying their magnetic anisotropies. In this paper we show how AC susceptibility may be used to obtain information regarding the influence of the dipolar interaction in a sample. We develop a model which includes both aspects of the dipolar interaction and may be fitted directly to the susceptibility data. The usual long-range nature of the interaction is implemented using a mean-field approximation, whereas the particle-particle aggregation is modeled using a distribution of anisotropy constants. The model is then applied to two samples studied at different concentrations. One consists of spherical magnetite nanoparticles dispersed in oil and the other of cubic magnetite nanoparticles embedded on polymeric nanospheres. We also introduce a simple technique to address the presence of the dipolar interaction in a given sample, based on the height of the AC susceptibility peaks for different driving frequencies. - Highlights: We discuss the importance of the dipolar interaction in magnetic nanoparticle samples. It is shown that AC susceptibility may be used to estimate the extent of this interaction. We develop a model that accounts for particle aggregation. The theoretical model is then fitted to distinct magnetite samples.

  1. Classical and quantum phases of low-dimensional dipolar systems

    Energy Technology Data Exchange (ETDEWEB)

    Cartarius, Florian

    2016-09-22

    In this thesis we present a detailed study of the phase diagram of ultracold bosonic atoms confined along a tight atomic wave guide, along which they experience an optical lattice potential. In this quasi-one dimensional model we analyse the interplay between interactions and quantum fluctuations in (i) determining the non-equilibrium steady state after a quench and (ii) giving rise to novel equilibrium phases, when the interactions combine the s-wave contact interaction and the anisotropic long range dipole-dipole interactions. In detail, in the first part of the thesis we study the depinning of a gas of impenetrable bosons following the sudden switch of of the optical lattice. By means of a Bose-Fermi mapping we infer the exact quantum dynamical evolution and show that in the thermodynamic limit the system is in a non-equilibrium steady state without quasi-long range order. In the second part of the thesis, we study the effect of quantum fluctuations on the linear-zigzag instability in the ground state of ultracold dipolar bosons, as a function of the strength of the transverse confinement. We first analyse the linear-zigzag instability in the classical regime, and then use our results to develop a multi-mode Bose-Hubbard model for the system. We then develop several numerical methods, to determine the ground state.

  2. 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.

  3. Focal mechanism of seismic events with a dipolar component

    Directory of Open Access Journals (Sweden)

    R. Console

    1995-06-01

    Full Text Available In this paper we model the geometry of a seismic source as a dislocation occurring on an elemental flat fault in an arbitrary direction with respect to the fault plane. This implies the use of a fourth parameter in addition to the three usual ones describing a simple double couple mechanism. We applied the radiation pattern obtained from the theory to a computer code written for the inversion of the observation data (amplitudes and polarities of the first onsets recorded by a network of stations. It allows the determination of the fault mechanism gener- alized in the above mentioned way. The computer code was verified on synthetic data and then applied to real data recorded by the seismic network operated by the Ente Nazionale per l'Energia Elettrica (ENEL, monitoring the geothermal field of Larderello. The experimental data show that for some events the source mechanism exhibits a significant dipolar component. However, due to the high standard deviation of the amplitude data, F-test applied to the results of the analysis shows that only for two events the confidence level for the general- ized model exceeds 90%.

  4. Conformations of a dipolar solute in a Stockmayer solvent channel.

    Science.gov (United States)

    Yi, Taeil; Wang, Qian; Lichter, Seth

    2012-10-30

    A wide range of molecules, from inorganic to biological, self-assemble on surfaces. Previous studies have elucidated many features of solute reorganization on surfaces using coarse-grained modeling, implicit solvents, and constraints such as chemically bonding the solute to the surface. Using molecular dynamics simulations under various combinations of interaction parameters, solute fractions, and solute dipole moment, we study the redistribution of freely-rotating dipolar solute molecules solvated by a water-like Stockmayer solvent initially adhered to a face-centered cubic substrate. The balance of attractive and repulsive forces is essential for acquiring a particular stable conformation. Here we show that the adsorbed molecules redistribute into different conformations--wetting film, nonwetting, partial wetting, and pseudopartial wetting drops--depending on the parameter values. We observe that the pseudopartial wetting drop is transient and its rate of spreading fluctuates, slowing to nearly zero as it passes through particular conformations before reaching an equilibrium thin film. Strong attraction between solute molecules yields a droplet with a net dipole moment. A high solute fraction leads to a pancake-like conformation arising from a balance of surface tension and van der Waals forces. This study augments our understanding of the evolution of aggregates in biological systems and also the design of polymers for self-assembled monolayers for industrial applications.

  5. Numerical simulation on the multiple dipolarization fronts in the magnetotail

    Science.gov (United States)

    Lu, Haoyu; Li, Yun; Cao, Jinbin; Ge, Yasong; Zhang, Tielong; Yu, Yiqun

    2017-10-01

    Using an extended MHD model including the Hall effect and finite Larmor radius effect, we reproduce multiple dipolarization fronts (DFs) associated with the interchange instability in the braking region of bursty bulk flow in the plasma sheet. Our simulations reveal that the multiple DFs produced by the interchange instability are "growing" type DFs because the maximum plasma flow speeds are behind the fronts. Both the earthward and tailward moving DFs can be produced by interchange instability in the near-Earth region. The Hall electric field is the dominant electric field component in the dip region and the DF layer. The convective and the electron pressure gradient electric field components are smaller. The sharp Bz changes in both the dip region and DF layer correspond to the oppositely directed currents that are primarily associated with electrons. The ion diamagnetic current due to the strong ion pressure gradient causes an intense downward current in the dip region, which can produce the dip ahead of the front. The energy dissipations in the dip region and DF layer are dominated by ions through the work done by the Lorentz force. Our simulation results indicate that the magnetic energy can be converted to plasmas on the DF layer, and vice versa in the dip region.

  6. Pollux: a stable weak dipolar magnetic field but no planet?

    Science.gov (United States)

    Aurière, Michel; Konstantinova-Antova, Renada; Espagnet, Olivier; Petit, Pascal; Roudier, Thierry; Charbonnel, Corinne; Donati, Jean-François; Wade, Gregg A.

    2014-08-01

    Pollux is considered as an archetype of a giant star hosting a planet: its radial velocity (RV) presents sinusoidal variations with a period of about 590 d, which have been stable for more than 25 years. Using ESPaDOnS and Narval we have detected a weak (sub-gauss) magnetic field at the surface of Pollux and followed up its variations with Narval during 4.25 years, i.e. more than for two periods of the RV variations. The longitudinal magnetic field is found to vary with a sinusoidal behaviour with a period close to that of the RV variations and with a small shift in phase. We then performed a Zeeman Doppler imaging (ZDI) investigation from the Stokes V and Stokes I least-squares deconvolution (LSD) profiles. A rotational period is determined, which is consistent with the period of variations of the RV. The magnetic topology is found to be mainly poloidal and this component almost purely dipolar. The mean strength of the surface magnetic field is about 0.7 G. As an alternative to the scenario in which Pollux hosts a close-in exoplanet, we suggest that the magnetic dipole of Pollux can be associated with two temperature and macroturbulent velocity spots which could be sufficient to produce the RV variations. We finally investigate the scenarii of the origin of the magnetic field which could explain the observed properties of Pollux.

  7. Quantum dynamics and topological excitations in interacting dipolar particles

    Science.gov (United States)

    Rey, Ana

    2016-05-01

    Dipole-dipole interactions, long-range and anisotropic interactions that arise due to the virtual exchange of photons, are of fundamental importance in optical physics, and are enabling a range of new quantum technologies including quantum networks and optical lattice atomic clocks. In this talk I will first discuss how arrays of dipolar particles with a simple J = 0- J = 1 internal level structure can naturally host topological and chiral excitations including Weyl quasi-particles. Weyl fermions were first predicted to exist in the context of high energy physics but only recently have been observed in solid state systems. I will discuss a proposal of using Mott insulators of Sr atoms to observe and probe the Weyl excitation spectrum and its non-trivial chirality. Finally I will report on a recent experiment done at JILA which validates the underlying microscopic model that predicts the existence of these excitations. The experiment measured the collective emission from a coherently driven gas of ultracold 88 Sr atoms and observed a highly directional and anisotropic emission intensity and a substantial broadening of the atomic spectral lines. All of the measurements are well reproduced by the theoretical model. These investigations open the door for the exploration of novel quantum many-body systems involving strongly interacting atoms and photons, and are useful guides for further developments of optical atomic clocks and other applications involving dense atomic ensembles. AFOSR, MURI-AFOSR, ARO,NSF-PHY-1521080, JILA-NSF-PFC-1125844.

  8. Energetic Electrons in Dipolarization Events: Spatial Properties and Anisotropy

    Science.gov (United States)

    Birn, J.; Runov, A.; Hesse, M.

    2014-01-01

    Using the electromagnetic fields of an MHD simulation of magnetotail reconnection, flow bursts, and dipolarization, we further investigate the acceleration of electrons to suprathermal energies. Particular emphasis is on spatial properties and anisotropies as functions of energy and time. The simulation results are compared with Time History of Events and Macroscale Interactions during Substorms observations. The test particle approach successfully reproduces several observed injection features and puts them into a context of spatial maps of the injection region(s): a dominance of perpendicular anisotropies farther down the tail and closer to the equatorial plane, an increasing importance of parallel anisotropy closer to Earth and at higher latitudes, a drop in energy fluxes at energies below approximately 10 keV, coinciding with the plasma density drop, together with increases at higher energy, a triple peak structure of flux increases near 0 deg, 90 deg, and 180 deg, and a tendency of flux increases to extend to higher energy closer to Earth and at lower latitudes. We identified the plasma sheet boundary layers and adjacent lobes as a main source region for both increased and decreased energetic electron fluxes, related to the different effects of adiabatic acceleration at high and low energies. The simulated anisotropies tend to exceed the observed ones, particularly for perpendicular fluxes at high energies. The most plausible reason is that the MHD simulation lacks the effects of anisotropy-driven microinstabilities and waves, which would reduce anisotropies.

  9. Physics of Substorm Growth Phase, Onset, and Dipolarization

    Energy Technology Data Exchange (ETDEWEB)

    C.Z. Cheng

    2003-10-22

    A new scenario of substorm growth phase, onset, and depolarization during expansion phase and the corresponding physical processes are presented. During the growth phase, as a result of enhanced plasma convection, the plasma pressure and its gradient are continued to be enhanced over the quiet-time values in the plasma sheet. Toward the late growth phase, a strong cross-tail current sheet is formed in the near-Earth plasma sheet region, where a local magnetic well is formed, the plasma beta can reach a local maximum with value larger than 50 and the cross-tail current density can be enhanced to over 10nA/m{sup 2} as obtained from 3D quasi-static magnetospheric equilibrium solutions for the growth phase. The most unstable kinetic ballooning instabilities (KBI) are expected to be located in the tailward side of the strong cross-tail current sheet region. The field lines in the most unstable KBI region map to the transition region between the region-1 and region-2 currents in the ionosphere, which is consistent with the observed initial brightening location of the breakup arc in the intense proton precipitation region. The KBI explains the AMPTE/CCE observations that a low-frequency instability with a wave period of 50-75 seconds is excited about 2-3 minutes prior to substorm onset and grows exponentially to a large amplitude at the onset of current disruption (or current reduction). At the current disruption onset higher frequency instabilities are excited so that the plasma and electromagnetic field fluctuations form a strong turbulent state. Plasma transport takes place due to the strong turbulence to relax the ambient plasma pressure profile so that the plasma pressure and current density are reduced and the ambient magnetic field intensity increases by more than a factor of 2 in the high-beta(sub)eq region and the field line geometry recovers from tail-like to dipole-like dipolarization.

  10. Generation of circularly polarized XUV and soft-x-ray high-order harmonics by homonuclear and heteronuclear diatomic molecules subject to bichromatic counter-rotating circularly polarized intense laser fields

    Science.gov (United States)

    Heslar, John; Telnov, Dmitry A.; Chu, Shih-I.

    2017-12-01

    Recently, studies of bright circularly polarized high-harmonic beams from atoms in the soft-x-ray region as a source for x-ray magnetic circular dichroism measurement in a tabletop-scale setup have received considerable attention. In this paper, we address the problem with molecular targets and perform a detailed quantum study of H2 +, CO, and N2 molecules in bichromatic counter-rotating circularly polarized laser fields where we adopt wavelengths (1300 and 790 nm) and intensities (2 ×1014W /cm2 ) reported in a recent experiment [Proc. Natl. Acad. Sci. USA 112, 14206 (2015), 10.1073/pnas.1519666112]. Our treatment of multiphoton processes in homonuclear and heteronuclear diatomic molecules is nonperturbative and based on the time-dependent density-functional theory for multielectron systems. The calculated radiation spectrum contains doublets of left and right circularly polarized harmonics with high-energy photons in the XUV and soft-x-ray ranges. Our results reveal intriguing and substantially different nonlinear optical responses for homonuclear and heteronuclear diatomic molecules subject to circularly polarized intense laser fields. We study in detail the below- and above-threshold harmonic regions and analyze the ellipticity and phase of the generated harmonic peaks.

  11. Vortices of a rotating two-component dipolar Bose–Einstein condensate in an optical lattice

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lin-Xue [College of Physics and Electronic Engineering, Northwest Normal University, Lanzhou 730070 (China); Key Laboratory of Time and Frequency Primary Standards, National Time Service Center, Chinese Academy of Sciences, Xi' an 710600 (China); Dong, Biao; Chen, Guang-Ping [Key Laboratory of Time and Frequency Primary Standards, National Time Service Center, Chinese Academy of Sciences, Xi' an 710600 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Han, Wei; Zhang, Shou-Gang [Key Laboratory of Time and Frequency Primary Standards, National Time Service Center, Chinese Academy of Sciences, Xi' an 710600 (China); Shi, Yu-Ren, E-mail: shiyr@nwnu.edu.cn [College of Physics and Electronic Engineering, Northwest Normal University, Lanzhou 730070 (China); Zhang, Xiao-Fei, E-mail: xfzhang@ntsc.ac.cn [Key Laboratory of Time and Frequency Primary Standards, National Time Service Center, Chinese Academy of Sciences, Xi' an 710600 (China)

    2016-01-28

    We consider a two-component Bose–Einstein condensate, which consists of both dipolar and scalar bosonic atoms, in a confinement that is composed of a harmonic oscillator and an underlying optical lattice set rotation. When the dipoles are polarized along the symmetry axis of the harmonic potential, the ground-state density distributions of such a system are investigated as a function of the relative strength between the dipolar and contact interactions, and of the rotation frequency. Our results show that the number of vortices and its related vortex structures of such a system depend strongly on such system parameters. The special two-component system considered here opens up alternate ways for exploring the rich physics of dipolar quantum gases. - Highlights: • Only one component possesses dipole moment. • Spin-dependent optical lattices support exotic vortex structures. • Both the dipole–dipole interaction and rotation frequency are discussed in detail.

  12. Energy landscapes, structural topologies and rearrangement mechanisms in clusters of dipolar particles

    Science.gov (United States)

    Farrell, James D.; Lines, Christabel; Shepherd, James J.; Chakrabarti, Dwaipayan; Miller, Mark A.; Wales, David J.

    Clusters of spherical particles with isotropic attraction favour compact structures that maximise the number of energetically optimal nearest-neighbour interactions. In contrast, dipolar interactions lead to the formation of chains with a low coordination number. When both isotropic and dipolar interactions are present, the competition between them can lead to intricate knot, link and coil structures. Here, we investigate how these structures may self-organise and interconvert in clusters bound by the Stockmayer potential (Lennard-Jones plus point dipole). We map out the low-lying region of the energy landscape using disconnectivity graphs to follow how it evolves as the strength of the dipolar interactions increases. From comprehensive surveys of isomerisation pathways, we identify a number of rearrangement mechanisms that allow the topology of chain-like structures to interconvert.

  13. Assessment of molecular structure using frame-independent orientational restraints derived from residual dipolar couplings

    Energy Technology Data Exchange (ETDEWEB)

    Skrynnikov, Nikolai R.; Kay, Lewis E. [University of Toronto, Protein Engineering Network Centers of Excellence and Departments of Medical Genetics, Biochemistry and Chemistry (Canada)

    2000-11-15

    Residual dipolar couplings measured in weakly aligning liquid-crystalline solvent contain valuable information on the structure of biomolecules in solution. Here we demonstrate that dipolar couplings (DCs) can be used to derive a comprehensive set of pairwise angular restraints that do not depend on the orientation of the alignment tensor principal axes. These restraints can be used to assess the agreement between a trial protein structure and a set of experimental dipolar couplings by means of a graphic representation termed a 'DC consistency map'. Importantly, these maps can be used to recognize structural elements consistent with the experimental DC data and to identify structural parameters that require further refinement, which could prove important for the success of DC-based structure calculations. This approach is illustrated for the 42 kDa maltodextrin-binding protein.

  14. Internal structure and stability of vortices in a dipolar spinor Bose-Einstein condensate

    Science.gov (United States)

    Borgh, Magnus O.; Lovegrove, Justin; Ruostekoski, Janne

    2017-05-01

    We demonstrate how dipolar interactions can have pronounced effects on the structure of vortices in atomic spinor Bose-Einstein condensates and illustrate generic physical principles that apply across dipolar spinor systems. We then find and analyze the cores of singular vortices with non-Abelian charges in the point-group symmetry of a spin-3 52Cr condensate. Using a simpler model system, we analyze the underlying dipolar physics and show how a characteristic length scale arising from the magnetic dipolar coupling interacts with the hierarchy of healing lengths of the s -wave scattering and leads to simple criteria for the core structure: When the interactions both energetically favor the ground-state spin condition, such as in the spin-1 ferromagnetic phase, the size of singular vortices is restricted to the shorter spin-dependent healing length (s -wave or dipolar). Conversely, when the interactions compete (e.g., in the spin-1 polar phase), we find that the core of a singular vortex is enlarged by increasing dipolar coupling. We further demonstrate how the spin alignment arising from the interaction anisotropy is manifest in the appearance of a ground-state spin-vortex line that is oriented perpendicularly to the condensate axis of rotation, as well as in potentially observable internal core spin textures. We also explain how it leads to an interaction-dependent angular momentum in nonsingular vortices as a result of competition with rotation-induced spin ordering. When the anisotropy is modified by a strong magnetic field, we show how it gives rise to a symmetry-breaking deformation of a vortex core into a spin-domain wall.

  15. 1,3-Dipolar Cycloadditions of Benzonitrile Oxide with Various Dipolarophiles in Aqueous Solutions. A Kinetic Study

    NARCIS (Netherlands)

    Mersbergen, Dick van; Wijnen, Jan W.; Engberts, Jan B.F.N.

    1998-01-01

    The second-order rate constants for the 1,3-dipolar cycloaddition of benzonitrile oxide (1) with various dipolarophiles (2a-e) were determined in aqueous media and in organic solvents to gain more insight into the influence of an aqueous medium on pericyclic reactions. 1,3-Dipolar cycloadditions

  16. Refocused continuous-wave decoupling: A new approach to heteronuclear dipolar decoupling in solid-state NMR spectroscopy

    DEFF Research Database (Denmark)

    Vinther, Joachim Møllesøe; Nielsen, Anders B.; Bjerring, Morten

    2012-01-01

    from dipolar coupling in heteronuclear spin systems is rationalized by effective Hamiltonian calculations to third order. In some variants the π pulse refocusing is supplemented by insertion of rotor-synchronized π/2 purging pulses to further reduce the residual dipolar coupling effects. Five different...

  17. Vibration spectrum of a two-soliton molecule in dipolar Bose–Einstein condensates

    Energy Technology Data Exchange (ETDEWEB)

    Turmanov, B.Kh. [Physical–Technical Institute, Uzbek Academy of Sciences, 100084, Tashkent (Uzbekistan); Baizakov, B.B., E-mail: baizakov@uzsci.net [Physical–Technical Institute, Uzbek Academy of Sciences, 100084, Tashkent (Uzbekistan); Umarov, B.A.; Abdullaev, F.Kh. [Department of Physics, Kulliyyah of Science, International Islamic University Malaysia, 25200 Kuantan, Pahang (Malaysia)

    2015-09-11

    We study the vibration of soliton molecules in dipolar Bose–Einstein condensates by variational approach and numerical simulations of the nonlocal Gross–Pitaevskii equation. We employ the periodic variation of the strength of dipolar atomic interactions to excite oscillations of solitons near their equilibrium positions. When the parametric perturbation is sufficiently strong the molecule breaks up into individual solitons, like the dissociation of ordinary molecules. The waveform of the molecule and resonance frequency, predicted by the developed model, are confirmed by numerical simulations of the governing equation.

  18. Multiply quantized and fractional skyrmions in a binary dipolar Bose-Einstein condensate under rotation

    Science.gov (United States)

    Dong, Biao; Sun, Qing; Liu, Wu-Ming; Ji, An-Chun; Zhang, Xiao-Fei; Zhang, Shou-Gang

    2017-07-01

    We consider a binary dipolar Bose-Einstein condensate with repulsive contact and dipolar interactions under rotation. Our results show that the interplay among short-range interaction, long-range interaction, and rotation can give rise to a rich variety of topological configurations, including giant skyrmions with multiply topological charges and skyrmion-vortex lattices. In particular, we find that for fixed rotation frequencies, tuning the short- and long-range interactions can derive novel ground-state phases, such as a meron pair composed of two fractional skyrmions and a skyrmion with topological charge Q =2 centered in giant skyrmions.

  19. Pressure-stability of phospholipid bicelles: Measurement of residual dipolar couplings under extreme conditions

    Energy Technology Data Exchange (ETDEWEB)

    Brunner, E.; Arnold, M.R.; Kremer, W.; Kalbitzer, H.R. [University of Regensburg, Institute of Biophysics and Physical Biochemistry (Germany)

    2001-10-15

    High-pressure NMR of proteins in solutions currently gains increasing interest. 3D structure determination of proteins under high pressure is, however, so far impossible due to the lack of NOE information. Residual dipolar couplings induced by the addition of magnetically orienting media are known to be capable of replacing NOE information to a very high extent. In the present contribution we study the pressure-wstability of dimyristoylphosphatidylcholine (DMPC)/ dihexanoylphosphatidylcholine (DHPC) bicelles and demonstrate the feasibility of measuring residual dipolar couplings in proteins under high pressure.

  20. Spin correlations in Ho2Ti2O7: A dipolar spin ice system

    DEFF Research Database (Denmark)

    Bramwell, S.T.; Harris, M.J.; Hertog, B.C. den

    2001-01-01

    described by a nearest neighbor spin ice model and very accurately described by a dipolar spin ice model. The heat capacity is well accounted for by the sum of a dipolar spin ice contribution and an expected nuclear spin contribution, known to exist in other Ho(3+) salts. These results settle the question......The pyrochlore material Ho(2)Ti(2)O(7) has been suggested to show "spin ice" behavior. We present neutron scattering and specific heat results that establish unambiguously that Ho(2)Ti(2)O(7) exhibits spin ice correlations at low temperature. Diffuse magnetic neutron scattering is quite well...

  1. Lorentz microscopy sheds light on the role of dipolar interactions in magnetic hyperthermia

    Science.gov (United States)

    Campanini, M.; Ciprian, R.; Bedogni, E.; Mega, A.; Chiesi, V.; Casoli, F.; de Julián Fernández, C.; Rotunno, E.; Rossi, F.; Secchi, A.; Bigi, F.; Salviati, G.; Magén, C.; Grillo, V.; Albertini, F.

    2015-04-01

    Monodispersed Fe3O4 nanoparticles with comparable size distributions have been synthesized by two different synthesis routes, co-precipitation and thermal decomposition. Thanks to the different steric stabilizations, the described samples can be considered as a model system to investigate the effects of magnetic dipolar interactions on the aggregation states of the nanoparticles. Moreover, the presence of magnetic dipolar interactions can strongly affect the nanoparticle efficiency as a hyperthermic mediator. In this paper, we present a novel way to visualize and map the magnetic dipolar interactions in different kinds of nanoparticle aggregates by the use of Lorentz microscopy, an easy and reliable in-line electron holographic technique. By exploiting Lorentz microscopy, which is complementary to the magnetic measurements, it is possible to correlate the interaction degrees of magnetic nanoparticles with their magnetic behaviors. In particular, we demonstrate that Lorentz microscopy is successful in visualizing the magnetic configurations stabilized by dipolar interactions, thus paving the way to the comprehension of the power loss mechanisms for different nanoparticle aggregates.Monodispersed Fe3O4 nanoparticles with comparable size distributions have been synthesized by two different synthesis routes, co-precipitation and thermal decomposition. Thanks to the different steric stabilizations, the described samples can be considered as a model system to investigate the effects of magnetic dipolar interactions on the aggregation states of the nanoparticles. Moreover, the presence of magnetic dipolar interactions can strongly affect the nanoparticle efficiency as a hyperthermic mediator. In this paper, we present a novel way to visualize and map the magnetic dipolar interactions in different kinds of nanoparticle aggregates by the use of Lorentz microscopy, an easy and reliable in-line electron holographic technique. By exploiting Lorentz microscopy, which is

  2. Interaction of Rayleigh waves with 2D dipolar exciton gas: impact of Bose–Einstein condensation

    Science.gov (United States)

    Boev, M. V.; Chaplik, A. V.; Kovalev, V. M.

    2017-12-01

    The theory of the interaction of a two-dimensional gas of indirect dipolar excitons with Rayleigh surface elastic waves has been developed. The absorption and renormalization of the phase velocity of a surface wave, as well as the drag of excitons by the surface acoustic wave and the generation of bulk acoustic waves by a two dimensional gas of dipolar excitons irradiated by external electromagnetic radiation, have been considered. These effects have been studied both in a normal phase at high temperatures and in a condensed phase of the exciton gas. The calculations have been performed in the ballistic and diffusion limits for both phases.

  3. Isolation of the Mutual Transverse Dipolar Relaxation of a Pair of Coupled Spins

    Science.gov (United States)

    Norwood, T. J.; Pereira, J.

    The potential of relaxation measurements to provide dynamic information about a molecule often goes unrealized due to the complexity of the processes which occur and the difficulty in separating them. Generalized expressions for several elements of the dipolar relaxation matrix are derived. It is shown that by taking the appropriate linear combination of these relaxation rates it is possible to isolate the mutual dipolar relaxation of a pair of coupled spins, even when both also relax with an arbitrary number of others. The technique is demonstrated experimentally using 5,7-dimethoxy coumarin.

  4. Dipolar Quinoidal Acene Analogues as Stable Isoelectronic Structures of Pentacene and Nonacene

    KAUST Repository

    Shi, Xueliang

    2015-10-08

    Quinoidal thia-acene analogues, as the respective isoelectronic structures of pentacene and nonacene, were synthesized and an unusual 1,2-sulfur migration was observed during the Friedel-Crafts alkylation reaction. The analogues display a closed-shell quinoidal structure in the ground state with a distinctive dipolar character. In contrast to their acene isoelectronic structures, both compounds are stable because of the existence of more aromatic sextet rings, a dipolar character, and kinetic blocking. They exhibit unique packing in single crystals resulting from balanced dipole-dipole and [C-H⋯π]/[C-H⋯S] interactions.

  5. Simulation of transverse beam splitting using time-dependent dipolar or quadrupolar kicks

    CERN Document Server

    Capoani, Federico

    2017-01-01

    Two simple systems with high relevance for accelerator physics have been studied in detail in the context of this Summer Student Project. These systems describe the motion under the influence of detuning with amplitude due to non-linear magnets and an external, time-dependent force of dipolar or quadrupolar nature.Two simple systems with high relevance for accelerator physics have been studied in detail in the context of this Summer Student Project. These systems describe the motion under the influence of detuning with amplitude due to non-linear magnets and an external, time-dependent force of dipolar or quadrupolar nature.

  6. Dipolar Bose gas with three-body interactions at finite temperature

    Science.gov (United States)

    Boudjemâa, Abdelâali

    2018-01-01

    We investigate effects of three-body contact interactions on a trapped dipolar Bose gas at finite temperature using the Hartree–Fock–Bogoliubov approximation. We analyze numerically the behavior of the transition temperature and the condensed fraction. Effects of the three-body interactions, anomalous pair correlations and temperature on the collective modes are discussed.

  7. Nonlinear localized modes in dipolar Bose–Einstein condensates in two-dimensional optical lattices

    Energy Technology Data Exchange (ETDEWEB)

    Rojas-Rojas, Santiago, E-mail: srojas@cefop.cl [Center for Optics and Photonics and MSI-Nucleus on Advanced Optics, Universidad de Concepción, Casilla 160-C, Concepción (Chile); Departamento de Física, Universidad de Concepción, Casilla 160-C, Concepción (Chile); Naether, Uta [Instituto de Ciencia de Materiales de Aragón and Departamento de Física de la Materia Condensada, CSIC-Universidad de Zaragoza, 50009 Zaragoza (Spain); Delgado, Aldo [Center for Optics and Photonics and MSI-Nucleus on Advanced Optics, Universidad de Concepción, Casilla 160-C, Concepción (Chile); Departamento de Física, Universidad de Concepción, Casilla 160-C, Concepción (Chile); Vicencio, Rodrigo A. [Center for Optics and Photonics and MSI-Nucleus on Advanced Optics, Universidad de Concepción, Casilla 160-C, Concepción (Chile); Departamento de Física, Facultad de Ciencias, Universidad de Chile, Santiago (Chile)

    2016-09-16

    Highlights: • We study discrete two-dimensional breathers in dipolar Bose–Einstein Condensates. • Important differences in the properties of three fundamental modes are found. • Norm threshold for existence of 2D breathers varies with dipolar interaction. • The Effective Potential Method is implemented for stability analysis. • Uncommon mobility of 2D discrete solitons is observed. - Abstract: We analyze the existence and properties of discrete localized excitations in a Bose–Einstein condensate loaded into a periodic two-dimensional optical lattice, when a dipolar interaction between atoms is present. The dependence of the Number of Atoms (Norm) on the energy of solutions is studied, along with their stability. Two important features of the system are shown, namely, the absence of the Norm threshold required for localized solutions to exist in finite 2D systems, and the existence of regions in the parameter space where two fundamental solutions are simultaneously unstable. This feature enables mobility of localized solutions, which is an uncommon feature in 2D discrete nonlinear systems. With attractive dipolar interaction, a non-trivial behavior of the Norm dependence is obtained, which is well described by an analytical model.

  8. Expanding stereochemical and skeletal diversity using petasis reactions and 1,3-dipolar cycloadditions.

    Science.gov (United States)

    Muncipinto, Giovanni; Kaya, Taner; Wilson, J Anthony; Kumagai, Naoya; Clemons, Paul A; Schreiber, Stuart L

    2010-11-19

    A short and modular synthetic pathway using intramolecular 1,3-dipolar cycloaddition reactions and yielding functionalized isoxazoles, isoxazolines, and isoxazolidines is described. The change in shape of previous compounds and those in this study is quantified and compared using principal moment-of-inertia shape analysis.

  9. Theoretical Study of Dipolar Relaxation of Coupled Nuclear Spins at Variable Magnetic Field

    NARCIS (Netherlands)

    Pravdivtsev, A.N.; Ivanov, K.L.; Kaptein, R.|info:eu-repo/dai/nl/074334603; Yurkovskaya, A.V.

    2013-01-01

    A theoretical study was made of magnetic field-dependent dipolar relaxation in two- and three-spin systems. The results for the nuclear magnetic relaxation dispersion (NMRD) curves were compared with those for the simpler model of fluctuating local fields. For both models it was found that at low

  10. MAGNETIC-X-RAY DICHROISM - GENERAL FEATURES OF DIPOLAR AND QUADRUPOLAR SPECTRA

    NARCIS (Netherlands)

    CARRA, P; KONIG, H; THOLE, BT; ALTARELLI, M

    1993-01-01

    Sum rules are derived for dipolar linear and quadrupolar circular dichroism in the X-ray region. They relate the intensity of the dichroic signal to the ground state expectation values of orbital and spin dependent effective operators, which act on the valence electrons. The results obtained are

  11. Decay of Rabi Oscillations by Dipolar-Coupled Dynamical Spin Environments

    NARCIS (Netherlands)

    Dobrovitski, V.V.; Feiguin, A.E.; Hanson, R.; Awschalom, D.D.

    2009-01-01

    We study the Rabi oscillations decay of a spin decohered by a spin bath whose internal dynamics is caused by dipolar coupling between the bath spins. The form and rate of decay as a function of the intrabath coupling is obtained analytically, and confirmed numerically. The complex form of decay

  12. High electronegativity multi-dipolar electron cyclotron resonance plasma source for etching by negative ions

    DEFF Research Database (Denmark)

    Stamate, Eugen; Draghici, M.

    2012-01-01

    A large area plasma source based on 12 multi-dipolar ECR plasma cells arranged in a 3 x 4 matrix configuration was built and optimized for silicon etching by negative ions. The density ratio of negative ions to electrons has exceeded 300 in Ar/SF6 gas mixture when a magnetic filter was used to re...

  13. Electron dynamics during substorm dipolarization in Mercury's magnetosphere

    Directory of Open Access Journals (Sweden)

    D. C. Delcourt

    2005-11-01

    Full Text Available We examine the nonlinear dynamics of electrons during the expansion phase of substorms at Mercury using test particle simulations. A simple model of magnetic field line dipolarization is designed by rescaling a magnetic field model of the Earth's magnetosphere. The results of the simulations demonstrate that electrons may be subjected to significant energization on the time scale (several seconds of the magnetic field reconfiguration. In a similar manner to ions in the near-Earth's magnetosphere, it is shown that low-energy (up to several tens of eV electrons may not conserve the second adiabatic invariant during dipolarization, which leads to clusters of bouncing particles in the innermost magnetotail. On the other hand, it is found that, because of the stretching of the magnetic field lines, high-energy electrons (several keVs and above do not behave adiabatically and possibly experience meandering (Speiser-type motion around the midplane. We show that dipolarization of the magnetic field lines may be responsible for significant, though transient, (a few seconds precipitation of energetic (several keVs electrons onto the planet's surface. Prominent injections of energetic trapped electrons toward the planet are also obtained as a result of dipolarization. These injections, however, do not exhibit short-lived temporal modulations, as observed by Mariner-10, which thus appear to follow from a different mechanism than a simple convection surge.

  14. Spontaneous generation of spin-orbit coupling in magnetic dipolar Fermi gases

    OpenAIRE

    Sogo, T; M. Urban; Schuck, P.; Miyakawa, T

    2011-01-01

    The stability of an unpolarized two-component dipolar Fermi gas is studied within mean-field theory. Besides the known instability towards spontaneous magnetization with Fermi sphere deformation, another instability towards spontaneous formation of a spin-orbit coupled phase with a Rashba-like spin texture is found. A phase diagram is presented and consequences are briefly discussed.

  15. Numerical simulation of trapped dipolar quantum gases: Collapse studies and vortex dynamics

    KAUST Repository

    Sparber, Christof

    2010-01-01

    We numerically study the three dimensional Gross-Pitaevskii equation for dipolar quantum gases using a time-splitting algorithm. We are mainly concerned with numerical investigations of the possible blow-up of solutions, i.e. collapse of the condensate, and the dynamics of vortices. © American Institute of Mathematical Sciences.

  16. On the Gross–Pitaevskii equation for trapped dipolar quantum gases

    KAUST Repository

    Carles, Rémi

    2008-09-29

    We study the time-dependent Gross-Pitaevskii equation describing Bose-Einstein condensation of trapped dipolar quantum gases. Existence and uniqueness as well as the possible blow-up of solutions are studied. Moreover, we discuss the problem of dimension reduction for this nonlinear and nonlocal Schrödinger equation. © 2008 IOP Publishing Ltd and London Mathematical Society.

  17. Wave Vector Dependent Susceptibility at T>Tc in a Dipolar Ising Ferromagnet

    DEFF Research Database (Denmark)

    Als-Nielsen, Jens Aage; Holmes, L. M:; Guggenheim, H. J.

    1974-01-01

    The wave-vector-dependent susceptibility of LiTbF4 has been investigated by means of neutron scattering. The observations show a singularity of the susceptibility near wave vector Q=0 which is characteristic of the dipolar Coulomb interaction and good agreement with theory is obtained...

  18. Kinetic solvent effects on 1,3-dipolar cycloadditions of benzonitrile oxide

    NARCIS (Netherlands)

    Rispens, T; Engberts, JBFN

    The kinetics of 1,3-dipolar cycloadditions of benzonitrile oxide with a series of N-substituted maleimides and with cyclopentene are reported for water, a wide range of organic solvents and binary solvent mixtures. The results indicate the importance of both solvent polarity and specific

  19. The Plasma Sheet as Natural Symmetry Plane for Dipolarization Fronts in the Earth's Magnetotail

    Science.gov (United States)

    Frühauff, D.; Glassmeier, K.-H.

    2017-11-01

    In this work, observations of multispacecraft mission Time History of Events and Macroscale Interactions during Substorms are used for statistical investigation of dipolarization fronts in the near-Earth plasma sheet of the magnetotail. Using very stringent criteria, 460 events are detected in almost 10 years of mission data. Minimum variance analysis is used to determine the normal directions of the phase fronts, providing evidence for the existence of a natural symmetry of these phenomena, given by the neutral sheet of the magnetotail. This finding enables the definition of a local coordinate system based on the Tsyganenko model, reflecting the intrinsic orientation of the neutral sheet and, therefore, the dipolarization fronts. In this way, the comparison of events with very different background conditions is improved. Through this study, the statistical results of Liu, Angelopoulos, Runov, et al. (2013) are both confirmed and extended. In a case study, the knowledge of this plane of symmetry helps to explain the concave curvature of dipolarization fronts in the XZ plane through phase propagation speeds of magnetoacoustic waves. A second case study is presented to determine the central current system of a passing dipolarization front through a constellation of three spacecraft. With this information, a statistical analysis of spacecraft observations above and below the neutral sheet is used to provide further evidence for the neutral sheet as the symmetry plane and the central current system. Furthermore, it is shown that the signatures of dipolarization fronts are under certain conditions closely related to that of flux ropes, indicating a possible relationship between these two transient phenomena.

  20. Brightening of onset arc precedes the dipolarization onset: THEMIS observations of two events on 1 March 2008

    Directory of Open Access Journals (Sweden)

    J. R. Kan

    2011-11-01

    Full Text Available We present a new M-I coupling model of substorm during southward IMF based on the THEMIS observations of two events on 1 March 2008. The first event (E-1 was classified as a pseudo-breakup: brightening of the onset arc preceded the first dipolarization onset by ∼71 ± 3 s, but the breakup arcs faded within ∼5 min without substantial poleward expansion and the dipolarization stopped and reversed to thinning. The second event (E-2 was identified as a substorm: brightening of the second onset arc preceded the second dipolarization onset by ∼80 ± 3 s, leading to a full-scale expanding auroral bulge during the substorm expansion phase for ∼20 min. The Alfvén travel time from the ionosphere to the dipolarization onset region is estimated at ∼69.3 s in E-1; at ∼80.3 s in E-2, which matched well with the observed time delay of the dipolarization onset after the brightening of the onset arc, respectively in E-1 and E-2. Brightening of the onset arc precedes the dipolarization onset suggest that the onset arc brightening is caused by the intense upward field-aligned currents originating from the divergence of the Cowling electrojet in the ionosphere. The Cowling electrojet current loop (CECL is formed to close the field-aligned currents at all times. The closure current in the Alfvén wavefront is anti-parallel to the cross-tail current. Dipolarization onset occurs when the Alfvén wavefront incident on the near-Earth plasma sheet to disrupt the cross-tail current in the dipolarization region. Slow MHD waves dominate the disruption of the cross-tail current in the dipolarization region.

  1. Time-reversal-based SU(2) x Sn scalar invariants as (Lie Algebraic) group measures: a structured overview of generalised democratic-recoupled, uniform non-Abelian [AX]n NMR spin systems, as abstract [Formula: see text] chain networks.

    Science.gov (United States)

    Temme, F P

    2004-03-01

    The physics of dual group scalar invariants (SIs) as (Lie algebraic) group measures (L-GMs) and its significance to non-Abelian NMR spin systems motivates this overview of uniform general-2n [AX](2n) spin evolution, which represents an extensive addendum to Corio's earlier (essentially restricted) view of Abelian spin system SU(2)-based SI-cardinalities. The [Formula: see text] values in [J. Magn. Reson., 134 (1998) 131] arise from strictly linear recoupled time-reversal invariance (TRI) models. In contrast, here we discuss the physical significance of an alternative polyhedral combinatorics approach to democratic recoupling (DR), a property inherent in both the TRI and statistical sampling. Recognition of spin ensemble SIs as being L-GMs over isomorphic algebras is invaluable in many DR-based NMR problems. Various [AX]n model spin systems, including the [AX]3 bis odd-odd parity spin system, are examined as direct applications of these L-GM- and combinatorial-based SI ideas. Hence in place of /SI/=15 (implied by Corio's [Formula: see text] approach), the bis 3-fold spin system cardinality is seen now as constrained to a single invariant on an isomorphic product algebra under L-GMs, in accord with the subspectral analysis of Jones et al. [Canad. J. Chem., 43 (1965) 683]. The group projective ideas cited here for DR (as cf. to graph theoretic views) apply to highly degenerate non-Abelian problems. Over dual tensorial bases, they define models of spin dynamical evolution whose (SR) quasiparticle superboson carrier (sub)spaces are characterised by SIs acting as explicit auxiliary labels [Physica, A198 (1993) 245; J. Math. Chem., 31 (2002) 281]. A deeper [Formula: see text] network-based view of spin-alone space developed in Balasubramanian's work [J. Chem. Phys., 78 (1983) 6358] is especially important, (e.g.) in the study of spin waves [J. Math. Chem., 31 (2002) 363]. Beyond the specific NMR SIs derived here, there are DR applications where a sporadic, still higher, 2

  2. Dielectric relaxation in ionic liquid/dipolar solvent binary mixtures: A semi-molecular theory

    Science.gov (United States)

    Daschakraborty, Snehasis; Biswas, Ranjit

    2016-03-01

    A semi-molecular theory is developed here for studying dielectric relaxation (DR) in binary mixtures of ionic liquids (ILs) with common dipolar solvents. Effects of ion translation on DR time scale, and those of ion rotation on conductivity relaxation time scale are explored. Two different models for the theoretical calculations have been considered: (i) separate medium approach, where molecularities of both the IL and dipolar solvent molecules are retained, and (ii) effective medium approach, where the added dipolar solvent molecules are assumed to combine with the dipolar ions of the IL, producing a fictitious effective medium characterized via effective dipole moment, density, and diameter. Semi-molecular expressions for the diffusive DR times have been derived which incorporates the effects of wavenumber dependent orientational static correlations, ion dynamic structure factors, and ion translation. Subsequently, the theory has been applied to the binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) with water (H2O), and acetonitrile (CH3CN) for which experimental DR data are available. On comparison, predicted DR time scales show close agreement with the measured DR times at low IL mole fractions (xIL). At higher IL concentrations (xIL > 0.05), the theory over-estimates the relaxation times and increasingly deviates from the measurements with xIL, deviation being the maximum for the neat IL by almost two orders of magnitude. The theory predicts negligible contributions to this deviation from the xIL dependent collective orientational static correlations. The drastic difference between DR time scales for IL/solvent mixtures from theory and experiments arises primarily due to the use of the actual molecular volume ( Vmol dip ) for the rotating dipolar moiety in the present theory and suggests that only a fraction of Vmol dip is involved at high xIL. Expectedly, nice agreement between theory and experiments appears when experimental

  3. Dielectric relaxation in ionic liquid/dipolar solvent binary mixtures: A semi-molecular theory.

    Science.gov (United States)

    Daschakraborty, Snehasis; Biswas, Ranjit

    2016-03-14

    A semi-molecular theory is developed here for studying dielectric relaxation (DR) in binary mixtures of ionic liquids (ILs) with common dipolar solvents. Effects of ion translation on DR time scale, and those of ion rotation on conductivity relaxation time scale are explored. Two different models for the theoretical calculations have been considered: (i) separate medium approach, where molecularities of both the IL and dipolar solvent molecules are retained, and (ii) effective medium approach, where the added dipolar solvent molecules are assumed to combine with the dipolar ions of the IL, producing a fictitious effective medium characterized via effective dipole moment, density, and diameter. Semi-molecular expressions for the diffusive DR times have been derived which incorporates the effects of wavenumber dependent orientational static correlations, ion dynamic structure factors, and ion translation. Subsequently, the theory has been applied to the binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) with water (H2O), and acetonitrile (CH3CN) for which experimental DR data are available. On comparison, predicted DR time scales show close agreement with the measured DR times at low IL mole fractions (x(IL)). At higher IL concentrations (x(IL) > 0.05), the theory over-estimates the relaxation times and increasingly deviates from the measurements with x(IL), deviation being the maximum for the neat IL by almost two orders of magnitude. The theory predicts negligible contributions to this deviation from the x(IL) dependent collective orientational static correlations. The drastic difference between DR time scales for IL/solvent mixtures from theory and experiments arises primarily due to the use of the actual molecular volume (V(mol)(dip)) for the rotating dipolar moiety in the present theory and suggests that only a fraction of V(mol)(dip) is involved at high x(IL). Expectedly, nice agreement between theory and experiments appears when

  4. A One-Pot Multicomponent 1,3-Dipolar Cycloaddition Strategy: Combinatorial Synthesis of Dihydrothiophenone-Engrafted Dispiro Hybrid Heterocycles.

    Science.gov (United States)

    Anusha Rani, Mani; Vivek Kumar, Sundaravel; Malathi, Karuppiah; Muthu, Muthumani; Almansour, Abdulrahman I; Suresh Kumar, Raju; Ranjith Kumar, Raju

    2017-05-08

    The combinatorial syntheses of a library of novel dihydrothiophenone-engrafted dispiro oxindole/indenoquinoxaline-pyrrolidine/pyrrolothiazole/indolizine hybrid heterocycles have been realized through a chemo-, regio-, and stereoselective multicomponent 1,3-dipolar cycloaddition strategy.

  5. Multicomponent synthesis of spiropyrrolidine analogues derived from vinylindole/indazole by a 1,3-dipolar cycloaddition reaction

    Directory of Open Access Journals (Sweden)

    Manjunatha Narayanarao

    2016-12-01

    Full Text Available A new series of spiropyrrolidine compounds containing indole/indazole moieties as side chains have been accomplished via a one-pot multicomponent synthesis. The method uses the 1,3-dipolar cycloaddition reaction between N-alkylvinylindole/indazole and azomethine ylides, prepared in situ from cyclic/acyclic amino acids. The 1,3-dipolar cycloaddition proceeds efficiently under thermal conditions to afford the regio- and stereospecific cyclic adducts.

  6. Finslerian dipolar modulation of the CMB power spectra at scales 2 < l < 600

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xin [Chongqing University, Department of Physics, Chongqing (China); Chinese Academy of Sciences, CAS Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Beijing (China); Lin, Hai-Nan [Chongqing University, Department of Physics, Chongqing (China)

    2017-05-15

    A common explanation for the CMB power asymmetry is to introduce a dipolar modulation at the stage of inflation, where the primordial power spectrum is spatially varying. If the universe in the stage of inflation is Finslerian, and if the Finsler spacetime is non-reversible under parity flip, x → -x, then a three dimensional spectrum which is a function of wave vector and direction is valid. In this paper, a three dimensional primordial power spectrum with preferred direction is derived in the framework of Finsler spacetime. It is found that the amplitude of dipolar modulation is related to the Finslerian parameter, which in turn is a function of wave vector. The angular correlation coefficients are presented, and the numerical results for the anisotropic correlation coefficients over the multipole range 2 < l < 600 are given. (orig.)

  7. Analytical approximations for the orientation distribution of small dipolar particles in steady shear flows

    DEFF Research Database (Denmark)

    Bees, Martin Alan; Hill, N.A.; Pedley, T.J.

    1998-01-01

    Analytical approximations are obtained to solutions of the steady Fokker-Planck equation describing the probability density function for the orientation of dipolar particles in a steady, low-Reynolds-number shear flow and a uniform external field. Exact computer algebra is used to solve the equat......Analytical approximations are obtained to solutions of the steady Fokker-Planck equation describing the probability density function for the orientation of dipolar particles in a steady, low-Reynolds-number shear flow and a uniform external field. Exact computer algebra is used to solve...... to swimming cells in bioconvection are discussed. A separate symptotic expansion is performed for the case in which spherical particles are in a flow with high vorticy, and the results are compared with the truncated spherical harmonic expansion. Agreement between the two methods is excellent....

  8. Two dimensional dipolar coupling in monolayers of silver and gold nanoparticles on a dielectric substrate.

    Science.gov (United States)

    Liu, Yu; Begin-Colin, Sylvie; Pichon, Benoît P; Leuvrey, Cedric; Ihiawakrim, Dris; Rastei, Mircea; Schmerber, Guy; Vomir, Mircea; Bigot, Jean Yves

    2014-10-21

    The dimensionality of assembled nanoparticles plays an important role in their optical and magnetic properties, via dipolar effects and the interaction with their environment. In this work we develop a methodology for distinguishing between two (2D) and three (3D) dimensional collective interactions on the surface plasmon resonance of assembled metal nanoparticles. Towards that goal, we elaborate different sets of Au and Ag nanoparticles as suspensions, random 3D arrangements and well organized 2D arrays. Then we model their scattering cross-section using effective field methods in dimension n, including interparticle as well as particle-substrate dipolar interactions. For this modelling, two effective field medium approaches are employed, taking into account the filling factors of the assemblies. Our results are important for realizing photonic amplifier devices.

  9. Macroscopic order and electro-optic response of dipolar chromophore-polymer materials.

    Science.gov (United States)

    Pereverzev, Yuriy V; Prezhdo, Oleg V; Dalton, Larry R

    2004-12-10

    This Minireview considers the key factors that govern the organization of macroscopic polarization in nonlinear optical systems obtained by electric poling of organic dipolar chromophores dissolved in polymer matrices. The macroscopic electric polarization depends on the thermodynamic state of the dipole system. The dependence of the paraelectric and antiferroelectric states of dipolar chromophores on the chromophore concentration and the strength of the poling field is discussed. Phase transitions between the para- and antiferroelectric states are investigated within the limits of the Ising and isotropic models for the chromophore dipoles and are considered for varying chromophore concentration, poling field strength, and macroscopic shape of the sample used for poling. The macroscopic polarization and electro-optic coefficient of the material change drastically upon phase transition. The theories are compared with the experimental data on the electro-optic coefficient dependence on the chromophore concentration. The isotropic dipole model shows excellent agreement with experiment for the chromophore systems most commonly used in nonlinear optics.

  10. Partial alignment and measurement of residual dipolar couplings of proteins under high hydrostatic pressure.

    Science.gov (United States)

    Fu, Yinan; Wand, A Joshua

    2013-08-01

    High-pressure NMR spectroscopy has emerged as a complementary approach for investigating various structural and thermodynamic properties of macromolecules. Noticeably absent from the array of experimental restraints that have been employed to characterize protein structures at high hydrostatic pressure is the residual dipolar coupling, which requires the partial alignment of the macromolecule of interest. Here we examine five alignment media that are commonly used at ambient pressure for this purpose. We find that the spontaneous alignment of Pf1 phage, d(GpG) and a C12E5/n-hexnanol mixture in a magnetic field is preserved under high hydrostatic pressure. However, DMPC/DHPC bicelles and collagen gel are found to be unsuitable. Evidence is presented to demonstrate that pressure-induced structural changes can be identified using the residual dipolar coupling.

  11. Partial alignment and measurement of residual dipolar couplings of proteins under high hydrostatic pressure

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Yinan; Wand, A. Joshua, E-mail: wand@mail.med.upenn.edu [University of Pennsylvania, Department of Biochemistry and Biophysics, Johnson Research Foundation (United States)

    2013-08-15

    High-pressure NMR spectroscopy has emerged as a complementary approach for investigating various structural and thermodynamic properties of macromolecules. Noticeably absent from the array of experimental restraints that have been employed to characterize protein structures at high hydrostatic pressure is the residual dipolar coupling, which requires the partial alignment of the macromolecule of interest. Here we examine five alignment media that are commonly used at ambient pressure for this purpose. We find that the spontaneous alignment of Pf1 phage, d(GpG) and a C12E5/n-hexnanol mixture in a magnetic field is preserved under high hydrostatic pressure. However, DMPC/DHPC bicelles and collagen gel are found to be unsuitable. Evidence is presented to demonstrate that pressure-induced structural changes can be identified using the residual dipolar coupling.

  12. Direct Observation of Field and Temperature Induced Domain Replication in Dipolar Coupled Perpendicular Anisotropy Films

    Energy Technology Data Exchange (ETDEWEB)

    Hauet, T.; Gunther, C.M.; Pfau, B.; Eisebitt, S.; Fischer, P.; Rick, R. L.; Thiele, J.-U.; Hellwig, O.; Schabes, M.E.

    2007-07-01

    Dipolar interactions in a soft/Pd/hard [CoNi/Pd]{sub 30}/Pd/[Co/Pd]{sub 20} multilayer system, where a thick Pd layer between two ferromagnetic units prevents direct exchange coupling, are directly revealed by combining magnetometry and state-of-the-art layer resolving soft x-ray imaging techniques with sub-100-nm spatial resolution. The domains forming in the soft layer during external magnetic field reversal are found to match the domains previously trapped in the hard layer. The low Curie temperature of the soft layer allows varying its intrinsic parameters via temperature and thus studying the competition with dipolar fields due to the domains in the hard layer. Micromagnetic simulations elucidate the role of [CoNi/Pd] magnetization, exchange, and anisotropy in the duplication process. Finally, thermally driven domain replication in remanence during temperature cycling is demonstrated.

  13. A facile regioselective synthesis of novel spiroacenaphthene pyrroloisoquinolines through 1,3-dipolar cycloaddition reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sarrafi, Yaghoub; Asghari, Asieh; Sadatshahabi, Marzieh, E-mail: ysarrafi@umz.ac.ir [Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran (Iran, Islamic Republic of); Hamzehloueian, Mahshid [Department of Chemistry, Jouybar Branch, Islamic Azad University, Jouybar (Iran, Islamic Republic of); Alimohammadi, Kamal [Department of Chemistry, Dr. Shariati Branch, University of Farhangian, Sari (Iran, Islamic Republic of)

    2013-12-01

    An efficient one-pot three-component procedure for the synthesis of novel spiroacenaphthene pyrroloisoquinolines with high regioselectivity is described. These compounds were prepared from 1,3-dipolar cycloaddition of an azomethine ylide generated from acenaphthenequinone and 1,2,3,4-tetrahydroisoquinoline via [1,5]-H shift, with chalcone and nitrostyrene derivatives as dipolarophiles. The structure and stereochemistry of the cycloadducts have been established by single crystal X-ray structure and spectroscopic techniques. (author)

  14. Observation of Dipolar Spin-Exchange Interactions with Polar Molecules in a Lattice

    Science.gov (United States)

    2013-01-01

    specific quantization axis (B-field). Negative values (blue) correspond to attractive interactions, and positive values (red) to repulsive interactions...superfluidity, and topological phases 9–13. Ultracold gases of polar molecules provide highly controllable, long-lived, and strongly interacting dipolar...systems and have recently attracted intense scientific interest. Samples of fermionic 40K87Rb polar molecules, with an electric dipole moment of 0.57

  15. NMR studies on 1,3-dipolar cycloaddition of nitrile oxides to norbornenes

    Energy Technology Data Exchange (ETDEWEB)

    Gucma, Miroslaw; Golebiewski, W. Marek; Krawczyk, Maria, E-mail: golebiewski@ipo.waw.pl [Institute of Industrial Organic Chemistry, Warsaw (Poland)

    2013-05-15

    The 1,3-dipolar cycloaddition reaction of nitrile oxides to norbornenes substituted with an acrylate-derived moiety was examined. Only adducts to norbornene system were formed with a good exo selectivity and complete site-selectivity. Structures of the products were elucidated by an extensive application of electrospray ionization-mass spectrometry (ESI-MS) and 2D {sup 1}H and {sup 13}C nuclear magnetic resonance (NMR). (author)

  16. Long-range dipolar order and dispersion forces in polar liquids.

    Science.gov (United States)

    Besford, Quinn Alexander; Christofferson, Andrew Joseph; Liu, Maoyuan; Yarovsky, Irene

    2017-11-21

    Complex solvation phenomena, such as specific ion effects, occur in polar liquids. Interpretation of these effects in terms of structure and dispersion forces will lead to a greater understanding of solvation. Herein, using molecular dynamics, we probe the structure of polar liquids through specific dipolar pair correlation functions that contribute to the potential of mean force that is "felt" between thermally rotating dipole moments. It is shown that unique dipolar order exists at separations at least up to 20 Å for all liquids studied. When the structural order is compared with a dipolar dispersion force that arises from local co-operative enhancement of dipole moments, a strong agreement is found. Lifshitz theory of dispersion forces was compared with the structural order, where the theory is validated for all liquids that do not have significant local dipole correlations. For liquids that do have significant local dipole correlations, specifically liquid water, Lifshitz theory underestimates the dispersion force by a factor of 5-10, demonstrating that the force that leads to the increased structure in liquid water is missed by Lifshitz theory of van der Waals forces. We apply similar correlation functions to an ionic aqueous system, where long-range order between water's dipole moment and a single chloride ion is found to exist at 20 Å of separation, revealing a long-range perturbation of water's structure by an ion. Furthermore, we found that waters within the 1st, 2nd, and 3rd solvation shells of a chloride ion exhibit significantly enhanced dipolar interactions, particularly with waters at larger distances of separation. Our results provide a link between structures, dispersion forces, and specific ion effects, which may lead to a more robust understanding of solvation.

  17. Long-range dipolar order and dispersion forces in polar liquids

    Science.gov (United States)

    Besford, Quinn Alexander; Christofferson, Andrew Joseph; Liu, Maoyuan; Yarovsky, Irene

    2017-11-01

    Complex solvation phenomena, such as specific ion effects, occur in polar liquids. Interpretation of these effects in terms of structure and dispersion forces will lead to a greater understanding of solvation. Herein, using molecular dynamics, we probe the structure of polar liquids through specific dipolar pair correlation functions that contribute to the potential of mean force that is "felt" between thermally rotating dipole moments. It is shown that unique dipolar order exists at separations at least up to 20 Å for all liquids studied. When the structural order is compared with a dipolar dispersion force that arises from local co-operative enhancement of dipole moments, a strong agreement is found. Lifshitz theory of dispersion forces was compared with the structural order, where the theory is validated for all liquids that do not have significant local dipole correlations. For liquids that do have significant local dipole correlations, specifically liquid water, Lifshitz theory underestimates the dispersion force by a factor of 5-10, demonstrating that the force that leads to the increased structure in liquid water is missed by Lifshitz theory of van der Waals forces. We apply similar correlation functions to an ionic aqueous system, where long-range order between water's dipole moment and a single chloride ion is found to exist at 20 Å of separation, revealing a long-range perturbation of water's structure by an ion. Furthermore, we found that waters within the 1st, 2nd, and 3rd solvation shells of a chloride ion exhibit significantly enhanced dipolar interactions, particularly with waters at larger distances of separation. Our results provide a link between structures, dispersion forces, and specific ion effects, which may lead to a more robust understanding of solvation.

  18. Dipolar cycloaddition of rhodium-generated carbonyl ylides with p-quinones.

    Science.gov (United States)

    Pirrung, M C; Kaliappan, K P

    2000-02-10

    [reaction: see text] The dipolar cycloaddition of carbonyl ylides generated by the rhodium-catalyzed decomposition of delta- and epsilon-carbonyl-alpha-diazoketones with p-quinones leads to both C=O and C=C addition products. The product ratio is solvent- and catalyst-dependent and has been optimized to favor formation of either product. The C=C addition products of naphthoquinones are used in the assembly of structures hybridizing the illudin and anthraquinone anticancer agents.

  19. Magnetic fluctuations embedded in dipolarization inside geosynchronous orbit and their associated selective acceleration of O+ ions

    Science.gov (United States)

    Nosé, M.; Takahashi, K.; Keika, K.; Kistler, L. M.; Koga, K.; Koshiishi, H.; Matsumoto, H.; Shoji, M.; Miyashita, Y.; Nomura, R.

    2014-06-01

    We study magnetic fluctuations embedded in dipolarizations in the inner magnetosphere (a geocentric distance of ≤6.6 RE) and their associated ion flux changes, using the Engineering Test Satellite VIII and Active Magnetospheric Particle Tracer Explorers/CCE satellites. We select seven events of dipolarization that occur during the main phase of magnetic storms having a minimum value of the Dst index less than -40 nT. It is found that (1) all of the dipolarization events are accompanied by strong magnetic fluctuations with the major frequency close to the local O+ gyrofrequency; (2) the magnetic fluctuations appear with significant amplitude in the component nearly parallel to the local magnetic field; (3) the strong flux enhancement is seen in the energy range of 1-10 keV only for O+ ions. In terms of frequency and dominant components of the magnetic fluctuations, they are considered to be excited by the drift-driven electromagnetic ion cyclotron (EMIC) instability that is recently identified with the linear theory. We perform particle tracing for H+ and O+ ions in the electromagnetic fields modeled by the linear dispersion relation of the drift-driven EMIC instability. Results show that the O+ ions are accelerated to the energy range of 0.5-5 keV and undergo a significant modification of the spectral shape, while the H+ ions have no clear change of spectral shape, being consistent with the observations. We therefore suggest that the electromagnetic fluctuations associated with the dipolarizations can accelerate O+ ions locally and nonadiabatically in the inner magnetosphere. This selective acceleration of O+ ions may play a role in enhancing the O+ energy density in the storm time ring current.

  20. Synthesis of pyrrolizidine alkaloids via 1,3-dipolar cycloaddition involving cyclic nitrones and unsaturated lactones.

    Science.gov (United States)

    Stecko, Sebastian; Jurczak, Margarita; Urbańczyk-Lipkowska, Zofia; Solecka, Jolanta; Chmielewski, Marek

    2008-09-08

    The 1,3-dipolar cycloaddition of cyclic nitrone derived from tartaric acid and (S)-5-hydroxymethyl-2(5H)-furanone leads to a single adduct which was transformed into 2,6-dihydroxyhastanecine via reaction sequence involving reduction of the lactone moiety, glycolic cleavage of the terminal diol, and the N-O hydrogenolysis followed by the intramolecular alkylation of the nitrogen atom.

  1. 1,3-Dipolar Cycloaddition Reactions of Substituted Benzyl Azides with Acetylenic Compounds

    Directory of Open Access Journals (Sweden)

    Sultan T. Abu-Orabi

    2002-02-01

    Full Text Available We review in this article some of our work which has been published over the last fifteen years in the area of 1,3-dipolar cycloaddition reactions of substituted benzyl azides with acetylenic compounds to form the corresponding 1,2-3-triazoles. Several triazole derivatives were transformed into triazolopyridazine and triazolo-1,3,4-oxadiazole derivatives upon their reactions with hydrazine.

  2. Luttinger hydrodynamics of confined one-dimensional Bose gases with dipolar interactions

    Energy Technology Data Exchange (ETDEWEB)

    Citro, R [Dipartimento di Fisica ' E R Caianiello' and CNISM, Universita degli Studi di Salerno, Salerno (Italy); Palo, S De [DEMOCRITOS INFM-CNR and Dipartimento di Fisica Teorica, Universita Trieste, Trieste (Italy); Orignac, E [Laboratoire de Physique de l' Ecole Normale Superieure de Lyon, CNRS-UMR5672, Lyon (France); Pedri, P [Laboratoire de Physique Theorique et Modeles Statistiques, Universite Paris-Sud, CNRS-UMR8626, Orsay (France); Chiofalo, M-L [INFN, Department of Mathematics and Faculty of Pharmacy, University of Pisa, Pisa (Italy)], E-mail: chiofalo@dm.unipi.it

    2008-04-15

    Ultracold bosonic and fermionic quantum gases confined to quasi-one-dimensional (1D) geometry are promising candidates for probing fundamental concepts of Luttinger liquid (LL) physics. They can also be exploited for devising applications in quantum information processing and precision measurements. Here, we focus on 1D dipolar Bose gases, where evidence of super-strong coupling behavior has been demonstrated by analyzing the low-energy static and dynamical structures of the fluid at zero temperature by a combined reptation quantum Monte Carlo (RQMC) and bosonization approach. Fingerprints of LL behavior emerge in the whole crossover from the already strongly interacting Tonks-Girardeau at low density to a dipolar density wave regime at high density. We have also shown that a LL framework can be effectively set up and utilized to describe this strongly correlated crossover physics in the case of confined 1D geometries after using the results for the homogeneous system in LL hydrodynamic equations within a local density approximation. This leads to the prediction of observable quantities such as the frequencies of the collective modes of the trapped dipolar gas under the more realistic conditions that could be found in ongoing experiments. The present paper provides a description of the theoretical framework in which the above results have been worked out, making available all the detailed derivations of the hydrodynamic Luttinger equations for the inhomogeneous trapped gas and of the correlation functions for the homogeneous system.

  3. Topological defect formation in rotating binary dipolar Bose–Einstein condensate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xiao-Fei, E-mail: xfzhang@ntsc.ac.cn [Key Laboratory of Time and Frequency Primary Standards, National Time Service Center, Chinese Academy of Sciences, Xi’an 710600 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Department of Engineering Science, University of Electro-Communications, Tokyo 182-8585 (Japan); Han, Wei [Key Laboratory of Time and Frequency Primary Standards, National Time Service Center, Chinese Academy of Sciences, Xi’an 710600 (China); Jiang, Hai-Feng [Key Laboratory of Time and Frequency Primary Standards, National Time Service Center, Chinese Academy of Sciences, Xi’an 710600 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Liu, Wu-Ming [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Saito, Hiroki [Department of Engineering Science, University of Electro-Communications, Tokyo 182-8585 (Japan); Zhang, Shou-Gang [Key Laboratory of Time and Frequency Primary Standards, National Time Service Center, Chinese Academy of Sciences, Xi’an 710600 (China); University of Chinese Academy of Sciences, Beijing 100049 (China)

    2016-12-15

    We investigate the topological defects and spin structures of a rotating binary Bose–Einstein condensate, which consists of both dipolar and scalar bosonic atoms confined in spin-dependent optical lattices, for an arbitrary orientation of the dipoles with respect to their plane of motion. Our results show that the tunable dipolar interaction, especially the orientation of the dipoles, can be used to control the direction of stripe phase and its related half-vortex sheets. In addition, it can also be used to obtain a regular arrangement of various topological spin textures, such as meron, circular and cross disgyration spin structures. We point out that such topological defects and regular arrangement of spin structures arise primarily from the long-range and anisotropic nature of dipolar interaction and its competition with the spin-dependent optical lattices and rotation. - Highlights: • Effects of both strength and orientation of the dipoles are discussed. • Various topological defects can be formed in different parameter regions. • Present one possible way to obtain regular arrangements of spin textures.

  4. Thermodynamics of dipolar hard spheres with low-to-intermediate coupling constants.

    Science.gov (United States)

    Elfimova, Ekaterina A; Ivanov, Alexey O; Camp, Philip J

    2012-08-01

    The thermodynamic properties of the dipolar hard-sphere fluid are studied using theory and simulation. A new theory is derived using a convenient mathematical approximation for the Helmholtz free energy relative to that for the hard-sphere fluid. The approximation is designed to give the correct low-density virial expansion. New theoretical and numerical results for the fourth virial coefficient are given. Predictions of thermodynamic functions for dipolar coupling constants λ=1 and 2 show excellent agreement with simulation results, even at the highest value of the particle volume fraction φ. For higher values of λ, there are deviations at high volume fractions, but the correct low-density behavior is retained. The theory is compared critically against the established thermodynamic perturbation theory; it gives significant improvements at low densities and is more convenient in terms of the required numerics. Dipolar hard spheres provide a basic model for ferrofluids, and the theory is accurate for typical experimental parameters λ

  5. Oxygen Ions O+ Energized by Kinetic Alfvén Eigenmode During Dipolarizations of Intense Substorms

    Science.gov (United States)

    Duan, Suping; Dai, Lei; Wang, Chi; He, Zhaohai; Cai, Chunlin; Zhang, Y. C.; Dandouras, I.; Reme, H.; André, M.; Khotyaintsev, Y. V.

    2017-11-01

    Singly charged oxygen ions, O+, energized by kinetic Alfvén wave eigenmode (KAWE) in the plasma sheet boundary layer during dipolarizations of two intense substorms, 10:07 UT on 31 August 2004 and 18:24 UT on 14 September 2004, are investigated by Cluster spacecraft in the magnetotail. It is found that after the beginning of the expansion phase of substorms, O+ ions are clearly energized in the direction perpendicular to the magnetic field with energy larger than 1 keV in the near-Earth plasma sheet during magnetic dipolarizations. The pitch angle distribution of these energetic O+ ions is significantly different from that of O+ ions with energy less than 1 keV before substorm onset that is in the quasi-parallel direction along the magnetic field. The KAWE with the large perpendicular unipolar electric field, Ez -20 mV/m, significantly accelerates O+ ions in the direction perpendicular to the background magnetic field. We present good evidences that O+ ion origin from the ionosphere along the magnetic field line in the northward lobe can be accelerated in the perpendicular direction during substorm dipolarizations. The change of the move direction of O+ ions is useful for O+ transferring from the lobe into the central plasma sheet in the magnetotail. Thus, KAWE can play an important role in O+ ion transfer process from the lobe into the plasma sheet during intense substorms.

  6. Fundamental measure density functional theory study of liquid-vapor interface of dipolar and quadrupolar fluids.

    Science.gov (United States)

    Warshavsky, V B; Zeng, X C

    2013-10-07

    We have studied interfacial structure and properties of liquid-vapor interfaces of dipolar fluids and quadrupolar fluids, respectively, using the classical density functional theory (DFT). Towards this end, we employ the fundamental measure DFT for a reference hard-sphere (HS) part of free energy and the modified mean field approximation for the correlation function of dipolar or quadrupolar fluid. At low temperatures we find that both the liquid-vapor interfacial density profile and orientational order parameter profile exhibit weakly damped oscillatory decay into the bulk liquid. At high temperatures the decay of interfacial density and order parameter profiles is entirely monotonic. The scaled temperature τ = 1 - T/T(c) that separates the two qualitatively different interfacial structures is in the range 0.10-0.15. At a given (dimensionless) temperature, increasing the dipolar or quadrupolar moment enhances the density oscillations. Application of an electric field (normal to the interface) will damp the oscillations. Likewise, at the given temperature, increasing the strength of any multipolar moment also increases the surface tensions while increasing the strength of the applied electric field will reduce the surface tensions. The results are compared with those based on the local-density approximations (LDA) for the reference HS part of free energy as well as with results of numerical experiments.

  7. Ion velocity distributions in dipolarization events: Distributions in the central plasma sheet

    Science.gov (United States)

    Birn, J.; Runov, A.; Zhou, X.-Z.

    2017-08-01

    Using combined MHD/test particle simulations, we further explore characteristic ion velocity distributions in the central plasma sheet (CPS) in relation to dipolarization events. Distributions in the CPS within the dipolarized flux bundle (DFB) that follows the passage of a dipolarization front typically show two opposing low subthermal-energy beams with a ring-like component perpendicular to the magnetic field at about twice the thermal energy. The dominance of the perpendicular anisotropy and a field-aligned peak at lower energy agree qualitatively with ion distribution functions derived from "Time History of Events and Macroscale Interactions during Substorms" observations. At locations somewhat off the equatorial plane the field-aligned peaks are shifted by a field-aligned component of the bulk flow, such that one peak becomes centered near zero net velocity, which makes it less likely to be observed. The origins of the field-aligned peaks are low-energy lobe (or near plasma sheet boundary layer) regions, while the ring distribution originates mostly from thermal plasma sheet particles on extended field lines. The acceleration mechanisms are also quite different: the beam ions are accelerated first by the E × B drift motion of the DFB and then by a slingshot effect of the earthward convecting DFB (akin to first-order Fermi, type B, acceleration), which causes an increase in field-aligned speed. In contrast, the ring particles are accelerated by successive, betatron-like acceleration after entering the high electric field region of an earthward propagating DFB.

  8. Competition between anisotropy and dipolar interaction in multicore nanoparticles: Monte Carlo simulation

    Directory of Open Access Journals (Sweden)

    Juanita Londoño-Navarro

    2015-01-01

    Full Text Available Se realizaron simulaciones computacionales empleando Monte Carlo combinado con el modelo de Heisenberg y el algoritmo de Metropolis con el fin de estudiar las propiedades de equilibrio magnético en nano partículas multi-núcleo de magnetita. Se consideraron tres tipos de efectos: Interacción Zeeman, anisotropía magneto cristalina e interacción dipolar. Se observó una reducción en la magnetización debido a la influencia de la interacción dipolar y la anisotropía. Se estudió el efecto de la distribución de tamaños (diámetro medio y desviación estándar en la magnetización de las nano partículas, obteniéndose un mejor comportamiento magnético para tamaños grandes, ya que, en este caso se reduce la influencia del término de interacción dipolar. Se estudió además el efecto de la temperatura y de la dirección del eje fácil de magnetización sobre las propiedades magnéticas.

  9. Nuclear magnetic resonance signal dynamics of liquids in the presence of distant dipolar fields, revisited.

    Science.gov (United States)

    Barros, Wilson; Gochberg, Daniel F; Gore, John C

    2009-05-07

    The description of the nuclear magnetic resonance magnetization dynamics in the presence of long-range dipolar interactions, which is based upon approximate solutions of Bloch-Torrey equations including the effect of a distant dipolar field, has been revisited. New experiments show that approximate analytic solutions have a broader regime of validity as well as dependencies on pulse-sequence parameters that seem to have been overlooked. In order to explain these experimental results, we developed a new method consisting of calculating the magnetization via an iterative formalism where both diffusion and distant dipolar field contributions are treated as integral operators incorporated into the Bloch-Torrey equations. The solution can be organized as a perturbative series, whereby access to higher order terms allows one to set better boundaries on validity regimes for analytic first-order approximations. Finally, the method legitimizes the use of simple analytic first-order approximations under less demanding experimental conditions, it predicts new pulse-sequence parameter dependencies for the range of validity, and clarifies weak points in previous calculations.

  10. Acceleration and particle transport in collisionless plasma in the process of dipolarization and nonstationary turbulence

    Science.gov (United States)

    Zhukova, E. I.; Malova, Kh. V.; Popov, V. Yu.; Grigorenko, E. E.; Petrukovich, A. A.; Zelenyi, L. M.

    2017-11-01

    This work is devoted to studying the processes of the acceleration of plasma particles in thin current sheets that appear during magnetospheric substorms in the Earth's magnetosphere tail. A numerical model of magnetic dipolarization accompanied by plasma turbulence has been constructed and studied. The model allows one to investigate the particle acceleration due to the action of three principal mechanisms: (1) plasma turbulence; (2) magnetic dipolarization; (3) their simultaneous action. For the given velocity kappa-distributions, we obtained energy spectra of three types of accelerated particles, i.e., protons p +, ions of oxygen O+, and electrons e -. It has been shown that the combined mechanism of dipolarization with turbulence (3) makes the largest contribution to the increase in the energy of protons and heavy ions as compared with a separate action of each of mechanisms (1) and (2); in this case, electrons accelerate less. The consideration of the joint action of acceleration mechanisms (1) and (2) can explain the apparition of particles with energies on the order of magnitude equal to hundreds keV in the Earth's magnetosphere tail.

  11. Phase transitions to dipolar clusters and charge density waves in high T{sub c} superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Saarela, M., E-mail: Mikko.Saarela@oulu.fi [Department of Physics, University of Oulu, P.O. Box 3000, FIN-90014 (Finland); Kusmartsev, F.V. [Department of Physics, Loughborough University, LE11 3TU (United Kingdom)

    2017-02-15

    We show that doping of hole charge carriers leads to formation of electric dipolar clusters in cuprates. They are created by many-body interactions between the dopant ion outside and holes inside the CuO planes. Because of the two-fold degeneracy holes in the CuO plane cluster into four-particles resonance valence bond plaquettes bound with dopant ions. Such dipoles may order into charge-density waves (CDW) or stripes or form a disordered state depending on doping and temperature. The lowest energy of the ordered system corresponds to a local anti-ferroelectric ordering. The mobility of individual disordered dipoles is very low at low temperatures and they prefer first to bind into dipole-dipole pairs. Electromagnetic radiation interacts strongly with electric dipoles and when the sample is subjected to it the mobility changes significantly. This leads to a fractal growth of dipolar clusters. The existence of electric dipoles and CDW induce two phase transitions with increasing temperature, melting of the ordered state and disappearance of the dipolar state. Ferroelectricity at low doping is a natural consequence of such dipole moments. We develop a theory based on two-level systems and dipole-dipole interaction to explain the behavior of the polarization as a function of temperature and electric field.

  12. The [3 + 3]-cycloaddition alternative for heterocycle syntheses: catalytically generated metalloenolcarbenes as dipolar adducts.

    Science.gov (United States)

    Xu, Xinfang; Doyle, Michael P

    2014-04-15

    The combination of two or more unsaturated structural units to form cyclic organic compounds is commonly referred to as cycloaddition, and the combination of two unsaturated structural units that forms a six-membered ring is formally either a [5 + 1]-, [4 + 2]-, [2 + 2 + 2]-, or [3 + 3]-cycloaddition. Occurring as concerted or stepwise processes, cycloaddition reactions are among the most useful synthetic constructions in organic chemistry. Of these transformations, the concerted [4 + 2]-cycloaddition, the Diels-Alder reaction, is by far the best known and most widely applied. However, although symmetry disallowed as a concerted process and lacking certifiable examples until recently, stepwise [3 + 3]-cycloadditions offer advantages for the synthesis of a substantial variety of heterocyclic compounds, and they are receiving considerable attention. In this Account, we present the development of stepwise [3 + 3]-cycloaddition reactions from virtual invisibility in the 1990s to a rapidly growing synthetic methodology today, involving organocatalysis or transition metal catalysis. With origins in organometallic or vinyliminium ion chemistry, this area has blossomed into a viable synthetic transformation for the construction of six-membered heterocyclic compounds containing one or more heteroatoms. The development of [3 + 3]-cycloaddition transformations has been achieved through identification of suitable and compatible reactive dipolar adducts and stable dipoles. The reactive dipolar species is an energetic dipolar intermediate that is optimally formed catalytically in the reaction. The stepwise process occurs with the reactive dipolar adduct reacting as an electrophile or as a nucleophile to form the first covalent bond, and this association provides entropic assistance for the construction of the second covalent bond and the overall formal [3 + 3]-cycloaddition. Organocatalysis is well developed for both inter- and intramolecular synthetic transformations, but the

  13. EPR characterization of Mn(ii) complexes for distance determination with pulsed dipolar spectroscopy.

    Science.gov (United States)

    Keller, Katharina; Zalibera, Michal; Qi, Mian; Koch, Vanessa; Wegner, Julia; Hintz, Henrik; Godt, Adelheid; Jeschke, Gunnar; Savitsky, Anton; Yulikov, Maxim

    2016-09-14

    The four Mn(ii) complexes Mn-DOTA, Mn-TAHA, Mn-PyMTA, and Mn-NO3Py were characterized by electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR), and relaxation measurements, to predict their relative performance in the EPR pulse dipolar spectroscopy (PDS) experiments. High spin density localization on the metal ions was proven by ENDOR on 1H, D, 14N, and 55Mn nuclei. The transverse relaxation of the Mn(ii) complexes appears to be slow enough for PDS-based spin-spin distance determination. Rather advantageous ratios of T1/Tm were measured allowing for good relaxation induced dipolar modulation enhancement (RIDME) performance and, in general, fast shot repetitions in any PDS experiment. Relaxation properties of the Mn(ii) complexes correlate with the strengths of their zero field splitting (ZFS). Further, a comparison of Mn(ii)-DOTA and Gd(iii)-DOTA based spin labels is presented. The RIDME technique to measure nanometer-range Mn(ii)-Mn(ii) distances in biomolecules is discussed as an alternative to the well-known DEER technique that often appears challenging in cases of metal-metal distance measurements. The use of a modified kernel function that includes dipolar harmonic overtones allows model-free computation of the Mn(ii)-Mn(ii) distance distributions. Mn(ii)-Mn(ii) distances are computed from RIDME data of Mn-rulers consisting of two Mn-PyMTA complexes connected by a rodlike spacer of defined length. Level crossing effects seem to have only a weak influence on the distance distributions computed from this set of Mn(ii)-Mn(ii) RIDME data.

  14. Ultrafast responses of dipolar and octupolar compounds with dipicolinate as an electron acceptor

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yaochuan, E-mail: ycwang@dlmu.edu.cn [Department of Physics, Dalian Maritime University, Dalian 116026 (China); State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Liu, Siyuan; Liu, Dajun; Wang, Guiqiu [Department of Physics, Dalian Maritime University, Dalian 116026 (China); Xiao, Haibo [Department of Chemistry, Shanghai Normal University, Shanghai 200234 (China)

    2016-11-01

    Two dipolar compounds with dipicolinate as electron acceptor group named trans-dimethyl-4-[4’-(N,N-dimethylamino)-styry1]-pyridin-2,6-dicarboxylate (M-1), trans-dimethyl-4-[4'-(N,N-diphenylamino)-styry1]-pyridin-2,6-dicarboxylate (P-1) as well as a P-1 based multi-branched octupolar compound {4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl) vinyl]}-N,N-bis{4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl)vinylphenyl]} aniline (P-3) with intense two-photon fluorescence emission properties are systematically investigated by using steady-state absorption and fluorescence spectroscopy, Z-scan, and two-photon excited fluorescence (TPF) method. The two-photon absorption cross section of octupolar compound P-3 in THF solution is determined to be 376 GM, which is approximately 12 times greater than that of dipolar counterpart P-1 (32 GM). Transient absorption spectroscopy is employed to investigate the excited state dynamics of the dipolar and octupolar compounds. The formation and relaxation lifetimes of the intra-molecular charge transfer (ICT) state are determined to be in the ranges of several picoseconds and several-hundreds of picoseconds, respectively, for all the three compounds in THF solutions. An extended π-conjugated system and increased intra-molecular cooperative effect are responsible for the observed large two-photon absorption character. - Highlights: • Octupolar compound gain 12-fold enhancement of two photon absorption. • Dynamic properties of intra-molecular charge transfer state are determined. • Cooperative effect is responsible for great increase of two photon character.

  15. Different approaches to analyze the dipolar interaction effects on diluted and concentrated granular superparamagnetic systems

    Energy Technology Data Exchange (ETDEWEB)

    Moscoso-Londoño, O., E-mail: omoscoso@ifi.unicamp.br [Instituto de Física ‘Gleb Wataghin’, Universidade Estadual de Campinas (UNICAMP), CEP13083-859 Campinas, São Paulo (Brazil); Tancredi, P. [Laboratorio de Sólidos Amorfos, INTECIN, Facultad de Ingeniería, Universidad de Buenos Aires (UBA), CONICET, C1063ACV Buenos Aires (Argentina); Muraca, D. [Instituto de Física ‘Gleb Wataghin’, Universidade Estadual de Campinas (UNICAMP), CEP13083-859 Campinas, São Paulo (Brazil); Centro de Ciencias Naturais e Humanas, Universidade Federal do ABC (UFABC), Av. Dos Estados, 5001, Santo André, SP (Brazil); Mendoza Zélis, P.; Coral, D.; Fernández van Raap, M.B. [Instituto de Física, Universidad Nacional de La Plata (UNLP), CONICET, CC.67, 1900 La Plata, Buenos Aires (Argentina); Wolff, U.; Neu, V.; Damm, C. [IFW Dresden, Leibniz Institute for Solid State and Materials Research, Dresden, Helmholtzstrasse 20, 01069 Dresden (Germany); Oliveira, C.L.P. de [Instituto de Física, Universidade de São Paulo, São Paulo 05314970 (Brazil); Pirota, K.R. [Instituto de Física ‘Gleb Wataghin’, Universidade Estadual de Campinas (UNICAMP), CEP13083-859 Campinas, São Paulo (Brazil); and others

    2017-04-15

    Controlled magnetic granular materials with different concentrations of magnetite nanoparticles immersed in a non-conducting polymer matrix were synthesized and, their macroscopic magnetic observables analyzed in order to advance towards a better understanding of the magnetic dipolar interactions and its effects on the obtained magnetic parameters. First, by means of X-ray diffraction, transmission electron microscopy, small angle X-ray scattering and X-ray absorption fine structure an accurate study of the structural properties was carried out. Then, the magnetic properties were analyzed by means of different models, including those that consider the magnetic interactions through long-range dipolar forces as: the Interacting Superparamagnetic Model (ISP) and the Vogel-Fulcher law (V-F). In systems with larger nanoparticle concentrations, magnetic results clearly indicate that the role played by the dipolar interactions affects the magnetic properties, giving rise to obtaining magnetic and structural parameters without physical meaning. Magnetic parameters as the effective anisotropic constant, magnetic moment relaxation time and mean blocking temperature, extracted from the application of the ISP model and V-F Law, were used to simulate the zero-field-cooling (ZFC) and field-cooling curves (FC). A comparative analysis of the simulated, fitted and experimental ZFC/FC curves suggests that the current models depict indeed our dilute granular systems. Notwithstanding, for concentrated samples, the ISP model infers that clustered nanoparticles are being interpreted as single entities of larger magnetic moment and volume, effect that is apparently related to a collective and complex magnetic moment dynamics within the cluster. - Highlights: • Nanoparticle architecture into matrices determines the composite magnetic response. • Magnetically diluted or compacted systems are useful to study magnetism at nanoscale. • Particle aggregation into the matrices was examined

  16. Quasi-parallel whistler mode waves observed by THEMIS during near-earth dipolarizations

    Directory of Open Access Journals (Sweden)

    O. Le Contel

    2009-06-01

    Full Text Available We report on quasi-parallel whistler emissions detected by the near-earth satellites of the THEMIS mission before, during, and after local dipolarization. These emissions are associated with an electron temperature anisotropy α=Te/T||e>1 consistent with the linear theory of whistler mode anisotropy instability. When the whistler mode emissions are observed the measured electron anisotropy varies inversely with β||e (the ratio of the electron parallel pressure to the magnetic pressure as predicted by Gary and Wang (1996. Narrow band whistler emissions correspond to the small α existing before dipolarization whereas the broad band emissions correspond to large α observed during and after dipolarization. The energy in the whistler mode is leaving the current sheet and is propagating along the background magnetic field, towards the Earth. A simple time-independent description based on the Liouville's theorem indicates that the electron temperature anisotropy decreases with the distance along the magnetic field from the equator. Once this variation of α is taken into account, the linear theory predicts an equatorial origin for the whistler mode. The linear theory is also consistent with the observed bandwidth of wave emissions. Yet, the anisotropy required to be fully consistent with the observations is somewhat larger than the measured one. Although the discrepancy remains within the instrumental error bars, this could be due to time-dependent effects which have been neglected. The possible role of the whistler waves in the substorm process is discussed.

  17. Unconventional symmetries of Fermi liquid and Cooper pairing properties with electric and magnetic dipolar fermions.

    Science.gov (United States)

    Li, Yi; Wu, Congjun

    2014-12-10

    The rapid experimental progress of ultra-cold dipolar fermions opens up a whole new opportunity to investigate novel many-body physics of fermions. In this article, we review theoretical studies of the Fermi liquid theory and Cooper pairing instabilities of both electric and magnetic dipolar fermionic systems from the perspective of unconventional symmetries. When the electric dipole moments are aligned by the external electric field, their interactions exhibit the explicit d(r(2)-3z(2)) anisotropy. The Fermi liquid properties, including the single-particle spectra, thermodynamic susceptibilities and collective excitations, are all affected by this anisotropy. The electric dipolar interaction provides a mechanism for the unconventional spin triplet Cooper pairing, which is different from the usual spin-fluctuation mechanism in solids and the superfluid (3)He. Furthermore, the competition between pairing instabilities in the singlet and triplet channels gives rise to a novel time-reversal symmetry breaking superfluid state. Unlike electric dipole moments which are induced by electric fields and unquantized, magnetic dipole moments are intrinsic proportional to the hyperfine-spin operators with a Lande factor. Its effects even manifest in unpolarized systems exhibiting an isotropic but spin-orbit coupled nature. The resultant spin-orbit coupled Fermi liquid theory supports a collective sound mode exhibiting a topologically non-trivial spin distribution over the Fermi surface. It also leads to a novel p-wave spin triplet Cooper pairing state whose spin and orbital angular momentum are entangled to the total angular momentum J = 1 dubbed the J-triplet pairing. This J-triplet pairing phase is different from both the spin-orbit coupled (3)He-B phase with J = 0 and the spin-orbit decoupled (3)He-A phase.

  18. Fluctuation-dissipation theorem in an isolated system of quantum dipolar bosons after a quench.

    Science.gov (United States)

    Khatami, Ehsan; Pupillo, Guido; Srednicki, Mark; Rigol, Marcos

    2013-08-02

    We examine the validity of fluctuation-dissipation relations in isolated quantum systems taken out of equilibrium by a sudden quench. We focus on the dynamics of trapped hard-core bosons in one-dimensional lattices with dipolar interactions whose strength is changed during the quench. We find indications that fluctuation-dissipation relations hold if the system is nonintegrable after the quench, as well as if it is integrable after the quench if the initial state is an equilibrium state of a nonintegrable Hamiltonian. On the other hand, we find indications that they fail if the system is integrable both before and after quenching.

  19. A Time-Splitting and Sine Spectral Method for Dynamics of Dipolar Bose-Einstein Condensate

    Directory of Open Access Journals (Sweden)

    Si-Qi Li

    2013-01-01

    Full Text Available A two-component Bose-Einstein condensate (BEC described by two coupled a three-dimension Gross-Pitaevskii (GP equations is considered, where one equation has dipole-dipole interaction while the other one has only the usual s-wave contact interaction, in a cigar trap. The time-splitting and sine spectral method in space is proposed to discretize the time-dependent equations for computing the dynamics of dipolar BEC. The singularity in the dipole-dipole interaction brings significant difficulties both in mathematical analysis and in numerical simulations. Numerical results are given to show the efficiency of this method.

  20. Fluctuation-Dissipation Theorem in an Isolated System of Quantum Dipolar Bosons after a Quench

    Science.gov (United States)

    Khatami, Ehsan; Pupillo, Guido; Srednicki, Mark; Rigol, Marcos

    2013-08-01

    We examine the validity of fluctuation-dissipation relations in isolated quantum systems taken out of equilibrium by a sudden quench. We focus on the dynamics of trapped hard-core bosons in one-dimensional lattices with dipolar interactions whose strength is changed during the quench. We find indications that fluctuation-dissipation relations hold if the system is nonintegrable after the quench, as well as if it is integrable after the quench if the initial state is an equilibrium state of a nonintegrable Hamiltonian. On the other hand, we find indications that they fail if the system is integrable both before and after quenching.

  1. Triazol-substituted titanocenes by strain-driven 1,3-dipolar cycloadditions

    Directory of Open Access Journals (Sweden)

    Andreas Gansäuer

    2014-07-01

    Full Text Available An operationally simple, convenient, and mild strategy for the synthesis of triazole-substituted titanocenes via strain-driven 1,3-dipolar cycloadditions between azide-functionalized titanocenes and cyclooctyne has been developed. It features the first synthesis of titanocenes containing azide groups. These compounds constitute ‘second-generation’ functionalized titanocene building blocks for further synthetic elaboration. Our synthesis is modular and large numbers of the complexes can in principle be prepared in short periods of time. Some of the triazole-substituted titanocenes display high cyctotoxic activity against BJAB cells. Comparison of the most active complexes allows the identification of structural features essential for biological activity.

  2. Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions

    Directory of Open Access Journals (Sweden)

    Wilson Silva do Nascimento

    2010-04-01

    Full Text Available Naphthoquinones are known according to their important bio-activities, such as their antitumoral and topoisomerase inhibition properties. From 2-azido (3 or 2,3-diacetylene-1,4-naphthoquinone (4 it was possible to obtain triazole derivatives (naphthoquinonic. This work describes the synthesis of two novel molecules, with triazole groups linked to 1,4-naphthoquinone using the 1,3-dipolar cycloaddition and Sonogashira reactions. The synthetic strategy followed two routes (Scheme 1. First, we synthesized the 2-bromo-1,4-naphthoquinone (2, yield 98% by using Br2 and CH3CO2H, and then used it to obtain 2-azido-1,4-naphthoquinone (3, yield 62% from compound 1, along with ethanolic solution (reflux and NaN3. Finally, we prepared 1,2,3-triazole compounds (4a, b by 1,3-dipolar cycloaddition, involving compound (3 and terminal acetylenes (phenylacetylene, a and glycoside (b using Cu(OAc2 and ascorbate, under argon atmosphere. During the second step, 2,3-dibromo-1,4-naphthoquinone was prepared using Br2/CH2Cl2 at room temperature. From compound (5 it was possible to synthesize (6, catalyzed by Pd(PPh32Cl2/CuI/Et3N, under argon atmosphere, in 40% yield. The 1,3-dipolar cycloaddition reactions involving 2-azido-1,4-naphthoquinone (3 and alkynes (a, yield 23% and b, yield 30% were conducted using the solvent system, (1:1 terc-BuOH/H2O/r.t/ 20 mol% of Cu(OAc2 and sodium ascorbate, under stirring during 24 hours. The reaction involving 2,3-dibromo-1,4-naphthoquinone (5, yield 65% and phenylacetylene was prepared using the solvent mixture (2:1 DMSO/CHCl3 and catalytic amount of CuI/Pd(PPh32Cl2. The final products were characterized by elemental analysis and spectrometric techniques (IR, NMR 1H and 13C. Two novel triazole compounds were synthesized from naphthoquinones by 1,3-dipolar cycloaddition from suitable 1,4-naphthoquinones obtained by Sonogashira couplings.

  3. Dipolar and quadrupolar freezing in (NaCN)1-x(KCN)x

    DEFF Research Database (Denmark)

    Loidl, A.; Schräder, T.; Böhmer, R.

    1986-01-01

    , the slowing down of the dipolar and the quadrupolar relaxation behaves very differently in the two samples investigated. In (NaCN)0.15(KCN)0.85 the freezing-in of the quadrupolar degrees of freedom is a cooperative effect which is dominated by strain-mediated interactions. The resulting low-temperature state...... is characterized by frozen-in orientational correlations and frozen-in lattice strains. In (NaCN)0.41(KCN)0.59 the experimental results on the dynamics of the quadrupolar freezing are indicative of single-ion behavior where the slowing down of the molecular reorientations is completely due to thermal activation...

  4. Persistent superfluid flow arising from the He-McKellar-Wilkens effect in molecular dipolar condensates

    CERN Document Server

    Wood, A A; Martin, A M

    2016-01-01

    We show that the He-McKellar-Wilkens effect can induce a persistent flow in a Bose-Einstein condensate of polar molecules confined in a toroidal trap, with the dipolar interaction mediated via an electric dipole moment. For Bose-Einstein condensates of atoms with a magnetic dipole moment, we show that although it is theoretically possible to induce persistent flow via the Aharonov-Casher effect, the strength of electric field required is prohibitive. We also outline an experimental geometry tailored specifically for observing the He-McKellar-Wilkens effect in toroidally-trapped condensates.

  5. Calculation of Vibrational Spectra of Coordinated Perchlorate Ion in Dipolar Aprotic Solvents

    Science.gov (United States)

    Mikhailov, G. P.

    2014-09-01

    The vibrational spectrum of perchlorate ion coordinated to Li+, Na+, and Mg2+ cations in dipolar aprotic solvents (DAS) was studied using Hartree-Fock methods not taking into account (RHF) and accounting partially for electron correlation (MP2) and B3LYP density functional theory within the polarized continuum model (PCM). Experimental and calculated spectrum-structure correlations for coordinated perchlorate-ion complexes in DAS were analyzed. It was found that the best fi t of the experimental and calculated vibrational spectra was achieved by taking into account the electron correlation and non-specific solvation.

  6. Synthesis and 1,3-Dipolar Cycloaddition Reactions of Chiral Maleimides

    Directory of Open Access Journals (Sweden)

    Lubor Fisera

    1997-02-01

    Full Text Available New routes to the synthesis of various novel chiral maleimides are described. The oxabicyclic anhydride 2 readily available exo-Diels-Alder adduct of furan and maleic anhydride was used as a vehicle, which in turn reacted with hydrochlorides of amino acids 3a-f in the presence of Et3N with release of furan to give the requisite novel chiral imides 4a-f in good to moderate yields. The stereoselectivity of 1,3-dipolar cycloaddition of nitrile oxides with prepared chiral imides 4a-f is investigated.

  7. 1,3-Dipolar Cycloaddition Reactions of Azomethine Ylides with Carbonyl Dipolarophiles Yielding Oxazolidine Derivatives

    Directory of Open Access Journals (Sweden)

    Adam G. Meyer

    2016-07-01

    Full Text Available We provide a comprehensive account of the 1,3-dipolar cycloaddition reactions of azomethine ylides with carbonyl dipolarophiles. Many different azomethine ylides have been studied, including stabilized and non-stabilized ylides. Of the carbonyl dipolarophiles, aldehydes including formaldehyde are the most studied, although there are now examples of cycloadditions with ketones, ketenes and carboxyl systems, in particular isatoic anhydrides and phthalic anhydrides. Intramolecular cycloadditions with esters can also occur under certain circumstances. The oxazolidine cycloadducts undergo a range of reactions triggered by the ring-opening of the oxazolidine ring system.

  8. Isoxazolodihydropyridinones: 1,3-dipolar cycloaddition of nitrile oxides onto 2,4-dioxopiperidines

    Science.gov (United States)

    Coffman, Keith C.; Hartley, Timothy P.; Dallas, Jerry L.; Kurth, Mark J.

    2012-01-01

    Practical and efficient methods have been developed for the diversity-oriented synthesis of isoxazolodihydropyridinones via the 1,3-dipolar cycloaddition of nitrile oxides onto 2,4-dioxopiperidines. A select few of these isoxazolodihydropyridinones were further elaborated with triazoles by copper catalyzed azide-alkyne cycloaddition reactions. A total of 70 compounds and intermediates were synthesized and analyzed for drug likeness. Sixty-four of these novel compounds were submitted to the NIH Molecular Libraries Small Molecule Repository for high-throughput biological screening. PMID:22352295

  9. Dipolar Self-Assembling in Mixtures of Propylene Carbonate and Dimethyl Sulfoxide as Revealed by the Orientational Entropy.

    Science.gov (United States)

    Płowaś, Iwona; Świergiel, Jolanta; Jadżyn, Jan

    2016-08-18

    This article presents the results of static dielectric studies performed on mixtures of two strongly polar liquids important from a technological point of view: propylene carbonate (PC) and dimethyl sulfoxide (DMSO). The dielectric data were analyzed in terms of the molar orientational entropy increment induced by the probing electric field. It was found that the two polar liquids in the neat state reveal quite different molecular organization in terms of dipole-dipole self-assembling: PC exhibits a dipolar coupling of the head-to-tail type, whereas in DMSO one observes extreme restriction of dipolar association in any form. In PC + DMSO mixtures, the disintegration of the dipolar ensembles of PC molecules takes place and the progress of that process is strictly proportional to the concentration of DMSO. The static permittivity of mixtures of such differently self-organized liquids exhibits a positive deviation from the additive rule and the deviation develops symmetrically within the concentration scale.

  10. Dynamics of 1,3-dipolar cycloadditions: energy partitioning of reactants and quantitation of synchronicity.

    Science.gov (United States)

    Xu, Lai; Doubleday, Charles E; Houk, K N

    2010-03-10

    The dynamics of 1,3-dipolar cycloadditions of nine 1,3-dipoles with ethylene and acetylene have been explored by quasiclassical trajectory and single trajectory calculations in the retro-cycloaddition direction to compute energy partitioning of reactants among relative translation, vibration, and rotation. The results are interpreted with an expanded version of Polanyi's Rules for bimolecular reactions, and three trends are evident. (1) Relative translation of reactants is the main contributor to surmounting the barrier, since all transition states (TSs) are early with respect to sigma bond formation. (2) Vibrational excitation in the 1,3-dipole bending modes required for reaction is related to the lateness of the TS with respect to dipole bending: diazonium betaines (late TS, dipole bending required) > nitrilium betaines > azomethine betaines (early TS, dipole bending least important). This is also the order of the activation barriers (high --> low). (3) The previously reported linear correlation between activation barriers and the energy required to distort reactants to their TS geometries are understandable in terms of the requirements for vibrational excitation computed here. For the 1,3-dipolar cycloadditions, single trajectory calculations, which contain no zero point vibrational energy, give reasonable estimates of the mean energy partitioning of reactants derived from potential energy barrier release. The timing of bond formation and relative reactivities of different 1,3-dipoles are discussed.

  11. Conformational studies of blood group A and blood group B oligosaccharides using NMR residual dipolar couplings.

    Science.gov (United States)

    Azurmendi, Hugo F; Bush, C Allen

    2002-05-13

    The conformations of two synthetic trisaccharides of blood group A and B (alpha-L-Fucp-(1-->2)-[alpha-D-GalpNAc-(1-->3)]-alpha-D-Galp and alpha-L-Fucp-(1-->2)-[alpha-D-Galp-(1-->3)]-alpha-D-Galp, respectively) and of a type A tetrasaccharide alditol, Fucp-(1-->2)-[alpha-D-GalpNAc-(1-->3)]-beta-D-Galp-(1-->3)-GalNAc-ol, were studied by NMR measurements of one-bond C-H residual dipolar couplings in partially oriented liquid crystal solutions. The conformations of the three oligosaccharides were analyzed by generating thousands of structures using a Monte-Carlo method. Two different strategies were applied to calculate theoretical dipolar couplings for these structures. In the first method, the orientation of the molecule was calculated from the optimal fit of the molecular model to the experimental data, while in the second method the orientation tensor was calculated directly from the moment of inertia of the molecular model. Both methods of analysis give similar results but with slightly better agreement with experiment for the former one. The analysis of the results implies a single unique conformation for both blood group epitopes in solution in disagreement with theoretical models suggesting the existence of two conformers in solution.

  12. Non-Arrhenius relaxation of the Heisenberg model with dipolar and anisotropic interactions

    Energy Technology Data Exchange (ETDEWEB)

    Diaz-Mendez, Rogelio, E-mail: rogelio@electrica.cujae.edu.cu [Nanophysics Group, Department of Physics, Electric Engineering Faculty, CUJAE, ave 114 final, La Habana (Cuba); ' Henri Poincare' Group of Complex Systems, Physics Faculty, University of Havana, La Habana, CP 10400 (Cuba); Mulet, Roberto [' Henri Poincare' Group of Complex Systems, Physics Faculty, University of Havana, La Habana, CP 10400 (Cuba); Department of Theoretical Physics, Physics Faculty, University of Havana, La Habana, CP 10400 (Cuba)

    2012-01-15

    The dynamical properties of a 2D Heisenberg model with dipolar interactions and perpendicular anisotropy are studied using Monte Carlo simulations in two different ordered regions of the equilibrium phase diagram. We find a temperature defining a dynamical transition below which the relaxation suddenly slows down and the system apart from the typical Arrhenius relaxation to a Vogel-Fulcher-Tamann law. This anomalous behavior is observed in the scaling of the magnetic relaxation and may eventually lead to a freezing of the system. Through the analysis of the domain structures we explain this behavior in terms of the domains dynamics. Moreover, we calculate the energy barriers distribution obtained from the data of the magnetic viscosity. Its shape supports our comprehension of both, the Vogel-Fulcher-Tamann dynamical slowing down and the freezing mechanism. - Highlights: > We make Monte Carlo simulations in a dipolar Heisenberg model with anisotropy. > We find a dynamical transition temperature below which the relaxation is VFT-like. > An interpretation is done by analyzing the domains structure and energy barriers.

  13. Non-dipolar Wilson links for transverse-momentum-dependent wave functions

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hsiang-nan [Institute of Physics, Academia Sinica,Taipei, Taiwan 115 (China); Department of Physics, National Cheng-Kung University,Tainan, Taiwan 701 (China); Department of Physics, National Tsing-Hua University,Hsinchu, Taiwan 300 (China); Wang, Yu-Ming [Institut für Theoretische Teilchenphysik und Kosmologie RWTH Aachen,D-52056 Aachen (Germany); Physik Department T31, James-Franck-Straße, Technische Universität München,D-85748 Garching (Germany)

    2015-06-03

    We propose a new definition of a transverse-momentum-dependent (TMD) wave function with simpler soft subtraction for k{sub T} factorization of hard exclusive processes. The un-subtracted wave function involves two pieces of non-light-like Wilson links oriented in different directions, so that the rapidity singularity appearing in usual k{sub T} factorization is regularized, and the pinched singularity from Wilson-link self-energy corrections is alleviated to a logarithmic one. In particular no soft function is needed, when the two pieces of Wilson links are orthogonal to each other. We show explicitly at one-loop level that the simpler definition with the non-dipolar Wilson links exhibits the same infrared behavior as the one with the dipolar Wilson links and complicated soft subtraction. It is pointed out that both definitions reduce to the naive TMD wave function as the non-light-like Wilson links approach to the light cone. Their equivalence is then extended to all orders by considering the evolution in the Wilson-link rapidity.

  14. Charge carrier transport in molecularly doped polycarbonate as a test case for the dipolar glass model.

    Science.gov (United States)

    Novikov, S V; Tyutnev, A P

    2013-03-14

    We present the results of Monte Carlo simulations of the charge carrier transport in a disordered molecular system containing spatial and energetic disorders using the dipolar glass model. Model parameters of the material were chosen to fit a typical polar organic photoconductor polycarbonate doped with 30% of aromatic hydrazone, whose transport properties are well documented in literature. Simulated carrier mobility demonstrates a usual Poole-Frenkel field dependence and its slope is very close to the experimental value without using any adjustable parameter. At room temperature transients are universal with respect to the electric field and transport layer thickness. At the same time, carrier mobility does not depend on the layer thickness and transients develop a well-defined plateau where the current does not depend on time, thus demonstrating a non-dispersive transport regime. Tails of the transients decay as power law with the exponent close to -2. This particular feature indicates that transients are close to the boundary between dispersive and non-dispersive transport regimes. Shapes of the simulated transients are in very good agreement with the experimental ones. In summary, we provide a first verification of a self-consistency of the dipolar glass transport model, where major transport parameters, extracted from the experimental transport data, are then used in the transport simulation, and the resulting mobility field dependence and transients are in very good agreement with the initial experimental data.

  15. Condensation to a strongly correlated dark fluid of two dimensional dipolar excitons

    Science.gov (United States)

    Mazuz-Harpaz, Yotam; Cohen, Kobi; Rapaport, Ronen

    2017-08-01

    Recently we reported on the condensation of cold, electrostatically trapped dipolar excitons in GaAs bilayer heterostructure into a new, dense and dark collective phase. Here we analyze and discuss in detail the experimental findings and the emerging evident properties of this collective liquid-like phase. We show that the phase transition is characterized by a sharp increase of the number of non-emitting dipoles, by a clear contraction of the fluid spatial extent into the bottom of the parabolic-like trap, and by spectral narrowing. We extract the total density of the condensed phase which we find to be consistent with the expected density regime of a quantum liquid. We show that there are clear critical temperature and excitation power onsets for the phase transition and that as the power further increases above the critical power, the strong darkening is reduced down until no clear darkening is observed. At this point another transition appears which we interpret as a transition to a strongly repulsive yet correlated e-h plasma. Based on the experimental findings, we suggest that the physical mechanism that may be responsible for the transition is a dynamical final-state stimulation of the dipolar excitons to their dark spin states, which have a long lifetime and thus support the observed sharp increase in density. Further experiments and modeling will hopefully be able to unambiguously identify the physical mechanism behind these recent observations.

  16. Solar Micro-Type III Burst Storms and Long Dipolar Magnetic Field in the Outer Corona

    Science.gov (United States)

    Morioka, A.; Miyoshi, Y.; Iwai, K.; Kasaba, Y.; Masuda, S.; Misawa, H.; Obara, T.

    2015-08-01

    Solar micro-type III radio bursts are elements of the so-called type III storms and are characterized by short-lived, continuous, and weak emissions. Their frequency of occurrence with respect to radiation power is quite different from that of ordinary type III bursts, suggesting that the generation process is not flare-related, but due to some recurrent acceleration processes around the active region. We examine the relationship of micro-type III radio bursts with coronal streamers. We also explore the propagation channel of bursts in the outer corona, the acceleration process, and the escape route of electron beams. It is observationally confirmed that micro-type III bursts occur near the edge of coronal streamers. The magnetic field line of the escaping electron beams is tracked on the basis of the frequency drift rate of micro-type III bursts and the electron density distribution model. The results demonstrate that electron beams are trapped along closed dipolar field lines in the outer coronal region, which arise from the interface region between the active region and the coronal hole. A 22 year statistical study reveals that the apex altitude of the magnetic loop ranges from 15 to 50 RS. The distribution of the apex altitude has a sharp upper limit around 50 RS suggesting that an unknown but universal condition regulates the upper boundary of the streamer dipolar field.

  17. Numerical simulations of motion-insensitive diffusion imaging based on the distant dipolar field effects.

    Science.gov (United States)

    Lin, Tao; Sun, Huijun; Chen, Zhong; You, Rongyi; Zhong, Jianhui

    2007-12-01

    Diffusion weighting in MRI is commonly achieved with the pulsed-gradient spin-echo (PGSE) method. When combined with spin-warping image formation, this method often results in ghosts due to the sample's macroscopic motion. It has been shown experimentally (Kennedy and Zhong, MRM 2004;52:1-6) that these motion artifacts can be effectively eliminated by the distant dipolar field (DDF) method, which relies on the refocusing of spatially modulated transverse magnetization by the DDF within the sample itself. In this report, diffusion-weighted images (DWIs) using both DDF and PGSE methods in the presence of macroscopic sample motion were simulated. Numerical simulation results quantify the dependence of signals in DWI on several key motion parameters and demonstrate that the DDF DWIs are much less sensitive to macroscopic sample motion than the traditional PGSE DWIs. The results also show that the dipolar correlation distance (d(c)) can alter contrast in DDF DWIs. The simulated results are in good agreement with the experimental results reported previously.

  18. Long-Lived Spin-Orbit-Coupled Degenerate Dipolar Fermi Gas

    Directory of Open Access Journals (Sweden)

    Nathaniel Q. Burdick

    2016-08-01

    Full Text Available We describe the creation of a long-lived spin-orbit-coupled gas of quantum degenerate atoms using the most magnetic fermionic element, dysprosium. Spin-orbit coupling arises from a synthetic gauge field created by the adiabatic following of degenerate dressed states composed of optically coupled components of an atomic spin. Because of dysprosium’s large electronic orbital angular momentum and large magnetic moment, the lifetime of the gas is limited not by spontaneous emission from the light-matter coupling, as for gases of alkali-metal atoms, but by dipolar relaxation of the spin. This relaxation is suppressed at large magnetic fields due to Fermi statistics. We observe lifetimes up to 400 ms, which exceeds that of spin-orbit-coupled fermionic alkali atoms by a factor of 10–100 and is close to the value obtained from a theoretical model. Elastic dipolar interactions are also observed to influence the Rabi evolution of the spin, revealing an interacting fermionic system. The long lifetime of this weakly interacting spin-orbit-coupled degenerate Fermi gas will facilitate the study of quantum many-body phenomena manifest at longer time scales, with exciting implications for the exploration of exotic topological quantum liquids.

  19. Subradiant dipolar interactions in plasmonic nanoring resonator array for integrated label-free biosensing.

    Science.gov (United States)

    Liang, Yuzhang; Zhang, Hui; Zhu, Wenqi; Agrawal, Amit; Lezec, Henri J; Li, Lixia; Peng, Wei; Zou, Yi; Lu, Yan-Qing; Xu, Ting

    2017-11-15

    With the development of advanced nanofabrication technologies over the last decade, plasmonic nanostructures have attracted wide attention for their potential in label-free biosensing applications. However, the sensing performance of nanostructured plasmonic sensors is primarily limited by the broad-linewidth features with low peak-to-dip signal ratio in the extinction spectra that result from strong radiative damping. Here, we propose and systematically investigate the in-plane and out-of-plane dipolar interactions in an array of plasmonic nanoring resonators that are from the spatial combination of classic nanohole and nanodisk structures. Originating from the strong coupling of the dipolar modes from parent nanohole and nanodisk structures, the subradiant lattice plasmon resonance in the nanoring resonator array exhibits narrow-linewidth spectral features with high peak-to-dip signal ratio and strong near-field electromagnetic enhancement, making it an ideal platform for high-sensitivity chemical and bio-medical sensing. We experimentally demonstrate that the plasmonic nanoring resonator array can be used for high-sensitivity refractive index sensing and real-time monitoring of biomolecular specific binding interactions at nanomolar concentration. Moreover, thanks to its simple normal incident illumination scheme and polarization independent optical response, we further transfer the plasmonic nanoring resonator array onto the optical fiber tip to demonstrate an integrated and miniaturized platform for label-free remote biosensing, which implies that the plasmonic nanoring resonator array may be a potential candidate for developing high performance and highly-integrated photonic biosensing systems.

  20. A long-lived spin-orbit-coupled degenerate dipolar Fermi gas

    CERN Document Server

    Burdick, Nathaniel Q; Lev, Benjamin L

    2016-01-01

    We describe the creation of a long-lived spin-orbit-coupled gas of quantum degenerate atoms using the most magnetic fermionic element, dysprosium. Spin-orbit-coupling arises from a synthetic gauge field created by the adiabatic following of degenerate dressed states comprised of optically coupled components of an atomic spin. Because of dysprosium's large electronic orbital angular momentum and large magnetic moment, the lifetime of the gas is limited not by spontaneous emission from the light-matter coupling, as for gases of alkali-metal atoms, but by dipolar relaxation of the spin. This relaxation is suppressed at large magnetic fields due to Fermi statistics. We observe lifetimes up to 400 ms, which exceeds that of spin-orbit-coupled fermionic alkali atoms by a factor of 10-100, and is close to the value obtained from a theoretical model. Elastic dipolar interactions are also observed to influence the Rabi evolution of the spin, revealing an interacting fermionic system. The long lifetime of this weakly in...

  1. Ion velocity distributions in dipolarization events: Beams in the vicinity of the plasma sheet boundary

    Science.gov (United States)

    Birn, J.; Chandler, M.; Moore, T.; Runov, A.

    2017-08-01

    Using combined MHD/test particle simulations, we further explore characteristic ion velocity distributions in relation to magnetotail reconnection and dipolarization events, focusing on distributions at and near the plasma sheet boundary layer (PSBL). Simulated distributions right at the boundary are characterized by a single earthward beam, as discussed earlier. However, farther inside, the distributions consist of multiple beams parallel and antiparallel to the magnetic field, remarkably similar to recent Magnetospheric Multiscale observations. The simulations provide insight into the mechanisms: the lowest earthward beam results from direct acceleration at an earthward propagating dipolarization front (DF), with a return beam at somewhat higher energy. A higher-energy earthward beam results from dual acceleration, first near the reconnection site and then at the DF, again with a corresponding return beam resulting from mirroring closer to Earth. Multiple acceleration at the X line or the propagating DF with intermediate bounces may produce even higher-energy beams. Particles contributing to the lower energy beams are found to originate from the PSBL with thermal source energies, increasing with increasing beam energy. In contrast, the highest-energy beams consist mostly of particles that have entered the acceleration region via cross-tail drift with source energies in the suprathermal range.

  2. Stability of Neel skyrmions in ultra-thin nanodots considering Dzyaloshinskii-Moriya and dipolar interactions

    Science.gov (United States)

    Vidal-Silva, Nicolás; Riveros, Alejandro; Escrig, Juan

    2017-12-01

    An analytical expression for the energy of Neel skyrmions in ultra-thin nanodots considering exchange, uniaxial anisotropy, Dzyaloshinskii-Moriya, and dipolar contributions has been obtained. In particular, we have proposed for the Neel skyrmion, a general ansatz for the magnetization component perpendicular to the dot, given by mz (r) = [ 1 -(r /Rs) n ] / [ 1 +(r /Rs) n ] , where Rs is the radius of the skyrmion and n is an even integer number. As proof of concept, we calculate the energy of a Neel skyrmion in an ultra-thin Co/Pt cylinder, and we find that the dipolar contribution cannot be neglected and that both Dzyaloshinskii-Moriya interaction and anisotropy play an important role to stabilize the skyrmion. Additionally, we have obtained a good agreement between our analytical calculations and previously published micromagnetic simulations for n = 10 . For this reliable value of n, we have obtained that for a Dzyaloshinski Moriya constant D = 5.5 (mJ/m2), it is possible to stabilize a Neel skyrmion for Ku in the range 0.4 (MJ/m3) < Ku < 1.3 (MJ/m3), whereas for Ku = 0.8 (MJ /m3) , the skyrmion stabilizes for 5.0 (mJ/m2) < D < 6.0 (mJ/m2). Thus, this analytical equation can be widely used to predict stability ranges for the Neel skyrmion in spintronic devices.

  3. Nanoscale control of competing interactions and geometrical frustration in a dipolar trident lattice.

    Science.gov (United States)

    Farhan, Alan; Petersen, Charlotte F; Dhuey, Scott; Anghinolfi, Luca; Qin, Qi Hang; Saccone, Michael; Velten, Sven; Wuth, Clemens; Gliga, Sebastian; Mellado, Paula; Alava, Mikko J; Scholl, Andreas; van Dijken, Sebastiaan

    2017-10-17

    Geometrical frustration occurs when entities in a system, subject to given lattice constraints, are hindered to simultaneously minimize their local interactions. In magnetism, systems incorporating geometrical frustration are fascinating, as their behavior is not only hard to predict, but also leads to the emergence of exotic states of matter. Here, we provide a first look into an artificial frustrated system, the dipolar trident lattice, where the balance of competing interactions between nearest-neighbor magnetic moments can be directly controlled, thus allowing versatile tuning of geometrical frustration and manipulation of ground state configurations. Our findings not only provide the basis for future studies on the low-temperature physics of the dipolar trident lattice, but also demonstrate how this frustration-by-design concept can deliver magnetically frustrated metamaterials.Artificial magnetic nanostructures enable the study of competing frustrated interactions with more control over the system parameters than is possible in magnetic materials. Farhan et al. present a two-dimensional lattice geometry where the frustration can be controlled by tuning the unit cell parameters.

  4. Direct observation of dipolar chains in ferrofluids in zero field using cryogenic electron microscopy

    CERN Document Server

    Butter, K; Frederik, P M; Vroege, G J; Philipse, A P

    2003-01-01

    The particle structure of ferrofluids is studied in situ, by cryogenic electron microscopy, on vitrified films of iron and magnetite dispersions. By means of synthesis of iron colloids with controlled particle size and different types of surfactant, dipolar particle interactions can be varied over a broad range, which significantly influences the ferrofluid particle structure. Our experiments on iron dispersions (in contrast to magnetite dispersions) for the first time demonstrate, in ferrofluids in zero field, a transition with increasing particle size from separate particles to linear chains of particles (Butter K, Bomans P H, Frederik P M, Vroege G J and Philipse A P 2003 Nature Mater. 2 88). These chains, already predicted theoretically by de Gennes and Pincus (de Gennes P G and Pincus P A 1970 Phys. Kondens. Mater. 11 189), very much resemble the fluctuating chains found in simulations of dipolar fluids (Weis J J 1998 Mol. Phys. 93 361, Chantrell R W, Bradbury A, Popplewell J and Charles S W 1982 J. Appl...

  5. NMR experiments for the measurement of proton-proton and carbon-carbon residual dipolar couplings in uniformly labelled oligosaccharides

    Energy Technology Data Exchange (ETDEWEB)

    Martin-Pastor, Manuel [Universidad de Santiago de Compostela, Laboratorio Integral de Estructura de Biomoleculas Jose. R. Carracido, Unidade de Resonancia Magnetica, RIAIDT (Spain)], E-mail: mmartin@usc.es; Canales-Mayordomo, Angeles; Jimenez-Barbero, Jesus [Departamento de Estructura y funcion de proteinas, Centro de Investigaciones Biologicas, CSIC (Spain)], E-mail: jjbarbero@cib.csic.es

    2003-08-15

    A 2D-HSQC-carbon selective/proton selective-constant time COSY, 2D-HSQC-(sel C, sel H)-CT COSY experiment, which is applicable to uniformly {sup 13}C isotopically enriched samples (U-{sup 13}C) of oligosaccharides or oligonucleotides is proposed for the measurement of proton-proton RDC in crowded regions of 2D-spectra. In addition, a heteronuclear constant time-COSY experiment, {sup 13}C-{sup 13}C CT-COSY, is proposed for the measurement of one bond carbon-carbon RDC in these molecules. These two methods provide an extension, to U-{sup 13}C molecules, of the original homonuclear constant time-COSY experiment proposed by Tian et al. (1999) for saccharides. The combination of a number of these RDC with NOE data may provide the method of choice to study oligosaccharide conformation in the free and receptor-bound state.

  6. Dynamics of 1,3-dipolar cycloaddition reactions of diazonium betaines to acetylene and ethylene: bending vibrations facilitate reaction.

    Science.gov (United States)

    Xu, Lai; Doubleday, Charles E; Houk, K N

    2009-01-01

    Getting the bends: The dynamics of 1,3-dipolar cycloaddition reactions have been explored by decomposing transition vector, quasi-classical trajectories, and single trajectories. Dipole bending (see picture) makes the largest contribution to the TS distortion energy and constitutes the major part of transition-state distortion energy in the favored concerted pathway.

  7. Minute splitting of magnetic excitations in CsFeCl{sub 3} due to dipolar interaction observed by polarised neutrons

    Energy Technology Data Exchange (ETDEWEB)

    Dorner, B. [Institut Max von Laue - Paul Langevin (ILL), 38 - Grenoble (France); Baehr, M. [HMI, Berlin (Germany); Petitgrand, D. [Laboratoire Leon Brillouin (LLB) - Centre d`Etudes de Saclay, 91 - Gif-sur-Yvette (France)

    1997-04-01

    Using inelastic neutron scattering with polarisation analysis it was possible, for the first time, to observe simultaneously the two magnetic modes split due to dipolar interaction. This would not have been possible with energy resolution only. An analysis of eigenvectors was also performed. (author). 4 refs.

  8. Magnetization reversal of two-dimensional superlattices of Mn3O4 nanocubes and their collective dipolar interaction effects

    Science.gov (United States)

    Chen, Weimeng; Chen, Chinping; Guo, Lin

    2010-08-01

    Magnetic properties of two-dimensional (2D) paddy-field like superlattices of Mn3O4 cubic nanoparticles have been investigated by magnetization measurements. The 2D ordered structure extends over several microns in size. Each nanocube is of single-crystal about 6 nm in size. The magnetic properties are investigated with the powders dispersed in nonmagnetic n-eicosane to "dilute" the dipolar interaction. By accounting for the temperature variation effect of the magnetocrystalline anisotropy, Kmag(T), the temperature dependent coercivity, HC(T), can be well described by the equation, HC(T)=H0kmag(T)/mS(T){1-[kBT ln(t /t0)/E0kmag(T)]3/4}, in which kmag(T)=Kmag(T)/Kmag(0) is the reduced temperature dependent magnetocrystalline anisotropy and mS(T)=MS(T)/MS(0) is the reduced saturation magnetization. The effects of collective dipolar interaction on the magnetic properties are also studied with the as-prepared powder sample. The apparent magnetic anisotropy is seriously reduced with the presence of dipolar interaction. The switching volume is determined by the analysis on the magnetic measurements both with and without the dipolar interaction effect. There is a discrepancy in the value of switching volume determined by the two different analysis methods. Possible reasons are discussed.

  9. Dimerization of propargyl and homopropargyl 6-azido-6-deoxy-glycosides upon 1,3-dipolar cycloaddition

    Directory of Open Access Journals (Sweden)

    2008-08-01

    Full Text Available Copper-catalyzed, thermal or microwave promoted 1,3-dipolar cycloaddition (Click Reaction of 2-propynyl and 3-butynyl 2,3,4-tri-O-acetyl-6-azido-6-deoxy-glycopyranosides in the D-gluco, D-galacto and D-manno series afford the corresponding dimeric cycloaddition products.

  10. Does Synergism in Microscopic Polarity Correlate with Extrema in Macroscopic Properties for Aqueous Mixtures of Dipolar Aprotic Solvents?

    Science.gov (United States)

    Duereh, Alif; Sato, Yoshiyuki; Smith, Richard Lee; Inomata, Hiroshi; Pichierri, Fabio

    2017-06-22

    Aqueous mixtures of dipolar aprotic solvents (acetonitrile, γ-valerolactone, γ-butyrolactone, tetrahydrofuran, 1,4-dioxane, acetone, pyridine, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide) show synergism in microscopic polarity and extrema in macroscopic viscosity (η) and molar excess enthalpy (H E ) in water-rich compositions that correlate with solvent functional group electrostatic basicity (β 2 H ). Microscopic polarities of aqueous solvent mixtures were estimated by measuring the spectral shift (λ max ) of 4-nitroaniline with UV-vis spectroscopy at 25 °C. Dynamic viscosities (η) and densities were measured for eight aqueous dipolar aprotic mixtures over the full range of compositions at (25 to 45) °C. The λ max , η, and H E values of the aqueous mixtures showed a linear trend with increasing electrostatic basicity of the solvent functional groups that is attributed to the size and strength of the hydration shell of water. Density functional theory (DFT) calculations were performed for 1:3 complexes (solvent: (H 2 O) 3 ) and it was found that aqueous mixtures with high basicity have high binding energies and short hydrogen bonding distances implying that the size and strength of the hydration shell of water is proportional to functional group basicity. Consideration of functional group basicity of dipolar aprotic solvents allows one to relate synergism in microscopic polarity to extrema in macroscopic properties for a wide range of aqueous dipolar aprotic solvent mixtures.

  11. Multicomponent Dipolar Cycloaddition Strategy: Combinatorial Synthesis of Novel Spiro-Tethered Pyrazolo[3,4-b]quinoline Hybrid Heterocycles.

    Science.gov (United States)

    Sumesh, Remani Vasudevan; Muthu, Muthumani; Almansour, Abdulrahman I; Suresh Kumar, Raju; Arumugam, Natarajan; Athimoolam, S; Jeya Yasmi Prabha, E Arockia; Kumar, Raju Ranjith

    2016-05-09

    The stereoselective syntheses of a library of novel spiro-tethered pyrazolo[3,4-b]quinoline-pyrrolidine/pyrrolothiazole/indolizine-oxindole/acenaphthene hybrid heterocycles have been achieved through the 1,3-dipolar cycloaddition of azomethine ylides generated in situ from α-amino acids and 1,2-diketones to dipolarophiles derived from pyrazolo[3,4-b]quinoline derivatives.

  12. Inclusion Compound Based Approach to Forming Arrays of Artificial Dipolar Molecular Rotors: A Search for Optimal Rotor Structures

    Czech Academy of Sciences Publication Activity Database

    Kobr, L.; Zhao, K.; Shen, X.; Shoemaker, R. K.; Rogers, C. T.; Michl, Josef

    2013-01-01

    Roč. 25, č. 3 (2013), s. 443-448 ISSN 0935-9648 EU Projects: European Commission(XE) 227756 - DIPOLAR ROTOR ARRAY Grant - others:NSF(US) CHE 0848663 Institutional support: RVO:61388963 Keywords : inclusion compounds * molecular rotors * ferroelectricity * two-dimensional arrays Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 15.409, year: 2013

  13. Existence of a Thermodynamic Spin-Glass Phase in the Zero-Concentration Limit of Anisotropic Dipolar Systems

    Directory of Open Access Journals (Sweden)

    Juan Carlos Andresen

    2014-10-01

    Full Text Available The nature of ordering in dilute dipolar interacting systems dates back to the work of Debye and is one of the most basic, oldest and as-of-yet unsettled problems in magnetism. While spin-glass order is readily observed in several RKKY-interacting systems, dipolar spin glasses are the subject of controversy and ongoing scrutiny, e.g., in LiHo_{x}Y_{1−x}F_{4}, a rare-earth randomly diluted uniaxial (Ising dipolar system. In particular, it is unclear if the spin-glass phase in these paradigmatic materials persists in the limit of zero concentration or not. We study an effective model of LiHo_{x}Y_{1−x}F_{4} using large-scale Monte Carlo simulations that combine parallel tempering with a special cluster algorithm tailored to overcome the numerical difficulties that occur at extreme dilutions. We find a paramagnetic to spin-glass phase transition for all Ho^{+} ion concentrations down to the smallest concentration numerically accessible, 0.1%, and including Ho^{+} ion concentrations that coincide with those studied experimentally up to 16.7%. Our results suggest that randomly diluted dipolar Ising systems have a spin-glass phase in the limit of vanishing dipole concentration, with a critical temperature vanishing linearly with concentration. The agreement of our results with mean-field theory testifies to the irrelevance of fluctuations in interactions strengths, albeit being strong at small concentrations, to the nature of the low-temperature phase and the functional form of the critical temperature of dilute anisotropic dipolar systems. Deviations from linearity in experimental results at the lowest concentrations are discussed.

  14. Influence of static and dynamic dipolar fields in bulk YIG/thin film NiFe systems probed via spin rectification effect

    Energy Technology Data Exchange (ETDEWEB)

    Soh, Wee Tee, E-mail: a0046479@u.nus.edu [Center for Superconducting and Magnetic Materials, Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); Tay, Z.J. [Center for Superconducting and Magnetic Materials, Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); Yakovlev, N.L. [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3 Research Link, Singapore 117602 (Singapore); Peng, Bin [State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of China, Chengdu 610054 (China); Ong, C.K. [Center for Superconducting and Magnetic Materials, Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); Temasek Laboratories, National University of Singapore, 5A Engineering Drive 2, Singapore 117411 (Singapore)

    2017-03-15

    The characteristics of the static and dynamic components of the dipolar fields originating from a bulk polycrystalline yttrium iron garnet (YIG) substrate are probed by depositing a NiFe (Permalloy) layer on it, which acts as a detector. By measuring dc voltages generated via spin rectification effect (SRE) within the NiFe layer under microwave excitation, we characterize the influence of dipolar fields from bulk YIG on the NiFe layer. It is found that the dynamic YIG dipolar fields modify the self-SRE of NiFe, driving its own rectification voltages within the NiFe layer, an effect we term as non-local SRE. This non-local SRE only occurs near the simultaneous resonance of both YIG and NiFe. On the other hand, the static dipolar field from YIG manifests itself as a negative anisotropy in the NiFe layer which shifts the latter’s ferromagnetic resonance frequency. - Highlights: • We demonstrate the quantification of both the static and dynamic components of the dipolar fields due to a YIG slab. • The detection and characterisation of such dipolar fields are important in many magnetic applications such as magnonics. • The dipolar fields can pose potential pitfalls if not properly considered in certain spin-electronics systems.

  15. Dipolar colloids in apolar media: direct microscopy of two-dimensional suspensions

    Science.gov (United States)

    Janai, Erez; Cohen, Avner P.; Butenko, Alexander V.; Schofield, Andrew B.; Schultz, Moty; Sloutskin, Eli

    2016-06-01

    Spherical colloids, in an absence of external fields, are commonly assumed to interact solely through rotationally-invariant potentials, u(r). While the presence of permanent dipoles in aqueous suspensions has been previously suggested by some experiments, the rotational degrees of freedom of spherical colloids are typically neglected. We prove, by direct experiments, the presence of permanent dipoles in commonly used spherical poly(methyl methacrylate) (PMMA) colloids, suspended in an apolar organic medium. We study, by a combination of direct confocal microscopy, computer simulations, and theory, the structure and other thermodynamical properties of organic suspensions of colloidal spheres, confined to a two-dimensional (2D) monolayer. Our studies reveal the effects of the dipolar interactions on the structure and the osmotic pressure of these fluids. These observations have far-reaching consequences for the fundamental colloidal science, opening new directions in self-assembly of complex colloidal clusters.

  16. Mutual capture of dipolar molecules at low and very low energies. II. Numerical study.

    Science.gov (United States)

    Auzinsh, M; Dashevskaya, E I; Litvin, I; Nikitin, E E; Troe, J

    2011-05-26

    The low-energy rate coefficients of capture of two identical dipolar polarizable rigid rotors in their lowest nonresonant (j(1) = 0 and j(2) = 0) and resonant (j(1) = 0, 1 and j(2) = 1, 0) states are calculated accurately within the close-coupling (CC) approach. The convergence of the quantum rate coefficients to their quantum-classical counterparts is studied. A comparison of the present accurate numerical with approximate analytical results (Nikitin, E. E.; Troe, J. J. Phys. Chem. A 2010, 114, 9762) indicates a good performance of the previous approach which was based on the interpolation between s-wave fly wheel quantal and all-wave classical adiabatic channel limits. The results obtained apply as well to the formation of transient molecular species in the encounter of two atoms at very low collision energy interacting via resonance dipole-dipole interaction.

  17. Proterozoic low orbital obliquity and axial-dipolar geomagnetic field from evaporite palaeolatitudes.

    Science.gov (United States)

    Evans, David A D

    2006-11-02

    Palaeomagnetism of climatically sensitive sedimentary rock types, such as glacial deposits and evaporites, can test the uniformitarianism of ancient geomagnetic fields and palaeoclimate zones. Proterozoic glacial deposits laid down in near-equatorial palaeomagnetic latitudes can be explained by 'snowball Earth' episodes, high orbital obliquity or markedly non-uniformitarian geomagnetic fields. Here I present a global palaeomagnetic compilation of the Earth's entire basin-scale evaporite record. Magnetic inclinations are consistent with low orbital obliquity and a geocentric-axial-dipole magnetic field for most of the past two billion years, and the snowball Earth hypothesis accordingly remains the most viable model for low-latitude Proterozoic ice ages. Efforts to reconstruct Proterozoic supercontinents are strengthened by this demonstration of a consistently axial and dipolar geomagnetic reference frame, which itself implies stability of geodynamo processes on billion-year timescales.

  18. Simulation study of localization of electromagnetic waves in two-dimensional random dipolar systems.

    Science.gov (United States)

    Wang, Ken Kang-Hsin; Ye, Zhen

    2003-12-01

    We study the propagation and scattering of electromagnetic waves by random arrays of dipolar cylinders in a uniform medium. A set of self-consistent equations, incorporating all orders of multiple scattering of the electromagnetic waves, is derived from first principles and then solved numerically for electromagnetic fields. For certain ranges of frequencies, spatially localized electromagnetic waves appear in such a simple but realistic disordered system. Dependence of localization on the frequency, radiation damping, and filling factor is shown. The spatial behavior of the total, coherent, and diffusive waves is explored in detail, and found to comply with a physical intuitive picture. A phase diagram characterizing localization is presented, in agreement with previous investigations on other systems.

  19. Attraction-driven aggregation of dipolar particles in an external magnetic field.

    Science.gov (United States)

    Pál, Gergo; Kun, Ferenc; Varga, Imre; Sohler, Dóra; Sun, Gang

    2011-06-01

    We present a detailed experimental study of the aggregation of particles of permanent magnetic moment in an external magnetic field. The experiments are performed with millimeter-sized particles floating on the surface of water. Due to the large size of the particles, thermal noise does not have any relevance in the system; the particles undergo deterministic motion. Experiments are carried out varying the concentration which also controls the relative importance of the dipole-external field and the dipole-dipole interactions. We determined the exponents characterizing the aggregation process and found that the attraction driven aggregation of dipolar particles obeys the Vicsek-Family dynamic scaling. The exponents are found to have a concentration dependence which can be attributed to the change of mobility of clusters and their interaction at higher concentrations.

  20. Molecular dynamics simulations of a silver atom in water: evidence for a dipolar excitonic state.

    Science.gov (United States)

    Spezia, Riccardo; Nicolas, Cédric; Boutin, Anne; Vuilleumier, Rodolphe

    2003-11-14

    The properties of a silver atom in bulk water were studied for the first time by molecular dynamics simulations using two complementary mixed quantum-classical approaches. The first one consists of treating by quantum mechanics one electron only, which interacts with a classical silver cation and solvent through one-electron pseudopotentials. The second one is Car-Parrinello molecular dynamics that treats all the valence electrons quantum-mechanically. Very good agreement is obtained between these two methods, and the calculated absorption spectrum of the solvated silver atom agrees very well with experimental data. Both simulations reveal that the silver atom is in the critical region for the appearance of a dipolar excitonic state and exhibits a dipole moment of approximately 2 D with large fluctuations of +/-1 D. The structure of the solvation shell is also analyzed.

  1. Microwave-assisted multicomponent diastereoselective 1,3-dipolar cycloaddition of ethyl glyoxylate derived azomethine ylides.

    Science.gov (United States)

    Mancebo-Aracil, Juan; Nájera, Carmen; Sansano, José M

    2013-01-28

    The thermal multicomponent 1,3-dipolar cycloaddition (1,3-DC) of diethyl aminomalonate or α-amino esters (derived from glycine, alanine, phenylalanine, and phenylglycine) with ethyl glyoxylate and the corresponding dipolarophile such as maleimides, methyl acrylate, methyl fumarate, (E)-1,2-bis(phenylsulfonyl)ethylene, and electron deficient alkynes allows the diastereoselective synthesis of new polysubstituted pyrrolidine derivatives. Microwave-assisted heating processes give better results than conventional heating ones, affording endo-cycloadducts as major stereoisomers. In general, 2,5-cis-cycloadducts are preferentially formed according to the previous formation of the W-shaped dipole. Only in the 1,3-DC of the disulfone with phenylglycine and ethyl glyoxylate the corresponding exo-trans-cycloadduct was isolated. The compound endo-cis-4b, derived from phenylalanine, ethyl glyoxylate and N-benzylmaleimide, has been further transformed into a very complex diazabicyclo[2.2.1]octane skeleton with potential biological activity.

  2. Superfluidity of dipolar excitons in a transition metal dichalcogenide double layer

    Science.gov (United States)

    Berman, Oleg L.; Kezerashvili, Roman Ya.

    2017-09-01

    We study formation and superfluidity of dipolar excitons in double layer heterostructures formed by two transition metal dichalcogenide (TMDC) atomically thin layers. Considering screening effects for an electron-hole interaction via the harmonic oscillator approximation for the Keldysh potential, the analytical expressions for the exciton energy spectrum and the mean field critical temperature Tc for the superfluidity are obtained. It is shown that binding energies of A excitons are larger than for B excitons. The mean field critical temperature for a two-component dilute exciton system in a TMDC double layer is analyzed and shown that the latter is an increasing function of the factor Q , determined by the effective masses of A and B excitons and their reduced mass. Comparison of the calculations for Tc performed by employing the Coulomb and Keldysh interactions demonstrates the importance of screening effects in TMDC.

  3. Radiación sincrotronica en un campo magnético dipolar

    Directory of Open Access Journals (Sweden)

    J. Bonatti

    2016-03-01

    Full Text Available Se estudia la variación de la energía emitida por un electrón en una transición entre los niveles de Landau Ni=1 a Nf=0 en un campo magnético dipolar fuerte. Se toma como primera aproximación la dependencia funcional del campo  B=r3*(r*+z-3 Bsup. para representar a éste cerca de los polos en la superficie de una estrella de neutrones y se analiza la variación de la energía emitida para esa trasmisión en función de la altitud.

  4. A Bis-Manganese(II)-DOTA Complex for Pulsed Dipolar Spectroscopy.

    Science.gov (United States)

    Demay-Drouhard, Paul; Ching, H Y Vincent; Akhmetzyanov, Dmitry; Guillot, Régis; Tabares, Leandro C; Bertrand, Hélène C; Policar, Clotilde

    2016-07-04

    High-spin gadolinium(III) and manganese(II) complexes have emerged as alternatives to standard nitroxide radical spin labels for measuring nanometric distances by using pulsed electron-electron double resonance (PELDOR or DEER) at high fields/frequencies. For certain complexes, particularly those with relatively small zero-field splitting (ZFS) and short distances between the two metal centers, the pseudosecular term of the dipolar coupling Hamiltonian is non-negligible. However, in general, the contribution from this term during conventional data analysis is masked by the flexibility of the molecule of interest and/or the long tethers connecting them to the spin labels. The efficient synthesis of a model system consisting of two [Mn(dota)](2-) (MnDOTA; DOTA(4-) =1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate) directly connected to the ends of a central rodlike oligo(phenylene-ethynylene) (OPE) spacer is reported. The rigidity of the OPE is confirmed by Q-band PELDOR measurements on a bis-nitroxide analogue. The Mn(II) -Mn(II) distance distribution profile determined by W-band PELDOR is in reasonable agreement with one simulated by using a simple rotamer analysis. The small degree of flexibility arising from the linking MnDOTA arm appears to outweigh the contribution from the pseudosecular term at this interspin distance. This study illustrates the potential of MnDOTA-based spin labels for measuring fairly short nanometer distances, and also presents an interesting candidate for in-depth studies of pulsed dipolar spectroscopy methods on Mn(II) -Mn(II) systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Multi-spacecraft observation of plasma dipolarization/injection in the inner magnetosphere

    Directory of Open Access Journals (Sweden)

    S. V. Apatenkov

    2007-03-01

    Full Text Available Addressing the origin of the energetic particle injections into the inner magnetosphere, we investigate the 23 February 2004 substorm using a favorable constellation of four Cluster (near perigee, LANL and Geotail spacecraft. Both an energy-dispersed and a dispersionless injection were observed by Cluster crossing the plasma sheet horn, which mapped to 9–12 RE in the equatorial plane close to the midnight meridian. Two associated narrow equatorward auroral tongues/streamers propagating from the oval poleward boundary could be discerned in the global images obtained by IMAGE/WIC. As compared to the energy-dispersed event, the dispersionless injection front has important distinctions consequently repeated at 4 spacecraft: a simultaneous increase in electron fluxes at energies ~1..300 keV, ~25 nT increase in BZ and a local increase by a factor 1.5–1.7 in plasma pressure. The injected plasma was primarily of solar wind origin. We evaluated the change in the injected flux tube configuration during the dipolarization by fitting flux increases observed by the PEACE and RAPID instruments, assuming adiabatic heating and the Liouville theorem. Mapping the locations of the injection front detected by the four spacecraft to the equatorial plane, we estimated the injection front thickness to be ~1 RE and the earthward propagation speed to be ~200–400 km/s (at 9–12 RE. Based on observed injection properties, we suggest that it is the underpopulated flux tubes (bubbles with enhanced magnetic field and sharp inner front propagating earthward, which accelerate and transport particles into the strong-field dipolar region.

  6. Fluorine detected 2D NMR experiments for the practical determination of size and sign of homonuclear F-F and heteronuclear C-F multiple bond J-coupling constants in multiple fluorinated compounds

    Science.gov (United States)

    Aspers, Ruud L. E. G.; Ampt, Kirsten A. M.; Dvortsak, Peter; Jaeger, Martin; Wijmenga, Sybren S.

    2013-06-01

    The use of fluorine in molecules obtained from chemical synthesis has become increasingly important within the pharmaceutical and agricultural industry. NMR characterization of these compounds is of great value with respect to their structure elucidation, their screening in metabolomics investigations and binding studies. The favorable NMR properties of the fluorine nucleus make NMR with fluorine detection of great value in this respect. A suite of NMR 2D F-F- and F-C-correlation experiments with fluorine detection was applied to the assignment of resonances, nJCF- and nJFF-couplings as well as the determination of their size and sign. The utilization of this experiment suite was exemplarily demonstrated for a highly fluorinated vinyl alkyl ether. Especially F-C HSQC and J-scaled F-C HMBC experiments allowed determining the size of the J-couplings of this compound. The relative sign of its homo- and heteronuclear couplings was achieved by different combinations of 2D NMR experiments, including non-selective and F2-selective F-C XLOC, F2-selective F-C HMQC, and F-F COSY. The F2-one/two-site selective F-C XLOC versions were found highly useful, as they led to simplifications of the common E.COSY patterns and resulted in a higher confidence level of the assignment by using selective excitation. The combination of F2-one/two-site selective F-C XLOC experiments with a F2-one-site selective F-C HMQC experiment provided the signs of all nJCF- and nJFF-couplings in the vinyl moiety of the test compound. Other combinations of experiments were found useful as well for special purposes when focusing for example on homonuclear couplings a combination of F-F COSY-10 with a F2-one-site selective F-C HMQC could be used. The E.COSY patterns in the spectra demonstrated were analyzed by use of the spin-selective displacement vectors, and in case of the XLOC also by use of the DQ- and ZQ-displacement vectors. The variety of experiments presented shall contribute to facilitate the

  7. Interresidue carbonyl-carbonyl polarization transfer experiments in uniformly 13C, 15N-labeled peptides and proteins

    Science.gov (United States)

    Janik, Rafal; Ritz, Emily; Gravelle, Andrew; Shi, Lichi; Peng, Xiaohu; Ladizhansky, Vladimir

    2010-03-01

    In this work, we demonstrate that Homonuclear Rotary Resonance Recoupling (HORROR) can be used to reintroduce carbonyl-carbonyl interresidue dipolar interactions and to achieve efficient polarization transfer between carbonyl atoms in uniformly 13C, 15N-labeled peptides and proteins. We show that the HORROR condition is anisotropically broadened and overall shifted to higher radio frequency intensities because of the CSA effects. These effects are analyzed theoretically using Average Hamiltonian Theory. At spinning frequencies used in this study, 22 kHz, this broadening is experimentally found to be on the order of a kilohertz at a proton field of 600 MHz. To match HORROR condition over all powder orientations, variable amplitude radio frequency (RF) fields are required, and efficient direct transfers on the order of 20-30% can be straightforwardly established. Two- and three-dimensional chemical shift correlation experiments establishing long-range interresidue connectivities (e.g., (N[i]-CO[i - 2])) are demonstrated on the model peptide N-acetyl-valine-leucine, and on the third immunoglobulin binding domain of protein G. Possible future developments are discussed.

  8. Quantum-Fluctuation-Driven Crossover from a Dilute Bose-Einstein Condensate to a Macrodroplet in a Dipolar Quantum Fluid

    Directory of Open Access Journals (Sweden)

    L. Chomaz

    2016-11-01

    Full Text Available In a joint experimental and theoretical effort, we report on the formation of a macrodroplet state in an ultracold bosonic gas of erbium atoms with strong dipolar interactions. By precise tuning of the s-wave scattering length below the so-called dipolar length, we observe a smooth crossover of the ground state from a dilute Bose-Einstein condensate to a dense macrodroplet state of more than 2×10^{4}  atoms. Based on the study of collective excitations and loss features, we prove that quantum fluctuations stabilize the ultracold gas far beyond the instability threshold imposed by mean-field interactions. Finally, we perform expansion measurements, showing that although self-bound solutions are prevented by losses, the interplay between quantum stabilization and losses results in a minimal time-of-flight expansion velocity at a finite scattering length.

  9. Frustrated Magnetism of Dipolar Molecules on a Square Optical Lattice: Prediction of a Quantum Paramagnetic Ground State

    Science.gov (United States)

    Zou, Haiyuan; Zhao, Erhai; Liu, W. Vincent

    2017-08-01

    Motivated by the experimental realization of quantum spin models of polar molecule KRb in optical lattices, we analyze the spin 1 /2 dipolar Heisenberg model with competing anisotropic, long-range exchange interactions. We show that, by tilting the orientation of dipoles using an external electric field, the dipolar spin system on square lattice comes close to a maximally frustrated region similar, but not identical, to that of the J1-J2 model. This provides a simple yet powerful route to potentially realize a quantum spin liquid without the need for a triangular or kagome lattice. The ground state phase diagrams obtained from Schwinger-boson and spin-wave theories consistently show a spin disordered region between the Néel, stripe, and spiral phase. The existence of a finite quantum paramagnetic region is further confirmed by an unbiased variational ansatz based on tensor network states and a tensor renormalization group.

  10. The Relationship Between Dipolarization Fronts and Pi2 Pulsations in the Near-Earth Magnetotail - A MHD Case Study

    Science.gov (United States)

    Ream, J. B.; Walker, R. J.; Ashour-Abdalla, M.; El-Alaoui, M.

    2011-12-01

    We performed a global MHD simulation of a substorm event on 14 September 2004 in order to investigate the link between Pi2 generation and dipolarization fronts. Pi2 pulsations (T = 40-150 s) measured by ground-based instruments are typically used as an indicator of substorm onset, therefore, understanding how and where they are generated is vital to understanding the series of events leading up to onset. Kepko et al. [1999] suggested that the compression regions and velocity variations associated with earthward propagating dipolarization fronts directly drive Pi2 pulsations. Similarly, Panov et al. [2011] suggested that Pi2 pulsations are generated by the overshoot and rebound of bursty bulk flows. Dipolarization fronts are step-wise enhancements in Bz which are associated with fast (>100km/s) earthward flows and are followed by tailward expansion due to pile-up at the high pressure region where the magnetic field lines transition from a stretched to a dipolar configuration. Cao et al. [2009] have presented observations from Double Star (TC1), Cluster 4 and Polar of a substorm with onset at 18:22 UT. During this event a dipolarization front was observed by Double Star at ~18:25, and dipolarization associated expansion was observed by Cluster 4 at ~18:50 and Polar at ~18:55 UT. The spacecraft were positioned at (-10.2, -1.6, 1.2), (-16.4, 1.6, 2.2) and (-7.5, -1.8, -4.9) RE in GSM coordinates respectively. The simulation was carried out with the UCLA global MHD code [El-Alaoui (2001), Raeder (1998)], using Geotail, located near the bow shock at ~24 RE, as the solar wind monitor. The solar wind magnetic field data were rotated into a minimum variance frame to be used as input for the simulation. The results from the simulation have been compared to observations and do a good job reproducing the structures observed by all three satellites. Around the time of onset, we have identified a dipolarization front near midnight which originates at ~12 RE. We show that as the

  11. Frustrated Magnetism of Dipolar Molecules on a Square Optical Lattice: Prediction of a Quantum Paramagnetic Ground State.

    Science.gov (United States)

    Zou, Haiyuan; Zhao, Erhai; Liu, W Vincent

    2017-08-04

    Motivated by the experimental realization of quantum spin models of polar molecule KRb in optical lattices, we analyze the spin 1/2 dipolar Heisenberg model with competing anisotropic, long-range exchange interactions. We show that, by tilting the orientation of dipoles using an external electric field, the dipolar spin system on square lattice comes close to a maximally frustrated region similar, but not identical, to that of the J_{1}-J_{2} model. This provides a simple yet powerful route to potentially realize a quantum spin liquid without the need for a triangular or kagome lattice. The ground state phase diagrams obtained from Schwinger-boson and spin-wave theories consistently show a spin disordered region between the Néel, stripe, and spiral phase. The existence of a finite quantum paramagnetic region is further confirmed by an unbiased variational ansatz based on tensor network states and a tensor renormalization group.

  12. Low-lying excitation modes of trapped dipolar Fermi gases: From the collisionless to the hydrodynamic regime

    Science.gov (United States)

    Wächtler, Falk; Lima, Aristeu R. P.; Pelster, Axel

    2017-10-01

    By means of the Boltzmann-Vlasov kinetic equation we investigate dynamical properties of a trapped one-component Fermi gas at zero temperature, featuring the anisotropic and long-range dipole-dipole interaction. To this end, we determine an approximate solution by rescaling both space and momentum variables of the equilibrium distribution, thereby obtaining coupled ordinary differential equations for the corresponding scaling parameters. Based on previous results on how the Fermi sphere is deformed in the hydrodynamic regime of a dipolar Fermi gas, we are able to implement the relaxation-time approximation for the collision integral. Then, we proceed by linearizing the equations of motion around the equilibrium in order to study both the frequencies and the damping of the low-lying excitation modes all the way from the collisionless to the hydrodynamic regime. Our theoretical results are expected to be relevant for understanding current experiments with trapped dipolar Fermi gases.

  13. Synthesis with Perfect Atom Economy: Generation of Furan Derivatives by 1,3-Dipolar Cycloaddition of Acetylenedicarboxylates at Cyclooctynes

    Directory of Open Access Journals (Sweden)

    Klaus Banert

    2014-09-01

    Full Text Available Cyclooctyne and cycloocten-5-yne undergo, at room temperature, a 1,3-dipolar cycloaddition with dialkyl acetylenedicarboxylates 1a,b to generate furan-derived short-lived intermediates 2, which can be trapped by two additional equivalents of 1a,b or alternatively by methanol, phenol, water or aldehydes to yield polycyclic products 3b–d, orthoesters 4a–c, ketones 5 or epoxides 6a,b, respectively. Treatment of bis(trimethylsilyl acetylenedicarboxylate (1c with cyclooctyne leads to the ketone 7 via retro-Brook rearrangement of the dipolar intermediate 2c. In all cases, the products are formed with perfect atom economy.

  14. Nuclear magnetic resonance studies of quadrupolar nuclei and dipolar field effects

    Energy Technology Data Exchange (ETDEWEB)

    Urban, Jeffry Todd [Univ. of California, Berkeley, CA (United States)

    2004-01-01

    Experimental and theoretical research conducted in two areas in the field of nuclear magnetic resonance (NMR) spectroscopy is presented: (1) studies of the coherent quantum-mechanical control of the angular momentum dynamics of quadrupolar (spin I > 1/2) nuclei and its application to the determination of molecular structure; and (2) applications of the long-range nuclear dipolar field to novel NMR detection methodologies.The dissertation is organized into six chapters. The first two chapters and associated appendices are intended to be pedagogical and include an introduction to the quantum mechanical theory of pulsed NMR spectroscopy and the time dependent theory of quantum mechanics. The third chapter describes investigations of the solid-state multiple-quantum magic angle spinning (MQMAS) NMR experiment applied to I = 5/2 quadrupolar nuclei. This work reports the use of rotary resonance-matched radiofrequency irradiation for sensitivity enhancement of the I = 5/2 MQMAS experiment. These experiments exhibited certain selective line narrowing effects which were investigated theoretically.The fourth chapter extends the discussion of multiple quantum spectroscopy of quadrupolar nuclei to a mostly theoretical study of the feasibility of enhancing the resolution of nitrogen-14 NMR of large biomolecules in solution via double-quantum spectroscopy. The fifth chapter continues to extend the principles of multiple quantum NMR spectroscopy of quadrupolar nuclei to make analogies between experiments in NMR/nuclear quadrupolar resonance (NQR) and experiments in atomic/molecular optics (AMO). These analogies are made through the Hamiltonian and density operator formalism of angular momentum dynamics in the presence of electric and magnetic fields.The sixth chapter investigates the use of the macroscopic nuclear dipolar field to encode the NMR spectrum of an analyte nucleus indirectly in the magnetization of a sensor nucleus. This technique could potentially serve as an

  15. Non-dipolar magnetic field models and patterns of radio emission: Uranus and Neptune compared

    Science.gov (United States)

    Evans, D. R.

    1994-01-01

    The magnetic field geometries of Uranus and Neptune are superficially similar, and are similarly unlike those of other planets: the field strengths are similar, and they contain extraordinarily large non-dipolar components. As a corollary, the best dipolar field models of each of the two planets comprises a dipole that is considerably offset from the planetary center and tilted away from the rotational axis. However, in other respects the best field models of the two planets are quite different. Uranus has a quadrupole model in which all the terms are well determined and in which none of the higher order terms is determined. To represent the magnetometer data acquired during Voyager's Neptune encounter requires a model of order 8 (instead of Uranus' order 2), yet many of the coefficients are poorly determined. A second model, an octupole model comprising the terms up to order three of the order 8 model, has been suggested by the magnetometer team as being useful; its use, however, is limited only to the region outside of about 2R(exp N), whereas planetary radio emissions have their sources well inside this surface. Computer code has been written that permits an analysis of the detailed motion of low energy charged particles moving in general planetary magnetic fields. At Uranus, this code reveals the existence of an isolated region of the inner magnetosphere above the day side in which particles may be trapped, separate from the more general magnetospheric trapping. An examination of the so-call ordinary mode uranian radio emissions leads us to believe that these emissions are in fact extraordinary mode emissions coming from particles trapped in this isolated region. A similar attempt to discover trapping regions at Neptune has proved, unfortunately, to be impossible. This arises from three factors: (1) the computation needed to track particles in an eighth order field is more than an order of magnitude greater than that needed to perform a similar calculation in a

  16. Numerical and analytical investigation of the synchronization of dipolarly coupled vortex spin-torque nano-oscillators

    OpenAIRE

    Belanovsky A.D.; Locatelli N.; Skirdkov P.N.; Abreu Araujo F.; Zvezdin K.A.; Grollier J.; Cros V.; Zvezdin A.K.

    2013-01-01

    We investigate analytically and numerically the synchronization dynamics of dipolarly coupled vortex based Spin-Torque Nano Oscillators with different pillar diameters. We identify the critical interpillar distances on which synchronization occurs as a function of their diameter mismatch. We obtain numerically a phase diagram showing the transition between unsynchronized and synchronized states and compare it to analytical predictions we make using the Thiele approach. Our study demonstrates ...

  17. A regio- and stereoselective 1,3-dipolar cycloaddition for the synthesis of new-fangled dispiropyrrolothiazoles as antimycobacterial agents.

    Science.gov (United States)

    Almansour, Abdulrahman I; Ali, Sadath; Ali, Mohamed Ashraf; Ismail, Rusli; Choon, Tan Soo; Sellappan, Velmurugan; Elumalai, Karthi Keyan; Pandian, Suresh

    2012-12-15

    A series of dispiropyrrolothiazoles compounds were synthesized using 1,3-dipolar cycloaddition and were screened for antimycobacterial activity against Mycobacterium tuberculosis H(37)Rv and INH resistant M. tuberculosis strains. Two of them were showing good activity with MIC of less than 1 μM. Compound (5f) was found to be the most active with MIC of 0.210 and 8.312 μM respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

  18. Freezing point and solid-liquid interfacial free energy of Stockmayer dipolar fluids: a molecular dynamics simulation study.

    Science.gov (United States)

    Wang, Jun; Apte, Pankaj A; Morris, James R; Zeng, Xiao Cheng

    2013-09-21

    Stockmayer fluids are a prototype model system for dipolar fluids. We have computed the freezing temperatures of Stockmayer fluids at zero pressure using three different molecular-dynamics simulation methods, namely, the superheating-undercooling method, the constant-pressure and constant-temperature two-phase coexistence method, and the constant-pressure and constant-enthalpy two-phase coexistence method. The best estimate of the freezing temperature (in reduced unit) for the Stockmayer (SM) fluid with the dimensionless dipole moment μ*=1, √2, √3 is 0.656 ± 0.001, 0.726 ± 0.002, and 0.835 ± 0.005, respectively. The freezing temperature increases with the dipolar strength. Moreover, for the first time, the solid-liquid interfacial free energies γ of the fcc (111), (110), and (100) interfaces are computed using two independent methods, namely, the cleaving-wall method and the interfacial fluctuation method. Both methods predict that the interfacial free energy increases with the dipole moment. Although the interfacial fluctuation method suggests a weaker interfacial anisotropy, particularly for strongly dipolar SM fluids, both methods predicted the same trend of interfacial anisotropy, i.e., γ100 > γ110 > γ111.

  19. Reflection and transmission of thermo-elastic waves without energy dissipation at the interface of two dipolar gradient elastic solids.

    Science.gov (United States)

    Li, Yueqiu; Wei, Peijun

    2018-01-01

    The reflection and transmission of thermal elastic waves at the interface between two different dipolar gradient elastic solids are studied based on the generalized thermo-elastic theory of Green and Naghdi [(1993). J. Elasticity 31, 189-208] (type II of no energy dissipation). First, some thermodynamic formulas are generalized to a dipolar gradient elastic solid and the function of free energy density is postulated. Second, equations of thermal motion and constitutive relations in a dipolar gradient elasticity are derived. Then the nontraditional interfacial conditions are used to determine the amplitude ratio of the reflection and transmission waves with respect to the incident wave. Some numerical results of the reflection and transmission coefficients in the form of an energy flux ratio are given for different microstructure parameters while thermal parameters are fixed. The numerical results are validated by the consideration of energy conservation. It is found that there are a total of five modes of dispersive waves, namely, coupled MT1 wave, coupled MT2 wave, coupled MT3 wave, SV wave, and one evanescent wave which reduces to the surface waves at an interface, namely, SS wave. The thermal parameters mainly affect the coupled MT2 wave while the microstructure parameters affect not only the coupled waves but also the SS surface waves.

  20. Near-Earth injection of MeV electrons associated with intense dipolarization electric fields: Van Allen Probes observations.

    Science.gov (United States)

    Dai, Lei; Wang, Chi; Duan, Suping; He, Zhaohai; Wygant, John R; Cattell, Cynthia A; Tao, Xin; Su, Zhenpeng; Kletzing, Craig; Baker, Daniel N; Li, Xinlin; Malaspina, David; Blake, J Bernard; Fennell, Joseph; Claudepierre, Seth; Turner, Drew L; Reeves, Geoffrey D; Funsten, Herbert O; Spence, Harlan E; Angelopoulos, Vassilis; Fruehauff, Dennis; Chen, Lunjin; Thaller, Scott; Breneman, Aaron; Tang, Xiangwei

    2015-08-16

    Substorms generally inject tens to hundreds of keV electrons, but intense substorm electric fields have been shown to inject MeV electrons as well. An intriguing question is whether such MeVelectron injections can populate the outer radiation belt. Here we present observations of a substorm injection of MeV electrons into the inner magnetosphere. In the premidnight sector at L ∼ 5.5, Van Allen Probes (Radiation Belt Storm Probes)-A observed a large dipolarization electric field (50 mV/m) over ∼40 s and a dispersionless injection of electrons up to ∼3 MeV. Pitch angle observations indicated betatron acceleration of MeV electrons at the dipolarization front. Corresponding signals of MeV electron injection were observed at LANL-GEO, THEMIS-D, and GOES at geosynchronous altitude. Through a series of dipolarizations, the injections increased the MeV electron phase space density by 1 order of magnitude in less than 3 h in the outer radiation belt ( L > 4.8). Our observations provide evidence that deep injections can supply significant MeV electrons.

  1. An Intramolecular Nitrone-Olefin Dipolar Cycloaddition-Based Approach to Total Synthesis of the Cylindricine and Lepadiformine Marine Alkaloids.

    Science.gov (United States)

    Werner, Kim M.; de Los Santos, Jesus M.; Weinreb, Steven M.; Shang, Maoyu

    1999-06-25

    A synthetic route to the cylindricine skeleton as well as to the reported structure of the marine alkaloid lepadiformine has been achieved using an intramolecular nitrone/1,3-diene dipolar cycloaddition as the key step. The synthesis began with sequential alkylations of acetone oxime to afford key intermediate oxime 30, which contains all of the carbons necessary to form the tricyclic skeleton of the alkaloids. Nitrone 40, available from oxime 30 by standard transformations, underwent an intramolecular 1,3-dipolar cycloaddition to provide isoxazolidine 43. Related 1,3-dipolar cycloadditions were also explored on two additional nitrone-olefin substrates 41 and 42, which were prepared in a manner similar to that of 40. The tricyclic alkaloid core 52 was formed stereoselectively by a tandem oxidation-Michael addition of amino alcohol 49 derived from isoxazolidine 43. Cleavage of the O-phenyl ether of 52 provided 2-epi-cylindricine C (53). Several unsuccessful attempts were made to convert 52 to cylindricine C by epimerization at C2. Tricyclic ketone 52 was deoxygenated to give amine 59, whose structure and relative stereochemistry were confirmed by single-crystal X-ray analysis of its picrate salt. Removal of the O-phenyl protecting group from 59 provided tricyclic amino alcohol 60 having the putative structure of lepadiformine, but whose NMR data did not correspond to those of the natural product.

  2. A new dipolar potential for numerical simulations of polar fluids on the 4D hypersphere

    Science.gov (United States)

    Caillol, Jean-Michel; Trulsson, Martin

    2014-09-01

    We present a new method for Monte Carlo or Molecular Dynamics numerical simulations of three-dimensional polar fluids. The simulation cell is defined to be the surface of the northern hemisphere of a four-dimensional (hyper)sphere. The point dipoles are constrained to remain tangent to the sphere and their interactions are derived from the basic laws of electrostatics in this geometry. The dipole-dipole potential has two singularities which correspond to the following boundary conditions: when a dipole leaves the northern hemisphere at some point of the equator, it reappears at the antipodal point bearing the same dipole moment. We derive all the formal expressions needed to obtain the thermodynamic and structural properties of a polar liquid at thermal equilibrium in actual numerical simulation. We notably establish the expression of the static dielectric constant of the fluid as well as the behavior of the pair correlation at large distances. We report and discuss the results of extensive numerical Monte Carlo simulations for two reference states of a fluid of dipolar hard spheres and compare these results with previous methods with a special emphasis on finite size effects.

  3. Highly efficient square wave distant dipolar field and its application for in vivo MRI.

    Science.gov (United States)

    Cai, Congbo; Gao, Fenglian; Cai, Shuhui; Zhong, Jianhui; Chen, Zhong

    2010-10-01

    Intermolecular multiple quantum coherences generated by distant dipolar field (DDF) have some attractive properties, but the intrinsic weak signal intensity prevents their widespread applications. Recently, Branca et al. (J Chem Phys 2008;129:054502) suggested that square wave DDF was more efficient than conventional sinusoidal DDF because it could simultaneously produce intermolecular multiple quantum coherences signal with various major orders. In this article, instead of a series of adiabatic inversion pulses proposed previously, a more efficient composite adiabatic inversion pulse was applied to create square wave DDF. The square wave DDF was applied to in vivo MRI for the first time, and the corresponding simulations were performed. Both experimental and simulated results show that square wave DDF with composite adiabatic inversion pulse improves over the original Z-modulation enhanced to binary for self-refocused acquisition implementation and can enhance the signal intensity to about 2-fold of that from conventional correlation spectroscopy (COSY) revamped with asymmetric Z-gradient echo detection sequence for in vivo MRI, close to the theoretical prediction.

  4. Dipolar modulation in the size of galaxies: the effect of Doppler magnification

    Science.gov (United States)

    Bonvin, Camille; Andrianomena, Sambatra; Bacon, David; Clarkson, Chris; Maartens, Roy; Moloi, Teboho; Bull, Philip

    2017-12-01

    Objects falling into an overdensity appear larger on its near side and smaller on its far side than other objects at the same redshift. This produces a dipolar pattern of magnification, primarily as a consequence of the Doppler effect. At low redshift, this Doppler magnification completely dominates the usual integrated gravitational lensing contribution to the lensing magnification. We show that one can optimally observe this pattern by extracting the dipole in the cross-correlation of number counts and galaxy sizes. This dipole allows us to almost completely remove the contribution from gravitational lensing up to redshift ≲0.5, and even at high redshift z ≃ 1, the dipole picks up the Doppler magnification predominantly. Doppler magnification should be easily detectable in current and upcoming optical and radio surveys; by forecasting for telescopes such as the SKA, we show that this technique is competitive with using peculiar velocities via redshift-space distortions to constrain dark energy. It produces similar yet complementary constraints on the cosmological model to those found using measurements of the cosmic shear.

  5. Atomic-scale sensing of the magnetic dipolar field from single atoms

    Science.gov (United States)

    Choi, Taeyoung; Paul, William; Rolf-Pissarczyk, Steffen; MacDonald, Andrew J.; Natterer, Fabian D.; Yang, Kai; Willke, Philip; Lutz, Christopher P.; Heinrich, Andreas J.

    2017-05-01

    Spin resonance provides the high-energy resolution needed to determine biological and material structures by sensing weak magnetic interactions. In recent years, there have been notable achievements in detecting and coherently controlling individual atomic-scale spin centres for sensitive local magnetometry. However, positioning the spin sensor and characterizing spin-spin interactions with sub-nanometre precision have remained outstanding challenges. Here, we use individual Fe atoms as an electron spin resonance (ESR) sensor in a scanning tunnelling microscope to measure the magnetic field emanating from nearby spins with atomic-scale precision. On artificially built assemblies of magnetic atoms (Fe and Co) on a magnesium oxide surface, we measure that the interaction energy between the ESR sensor and an adatom shows an inverse-cube distance dependence (r-3.01±0.04). This demonstrates that the atoms are predominantly coupled by the magnetic dipole-dipole interaction, which, according to our observations, dominates for atom separations greater than 1 nm. This dipolar sensor can determine the magnetic moments of individual adatoms with high accuracy. The achieved atomic-scale spatial resolution in remote sensing of spins may ultimately allow the structural imaging of individual magnetic molecules, nanostructures and spin-labelled biomolecules.

  6. Phase transitions and multicritical behavior in the Ising model with dipolar interactions.

    Science.gov (United States)

    Bab, M A; Horowitz, C M; Rubio Puzzo, M L; Saracco, G P

    2016-10-01

    In this work, the phase diagram of the ferromagnetic Ising model with dipole interactions is revisited with the aim of determining the nature of the phase transition between stripe-ordered phases with width n (h_{n}) and tetragonal liquid (TL) phases. Extensive Monte Carlo simulations are performed in order to study the short-time dynamic behavior of the observables for selected values of the ratio between the ferromagnetic exchange and dipolar constants δ. The obtained results indicate that the h_{1}-TL phase transition line is continuous up to δ=1.2585, while for the h_{2}-TL line a weak first-order character is found in the interval 1.2585≤δ≤1.36 and becomes continuous for 1.37≤δ≤1.9. This result suggests the existence of a tricritical point close to δ=1.37. When it is appropriate, the complete set of critical exponents is obtained, and in all the studied cases they depend on δ but do not belong to the Ising universality class. Furthermore, short-time dynamic studies reveal that at the point where the mentioned lines meet the h_{1}-h_{2} line, i.e., at δ=1.2585, the critical phase corresponding to the h_{1}-TL transition coexists with the h_{2} phase.

  7. Characteristics of ion distribution functions in dipolarizing flux bundles: Event studies

    Science.gov (United States)

    Runov, A.; Angelopoulos, V.; Artemyev, A.; Birn, J.; Pritchett, P. L.; Zhou, X.-Z.

    2017-06-01

    Taking advantage of multipoint observations from a repeating configuration of the five Time History of Events and Macroscale Interactions during Substorms (THEMIS) probes separated by 1 to 2 Earth radii (RE) along X, Y, and Z in the geocentric solar magnetospheric system (GSM), we study ion distribution functions collected by the probes during three dipolarizing flux bundle (DFB) events observed at geocentric distances 9 GSM directions and |Bx| levels, which characterize the distance from the neutral sheet. We found that the characteristics of the ion distribution functions strongly depended on the |Bx| level, whereas changes with respect to X and Y were minor. In all three events, ion distribution functions f(v) observed inside DFBs were organized by magnetic and electric fields. The probes near the magnetic equator observed perpendicular anisotropy of the phase space density in the range between thermal energy and twice the thermal energy, although the distribution in the ambient plasma sheet was isotropic. The anisotropic ion distribution in DFBs injected toward the inner magnetosphere may provide the free energy for waves and instabilities, which are important elements of particle energization.

  8. Open Boundary Particle-in-Cell Simulation of Dipolarization Front Propagation

    Science.gov (United States)

    Klimas, Alex; Hwang, Kyoung-Joo; Vinas, Adolfo F.; Goldstein, Melvyn L.

    2014-01-01

    First results are presented from an ongoing open boundary 2-1/2D particle-in-cell simulation study of dipolarization front (DF) propagation in Earth's magnetotail. At this stage, this study is focused on the compression, or pileup, region preceding the DF current sheet. We find that the earthward acceleration of the plasma in this region is in general agreement with a recent DF force balance model. A gyrophase bunched reflected ion population at the leading edge of the pileup region is reflected by a normal electric field in the pileup region itself, rather than through an interaction with the current sheet. We discuss plasma wave activity at the leading edge of the pileup region that may be driven by gradients, or by reflected ions, or both; the mode has not been identified. The waves oscillate near but above the ion cyclotron frequency with wavelength several ion inertial lengths. We show that the waves oscillate primarily in the perpendicular magnetic field components, do not propagate along the background magnetic field, are right handed elliptically (close to circularly) polarized, exist in a region of high electron and ion beta, and are stationary in the plasma frame moving earthward. We discuss the possibility that the waves are present in plasma sheet data, but have not, thus far, been discovered.

  9. Calculation of the second virial coefficient for dipolar and quadrupolar polyatomic gases

    Energy Technology Data Exchange (ETDEWEB)

    Burns, H.A.

    1976-01-01

    The classical statistical mechanical development of the equation of state for polyatomic gases is reviewed and a historical background of work of interest to the present study is given. Equations for the second virial coefficient for dipolar and quadrupolar gases are derived from an assumed model of interaction. The model consists of two rigid cores interacting via a soft potential which is a sum of valence repulsion, dispersion and electrostatic interaction potentials and which is parameterized by the shortest distance between the hard cores. This parameterization is accomplished by expanding the electrostatic potential about multipole centers which ''float'' on the surfaces of the hard cores, and by assuming the valence repulsion and dispersion potentials to be of a Kihara type. Model parameters for this potential are given for CO, N/sub 2/O, HCl, propyne, SO/sub 2/, H/sub 2/O, H/sub 2/S, fluorobenzene, pyridine, CH/sub 3/F, CH/sub 3/Cl, CF/sub 3/Cl, CCl/sub 3/H, CCl/sub 3/F and CO/sub 2/. A comparison of the present work is made to that of several other investigators. (auth)

  10. Characterization of magnetically oriented phospholipid micelles for measurement of dipolar couplings in macromolecules

    Energy Technology Data Exchange (ETDEWEB)

    Ottiger, Marcel; Bax, Ad [National Institutes of Health, Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases (United States)

    1998-10-15

    Weak alignment of solute molecules with the magnetic field can be achieved in a dilute liquid crystalline medium, consisting of an aqueous mixture of dimyristoyl-phosphatidylcholine (DMPC) and dihexanoyl-phosphatidylcholine (DHPC). For a certain range of molar ratios, DMPC and DHPC can form large, disc-shaped particles, commonly referred to as bicelles (Sanders and Schwonek, 1992), which cooperatively align in the magnetic field and induce a small degree of alignment on asymmetrically shaped solute molecules. As a result, dipolar couplings between pairs of {sup 1}H, {sup 13}C or {sup 15}N nuclei are no longer averaged to zero by rotational diffusion and they can be readily measured, providing valuable structural information. The stability of these liquid crystals and the degree of alignment of the solute molecules depend strongly on experimental variables such as the DMPC:DHPC ratio and concentration, the preparation protocol of the DMPC/DHPC mixtures, as well as salt, temperature, and pH. The lower temperature limit for which the liquid crystalline phase is stable can be reduced to 20 deg. C by using a ternary mixture of DHPC, DMPC, and 1-myristoyl-2-myristoleoyl-sn-glycero-3-phosphocholine, or a binary mixture of DHPC and ditridecanoyl-phosphatidylcholine. These issues are discussed, with an emphasis on the use of the medium for obtaining weak alignment of biological macromolecules.

  11. Characterization of magnetically oriented phospholipid micelles for measurement of dipolar couplings in macromolecules.

    Science.gov (United States)

    Ottiger, M; Bax, A

    1998-10-01

    Weak alignment of solute molecules with the magnetic field can be achieved in a dilute liquid crystalline medium, consisting of an aqueous mixture of dimyristoyl-phosphatidylcholine (DMPC) and dihexanoyl-phosphatidylcholine (DHPC). For a certain range of molar ratios, DMPC and DHPC can form large, disc-shaped particles, commonly referred to as bicelles (Sanders and Schwonek, 1992), which cooperatively align in the magnetic field and induce a small degree of alignment on asymmetrically shaped solute molecules. As a result, dipolar couplings between pairs of 1H, 13C or 15N nuclei are no longer averaged to zero by rotational diffusion and they can be readily measured, providing valuable structural information. The stability of these liquid crystals and the degree of alignment of the solute molecules depend strongly on experimental variables such as the DMPC:DHPC ratio and concentration, the preparation protocol of the DMPC/DHPC mixtures, as well as salt, temperature, and pH. The lower temperature limit for which the liquid crystalline phase is stable can be reduced to 20 degrees C by using a ternary mixture of DHPC, DMPC, and 1-myristoyl-2-myristoleoyl-sn-glycero-3-phosphocholine, or a binary mixture of DHPC and ditridecanoyl-phosphatidylcholine. These issues are discussed, with an emphasis on the use of the medium for obtaining weak alignment of biological macromolecules.

  12. Van der Waals versus dipolar forces controlling mesoscopic organizations of magnetic nanocrystals.

    Science.gov (United States)

    Lalatonne, Y; Richardi, J; Pileni, M P

    2004-02-01

    The structure, thermodynamics and dynamics in many physical and chemical systems are determined by interplay of short-range isotropic and long-range anisotropic forces. Magnetic nanoparticles dispersed in solution are ideal model systems to study this interplay, as they are subjected to both isotropic van der Waals and anisotropic dipolar forces. Here we show from experiment an abrupt transition of maghemite nanocrystal organization from chain-like to random structures when nanoparticle solutions are evaporated under a magnetic field. This is explained by brownian dynamics simulations in terms of a variation of the strength of van der Waals interactions with the particle contact distance, which is tuned by the length of the molecules coating the particles. The weak dipole-dipole interactions between the maghemite particles are usually not sufficient to result in the chain formation observed here. However, due to the van der Waals interactions, when the nanocrystal contact distance is short enough, clusters of nanocrystals are formed during the evaporation process. These clusters exhibit large dipole moments compared with a single particle, which explains the formation of chain-like structures. Conversely, when the nanocrystal contact distance is too long, no nanocrystal aggregation occurs, and a random distribution of maghemite nanocrystals is obtained.

  13. Backbone Solution Structures of Proteins Using Residual Dipolar Couplings: Application to a Novel Structural Genomics Target

    Science.gov (United States)

    Valafar, H.; Mayer, K. L.; Bougault, C. M.; LeBlond, P. D.; Jenney, F. E.; Brereton, P. S.; Adams, M.W.W.; Prestegard, J.H.

    2006-01-01

    Structural genomics (or proteomics) activities are critically dependent on the availability of high-throughput structure determination methodology. Development of such methodology has been a particular challenge for NMR based structure determination because of the demands for isotopic labeling of proteins and the requirements for very long data acquisition times. We present here a methodology that gains efficiency from a focus on determination of backbone structures of proteins as opposed to full structures with all side chains in place. This focus is appropriate given the presumption that many protein structures in the future will be built using computational methods that start from representative fold family structures and replace as many as 70% of the side chains in the course of structure determination. The methodology we present is based primarily on residual dipolar couplings (RDCs), readily accessible NMR observables that constrain the orientation of backbone fragments irrespective of separation in space. A new software tool is described for the assembly of backbone fragments under RDC constraints and an application to a structural genomics target is presented. The target is an 8.7 kDa protein from Pyrococcus furiosus, PF1061, that was previously not well annotated, and had a nearest structurally characterized neighbor with only 33% sequence identity. The structure produced shows structural similarity to this sequence homologue, but also shows similarity to other proteins that suggests a functional role in sulfur transfer. Given the backbone structure and a possible functional link this should be an ideal target for development of modeling methods. PMID:15704012

  14. Cluster-cluster aggregation of Ising dipolar particles under thermal noise

    KAUST Repository

    Suzuki, Masaru

    2009-08-14

    The cluster-cluster aggregation processes of Ising dipolar particles under thermal noise are investigated in the dilute condition. As the temperature increases, changes in the typical structures of clusters are observed from chainlike (D1) to crystalline (D2) through fractal structures (D1.45), where D is the fractal dimension. By calculating the bending energy of the chainlike structure, it is found that the transition temperature is associated with the energy gap between the chainlike and crystalline configurations. The aggregation dynamics changes from being dominated by attraction to diffusion involving changes in the dynamic exponent z=0.2 to 0.5. In the region of temperature where the fractal clusters grow, different growth rates are observed between charged and neutral clusters. Using the Smoluchowski equation with a twofold kernel, this hetero-aggregation process is found to result from two types of dynamics: the diffusive motion of neutral clusters and the weak attractive motion between charged clusters. The fact that changes in structures and dynamics take place at the same time suggests that transitions in the structure of clusters involve marked changes in the dynamics of the aggregation processes. © 2009 The American Physical Society.

  15. Protein Structure Validation and Identification from Unassigned Residual Dipolar Coupling Data Using 2D-PDPA

    Science.gov (United States)

    Fahim, Arjang; Mukhopadhyay, Rishi; Yandle, Ryan; Prestegard, James H.; Valafar, Homayoun

    2014-01-01

    More than 90% of protein structures submitted to the PDB each year are homologous to some previously characterized protein structure. The extensive resources that are required for structural characterization of proteins can be justified for the 10% of the novel structures, but not for the remaining 90%. This report presents the 2D-PDPA method, which utilizes unassigned residual dipolar coupling in order to address the economics of structure determination of routine proteins by reducing the data acquisition and processing time. 2D-PDPA has been demonstrated to successfully identify the correct structure of an array of proteins that range from 46 to 445 residues in size from a library of 619 decoy structures by using unassigned simulated RDC data. When using experimental data, 2D-PDPA successfully identified the correct NMR structures from the same library of decoy structures. In addition, the most homologous X-ray structure was also identified as the second best structural candidate. Finally, success of 2D-PDPA in identifying and evaluating the most appropriate structure from a set of computationally predicted structures in the case of a previously uncharacterized protein Pf2048.1 has been demonstrated. This protein exhibits less than 20% sequence identity to any protein with known structure and therefore presents a compelling and practical application of our proposed work. PMID:23973992

  16. Persistence of the flat band in a kagome magnet with dipolar interactions

    Science.gov (United States)

    Maksymenko, Mykola; Moessner, Roderich; Shtengel, Kirill

    2017-10-01

    The weathervane modes of the classical Heisenberg antiferromagnet on the kagome lattice constitute possibly the earliest and certainly the most celebrated example of a flat band of zero-energy excitations. Such modes arise from the underconstraint that has since become a defining criterion of strong geometrical frustration. We investigate the fate of this flat band when dipolar interactions are added. These change the nearest-neighbor model fundamentally as they remove the Heisenberg spin-rotational symmetry while also introducing a long-range component to the interaction. We explain how the modes continue to remain approximately dispersionless, while being lifted to finite energy as well as being squeezed: they change their ellipticity described by the ratio of the amplitudes of the canonically conjugate variables comprising them. This phenomenon provides interesting connections between concepts such as constraint counting and self-screening underpinning the field of frustrated magnetism. Moreover, this property is found to be remarkably stable to a wide range of additional interactions.

  17. Dipolarization fronts as Earthward Propagating Flux Ropes: A Three-dimensional Global Hybrid Simulation

    Science.gov (United States)

    Lu, Q.; Lu, S.; Lin, Y.; Wang, X.

    2016-12-01

    Dipolarization fronts (DFs) as earthward propagating flux ropes (FRs) in the Earth's magnetotailare presented and investigated with a three-dimensional (3-D) global hybrid simulation for the first time. In thesimulation, several small-scale earthward propagating FRs are found to be formed by multiple X line reconnectionin the near tail. During their earthward propagation, the magnetic field Bz of the FRs becomes highly asymmetricdue to the imbalance of the reconnection rates between the multiple X lines. At the later stage, when the FRsapproach the near-Earth dipole-like region, the antireconnection between the southward/negative Bz ofthe FRs and the northward geomagnetic field leads to the erosion of the southward magnetic flux of theFRs, which further aggravates the Bz asymmetry. Eventually, the FRs merge into the near-Earth regionthrough the antireconnection. These earthward propagating FRs can fully reproduce the observationalfeatures of the DFs, e.g., a sharp enhancement of Bz preceded by a smaller amplitude Bz dip, an earthwardflow enhancement, the presence of the electric field components in the normal and dawn-dusk directions,and ion energization. Our results show that the earthward propagating FRs can be used to explain the DFsobserved in the magnetotail. The thickness of the DFs is on the order of several ion inertial lengths, and theelectric field normal to the front is found to be dominated by the Hall physics. During the earthward propagationfrom the near-tail to the near-Earth region, the speed of the FR/DFs increases from 150km/s to 1000 km/s. TheFR/DFs can be tilted in the GSM (x, y) plane with respect to the y (dawn-dusk) axis and only extend several Earthradii in this direction. Moreover, the structure and evolution of the FRs/DFs are nonuniform in the dawn-duskdirection, which indicates that the DFs are essentially 3-D.

  18. Occurrence rate of dipolarization fronts in the plasma sheet: Cluster observations

    Directory of Open Access Journals (Sweden)

    S. Xiao

    2017-08-01

    Full Text Available We investigate the occurrence rate of dipolarization fronts (DFs in the plasma sheet by taking full advantage of all four Cluster satellites (C1–4 from years 2001 to 2009. In total, we select 466 joint-observation DF events, in which 318, 282, 254, and 236 DFs are observed by C1, C2, C3, and C4, respectively. Our findings are as follows: (1 the maximum occurrence rate is ∼ 15.3 events per day at X ∼ 15 RE in the XY plane, and the average occurrence rate is ∼ 5.4 events per day over the whole observation period; (2 the occurrence rate on the dusk side of the plasma sheet is larger and decreases with increasing BXY∕BLobe; (3 the occurrence rate within |Y|  <  6 RE increases gradually from X ≈ −19 to −15 RE and then decreases from X ≈ −15 to −10 RE; (4 the occurrence rate when AE > 200 nT is much larger than that when AE < 200 nT, indicating that DFs preferentially occur during high geomagnetic activity. The magnetic pileup and earthward and duskward ion flows could contribute to the increases in the occurrence rate from X ≈ −19 to −15 RE. We suggest that both geomagnetic activity and multiple DFs contribute to the high occurrence rate of the DFs. In addition, the finite length of the DF in the dawn–dusk direction can affect the chance that a satellite observes the DF.

  19. A Tailward Moving Current Sheet Normal Magnetic Field Front Followed by an Earthward Moving Dipolarization Front

    Science.gov (United States)

    Hwang, K.-J.; Goldstein, M. L.; Moore, T. E.; Walsh, B. M.; Baishev, D. G.; Moiseyev, A. V.; Shevtsov, B. M.; Yumoto, K.

    2014-01-01

    A case study is presented using measurements from the Cluster spacecraft and ground-based magnetometers that show a substorm onset propagating from the inner to outer plasma sheet. On 3 October 2005, Cluster, traversing an ion-scale current sheet at the near-Earth plasma sheet, detected a sudden enhancement of Bz, which was immediately followed by a series of flux rope structures. Both the local Bz enhancement and flux ropes propagated tailward. Approximately 5 min later, another Bz enhancement, followed by a large density decrease, was observed to rapidly propagate earthward. Between the two Bz enhancements, a significant removal of magnetic flux occurred, possibly resulting from the tailward moving Bz enhancement and flux ropes. In our scenario, this flux removal caused the magnetotail to be globally stretched so that the thinnest sheet formed tailward of Cluster. The thinned current sheet facilitated magnetic reconnection that quickly evolved from plasma sheet to lobe and generated the later earthward moving dipolarization front (DF) followed by a reduction in density and entropy. Ground magnetograms located near the meridian of Cluster's magnetic foot points show two-step bay enhancements. The positive bay associated with the first Bz enhancement indicates that the substorm onset signatures propagated from the inner to the outer plasma sheet, consistent with the Cluster observation. The more intense bay features associated with the later DF are consistent with the earthward motion of the front. The event suggests that current disruption signatures that originated in the near-Earth current sheet propagated tailward, triggering or facilitating midtail reconnection, thereby preconditioning the magnetosphere for a later strong substorm enhancement.

  20. Experimental quantification of decoherence via the Loschmidt echo in a many spin system with scaled dipolar Hamiltonians

    Energy Technology Data Exchange (ETDEWEB)

    Buljubasich, Lisandro; Dente, Axel D.; Levstein, Patricia R.; Chattah, Ana K.; Pastawski, Horacio M. [Instituto de Física Enrique Gaviola (IFEG-CONICET), Córdoba 5000 (Argentina); Facultad de Matemática, Astronomía y Física, Universidad Nacional de Córdoba, Ciudad Universitaria, Córdoba 5000 (Argentina); Sánchez, Claudia M. [Facultad de Matemática, Astronomía y Física, Universidad Nacional de Córdoba, Ciudad Universitaria, Córdoba 5000 (Argentina)

    2015-10-28

    We performed Loschmidt echo nuclear magnetic resonance experiments to study decoherence under a scaled dipolar Hamiltonian by means of a symmetrical time-reversal pulse sequence denominated Proportionally Refocused Loschmidt (PRL) echo. The many-spin system represented by the protons in polycrystalline adamantane evolves through two steps of evolution characterized by the secular part of the dipolar Hamiltonian, scaled down with a factor |k| and opposite signs. The scaling factor can be varied continuously from 0 to 1/2, giving access to a range of complexity in the dynamics. The experimental results for the Loschmidt echoes showed a spreading of the decay rates that correlate directly to the scaling factors |k|, giving evidence that the decoherence is partially governed by the coherent dynamics. The average Hamiltonian theory was applied to give an insight into the spin dynamics during the pulse sequence. The calculations were performed for every single radio frequency block in contrast to the most widely used form. The first order of the average Hamiltonian numerically computed for an 8-spin system showed decay rates that progressively decrease as the secular dipolar Hamiltonian becomes weaker. Notably, the first order Hamiltonian term neglected by conventional calculations yielded an explanation for the ordering of the experimental decoherence rates. However, there is a strong overall decoherence observed in the experiments which is not reflected by the theoretical results. The fact that the non-inverted terms do not account for this effect is a challenging topic. A number of experiments to further explore the relation of the complete Hamiltonian with this dominant decoherence rate are proposed.

  1. Nuclear magnetic relaxation by the dipolar EMOR mechanism: General theory with applications to two-spin systems.

    Science.gov (United States)

    Chang, Zhiwei; Halle, Bertil

    2016-02-28

    In aqueous systems with immobilized macromolecules, including biological tissue, the longitudinal spin relaxation of water protons is primarily induced by exchange-mediated orientational randomization (EMOR) of intra- and intermolecular magnetic dipole-dipole couplings. We have embarked on a systematic program to develop, from the stochastic Liouville equation, a general and rigorous theory that can describe relaxation by the dipolar EMOR mechanism over the full range of exchange rates, dipole coupling strengths, and Larmor frequencies. Here, we present a general theoretical framework applicable to spin systems of arbitrary size with symmetric or asymmetric exchange. So far, the dipolar EMOR theory is only available for a two-spin system with symmetric exchange. Asymmetric exchange, when the spin system is fragmented by the exchange, introduces new and unexpected phenomena. Notably, the anisotropic dipole couplings of non-exchanging spins break the axial symmetry in spin Liouville space, thereby opening up new relaxation channels in the locally anisotropic sites, including longitudinal-transverse cross relaxation. Such cross-mode relaxation operates only at low fields; at higher fields it becomes nonsecular, leading to an unusual inverted relaxation dispersion that splits the extreme-narrowing regime into two sub-regimes. The general dipolar EMOR theory is illustrated here by a detailed analysis of the asymmetric two-spin case, for which we present relaxation dispersion profiles over a wide range of conditions as well as analytical results for integral relaxation rates and time-dependent spin modes in the zero-field and motional-narrowing regimes. The general theoretical framework presented here will enable a quantitative analysis of frequency-dependent water-proton longitudinal relaxation in model systems with immobilized macromolecules and, ultimately, will provide a rigorous link between relaxation-based magnetic resonance image contrast and molecular parameters.

  2. Quantum effects in the capture of charged particles by dipolar polarizable symmetric top molecules. I. General axially nonadiabatic channel treatment.

    Science.gov (United States)

    Auzinsh, M; Dashevskaya, E I; Litvin, I; Nikitin, E E; Troe, J

    2013-08-28

    The rate coefficients for capture of charged particles by dipolar polarizable symmetric top molecules in the quantum collision regime are calculated within an axially nonadiabatic channel approach. It uses the adiabatic approximation with respect to rotational transitions of the target within first-order charge-dipole interaction and takes into account the gyroscopic effect that decouples the intrinsic angular momentum from the collision axis. The results are valid for a wide range of collision energies (from single-wave capture to the classical limit) and dipole moments (from the Vogt-Wannier and fly-wheel to the adiabatic channel limit).

  3. Thermal Entanglement of Two Qubits with Dipolar Ordered Initial State Coupled to a Spin Chain in MQ NMR System

    Science.gov (United States)

    Eskandari, M. R.; Rezaee, Ladan

    2012-12-01

    In this paper, we aim to provide a theoretical study of thermal entanglement of two qubits coupled to a spin chain with considering multiple-spin correlations which accompanies decay in multiple quantum nuclear magnetic resonance (MQ NMR) system. We show an explicit connection between the coherence factor and entanglement, and numerically and analytically study the dynamical process of entanglement in weak coupling cases for dipolar ordered initial states. We provide results that the entanglement evolution depends not only on the coupling constant between central two qubits and the system-environment couplings but also on temperature and the number of spins in chain.

  4. Radiation from charged particles on eccentric orbits in a dipolar magnetic field around a Schwarzschild black hole

    CERN Document Server

    Papadopoulos, Demetrios B; Kokkotas, Kostas D; Stergioulas, Nikolaos

    2015-01-01

    We obtain an approximate solution for the motion of a charged particle around a Schwarzschild black hole immersed in a weak dipolar magnetic field. We focus on eccentric bound orbits in the equatorial plane of the Schwarzschild black hole and derive an analytic expression for the spectral distribution of the electromagnetic emission from a charged particle on such an orbit. Two sets of harmonic contributions appear, with specific frequency spacing. The expression can be written in compact form, if it is truncated up to the lowest order harmonic contributions.

  5. Generation of electromagnetic ion cyclotron waves in the near-Earth magnetotail during dipolarization: two-dimensional global hybrid simulation

    Science.gov (United States)

    Guo, Zhifang; Wu, Mingyu; Du, Amin

    2017-04-01

    We employ two-dimensional global hybrid simulations to study the generation, propagation and polarization of electromagnetic ion cyclotron (EMIC) waves in the near-Earth magnetotail during dipolarization. In our simulation, EMIC waves with left-hand polarized signals originate in the low-latitude magnetotail as a result of the ion temperature anisotropy which is due to ion heating by Alfvén waves. Subsequently, EMIC waves can propagate along the ambient magnetic field toward high-latitudes. Our work provides one possible mechanism for the generation of EMIC waves observed in the near-Earth magnetotail.

  6. New Chiral Bis-Dipolar 6,6'-Disubstituted-Binaphthol Derivatives for Second-Order Nonlinear Optics

    DEFF Research Database (Denmark)

    Deussen, Heinz-Josef; Boutton, Carlo; Thorup, Niels

    1998-01-01

    two equal donor-acceptor (D-A) systems linked together to give a bis(dipolar) V-shaped system. The dihedral angle a between the two connected D-A sys tems has been controlled by chemical methods; this leads to distinct changes in the optical spectra of the connected D-A chromophores, primarily changes......-Perry powder test to evaluate the second-order nonlinear optical (NLO) properties of polycrystalline samples. Although chirality ensures noncentrosymmetric crystals, only modest (approximate to 2-methyl-4-nitroaniline) or no nonlinearities were observed in the powder test, For a representative selection...

  7. Near?Earth injection of MeV electrons associated with intense dipolarization electric fields: Van Allen Probes observations

    OpenAIRE

    Dai, Lei; Wang, Chi; Duan, Suping; He, Zhaohai; Wygant, John R.; Cattell, Cynthia A.; Tao, Xin; Su, Zhenpeng; Kletzing, Craig; Baker, Daniel N.; Li, Xinlin; Malaspina, David; Blake, J. Bernard; Fennell, Joseph; Claudepierre, Seth

    2015-01-01

    Abstract Substorms generally inject tens to hundreds of keV electrons, but intense substorm electric fields have been shown to inject MeV electrons as well. An intriguing question is whether such MeVelectron injections can populate the outer radiation belt. Here we present observations of a substorm injection of MeV electrons into the inner magnetosphere. In the premidnight sector at L ? 5.5, Van Allen Probes (Radiation Belt Storm Probes)?A observed a large dipolarization electric field (50?m...

  8. Magnetic dipolar coupling and collective effects for binary information codification in cost-effective logic devices

    Energy Technology Data Exchange (ETDEWEB)

    Chiolerio, Alessandro, E-mail: alessandro.chiolerio@iit.it [Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, IT-10129 Torino (Italy); Center for Space Human Robotics, Istituto Italiano di Tecnologia, Corso Trento 21, IT-10129 Torino (Italy); Allia, Paolo [Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, IT-10129 Torino (Italy); Graziano, Mariagrazia [Electronic and Telecommunication Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, IT-10129 Torino (Italy)

    2012-09-15

    Physical limitations foreshadow the eventual end to traditional Complementary Metal Oxide Semiconductor (CMOS) scaling. Therefore, interest has turned to various materials and technologies aimed to succeed to traditional CMOS. Magnetic Quantum dot Cellular Automata (MQCA) are one of these technologies. Working MQCA arrays require very complex techniques and an excellent control on the geometry of the nanomagnets and on the quality of the magnetic thin film, thus limiting the possibility for MQCA of representing a definite solution to cost-effective, high density and low power consumption device demand. Counter-intuitively, moving towards bigger sizes and lighter technologies it is still possible to develop multi-state logic devices, as we demonstrated, whose main advantage is cost-effectiveness. Applications may be seen in low cost logic devices where integration and computational power are not the main issue, eventually using flexible substrates and taking advantage of the intrinsic mechanical toughness of systems where long range interactions do not need wirings. We realized cobalt micrometric MQCA arrays by means of Electron Beam Lithography, exploiting cost-effective processes such as lift-off and RF sputtering that usually are avoided due to their low control on array geometry and film roughness. Information relative to the magnetic configuration of MQCA elements including their eventual magnetic interactions was obtained from Magnetic Force Microscope (MFM) images, enhanced by means of a numerical procedure and presented in differential maps. We report the existence of bi-stable magnetic patterns, as detected by MFM while sampling the z-component of magnetic induction field, arising from dipolar inter-element magnetostatic coupling, able to store and propagate binary information. This is achieved despite the array quality and element magnetic state, which are low and multi-domain, respectively. We discuss in detail shape, inter-element spacing and dot profile

  9. Extensive electron transport and energization via multiple, localized dipolarizing flux bundles

    Science.gov (United States)

    Gabrielse, Christine; Angelopoulos, Vassilis; Harris, Camilla; Artemyev, Anton; Kepko, Larry; Runov, Andrei

    2017-05-01

    Using an analytical model of multiple dipolarizing flux bundles (DFBs) embedded in earthward traveling bursty bulk flows, we demonstrate how equatorially mirroring electrons can travel long distances and gain hundreds of keV from betatron acceleration. The model parameters are constrained by four Time History of Events and Macroscale Interactions during Substorms satellite observations, putting limits on the DFBs' speed, location, and magnetic and electric field magnitudes. We find that the sharp, localized peaks in magnetic field have such strong spatial gradients that energetic electrons ∇B drift in closed paths around the peaks as those peaks travel earthward. This is understood in terms of the third adiabatic invariant, which remains constant when the field changes on timescales longer than the electron's drift timescale: An energetic electron encircles a sharp peak in magnetic field in a closed path subtending an area of approximately constant flux. As the flux bundle magnetic field increases the electron's drift path area shrinks and the electron is prevented from escaping to the ambient plasma sheet, while it continues to gain energy via betatron acceleration. When the flux bundles arrive at and merge with the inner magnetosphere, where the background field is strong, the electrons suddenly gain access to previously closed drift paths around the Earth. DFBs are therefore instrumental in transporting and energizing energetic electrons over long distances along the magnetotail, bringing them to the inner magnetosphere and energizing them by hundreds of keV.Plain Language SummaryScientists have wondered how narrow flow channels in space could transport and energize electrons enough before the electrons escape the channel. They also wondered how narrow, localized magnetic field peaks (and their electric fields) contribute to electron energization in comparison to wide, large-scale electromagnetic fields. We show that it is actually because these fields are so

  10. High Temperature and High Energy Density Dipolar GlassPolymers Based on Sulfonyl Poly(2,6-Dimethyl-1,4-Phenylene (Preprint)

    Science.gov (United States)

    2017-12-06

    AFRL-RX-WP-JA-2017-0520 HIGH TEMPERATURE AND HIGH ENERGY DENSITY DIPOLAR GLASSPOLYMERS BASED ON SULFONYL POLY(2,6-DIMETHYL-1,4... ENERGY DENSITY DIPOLAR GLASSPOLYMERS BASED ON SULFONYL POLY(2,6-DIMETHYL-1,4-PHENYLENE (PREPRINT) 5a. CONTRACT NUMBER FA8650-15-D-5405-0002 5b... energy density reached as high as 22 J·cm-3 at the breakdown field. Due to the high Tg, the SO2-PPO25 sample also exhibited low dielectric losses. For

  11. Solid state 13C NMR of unlabeled phosphatidylcholine bilayers: spectral assignments and measurement of carbon-phosphorus dipolar couplings and 13C chemical shift anisotropies.

    Science.gov (United States)

    Sanders, C R

    1993-01-01

    The direct measurement of 13C chemical shift anisotropies (CSA) and 31P-13C dipolar splitting in random dispersions of unlabeled L alpha-phase phosphatidylcholine (PC) has traditionally been difficult because of extreme spectral boradening due to anisotropy. In this study, mixtures of dimyristoyl phosphatidylcholine (DMPC) with three different detergents known to promote the magnetic orientation of DMPC were employed to eliminate the powder-pattern nature of signals without totally averaging out spectral anisotropy. The detergents utilized were CHAPSO, Triton X-100, and dihexanoylphosphatidylcholine (DHPC). Using such mixtures, many of the individual 13C resonances from DMPC were resolved and a number of 13C-31P dipolar couplings were evident. In addition, differing line widths were observed for the components of some dipolar doublets, suggestive of dipolar/chemical shift anisotropy (CSA) relaxation interference effects. Oriented sample resonance assignments were made by varying the CHAPSO or DHPC to DMPC ratio to systematically scale overall bilayer order towards the isotropic limit. In this manner, peaks could be identified based upon extrapolation to their isotropic positions, for which assignments have previously been made (Lee, C.W.B., and R.G. Griffin. 1989. Biophys. J. 55:355-358; Forbes, J., J. Bowers, X. Shan, L. Moran, E. Oldfield, and M.A. Moscarello. 1988. J. Chem. Soc., Faraday, Trans. 1 84:3821-3849). It was observed that the plots of CSA or dipolar coupling versus overall bilayer order obtained from DHPC and CHAPSO titrations were linear. Estimates of the intrinsic dipolar couplings and chemical shift anisotropies for pure DMPC bilayers were made by extrapolating shifts and couplings from the detergent titrations to zero detergent. Both detergent titrations led to similar "intrinsic" CSAs and dipolar couplings. Results extracted from an oriented Triton-DMPC mixture also led to similar estimates for the detergent-free DMPC shifts and couplings. The

  12. Transition from spin-orbit to hyperfine interaction dominated spin relaxation in a cold fluid of dipolar excitons

    Science.gov (United States)

    Finkelstein, Ran; Cohen, Kobi; Jouault, Benoit; West, Ken; Pfeiffer, Loren N.; Vladimirova, Masha; Rapaport, Ronen

    2017-08-01

    We measure the spin-resolved transport of dipolar excitons in a biased GaAs double quantum well structure. From these measurements we extract both spin lifetime and mobility of the excitons. We find that below a temperature of 4.8 K there is a sharp increase in the spin lifetime of the excitons, together with a sharp reduction in their mobility. Below a critical power the spin lifetime increases with increasing mobility and density, while above the critical power the opposite trend is observed. We interpret this transition as evidence of the interplay between two different spin dephasing mechanisms: at low mobility the dephasing is dominated by the hyperfine interaction with the lattice nuclei spins, while at higher mobility the spin-orbit interaction dominates and a Dyakonov-Perel spin relaxation takes over. The excitation power and temperature regime where the hyperfine interaction induced spin dephasing is observed correlates with the regime where a dark dipolar quantum liquid was reported recently on a similar sample.

  13. Diffraction-like phenomena in a periodic magnetization distribution at 1.5 T using the distant dipolar field (DDF).

    Science.gov (United States)

    Kirsch, Stefan; Bachert, Peter

    2007-04-01

    In the CRAZED experiment (COSY revamped by asymmetric Z-gradient echo detection, Warren et al.), a spatially anisotropic magnetization distribution is created by application of a magnetic field gradient (strength G, duration tau) which in turn generates a response called the distant dipolar field (DDF). The DDF is a source of intermolecular multiple-quantum coherences (iMQC) which contain information on the distance d=pi/(gammaGtau) between pairs of dipolar-coupled spins. Diffraction-like phenomena may result for periodically structured samples. In this study, we report the observation of diffraction owing to the DDF at 1.5 T using a clinical whole-body tomograph. Based on the semi-classical treatment of the problem by Robyr and Bowtell, diffraction conditions were obtained for a CRAZED-type pulse sequence that selects iMQC of order N. The predicted distinct difference in N=2 and N not equal2 coherences, i.e., a dominant continuous course as a function of tau (N=2) and prominent diffraction peaks otherwise, could be verified in CRAZED experiments in a periodically structured sample selecting coherence orders N=2 and N=3. The diffractive signal component contains information on the geometric structure of the sample. Applications of this technique may permit the detection of changes in composition and geometry of periodic structures.

  14. Dipolar electrostatic energy effect on relaxation process of monolayers at air-water interface: analysis of thermodynamics and kinetics.

    Science.gov (United States)

    Ou-Yang, Wei; Weis, Martin; Lee, Keanchuan; Manaka, Takaaki; Iwamoto, Mitsumasa

    2009-12-28

    In order to understand the effect of electrostatic energy on phase transition from monolayer to multilayer, isobaric relaxation process of Langmuir monolayers composed of stearic acid or ferroelectric polyvinylidene fluoride and trifluoroethylene copolymer with various vinylidene fluoride (VDF) ratios is investigated in terms of thermodynamic and kinetic analysis. A monotonous decreasing tendency of material loss with respect to temperature is observed for stearic acid monolayer, which is due to thermal activation effect on phase transition from monolayer to multilayer. In contrast, for the ferroelectric monolayer it presents a nonmonotonous behavior of losing materials with a peak position near the Curie temperature, which is not only owing to thermal activation but also dipole moment change. This observation is confirmed for the copolymer monolayers with other VDF content ratios. Amazingly, for the ferroelectric monolayers a good correspondence is found for critical temperatures evaluated from several independent methods including the analysis on slow collapse. This finding again tells the fact that the relaxation process, namely phase transition from monolayer to multilayer, is greatly influenced by dipolar electrostatic energy. Moreover, the study of time dependent relaxation process reveals a diffusionlike behavior of multilayer structure formation, which cannot be interpreted by classical models. Hence a new model based on diffusion-driven material transfer is proposed and diffusivity of the copolymer molecules is estimated with a value of 0.4x10(-5) cm(2)/s. As a whole, this research reflects the importance of dipolar electrostatic energy for phase transition of monolayers at air-water interface.

  15. BaZr.sub.0.5./sub.Ti.sub.0.5./sub.O.sub.3./sub.: Lead-free relaxor ferroelectric or dipolar glass

    Czech Academy of Sciences Publication Activity Database

    Filipič, C.; Kutnjak, Z.; Pirc, R.; Canu, G.; Petzelt, Jan

    2016-01-01

    Roč. 93, č. 22 (2016), 1-7, č. článku 224105. ISSN 2469-9950 Institutional support: RVO:68378271 Keywords : relaxor ferroelectric * dipolar glass * dielectric relaxation * Edwards-Anderson parameter Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.836, year: 2016

  16. Synthesis of isofagomine-pyrrolidine hybrid sugars and analogues of (-)-steviamine and (+)-hyacinthacine C5 using 1,3-dipolar cycloaddition reactions.

    Science.gov (United States)

    Lahiri, Rima; Palanivel, Ashokkumar; Kulkarni, Sudhir A; Vankar, Yashwant D

    2014-11-21

    Highly regioselective 1,3-dipolar cycloadditions between d-arabinose-derived nitrones and d-mannitol-derived trans-olefins have been utilized to synthesize isofagomine-pyrrolidine hybrid sugars, hydroxymethylated analogues of (-)-steviamine and analogues of (+)-hyacinthacine C5. All of the new compounds were subsequently tested against several commercially available glycosidases, and some of them showed good and selective glycosidase inhibition.

  17. Dipolar and chain-linking effects on the rheology of grafted chains in a nanopore under shear at different grafting densities

    DEFF Research Database (Denmark)

    Jensen, Morten Østergaard; Mouritsen, Ole G.; Peters, Günther H.J.

    2001-01-01

    this modification of the interfacial region could specifically control the mechanical properties. By considering two different grafting densities, the effect of dipolar forces across the nanopore with increasing load was addressed. In general, it was found that interfacial viscosities and friction forces increase...

  18. Thiourea-Quaternary Ammonium Salt Catalyzed Asymmetric 1, 3-Dipolar Cycloaddition of Imino Esters To Construct Spiro[pyrrolidin-3,3'-oxindoles].

    Science.gov (United States)

    Zhang, Jia-Xing; Wang, Hong-Yu; Jin, Qiao-Wen; Zheng, Chang-Wu; Zhao, Gang; Shang, Yong-Jia

    2016-10-07

    A highly enantioselective 1,3-dipolar cycloaddition of imino esters with methyleneindolinones has been realized by using readily available thiourea-quaternary ammonium salts as phase-transfer catalysts, enabling efficient construction of a range of chiral spiro[pyrrolidin-3,3'-oxindoles] in good yields with excellent enantioselectivities under mild conditions.

  19. Conformational response of the phosphatidylcholine headgroup to bilayer surface charge: torsion angle constraints from dipolar and quadrupolar couplings in bicelles.

    Science.gov (United States)

    Semchyschyn, Darlene J; Macdonald, Peter M

    2004-02-01

    The effects of bilayer surface charge on the conformation of the phosphocholine group of phosphatidylcholine were investigated using a torsion angle analysis of quadrupolar and dipolar splittings in, respectively, (2)H and (13)C NMR spectra of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) labelled in the phosphocholine group with either deuterons (POPC-alpha-d(2), POPC-beta-d(2) and POPC-gamma-d(9)) or carbon-13 (POPC-alpha-(13)C and POPC-alphabeta-(13)C(2)) and incorporated into magnetically aligned bicelles containing various amounts of either the cationic amphiphile 1,2-dimyristoyl-3-trimethylammoniumpropane (DMTAP) or the anionic amphiphile 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG). Three sets of quadrupolar splittings, one from each of the three deuteron labelling positions, and three sets of dipolar splittings ((13)C(alpha)-(31)P, (13)C(alpha)-(13)C(beta), (13)C(beta)-(14)N), were measured at each surface charge, along with the (31)P residual chemical shift anisotropy. The torsion angle analysis assumed fast anisotropic rotation of POPC about its long molecular axis, thus projecting all NMR interactions onto that director axis of motion. Dipolar, quadrupolar and chemical shift anisotropies were calculated as a function of the phosphocholine internal torsion angles by first transforming into a common reference frame affixed to the phosphocholine group prior to motional averaging about the director axis. A comparison of experiment and calculation provided the two order parameters specifying the director orientation relative to the molecule, plus the torsion angles alpha(3), alpha(4) and alpha(5). Surface charge was found to have little effect on the torsion angle alpha(5) (rotations about C(alpha)-C(beta)), but to have large and inverse effects on torsion angles alpha(3) [rotations about P-O(11)] and alpha(4) [rotations about O(11)-C(alpha)], yielding a net upwards tilt of the P-N vector in the presence of cationic surface charge, and a

  20. Molecular-Based Fluorescent Nanoparticles Built from Dedicated Dipolar Thienothiophene Dyes as Ultra-Bright Green to NIR Nanoemitters

    Directory of Open Access Journals (Sweden)

    Cristiano Mastrodonato

    2016-09-01

    Full Text Available Fluorescent Organic Nanoparticles (FONs, prepared by self-aggregation of dedicated dyes in water, represent a promising green alternative to the toxic quantum dots (QDs for bioimaging purposes. In the present paper, we describe the synthesis and photophysical properties of new dipolar push-pull derivatives built from thieno[3,2-b]thiophene as a π-conjugated bridge that connects a triphenylamine moiety bearing various bulky substituents as electron-releasing moiety to acceptor end-groups of increasing strength (i.e., aldehyde, dicyanovinyl and diethylthiobarbiturate. All dyes display fluorescence properties in chloroform, which shifts from the green to the NIR range depending on the molecular polarization (i.e., strength of the end-groups as well as a large two-photon absorption (TPA band response in the biological spectral window (700–1000 nm. The TPA bands show a bathochromic shift and hyperchromic effect with increasing polarization of the dyes with maximum TPA cross-section reaching 2000 GM for small size chromophore. All dyes are found to form stable and deeply colored nanoparticles (20–45 nm in diameter upon nanoprecipitation in water. Although their fluorescence is strongly reduced upon aggregation, all nanoparticles show large one-photon (up to 108 M−1·cm−1 in the visible region and two-photon (up to 106 GM in the NIR brightness. Interestingly, both linear and non-linear optical properties are significantly affected by interchromophoric interactions, which are promoted by the molecular confinement and modulated by both the dipolar strength and the presence of the bulky groups. Finally, we exploited the photophysical properties of the FONs to design optimized core-shell nanoparticles built from a pair of complementary dipolar dyes that promotes an efficient core-to-shell FRET process. The resulting molecular-based core-shell nanoparticles combine large two-photon absorption and enhanced emission both located in the NIR spectral

  1. Dipolar interaction and demagnetizing effects in magnetic nanoparticle dispersions: Introducing the mean-field interacting superparamagnet model

    Science.gov (United States)

    Sánchez, F. H.; Mendoza Zélis, P.; Arciniegas, M. L.; Pasquevich, G. A.; Fernández van Raap, M. B.

    2017-04-01

    Aiming to analyze relevant aspects of interacting magnetic nanoparticle systems (frequently called interacting superparamagnets), a model is built from magnetic dipolar interaction and demagnetizing mean-field concepts. By making reasonable simplifying approximations, a simple and useful expression for effective demagnetizing factors is achieved, which allows the analysis of uniform and nonuniform spatial distributions of nanoparticles, in particular the occurrence of clustering. This expression is a function of demagnetizing factors associated with specimen shape and clusters shape, and of the mean distances between near neighbor nanoparticles and between clusters, relative to the characteristic sizes of each of these two types of objects, respectively. The model explains effects of magnetic dipolar interactions, such as the observation of apparent nanoparticle magnetic moments smaller than real ones and approaching to zero as temperature decreases. It is shown that by performing a minimum set of experimental determinations along principal directions of geometrically well-defined specimens, model application allows retrieval of nanoparticle intrinsic properties, like mean volume, magnetic moment, and susceptibility in the absence of interactions. It also permits the estimation of mean interparticle and intercluster relative distances, as well as mean values of demagnetizing factors associated with clusters shape. An expression for average magnetic dipolar energy per nanoparticle is also derived, which is a function of specimen effective demagnetizing factor and magnetization. Experimental test of the model was performed by analysis of results reported in the literature and of original results reported here. The first case corresponds to oleic-acid-coated 8-nm magnetite particles dispersed in PEGDA-600 polymer, and the second one to polyacrilic-acid-coated 13-nm magnetite particles dispersed in PVA solutions from which ferrogels were later produced by a physical

  2. Acousto-exciton interaction in a gas of 2D indirect dipolar excitons in the presence of disorder

    Energy Technology Data Exchange (ETDEWEB)

    Kovalev, V. M.; Chaplik, A. V., E-mail: chaplik@isp.nsc.ru [Russian Academy of Sciences, Rzhanov Institute of Semiconductor Physics, Siberian Branch (Russian Federation)

    2016-03-15

    A theory for the linear and quadratic responses of a 2D gas of indirect dipolar excitons to an external surface acoustic wave perturbation in the presence of a static random potential is considered. The theory is constructed both for high temperatures, definitely greater than the exciton gas condensation temperature, and at zero temperature by taking into account the Bose–Einstein condensation effects. The particle Green functions, the density–density correlation function, and the quadratic response function are calculated by the “cross” diagram technique. The results obtained are used to calculate the absorption of Rayleigh surface waves and the acoustic exciton gas drag by a Rayleigh wave. The damping of Bogoliubov excitations in an exciton condensate due to theirs scattering by a random potential has also been determined.

  3. Polarimetry-based analysis of dipolar transitions of single colloidal CdSe/CdS dot-in-rods

    CERN Document Server

    Lethiec, Clotilde; Carbone, Luigi; Bramati, Alberto; Coolen, Laurent; Maître, Agnès

    2014-01-01

    We prove experimentally, upon polarization analysis performed on a large statistic of single nanoemitters, that high quality core/shell CdSe/CdS dot-in-rods behave as linear dipoles. Moreover, the dipole in-plane and out-of-plane orientations could be assessed. We demonstrate in particular that, contrary to expectations, the emitting dipole is not aligned with the elongated axis of the dot-in-rod. Besides, the polarimetric measurements prove that the excitation transition cannot be approximated by a single linear dipole, contrary to the emission transition. Finally, we highlight that non-radiative channels of charge carrier recombination do not affect the dipolar nature of the radiative transitions.

  4. Theoretical analysis of the sensitivity of dipolar field signal to local field variations by perturbative expansion of the magnetization

    Science.gov (United States)

    Wong, Chung Ki

    2010-03-01

    A perturbation method based on the integral form of the Bloch equation is used to calculate the distant dipolar field (DDF) signal formed by the correlation spectroscopy revamped by asymmetric z-gradient echo detection (CRAZED) sequence in the presence of a susceptibility-induced field. The properties of the DDF signal are analyzed through the series expansion of the magnetization, and the first order DDF result is applied to study the use of the DDF effect to probe sub-voxel field distributions. Numerical calculations are carried out with the sub-voxel field distributions modeled by rectangular tubes of uniform frequency shifts (the block model) and cylinders of a finite susceptibility difference (the blood vessel model) using the parameters for brain at 9.4 T. The DDF signal is found to exhibit features arising from the sub-voxel structures.

  5. Stark Effects on Rigid-Rotor Wavefunctions: A Quantum Description of Dipolar Rotors Trapped in Electric Fields

    Science.gov (United States)

    Henderson, Giles; Logsdon, Brad

    1995-11-01

    Chemists have had few opportunities to study the effects of molecular orientations on reactions. At ordinary temperatures, it is impractical to orient gas phase molecules with electric fields because their rotational kinetic energies are large compared to the interaction energy of molecular dipoles with accessible laboratory fields. This study uses a variational matrix method and computer graphics to illustrate how orientational probability of molecules cooled by supersonic expansions are dramatically influenced by electric fields. These calculations reveal how free rotor wavefunctions evolve into harmonic oscillator type functions as dipolar molecules become trapped by the laboratory field as Stark pendulum oscillators. A supplement to this article that includes computer animated descriptions of the molecular motions described here are available at JCE Internet.

  6. Bicelle-based liquid crystals for NMR-measurement of dipolar couplings at acidic and basic pH values

    Energy Technology Data Exchange (ETDEWEB)

    Ottiger, Marcel; Bax, Ad [National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Laboratory of Chemical Physics (United States)

    1999-02-15

    It is demonstrated that mixtures of ditetradecyl- phosphatidylcholine or didodecyl-phoshatidylcholine and dihexyl- phosphatidylcholine in water form lyotropic liquid crystalline phases under similar conditions as previously reported for bicelles consisting of dimyristoyl-phosphatidylcholine (DMPC) and dihexanoyl- phosphatidylcholine (DHPC). The carboxy-ester bonds present in DMPC and DHPC are replaced by ether linkages in their alkyl analogs, which prevents acid- or base-catalyzed hydrolysis of these compounds. 15N-1H dipolar couplings measured for ubiquitin over the 2.3-10.4pH range indicate that this protein retains a backbone conformation which is very similar to its structure at pH 6.5 over this entire range.

  7. Probing mutation-induced structural perturbations by refinement against residual dipolar couplings: application to the U4 spliceosomal RNP complex.

    Science.gov (United States)

    Kirkpatrick, John P; Li, Ping; Carlomagno, Teresa

    2009-04-17

    Confident interpretation of biochemical experiments performed with mutated proteins relies on verification of the integrity of the mutant structures. We present a simple and rapid refinement protocol for comparing the structures of mutated and wild-type proteins. Our approach involves measurement of residual dipolar couplings, and only requires assignment of the backbone resonances of the mutant species. We demonstrate application of the protocol to a mutant of the 15.5K protein, a core component of the U4 spliceosomal ribonucleoprotein (RNP) complex. Confirmation of the unperturbed structure of the mutated protein prompted re-examination of a previous mutagenesis study and indicated that the interpretation of mutant binding affinities in terms of direct interfacial contacts should be applied with caution.

  8. Stretched Gelatin Phantom for Detection of Residual Dipolar Couplings in MR Spectra and Data Analysis of Carnosine

    Directory of Open Access Journals (Sweden)

    Karel Bernášek

    2016-01-01

    Full Text Available Peak splitting due to the residual dipolar coupling (RDC represents a potentially applicable spectral parameter for diagnostic purposes. Several of the skeletal muscle metabolites were previously reported to display the RDC splitting in in vivo MR spectra. We constructed an in vitro model consisting of mechanically stretched gelatin cylinder soaked with the muscle metabolite carnosine. We describe the preparation procedure of an upscaled 50 mL stretched gelatin sample with carnosine that can be used as a phantom for setting-up and testing of spectroscopic measurements of RDC in a MR scanner. We also report on analysis of the RDC splittings in 1H and 13C high resolution MR spectra of carnosine.

  9. Compiled data set of exact NOE distance limits, residual dipolar couplings and scalar couplings for the protein GB3

    Directory of Open Access Journals (Sweden)

    Beat Vögeli

    2015-12-01

    Full Text Available We compiled an NMR data set consisting of exact nuclear Overhauser enhancement (eNOE distance limits, residual dipolar couplings (RDCs and scalar (J couplings for GB3, which forms one of the largest and most diverse data set for structural characterization of a protein to date. All data have small experimental errors, which are carefully estimated. We use the data in the research article Vogeli et al., 2015, Complementarity and congruence between exact NOEs and traditional NMR probes for spatial decoding of protein dynamics, J. Struct. Biol., 191, 3, 306–317, doi:10.1016/j.jsb.2015.07.008 [1] for cross-validation in multiple-state structural ensemble calculation. We advocate this set to be an ideal test case for molecular dynamics simulations and structure calculations.

  10. Temperature- and pressure-dependent infrared spectroscopy of 1-butyl-3-methylimidazolium trifluoromethanesulfonate: A dipolar coupling theory analysis.

    Science.gov (United States)

    Burba, Christopher M; Chang, Hai-Chou

    2018-03-15

    Continued growth and development of ionic liquids requires a thorough understanding of how cation and anion molecular structure defines the liquid structure of the materials as well as the various properties that make them technologically useful. Infrared spectroscopy is frequently used to assess molecular-level interactions among the cations and anions of ionic liquids because the intramolecular vibrational modes of the ions are sensitive to the local potential energy environments in which they reside. Thus, different interaction modes among the ions may lead to different spectroscopic signatures in the vibrational spectra. Charge organization present in ionic liquids, such as 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C 4 mim]CF 3 SO 3 ), is frequently modeled in terms of a quasicrystalline structure. Highly structured quasilattices enable the dynamic coupling of vibrationally-induced dipole moments to produce optical dispersion and transverse optical-longitudinal optical (TO-LO) splitting of vibrational modes of the ionic liquid. According to dipolar coupling theory, the degree of TO-LO splitting is predicted to have a linear dependence on the number density of the ionic liquid. Both temperature and pressure will affect the number density of the ionic liquid and, therefore, the amount of TO-LO splitting for this mode. Therefore, we test these relationships through temperature- and pressure-dependent FT-IR spectroscopic studies of [C 4 mim]CF 3 SO 3 , focusing on the totally symmetric SO stretching mode for the anion, ν s (SO 3 ). Increased temperature decreases the amount of TO-LO splitting for ν s (SO 3 ), whereas elevated pressure is found to increase the amount of band splitting. In both cases, the experimental observations follow the general predictions of dipolar coupling theory, thereby supporting the quasilattice model for this ionic liquid. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Bounce-averaged Fokker-Planck diffusion equation in non-dipolar magnetic fields with applications to the Dungey magnetosphere

    Directory of Open Access Journals (Sweden)

    B. Ni

    2012-04-01

    Full Text Available We perform a detailed derivation of the bounce-averaged relativistic Fokker-Planck diffusion equation applicable to arbitrary magnetic field at a constant Roederer L. The form of the bounce-averaged diffusion equation is found regardless of details of the mirror geometry, suggesting that the numerical schemes developed for solving the modified two-dimensional (2-D Fokker-Planck equation in a magnetic dipole should be feasible for similar computation efforts on modeling wave-induced particle diffusion processes in any non-dipolar magnetic field. However, bounce period related terms and bounce-averaged diffusion coefficients are required to be computed in realistic magnetic fields. With the application to the Dungey magnetosphere that is controlled by the intensity of southward interplanetary magnetic field (IMF, we show that with enhanced southward IMF the normalized bounce period related term decreases accordingly, and bounce-averaged diffusion coefficients cover a broader range of electron energy and equatorial pitch angle with a tendency of increased magnitude and peaking at lower energies. The compression of the Dungey magnetosphere can generally produce scattering loss of plasma sheet electrons ~100 keV on a timescale shorter than that in a dipolar field, and induce momentum diffusion at high pitch angles closer to 90°. Correspondingly, the strong diffusion rate drops considerably as a product of changes in both the equatorial loss cone and the bounce period. The extent of differences in all the parameters introduced by the southward IMF intensification also becomes larger for a field line with higher equatorial crossing. With the derived general formulism of bounce-averaged diffusion equation for arbitrary 2-D magnetic field, our results confirm the need for the adoption of realistic magnetic fields to perform accurate determination of electron resonant scattering rates and precise multi-dimensional diffusion simulations of magnetospheric

  12. Theoretical Studies of Observable Transitions to Recoupled Pair Bonded States of Sulfur Halide Compounds: SF/SCl (X^2{Π}{→}A^2{Σ}^-), SF_2/SCl_2 (X^1A_1{→}1^1B_1, X^1A_1{→}1^1A_2), and SFCl (X^1A'{→}A^1A{'{'}})

    Science.gov (United States)

    Leiding, Jeff; Woon, David E.; Dunning, Thom H.; , Jr.

    2011-06-01

    In previous studies regarding the nature of hypervalent behavior, we identified low-lying excited states of SF(a^4{Σ}^-), SCl(a^4{Σ}^-), SF_2(a^3B_1,b^3A_2), SFCl(a^3A{'{'}}) and SCl_2(a^3B_1) that involve recoupled pair bonding (rpb), where the electrons of the S 3p^2 pair are made available to form bonds. While the transitions from the ground states to the quartet states of SF/SCl and the triplet states of SF_2/SFCl/SCl_2 are spin-forbidden, each of these excited states have analogs with formally spin- and dipole-allowed transitions (except ^1A_2). We performed high level MRCI+Q/aug-cc-pV(Q+d)Z calculations in order to characterize the electronic spectra, spectroscopic constants, and bonding of these species, and made comparisons to available experimental data. We found that excitation into the experimentally known and dipole-forbidden singlet rpb state, SCl_2(B^1A_2), can explain the well-known photodissociation behavior of SCl_2 used to produce SCl(X^2{Π}) radicals in the laboratory. Finally, we have also found a possible system of bond-stretch isomers on the SFCl(A^1A{'{'}}) potential energy surface that is analogous to the behavior on the triplet surface reported in our previous study. Howe, J. D.; Ashfold, M. N. R.; Morgan, R. A.;Western, C. M.; Buma, W. J.; Milan, J. B. and de Lang, C. A. J. Chem. Soc. Faraday Trans. 1995, 91, 773. Leiding, J.; Woon, D. E., and Dunning, T. H., Jr. J. Phys. Chem. A 2011, 115, 329.

  13. Characterization and modeling of multi-dipolar microwave plasmas: application to multi-dipolar plasma assisted sputtering; Caracterisation et modelisation des plasmas micro-onde multi-dipolaires: application a la pulverisation assistee par plasma multi-dipolaire

    Energy Technology Data Exchange (ETDEWEB)

    Tran, T.V

    2006-12-15

    The scaling up of plasma processes in the low pressure range remains a question to be solved for their rise at the industrial level. One solution is the uniform distribution of elementary plasma sources where the plasma is produced via electron cyclotron resonance (ECR) coupling. These elementary plasma sources are made up of a cylindrical permanent magnet (magnetic dipole) set at the end of a coaxial microwave line. Although of simple concept, the optimisation of these dipolar plasma sources is in fact a complex problem. It requires the knowledge, on one hand, of the configurations of static magnetic fields and microwave electric fields, and, on the other hand, of the mechanisms of plasma production in the region of high intensity magnetic field (ECR condition), and of plasma diffusion. Therefore, the experimental characterisation of the operating ranges and plasma parameters has been performed by Langmuir probes and optical emission spectroscopy on different configurations of dipolar sources. At the same time, in a first analytical approach, calculations have been made on simple magnetic field configurations, motion and trajectory of electrons in these magnetic fields, and the acceleration of electrons by ECR coupling. Then, the results have been used for the validation of the numerical modelling of the electron trajectories by using a hybrid PIC (particle-in-cell) / MC (Monte Carlo) method. The experimental study has evidenced large operating domains, between 15 and 200 W of microwave power, and from 0.5 to 15 mtorr argon pressure. The analysis of plasma parameters has shown that the region of ECR coupling is localised near the equatorial plane of the magnet and dependent on magnet geometry. These characterizations, applied to a cylindrical reactor using 48 sources, have shown that densities between 10{sup 11} and 10{sup 12} cm{sup -3} could be achieved in the central part of the volume at a few mtorr argon pressures. The modelling of electron trajectories near

  14. Copper-catalyzed Huisgen 1,3-dipolar cycloaddition under oxidative conditions: polymer-assisted assembly of 4-acyl-1-substituted-1,2,3-triazoles.

    Science.gov (United States)

    Diz, Paula M; Coelho, Alberto; El Maatougui, Abdelaziz; Azuaje, Jhonny; Caamaño, Olga; Gil, Álvaro; Sotelo, Eddy

    2013-07-05

    We herein document the first example of a reliable copper-catalyzed Huisgen 1,3-dipolar cycloaddition under oxidative conditions. The combined use of two polymer-supported reagents (polystyrene-1,5,7-triazabicyclo[4,4,0]dec-5-ene/Cu and polystyrene-2-iodoxybenzamide) overcomes the thermodynamic instability of copper(I) species toward oxidation, enabling the reliable Cu-catalyzed Huisgen 1,3-dipolar cycloadditions in the presence of an oxidant agent. This polymer-assisted pathway, not feasible under conventional homogeneous conditions, provides a direct assembly of 4-acyl-1-substituted-1,2,3-triazoles, contributing to expand the reliability and scope of Cu(I)-catalyzed alkyne-azide cycloaddition.

  15. Interlayer exchange coupling, dipolar coupling and magnetoresistance in Fe/MgO/Fe trilayers with a subnanometer MgO barrier

    Energy Technology Data Exchange (ETDEWEB)

    Kozioł-Rachwał, A. [AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, al. Mickiewicza 30, 30-059 Kraków (Poland); National Institute of Advanced Industrial Science and Technology, Spintronics Research Center, Tsukuba, Ibaraki 305-8568 (Japan); Skowroński, W.; Frankowski, M. [AGH University of Science and Technology, Department of Electronics, al. Mickiewicza 30, 30-059 Kraków (Poland); Chęciński, J. [AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, al. Mickiewicza 30, 30-059 Kraków (Poland); AGH University of Science and Technology, Department of Electronics, al. Mickiewicza 30, 30-059 Kraków (Poland); Ziętek, S.; Rzeszut, P. [AGH University of Science and Technology, Department of Electronics, al. Mickiewicza 30, 30-059 Kraków (Poland); Ślęzak, M.; Matlak, K.; Ślęzak, T. [AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, al. Mickiewicza 30, 30-059 Kraków (Poland); Stobiecki, T. [AGH University of Science and Technology, Department of Electronics, al. Mickiewicza 30, 30-059 Kraków (Poland); Korecki, J. [AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, al. Mickiewicza 30, 30-059 Kraków (Poland); Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek 8, 30-239 Kraków (Poland)

    2017-02-15

    Fe/MgO/Fe trilayers with a subnanometer MgO tunnel barrier were grown by molecular beam epitaxy. Longitudinal magnetooptic Kerr effect measurements confirmed the existence of the antiferromagnetic interlayer exchange coupling (IEC) between the Fe layers for 2 Ådipolar coupling that appeared after the nanofabrication process modified the effective coupling between layers, and we determined dependence of the dipolar coupling on the pillar diameter. Finally, magnetoresistance (MR) was measured as a function of MgO thickness (d{sub MgO}), and a non-zero MR was found for the MgO as thin as 3.4 Å. Extrapolation of the MR (d{sub MgO}) dependence to MR=0 allowed us to determine the length of the pinholes in our sample, which was estimated to be (3.2±0.5) Å. - Highlights: • Strong antiferromagnetic (AFM) interlayer exchange coupling (IEC) between Fe layers in Fe/MgO/Fe. • After nanofabrication the effective AFM IEC is enhanced due to the dipolar coupling. • The dipolar coupling that appeared after the nanofabrication process modified the effective coupling between layers. • Non-zero magnetoresistance values registered for the Fe/MgO/Fe trilayers with the MgO spacers as thin as 3.4 Å.

  16. Direct oxidation of Δ2-isoxazolines synthesis by metal ion-mediated diastereoface-selective 1,3-dipolar cycloaddition with “activated” DMSO

    OpenAIRE

    Naoufel Ben Hamadi; Moncef Msaddek

    2017-01-01

    A series of 4-hydroxyl-Δ2-isoxazol-6(6aH)-one derivatives was prepared by magnesium ion-mediated diastereoface-selective 1,3-dipolar cycloaddition of aromatic nitrile oxides with pyrrolidinone derivatives. The reaction of 4-hydroxyl-Δ2-isoxazol-6(6aH)-one derivatives with dimethylsulfoxide and oxalyl chloride under Swern conditions led to a Δ2-isoxazole-4,6(5H,6aH)-dione.

  17. Direct oxidation of Δ2-isoxazolines synthesis by metal ion-mediated diastereoface-selective 1,3-dipolar cycloaddition with “activated” DMSO

    Directory of Open Access Journals (Sweden)

    Naoufel Ben Hamadi

    2017-02-01

    Full Text Available A series of 4-hydroxyl-Δ2-isoxazol-6(6aH-one derivatives was prepared by magnesium ion-mediated diastereoface-selective 1,3-dipolar cycloaddition of aromatic nitrile oxides with pyrrolidinone derivatives. The reaction of 4-hydroxyl-Δ2-isoxazol-6(6aH-one derivatives with dimethylsulfoxide and oxalyl chloride under Swern conditions led to a Δ2-isoxazole-4,6(5H,6aH-dione.

  18. ESTUDIO DE LA COOPERATIVIDAD ELECTRONICA EN CROMOFOROS DIPOLARES CONSTITUIDOS POR GRUPOS ORGANOMETALICOS ACEPTORES Y DADORES CONECTADOS POR UN COMPLEJO BASE DE SCHIFF.

    OpenAIRE

    TRUJILLO MANDIOLA, ALEXANDER

    2008-01-01

    El presente trabajo de tesis doctoral tuvo como objetivo el diseño y síntesis de cromóforos dipolares trinucleares del tipo A-it-D, donde los grupos aceptor A. [Cp*Ru(areno)]. y dador D. [CpFe( 5 -CH4 )-], (Cp* = i 5 -05 (CH3 ) 5y Cp = 5 -05 H5) se encuen 142p.

  19. (1)H-(31)P CPVC NMR method under Very Fast Magic Angle Spinning for analysis of dipolar interactions and dynamics processes in the crystalline phosphonium tetrafluoroborate salts.

    Science.gov (United States)

    Paluch, Piotr; Trébosc, Julien; Amoureux, Jean-Paul; Potrzebowski, Marek J

    2017-06-01

    We present an NMR methodology which can be used to study the dynamical processes occurring in organophosphorus compounds that belong to the group of the organic ionic plastic crystals (OIPCs). As model samples we employed two phosphonium tetrafluoroborate salts; (t-Bu)3PH(+)BF4(-) (1) and (Me)3PH(+)BF4(-) (2). Both samples possess in their structures direct H-P bonds, and both undergo complex thermal processes in the solid state, forming below the melting point three or four phases, respectively. (1)H-(31)P CPVC (Cross-Polarization Variable Contact) measurements were performed under Very Fast Magic Angle Spinning with speed equal to 50 or 60 kHz, in order (i) to establish the hydrogen-phosphorus dipolar couplings, and (ii) to correlate the dipolar splitting values with molecular motions of the cation. Our project is divided into three sections. In the first part we present DSC studies of (1) and (2), to verify whether these samples fulfill the requirements that define them as OIPC. The second part is dedicated to a discussion of the theoretical aspects of (1)H-(31)P CPVC and especially an analysis of the influence of different parameters, e.g. CSA31P, H-H mismatch, rf-inhomogeneity, dipolar truncation, and the type of dynamics through the motionally averaged asymmetry value on the NMR response. The third part shows experimental (1)H-(31)P CPVC data and applicability of these measurements to study H-P distances and dynamics. The complex molecular motion for sample (2), including rotation and diffusion, versus temperature is then postulated on the bases of the changes of H-P dipolar splitting. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Synthesis of novel isatin-type 5'-(4-Alkyl/Aryl-1H-1,2,3-triazoles) via 1,3-dipolar cycloaddition reactions

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Bianca N. M.; Silva, Barbara V.; Pinto, Angelo C., E-mail: biancanascimento@iq.ufrj.br [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica; Silva, Fernando C.; Gonzaga, Daniel T. G.; Ferreira, Vitor F. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Instituto de Quimica

    2013-02-15

    Isatin and 1H-1,2,3-triazoles are two classes of compounds with great prominence in organic synthesis and medicinal chemistry as they are heterocycle nuclei with a high reactivity allowing to obtain several compounds with important biological properties. Herein, the synthesis of novel 5'-(4-alquil/aril-1H-1,2,3-triazole)-isatin via reaction of 1,3-dipolar cycloaddition catalyzed by acetic acid is reported. (author)

  1. A theoretical study on the reaction pathways and the mechanism of 1,3- dipolar cycloaddition of vinyl acetylene and methyl azide.

    Science.gov (United States)

    Siadati, Seyyed Amir; Mahboobifar, Ali; Nasiri, Ramin

    2014-01-01

    1,3-dipolar cycloaddition procedure is one of the most widely practiced methods in order to synthesize heterocyclic compounds. Although, it seems very simple, but, there are numerous precursors of heterocyclic molecules who have more than one positions to react with a 1,3-dipole species. As a result, while using a precursor with more than one position for reaction, it is probable to synthesize several products with different structures. This paper studies all possible interactions of vinyl acetylene, which has two positions for reaction, with methyl azide. This reaction could lead to the emergence of any 1,3-dipolar cycloaddition products. Our ultimate goal is to help researchers to find out how precursors containing both carbon-carbon double, and the triple bonds interact with 1,3- dipolar species. The present study used the DFT calculations at B3LYP/6-311++G(3df,pd) level to check all probable interactions between vinyl acetylene and methyl azide, and determined Potential Energy Surface, and optimized all species.

  2. Relaxation dynamics of a driven two-level system coupled to a Bose–Einstein condensate: application to quantum dot-dipolar exciton gas hybrid systems

    Science.gov (United States)

    Kovalev, Vadim M.; Tse, Wang-Kong

    2017-11-01

    We develop a microscopic theory for the relaxation dynamics of an optically pumped two-level system (TLS) coupled to a bath of weakly interacting Bose gas. Using Keldysh formalism and diagrammatic perturbation theory, expressions for the relaxation times of the TLS Rabi oscillations are derived when the boson bath is in the normal state and the Bose–Einstein condensate (BEC) state. We apply our general theory to consider an irradiated quantum dot coupled with a boson bath consisting of a two-dimensional dipolar exciton gas. When the bath is in the BEC regime, relaxation of the Rabi oscillations is due to both condensate and non-condensate fractions of the bath bosons for weak TLS-light coupling and pre dominantly due to the non-condensate fraction for strong TLS-light coupling. Our theory also shows that a phase transition of the bath from the normal to the BEC state strongly influences the relaxation rate of the TLS Rabi oscillations. The TLS relaxation rate is approximately independent of the pump field frequency and monotonically dependent on the field strength when the bath is in the low-temperature regime of the normal phase. Phase transition of the dipolar exciton gas leads to a non-monotonic dependence of the TLS relaxation rate on both the pump field frequency and field strength, providing a characteristic signature for the detection of BEC phase transition of the coupled dipolar exciton gas.

  3. On the theory of the proton dipolar-correlation effect as a method for investigation of segmental displacement in polymer melts

    Science.gov (United States)

    Lozovoi, A.; Petrova, L.; Mattea, C.; Stapf, S.; Rössler, E. A.; Fatkullin, N.

    2017-08-01

    A thorough theoretical description of the recently suggested method [A. Lozovoi et al. J. Chem. Phys. 144, 241101 (2016)] based on the proton NMR dipolar-correlation effect allowing for the investigation of segmental diffusion in polymer melts is presented. It is shown that the initial rise of the proton dipolar-correlation build-up function, constructed from Hahn Echo signals measured at times t and t/2, contains additive contributions from both inter- and intramolecular magnetic dipole-dipole interactions. The intermolecular contribution depends on the relative mean-squared displacement of polymer segments from different macromolecules, which provides an opportunity for an experimental study of segmental translational motions at the millisecond range that falls outside the typical range accessible by other methods, i.e., neutron scattering or NMR spin echo with the magnetic field gradients. A comparison with the other two proton NMR methods based on transverse spin relaxation phenomena, i.e., solid echo and double quantum resonance, shows that the initial rise of the build-up functions in all the discussed methods is essentially identical and differs only in numerical coefficients. In addition, it is argued that correlation functions constructed in the same manner as the dipolar-correlation build-up function can be applied for an experimental determination of a mean relaxation rate in the case of systems possessing multi-exponential magnetization decay.

  4. Theoretical studies of the properties of magnetic resonance signal formed under the influence of distant dipolar field

    Science.gov (United States)

    Wong, Chung Ki

    This dissertation studies the properties of nuclear magnetic resonance (NMR) signals of biological samples formed under the influence of distant dipolar field (DDF). The use of DDF effect for magnetic resonance imaging (MRI) has aroused substantial research interests in recent years because of the unique contrast features of DDF signal. The main research activities on this topic are to improve the DDF signal level, and to characterize the use of DDF effect on probing tissue structures and functional MRI in brain studies. Issues of both directions are addressed in this dissertation. After a brief introduction to basic spin dynamics related to MR, the classical Bloch equation with the nonlinear DDF effect incorporated is solved analytically. The mechanism of separating the DDF signal from the whole signal of the sample based on the correlation spectroscopy revamped by asymmetric z-gradient echo detection (CRAZED) is first reviewed. That the sensitivity of the signal to physical parameters such as static magnetic field and transverse relaxation time are examined, and parameters for optimal signal-to-noise and contrast are obtained. The technique of multiple spin-echo acquisition to increase the signal magnitude and time efficiency is analyzed, and optimal conditions are found. Finally the problem of the sensitivity of DDF signal to variations in local magnetic field on a particular length scale is treated using a perturbation method. The results suggest that such sensitivity exists in a simple field distribution.

  5. Quasi-one-dimensional spin-orbit- and Rabi-coupled bright dipolar Bose-Einstein-condensate solitons

    Science.gov (United States)

    Chiquillo, Emerson

    2018-01-01

    We study the formation of stable bright solitons in quasi-one-dimensional (quasi-1D) spin-orbit- (SO-) and Rabi-coupled two pseudospinor dipolar Bose-Einstein condensates (BECs) of 164Dy atoms in the presence of repulsive contact interactions. As a result of the combined attraction-repulsion effect of both interactions and the addition of SO and Rabi couplings, two kinds of ground states in the form of self-trapped bright solitons can be formed, a plane-wave soliton (PWS) and a stripe soliton (SS). These quasi-1D solitons cannot exist in a condensate with purely repulsive contact interactions and SO and Rabi couplings (no dipole). Neglecting the repulsive contact interactions, our findings also show the possibility of creating PWSs and SSs. When the strengths of the two interactions are close to each other, the SS develops an oscillatory instability indicating a possibility of a breather solution, eventually leading to its destruction. We also obtain a phase diagram showing regions where the solution is a PWS or SS.

  6. Collective excitations in liquid dimethyl sulfoxide (DMSO): FIR spectrum, low frequency vibrational density of states, and ultrafast dipolar solvation dynamics

    Science.gov (United States)

    Hazra, Milan K.; Bagchi, Biman

    2017-01-01

    Valuable dynamical and structural information about neat liquid DMSO at ambient conditions can be obtained through a study of low frequency vibrations in the far infrared (FIR), that is, terahertz regime. For DMSO, collective excitations as well as single molecule stretches and bends have been measured by different kinds of experiments such as OHD-RIKES and terahertz spectroscopy. In the present work, we investigate the intermolecular vibrational spectrum of DMSO through three different computational techniques namely (i) the far-infrared spectrum obtained through the Fourier transform of total dipole moment auto-time correlation function, (ii) from the Fourier transform of the translational and angular velocity time autocorrelation functions, and (iii) a quenched normal mode analysis of the parent liquid at 300 K. The three spectra, although exhibit differences among each other, reveal similar features which are in good, semi-quantitative, agreement with experimental results. The study of participation ratio of the density of states obtained from the normal mode analysis shows that the broad spectrum around 100 cm-1 involves collective oscillations of 300-400 molecules. Dipolar solvation dynamics exhibit ultrafast energy relaxation with an initial time constant around 157 fs which can be attributed to the coupling to the collective excitations. We compare the properties of DMSO with those of water vis-a-vis the existence of the low frequency collective modes. Last, we find that the collective excitation spectrum exhibits strong temperature dependence.

  7. Collective excitations in liquid dimethyl sulfoxide (DMSO): FIR spectrum, low frequency vibrational density of states, and ultrafast dipolar solvation dynamics.

    Science.gov (United States)

    Hazra, Milan K; Bagchi, Biman

    2017-01-14

    Valuable dynamical and structural information about neat liquid DMSO at ambient conditions can be obtained through a study of low frequency vibrations in the far infrared (FIR), that is, terahertz regime. For DMSO, collective excitations as well as single molecule stretches and bends have been measured by different kinds of experiments such as OHD-RIKES and terahertz spectroscopy. In the present work, we investigate the intermolecular vibrational spectrum of DMSO through three different computational techniques namely (i) the far-infrared spectrum obtained through the Fourier transform of total dipole moment auto-time correlation function, (ii) from the Fourier transform of the translational and angular velocity time autocorrelation functions, and (iii) a quenched normal mode analysis of the parent liquid at 300 K. The three spectra, although exhibit differences among each other, reveal similar features which are in good, semi-quantitative, agreement with experimental results. The study of participation ratio of the density of states obtained from the normal mode analysis shows that the broad spectrum around 100 cm -1 involves collective oscillations of 300-400 molecules. Dipolar solvation dynamics exhibit ultrafast energy relaxation with an initial time constant around 157 fs which can be attributed to the coupling to the collective excitations. We compare the properties of DMSO with those of water vis-a-vis the existence of the low frequency collective modes. Last, we find that the collective excitation spectrum exhibits strong temperature dependence.

  8. Monovalent Ions and Water Dipoles in Contact with Dipolar Zwitterionic Lipid Headgroups-Theory and MD Simulations

    Science.gov (United States)

    Velikonja, Aljaž; Perutkova, Šarka; Gongadze, Ekaterina; Kramar, Peter; Polak, Andraž; Maček-Lebar, Alenka; Iglič, Aleš

    2013-01-01

    The lipid bilayer is a basic building block of biological membranes and can be pictured as a barrier separating two compartments filled with electrolyte solution. Artificial planar lipid bilayers are therefore commonly used as model systems to study the physical and electrical properties of the cell membranes in contact with electrolyte solution. Among them the glycerol-based polar phospholipids which have dipolar, but electrically neutral head groups, are most frequently used in formation of artificial lipid bilayers. In this work the electrical properties of the lipid layer composed of zwitterionic lipids with non-zero dipole moments are studied theoretically. In the model, the zwitterionic lipid bilayer is assumed to be in contact with aqueous solution of monovalent salt ions. The orientational ordering of water, resulting in spatial variation of permittivity, is explicitly taken into account. It is shown that due to saturation effect in orientational ordering of water dipoles the relative permittivity in the zwitterionic headgroup region is decreased, while the corresponding electric potential becomes strongly negative. Some of the predictions of the presented mean-field theoretical consideration are critically evaluated using the results of molecular dynamics (MD) simulation. PMID:23434651

  9. Monovalent Ions and Water Dipoles in Contact with Dipolar Zwitterionic Lipid Headgroups-Theory and MD Simulations

    Directory of Open Access Journals (Sweden)

    Aljaž Velikonja

    2013-01-01

    Full Text Available The lipid bilayer is a basic building block of biological membranes and can be pictured as a barrier separating two compartments filled with electrolyte solution. Artificial planar lipid bilayers are therefore commonly used as model systems to study the physical and electrical properties of the cell membranes in contact with electrolyte solution. Among them the glycerol-based polar phospholipids which have dipolar, but electrically neutral head groups, are most frequently used in formation of artificial lipid bilayers. In this work the electrical properties of the lipid layer composed of zwitterionic lipids with non-zero dipole moments are studied theoretically. In the model, the zwitterionic lipid bilayer is assumed to be in contact with aqueous solution of monovalent salt ions. The orientational ordering of water, resulting in spatial variation of permittivity, is explicitly taken into account. It is shown that due to saturation effect in orientational ordering of water dipoles the relative permittivity in the zwitterionic headgroup region is decreased, while the corresponding electric potential becomes strongly negative. Some of the predictions of the presented mean-field theoretical consideration are critically evaluated using the results of molecular dynamics (MD simulation.

  10. J-Spectroscopy in the presence of residual dipolar couplings: determination of one-bond coupling constants and scalable resolution

    Energy Technology Data Exchange (ETDEWEB)

    Furrer, Julien [Universitaet Heidelberg, Organisch-Chemisches Institut (Germany); John, Michael; Kessler, Horst; Luy, Burkhard [Technische Universitaet Muenchen, Department Chemie: Organische Chemie II (Germany)], E-mail: Burkhard.Luy@ch.tum.de

    2007-03-15

    The access to weak alignment media has fuelled the development of methods for efficiently and accurately measuring residual dipolar couplings (RDCs) in NMR-spectroscopy. Among the wealth of approaches for determining one-bond scalar and RDC constants only J-modulated and J-evolved techniques retain maximum resolution in the presence of differential relaxation. In this article, a number of J-evolved experiments are examined with respect to the achievable minimum linewidth in the J-dimension, using the peptide PA{sub 4} and the 80-amino-acid-protein Saposin C as model systems. With the JE-N-BIRD{sup d,X}-HSQC experiment, the average full-width at half height could be reduced to approximately 5 Hz for the protein, which allows the additional resolution of otherwise unresolved peaks by the active (J+D)-coupling. Since RDCs generally can be scaled by the choice of alignment medium and alignment strength, the technique introduced here provides an effective resort in cases when chemical shift differences alone are insufficient for discriminating signals. In favorable cases even secondary structure elements can be distinguished.

  11. 1,3-dipolar cyclo addition of benzyl aside to alpha-beta-unsaturated five-membered lactones

    Energy Technology Data Exchange (ETDEWEB)

    Alonso-Perarnau, D.; March, P. de; Figueredo, M.; Font, J. [Departamento de Quimica, Universidad Autonoma de Barcelona, Barcelona (Spain)

    1994-12-31

    The 1,3-dipolar cyclo addition reactions between benzyl azide and the alpha,beta-unsaturated lactones crotonolactone, alpha-methylenebutyrolactone and Beta-angelica lactone have been performed. The best yields of cycloadducts were obtained by working without solvent, at 60 degree centigree in a sealed tube under nitrogen atmosphere. (3aRS,6aSR)-1-Benzyl-3 a, 4,6,6a-tetrahydro-1H-furo[3,4-d]-1,2,3-triazol-4-one and 3-benzyl-7-oxa-1,2,3-triazaspiro[4.4] non-1-en-6-one have been isolated in 36% and 78% yield from the reactions of the two first lactones respectively. The second product is the first example of this heterocyclic system. The reaction with Beta-angelica lactone yielded the primary cycloadducts (3aR,S,6RS,6aSR)-and (3aRS,6SR,6aSR)-1-benzyl-3a,4,6,6a-tetrahydro-6-methyl-1H-furo[3,4-d]-1,1,3-triazol-4-one and the nitrogen elimination product 4-benzylamino-5-methyl 1-2(5H)-furanone in 44%, 11%, and 7% yield respectively. 26 refs.

  12. Detection of Ketones by a Novel Technology: Dipolar Proton Transfer Reaction Mass Spectrometry (DP-PTR-MS).

    Science.gov (United States)

    Pan, Yue; Zhang, Qiangling; Zhou, Wenzhao; Zou, Xue; Wang, Hongmei; Huang, Chaoqun; Shen, Chengyin; Chu, Yannan

    2017-05-01

    Proton transfer reaction mass spectrometry (PTR-MS) has played an important role in the field of real-time monitoring of trace volatile organic compounds (VOCs) due to its advantages such as low limit of detection (LOD) and fast time response. Recently, a new technology of proton extraction reaction mass spectrometry (PER-MS) with negative ions OH- as the reagent ions has also been presented, which can be applied to the detection of VOCs and even inorganic compounds. In this work, we combined the functions of PTR-MS and PER-MS in one instrument, thereby developing a novel technology called dipolar proton transfer reaction mass spectrometry (DP-PTR-MS). The selection of PTR-MS mode and PER-MS mode was achieved in DP-PTR-MS using only water vapor in the ion source and switching the polarity. In this experiment, ketones (denoted by M) were selected as analytes. The ketone (molecular weight denoted by m) was ionized as protonated ketone [M + H]+ [mass-to-charge ratio (m/z) m + 1] in PTR-MS mode and deprotonated ketone [M - H]- (m/z m - 1) in PER-MS mode. By comparing the m/z value of the product ions in the two modes, the molecular weight of the ketone can be positively identified as m. Results showed that whether it is a single ketone sample or a mixed sample of eight kinds of ketones, the molecular weights can be detected with DP-PTR-MS. The newly developed DP-PTR-MS not only maintains the original advantages of PTR-MS and PER-MS in sensitive and rapid detection of ketones, but also can estimate molecular weight of ketones. Graphical Abstract ᅟ.

  13. Detection of Ketones by a Novel Technology: Dipolar Proton Transfer Reaction Mass Spectrometry (DP-PTR-MS)

    Science.gov (United States)

    Pan, Yue; Zhang, Qiangling; Zhou, Wenzhao; Zou, Xue; Wang, Hongmei; Huang, Chaoqun; Shen, Chengyin; Chu, Yannan

    2017-05-01

    Proton transfer reaction mass spectrometry (PTR-MS) has played an important role in the field of real-time monitoring of trace volatile organic compounds (VOCs) due to its advantages such as low limit of detection (LOD) and fast time response. Recently, a new technology of proton extraction reaction mass spectrometry (PER-MS) with negative ions OH- as the reagent ions has also been presented, which can be applied to the detection of VOCs and even inorganic compounds. In this work, we combined the functions of PTR-MS and PER-MS in one instrument, thereby developing a novel technology called dipolar proton transfer reaction mass spectrometry (DP-PTR-MS). The selection of PTR-MS mode and PER-MS mode was achieved in DP-PTR-MS using only water vapor in the ion source and switching the polarity. In this experiment, ketones (denoted by M) were selected as analytes. The ketone (molecular weight denoted by m) was ionized as protonated ketone [M + H]+ [mass-to-charge ratio ( m/z) m + 1] in PTR-MS mode and deprotonated ketone [M - H]- ( m/z m - 1) in PER-MS mode. By comparing the m/z value of the product ions in the two modes, the molecular weight of the ketone can be positively identified as m. Results showed that whether it is a single ketone sample or a mixed sample of eight kinds of ketones, the molecular weights can be detected with DP-PTR-MS. The newly developed DP-PTR-MS not only maintains the original advantages of PTR-MS and PER-MS in sensitive and rapid detection of ketones, but also can estimate molecular weight of ketones.

  14. Critical evaluation of dipolar, acid-base and charge interactions I. Electron displacement within and between molecules, liquids and semiconductors.

    Science.gov (United States)

    Rosenholm, Jarl B

    2017-09-01

    Specific dipolar, acid-base and charge interactions involve electron displacements. For atoms, single bonds and molecules electron displacement is characterized by electronic potential, absolute hardness, electronegativity and electron gap. In addition, dissociation, bonding, atomization, formation, ionization, affinity and lattice enthalpies are required to quantify the electron displacement in solids. Semiconductors are characterized by valence and conduction band energies, electron gaps and average Fermi energies which in turn determine Galvani potentials of the bulk, space charge layer and surface states. Electron displacement due to interaction between (probe) molecules, liquids and solids are characterized by parameters such as Hamaker constant, solubility parameter, exchange energy density, surface tension, work of adhesion and immersion. They are determined from permittivity, refractive index, enthalpy of vaporization, molar volume, surface pressure and contact angle. Moreover, acidic and basic probes may form adducts which are adsorbed on target substrates in order to establish an indirect measure of polarity, acidity, basicity or hydrogen bonding. Acidic acceptor numbers (AN), basic donor numbers (DN), acidic and basic "electrostatic" (E) and "covalent" (C) parameters determined by enthalpy of adduct formation are considered as general acid-base scales. However, the formal grounds for assignments as dispersive, Lifshitz-van der Waals, polar, acid, base and hydrogen bond interactions are inconsistent. Although correlations are found no of the parameters are mutually fully compatible and moreover the enthalpies of acid-base interaction do not correspond to free energies. In this review the foundations of different acid-base parameters relating to electron displacement within and between (probe) molecules, liquids and (semiconducting) solids are thoroughly investigated and their mutual relationships are evaluated. Copyright © 2017 Elsevier B.V. All rights

  15. Evidence of magnetic dipolar interaction in micrometric powders of the Fe{sub 50}Mn{sub 10}Al{sub 40} system: Melted alloys

    Energy Technology Data Exchange (ETDEWEB)

    Perez Alcazar, G.A., E-mail: gpgeperez@gmail.com [Departamento de Fisica, Universidad del Valle, A. A. 25360, Cali (Colombia); Unidad Asociada ICMM-IMA, Apdo. 155, 28230 Las Rozas, Madrid (Spain); Zamora, L.E. [Departamento de Fisica, Universidad del Valle, A. A. 25360, Cali (Colombia); Unidad Asociada ICMM-IMA, Apdo. 155, 28230 Las Rozas, Madrid (Spain); Tabares, J.A.; Piamba, J.F. [Departamento de Fisica, Universidad del Valle, A. A. 25360, Cali (Colombia); Gonzalez, J.M. [Unidad Asociada ICMM-IMA, Apdo. 155, 28230 Las Rozas, Madrid (Spain); Greneche, J.M. [LUNAM, Universite du Maine, Institut des Molecules et Materiaux du Mans, UMR CNRS 6283, 72085 Le Mans Cedex 9 (France); Martinez, A. [Instituto de Magnetismo Aplicado, P.O. Box 155, 28230 Las Rozas (Spain); Romero, J.J. [Instituto de Ceramica y Vidrio, CSIC, C/Kelsen 5, 28049, Madrid (Spain); Marco, J.F. [Instituto de Quimica Fisica Rocasolano, CSIC, C/Serrano 119, 28006 Madrid (Spain)

    2013-02-15

    Powders of melted disordered Fe{sub 50}Mn{sub 10}Al{sub 40} alloy were separated at different mean particle sizes as well as magnetically and structurally characterized. All the samples are BCC and show the same nanostructure. Particles larger than 250 {mu}m showed a lamellar shape compared to smaller particles, which exhibited a more regular form. All the samples are ferromagnetic at room temperature and showed reentrant spin-glass (RSG) and superparamagnetic (SP)-like behaviors between 30 and 60 K and 265 and > 280 K, respectively, as a function of frequency and particle size. The freezing temperature increases with increasing particle size while the blocking one decreases with particle size. The origin of these magnetic phenomena relies in the internal disordered character of samples and the competitive interaction of Fe and Mn atoms. The increase of their critical freezing temperature with increasing mean particle size is due to the increase of the magnetic dipolar interaction between the magnetic moment of each particle with the field produced by the other magnetic moments of their surrounding particles. - Highlights: Black-Right-Pointing-Pointer The effect of particle size in microsized powders of Fe{sub 50}Mn{sub 10}Al{sub 40} melted disordered alloy is studied. Black-Right-Pointing-Pointer Dipolar magnetic interaction between particles exists and this changes with the particle size. Black-Right-Pointing-Pointer For all the particle sizes the reentrant spin- glass and the superparamagnetic-like phases exist. Black-Right-Pointing-Pointer RSG and SP critical temperatures increase with increasing the dipolar magnetic interaction (the mean particle size).

  16. Inverse Dipolar Magnetic Anomaly Over the Volcanic Cone Linked to Reverse Polarity Magnetizations in Lavas and Tuffs - Implications for the Conduit System

    Science.gov (United States)

    Fucugauchi, J. U.; Perez-Cruz, L. L.; Trigo-Huesca, A.

    2012-12-01

    A combined magnetics and paleomagnetic study of Toluquilla monogenetic volcano and associated lavas and tuffs from Valsequillo basin in Central Mexico provides evidence on a magnetic link between lavas, ash tuffs and the underground volcanic conduit system. Paleomagnetic analyses show that lavas and ash tuffs carry reverse polarity magnetizations, which correlate with the inversely polarized dipolar magnetic anomaly over the volcano. The magnetizations in the lava and tuff show similar southward declinations and upward inclinations, supporting petrological inferences that the tuff was emplaced while still hot and indicating a temporal correlation for lava and tuff emplacement. Conduit geometry is one of the important controlling factors in eruptive dynamics of basaltic volcanoes. However volcanic conduits are often not, or only partly, exposed. Modeling of the dipolar anomaly gives a reverse polarity source magnetization associated with a vertical prismatic body with southward declination and upward inclination, which correlates with the reverse polarity magnetizations in the lava and tuff. The study documents a direct correlation of the paleomagnetic records with the underground magmatic conduit system of the monogenetic volcano. Time scale for cooling of the volcanic plumbing system involves a longer period than the one for the tuff and lava, suggesting that magnetization for the source of dipolar anomaly may represent a long time average as compared to the spot readings in the lava and tuff. The reverse polarity magnetizations in lava and tuff and in the underground source body for the magnetic anomaly are interpreted in terms of eruptive activity of Toluquilla volcano at about 1.3 Ma during the Matuyama reverse polarity C1r.2r chron.

  17. Azide-enolate 1,3-dipolar cycloaddition in the synthesis of novel triazole-based miconazole analogues as promising antifungal agents.

    Science.gov (United States)

    González-Calderón, Davir; Mejía-Dionicio, María G; Morales-Reza, Marco A; Ramírez-Villalva, Alejandra; Morales-Rodríguez, Macario; Jauregui-Rodríguez, Bertha; Díaz-Torres, Eduardo; González-Romero, Carlos; Fuentes-Benítes, Aydeé

    2016-04-13

    Seven miconazole analogs involving 1,4,5-tri and 1,5-disubstituted triazole moieties were synthesized by azide-enolate 1,3-dipolar cycloaddition. The antifungal activity of these compounds was evaluated in vitro against four filamentous fungi, including Aspergillus fumigatus, Trichosporon cutaneum, Rhizopus oryzae, and Mucor hiemalis as well as three species of Candida spp. as yeast specimens. These pre-clinical studies suggest that compounds 4b, 4d and 7b can be considered as drug candidates for future complementary biological studies due to their good/excellent antifungal activities. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  18. Investigation of quantitative structure-reactivity relationships in the aliphatic Claisen rearrangement of bis-vinyl ethers reveals a dipolar, dissociative mechanism.

    Science.gov (United States)

    O'Rourke, Natasha F; Wulff, Jeremy E

    2014-02-28

    Kinetic investigations of substituent effects in the thermal rearrangement of bis-vinyl ether substrates are reported. Findings indicate that the influence of the various substituent patterns on the rate of rearrangement in these compounds differs from that documented in the literature for the analogous [3,3]-sigmatropic rearrangement of allyl vinyl ethers. In addition, the thermochemical data collected suggests the existence of a dissociative transition state with significant dipolar character. These findings provide a unique contribution to the already extensive body of literature dedicated to mechanistic investigation of the Claisen rearrangement of aliphatic allyl vinyl ethers.

  19. A novel one-pot green synthesis of dispirooxindolo-pyrrolidines via 1,3-dipolar cycloaddition reactions of azomethine ylides.

    Science.gov (United States)

    Almansour, Abdulrahman I; Arumugam, Natarajan; Kumar, Raju Suresh; Periyasami, Govindasami; A Ghabbour, Hazem; Fun, Hoong-Kun

    2015-01-07

    A facile synthesis of dispirooxindolopyrrolidines has been accomplished via a one-pot three component 1,3-dipolar cycloaddition reaction. The reaction of azomethine ylides generated in situ from L-phenylalanine and substituted isatins with a series of unusual (E)-2-oxoindolino-3-ylidene acetophenone dipolarophiles in the ionic liquid 1-butyl-3-methylimidazolium bromide [bmim]BF4, furnished the cycloadducts in good yields, with the regioisomers 5a-f being obtained with high selectivity. Furthermore, the recyclability of [bmim]BF4, up to five times, was also investigated.

  20. A Novel One-Pot Green Synthesis of Dispirooxindolo-pyrrolidines via 1,3-Dipolar Cycloaddition Reactions of Azomethine Ylides

    Directory of Open Access Journals (Sweden)

    Abdulrahman I. Almansour

    2015-01-01

    Full Text Available A facile synthesis of dispirooxindolopyrrolidines has been accomplished via a one-pot three component 1,3-dipolar cycloaddition reaction. The reaction of azomethine ylides generated in situ from L-phenylalanine and substituted isatins with a series of unusual (E-2-oxoindolino-3-ylidene acetophenone dipolarophiles in the ionic liquid 1-butyl-3-methylimidazolium bromide [bmim]BF4, furnished the cycloadducts in good yields, with the regioisomers 5a–f being obtained with high selectivity. Furthermore, the recyclability of [bmim]BF4, up to five times, was also investigated.

  1. Synthesis of casuarine-related derivatives via 1,3-dipolar cycloaddition between a cyclic nitrone and an unsaturated gamma-lactone.

    Science.gov (United States)

    Stecko, Sebastian; Solecka, Jolanta; Chmielewski, Marek

    2009-01-26

    The 1,3-dipolar cycloaddition of the cyclic nitrone derived from tartaric acid and (S)-5-hydroxymethyl-2(5H)-furanone leads to the single adduct 7 which can be transformed into the 3-epi-1-homo-casuarine via a reaction sequence involving reduction of the lactone moiety and N-O bond hydrogenolysis, followed by intramolecular alkylation of the nitrogen atom. The adduct 7 can also be used in the synthesis of 1-methyl- or 3-methyl analogues of 3-epi-casuarine.

  2. 1,3-Dipolar cycloaddition of a cyclic nitrone derived from 2-deoxy-D-ribose to α,β-unsaturated lactones: An entry to carbapenem antibiotics.

    Science.gov (United States)

    Pieczykolan, Michał; Staszewska-Krajewska, Olga; Furman, Bartłomiej; Chmielewski, Marek

    2016-10-04

    1,3-Dipolar cycloadditions of 2-deoxy-D-ribose-derived L-threo five-membered cyclic nitrone to α,β-unsaturated γ- and δ-lactones were investigated. Cycloadducts obtained from δ-lactones, after NO bond cleavage, opening of the lactone ring, and protection of hydroxyl groups were subjected to β-lactam ring formation by using Mukaiyama's salt. Cycloadducts from γ-lactones subjected to the same reaction sequence undergo β-elimination of a water molecule to provide pyrrolidine-substituted unsaturated γ-lactones. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Mono and dinuclear arene ruthenium(II) triazoles by 1,3-dipolar cycloadditions to a coordinated azide in ruthenium(II) compounds

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Svitlyk, V.; Mozharivskyj, Y.

    reaction of [(η 6 - C 6 Me 6 )Ru(L 2 )Cl] with sodium azide. Notably, as mentioned earlier, a direct reaction of [(η 6 -C 6 Me 6 ) Ru(L 1 )Cl] (1) with NaN 3 in ethanol yielded tetra azido compound of formulation [{(η 6 - C 6 Me 6 )Ru(N 3 )(N 3 )} 2... sodium azide. As a part of our study on arene ruthenium (II) azide compounds, 11 herein, we would like to report, the synthesis of (η 6 -C 6 Me 6 ) ruthenium (II) azido compound 2 and the subsequent 1,3-dipolar cycloaddition reaction of 1 and 2...

  4. Single-ion versus dipolar origin of the magnetic anisotropy in iron(III)-oxo clusters: a case study.

    Science.gov (United States)

    Abbati, G L; Brunel, L C; Casalta, H; Cornia, A; Fabretti, A C; Gatteschi, D; Hassan, A K; Jansen, A G; Maniero, A L; Pardi, L; Paulsen, C; Segre, U

    2001-04-17

    A multitechnique approach has allowed the first experimental determination of single-ion anisotropies in a large iron(III)-oxo cluster, namely [NaFe6(OCH3)12(pmdbm)6ClO4 (1) in which Hpmdbm = 1,3-bis(4-methoxyphenyl)-1,3-propanedione. High-frequency EPR (HF-EPR). bulk susceptibility measurements, and high-field cantilever torque magnetometry (HF-CTM) have been applied to iron-doped samples of an isomorphous hexagallium(III) cluster [NaGa6(OCH3)12-(pmdbm)6]ClO4, whose synthesis and X-ray structure are also presented. HF-EPR at 240 GHz and susceptibility data have shown that the iron(III) ions have a hard-axis type anisotropy with DFe = 0.43(1) cm(-1) and EFe = 0.066(3) cm(-1) in the zero-field splitting (ZFS) Hamiltonian H = DFe[S2(z) - S(S + 1)/3] + Fe[S2(x) - S2(y)]. HF-CTM at 0.4 K has then been used to establish the orientation of the ZFS tensors with respect to the unique molecular axis of the cluster, Z. The hard magnetic axes of the iron(III) ions are found to be almost perpendicular to Z, so that the anisotropic components projected onto Z are negative, DFe(ZZ)= -0.164(4) cm(-1). Due to the dominant antiferromagnetic coupling, a negative DFe(ZZ) value determines a hard-axis molecular anisotropy in 1, as experimentally observed. By adding point-dipolar interactions between iron(III) spins, the calculated ZFS parameter of the triplet state, D1 = 4.70(9) cm(-1), is in excellent agreement with that determined by inelastic neutron scattering experiments at 2 K, D1 = 4.57(2) cm(-1). Iron-doped samples of a structurally related compound, the dimer [Ga2(OCH3)2(dbm)4] (Hdbm = dibenzoylmethane), have also been investigated by HF-EPR at 525 GHz. The single-ion anisotropy is of the hard-axis type as well, but the DFe parameter is significantly larger [DFe = 0.770(3) cm(-1). EFe = 0.090(3) cm(-1)]. We conclude that, although the ZFS tensors depend very unpredictably on the coordination environment of the metal ions, single-ion terms can contribute significantly to the

  5. On the outside looking in: rethinking the molecular mechanism of 1,3-dipolar cycloadditions from the perspective of bonding evolution theory. The reaction between cyclic nitrones and ethyl acrylate

    OpenAIRE

    Abel idrice, ADJIEUFACK; MBOUOMBOUO NDASSA, Ibrahim; Patouossa, I.; Joseph, KETCHA MBADCAM; Safont Villarreal, Vicent Sixte; Oliva, Mónica; Andrés, Juan

    2017-01-01

    In this work we report on the progress that has been made towards gaining an understanding of the molecular mechanism of 1,3-dipolar cycloadditions using the bonding evolution theory (BET). A detailed analysis of the flow of electron density along the reaction pathway of the formal 1,3-dipolar cycloaddition reaction between cyclic nitrones (pyrroline-1-oxide and 2,3,4,5-tetrahydropyridine-1-oxide) and ethyl acrylate, as a case study, allowed the nature of the molecular mechanisms to be charac...

  6. Complex Dipolar Matter

    Science.gov (United States)

    2014-11-10

    grant began in August 2011. The basic timeline of activities over the last three years are as follows. In 2011-2012 I was on sabbatical on a Humboldt...Calculations in this paper came out of my sabbatical in Heidelberg, and in many cases were personally requested by leading researchers, including my host

  7. The Roles of Molecular Structure and Effective Optical Symmetry in Evolving Dipolar Chromophoric Building Blocks to Potent Octopolar NLO Chromophores

    Science.gov (United States)

    Ishizuka, Tomoya; Sinks, Louise E.; Song, Kai; Hung, Sheng-Ting; Nayak, Animesh; Clays, Koen; Therien, Michael J.

    2011-01-01

    A series of mono-, bis-, tris-, and tetrakis-(porphinato)zinc(II) (PZn)-elaborated ruthenium(II) bis(terpyridine) (Ru) complexes has been synthesized in which an ethyne unit connects the macrocycle meso carbon atom to terpyridyl (tpy) 4-, 4′-, and 4″- positions. These supermolecular chromophores, based on the ruthenium(II) [5-(4′-ethynyl-(2,2′;6′,2″-terpyridinyl))-10,20-bis(2′,6′-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2′;6′,2″-terpyridine)2+ bis-hexafluorophosphate (RuPZn) archetype, evince strong mixing of the PZn-based oscillator strength with ruthenium terpyridyl charge resonance bands. Potentiometric and linear absorption spectroscopic data indicate that for structures in which multiple PZn moieties are linked via ethynes to a [Ru(tpy)2]2+ core, little electronic coupling is manifest between PZn units, regardless of whether they are located on the same or opposite tpy ligand. Congruent with these experiments, pump-probe transient absorption studies suggest that the individual RuPZn fragments of these structures exhibit, at best, only modest excited-state electronic interactions that derive from factors other than the dipole-dipole interactions of these strong oscillators; this approximate independent character of the component RuPZn oscillators enables fabrication of NLO multipoles with extraordinary hyperpolarizabilities. Dynamic hyperpolarizability (βλ) values and depolarization ratios (ρ) were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at an incident irradiation wavelength (λinc) of 1300 nm. The depolarization ratio data provide an experimental measure of chromophore optical symmetry; appropriate coupling of multiple charge-transfer oscillators produces structures having enormous averaged hyperpolarizabilities (βHRS values), while evolving the effective chromophore symmetry from purely dipolar (e.g., Ru(tpy)[4-(Znporphyrin)ethynyl-tpy](PF6)2, βHRS = 1280 × 10−30 esu, ρ = 3

  8. A refined model of the chlorosomal antennae of the green bacterium chlorobium tepidum from proton chemical shift constraints obtained with high-field 2-D and 3-D MAS NMR dipolar correlation spectroscopy

    NARCIS (Netherlands)

    Rossum, van B.E.J.; Steengaard, D.B.; Boender, G.J.; Schaffner, K.; Holzwarth, A.R.; Groot, de H.J.M.

    2001-01-01

    Heteronuclear 2-D and 3-D magic-angle spinning NMR dipolar correlation spectroscopy was applied to determine solid-state 1H shifts for aggregated bacteriochlorophyll c (BChl c) in uniformly 13C-enriched light harvesting chlorosomes of the green photosynthetic bacterium Chlorobium tepidum. A complete

  9. Tandem synthesis of novel 4-(azidocarbonylphenylazide from 3-(4-hydrazinocarbonylphenylsydnone and its chemoselective 1,3 dipolar cycloaddition reaction and Curtius rearrangement

    Directory of Open Access Journals (Sweden)

    Prashant R. Latthe

    2011-01-01

    Full Text Available C The 4-(azidocarbonylphenylazide 3 obtained from 4-(hydrazinocarbonyl phenylsydnone 1 by tandem hydrolysis – diazotisation, is used as the key intermediate for the chemoselective one-pot 1,3- dipolar cycloaddition reaction with dimethylacetylene dicarboxylate (DMAD along with Curtius rearrangement affording the carbamates 5a-c and the isocyanate 6. These compounds were further used as building blocks for the triheterocyclic carbamates 9a-c and 10a-c and 4- triazolophenylaryl ureas 7a-f. The ethyl carbamate derivative 5a exhibited antibacterial inhibition selectively against B.subtilis almost one and half times more than Norfloxacin while compounds 5a, 7b and 10c were as active as Griseofulvin against A.flavus

  10. Synthetic scope and DFT analysis of the chiral binap–gold(I complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

    Directory of Open Access Journals (Sweden)

    María Martín-Rodríguez

    2013-11-01

    Full Text Available The 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(Sa-Binap·AuTFA]2. The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described.

  11. Asymmetric synthesis of pyrrolo[2,1-a]isoquinoline derivatives by 1,3-dipolar cycloadditions of stabilized isoquinolinium N-ylides with sulfinyl dipolarophiles.

    Science.gov (United States)

    Ruano, José Luis García; Fraile, Alberto; Martín, M Rosario; González, Gemma; Fajardo, Cristina; Martín-Castro, Ana María

    2011-05-06

    Enantiomerically pure pyrrolo[2,1-a]isoquinoline derivatives are obtained by 1,3-dipolar reactions of isoquinolinium azomethine ylides with enantiopure 3-p-tolylsulfinylacrylonitriles, tert-butyl (2E)-4,4-diethoxy-2-p-tolylsulfinylbut-2-enoate, and 5-ethoxy-3-p-tolylsulfinylfuran-2(5H)-ones. Reactions evolve through the anti conformation of the ylide with complete regioselectivity. The facial selectivity is completely controlled by the configuration of the sulfinyl sulfur for acyclic dipolarophiles, whereas it is high (dr 83/17 or 89/11) but controlled by the C-5 configuration for sulfinylfuranones. Complete endo selectivity is observed with cyclic dipolarophiles and substituted acrylonitriles, but it is low with butenoate. The sulfinyl group also exerts a positive influence on the dipolarophilic reactivity toward these ylides. © 2011 American Chemical Society

  12. Head-to-Tail Zig-Zag Packing of Dipolar Merocyanine Dyes Affords High-Performance Organic Thin-Film Transistors.

    Science.gov (United States)

    Lv, Aifeng; Stolte, Matthias; Würthner, Frank

    2015-09-01

    Attachment of bulky substituents at both thiophene donor (D) and thiazole acceptor (A) heterocycles of a dipolar (μ(g)=10.4 D) D-π-A merocyanine dye affords a more than 1 Å expansion of the common antiparallel supramolecular dimer motif in the solid state, enabling very close π-contacts (3.36 Å) to two other neighbor molecules on each of the two remaining π-faces. This unusual packing motif leads to three-dimensional percolation pathways for hole transport and affords thin-film transistors with mobility up to 0.64 cm(2)  V(-1)  s(-1). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Micelle-induced curvature in a water-insoluble HIV-1 Env peptide revealed by NMR dipolar coupling measurement in stretched polyacrylamide gel.

    Science.gov (United States)

    Chou, James J; Kaufman, Joshua D; Stahl, Stephen J; Wingfield, Paul T; Bax, Ad

    2002-03-20

    The structure of a water-insoluble fragment encompassing residues 282-304 of the HIV envelope protein gp41 is studied when solubilized by dihexanoyl phosphatidylcholine (DHPC) and by small bicelles, consisting of a 4:1 molar ratio of DHPC and dimyristoyl phosphatidylcholine (DMPC). Weak alignment with the magnetic field was accomplished in a stretched polyacrylamide gel, permitting measurement of one-bond (1)H-(15)N, (13)Ca-(13)C', and (13)C'-(15)N dipolar couplings, which formed the basis for determining the peptide structure. In both detergent systems, the peptide adopts an alpha-helical conformation from residue 4 through 18. In the presence of the DHPC micelles the helix is strongly curved towards the hydrophobic surface, whereas in the presence of bicelles a much weaker curvature in the opposite direction is observed.

  14. An encodable lanthanide binding tag with reduced size and flexibility for measuring residual dipolar couplings and pseudocontact shifts in large proteins

    Science.gov (United States)

    Barb, Adam W.; Subedi, Ganesh P.

    2016-01-01

    Metal ions serve important roles in structural biology applications from long-range perturbations seen in magnetic resonance experiments to electron-dense signatures in x-ray crystallography data; however, the metal ion must be secured in a molecular framework to achieve the maximum benefit. Polypeptide-based lanthanide-binding tags (LBTs) represent one option that can be directly encoded within a recombinant protein expression construct. However, LBTs often exhibit significant mobility relative to the target molecule. Here we report the characterization of improved LBTs sequences for insertion into a protein loop. These LBTs were inserted to connect two parallel alpha helices of an immunoglobulin G (IgG)-binding Z domain platform. Variants A and B bound Tb3+ with high affinity (0.70 and 0.13 µM, respectively) and displayed restricted LBT motion. Compared to the parent construct, the metal-bound A experienced a 2.5-fold reduction in tag motion as measured by magnetic field-induced residual dipolar couplings and was further studied in a 72.2 kDa complex with the human IgG1 fragment crystallizable (IgG1 Fc) glycoprotein. The appearance of both pseudo-contact shifts (-0.221 to 0.081 ppm) and residual dipolar couplings (-7.6 to 14.3 Hz) of IgG1 Fc resonances in the IgG1 Fc:(variant A:Tb3+)2 complex indicated structural restriction of the LBT with respect to the Fc. These studies highlight the applicability of improved LBT sequences with reduced mobility to probe the structure of macromolecular systems. PMID:26728077

  15. An encodable lanthanide binding tag with reduced size and flexibility for measuring residual dipolar couplings and pseudocontact shifts in large proteins

    Energy Technology Data Exchange (ETDEWEB)

    Barb, Adam W., E-mail: abarb@iastate.edu; Subedi, Ganesh P. [Iowa State University, Roy J. Carver Department of Biochemistry, Biophysics and Molecular Biology (United States)

    2016-01-15

    Metal ions serve important roles in structural biology applications from long-range perturbations seen in magnetic resonance experiments to electron-dense signatures in X-ray crystallography data; however, the metal ion must be secured in a molecular framework to achieve the maximum benefit. Polypeptide-based lanthanide-binding tags (LBTs) represent one option that can be directly encoded within a recombinant protein expression construct. However, LBTs often exhibit significant mobility relative to the target molecule. Here we report the characterization of improved LBTs sequences for insertion into a protein loop. These LBTs were inserted to connect two parallel alpha helices of an immunoglobulin G (IgG)-binding Z domain platform. Variants A and B bound Tb{sup 3+} with high affinity (0.70 and 0.13 μM, respectively) and displayed restricted LBT motion. Compared to the parent construct, the metal-bound A experienced a 2.5-fold reduction in tag motion as measured by magnetic field-induced residual dipolar couplings and was further studied in a 72.2 kDa complex with the human IgG1 fragment crystallizable (IgG1 Fc) glycoprotein. The appearance of both pseudo-contact shifts (−0.221 to 0.081 ppm) and residual dipolar couplings (−7.6 to 14.3 Hz) of IgG1 Fc resonances in the IgG1 Fc:(variant A:Tb{sup 3+}){sub 2} complex indicated structural restriction of the LBT with respect to the Fc. These studies highlight the applicability of improved LBT sequences with reduced mobility to probe the structure of macromolecular systems.

  16. Exchange bias properties of 140 nm-sized dipolarly interacting circular dots with ultrafine IrMn and NiFe layers

    Energy Technology Data Exchange (ETDEWEB)

    Spizzo, F., E-mail: spizzo@fe.infn.it [Dipartimento di Fisica e Scienze della Terra and CNISM, Università di Ferrara, I-44122 Ferrara (Italy); Tamisari, M. [Dipartimento di Fisica e Scienze della Terra and CNISM, Università di Ferrara, I-44122 Ferrara (Italy); Dipartimento di Fisica e Geologia and CNISM, Università di Perugia, I-06123 Perugia (Italy); Chinni, F.; Bonfiglioli, E. [Dipartimento di Fisica e Scienze della Terra and CNISM, Università di Ferrara, I-44122 Ferrara (Italy); Gerardino, A. [Istituto di Fotonica e Nanotecnologie, CNR, I-00156 Roma (Italy); Barucca, G. [Dipartimento SIMAU, Università Politecnica delle Marche, I-60131 Ancona (Italy); Bisero, D.; Fin, S.; Del Bianco, L. [Dipartimento di Fisica e Scienze della Terra and CNISM, Università di Ferrara, I-44122 Ferrara (Italy)

    2016-02-15

    We studied the exchange bias effect in an array of IrMn(3 nm)/NiFe(3 nm) circular dots (size ~140 nm and center-to-center distance ~200 nm, as revealed by microscopy analyses), prepared on a large area (3×3 mm{sup 2}) by electron beam lithography and lift-off, using dc sputtering deposition. Hysteresis loops were measured by SQUID magnetometer at increasing values of temperature T (in the 5–300 K range) after cooling from 300 K down to 5 K in zero field (ZFC mode) and in a saturating magnetic field (FC mode). The exchange bias effect disappears above T~200 K and, at each temperature, the exchange field H{sub EX} measured in ZFC is substantially lower than the FC one. Micromagnetic calculations indicate that, at room temperature, each dot is in high-remanence ground state, but magnetic dipolar interactions establish a low-remanence configuration of the array as a whole. Hence, at low temperature, following the ZFC procedure, the exchange anisotropy in the dot array is averaged out, tending to zero. However, even the FC values of H{sub EX} and of the coercivity H{sub C} are definitely smaller compared to those measured in a reference continuous film with the same stack configuration (at T=5 K, H{sub EX}~90 Oe and H{sub C}~180 Oe in the dots and H{sub EX}~1270 Oe and H{sub C}~860 Oe in the film). Our explanation is based on the proven glassy magnetic nature of the ultrathin IrMn layer, implying the existence of magnetic correlations among the spins, culminating in a collective freezing below T~100 K. We propose, also by the light of micromagnetic simulations, that the small dot size imposes a spatial constraint on the magnetic correlation length among the IrMn spins so that, even at the lowest temperature, their thermal stability, especially at the dot border, is compromised. - Highlights: • Exchange bias in 140 nm-sized IrMn(3 nm)/NiFe(3 nm) dots much weaker than in a film. • Glassy magnetic nature of the IrMn phase and collective spin freezing at T<100 K

  17. OpenMP, OpenMP/MPI, and CUDA/MPI C programs for solving the time-dependent dipolar Gross-Pitaevskii equation

    Science.gov (United States)

    Lončar, Vladimir; Young-S., Luis E.; Škrbić, Srdjan; Muruganandam, Paulsamy; Adhikari, Sadhan K.; Balaž, Antun

    2016-12-01

    We present new versions of the previously published C and CUDA programs for solving the dipolar Gross-Pitaevskii equation in one, two, and three spatial dimensions, which calculate stationary and non-stationary solutions by propagation in imaginary or real time. Presented programs are improved and parallelized versions of previous programs, divided into three packages according to the type of parallelization. First package contains improved and threaded version of sequential C programs using OpenMP. Second package additionally parallelizes three-dimensional variants of the OpenMP programs using MPI, allowing them to be run on distributed-memory systems. Finally, previous three-dimensional CUDA-parallelized programs are further parallelized using MPI, similarly as the OpenMP programs. We also present speedup test results obtained using new versions of programs in comparison with the previous sequential C and parallel CUDA programs. The improvements to the sequential version yield a speedup of 1.1-1.9, depending on the program. OpenMP parallelization yields further speedup of 2-12 on a 16-core workstation, while OpenMP/MPI version demonstrates a speedup of 11.5-16.5 on a computer cluster with 32 nodes used. CUDA/MPI version shows a speedup of 9-10 on a computer cluster with 32 nodes.

  18. Synthesis of highly substituted spiropyrrolidines via 1, 3-dipolar cycloaddition reaction of N-metalated azomethine ylides. A new access to spiropyrroline derivatives

    Directory of Open Access Journals (Sweden)

    Chourouk Mhiri

    2015-02-01

    Full Text Available 1,3-dipolar cycloaddition of (E-arylidene-(2H-indanones 1 (Ar = Ph, p-MeC6H4, p-MeOC6H4, p-ClC6H4 and (E-2-arylidene-(2H-tetralones 2 (Ar = Ph, p-MeC6H4, p-MeOC6H4, p-ClC6H4 to N-metalated azomethine ylides 3 generated from methyl N-arylideneglycinate in the presence of silver acetate produces in good yields novel spiro[3,5-(diaryl-2-carbomethoxypyrrolidine-4:2’-indanones] 4 and spiro[3,5-(diaryl-2-carbomethoxypyrrolidine-4:2’-tetral-1-ones] 5. The cycloaddition proceeds in regio- and stereoselective manner (100% at room temperature to afford respectively the syn-endo cycloadducts 4 and 5 via metallo-azomethine ylides. The regio- and stereochemistry of the spiranic adducts has been established on the basis of spectroscopic data and elemental analyses, corroborated by single-crystal X-ray crystallographic analysis of the heterocycles 4cd, 4bb and 5bd. The endo-pyrrolidines 4 were brominated by N-bromosuccinimide to give finally the dehydrobrominated 3,4-dihydro-2H-pyrrole derivatives 6. The spiro-adducts 4 and their corresponding oxidation products 6 are fluorescent in solution. 

  19. Protein resonance assignment at MAS frequencies approaching 100 kHz: a quantitative comparison of J-coupling and dipolar-coupling-based transfer methods

    Energy Technology Data Exchange (ETDEWEB)

    Penzel, Susanne; Smith, Albert A.; Agarwal, Vipin; Hunkeler, Andreas [ETH Zürich, Physical Chemistry (Switzerland); Org, Mai-Liis; Samoson, Ago, E-mail: ago.samoson@ttu.ee [Tallinn University of Technology, NMR Instituut, Tartu Teadus, Tehnomeedikum (Estonia); Böckmann, Anja, E-mail: a.bockmann@ibcp.fr [UMR 5086 CNRS/Université de Lyon 1, Institut de Biologie et Chimie des Protéines (France); Ernst, Matthias, E-mail: maer@ethz.ch; Meier, Beat H., E-mail: beme@ethz.ch [ETH Zürich, Physical Chemistry (Switzerland)

    2015-10-15

    We discuss the optimum experimental conditions to obtain assignment spectra for solid proteins at magic-angle spinning (MAS) frequencies around 100 kHz. We present a systematic examination of the MAS dependence of the amide proton T{sub 2}′ times and a site-specific comparison of T{sub 2}′ at 93 kHz versus 60 kHz MAS frequency. A quantitative analysis of transfer efficiencies of building blocks, as they are used for typical 3D experiments, was performed. To do this, we compared dipolar-coupling and J-coupling based transfer steps. The building blocks were then combined into 3D experiments for sequential resonance assignment, where we evaluated signal-to-noise ratio and information content of the different 3D spectra in order to identify the best assignment strategy. Based on this comparison, six experiments were selected to optimally assign the model protein ubiquitin, solely using spectra acquired at 93 kHz MAS. Within 3 days of instrument time, the required spectra were recorded from which the backbone resonances have been assigned to over 96 %.

  20. A theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives

    Directory of Open Access Journals (Sweden)

    Hamzehloueian Mahshid

    2014-01-01

    Full Text Available The present study reports a systematic computational analysis of the two possible pathways, fused and bridged, for an intramolecular hetero Diels-Alder (IMHDA and an intramolecular 1,3-dipolar cycloaddition (IMDCA of 2-vinyloxybenzaldehyde derivatives. The potential energy surface analysis for both reactions is in agreement with experimental observations. The activation energies associated with the two regioisomeric channels in IMHDA reaction show that the bridged product is favored, although in IMDCA, the most stable TS results the fused product. The global electronic properties of fragments within each molecule were studied to discuss the reactivity patterns and charge transfer direction in the intramolecular processes. The asynchronicity of the bond formation and aromaticity of the optimized TSs in the Diels-Alder reaction as well as cycloaddition reaction were evaluated. Finally, 1H NMR chemical shifts of the possible regioisomers have been calculated using the GIAO method which of the most stable products are in agreement with the experimental data in the both reaction.

  1. Cross-Correlated Relaxation of Dipolar Coupling and Chemical-Shift Anisotropy in Magic-Angle Spinning R1ρ NMR Measurements: Application to Protein Backbone Dynamics Measurements

    Science.gov (United States)

    Kurauskas, Vilius; Weber, Emmanuelle; Hessel, Audrey; Ayala, Isabel; Marion, Dominique; Schanda, Paul

    2016-01-01

    Transverse relaxation rate measurements in MAS solid-state NMR provide information about molecular motions occurring on nanoseconds-to-milliseconds (ns-ms) time scales. The measurement of heteronuclear (13C, 15N) relaxation rate constants in the presence of a spin-lock radio-frequency field (R1ρ relaxation) provides access to such motions, and an increasing number of studies involving R1ρ relaxation in proteins has been reported. However, two factors that influence the observed relaxation rate constants have so far been neglected, namely (i) the role of CSA/dipolar cross-correlated relaxation (CCR), and (ii) the impact of fast proton spin flips (i.e. proton spin diffusion and relaxation). We show that CSA/D CCR in R1ρ experiments is measurable, and that this cross-correlated relaxation rate constant depends on ns-ms motions, and can thus itself provide insight into dynamics. We find that proton spin-diffusion attenuates this cross-correlated relaxation, due to its decoupling effect on the doublet components. For measurements of dynamics, the use of R1ρ rate constants has practical advantages over the use of CCR rates, and the present manuscript reveals factors that have so far been disregarded and which are important for accurate measurements and interpretation. PMID:27500976

  2. Transient magnetization dynamics of spin-torque oscillator and magnetic dot coupled by magnetic dipolar interaction: Reading of magnetization direction using magnetic resonance

    Science.gov (United States)

    Kanao, Taro; Suto, Hirofumi; Kudo, Kiwamu; Nagasawa, Tazumi; Mizushima, Koichi; Sato, Rie

    2018-01-01

    We study the magnetization dynamics of a spin-torque oscillator (STO) and a magnetic dot coupled by a magnetic dipolar field using micromagnetic simulation with the aim of developing a read method in magnetic recording that uses magnetic resonance. We propose an STO with a perpendicularly magnetized free layer and an in-plane-magnetized fixed layer as a suitable STO for this resonance read method. When the oscillation frequency of the STO is near the ferromagnetic resonance (FMR) frequency of the magnetic dot, the oscillation amplitude of the STO decreases because FMR excited in the magnetic dot causes additional dissipation. To estimate the read rate of the resonance read method, we study the transient magnetization dynamics to the coupled oscillation state from an initial state where the STO is in a free-running state and the magnetic dot is in a stationary stable state. The STO shows transient dynamics within a time scale of 1 ns, which means that the STO can perform resonance reading with a response time within this time scale. This response time is shorter when the separation length between the STO and the magnetic dot is shorter, which indicates that the response speed can become faster by increasing the strength of the interaction between the STO and the magnetic dot. Successive reads are demonstrated by moving the STO over an array of magnetic dots.

  3. Magneto-thermally activated spin-state transition in La0.95Ca0.05CoO3: magnetically-tunable dipolar glass and giant magneto-electricity.

    Science.gov (United States)

    Pandey, Suchita; Kumar, Jitender; Awasthi, A M

    2016-03-07

    The magneto-dielectric spectroscopy of La0.95Ca0.05CoO3 covering the crossover of spin states reveals the strong coupling of its spin and dipolar degrees of freedom. The signature of the spin-state transition at 30 K clearly manifests in the magnetization data at a 1 Tesla optimal field. Our Co L3,2-edge X-ray absorption spectrum on the doped specimen is consistent with its suppressed low-to-intermediate spin-state transition temperature at ∼30 K compared to ∼150 K, documented for pure LaCoO3. The dispersive activation step in the dielectric constant with the associated relaxation peak in imaginary permittivity characterize the allied influence of coexistent spin-states on the dielectric character. Dipolar relaxation in the low-spin regime below the transition temperature is partly segmental (Vogel-Fulcher-Tamman (VFT) kinetics) and features magnetic-field tunability, whereas in the low/intermediate-spin disordered state above ∼30 K, it is uncorrelated (Arrhenic kinetics) and almost impervious to the magnetic field H. Kinetics-switchover defines the dipolar-glass transition temperature Tg(H) (=27 K|0T), below which their magneto-thermally-activated cooperative relaxations freeze out by the VFT temperature T0(H) (=15 K|0T). An applied magnetic field facilitates thermal activation in toggling the low spins up into the intermediate states. Consequently, the downsized dipolar-glass segments in the low-spin state and the independent dipoles in the intermediate state exhibit accelerated dynamics. A critical 5 Tesla field collapses the entire relaxation kinetics into a single Arrhenic behaviour, signaling that the dipolar glass is completely devitrified under all higher fields. The magneto-electricity (ME) spanning sizeable thermo-spectral range registers diverse signatures here in kinetic, spectral, and field behaviors, in contrast to the static/perturbative ME observed close to the spin-ordering in typical multiferroics. Intrinsic magneto-dielectricity (50%) along

  4. A theoretical and experimental exploration of the mechanism of microwave assisted 1,3-dipolar cycloaddition of pyridinium ylides to single walled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Bayazit, Mustafa K., E-mail: m.bayazit@imperial.ac.uk [Department of Chemistry, University of Durham, Durham DH1 3LE (United Kingdom); Celebi, Nihat [Department of Chemistry, Abant Izzet Baysal University, Bolu 14280 (Turkey); Coleman, Karl S. [Department of Chemistry, University of Durham, Durham DH1 3LE (United Kingdom)

    2014-05-01

    Cycloaddition reactions have widely been used for surface functionalization of single walled carbon nanotubes (SWNTs). Here, 1,3-dipolar cycloaddition (1,3-DC) of two new pyridinium ylides, generated in-situ via the addition of triethylamine (NEt{sub 3}) to the Kröhnke salts N-(4-methyl sodium benzene sulfonate)-pyridinium bromide and N-(4-nitrobenzyl)-pyridinium bromide, to SWNTs under microwave conditions are assessed both theoretically using PM3 (RHF) type calculations and experimentally. Evidence of covalent surface modification is provided by FTIR, UV–vis–NIR and resonance Raman spectroscopy. Solubility of the modified SWNTs increases when compared to as-received SWNTs. Quantification of surface groups is performed via TGA-MS and XPS. 1,3-DC of pyridinium ylides with smaller HOMO–LUMO energy gap is found to be more selective to large diameter SWNTs. Theoretically predicted smaller energy gaps between HOMO{sub ylides} and LUMO{sub (8,8)} SWNT suggest that the charges are probably transferred from pyridinium ylides to SWNTs indicating HOMO{sub ylide}–LUMO{sub (8,8)} {sub SWNT} controlled 1,3-DC. Regioselectivity of second ylide addition as addendum to ylide–SWNT adduct is also discussed. - Graphical abstract: Display Omitted - Highlights: • PM3 (RHF) type calculations suggest that charges are probably transferred from HOMO of pyridinium ylides to LUMO of SWNTs. • Theoretical predictions indicate a HOMO{sub ylide}–LUMO{sub (8,8)} {sub SWNT} controlled 1,3-DC reaction (Type I). • Pyridinium ylides with smaller HOMO–LUMO energy gap is experimentally found to be more selective to large diameter SWNTs. • Reactivity of pyridinium ylide might be manipulated using strong electron withdrawing groups. • Graphene surface modification may be anticipated using the same approach.

  5. Exchange bias properties of 140 nm-sized dipolarly interacting circular dots with ultrafine IrMn and NiFe layers

    Science.gov (United States)

    Spizzo, F.; Tamisari, M.; Chinni, F.; Bonfiglioli, E.; Gerardino, A.; Barucca, G.; Bisero, D.; Fin, S.; Del Bianco, L.

    2016-02-01

    We studied the exchange bias effect in an array of IrMn(3 nm)/NiFe(3 nm) circular dots (size 140 nm and center-to-center distance 200 nm, as revealed by microscopy analyses), prepared on a large area (3×3 mm2) by electron beam lithography and lift-off, using dc sputtering deposition. Hysteresis loops were measured by SQUID magnetometer at increasing values of temperature T (in the 5-300 K range) after cooling from 300 K down to 5 K in zero field (ZFC mode) and in a saturating magnetic field (FC mode). The exchange bias effect disappears above T 200 K and, at each temperature, the exchange field HEX measured in ZFC is substantially lower than the FC one. Micromagnetic calculations indicate that, at room temperature, each dot is in high-remanence ground state, but magnetic dipolar interactions establish a low-remanence configuration of the array as a whole. Hence, at low temperature, following the ZFC procedure, the exchange anisotropy in the dot array is averaged out, tending to zero. However, even the FC values of HEX and of the coercivity HC are definitely smaller compared to those measured in a reference continuous film with the same stack configuration (at T=5 K, HEX 90 Oe and HC 180 Oe in the dots and HEX 1270 Oe and HC 860 Oe in the film). Our explanation is based on the proven glassy magnetic nature of the ultrathin IrMn layer, implying the existence of magnetic correlations among the spins, culminating in a collective freezing below T 100 K. We propose, also by the light of micromagnetic simulations, that the small dot size imposes a spatial constraint on the magnetic correlation length among the IrMn spins so that, even at the lowest temperature, their thermal stability, especially at the dot border, is compromised.

  6. Thermodynamics of Dipolar Chain Systems

    DEFF Research Database (Denmark)

    R. Armstrong, J.; Zinner, Nikolaj Thomas; V. Fedorov, D.

    2012-01-01

    of the intralayer repulsion and quantum statistical requirements in systems with more than one chain. Specifically, we consider the case of two chains and solve the problem analytically within the harmonic Hamiltonian approach which is accurate for large dipole moments. The case of three chains is calculated...

  7. Independent EEG sources are dipolar

    National Research Council Canada - National Science Library

    Delorme, Arnaud; Palmer, Jason; Onton, Julie; Oostenveld, Robert; Makeig, Scott

    2012-01-01

    Independent component analysis (ICA) and blind source separation (BSS) methods are increasingly used to separate individual brain and non-brain source signals mixed by volume conduction in electroencephalographic (EEG...

  8. Comparative Monte-Carlo simulations of charge carrier transport in amorphous molecular solids as given by three most common models of disorder: The dipolar glass, the Gaussian disorder, and their mix

    Science.gov (United States)

    Tyutnev, A. P.; Novikov, S. V.; Saenko, V. S.; Pozhidaev, E. D.

    2017-09-01

    We have performed Monte-Carlo simulations of the charge carrier transport in a model molecularly doped polymer using three most popular hopping theories (the dipolar glass model, the Gaussian disorder model, and an intermediate between them) in a wide range of applied electric fields and temperatures. Time of flight transients have been computed and analyzed in logarithmic coordinates to study the Poole-Frenkel field dependence, the non-Arrhenius mobility temperature dependence, and the nondispersive versus dispersive current shapes. We also have made an attempt to estimate the total disorder energy directly from simulation data at the lowest electric field thus checking the consistency of the model fitting. Computational results have been compared with the analytical and experimental information available in the literature.

  9. A 13C and 1H NMR spectroscopic investigation of the structure of the iminium ion with a dipolar form in metal complexes of 2-N-substituted N-confused porphyrins.

    Science.gov (United States)

    Chang, Wen-Pin; Lin, Wen-Chain; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu

    2012-11-21

    The crystal structures of chloro(2-aza-2-ethoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) zinc(II) [Zn(2-NCH2COOC2H5NCTPP)Cl; 4], (2-aza-2-ethoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) palladium(II) [Pd(2-NCH2COOC2H5NCTPP); 5], bromo(2-aza-2-ethoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) manganese(III) [Mn(2-NCH2COOC2H5NCTPP)Br; 6], [2-aza-(3′-phenoxypropyl)-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′] nickel(II) [Ni(2-NCH2CH2CH2OC6H5NCTPP); 7] and chloro(2-aza-2-methoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) zinc(II) [Zn(2-NCH2COOCH3NCTPP)Cl; 8] have been established. The g value of 9.54, which was measured from the parallel polarization of the X-band EPR spectra in CHCl3 at 4 K, is consistent with the high spin mononuclear manganese(III) centre (S = 2) in 6. The magnitude of the axial (D) zero-field splitting (ZFS) for the mononuclear Mn(III) centre in 6 was determined approximately to be 1.63 cm(−1) by paramagnetic susceptibility measurements. The NMR spectroscopic investigation of the iminium ion with a dipolar canonical contribution to the metal complexes 5–7, Pd(2-NCH2C6H5NCTPP) (10) and Ni(2-NCH2C6H5NCTPP) (11) in CDCl3 is reported. A resonance between the dipolar canonical form II and covalent canonical form I exists for complexes 5–7, 10 and 11 in CDCl3. To develop the correlations between δ13C [C(3)], δ1H [H(3)] and the canonical form II in 5–7, 10 and 11, this work thoroughly examines the 13C and 1H NMR of N+=CH(Ar) fragment on seven metal complexes of 2-N substituted N-confused porphyrin. According to these results, the 13C [C(3)] and 1H [H(3)] chemical shifts of the N+=CH(Ar) fragment at 20 °C in CDCl3 are separately located at 152.6 ± 0.5 and 8.30 ± 0.15 ppm respectively for the iminium ion. This exists as a dipolar canonical form II for complexes 5–7, 10 and 11, and the N–CH(Ar) group

  10. H-ferrierite zeolite: As an effective and reusable heterogeneous catalyst for synthesis of 1,5-benzothiazepine under solvent free condition and 1,3-dipolar cycloaddition in water

    Directory of Open Access Journals (Sweden)

    Thoraya A. Farghaly

    2017-05-01

    Full Text Available An efficient synthesis of new derivatives of 1,5-benzothiazepine has been developed by the reaction of various chalcones (1,3-diaryl-2-propenones with 2-amino-thiophenol in the presence of H-ferrierite zeolite as acidic catalyst without solvent. In addition, 1,3-dipolar cycloaddition of hydrazonoyl chlorides on CN bond of 1,5-benzothiazepines in water in the presence of Na2CO3/THAC as a base catalyst afforded 1,2,4-triazolo[3,4-d][1,5]benzothiazepines. The structure of all the newly synthesized compounds was established on the basis of spectral data (Mass, IR, 1H NMR, 13C NMR and elemental analysis.

  11. A solvent free, four-component synthesis and 1,3-dipolar cycloaddition of 4(H)-pyrans with nitrile oxides: synthesis and discovery of antimycobacterial activity of enantiomerically pure 1,2,4-oxadiazoles.

    Science.gov (United States)

    Almansour, Abdulrahman I; Suresh Kumar, Raju; Arumugam, Natarajan; Sriram, Dharmarajan

    2012-07-01

    Four-component reactions of (R)-1-(1-phenylethyl)tetrahydro-4(1H)-pyridinone, aromatic aldehydes and malononitrile in a 1:2:1 molar ratio in the presence of solid sodium ethoxide under solvent free conditions afforded an inseparable mixture of two diastereomeric 4(H)-pyrans in near quantitative yields. These compounds upon 1,3-dipolar cycloaddition with nitrile oxides furnished two enantiomerically pure 1,2,4-oxadiazoles in moderate yields, which were screened for in vitro activity against Mycobacterium tuberculosis H37Rv (MTB) and multi-drug resistant M. tuberculosis (MDR-TB). Among the compounds screened, compound 10h was found to be the most active in vitro with a MIC value of 0.07 and 0.14 μM against MTB and MDR-TB respectively. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  12. On the outside looking in: rethinking the molecular mechanism of 1,3-dipolar cycloadditions from the perspective of bonding evolution theory. The reaction between cyclic nitrones and ethyl acrylate.

    Science.gov (United States)

    Adjieufack, A I; Ndassa, I M; Patouossa, I; Mbadcam, J K; Safont, V S; Oliva, M; Andrés, J

    2017-07-19

    In this work we report on the progress that has been made towards gaining an understanding of the molecular mechanism of 1,3-dipolar cycloadditions using the bonding evolution theory (BET). A detailed analysis of the flow of electron density along the reaction pathway of the formal 1,3-dipolar cycloaddition reaction between cyclic nitrones (pyrroline-1-oxide and 2,3,4,5-tetrahydropyridine-1-oxide) and ethyl acrylate, as a case study, allowed the nature of the molecular mechanisms to be characterized. The present study provides a deep insight into the reaction mechanism, based on the electron density rearrangements given by the structural stability domains, and their connection with the bond breaking/forming processes along the reaction pathway. The electron pushing formalism is a powerful tool to describe chemical reactivity. Here, we show how the Lewis structures can be recovered and how curly arrows describe electron density transfers in chemical reaction mechanisms based on the BET results. The reaction mechanism is described by four consecutive events taking place as the reaction progresses: (1) the population of the initial N-C double bond is transferred to the N and C atoms; (2) the population of the initial double C-C bond is transferred to the C atoms. Along the ortho pathway the next steps are: (3) the C-C bond-forming process, and (4) the O-C bond-forming process. The order of (3) and (4) is inverted in the meta channel. Based on the sequence of the structural stability domains along the intrinsic reaction coordinate, a new synchronicity index is proposed, allowing us to classify and quantify the (a)synchronicity of the 1,3-DC reactions and, therefore, the nature of the reaction mechanism.

  13. Characterization and modelling of microwave multi dipole plasmas. Application to multi dipolar plasma assisted sputtering; Caracterization et modelisation des plasmas micro-onde multi-dipolaires. Application a la pulverisation assistee par plasma multi-dipolaire

    Energy Technology Data Exchange (ETDEWEB)

    Tran, Tan Vinh [Universite Joseph Fourier/CNRS-IN2P3, 53 Avenue des Martyrs, F-38026 Grenoble (France)

    2006-07-01

    The scaling up of plasma processes in the low pressure range remains a question to be solved for their rise at the industrial level. One solution is the uniform distribution of elementary plasma sources where the plasma is produced via electron cyclotron resonance (ECR) coupling. These elementary plasma sources are made up of a cylindrical permanent magnet (magnetic dipole) set at the end of a coaxial microwave line. Although of simple concept, the optimisation of these dipolar plasma sources is in fact a complex problem. It requires the knowledge, on one hand, of the configurations of static magnetic fields and microwave electric fields, and, on the other hand, of the mechanisms of plasma production in the region of high intensity magnetic field (ECR condition), and of plasma diffusion. Therefore, the experimental characterisation of the operating ranges and plasma parameters has been performed by Langmuir probes and optical emission spectroscopy on different configurations of dipolar sources. At the same time, in a first analytical approach, calculations have been made on simple magnetic field configurations, motion and trajectory of electrons in these magnetic fields, and the acceleration of electrons by ECR coupling. Then, the results have been used for the validation of the numerical modelling of the electron trajectories by using a hybrid PIC (particle-in-cell) / MC (Monte Carlo) method. The experimental study has evidenced large operating domains, between 15 and 200 W of microwave power, and from 0.5 to 15 mTorr argon pressure. The analysis of plasma parameters has shown that the region of ECR coupling is localised near the equatorial plane of the magnet and dependent on magnet geometry. These characterizations, applied to a cylindrical reactor using 48 sources, have shown that densities between 10{sup 11} and 10{sup 12} cm{sup -3} could be achieved in the central part of the volume at a few mTorr argon pressures. The modelling of electron trajectories near

  14. Proton-detected 3D (1)H/(13)C/(1)H correlation experiment for structural analysis in rigid solids under ultrafast-MAS above 60 kHz.

    Science.gov (United States)

    Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

    2015-10-28

    A proton-detected 3D (1)H/(13)C/(1)H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of (13)C-(1)H connectivities, and proximities of (13)C-(1)H and (1)H-(1)H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including (1)H-(1)H dipolar couplings, while the finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used to recouple dipolar couplings among protons and the insensitive nuclei enhanced by polarization transfer technique is used to transfer magnetization between heteronuclear spins. The 3D experiment eliminates signals from non-carbon-bonded protons and non-proton-bonded carbons to enhance spectral resolution. The 2D (F1/F3) (1)H/(1)H and 2D (13)C/(1)H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of (1)H-(1)H proximity and (13)C-(1)H connectivity. In addition, the 2D (F1/F2) (1)H/(13)C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of (1)H-(1)H dipolar couplings, enables the measurement of proximities between (13)C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of (1)H-(1)H-(13)C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ⋅ H2O ⋅ HCl demonstrate the efficiency of the 3D experiment.

  15. The Myth Incarnate: Recoupling Processes, Turmoil, and Inhabited Institutions in an Urban Elementary School

    Science.gov (United States)

    Hallett, Tim

    2010-01-01

    The study of institutional myths has been central to organizational sociology, cultural sociology, and the sociology of education for 30 years. This article examines how the myth concept has been used and develops neglected possibilities by asking: What happens when myths become incarnate, and how does this occur? In other words, what happens when…

  16. Exploring the Dynamics of Decoupling and Recoupling in Corporate Responsibility Standardization

    DEFF Research Database (Denmark)

    Haack, Patrick; Martignoni, Dirk; Schoeneborn, Dennis

    -state Markov chain model, we explore the boundary conditions under which initial opacity paired with an endogenous change towards transparency (characterized by the relative ease or possibility of evaluation) maximizes the overall number of substantive adoptions. We show that the hypocritical adoption...... of formal policies might prove instable and yield long-term institutional consequences, not only because of instability of decoupling within a single organization, but also because of sequence and endogeneity effects at the institutional field level. We illustrate our arguments by drawing on the case......Organizations adopt formal policies often ceremonially, meaning that policy adoption is not substantive and lacks alignment with actual practice. Prior research in institutional theory has largely assumed as static view of adoption and suggests that a situation of opacity (characterized...

  17. Highly resolved HSQC experiments for the fast and accurate measurement of homonuclear and heteronuclear coupling constants

    Science.gov (United States)

    Souza, Alexandre A.; Gil, Roberto R.; Parella, Teodor

    2017-09-01

    A number of J-upscaled NMR experiments are currently available to measure coupling constants along the indirect F1 dimension of a 2D spectrum. A major drawback is the limited F1 digital resolution that requires long acquisition times in order to achieve reasonably accurate measures. Here is shown how high levels of F1 digital resolution in a multiple-purpose HSQC experiment can be easily achieved by implementing a general J/δ-scaling strategy. In particular, a set of new J-resolved HSQC experiments is presented for a faster and much more accurate J determination in small molecules. Several options and practical aspects are discussed and exemplified by measuring the magnitude and/or the sign of several homo- and heteronuclear coupling constants in one shot.

  18. Van der Waals universality in homonuclear atom-dimer elastic collisions

    CERN Document Server

    Giannakeas, P

    2016-01-01

    The universal aspects of atom-dimer elastic collisions are investigated within the framework of Faddeev equations. The two-body interactions between the neutral atoms are approximated by the separable potential approach. Our analysis considers a pure van der Waals potential tail as well as soft-core van der Waals interactions permitting us in this manner to address the universally general features of atom-dimer resonant spectra. In particular, we show that the atom-dimer resonances are solely associated with the {\\it excited} Efimov states. Furthermore, the positions of the corresponding resonances for a soft-core potentials with more than 5 bound states are in good agreement with the corresponding results from an infinitely deep pure van der Waals tail potential.

  19. Exploring the Bermuda triangle of homonuclear diatomic spectroscopy: The electronic spectrum and structure of Ge2

    Science.gov (United States)

    Hostutler, David A.; Li, Haiyang; Clouthier, Dennis J.; Wannous, Ghassan

    2002-03-01

    The optical spectrum of jet-cooled Ge2 has been observed for the first time. Laser-induced fluorescence (LIF) and wavelength resolved emission spectra were recorded using the pulsed discharge technique with a tetramethylgermane precursor. Analysis of the spectra yielded the vibrational constants ωe″=287.9(47), ωexe″=0.81(55), ωeye″=0.0037(18), ωe'=189.0(15), ωexe'=6.41(30), and Te'=20 610.8(16) cm-1. High-resolution rotationally resolved spectra of several bands of 74Ge2 show two strong P and R branches and two very weak Q branches. We have assigned the band system as a Hund's case (c) Ω'=1-Ω″=1 transition from the ground 3Σg- state to a 3Σu- excited state. The bond lengths derived from the rotational constants are r0″=2.3680(1) Å and re'=2.5244(18) Å, an ˜0.16 Å increase on electronic excitation. Arguments are presented for assigning the transition to a σg2πu2→σg2πuπg electron promotion, although the observed increase in the bond length is much less than predicted by previous ab initio calculations. The absence of the 0u+-0g+ component in the spectra has been attributed to an excited state predissociation.

  20. Spectroscopic Constants for Selected Homonuclear Diatomic Molecules. Volume 2. K through Z

    Science.gov (United States)

    1976-02-16

    Characteristic Bands, X R R 6883.9(2,0) 4800, 6(3, 1) 4778. 8(2,0) 3358. 6(0,2) 3315.6(0, 1) Remarks Several bands of the isotopic ape cies...64. 47) (64. 47a) (64, 48) (64. 49) (65. 50) (65. 51) (65. 52) (65. 53) (65. 54) Isotope Displacements and Vibrational Structure, D... Radium 20, 915-7 (60. 33) Raman Spectrum, A. Weber and E. A. MacGinnis, J. Molec. Spectrosc. 4, 195-200 0-19 i 71 o. (61. 34

  1. Trapping mode dipolar DC collisional activation in the RF-only ion guide of a linear ion trap/time-of-flight instrument for gaseous bio-ion declustering.

    Science.gov (United States)

    Webb, Ian K; Gao, Yang; Londry, Frank A; McLuckey, Scott A

    2013-09-01

    The application of dipolar direct current (DDC) to the radio frequency-only ion guide (Q0) of a hybrid quadrupole/time-of-flight mass spectrometer for collision-induced declustering of large bio-ions is described. As a broadband technique, ion trap DDC collisional activation (CA) is employed to decluster ions simultaneously over a relatively broad mass-to-charge (m/z) range. Declustering DDC CA can yield significantly narrower peaks relative to those observed in the absence of declustering methods, depending upon the extent of noncovalent adduction associated with the ions, and can also be used in conjunction with other methods, such as nozzle-skimmer CA. The key experimental variables in the DDC experiment are the DDC voltage (VDDC), VRF , and the time over which VDDC is applied. The VDDC/VRF ratio is key to the extent to which ion temperatures are elevated and also influences the upper m/z limit for ion storage. The VDDC/VRF ratio affects ion temperatures and the upper m/z limit in opposing directions. That is, as the ratio increases, the ion temperature also increases, whereas the upper m/z storage limit decreases. However, for a given VDDC /VRF ratio, the upper m/z storage limit can be increased by increasing VRF, at the expense of the lower m/z limit for ion storage. The key value of the approach is that it affords a relatively precise degree of control over ion temperatures as well as the time over which they are elevated to a higher temperature. The utility of the method is illustrated by the application of ion trap DDC CA in Q0 to oligonucleotide, protein, and multimeric protein complex analyte ions. Copyright © 2013 John Wiley & Sons, Ltd.

  2. Modeling liquid-vapor equilibria with an equation of state taking into account dipolar interactions and association by hydrogen bonding; Modelisation des proprietes PVTX des fluides du systeme H{sub 2}O-gaz prenant en compte l'association par liaisons hydrogenes et les interactions dipolaires

    Energy Technology Data Exchange (ETDEWEB)

    Perfetti, E

    2006-11-15

    Modelling fluid-rock interactions as well as mixing and unmixing phenomena in geological processes requires robust equations of state (EOS) which must be applicable to systems containing water, gases over a broad range of temperatures and pressures. Cubic equations of state based on the Van der Waals theory (e. g. Soave-Redlich-Kwong or Peng-Robinson) allow simple modelling from the critical parameters of the studied fluid components. However, the accuracy of such equations becomes poor when water is a major component of the fluid since neither association trough hydrogen bonding nor dipolar interactions are accounted for. The Helmholtz energy of a fluid may be written as the sum of different energetic contributions by factorization of partition function. The model developed in this thesis for the pure H{sub 2}O and H{sub 2}S considers three contributions. The first contribution represents the reference Van der Waals fluid which is modelled by the SRK cubic EOS. The second contribution accounts for association through hydrogen bonding and is modelled by a term derived from Cubic Plus Association (CPA) theory. The third contribution corresponds to the dipolar interactions and is modelled by the Mean Spherical Approximation (MSA) theory. The resulting CPAMSA equation has six adjustable parameters, which three represent physical terms whose values are close to their experimental counterpart. This equation results in a better reproduction of the thermodynamic properties of pure water than obtained using the classical CPA equation along the vapour-liquid equilibrium. In addition, extrapolation to higher temperatures and pressure is satisfactory. Similarly, taking into account dipolar interactions together with the SRK cubic equation of state for calculating molar volume of H{sub 2}S as a function of pressure and temperature results in a significant improvement compared to the SRK equation alone. Simple mixing rules between dipolar molecules are proposed to model the H

  3. From spin induced ferroelectricity to spin and dipolar glass in a triangular lattice: The CuCr{sub 1−x}V{sub x}O{sub 2} (0≤x≤0.5) delafossite

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, S.; Singh, K. [Laboratoire CRISMAT, CNRS UMR 6508, ENSICAEN, 6 Boulevard du Marechal Juin, 14050 Caen Cedex (France); Miclau, M. [Analysis and Characterization Department, National Institute for R and D in Electrochemistry and Condensed Matter, Timisoara 30024 (Romania); Simon, Ch.; Martin, C. [Laboratoire CRISMAT, CNRS UMR 6508, ENSICAEN, 6 Boulevard du Marechal Juin, 14050 Caen Cedex (France); Maignan, A., E-mail: antoine.maignan@ensicaen.fr [Laboratoire CRISMAT, CNRS UMR 6508, ENSICAEN, 6 Boulevard du Marechal Juin, 14050 Caen Cedex (France)

    2013-07-15

    The change from antiferromagnetism induced ferroelectricity to spin glass ferroelectric relaxor has been studied along the CuCr{sub 1−x}V{sub x}O{sub 2} (0≤x≤0.5) solid solution of polycrystalline samples. As x increases from CuCrO{sub 2} (x=0) to CuCr{sub 0.82}V{sub 0.18}O{sub 2}, it is found that the Néel temperature decreases from ∼24 K down to ∼13 K. This progressive weakening of the antiferromagnetism of CuCrO{sub 2} induces a rapid decrease of the spin induced ferroelectricity with polarization values going from ∼44 μC/m{sup 2} down to ∼1.5 μC/m{sup 2} for x=0.04 and x=0.08, respectively. Beyond x=0.18 (0.20≤x≤0.50), ac-magnetic susceptibility and magnetization measurements evidence a spin glass state while dielectric permittivity and polarization measurements point towards a relaxor behaviour. This shows that competing magnetic interactions in delafossites are an efficient way to transform a spin induced magnetoelectric into a multiglass (spin and dipolar) state. - Graphical abstract: The P(T) curves evidencing the aging effect on polarization in CuCr{sub 0.5}V{sub 0.5}O{sub 2}: E=135 kV/m is applied during cooling at different temperatures. The P values and the inflection point of the transition depend on the poling temperature suggesting a relaxor behaviour. This effect related to the spin glass state is not observed for the lowest vanadium content. - Highlights: • Samples of the CuCr{sub 1−x}V{sub x}O{sub 2} series have been studied. • The V content increase induces a change from antiferromagnetism to spin glass. • A behavior characterisitic of a spin and dipole glass is demonstrated. • The ferroelectricity is shown to go from spin induced to relaxor. • Competing magnetic interactions are efficient way to generate multiglass state.

  4. Double quantum 1H MAS NMR studies of hydrogen-bonded protons and water dynamics in materials.

    Science.gov (United States)

    Alam, Todd M; Nyman, May; McIntyre, Sarah K

    2007-03-15

    Two-dimensional double quantum (DQ) 1H MAS NMR was used to investigate different proton environments in a series of alkali (Na, K, Rb, Cs) [Nb6O19]8- Lindqvist salts, with the water and hydrogen-bound intercluster protons being clearly resolved. Through the analysis of the DQ 1H NMR spinning sideband pattern, it is possible to extract both the mean and distribution of the motionally averaged intramolecular homonuclear 1H-1H dipolar coupling for the different water environments and the intercluster protons. Motional order parameters for the water environments were then calculated from the averaged dipolar couplings. The influence of additional intermolecular dipolar couplings due to multispin interactions were simulated and discussed.

  5. Magnetic properties of dipolar chains in ferrofluids

    Energy Technology Data Exchange (ETDEWEB)

    Avgin, I., E-mail: ihavgin@gmail.com [Department of Electrical Engineering, Ege University, Izmir (Turkey); Huber, D.L. [Physics Department, University of Wisconsin-Madison, Madison, WI (United States)

    2014-07-01

    We have investigated the dipole interaction energies per particle and the local dipole field distributions in a frozen magnetization model of a ferrofluid chain in a saturating magnetic field. A lognormal distribution of particle diameters was assumed. The interaction energies were calculated for one dimensional arrays of dipoles with moments parallel to the chain. We have computed the energies by various approximations related to the hard sphere particle diameter distribution. A similar approach was followed for the local field distributions. It was found that the energy per particle and mean local field were largely determined by the mean particle diameter, but the distribution of local fields was sensitive to both the mean diameter and the assumptions about spatial correlations between particles of different size. Detailed results are presented for water-soluble Fe{sub 3}O{sub 4}/PAA (polyacrylic acid). (author)

  6. Dipolar source localization from intracerebral SEEG recordings.

    Science.gov (United States)

    Caune, Vairis; Le Cam, Steven; Ranta, Radu; Maillard, Louis; Louis-Dorr, Valérie

    2013-01-01

    This paper aims at exploring the feasibility of a brain source localization method from intracerebral stereo-electroencephalography (SEEG) measurements. The SEEG setup consists in multi-contact electrodes inserted in the brain volume, each containing about 10 collinear measuring contacts. In clinical context, these signals are usually observed using a bipolar montage (potential differences between neighbouring contacts of a SEEG electrode). The propagation of distant activity is thus suppressed, resulting in the observation of local activities around the contacts. We propose in this paper to take benefit of the propagation information by considering the original SEEG recordings (common reference montage), with the objective to localize sources possibly distant from the electrode contacts, and whose activities are propagating through the volume. Our method is based on an equivalent dipole model for the source and homogeneous infinite models for the propagation environment. This simple approach shows satisfactory localization performance under appropriate conditions, described in this paper. The proposed method is validated on real SEEG signals for the localisation of an intra-cortical electrical stimulation (ICS) generator.

  7. Experimental study of resolution of proton chemical shifts in solids: Combined multiple pulse NMR and magic-angle spinning

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, L.M.; Taylor, R.E.; Paff, A.J.; Gerstein, B.C.

    1980-01-01

    High-resolution nuclear magnetic resonance spectra of protons in rigid, randomly oriented solids have been measured using combined homonuclear dipolar decoupling (via multiple pulse techniques) and attenuation of chemical shift anisotropies (via magic-angle sample spinning). Under those conditions, isotropic proton chemical shifts were recorded for a variety of chemical species, with individual linewidths varying from about 55 to 110 Hz (1--2 ppm). Residual line broadening was due predominately to (i) magnetic-field instability and inhomogeneity, (ii) unresolved proton--proton spin couplings, (iii) chemical shift dispersion, (iv) residual dipolar broadening, and (v) lifetime broadening under the multiple pulse sequences used. The magnitudes of those effects and the current limits of resolution for this experiment in our spectrometer have been investigated. The compounds studied included organic solids (4, 4'-dimethylbenzophenone, 2, 6-dimethylbenzoic acid, and aspirin), polymers (polystyrene and polymethylmethacrylate), and the vitrain portion of a bituminous coal.

  8. Revealing the Local Proton Network through Three-Dimensional 13C/1H Double-Quantum/1H Single-Quantum and 1H Double-Quantum/13C/1H Single-Quantum Correlation Fast Magic-Angle Spinning Solid-State NMR Spectroscopy at Natural Abundance.

    Science.gov (United States)

    Malon, Michal; Pandey, Manoj Kumar; Nishiyama, Yusuke

    2017-08-31

    1H double quantum (DQ)/1H single quantum (SQ) correlation solid-state NMR spectroscopy is widely used to obtain internuclear 1H-1H proximities, especially at fast magic-angle spinning (MAS) rate (>60 kHz). However, to date, 1H signals are not well-resolved because of intense 1H-1H homonuclear dipolar interactions even at the attainable maximum MAS frequencies of ∼100 kHz and/or under 1H-1H homonuclear dipolar decoupling irradiations. Here we introduce novel three-dimensional (3D) experiments to resolve the 1H DQ/1H SQ correlation peaks using the additional 13C dimension. Although the low natural abundance of 13C (1.1%) significantly reduces the sensitivities, the 1H indirect measurements alleviate this issue and make this experiment possible even in naturally abundant samples. The two different implementations of 13C/1H DQ/1H SQ correlations and 1H DQ/13C/1H SQ correlations are discussed and demonstrated using l-histidine·HCl·H2O at natural abundance to reveal the local 1H-1H networks near each 13C. In addition, the complete 1H resonance assignments are achieved from a single 3D 13C/1H DQ/1H SQ experiment. We have also demonstrated the applicability of our proposed method on a biologically relevant molecule, capsaicin.

  9. Fulde-Ferrell-Larkin-Ovchinnikov state in bilayer dipolar systems

    NARCIS (Netherlands)

    Lee, H.; Matveenko, S.I.; Wang, D.-W.; Shlyapnikov, G.V.

    2017-01-01

    We study the phase diagram of fermionic polar molecules in a bilayer system, with an imbalance of molecular densities of the layers. For the imbalance exceeding a critical value, the system undergoes a transition from the uniform interlayer superfluid to the Fulde-Ferrell-Larkin-Ovchinnikov (FFLO)

  10. Adiabatic Shear Bands in Simple and Dipolar Viscoplastic Materials

    Science.gov (United States)

    1991-08-01

    in metals tMeyer, M. A., Murr, L E.. ed&.i. pp. 299 — .J 12. Xew York: Plenum Press 1981. [12] Cootin. L. S , I’risman. E. E.. Hawley. R H...Sympoaium on Macro-.Micro-Mechanics of High Velocity Deformation und Fracture (Kawata. K., Shioiri, J., eds.). pp. 189 —201. Berlin — Heidelberg- Xew

  11. Direct observation of localized dipolar excitations on rough nanostructured surfaces

    DEFF Research Database (Denmark)

    Bozhevolnyi, Sergey I.; Markel, V.A.; Coello, V.

    1998-01-01

    Using a photon scanning tunneling microscope (operating alternatively at the wavelengths of 594 and 633 nm) with shear-force feedback we image the topography of silver colloid fractals simultaneously with a near-field intensity distribution. We observe that near-field optical images exhibit spati...

  12. Layers of Cold Dipolar Molecules in the Harmonic Approximation

    DEFF Research Database (Denmark)

    R. Armstrong, J.; Zinner, Nikolaj Thomas; V. Fedorov, D.

    2012-01-01

    and their energies and radii determined. We extract the normal modes of the various systems as measures of their volatility and eventually of instability, and compare our findings to the excitations in crystals. We find modes that can be classified as either chains vibrating in phase or as layers vibrating against...

  13. Kinetic approach to condensation: Diatomic gases with dipolar molecules

    Science.gov (United States)

    Benilov, E. S.; Benilov, M. S.

    2017-10-01

    We derive a kinetic equation for rarefied diatomic gases whose molecules have a permanent dipole moment. Estimating typical parameters of such gases, we show that quantum effects cannot be neglected when describing the rotation of molecules, which we thus approximate by quantum rotators. The intermolecular potential is assumed to involve an unspecified short-range repulsive component and a long-range dipole-dipole Coulomb interaction. In the kinetic equation derived, the former and the latter give rise, respectively, to the collision integral and a self-consistent electric field generated collectively by the dipoles (as in the Vlasov model of plasma). It turns out that the characteristic period of the molecules' rotation is much shorter than the time scale of the collective electric force and the latter is much shorter than the time scale of the collision integral, which allows us to average the kinetic equation over rotation. In the averaged model, collisions and interaction with the collective field affect only those rotational levels of the molecules that satisfy certain conditions of synchronism. It is then shown that the derived model does not describe condensation; i.e., permanent dipoles of molecules cannot exert the level of intermolecular attraction necessary for condensation. It is argued that an adequate model of condensation must include the temporary dipoles that molecules induce on each other during interaction, and that this model must be quantum, not classical.

  14. Dynamic mesoscale model of dipolar fluids via fluctuating hydrodynamics.

    Science.gov (United States)

    Persson, Rasmus A X; Voulgarakis, Nikolaos K; Chu, Jhih-Wei

    2014-11-07

    Fluctuating hydrodynamics (FHD) is a general framework of mesoscopic modeling and simulation based on conservational laws and constitutive equations of linear and nonlinear responses. However, explicit representation of electrical forces in FHD has yet to appear. In this work, we devised an Ansatz for the dynamics of dipole moment densities that is linked with the Poisson equation of the electrical potential ϕ in coupling to the other equations of FHD. The resulting ϕ-FHD equations then serve as a platform for integrating the essential forces, including electrostatics in addition to hydrodynamics, pressure-volume equation of state, surface tension, and solvent-particle interactions that govern the emergent behaviors of molecular systems at an intermediate scale. This unique merit of ϕ-FHD is illustrated by showing that the water dielectric function and ion hydration free energies in homogeneous and heterogenous systems can be captured accurately via the mesoscopic simulation. Furthermore, we show that the field variables of ϕ-FHD can be mapped from the trajectory of an all-atom molecular dynamics simulation such that model development and parametrization can be based on the information obtained at a finer-grained scale. With the aforementioned multiscale capabilities and a spatial resolution as high as 5 Å, the ϕ-FHD equations represent a useful semi-explicit solvent model for the modeling and simulation of complex systems, such as biomolecular machines and nanofluidics.

  15. Dynamic mesoscale model of dipolar fluids via fluctuating hydrodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Persson, Rasmus A. X.; Chu, Jhih-Wei, E-mail: jwchu@nctu.edu.tw [Institute of Bioinformatics and Systems Biology, National Chiao Tung University, Hsinchu 30068, Taiwan (China); Department of Biological Science and Technology, National Chiao Tung University, Hsinchu 30068, Taiwan (China); Voulgarakis, Nikolaos K. [Department of Mathematics, Washington State University, Richland, Washington 99372 (United States)

    2014-11-07

    Fluctuating hydrodynamics (FHD) is a general framework of mesoscopic modeling and simulation based on conservational laws and constitutive equations of linear and nonlinear responses. However, explicit representation of electrical forces in FHD has yet to appear. In this work, we devised an Ansatz for the dynamics of dipole moment densities that is linked with the Poisson equation of the electrical potential ϕ in coupling to the other equations of FHD. The resulting ϕ-FHD equations then serve as a platform for integrating the essential forces, including electrostatics in addition to hydrodynamics, pressure-volume equation of state, surface tension, and solvent-particle interactions that govern the emergent behaviors of molecular systems at an intermediate scale. This unique merit of ϕ-FHD is illustrated by showing that the water dielectric function and ion hydration free energies in homogeneous and heterogenous systems can be captured accurately via the mesoscopic simulation. Furthermore, we show that the field variables of ϕ-FHD can be mapped from the trajectory of an all-atom molecular dynamics simulation such that model development and parametrization can be based on the information obtained at a finer-grained scale. With the aforementioned multiscale capabilities and a spatial resolution as high as 5 Å, the ϕ-FHD equations represent a useful semi-explicit solvent model for the modeling and simulation of complex systems, such as biomolecular machines and nanofluidics.

  16. Dipolar correlations and the dielectric permittivity of water.

    Science.gov (United States)

    Sharma, Manu; Resta, Raffaele; Car, Roberto

    2007-06-15

    The static dielectric properties of liquid and solid water are investigated within linear response theory in the context of ab initio molecular dynamics. Using maximally localized Wannier functions to treat the macroscopic polarization we formulate a first-principles, parameter-free, generalization of Kirkwood's phenomenological theory. Our calculated static permittivity is in good agreement with experiment. Two effects of the hydrogen bonds, i.e., a significant increase of the average local moment and a local alignment of the molecular dipoles, contribute in almost equal measure to the unusually large dielectric constant of water.

  17. Bound states of Dipolar Bosons in One-dimensional Systems

    DEFF Research Database (Denmark)

    G. Volosniev, A.; R. Armstrong, J.; V. Fedorov, D.

    2013-01-01

    We consider one-dimensional tubes containing bosonic polar molecules. The long-range dipole-dipole interactions act both within a single tube and between different tubes. We consider arbitrary values of the externally aligned dipole moments with respect to the symmetry axis of the tubes. The few-...

  18. Mechanism and regioselectivity of 1,3-dipolar cycloaddition ...

    Indian Academy of Sciences (India)

    The present analysis reveals that the cycloaddition ... step, five-centre cycloaddition, and involves 4π elec- trons from the 1,3-dipole and ..... S(1,5) = ( s. −. X3 − s. +. C4. )2 +. ( s. −. C1 − s. +. C5. )2 . (10b). As the values of S reveal, the reaction channel with lower activation energy corresponding to predominant regioisomer is ...

  19. Dipolar rotors orderly aligned in mesoporous fluorinated organosilica architectures

    KAUST Repository

    Bracco, Silvia

    2015-02-16

    New mesoporous covalent frameworks, based on hybrid fluorinated organosilicas, were prepared to realize a periodic architecture of fast molecular rotors containing dynamic dipoles in their structure. The mobile elements, designed on the basis of fluorinated p-divinylbenzene moieties, were integrated into the robust covalent structure through siloxane bonds, and showed not only the rapid dynamics of the aromatic rings (ca. 108 Hz at 325 K), as detected by solid-state NMR spectroscopy, but also a dielectric response typical of a fast dipole reorientation under the stimuli of an applied electric field. Furthermore, the mesochannels are open and accessible to diffusing in gas molecules, and rotor mobility could be individually regulated by I2 vapors. The iodine enters the channels of the periodic structure and reacts with the pivotal double bonds of the divinyl-fluoro-phenylene rotors, affecting their motion and the dielectric properties. Oriented molecular rotors: Fluorinated molecular rotors (see picture) were engineered in mesoporous hybrid organosilica architectures with crystalline order in their walls. The rotor dynamics was established by magic angle spinning NMR and dielectric measurements, indicating a rotational correlation time as short as 10-9 s at 325 K. The dynamics was modulated by I2 vapors entering the pores.

  20. Optical absorption in dipolar aggregates with a biological application

    Science.gov (United States)

    Apell, P.; Brånander, J.-O.; Gillbro, T.

    1993-07-01

    Based on a two-dimensional description of interacting dipoles and a standard optical effective medium model we estimate structural properties of bacteriochlorophyll c in chlorosome aggregates of Chloroflexus bacteria. The main aim is to see what detailed structural information one can get out of an optical experiment. The measured optical spectrum turns out to be compatible with a distribution of aggregated pigment molecules approximately 9 Å apart from each other. Their interaction is responsible for the red-shift in peak position. A more random distribution of the aggregates in turn gives a broader and slightly asymmetric line shape. These results are in line with available structural determinations using other methods.

  1. Magnetic dipolar ordering and hysteresis of geometrically defined nanoparticle clusters

    DEFF Research Database (Denmark)

    Kure, Mathias; Beleggia, Marco; Frandsen, Cathrine

    2017-01-01

    Magnetic nanoparticle clusters have several biomedical and engineering applications, and revealing the basic interplay between particle configuration and magnetic properties is important for tuning the clusters for specific uses. Here, we consider the nanoparticles as macrospins and use computer...... simulations to determine their magnetic configuration when placed at the vertices of various polyhedra. We find that magnetic dipoles of equal magnitude arrange in flux-closed vortices on a layer basis, giving the structures a null remanent magnetic moment. Assigning a toroidal moment to each layer, we find...

  2. Theory of a Nearly Two-Dimensional Dipolar Bose Gas

    Science.gov (United States)

    2016-05-11

    class: neutrons , protons, and elec- trons. Bosons are generally seen as force-carrier particles, or particles that propagate the four fundamental...mensional (2D) geometries, with the dipoles polarized perpendicular to the 2D plane. This results in a configuration where the dipoles are oriented...interactions are repulsive in the x-y plane, but are attractive in the z-direction, so two dipoles will attract if aligned in a “head-to-tail” configuration

  3. Magnetic dipolar ordering and hysteresis of geometrically defined nanoparticle clusters

    Science.gov (United States)

    Kure, Mathias; Beleggia, Marco; Frandsen, Cathrine

    2017-10-01

    Magnetic nanoparticle clusters have several biomedical and engineering applications, and revealing the basic interplay between particle configuration and magnetic properties is important for tuning the clusters for specific uses. Here, we consider the nanoparticles as macrospins and use computer simulations to determine their magnetic configuration when placed at the vertices of various polyhedra. We find that magnetic dipoles of equal magnitude arrange in flux-closed vortices on a layer basis, giving the structures a null remanent magnetic moment. Assigning a toroidal moment to each layer, we find that the geometrical arrangement, i.e., "triangular packing" vs. "square packing," of the moments in the adjacent layer determines whether the flux-closed layers are ferrotoroidal (co-rotating vortices) or antiferrotoroidal (counter-rotating vortices). Interestingly, upon adding a single magnetic moment at the center of the polyhedra, the central moment relaxes along one of the principal axes and induces partial alignment of the surrounding moments. The resulting net moment is up to nearly four times that of the single moment added. Furthermore, we model quasi-static hysteresis loops for structures with and without a central moment. We find that a central moment ensures an opening of the hysteresis loop, and the resultant loop areas are typically many-fold larger compared to the same structure without a central moment.

  4. Magnetic dipolar ordering and hysteresis of geometrically defined nanoparticle clusters

    DEFF Research Database (Denmark)

    Kure, Mathias; Beleggia, Marco; Frandsen, Cathrine

    2017-01-01

    Magnetic nanoparticle clusters have several biomedical and engineering applications, and revealing the basic interplay between particle configuration and magnetic properties is important for tuning the clusters for specific uses. Here, we consider the nanoparticles as macrospins and use computer...

  5. Condensed aromatic rings and E{sub 4}/E{sub 6} ratio: humic acids in gleysoils studied by NMR CP/MAS{sup 13}C, and dipolar dephasing; Aneis aromaticos condensados e relacao E{sub 4}/E{sub 6}: estudo de acidos humicos de gleissolos por RMN de {sup 13}C no estado solido utilizando a tecnica CP/MAS desacoplamento defasado

    Energy Technology Data Exchange (ETDEWEB)

    Saab, Sergio da Costa [Universidade Estadual de Ponta Grossa, PR (Brazil). Dept. de Fisica]. E-mail: scsaab@uepg.br; Martin-Neto, Ladislau [Empresa Brasileira de Pesquisa Agropecuaria, Sao Carlos, SP (Brazil)

    2007-03-15

    In this work, seven samples of humic acids extracted from gleysoils were investigated. These studies, using NMR CP/MAS {sup 13}C techniques, did not show significant correlation between the E{sub 4}/E{sub 6} ratio and the degree of aromaticity. However, dipolar dephasing (DD) measurements of condensed aromatic or substituted carbons showed a negative correlation of 0.94. Also, there was a good correlation between the amount of semiquinone free radicals measured by the EPR technique and condensed aromatic rings measured by NMR CP/MAS {sup 13}C with the DD technique. The content of semiquinone free radicals was quantified by EPR spectroscopy and was correlated with the humification (degree of aromaticity) of the humic substances. The results indicated that the E{sub 4}/E{sub 6} ratio identifies the degree of aromatic rings condensation. It was also found that the degree of aromaticity, measured by NMR, as frequently presented in the literature (by conventional CP/MAS), underestimates aromatic rings in condensed structures. (author)

  6. Electromyographic identification of spinal oscillator patterns and recouplings in a patient with incomplete spinal cord lesion: oscillator formation training as a method to improve motor activities.

    Science.gov (United States)

    Schalow, G; Blanc, Y; Jeltsch, W; Zäch, G A

    1996-08-01

    A patient with a strongly lesioned spinal cord, sub C5, relearned running, besides improving other movements, by an oscillator formation training (rhythmic, dynamic, stereotyped exercise). After 45 days of jumping on a springboard and other rhythm trainings, the patient was able to run 90 m in 41 s (7.9 km/h) (even 9.3 km/h 3 years after the lesion) besides marching (5.7 km/h), cycling, playing tennis and skiing. FF-type (alpha 1) (f = 8.3-11.4 Hz) and FR-type (alpha 2) (f = 6.7 Hz) motor unit firings were identified by electromyography (EMG) with surface electrodes by their oscillatory firing patterns in this patient. In EMG literature, the alpha 2-oscillatory firing is called "myokymic discharging". Alternating long and short oscillation periods were measured in FF-type motor units, with changing focus (change from long/short to short/long oscillation periods). The alternating mean period durations differed by approximately 10 ms. Transient synchronization of oscillatory firing FF-type motor units was observed with up to two phase relations per oscillation cycle. In recumbent position, the phase change in synchronization of two oscillatory firing motor units in the soleus muscle of one leg correlated with the change from alternating to symmetrical oscillatory firing of a third motor unit in the soleus muscle of the other leg. This measurement indicates that the alternating oscillatory firing of premotor neuronal networks is correlated with synchronization of oscillatory firing neuronal subnetworks, i.e., with coupling changes of oscillators, and is not due to reciprocal inhibition of half-centre oscillators as suggested by the change from alternating to symmetrical oscillatory firing. Coupling changes of oscillatory firing subnetworks to generate macroscopic (integrative) network functions are therefore a general organization form of the central nervous system (CNS), and are not related to rhythmic movements like walking or running only. It is proposed that synchronization of spinal oscillators, phase changes in synchronization, changes from alternating to symmetrical firing and backwards, and changes in the focus of alternating oscillatory firing are, among others, physiologic coupling rules of the human CNS to generate, by ongoing coupling changes of oscillatory firing subnetworks, integrative functions such as rhythmic and non-rhythmic movements. One phase relation between two oscillatory firing alpha 1-motor units was preserved from one volitional leg muscle activation (isometric contraction) to the subsequent one. Since running times improved upon successive runs for 90 m, the spinal cord seems to be able to store pattern organization for seconds up to minutes. Controlled and uncontrolled oscillatory firing of alpha 1-motor units in volitionally activated leg muscles were observed in this patient, which indicated that there still were pathologic recruitments of subnetworks after re-learning running and other movements. During walking, running, and jumping on a springboard, the activation patterns of the vastus lateralis, hamstrings, tibialis anterior, peronaeus longus, peronaeus brevis and soleus muscles were recorded (surface electromyography) to be still pathologic in accordance with partly still pathologic joint rotation angles measured kinematically. Especially upon running, the left knee joint flexion was reduced in swing by a rather permanent activity of the rectus femoris combined with an extra burst of the vastus lateralis in mid-swing. The recorded abnormalities are due to modification of the motor program rather than to muscle weakness per se. A further improvement of the movements of the patient seems possible by improving the motor program, i.e., by improving the functioning of the spinal pattern generators.(ABSTRACT TRUNCATED)

  7. Does the recoupling of dairy and crop production via cooperation between farms generate environmental benefits? A case-study approach in Europe

    NARCIS (Netherlands)

    Regan, John T.; Marton, Silvia; Barrantes, Olivia; Ruane, Eimear; Hanegraaf, Marjoleine; Berland, Jérémy; Korevaar, Hein; Pellerin, Sylvain; Nesme, Thomas

    2017-01-01

    The intensification of agriculture in Europe has contributed significantly to the decline of mixed crop-livestock farms in favour of specialised farms. Specialisation, when accompanied by intensive farming practices, leaves farms poorly equipped to sustainably manage by-products of production,

  8. A solid-state NMR method for solution of zeolite crystal structures.

    Science.gov (United States)

    Brouwer, Darren H; Darton, Richard J; Morris, Russell E; Levitt, Malcolm H

    2005-07-27

    Since zeolites are notoriously difficult to prepare as large single crystals, structure determination usually relies on powder X-ray diffraction (XRD). However, structure solution (i.e., deriving an initial structural model) directly from powder XRD data is often very difficult due to the diffraction phase problem and the high degree of overlap between the individual reflections, particularly for materials with the structural complexity of most zeolites. Here, we report a method for structure determination of zeolite crystal structures that combines powder XRD and nuclear magnetic resonance (NMR) spectroscopy in which the crucial step of structure solution is achieved using solid-state (29)Si double-quantum dipolar recoupling NMR, which probes the distance-dependent dipolar interactions between naturally abundant (29)Si nuclei in the zeolite framework. For two purely siliceous zeolite blind test samples, we demonstrate that the NMR data can be combined with the unit cell parameters and space group to solve structural models that refine successfully against the powder XRD data.

  9. Measurement of aluminum-carbon distances using S-RESPDOR NMR experiments.

    Science.gov (United States)

    Pourpoint, Frédérique; Trébosc, Julien; Gauvin, Régis M; Wang, Qiang; Lafon, Olivier; Deng, Feng; Amoureux, Jean-Paul

    2012-11-12

    It is demonstrated that reliable aluminum-carbon distances can be measured in samples with (13)C natural abundance by NMR spectroscopy. Overcoupled resonators, with only one radio-frequency synthesizer and one amplifier, are used to irradiate in the same pulse sequence (27)Al and (13)C nuclei, which differ by only 3.6 % in Larmor frequencies. The combination of (27)Al saturation pulse with heteronuclear dipolar recoupling yields dipolar dephasing of the (13)C signal, which only depends on the Al-C distance and the efficiency of the saturation pulse. Therefore, reliable distances can be obtained by rapid fitting of experimental data to an analytical expression. It is demonstrated that with natural isotopic abundance this approach allows recovery of Al-C distances of 216 pm for the covalent bond in lithium tetraalkyl aluminates, commonly used as a co-catalyst in olefin polymerization processes, and which range from 274 to 381 pm for the three carbon atoms in aluminum lactate. The accuracy of the measured internuclear distances is carefully estimated. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Modelling and Experimental Studies of the Effect of Water at the Polymer-Filler Interface in Silica-Filled Siloxane Rubbers

    Energy Technology Data Exchange (ETDEWEB)

    Dinh, L N; Schildbach, M A; Balazs, G B; Gee, R; Maxwell, R S

    2004-08-23

    Silica-filled polydimethylsiloxane (PDMS) composite systems find a broad range of applications due to their chemical and environmental resilience and the ability to fine tune, through chemical and processing modifications, the chemical and mechanical properties resulting in a precise engineering property for the final component. Thus, requirements for, and life-performance predictions of, these materials require an understanding of the interaction between the silica filler and the polymer network. Because silica surfaces are well known to have a high affinity for water adsorption, and this water is a critical part of the interface between the silica particles and the polymer matrix, water at this interface has important consequences on the nature of the silica-polymer bonding and subsequently the mechanical behaviour. Previous studies have reported on the water speciation and long-term outgassing kinetics of common fumed and precipitated silicas used in silicone elastomers, and of one such copolymer system in particular. Several different water species were observed to be present with a range of desorption activation energies. The amount and type of species present were observed to be dependent on the thermal and chemical history of the filler and the composite. Solid state Nuclear Magnetic Resonance (NMR) methods based on quantification of residual magnetic dipolar couplings have also been applied, as these measurements have been shown to be quite sensitive to dynamic and morphological changes in elastomer systems. These residual dipolar couplings in elastomeric materials arise due to polymer network constraints (on the NMR timescale) that prevent the averaging, due to reorientations, of the homonuclear dipolar couplings to zero. Residual dipolar couplings, as a result, can be used to test theories of elasticity, gelation, and polymer conformation. In addition, Molecular Dynamics (MD) investigations have found that the removal of water from the polymer

  11. Determining relative proton-proton proximities from the build-up of two-dimensional correlation peaks in 1H double-quantum MAS NMR: insight from multi-spin density-matrix simulations.

    Science.gov (United States)

    Bradley, Jonathan P; Tripon, Carmen; Filip, Claudiu; Brown, Steven P

    2009-08-28

    The build-up of intensity-as a function of the number, n(rcpl), of POST-C7 elements used for the excitation and reconversion of double-quantum (DQ) coherence (DQC)-is analysed for the fifteen distinct DQ correlation peaks that are observed experimentally for the eight separate (1)H resonances in a (1)H (500 MHz) DQ CRAMPS solid-state (12.5 kHz MAS) NMR spectrum of the dipeptide beta-AspAla (S. P. Brown, A. Lesage, B. Elena, and L. Emsley, J. Am. Chem. Soc., 2004, 126, 13230). The simulation in SPINEVOLUTION (M. Veshtort and R. G. Griffin, J. Magn. Reson., 2006, 178, 248) of t(1) ((1)H DQ evolution) FIDs for clusters of eight dipolar-coupled protons gives separate simulated (1)H DQ build-up curves for the CH(2)(a), CH(2)(b), CH(Asp), CH(Ala), NH and OH (1)H single-quantum (SQ) (1)H resonances. An analysis of both the simulated and experimental (1)H DQ build-up leads to the following general observations: (i) considering the build-up of (1)H DQ peaks at a particular SQ frequency, maximum intensity is observed for the DQC corresponding to the shortest H-H distance; (ii) for the maximum intensity (1)H DQ peak at a particular SQ frequency, the recoupling time for the observed maximum intensity depends on the corresponding H-H distance, e.g., maximum intensity for the CH(2)(a)-CH(2)(b) (H-H distance = 1.55 A) and OH-CH(Asp) (H-H distance = 2.49 A) DQ peaks is observed at n(rcpl) = 2 and 3, respectively; (iii) for DQ peaks involving a CH(2) proton at a non-CH(2) SQ frequency, there is much reduced intensity and a maximum intensity at a short recoupling time; (iv) for the other lower intensity (1)H DQ peaks at a particular SQ frequency, maximum intensity is observed for the same (or close to the same) recoupling time, but the relative intensity of the DQ peaks is a reliable indicator of the relative H-H distance-the ratio of the maximum intensities for the peaks at the CH(Ala) SQ frequency due to the two DQCs with the NH and OH protons are found to be approximately in the

  12. Site-resolved multiple-quantum filtered correlations and distance measurements by magic-angle spinning NMR: Theory and applications to spins with weak to vanishing quadrupolar couplings.

    Science.gov (United States)

    Eliav, U; Haimovich, A; Goldbourt, A

    2016-01-14

    We discuss and analyze four magic-angle spinning solid-state NMR methods that can be used to measure internuclear distances and to obtain correlation spectra between a spin I = 1/2 and a half-integer spin S > 1/2 having a small quadrupolar coupling constant. Three of the methods are based on the heteronuclear multiple-quantum and single-quantum correlation experiments, that is, high rank tensors that involve the half spin and the quadrupolar spin are generated. Here, both zero and single-quantum coherence of the half spins are allowed and various coherence orders of the quadrupolar spin are generated, and filtered, via active recoupling of the dipolar interaction. As a result of generating coherence orders larger than one, the spectral resolution for the quadrupolar nucleus increases linearly with the coherence order. Since the formation of high rank tensors is independent of the existence of a finite quadrupolar interaction, these experiments are also suitable to materials in which there is high symmetry around the quadrupolar spin. A fourth experiment is based on the initial quadrupolar-driven excitation of symmetric high order coherences (up to p = 2S, where S is the spin number) and subsequently generating by the heteronuclear dipolar interaction higher rank (l + 1 or higher) tensors that involve also the half spins. Due to the nature of this technique, it also provides information on the relative orientations of the quadrupolar and dipolar interaction tensors. For the ideal case in which the pulses are sufficiently strong with respect to other interactions, we derive analytical expressions for all experiments as well as for the transferred echo double resonance experiment involving a quadrupolar spin. We show by comparison of the fitting of simulations and the analytical expressions to experimental data that the analytical expressions are sufficiently accurate to provide experimental (7)Li-(13)C distances in a complex of lithium, glycine, and water. Discussion

  13. Acid epimerization of 20-keto pregnane glycosides is determined by 2D-NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, Victor P., E-mail: vpergarw@gobiernodecanarias.org [Instituto de Productos Naturales de Canarias, Departamento de Quimica de Productos Naturales y Biotecnologia (Spain)

    2011-05-15

    Carbohydrates influence many essential biological events such as apoptosis, differentiation, tumor metastasis, cancer, neurobiology, immunology, development, host-pathogen interactions, diabetes, signal transduction, protein folding, and many other contexts. We now report on the structure determination of pregnane glycosides isolated from the aerial parts of Ceropegia fusca Bolle (Asclepiadaceae). The observation of cicatrizant, vulnerary and cytostatic activities in some humans and animals of Ceropegia fusca Bolle, a species endemic to the Canary Islands, encouraged us to begin a pharmacological study to determine their exact therapeutic properties. High resolution {sup 1}H-NMR spectra of pregnane glycosides very often display well-resolved signals that can be used as starting points in several selective NMR experiments to study scalar (J coupling), and dipolar (NOE) interactions. ROESY is especially suited for molecules such that {omega}{tau}{sub c} {approx} 1, where {tau}{sub c} are the motional correlation times and {omega} is the angular frequency. In these cases the NOE is nearly zero, while the rotating-frame Overhauser effect spectroscopy (ROESY) is always positive and increases monotonically for increasing values of {tau}{sub c}. The ROESY shows dipolar interactions cross peaks even in medium-sized molecules which are helpful in unambiguous assignment of all the interglycosidic linkages. Selective excitation was carried out using a double pulsed-field gradient spin-echo sequence (DPFGSE) in which 180 Degree-Sign Gaussian pulses are sandwiched between sine shaped z-gradients. Scalar interactions were studied by homonuclear DPFGSE-COSY and DPFGSE-TOCSY experiments, while DPFGSE-ROESY was used to monitor the spatial environment of the selectively excited proton. Dipolar interactions between nuclei close in space can be detected by the 1D GROESY experiment, which is a one-dimensional counterpart of the 2D ROESY method. The C-12 and C-17 configurations were

  14. Characterization of oil shale, isolated kerogen, and post-pyrolysis residues using advanced 13 solid-state nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Cao, Xiaoyan; Birdwell, Justin E.; Chappell, Mark A.; Li, Yuan; Pignatello, Joseph J.; Mao, Jingdong

    2013-01-01

    Characterization of oil shale kerogen and organic residues remaining in postpyrolysis spent shale is critical to the understanding of the oil generation process and approaches to dealing with issues related to spent shale. The chemical structure of organic matter in raw oil shale and spent shale samples was examined in this study using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Oil shale was collected from Mahogany zone outcrops in the Piceance Basin. Five samples were analyzed: (1) raw oil shale, (2) isolated kerogen, (3) oil shale extracted with chloroform, (4) oil shale retorted in an open system at 500°C to mimic surface retorting, and (5) oil shale retorted in a closed system at 360°C to simulate in-situ retorting. The NMR methods applied included quantitative direct polarization with magic-angle spinning at 13 kHz, cross polarization with total sideband suppression, dipolar dephasing, CHn selection, 13C chemical shift anisotropy filtering, and 1H-13C long-range recoupled dipolar dephasing. The NMR results showed that, relative to the raw oil shale, (1) bitumen extraction and kerogen isolation by demineralization removed some oxygen-containing and alkyl moieties; (2) unpyrolyzed samples had low aromatic condensation; (3) oil shale pyrolysis removed aliphatic moieties, leaving behind residues enriched in aromatic carbon; and (4) oil shale retorted in an open system at 500°C contained larger aromatic clusters and more protonated aromatic moieties than oil shale retorted in a closed system at 360°C, which contained more total aromatic carbon with a wide range of cluster sizes.

  15. Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state 13C nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Cao, X.; Mastalerz, Maria; Chappell, M.A.; Miller, L.F.; Li, Y.; Mao, J.

    2011-01-01

    Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CHn selection, and recoupled C-H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO2 adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO2 saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%-86.1%), nonpolar alkyl groups (9.0%-28.9%), and aromatic C-O carbons (4.1%-9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO2 saturation. After exposure to high pressure CO2, vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO2 adsorption samples compared to the original lithotypes. These observations suggested chemical CO2-coal interactions at high pressure and the selectivity of lithotypes in response to CO2 adsorption. ?? 2011 Elsevier B.V.

  16. High-resolution NMR characterization of low abundance oligomers of amyloid-β without purification.

    Science.gov (United States)

    Kotler, Samuel A; Brender, Jeffrey R; Vivekanandan, Subramanian; Suzuki, Yuta; Yamamoto, Kazutoshi; Monette, Martine; Krishnamoorthy, Janarthanan; Walsh, Patrick; Cauble, Meagan; Holl, Mark M Banaszak; Marsh, E Neil G; Ramamoorthy, Ayyalusamy

    2015-07-03

    Alzheimer's disease is characterized by the misfolding and self-assembly of the amyloidogenic protein amyloid-β (Aβ). The aggregation of Aβ leads to diverse oligomeric states, each of which may be potential targets for intervention. Obtaining insight into Aβ oligomers at the atomic level has been a major challenge to most techniques. Here, we use magic angle spinning recoupling (1)H-(1)H NMR experiments to overcome many of these limitations. Using (1)H-(1)H dipolar couplings as a NMR spectral filter to remove both high and low molecular weight species, we provide atomic-level characterization of a non-fibrillar aggregation product of the Aβ1-40 peptide using non-frozen samples without isotopic labeling. Importantly, this spectral filter allows the detection of the specific oligomer signal without a separate purification procedure. In comparison to other solid-state NMR techniques, the experiment is extraordinarily selective and sensitive. A resolved 2D spectra could be acquired of a small population of oligomers (6 micrograms, 7% of the total) amongst a much larger population of monomers and fibers (93% of the total). By coupling real-time (1)H-(1)H NMR experiments with other biophysical measurements, we show that a stable, primarily disordered Aβ1-40 oligomer 5-15 nm in diameter can form and coexist in parallel with the well-known cross-β-sheet fibrils.

  17. Analysis of the Electronic Structure of the Special Pair of a Bacterial Photosynthetic Reaction Center by 13 C Photochemically Induced Dynamic Nuclear Polarization Magic-Angle Spinning NMR Using a Double-Quantum Axis.

    Science.gov (United States)

    Najdanova, Marija; Gräsing, Daniel; Alia, A; Matysik, Jörg

    2018-01-01

    The origin of the functional symmetry break in bacterial photosynthesis challenges since several decades. Although structurally very similar, the two branches of cofactors in the reaction center (RC) protein complex act very differently. Upon photochemical excitation, an electron is transported along one branch, while the other remains inactive. Photochemically induced dynamic nuclear polarization (photo-CIDNP) magic-angle spinning (MAS) 13 C NMR revealed that the two bacteriochlorophyll cofactors forming the "Special Pair" donor dimer are already well distinguished in the electronic ground state. These previous studies are relying solely on 13 C-13 C correlation experiments as radio-frequency-driven recoupling (RFDR) and dipolar-assisted rotational resonance (DARR). Obviously, the chemical-shift assignment is difficult in a dimer of tetrapyrrole macrocycles, having eight pyrrole rings of similar chemical shifts. To overcome this problem, an INADEQUATE type of experiment using a POST C7 symmetry-based approach is applied to selectively isotope-labeled bacterial RC of Rhodobacter (R.) sphaeroides wild type (WT). We, therefore, were able to distinguish unresolved sites of the macromolecular dimer. The obtained chemical-shift pattern is in-line with a concentric assembly of negative charge within the common center of the Special Pair supermolecule in the electronic ground state. © 2017 The American Society of Photobiology.

  18. 2D {sup 31}P solid state NMR spectroscopy, electronic structure and thermochemistry of PbP{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Benndorf, Christopher [Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster (Germany); Institut für Physikalische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster (Germany); Hohmann, Andrea; Schmidt, Peer [Brandenburgische Technische Universität Cottbus-Senftenberg, Fakultät für Naturwissenschaften, Postfach 101548, 01958 Senftenberg (Germany); Eckert, Hellmut, E-mail: eckerth@uni-muenster.de [Institut für Physikalische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster (Germany); Instituto de Física de Sao Carlos, Universidade de Sao Paulo, CEP 369, Sao Carlos, SP 13560-590 (Brazil); Johrendt, Dirk [Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstraße 5-13, D-81377 München (Germany); and others

    2016-03-15

    Phase pure polycrystalline PbP{sub 7} was prepared from the elements via a lead flux. Crystalline pieces with edge-lengths up to 1 mm were obtained. The assignment of the previously published {sup 31}P solid state NMR spectrum to the seven distinct crystallographic sites was accomplished by radio-frequency driven dipolar recoupling (RFDR) experiments. As commonly found in other solid polyphosphides there is no obvious correlation between the {sup 31}P chemical shift and structural parameters. PbP{sub 7} decomposes incongruently under release of phosphorus forming liquid lead as remainder. The thermal decomposition starts at T>550 K with a vapor pressure almost similar to that of red phosphorus. Electronic structure calculations reveal PbP{sub 7} as a semiconductor according to the Zintl description and clearly shows the stereo-active Pb-6s{sup 2} lone pairs in the electron localization function ELF. - Graphical abstract: Coordination of the lead atoms in PbP{sub 7}.

  19. Yeast prion architecture explains how proteins can be genes

    Science.gov (United States)

    Wickner, Reed

    2013-03-01

    Prions (infectious proteins) transmit information without an accompanying DNA or RNA. Most yeast prions are self-propagating amyloids that inactivate a normally functional protein. A single protein can become any of several prion variants, with different manifestations due to different amyloid structures. We showed that the yeast prion amyloids of Ure2p, Sup35p and Rnq1p are folded in-register parallel beta sheets using solid state NMR dipolar recoupling experiments, mass-per-filament-length measurements, and filament diameter measurements. The extent of beta sheet structure, measured by chemical shifts in solid-state NMR and acquired protease-resistance on amyloid formation, combined with the measured filament diameters, imply that the beta sheets must be folded along the long axis of the filament. We speculate that prion variants of a single protein sequence differ in the location of these folds. Favorable interactions between identical side chains must hold these structures in-register. The same interactions must guide an unstructured monomer joining the end of a filament to assume the same conformation as molecules already in the filament, with the turns at the same locations. In this way, a protein can template its own conformation, in analogy to the ability of a DNA molecule to template its sequence by specific base-pairing. Bldg. 8, Room 225, NIH, 8 Center Drive MSC 0830, Bethesda, MD 20892-0830, wickner@helix.nih.gov, 301-496-3452

  20. Solvent-free one-pot 1,3-dipolar cycloaddition reactions of ...

    Indian Academy of Sciences (India)

    Int. Ed. 43 6250. 3. Perreux L and Loupy A 2001 Tetrahedron 57 9199. 4. Loupy A, Petti A, Hamelin J, Texier-Boullet F, Jacquault. P and Mathé D 1998 Synthesis 9 1213. 5. Loupy A 2006 Microwaves in organic synthesis. (Weinheim, Germany: Wiley-VCH) 2nd edn. 6. Kabalka G W and Pagni R M 1997 Tetrahedron 53 7999.

  1. Parametric amplification of matter waves in dipolar spinor Bose-Einstein condensates

    DEFF Research Database (Denmark)

    Deuretzbacher, F.; Gebreyesus, G.; Topic, O.

    2010-01-01

    Spin-changing collisions may lead under proper conditions to the parametric amplification of matter waves in spinor Bose-Einstein condensates. Magnetic dipole-dipole interactions, although typically very weak in alkali-metal atoms, are shown to play a very relevant role in the amplification process...

  2. Liquid ammonia as a dipolar aprotic solvent for aliphatic nucleophilic substitution reactions.

    Science.gov (United States)

    Ji, Pengju; Atherton, John; Page, Michael I

    2011-03-04

    The rate constants for the reactions of a variety of nucleophiles reacting with substituted benzyl chlorides in liquid ammonia (LNH(3)) have been determined. To fully interpret the associated linear free-energy relationships, the ionization constants of phenols ions in liquid ammonia were obtained using UV spectra. These equilibrium constants are the product of those for ion-pair formation and dissociation to the free ions, which can be separated by evaluating the effect of added ammonium ions. There is a linear relationship between the pK(a) of phenols in liquid ammonia and those in water of slope 1.68. Aminium ions exist in their unprotonated free base form in liquid ammonia and their ionization constants could not be determined by NMR. The rates of solvolysis of substituted benzyl chlorides in liquid ammonia at 25 °C show a Hammett ρ of zero, having little or no dependence upon ring substituents, which is in stark contrast with the hydrolysis rates of substituted benzyl halides in water, which vary 10(7) fold. The rate of substitution of benzyl chloride by substituted phenoxide ions is first order in the concentration of the nucleophile indicative of a S(N)2 process, and the dependence of the rate constants on the pK(a) of the phenol in liquid ammonia generates a Brønsted β(nuc) = 0.40. Contrary to the solvolysis reaction, the reaction of phenoxide ion with 4-substituted benzyl chlorides gives a Hammett ρ = 1.1, excluding the 4-methoxy derivative, which shows the normal positive deviation. The second order rate constants for the substitution of benzyl chlorides by neutral and anionic amines show a single Brønsted β(nuc) = 0.21 (based on the aqueous pK(a) of amine), but their dependence on the substituent in substituted benzyl chlorides varies with a Hammett ρ of 0 for neutral amines, similar to that seen for solvolysis, whereas that for amine anions is 0.93, similar to that seen for phenoxide ion.

  3. Silicone elastomers with high dielectric permittivity and high dielectric breakdown strength based on dipolar copolymers

    DEFF Research Database (Denmark)

    Madsen, Frederikke Bahrt; Yu, Liyun; Daugaard, Anders Egede

    2014-01-01

    Dielectric elastomers (DES) are a promising new transducer technology, but high driving voltages limit their current commercial potential. One method used to lower driving voltage is to increase dielectric permittivity of the elastomer. A novel silicone elastomer system with high dielectric......-4-nitrobenzene. Here, a high increase in dielectric permittivity (similar to 70%) was obtained without compromising other favourable DE properties such as elastic modulus, gel fraction, dielectric loss and electrical breakdown strength. © 2014 Elsevier Ltd. All rights reserved....

  4. Tunable negligible-loss energy transfer between dipolar-coupled magnetic disks by stimulated vortex gyration

    OpenAIRE

    Hyunsung Jung; Ki-Suk Lee; Dae-Eun Jeong; Youn-Seok Choi; Young-Sang Yu; Dong-Soo Han; Andreas Vogel; Lars Bocklage; Guido Meier; Mi-Young Im; Peter Fischer; Sang-Koog Kim

    2011-01-01

    A wide variety of coupled harmonic oscillators exist in nature. Coupling between different oscillators allows for the possibility of mutual energy transfer between them and the information-signal propagation. Low-energy input signals and their transport with negligible energy loss are the key technological factors in the design of information-signal processing devices. Here, utilizing the concept of coupled oscillators, we experimentally demonstrated a robust new mechanism for energy transfer...

  5. Tunable energy transfer between dipolar-coupled magnetic disks by stimulated vortex gyration

    OpenAIRE

    Jung, Hyunsung; Lee, Ki-Suk; Jeong, Dae-Eun; Choi, Youn-Seok; Yu, Young-Sang; Han, Dong-Soo; Vogel, Andreas; Bocklage, Lars; Meier, Guido; Im, Mi-Young; Fischer, Peter; Kim, Sang-Koog

    2010-01-01

    A wide variety of coupled harmonic oscillators exist in nature1. Coupling between different oscillators allows for the possibility of mutual energy transfer between them2-4 and the information-signal propagation5,6. Low-energy input signals and their transport with low-energy dissipation are the key technical factors in the design of information processing devices7. Here, utilizing the concept of coupled oscillators, we experimentally demonstrated a robust new mechanism for energy transfer be...

  6. Trapped fermions with short-range and dipolar interactions in 2D optical lattices

    DEFF Research Database (Denmark)

    Larsen, Anne-Louise G.

    Ultracold atoms in optical lattices are ideal quantum simulators of complex many-body Hamiltonians that arise in condensed matter systems. Manipulation of these model systems allows us to explore a variety of physical phenomena taking place in solid state systems. Here, we present mean...

  7. Superfluidity of a dipolar Fermi gas in 2D optical lattices bilayer

    Energy Technology Data Exchange (ETDEWEB)

    Camacho-Guardian, A.; Paredes, R. [Instituto de Fisica, Universidad Nacional Autonoma de Mexico (Mexico)

    2016-12-15

    Ultracold Fermi molecules lying in 2D square optical lattices bilayers with its dipole moment perpendicularly aligned to the layers, having interlayer finite range s-wave interactions, are shown to form superfluid phases, both, in the Bardeen, Cooper and Schrieffer (BCS) regime of Cooper pairs, and in the condensate regime of bound dimeric molecules. We demonstrate this result using a functional integral scheme within the Ginzburg-Landau theory. For the deep Berezinskii-Kosterlitz-Thouless (BKT) phase transition, we predict critical temperatures around 5 nK and 20 nK for {sup 23}Na{sup 40}K and OH molecules, which are within reach of current experiments [J. W. Park, S. Will and M. Zwierlein, Phys. Rev. Lett. 114, 205302 (2015)]. (copyright 2016 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Coupling of a dipolar emitter into one-dimensional surface plasmon.

    Science.gov (United States)

    Barthes, Julien; Bouhelier, Alexandre; Dereux, Alain; Colas des Francs, Gérard

    2013-01-01

    Quantum plasmonics relies on a new paradigm for light-matter interaction. It benefits from strong confinement of surface plasmon polaritons (SPP) that ensures efficient coupling at a deep subwavelength scale, instead of working with a long lifetime cavity polariton that increases the duration of interaction. The large bandwidth and the strong confinement of one dimensional SPP enable controlled manipulation of a nearby quantum emitter. This paves the way to ultrafast nanooptical devices. However, the large SPP bandwidth originates from strong losses so that a clear understanding of the coupling process is needed. In this report, we investigate in details the coupling between a single emitter and a plasmonic nanowire, but also SPP mediated coupling between two emitters. We notably clarify the role of losses in the Purcell factor, unavoidable to achieve nanoscale confinement down to 10(-4)(λ/n)(3). Both the retarded and band-edge quasi-static regimes are discussed.

  9. Multi-ion sensing of dipolar noise sources in ion traps

    Science.gov (United States)

    Galve, F.; Alonso, J.; Zambrini, R.

    2017-09-01

    Trapped-ion quantum platforms are subject to "anomalous" heating due to interactions with electric-field noise sources of nature not yet completely known. There is ample experimental evidence that this noise originates at the surfaces of the trap electrodes, and models assuming fluctuating pointlike dipoles are consistent with observations, but the exact microscopic mechanisms behind anomalous heating remain undetermined. Here we show how a two-ion probe displays a transition in its dissipation properties, enabling experimental access to the mean orientation of the dipoles and the spatial extent of dipole-dipole correlations. This information can be used to test the validity of candidate microscopic models, which predict correlation lengths spanning several orders of magnitude. Furthermore, we propose an experiment to measure these effects with currently available traps and techniques.

  10. Charged perfect fluid tori in strong central gravitational and dipolar magnetic fields

    Czech Academy of Sciences Publication Activity Database

    Kovář, J.; Slaný, P.; Cremaschini, C.; Stuchlík, Z.; Karas, Vladimír; Trova, Audrey

    2016-01-01

    Roč. 93, June (2016), 124055/1-124055/20 ISSN 1550-7998 R&D Projects: GA ČR GB14-37086G; GA MŠk(CZ) LH14049 Grant - others:GA ČR(CZ) GP14-07753P Institutional support: RVO:67985815 Keywords : black holes * accretion discscretion discs Subject RIV: BN - Astronomy, Celestial Mechanics, Astrophysics Impact factor: 4.643, year: 2014

  11. Bilayered smectic phase polymorphism in the dipolar Gay-Berne liquid crystal model.

    Science.gov (United States)

    Houssa, Mohammed; Rull, Luis F; Romero-Enrique, Jose M

    2009-04-21

    We present computer simulations of the Gay-Berne model with a strong terminal dipole. We report the existence of different stable antiferroelectric interdigitated bilayered phases in this model with diverse in-plane organization. The occurrence of these phases depends crucially on the value of the molecular elongation kappa. For kappa=3 we find an interdigitated bilayered smectic-A phase (absent when there is no dipole) and a bilayered smectic-T (or crystal) with positional in-plane tetragonal ordering, different from the hexatic observed in the absence of the molecular dipole. For kappa=4, bilayered smectic-A and in-plane hexatic-ordered smectic-B (or crystal) phases are observed.

  12. Effects of electric field on thermodynamics and ordering of a dipolar liquid

    Science.gov (United States)

    Johari, G. P.

    2016-10-01

    We propose that an electric field's role in changing the structural disorder may be investigated by comparing the field-induced entropy decrease, ΔES, against the pressure-induced and cooling-induced entropy decreases, ΔpS and ΔTS, respectively, for the same increase in the dielectric α-relaxation time, Δτα, or in the viscosity. If these three quantities are found to be the same, the change in the number of microstates, Δln Ω = ΔS/R, would be the same whether there is an electric field-induced dipole vector alignment, or not. The available data [S. Samanta and R. Richert, J. Chem. Phys. 142, 044504 (2015)] show that ΔES ≅ ΔpS, and ΔES ≅ ΔTS. We further argue that in the case of conformational disorder without hydrodynamics, as for a flexible molecule's orientationally disordered or plastic crystal, ΔTS would be more negative than ΔES for the same increase in Δτα. For cyclo-octanol plastic crystal, whose octyl-ring would lose some of its dielectrically inactive conformational degrees of freedom on cooling, ΔTS is five-times ΔES. Hence the entropy of such crystals may not be related to their τα, an aspect relevant to certain biopolymer crystals. We also mention other effects of E. The findings are relevant to a number of recent studies on the analysis of the effect of electric field on a liquid's properties. The method can be used to study the role of other entropy-altering variables in liquid crystals and ferromagnetic liquids.

  13. Rapid measurement of residual dipolar couplings for fast fold elucidation of proteins

    Energy Technology Data Exchange (ETDEWEB)

    Rasia, Rodolfo M. [Jean-Pierre Ebel CNRS/CEA/UJF, Institut de Biologie Structurale (France); Lescop, Ewen [CNRS, Institut de Chimie des Substances Naturelles (France); Palatnik, Javier F. [Universidad Nacional de Rosario, Instituto de Biologia Molecular y Celular de Rosario, Facultad de Ciencias Bioquimicas y Farmaceuticas (Argentina); Boisbouvier, Jerome, E-mail: jerome.boisbouvier@ibs.fr; Brutscher, Bernhard, E-mail: Bernhard.brutscher@ibs.fr [Jean-Pierre Ebel CNRS/CEA/UJF, Institut de Biologie Structurale (France)

    2011-11-15

    It has been demonstrated that protein folds can be determined using appropriate computational protocols with NMR chemical shifts as the sole source of experimental restraints. While such approaches are very promising they still suffer from low convergence resulting in long computation times to achieve accurate results. Here we present a suite of time- and sensitivity optimized NMR experiments for rapid measurement of up to six RDCs per residue. Including such an RDC data set, measured in less than 24 h on a single aligned protein sample, greatly improves convergence of the Rosetta-NMR protocol, allowing for overnight fold calculation of small proteins. We demonstrate the performance of our fast fold calculation approach for ubiquitin as a test case, and for two RNA-binding domains of the plant protein HYL1. Structure calculations based on simulated RDC data highlight the importance of an accurate and precise set of several complementary RDCs as additional input restraints for high-quality de novo structure determination.

  14. Synthesis of aryl-1H-1,2,3-triazoles via 1,3-dipolar cycloaddition

    Directory of Open Access Journals (Sweden)

    Wagner O. Valença

    2012-06-01

    Full Text Available A series of Aryl-1H-1,2,3-triazoles were prepared from the reaction between aril-azide (1 with 1.5 equiv. of terminal alkynes (2a-o. The reactions carried out at room temperature and in the presence of CuI (10 mol% in acetonitrile. The compounds (3a-o were obtained in moderate-to-good yields (50-94%. In general, not was observed significant inductive effect on the reactivity of the alkynes (2a-f. The alcohol alkynes (2i-k showed moderate yields 50-72%. On the other hand, the reaction with alkyl alkynes (2m,n furnished the compounds (3m and (3n in excellent yields of 89% and 90%, respectively.

  15. Quantum few-body bound states of dipolar particles in a helical geometry

    DEFF Research Database (Denmark)

    Pedersen, Jakob Knorborg; Fedorov, Dmitri Vladimir; Jensen, Aksel Stenholm

    2016-01-01

    We study a quantum mechanical system consisting of up to three identical dipoles confined to move along a helical shaped trap. The long-range interactions between particles confined to move in this one dimension leads to an interesting effective two-particle potential with an oscillating behavior...

  16. Electromagnetic Low-Frequency Dipolar Excitation of Two Metal Spheres in a Conductive Medium

    Directory of Open Access Journals (Sweden)

    Panayiotis Vafeas

    2012-01-01

    Full Text Available This work concerns the low-frequency interaction of a time-harmonic magnetic dipole, arbitrarily orientated in the three-dimensional space, with two perfectly conducting spheres embedded within a homogeneous conductive medium. In such physical applications, where two bodies are placed near one another, the 3D bispherical geometry fits perfectly. Considering two solid impenetrable (metallic obstacles, excited by a magnetic dipole, the scattering boundary value problem is attacked via rigorous low-frequency expansions in terms of integral powers (ikn, where n≥0, k being the complex wave number of the exterior medium, for the incident, scattered, and total non-axisymmetric electric and magnetic fields. We deal with the static (n=0 and the dynamic (n=1,2,3 terms of the fields, while for n≥4 the contribution has minor significance. The calculation of the exact solutions, satisfying Laplace’s and Poisson’s differential equations, leads to infinite linear systems, solved approximately within any order of accuracy through a cut-off procedure and via numerical implementation. Thus, we obtain the electromagnetic fields in an analytically compact fashion as infinite series expansions of bispherical eigenfunctions. A simulation is developed in order to investigate the effect of the radii ratio, the relative position of the spheres, and the position of the dipole on the real and imaginary parts of the calculated scattered magnetic field.

  17. Dipolar degrees of freedom and Isospin equilibration processes in Heavy Ion collisions

    CERN Document Server

    Papa, M; Acosta, L; Amorini, F; Agodi, C; Anzalone, A; Auditore, L; Cardella, G; Cavallaro, S; Chatterjee, M B; De Filippo, E; Francalanza, L; Geraci, E; Grassi, L; Gnoffo, B; Han, J; La Guidara, E; Lanzalone, G; Lombardo, I; Pagano, C Maiolino T Minniti A; Pagano, E V; Pirrone, S; Politi, G; Porto, F; Quattrocchi, L; Rizzo, F; Rosato, E; Russotto, P; Trifirò, A; Trimarchi, M; Verde, G; Vigilante, and M

    2015-01-01

    Background: In heavy ion collision at the Fermi energies Isospin equilibration processes occur- ring when nuclei with different charge/mass asymmetries interacts have been investigated to get information on the nucleon-nucleon Iso-vectorial effective interaction. Purpose: In this paper, for the system 48Ca +27 Al at 40 MeV/nucleon, we investigate on this process by means of an observable tightly linked to isospin equilibration processes and sensitive in exclusive way to the dynamical stage of the collision. From the comparison with dynamical model calculations we want also to obtain information on the Iso-vectorial effective microscopic interaction. Method: The average time derivative of the total dipole associated to the relative motion of all emitted charged particles and fragments has been determined from the measured charges and velocities by using the 4? multi-detector CHIMERA. The average has been determined for semi- peripheral collisions and for different charges Zb of the biggest produced fragment. E...

  18. Revisiting the Low-Frequency Dipolar Perturbation by an Impenetrable Ellipsoid in a Conductive Surrounding

    Directory of Open Access Journals (Sweden)

    Panayiotis Vafeas

    2017-01-01

    Full Text Available This contribution deals with the scattering by a metallic ellipsoidal target, embedded in a homogeneous conductive medium, which is stimulated when a 3D time-harmonic magnetic dipole is operating at the low-frequency realm. The incident, the scattered, and the total three-dimensional electromagnetic fields, which satisfy Maxwell’s equations, yield low-frequency expansions in terms of positive integral powers of the complex-valued wave number of the exterior medium. We preserve the static Rayleigh approximation and the first three dynamic terms, while the additional terms of minor contribution are neglected. The Maxwell-type problem is transformed into intertwined potential-type boundary value problems with impenetrable boundary conditions, whereas the environment of a genuine ellipsoidal coordinate system provides the necessary setting for tackling such problems in anisotropic space. The fields are represented via nonaxisymmetric infinite series expansions in terms of harmonic eigenfunctions, affiliated with the ellipsoidal system, obtaining analytical closed-form solutions in a compact fashion. Until nowadays, such problems were attacked by using the very few ellipsoidal harmonics exhibiting an analytical form. In the present article, we address this issue by incorporating the full series expansion of the potentials and utilizing the entire subspace of ellipsoidal harmonic eigenfunctions.

  19. Dipolar cross-linkers for PDMS networks with enhanced dielectric permittivity and low dielectric loss

    DEFF Research Database (Denmark)

    Bahrt, Frederikke; Daugaard, Anders Egede; Hvilsted, Søren

    2013-01-01

    -(4-((4-nitrophenyl)diazenyl)phenoxy)-prop-1-yn-1-ylium, with a synthesized silicone compatible azide-functional cross-linker by click chemistry. The thermal, mechanical and electromechanical properties were investigated for PDMS films with 0 to 3.6 wt% of dipole-cross-linker. The relative dielectric permittivity...

  20. Ordering, thermal excitations and phase transitions in dipolar coupled mono-domain magnet arrays

    Science.gov (United States)

    Kapaklis, Vassilios

    2015-03-01

    Magnetism has provided a fertile test bed for physical models, such as the Heisenberg and Ising models. Most of these investigations have focused on solid materials and relate to their atomic properties such as the atomic magnetic moments and their interactions. Recently, advances in nanotechnology have enabled the controlled patterning of nano-sized magnetic particles, which can be arranged in extended lattices. Tailoring the geometry and the magnetic material of these lattices, the magnetic interactions and magnetization reversal energy barriers can be tuned. This enables interesting interaction schemes to be examined on adjustable length and energy scales. As a result such nano-magnetic systems represent an ideal playground for the study of physical model systems, being facilitated by direct magnetic imaging techniques. One particularly interesting case is that of systems exhibiting frustration, where competing interactions cannot be simultaneously satisfied. This results in a degeneracy of the ground state and intricate thermodynamic properties. An archetypical frustrated physical system is water ice. Similar physics can be mirrored in nano-magnetic arrays, by tuning the arrangement of neighboring magnetic islands, referred to as artificial spin ice. Thermal excitations in such systems resemble magnetic monopoles. In this presentation key concepts related to nano-magnetism and artificial spin ice will be introduced and discussed, along with recent experimental and theoretical developments.

  1. Structural and dipolar fluctuations in liquid water: a Car–Parrinello molecular dynamics study

    OpenAIRE

    Skarmoutsos, Ioannis; Masia, Marco; Guàrdia Manuel, Elvira

    2016-01-01

    A Car–Parrinello molecular dynamics simulation was performed to investigate the local tetrahedral order, molecular dipole fluctuations and their interrelation with hydrogen bonding in liquid water. Water molecules were classified in three types, exhibiting low, intermediate and high tetrahedral order. Transitions from low to high tetrahedrally ordered structures take place only through transitions to the intermediate state. The molecular dipole moments depend strongly on the tetrahedral order...

  2. Terahertz response of dipolar impurities in polar liquids: on anomalous dielectric absorption of protein solutions.

    Science.gov (United States)

    Matyushov, Dmitry V

    2010-02-01

    A theory of radiation absorption by dielectric mixtures is presented. The coarse-grained formulation is based on the wave-vector-dependent correlation functions of molecular dipoles of the host polar liquid and a density structure factor of the solutes. A nonlinear dependence of the dielectric absorption coefficient on the solute concentration is predicted and originates from the mutual polarization of the liquid surrounding the solutes by the collective field of the solute dipoles aligned along the radiation field. The theory is applied to terahertz absorption of hydrated saccharides and proteins. While the theory gives an excellent account of the observations for saccharides, without additional assumptions and fitting parameters, experimental absorption coefficient of protein solutions significantly exceeds theoretical calculations with dipole moment of the bare protein assigned to the solute and shows a peak against the protein concentration. A substantial polarization of protein's hydration shell, resulting in a net dipole moment, is required to explain the disagreement between theory and experiment. When the correlation function of the total dipole moment of the protein with its hydration shell from numerical simulations is used in the analytical model, an absorption peak, qualitatively similar to that seen in experiment, is obtained. The existence and position of the peak are sensitive to the specifics of the protein-protein interactions. Numerical testing of the theory requires the combination of dielectric and small-angle scattering measurements. The calculations confirm that "elastic ferroelectric bag" of water shells observed in previous numerical simulations is required to explain terahertz dielectric measurements.

  3. Structural and dipolar fluctuations in liquid water: A Car-Parrinello molecular dynamics study

    Science.gov (United States)

    Skarmoutsos, Ioannis; Masia, Marco; Guardia, Elvira

    2016-03-01

    A Car-Parrinello molecular dynamics simulation was performed to investigate the local tetrahedral order, molecular dipole fluctuations and their interrelation with hydrogen bonding in liquid water. Water molecules were classified in three types, exhibiting low, intermediate and high tetrahedral order. Transitions from low to high tetrahedrally ordered structures take place only through transitions to the intermediate state. The molecular dipole moments depend strongly on the tetrahedral order and hydrogen bonding. The average dipole moment of water molecules with a strong tetrahedral order around them comes in excellent agreement with previous estimations of the dipole moment of ice Ih molecules.

  4. From spin induced ferroelectricity to dipolar glasses: Spinel chromites and mixed delafossites

    Science.gov (United States)

    Maignan, A.; Martin, C.; Singh, K.; Simon, Ch.; Lebedev, O. I.; Turner, S.

    2012-11-01

    Magnetoelectric multiferroics showing coupling between polarization and magnetic order are attracting much attention. For instance, they could be used in memory devices. Metal-transition oxides are provided several examples of inorganic magnetoelectric multiferroics. In the present short review, spinel and delafossite chromites are described. For the former, an electric polarization is evidenced in the ferrimagnetic state for ACr2O4 polycrystalline samples (A=Ni, Fe, Co). The presence of a Jahn-Teller cation such as Ni2+ at the A site is shown to yield larger polarization values. In the delafossites, substitution by V3+ at the Cr or Fe site in CuCrO2 (CuFeO2) suppresses the complex antiferromagnetic structure at the benefit of a spin glass state. The presence of cation disorder, probed by transmission electron microscopy, favors relaxor-like ferroelectricity. The results on the ferroelectricity of ferrimagnets and insulating spin glasses demonstrate that, in this research field, transition-metal oxides are worth to be studied.

  5. Systematic Investigation of Organic Photovoltaic Cell Charge Injection/Performance Modulation by Dipolar Organosilane Interfacial Layers

    Science.gov (United States)

    2013-08-13

    room temperature. The solution was diluted with distilled water (40 mL) and the product was extracted with ethyl acetate (3 × 15 mL). The organic...character of the products and highly reactive nature of the −SiCl3 moieties. The 1H, 13C, and 19F NMR spectra of all new compounds are provided in the...layer = poly(3-hexylthiophene):phenyl- C71-butyric acid methyl ester (P3HT:PC71BM) or poly[[4,8-bis[(2-ethylhexyl)- oxy]benzo[1,2-b:4,5-b’]dithiophene

  6. Enhanced reactivity of dinuclear Copper(I) acetylides in dipolar cycloadditions

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Fokin, V.V.

    2007-01-01

    Dinuclear alkynyl copper(I) complexes exhibit superior reactivity toward organic azides compared to their monomeric analogues. DFT studies indicate that the second copper center facilitates the formation of the cupracycle in the rate-determining step and stabilizes the metallacycle intermediate i...

  7. Measurement of the Spin-Dipolar Part of the Tensor Polarizability of Rb 87

    Science.gov (United States)

    Dallal, Yehonatan; Ozeri, Roee

    2015-10-01

    We report on the measurement of the contribution of the magnetic-dipole hyperfine interaction to the tensor polarizaility of the electronic ground state in Rb 87 . This contribution was isolated by measuring the differential shift of the clock transition frequency in Rb 87 atoms that were optically trapped in the focus of an intense CO2 laser beam. By comparing to previous tensor polarizability measurements in Rb 87 , the contribution of the interaction with the nuclear electric-quadrupole moment was isolated as well. Our measurement will enable better estimation of blackbody shifts in Rb atomic clocks. The methods reported here are applicable for future spectroscopic studies of atoms and molecules under strong quasistatic fields.

  8. DFT study of the mechanism and stereoselectivity of the 1,3-dipolar ...

    Indian Academy of Sciences (India)

    electron-rich cyclic dipolarophiles: α, β-unsaturated lactones and vinyl ethers. Different reaction channels and reactants approaches, effective in regio- and stereo- chemical preferences are discussed; the results were compared to experimental data and found in good agreement.14 Recently, Acharjee and Banerji15.

  9. On the Electric Fields Produced by Dipolar Coulomb Charges of an Individual Thundercloud in the Ionosphere

    Directory of Open Access Journals (Sweden)

    Vitaly P. Kim

    2015-06-01

    Full Text Available In this paper we study the transmission of the electrostatic field due to coulomb charges of an individual thundercloud into the midlatitude ionosphere, taking into account the total geomagnetic field integrated Pedersen conductivity of the ionosphere. It is shown that at ionospheric altitudes, a typical thundercloud produces an insignificant electrostatic field whereas a giant thundercloud can drive the horizontal electrostatic field with a magnitude of ~270 μV/m for nighttime conditions.

  10. Effects of dipolar interactions on magnetic properties of Co nanowire arrays

    Science.gov (United States)

    Li, Hong-Jian; Yue, Ming; Wu, Qiong; Peng, Yi; Li, Yu-Qing; Liu, Wei-Qiang; Zhang, Dong-Tao; Zhang, Jiu-Xing

    2017-10-01

    Not Available Project supported by the National Natural Science Foundation of China (Grant Nos. 51401001, 51371002, and 51331003) and the International S&T Cooperation Program of China (Grant No. 2015DFG52020).

  11. Dipolar Relaxation Dynamics at the Active Site of an ATPase Regulated by Membrane Lateral Pressure

    Czech Academy of Sciences Publication Activity Database

    Fischermeier, E.; Pospíšil, Petr; Sayed, A.; Hof, Martin; Solioz, M.; Fahmy, K.

    2017-01-01

    Roč. 56, č. 5 (2017), s. 1269-1272 ISSN 1433-7851 R&D Projects: GA ČR(CZ) GBP208/12/G016 Institutional support: RVO:61388955 Keywords : fluorescence * ion pump * membrane proteins * nanodiscs * time-resolved emission Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 11.994, year: 2016

  12. Versatile Scope of a Masked Aldehyde Nitrone in 1,3-Dipolar Cycloadditions

    NARCIS (Netherlands)

    Hoogenboom, Jorin; Zuilhof, Han; Wennekes, Tom

    2015-01-01

    A new masked aldehyde-containing nitrone 1 that is easily available through a facile one-step procedure has been developed. It undergoes a [3 + 2]-thermal cycloaddition with a wide range of dipolarophiles, affording isoxazolidine cycloadducts that are suitable for versatile postcycloaddition

  13. Dynamo Scaling Laws for Uranus and Neptune: The Role of Convective Shell Thickness on Dipolarity

    Science.gov (United States)

    Stanley, Sabine; Yunsheng Tian, Bob

    2017-10-01

    Previous dynamo scaling law studies (Christensen and Aubert, 2006) have demonstrated that the morphology of a planet’s magnetic field is determined by the local Rossby number (Ro_l): a non-dimensional diagnostic variable that quantifies the ratio of inertial forces to Coriolis forces on the average length scale of the flow. Dynamos with Ro_l ~ 0.1 produce multipolar magnetic fields. Scaling studies have also determined the dependence of the local Rossby number on non-dimensional parameters governing the system - specifically the Ekman, Prandtl, magnetic Prandtl and flux-based Rayleigh numbers (Olson and Christensen, 2006). When these scaling laws are applied to the planets, it appears that Uranus and Neptune should have dipole-dominated fields, contrary to observations. However, those scaling laws were derived using the specific convective shell thickness of the Earth’s core. Here we investigate the role of convective shell thickness on dynamo scaling laws. We find that the local Rossby number depends exponentially on the convective shell thickness. Including this new dependence on convective shell thickness, we find that the dynamo scaling laws now predict that Uranus and Neptune reside deeply in the multipolar regime, thereby resolving the previous contradiction with observations.

  14. Manipulating the dipolar magnetic interactions in FePt square arrays: The role of edge roughness

    Science.gov (United States)

    Norpoth, J.; Dreyer, S.; Jooss, Ch.; Sievers, S.

    2007-05-01

    The high magnetocrystalline anisotropy energy in hard magnetic materials may sustain magnetization distributions in the remanent state, which exhibit a high number of magnetic surface charges and thus significant magnetic stray fields. Here, we focus onto the stray field distribution in the exterior and the demagnetization field distribution in the interior of hard magnetic FePt elements without and with artificial saw tooth edge roughness. Our experiments and calculations reveal that external stray fields and internal demagnetization fields are considerably modified by the artificial edge roughness.

  15. DFT study of the mechanism and stereoselectivity of the 1, 3-dipolar ...

    Indian Academy of Sciences (India)

    Khadija Marakchi1 Rachida Ghailane2 Oum Kaltoum Kabbaj1 Najia Komiha1. Laboratoire de Spectroscopie, Modélisation Moléculaire, Matériaux et Environnement (LS3ME) Université Mohammed V-Agdal Faculté des Sciences, BP 1014 Rabat, Maroc; Laboratoire de Synthèse Organique, Organomtallique et Théorique.

  16. Quantum Factorization of 143 on a Dipolar-Coupling NMR system

    OpenAIRE

    Xu, Nanyang; Zhu, Jing; Lu, Dawei; Zhou, Xianyi; Peng, Xinhua; Du, Jiangfeng

    2011-01-01

    Quantum algorithms could be much faster than classical ones in solving the factoring problem. Adiabatic quantum computation for this is an alternative approach other than Shor's algorithm. Here we report an improved adiabatic factoring algorithm and its experimental realization to factor the number 143 on a liquid crystal NMR quantum processor with dipole-dipole couplings. We believe this to be the largest number factored in quantum-computation realizations, which shows the practical importan...

  17. Ion-dipole interactions are asymptotically unscreened by water in dipolar nanopores, yielding patterned ion distributions

    OpenAIRE

    Leung, Kevin

    2008-01-01

    The permeation, rejection, and transport of electrolytes in water-filled nanopores are critical to ion current gating and desalinalion processes in synthetic porous membranes and the functions of biological ion channels. Mile the effects of confinement pore polarizability, and discrete channel charge sites have been much studied, the potentially dramatic impact of dipole-lined synthetic pores on electrolytes has seldom been addressed. Dipole layers naturally occur on the interior surfaces of ...

  18. Cross-correlated relaxation rates between protein backbone H–X dipolar interactions

    Energy Technology Data Exchange (ETDEWEB)

    Vögeli, Beat, E-mail: beat.vogeli@ucdenver.edu [University of Colorado Denver, Department of Biochemistry and Molecular Genetics (United States)

    2017-03-15

    The relaxation interference between dipole–dipole interactions of two separate spin pairs carries structural and dynamics information. In particular, when compared to individual dynamic behavior of those spin pairs, such cross-correlated relaxation (CCR) rates report on the correlation between the spin pairs. We have recently mapped out correlated motion along the backbone of the protein GB3, using CCR rates among and between consecutive H{sup N}–N and H{sup α}–C{sup α} dipole–dipole interactions. Here, we provide a detailed account of the measurement of the four types of CCR rates. All rates were obtained from at least two different pulse sequences, of which the yet unpublished ones are presented. Detailed comparisons between the different methods and corrections for unwanted pathways demonstrate that the averaged CCR rates are highly accurate and precise with errors of 1.5–3% of the entire value ranges.

  19. Formation of classical crystals of dipolar particles in a helical geometry

    DEFF Research Database (Denmark)

    K. Pedersen, J.; V. Fedorov, D.; S. Jensen, A.

    2014-01-01

    We consider crystal formation of particles with dipole-dipole interactions that are confined to move in a one-dimensional helical geometry with their dipole moments oriented along the symmetry axis of the confining helix. The stable classical lowest energy configurations are found to be chain str......-to-tail attraction in the system. The speed of sound propagates along the chains. It is independent of the number of chains although depending on geometry....

  20. Spontaneous Magnetization in the Dipolar Ising Ferromagnet LiTbF4

    DEFF Research Database (Denmark)

    Als-Nielsen, Jens Aage; Holmes, L. M.; Krebs Larsen, F.

    1975-01-01

    The spontaneous magnetization μ in Bohr magnetons below TC=2.874 K in LiTbF4 has been measured by magnetic Bragg scattering of neutrons. The data were normalized by comparing the magnetic Bragg scattering to the nuclear Bragg scattering at T>TC. The nuclear structure factors as well as the extinc...

  1. Experimental test of renormalization group theory on the uniaxial, dipolar coupled ferromagnet LiTbf4

    DEFF Research Database (Denmark)

    Als-Nielsen, Jens Aage

    1976-01-01

    The transverse correlation range ξ and the susceptibility in the critical region has been measured by neutron scattering. A special technique required to resolve the superdiverging longitudinal correlation range has been utilized. The results for ξ together with existing specific-heat data are in...

  2. Quantum factorization of 143 on a dipolar-coupling nuclear magnetic resonance system.

    Science.gov (United States)

    Xu, Nanyang; Zhu, Jing; Lu, Dawei; Zhou, Xianyi; Peng, Xinhua; Du, Jiangfeng

    2012-03-30

    Quantum algorithms could be much faster than classical ones in solving the factoring problem. Adiabatic quantum computation for this is an alternative approach other than Shor's algorithm. Here we report an improved adiabatic factoring algorithm and its experimental realization to factor the number 143 on a liquid-crystal NMR quantum processor with dipole-dipole couplings. We believe this to be the largest number factored in quantum-computation realizations, which shows the practical importance of adiabatic quantum algorithms.

  3. Richard Gans y la cuantificación del momento dipolar magnético

    OpenAIRE

    Bibiloni, Aníbal Guillermo; Civitarese, Osvaldo E.; Reichenbach, María Cecilia von

    2002-01-01

    Richard Gans, físico de origen alemán, fue el sucesor de Emil Bose en la dirección-organización del Departamento de Física de la Universidad de La Plata. Su llegada, en 1912, constituyó un aporte significativo, para la incipiente actividad científica en la UNLP. Richard Gans, en el momento de su llegada a la Plata, había adquirido ya una sólida reputación científica y estaba en contacto con centros muy activos de investigación. Su trabajo, en problemas relacionados con el magnetismo, era bien...

  4. Branched Polyhedral Oligomeric Silsesquioxane Nanoparticles Prepared via Strain-Promoted 1,3-Dipolar Cycloadditions

    NARCIS (Netherlands)

    Ledin, Petr A.; Xu, Weinan; Friscourt, Frédéric; Boons, Geert Jan; Tsukruk, Vladimir V.

    2015-01-01

    Conjugation of small organic molecules and polymers to polyhedral oligosilsesquioxane (POSS) cores results in novel hybrid materials with unique physical characteristics. We report here an approach in which star-shaped organic-inorganic scaffolds bearing eight cyclooctyne moieties can be rapidly

  5. Transverse relaxation of scalar-coupled protons.

    Science.gov (United States)

    Segawa, Takuya F; Baishya, Bikash; Bodenhausen, Geoffrey

    2010-10-25

    In a preliminary communication (B. Baishya, T. F. Segawa, G. Bodenhausen, J. Am. Chem. Soc. 2009, 131, 17538-17539), we recently demonstrated that it is possible to obtain clean echo decays of protons in biomolecules despite the presence of homonuclear scalar couplings. These unmodulated decays allow one to determine apparent transverse relaxation rates R(2) (app) of individual protons. Herein, we report the observation of R(2) (app) for three methyl protons, four amide H(N) protons, and all 11 backbone H(α) protons in cyclosporin A. If the proton resonances overlap, their R(2) (app) rates can be measured by transferring their magnetization to neighboring (13)C nuclei, which are less prone to overlap. The R(2) (app) rates of protons attached to (13)C are faster than those attached to (12)C because of (13)C-(1)H dipolar interactions. The differences of these rates allow the determination of local correlation functions. Backbone H(N) and H(α) protons that have fast decay rates R(2) (app) also feature fast longitudinal relaxation rates R(1) and intense NOESY cross peaks that are typical of crowded environments. Variations of R(2) (app) rates of backbone H(α) protons in similar amino acids reflect differences in local environments.

  6. Updated methodology for nuclear magnetic resonance characterization of shales

    Science.gov (United States)

    Washburn, Kathryn E.; Birdwell, Justin E.

    2013-08-01

    Unconventional petroleum resources, particularly in shales, are expected to play an increasingly important role in the world's energy portfolio in the coming years. Nuclear magnetic resonance (NMR), particularly at low-field, provides important information in the evaluation of shale resources. Most of the low-field NMR analyses performed on shale samples rely heavily on standard T1 and T2 measurements. We present a new approach using solid echoes in the measurement of T1 and T1-T2 correlations that addresses some of the challenges encountered when making NMR measurements on shale samples compared to conventional reservoir rocks. Combining these techniques with standard T1 and T2 measurements provides a more complete assessment of the hydrogen-bearing constituents (e.g., bitumen, kerogen, clay-bound water) in shale samples. These methods are applied to immature and pyrolyzed oil shale samples to examine the solid and highly viscous organic phases present during the petroleum generation process. The solid echo measurements produce additional signal in the oil shale samples compared to the standard methodologies, indicating the presence of components undergoing homonuclear dipolar coupling. The results presented here include the first low-field NMR measurements performed on kerogen as well as detailed NMR analysis of highly viscous thermally generated bitumen present in pyrolyzed oil shale.

  7. Pulsed zero field NMR of solids and liquid crystals

    Energy Technology Data Exchange (ETDEWEB)

    Thayer, A.M.

    1987-02-01

    This work describes the development and applications to solids and liquid crystals of zero field nuclear magnetic resonance (NMR) experiments with pulsed dc magnetic fields. Zero field NMR experiments are one approach for obtaining high resolution spectra of amorphous and polycrystalline materials which normally (in high field) display broad featureless spectra. The behavior of the spin system can be coherently manipulated and probed in zero field with dc magnetic field pulses which are employed in a similar manner to radiofrequency pulses in high field NMR experiments. Nematic phases of liquid crystalline systems are studied in order to observe the effects of the removal of an applied magnetic field on sample alignment and molecular order parameters. In nematic phases with positive and negative magnetic susceptibility anisotropies, a comparison between the forms of the spin interactions in high and low fields is made. High resolution zero field NMR spectra of unaligned smectic samples are also obtained and reflect the symmetry of the liquid crystalline environment. These experiments are a sensitive measure of the motionally induced asymmetry in biaxial phases. Homonuclear and heteronuclear solute spin systems are compared in the nematic and smectic phases. Nonaxially symmetric dipolar couplings are reported for several systems. The effects of residual fields in the presence of a non-zero asymmetry parameter are discussed theoretically and presented experimentally. Computer programs for simulations of these and other experimental results are also reported. 179 refs., 75 figs.

  8. Selective excitation enables assignment of proton resonances and {sup 1}H-{sup 1}H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu [Biophysics and Department of Chemistry, The University of Michigan, Ann Arbor, Michigan 48109-1055 (United States)

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of {sup 1}H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as {sup 13}C or {sup 15}N. In this method, after the initial preparation of proton magnetization and cross-polarization to {sup 13}C nuclei, transverse magnetization of desired {sup 13}C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific {sup 13}C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of {sup 1}H-{sup 1}H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  9. Stepwise transition of a topological defect from the smectic film to the boundary of a dipolar inclusion

    Science.gov (United States)

    Dolganov, P. V.; Kats, E. I.; Cluzeau, P.

    2010-03-01

    Cholesteric droplets accompanied by a topological defect are studied in free standing smectic C∗ films. We observed a transition between two droplet-defect configurations with the defect in the film and on the droplet boundary. We found that the distance between the droplet surface and the topological defect decreases continuously with increasing temperature and above a certain critical temperature the defect jumps to the droplet boundary. We relate this stepwise change in the defect position to the change in the anchoring on the droplet boundary. This transformation leads to a decrease in the interparticle distances in self-organized chains from droplets. Our simple theory allows us to estimate the value of the anchoring energy.

  10. In situ SHG monitoring of dipolar orientation and relaxation in Disperse Red type/derivative urethane-urea copolymer

    Science.gov (United States)

    Samoc, A.; Holland, A.; Tsuchimori, M.; Watanabe, O.; Samoc, M.; Luther-Davies, B.; Kolev, V. Z.

    2005-09-01

    We investigated linear optical and second-order nonlinear optical (NLO) properties of films of urethane-urea copolymer (UU2) functionalised with a high concentration of an azobenzene chromophore. The polymer films on ITO-coated substrate were corona poled to induce a noncentrosymmetric organization of chromophore dipoles and data on the second harmonic generated with the laser beam (the fundamental wavelength 1053 nm, 6 ps/pulse, 20 Hz repetition rate) was acquired as a function of time and temperature. Second harmonic generation (SHG) was used to monitor in situ the polar alignment and relaxation of orientation of the side-chain Disperse Red-like chromophore molecules in the films poled at room temperature and high above the glass transition temperature (Tg 140-150oC). The deff coefficient was determined from the Maker-fringe method and corrected for absorption. A strong second harmonic effect with a fast relaxation was observed in "cold" (room temperature) poling experiments. A large second-order resonantly enhanced optical nonlinearity (d33 of the order of 200 pm/V) was obtained in high temperature poling. A strong and stable nonlinearity has persisted for years after the films were high-temperature poled.

  11. Dipolar relaxation of multiple-quantum NMR coherences in a linear homogeneous chain of 19F nuclei in calcium fluoroapatite

    Directory of Open Access Journals (Sweden)

    Bochkin G.A., Fel'dman E.B., Vasil'ev S.G.

    2016-12-01

    Full Text Available Experimental and theoretical investigations of dynamics and relaxation of multiple quantum (MQ nuclear magnetic resonance (NMR coherences of the zeroth and second orders are performed in a quasi-one-dimensional chain of nuclear spins of 19F in calcium fluorapatite. MQ NMR dynamics are studied on the preparation period of the MQ NMR experiment in the approximation of nearest neighbor interactions. The density matrix of the system at the end of the preparation period is used as the initial condition for the study of the relaxation process on the evolution period of the MQ NMR experiment. The relaxation asymptotics of the intensity of the MQ NMR coherence of the zeroth order is obtained. Relaxation of the MQ NMR coherence of the second order is investigated with ZZ part of the dipole-dipole interactions. The experimental data qualitatively agree with the results of the developed theory.

  12. Synthesis and Antimicrobial Studies of New Series of Pyrazoline Bearing Bis-Heterocycles via 1,3-Dipolar Cycloaddition Reactions

    Directory of Open Access Journals (Sweden)

    B. Jayashankara

    2008-01-01

    Full Text Available Biologically interesting bis-heterocycles bearing pyrazoline and imidazole moieties have been synthesized. 1H NMR, 13C NMR, IR and elemental analyses characterized the newly synthesized compounds. All the synthesized compounds were evaluated for their antimicrobial activity and were compared with the standard drugs. All the compounds demonstrated potent to weak antimicrobial activity.

  13. Dipolar effects on propagation of ultrashort laser pulse in one-dimensional para-nitroaniline (pNA) molecules

    Science.gov (United States)

    Zhao, Ke; Li, Hong-Yu; Liu, Ji-Cai; Wang, Chuan-Kui; Luo, Yi

    2005-12-01

    The dynamic behaviour of ultrashort (femtosecond) laser pulses in a molecular medium is studied by solving the full Maxwell-Bloch equations beyond the limits of the slowly varying envelope approximation and the rotating-wave approximation under the resonant and the non-resonant conditions. A one-dimensional asymmetric charge-transfer molecule, para-nitroaniline, is used as a model molecule whose electronic properties are calculated with the time-dependent hybrid density functional theory. Under the one-photon resonant condition, 4π pulse is separated into two sub-pulses. The weight of the second-harmonic component mainly contributed by the two-photon excitation becomes stronger with longer propagation time. Under the two-photon resonant condition, the separation of 4π pulse is not induced and many higher-order spectral components beyond the second-harmonic generation occur. Interestingly, when the pulse propagates for long enough, the carrier modification becomes so significant that a continuous spectrum is generated. The Fourier transform of the high-harmonic spectrum demonstrates that an even shorter laser pulse can be produced in both resonant and non-resonant propagations. The effects of permanent dipole moments on the pulse evolution are discussed.

  14. Dipolar effects on propagation of ultrashort laser pulse in one-dimensional para-nitroaniline (pNA) molecules

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Ke [College of Physics and Electronics, Shandong Normal University, Jinan 250014 (China); Li Hongyu [College of Physics and Electronics, Shandong Normal University, Jinan 250014 (China); Liu Jicai [College of Physics and Electronics, Shandong Normal University, Jinan 250014 (China); Wang Chuankui [College of Physics and Electronics, Shandong Normal University, Jinan 250014 (China); Luo Yi [Theoretical Chemistry, Royal Institute of Technology, AlbaNova, S-10691 Stockholm (Sweden)

    2005-12-14

    The dynamic behaviour of ultrashort (femtosecond) laser pulses in a molecular medium is studied by solving the full Maxwell-Bloch equations beyond the limits of the slowly varying envelope approximation and the rotating-wave approximation under the resonant and the non-resonant conditions. A one-dimensional asymmetric charge-transfer molecule, para-nitroaniline, is used as a model molecule whose electronic properties are calculated with the time-dependent hybrid density functional theory. Under the one-photon resonant condition, 4{pi} pulse is separated into two sub-pulses. The weight of the second-harmonic component mainly contributed by the two-photon excitation becomes stronger with longer propagation time. Under the two-photon resonant condition, the separation of 4{pi} pulse is not induced and many higher-order spectral components beyond the second-harmonic generation occur. Interestingly, when the pulse propagates for long enough, the carrier modification becomes so significant that a continuous spectrum is generated. The Fourier transform of the high-harmonic spectrum demonstrates that an even shorter laser pulse can be produced in both resonant and non-resonant propagations. The effects of permanent dipole moments on the pulse evolution are discussed.

  15. A continuous-time random-walk approach to the Cole-Davidson dielectric response of dipolar liquids

    DEFF Research Database (Denmark)

    Szabat, B.; Langner, K. M.; Klösgen-Buchkremer, Beate Maria

    2004-01-01

    We show how the Cole-Davidson relaxation response, characteristic of alcoholic systems, can be derived within the framework of the continuous-time random walk (CTRW). Using the random-variable formalism, we indicate that the high-frequency power law of dielectric spectra is determined by the heavy...

  16. A continuous-time random-walk approach to the Cole-Davidson dielectric response of dipolar liquids

    DEFF Research Database (Denmark)

    Szabat, Bozena; Langner, Karol M.; Klösgen, Beate Maria

    2005-01-01

    We show how the Cole-Davidson relaxation response, characteristic of alcoholic systems, can be derived within the framework of the continuous-time random walk 4CTRW). Using the random-variable formalism, we indicate that the high-frequency power law of dielectric spectra is determined by the heavy...

  17. Synthesis of pyrrolizines by intramolecular capture of 1,4-dipolar intermediates in reactions of enamines with dimethyl acetylenedicarboxylate

    NARCIS (Netherlands)

    Verboom, Willem; Visser, G.W.; Trompenaars, W.P.; Reinhoudt, David; Harkema, Sybolt; van Hummel, G.J.

    1981-01-01

    Solvent polarity and reaction temperature strongly influence the reactions of dimethyl acetylenedicar-boxylate (DMAD) with 1-pyrrolidinyl enamines of acyclic and cyclic ketones. Whereas DMAD and 1-[1-phenyl-2-(phenylthio)ethenyl]pyrrolidine (3) give only a mixture of the isomeric 1,3-butadienes (5)

  18. Collective excitations in liquid DMSO : FIR spectrum, Low frequency vibrational density of states and ultrafast dipolar solvation dynamics

    OpenAIRE

    Hazra, Milan; Bagchi, Biman

    2016-01-01

    Valuable dynamical and structural information about neat liquid DMSO at ambient conditions can be obtained through study of low frequency vibrations in the far infrared (FIR), that is, terahertz regime. For DMSO, collective excitations as well as single molecule stretches and bends have been measured by different kinds of experiments such as OHD-RIKES and terahertz spectroscopy. In the present work we investigate the intermolecular vibrational spectrum of DMSO through three different computat...

  19. Quantum-Fluctuation-Driven Crossover from a Dilute Bose-Einstein Condensate to a Macrodroplet in a Dipolar Quantum Fluid

    National Research Council Canada - National Science Library

    Chomaz, L; Baier, S; Petter, D; Mark, M. J; Wächtler, F; Santos, L; Ferlaino, F

    2016-01-01

    ... state of more than 2×10^{4}  atoms. Based on the study of collective excitations and loss features, we prove that quantum fluctuations stabilize the ultracold gas far beyond the instability threshold imposed by mean-field interactions...

  20. The spin glass delafossite CuFe0.5V0.5O2: a dipolar glass?

    Science.gov (United States)

    Singh, Kiran; Maignan, Antoine; Simon, Charles; Hardy, Vincent; Pachoud, Elise; Martin, Christine

    2011-03-01

    The ferroelectric and spin glass properties of CuFe0.5V0.5O2 have been studied. Magnetization, ac magnetic susceptibility and specific heat measurements reveal a spin glass behavior (Tf = 20.5 K) for this delafossite. In CuFeO2, substitution of trivalent diamagnetic cations for Fe3 + is known to change the antiferromagnetic state and induce ferroelectricity. But partial occupation of the Fe3 + site by V3 + is responsible for disordered magnetism in CuFe0.5V0.5O2. The dielectric permittivity shows a frequency dependence reminiscent of relaxor ferroelectrics in which different cations occupy the same crystallographic site. Polarization measurements show the existence of a ferroelectric state below Tf with P5 K≈1.3 µC m - 2. These results point towards a relaxor-type ferroelectricity originating from a disordered array of magnetic cations. A clear coupling between electronic charges and spins is evidenced by the magnetodielectric effect.

  1. Facile measurement of {sup 1}H-{sup 15}N residual dipolar couplings in larger perdeuterated proteins

    Energy Technology Data Exchange (ETDEWEB)

    Fitzkee, Nicholas C.; Bax, Ad, E-mail: bax@nih.go [National Institutes of Health, Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases (United States)

    2010-10-15

    We present a simple method, ARTSY, for extracting {sup 1}J{sub NH} couplings and {sup 1}H-{sup 15}N RDCs from an interleaved set of two-dimensional {sup 1}H-{sup 15}N TROSY-HSQC spectra, based on the principle of quantitative J correlation. The primary advantage of the ARTSY method over other methods is the ability to measure couplings without scaling peak positions or altering the narrow line widths characteristic of TROSY spectra. Accuracy of the method is demonstrated for the model system GB3. Application to the catalytic core domain of HIV integrase, a 36 kDa homodimer with unfavorable spectral characteristics, demonstrates its practical utility. Precision of the RDC measurement is limited by the signal-to-noise ratio, S/N, achievable in the 2D TROSY-HSQC spectrum, and is approximately given by 30/(S/N) Hz.

  2. The spin glass delafossite CuFe(0.5)V(0.5)O(2): a dipolar glass?

    Science.gov (United States)

    Singh, Kiran; Maignan, Antoine; Simon, Charles; Hardy, Vincent; Pachoud, Elise; Martin, Christine

    2011-03-30

    The ferroelectric and spin glass properties of CuFe(0.5)V(0.5)O(2) have been studied. Magnetization, ac magnetic susceptibility and specific heat measurements reveal a spin glass behavior (T(f) = 20.5 K) for this delafossite. In CuFeO(2), substitution of trivalent diamagnetic cations for Fe(3 + ) is known to change the antiferromagnetic state and induce ferroelectricity. But partial occupation of the Fe(3 + ) site by V(3 + ) is responsible for disordered magnetism in CuFe(0.5)V(0.5)O(2). The dielectric permittivity shows a frequency dependence reminiscent of relaxor ferroelectrics in which different cations occupy the same crystallographic site. Polarization measurements show the existence of a ferroelectric state below T(f) with P(5 K)≈1.3 µC m( - 2). These results point towards a relaxor-type ferroelectricity originating from a disordered array of magnetic cations. A clear coupling between electronic charges and spins is evidenced by the magnetodielectric effect.

  3. Dipolar structures in magnetite ferrofluids studied with small-angle neutron scattering with and without applied magnetic field

    NARCIS (Netherlands)

    Klokkenburg, M.; Erne, B.H.; Wiedenmann, A.; Petukhov, A.V.; Philipse, A.P.

    2007-01-01

    Field-induced structure formation in a ferrofluid with well-defined magnetite nanoparticles with a permanent magnetic dipole moment was studied with small-angle neutron scattering (SANS) as a function of the magnetic interactions. The interactions were tuned by adjusting the size of the

  4. Giant resonance and dipolar states of light nuclei; La resonance geante et les etats dipolaires des noyaux legers

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1965-07-01

    Cross-section for ({gamma},n) reactions on C{sup 12},, O{sup 10}, Mg{sup 24} and Ca{sup 40} have been measured using 'monochromatic' gamma rays of variable energy obtained from the annihilation in flight of fast positrons. We compare the observed structure with the shell model of nucleus, including residual interaction between nucleons by 'hole particle' techniques. (author) [French] Les photons 'monochromatiques', d'energie variable, produits par l'annihilation en vol de positons, sont utilises pour mesurer la section efficace ({gamma},n) de {sup 12}C, {sup 16}O, {sup 21}Mg et {sup 40}Ca. La structure observee est comparee aux previsions theoriques du modele a particules independantes, tenant compte de l'interaction residuelle entre nucleons par la methode 'trou-particule'. (auteur)

  5. Surface-enhanced Raman scattering of dipolar molecules by the graphene Fermi surface modulation with different dipole moments

    Science.gov (United States)

    Zhang, Mingjia; Leng, Yandan; Huang, Jing; Yu, JiaoJiao; Lan, Zhenggang; Huang, Changshui

    2017-12-01

    We report the modulation of Raman scattering spectrum of chromophore/graphene hybrids by tunning the molecular polarization with different terminal groups (methyl, methoxy, nitrile, and two nitros). Based on the density functional theory, the specific dipole moment values of the chromophore molecules are calculated. An obvious surface-enhanced Raman scattering (SERS) was observed and the scattering intensity of molecule increases with enlarged dipole moment. According to the analysis of G band Raman shifts of graphene, the enhancement of the Raman signal can be attributed to strong electronic coupling between graphene and chromophore, which is closely related with the modulation of graphene Fermi surface by changing the dipole moment of the molecule. Besides, the optimization of the ground state geometry and the binding energy of the hybrids were also calculated with the Density Functional Based Tight Bonding (DFTB) method, which confirms that the enhanced Raman scattering of molecules on graphene arises from the improved energy level matching between graphene Fermi surface and molecular band, further providing a new way to design novel SERS devices.

  6. Collective excitations in liquid DMSO : FIR spectrum, Low frequency vibrational density of states and ultrafast dipolar solvation dynamics

    CERN Document Server

    Hazra, Milan

    2016-01-01

    Valuable dynamical and structural information about neat liquid DMSO at ambient conditions can be obtained through study of low frequency vibrations in the far infrared (FIR), that is, terahertz regime. For DMSO, collective excitations as well as single molecule stretches and bends have been measured by different kinds of experiments such as OHD-RIKES and terahertz spectroscopy. In the present work we investigate the intermolecular vibrational spectrum of DMSO through three different computational techniques namely (i) the far-infra red spectrum obtained through Fourier transform of total dipole moment auto time correlation function, (ii) from Fourier transform of the translational and angular velocity time autocorrelation functions and a (iii) quenched normal mode analysis of the parent liquid at 300K. The three spectrum, although exhibit differences among each other, reveal similar features which are in good, semi-quantitative, agreement with experimental results. Study of participation ratio of the density...

  7. Two-Level Dipolar System in a Heat Bath: High-Pump Power Effects in the Nonlinear Optical Responses

    Science.gov (United States)

    Paz, J. L.; León-Torres, J. R.; Lascano, Luis; Alvarado, Ysaias J.; Costa-Vera, Cesar

    2017-06-01

    Using the four-wave mixing spectroscopy, we analyze the nonlinear optical properties in a strongly driven two-level system, using a perturbative treatment where, the pump field is considered at all orders, second order in the probe, and first order for the signal field, when the stochastic effects of the solvent are considered. Significant variations in the nonlinear optical properties due mainly to changes in the probe intensity, chemical concentrations, and transversal relaxation times are observed.

  8. Effects of microwave electric fields on the translational diffusion of dipolar molecules in surface potential: A simulation study

    Science.gov (United States)

    Kapranov, Sergey V.; Kouzaev, Guennadi A.

    2018-01-01

    Variations of effective diffusion coefficient of polar molecules exposed to microwave electric fields in a surface potential are studied by solving coupled stochastic differential equations of motion with a deterministic component of the surface force. Being an essential tool for the simulation interpretation, a theoretical approach to effective diffusion in surface potential is first developed. The effective diffusion coefficient is represented as the product of the normal diffusion coefficient and potential-dependent correction function, whose temperature dependence is close to the Arrhenius form. The analytically found zero-diffusion condition defines the state of thermal equilibrium at the surface. The diffusion of a water-like dipole molecule in the potential of graphite surface is simulated in the field-free conditions and in the presence of the alternating electric fields of various magnitude intensities and frequencies. Temperature dependence of the correction function exhibits field-induced variations of the effective Lennard-Jones energy parameter. It demonstrates maximum departure from the zero-field value at certain frequencies and intensities, which is associated with variations in the rotational dynamics. A concept of the amplitude-frequency resonance put forward to interpret the simulation results is explained using a heuristic reasoning and is corroborated by semi-quantitative considerations in terms of the Dissado-Hill cluster theory of dielectric relaxation.

  9. statistical fluid theory for associating fluids containing alternating ...

    Indian Academy of Sciences (India)

    Abstract. Statistical associating fluid theory of homonuclear dimerized chain fluids and homonuclear monomer-dimer mixture chain fluids are extended to fluids containing al- ternating heteronuclear chain molecules separately. The proposed models account for the appropriate site-site correlation functions at contact.

  10. Preparation and measurement of TFBG based vibration sensor

    Science.gov (United States)

    Helan, Radek; Urban, Frantisek; Mikel, Bretislav; Urban, Frantisek

    2014-08-01

    We present vibration fiber sensor set up based on tilted fiber Bragg grating (TFBG) and fiber taper. The sensor uses the TFBG as a cladding modes reflector and fiber taper as a bend-sensitive recoupling member. The lower cladding modes (ghost), reflected from TFBG, is recoupled back into the fiber core via tapered fiber section. We focused on optimization of TFBG tilt angle to reach maximum reflection of the ghost and taper parameters. Comparative measurements were made using optical spectrum analyzer and superluminiscent diode as broadband light source. We present dependence between intensity of recoupled ghost mode and sensor deflection.

  11. Resolution Improvement in Multidimensional Nuclear Magnetic Resonance Spectroscopy of Proteins; Amelioration de la resolution dans la resonance magnetique nucleaire multidimensionnelle des proteines

    Energy Technology Data Exchange (ETDEWEB)

    Duma, L

    2004-07-01

    The work presented in this thesis is concerned with both liquid-state and solid-state nuclear magnetic resonance (NMR) spectroscopy. Most of this work is devoted to the investigation by solid-state NMR of C{sup 13}-enriched compounds with the principal aim of presenting techniques devised for further improving the spectral resolution in multidimensional NMR of microcrystalline proteins. In fully C{sup 13}-labelled compounds, the J-coupling induces a broadening of the carbon lineshapes. We show that spin-state-selective technique called IPAP can be successfully combined with standard polarisation transfer schemes in order to remove the J-broadening in multidimensional solid-state NMR correlation experiments of fully C{sup 13}-enriched proteins. We present subsequently two techniques tailored for liquid-state NMR spectroscopy. The carbon directly detected techniques provide chemical shift information for all backbone hetero-nuclei. They are very attracting for the study of large bio-molecular systems or for the investigation of paramagnetic proteins. In the last part of this thesis, we study the spin-echo J-modulation for homonuclear two-spin 1/2 systems. Under magic-angle spinning, the theory of J-induced spin-echo modulation allows to derive a set of modulation regimes which give a spin-echo modulation exactly equal to the J-coupling. We show that the chemical-shift anisotropy and the dipolar interaction tend to stabilize the spin-echo J-modulation. The theoretical conclusions are supported by numerical simulations and experimental results obtained for three representative samples containing C{sup 13} spin pairs. (author)

  12. Design and construction of a quadruple-resonance MAS NMR probe for investigation of extensively deuterated biomolecules.

    Science.gov (United States)

    Collier, Kelsey A; Sengupta, Suvrajit; Espinosa, Catalina A; Kelly, John E; Kelz, Jessica I; Martin, Rachel W

    2017-12-01

    Extensive deuteration is frequently used in solid-state NMR studies of biomolecules because it dramatically reduces both homonuclear ( 1 H- 1 H) and heteronuclear ( 1 H- 13 C and 1 H- 15 N) dipolar interactions. This approach greatly improves resolution, enables low-power rf decoupling, and facilitates 1 H-detected experiments even in rigid solids at moderate MAS rates. However, the resolution enhancement is obtained at some cost due the reduced abundance of protons available for polarization transfer. Although deuterium is a useful spin-1 NMR nucleus, in typical experiments the deuterons are not directly utilized because the available probes are usually triple-tuned to 1 H, 13 C and 15 N. Here we describe a 1 H/ 13 C/ 2 H/ 15 N MAS ssNMR probe designed for solid-state NMR of extensively deuterated biomolecules. The probe utilizes coaxial coils, with a modified Alderman-Grant resonator for the 1 H channel, and a multiply resonant solenoid for 13 C/ 2 H/ 15 N. A coaxial tuning-tube design is used for all four channels in order to efficiently utilize the constrained physical space available inside the magnet bore. Isolation among the channels is likewise achieved using short, adjustable transmission line elements. We present benchmarks illustrating the tuning of each channel and isolation among them and the magnetic field profiles at each frequency of interest. Finally, representative NMR data are shown demonstrating the performance of both the detection and decoupling circuits. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Indirectly detected chemical shift correlation NMR spectroscopy in solids under fast magic angle spinning

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Kanmi [Iowa State Univ., Ames, IA (United States)

    2011-01-01

    on decoupling efficiency as well as scaling factors. Indirect detection with assistance of PMLGm$\\bar{x}$ during INEPTR transfer proved to offer the highest sensitivity gains of 3-10. In addition, the CRAMPS sequence was applied under fast MAS to increase the 1H resolution during t1 evolution in the traditional, 13C detected HETCOR scheme. Two naturally abundant solids, tripeptide N-formyl-L-methionyl-L-leucyl-L-phenylalanine (f-MLF-OH) and brown coal, with well ordered and highly disordered structures, respectively, are studied to confirm the capabilities of these techniques. Concomitantly, a simple optimization of 1H homonuclear dipolar decoupling at MAS rates exceeding 10 kHz was developed (Chapter 4). The fine-tuned decoupling efficiency can be obtained by minimizing the signal loss due to transverse relaxation in a simple spin-echo experiment, using directly the sample of interest. The excellent agreement between observed decoupling pattern and earlier theoretical predictions confirmed the utility of this strategy. The properties of naturally abundant surface-bound fluorocarbon groups in mesoporous silica nanoparticles (MSNs) were investigated by the above-mentioned multidimensional solid-state NMR experiments and theoretical modeling (Chapter 5). Two conformations of (pentafluorophenyl)propyl groups (abbreviated as PFP) were determined as PFP-prone and PFP-upright, whose aromatic rings are located above the siloxane bridges and in roughly upright position, respectively. Several 1D and 2D NMR techniques were implemented in the characterizations, including indirectly detected 1H{l_brace}13C{r_brace} and 19F{l_brace}13C{r_brace} 2D HETCOR, Carr-Purcell-Meiboom-Gill (CPMG) assisted 29Si direct polarization and 29Si19F 2D experiments, 2D double-quantum (DQ) 19F MAS NMR spectra and spin-echo measurements

  14. La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2}. Synthesis, structure and {sup 31}P solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, Timo; Eul, Matthias; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Benndorf, Christopher; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. of Physics

    2016-04-01

    The phosphide oxides La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2} were synthesized from lanthanum, copper(I) oxide, red phosphorus, and lanthanum(III) chloride through a ceramic technique. Single crystals can be grown in a NaCl/KCl flux. Both structures were refined from single crystal X-ray diffractometer data: I4/mmm, a = 403.89(4), c = 2681.7(3) pm, wR2 = 0.0660, 269 F{sup 2} values, 19 variables for La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and a = 407.52(5), c = 4056.8(7) pm, wR2 = 0.0905, 426 F{sup 2} values, 27 variables for La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2}. Refinement of the occupancy parameters revealed full occupancy for the oxygen sites in both compounds. The structures are composed of cationic (La{sub 2}O{sub 2}){sup 2+} layers and covalently bonded (Cu{sub 4}P{sub 4}){sup 5-} polyanionic layers with metallic characteristics, and an additional La{sup 3+} between two adjacent (Cu{sub 4}P{sub 4}){sup 5-} layers. The structure of La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2} comprises two additional LaOCl slabs per unit cell. Temperature-dependent magnetic susceptibility studies revealed Pauli paramagnetism. The phosphide substructure of La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} was studied by {sup 31}P solid state NMR spectroscopy. By using a suitable dipolar re-coupling approach the two distinct resonances belonging to the P{sub 2}{sup 4-} and the P{sup 3-} units could be identified.

  15. Ultrasonic Synthesis, Molecular Structure and Mechanistic Study of 1,3-Dipolar Cycloaddition Reaction of 1-Alkynylpyridinium-3-olate and Acetylene Derivatives

    Directory of Open Access Journals (Sweden)

    Asmaa Aboelnaga

    2016-06-01

    Full Text Available Regioselectively, ethyl propiolate reacted with 1-(propergyl-pyridinium-3-olate to give two regioisomers; ethyl 4-oxo-8-(prop-2-ynyl-8-aza-bicyclo(3.2.1octa-2,6-diene-6-carboxylate 4, ethyl 2-oxo-8-(prop-2-ynyl-8-aza-bicyclo(3.2.1octa-3,6-diene-6-carboxylate 5 as well as ethyl 2,6-dihydro-6-(prop-2-ynylfuro(2,3-cpyridine-3-carboxylate 6. The obtained compounds were identified by their spectral (IR, mass and NMR data. Moreover, DFT quantum chemical calculations were used to study the mechanism of the cycloaddition reaction. The regioselectivity was explained using transition state calculations, where the calculations agreed with the formation of products 4 and 5 in almost the same ratio. The reaction was also extended for diphenylaceylene as dipolarophile to give only two products instead of three.

  16. Ultrasonic Synthesis, Molecular Structure and Mechanistic Study of 1,3-Dipolar Cycloaddition Reaction of 1-Alkynylpyridinium-3-olate and Acetylene Derivatives.

    Science.gov (United States)

    Aboelnaga, Asmaa; Hagar, Mohamed; Soliman, Saied M

    2016-06-29

    Regioselectively, ethyl propiolate reacted with 1-(propergyl)-pyridinium-3-olate to give two regioisomers; ethyl 4-oxo-8-(prop-2-ynyl)-8-aza-bicyclo(3.2.1)octa-2,6-diene-6-carboxylate 4, ethyl 2-oxo-8-(prop-2-ynyl)-8-aza-bicyclo(3.2.1)octa-3,6-diene-6-carboxylate 5 as well as ethyl 2,6-dihydro-6-(prop-2-ynyl)furo(2,3-c)pyridine-3-carboxylate 6. The obtained compounds were identified by their spectral (IR, mass and NMR) data. Moreover, DFT quantum chemical calculations were used to study the mechanism of the cycloaddition reaction. The regioselectivity was explained using transition state calculations, where the calculations agreed with the formation of products 4 and 5 in almost the same ratio. The reaction was also extended for diphenylaceylene as dipolarophile to give only two products instead of three.

  17. Was the Devonian geomagnetic field dipolar or multipolar? Palaeointensity studies of Devonian igneous rocks from the Minusa Basin (Siberia) and the Kola Peninsula dykes, Russia

    Science.gov (United States)

    Shcherbakova, V. V.; Biggin, A. J.; Veselovskiy, R. V.; Shatsillo, A. V.; Hawkins, L. M. A.; Shcherbakov, V. P.; Zhidkov, G. V.

    2017-05-01

    Defining variations in the behaviour of the geomagnetic field through geological time is critical to understanding the dynamics of Earth's core and its response to mantle convection and planetary evolution. Furthermore, the question of whether the axial dipole dominance of the recent palaeomagnetic field persists through the whole of Earth's history is fundamental to determining the reliability of palaeogeographic reconstructions and the efficacy of the magnetosphere in shielding Earth from solar wind radiation. Previous palaeomagnetic directional studies have suggested that the palaeofield had a complex configuration in the Devonian period (419-359 Ma). Here we present new high-quality palaeointensity determinations from rocks aged between 408 and 375 Ma from the Minusa Basin (southern Siberia), and the Kola Peninsula that enable the first reliable investigation of the strength of the field during this enigmatic period. Palaeointensity experiments were performed using the thermal Thellier, microwave Thellier and Wilson methods on 165 specimens from 25 sites. Six out of eight successful sites from the Minusa Basin and all four successful sites from the Kola Peninsula produced extremely low palaeointensities (<10 μT). These findings challenge the uniformitarian view of the palaeomagnetic field: field intensities of nearly an order of magnitude lower than Neogene values (except during relatively rare geomagnetic excursions and reversals) together with the widespread appearance of strange directions found in the Devonian suggest that the Earth's field during this time may have had a dominantly multipolar geometry. A persistent, low intensity multipolar magnetic field and associated diminished magnetosphere would increase the impact of solar particles on the Earth's magnetosphere, ionosphere and atmosphere with potential major implications for Earth's climate and biosphere.

  18. 1,3-Dipolar Cycloaddition Reactions of 1-(4-Phenylphenacyl-1,10-phenanthrolinium N-Ylide with Activated Alkynes and Alkenes

    Directory of Open Access Journals (Sweden)

    A. Badoiu

    2005-02-01

    Full Text Available The 3 2 cycloaddition reaction of 1-(4-phenylphenacyl-1,10-phenanthrolinium ylide with activated alkynes gave pyrrolo[1,2- 4a][1,10]phenanthrolines 6a-d. The "one pot" synthesis of 6a,b,d from 4, activatedalkenes, Et3N and tetrakis-pyridine cobalt (II dichromate (TPCD is described. Thehelical chirality of pyrrolophenanthrolines 6b-d was put in evidence by NMRspectroscopy.

  19. A laser-T-jump study of the adsorption of dipolar molecules to planar lipid membranes. II. Phloretin and phloretin analogues.

    Science.gov (United States)

    Awiszus, R; Stark, G

    1988-01-01

    Phloretin and structurally related neutral molecules adsorb to the interface of lipid membranes and modify the electric dipole potential of the membrane/water interface. The adsorption process has been studied using a laser-T-jump relaxation technique in combination with an analysis of nonactin mediated potassium transport (see part I, Awiszus and Stark 1988). Deviations from the Langmuir isotherm were observed for most of the substances. The discrepancies were most pronounced at large surface densities, whereas good agreement was found at low concentrations in many cases. The partition coefficient in the limit of low concentrations was compared with that of octanol/water bulk phases. No correlation was found. The individual values of the two partition coefficients differed by more than three orders of magnitude. The contribution, b, of a single adsorbed molecule to the dipole potential could not be predicted from the dipole moment, microL, of the molecule measured in the bulk phase. Different values of b were found at identical values of microL. The study shows the limitations of the use of bulk phase data to predict molecular properties in lipid membranes.

  20. The Influence of Dipolar Interactions between Mesogenic Units on the Aggregation Behavior of a Series of Isomeric Double-Chained Ammonium Amphotropes

    NARCIS (Netherlands)

    Everaars, M.D.; Marcelis, A.T.M.; Sudhölter, E.J.R.; Jerôme, B.

    2000-01-01

    A series of novel double-chained ammonium amphotropes has been synthesized which differ in the dipole orientation of their mesogenic units along the long molecular axis. The mesogenic units consist of an azobenzene core which has an electron donating oxy unit at the 4-position and an electron

  1. Out-of-Plane and In-Plane Magnetization Behavior of Dipolar Interacting FeNi Nanoislands around the Percolation Threshold

    OpenAIRE

    A. Stupakov; Bagdinov, A. V.; V. V. Prokhorov; Bagdinova, A. N.; Demikhov, E. I.; Dejneka, A.; Kugel, K. I.; Gorbatsevich, A. A.; Pudonin, F. A.; Kovaleva, N. N.

    2016-01-01

    Magnetic properties of inhomogeneous nanoisland FeNi films were studied by SQUID magnetometry. The FeNi films with nominal thickness ranging from 0.6 to 2.0 nm were deposited by rf sputtering on Sitall glass substrates and covered by a protecting Al2O3 layer on the top. The SQUID data indicate pronounced irreversibility behavior for the out-of-plane temperature dependent magnetization response (measured at H = 100 Oe) using zero-field cooling (ZFC) and field cooled warming (FCW) after the app...

  2. Out-of-Plane and In-Plane Magnetization Behavior of Dipolar Interacting FeNi Nanoislands around the Percolation Threshold

    Directory of Open Access Journals (Sweden)

    A. Stupakov

    2016-01-01

    Full Text Available Magnetic properties of inhomogeneous nanoisland FeNi films were studied by SQUID magnetometry. The FeNi films with nominal thickness ranging from 0.6 to 2.0 nm were deposited by rf sputtering on Sitall glass substrates and covered by a protecting Al2O3 layer on the top. The SQUID data indicate pronounced irreversibility behavior for the out-of-plane temperature-dependent magnetization response (measured at H≃100 Oe using zero-field cooling (ZFC and field-cooled warming (FCW after the applied dc magnetizing field Hm≃2 T for the FeNi samples with nominal thickness 1.1 nm ≲d≲1.8 nm, below the percolation threshold. The positive difference between the FCW and ZFC data identifies two irreversibility temperature scales, TB≈50 K and T⁎≈200 K, which can be associated with the superparamagnetic and superferromagnetic behavior in inhomogeneous nanoisland FeNi films, respectively. However, above the film percolation threshold, we observed a crossover from the out-of-plane to in-plane magnetization orientation. Here, the in-plane FCW-ZFC difference implies negative remanent magnetization response in the temperature range TB≲T≲T⁎. The observed magnetization properties can be associated with the presence of the superferromagnetic phase in self-assembled clusters of quasi-2D metallic magnetic FeNi nanoislands.

  3. PhI(OAc)2 -mediated novel 1,3-dipolar cycloaddition of methylenecyclopropanes (MCPs), vinylidenecyclopropanes (VCPs), and methylenecyclobutane (MCB) with phthalhydrazide.

    Science.gov (United States)

    Liu, Le-Ping; Lu, Jian-Mei; Shi, Min

    2007-03-29

    [structure: see text]. Iodobenzene diacetate-mediated reactions of methylenecyclopropanes 1, vinylidenecyclopropanes 2, and a methylenecyclobutane 3a with phthalhydrazide give the corresponding [3+2] cycloaddition products in good yields under mild conditions. In these reactions, phthalhydrazide was transformed to a 1,3-dipole intermediate in the presence of iodobenzene diacetate. A plausible reaction mechanism has been proposed.

  4. The spin glass delafossite CuFe{sub 0.5}V{sub 0.5}O{sub 2}: a dipolar glass?

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Kiran; Maignan, Antoine; Simon, Charles; Hardy, Vincent; Pachoud, Elise; Martin, Christine, E-mail: antoine.maignan@ensicaen.fr [Laboratoire CRISMAT, CNRS UMR 6508, ENSICAEN, 6 Boulevard du Marechal Juin, 14050 Caen Cedex (France)

    2011-03-30

    The ferroelectric and spin glass properties of CuFe{sub 0.5}V{sub 0.5}O{sub 2} have been studied. Magnetization, ac magnetic susceptibility and specific heat measurements reveal a spin glass behavior (T{sub f} = 20.5 K) for this delafossite. In CuFeO{sub 2}, substitution of trivalent diamagnetic cations for Fe{sup 3+} is known to change the antiferromagnetic state and induce ferroelectricity. But partial occupation of the Fe{sup 3+} site by V{sup 3+} is responsible for disordered magnetism in CuFe{sub 0.5}V{sub 0.5}O{sub 2}. The dielectric permittivity shows a frequency dependence reminiscent of relaxor ferroelectrics in which different cations occupy the same crystallographic site. Polarization measurements show the existence of a ferroelectric state below T{sub f} with P{sub 5K{approx}}1.3 {mu}C m{sup -2}. These results point towards a relaxor-type ferroelectricity originating from a disordered array of magnetic cations. A clear coupling between electronic charges and spins is evidenced by the magnetodielectric effect.

  5. Influence of the properties of soft collective spin wave modes on the magnetization reversal in finite arrays of dipolarly coupled magnetic dots

    Energy Technology Data Exchange (ETDEWEB)

    Stebliy, Maxim; Ognev, Alexey; Samardak, Alexander; Chebotkevich, Ludmila [School of Natural Sciences, Far Eastern Federal University, Vladivostok 690950 (Russian Federation); Verba, Roman, E-mail: verrv@ukr.net [Institute of Magnetism, National Academy of Sciences of Ukraine, Kyiv 03142 (Ukraine); Melkov, Gennadiy [Faculty of Radiophysics, Electronics and Computer Systems, Taras Shevchenko National University of Kyiv, Kyiv 01601 (Ukraine); Tiberkevich, Vasil; Slavin, Andrei [Department of Physics, Oakland University, Rochester, MI 48309 (United States)

    2015-06-15

    Magnetization reversal in finite chains and square arrays of closely packed cylindrical magnetic dots, having vortex ground state in the absence of the external bias field, has been studied experimentally by measuring static hysteresis loops, and also analyzed theoretically. It has been shown that the field B{sub n} of a vortex nucleation in a dot as a function of the finite number N of dots in the array's side may exhibit a monotonic or an oscillatory behavior depending on the array geometry and the direction of the external bias magnetic field. The oscillations in the dependence B{sub n}(N) are shown to be caused by the quantization of the collective soft spin wave mode, which corresponds to the vortex nucleation in a finite array of dots. These oscillations are directly related to the form and symmetry of the dispersion law of the soft SW mode: the oscillation could appear only if the minimum of the soft mode spectrum is not located at any of the symmetric points inside the first Brillouin zone of the array's lattice. Thus, the purely static measurements of the hysteresis loops in finite arrays of coupled magnetic dots can yield important information about the properties of the collective spin wave excitations in these arrays. - Highlights: • Magnetization reversal in finite arrays of vortex state magnetic dots is studied. • The vortex nucleation field could change nonmonotonically with array size. • This behavior is caused by the quantization of the collective soft spin wave mode.

  6. The Effect of an Offset Polar Cap Dipolar Magnetic Field on the Modeling of the Vela Pulsar’s γ-Ray Light Curves

    Science.gov (United States)

    Barnard, M.; Venter, C.; Harding, A. K.

    2016-12-01

    We performed geometric pulsar light curve modeling using static, retarded vacuum, and offset polar cap (PC) dipole B-fields (the latter is characterized by a parameter ɛ), in conjunction with standard two-pole caustic (TPC) and outer gap (OG) emission geometries. The offset-PC dipole B-field mimics deviations from the static dipole (which corresponds to ɛ =0). In addition to constant-emissivity geometric models, we also considered a slot gap (SG) E-field associated with the offset-PC dipole B-field and found that its inclusion leads to qualitatively different light curves. Solving the particle transport equation shows that the particle energy only becomes large enough to yield significant curvature radiation at large altitudes above the stellar surface, given this relatively low E-field. Therefore, particles do not always attain the radiation-reaction limit. Our overall optimal light curve fit is for the retarded vacuum dipole field and OG model, at an inclination angle α ={78}-1+{1^\\circ } and observer angle \\zeta ={69}-1+{2^\\circ }. For this B-field, the TPC model is statistically disfavored compared to the OG model. For the static dipole field, neither model is significantly preferred. We found that smaller values of ɛ are favored for the offset-PC dipole field when assuming constant emissivity, and larger ɛ values favored for variable emissivity, but not significantly so. When multiplying the SG E-field by a factor of 100, we found improved light curve fits, with α and ζ being closer to best fits from independent studies, as well as curvature radiation reaction at lower altitudes.

  7. Ruido 1/f y reversiones del momento dipolar magnético para diferentes dínamos esféricos

    OpenAIRE

    Fontana, Mauro

    2017-01-01

    Hace más de un siglo que Bernard Brunhes propuso la existencia de reversiones del campo magnético terrestre en escalas de tiempo geológicas. Esta teoría, hacia mediados del siglo XX, logró la aceptación de la comunidad científica. No obstante, aún no ha sido posible establecer mecanismos precisos que permitan explicar las reversiones geomagnéticas. El presente trabajo muestra que, aún en una geometría sencilla, las ecuaciones de la magnetohidrodinámica difusiva y rotante contienen todos los i...

  8. External dc bias-field effects in the nonlinear ac stationary response of dipolar particles in a mean-field potential.

    Science.gov (United States)

    Wei, Nijun; Déjardin, Pierre-Michel; Kalmykov, Yuri P; Coffey, William T

    2016-04-01

    External dc bias-field effects on the nonlinear dielectric relaxation and dynamic Kerr effect of a system of permanent dipoles in a uniaxial mean-field potential are studied via the rotational Brownian motion model postulated in terms of the infinite hierarchy of differential-recurrence equations for the statistical moments f_{n}(t)=〈P_{n}〉(t) (the expectation value of the Legendre polynomials P_{n}). By solving these equations, the nonlinear dielectric and Kerr-effect ac stationary responses are evaluated for arbitrary dc field strength via perturbation theory in the ac field. Simple analytic equations based on the large separation of the time scales of the fast intrawell and slow overbarrier (interwell) relaxation processes are also derived.

  9. Exactly solvable models for multiatomic molecular Bose-Einstein condensates

    Energy Technology Data Exchange (ETDEWEB)

    Santos, G, E-mail: gfilho@if.ufrgs.br, E-mail: gfilho@cbpf.br [Instituto de Fisica da UFRGS, Av. Bento Goncalves, 9500, Agronomia, Porto Alegre, RS (Brazil)

    2011-08-26

    I introduce two families of exactly solvable models for multiatomic hetero-nuclear and homo-nuclear molecular Bose-Einstein condensates through the algebraic Bethe ansatz method. The conserved quantities of the respective models are also shown. (paper)

  10. EXPERIMENTAL AND THEORETICAL NMR STUDY OF 4-(1 ...

    African Journals Online (AJOL)

    Preferred Customer

    experimental and theoretical data have showed that the molecular geometry and the ... 1D and 2D hetero- and homonuclear NMR methods enable to ... The essence of this study is briefly to report experimental and theoretical NMR features of.

  11. A new laboratory approach to shale analysis using NMR relaxometry

    Science.gov (United States)

    Washburn, Kathryn E.; Birdwell, Justin E.; Baez, Luis; Beeney, Ken; Sonnenberg, Steve

    2013-01-01

    Low-field nuclear magnetic resonance (LF-NMR) relaxometry is a non-invasive technique commonly used to assess hydrogen-bearing fluids in petroleum reservoir rocks. Measurements made using LF-NMR provide information on rock porosity, pore-size distributions, and in some cases, fluid types and saturations (Timur, 1967; Kenyon et al., 1986; Straley et al., 1994; Brown, 2001; Jackson, 2001; Kleinberg, 2001; Hurlimann et al., 2002). Recent improvements in LF-NMR instrument electronics have made it possible to apply methods used to measure pore fluids to assess highly viscous and even solid organic phases within reservoir rocks. T1 and T2 relaxation responses behave very differently in solids and liquids; therefore the relationship between these two modes of relaxation can be used to differentiate organic phases in rock samples or to characterize extracted organic materials. Using T1-T2 correlation data, organic components present in shales, such as kerogen and bitumen, can be examined in laboratory relaxometry measurements. In addition, implementation of a solid-echo pulse sequence to refocus T2 relaxation caused by homonuclear dipolar coupling during correlation measurements allows for improved resolution of solid-phase protons. LF-NMR measurements of T1 and T2 relaxation time distributions were carried out on raw oil shale samples from the Eocene Green River Formation and pyrolyzed samples of these shales processed by hydrous pyrolysis and techniques meant to mimic surface and in-situ retorting. Samples processed using the In Situ Simulator approach ranged from bitumen and early oil generation through to depletion of petroleum generating potential. The standard T1-T2 correlation plots revealed distinct peaks representative of solid- and liquid-like organic phases; results on the pyrolyzed shales reflect changes that occurred during thermal processing. The solid-echo T1 and T2 measurements were used to improve assessment of the solid organic phases, specifically

  12. Hydrogen and deuterium NMR of solids by magic angle spinning

    Energy Technology Data Exchange (ETDEWEB)

    Eckman, Richard Raymond [Univ. of California, Berkeley, CA (United States)

    1982-10-01

    The nuclear magnetic resonance of solids has long been characterized by very large spectral broadening which arises from internuclear dipole-dipole coupling or the nuclear electric quadrupole interaction. These couplings can obscure the smaller chemical shift interaction and make that information unavailable. Two important and difficult cases are that of hydrogen and deuterium. For example, the homonuclear dipolar broadening, HD, for hydrogen is usually several tens of kilohertz. For deuterium, HD is relatively small; however, the quadrupole interaction causes a broadening which can be hundreds of kilohertz in polycrystalline or amorphous solids. The development of cross polarization, heteronuclear radiofrequency decoupling, and coherent averaging of nuclear spin interactions has provided measurement of chemical shift tensors in solids. Recently, double quantum NMR and double quantum decoupling have led to measurement of deuterium and proton chemical shift tensors, respectively. A general problem of these experiments is the overlapping of the tensor powder pattern spectra of magnetically distinct sites which cannot be resolved. In this work, high resolution NMR of hydrogen and deuterium in solids is demonstrated. For both nuclei, the resonances are narrowed to obtain liquid-like isotropic spectra by high frequency rotation of the sample about an axis inclined at the magic angle, βm = Arccos(3-1/2), with respect to the direction of the external magnetic field. Two approaches have been developed for each nucleus. For deuterium, the powder spectra were narrowed by over three orders of magnitude by magic angle rotation with precise control of β. A second approach was the observation of deuterium double quantum transitions under magic angle rotation. For hydrogen, magic angle rotation alone could be applied to obtain the isotropic spectrum when HD was small. This often occurs naturally when the nuclei are semi-dilute or involved in

  13. On the Integration of Academic and Artistic Methodologies

    DEFF Research Database (Denmark)

    Heinrich, Falk

    2013-01-01

    The paper reflects upon the integration of academic-scientific methods and artistic strategies for art and technology projects that address user participation in a socially defined domain. The paper begins by describing its field of inquiry as an extended art field in which artistic enterprises...... (tightly coupled constituents) as a theoretical and heuristic tool for productive interferences between artistic and scientific methods. Art and technology projects operate within a field of existing forms (social patterns, urban spaces, etc.), which must be de-coupled prior to decisions related to new...... forms. Novel recoupling is often seen as the artistic impetus per se, but recoupling is intrinsically bound to the decoupling process. The decoupling-recoupling process necessitates a project dependent combination of various scientific and artistic methods due to the complexity and aim of these projects...

  14. Optimization of identity operation in NMR spectroscopy via genetic algorithm: Application to the TEDOR experiment

    Science.gov (United States)

    Manu, V. S.; Veglia, Gianluigi

    2016-12-01

    Identity operation in the form of π pulses is widely used in NMR spectroscopy. For an isolated single spin system, a sequence of even number of π pulses performs an identity operation, leaving the spin state essentially unaltered. For multi-spin systems, trains of π pulses with appropriate phases and time delays modulate the spin Hamiltonian to perform operations such as decoupling and recoupling. However, experimental imperfections often jeopardize the outcome, leading to severe losses in sensitivity. Here, we demonstrate that a newly designed Genetic Algorithm (GA) is able to optimize a train of π pulses, resulting in a robust identity operation. As proof-of-concept, we optimized the recoupling sequence in the transferred-echo double-resonance (TEDOR) pulse sequence, a key experiment in biological magic angle spinning (MAS) solid-state NMR for measuring multiple carbon-nitrogen distances. The GA modified TEDOR (GMO-TEDOR) experiment with improved recoupling efficiency results in a net gain of sensitivity up to 28% as tested on a uniformly 13C, 15N labeled microcrystalline ubiquitin sample. The robust identity operation achieved via GA paves the way for the optimization of several other pulse sequences used for both solid- and liquid-state NMR used for decoupling, recoupling, and relaxation experiments.

  15. Efficient 2D double-quantum solid-state NMR spectroscopy with large spectral widths.

    Science.gov (United States)

    Märker, Katharina; Hediger, Sabine; De Paëpe, Gaël

    2017-08-10

    2D double-quantum single-quantum correlation spectra with arbitrary spectral widths can be recorded with SR26 and related supercycled recoupling sequences when applying Supercycle-Timing-Compensation (STiC) phase shifts. This concept widely extends the applicability of supercycled sequences, most importantly for obtaining long-range distance constraints for structure determination with solid-state NMR.

  16. Vaccination of High-Risk Breast Cancer Patients with Carbohydrate Mimicking Peptides

    Science.gov (United States)

    2008-05-01

    for coupling cycle. The extent of coupling of each amino acid will be monitored by the ninhydrin test3 and recoupling will be performed if a...positive ninhydrin test result is obtained. After completion of the last coupling step (first amino acid in the peptide sequence), the resin will be

  17. Corporate Responsibility as Myth and Ceremony

    DEFF Research Database (Denmark)

    Haack, Patrick; Martignoni, Dirk; Schoeneborn, Dennis

    Organizations adopt corporate responsibility (CR) policies often ceremonially, meaning that policy adoption is not substantive and lacks alignment with actual practice. Prior research in institutional theory has largely assumed as static view of adoption and suggests that a situation of opacity (i...... governance mechanism and (2) the institutional theory concepts of decoupling and (re-)coupling....

  18. Optimization of identity operation in NMR spectroscopy via genetic algorithm: Application to the TEDOR experiment.

    Science.gov (United States)

    Manu, V S; Veglia, Gianluigi

    2016-12-01

    Identity operation in the form of π pulses is widely used in NMR spectroscopy. For an isolated single spin system, a sequence of even number of π pulses performs an identity operation, leaving the spin state essentially unaltered. For multi-spin systems, trains of π pulses with appropriate phases and time delays modulate the spin Hamiltonian to perform operations such as decoupling and recoupling. However, experimental imperfections often jeopardize the outcome, leading to severe losses in sensitivity. Here, we demonstrate that a newly designed Genetic Algorithm (GA) is able to optimize a train of π pulses, resulting in a robust identity operation. As proof-of-concept, we optimized the recoupling sequence in the transferred-echo double-resonance (TEDOR) pulse sequence, a key experiment in biological magic angle spinning (MAS) solid-state NMR for measuring multiple carbon-nitrogen distances. The GA modified TEDOR (GMO-TEDOR) experiment with improved recoupling efficiency results in a net gain of sensitivity up to 28% as tested on a uniformly (13)C, (15)N labeled microcrystalline ubiquitin sample. The robust identity operation achieved via GA paves the way for the optimization of several other pulse sequences used for both solid- and liquid-state NMR used for decoupling, recoupling, and relaxation experiments. Copyright © 2016 Elsevier Inc. All rights reserved.

  19. Cu-free 1,3-dipolar cycloaddition click reactions to form isoxazole linkers in chelating ligands for fac-[M(I)(CO)3]+ centers (M = Re, 99mTc).

    Science.gov (United States)

    Bottorff, Shalina C; Kasten, Benjamin B; Stojakovic, Jelena; Moore, Adam L; MacGillivray, Leonard R; Benny, Paul D

    2014-02-17

    Isoxazole ring formation was examined as a potential Cu-free alternative click reaction to Cu(I)-catalyzed alkyne/azide cycloaddition. The isoxazole reaction was explored at macroscopic and radiotracer concentrations with the fac-[M(I)(CO)3](+) (M = Re, (99m)Tc) core for use as a noncoordinating linker strategy between covalently linked molecules. Two click assembly methods (click, then chelate and chelate, then click) were examined to determine the feasibility of isoxazole ring formation with either alkyne-functionalized tridentate chelates or their respective fac-[M(I)(CO)3](+) complexes with a model nitrile oxide generator. Macroscale experiments, alkyne-functionalized chelates, or Re complexes indicate facile formation of the isoxazole ring. (99m)Tc experiments demonstrate efficient radiolabeling with click, then chelate; however, the chelate, then click approach led to faster product formation, but lower yields compared to the Re analogues.

  20. Propriedades magnéticas de memória e envelhecimento, exchange bias e treinamento de nanopartículas do tipo core-shell em regimes de interações dipolares fracas e fortes

    OpenAIRE

    Leite, Rodolpho Carvalho

    2017-01-01

    Investigamos as propriedades magnéticas de nanopartículas core-shell (NPs-CS) ultrapequenas de CoFe2O4@γ-Fe2O3 com diâmetro médio de dRX = 2.7 nm em amostras de ferrofluido diluído e pó compacto. Utilizamos a abordagem proposta por Thamm e Hesse para definir os dois regimes de interações fracas, para amostra de ferrofluido diluído, e fortes, para amostra pó, presentes a 5 K. A energia de anisotropia magnética, nestes regimes, é sondada pela curva de primeira magnetização, dependência térmica ...