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Sample records for multiple chiral centers

  1. (Thio)urea-mediated synthesis of functionalized six-membered rings with multiple chiral centers

    PubMed Central

    Koutoulogenis, Giorgos; Kaplaneris, Nikolaos

    2016-01-01

    Summary Organocatalysis, now running its second decade of life, is being considered one of the main tools a synthetic chemist has to perform asymmetric catalysis. In this review the synthesis of six-membered rings, that contain multiple chiral centers, either by a ring closing process or by a functionalization reaction on an already existing six-membered ring, utilizing bifunctional (thio)ureas will be summarized. Initially, the use of primary amine-thioureas as organocatalysts for the above transformation is being discussed, followed by the examples employing secondary amine-thioureas. Finally, the use of tertiary amine-thioureas and miscellaneous examples are presented. PMID:27340441

  2. Chiral geometry in multiple chiral doublet bands

    NASA Astrophysics Data System (ADS)

    Zhang, Hao; Chen, Qibo

    2016-02-01

    The chiral geometry of multiple chiral doublet bands with identical configuration is discussed for different triaxial deformation parameters γ in the particle rotor model with . The energy spectra, electromagnetic transition probabilities B(M1) and B(E2), angular momenta, and K-distributions are studied. It is demonstrated that the chirality still remains not only in the yrast and yrare bands, but also in the two higher excited bands when γ deviates from 30°. The chiral geometry relies significantly on γ, and the chiral geometry of the two higher excited partner bands is not as good as that of the yrast and yrare doublet bands. Supported by Plan Project of Beijing College Students’ Scientific Research and Entrepreneurial Action, Major State 973 Program of China (2013CB834400), National Natural Science Foundation of China (11175002, 11335002, 11375015, 11461141002), National Fund for Fostering Talents of Basic Science (NFFTBS) (J1103206), Research Fund for Doctoral Program of Higher Education (20110001110087) and China Postdoctoral Science Foundation (2015M580007)

  3. Examination of the potential for adaptive chirality of the nitrogen chiral center in aza-aspartame.

    PubMed

    Bouayad-Gervais, Samir H; Lubell, William D

    2013-01-01

    The potential for dynamic chirality of an azapeptide nitrogen was examined by substitution of nitrogen for the α-carbon of the aspartate residue in the sweetener S,S-aspartame. Considering that S,S- and R,S-aspartame possess sweet and bitter tastes, respectively, a bitter-sweet taste of aza-aspartame 9 could be indicative of a low isomerization barrier for nitrogen chirality inter-conversion. Aza-aspartame 9 was synthesized by a combination of hydrazine and peptide chemistry. Crystallization of 9 indicated a R,S-configuration in the solid state; however, the aza-residue chiral center was considerably flattened relative to its natural amino acid counterpart. On tasting, the authors considered aza-aspartame 9 to be slightly bitter or tasteless. The lack of bitter sweet taste of aza-aspartame 9 may be due to flattening from sp2 hybridization in the urea as well as a high barrier for sp3 nitrogen inter-conversion, both of which may interfere with recognition by taste receptors. PMID:24288001

  4. Examination of the potential for adaptive chirality of the nitrogen chiral center in aza-aspartame.

    PubMed

    Bouayad-Gervais, Samir H; Lubell, William D

    2013-11-28

    The potential for dynamic chirality of an azapeptide nitrogen was examined by substitution of nitrogen for the α-carbon of the aspartate residue in the sweetener S,S-aspartame. Considering that S,S- and R,S-aspartame possess sweet and bitter tastes, respectively, a bitter-sweet taste of aza-aspartame 9 could be indicative of a low isomerization barrier for nitrogen chirality inter-conversion. Aza-aspartame 9 was synthesized by a combination of hydrazine and peptide chemistry. Crystallization of 9 indicated a R,S-configuration in the solid state; however, the aza-residue chiral center was considerably flattened relative to its natural amino acid counterpart. On tasting, the authors considered aza-aspartame 9 to be slightly bitter or tasteless. The lack of bitter sweet taste of aza-aspartame 9 may be due to flattening from sp2 hybridization in the urea as well as a high barrier for sp3 nitrogen inter-conversion, both of which may interfere with recognition by taste receptors.

  5. Enantiomeric resolution of multiple chiral centres racemates by capillary electrophoresis.

    PubMed

    Ali, Imran; Suhail, Mohd; Al-Othman, Zeid A; Alwarthan, Abdulrahman; Aboul-Enein, Hassan Y

    2016-05-01

    Enantiomeric resolution of multichiral centre racemates is an important area as some multichiral centre racemates are of great medicinal importance. However, enantioseparation of such types of racemates is a challenging task. Amongst many analytical techniques, capillary electrophoresis is a powerful technique and may be used to resolve such racemates. Only few papers are available describing enantiomeric resolution of such racemates. Therefore, efforts have been made to describe the enantiomeric resolution of multichiral centre racemates by capillary electrophoresis. This article discusses the importance of multichiral racemates, the need for capillary electrophoresis in enantiomeric resolution and chiral resolution of multichiral centre racemates using various chiral selectors. Further, attempts have been made to discuss the future challenges and prospects of enantiomeric resolution of multichiral racemates. The various chiral selectors used for the purpose are chiral crown ether, cyclodextrins, polysaccharides, macrocyclic glycopeptide antibiotics and ligand exchange.

  6. Chiral rotational spectroscopy

    NASA Astrophysics Data System (ADS)

    Cameron, Robert P.; Götte, Jörg B.; Barnett, Stephen M.

    2016-09-01

    We introduce chiral rotational spectroscopy, a technique that enables the determination of the orientated optical activity pseudotensor components BX X, BY Y, and BZ Z of chiral molecules, in a manner that reveals the enantiomeric constitution of a sample and provides an incisive signal even for a racemate. Chiral rotational spectroscopy could find particular use in the analysis of molecules that are chiral solely by virtue of their isotopic constitution and molecules with multiple chiral centers. A basic design for a chiral rotational spectrometer together with a model of its functionality is given. Our proposed technique offers the more familiar polarizability components αX X, αY Y, and αZ Z as by-products, which could see it find use even for achiral molecules.

  7. Remote control of helical chirality: thermodynamic resolution of a racemic mixture of CTV units by remote stereogenic centers.

    PubMed

    Chatelet, Bastien; Joucla, Lionel; Padula, Daniele; Di Bari, Lorenzo; Pilet, Guillaume; Robert, Vincent; Dufaud, Véronique; Dutasta, Jean-Pierre; Martinez, Alexandre

    2015-02-01

    Enantiopure hemicryptophanes designed from the cyclotriveratrylene (CTV) unit display remarkable properties in selective host-guest recognition or as supramolecular catalysts. The unprecedented control of the helical chirality of the CTV unit by remote stereogenic centers of a tren moiety is reported, providing an original access to this highly promising class of host molecules. Although the chiral centers and the CTV unit are separated by more than 10 Å, one single diastereomer is formed; the nature of the diastereoselective process is discussed and the procedure is exemplified using different enantiopure tren derivatives. This work also highlights the influence of the chirality of the CTV unit on the whole cage structure. PMID:25629235

  8. Olfactory discrimination ability of human subjects for enantiomers with an isopropenyl group at the chiral center.

    PubMed

    Laska, Matthias

    2004-02-01

    The ability of 20 human subjects to distinguish between nine enantiomeric odor pairs sharing an isopropenyl group at the chiral center was tested in a forced-choice triangular test procedure. I found (i). that as a group, the subjects were only able to significantly discriminate the optical isomers of limonene, carvone, dihydrocarvone, dihydrocarveol and dihydrocarvyl acetate, whereas they failed to distinguish between the (+)- and (-)-forms of perillaalcohol, perillaaldehyde, isopulegol and limonene oxide; (ii). marked interindividual differences in discrimination performance, ranging from subjects who were able to significantly discriminate between eight of the nine odor pairs to subjects who failed to do so with six of the nine tasks; and (iii). that with none of the nine odor pairs the antipodes were reported to differ significantly in subjective intensity when presented at equal concentrations. Additional tests of the chemesthetic potency and threshold measurements of the optical isomers of dihydrocarvone, dihydrocarveol, and dihydrocarvyl acetate suggest that the discriminability of these three enantiomeric odor pairs is indeed due to differences in odor quality. Analysis of structure-activity relationships suggest that the combined presence of (i). an isopropenyl group at the chiral center; (ii). a methyl group at the para-position; and/or (iii). an oxygen-containing group at the meta-position allows for the discrimination of enantiomeric odor pairs. PMID:14977811

  9. Stereogenic Centers and Axes: A Comparison of the Chiral Topologies Available to Cabcd and AbC=C=Ccd

    ERIC Educational Resources Information Center

    Lloyd-Williams, Paul; Giralt, Ernest

    2005-01-01

    A clarification of concepts and a comparative analysis of chirality as a consequence of stereogenic center and axes are provided by considering the different possibilities for the archetypical molecule Cabcd. The key difference between Cabcd and abC=C=Ccd and, by extension, between molecules incorporating a stereogenic axis, is in the number of…

  10. Multiple scattering in chiral media: border effects, reduced depolarization, and sensitivity limit

    NASA Astrophysics Data System (ADS)

    Delplancke, Francoise; Badoz, Jacques P.; Boccara, A. Claude

    1997-10-01

    Suspensions of polystyrene latex beads in chiral solutions were investigated. The rotatory power, induced by solubilized sucrose, in near-forward scattering was measured via a method using polarization modulation by photo-elastic modulator. The sensitivity of the measurement was enhanced and optimized in order to measure sucrose concentrations as low as 5 mg/ml in a cell 5 mm thick only. Different concentrations and diameters of latex particles were used in combination with different sucrose concentrations going from 1 mg/ml up to saturation. The experiments showed that the apparent rotatory power is enhanced by multiple scattering, that depolarization effects are less important with highly concentrated sucrose solutions and that attention has to be paid to cell border effects in order to avoid important artifacts, in case of highly scattering suspensions. Qualitative and theoretical explanations of those observations are presented. One possible application of this method is to measure the sugar content in human blood, in vivo, non-invasively, through the skin. The concentration to be evaluated is at the sensitivity limit. So any artifact has to be removed carefully, e.g. skin cell birefringence or chirality.

  11. Multiple chiral topological states in liquid crystals from unstructured light beams

    SciTech Connect

    Loussert, Charles; Brasselet, Etienne

    2014-02-03

    It is shown experimentally that unstructured light beams can generate a wealth of distinct metastable defect structures in thin films of chiral liquid crystals. Various kinds of individual chiral topological states are obtained as well as dimers and trimers, which correspond to the entanglement of several topological unit cells. Self-assembled nested assemblies of several metastable particle-like topological states can also be formed. Finally, we propose and experimentally demonstrate an opto-electrical approach to generate tailor-made architectures.

  12. Three-dimensional Chiral Plasmonic Oligomers

    NASA Astrophysics Data System (ADS)

    Hentschel, Mario

    2013-03-01

    We demonstrate chiral optical response in stacked arrangements of plasmonic nanostructures. We show that three-dimensional arrangements of plasmonic ``meta-atoms'' only exhibit a chiral optical response if similar plasmonic ``atoms'' are arranged in a handed fashion as we require resonant plasmonic coupling. Moreover, we demonstrate that such particle groupings, similarly to molecular systems, possess the capability to encode their three-dimensional arrangement in unique and well-modulated spectra, making them ideal candidates for a three-dimensional chiral plasmon ruler. Furthermore, we discuss the onset of a broadband chiral optical response in the wavelength regime between 700 nm and 3500 nm upon charge transfer between the nanoparticles. We show in experiment and simulation that this response is due to the ohmic contact between adjacent particles which causes a strong red-shift of the fundamental mode. The geometrical shape of the resulting fused particles allows for efficient excitation of higher order modes. Calculated spectra and field distributions confirm our interpretation and show a number of interacting plasmonic modes. Finally, we will discuss plasmonic diastereomers which consist of multiple chiral centers. We find that the chiral optical response of the composite molecules can be traced back to the properties of the constituting building blocks. We demonstrate that the optical response of complex chiral plasmonic systems can be decomposed and understood in terms of fundamental building blocks, offering simple and straightforward design rules for future applications such as chiral optical elements and enantiomer sensors.

  13. From an α-functionalized silicon-stereogenic N,O-silane to a monomeric and tetracoordinate tBuLi adduct with lithium-centered chirality.

    PubMed

    Bauer, Jonathan O; Strohmann, Carsten

    2014-07-28

    Donor-functionalized silanes with stereogenic silicon centers are extremely rare. A convenient stereocontrolled route to a nitrogen-oxygen-functionalized silicon-chiral compound with an additional aminomethyl function is presented. This silane was directly achieved in stereochemically pure form by a simple nucleophilic substitution reaction. Owing to the unique asymmetry of this silane and the presence of three donor functions, the first monomeric butyllithium compound with lithium-centered chirality could be isolated; the configuration was assigned by X-ray crystallography. This [silane⋅ tBuLi] complex undergoes an unexpected deprotonation/stereospecific substitution sequence in toluene, leading to the development of a convenient one-pot synthesis of a functionalized silicon-chiral benzylsilane, which proceeds with inversion of configuration and complete preservation of the stereochemical integrity at silicon.

  14. Novel oxygen chirality induced by asymmetric coordination of an ether oxygen atom to a metal center in a series of sugar-pendant dipicolylamine copperII complexes.

    PubMed

    Mikata, Yuji; Sugai, Yuko; Obata, Makoto; Harada, Masafumi; Yano, Shigenobu

    2006-02-20

    Six sugar-pendant 2,2'-dipicolylamine (DPA) ligands (L1-3 and L'1-3) have been prepared. OH-protected and unprotected D-glucose, D-mannose, and D-xylose were attached to a DPA moiety via an O-glycoside linkage. X-ray crystallography of the copper(II) complexes (1-5) with these ligands revealed that the anomeric oxygen atom is coordinated to the metal center in the solid state, generating a chiral center at the oxygen atom. The CD spectra of these copper complexes in methanol or aqueous solution exhibit Cotton effects in the d-d transition region, which indicates that the ether oxygen atoms remain coordinated to the metal center and the oxygen-atom chirality is preserved even in solution. For complexes 1 and 2, the inverted oxygen-atom chirality and chelate-ring conformation in the solid state are well correlated with the mirror-image CD spectra in methanol solution. The concomitant inversion of the asymmetric configuration around the copper center was also observed in a methanol solution of complex 3 and a pyridine solution of complex 2. The square-pyramidal/octahedral copper(II) centers also exhibited characteristic absorption and CD spectra.

  15. Engineering chiral density waves and topological band structures by multiple-Q superpositions of collinear up-up-down-down orders

    NASA Astrophysics Data System (ADS)

    Hayami, Satoru; Ozawa, Ryo; Motome, Yukitoshi

    2016-07-01

    Magnetic orders characterized by multiple ordering vectors harbor noncollinear and noncoplanar spin textures and can be a source of unusual electronic properties through the spin Berry phase mechanism. We theoretically show that such multiple-Q states are stabilized in itinerant magnets in the form of superpositions of collinear up-up-down-down (UUDD) spin states, which accompany the density waves of vector and scalar chirality. The result is drawn by examining the ground state of the Kondo lattice model with classical localized moments, especially when the Fermi surface is tuned to be partially nested by the symmetry-related commensurate vectors. We unveil the instability toward a double-Q UUDD state with vector chirality density waves on the square lattice and a triple-Q UUDD state with scalar chirality density waves on the triangular lattice, using the perturbative theory and variational calculations. The former double-Q state is also confirmed by large-scale Langevin dynamics simulations. We also show that, for a sufficiently large exchange coupling, the chirality density waves can induce rich nontrivial topology of electronic structures, such as the massless Dirac semimetal, Chern insulator with quantized topological Hall response, and peculiar edge states which depend on the phase of chirality density waves at the edges.

  16. GMTI Direction of Arrival Measurements from Multiple Phase Centers.

    SciTech Connect

    Doerry, Armin W.; Bickel, Douglas L.

    2015-03-01

    Ground Moving Target Indicator (GMTI) radar attempts to detect and locate targets with unknown motion. Very slow-moving targets are difficult to locate in the presence of surrounding clutter. This necessitates multiple antenna phase centers (or equivalent) to offer independent Direction of Arrival (DOA) measurements. DOA accuracy and precision generally remains dependent on target Signal-to-Noise Ratio (SNR), Clutter-toNoise Ratio (CNR), scene topography, interfering signals, and a number of antenna parameters. This is true even for adaptive techniques like Space-Time-AdaptiveProcessing (STAP) algorithms.

  17. The ribosome can discriminate the chirality of amino acids within its peptidyl-transferase center

    PubMed Central

    Englander, Michael T.; Avins, Joshua L.; Fleisher, Rachel C.; Liu, Bo; Effraim, Philip R.; Wang, Jiangning; Schulten, Klaus; Leyh, Thomas S.; Gonzalez, Ruben L.; Cornish, Virginia W.

    2015-01-01

    The cellular translational machinery (TM) synthesizes proteins using exclusively L- or achiral aminoacyl-tRNAs (aa-tRNAs), despite the presence of D-amino acids in nature and their ability to be aminoacylated onto tRNAs by aa-tRNA synthetases. The ubiquity of L-amino acids in proteins has led to the hypothesis that D-amino acids are not substrates for the TM. Supporting this view, protein engineering efforts to incorporate D-amino acids into proteins using the TM have thus far been unsuccessful. Nonetheless, a mechanistic understanding of why D-aa-tRNAs are poor substrates for the TM is lacking. To address this deficiency, we have systematically tested the translation activity of D-aa-tRNAs using a series of biochemical assays. We find that the TM can effectively, albeit slowly, accept D-aa-tRNAs into the ribosomal aa-tRNA binding (A) site, use the A-site D-aa-tRNA as a peptidyl-transfer acceptor, and translocate the resulting peptidyl-D-aa-tRNA into the ribosomal peptidyl-tRNA binding (P) site. During the next round of continuous translation, however, we find that ribosomes carrying a P-site peptidyl-D-aa-tRNA partition into subpopulations that are either translationally arrested or that can continue translating. Consistent with its ability to arrest translation, chemical protection experiments and molecular dynamics simulations show that P site-bound peptidyl-D-aa-tRNA can trap the ribosomal peptidyl-transferase center in a conformation in which peptidyl transfer is impaired. Our results reveal a novel mechanism through which D-aa-tRNAs interfere with translation, provide insight into how the TM might be engineered to use D-aa-tRNAs, and increase our understanding of the physiological role of a widely distributed enzyme that clears D-aa-tRNAs from cells. PMID:25918365

  18. The ribosome can discriminate the chirality of amino acids within its peptidyl-transferase center.

    PubMed

    Englander, Michael T; Avins, Joshua L; Fleisher, Rachel C; Liu, Bo; Effraim, Philip R; Wang, Jiangning; Schulten, Klaus; Leyh, Thomas S; Gonzalez, Ruben L; Cornish, Virginia W

    2015-05-12

    The cellular translational machinery (TM) synthesizes proteins using exclusively L- or achiral aminoacyl-tRNAs (aa-tRNAs), despite the presence of D-amino acids in nature and their ability to be aminoacylated onto tRNAs by aa-tRNA synthetases. The ubiquity of L-amino acids in proteins has led to the hypothesis that D-amino acids are not substrates for the TM. Supporting this view, protein engineering efforts to incorporate D-amino acids into proteins using the TM have thus far been unsuccessful. Nonetheless, a mechanistic understanding of why D-aa-tRNAs are poor substrates for the TM is lacking. To address this deficiency, we have systematically tested the translation activity of D-aa-tRNAs using a series of biochemical assays. We find that the TM can effectively, albeit slowly, accept D-aa-tRNAs into the ribosomal aa-tRNA binding (A) site, use the A-site D-aa-tRNA as a peptidyl-transfer acceptor, and translocate the resulting peptidyl-D-aa-tRNA into the ribosomal peptidyl-tRNA binding (P) site. During the next round of continuous translation, however, we find that ribosomes carrying a P-site peptidyl-D-aa-tRNA partition into subpopulations that are either translationally arrested or that can continue translating. Consistent with its ability to arrest translation, chemical protection experiments and molecular dynamics simulations show that P site-bound peptidyl-D-aa-tRNA can trap the ribosomal peptidyl-transferase center in a conformation in which peptidyl transfer is impaired. Our results reveal a novel mechanism through which D-aa-tRNAs interfere with translation, provide insight into how the TM might be engineered to use D-aa-tRNAs, and increase our understanding of the physiological role of a widely distributed enzyme that clears D-aa-tRNAs from cells.

  19. The Decker Family Development Center: Supportive Data of an Intervention Model for Multiple-Risk Families.

    ERIC Educational Resources Information Center

    Newman, Carole; And Others

    The Decker Family Development Center in Barberton (Ohio) is a holistic "one-stop shop" that provides services to families who are at multiple risk. During its 5 years of operation, this center has developed a model that goes beyond cooperation into co-construction to empower stakeholders. This paper describes the center and its successes and…

  20. Supporting Multiple Programs and Projects at NASA's Kennedy Space Center

    NASA Technical Reports Server (NTRS)

    Stewart, Camiren L.

    2014-01-01

    With the conclusion of the shuttle program in 2011, the National Aeronautics and Space Administration (NASA) had found itself at a crossroads for finding transportation of United States astronauts and experiments to space. The agency would eventually hand off the taxiing of American astronauts to the International Space Station (ISS) that orbits in Low Earth Orbit (LEO) about 210 miles above the earth under the requirements of the Commercial Crew Program (CCP). By privatizing the round trip journey from Earth to the ISS, the space agency has been given the additional time to focus funding and resources to projects that operate beyond LEO; however, adding even more stress to the agency, the premature cancellation of the program that would succeed the Shuttle Program - The Constellation Program (CxP) -it would inevitably delay the goal to travel beyond LEO for a number of years. Enter the Space Launch System (SLS) and the Orion Multipurpose Crew Vehicle (MPCV). Currently, the SLS is under development at NASA's Marshall Spaceflight Center in Huntsville, Alabama, while the Orion Capsule, built by government contractor Lockheed Martin Corporation, has been assembled and is currently under testing at the Kennedy Space Center (KSC) in Florida. In its current vision, SLS will take Orion and its crew to an asteroid that had been captured in an earlier mission in lunar orbit. Additionally, this vehicle and its configuration is NASA's transportation to Mars. Engineers at the Kennedy Space Center are currently working to test the ground systems that will facilitate the launch of Orion and the SLS within its Ground Services Development and Operations (GSDO) Program. Firing Room 1 in the Launch Control Center (LCC) has been refurbished and outfitted to support the SLS Program. In addition, the Spaceport Command and Control System (SCCS) is the underlying control system for monitoring and launching manned launch vehicles. As NASA finds itself at a junction, so does all of its

  1. Rational Design of Chiral Nanostructures from Self-Assembly of a Ferrocene-Modified Dipeptide.

    PubMed

    Wang, Yuefei; Qi, Wei; Huang, Renliang; Yang, Xuejiao; Wang, Mengfan; Su, Rongxin; He, Zhimin

    2015-06-24

    We report a new paradigm for the rational design of chiral nanostructures that is based on the hierarchical self-assembly of a ferrocene (Fc)-modified dipeptide, ferrocene-L-Phe-L-Phe-OH (Fc-FF). Compared to other chiral self-assembling systems, Fc-FF is unique because of its smaller size, biocompatibility, multiple functions (a redox center), and environmental responsiveness. X-ray and spectroscopic analyses showed that the incorporation of counterions during the hierarchical self-assembly of Fc-FF changed the conformations of the secondary structures from flat β sheets into twisted β sheets. This approach enables chiral self-assembly and the formation of well-defined chiral nanostructures composed of helical twisted β sheets. We identified two elementary forms for the helical twist of the β sheets, which allowed us to create a rich variety of rigid chiral nanostructures over a wide range of scales. Furthermore, through subtle modulations in the counterions, temperature, and solvent, we are able to precisely control the helical pitch, diameter, and handedness of the self-assembled chiral nanostructures. This unprecedented level of control not only offers insights into how rationally designed chiral nanostructures can be formed from simple molecular building blocks but also is of significant practical value for the use in chiroptics, templates, chiral sensing, and separations.

  2. Chiral squaring

    NASA Astrophysics Data System (ADS)

    Nagy, S.

    2016-07-01

    We construct the states and symmetries of N = 4 super-Yang-Mills by tensoring two N = 1 chiral multiplets and introducing two extra SUSY generators. This allows us to write the maximal N = 8 supergravity as four copies of the chiral multiplet. We extend this to higher dimensions and discuss applications to scattering amplitudes.

  3. One-pot multiple reactions: asymmetric synthesis of 2,6-cis-disubstituted piperidine alkaloids from chiral aziridine.

    PubMed

    Yadav, Nagendra Nath; Choi, Jihye; Ha, Hyun-Joon

    2016-07-01

    A divergent, new, and highly stereoselective synthesis of cis-2,6-disubstituted piperidine natural products including isosolenopsins, deoxocassine, and spectaline was achieved from chiral aziridine decorated with appropriate alkyl chains for isosolenopsins or alkynyl groups for deoxocassine and spectaline at C2. The characteristic feature of this synthesis is one-pot sequential reactions under atmospheric hydrogen including the reduction of alkyne (for deoxocassine and spectaline), reductive ring-opening of aziridine, debenzylation, and intramolecular reductive amination in high yields. The prerequisite aziridines were elaborated from commercially available (2S)-hydroxymethylaziridine through oxidation, Wittig olefination, and the Grignard reaction for isosolenopsins or substrate-controlled lithium alkynylate addition for deoxocassine and spectaline. PMID:27189444

  4. Nuclear Chirality

    SciTech Connect

    Starosta, Krzysztof

    2005-04-05

    Nuclear chirality is a novel manifestation of spontaneous symmetry breaking resulting from an orthogonal coupling of angular momentum vectors in triaxial nuclei. Three perpendicular angular momenta can form two systems of opposite handedness; the time reversal operator, which reverses orientation of each of the angular momentum components, relates these two systems. The status of current experimental searches for chiral doubling of states, as well as recent progress on the theoretical side is reviewed.

  5. Isotopic chirality

    SciTech Connect

    Floss, H.G.

    1994-12-01

    This paper deals with compounds that are chiral-at least in part, due to isotope substitution-and their use in tracing the steric course of enzyme reaction in vitro and in vivo. There are other applications of isotopically chiral compounds (for example, in analyzing the steric course of nonenzymatic reactions and in probing the conformation of biomolecules) that are important but they will not be discussed in this context.

  6. The US Network of Pediatric Multiple Sclerosis Centers: Development, Progress, and Next Steps

    PubMed Central

    Casper, T. Charles; Rose, John W.; Roalstad, Shelly; Waubant, Emmanuelle; Aaen, Gregory; Belman, Anita; Chitnis, Tanuja; Gorman, Mark; Krupp, Lauren; Lotze, Timothy E.; Ness, Jayne; Patterson, Marc; Rodriguez, Moses; Weinstock-Guttman, Bianca; Browning, Brittan; Graves, Jennifer; Tillema, Jan-Mendelt; Benson, Leslie; Harris, Yolanda

    2014-01-01

    Multiple sclerosis and other demyelinating diseases in the pediatric population have received an increasing level of attention by clinicians and researchers. The low incidence of these diseases in children creates a need for the involvement of multiple clinical centers in research efforts. The Network of Pediatric Multiple Sclerosis Centers was created initially in 2006 to improve the diagnosis and care of children with demyelinating diseases. In 2010, the Network shifted its focus to multicenter research while continuing to advance the care of patients. The Network has obtained support from the National Multiple Sclerosis Society, the Guthy-Jackson Charitable Foundation, and the National Institutes of Health. The Network will continue to serve as a platform for conducting impactful research in pediatric demyelinating diseases of the central nervous system. This article provides a description of the history and development, organization, mission, research priorities, current studies, and future plans of the Network. PMID:25270659

  7. The US Network of Pediatric Multiple Sclerosis Centers: Development, Progress, and Next Steps.

    PubMed

    Casper, T Charles; Rose, John W; Roalstad, Shelly; Waubant, Emmanuelle; Aaen, Gregory; Belman, Anita; Chitnis, Tanuja; Gorman, Mark; Krupp, Lauren; Lotze, Timothy E; Ness, Jayne; Patterson, Marc; Rodriguez, Moses; Weinstock-Guttman, Bianca; Browning, Brittan; Graves, Jennifer; Tillema, Jan-Mendelt; Benson, Leslie; Harris, Yolanda

    2015-09-01

    Multiple sclerosis and other demyelinating diseases in the pediatric population have received an increasing level of attention by clinicians and researchers. The low incidence of these diseases in children creates a need for the involvement of multiple clinical centers in research efforts. The Network of Pediatric Multiple Sclerosis Centers was created initially in 2006 to improve the diagnosis and care of children with demyelinating diseases. In 2010, the Network shifted its focus to multicenter research while continuing to advance the care of patients. The Network has obtained support from the National Multiple Sclerosis Society, the Guthy-Jackson Charitable Foundation, and the National Institutes of Health. The Network will continue to serve as a platform for conducting impactful research in pediatric demyelinating diseases of the central nervous system. This article provides a description of the history and development, organization, mission, research priorities, current studies, and future plans of the Network.

  8. The Assignment of the Absolute Configuration of C-22 Chiral Center in the Aglycones of Triterpene Glycosides from the Sea Cucumber Cladolabes schmeltzi and Chemical Transformations of Cladoloside C.

    PubMed

    Kalinovsky, Anatoly I; Silchenko, Alexandra S; Avilov, Sergey A; Kalinin, Vladimir I

    2015-07-01

    The absolute R-configuration of the C-22 chiral center in cladoloside C (1) and therefore in all related glycosides isolated from the sea cucumber Cladolabes schmeltzii has been assigned by Mosher's method. Some chemical transformations of the native glycoside 1 were carried out to apply this method. This resulted in the isolation and elucidation of chemical structures of progenin 2 and artefact aglycones 3 and 4, obtained from 1 and assignment of the absolute R-configuration of C-22 in the progenin 2. The coincidence of C-22 configurations in the studied compounds with those of the earlier known lanostane-type aglycone of frondoside C and holostane-type aglycone of cladoloside C (1) confirms the generic biosynthetic pathways to different types of sea cucumber glycoside aglycones. It suggests the same R-configuration of C-22 chiral centers in all the sea cucumber glycosides having C-22 functionalities.

  9. Generation mechanism of the ENSO rainfall center in the tropical Pacific: Multiple-timescale processes

    NASA Astrophysics Data System (ADS)

    Chen, M. T.-C.

    2009-04-01

    The tropical Pacific rainfall center associated with the ENSO cycle exhibits an interannual east-west seesaw following the corresponding sea surface temperatures (SSTs). It has been perceived in the past several decades by the climate research community that this east-west seesaw of the ENSO rainfall center is a direct response of the tropical atmospheric to the SST anomalies. It is analyzed by this study that this ENSO rainfall center is actually generated by a modulation of the equatorward cold air intrusion of midlatitude anticyclones by the ENSO east-west seesaw of the tropical Pacific SSTs through the multiple-timescale processes in the tropics-midlatitude interaction.

  10. Evaluation of the effect of the chiral centers of Taxol on binding to β-tubulin: A docking and molecular dynamics simulation study.

    PubMed

    Ghadari, Rahim; Alavi, Fatemeh S; Zahedi, Mansour

    2015-06-01

    Taxol is one of the most important anti-cancer drugs. The interaction between different variants of Taxol, by altering one of its chiral centers at a time, with β-tubulin protein has been investigated. To achieve such goal, docking and molecular dynamics (MD) simulation studies have been performed. In docking studies, the preferred conformers have been selected to further study by MD method based on the binding energies reported by the AutoDock program. The best result of docking study which shows the highest affinity between ligand and protein has been used as the starting point of the MD simulations. All of the complexes have shown acceptable stability during the simulation process, based on the RMSDs of the backbone of the protein structure. Finally, MM-GBSA calculations have been carried out to select the best ligand, considering the binding energy criteria. The results predict that two of the structures have better affinity toward the mentioned protein, in comparison with Taxol. Three of the structures have affinity similar to that of the Taxol toward the β-tubulin.

  11. Evaluation of the Multiple Careers Magnet and Assessment Centers at William B. Carrell, 1978-79.

    ERIC Educational Resources Information Center

    Maples, Wayne; And Others

    The report evaluates Texas' Multiple Careers Magnet Center (MCMC), a part time program to provide special education secondary students with career training. It is explained that students enter one of six career education clusters: furniture repair and upholstery, general construction trades, building and grounds maintenance, laundry and dry…

  12. Leaders' Experiences with High School-College Writing Center Collaborations: A Qualitative Multiple-Case Study

    ERIC Educational Resources Information Center

    Story, Julie A.

    2014-01-01

    The purpose of this qualitative multiple-case study was to explore academic leaders' experiences with the organizational elements of their own high school-college writing center collaborations. Conjoining theories framed this study: collaborative leadership theory, Kenneth Bruffee's notion of social constructionism and collaborative learning…

  13. NATIONAL SURVEYS OF MULTIPLE ENVIRONMENTAL HAZARDS TO YOUNG CHILDREN IN HOMES AND CHILD CARE CENTERS

    EPA Science Inventory

    The Department of Housing and Urban Development (HUD) has teamed with other federal agencies to characterize exposure of multiple environmental hazards to young children in two main indoor environments, homes and daycare centers. Under the co-sponsorship of HUD and the Nationa...

  14. Multiple emotions: a person-centered approach to the relationship between intergroup emotion and action orientation.

    PubMed

    Fernando, Julian W; Kashima, Yoshihisa; Laham, Simon M

    2014-08-01

    Although a great deal of research has investigated the relationship between emotions and action orientations, most studies to date have used variable-centered techniques to identify the best emotion predictor(s) of a particular action. Given that people frequently report multiple or blended emotions, a profitable area of research may be to adopt person-centered approaches to examine the action orientations elicited by a particular combination of emotions or "emotion profile." In two studies, across instances of intergroup inequality in Australia and Canada, we examined participants' experiences of six intergroup emotions: sympathy, anger directed at three targets, shame, and pride. In both studies, five groups of participants with similar emotion profiles were identified by cluster analysis and their action orientations were compared; clusters indicated that the majority of participants experienced multiple emotions. Each action orientation was also regressed on the six emotions. There were a number of differences in the results obtained from the person-centered and variable-centered approaches. This was most apparent for sympathy: the group of participants experiencing only sympathy showed little inclination to perform prosocial actions, yet sympathy was a significant predictor of numerous action orientations in regression analyses. These results imply that sympathy may only prompt a desire for action when experienced in combination with other emotions. We suggest that the use of person-centered and variable-centered approaches as complementary analytic strategies may enrich research into not only the affective predictors of action, but emotion research in general.

  15. Prebiotic chirality

    NASA Astrophysics Data System (ADS)

    Mekki-Berrada, Ali

    Bringing closer phospholipids each other on a bilayer of liposome, causes their rotation around their fatty acids axis, generating a force which brings closer the two sheets of the bilayer. In this theoretical study I show that for getting the greater cohesion of the liposome, by these forces, the serine in the hydrophilic head must have a L chirality. In the case where the hydrophilic head is absent amino acids with L chirality could contribute to this cohesion by taking the place of L-serine. Some coenzymes having a configuration similar to ethanolamine may also contribute. This is the case of pyridoxamine, thiamine and tetrahydrofolic acid. The grouping of amino acids of L chirality and pyridoxamine on the wall could initialize the prebiotic metabolism of these L amino acids only. This would explain the origin of the homo-chirality of amino acids in living world. Furthermore I show that in the hydrophilic head, the esterification of glycerol-phosphate by two fatty acids go through the positioning of dihydroxyacetone-phosphate and L-glyceraldehyde-3-phosphate, but not of D-glyceraldehyde-3-phosphate, prior their hydrogenation to glycerol-3- phosphate. The accumulation of D-glyceraldehyde-3-phosphate in the cytoplasm displace the thermodynamic equilibria towards the synthesis of D-dATP from D-glyceraldehyde-3-phosphate, acetaldehyde and prebiotic adenine, a reaction which does not require a coenzyme in the biotic metabolism. D-dATP and thiamine, more prebiotic metabolism of L-amino acids on the wall, would initialize D-pentoses phosphate and D-nucleotides pathways from the reaction of D-glyceraldehyde-3-phosphate + dihydroxyacetone-phosphate + prebiotic nucleic bases. The exhaustion of the prebiotic glyceraldehyde (racemic) and the nascent biotic metabolism dominated by D-glyceraldehyde-3-phosphate, would explain the origin of homo-chirality of sugars in living world. References: http://en.wikiversity.org/wiki/Prebiotic_chirality

  16. Chiral streamers

    SciTech Connect

    Zou, Dandan; Cao, Xin; Lu, Xinpei; Ostrikov, Kostya

    2015-10-15

    The interaction of time-varying electromagnetic fields and solid, liquid, and gaseous matter may lead to electrical breakdown phenomena through the excitation of ionization waves or streamers that control the dynamics of localized plasma propagation through the media. The streamers usually propagate along straight lines, either between random points in space or along a certain direction in a guided mode. Here, we report on a new type of plasma discharges with the regular helical propagation pattern driven by a pulsed dc voltage in nitrogen at sub-atmospheric-pressure conditions. The helical guided streamers, named chiral streamers or chi-streamers, are excited without any external magnetic fields, which commonly cause helical plasma motions. We also demonstrate a hybrid propagation mode involving the interchangeable chiral streamers and the straight-line propagating plasmas. High-speed, time-resolved optical imaging reveals that the chiral streamers and the hybrid patterns are made of spatially localized discrete plasma bullets, similar to the straight-line guided streamers. These results may enable effective control of propagation of confined plasmas and electromagnetic energy along pre-determined, potentially deterministic paths, which have important implications for the development of next-generation plasma-based radiation sources, communication devices, and medical treatments.

  17. Improved accuracy of acute graft-versus-host disease staging among multiple centers.

    PubMed

    Levine, John E; Hogan, William J; Harris, Andrew C; Litzow, Mark R; Efebera, Yvonne A; Devine, Steven M; Reshef, Ran; Ferrara, James L M

    2014-01-01

    The clinical staging of acute graft-versus-host disease (GVHD) varies significantly among bone marrow transplant (BMT) centers, but adherence to long-standing practices poses formidable barriers to standardization among centers. We have analyzed the sources of variability and developed a web-based remote data entry system that can be used by multiple centers simultaneously and that standardizes data collection in key areas. This user-friendly, intuitive interface resembles an online shopping site and eliminates error-prone entry of free text with drop-down menus and pop-up detailed guidance available at the point of data entry. Standardized documentation of symptoms and therapeutic response reduces errors in grade assignment and allows creation of confidence levels regarding the diagnosis. Early review and adjudication of borderline cases improves consistency of grading and further enhances consistency among centers. If this system achieves widespread use it may enhance the quality of data in multicenter trials to prevent and treat acute GVHD.

  18. Improved accuracy of acute graft-versus-host disease staging among multiple centers.

    PubMed

    Levine, John E; Hogan, William J; Harris, Andrew C; Litzow, Mark R; Efebera, Yvonne A; Devine, Steven M; Reshef, Ran; Ferrara, James L M

    2014-01-01

    The clinical staging of acute graft-versus-host disease (GVHD) varies significantly among bone marrow transplant (BMT) centers, but adherence to long-standing practices poses formidable barriers to standardization among centers. We have analyzed the sources of variability and developed a web-based remote data entry system that can be used by multiple centers simultaneously and that standardizes data collection in key areas. This user-friendly, intuitive interface resembles an online shopping site and eliminates error-prone entry of free text with drop-down menus and pop-up detailed guidance available at the point of data entry. Standardized documentation of symptoms and therapeutic response reduces errors in grade assignment and allows creation of confidence levels regarding the diagnosis. Early review and adjudication of borderline cases improves consistency of grading and further enhances consistency among centers. If this system achieves widespread use it may enhance the quality of data in multicenter trials to prevent and treat acute GVHD. PMID:25455279

  19. Family-centered care coordination for children with special needs across multiple settings.

    PubMed

    Lindeke, Linda L; Leonard, Barbara J; Presler, Betty; Garwick, Ann

    2002-01-01

    Care coordination is a process that involves assessment, planning, implementation, evaluation, education, monitoring, support, and advocacy. Pediatric nurse practitioners (PNPs) are well positioned to coordinate care but may not be well educated about potential conflicts of interest in balancing cost-containment constraints with obtaining maximum quality and quantity of care for children and families with complex needs. The philosophy of family-centered care is embodied in some care coordination models and absent in others. PNPs who aim to support families of children with special health care needs need to understand the complexity of interacting with multiple care coordination models across health and educational settings. PNPs may act as change agents to infuse family-centered care principles into existing and future care coordination models. PMID:12436098

  20. Model of fluorescence intermittency of single colloidal semiconductor quantum dots using multiple recombination centers.

    PubMed

    Frantsuzov, Pavel A; Volkán-Kacsó, Sándor; Jankó, Bolizsár

    2009-11-13

    We present a new physical model resolving a long-standing mystery of the power-law distributions of the blinking times in single colloidal quantum dot fluorescence. The model considers the nonradiative relaxation of the exciton through multiple recombination centers. Each center is allowed to switch between two quasistationary states. We point out that the conventional threshold analysis method used to extract the exponents of the distributions for the on times and off times has a serious flaw: the qualitative properties of the distributions strongly depend on the threshold value chosen for separating the on and off states. Our new model explains naturally this threshold dependence, as well as other key experimental features of the single quantum dot fluorescence trajectories, such as the power-law power spectrum (1/f noise).

  1. Disordered two-dimensional electron systems with chiral symmetry

    NASA Astrophysics Data System (ADS)

    Markoš, P.; Schweitzer, L.

    2012-10-01

    We review the results of our recent numerical investigations on the electronic properties of disordered two dimensional systems with chiral unitary, chiral orthogonal, and chiral symplectic symmetry. Of particular interest is the behavior of the density of states and the logarithmic scaling of the smallest Lyapunov exponents in the vicinity of the chiral quantum critical point in the band center at E=0. The observed peaks or depressions in the density of states, the distribution of the critical conductances, and the possible non-universality of the critical exponents for certain chiral unitary models are discussed.

  2. Chiral cardiovascular drugs: an overview.

    PubMed

    Ranade, Vasant V; Somberg, John C

    2005-01-01

    Stereochemistry in drug molecules is rapidly becoming an important aspect in drug research, design, and development. Recently, individual stereoisomers of drug molecules with asymmetric centers such as fexofenadine, cetirizine, verapamil, fluoxetine, levalbutarol, and amphetamine, for example, have been separated and developed as individual drugs. These stereoisomers have different therapeutic activity, and each isomer has contributed differently with respect to its formulation's pharmacologic activity, side effects, and toxicity. The present overview discusses chirality among a select group of cardiovascular drugs, their stereochemical synthesis/preparation, isolation techniques using chiral chromatography, methods for confirmation of their enantiomeric purity, pharmacodynamics, and pharmacokinetics. Chirality has been visualized as an important factor in cardiovascular research. It is also becoming evident in other areas of therapeutics.

  3. Stereoselective introduction of two chiral centers by a single diketoreductase: an efficient biocatalytic route for the synthesis of statin side chains.

    PubMed

    Wu, Xuri; Wang, Lili; Wang, Shuzhen; Chen, Yijun

    2010-06-01

    Statins, including atorvastatin (Lipitor), are the top-selling drugs in the world. The biocatalytic production of chiral side chains of statin drugs is of great interest to academia and industry. Stereoselective double reduction of a beta,delta-diketo ester catalyzed by a diketoreductase offers a simple and efficient route for the preparation of statin side chains. Comparison of different cofactor regeneration systems resulted in an easy and cost-effective process for this enzymatic reduction.

  4. Chiral mirrors

    NASA Astrophysics Data System (ADS)

    Plum, Eric; Zheludev, Nikolay I.

    2015-06-01

    Mirrors are used in telescopes, microscopes, photo cameras, lasers, satellite dishes, and everywhere else, where redirection of electromagnetic radiation is required making them arguably the most important optical component. While conventional isotropic mirrors will reflect linear polarizations without change, the handedness of circularly polarized waves is reversed upon reflection. Here, we demonstrate a type of mirror reflecting one circular polarization without changing its handedness, while absorbing the other. The polarization-preserving mirror consists of a planar metasurface with a subwavelength pattern that cannot be superimposed with its mirror image without being lifted out of its plane, and a conventional mirror spaced by a fraction of the wavelength from the metasurface. Such mirrors enable circularly polarized lasers and Fabry-Pérot cavities with enhanced tunability, gyroscopic applications, polarization-sensitive detectors of electromagnetic waves, and can be used to enhance spectroscopies of chiral media.

  5. Chiral shielding

    SciTech Connect

    Babukhadia, L.; Berdnikov, Ya. A.; Ivanov, A. N.; Scadron, M. D.

    2000-08-01

    We demonstrate how a chiral soft pion theorem (SPT) shields the scalar meson ground-state isoscalar {sigma}(600-700) and isospinor {kappa}(800-900) from detection in a{sub 1}{yields}{pi}({pi}{pi}){sub swave}, {gamma}{gamma}{yields}2{pi}{sup 0}, {pi}{sup -}p{yields}{pi}{sup -}{pi}{sup +}n and K{sup -}p{yields}K{sup -}{pi}{sup +}n processes. While pseudoscalar meson PVV transitions are known to be determined by (only) quark loop diagrams, the above SPT also constrains scalar meson SVV transitions to be governed (only) by meson loop diagrams. We apply this latter SVV theorem to a{sub 0}{yields}{gamma}{gamma} and f{sub 0}{yields}{gamma}{gamma} decays. (c) 2000 The American Physical Society.

  6. Understanding complex chiral plasmonics.

    PubMed

    Duan, Xiaoyang; Yue, Song; Liu, Na

    2015-11-01

    Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the 'host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant and simple analytical model, which can describe, predict, and comprehend the chiroptical spectra in detail. Our study will shed light on designing well-controlled chiral-achiral coupling platforms for reliable chiral sensing.

  7. A multiple chemical equilibria approach to modeling and interpreting the separation of amino acid enantiomers by chiral ligand-exchange chromatography.

    PubMed

    Sanaie, Nooshafarin; Haynes, Charles A

    2006-11-01

    A model of chiral ligand-exchange chromatography (CLEC) is presented that combines the non-ideal equilibrium-dispersion equation for solute transport with equations describing all chemical equilibria within the column. The model connects elution band profiles to the time and space resolved formation of diastereomeric complexes in both the mobile and stationary phases, thereby providing insights into the overall separation mechanism. The stoichiometries and formation constants for all equilibrium complexes formed in the mobile phase are taken from standard thermodynamic databases and independent potentiometric titration experiments. Formation constants for complexes formed with the stationary phase ligand are determined from potentiometric titration data for a water-soluble analogue of the ligand. Together this set of pure thermodynamic parameters can be used to calculate the equilibrium composition of the system at any operating condition. The model includes a temperature-dependent pure-component parameter, determined by regression to a single elution band for the pure component, that corrects for subtle effects associated with immobilizing the ligand (i.e., the chiral selector) onto the stationary phase. Model performance is assessed through comparison with chromatograms for two hydrophobic amino acid racemates loaded on the Nucleosil Chiral-1 CLEC column. The model is also applied to a restricted optimization of column operating conditions to assess its predictive power. In both cases, model predictions compare well with experiment while also providing a molecular understanding of the separation process and its dependence on column operating conditions.

  8. Chiral structures from achiral liquid crystals in cylindrical capillaries.

    PubMed

    Jeong, Joonwoo; Kang, Louis; Davidson, Zoey S; Collings, Peter J; Lubensky, Tom C; Yodh, A G

    2015-04-14

    We study chiral symmetry-broken configurations of nematic liquid crystals (LCs) confined to cylindrical capillaries with homeotropic anchoring on the cylinder walls (i.e., perpendicular surface alignment). Interestingly, achiral nematic LCs with comparatively small twist elastic moduli relieve bend and splay deformations by introducing twist deformations. In the resulting twisted and escaped radial (TER) configuration, LC directors are parallel to the cylindrical axis near the center, but to attain radial orientation near the capillary wall, they escape along the radius through bend and twist distortions. Chiral symmetry-breaking experiments in polymer-coated capillaries are carried out using Sunset Yellow FCF, a lyotropic chromonic LC with a small twist elastic constant. Its director configurations are investigated by polarized optical microscopy and explained theoretically with numerical calculations. A rich phenomenology of defects also arises from the degenerate bend/twist deformations of the TER configuration, including a nonsingular domain wall separating domains of opposite twist handedness but the same escape direction and singular point defects (hedgehogs) separating domains of opposite escape direction. We show the energetic preference for singular defects separating domains of opposite twist handedness compared with those of the same handedness, and we report remarkable chiral configurations with a double helix of disclination lines along the cylindrical axis. These findings show archetypally how simple boundary conditions and elastic anisotropy of confined materials lead to multiple symmetry breaking and how these broken symmetries combine to create a variety of defects. PMID:25825733

  9. Chiral structures from achiral liquid crystals in cylindrical capillaries

    NASA Astrophysics Data System (ADS)

    Jeong, Joonwoo; Kang, Louis; Davidson, Zoey S.; Collings, Peter J.; Lubensky, Tom C.; Yodh, A. G.

    2015-04-01

    We study chiral symmetry-broken configurations of nematic liquid crystals (LCs) confined to cylindrical capillaries with homeotropic anchoring on the cylinder walls (i.e., perpendicular surface alignment). Interestingly, achiral nematic LCs with comparatively small twist elastic moduli relieve bend and splay deformations by introducing twist deformations. In the resulting twisted and escaped radial (TER) configuration, LC directors are parallel to the cylindrical axis near the center, but to attain radial orientation near the capillary wall, they escape along the radius through bend and twist distortions. Chiral symmetry-breaking experiments in polymer-coated capillaries are carried out using Sunset Yellow FCF, a lyotropic chromonic LC with a small twist elastic constant. Its director configurations are investigated by polarized optical microscopy and explained theoretically with numerical calculations. A rich phenomenology of defects also arises from the degenerate bend/twist deformations of the TER configuration, including a nonsingular domain wall separating domains of opposite twist handedness but the same escape direction and singular point defects (hedgehogs) separating domains of opposite escape direction. We show the energetic preference for singular defects separating domains of opposite twist handedness compared with those of the same handedness, and we report remarkable chiral configurations with a double helix of disclination lines along the cylindrical axis. These findings show archetypally how simple boundary conditions and elastic anisotropy of confined materials lead to multiple symmetry breaking and how these broken symmetries combine to create a variety of defects.

  10. Chiral structures from achiral liquid crystals in cylindrical capillaries

    PubMed Central

    Jeong, Joonwoo; Kang, Louis; Davidson, Zoey S.; Collings, Peter J.; Lubensky, Tom C.; Yodh, A. G.

    2015-01-01

    We study chiral symmetry-broken configurations of nematic liquid crystals (LCs) confined to cylindrical capillaries with homeotropic anchoring on the cylinder walls (i.e., perpendicular surface alignment). Interestingly, achiral nematic LCs with comparatively small twist elastic moduli relieve bend and splay deformations by introducing twist deformations. In the resulting twisted and escaped radial (TER) configuration, LC directors are parallel to the cylindrical axis near the center, but to attain radial orientation near the capillary wall, they escape along the radius through bend and twist distortions. Chiral symmetry-breaking experiments in polymer-coated capillaries are carried out using Sunset Yellow FCF, a lyotropic chromonic LC with a small twist elastic constant. Its director configurations are investigated by polarized optical microscopy and explained theoretically with numerical calculations. A rich phenomenology of defects also arises from the degenerate bend/twist deformations of the TER configuration, including a nonsingular domain wall separating domains of opposite twist handedness but the same escape direction and singular point defects (hedgehogs) separating domains of opposite escape direction. We show the energetic preference for singular defects separating domains of opposite twist handedness compared with those of the same handedness, and we report remarkable chiral configurations with a double helix of disclination lines along the cylindrical axis. These findings show archetypally how simple boundary conditions and elastic anisotropy of confined materials lead to multiple symmetry breaking and how these broken symmetries combine to create a variety of defects. PMID:25825733

  11. Chiral Analysis of Isopulegol by Fourier Transform Molecular Rotational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Evangelisti, Luca; Seifert, Nathan A.; Spada, Lorenzo; Pate, Brooks

    2016-06-01

    Chiral analysis on molecules with multiple chiral centers can be performed using pulsed-jet Fourier transform rotational spectroscopy. This analysis includes quantitative measurement of diastereomer products and, with the three wave mixing methods developed by Patterson, Schnell, and Doyle (Nature 497, 475-477 (2013)), quantitative determination of the enantiomeric excess of each diastereomer. The high resolution features enable to perform the analysis directly on complex samples without the need for chromatographic separation. Isopulegol has been chosen to show the capabilities of Fourier transform rotational spectroscopy for chiral analysis. Broadband rotational spectroscopy produces spectra with signal-to-noise ratio exceeding 1000:1. The ability to identify low-abundance (0.1-1%) diastereomers in the sample will be described. Methods to rapidly identify rotational spectra from isotopologues at natural abundance will be shown and the molecular structures obtained from this analysis will be compared to theory. The role that quantum chemistry calculations play in identifying structural minima and estimating their spectroscopic properties to aid spectral analysis will be described. Finally, the implementation of three wave mixing techniques to measure the enantiomeric excess of each diastereomer and determine the absolute configuration of the enantiomer in excess will be described.

  12. Introduction to chiral symmetry

    SciTech Connect

    Koch, V.

    1996-01-08

    These lectures are an attempt to a pedagogical introduction into the elementary concepts of chiral symmetry in nuclear physics. Effective chiral models such as the linear and nonlinear sigma model will be discussed as well as the essential ideas of chiral perturbation theory. Some applications to the physics of ultrarelativistic heavy ion collisions will be presented.

  13. Massive parallel IGHV gene sequencing reveals a germinal center pathway in origins of human multiple myeloma.

    PubMed

    Cowan, Graeme; Weston-Bell, Nicola J; Bryant, Dean; Seckinger, Anja; Hose, Dirk; Zojer, Niklas; Sahota, Surinder S

    2015-05-30

    Human multiple myeloma (MM) is characterized by accumulation of malignant terminally differentiated plasma cells (PCs) in the bone marrow (BM), raising the question when during maturation neoplastic transformation begins. Immunoglobulin IGHV genes carry imprints of clonal tumor history, delineating somatic hypermutation (SHM) events that generally occur in the germinal center (GC). Here, we examine MM-derived IGHV genes using massive parallel deep sequencing, comparing them with profiles in normal BM PCs. In 4/4 presentation IgG MM, monoclonal tumor-derived IGHV sequences revealed significant evidence for intraclonal variation (ICV) in mutation patterns. IGHV sequences of 2/2 normal PC IgG populations revealed dominant oligoclonal expansions, each expansion also displaying mutational ICV. Clonal expansions in MM and in normal BM PCs reveal common IGHV features. In such MM, the data fit a model of tumor origins in which neoplastic transformation is initiated in a GC B-cell committed to terminal differentiation but still targeted by on-going SHM. Strikingly, the data parallel IGHV clonal sequences in some monoclonal gammopathy of undetermined significance (MGUS) known to display on-going SHM imprints. Since MGUS generally precedes MM, these data suggest origins of MGUS and MM with IGHV gene mutational ICV from the same GC B-cell, arising via a distinctive pathway.

  14. Model of complex chiral drug metabolic systems and numerical simulation of the remaining chirality toward analysis of dynamical pharmacological activity.

    PubMed

    Ogino, Yoshiyuki; Asahi, Toru

    2015-05-21

    In this study, systems of complicated pathways involved in chiral drug metabolism were investigated. The development of chiral drugs resulted in significant improvement in the remedies available for the treatment of various severe sicknesses. Enantiopure drugs undergo various biological transformations that involve chiral inversion and thus result in the generation of multiple enantiomeric metabolites. Identification of the specific active substances determining a given drug׳s efficacy among such a mixture of different metabolites remains a challenge. To comprehend this complexity, we constructed a mathematical model representing the complicated metabolic pathways simultaneously involving chiral inversion. Moreover, this model is applied to the metabolism of thalidomide, which has recently been revived as a potentially effective prescription drug for a number of intractable diseases. The numerical simulation results indicate that retained chirality in the metabolites reflects the original chirality of the unmetabolized drug, and a higher level of enantiomeric purity is preserved during spontaneous degradation. In addition, chirality remaining after equilibration is directly related to the rate constant not only for chiral inversion but also for generation and degradation. Furthermore, the retention of chirality is quantitatively predictable using this combination of kinetic parameters. Our simulation results well explain the behavior of thalidomide in the practical biological experimental data. Therefore, this model promises a comprehensive understanding of dynamic metabolic systems involving chiral drugs that express multiple enantiospecific drug efficacies.

  15. Model of complex chiral drug metabolic systems and numerical simulation of the remaining chirality toward analysis of dynamical pharmacological activity.

    PubMed

    Ogino, Yoshiyuki; Asahi, Toru

    2015-05-21

    In this study, systems of complicated pathways involved in chiral drug metabolism were investigated. The development of chiral drugs resulted in significant improvement in the remedies available for the treatment of various severe sicknesses. Enantiopure drugs undergo various biological transformations that involve chiral inversion and thus result in the generation of multiple enantiomeric metabolites. Identification of the specific active substances determining a given drug׳s efficacy among such a mixture of different metabolites remains a challenge. To comprehend this complexity, we constructed a mathematical model representing the complicated metabolic pathways simultaneously involving chiral inversion. Moreover, this model is applied to the metabolism of thalidomide, which has recently been revived as a potentially effective prescription drug for a number of intractable diseases. The numerical simulation results indicate that retained chirality in the metabolites reflects the original chirality of the unmetabolized drug, and a higher level of enantiomeric purity is preserved during spontaneous degradation. In addition, chirality remaining after equilibration is directly related to the rate constant not only for chiral inversion but also for generation and degradation. Furthermore, the retention of chirality is quantitatively predictable using this combination of kinetic parameters. Our simulation results well explain the behavior of thalidomide in the practical biological experimental data. Therefore, this model promises a comprehensive understanding of dynamic metabolic systems involving chiral drugs that express multiple enantiospecific drug efficacies. PMID:25791284

  16. Improving the Spelling of High Frequency Words in Daily Writing through the Use of Multiple Intelligence Centers.

    ERIC Educational Resources Information Center

    Shah, Tejal; Thomas, Alexis

    This study describes a 12-week program developed with the intent of improving the spelling of high frequency words using centers that will activate each of the eight multiple intelligences. The targeted population consists of second and third graders in a suburban community in northeast Illinois. Parent surveys, teacher interviews, observations,…

  17. The Use of Prison Confinement for the Treatment of Multiple Drunken Driver Offenders: An Evaluation of the Longwood Treatment Center.

    ERIC Educational Resources Information Center

    LeClair, Daniel P.; And Others

    In March of 1985, the Massachusetts Department of Correction opened Longwood Treatment Center, the state's first minimum security prison designed exclusively to detain and provide alcoholism education and treatment to multiple drunken driving offenders. A process evaluation of the program revealed that the program was implemented as planned and…

  18. Influence of the solvent and metal center on supramolecular chirality induction with bisporphyrin tweezer receptors. Strong metal modulation of effective molarity values.

    PubMed

    Pintre, Inmaculada C; Pierrefixe, Simon; Hamilton, Alex; Valderrey, Virginia; Bo, Carles; Ballester, Pablo

    2012-04-16

    We describe the synthesis of a bisporphyrin tweezer receptor 1·H(4) and its metalation with Zn(II) and Rh(III) cations. We report the thermodynamic characterization of the supramolecular chirality induction process that takes place when the metalated bisporphyrin receptors coordinate to enantiopure 1,2-diaminocyclohexane in two different solvents, toluene and dichloromethane. We also performed a thorough study of several simpler systems that were used as models for the thermodynamic characterization of the more complex bisporphyrin systems. The initial complexation of the chiral diamine with the bisporphyrins produces a 1:1 sandwich complex that opens up to yield a simple 1:2 complex in the presence of excess diamine. The CD spectra associated with the 1:1 and 1:2 complexes of both metalloporphyrins, 1·Zn(2) and 1·Rh(2), display bisignate Cotton effects when the chirogenesis process is studied in toluene solutions. On the contrary, in dichloromethane solutions, only 1·Zn(2) yields CD-active 1:1 and 1:2 complexes, while the 1:2 complex of 1·Rh(2) is CD-silent. In both solvents, porphyrin 1·Zn(2) features a stoichiometrically controlled chirality inversion process, which is the sign of the Cotton effect of the 1:1 complex is opposite to that of the 1:2 complex. In contrast, porphyrin 1·Rh(2) affords 1:1 and 1:2 complexes in toluene solutions with the same sign for their CD couplets. Interestingly, in both solvents, the signs of the CD couplets associated with the 1:1 sandwich complexes of 1·Zn(2) and 1·Rh(2) are opposite. The amplitudes of the CD couplets are higher for 1·Zn(2) than for 1·Rh(2). This observation is in agreement with 1·Rh(2) having a smaller extinction coefficient than 1·Zn(2). We performed DFT-based calculations and assigned molecular structures to the 1:1 and 1:2 complexes that explain the observed signs for their CD couplets. Unexpectedly, the quantification of the thermodynamic stability of the two metallobisporphyrin/diamine 1

  19. Chiral symmetry and chiral-symmetry breaking

    SciTech Connect

    Peskin, M.E.

    1982-12-01

    These lectures concern the dynamics of fermions in strong interaction with gauge fields. Systems of fermions coupled by gauge forces have a very rich structure of global symmetries, which are called chiral symmetries. These lectures will focus on the realization of chiral symmetries and the causes and consequences of thier spontaneous breaking. A brief introduction to the basic formalism and concepts of chiral symmetry breaking is given, then some explicit calculations of chiral symmetry breaking in gauge theories are given, treating first parity-invariant and then chiral models. These calculations are meant to be illustrative rather than accurate; they make use of unjustified mathematical approximations which serve to make the physics more clear. Some formal constraints on chiral symmetry breaking are discussed which illuminate and extend the results of our more explicit analysis. Finally, a brief review of the phenomenological theory of chiral symmetry breaking is presented, and some applications of this theory to problems in weak-interaction physics are discussed. (WHK)

  20. Automated vessel shadow segmentation of fovea-centered spectral-domain images from multiple OCT devices

    NASA Astrophysics Data System (ADS)

    Wu, Jing; Gerendas, Bianca S.; Waldstein, Sebastian M.; Simader, Christian; Schmidt-Erfurth, Ursula

    2014-03-01

    ground truth vessel shadow regions identified by expert graders at the Vienna Reading Center (VRC). The results presented here are intended to show the feasibility of this method for the accurate and precise extraction of suitable retinal vessel shadows from multiple vendor 3D SD-OCT scans for use in intra-vendor and cross-vendor 3D OCT registration, 2D fundus registration and actual retinal vessel segmentation. The resulting percentage of true vessel shadow segments to false positive segments identified by the proposed system compared to mean grader ground truth is 95%.

  1. Safety and efficacy of dimethyl fumarate in multiple sclerosis: a multi-center observational study.

    PubMed

    Miclea, A; Leussink, V I; Hartung, H P; Gold, R; Hoepner, R

    2016-08-01

    Dimethyl fumarate (DMF) was recently approved for treating patients with relapsing-remitting multiple sclerosis (RRMS) based on two phase III clinical trials demonstrating its efficacy. This prompts the need for demonstrating the clinical efficacy and safety of DMF in the real world. By retrospective analysis of medical records at two German MS centers, 644 MS patients treated with DMF were identified. All were included in a safety analysis, and a subgroup of patients with available efficacy data during previous MS therapies (n = 352) was further analyzed for annualized relapse rate and disability progression assessed by the EDSS. In the overall DMF population studied, the annualized relapse rate decreased from 0.52 at baseline to 0.35, and the annualized disability progression from 0.15 to 0.10. Patients who were switched from interferons or glatiramer acetate to DMF revealed a greater benefit, whereas patients pretreated with more potent immunotherapies did not respond that well. Interestingly, patients with a lymphocyte count ≥2000/µl after 0.52 years (mean, SD 0.2) of DMF treatment did not benefit compared to those with lower lymphocyte counts. In total, 22.2 % of the patients withdrew from DMF due to side effects, with gastrointestinal discomfort (12.7 %) and lymphopenia (5.3 %) as most frequently reported reasons. Our study corroborates that DMF is an overall safe and effective drug that reduces relapse rate as well as disability progression in MS patients. Further prospective studies are warranted to establish the additional parameters predicting DMF response, especially in patients switching from other first-line immunotherapies. PMID:27260297

  2. Development of chiral sulfoxide ligands for asymmetric catalysis.

    PubMed

    Trost, Barry M; Rao, Meera

    2015-04-20

    Nitrogen-, phosphorus-, and oxygen-based ligands with chiral backbones have been the historic workhorses of asymmetric transition-metal-catalyzed reactions. On the contrary, sulfoxides containing chirality at the sulfur atom have mainly been used as chiral auxiliaries for diastereoselective reactions. Despite several distinct advantages over traditional ligand scaffolds, such as the proximity of the chiral information to the metal center and the ability to switch between S and O coordination, these compounds have only recently emerged as a versatile class of chiral ligands. In this Review, we detail the history of the development of chiral sulfoxide ligands for asymmetric catalysis. We also provide brief descriptions of metal-sulfoxide bonding and strategies for the synthesis of enantiopure sulfoxides. Finally, insights into the future development of this underutilized ligand class are discussed.

  3. Chiral Hydroxylation at the Mononuclear Nonheme Fe(II) Center of 4-(S) Hydroxymandelate Synthase – A Structure-Activity Relationship Analysis

    PubMed Central

    Di Giuro, Cristiana M. L.; Konstantinovics, Cornelia; Rinner, Uwe; Nowikow, Christina; Leitner, Erich; Straganz, Grit D.

    2013-01-01

    (S)-Hydroxymandelate synthase (Hms) is a nonheme Fe(II) dependent dioxygenase that catalyzes the oxidation of 4-hydroxyphenylpyruvate to (S)-4-hydroxymandelate by molecular oxygen. In this work, the substrate promiscuity of Hms is characterized in order to assess its potential for the biosynthesis of chiral α-hydroxy acids. Enzyme kinetic analyses, the characterization of product spectra, quantitative structure activity relationship (QSAR) analyses and in silico docking studies are used to characterize the impact of substrate properties on particular steps of catalysis. Hms is found to accept a range of α-oxo acids, whereby the presence of an aromatic substituent is crucial for efficient substrate turnover. A hydrophobic substrate binding pocket is identified as the likely determinant of substrate specificity. Upon introduction of a steric barrier, which is suspected to obstruct the accommodation of the aromatic ring in the hydrophobic pocket during the final hydroxylation step, the racemization of product is obtained. A steady state kinetic analysis reveals that the turnover number of Hms strongly correlates with substrate hydrophobicity. The analysis of product spectra demonstrates high regioselectivity of oxygenation and a strong coupling efficiency of C-C bond cleavage and subsequent hydroxylation for the tested substrates. Based on these findings the structural basis of enantioselectivity and enzymatic activity is discussed. PMID:23935907

  4. A molecular propeller effect for chiral separation and analysis

    NASA Astrophysics Data System (ADS)

    Clemens, Jonathon B.; Kibar, Osman; Chachisvilis, Mirianas

    2015-07-01

    Enantiomers share nearly identical physical properties but have different chiral geometries, making their identification and separation difficult. Here we show that when exposed to a rotating electric field, the left- and right-handed chiral molecules rotate with the field and act as microscopic propellers; moreover, owing to their opposite handedness, they propel along the axis of field rotation in opposite directions. We introduce a new molecular parameter called hydrodynamic chirality to characterize the coupling of rotational motion of a chiral molecule into its translational motion and quantify the direction and velocity of such motion. We demonstrate >80% enrichment level of counterpart enantiomers in solution without using chiral selectors or circularly polarized light. We expect our results to have an impact on multiple applications in drug discovery, analytical and chiral chemistry, including determination of absolute configuration, as well as in influencing the understanding of artificial and natural molecular systems where rotational motion of the molecules is involved.

  5. A molecular propeller effect for chiral separation and analysis

    PubMed Central

    Clemens, Jonathon B.; Kibar, Osman; Chachisvilis, Mirianas

    2015-01-01

    Enantiomers share nearly identical physical properties but have different chiral geometries, making their identification and separation difficult. Here we show that when exposed to a rotating electric field, the left- and right-handed chiral molecules rotate with the field and act as microscopic propellers; moreover, owing to their opposite handedness, they propel along the axis of field rotation in opposite directions. We introduce a new molecular parameter called hydrodynamic chirality to characterize the coupling of rotational motion of a chiral molecule into its translational motion and quantify the direction and velocity of such motion. We demonstrate >80% enrichment level of counterpart enantiomers in solution without using chiral selectors or circularly polarized light. We expect our results to have an impact on multiple applications in drug discovery, analytical and chiral chemistry, including determination of absolute configuration, as well as in influencing the understanding of artificial and natural molecular systems where rotational motion of the molecules is involved. PMID:26216219

  6. Complications in multiple gestation pregnancy: A cross-sectional study of ten maternal-fetal medicine centers in China

    PubMed Central

    Wei, Jun; Wu, Qi-Jun; Zhang, Tie-Ning; Shen, Zi-Qi; Liu, Hao; Zheng, Dong-Ming; Cui, Hong; Liu, Cai-Xia

    2016-01-01

    Complications in women with multiple gestation pregnancy have not been studied in China. We aimed to establish a database of women with multiple gestation pregnancy and investigate the complications related to multiple pregnancy. We conducted a cross-sectional study that included 3246 women with multiple gestation pregnancy and who had multiple live-birth deliveries; the women were registered at ten maternal-fetal medicine centers in China in 2013. All participants completed a detailed questionnaire that included basic demographic information, history of gestation and abnormal fetal development, risk factors during pregnancy, and pregnancy outcomes. Overall, 1553 (47.8%) women experienced pregnancy complications; these women were more likely to have lower height and less education than women who did not experience complications. However, women who experienced complications had a higher twin birth rate and were more likely to have received regular antenatal care and assisted reproductive technology than women without complications (P < 0.05). Notably, preterm birth was a primary complication in multiple pregnancy (n = 960). In conclusion, pregnancy complications, especially preterm birth, were relatively common in women with multiple gestation pregnancy. The findings from this cross-sectional study in China may be used as a foundation for investigating risk factors for complications in women with multiple gestation pregnancy in the future. PMID:27127170

  7. Complications in multiple gestation pregnancy: A cross-sectional study of ten maternal-fetal medicine centers in China.

    PubMed

    Wei, Jun; Wu, Qi-Jun; Zhang, Tie-Ning; Shen, Zi-Qi; Liu, Hao; Zheng, Dong-Ming; Cui, Hong; Liu, Cai-Xia

    2016-05-24

    Complications in women with multiple gestation pregnancy have not been studied in China. We aimed to establish a database of women with multiple gestation pregnancy and investigate the complications related to multiple pregnancy. We conducted a cross-sectional study that included 3246 women with multiple gestation pregnancy and who had multiple live-birth deliveries; the women were registered at ten maternal-fetal medicine centers in China in 2013. All participants completed a detailed questionnaire that included basic demographic information, history of gestation and abnormal fetal development, risk factors during pregnancy, and pregnancy outcomes. Overall, 1553 (47.8%) women experienced pregnancy complications; these women were more likely to have lower height and less education than women who did not experience complications. However, women who experienced complications had a higher twin birth rate and were more likely to have received regular antenatal care and assisted reproductive technology than women without complications (P < 0.05). Notably, preterm birth was a primary complication in multiple pregnancy (n = 960). In conclusion, pregnancy complications, especially preterm birth, were relatively common in women with multiple gestation pregnancy. The findings from this cross-sectional study in China may be used as a foundation for investigating risk factors for complications in women with multiple gestation pregnancy in the future. PMID:27127170

  8. Monthly Themes and Learning Centers for Young Children with Visual and Multiple Impairments.

    ERIC Educational Resources Information Center

    Hamilton, Paula J.

    This paper describes the learning center approach of the preschool and kindergarten programs at the Maryland School for the Blind. Units are presented in monthly themes suggested by the local school curriculum, and this thematic approach is incorporated into the specific learning centers. The classroom is divided into six main learning areas: (1)…

  9. Chiral atomically thin films

    NASA Astrophysics Data System (ADS)

    Kim, Cheol-Joo; Sánchez-Castillo, A.; Ziegler, Zack; Ogawa, Yui; Noguez, Cecilia; Park, Jiwoong

    2016-06-01

    Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm–1) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.

  10. Characterizing optical chirality

    SciTech Connect

    Bliokh, Konstantin Y.; Nori, Franco

    2011-02-15

    We examine the recently introduced measure of chirality of a monochromatic optical field [Y. Tang and A. E. Cohen, Phys. Rev. Lett. 104, 163901 (2010)] using the momentum (plane-wave) representation and helicity basis. Our analysis clarifies the physical meaning of the measure of chirality and unveils its close relation to the polarization helicity, spin angular momentum, energy density, and Poynting energy flow. We derive the operators of the optical chirality and of the corresponding chiral momentum, which acquire remarkably simple forms in the helicity representation.

  11. Chiral atomically thin films

    NASA Astrophysics Data System (ADS)

    Kim, Cheol-Joo; Sánchez-Castillo, A.; Ziegler, Zack; Ogawa, Yui; Noguez, Cecilia; Park, Jiwoong

    2016-06-01

    Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm-1) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.

  12. Molecular-Level Design of Heterogeneous Chiral Catalysis

    SciTech Connect

    Francisco Zaera

    2012-03-21

    , and the development of ways to imprint chiral centers on achiral solid surfaces. Chiral catalysis is not only a problem of great importance in its own right, but also the ultimate test of how to control selectivity in catalysis. The time is ripe for fundamental work in heterogeneous chiral catalysis to provide the U.S. with a leadership role in developing the next generation of catalytic processes for medicinal and agrochemical manufacturing. Our team provides the required expertise for a synergistic and comprehensive integration of physical and chemical experimentation with solid state and molecular reactivity theories to solve this problem.

  13. Axially chiral allenyl gold complexes.

    PubMed

    Johnson, Alice; Laguna, Antonio; Gimeno, M Concepción

    2014-09-17

    Unprecedented allenyl gold complexes have been achieved starting from triphenylpropargylphosphonium bromide. Two different coordination modes of the allene isomer of triphenylphosphoniumpropargylide to gold have been found depending on the gold oxidation state. Bromo-, pentafluorophenyl-, and triphenylphosphine-gold(I) allenyl complexes were prepared in which the α carbon coordinates to the gold(I) center. A chiral pentafluorophenyl-gold(III) allenyl complex with the gold atoms coordinated to the γ carbon was also prepared. All the complexes have been structurally characterized by X-ray diffraction showing the characteristic distances for a C═C═C unit.

  14. Bridged bis(beta-cyclodextrin)s possessing coordinated metal center(s) and their inclusion complexation behavior with model substrates: enhanced molecular binding ability by multiple recognition.

    PubMed

    Liu, Y; Chen, Y; Li, L; Zhang, H Y; Liu, S X; Guan, X D

    2001-12-14

    To investigate quantitatively the cooperative binding ability of several beta-cyclodextrin oligomers bearing single or multiligated metal center(s), the inclusion complexation behavior of four bis(beta-cyclodextrin)s (2-5) linked by 2,2'-bipyridine-4,4'-dicarboxy tethers and their copper(II) complexes (6-9) with representative dye guests, i.e., methyl orange (MO), acridine red (AR), rhodamine B (RhB), ammonium 8-anilino-1-naphthalenesulfonic acid (ANS), and sodium 6-(p-toludino)-2-naphthalenesulfonate (TNS), have been examined in aqueous solution at 25 degrees C by means of UV-vis, circular dichroism, fluorescence, and 2D NMR spectroscopy. The results obtained indicate that bis(beta-cyclodextrin)s 2-5 can associate with one or three copper(II) ion(s) producing 2:1 or 2:3 bis(beta-cyclodextrin)-copper(II) complexes. These metal-ligated oligo(beta-cyclodextrin)s can bind two model substrates to form intramolecular 2:2 host-guest inclusion complexes and thus significantly enhance the original binding abilities of parent beta-cyclodextrin and bis(beta-cyclodextrin) toward model substrates through the cooperative binding of two guest molecules by four tethered cyclodextrin moieties, as well as the additional binding effect supplied by ligated metal center(s). Host 6 showed the highest enhancement of the stability constant, up to 38.3 times for ANS as compared with parent beta-cyclodextrin. The molecular binding mode and stability constant of substrates by bridged bis- and oligo(beta-cyclodextrin)s 2-9 are discussed from the viewpoint of the size/shape-fit interaction and molecular multiple recognition between host and guest.

  15. Disentangling Multiple Sclerosis and depression: an adjusted depression screening score for patient-centered care.

    PubMed

    Gunzler, Douglas D; Perzynski, Adam; Morris, Nathan; Bermel, Robert; Lewis, Steven; Miller, Deborah

    2015-04-01

    Screening for depression can be challenging in Multiple Sclerosis (MS) patients due to the overlap of depressive symptoms with other symptoms, such as fatigue, cognitive impairment and functional impairment, for MS patients. The aim of this study was to understand these overlapping symptoms and subsequently develop an adjusted depression screening tool for better clinical assessment of depressive symptoms in MS patients. We evaluated 3,507 MS patients with a self-reported depression screening (PHQ-9) score using a multiple indicator multiple cause modeling approach. Our models showed significant differential item functioning effects denoting significant overlap of depressive symptoms with all MS symptoms under study and good model fit. The magnitude of the overlap was especially large for fatigue. Adjusted depression screening scales were formed based on factor scores and loadings that will allow clinicians to understand the depressive symptoms separate from other symptoms for MS patients for improved patient care.

  16. Molecular model for chirality phenomena

    NASA Astrophysics Data System (ADS)

    Latinwo, Folarin; Stillinger, Frank H.; Debenedetti, Pablo G.

    2016-10-01

    Chirality is a hallmark feature for molecular recognition in biology and chemical physics. We present a three-dimensional continuum model for studying chirality phenomena in condensed phases using molecular simulations. Our model system is based upon a simple four-site molecule and incorporates non-trivial kinetic behavior, including the ability to switch chirality or racemize, as well as thermodynamics arising from an energetic preference for specific chiral interactions. In particular, we introduce a chiral renormalization parameter that can locally favor either homochiral or heterochiral configurations. Using this model, we explore a range of chirality-specific phenomena, including the kinetics of chiral inversion, the mechanism of spontaneous chiral symmetry breaking in the liquid, chirally driven liquid-liquid phase separation, and chiral crystal structures.

  17. The significance of chirality in drug design and development.

    PubMed

    Brooks, W H; Guida, W C; Daniel, K G

    2011-01-01

    Proteins are often enantioselective towards their binding partners. When designing small molecules to interact with these targets, one should consider stereoselectivity. As considerations for exploring structure space evolve, chirality is increasingly important. Binding affinity for a chiral drug can differ for diastereomers and between enantiomers. For the virtual screening and computational design stage of drug development, this problem can be compounded by incomplete stereochemical information in structure libraries leading to a "coin toss" as to whether or not the "ideal" chiral structure is present. Creating every stereoisomer for each chiral compound in a structure library leads to an exponential increase in the number of structures resulting in potentially unmanageable file sizes and screening times. Therefore, only key chiral structures, enantiomeric pairs based on relative stereochemistry need be included, and lead to a compromise between exploration of chemical space and maintaining manageable libraries. In clinical environments, enantiomers of chiral drugs can have reduced, no, or even deleterious effects. This underscores the need to avoid mixtures of compounds and focus on chiral synthesis. Governmental regulations emphasizing the need to monitor chirality in drug development have increased. The United States Food and Drug Administration issued guidelines and policies in 1992 concerning the development of chiral compounds. These guidelines require that absolute stereochemistry be known for compounds with chiral centers and that this information should be established early in drug development in order that the analysis can be considered valid. From exploration of structure space to governmental regulations it is clear that the question of chirality in drug design is of vital importance. PMID:21291399

  18. The significance of chirality in drug design and development.

    PubMed

    Brooks, W H; Guida, W C; Daniel, K G

    2011-01-01

    Proteins are often enantioselective towards their binding partners. When designing small molecules to interact with these targets, one should consider stereoselectivity. As considerations for exploring structure space evolve, chirality is increasingly important. Binding affinity for a chiral drug can differ for diastereomers and between enantiomers. For the virtual screening and computational design stage of drug development, this problem can be compounded by incomplete stereochemical information in structure libraries leading to a "coin toss" as to whether or not the "ideal" chiral structure is present. Creating every stereoisomer for each chiral compound in a structure library leads to an exponential increase in the number of structures resulting in potentially unmanageable file sizes and screening times. Therefore, only key chiral structures, enantiomeric pairs based on relative stereochemistry need be included, and lead to a compromise between exploration of chemical space and maintaining manageable libraries. In clinical environments, enantiomers of chiral drugs can have reduced, no, or even deleterious effects. This underscores the need to avoid mixtures of compounds and focus on chiral synthesis. Governmental regulations emphasizing the need to monitor chirality in drug development have increased. The United States Food and Drug Administration issued guidelines and policies in 1992 concerning the development of chiral compounds. These guidelines require that absolute stereochemistry be known for compounds with chiral centers and that this information should be established early in drug development in order that the analysis can be considered valid. From exploration of structure space to governmental regulations it is clear that the question of chirality in drug design is of vital importance.

  19. The covariant chiral ring

    NASA Astrophysics Data System (ADS)

    Bourget, Antoine; Troost, Jan

    2016-03-01

    We construct a covariant generating function for the spectrum of chiral primaries of symmetric orbifold conformal field theories with N = (4 , 4) supersymmetry in two dimensions. For seed target spaces K3 and T 4, the generating functions capture the SO(21) and SO(5) representation theoretic content of the chiral ring respectively. Via string dualities, we relate the transformation properties of the chiral ring under these isometries of the moduli space to the Lorentz covariance of perturbative string partition functions in flat space.

  20. Synthesis of Chiral Cyclopentenones.

    PubMed

    Simeonov, Svilen P; Nunes, João P M; Guerra, Krassimira; Kurteva, Vanya B; Afonso, Carlos A M

    2016-05-25

    The cyclopentenone unit is a very powerful synthon for the synthesis of a variety of bioactive target molecules. This is due to the broad diversity of chemical modifications available for the enone structural motif. In particular, chiral cyclopentenones are important precursors in the asymmetric synthesis of target chiral molecules. This Review provides an overview of reported methods for enantioselective and asymmetric syntheses of cyclopentenones, including chemical and enzymatic resolution, asymmetric synthesis via Pauson-Khand reaction, Nazarov cyclization and organocatalyzed reactions, asymmetric functionalization of the existing cyclopentenone unit, and functionalization of chiral building blocks. PMID:27101336

  1. Efficient Molecular Dynamics Simulations of Multiple Radical Center Systems Based on the Fragment Molecular Orbital Method

    SciTech Connect

    Nakata, Hiroya; Schmidt, Michael W; Fedorov, Dmitri G; Kitaura, Kazuo; Nakamura, Shinichiro; Gordon, Mark S

    2014-10-16

    The fully analytic energy gradient has been developed and implemented for the restricted open-shell Hartree–Fock (ROHF) method based on the fragment molecular orbital (FMO) theory for systems that have multiple open-shell molecules. The accuracy of the analytic ROHF energy gradient is compared with the corresponding numerical gradient, illustrating the accuracy of the analytic gradient. The ROHF analytic gradient is used to perform molecular dynamics simulations of an unusual open-shell system, liquid oxygen, and mixtures of oxygen and nitrogen. These molecular dynamics simulations provide some insight about how triplet oxygen molecules interact with each other. Timings reveal that the method can calculate the energy gradient for a system containing 4000 atoms in only 6 h. Therefore, it is concluded that the FMO-ROHF method will be useful for investigating systems with multiple open shells.

  2. Efficient molecular dynamics simulations of multiple radical center systems based on the fragment molecular orbital method.

    PubMed

    Nakata, Hiroya; Schmidt, Michael W; Fedorov, Dmitri G; Kitaura, Kazuo; Nakamura, Shinichiro; Gordon, Mark S

    2014-10-16

    The fully analytic energy gradient has been developed and implemented for the restricted open-shell Hartree-Fock (ROHF) method based on the fragment molecular orbital (FMO) theory for systems that have multiple open-shell molecules. The accuracy of the analytic ROHF energy gradient is compared with the corresponding numerical gradient, illustrating the accuracy of the analytic gradient. The ROHF analytic gradient is used to perform molecular dynamics simulations of an unusual open-shell system, liquid oxygen, and mixtures of oxygen and nitrogen. These molecular dynamics simulations provide some insight about how triplet oxygen molecules interact with each other. Timings reveal that the method can calculate the energy gradient for a system containing 4000 atoms in only 6 h. Therefore, it is concluded that the FMO-ROHF method will be useful for investigating systems with multiple open shells.

  3. Catalysis of dynamical chiral symmetry breaking by chiral chemical potential

    NASA Astrophysics Data System (ADS)

    Braguta, V. V.; Kotov, A. Yu.

    2016-05-01

    In this paper, we study the properties of media with chiral imbalance parametrized by chiral chemical potential. It is shown that depending on the strength of interaction between constituents in the media the chiral chemical potential either creates or enhances dynamical chiral symmetry breaking. Thus, the chiral chemical potential plays the role of the catalyst of dynamical chiral symmetry breaking. Physically, this effect results from the appearance of the Fermi surface and additional fermion states on this surface, which take part in dynamical chiral symmetry breaking. An interesting conclusion which can be drawn is that at sufficiently small temperature chiral plasma is unstable with respect to condensation of Cooper pairs and dynamical chiral symmetry breaking even for vanishingly small interactions between constituents.

  4. Luminescent chiral lanthanide(III) complexes as potential molecular probes

    PubMed Central

    Muller, Gilles

    2009-01-01

    This perspective gives an introduction into the design of luminescent lanthanide(III)-containing complexes possessing chiral properties and used to probe biological materials. The first part briefly describes general principles, focusing on the optical aspect (i.e. lanthanide luminescence, sensitization processes) of the most emissive trivalent lanthanide ions, europium and terbium, incorporated into molecular luminescent edifices. This is followed by a short discussion on the importance of chirality in the biological and pharmaceutical fields. The second part is devoted to the assessment of the chiroptical spectroscopic tools available (typically circular dichroism and circularly polarized luminescence) and the strategies used to introduce a chiral feature into luminescent lanthanide(III) complexes (chiral structure resulting from a chiral arrangement of the ligand molecules surrounding the luminescent center or presence of chiral centers in the ligand molecules). Finally, the last part illustrates these fundamental principles with recent selected examples of such chiral luminescent lanthanide-based compounds used as potential probes of biomolecular substrates. PMID:19885510

  5. Spintronics: Chiral damping

    PubMed Central

    Kim, Kyoung-Whan; Lee, Hyun-Woo

    2016-01-01

    The analysis of the magnetic domain wall motion in a nanostructured magnetic system with strong spin-orbit coupling shows that the energy dissipation can be chiral when the inversion symmetry is broken. PMID:26906956

  6. Nonlinear chiral transport phenomena

    NASA Astrophysics Data System (ADS)

    Chen, Jiunn-Wei; Ishii, Takeaki; Pu, Shi; Yamamoto, Naoki

    2016-06-01

    We study the nonlinear responses of relativistic chiral matter to the external fields such as the electric field E , gradients of temperature and chemical potential, ∇T and ∇μ . Using the kinetic theory with Berry curvature corrections under the relaxation time approximation, we compute the transport coefficients of possible new electric currents that are forbidden in usual chirally symmetric matter but are allowed in chirally asymmetric matter by parity. In particular, we find a new type of electric current proportional to ∇μ ×E due to the interplay between the effects of the Berry curvature and collisions. We also derive an analog of the "Wiedemann-Franz" law specific for anomalous nonlinear transport in relativistic chiral matter.

  7. The quest for chirality

    SciTech Connect

    Bonner, W.A.

    1996-07-01

    The indispensable role played by homochirality and chiral homogeneity in the self-replication of crucial biomolecules is stressed, with the conclusion that life could neither exist nor originate without these chiral molecular attributes. Hypotheses historically proposed for the origin of chiral molecules on Earth are reviewed, including biogenic theories as well as abiotic theories embracing both indeterminate and determinate mechanisms. Indeterminate mechanisms, including autocatalytic symmetry breaking, asymmetric adsorption on quartz and clay minerals, and asymmetric syntheses in chiral crystals, are discussed and evaluated in the context of the prebiotic environment. Abiotic determinate mechanisms based on electric, magnetic and gravitational fields, on circularly polarized light (CPL), and on parity violation effects are summarized, with the emphasis that only CPL has proved practicable experimentally, but that it would be implausible on the primitive Earth. Mechanisms for the amplification of small, indigenous enantiomeric excesses are discussed, with one involving the partial polymerization of amino acids and the partial hydrolysis of polypeptides suggested as potentially viable prebiotically. Aspects of the turbulent, chirality-destructive primeval environment are described, with the conclusion that all of the above mechanisms for the {ital terrestrial} prebiotic origin of chirality would be non-viable, and that an alternative extraterrestrial source for the accumulation of chiral molecules on primitive Earth must have been operative. A scenario for this is outlined, in which we postulate that asymmetric photolysis of the organic mantles on interstellar grains in molecular clouds by circularly polarized ultraviolet synchrotron radiation from the neutron star remnants of supernovae produces chiral molecules in the grain mantles. (Abstract Truncated)

  8. Human-Centered Design and Evaluation of Haptic Cueing for Teleoperation of Multiple Mobile Robots.

    PubMed

    Son, Hyoung Il; Franchi, Antonio; Chuang, Lewis L; Kim, Junsuk; Bulthoff, Heinrich H; Giordano, Paolo Robuffo

    2013-04-01

    In this paper, we investigate the effect of haptic cueing on a human operator's performance in the field of bilateral teleoperation of multiple mobile robots, particularly multiple unmanned aerial vehicles (UAVs). Two aspects of human performance are deemed important in this area, namely, the maneuverability of mobile robots and the perceptual sensitivity of the remote environment. We introduce metrics that allow us to address these aspects in two psychophysical studies, which are reported here. Three fundamental haptic cue types were evaluated. The Force cue conveys information on the proximity of the commanded trajectory to obstacles in the remote environment. The Velocity cue represents the mismatch between the commanded and actual velocities of the UAVs and can implicitly provide a rich amount of information regarding the actual behavior of the UAVs. Finally, the Velocity+Force cue is a linear combination of the two. Our experimental results show that, while maneuverability is best supported by the Force cue feedback, perceptual sensitivity is best served by the Velocity cue feedback. In addition, we show that large gains in the haptic feedbacks do not always guarantee an enhancement in the teleoperator's performance.

  9. Diffraction gratings for chiral molecules and their applications.

    PubMed

    Cameron, Robert P; Yao, Alison M; Barnett, Stephen M

    2014-05-15

    We suggest the use of certain readily producible types of light to exert a force that points in opposite directions for the enantiomers of a chiral molecule and propose multiple devices based upon this novel manifestation of optical activity: in particular, our discriminatory chiral diffraction grating; a device that could be employed, for example, to measure the enantiomeric excess of a sample of chiral molecules simply and to high precision. Our work is relevant for many types of molecules and our proposed devices may be realizable using currently existing technology.

  10. Syntheses and some features of five new cyclohexane-1,3-dicarboxylates with multiple stereogenic centers

    NASA Astrophysics Data System (ADS)

    Ismiyev, Arif M.; Maharramov, Abel M.; Aliyeva, Rafiga A.; Askerov, Rizvan K.; Mahmudov, Kamran T.; Kopylovich, Maximilian N.; Naïli, Houcine; Pombeiro, Armando J. L.

    2013-01-01

    The condensation of diethyl 4-hydroxy-4-methyl-6-oxo-2-(4-substitutedphenyl)-cyclohexane-1,3-dicarboxylates and N'-(2-chloropropyl)ethane-1,2-diamine leads to diethyl 1-(2-chloropropyl)-9-hydroxy-9-methyl-7-phenyl-1,4-diazaspiro[4.5]decane-6,8-dicarboxylate (2) and its para-substituted methyl (1), chloro (3), bromo (4), and nitro (5) derivatives with a new stereogenic center, which were fully characterized by elemental analysis, ESI-MS, IR, 1H and 13C NMR spectroscopies and X-ray single-crystal analysis (for 2). The condensation reaction is regioselective, only cyclohexanone carbonyl moiety undergoes the transformation, leaving the β-keto ester carbonyls unreacted. Withing the compounds 1-5, the increase in the Hammett's σp, related normal σpn, inductive σI, negative σp- and positive σp+ polar conjugation and Taft's σpo substituent constants generally leads to the corresponding drift of δOsbnd H and δNsbnd H NMR chemical shifts to lower field.

  11. Cerebrospinal fluid B cells from Multiple Sclerosis patients are subject to normal germinal center selection

    PubMed Central

    Harp, Christopher; Lee, Jane; Lambracht-Washington, Doris; Cameron, Elizabeth; Olsen, Gregory; Frohman, Elliot; Racke, Michael; Monson, Nancy

    2007-01-01

    Previous findings from our laboratory demonstrated that some clonally expanded cerebrospinal fluid (CSF) B cells from MS patients exhibit diminished mutation targeting patterns in comparison to typical B cells selected in the context of germinal centers (GCs). In order to determine whether the overall CSF B cell repertoires adhered to mutation patterns typical of GC-selected B cells, we analyzed the immunoglobulin repertoires from CSF B cells of 8 MS patients for mutation characteristics typical of GC-derived B cells. Mutation targeting was preserved. Thus, clonal expansion of some CSF B cells may occur independently of GC, but the CSF B cell pool is governed by typical GC selection. Interestingly, the heavy chain CDR3’s of CSF B cells from MS patients had a net acidic charge, similar to GC-derived B cells, but a tendency towards longer CDR3’s, consistent with autoreactive B cells. How these findings may support current hypotheses regarding the origin of CSF B cells is discussed. PMID:17169437

  12. Cerebrospinal fluid B cells from multiple sclerosis patients are subject to normal germinal center selection.

    PubMed

    Harp, Christopher; Lee, Jane; Lambracht-Washington, Doris; Cameron, Elizabeth; Olsen, Gregory; Frohman, Elliot; Racke, Michael; Monson, Nancy

    2007-02-01

    Previous findings from our laboratory demonstrated that some clonally expanded cerebrospinal fluid (CSF) B cells from MS patients exhibit diminished mutation targeting patterns in comparison to typical B cells selected in the context of germinal centers (GCs). In order to determine whether the overall CSF B cell repertoires adhered to mutation patterns typical of GC-selected B cells, we analyzed the immunoglobulin repertoires from CSF B cells of 8 MS patients for mutation characteristics typical of GC-derived B cells. Mutation targeting was preserved. Thus, clonal expansion of some CSF B cells may occur independently of GC, but the CSF B cell pool is governed by typical GC selection. Interestingly, the heavy chain CDR3's of CSF B cells from MS patients had a net acidic charge, similar to GC-derived B cells, but a tendency towards longer CDR3's, consistent with autoreactive B cells. How these findings may support current hypotheses regarding the origin of CSF B cells is discussed. PMID:17169437

  13. Outcome in Multiple Myeloma Patients Eligible for Stem Cell Transplantation: A Single-Center Experience.

    PubMed

    Lamm, Wolfgang; Wohlfarth, Philipp; Bojic, Marija; Schörgenhofer, Christian; Drach, Johannes; Gisslinger, Heinz; Worel, Nina; Schiefer, Ana; Schulenburg, Axel; Agis, Hermine; Kalhs, Peter; Greinix, Hildegard T; Schellongowski, Peter; Rabitsch, Werner

    2015-01-01

    Autologous hematopoietic stem cell transplantation (ASCT) is the standard of care for selected patients with multiple myeloma (MM). Many data exist on ASCT in the era of novel agents. We retrospectively analyzed 189 patients (108 males and 81 females) with biopsy-proven MM, who had received ASCT after induction therapy with either conventional chemotherapy alone or in combination with novel agents at our department. The outcomes of both groups and the risk factors for shorter survival were investigated. The most commonly used induction chemotherapy prior to ASCT was VAD (vincristine, doxorubicin and dexamethasone, 42%), followed by PAD (bortezomib, doxorubicin and dexamethasone, 21%). One-hundred and twenty-nine patients (68%) received cyclophosphamide-recombinant human granulocyte colony-stimulating factor for stem cell mobilization. No differences were observed for progression-free survival in terms of the number of transplanted CD34+ cells (p = 0.261). A trend in improved overall survival (OS) was seen for the use of novel agents when compared to conventional chemotherapy (164.3 vs. 82.0 months; p = 0.046). The International Staging System stages had a significant (p = 0.036) impact on OS. The novel agents improved OS in our patients with MM undergoing ASCT when compared to conventional chemotherapy regimens. The number of transplanted CD34+ cells had no significant impact on hematopoietic reconstitution.

  14. TADDOLs, Their Derivatives, and TADDOL Analogues: Versatile Chiral Auxiliaries.

    PubMed

    Seebach, Dieter; Beck, Albert K.; Heckel, Alexander

    2001-01-01

    TADDOLs, which contain two adjacent diarylhydroxymethyl groups in a trans relationship on a 1,3-dioxolane ring, can be prepared from acetals or ketals of tartrate esters by reaction of the latter with aromatic Grignard reagents. They are extraordinarily versatile chiral auxiliaries. Here, a historical review of the subject is followed by discussion of the preparation of TADDOLs and analogous systems, including TADDOLs with N-, P-, O-, and S-heteroatom ligands appropriate for metals. Crystal structure analysis reveals that the heteroatoms on the diarylmethyl groups are almost always in close proximity to each other, joined together by H-bonds, and predisposed to form chelate complexes in which the metallic centers reside in propeller-like chiral environments. Applications of TADDOL derivatives in enantioselective synthesis extend from utilization as stoichiometric chiral reagents or in Lewis acid mediated reactions, to roles in catalytic hydrogenation and stereoregular metathesis polymerization. Derivatives and complexes based on the following metals have so far been investigated: Li, B, Mg, Al, Si, Cu, Zn, Ce, Ti, Zr, Mo, Rh, Ir, Pd, Pt. The number of stereoselective reactions already accomplished with TADDOLs is correspondingly large. It is also easy to prepare TADDOL derivatives that are readily polymerizable and graftable, and to transform them into immobilized solid-phase catalysts. The result is catalysts, simply or dendritically immobilized in polystyrene or on silica gel and characterized by unexpected stability even after multiple use in titanium TADDOLate mediated reactions. TADDOLs show further unusual characteristics that make them useful for applications in material science and supramolecular chemistry: they are the most effective doping agents known for phase transformations of achiral (nematic) into chiral (cholesteric) liquid crystals. The TADDOL OH group that is not involved in intramolecular H-bonding shows a strong tendency to associate

  15. Chiral anomalies and differential geometry

    SciTech Connect

    Zumino, B.

    1983-10-01

    Some properties of chiral anomalies are described from a geometric point of view. Topics include chiral anomalies and differential forms, transformation properties of the anomalies, identification and use of the anomalies, and normalization of the anomalies. 22 references. (WHK)

  16. Active Chiral Plasmonics.

    PubMed

    Yin, Xinghui; Schäferling, Martin; Michel, Ann-Katrin U; Tittl, Andreas; Wuttig, Matthias; Taubner, Thomas; Giessen, Harald

    2015-07-01

    Active control over the handedness of a chiral metamaterial has the potential to serve as key element for highly integrated polarization engineering approaches, polarization sensitive imaging devices, and stereo display technologies. However, this is hard to achieve as it seemingly involves the reconfiguration of the metamolecule from a left-handed into a right-handed enantiomer and vice versa. This type of mechanical actuation is intricate and usually neither monolithically realizable nor viable for high-speed applications. Here, enabled by the phase change material Ge3Sb2Te6 (GST-326), we demonstrate a tunable and switchable mid-infrared plasmonic chiral metamaterial in a proof-of-concept experiment. A large tunability range of the circular dichroism response from λ = 4.15 to 4.90 μm is achieved, and we experimentally demonstrate that the combination of a passive bias-type chiral layer with the active chiral metamaterial allows for switchable chirality, that is, the reversal of the circular dichroism sign, in a fully planar, layered design without the need for geometrical reconfiguration. Because phase change materials can be electrically and optically switched, our designs may open up a path for highly integrated mid-IR polarization engineering devices that can be modulated on ultrafast time scales.

  17. Application of rifampicin as a chiral selector for enantioresolution of basic drugs using capillary electrophoresis.

    PubMed

    Dixit, Shuchi; Park, Jung Hag

    2016-07-01

    Rifampicin, a member of rifamycin sub-class of antibiotics which belongs to the naphthalenic ansamycin class of antibiotics, has a characteristic ansa structure, i.e., a ring structure or chromophore spanned by an aliphatic chain. The present work was designed to evaluate its potential as a chiral selector (CS) as its structure consisting of nine stereogenic centers, an aromatic moiety and several functional groups (i.e., one imine, one amide, one acetoxy residue, two aliphatic hydroxyl and three phenolic hydroxyl groups) was expected to instigate multiple enantioselective interactions, namely, hydrogen bonding and inclusion complexation with chiral analytes, and therefore resulting in efficient enantioseparations. Systematic experiments were performed to investigate the effects of concentration of CS, composition of background electrolyte (BGE) and applied voltage on chiral separation. Enantiomers of propranolol and metoprolol were baseline resolved using a BGE consisting of 20mM CS and 50/50 (v/v) iso-propanol/phosphate buffer (100mM, pH 7.0) whereas for enantiomers of sertraline, a BGE consisting of 23mM CS and 40/60 (v/v) iso-propanol/phosphate buffer (100mM, pH 7.0) resulted in baseline resolutions. PMID:27240943

  18. Simple chiral urea gelators, (R)- and (S)-2-heptylurea: their gelling ability enhanced by chirality.

    PubMed

    Kim, Jong-Uk; Schollmeyer, Dieter; Brehmer, Martin; Zentel, Rudolf

    2011-05-15

    We present the first report on the synthesis of chiral ureas, (R)- and (S)-2-heptylurea, and their gelling behaviors. The ureas were prepared by the reactions of chiral amines and phenyl carbamate in the presence of triethylamine. On cooling from homogeneous solutions, the chiral ureas form gels in water and various nonpolar organic solvents, such as cyclohexane, toluene, and tetrachloromethane, while the racemate gelatinize only toluene and tetrachloromethane among the solvents we examined. The gelling ability of the enantiomeric urea is higher than the racemate, as the critical gelling concentrations in toluene, for example, were 0.2% and 0.7% (wt/wt), respectively. The enhanced gelling ability of the enantiomeric ureas is due to the 1D supramolecular structure formed during gelation. In contrast, the racemate crystallizes into two-dimensional lamellae, where the (R)- and (S)-2-heptylurea exist alternatingly in a plane (P2(1)/c space group). Powder X-ray diffraction pattern of the enantiomeric urea showed that it has a different crystal lattice from that of the racemate, implying that the steric effect by the methyl group at the chiral center prevents the pure enantiomers from having 2D hydrogen bonding networks, which lead to sheet-like structures for the racemate and the achiral analog. Thus the pure enantiomers self-organize into one-dimensional fibrous structures. The simplicity and the ambidextrous gelling behaviors of the chiral ureas in forming both hydrogels and organogels present numerous possibilities for future applications. PMID:21396655

  19. Chiral Sensitivity in the Dissociative Electron Attachment of Halocamphor Molecules

    NASA Astrophysics Data System (ADS)

    Dreiling, Joan

    2016-05-01

    We have demonstrated chirally-dependent molecular destruction when incident longitudinally-spin-polarized (chiral) electrons break bonds in chiral molecules. This chiral sensitivity was observed through an asymmetry in the dissociative electron attachment (DEA) reaction rate with chiral 3-bromocamphor (C10 H15 BrO). Such an observation provides an unambiguous demonstration of the idea underlying the Vester-Ulbricht hypothesis, which attempts to explain the origins of the homochirality that is observed in many biological systems. While the lack of inversion symmetry in these reactions allows the effects we observe to occur, their dynamic causes are poorly understood. We have further studied the asymmetries in the DEA rates for two additional halocamphor molecules, 3-iodocamphor (C10 H15 IO) and 10-iodocamphor, in a systematic effort to illuminate the mechanisms responsible for the chiral sensitivity. The DEA signal depends on the sign of the incident electron helicity for a given target handedness in all molecules, and it varies with both the atomic number and the location of the heaviest atom in the molecule. Surprisingly, the DEA asymmetries for 10-iodocamphor, in which the heaviest atom is farther from a chiral center than for the other molecules, produced the largest asymmetries. This work was performed at the University of Nebraska-Lincoln. This project was funded by NSF Grant PHY-1206067.

  20. Chirality, quantum mechanics, and biological determinism

    NASA Astrophysics Data System (ADS)

    Davies, P. C. W.

    2006-08-01

    life with biochemical make-up resembling that of known life. Whilst the experimental search for a second sample of life - possibly by detecting a chiral "anomaly" - continues, some theoretical investigations may be pursued to narrow down the options. Chiral determinism would be an intrinsically quantum process. There are hints that quantum mechanics plays a key role in biology, but the claim remains contentious. Here I review some of the evidence for quantum aspects of biology. I also summarize some proposals for testing biological determinism by seeking evidence for a multiple genesis events on Earth, and for identifying extant "alien microbes" - micro-organisms descended from an independent origin from familiar life.

  1. Patient- and family-centered care coordination: a framework for integrating care for children and youth across multiple systems.

    PubMed

    2014-05-01

    Understanding a care coordination framework, its functions, and its effects on children and families is critical for patients and families themselves, as well as for pediatricians, pediatric medical subspecialists/surgical specialists, and anyone providing services to children and families. Care coordination is an essential element of a transformed American health care delivery system that emphasizes optimal quality and cost outcomes, addresses family-centered care, and calls for partnership across various settings and communities. High-quality, cost-effective health care requires that the delivery system include elements for the provision of services supporting the coordination of care across settings and professionals. This requirement of supporting coordination of care is generally true for health systems providing care for all children and youth but especially for those with special health care needs. At the foundation of an efficient and effective system of care delivery is the patient-/family-centered medical home. From its inception, the medical home has had care coordination as a core element. In general, optimal outcomes for children and youth, especially those with special health care needs, require interfacing among multiple care systems and individuals, including the following: medical, social, and behavioral professionals; the educational system; payers; medical equipment providers; home care agencies; advocacy groups; needed supportive therapies/services; and families. Coordination of care across settings permits an integration of services that is centered on the comprehensive needs of the patient and family, leading to decreased health care costs, reduction in fragmented care, and improvement in the patient/family experience of care.

  2. Diastereodivergent Catalytic Asymmetric Michael Addition of 2-Oxindoles to α,β-Unsaturated Ketones by Chiral Diamine Catalysts.

    PubMed

    Wei, Yuan; Wen, Shigang; Liu, Zunwu; Wu, Xinxin; Zeng, Bubing; Ye, Jinxing

    2015-06-01

    A diastereodivergent catalytic asymmetric Michael addition of 2-oxindoles to α,β-unsaturated ketones has been successfully developed with two complementary chiral diamine catalysts, affording chiral 3,3-disubstituted oxindoles with two adjacent chiral centers. Diastereodivergence has been realized through modifying substrates and utilizing different catalysts. Either anti-or syn-configured products possessing vicinal quaternary and tertiary stereogenic centers were produced with high enantioselectivities. PMID:25973971

  3. Multiple perpetrator rape among girls evaluated at a hospital-based Child Advocacy Center: Seven years of reviewed cases

    PubMed Central

    Edinburgh, Laurel; Pape-Blabolil, Julie; Harpin, Scott B.; Saewyc, Elizabeth

    2015-01-01

    The aim of this study was to describe contextual events, abuse experiences, and disclosure processes of adolescents who presented to a hospital-based Child Advocacy Center for medical evaluation and evidentiary collection as indicated after experiencing multiple perpetrator rape during a single event (n = 32) and to compare these findings to a group of single perpetrator sexual assaults (n = 534). This study used a retrospective mixed-methods design with in-depth, forensic interviews and complete physical examinations of gang-raped adolescents. Patients ranged from 12 to 17 years (M = 14 years). Girls who experienced multiple perpetrator rape during a single event were more likely to have run away, to have drunk alcohol in the past month, and to have participated in binge drinking in the past 2 weeks. Acute presentation of these victims were rare but 30% had hymenal transections and 38% had sexually transmitted infections (STIs). Forensic interviews revealed alcohol was a common weapon used by offenders, and its use resulted in victims experiencing difficulty in remembering and reporting details for police investigation or physical and mental health care. Most victims were raped at parties they attended with people they thought they could trust, and they felt let down by witnesses who could have helped but did not intervene. Although relatively rare, multiple perpetrator rape during a single event is a type of severe sexual assault experience and has significant risks for deleterious health outcomes. These victims require health care by trained providers to diagnose physical findings, treat STIs, screen for trauma, and support victims. PMID:24933707

  4. Multiple perpetrator rape among girls evaluated at a hospital-based child advocacy center: seven years of reviewed cases.

    PubMed

    Edinburgh, Laurel; Pape-Blabolil, Julie; Harpin, Scott B; Saewyc, Elizabeth

    2014-09-01

    The aim of this study was to describe contextual events, abuse experiences, and disclosure processes of adolescents who presented to a hospital-based Child Advocacy Center for medical evaluation and evidentiary collection as indicated after experiencing multiple perpetrator rape during a single event (n=32) and to compare these findings to a group of single perpetrator sexual assaults (n=534). This study used a retrospective mixed-methods design with in-depth, forensic interviews and complete physical examinations of gang-raped adolescents. Patients ranged from 12 to 17 years (M=14 years). Girls who experienced multiple perpetrator rape during a single event were more likely to have run away, to have drunk alcohol in the past month, and to have participated in binge drinking in the past 2 weeks. Acute presentation of these victims were rare but 30% had hymenal transections and 38% had sexually transmitted infections (STIs). Forensic interviews revealed alcohol was a common weapon used by offenders, and its use resulted in victims experiencing difficulty in remembering and reporting details for police investigation or physical and mental health care. Most victims were raped at parties they attended with people they thought they could trust, and they felt let down by witnesses who could have helped but did not intervene. Although relatively rare, multiple perpetrator rape during a single event is a type of severe sexual assault experience and has significant risks for deleterious health outcomes. These victims require health care by trained providers to diagnose physical findings, treat STIs, screen for trauma, and support victims.

  5. Polar Superhelices in Ferroelectric Chiral Nanosprings

    NASA Astrophysics Data System (ADS)

    Shimada, Takahiro; Lich, Le Van; Nagano, Koyo; Wang, Jian-Shan; Wang, Jie; Kitamura, Takayuki

    2016-10-01

    Topological objects of nontrivial spin or dipolar field textures, such as skyrmions, merons, and vortices, interacting with applied external fields in ferroic materials are of great scientific interest as an intriguing playground of unique physical phenomena and novel technological paradigms. The quest for new topological configurations of such swirling field textures has primarily been done for magnets with Dzyaloshinskii-Moriya interactions, while the absence of such intrinsic chiral interactions among electric dipoles left ferroelectrics aside in this quest. Here, we demonstrate that a helical polarization coiled into another helix, namely a polar superhelix, can be extrinsically stabilized in ferroelectric nanosprings. The interplay between dipolar interactions confined in the chiral geometry and the complex strain field of mixed bending and twisting induces the superhelical configuration of electric polarization. The geometrical structure of the polar superhelix gives rise to electric chiralities at two different length scales and the coexistence of three order parameters, i.e., polarization, toroidization, and hypertoroidization, both of which can be manipulated by homogeneous electric and/or mechanical fields. Our work therefore provides a new geometrical configuration of swirling dipolar fields, which offers the possibility of multiple order-parameters, and electromechanically controllable dipolar chiralities and associated electro-optical responses.

  6. Polar Superhelices in Ferroelectric Chiral Nanosprings

    PubMed Central

    Shimada, Takahiro; Lich, Le Van; Nagano, Koyo; Wang, Jian-Shan; Wang, Jie; Kitamura, Takayuki

    2016-01-01

    Topological objects of nontrivial spin or dipolar field textures, such as skyrmions, merons, and vortices, interacting with applied external fields in ferroic materials are of great scientific interest as an intriguing playground of unique physical phenomena and novel technological paradigms. The quest for new topological configurations of such swirling field textures has primarily been done for magnets with Dzyaloshinskii-Moriya interactions, while the absence of such intrinsic chiral interactions among electric dipoles left ferroelectrics aside in this quest. Here, we demonstrate that a helical polarization coiled into another helix, namely a polar superhelix, can be extrinsically stabilized in ferroelectric nanosprings. The interplay between dipolar interactions confined in the chiral geometry and the complex strain field of mixed bending and twisting induces the superhelical configuration of electric polarization. The geometrical structure of the polar superhelix gives rise to electric chiralities at two different length scales and the coexistence of three order parameters, i.e., polarization, toroidization, and hypertoroidization, both of which can be manipulated by homogeneous electric and/or mechanical fields. Our work therefore provides a new geometrical configuration of swirling dipolar fields, which offers the possibility of multiple order-parameters, and electromechanically controllable dipolar chiralities and associated electro-optical responses. PMID:27713540

  7. Chirality and Life

    NASA Astrophysics Data System (ADS)

    Barron, Laurence D.

    Chirality, meaning handedness, pervades much of modern science, from the physics of elementary particles to the chemistry of life. The amino acids and sugars from which the central molecules of life—proteins and nucleic acids—are constructed exhibit homochirality, which is expected to be a key biosignature in astrobiology. This article provides a brief review of molecular chirality and its significance for the detection of extant or extinct life on other worlds. Fundamental symmetry aspects are emphasized since these bring intrinsic physical properties of the universe to bear on the problem of the origin and role of homochirality in the living world.

  8. Chirality and Life

    NASA Astrophysics Data System (ADS)

    Barron, Laurence D.

    2008-03-01

    Chirality, meaning handedness, pervades much of modern science, from the physics of elementary particles to the chemistry of life. The amino acids and sugars from which the central molecules of life—proteins and nucleic acids—are constructed exhibit homochirality, which is expected to be a key biosignature in astrobiology. This article provides a brief review of molecular chirality and its significance for the detection of extant or extinct life on other worlds. Fundamental symmetry aspects are emphasized since these bring intrinsic physical properties of the universe to bear on the problem of the origin and role of homochirality in the living world.

  9. Increments to chiral recognition facilitating enantiomer separations of chiral acids, bases, and ampholytes using Cinchona-based zwitterion exchanger chiral stationary phases.

    PubMed

    Wernisch, Stefanie; Pell, Reinhard; Lindner, Wolfgang

    2012-07-01

    The intramolecular distances of anion and cation exchanger sites of zwitterionic chiral stationary phases represent potential tuning sites for enantiomer selectivity. In this contribution, we investigate the influence of alkanesulfonic acid chain length and flexibility on enantiomer separations of chiral acids, bases, and amphoteric molecules for six Cinchona alkaloid-based chiral stationary phases in comparison with structurally related anion and cation exchangers. Employing polar-organic elution conditions, we observed an intramolecular counterion effect for acidic analytes which led to reduced retention times but did not impair enantiomer selectivities. Retention of amphoteric analytes is based on simultaneous double ion pairing of their charged functional groups with the acidic and basic sites of the zwitterionic selectors. A chiral center in the vicinity of the strong cation exchanger site is vital for chiral separations of bases. Sterically demanding side chains are beneficial for separations of free amino acids. Enantioseparations of free (un-derivatized) peptides were particularly successful in stationary phases with straight-chain alkanesulfonic acid sites, pointing to a beneficial influence of more flexible moieties. In addition, we observed pseudo-enantiomeric behavior of quinine and quinidine-derived chiral stationary phases facilitating reversal of elution orders for all analytes.

  10. Diastereoselective zinco-cyclopropanation of chiral allylic alcohols with gem-dizinc carbenoids.

    PubMed

    Fournier, Jean-François; Mathieu, Simon; Charette, André B

    2005-09-28

    The highly diastereoselective zinco-cyclopropanation of chiral allylic alcohols using gem-dizinc carbenoids is described. The reaction produces three contiguous stereogenic centers, and the resulting chiral cyclopropylzinc derivatives can be trapped with electrophiles with retention of configuration. Simple functional group manipulations lead to the efficient synthesis of orthogonally protected 1,2,3-substituted cyclopropane derivatives. PMID:16173730

  11. Chiral holmium complex-catalyzed Diels-Alder reaction of silyloxyvinylindoles: stereoselective synthesis of hydrocarbazoles.

    PubMed

    Harada, Shinji; Morikawa, Takahiro; Nishida, Atsushi

    2013-10-18

    The catalytic and asymmetric cycloaddition between 3-[1-(silyloxy)vinyl]indoles and electron-deficient olefins gave substituted hydrocarbazoles in up to 99% yield and 94% ee. This reaction was catalyzed by a novel chiral holmium(III) complex. Alkylation of the cycloadduct gave a tricyclic compound with four continuous chiral centers, one of which was a quaternary carbon.

  12. Chiral discrimination in the confined environment of biological nanospace

    NASA Astrophysics Data System (ADS)

    Nandi, Nilashis

    Although chiral discrimination in biological systems is overwhelmingly present, its molecular mechanism remained a puzzle. Why the basic blocks of life like L-amino acid and D-sugar are not being scrambled and retain enantiomeric purity since evolution is an unresolved question. In the present review we focus on the recent experimental and computational studies on the chiral discrimination in reactions such as peptide synthesis and aminoacylation. Experimental studies have shown that a clear homochiral preference exists favouring L-amino acid. Recent combined quantum mechanical/molecular mechanical studies explain the high level of stereospecificity of the processes and revealed multiple factors responsible for the discrimination and concomitant retention of the biological homochirality. Chirality of the relevant molecular segments and the intricate interaction between them as well as with the surrounding residues are important. The confinement of the chiral reactants within the biological nanospaces like the peptidyl transferase centre in tRNA and active site of the aminoacyl transferase as well as the nanoscale proximity are important for the manifestation of the discrimination. Multiple favourable influences of the stereochemistry of the natural chirality (D-form) of the sugar ring are noted. This explains the heterochiral relationship of the D-sugar and L-amino acid in biology. In addition to factors such as chirality, confinement and nanoscale proximity of the molecular segments, the network of electrostatic interaction present in the active site plays a significant role in the chiral discrimination in aminoacylation. Chiral discriminations in the biological cavities of nucleic acid and cyclodextrin are also briefly reviewed.

  13. Detection of ectopic B-cell follicles with germinal centers in the meninges of patients with secondary progressive multiple sclerosis.

    PubMed

    Serafini, Barbara; Rosicarelli, Barbara; Magliozzi, Roberta; Stigliano, Egidio; Aloisi, Francesca

    2004-04-01

    Multiple sclerosis (MS) is characterized by synthesis of oligoclonal immunoglobulins and the presence of B-cell clonal expansions in the central nervous system (CNS). Because ectopic lymphoid tissue generated at sites of chronic inflammation is thought to be important in sustaining immunopathological processes, we have investigated whether structures resembling lymphoid follicles could be identified in the CNS of MS patients. Sections from post-mortem MS brains and spinal cords were screened using immunohistochemistry for the presence of CD20+ B-cells, CD3+ T-cells, CD138+ plasma cells and CD21+, CD35+ follicular dendritic cells, and for the expression of lymphoid chemokines (CXCL 13, CCL21) and peripheral node addressin (PNAd). Lymphoid follicle-like structures containing B-cells, T-cells and plasma cells, and a network of follicular dendritic cells producing CXCL13 were observed in the cerebral meninges of 2 out of 3 patients with secondary progressive MS, but not in relapsing remitting and primary progressive MS. We also show that proliferating B-cells are present in intrameningeal follicles, a finding which is suggestive of germinal center formation. No follicle-like structures were detected in parenchymal lesions. The formation of ectopic lymphoid follicies in the meninges of patients with MS could represent a critical step in maintaining humoral autoimmunity and in disease exacerbation.

  14. A retrospective analysis of cytogenetic alterations in patients with newly diagnosed multiple myeloma: a single center study in Korea

    PubMed Central

    Li, Shuhua; Lim, Hyeon-Ho; Woo, Kwang-Sook; Kim, Sung-Hyun

    2016-01-01

    Background The accurate identification of cytogenetic abnormalities in multiple myeloma (MM) has become more important over recent years for the development of new diagnostic and prognostic markers. In this study, we retrospectively analyzed the cytogenetic aberrations in MM cases as an initial assessment in a single institute. Methods We reviewed the cytogenetic results from 222 patients who were newly diagnosed with MM between January 2000 and December 2015. Chromosomal analysis was performed on cultured bone marrow samples by standard G-banding technique. At least 20 metaphase cells were analyzed for karyotyping. Results Clonal chromosome abnormalities were detected in 45.0% (100/222) of the patients. Among these results, 80 cases (80.0%) had both numerical and structural chromosome abnormalities. Overall hyperdiploidy with structural cytogenetic aberrations was the most common finding (44.0%), followed by hypodiploidy with structural aberrations (28.0%). Amplification of the long arm of chromosome 1 and -13/del(13q) were the most frequent recurrent abnormalities, and were detected in 50 patients (50.0%) and 40 patients (40.0%) with clonal abnormalities, respectively. The most common abnormality involving 14q32 was t(11;14)(q13;q32), which was observed in 19 cases. Conclusion These findings demonstrate that myeloma cells exhibit complex aberrations regardless of ploidy, even from a single center in Korea. Conventional cytogenetic analysis should be included in the initial diagnostic work-up for patients suspected of having MM. PMID:27382557

  15. Asymmetric Synthesis of Chiral α-Methyl-α,β-diamino Acid Derivatives via Group-Assisted Purification Chemistry Using N-Phosphonyl Imines and a Ni(II)-Complexed Alanine Schiff Base.

    PubMed

    Zhang, Haowei; Yang, Bing; Yang, Zhen; Lu, Hongjian; Li, Guigen

    2016-09-01

    The Mannich reaction between chiral N-phosphonyl imines and a Ni(II)-complexed alanine Schiff base (Ala-Ni) is reported. With a chiral phosphonyl auxiliary, a single isomer of α-methyl-α,β-diamino acid derivative containing vicinal chiral centers, including a chiral quaternary carbon center, can be obtained simply by washing the crude mixture with cosolvents. The absolute stereochemistry of the enantiomerically pure product has been unambiguously determined by X-ray crystallographic analysis. PMID:27459278

  16. Yang-Mills theories with chiral matter at strong coupling

    SciTech Connect

    Shifman, M.; Uensal, Mithat

    2009-05-15

    Strong coupling dynamics of Yang-Mills theories with chiral fermion content remained largely elusive despite much effort over the years. In this work, we propose a dynamical framework in which we can address nonperturbative properties of chiral, nonsupersymmetric gauge theories, in particular, chiral quiver theories on S{sub 1}xR{sub 3}. Double-trace deformations are used to stabilize the center-symmetric vacuum. This allows one to smoothly connect small-r(S{sub 1}) to large-r(S{sub 1}) physics (R{sub 4} is the limiting case) where the double-trace deformations are switched off. In particular, the occurrence of the mass gap in the gauge sector and linear confinement due to bions are analytically demonstrated. We find the pattern of the chiral symmetry realization which depends on the structure of the monopole-ring operators, a novel class of topological excitations. The deformed chiral theory, unlike the undeformed one, satisfies volume independence down to arbitrarily small volumes (a working Eguchi-Kawai reduction) in the large N limit. This equivalence may open new perspectives on strong coupling chiral gauge theories on R{sub 4}.

  17. Optical properties of chiral nanotubes

    NASA Astrophysics Data System (ADS)

    Cecilia, Noguez; Román-Velázquez Carlos, E.; Ariadna, Sánchez; Montes Lilia, Meza

    2004-03-01

    A recent theoretical model [1] is applied to study the optical properties chiral nanostructures like carbon nanotubes. We calculate the Circular Dichroism (CD) spectra for carbon nanotubes with different chirality. The calculated CD spectra show features that allow us to distinguish between nanotubes with different indexes of chirality. Other nanostructures, like chiral fullerenes are also investigated.These results provide theoretical support for the quantification of chirality and its measurement, using the CD lineshapes of chiral. This work has been partly financed by CONACyT grant No. 36651-E and by DGAPA-UNAM grants No. IN104201. [1] C. E. Roman-Velazquez, et al., J. of Phys. Chem. B (Letter) 107, 12035 (2003)

  18. ENANTIOMER-SPECIFIC EFFECTS OF CHIRAL POLLUTANTS

    EPA Science Inventory

    Enantiomers, the mirror image isomers of chiral pollutants, are known to be selective in their interaction with other chiral molecules, including enzymes and other biochemicals. Considerable research has shown, for example, that chiral pesticides are degraded selectively by micr...

  19. CHIRAL--A Computer Aided Application of the Cahn-Ingold-Prelog Rules.

    ERIC Educational Resources Information Center

    Meyer, Edgar F., Jr.

    1978-01-01

    A computer program is described for identification of chiral centers in molecules. Essential input to the program includes both atomic and bonding information. The program does not require computer graphic input-output. (BB)

  20. Chiral Dynamics 2006

    NASA Astrophysics Data System (ADS)

    Ahmed, Mohammad W.; Gao, Haiyan; Weller, Henry R.; Holstein, Barry

    2007-10-01

    pt. A. Plenary session. Opening remarks: experimental tests of chiral symmetry breaking / A. M. Bernstein. [Double pie symbols] scattering / H. Leutwyler. Chiral effective field theory in a [Triangle]-resonance region / V. Pascalutsa. Some recent developments in chiral perturbation theory / Ulf-G. Mei ner. Chiral extrapolation and nucleon structure from the lattice / R.D. Young. Recent results from HAPPEX / R. Michaels. Chiral symmetries and low energy searches for new physics / M.J. Ramsey-Musolf. Kaon physics: recent experimental progress / M. Moulson. Status of the Cabibbo angle / V. Cirigliano. Lattice QCD and nucleon spin structure / J.W. Negele. Spin sum rules and polarizabilities: results from Jefferson lab / J-P Chen. Compton scattering and nucleon polarisabilities / Judith A. McGovern. Virtual compton scattering at MIT-bates / R. Miskimen. Physics results from the BLAST detector at the BATES accelerator / R.P. Redwine. The [Pie sympbol]NN system, recent progress / C. Hanhart. Application of chiral nuclear forces to light nuclei / A. Nogga. New results on few-body experiments at low energy / Y. Nagai. Few-body lattice calculations / M.J. Savage. Research opportunities at the upgraded HI?S facility / H.R. Weller -- pt. B. Goldstone boson dynamics. Working group summary: Goldstone Boson dynamics / G. Colangelo and S. Giovannella. Recent results on radiative Kaon decays from NA48 and NA48/2 / S.G. López. Cusps in K-->3 [Pie symbol] decays / B. Kubis. Recent KTeV results on radiative Kaon decays / M.C. Ronquest. The [Double pie symbols] scattering amplitude / J.R. Peláez. Determination of the Regge parameters in the [Double pie symbols] scattering amplitude / I. Caprini. e+e- Hadronic cross section measurement at DA[symbol]NE with the KLOE detector / P. Beltrame. Measurement of the form factors of e+e- -->2([Pie symbol]+[Pie symbol]-), pp and the resonant parameters of the heavy charmonia at BES / H. Hu. Measurement of e+e- multihadronic cross section below 4

  1. Chiral symmetry and pentaquarks

    SciTech Connect

    Dmitri Diakonov

    2004-07-01

    Spontaneous chiral symmetry breaking, mesons and baryons are illustrated in the language of the Dirac theory. Various forces acting between quarks inside baryons are discussed. I explain why the naive quark models typically overestimate pentaquark masses by some 500 MeV and why in the fully relativistic approach to baryons pentaquarks turn out to be light. I discuss briefly why it can be easier to produce pentaquarks at low than at high energies.

  2. Chiral Biomarkers in Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2010-01-01

    The chirality of organic molecules with the asymmetric location of group radicals was discovered in 1848 by Louis Pasteur during his investigations of the rotation of the plane of polarization of light by crystals of sodium ammonium paratartrate. It is well established that the amino acids in proteins are exclusively Levorotary (L-aminos) and the sugars in DNA and RNA are Dextrorotary (D-sugars). This phenomenon of homochirality of biological polymers is a fundamental property of all life known on Earth. Furthermore, abiotic production mechanisms typically yield recemic mixtures (i.e. equal amounts of the two enantiomers). When amino acids were first detected in carbonaceous meteorites, it was concluded that they were racemates. This conclusion was taken as evidence that they were extraterrestrial and produced by abiologically. Subsequent studies by numerous researchers have revealed that many of the amino acids in carbonaceous meteorites exhibit a significant L-excess. The observed chirality is much greater than that produced by any currently known abiotic processes (e.g. Linearly polarized light from neutron stars; Circularly polarized ultraviolet light from faint stars; optically active quartz powders; inclusion polymerization in clay minerals; Vester-Ulbricht hypothesis of parity violations, etc.). This paper compares the measured chirality detected in the amino acids of carbonaceous meteorites with the effect of these diverse abiotic processes. IT is concluded that the levels observed are inconsistent with post-arrival biological contamination or with any of the currently known abiotic production mechanisms. However, they are consistent with ancient biological processes on the meteorite parent body. This paper will consider these chiral biomarkers in view of the detection of possible microfossils found in the Orgueil and Murchison carbonaceous meteorites. Energy dispersive x-ray spectroscopy (EDS) data obtained on these morphological biomarkers will be

  3. Generalized simplicial chiral models

    NASA Astrophysics Data System (ADS)

    Alimohammadi, Masoud

    2000-02-01

    Using the auxiliary field representation of the simplicial chiral models on a ( d-1)-dimensional simplex, the simplicial chiral models are generalized through replacing the term Tr (AA †) in the Lagrangian of these models by an arbitrary class function of AA †; V(AA †) . This is the same method used in defining the generalized two-dimensional Yang-Mills theories (gYM 2) from ordinary YM 2. We call these models the "generalized simplicial chiral models". Using the results of the one-link integral over a U( N) matrix, the large- N saddle-point equations for eigenvalue density function ρ( z) in the weak ( β> βc) and strong ( β< βc) regions are computed. In d=2, where the model is in some sense related to the gYM 2 theory, the saddle-point equations are solved for ρ( z) in the two regions, and the explicit value of critical point βc is calculated for V(B)= Tr B n(B=AA †) . For V(B)= Tr B 2, Tr B 3, and Tr B4, the critical behaviour of the model at d=2 is studied, and by calculating the internal energy, it is shown that these models have a third order phase transition.

  4. Chiral microemulsion electrokinetic chromatography with two chiral components: Improved separations via synergies between a chiral surfactant and a chiral cosurfactant.

    PubMed

    Kahle, Kimberly A; Foley, Joe P

    2006-02-01

    In this study, the combination of two chiral components in a microemulsion formulation for the separation of enantiomers via microemulsion EKC (MEEKC) was successfully accomplished. Previous publications of chiral microemulsions have utilized only one chiral entity; the surfactant, cosurfactant, or oil was chiral. This is the first study, to date, of the effects of using two chiral species in a single pseudostationary phase (PSP). The chiral surfactant dodecoxycarbonylvaline (DDCV) was used in conjunction with the chiral cosurfactant S-2-hexanol. Ethyl acetate was incorporated as the oil core of the microemulsion and the buffer was 50 mM phosphate at a pH of 7. Additionally, a microemulsion prepared with racemic 2-hexanol was used for comparison to a previous DDCV microemulsion and as a baseline for the newly formulated dual chiral microemulsion. The efficiencies, resolutions, and enantioselectivities for the S-2-hexanol, racemic 2-hexanol, and original 1-butanol DDCV microemulsions are compared. The hexanol-based PSPs provide improved efficiencies and resolutions. To evaluate the combination of each DDCV enantiomer (R and S) with S-2-hexanol, changes in Gibb's free energy were calculated. A synergistic effect was found when two chiral components were combined to form a microemulsion.

  5. Multiple Scattering X-Ray Absorption Studies of Zn2+ Binding Sites in Bacterial Photosynthetic Reaction Centers

    PubMed Central

    Giachini, Lisa; Francia, Francesco; Mallardi, Antonia; Palazzo, Gerardo; Carpenè, Emilio; Boscherini, Federico; Venturoli, Giovanni

    2005-01-01

    Binding of transition metal ions to the reaction center (RC) protein of the photosynthetic bacterium Rhodobacter sphaeroides has been previously shown to slow light-induced electron and proton transfer to the secondary quinone acceptor molecule, QB. On the basis of x-ray diffraction at 2.5 Å resolution a site, formed by AspH124, HisH126, and HisH128, has been identified at the protein surface which binds Cd2+ or Zn2+. Using Zn K-edge x-ray absorption fine structure spectroscopy we report here on the local structure of Zn2+ ions bound to purified RC complexes embedded into polyvinyl alcohol films. X-ray absorption fine structure data were analyzed by combining ab initio simulations and multiparameter fitting; structural contributions up to the fourth coordination shell and multiple scattering paths (involving three atoms) have been included. Results for complexes characterized by a Zn to RC stoichiometry close to one indicate that Zn2+ binds two O and two N atoms in the first coordination shell. Higher shell contributions are consistent with a binding cluster formed by two His, one Asp residue, and a water molecule. Analysis of complexes characterized by ∼2 Zn ions per RC reveals a second structurally distinct binding site, involving one O and three N atoms, not belonging to a His residue. The local structure obtained for the higher affinity site nicely fits the coordination geometry proposed on the basis of x-ray diffraction data, but detects a significant contraction of the first shell. Two possible locations of the second new binding site at the cytoplasmic surface of the RC are proposed. PMID:15613631

  6. Cyclotriphosphazene appended porphyrins and fulleropyrrolidine complexes as supramolecular multiple photosynthetic reaction centers: steady and excited states photophysical investigation.

    PubMed

    Nair, Vishnu Sukumaran; Pareek, Yogita; Karunakaran, Venugopal; Ravikanth, Mangalampalli; Ajayaghosh, Ayyappanpillai

    2014-06-01

    New multiple photosynthetic reaction centers were constructed from cyclophosphazene decorated multiporphyrin chromophores and a fulleropyrrolidine having a pyridine ligand (FPY). The excited state electron transfer in the self-assembled donor-acceptor assembly was investigated by using steady state absorption and emission, time-resolved emission spectroscopy and nanosecond laser flash photolysis. The effect of metal (Zn(2+)) coordination to porphyrin units in the multiporphyrin arrays on cyclophosphazine scaffold (P3N3Zn) was studied by comparing with metal free porphyrin assembly on a cyclophosphazene scaffold (P3N3). In P3N3Zn, the decrease of absorption and fluorescence intensity and the lowering of the amplitude of longer fluorescence lifetime with increase of FPY concentration reflect the formation of a ground state complex with an association constant of ∼14,910 M(-1). When compared to the metal-free complex P3N3, the metal-coordinated derivative P3N3Zn exhibited shortening of the singlet and triplet state lifetimes and lowering of the singlet and triplet quantum yields. The cause of the decrease of the triplet quantum yields by insertion of zinc metal is discussed along with the possible non-planarity of the porphyrin ring. From the fluorescence lifetime measurements for the P3N3Zn-FPY mixture, it is proposed that self-assembly of the donor-acceptor complex leads to charge separated species with a rate constant of 7.1 × 10(9) s(-1). The decrease of triplet state intensity and lifetime of the P3N3Zn in the P3N3Zn-FPY complex from the nanosecond transient absorption studies support the occurrence of intermolecular electron transfer in the triplet state.

  7. Chiral drag force

    NASA Astrophysics Data System (ADS)

    Rajagopal, Krishna; Sadofyev, Andrey V.

    2015-10-01

    We provide a holographic evaluation of novel contributions to the drag force acting on a heavy quark moving through strongly interacting plasma. The new contributions are chiral in the sense that they act in opposite directions in plasmas containing an excess of left- or right-handed quarks. The new contributions are proportional to the coefficient of the axial anomaly, and in this sense also are chiral. These new contributions to the drag force act either parallel to or antiparallel to an external magnetic field or to the vorticity of the fluid plasma. In all these respects, these contributions to the drag force felt by a heavy quark are analogous to the chiral magnetic effect (CME) on light quarks. However, the new contribution to the drag force is independent of the electric charge of the heavy quark and is the same for heavy quarks and antiquarks, meaning that these novel effects do not in fact contribute to the CME current. We show that although the chiral drag force can be non-vanishing for heavy quarks that are at rest in the local fluid rest frame, it does vanish for heavy quarks that are at rest in a suitably chosen frame. In this frame, the heavy quark at rest sees counterpropagating momentum and charge currents, both proportional to the axial anomaly coefficient, but feels no drag force. This provides strong concrete evidence for the absence of dissipation in chiral transport, something that has been predicted previously via consideration of symmetries. Along the way to our principal results, we provide a general calculation of the corrections to the drag force due to the presence of gradients in the flowing fluid in the presence of a nonzero chemical potential. We close with a consequence of our result that is at least in principle observable in heavy ion collisions, namely an anticorrelation between the direction of the CME current for light quarks in a given event and the direction of the kick given to the momentum of all the heavy quarks and

  8. Isothermal Titration Calorimetry of Chiral Polymeric Nanoparticles.

    PubMed

    Werber, Liora; Preiss, Laura C; Landfester, Katharina; Muñoz-Espí, Rafael; Mastai, Yitzhak

    2015-09-01

    Chiral polymeric nanoparticles are of prime importance, mainly due to their enantioselective potential, for many applications such as catalysis and chiral separation in chromatography. In this article we report on the preparation of chiral polymeric nanoparticles by miniemulsion polymerization. In addition, we describe the use of isothermal titration calorimetry (ITC) to measure the chiral interactions and the energetics of the adsorption of enantiomers from aqueous solutions onto chiral polymeric nanoparticles. The characterization of chirality in nano-systems is a very challenging task; here, we demonstrate that ITC can be used to accurately determine the thermodynamic parameters associated with the chiral interactions of nanoparticles. The use of ITC to measure the energetics of chiral interactions and recognition at the surfaces of chiral nanoparticles can be applied to other nanoscale chiral systems and can provide further insight into the chiral discrimination processes of nanomaterials.

  9. Chiral Crystallization of Ethylenediamine Sulfate

    ERIC Educational Resources Information Center

    Koby, Lawrence; Ningappa, Jyothi B.; Dakesssian, Maria; Cuccia, Louis A.

    2005-01-01

    The optimal conditions for the crystallization of achiral ethylenediamine sulfate into large chiral crystals that are ideal for polarimetry studies and observation using Polaroid sheets are presented. This experiment is an ideal undergraduate experiment, which clearly demonstrates the chiral crystallization of an achiral molecule.

  10. CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

    Like amino acids, certain pesticides exist in "left-handed" and "right-handed" (chiral) forms. Commercially available chiral pesticides are produced as racemic mixtures in which the ratio of the two forms (or enantiomers) is 1:1. Enantiomers have the same ...

  11. Chirality-Dependent Hall Effect in Weyl Semimetals.

    PubMed

    Yang, Shengyuan A; Pan, Hui; Zhang, Fan

    2015-10-01

    We generalize a semiclassical theory and use the argument of angular momentum conservation to examine the ballistic transport in lightly doped Weyl semimetals, taking into account various phase-space Berry curvatures. We predict universal transverse shifts of the wave-packet center in transmission and reflection, perpendicular to the direction in which the Fermi energy or velocities change adiabatically. The anomalous shifts are opposite for electrons with different chirality, and they can be made imbalanced by breaking inversion symmetry. We discuss how to utilize local gates, strain effects, and circularly polarized lights to generate and probe such a chirality-dependent Hall effect.

  12. Control of oxygen atom chirality and chelate ring conformation by protected/free sugar hydroxyl groups in glucose-pendant dipicolylamine-copper(II) complexes.

    PubMed

    Mikata, Yuji; Sugai, Yuko; Yano, Shigenobu

    2004-08-01

    A pair of copper(II) complexes 1 and 2 exhibit an enantiomeric chiral center at the oxygen atom that coordinates to the metal center. The configurations of the oxygen atom chirality and the chelate ring conformation are simply controlled by protected/free hydroxyl groups of the sugar moiety, yielding mirror image CD spectra. In this system, repulsive and attractive forces are used to regulate chirality on the copper-coordinated oxygen atom both in the solid state and in solution.

  13. Controlling Chirality of Entropic Crystals

    NASA Astrophysics Data System (ADS)

    Damasceno, Pablo F.; Karas, Andrew S.; Schultz, Benjamin A.; Engel, Michael; Glotzer, Sharon C.

    2015-10-01

    Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams.

  14. Controlling Chirality of Entropic Crystals.

    PubMed

    Damasceno, Pablo F; Karas, Andrew S; Schultz, Benjamin A; Engel, Michael; Glotzer, Sharon C

    2015-10-01

    Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams. PMID:26550757

  15. Chiral Shielding Revisited

    SciTech Connect

    Scadron, M. D.

    2008-08-31

    A model-independent chiral soft-pion theorem (SPT) shields the now observed scalar-meson ground-state isoscalar {sigma}(600) and isospinor {kappa}(800) resonances from detection in a{sub 1}{yields}{pi}({pi}{pi}){sub S-wave}, {gamma}{gamma}{yields}2{pi}{sup 0}, {pi}{sup -}P{yields}{pi}{sup -}{pi}{sup +}n, and K{sup -}P{yields}K{sup -}{pi}{sup +}n processes. Moreover, for pseudoscalar-to-vector-vector (PVV) decays, quark loops only are required.

  16. Candidates for twin chiral bands in 102Rh.

    PubMed

    Tonev, D; Yavahchova, M S; Goutev, N; de Angelis, G; Petkov, P; Bhowmik, R K; Singh, R P; Muralithar, S; Madhavan, N; Kumar, R; Kumar Raju, M; Kaur, J; Mohanto, G; Singh, A; Kaur, N; Garg, R; Shukla, A; Marinov, Ts K; Brant, S

    2014-02-01

    Excited states in 102Rh, populated in the fusion-evaporation reaction Zr94(11B,3n)102Rh at a beam energy of 36 MeV, were studied using the Indian National Gamma Array spectrometer at Inter University Accelerator Center, New Delhi. The angular correlations and the electromagnetic character of some of the gamma-ray transitions observed were investigated in detail. A new chiral candidate sister band was found. Lifetimes of exited states in both chiral candidate bands of 102Rh were measured for the first time in the A∼100 mass region by means of the Doppler-shift attenuation technique. The derived reduced transition probabilities are compared to the predictions of the two quasiparticles plus triaxial rotor model. Both experimental results and calculations do not support the presence of static chirality in 102Rh. PMID:24580588

  17. Multi-criteria clinical decision support: A primer on the use of multiple criteria decision making methods to promote evidence-based, patient-centered healthcare.

    PubMed

    Dolan, James G

    2010-01-01

    Current models of healthcare quality recommend that patient management decisions be evidence-based and patient-centered. Evidence-based decisions require a thorough understanding of current information regarding the natural history of disease and the anticipated outcomes of different management options. Patient-centered decisions incorporate patient preferences, values, and unique personal circumstances into the decision making process and actively involve both patients along with health care providers as much as possible. Fundamentally, therefore, evidence-based, patient-centered decisions are multi-dimensional and typically involve multiple decision makers.Advances in the decision sciences have led to the development of a number of multiple criteria decision making methods. These multi-criteria methods are designed to help people make better choices when faced with complex decisions involving several dimensions. They are especially helpful when there is a need to combine "hard data" with subjective preferences, to make trade-offs between desired outcomes, and to involve multiple decision makers. Evidence-based, patient-centered clinical decision making has all of these characteristics. This close match suggests that clinical decision support systems based on multi-criteria decision making techniques have the potential to enable patients and providers to carry out the tasks required to implement evidence-based, patient-centered care effectively and efficiently in clinical settings.The goal of this paper is to give readers a general introduction to the range of multi-criteria methods available and show how they could be used to support clinical decision-making. Methods discussed include the balance sheet, the even swap method, ordinal ranking methods, direct weighting methods, multi-attribute decision analysis, and the analytic hierarchy process (AHP).

  18. Pion and kaon masses in staggered chiral perturbation theory

    NASA Astrophysics Data System (ADS)

    Aubin, C.; Bernard, C.

    2003-08-01

    We show how to compute chiral logarithms that take into account both the O(a2) taste-symmetry breaking of staggered fermions and the fourth-root trick that produces one taste per flavor. The calculation starts from the Lee-Sharpe Lagrangian generalized to multiple flavors. An error in a previous treatment by one of us is explained and corrected. The one loop chiral logarithm corrections to the pion and kaon masses in the full (unquenched), partially quenched, and quenched cases are computed as examples.

  19. Chirality and catalysis with aromatic N-fused heterobicyclic carbenes.

    PubMed

    Iglesias-Sigüenza, Javier; Izquierdo, Cristina; Díez, Elena; Fernández, Rosario; Lassaletta, José M

    2016-06-21

    The benzoannulation of the most common families of aromatic NHCs, imidazol-2-ylidenes and 1,2,4-triazol-3-ylidenes, results in heterobicyclic imidazo[1,5-a]pyridin-3-ylidenes ('s) and [1,2,4]triazolo[4,3-a]pyridin-3-ylidenes ('s), characterized by a bridged N atom. These are versatile platforms that offer multiple possibilities for the modulation of the steric and electronic properties of the carbene ligand and/or organocatalyst, and offer also diverse opportunities for the introduction of several types of chiralities. In this paper the different families of chiral and carbenes and their application in asymmetric catalysis will be discussed.

  20. Chiral limit of QCD

    SciTech Connect

    Gupta, R.

    1994-12-31

    This talk contains an analysis of quenched chiral perturbation theory and its consequences. The chiral behavior of a number of quantities such as the pion mass m{sub pi}{sup 2}, the Bernard-Golterman ratios R and {sub X}, the masses of nucleons, and the kaon B-parameter are examined to see if the singular terms induced by the additional Goldstone boson, {eta}{prime}, are visible in present data. The overall conclusion (different from that presented at the lattice meeting) of this analysis is that even though there are some caveats attached to the indications of the extra terms induced by {eta}{prime} loops, the standard expressions break down when extrapolating the quenched data with m{sub q} < m{sub s}/2 to physical light quarks. I then show that due to the single and double poles in the quenched {eta}{prime}, the axial charge of the proton cannot be calculated using the Adler-Bell-Jackiw anomaly condition. I conclude with a review of the status of the calculation of light quark masses from lattice QCD.

  1. Phase diagrams for the blue phases of highly chiral liquid crystals

    NASA Astrophysics Data System (ADS)

    Bowling, Miriam B.; Collings, Peter J.; Booth, Christopher J.; Goodby, John W.

    1993-11-01

    Polarizing microscopy and optical-activity measurements are used to determine the phase diagram for the blue phases of chiral-racemic mixtures of terephthaloyloxy-bis-4-(2'-methylbutyl) benzoate. Contrary to an earlier report, it is the second blue phase (BP II) rather than the first blue phase (BP I) that is not stable relative to the other blue phases at high chirality. With this development, all phase diagrams for the blue phases reported to date have the same topology. Using similar data for two other highly chiral systems, it is found that a simple scaling of the temperature and chiral-fraction axes produces phase diagrams in quantitative agreement with the present results. Thus, in spite of differences in molecular structure, the number of chiral centers, and phase-transition temperatures, these three systems possess remarkably similar phase diagrams and lend evidence for a universal phase diagram for the blue phases.

  2. Chiral quantum dot based materials

    NASA Astrophysics Data System (ADS)

    Govan, Joseph; Loudon, Alexander; Baranov, Alexander V.; Fedorov, Anatoly V.; Gun'ko, Yurii

    2014-05-01

    Recently, the use of stereospecific chiral stabilising molecules has also opened another avenue of interest in the area of quantum dot (QD) research. The main goal of our research is to develop new types of technologically important quantum dot materials containing chiral defects, study their properties and explore their applications. The utilisation of chiral penicillamine stabilisers allowed the preparation of new water soluble white emitting CdS quantum nanostructures which demonstrated circular dichroism in the band-edge region of the spectrum. It was also demonstrated that all three types of QDs (D-, L-, and Rac penicillamine stabilised) show very broad emission bands between 400 and 700 nm due to defects or trap states on the surfaces of the nanocrystals. In this work the chiral CdS based quantum nanostructures have also been doped by copper metal ions and new chiral penicilamine stabilized CuS nanoparticles have been prepared and investigated. It was found that copper doping had a strong effect at low levels in the synthesis of chiral CdS nanostructures. We expect that this research will open new horizons in the chemistry of chiral nanomaterials and their application in biotechnology, sensing and asymmetric synthesis.

  3. Chiral perturbation theory with nucleons

    SciTech Connect

    Meissner, U.G.

    1991-09-01

    I review the constraints posed on the interactions of pions, nucleons and photons by the spontaneously broken chiral symmetry of QCD. The framework to perform these calculations, chiral perturbation theory, is briefly discussed in the meson sector. The method is a simultaneous expansion of the Greens functions in powers of external moments and quark masses around the massless case, the chiral limit. To perform this expansion, use is made of a phenomenological Lagrangian which encodes the Ward-identities and pertinent symmetries of QCD. The concept of chiral power counting is introduced. The main part of the lectures of consists in describing how to include baryons (nucleons) and how the chiral structure is modified by the fact that the nucleon mass in the chiral limit does not vanish. Particular emphasis is put on working out applications to show the strengths and limitations of the methods. Some processes which are discussed are threshold photopion production, low-energy compton scattering off nucleons, {pi}N scattering and the {sigma}-term. The implications of the broken chiral symmetry on the nuclear forces are briefly described. An alternative approach, in which the baryons are treated as very heavy fields, is touched upon.

  4. Fluid-Gravity Model for the Chiral Magnetic Effect

    SciTech Connect

    Kalaydzhyan, Tigran; Kirsch, Ingo

    2011-05-27

    We consider the STU model as a gravity dual of a strongly coupled plasma with multiple anomalous U(1) currents. In the bulk we add additional background gauge fields to include the effects of external electric and magnetic fields on the plasma. Reducing the number of chemical potentials in the STU model to two and interpreting them as quark and chiral chemical potential, we obtain a holographic description of the chiral magnetic and chiral vortical effects (CME and CVE) in relativistic heavy-ion collisions. These effects formally appear as first-order transport coefficients in the electromagnetic current. We compute these coefficients from our model using fluid-gravity duality. We also find analogous effects in the axial-vector current. Finally, we briefly discuss a variant of our model, in which the CME/CVE is realized in the late-time dynamics of an expanding plasma.

  5. Fluid-gravity model for the chiral magnetic effect.

    PubMed

    Kalaydzhyan, Tigran; Kirsch, Ingo

    2011-05-27

    We consider the STU model as a gravity dual of a strongly coupled plasma with multiple anomalous U(1) currents. In the bulk we add additional background gauge fields to include the effects of external electric and magnetic fields on the plasma. Reducing the number of chemical potentials in the STU model to two and interpreting them as quark and chiral chemical potential, we obtain a holographic description of the chiral magnetic and chiral vortical effects (CME and CVE) in relativistic heavy-ion collisions. These effects formally appear as first-order transport coefficients in the electromagnetic current. We compute these coefficients from our model using fluid-gravity duality. We also find analogous effects in the axial-vector current. Finally, we briefly discuss a variant of our model, in which the CME/CVE is realized in the late-time dynamics of an expanding plasma. PMID:21699286

  6. Nuclear chiral and magnetic rotation in covariant density functional theory

    NASA Astrophysics Data System (ADS)

    Meng, Jie; Zhao, Pengwei

    2016-05-01

    Excitations of chiral rotation observed in triaxial nuclei and magnetic and/or antimagnetic rotations (AMR) seen in near-spherical nuclei have attracted a lot of attention. Unlike conventional rotation in well-deformed or superdeformed nuclei, here the rotational axis is not necessary coinciding with any principal axis of the nuclear density distribution. Thus, tilted axis cranking (TAC) is mandatory to describe these excitations self-consistently in the framework of covariant density functional theory (CDFT). We will briefly introduce the formalism of TAC-CDFT and its application for magnetic and AMR phenomena. Configuration-fixed CDFT and its predictions for nuclear chiral configurations and for favorable triaxial deformation parameters are also presented, and the discoveries of the multiple chiral doublets in 133Ce and 103Rh are discussed.

  7. Chiral analysis by capillary electrophoresis using antibiotics as chiral selector.

    PubMed

    Desiderio, C; Fanali, S

    1998-05-20

    The separation of chiral compounds by capillary electrophoresis (CE) is a very interesting field of research in different areas such as pharmaceutical, environmental, agricultural analysis etc. The separation of two enantiomers can be achieved in CE using a chiral environment interacting with the two analytes on forming diastereoisomers with different stability constants and thus different mobilities. A wide number of chiral selectors have been employed in CE and among them glycopeptide antibiotics exhibited excellent enantioselective properties towards a wide number of racemic compounds. Vancomycin, ristocetin A, rifamycins, teicoplanin, kanamycin, streptomycin, fradiomycin, and two vancomycin analogues, added to the background electrolyte (BGE), are the antibiotics studied by CE running the separation in untreated and/or coated fused-silica capillary. Due to adsorption and absorption phenomena, some drawbacks can be expected when using bare fused-silica capillary, e.g., changes of electroosmotic flow (EOF), broaden peaks, reduced efficiency and low sensitivity. Coated capillary and counter current mode can be the solution to overcome the above mentioned problems. This review surveys the separation of enantiomers by CE when macrocyclic antibiotics are used as chiral selector. The enantioselectivity can be easily controlled modifying several parameters such as antibiotic type and concentration, pH, ionic strength and concentration of the background electrolyte, organic modifier etc. The paper also presents a list of the latest chiral separations achieved by CE where antibiotics were used as chiral selector.

  8. Chirality in photonic systems

    NASA Astrophysics Data System (ADS)

    Solnyshkov, Dmitry; Malpuech, Guillaume

    2016-10-01

    The optical modes of photonic structures are the so-called TE and TM modes that bring intrinsic spin-orbit coupling and chirality to these systems. This, combined with the unique flexibility of design of the photonic potential, and the possibility to mix photon states with excitonic resonances, sensitive to magnetic field and interactions, allows us to achieve many phenomena, often analogous to other solid-state systems. In this contribution, we review in a qualitative and comprehensive way several of these realizations, namely the optical spin Hall effect, the creation of spin currents protected by a non-trivial geometry, the Berry curvature for photons, and the photonic/polaritonic topological insulator.

  9. Amino Acids and Chirality

    NASA Technical Reports Server (NTRS)

    Cook, Jamie E.

    2012-01-01

    Amino acids are among the most heavily studied organic compound class in carbonaceous chondrites. The abundance, distributions, enantiomeric compositions, and stable isotopic ratios of amino acids have been determined in carbonaceous chondrites fi'om a range of classes and petrographic types, with interesting correlations observed between these properties and the class and typc of the chondritcs. In particular, isomeric distributions appear to correlate with parent bodies (chondrite class). In addition, certain chiral amino acids are found in enantiomeric excess in some chondrites. The delivery of these enantiomeric excesses to the early Earth may have contributed to the origin of the homochirality that is central to life on Earth today. This talk will explore the amino acids in carbonaceous chondritcs and their relevance to the origin of life.

  10. In situ synthesis of di-n-butyl l-tartrate-boric acid complex chiral selector and its application in chiral microemulsion electrokinetic chromatography.

    PubMed

    Hu, Shaoqiang; Chen, Yonglei; Zhu, Huadong; Zhu, Jinhua; Yan, Na; Chen, Xingguo

    2009-11-01

    A novel procedure for in situ assembling a complex chiral selector, di-n-butyl l-tartrate-boric acid complex, by the reaction of di-n-butyl l-tartrate with boric acid in a running buffer was reported and its application in the enantioseparation of beta-blockers and structural related compounds by chiral microemulsion electrokinetic chromatography (MEEKC) has been demonstrated. In order to achieve a good enantioseparation, the effect of dibutyl l-tartrate and sodium tetraborate concentration, surfactant identity and concentration, cosurfactant, buffer pH and composition, organic modifiers, as well as applied voltage and capillary length were investigated. Ten pairs of enantiomers that could not be separated with only dibutyl l-tartrate, obtained good chiral separation using the complex chiral selector; among them, seven pairs could be baseline resolved under optimized experimental conditions. The fixation of chiral centers by the formation of five-membered rings, and being oppositely charged with basic analytes were thought to be the key factors giving the complex chiral selector a superior chiral recognition capability. The effect of the molecular structure of analytes on enantioseparation was discussed in terms of molecular interaction.

  11. Chiral Bosonization of Superconformal Ghosts

    NASA Technical Reports Server (NTRS)

    Shi, Deheng; Shen, Yang; Liu, Jinling; Xiong, Yongjian

    1996-01-01

    We explain the difference of the Hilbert space of the superconformal ghosts (beta,gamma) system from that of its bosonized fields phi and chi. We calculate the chiral correlation functions of phi, chi fields by inserting appropriate projectors.

  12. Life's chirality from prebiotic environments

    NASA Astrophysics Data System (ADS)

    Gleiser, Marcelo; Walker, Sara Imari

    2012-10-01

    A key open question in the study of life is the origin of biomolecular homochirality: almost every life-form on Earth has exclusively levorotary amino acids and dextrorotary sugars. Will the same handedness be preferred if life is found elsewhere? We review some of the pertinent literature and discuss recent results suggesting that life's homochirality resulted from sequential chiral symmetry breaking triggered by environmental events. In one scenario, autocatalytic prebiotic reactions undergo stochastic fluctuations due to environmental disturbances, in a mechanism reminiscent of evolutionary punctuated equilibrium: short-lived destructive events may lead to long-term enantiomeric excess. In another, chiral-selective polymerization reaction rates influenced by environmental effects lead to substantial chiral excess even in the absence of autocatalysis. Applying these arguments to other potentially life-bearing platforms has implications to the search for extraterrestrial life: we predict that a statistically representative sampling of extraterrestrial stereochemistry will be racemic (chirally neutral) on average.

  13. Chiral metallohelical complexes enantioselectively target amyloid β for treating Alzheimer's disease.

    PubMed

    Li, Meng; Howson, Suzanne E; Dong, Kai; Gao, Nan; Ren, Jinsong; Scott, Peter; Qu, Xiaogang

    2014-08-20

    Stereochemistry is a very important issue for the pharmaceutical industry and can determine drug efficacy. The design and synthesis of small molecules, especially chiral molecules, which selectively target and inhibit amyloid-β (Aβ) aggregation, represent valid therapeutic strategies for treatment of Alzheimer's disease (AD). Herein we report that two triple-helical dinuclear metallosupramolecular complexes can act as a novel class of chiral amyloid-β inhibitors. Through targeting α/β-discordant stretches at the early steps of aggregation, these metal complexes can enantioselectively inhibit Aβ aggregation, which is demonstrated using fluorescent living cell-based screening and multiple biophysical and biochemical approaches. To the best of our knowledge, this is the first report of enantioselective inhibition of Aβ aggregation. Intriguingly, as a promising candidate for AD treatment, the chiral metal complex can cross the blood-brain barrier and have superoxide dismutase activity. It is well-known that chiral discrimination is important for understanding chiral drug action. Generally, one enantiomer is pharmaceutically active while the other is inactive or exerts severe side effects. Chiral discrimination should be important for AD treatment. Our work provides new insights into chiral inhibition of Aβ aggregation and opens a new avenue for design and screening of chiral agents as Aβ inhibitors against AD. PMID:25062433

  14. Application of chiral critical clusters to assymetric synthesis

    DOEpatents

    Ferrieri, Richard A.

    2002-01-01

    Disclosed is a composition, a method of making and a method of using critical clusters for asymmetric synthesis using substantially optically-pure chiral solvent molecules in a supercritical fluid. The solvent molecules are capable of forming a multipoint hydrogen bonded solvate as they encage at least one solute molecule. The encaged solute molecule is capable of reacting to form an optically active chiral center. In another aspect, there is disclosed a method of directing the position of bonding between a solute molecule and a ligand involving encaging the solute molecule and the ligand with polar solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to change electric charge distribution in the solute molecule. In yet another aspect, disclosed is a method of making pharmaceutical compounds involving encaging a solute molecule, which is capable of forming a chiral center, and a ligand with polar solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to change electric charge distribution of the solute molecule. The solute molecule and ligand are then reacted whereby the ligand bonds to the solute molecule forming a chiral center. Also disclosed is a method for racemic resolution using critical clusters involving encaging racemic mixtures of solute molecules with substantially optically-pure chiral solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to form critical clusters. The solvent molecules are capable of multipoint hydrogen bonding with the solute molecules. The encaged solute molecules are then nonenzymatically reacted to enhance the optical purity of the solute molecules.

  15. Discovery of the interstellar chiral molecule propylene oxide (CH3CHCH2O)

    NASA Astrophysics Data System (ADS)

    McGuire, Brett A.; Carroll, P. Brandon; Loomis, Ryan A.; Finneran, Ian A.; Jewell, Philip R.; Remijan, Anthony J.; Blake, Geoffrey A.

    2016-06-01

    Life on Earth relies on chiral molecules—that is, species not superimposable on their mirror images. This manifests itself in the selection of a single molecular handedness, or homochirality, across the biosphere. We present the astronomical detection of a chiral molecule, propylene oxide (CH3CHCH2O), in absorption toward the Galactic center. Propylene oxide is detected in the gas phase in a cold, extended molecular shell around the embedded, massive protostellar clusters in the Sagittarius B2 star-forming region. This material is representative of the earliest stage of solar system evolution in which a chiral molecule has been found.

  16. Discovery of the interstellar chiral molecule propylene oxide (CH₃CHCH₂O).

    PubMed

    McGuire, Brett A; Carroll, P Brandon; Loomis, Ryan A; Finneran, Ian A; Jewell, Philip R; Remijan, Anthony J; Blake, Geoffrey A

    2016-06-17

    Life on Earth relies on chiral molecules-that is, species not superimposable on their mirror images. This manifests itself in the selection of a single molecular handedness, or homochirality, across the biosphere. We present the astronomical detection of a chiral molecule, propylene oxide (CH3CHCH2O), in absorption toward the Galactic center. Propylene oxide is detected in the gas phase in a cold, extended molecular shell around the embedded, massive protostellar clusters in the Sagittarius B2 star-forming region. This material is representative of the earliest stage of solar system evolution in which a chiral molecule has been found.

  17. Discovery of the interstellar chiral molecule propylene oxide (CH₃CHCH₂O).

    PubMed

    McGuire, Brett A; Carroll, P Brandon; Loomis, Ryan A; Finneran, Ian A; Jewell, Philip R; Remijan, Anthony J; Blake, Geoffrey A

    2016-06-17

    Life on Earth relies on chiral molecules-that is, species not superimposable on their mirror images. This manifests itself in the selection of a single molecular handedness, or homochirality, across the biosphere. We present the astronomical detection of a chiral molecule, propylene oxide (CH3CHCH2O), in absorption toward the Galactic center. Propylene oxide is detected in the gas phase in a cold, extended molecular shell around the embedded, massive protostellar clusters in the Sagittarius B2 star-forming region. This material is representative of the earliest stage of solar system evolution in which a chiral molecule has been found. PMID:27303055

  18. Implementation of a Community-Based Family-Centered Program in Portugal: A Multiple Case Study Evaluation

    ERIC Educational Resources Information Center

    Teixeira de Melo, Ana; Alarcao, Madalena

    2012-01-01

    Family-centered, community-based programs are particularly suited to support families with at-risk children or maltreated children and achieve family preservation or reunification. In these child protection and child welfare cases, assessment is of great importance to inform decision making. But the implementation of services to support the…

  19. A Person-Centered Approach to P-E Fit Questions Using a Multiple-Trait Model.

    ERIC Educational Resources Information Center

    De Fruyt, Filip

    2002-01-01

    Employed college students (n=401) completed the Self-Directed Search and NEO Personality Inventory-Revised. Person-environment fit across Holland's six personality types predicted job satisfaction and skill development. Five-Factor Model traits significantly predicted intrinsic career outcomes. Use of the five-factor, person-centered approach to…

  20. Rotation of the chiral bag

    NASA Astrophysics Data System (ADS)

    Kahana, David E.; Jackson, A. D.; Ripka, G.

    1986-11-01

    Cranking of the chiral bag model is carried out in order to generate the correct quantum numbers for SU(2) baryons. The moment of inertia of the system is found to be divided between the meson and quark sectors. A numerical evaluation of the contributions to the moment of inertia from valence quarks and from mesons is presented. Finally, a discussion is given of the nucleon-delta mass splitting predicted in the chiral bag model.

  1. Gluons in the chiral bag

    NASA Astrophysics Data System (ADS)

    Kahana, D. E.; Milana, J.

    1987-07-01

    A perturbative QCD calculation of gluon exchange corrections to the cranking moment of inertia of the chiral bag model is done using the full time-dependent cavity propagators. Cranking is used to construct the nucleon and delta states and a value of the effective strong coupling constant is extracted by fitting the empirical Δ N mass splitting. The MIT bag limit (large bag radius) of the chiral bag model is also examined.

  2. Optical properties of chiral nanostructures

    NASA Astrophysics Data System (ADS)

    Cecilia, Noguez; Román-Velázquez, Carlos E.; Garzón, Ignacio L.

    2004-03-01

    We present a computational model to study the optical properties chiral nanostructures[1] . In this work the nanostructures of interest are composed by N atoms, where each one is represented by a polarizable point dipole located at theposition of the atom. We assume that the dipole located is characterized by a polarizability. The nanostructure is excited by a circularly polarized incident wave, such that, each dipole is subject to a total electric field due to: (i) the incident radiation field, plus (ii) the radiation field resulting from all of the other induced dipoles. Once we solve the complex-linear equations, the dipole moment on each atom in the cluster can be determined and we can find the extinction cross section of the whole nanoparticle. Circular dichroism (CD) spectra of chiral bare and thiol-passivated gold nanoclusters have been calculated within the dipole approximation. The calculated CD spectra show features that allow us to distinguish between clusters with different indexes of chirality. The main factor responsible of the differences in the CD lineshapes is the distribution of interatomic distances that characterize the chiral cluster geometry. These results provide theoretical support for the quantification of chirality and its measurement, using the CD lineshapes of chiral metal nanoclusters. [1] C. E. Roman-Velazquez, et al., J. of Phys. Chem. B (Letter) 107, 12035 (2003) This work has been partly supported by DGAPA-UNAM grants No. IN104201 and IN104402, and by CONACyT grant 36651-E.

  3. Chiral expression at the solid-liquid interface: a joint experimental and theoretical study of the self-assembly of chiral porphyrins on graphite.

    PubMed

    Linares, Mathieu; Iavicoli, Patrizia; Psychogyiopoulou, Krystallia; Beljonne, David; De Feyter, Steven; Amabilino, David B; Lazzaroni, Roberto

    2008-09-01

    The chiral organization of an enantiopure functional molecule on an achiral surface has been studied with the aim of understanding the influence of stereogenic centers on the self-assembly in two dimensions. A chiral tetra meso-amidophenyl-substituted porphyrin containing long hydrophobic tails at the periphery of the conjugated pi-electron system was prepared for this purpose. Scanning tunneling microscopy (STM) images of the compound at the graphite-heptanol interface reveal a chiral arrangement of the molecules, with the porphyrin rows tilted by 13 degrees with respect to the normal to the graphite axes. In terms of molecular modeling, a combination of molecular dynamics simulations on systems constrained by periodic boundary conditions and on unconstrained large molecular aggregates has been applied to reach a quantitative interpretation on both the density of the layer and its orientation with respect to the graphite surface. The results show clearly that (i) the methyl groups of the stereogenic point toward the graphite surface and (ii) the porphyrin molecules self-assemble into an interdigitated structure where the alkyl chains align along one of the graphite axes and the porphyrin cores are slightly shifted with respect to one another. The direction of this shift, which defines the chirality of the monolayer, is set by the chirality of the stereogenic centers. Such an arrangement results in the formation of a dense chiral monolayer that is further stabilized by hydrogen bonding with protic solvents.

  4. Bottom-up synthesis of chiral covalent organic frameworks and their bound capillaries for chiral separation

    PubMed Central

    Qian, Hai-Long; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2016-01-01

    Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application. PMID:27401541

  5. Bottom-up synthesis of chiral covalent organic frameworks and their bound capillaries for chiral separation

    NASA Astrophysics Data System (ADS)

    Qian, Hai-Long; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2016-07-01

    Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application.

  6. Bottom-up synthesis of chiral covalent organic frameworks and their bound capillaries for chiral separation.

    PubMed

    Qian, Hai-Long; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2016-07-12

    Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application.

  7. Correlation between structures of chiral polymers and their efficiency for chiral resolution by crystallization.

    PubMed

    Menahem, Tali; Pravda, Martin; Mastai, Yitzhak

    2009-10-01

    In this work, we describe the correlation between chiral polymer structures, particularly alpha-helical and random coil conformations, and their efficiency as chiral resolving agents in crystallization processes. A set of chiral block copolymers based on polyethylene oxide with chiral glutamic acid oligopeptide segments (PEG(113)-b-(+)-(S)-Glu(20)) were synthesized and employed as additives in the crystallization of rac-threonine. CD spectroscopy demonstrates that structures of chiral polymers could be switched between a helical and a disordered random coil by pH. The effect of these polymers at different conformations on the crystallization kinetics, crystal morphology, and chiral resolution of rac-threonine is reported. Our study demonstrates that only chiral polymers with alpha-helical conformations of the chiral segment are effective as additives for chiral resolution throughout crystallization. Overall, our results provide useful guidelines for the selection and design of chiral polymer additives that will act efficiently for chiral resolution by crystallization. PMID:19455618

  8. Lasing in chiral photonic structures [review article

    NASA Astrophysics Data System (ADS)

    Kopp, Victor I.; Zhang, Zhao-Qing; Genack, Azriel Z.

    This article presents a review of the lasing and photonic properties of periodic one-dimensional anisotropic structures with the symmetry of a double helix. Examples are self-organized cholesteric liquid crystals (CLCs) and sculptured thin films created by vapor deposition. A reflection band with sharp, closely spaced transmission peaks at its edges occurs for circularly polarized light with the same handedness as the helical structure. Within the reflection band, this wave is evanescent, corresponding to a vanishing density of states (DOS). Oppositely polarized light is uniformly transmitted. Since optical emission is proportional to the DOS, it is suppressed within the reflection band. However, it is enhanced at the band edge, where a series of narrow long-lived transmission modes are found. For this reason lasing in dye-doped CLCs occurs at the edge of the stop band rather than at its center, where reflection is highest. Introducing an additional rotation or an isotropic layer within a chiral structure creates a single circularly polarized localized mode with the same handedness as the structure. A resonance appears in the transmission of light of this polarization in thin samples. In thicker samples, the resonance appears instead in the reflection for oppositely polarized light. In contrast to strong modulation of the intensity within the sample on a wavelength scale, a characteristic of layered dielectric medium, the intensity within a chiral medium varies slowly when the sample is excited either at the band edge or at a localized mode. A transverse coherence is created in emission over a length scale proportional to the square root of the photon dwell time at resonance with long-lived modes. This makes possible spatially coherent lasing over a large area in thin films. The photonic properties of chiral thin films make them promising candidates for a variety of filter and laser applications.

  9. Chiral Separation of Indapamide Enantiomers by Capillary Electrophoresis

    PubMed Central

    Tero-Vescan, Amelia; Hancu, Gabriel; Oroian, Mihaela; Cârje, Anca

    2014-01-01

    Purpose: Indapamide is probably the most frequently prescribed diuretic drug, generally being used for the treatment of hypertension. It contains a chiral center in its molecule; is marketed as a racemic mixture; but there are rather few studies regarding the pharmacokinetic and the pharmacological effect differences of the two enantiomers. Our aim was the development of a simple, rapid and precise analytical procedure for the chiral separation of indapamide enantiomers. Methods: In this study capillary zone electrophoresis was used for the enantiomeric separation of indapamide using a systematic screening approach involving different native and derivatized; neutral and charged cyclodextrines as chiral selectors. The effects of pH value and composition of the background electrolyte, capillary temperature, running voltage and injection parameters have been investigated. Results: After preliminary analysis a charged derivatized CD, sulfobuthyl ether- β-CD, proved to be the optimum chiral selector for the enantioseparation. Using a buffer solution containing 25 mM disodium hydrogenophosphate – 25 mM sodium didydrogenophosphate and 5 mM sulfobuthyl ether- β-CD as chiral selector at a pH - 7, a voltage of + 25 kV, temperature 15°C and UV detection at 242 nm, we succeeded in the separation of the two enantiomers in approximately 6 minutes, with a resolution of 4.30 and a separation factor of 1.08. Conclusion: Capillary zone electrophoresis using cyclodextrines as chiral selectors proved to be a suitable method for the enantioseparation of indapamide. Our method is rapid, specific, reliable, and cost-effective and can be proposed for laboratories performing indapamide routine analysis. PMID:24754011

  10. "Her illness is a project we can work on together": developing a collaborative family-centered intervention model for newly diagnosed multiple sclerosis.

    PubMed

    Rintell, David; Melito, Richard

    2013-01-01

    This article presents a model for intervening with families that are addressing a new diagnosis of multiple sclerosis (MS) in one member. The model is collaborative, integrative, and family-centered. It involves both working with the family collaboratively and providing strategies to promote greater collaboration within the family. The model integrates elements of crisis intervention theory, psycho-education, and family-centered approaches. The model was developed with families addressing MS, and was piloted with three families. The intervention was found to improve family members' ability to collaborate with each other. Such increased collaboration may enhance the family's ability to manage long-term illness more effectively, help the family address the impact of the illness on all family members, and generally improve the family's quality of life. PMID:24453775

  11. Electron transfer kinetics in purified reaction centers from the green sulfur bacterium Chlorobium tepidum studied by multiple-flash excitation.

    PubMed

    Kusumoto, N; Sétif, P; Brettel, K; Seo, D; Sakurai, H

    1999-09-14

    Reaction center preparations from the green sulfur bacterium Chlorobium tepidum, which contain monoheme cytochrome c, were studied by flash-absorption spectroscopy in the near-UV, visible, and near-infrared regions. The decay kinetics of the photooxidized primary donor P840(+), together with the amount of photooxidized cytochrome c, were analyzed along a series of four flashes spaced by 1 ms: 95% of the P840(+) was reduced by cytochrome c with a t(1/2) of approximately 65 micros after the first flash, 80% with a t(1/2) of approximately 100 micros after the second flash, and 23% with a t(1/2) of approximately 100 micros after the third flash; after the fourth flash, almost no cytochrome c oxidation occurred. The observed rates, the establishment of redox equilibrium after each flash, and the total amount of photooxidizable cytochrome c are consistent with the presence of two equivalent cytochrome c molecules per photooxidizable P840. The data are well fitted assuming a standard free energy change DeltaG degrees of -53 meV for electron transfer from one cytochrome c to P840(+), DeltaG degrees being independent of the oxidation state of the other cytochrome c. These observations support a model with two monoheme cytochromes c which are symmetrically arranged around the reaction center core. From the ratio of menaquinone-7 to the bacteriochlorophyll pigment absorbing at 663 nm, it was estimated that our preparations contain 0.6-1.2 menaquinone-7 molecules per reaction center. However, no transient signal due to menaquinone could be observed between 360 and 450 nm in the time window from 10 ns to 4 micros. No recombination reaction between the primary partners P840(+) and A(0)(-) could be detected under normal conditions. Such a recombination was observed (t(1/2) approximately 19 ns) under highly reducing conditions or after accumulation of three electrons on the acceptor side during a series of flashes, showing that the secondary acceptors can stabilize three electrons

  12. Can a Non-Chiral Object Be Made of Two Identical Chiral Moieties?

    ERIC Educational Resources Information Center

    LeMarechal, Jean Francois

    2008-01-01

    Several pedagogical objects can be used to discuss chirality. Here, we use the cut of an apple to show that the association of identical chiral moieties can form a non-chiral object. Octahedral chirality is used to find situations equivalent to the cut of the apple. (Contains 5 figures.)

  13. Strange Disoriented Chiral Condensates

    NASA Astrophysics Data System (ADS)

    Abdel-Aziz, Mohamed; Gavin, Sean

    2002-10-01

    Enhancement of omega and anti-omega baryon production in Pb+Pb collisions at the CERN SPS can be explained by the formation of many small regions of disordered chiral condensate. This explanation implies that neutral and charged kaons as well as pions must exhibit novel isospin fluctuations. Fluctuations due to transient behavior of the Polyakov Loop condensate can produce similar phenomena. Kapusta and Gavin have computed the distribution of the fraction of neutral pions and kaons from such regions. We proposed robust statistical observables that can be used to extract the novel isospin fluctuations from background contributions in neutral/charged pion and K-short/K-charged correlation measurements at RHIC and LHC. The STAR experiment is currently examining K-short/K-charged correlations. Note that Pruneau, Voloshin and Gavin have proposed similar observables to study net-charge fluctuations. To obtain a baseline for comparison to RHIC and SPS experiments, Abdel-Aziz and Gavin compute these observables using numerical simulations using HIJING and URQMD event generators. We also obtain limits on the size and number of disordered regions by comparing to photon and charged-pion searches from WA98 and other SPS experiments. We will compare to the first results from STAR K-short/K-charged analysis.

  14. Phase diagram of chirally imbalanced QCD matter

    SciTech Connect

    Chernodub, M. N.; Nedelin, A. S.

    2011-05-15

    We compute the QCD phase diagram in the plane of the chiral chemical potential and temperature using the linear sigma model coupled to quarks and to the Polyakov loop. The chiral chemical potential accounts for effects of imbalanced chirality due to QCD sphaleron transitions which may emerge in heavy-ion collisions. We found three effects caused by the chiral chemical potential: the imbalanced chirality (i) tightens the link between deconfinement and chiral phase transitions; (ii) lowers the common critical temperature; (iii) strengthens the order of the phase transition by converting the crossover into the strong first order phase transition passing via the second order end point. Since the fermionic determinant with the chiral chemical potential has no sign problem, the chirally imbalanced QCD matter can be studied in numerical lattice simulations.

  15. Chiral Chlordane Components in Environmental Matrices

    EPA Science Inventory

    Chlordane, a persistent, bioaccumulative and toxic organochlorine pesticide, has been studied for many years. Since the advent of chiral analysis for environmental samples, over 2,400 measurements have been made of various chiral chlordane components. Chlordane enantiomer fractio...

  16. Tactoids of chiral liquid crystals

    NASA Astrophysics Data System (ADS)

    Palacio-Betancur, Viviana; Villada-Gil, Stiven; Zhou, Ye; Armas-Pérez, Julio C.; de Pablo, Juan José; Hernández-Ortiz, Juan Pablo

    The phase diagram of chiral liquid crystals confined in ellipsoids is obtained, by following a theoretically informed Monte Carlo relaxation of the tensor alignment field Q. The free energy of the system is described by a functional in the framework of the Landau-de Gennes formalism. This study also includes the effect of anchoring strength, curvature, and chirality of the system. In the low chirality region of the phase diagram we found the twist bipolar (BS) phase and some cholesteric phases such as the radial spherical structure (RSS), twist cylinder (TC) and double twist cylinder (DTC) whose axis of rotation is not necessarily aligned with the major axis of the geometry. For high chirality scenarios, the disclination lines are twisted or bent near the surface preventing the formation of symmetric networks of defects, although an hexagonal pattern is formed on the surface which might serve as open sites for collocation of colloids. By analyzing the free energies of isochoric systems, prolate geometries tend to be more favorable for high chirality and low anchoring conditions. Universidad Nacional de Colombia Ph.D. grant and COLCIENCIAS under the Contract No. 110-165-843-748. CONACYT for Postdoctoral Fellowships Nos. 186166 and 203840.

  17. Controlling Chirality of Entropic Crystals

    NASA Astrophysics Data System (ADS)

    Damasceno, Pablo; Karas, Andrew; Schultz, Benjamin; Engel, Michael; Glotzer, Sharon

    Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams. Work supported by the National Science Foundation, Division of Materials Research Award No. DMR 1120923, U.S. Army Research Office under Grant Award No. W911NF-10-1-0518, and also by the DOD/ASD (R&E) under Award No. N00244-09-1-0062.

  18. Chiral Thirring–Wess model

    SciTech Connect

    Rahaman, Anisur

    2015-10-15

    The vector type of interaction of the Thirring–Wess model was replaced by the chiral type and a new model was presented which was termed as chiral Thirring–Wess model in Rahaman (2015). The model was studied there with a Faddeevian class of regularization. Few ambiguity parameters were allowed there with the apprehension that unitarity might be threatened like the chiral generation of the Schwinger model. In the present work it has been shown that no counter term containing the regularization ambiguity is needed for this model to be physically sensible. So the chiral Thirring–Wess model is studied here without the presence of any ambiguity parameter and it has been found that the model not only remains exactly solvable but also does not lose the unitarity like the chiral generation of the Schwinger model. The phase space structure and the theoretical spectrum of this new model have been determined in the present scenario. The theoretical spectrum is found to contain a massive boson with ambiguity free mass and a massless boson.

  19. Multispectral Chiral Imaging with a Metalens.

    PubMed

    Khorasaninejad, M; Chen, W T; Zhu, A Y; Oh, J; Devlin, R C; Rousso, D; Capasso, F

    2016-07-13

    The vast majority of biologically active compounds, ranging from amino acids to essential nutrients such as glucose, possess intrinsic handedness. This in turn gives rise to chiral optical properties that provide a basis for detecting and quantifying enantio-specific concentrations of these molecules. However, traditional chiroptical spectroscopy and imaging techniques require cascading of multiple optical components in sophisticated setups. Here, we present a planar lens with an engineered dispersive response, which simultaneously forms two images with opposite helicity of an object within the same field-of-view. In this way, chiroptical properties can be probed across the visible spectrum using only the lens and a camera without the addition of polarizers or dispersive optical devices. We map the circular dichroism of the exoskeleton of a chiral beetle, Chrysina gloriosa, which is known to exhibit high reflectivity of left-circularly polarized light, with high spatial resolution limited by the numerical aperture of the planar lens. Our results demonstrate the potential of metasurfaces in realizing a compact and multifunctional device with unprecedented imaging capabilities. PMID:27267137

  20. Chirality: a relational geometric-physical property.

    PubMed

    Gerlach, Hans

    2013-11-01

    The definition of the term chirality by Lord Kelvin in 1893 and 1904 is analyzed by taking crystallography at that time into account. This shows clearly that chirality is a relational geometric-physical property, i.e., two relations between isometric objects are possible: homochiral or heterochiral. In scientific articles the relational term chirality is often mistaken for the two valued measure for the individual (absolute) sense of chirality, an arbitrary attributive term.

  1. Chiral lattice fermions with correct vacuum polarization and chiral anomaly

    SciTech Connect

    Pryor, C. )

    1991-04-15

    An action for chiral lattice fermions is proposed, which avoids the Nielsen-Ninomiya theorem by virtue of its nonlocality and nonbilinearity. The action is constructed by eliminating the extra fermion modes with a gauge-violating Majorana-type Wilson mass, which is then rendered invariant by an integration over gauge transformations. The free propagator is calculated, and the one-loop vacuum polarization is shown to be identical to that for Wilson fermions, even at nonzero lattice spacing. Also the chiral anomaly is shown to be the same as for Wilson fermions in the continuum limit.

  2. Field induced spin chirality and chirality switching in magnetic multilayers

    NASA Astrophysics Data System (ADS)

    Tartakovskaya, Elena V.

    2015-05-01

    The physical origin of the field-induced spin chirality experimentally observed in rare earth multilayers is determined. It is shown that the effect is possible due to the interplay between solid-state exchange interactions (the Ruderman-Kittel-Kasuya-Yosida and the Dsyaloshinsky-Moriya interactions), the external magnetic field and a special confinement of magnetic constituents. The presented model describes a certain temperature dependence of the chirality factor in agreement with experimental data and opens a new way to design nanostructured objects with predicted handedness.

  3. Structure Study of the Chiral Lactide Molecules by Chirped-Pulse Ftmw Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zaleski, Daniel P.; Neill, Justin L.; Pate, Brooks H.; Bialkowska-Jaworska, Ewa; Kisiel, Zbigniew

    2011-06-01

    Lactide is a six member cyclic diester with two chiral centers that forms from lactic acid in the presence of heat and an acid catalyst. It can form either a homo-chiral (RR) structure with both methyl groups equatorial or a hetero-chiral (RS) structure where one methyl group is equatorial and the other methyl group is axial. Structurally lactide is similar to lactic acid dimer; however, the kinked ring is covalently bonded and two waters are lost. And unlike lactic acid dimer, which has a very small dipole moment, the dipole moment of lactide is on the order of 3 Debye. Here the microwave spectra of the highly rigid homo- and hetero-chiral lactides are presented, which were first assigned in a heated lactic acid spectrum where the chemistry took place in the reservoir nozzles. Further isotopic information from a commercial sample of predominately homo-chiral lactide was obtained leading to a Kraitchman substitution structure of the homo-chiral lactide. Preliminary results of the cluster of homo-chiral lactide with one water molecule attached are also presented.

  4. Constructing diabatic states from adiabatic states: Extending generalized Mulliken-Hush to multiple charge centers with Boys localization

    NASA Astrophysics Data System (ADS)

    Subotnik, Joseph E.; Yeganeh, Sina; Cave, Robert J.; Ratner, Mark A.

    2008-12-01

    This article shows that, although Boys localization is usually applied to single-electron orbitals, the Boys method itself can be applied to many electron molecular states. For the two-state charge-transfer problem, we show analytically that Boys localization yields the same charge-localized diabatic states as those found by generalized Mulliken-Hush theory. We suggest that for future work in electron transfer, where systems have more than two charge centers, one may benefit by using a variant of Boys localization to construct diabatic potential energy surfaces and extract electronic coupling matrix elements. We discuss two chemical examples of Boys localization and propose a generalization of the Boys algorithm for creating diabatic states with localized spin density that should be useful for Dexter triplet-triplet energy transfer.

  5. Constructing diabatic states from adiabatic states: extending generalized Mulliken-Hush to multiple charge centers with boys localization.

    PubMed

    Subotnik, Joseph E; Yeganeh, Sina; Cave, Robert J; Ratner, Mark A

    2008-12-28

    This article shows that, although Boys localization is usually applied to single-electron orbitals, the Boys method itself can be applied to many electron molecular states. For the two-state charge-transfer problem, we show analytically that Boys localization yields the same charge-localized diabatic states as those found by generalized Mulliken-Hush theory. We suggest that for future work in electron transfer, where systems have more than two charge centers, one may benefit by using a variant of Boys localization to construct diabatic potential energy surfaces and extract electronic coupling matrix elements. We discuss two chemical examples of Boys localization and propose a generalization of the Boys algorithm for creating diabatic states with localized spin density that should be useful for Dexter triplet-triplet energy transfer.

  6. A disoriented chiral condensate search at the Fermilab Tevatron

    SciTech Connect

    Convery, M.E.

    1997-05-01

    MiniMax (Fermilab T-864) was a small test/experiment at the Tevatron designed to search for disoriented chiral condensates (DCC) in the forward direction. Relativistic quantum field theory treats the vacuum as a medium, with bulk properties characterized by long-range order parameters. This has led to suggestions that regions of {open_quotes}disoriented vacuum{close_quotes} might be formed in high-energy collision processes. In particular, the approximate chiral symmetry of QCD could lead to regions of vacuum which have chiral order parameters disoriented to directions which have non-zero isospin, i.e. disoriented chiral condensates. A signature of DCC is the resulting distribution of the fraction of produced pions which are neutral. The MiniMax detector at the C0 collision region of the Tevatron was a telescope of 24 multi-wire proportional chambers (MWPC`s) with a lead converter behind the eighth MWPC, allowing the detection of charged particles and photon conversions in an acceptance approximately a circle of radius 0.6 in pseudorapidity-azimuthal-angle space, centered on pseudorapidity {eta} {approx} 4. An electromagnetic calorimeter was located behind the MWPC telescope, and hadronic calorimeters and scintillator were located in the upstream anti-proton direction to tag diffractive events.

  7. Chirality and gravitational parity violation.

    PubMed

    Bargueño, Pedro

    2015-06-01

    In this review, parity-violating gravitational potentials are presented as possible sources of both true and false chirality. In particular, whereas phenomenological long-range spin-dependent gravitational potentials contain both truly and falsely chiral terms, it is shown that there are models that extend general relativity including also coupling of fermionic degrees of freedom to gravity in the presence of torsion, which give place to short-range truly chiral interactions similar to that usually considered in molecular physics. Physical mechanisms which give place to gravitational parity violation together with the expected size of the effects and their experimental constraints are discussed. Finally, the possible role of parity-violating gravity in the origin of homochirality and a road map for future research works in quantum chemistry is presented. PMID:25919812

  8. Chirality and gravitational parity violation.

    PubMed

    Bargueño, Pedro

    2015-06-01

    In this review, parity-violating gravitational potentials are presented as possible sources of both true and false chirality. In particular, whereas phenomenological long-range spin-dependent gravitational potentials contain both truly and falsely chiral terms, it is shown that there are models that extend general relativity including also coupling of fermionic degrees of freedom to gravity in the presence of torsion, which give place to short-range truly chiral interactions similar to that usually considered in molecular physics. Physical mechanisms which give place to gravitational parity violation together with the expected size of the effects and their experimental constraints are discussed. Finally, the possible role of parity-violating gravity in the origin of homochirality and a road map for future research works in quantum chemistry is presented.

  9. Shared Service Center vs. Shared Service Network: A Multiple Case Study Analysis of Factors Impacting on Shared Service Configurations

    NASA Astrophysics Data System (ADS)

    Becker, Jörg; Niehaves, Björn; Krause, Andreas

    Shared services have proven to be a key element when it comes to increasing government efficiency by collaboration. Here, we seek to investigate into the shared services phenomenon in the context of government reforms. For this purpose, an interview and document analysis-based multiple case study has been conducted in Germany. The qualitative analysis covers two shared service implementations on the local government level and identifies important preconditions for shared service emergence, namely cost pressure as motive, the existence of key actors promoting the topic and the existence of prior cooperation. Moreover, it is shown that the structure of such previous cooperation determines, if shared services are being organised in a centralised (shared service centre) or decentralised format (shared service network).

  10. Collisions in Chiral Kinetic Theory.

    PubMed

    Chen, Jing-Yuan; Son, Dam T; Stephanov, Mikhail A

    2015-07-10

    Using a covariant formalism, we construct a chiral kinetic theory Lorentz invariant to order O(ℏ), which includes collisions. We find a new contribution to the particle number current due to the side jumps required by the conservation of angular momentum during collisions. We also find a conserved symmetric stress-energy tensor as well as the H function obeying Boltzmann's H theorem. We demonstrate their use by finding a general equilibrium solution and the values of the anomalous transport coefficients characterizing the chiral vortical effect.

  11. Chiral symmetry on the lattice

    SciTech Connect

    Creutz, M.

    1994-11-01

    The author reviews some of the difficulties associated with chiral symmetry in the context of a lattice regulator. The author discusses the structure of Wilson Fermions when the hopping parameter is in the vicinity of its critical value. Here one flavor contrasts sharply with the case of more, where a residual chiral symmetry survives anomalies. The author briefly discusses the surface mode approach, the use of mirror Fermions to cancel anomalies, and finally speculates on the problems with lattice versions of the standard model.

  12. Human-centered approaches in geovisualization design: investigating multiple methods through a long-term case study.

    PubMed

    Lloyd, David; Dykes, Jason

    2011-12-01

    Working with three domain specialists we investigate human-centered approaches to geovisualization following an ISO13407 taxonomy covering context of use, requirements and early stages of design. Our case study, undertaken over three years, draws attention to repeating trends: that generic approaches fail to elicit adequate requirements for geovis application design; that the use of real data is key to understanding needs and possibilities; that trust and knowledge must be built and developed with collaborators. These processes take time but modified human-centred approaches can be effective. A scenario developed through contextual inquiry but supplemented with domain data and graphics is useful to geovis designers. Wireframe, paper and digital prototypes enable successful communication between specialist and geovis domains when incorporating real and interesting data, prompting exploratory behaviour and eliciting previously unconsidered requirements. Paper prototypes are particularly successful at eliciting suggestions, especially for novel visualization. Enabling specialists to explore their data freely with a digital prototype is as effective as using a structured task protocol and is easier to administer. Autoethnography has potential for framing the design process. We conclude that a common understanding of context of use, domain data and visualization possibilities are essential to successful geovis design and develop as this progresses. HC approaches can make a significant contribution here. However, modified approaches, applied with flexibility, are most promising. We advise early, collaborative engagement with data – through simple, transient visual artefacts supported by data sketches and existing designs – before moving to successively more sophisticated data wireframes and data prototypes. PMID:22034371

  13. Human-centered approaches in geovisualization design: investigating multiple methods through a long-term case study.

    PubMed

    Lloyd, David; Dykes, Jason

    2011-12-01

    Working with three domain specialists we investigate human-centered approaches to geovisualization following an ISO13407 taxonomy covering context of use, requirements and early stages of design. Our case study, undertaken over three years, draws attention to repeating trends: that generic approaches fail to elicit adequate requirements for geovis application design; that the use of real data is key to understanding needs and possibilities; that trust and knowledge must be built and developed with collaborators. These processes take time but modified human-centred approaches can be effective. A scenario developed through contextual inquiry but supplemented with domain data and graphics is useful to geovis designers. Wireframe, paper and digital prototypes enable successful communication between specialist and geovis domains when incorporating real and interesting data, prompting exploratory behaviour and eliciting previously unconsidered requirements. Paper prototypes are particularly successful at eliciting suggestions, especially for novel visualization. Enabling specialists to explore their data freely with a digital prototype is as effective as using a structured task protocol and is easier to administer. Autoethnography has potential for framing the design process. We conclude that a common understanding of context of use, domain data and visualization possibilities are essential to successful geovis design and develop as this progresses. HC approaches can make a significant contribution here. However, modified approaches, applied with flexibility, are most promising. We advise early, collaborative engagement with data – through simple, transient visual artefacts supported by data sketches and existing designs – before moving to successively more sophisticated data wireframes and data prototypes.

  14. Brilliant Sm, Eu, Tb and Dy chiral lanthanide complexes withstrong circularly polarized luminescence

    SciTech Connect

    Petoud, Stephane; Muller, Gilles; Moore, Evan G.; Xu, Jide; Sokolnicki, Jurek; Riehl, James P.; Le, Uyen; Cohen, Seth M.; Raymond,Kenneth N.

    2006-07-10

    The synthesis, characterization and luminescent behavior of trivalent Sm, Eu, Dy and Tb complexes of two enantiomeric, octadentate, chiral, 2-hydroxyisophthalamide ligands are reported. These complexes are highly luminescent in solution. Functionalization of the achiral parent ligand with a chiral 1-phenylethylamine substituent on the open face of the complex in close proximity to the metal center yields complexes with strong circularly polarized luminescence (CPL) activity. This appears to be the first example of a system utilizing the same ligand architecture to sensitize four different lanthanide cations and display CPL activity. The luminescence dissymmetry factor, g{sub lum}, recorded for the Eu(III) complex is one of the highest values reported, and this is the first time the CPL effect has been demonstrated for a Sm(III) complex with a chiral ligand. The combination of high luminescence intensity with CPL activity should enable new bioanalytical applications of macromolecules in chiral environments.

  15. Random lasers from dye-doped chiral photonic crystal films

    NASA Astrophysics Data System (ADS)

    Huang, Yuhua; Zhou, Ying; Wu, Shin-Tson

    2007-02-01

    We have obtained a dye-doped chiral photonic crystal (PC) film with reflection band gap much wider than its original band gap without dye dopants by using multiple-step fabrication processes. Moreover, the dye-doped chiral PC films using our multiple-step fabrication processes exhibit many oscillations within the broadened reflection band gap. The abrupt change of the optical density of state (DOS) around the oscillations provides the possibility of generating laser emission when the dye-doped chiral PC film is pumped by a pulsed laser with wavelength in the absorption region of the laser dye. Based on this property, we demonstrated random lasers which exhibit different multiple-mode laser wavelength at different spatial positions. Different from the random lasers induced by the scattering mechanism, the random lasers from the dye-doped cholesteric polymer film exhibit Gaussian-like beam shape and specific propagation orientation which is normal to the cholesteric planar surface. It is foreseeable that a high efficiency and high power broadband laser can be generated using cholesteric polymer films.

  16. Chiral xenobiotics bioaccumulations and environmental health prospectives.

    PubMed

    Hussain, Iqbal; ALOthman, Zeid A; Alwarthan, Abdulrahman A; Sanagi, Mohd Marsin; Ali, Imran

    2015-08-01

    The chiral xenobiotics are very dangerous for all of us due to the different enantioselective toxicities of the enantiomers. Besides, these have different enantioselective bioaccumulations and behaviors in our body and other organisms. It is of urgent need to understand the enantioselective bioaccumulations, toxicities, and the health hazards of the chiral xenobiotics. The present article describes the classification, sources of contamination, distribution, enantioselective bioaccumulation, and the toxicities of the chiral xenobiotics. Besides, the efforts are also made to discuss the prevention and remedial measures of the havoc of the chiral xenobiotics. The challenges of the chiral xenobiotics have also been highlighted. Finally, future prospectives are also discussed.

  17. A single-center retrospective analysis of first-line therapy of multiple myeloma with bendamustine-bortezomib-dexamethasone.

    PubMed

    Zwickl, Hannes; Zwickl-Traxler, Elisabeth; Pecherstorfer, Martin

    2016-09-01

    The aim of this retrospective study was to evaluate the efficacy and toxicity profile of bendamustine, bortezomib, and dexamethasone (BBD) combination treatment of patients with newly diagnosed multiple myeloma (MM). BBD treatment had a response rate of 80% regarding patients with ≥ partial response (PR). Median time to best response was 87.5 days and PFS was 22 months. Median of OS was not reached. PFS of non-responding patients was significantly shortened compared to those with ≥ PR. No statistically significant differences were determined concerning age (≥ vs. < 68 years) and ISS stage (ISS stage I/II vs. III). Grade 3 hematological effects and grade 3/4 non-hematological effects occurred in 20% and 35% of patients, respectively. Most pronounced hematological adverse event was leukopenia, the most severe non-hematological ones affected the cardiovascular system. In summary, BBD treatment was of acceptable efficacy in patients with newly diagnosed MM and exhibited rather low toxicity. PMID:26901249

  18. Fumarate treatment in progressive forms of multiple sclerosis: first results of a single-center observational study

    PubMed Central

    Strassburger-Krogias, Katrin; Ellrichmann, Gisa; Krogias, Christos; Altmeyer, Peter; Chan, Andrew

    2014-01-01

    Objectives: Therapeutic options in progressive forms of multiple sclerosis (MS) are still limited. Dimethyl fumarate (DMF) has immunomodulatory properties but may also exert antioxidative cytoprotective effects. Hence, it may be a therapeutic option for progressive MS. The aim of this observational study was to evaluate safety, adherence and efficacy of fumarates in patients with primary progressive MS (PPMS) or secondary progressive MS. Methods: Patients with progressive MS whose condition had failed to respond to standard therapies and had worsened received the fumarate mixture Fumaderm, licensed for psoriasis therapy in Germany, or DMF by pharmaceutical preparation (Bochum ethics approval no. 4797-13). At regular follow-up visits, tolerability and disease course were assessed. Results: Twenty-six patients [age 54 ± 7.8 years; female = 13 (50%); PPMS = 12 (46.2%); Expanded Disability Status Scale (EDSS) = 6.0 ± 0.4 (range 3.5–8.0); disease duration = 14.1 ± 8.7 years] were initiated on treatment with Fumaderm (n = 18) or pharmacy-prepared DMF (n=8). During a mean follow-up period of 13.2 ± 7.5 months (range 6–30) only five patients (19.2%) reported minor complaints. In 15 patients (57.7%) EDSS remained stable. In five cases (19.2%) there was even a decrease in EDSS while in six patients (23.1%) there was an increase in EDSS of more than 0.5 points, reflecting deterioration. Laboratory values were controlled for lymphopenia, renal and hepatic values, without any safety problems. We observed no significant differences between the two pharmaceutical forms. Conclusion: Our pilot data indicate that fumarate therapy appears to be safe and well tolerated by patients with progressive MS. In more than 75% of cases no further disease progression was evident. However, controlled studies are warranted to evaluate the detailed therapeutic potential of fumarates and their long-term effects in progressive MS. PMID:25342977

  19. Chirality effect in disordered graphene ribbon junctions

    NASA Astrophysics Data System (ADS)

    Long, Wen

    2012-05-01

    We investigate the influence of edge chirality on the electronic transport in clean or disordered graphene ribbon junctions. By using the tight-binding model and the Landauer-Büttiker formalism, the junction conductance is obtained. In the clean sample, the zero-magnetic-field junction conductance is strongly chirality-dependent in both unipolar and bipolar ribbons, whereas the high-magnetic-field conductance is either chirality-independent in the unipolar or chirality-dependent in the bipolar ribbon. Furthermore, we study the disordered sample in the presence of magnetic field and find that the junction conductance is always chirality-insensitive for both unipolar and bipolar ribbons with adequate disorders. In addition, the disorder-induced conductance plateaus can exist in all chiral bipolar ribbons provided the disorder strength is moderate. These results suggest that we can neglect the effect of edge chirality in fabricating electronic devices based on the magnetotransport in a disordered graphene ribbon.

  20. Micropatterning of cells reveals chiral morphogenesis

    PubMed Central

    2013-01-01

    Invariant left-right (LR) patterning or chirality is critical for embryonic development. The loss or reversal of LR asymmetry is often associated with malformations and disease. Although several theories have been proposed, the exact mechanism of the initiation of the LR symmetry has not yet been fully elucidated. Recently, chirality has been detected within single cells as well as multicellular structures using several in vitro approaches. These studies demonstrated the universality of cell chirality, its dependence on cell phenotype, and the role of physical boundaries. In this review, we discuss the theories for developmental LR asymmetry, compare various in vitro cell chirality model systems, and highlight possible roles of cell chirality in stem cell differentiation. We emphasize that the in vitro cell chirality systems have great promise for helping unveil the nature of chiral morphogenesis in development. PMID:23672821

  1. Construction of a tunable multi-enzyme-coordinate expression system for biosynthesis of chiral drug intermediates

    PubMed Central

    Jiang, Wei; Fang, Baishan

    2016-01-01

    Systems that can regulate and coordinate the expression of multiple enzymes for metabolic regulation and synthesis of important drug intermediates are poorly explored. In this work, a strategy for constructing a tunable multi-enzyme-coordinate expression system for biosynthesis of chiral drug intermediates was developed and evaluated by connecting protein-protein expressions, regulating the strength of ribosome binding sites (RBS) and detecting the system capacity for producing chiral amino acid. Results demonstrated that the dual-enzyme system had good enantioselectivity, low cost, high stability, high conversion rate and approximately 100% substrate conversion. This study has paved a new way of exploring metabolic mechanism of functional genes and engineering whole cell-catalysts for synthesis of chiral α-hydroxy acids or chiral amino acids. PMID:27456301

  2. Construction of a tunable multi-enzyme-coordinate expression system for biosynthesis of chiral drug intermediates.

    PubMed

    Jiang, Wei; Fang, Baishan

    2016-01-01

    Systems that can regulate and coordinate the expression of multiple enzymes for metabolic regulation and synthesis of important drug intermediates are poorly explored. In this work, a strategy for constructing a tunable multi-enzyme-coordinate expression system for biosynthesis of chiral drug intermediates was developed and evaluated by connecting protein-protein expressions, regulating the strength of ribosome binding sites (RBS) and detecting the system capacity for producing chiral amino acid. Results demonstrated that the dual-enzyme system had good enantioselectivity, low cost, high stability, high conversion rate and approximately 100% substrate conversion. This study has paved a new way of exploring metabolic mechanism of functional genes and engineering whole cell-catalysts for synthesis of chiral α-hydroxy acids or chiral amino acids. PMID:27456301

  3. Basics of Resonance Chiral Theory

    SciTech Connect

    Portoles, J.

    2010-12-28

    We review the main components that have to be considered, within Resonance Chiral Theory, in the study of processes whose dynamics is dominated by hadron resonances. We show its application in the study of the {tau}{yields}{pi}{pi}{pi}{nu}{sub {tau}} decay.

  4. Chiral asymmetry in spiral galaxies?

    PubMed

    Kondepudi, D K; Durand, D J

    2001-07-01

    Spiral galaxies are chiral entities when coupled with the direction of their recession velocity. As viewed from the Earth, the S-shaped and Z-shaped spiral galaxies are two chiral forms. What is the nature of chiral symmetry in spiral galaxies? In the Carnegie Atlas of Galaxies that lists photographs of a total of 1,168 galaxies, we found 540 galaxies, classified as normal or barred spirals, that are clearly identifiable as S- or Z- type. The recession velocities for 538 of these galaxies could be obtained from this atlas and other sources. A statistical analysis of this sample reveals no overall asymmetry but there is a significant asymmetry in certain subclasses: dominance of S-type galaxies in the Sb class of normal spiral galaxies and a dominance of Z-type in the SBb class of barred spiral galaxies. Both S- and Z-type galaxies seem to have similar velocity distribution, indicating no spatial segregation of the two chiral forms.

  5. Baryon and chiral symmetry breaking

    SciTech Connect

    Gorsky, A.; Krikun, A.

    2014-07-23

    We briefly review the generalized Skyrmion model for the baryon recently suggested by us. It takes into account the tower of vector and axial mesons as well as the chiral symmetry breaking. The generalized Skyrmion model provides the qualitative explanation of the Ioffe’s formula for the baryon mass.

  6. Chiral selectivity of amino acid adsorption on chiral surfaces—The case of alanine on Pt

    SciTech Connect

    Franke, J.-H.; Kosov, D. S.

    2015-02-07

    We study the binding pattern of the amino acid alanine on the naturally chiral Pt surfaces Pt(531), Pt(321), and Pt(643). These surfaces are all vicinal to the (111) direction but have different local environments of their kink sites and are thus a model for realistic roughened Pt surfaces. Alanine has only a single methyl group attached to its chiral center, which makes the number of possible binding conformations computationally tractable. Additionally, only the amine and carboxyl group are expected to interact strongly with the Pt substrate. On Pt(531), we study the molecule in its pristine as well as its deprotonated form and find that the deprotonated one is more stable by 0.47 eV. Therefore, we study the molecule in its deprotonated form on Pt(321) and Pt(643). As expected, the oxygen and nitrogen atoms of the deprotonated molecule provide a local binding “tripod” and the most stable adsorption configurations optimize the interaction of this “tripod” with undercoordinated surface atoms. However, the interaction of the methyl group plays an important role: it induces significant chiral selectivity of about 60 meV on all surfaces. Hereby, the L-enantiomer adsorbs preferentially to the Pt(321){sup S} and Pt(643){sup S} surfaces, while the D-enantiomer is more stable on Pt(531){sup S}. The binding energies increase with increasing surface density of kink sites, i.e., they are largest for Pt(531){sup S} and smallest for Pt(643){sup S}.

  7. Spherical β-cyclodextrin-silica hybrid materials for multifunctional chiral stationary phases.

    PubMed

    Wang, Litao; Dong, Shuqing; Han, Feng; Zhao, Yingwei; Zhang, Xia; Zhang, Xiaoli; Qiu, Hongdeng; Zhao, Liang

    2015-02-27

    Spherical β-CD-silica hybrid materials have been prepared successfully by simple one-pot polymerization, which provide a new strategy to construct new type of HPLC chiral stationary phases. Various β-CD, ethane, triazinyl and 3,5-dimethylphenyl functional groups that can provide multiple interactions were introduced into the pore channels and pore wall framework of mesoporous materials, respectively. The materials towards some chiral, acidic, anilines and phenols compounds showed multiple chromatographic separation functions including racemic resolution, anion exchange and achiral separations with a typical feature of normal/reversed phase chromatography. Multi-tasking including racemic resolution and achiral separations for selected compounds were performed simultaneously on a chiral chromatographic column. The multifunctional character of materials arises from the multiple interactions including hydrophobic interaction, π-π interaction, anion exchange, inclusion interaction and hydrogen bonding interaction. PMID:25637012

  8. Nuclear chiral dynamics and thermodynamics

    NASA Astrophysics Data System (ADS)

    Holt, Jeremy W.; Kaiser, Norbert; Weise, Wolfram

    2013-11-01

    This presentation reviews an approach to nuclear many-body systems based on the spontaneously broken chiral symmetry of low-energy QCD. In the low-energy limit, for energies and momenta small compared to a characteristic symmetry breaking scale of order 1 GeV, QCD is realized as an effective field theory of Goldstone bosons (pions) coupled to heavy fermionic sources (nucleons). Nuclear forces at long and intermediate distance scales result from a systematic hierarchy of one- and two-pion exchange processes in combination with Pauli blocking effects in the nuclear medium. Short distance dynamics, not resolved at the wavelengths corresponding to typical nuclear Fermi momenta, are introduced as contact interactions between nucleons. Apart from a set of low-energy constants associated with these contact terms, the parameters of this theory are entirely determined by pion properties and low-energy pion-nucleon scattering observables. This framework (in-medium chiral perturbation theory) can provide a realistic description of both isospin-symmetric nuclear matter and neutron matter, with emphasis on the isospin-dependence determined by the underlying chiral NN interaction. The importance of three-body forces is emphasized, and the role of explicit Δ(1232)-isobar degrees of freedom is investigated in detail. Nuclear chiral thermodynamics is developed and a calculation of the nuclear phase diagram is performed. This includes a successful description of the first-order phase transition from a nuclear Fermi liquid to an interacting Fermi gas and the coexistence of these phases below a critical temperature Tc. Density functional methods for finite nuclei based on this approach are also discussed. Effective interactions, their density dependence and connections to Landau Fermi liquid theory are outlined. Finally, the density and temperature dependences of the chiral (quark) condensate are investigated.

  9. Chirality at metal and helical ligand folding in optical isomers of chiral bis(naphthaldiminato)nickel(II) complexes.

    PubMed

    Enamullah, Mohammed; Quddus, Mohammad Abdul; Hasan, Mohammad Rezabul; Pescitelli, Gennaro; Berardozzi, Roberto; Makhloufi, Gamall; Vasylyeva, Vera; Janiak, Christoph

    2016-01-14

    Enantiopure bis[{(R or S)-N-1-(Ar)ethyl-2-oxo-1-naphthaldiminato-κ(2)N,O}]nickel(ii) complexes {Ar = C6H5 ( or ), p-OMeC6H4 ( or ), and p-BrC6H4 ( or )} are synthesized from the reactions between (R or S)-N-1-(Ar)ethyl-2-oxo-1-naphthaldimine and nickel(ii) acetate. Circular-dichroism spectra and their density-functional theoretical simulation reveal the expected mirror image relationship between the enantiomeric pairs / and / in solution. CD spectra are dominated by the metal-centered Λ- or Δ-chirality of non-planar four-coordinated nickel, this latter being in turn dictated by the ligand chirality. Single crystal structure determination for and shows that there are two symmetry-independent molecules (A and B) in each asymmetric unit that give a Z' = 2 structure. Two asymmetric and chiral bidentate N^O-chelate Schiff base ligands coordinate to the nickel atom in a distorted square planar N2O2-coordination sphere. The conformational difference between the symmetry-independent molecules arises from the "up-or-down" folding of the naphthaldiminato ligand with respect to the coordination plane, which creates right- (P) or left-handed (M) helical conformations. Overall, the combination of ligand chirality, chirality at the metal and ligand folding gives rise to discrete metal helicates of preferred helicity in a selective way. Cyclic voltammograms (CV) show an oxidation wave at ca. 1.30 V for the [Ni(L)2]/[Ni(L)2](+) couple, and a reduction wave at ca. -0.35 V for the [Ni(L)2]/[Ni(L)2](-) couple in acetonitrile. PMID:26619269

  10. Enhancement of quark number susceptibility with an alternative pattern of chiral symmetry breaking in dense matter

    SciTech Connect

    Harada, Masayasu; Takemoto, Shinpei; Sasaki, Chihiro

    2010-01-01

    We explore general features of thermodynamic quantities and hadron mass spectra in a possible phase where chiral SU(2){sub L}xSU(2){sub R} symmetry is spontaneously broken while its center Z{sub 2} symmetry remains unbroken. In this phase, chiral symmetry breaking is driven by a quartic quark condensate although a bilinear quark condensate vanishes. A Ginzburg-Landau free energy leads to a new tricritical point between the Z{sub 2} broken and unbroken phases. Furthermore, a critical point can appear even in the chiral limit where explicit breaking is turned off, instead of a tricritical point at which restoration of chiral and its center symmetries takes place simultaneously. The net quark number density exhibits an abrupt change near the restoration of the center symmetry rather than that of the chiral symmetry. Hadron masses in possible phases are also studied in a linear sigma model. We show that, in the Z{sub 2} symmetric phase, the qq-type scalar meson with zero isospin I=0 splits from the qq-type pseudoscalar meson with I=1.

  11. Local and global chirality at surfaces: succinic acid versus tartaric acid on Cu110.

    PubMed

    Humblot, Vincent; Lorenzo, Maria Ortega; Baddeley, Christopher J; Haq, Sam; Raval, Rasmita

    2004-05-26

    A detailed comparison of tartaric acid (HOOC-CHOH-CHOH-COOH) and succinic acid (HOOC-CH(2)-CH(2)-COOH) molecules on a Cu(110) surface is presented with a view to elucidate how the two-dimensional chirality exhibited by such robust, chemisorbed systems is affected when both OH groups of the former molecule are replaced with H groups, a stereochemical change that leaves the metal-bonding functionalities of the molecule untouched but destroys both chiral centers. It is found that this change does not significantly affect the thermodynamically preferred chemical forms that are adopted, namely the doubly deprotonated bicarboxylate at low coverages (theta chiral phases alter substantially. For both molecules, two-dimensional assembly is found to depend strongly on the nature of the local adsorption motif created, with each motif essentially acting as a "synthon" for the supramolecular assembly. In this respect, it seems that molecule-metal bonding interactions define the general self-assembly structure. The presence/absence of the OH groups, instead, cause a subtler, second-order effect on the finer details of the self-assembled structure. Finally, the creation of chirality in the achiral succinate system is shown to arise from adsorption-induced asymmetrization, inducing point chirality via molecular distortion and/or metal reconstruction of the local adsorption unit. This chiral adsorption unit is then responsible for creating chiral supramolecular through-space and through-metal interactions that propagate a chiral organization. However, the achirality of the succinate ensures that nucleation points of either chirality are equally created, producing a racemic conglomerate of coexisting mirror domains. It is in this aspect that the uniquely

  12. REVIEW ARTICLE: Chiral metamaterials: simulations and experiments

    NASA Astrophysics Data System (ADS)

    Wang, Bingnan; Zhou, Jiangfeng; Koschny, Thomas; Kafesaki, Maria; Soukoulis, Costas M.

    2009-11-01

    Electromagnetic metamaterials are composed of periodically arranged artificial structures. They show peculiar properties, such as negative refraction and super-lensing, which are not seen in natural materials. The conventional metamaterials require both negative epsilon and negative μ to achieve negative refraction. Chiral metamaterial is a new class of metamaterials offering a simpler route to negative refraction. In this paper, we briefly review the history of metamaterials and the developments on chiral metamaterials. We study the wave propagation properties in chiral metamaterials and show that negative refraction can be realized in chiral metamaterials with a strong chirality, with neither epsilon nor μ negative required. We have developed a retrieval procedure, adopting a uniaxial bi-isotropic model to calculate the effective parameters such as n ± , κ, epsilon and μ of the chiral metamaterials. Our work on the design, numerical calculations and experimental measurements of chiral metamaterials is introduced. Strong chiral behaviors such as optical activity and circular dichroism are observed and negative refraction is obtained for circularly polarized waves in these chiral metamaterials. We show that 3D isotropic chiral metamaterials can eventually be realized.

  13. Chiral sensing by nonchiral tetrapyrroles.

    PubMed

    Labuta, Jan; Hill, Jonathan P; Ishihara, Shinsuke; Hanyková, Lenka; Ariga, Katsuhiko

    2015-03-17

    Enantiomeric excess (ee) is a measure of the purity of an enantiomer of a chiral compound with respect to the presence of the complementary enantiomer. It is an important aspect of chemistry, especially in the fields of pharmaceuticals and asymmetric catalysis. Existing methods for determination of enantiomeric excesses using nuclear magnetic resonance (NMR) spectroscopy mostly rely on special chiral reagents (auxiliaries) that form two or more diastereomeric complexes with a chiral compound. As a result of this, the NMR spectrum of each enantiomer is different, allowing the determination of enantiomeric excess. In this Account, we describe a molecular design process that has allowed us to prepare prochiral solvating agents for NMR determination of ee of a wide variety of analyte types. At the outset of this work, we initially encountered the phenomenon of NMR peak splitting in the oxoporphyrinogen (OxP) host component of a supramolecular host-guest complex, where the extent of the splitting is apparently proportional to the guests' ee. Upon closer examination of the mechanism of action, it was found that several complicating factors, including prototropic tautomerism, macrocyclic inversion (ring-flipping), and 1:2 host-guest stoichiometry, obstruct potential applications of OxP as a chiral solvating agent. By considering the molecular conformation of the OxP host, a saddle-shaped calix[4]pyrrole, we moved to study the tetraphenylporphyrin (TPP) dication since it has a similar form, and it was found that it could also be used to probe ee. However, although TPP does not suffer from disadvantageous tautomeric processes, it is still subject to macrocyclic inversion and has the additional serious disadvantage of operating for ee sensing only at depressed temperatures. The intrinsic disadvantages of the OxP and TPP systems were finally overcome by covalently modifying the OxP chromophore by regioselective N-alkylation at one face of the molecule. This procedure yields a

  14. Molecular chirality and chiral capsule-type dimer formation of cyclic triamides via hydrogen-bonding interactions.

    PubMed

    Fujimoto, Noriko; Matsumura, Mio; Azumaya, Isao; Nishiyama, Shizuka; Masu, Hyuma; Kagechika, Hiroyuki; Tanatani, Aya

    2012-05-18

    Chiral properties of bowl-shaped cyclic triamides bearing functional groups with hydrogen-bonding ability were examined. Chiral induction of cyclic triamide 3a was observed by addition of chiral amine in solution, and chiral separation was achieved by simple crystallization to afford chiral capsule-type dimer structure of 4a.

  15. Chiral logarithms in quenched QCD

    SciTech Connect

    Y. Chen; S. J. Dong; T. Draper; I. Horvath; F. X. Lee; K. F. Liu; N. Mathur; and J. B. Zhang

    2004-08-01

    The quenched chiral logarithms are examined on a 163x28 lattice with Iwasaki gauge action and overlap fermions. The pion decay constant fpi is used to set the lattice spacing, a = 0.200(3) fm. With pion mass as low as {approx}180 MeV, we see the quenched chiral logarithms clearly in mpi2/m and fP, the pseudoscalar decay constant. The authors analyze the data to determine how low the pion mass needs to be in order for the quenched one-loop chiral perturbation theory (chiPT) to apply. With the constrained curve-fitting method, they are able to extract the quenched chiral logarithmic parameter delta together with other low-energy parameters. Only for mpi<=300 MeV do we obtain a consistent and stable fit with a constant delta which they determine to be 0.24(3)(4) (at the chiral scale Lambdachi = 0.8 GeV). By comparing to the 123x28 lattice, they estimate the finite volume effect to be about 2.7% for the smallest pion mass. They also fitted the pion mass to the form for the re-summed cactus diagrams and found that its applicable region is extended farther than the range for the one-loop formula, perhaps up to mpi {approx}500-600 MeV. The scale independent delta is determined to be 0.20(3) in this case. The authors study the quenched non-analytic terms in the nucleon mass and find that the coefficient C1/2 in the nucleon mass is consistent with the prediction of one-loop chiPT. They also obtain the low energy constant L5 from fpi. They conclude from this study that it is imperative to cover only the range of data with the pion mass less than {approx}300 MeV in order to examine the chiral behavior of the hadron masses and decay constants in quenched QCD and match them with quenched one-loop chiPT.

  16. Chirality and catalysis with aromatic N-fused heterobicyclic carbenes.

    PubMed

    Iglesias-Sigüenza, Javier; Izquierdo, Cristina; Díez, Elena; Fernández, Rosario; Lassaletta, José M

    2016-06-21

    The benzoannulation of the most common families of aromatic NHCs, imidazol-2-ylidenes and 1,2,4-triazol-3-ylidenes, results in heterobicyclic imidazo[1,5-a]pyridin-3-ylidenes ('s) and [1,2,4]triazolo[4,3-a]pyridin-3-ylidenes ('s), characterized by a bridged N atom. These are versatile platforms that offer multiple possibilities for the modulation of the steric and electronic properties of the carbene ligand and/or organocatalyst, and offer also diverse opportunities for the introduction of several types of chiralities. In this paper the different families of chiral and carbenes and their application in asymmetric catalysis will be discussed. PMID:27254732

  17. Mechanism of chirality conversion by periodic change of temperature: Role of chiral clusters

    NASA Astrophysics Data System (ADS)

    Katsuno, Hiroyasu; Uwaha, Makio

    2016-01-01

    By grinding crystals in a solution, the chirality of crystal structure (and the molecular chirality for the case of chiral molecules as well) can be converted, and the cause of the phenomenon is attributed to crystal growth with chiral clusters. We show that the recently found chirality conversion with a periodic change of temperature can also be explained by crystal growth with chiral clusters. With the use of a generalized Becker-Döring model, which includes enantio-selective incorporation of small chiral clusters to large solid clusters, the change of cluster distribution and the mass flow between clusters are studied. The chiral clusters act as a reservoir to pump out the minority species to the majority, and the exponential amplification of the enantiomeric excess found in the experiment is reproduced in the numerical calculation.

  18. On Yang--Mills Theories with Chiral Matter at Strong Coupling

    SciTech Connect

    Shifman, M.; Unsal, Mithat; /SLAC /Stanford U., Phys. Dept.

    2008-08-20

    Strong coupling dynamics of Yang-Mills theories with chiral fermion content remained largely elusive despite much effort over the years. In this work, we propose a dynamical framework in which we can address non-perturbative properties of chiral, non-supersymmetric gauge theories, in particular, chiral quiver theories on S{sub 1} x R{sub 3}. Double-trace deformations are used to stabilize the center-symmetric vacuum. This allows one to smoothly connect smaller(S{sub 1}) to larger(S{sub 1}) physics (R{sub 4} is the limiting case) where the double-trace deformations are switched off. In particular, occurrence of the mass gap in the gauge sector and linear confinement due to bions are analytically demonstrated. We find the pattern of the chiral symmetry realization which depends on the structure of the ring operators, a novel class of topological excitations. The deformed chiral theory, unlike the undeformed one, satisfies volume independence down to arbitrarily small volumes (a working Eguchi-Kawai reduction) in the large N limit. This equivalence, may open new perspectives on strong coupling chiral gauge theories on R{sub 4}.

  19. [Asymmetric intramolecular conjugate addition of chiral enolates via non-equilibrium].

    PubMed

    Monguchi, Daiki

    2006-08-01

    Optically active alpha,alpha-disubstituted alpha-amino acids belong to an important class of unnatural amino acids. Since the synthesis of such amino acids involves the creation of a quaternary stereocenter, methods for their synthesis have been extensively studied. We have reported that N-t-butoxycarbonyl(Boc)-N-methoxymethyl(MOM)-amino acid derivatives undergo asymmetric alpha-alkylation in up to 93% ee. Original chiral information on an amino acid is preserved in axially chiral enolate intermediates, and thus asymmetric induction is achieved without the aid of external chiral sources (i.e., memory of chirality). Recently, we have reported a new protocol for the asymmetric cyclization of amino acid derivatives, which enables straightforward synthesis of cyclic amino acids with a tetrasubstituted carbon center from the usual alpha-amino acids in up to 98% ee. Here we report the asymmetric construction of highly substituted chiral nitrogen heterocycles via intramolecular conjugate addition of chiral enolates generated from N-Boc-N-alkylylamino acid derivatives. This method is applicable to the asymmetric construction of pyrrolidine, piperidine, tetrahydroisoquinoline, and indoline derivatives with contiguous quaternary and tertiary stereocenters.

  20. Stable Pentaquarks from Strange Chiral Multiplets

    SciTech Connect

    Silas Beane

    2004-12-01

    The assumption of strong diquark correlations in the QCD spectrum suggests flavor multiplets of hadrons that are degenerate in the chiral limit. Generally it would be unnatural for there to be degeneracy in the hadron spectrum that is not protected by a QCD symmetry. Here we show--for pentaquarks constructed from diquarks--that these degeneracies can be naturally protected by the full chiral symmetry of QCD. The resulting chiral multiplet structure recovers the ideally-mixed pentaquark mass spectrum of the diquark model, and interestingly, requires that the axial couplings of the pentaquarks to states outside the degenerate multiplets vanish in the chiral limit. This result suggests that if these hadrons exist, they are stable in the chiral limit and therefore have widths that scale as the fourth power of the kaon mass over the chiral symmetry breaking scale. Natural-size widths are of order a few MeV.

  1. Asymmetric synthesis using chiral-encoded metal.

    PubMed

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-08-26

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity.

  2. Asymmetric synthesis using chiral-encoded metal.

    PubMed

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-01-01

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity. PMID:27562028

  3. Anomalous Maxwell equations for inhomogeneous chiral plasma

    NASA Astrophysics Data System (ADS)

    Gorbar, E. V.; Shovkovy, I. A.; Vilchinskii, S.; Rudenok, I.; Boyarsky, A.; Ruchayskiy, O.

    2016-05-01

    Using the chiral kinetic theory we derive the electric and chiral current densities in inhomogeneous relativistic plasma. We also derive equations for the electric and chiral chemical potentials that close the Maxwell equations in such a plasma. The analysis is done in the regimes with and without a drift of the plasma as a whole. In addition to the currents present in the homogeneous plasma (Hall current, chiral magnetic, chiral separation, and chiral electric separation effects, as well as Ohm's current) we derive several new terms associated with inhomogeneities of the plasma. Apart from various diffusionlike terms, we find also new dissipationless terms that are independent of relaxation time. Their origin can be traced to the Berry curvature modifications of the kinetic theory.

  4. Asymmetric synthesis using chiral-encoded metal

    PubMed Central

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-01-01

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity. PMID:27562028

  5. Asymmetric synthesis using chiral-encoded metal

    NASA Astrophysics Data System (ADS)

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-08-01

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity.

  6. Enantioselective recognition at mesoporous chiral metal surfaces

    PubMed Central

    Wattanakit, Chularat; Côme, Yémima Bon Saint; Lapeyre, Veronique; Bopp, Philippe A.; Heim, Matthias; Yadnum, Sudarat; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2014-01-01

    Chirality is widespread in natural systems, and artificial reproduction of chiral recognition is a major scientific challenge, especially owing to various potential applications ranging from catalysis to sensing and separation science. In this context, molecular imprinting is a well-known approach for generating materials with enantioselective properties, and it has been successfully employed using polymers. However, it is particularly difficult to synthesize chiral metal matrices by this method. Here we report the fabrication of a chirally imprinted mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and chiral template molecules. The porous platinum retains a chiral character after removal of the template molecules. A matrix obtained in this way exhibits a large active surface area due to its mesoporosity, and also shows a significant discrimination between two enantiomers, when they are probed using such materials as electrodes. PMID:24548992

  7. On chirality of slime mould.

    PubMed

    Dimonte, Alice; Adamatzky, Andrew; Erokhin, Victor; Levin, Michael

    2016-02-01

    Left-right patterning and lateralised behaviour is an ubiquitous aspect of plants and animals. The mechanisms linking cellular chirality to the large-scale asymmetry of multicellular structures are incompletely understood, and it has been suggested that the chirality of living cells is hardwired in their cytoskeleton. We examined the question of biased asymmetry in a unique organism: the slime mould Physarum polycephalum, which is unicellular yet possesses macroscopic, complex structure and behaviour. In laboratory experiment using a T-shape, we found that Physarum turns right in more than 74% of trials. The results are in agreement with previously published studies on asymmetric movement of muscle cells, neutrophils, liver cells and growing neural filaments, and for the first time reveal the presence of consistently-biased laterality in the fungi kingdom. Exact mechanisms of the slime mould's direction preference remain unknown.

  8. On chirality of slime mould.

    PubMed

    Dimonte, Alice; Adamatzky, Andrew; Erokhin, Victor; Levin, Michael

    2016-02-01

    Left-right patterning and lateralised behaviour is an ubiquitous aspect of plants and animals. The mechanisms linking cellular chirality to the large-scale asymmetry of multicellular structures are incompletely understood, and it has been suggested that the chirality of living cells is hardwired in their cytoskeleton. We examined the question of biased asymmetry in a unique organism: the slime mould Physarum polycephalum, which is unicellular yet possesses macroscopic, complex structure and behaviour. In laboratory experiment using a T-shape, we found that Physarum turns right in more than 74% of trials. The results are in agreement with previously published studies on asymmetric movement of muscle cells, neutrophils, liver cells and growing neural filaments, and for the first time reveal the presence of consistently-biased laterality in the fungi kingdom. Exact mechanisms of the slime mould's direction preference remain unknown. PMID:26747637

  9. On lattice chiral gauge theories

    NASA Technical Reports Server (NTRS)

    Maiani, L.; Rossi, G. C.; Testa, M.

    1991-01-01

    The Smit-Swift-Aoki formulation of a lattice chiral gauge theory is presented. In this formulation the Wilson and other non invariant terms in the action are made gauge invariant by the coupling with a nonlinear auxilary scalar field, omega. It is shown that omega decouples from the physical states only if appropriate parameters are tuned so as to satisfy a set of BRST identities. In addition, explicit ghost fields are necessary to ensure decoupling. These theories can give rise to the correct continuum limit. Similar considerations apply to schemes with mirror fermions. Simpler cases with a global chiral symmetry are discussed and it is shown that the theory becomes free at decoupling. Recent numerical simulations agree with those considerations.

  10. Optically controllable THz chiral metamaterials.

    PubMed

    Kenanakis, G; Zhao, R; Katsarakis, N; Kafesaki, M; Soukoulis, C M; Economou, E N

    2014-05-19

    Switchable and tunable chiral metamaterial response is numerically demonstrated here in different uniaxial chiral metamaterial structures operating in the THz regime. The structures are based on the bi-layer conductor design and the tunable/switchable response is achieved by replacing parts of the metallic components of the structures by photoconducting Si, which can be transformed from an insulating to an almost conducting state through photoexcitation, achievable under external optical pumping. All the structures proposed and discussed here exhibit frequency regions with giant tunable circular dichroism, as well as regions with giant tunable optical activity, showing unique potential in the achievement of active THz polarization components, like tunable polarizers and polarization filters. PMID:24921336

  11. Bootstrapping N=2 chiral correlators

    NASA Astrophysics Data System (ADS)

    Lemos, Madalena; Liendo, Pedro

    2016-01-01

    We apply the numerical bootstrap program to chiral operators in four-dimensional N=2 SCFTs. In the first part of this work we study four-point functions in which all fields have the same conformal dimension. We give special emphasis to bootstrapping a specific theory: the simplest Argyres-Douglas fixed point with no flavor symmetry. In the second part we generalize our setup and consider correlators of fields with unequal dimension. This is an example of a mixed correlator and allows us to probe new regions in the parameter space of N=2 SCFTs. In particular, our results put constraints on relations in the Coulomb branch chiral ring and on the curvature of the Zamolodchikov metric.

  12. Chiral anomaly, bosonization, and fractional charge

    SciTech Connect

    Mignaco, J.A.; Monteiro, M.A.R.

    1985-06-15

    We present a method to evaluate the Jacobian of chiral rotations, regulating determinants through the proper-time method and using Seeley's asymptotic expansion. With this method we compute easily the chiral anomaly for ..nu.. = 4,6 dimensions, discuss bosonization of some massless two-dimensional models, and handle the problem of charge fractionization. In addition, we comment on the general validity of Fujikawa's approach to regulate the Jacobian of chiral rotations with non-Hermitian operators.

  13. Thin-wire scatterers in chiral media.

    PubMed

    Jaggard, D L; Liu, J C; Grot, A; Pelet, P

    1991-06-01

    The effect of the handedness of chiral materials on the differential scattering cross section of embedded conducting wires is examined. The bow-tie-shaped induced current distributions and the resulting forbidden zone of radiation are explained through fundamental physical principles. We find that thin-wire scatterers can be divided into subchiral, chiral, and superchiral classes according to the degree of chirality of the host material and the electromagnetic length of the wire.

  14. Chirality operators for Heisenberg spin systems

    SciTech Connect

    Subrahmanyam, V. )

    1994-09-01

    The ground state of closed Heisenberg spin chains with an odd number of sites has a chiral degeneracy, in addition to a twofold Kramers degeneracy. A nonzero chirality implies that the spins are not coplanar, and is a measure of handedness. The chirality operator, which can be treated as a spin-1/2 operator, is explicitly constructed in terms of the spin operators, and is given as commutator of permutation operators.

  15. Flat-space chiral gravity.

    PubMed

    Bagchi, Arjun; Detournay, Stéphane; Grumiller, Daniel

    2012-10-12

    We provide the first evidence for a holographic correspondence between a gravitational theory in flat space and a specific unitary field theory in one dimension lower. The gravitational theory is a flat-space limit of topologically massive gravity in three dimensions at a Chern-Simons level of k=1. The field theory is a chiral two-dimensional conformal field theory with a central charge of c=24. PMID:23102291

  16. Anomalies and Discrete Chiral Symmetries

    SciTech Connect

    Creutz, M.

    2009-09-07

    The quantum anomaly that breaks the U(1) axial symmetry of massless multi-flavored QCD leaves behind a discrete flavor-singlet chiral invariance. With massive quarks, this residual symmetry has a close connection with the strong CP-violating parameter theta. One result is that if the lightest quarks are degenerate, then a first order transition will occur when theta passes through pi. The resulting framework helps clarify when the rooting prescription for extrapolating in the number of flavors is valid.

  17. Staggered chiral random matrix theory

    SciTech Connect

    Osborn, James C.

    2011-02-01

    We present a random matrix theory for the staggered lattice QCD Dirac operator. The staggered random matrix theory is equivalent to the zero-momentum limit of the staggered chiral Lagrangian and includes all taste breaking terms at their leading order. This is an extension of previous work which only included some of the taste breaking terms. We will also present some results for the taste breaking contributions to the partition function and the Dirac eigenvalues.

  18. Chiral symmetry and nucleon structure

    SciTech Connect

    Holstein, B.R. . Dept. of Physics and Astromony Washington Univ., Seattle, WA . Inst. for Nuclear Theory)

    1992-01-01

    Recently it has been realized that significant tests of the validity of QCD are available in low energy experiments (E < 500 MeV) by exploiting the property of (broken) chiral symmetry. This technique has been highly developed in The Goldstone boson sector by the work of Gasser and Leutwyler. Application to the nucleon system is much more difficult and is now being carefully developed.

  19. Chiral plasmons without magnetic field

    PubMed Central

    Song, Justin C. W.; Rudner, Mark S.

    2016-01-01

    Plasmons, the collective oscillations of interacting electrons, possess emergent properties that dramatically alter the optical response of metals. We predict the existence of a new class of plasmons—chiral Berry plasmons (CBPs)—for a wide range of 2D metallic systems including gapped Dirac materials. As we show, in these materials the interplay between Berry curvature and electron–electron interactions yields chiral plasmonic modes at zero magnetic field. The CBP modes are confined to system boundaries, even in the absence of topological edge states, with chirality manifested in split energy dispersions for oppositely directed plasmon waves. We unveil a rich CBP phenomenology and propose setups for realizing them, including in anomalous Hall metals and optically pumped 2D Dirac materials. Realization of CBPs will offer a powerful paradigm for magnetic field-free, subwavelength optical nonreciprocity, in the mid-IR to terahertz range, with tunable splittings as large as tens of THz, as well as sensitive all-optical diagnostics of topological bands. PMID:27071090

  20. Objects of Maximum Electromagnetic Chirality

    NASA Astrophysics Data System (ADS)

    Fernandez-Corbaton, Ivan; Fruhnert, Martin; Rockstuhl, Carsten

    2016-07-01

    We introduce a definition of the electromagnetic chirality of an object and show that it has an upper bound. Reciprocal objects attain the upper bound if and only if they are transparent for all the fields of one polarization handedness (helicity). Additionally, electromagnetic duality symmetry, i.e., helicity preservation upon interaction, turns out to be a necessary condition for reciprocal objects to attain the upper bound. We use these results to provide requirements for the design of such extremal objects. The requirements can be formulated as constraints on the polarizability tensors for dipolar objects or on the material constitutive relations for continuous media. We also outline two applications for objects of maximum electromagnetic chirality: a twofold resonantly enhanced and background-free circular dichroism measurement setup, and angle-independent helicity filtering glasses. Finally, we use the theoretically obtained requirements to guide the design of a specific structure, which we then analyze numerically and discuss its performance with respect to maximal electromagnetic chirality.

  1. Chiral plasmons without magnetic field.

    PubMed

    Song, Justin C W; Rudner, Mark S

    2016-04-26

    Plasmons, the collective oscillations of interacting electrons, possess emergent properties that dramatically alter the optical response of metals. We predict the existence of a new class of plasmons-chiral Berry plasmons (CBPs)-for a wide range of 2D metallic systems including gapped Dirac materials. As we show, in these materials the interplay between Berry curvature and electron-electron interactions yields chiral plasmonic modes at zero magnetic field. The CBP modes are confined to system boundaries, even in the absence of topological edge states, with chirality manifested in split energy dispersions for oppositely directed plasmon waves. We unveil a rich CBP phenomenology and propose setups for realizing them, including in anomalous Hall metals and optically pumped 2D Dirac materials. Realization of CBPs will offer a powerful paradigm for magnetic field-free, subwavelength optical nonreciprocity, in the mid-IR to terahertz range, with tunable splittings as large as tens of THz, as well as sensitive all-optical diagnostics of topological bands. PMID:27071090

  2. Chiral methyl-branched pheromones.

    PubMed

    Ando, Tetsu; Yamakawa, Rei

    2015-07-01

    Insect pheromones are some of the most interesting natural products because they are utilized for interspecific communication between various insects, such as beetles, moths, ants, and cockroaches. A large number of compounds of many kinds have been identified as pheromone components, reflecting the diversity of insect species. While this review deals only with chiral methyl-branched pheromones, the chemical structures of more than one hundred non-terpene compounds have been determined by applying excellent analytical techniques. Furthermore, their stereoselective syntheses have been achieved by employing trustworthy chiral sources and ingenious enantioselective reactions. The information has been reviewed here not only to make them available for new research but also to understand the characteristic chemical structures of the chiral pheromones. Since biosynthetic studies are still limited, it might be meaningful to examine whether the structures, particularly the positions and configurations of the branched methyl groups, are correlated with the taxonomy of the pheromone producers and also with the function of the pheromones in communication systems. PMID:25849023

  3. Depressive Symptoms Correlate with Disability and Disease Course in Multiple Sclerosis Patients: An Italian Multi-Center Study Using the Beck Depression Inventory

    PubMed Central

    Solaro, C.; Trabucco, E.; Signori, A.; Martinelli, V.; Radaelli, M.; Centonze, D.; Rossi, S.; Grasso, M. G.; Clemenzi, A.; Bonavita, S.; D’Ambrosio, A.; Patti, F.; D’Amico, E.; Cruccu, G.; Truini, A.

    2016-01-01

    Background Depression occurs in about 50% of patients with multiple sclerosis. The aims of this study was to investigate the prevalence of depressive symptoms in a multicenter MS population using the Beck Depression Inventory II (BDI II) and to identify possible correlations between the BDI II score and demographic and clinical variables. Methods Data were collected in a multi-center, cross-sectional study over a period of six months in six MS centers in Italy using BDI II. Results 1,011 MS patients participated in the study. 676 subjects were female, with a mean age of 34 years (SD 10.8), mean EDSS of 3.3 (0–8.5) and mean disease duration of 10.3 years (range 1–50 years). 668 (%) subjects scored lower than 14 on the BDI II and 343 (33.9%) scored greater than 14 (14 cut-off score). For patients with BDI>14 multivariate analysis showed a significant difference between EDSS and disease course. BDI II scores for subjects with secondary progressive (SP) MS were significantly different from primary progressive (PP) patients (p < 0.001) but similar to relapsing-remitting (RR) patients. Considering subjects with moderate to severe depressive symptoms (BDI II score from 20–63), in relation to disease course, 11.7% (83/710) had RR MS, 40.7% (96/236) SP and 13.6% (6/44) PP. Conclusions Using the BDI II, 30% of the current sample had depressive symptoms. BDI II score correlates with disability and disease course, particularly in subjects with SP MS. The BDI II scale can be a useful tool in clinical practice to screen depressive symptoms in people with MS. PMID:27632167

  4. C₅-symmetric chiral corannulenes: desymmetrization of bowl inversion equilibrium via "intramolecular" hydrogen-bonding network.

    PubMed

    Kang, Jiheong; Miyajima, Daigo; Itoh, Yoshimitsu; Mori, Tadashi; Tanaka, Hiroki; Yamauchi, Masahito; Inoue, Yoshihisa; Harada, Soichiro; Aida, Takuzo

    2014-07-30

    Because of a rapid conformational inversion, bowl-shaped C5-symmetric corannulenes, though geometrically chiral, have not been directly resolved into their enantiomers. However, if this inversion equilibrium can be desymmetrized, chiral corannulenes enriched in either enantiomer can be obtained. We demonstrated this possibility using pentasubstituted corannulenes 4 and 5 carrying amide-appended thioalkyl side chains. Compound 4 displays chiroptical activity in a chiral hydrocarbon such as limonene. Because compound 5 carries a chiral center in the side chains, its enantiomers 5R and 5S show chiroptical activity even in achiral solvents such as CHCl3 and methylcyclohexane. In sharp contrast, when the side chains bear no amide functionality (1 and 2R), no chiroptical activity emerges even in limonene or with a chiral center in the side chains. Detailed investigations revealed that the peripheral amide units in 4 and 5 are hydrogen-bonded only "intramolecularly" along the corannulene periphery, affording cyclic amide networks with clockwise and anticlockwise geometries. Although this networking gives rise to four stereoisomers, only two, which are enantiomeric to one another, are suggested computationally to exist in the equilibrated system. In a chiral environment (chiral solvent or side chain), their thermodynamic stabilities are certainly unequal, so the bowl-inversion equilibrium can be desymmetrized. However, this is not the case when the system contains a protic solvent that can deteriorate the hydrogen-bonding network. When the enantiomeric purity of limonene as the solvent is varied, the chiroptical activity of the corannulene core changes nonlinearly with its enantiomeric excess (majority rule). PMID:25046475

  5. Lateral chirality-sorting optical forces.

    PubMed

    Hayat, Amaury; Mueller, J P Balthasar; Capasso, Federico

    2015-10-27

    The transverse component of the spin angular momentum of evanescent waves gives rise to lateral optical forces on chiral particles, which have the unusual property of acting in a direction in which there is neither a field gradient nor wave propagation. Because their direction and strength depends on the chiral polarizability of the particle, they act as chirality-sorting and may offer a mechanism for passive chirality spectroscopy. The absolute strength of the forces also substantially exceeds that of other recently predicted sideways optical forces. PMID:26453555

  6. Generation of a Chiral Giant Micelle.

    PubMed

    Ito, Thiago H; Salles, Airton G; Priebe, Jacks P; Miranda, Paulo C M L; Morgon, Nelson H; Danino, Dganit; Mancini, Giovanna; Sabadini, Edvaldo

    2016-08-23

    Over the past few years, chiral supramolecular assemblies have been successfully used for recognition, sensing and enantioselective transformations. Several approaches are available to control chirality of discrete assemblies (e.g., cages and capsules), but few are efficient in assuring chirality for micellar aggregates. Optically active amino acid-derived surfactants are commonly used to generate chiral spherical micelles. To circumvent this limitation, we benefited from the uniaxial growth of spherical micelles into long cylindrical micelles usually called wormlike or giant micelles, upon the addition of cosolutes. This paper describes the unprecedented formation of chiral giant micelles in aqueous solutions of cetyltrimethylammonium bromide (CTAB) upon increasing addition of enantiopure sodium salt of 1,1'-bi-2-naphthol (Na-binaphtholate) as a cosolute. Depending on the concentrations of CTAB and Na-binaphtholate, chiral gel-like systems are obtained. The transition from spherical to giant micellar structures was probed using rheology, cryo-transmission electron microscopy, polarimetry, and electronic circular dichroism (CD). CD can be effectively used to monitor the incorporation of Na-binaphtholate into the micelle palisade as well as to determine its transition to giant micellar structures. Our approach expands the scope for chirality induction in micellar aggregates bringing the possibility to generate "smart" chiral systems and an alternative asymmetric chiral environment to perform enantioselective transformations. PMID:27499127

  7. Chiral selection on inorganic crystalline surfaces

    NASA Technical Reports Server (NTRS)

    Hazen, Robert M.; Sholl, David S.

    2003-01-01

    From synthetic drugs to biodegradable plastics to the origin of life, the chiral selection of molecules presents both daunting challenges and significant opportunities in materials science. Among the most promising, yet little explored, avenues for chiral molecular discrimination is adsorption on chiral crystalline surfaces - periodic environments that can select, concentrate and possibly even organize molecules into polymers and other macromolecular structures. Here we review experimental and theoretical approaches to chiral selection on inorganic crystalline surfaces - research that is poised to open this new frontier in understanding and exploiting surface-molecule interactions.

  8. Chiral Magnetic Effect in Hydrodynamic Approximation

    NASA Astrophysics Data System (ADS)

    Zakharov, Valentin I.

    We review derivations of the chiral magnetic effect (ChME) in hydrodynamic approximation. The reader is assumed to be familiar with the basics of the effect. The main challenge now is to account for the strong interactions between the constituents of the fluid. The main result is that the ChME is not renormalized: in the hydrodynamic approximation it remains the same as for non-interacting chiral fermions moving in an external magnetic field. The key ingredients in the proof are general laws of thermodynamics and the Adler-Bardeen theorem for the chiral anomaly in external electromagnetic fields. The chiral magnetic effect in hydrodynamics represents a macroscopic manifestation of a quantum phenomenon (chiral anomaly). Moreover, one can argue that the current induced by the magnetic field is dissipation free and talk about a kind of "chiral superconductivity". More precise description is a quantum ballistic transport along magnetic field taking place in equilibrium and in absence of a driving force. The basic limitation is the exact chiral limit while temperature—excitingly enough—does not seemingly matter. What is still lacking, is a detailed quantum microscopic picture for the ChME in hydrodynamics. Probably, the chiral currents propagate through lower-dimensional defects, like vortices in superfluid. In case of superfluid, the prediction for the chiral magnetic effect remains unmodified although the emerging dynamical picture differs from the standard one.

  9. The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol

    NASA Astrophysics Data System (ADS)

    Liriano, Melissa L.; Carrasco, Javier; Lewis, Emily A.; Murphy, Colin J.; Lawton, Timothy J.; Marcinkowski, Matthew D.; Therrien, Andrew J.; Michaelides, Angelos; Sykes, E. Charles H.

    2016-03-01

    The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule's intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our data

  10. The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol.

    PubMed

    Liriano, Melissa L; Carrasco, Javier; Lewis, Emily A; Murphy, Colin J; Lawton, Timothy J; Marcinkowski, Matthew D; Therrien, Andrew J; Michaelides, Angelos; Sykes, E Charles H

    2016-03-01

    The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule's intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our data

  11. The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol.

    PubMed

    Liriano, Melissa L; Carrasco, Javier; Lewis, Emily A; Murphy, Colin J; Lawton, Timothy J; Marcinkowski, Matthew D; Therrien, Andrew J; Michaelides, Angelos; Sykes, E Charles H

    2016-03-01

    The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule's intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our data

  12. Counting chiral operators in quiver gauge theories

    NASA Astrophysics Data System (ADS)

    Butti, Agostino; Forcella, Davide; Hanany, Amihay; Vegh, David; Zaffaroni, Alberto

    2007-11-01

    We discuss in detail the problem of counting BPS gauge invariant operators in the chiral ring of quiver gauge theories living on D-branes probing generic toric CY singularities. The computation of generating functions that include counting of baryonic operators is based on a relation between the baryonic charges in field theory and the Kähler moduli of the CY singularities. A study of the interplay between gauge theory and geometry shows that given geometrical sectors appear more than once in the field theory, leading to a notion of ``multiplicities". We explain in detail how to decompose the generating function for one D-brane into different sectors and how to compute their relevant multiplicities by introducing geometric and anomalous baryonic charges. The Plethystic Exponential remains a major tool for passing from one D-brane to arbitrary number N of D-branes. Explicit formulae are given for few examples, including Bbb C3/Bbb Z3, Bbb F0, and dP1.

  13. Chiral molecules in the ISM: the best candidates

    NASA Astrophysics Data System (ADS)

    Pilme, J.; Marloie, G.; Lattelais, M.; Pauzat, F.; Ellinger, Y.

    2011-05-01

    In this report we address the question of whether some chiral molecules have a probability of being detected in the interstellar medium (ISM). It is a crucial question since life on Earth, as we know it today, is inseparable from homochirality. Under these conditions, the identification of any chiral species in the interstellar medium (ISM) would be a considerable breakthrough in the pursuit of the origin of life. To this end we rely on the Minimum Energy Principle that states that the most abundant isomer of a given generic formula should be that of lowest energy (Lattelais et al. 2009). We present here computations of the relative stability of complex organic molecules (COMs) believed to be potentially able to exist in the ISM under a chiral isomeric form. Such a search is submitted to a number of constraints. The molecules we are looking for should present precise characteristics, namely: i) have no improper axis of rotation Sn; possess at least one asymmetric center ; ii) satisfy the Minimum Energy Principle; iii) be small with a large enough dipole moment to be possibly identified through their radio millimeter rotational spectra. The energies and dipole moments are calculated by means of quantum simulations based on density functional theory (DFT). The result is that no chiral isomer in the C3H6O (acetone), C2H5ON, C3H7ON (amides), C2H5O2N, C3H7O2N (amino acid) families is the most stable species. This is also true of the C2(H2O)2 and C3(H2O)3 species when restricted to the sugar families, but another chiral molecule of the same chemical formula, i.e. lactic acid HOCH(CH3)COOH is found to be the most stable of all structures. Two other molecules with an NH2 group, namely, NH2CH(CH3)CN, the precursor of α-alanine and NH2CH(CH3)OH, the simplest chiral molecule (beyond halogen or isotopically substituted methane curiosities) are also the most stable species in their respective families. These three molecules satisfy the conditions for being detected according

  14. Discovery of the First Interstellar Chiral Molecule: Propylene Oxide

    NASA Astrophysics Data System (ADS)

    Carroll, Brandon; McGuire, Brett A.; Loomis, Ryan; Finneran, Ian A.; Jewell, Philip; Remijan, Anthony; Blake, Geoffrey

    2016-06-01

    Life on Earth relies on chiral molecules, that is, species not superimposable on their mirror images. This manifests itself as a reliance on a single molecular handedness, or homochirality that is characteristic of life and perhaps most readily apparent in the large enhancement in biological activity of particular amino acid and sugar enantiomers. Yet, the ancestral origin of biological homochirality remains a mystery. The non-racemic ratios in some organics isolated from primitive meteorites hint at a primordial chiral seed but even these samples have experienced substantial processing during planetary assembly, obscuring their complete histories. To determine the underlying origin of any enantiomeric excess, it is critical to understand the molecular gas from which these molecules originated. Here, we present the first extra-solar, astronomical detection of a chiral molecule, propylene oxide (CH_3CHCH_2O), in absorption toward the Galactic Center. With the detection of propylene oxide, we at last have a target for broad-ranging searches for the possible cosmic origin of the homochirality of life.

  15. Evaluation of Dalbavancin as chiral selector for HPLC and comparison with Teicoplanin based chiral stationary phases

    PubMed Central

    ZHANG, XIAOTONG; BAO, YE; HUANG, KE; BARNETT-RUNDLETT, KIMBER L.; ARMSTRONG, DANIEL W.

    2015-01-01

    Dalbavancin is a new compound of the macrocyclic glycopeptide family. It was covalently linked to 5μm silica particles by using two different binding chemsitries. Approximately two hundred and fifty racemates including (A) heterocyclic compounds; (B) chiral acids; (C) chiral amines; (D) chiral alcohols; (E) chiral sulfoxides and sulfilimines; (F) amino acids and amino acid derivatives; and (G) other chiral compounds were tested on the two new chiral stationary phases (CSP) using three different mobile phases. As dalbavancin is structurally related to teicoplanin, the same set of chiral compounds was screened on two commercially available teicoplanin CSPs for comparison. The dalbavancin CSPs were able to separate some enantiomers that were not separated by the teicoplanin CSPs and also showed improved separations for many racemates. However, there were other compounds only separated or better separated on teicoplanin CSPS. Therefore, the dalbavancin CSPs are complementary to the teicoplanin CSPs. PMID:19676111

  16. Biomimetic Hierarchical Assembly of Helical Supraparticles from Chiral Nanoparticles.

    PubMed

    Zhou, Yunlong; Marson, Ryan L; van Anders, Greg; Zhu, Jian; Ma, Guanxiang; Ercius, Peter; Sun, Kai; Yeom, Bongjun; Glotzer, Sharon C; Kotov, Nicholas A

    2016-03-22

    Chiroptical materials found in butterflies, beetles, stomatopod crustaceans, and other creatures are attributed to biocomposites with helical motifs and multiscale hierarchical organization. These structurally sophisticated materials self-assemble from primitive nanoscale building blocks, a process that is simpler and more energy efficient than many top-down methods currently used to produce similarly sized three-dimensional materials. Here, we report that molecular-scale chirality of a CdTe nanoparticle surface can be translated to nanoscale helical assemblies, leading to chiroptical activity in the visible electromagnetic range. Chiral CdTe nanoparticles coated with cysteine self-organize around Te cores to produce helical supraparticles. D-/L-Form of the amino acid determines the dominant left/right helicity of the supraparticles. Coarse-grained molecular dynamics simulations with a helical pair-potential confirm the assembly mechanism and the origin of its enantioselectivity, providing a framework for engineering three-dimensional chiral materials by self-assembly. The helical supraparticles further self-organize into lamellar crystals with liquid crystalline order, demonstrating the possibility of hierarchical organization and with multiple structural motifs and length scales determined by molecular-scale asymmetry of nanoparticle interactions.

  17. Chiral Bosonic Mott Insulator on the Frustrated Triangular Lattice

    NASA Astrophysics Data System (ADS)

    Parameswaran, Siddharth; Zaletel, Michael; Rüegg, Andreas; Altman, Ehud

    2014-03-01

    We study the superfluid and insulating phases of interacting bosons on the triangular lattice with an inverted dispersion, corresponding to frustrated hopping between sites. The resulting single-particle dispersion has multiple minima at nonzero wavevectors in momentum space, in contrast to the unique zero-wavevector minimum of the unfrustrated problem. As a consequence, the superfluid phase is unstable against developing additional chiral order that breaks time reversal (T) and parity (P) symmetries by forming a condensate at nonzero wavevector. We demonstrate that the loss of superfluidity can lead to an even more exotic phase, the chiral Mott insulator, with nontrivial current order that breaks T, P. These results are obtained via variational estimates, as well as a combination of bosonization and DMRG of triangular ladders, which taken together permit a fairly complete characterization of the phase diagram. We discuss the relevance of these phases to optical lattice experiments, as well as signatures of chiral symmetry breaking in time-of-flight images. We acknowledge support from NSF Grants 1066293 (SP, EA) and DGE-1106400 (MPZ), the Simons Foundation (SP), the Swiss National Science Foundation (AR), the ISF, BSF, ERC Synergy UQUAM program and the Miller Institute at UC Berkeley (EA).

  18. Chiral bosonic Mott insulator on the frustrated triangular lattice

    NASA Astrophysics Data System (ADS)

    Zaletel, Michael P.; Parameswaran, S. A.; Rüegg, Andreas; Altman, Ehud

    2014-04-01

    We study the superfluid and insulating phases of interacting bosons on the triangular lattice with an inverted dispersion, corresponding to frustrated hopping between sites. The resulting single-particle dispersion has multiple minima at nonzero wave vectors in momentum space, in contrast to the unique zero-wave-vector minimum of the unfrustrated problem. As a consequence, the superfluid phase is unstable against developing additional chiral order that breaks time-reversal (T) and parity (P) symmetries by forming a condensate at nonzero wave vector. We demonstrate that the loss of superfluidity can lead to an even more exotic phase, the chiral Mott insulator, with nontrivial current order that breaks T ,P. These results are obtained via variational estimates, as well as a combination of bosonization and density-matrix renormalization group of triangular ladders, which, taken together, permit a fairly complete characterization of the phase diagram. We discuss the relevance of these phases to optical lattice experiments, as well as signatures of chiral symmetry breaking in time-of-flight images.

  19. Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes

    PubMed Central

    Krivickas, Sara Jane; Hashimoto, Chiho; Yoshida, Junya; Ueda, Akira; Takahashi, Kazuyuki; Wallis, John D

    2015-01-01

    Summary Chiral molecular crystals built up by chiral molecules without inversion centers have attracted much interest owing to their versatile functionalities related to optical, magnetic, and electrical properties. However, there is a difficulty in chiral crystal growth due to the lack of symmetry. Therefore, we made the molecular design to introduce intermolecular hydrogen bonds in chiral crystals. Racemic and enantiopure bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) derivatives possessing hydroxymethyl groups as the source of hydrogen bonds were designed. The novel racemic trans-vic-(hydroxymethyl)(methyl)-BEDT-TTF 1, and racemic and enantiopure trans-vic-bis(hydroxymethyl)-BEDT-TTF 2 were synthesized. Moreover, the preparations, crystal structure analyses, and electrical resistivity measurements of the novel achiral charge transfer salt θ21-[(S,S)-2]3[(R,R)-2]3(ClO4)2 and the chiral salt α’-[(R,R)-2]ClO4(H2O) were carried out. In the former θ21-[(S,S)-2]3[(R,R)-2]3(ClO4)2, there are two sets of three crystallographically independent donor molecules [(S,S)-2]2[(R,R)-2] in a unit cell, where the two sets are related by an inversion center. The latter α’-[(R,R)-2]ClO4(H2O) is the chiral salt with included solvent H2O, which is not isostructural with the reported chiral salt α’-[(S,S)-2]ClO4 without H2O, but has a similar donor arrangement. According to the molecular design by introduction of hydroxy groups and a ClO4 − anion, many intermediate-strength intermolecular hydrogen bonds (2.6–3.0 Å) were observed in these crystals between electron donor molecules, anions, and included H2O solvent, which improve the crystallinity and facilitate the extraction of physical properties. Both salts are semiconductors with relatively low resistivities at room temperature and activation energies of 1.2 ohm cm with E a = 86 meV for θ21-[(S,S)-2]3[(R,R)-2]3(ClO4)2 and 0.6 ohm cm with E a = 140 meV for α'-[(R,R)-2]2ClO4(H2O), respectively. The variety of donor

  20. A mechanism to pin skyrmions in chiral magnets.

    PubMed

    Liu, Ye-Hua; Li, You-Quan

    2013-02-20

    We propose a mechanism to pin skyrmions in chiral magnetic thin films by introducing local maxima of magnetic exchange strength as pinning centers. The local maxima can be realized by engineering the local density of itinerant electrons. The stationary properties and the dynamical pinning and depinning processes of an isolated skyrmion around a pinning center are studied. We carry out numerical simulations of the Landau-Lifshitz-Gilbert (LLG) equation and find a way to control the position of an isolated skyrmion in a pinning center lattice using electric current pulses. The results are verified by a Thiele equation analysis. We also find that the critical current to depin a skyrmion, which is estimated to have order of magnitude 10(7)-10(8) A m(-2), has linear dependence on the pinning strength.

  1. Chiral hypervalent iodine reagents: synthesis and reactivity.

    PubMed

    Parra, Alejandro; Reboredo, Silvia

    2013-12-16

    Chiral hypervalent iodine chemistry has been steadily increasing in importance in recent years. This review catalogues enantioselective transformations triggered by chiral hypervalent iodine(III/V) reagents, in stoichiometric or catalytic quantities, highlighting the different reactivities in terms of yield and enantioselectivity. Moreover, the synthesis of the most remarkable and successful catalysts has been illustrated in detail.

  2. A construction of lattice chiral gauge theories

    NASA Astrophysics Data System (ADS)

    Narayanan, Rajamani; Neuberger, Herbert

    1995-02-01

    Path integration over Euclidean chiral fermions is replaced by the quantum mechanics of an auxiliary system of non-interacting fermions. Our construction avoids the no-go theorem and faithfully maintains all the known important features of chiral fermions, including the violation of some perturbative conservation laws by gauge field configurations of non-trivial topology.

  3. Color Confinement and Dynamical Chiral Symmetry Breaking

    NASA Astrophysics Data System (ADS)

    Nakamura, Naoki; Suzuki, Tsuneo

    We study the relation between the quark confinement and the dynamical chiral symmetry breaking in SU(2) QCD by deriving an effective Lagrangian of a monopole field and the chiral fields from the dual Ginzburg-Landau type Lagrangian(DGL Lagrangian)…

  4. Quantization of the chiral soliton in medium

    NASA Astrophysics Data System (ADS)

    Nagai, S.; Sawado, N.; Shiiki, N.

    2006-01-01

    Chiral solitons coupled with quarks in medium are studied based on the Wigner-Seitz approximation. The chiral quark soliton model is used to obtain the classical soliton solutions. To investigate nucleon and Δ in matter, the semi-classical quantization is performed by the cranking method. The saturation for nucleon matter and Δ matter are observed.

  5. Generalized electromagnetic fields in a chiral medium

    NASA Astrophysics Data System (ADS)

    Bisht, P. S.; Singh, Jivan; Negi, O. P. S.

    2007-09-01

    The time-dependent Dirac-Maxwell's equations in the presence of electric and magnetic sources are reformulated in a chiral medium, and the solutions for the classical problem are obtained in a unique, simple and consistent manner. The quaternion reformulation of generalized electromagnetic fields in the chiral medium has also been discussed in a compact, simple and consistent manner.

  6. Chiral gravity, log gravity, and extremal CFT

    SciTech Connect

    Maloney, Alexander; Song Wei; Strominger, Andrew

    2010-03-15

    We show that the linearization of all exact solutions of classical chiral gravity around the AdS{sub 3} vacuum have positive energy. Nonchiral and negative-energy solutions of the linearized equations are infrared divergent at second order, and so are removed from the spectrum. In other words, chirality is confined and the equations of motion have linearization instabilities. We prove that the only stationary, axially symmetric solutions of chiral gravity are BTZ black holes, which have positive energy. It is further shown that classical log gravity--the theory with logarithmically relaxed boundary conditions--has finite asymptotic symmetry generators but is not chiral and hence may be dual at the quantum level to a logarithmic conformal field theories (CFT). Moreover we show that log gravity contains chiral gravity within it as a decoupled charge superselection sector. We formally evaluate the Euclidean sum over geometries of chiral gravity and show that it gives precisely the holomorphic extremal CFT partition function. The modular invariance and integrality of the expansion coefficients of this partition function are consistent with the existence of an exact quantum theory of chiral gravity. We argue that the problem of quantizing chiral gravity is the holographic dual of the problem of constructing an extremal CFT, while quantizing log gravity is dual to the problem of constructing a logarithmic extremal CFT.

  7. A lattice formulation of chiral gauge theories

    SciTech Connect

    Bodwin, G.T.

    1996-08-01

    We present a method for implementing gauge theories of chiral fermions on the lattice. Discussed topics include: the lattice as a UV regulator, a chiral QED model, modification of the fermion determinant, large gauge-field momenta, and a non-perturbative problem.

  8. Orientation-Dependent Handedness and Chiral Design

    NASA Astrophysics Data System (ADS)

    Efrati, Efi; Irvine, William T. M.

    2014-01-01

    Chirality occupies a central role in fields ranging from biological self-assembly to the design of optical metamaterials. The definition of chirality, as given by Lord Kelvin, associates chirality with the lack of mirror symmetry: the inability to superpose an object on its mirror image. While this definition has guided the classification of chiral objects for over a century, the quantification of handed phenomena based on this definition has proven elusive, if not impossible, as manifest in the paradox of chiral connectedness. In this work, we put forward a quantification scheme in which the handedness of an object depends on the direction in which it is viewed. While consistent with familiar chiral notions, such as the right-hand rule, this framework allows objects to be simultaneously right and left handed. We demonstrate this orientation dependence in three different systems—a biomimetic elastic bilayer, a chiral propeller, and optical metamaterial—and find quantitative agreement with chirality pseudotensors whose form we explicitly compute. The use of this approach resolves the existing paradoxes and naturally enables the design of handed metamaterials from symmetry principles.

  9. Study on the determination and chiral inversion of R-salbutamol in human plasma and urine by liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhou, Ting; Zeng, Jing; Liu, Shan; Zhao, Ting; Wu, Jie; Lai, Wenshi; He, Mingzhi; Xu, Beining; Qu, Shanshan; Xu, Ling; Tan, Wen

    2015-10-01

    The chiral inversion has been a concerned issue during the research and development of a chiral drug. In this study, a sensitive chiral liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for determination of salbutamol enantiomers in human plasma and urine. The chiral inversion mechanism of R-salbutamol was fully investigated for the first time by studying the effects of physicochemical factors, including pH, temperature and time. A fitted model to predict the chiral inversion ratio of R-salbutamol was proposed using a Box-Behnken design. All the samples were separated on an Astec Chirobiotic T column and detected by a tandem mass spectrometer in multiple reaction monitoring mode. Lower limit of quantification of 0.100ng/mL was achieved under the optimized conditions. The method was fully validated and successfully applied to the clinical pharmacokinetic study of R-salbutamol in healthy volunteers. Chiral inversion of R-salbutamol to S-salbutamol has been detected in urine samples. The results indicated that pH and temperature were two dominant factors that caused the chiral inversion of R-salbutamol, which should be taken into consideration during the analysis of chiral drugs. The chiral inversion of R-salbutamol determined in this study was confirmed resulted from the gastric acid in stomach rather than caused by the analysis conditions. Moreover, the calculated results of the fitted model matched very well with the enantioselective pharmacokinetic study of R-salbutamol, and the individual difference of the chiral inversion ratio of R-salbutamol was related to the individual gastric environment. On the basis of the results, this study provides important and concrete information not only for the chiral analysis but also for the metabolism research of chiral drugs.

  10. Stereoselective nucleophilic fluoromethylation of aryl ketones: dynamic kinetic resolution of chiral α-fluoro carbanions.

    PubMed

    Shen, Xiao; Miao, Wenjun; Ni, Chuanfa; Hu, Jinbo

    2014-01-13

    Although many methods are available for the synthesis of optically enriched monofluoromethyl secondary alcohols, synthesizing optically enriched monofluoromethyl tertiary alcohols remains a challenge. An efficient and easy-to-handle nucleophilic fluoromethylation protocol was developed. The current monofluoromethylation showed much higher facial selectivity than the corresponding difluoromethylation and proceeded via a different type of transition state. Excellent stereoselective control at the fluorinated carbon chiral center was found, an effect believed to be facilitated by the dynamic kinetic resolution of the chiral α-fluoro carbanions.

  11. Chiral THz metamaterial with tunable optical activity

    SciTech Connect

    Zhou, Jiangfeng; Taylor, Antoinette; O' Hara, John; Chowdhury, Roy; Zhao, Rongkuo; Soukoullis, Costas M

    2010-01-01

    Optical activity in chiral metamaterials is demonstrated in simulation and shows actively tunable giant polarization rotation at THz frequencies. Electric current distributions show that pure chirality is achieved by our bi-Iayer chiral metamaterial design. The chirality can be optically controlled by illumination with near-infrared light. Optical activity, occurring in chiral materials such as DNA, sugar and many other bio-molecules, is a phenomenon of great importance to many areas of science including molecular biology, analytical chemistry, optoelectronics and display applications. This phenomenon is well understood at an effective medium level as a magnetic/electric moment excited by the electric/magnetic field of the incident electromagnetic (EM) wave. Usually, natural chiral materials exhibit very weak optical activity e.g. a gyrotropic quartz crystal. The optical activity of chiral metamaterials, however, can be five orders of magnitude stronger. Chiral metamaterials are made of sub-wavelength resonators lacking symmetry planes. The asymmetry allows magnetic moments to be excited by the electric field of the incident EM wave and vice versa. Recently, chiral metamaterials have been demonstrated and lead to prospects in giant optical activity, circular dichroism, negative refraction and reversing the Casmir force. These fascinating optical properties require strong chirality, which may be designed through the microscopic structure of chiral metamaterials. However, these metamaterials have a fixed response function, defined by the geometric structuring, which limits their ability to manipulate EM waves. Active metamaterials realize dynamic control of response functions and have produced many influential applications such as ultra-fast switching devices, frequency and phase modulation and memory devices. Introducing active designs to chiral metamaterials will give additional freedom in controlling the optical activity, and therefore enable dynamic manipulation

  12. Tunable lithography masks using chiral nematic fluids

    NASA Astrophysics Data System (ADS)

    Jeong, Hyeon Su; Srinivasarao, Mohan; Jung, Hee-Tae

    2013-03-01

    We present a facile route for pattern formation using chiral nematic fluids as tunable masks in lithography process. The chiral nematic phase prepared by adding a chiral dopant (CB15) to 5CB acted as a set of parallel cylindrical lenses and as a polarization selective photomask for the preparation of periodic line patterns. The pitch of the helical twist was easily controlled by the concentration of chiral agent and the feature size of the resulting pattern was easily tuned. Because of the high mobility of the small liquid crystalline compound, the preparation of chiral nematic fluids based lithography masks requires only a few seconds. This approach has significant advantages including facility, range of surface ordering, and rate of forming periodic arrays. Current affiliation: SK Innovation, Daejeon, Korea

  13. Enantioselective environmental toxicology of chiral pesticides.

    PubMed

    Ye, Jing; Zhao, Meirong; Niu, Lili; Liu, Weiping

    2015-03-16

    The enantioselective environmental toxic effect of chiral pesticides is becoming more important. As the industry develops, increasing numbers of chiral insecticides and herbicides will be introduced into use, potentially posing toxic effects on nontarget living beings. Chiral pesticides, including herbicides such as acylanilides, phenoxypropanoic acids, and imidazolinones, and insecticides such as synthetic pyrethroids, organophosphates, and DDT often behave enantioselectively during agricultural use. These compounds also pose unpredictable enantioselective ecological threats to nontarget living beings and/or humans, affecting the food chain and entire ecosystems. Thus, to investigate the enantioselective toxic effects of chiral insecticides and herbicides is necessary during environmental protection. The environmental toxicology of chiral pesticides, especially the findings obtained from studies conducted in our laboratory during the past 10 years, is reviewed. PMID:25643169

  14. Chiral magnetic effect in condensed matter systems

    DOE PAGESBeta

    Li, Qiang; Kharzeev, Dmitri E.

    2016-12-01

    The chiral magnetic effect is the generation of electrical current induced by chirality imbalance in the presence of magnetic field. It is a macroscopic manifestation of the quantum anomaly in relativistic field theory of chiral fermions. In the quark-gluon plasma, the axial anomaly induces topological charge changing transition that results in the generation of electrical current along the magnetic field. In condensed matter systems, the chiral magnetic effect was first predicted in the gapless semiconductors with tow energy bands having pointlike degeneracies. In addition, thirty years later after this prediction, the chiral magnetic effect was finally observed in the 3Dmore » Dirac/Weyl semimetals.« less

  15. A liquid crystalline chirality balance for vapours

    NASA Astrophysics Data System (ADS)

    Ohzono, Takuya; Yamamoto, Takahiro; Fukuda, Jun-Ichi

    2014-04-01

    Chiral discrimination of vapours plays an important role in olfactory perception of biological systems and its realization by artificial sensors has been an intriguing challenge. Here, we report a simple method that tangibly visualizes the chirality of a diverse variety of molecules dissolved from vapours with high sensitivity, by making use of a structural change in a periodic microstructure of a nematic liquid crystal confined in open microchannels. This microstructure is accompanied by a topological line defect of a zigzag form with equal lengths of ‘zig’ and ‘zag.’ We find that a tiny amount of vapour of chiral molecules injected onto the liquid crystal induces the imbalance of ‘zig’ and ‘zag’ depending on its enantiomeric excess within a few seconds. Our liquid-crystal-based ‘chirality balance’ offers a simple, quick and versatile chirality-sensing/-screening method for gas-phase analysis (for example, for odours, environmental chemicals or drugs).

  16. Effects on Jc of pinning center morphology for multiple-in-line-damage in coated conductor and bulk, melt-textured HTS

    NASA Astrophysics Data System (ADS)

    Weinstein, R.; Parks, D.; Sawh, R.-P.; Mayes, B.; Gandini, A.; Goyal, A.; Chen, Y.; Selvamanickam, V.

    2009-12-01

    The properties of discontinuous aligned pinning centers (PCs) created by high-energy heavy-ions are compared for bulk melt-textured and coated conductor HTS. Properties of PCs, which increase Jc (pinning potential and entanglement), and negative properties which decrease Jc (e.g., decreased Tc and percolation paths) are evaluated. Mechanisms are proposed to explain the very large increases in Jc resulting from multiple-in-line-damage (MILD) compared to continuous columnar pinning centers (CCPC). In particular, a mechanism which results in fluxoid entanglement, even for parallel (unsplayed) PCs, is discussed. The same mechanism is found to also account for restoration of much of the pinning potential expected to be lost due to the gaps in MILD PCs. It also accounts for the fact that at high fluence, Jc increases as fluence is increased, instead of decreasing as expected. The very low self-field in coated conductor permits separation of the negative and positive effects of PCs. It is found that parameters developed to quantify the negative effects in bulk melt-textured YBCO, by 63 GeV U 238 ions, successfully describe damage to 2.1 μm thick coated conductor by 1 GeV Ru 44 ions. Coated conductor at 77 K and self-field is generally known to have Jc about 100 times that of melt-textured YBCO. However, at 77 K and applied field of 1 T, when both forms of HTS are processed with comparable numbers of near-optimum MILD PCs, the difference in Jc is reduced to a factor of 1.3-2. Whereas Jc for melt-textured YBCO increased sharply, by a factor of up to 16.8 for high-fluence MILD PCs, Jc in coated conductor increased by a smaller factor of 2.5-3.0. Nevertheless, 2.1 μm thick coated conductor, with near-optimum MILD PCs, exhibits Jc = 543 kA/cm 2 at 77 K and applied field of 1.0 T, and Ic = 114 A/cm-width of conductor. This is the highest value we find in the literature. The phenomenology developed indicates that for optimum MILD PCs in coated conductor, Jc ∼ 700 ± 70 k

  17. Nuclear forces and chiral theories

    SciTech Connect

    Friar, J.L. |

    1995-09-01

    Recent successes in ab initio calculations of light nuclei (A=2-6) will be reviewed and correlated with the dynamical consequences of chiral symmetry. The tractability of nuclear physics evinced by these results is evidence for that symmetry. The relative importance of three-nucleon forces, four-nucleon forces, multi-pion exchanges, and relativistic corrections will be discussed in the context of effective field theories and dimensional power counting. Isospin violation in the nuclear force will also be discussed in this context.

  18. Langmuir Films of Chiral Molecules on Mercury

    SciTech Connect

    Tamam, L.; Menahem, T; Mastai, Y; Sloutskin, E; Yefet, S; Deustch, M

    2009-01-01

    Homo- and heterochiral Langmuir films of a chiral derivative of stearic acid are studied in situ on the surface of liquid mercury as a function of surface coverage by surface tensiometry and surface-specific synchrotron X-ray diffraction and reflectivity. A transition from a phase of surface-parallel molecules to a phase of standing-up molecules is found. The former shows no surface-parallel long-range order. The standing-up phase of both homochiral and heterochiral compositions exhibit long-range order. However, the former has an oblique unit cell with parallel molecular planes, and the later has a centered rectangular unit cell with a herringbone molecular packing. For both cases, the standing-up molecules are tilted by 44 from the surface normal and pack at a density of 19.5 Angstroms2/molecule in the plane normal to the molecular long axis. Important differences are found, and discussed, between this behavior and that of a Langmuir film of the nonchiral stearic acid on mercury.

  19. Patient-reported adverse effects of high-dose intravenous methylprednisolone treatment: a prospective web-based multi-center study in multiple sclerosis patients with a relapse.

    PubMed

    Jongen, Peter Joseph; Stavrakaki, Ioanna; Voet, Bernard; Hoogervorst, Erwin; van Munster, Erik; Linssen, Wim H; Sinnige, Ludovicus G; Verhagen, Wim I; Visser, Leo H; van der Kruijk, Ruud; Verheul, Freek; Boringa, Jan; Heerings, Marco; Gladdines, Werner; Lönnqvist, Fredrik; Gaillard, Pieter

    2016-08-01

    In a prospective multi-center observational study, we evaluated the frequency, severity, and impact on activities of daily living (ADL) of adverse effects (AEs) of high-dose intravenous methylprednisolone (IVMP) in relapsing remitting multiple sclerosis (MS) patients with a relapse. Online self-report questionnaires stating IVMP's most common AEs were completed at baseline, the 2nd day of treatment, and 1 day and 1 week after treatment. Eighty-five patients were included, 66 completed the baseline questionnaire, and 59 completed at least one post-baseline questionnaire. Patients reported on average 4 (median) AEs; two (3.4 %) reported no AE. Most frequent was change in taste (61 %), facial flushing (61 %), sick/stomach pain (53 %), sleep disturbance (44 %), appetite change (37 %), agitation (36 %), and behavioral changes (36 %). Of all AEs, 34.3 % were severe and 37.9 % impacted on ADL. A 3-day course resulted in 4 (median) AEs and a 5-day course in 7. All patients with high disease impact had two or more AEs, compared with 79 % of those with low impact (p < 0.01). Of patients with high disability, 45 % had severe AEs, compared with 16 % of those with low disability. Severe central nervous system (CNS)-related AEs occurred two times more frequently in patients with high disease impact, and two-and-a-half times more frequently in patients with high disability. Therefore, in virtually all patients, high-dose IVMP leads to AEs, with about one of three AEs being severe with impact on ADL. Patients with high disease impact or high disability may experience more (severe) AEs, due to a higher occurrence of severe CNS-related AEs. PMID:27272956

  20. Chiral Potts spin glass in d =2 and 3 dimensions

    NASA Astrophysics Data System (ADS)

    Ćaǧlar, Tolga; Berker, A. Nihat

    2016-09-01

    The chiral spin-glass Potts system with q =3 states is studied in d =2 and 3 spatial dimensions by renormalization-group theory and the global phase diagrams are calculated in temperature, chirality concentration p , and chirality-breaking concentration c , with determination of phase chaos and phase-boundary chaos. In d =3 , the system has ferromagnetic, left-chiral, right-chiral, chiral spin-glass, and disordered phases. The phase boundaries to the ferromagnetic, left- and right-chiral phases show, differently, an unusual, fibrous patchwork (microreentrances) of all four (ferromagnetic, left-chiral, right-chiral, chiral spin-glass) ordered phases, especially in the multicritical region. The chaotic behavior of the interactions, under scale change, are determined in the chiral spin-glass phase and on the boundary between the chiral spin-glass and disordered phases, showing Lyapunov exponents in magnitudes reversed from the usual ferromagnetic-antiferromagnetic spin-glass systems. At low temperatures, the boundaries of the left- and right-chiral phases become thresholded in p and c . In d =2 , the chiral spin-glass Potts system does not have a spin-glass phase, consistently with the lower-critical dimension of ferromagnetic-antiferromagnetic spin glasses. The left- and right-chirally ordered phases show reentrance in chirality concentration p .

  1. Static and dynamic effects of chirality in dielectric media

    NASA Astrophysics Data System (ADS)

    Lakes, R. S.

    2016-09-01

    Chiral dielectrics are considered from the perspective of continuum representations of spatial heterogeneity. Static effects in isotropic chiral dielectrics are predicted, provided the electric field has nonzero third spatial derivatives. The effects are compared with static chiral phenomena in Cosserat elastic materials which obey generalized continuum constitutive equations. Dynamic monopole-like magnetic induction is predicted in chiral dielectric media.

  2. Chiral Aminophosphines as Catalysts for Enantioselective Double-Michael Indoline Syntheses

    PubMed Central

    Khong, San N.; Kwon, Ohyun

    2014-01-01

    The bisphosphine-catalyzed double-Michael addition of dinucleophiles to electron-deficient acetylenes is an efficient process for the synthesis of many nitrogen-containing heterocycles. Because the resulting heterocycles contain at least one stereogenic center, this double-Michael reaction would be even more useful if an asymmetric variant of the reaction were to be developed. Aminophosphines can also facilitate the double-Michael reaction and chiral amines are more readily available in Nature and synthetically; therefore, in this study we prepared several new chiral aminophosphines. When employed in the asymmetric double-Michael reaction between ortho-tosylamidophenyl malonate and 3-butyn-2-one, the chiral aminophosphines produced indolines in excellent yields with moderate asymmetric induction. PMID:22580397

  3. Remarkably diastereoselective synthesis of a chiral biphenyl diphosphine ligand and its application in asymmetric hydrogenation

    PubMed Central

    Qiu, Liqin; Wu, Jing; Chan, Shusun; Au-Yeung, Terry T.-L.; Ji, Jian-Xin; Guo, Rongwei; Pai, Cheng-Chao; Zhou, Zhongyuan; Li, Xingshu; Fan, Qing-Hua; Chan, Albert S. C.

    2004-01-01

    Essentially complete atropdiastereoselectivity was realized in the preparation of biaryl diphosphine dioxide by asymmetric intramolecular Ullmann coupling and oxidative coupling with central-to-axial chirality transfer. A bridged C2-symmetric biphenyl phosphine ligand possessing additional chiral centers on the linking unit of the biphenyl groups was synthesized. No resolution step was required for the preparation of the enantiomerically pure chiral ligand. These findings offer a general and practical tool for the development of previously uninvestigated atropdiastereomeric biaryl phosphine ligands. The diphosphine ligand was found to be highly effective in the asymmetric hydrogenation of α- and β-ketoesters, 2-(6′-methoxy-2′-naphthyl)propenoic acid, β-(acylamino)acrylates, and enol acetates. PMID:15067137

  4. Chiral magnetism at oxide interfaces

    NASA Astrophysics Data System (ADS)

    Randeria, Mohit

    2014-03-01

    There are tantalizing hints of magnetism at the n-type LaAlO3/SrTiO3 interface, but the experimental evidence remains controversial in view of some of the differences between different samples and probes. I will argue that if magnetism exists at interfaces, symmetry arguments imply chiral interactions that lead to a spiral ground state in zero external field and skyrmion crystals for H ≠ 0 . I will next present a microscopic model that provides a possible mechanism for the formation of local moments. I will show that the coupling of these moments to itinerant electrons leads to ferromagnetic double exchange together with Dzyaloshinskii-Moriya (DM) interactions and an easy-plane ``compass'' anisotropy, which arise from Rashba spin-orbit coupling (SOC) due to the lack of inversion symmetry at the interface. The compass term, often ignored in the literature on chiral magnetism, is shown to play a crucial role in determining the magnetic ground state. I will compare our results with existing torque magnetometry data on LAO/STO and try to reconcile it with scanning SQUID magnetometry. Finally, I will present the phase diagram in a field and show that easy-plane anisotropy stabilizes an unexpectedly large skyrmion crystal phase and describe its properties. (Work done in collaboration with Sumilan Banerjee, Onur Erten, Daniel Kestner and James Rowland). Supported by DOE-BES DE-SC0005035, NSF-DMR-1006532 and NSF MRSEC DMR-0820414.

  5. Nucleic acids, proteins, and chirality

    NASA Technical Reports Server (NTRS)

    Usher, D. A.; Profy, A. T.; Walstrum, S. A.; Needels, M. C.; Bulack, S. C.; Lo, K. M.

    1984-01-01

    The present investigation is concerned with experimental results related, in one case, to the chirality of nucleotides, and, in another case, to the possibility of a link between the chirality of nucleic acids, and that of peptides. It has been found that aminoacylation of the 'internal' hydroxyl group of a dinucleoside monophosphate can occur stereoselectively. However, this reaction has not yet been made a part of a working peptide synthesis scheme. The formation and cleavage of oligonucleotides is considered. In the event of the formation of a helical complex between the oligonucleotide and the polymer, 1-prime,5-prime-bonds in the oligomer are found to become more resistant towards cleavage. The conditions required for peptide bond formation are examined, taking into account the known structures of RNA and possible mechanisms for prebiotic peptide bond formation. The possibility is considered that the 2-prime,5-prime-internucleotide linkage could have played an important part in the early days of biological peptide synthesis.

  6. P08.11SURGICAL MANAGEMENT OF BRAIN METASTASES FROM LUNG ADENOCARCINOMA: A SINGLE CENTER EXPERIENCE AND REFLECTIONS ON MULTIPLE LESIONS

    PubMed Central

    Fornaro, R.; Agnoletti, A.; Specchia, F.M. Calamo; Garbossa, D.; Lanotte, M.; Ducati, A.

    2014-01-01

    INTRODUCTION: Metastases are the most common intracerebral tumors, and they're expected to increase in the next years. Prognosis is linked to the progression of systemic and cerebral disease. Among patients in good conditions, removal of the cerebral metastasis represents the first treatment to apply. To evaluate the ideal conditions for surgery and its results we performed this single-center study on patients with solitary and multiple cerebral metastases. MATERIALS AND METHODS: We analyzed patients treated for cerebral metastasis between January 2004 and 2011. We considered only cases with non-small cell lung carcinoma (NSCLC) as primary tumor. We collected mortality and complication rates and analyzed the early outcomes before adjuvant therapy. Finally we used a χ2 test (p = 0.05) to assess if better early outcomes (improved or stable KPS) were significantly related to the presence of solitary VS multiple lesions. RESULTS: Our series included 199 patients; mean survival was 11.08 months. 95 patients harbored a single brain metastasis (Group 1) and 104 had more than one localization (Group 2). 67 patients underwent surgical operation. The mean pre-operative KPS was 75/100 in Group 1 and 65/100 in Group 2. After surgery in Group 1 the score improved in 69% of patients, was unchanged in 20% and worsened in 11%. In Group 2 the post-operative KPS was increased in 66% of cases, unchanged in 17% and worsened in 17% of cases. Statistical analysis did not show significant differences in the rates of good (KPS improved or stable) and poor outcomes in the two groups of operated patients. Patients with lesions in the posterior fossa improved after surgery more than those with supratentorial metastases. DISCUSSION: Observation of an high mortality for not-neurological causes confirms that modern treatments allow a significant control of the disease within the nervous system. Surgery entails the additional advantage of large tissue-samples availability for histological

  7. Hierarchical chirality transfer in the growth of Towel Gourd tendrils

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Shan; Wang, Gang; Feng, Xi-Qiao; Kitamura, Takayuki; Kang, Yi-Lan; Yu, Shou-Wen; Qin, Qing-Hua

    2013-10-01

    Chirality plays a significant role in the physical properties and biological functions of many biological materials, e.g., climbing tendrils and twisted leaves, which exhibit chiral growth. However, the mechanisms underlying the chiral growth of biological materials remain unclear. In this paper, we investigate how the Towel Gourd tendrils achieve their chiral growth. Our experiments reveal that the tendrils have a hierarchy of chirality, which transfers from the lower levels to the higher. The change in the helical angle of cellulose fibrils at the subcellular level induces an intrinsic torsion of tendrils, leading to the formation of the helical morphology of tendril filaments. A chirality transfer model is presented to elucidate the chiral growth of tendrils. This present study may help understand various chiral phenomena observed in biological materials. It also suggests that chirality transfer can be utilized in the development of hierarchically chiral materials having unique properties.

  8. Hierarchical chirality transfer in the growth of Towel Gourd tendrils.

    PubMed

    Wang, Jian-Shan; Wang, Gang; Feng, Xi-Qiao; Kitamura, Takayuki; Kang, Yi-Lan; Yu, Shou-Wen; Qin, Qing-Hua

    2013-01-01

    Chirality plays a significant role in the physical properties and biological functions of many biological materials, e.g., climbing tendrils and twisted leaves, which exhibit chiral growth. However, the mechanisms underlying the chiral growth of biological materials remain unclear. In this paper, we investigate how the Towel Gourd tendrils achieve their chiral growth. Our experiments reveal that the tendrils have a hierarchy of chirality, which transfers from the lower levels to the higher. The change in the helical angle of cellulose fibrils at the subcellular level induces an intrinsic torsion of tendrils, leading to the formation of the helical morphology of tendril filaments. A chirality transfer model is presented to elucidate the chiral growth of tendrils. This present study may help understand various chiral phenomena observed in biological materials. It also suggests that chirality transfer can be utilized in the development of hierarchically chiral materials having unique properties. PMID:24173107

  9. Hierarchical chirality transfer in the growth of Towel Gourd tendrils

    PubMed Central

    Wang, Jian-Shan; Wang, Gang; Feng, Xi-Qiao; Kitamura, Takayuki; Kang, Yi-Lan; Yu, Shou-Wen; Qin, Qing-Hua

    2013-01-01

    Chirality plays a significant role in the physical properties and biological functions of many biological materials, e.g., climbing tendrils and twisted leaves, which exhibit chiral growth. However, the mechanisms underlying the chiral growth of biological materials remain unclear. In this paper, we investigate how the Towel Gourd tendrils achieve their chiral growth. Our experiments reveal that the tendrils have a hierarchy of chirality, which transfers from the lower levels to the higher. The change in the helical angle of cellulose fibrils at the subcellular level induces an intrinsic torsion of tendrils, leading to the formation of the helical morphology of tendril filaments. A chirality transfer model is presented to elucidate the chiral growth of tendrils. This present study may help understand various chiral phenomena observed in biological materials. It also suggests that chirality transfer can be utilized in the development of hierarchically chiral materials having unique properties. PMID:24173107

  10. Spontaneous Planar Chiral Symmetry Breaking in Cells

    NASA Astrophysics Data System (ADS)

    Hadidjojo, Jeremy; Lubensky, David

    Recent progress in animal development has highlighted the central role played by planar cell polarity (PCP) in epithelial tissue morphogenesis. Through PCP, cells have the ability to collectively polarize in the plane of the epithelium by localizing morphogenetic proteins along a certain axis. This allows direction-dependent modulation of tissue mechanical properties that can translate into the formation of complex, non-rotationally invariant shapes. Recent experimental observations[1] show that cells, in addition to being planar-polarized, can also spontaneously develop planar chirality, perhaps in the effort of making yet more complex shapes that are reflection non-invariant. In this talk we will present our work in characterizing general mechanisms that can lead to spontaneous chiral symmetry breaking in cells. We decompose interfacial concentration of polarity proteins in a hexagonal cell packing into irreducible representations. We find that in the case of polar concentration distributions, a chiral state can only be reached from a secondary instability after the cells are polarized. However in the case of nematic distributions, we show that a finite-amplitude (subcritical, or ``first-order'') nematic transition can send the system from disorder directly to a chiral state. In addition, we find that perturbing the system by stretching the hexagonal packing enables direct (supercritical, or ``second-order'') chiral transition in the nematic case. Finally, we do a Landau expansion to study competition between stretch-induced chirality and the tendency towards a non-chiral state in packings that have retained the full 6-fold symmetry.

  11. Broken chiral symmetry on a null plane

    SciTech Connect

    Beane, Silas R.

    2013-10-15

    On a null-plane (light-front), all effects of spontaneous chiral symmetry breaking are contained in the three Hamiltonians (dynamical Poincaré generators), while the vacuum state is a chiral invariant. This property is used to give a general proof of Goldstone’s theorem on a null-plane. Focusing on null-plane QCD with N degenerate flavors of light quarks, the chiral-symmetry breaking Hamiltonians are obtained, and the role of vacuum condensates is clarified. In particular, the null-plane Gell-Mann–Oakes–Renner formula is derived, and a general prescription is given for mapping all chiral-symmetry breaking QCD condensates to chiral-symmetry conserving null-plane QCD condensates. The utility of the null-plane description lies in the operator algebra that mixes the null-plane Hamiltonians and the chiral symmetry charges. It is demonstrated that in a certain non-trivial limit, the null-plane operator algebra reduces to the symmetry group SU(2N) of the constituent quark model. -- Highlights: •A proof (the first) of Goldstone’s theorem on a null-plane is given. •The puzzle of chiral-symmetry breaking condensates on a null-plane is solved. •The emergence of spin-flavor symmetries in null-plane QCD is demonstrated.

  12. Chirally symmetric but confining dense, cold matter

    NASA Astrophysics Data System (ADS)

    Glozman, L. Ya.; Wagenbrunn, R. F.

    2008-03-01

    The folklore tradition about the QCD phase diagram is that at the chiral restoration phase transition at finite density hadrons are deconfined and there appears the quark matter. We address this question within the only known exactly solvable confining and chirally symmetric model. It is postulated within this model that there exists linear Coulomb-like confining interaction. The chiral symmetry breaking and the quark Green function are obtained from the Schwinger-Dyson (gap) equation while the color-singlet meson spectrum results from the Bethe-Salpeter equation. We solve this model at T=0 and finite chemical potential μ and obtain a clear chiral restoration phase transition at the critical value μcr. Below this value the spectrum is similar to the previously obtained one at μ=0. At μ>μcr the quarks are still confined and the physical spectrum consists of bound states which are arranged into a complete set of exact chiral multiplets. This explicitly demonstrates that a chirally symmetric matter consisting of confined but chirally symmetric hadrons at finite chemical potential is also possible in QCD. If so, there must be nontrivial implications for astrophysics.

  13. Chirally symmetric but confining dense, cold matter

    SciTech Connect

    Glozman, L. Ya.; Wagenbrunn, R. F.

    2008-03-01

    The folklore tradition about the QCD phase diagram is that at the chiral restoration phase transition at finite density hadrons are deconfined and there appears the quark matter. We address this question within the only known exactly solvable confining and chirally symmetric model. It is postulated within this model that there exists linear Coulomb-like confining interaction. The chiral symmetry breaking and the quark Green function are obtained from the Schwinger-Dyson (gap) equation while the color-singlet meson spectrum results from the Bethe-Salpeter equation. We solve this model at T=0 and finite chemical potential {mu} and obtain a clear chiral restoration phase transition at the critical value {mu}{sub cr}. Below this value the spectrum is similar to the previously obtained one at {mu}=0. At {mu}>{mu}{sub cr} the quarks are still confined and the physical spectrum consists of bound states which are arranged into a complete set of exact chiral multiplets. This explicitly demonstrates that a chirally symmetric matter consisting of confined but chirally symmetric hadrons at finite chemical potential is also possible in QCD. If so, there must be nontrivial implications for astrophysics.

  14. Chiral Alfvén Wave in Anomalous Hydrodynamics.

    PubMed

    Yamamoto, Naoki

    2015-10-01

    We study the hydrodynamic regime of chiral plasmas at high temperature. We find a new type of gapless collective excitation induced by chiral effects in an external magnetic field. This is a transverse wave, and it is present even in incompressible fluids, unlike the chiral magnetic and chiral vortical waves. The velocity is proportional to the coefficient of the gravitational anomaly. We briefly discuss the possible relevance of this "chiral Alfvén wave" in physical systems. PMID:26551804

  15. Elastic waves in structurally chiral composites

    SciTech Connect

    Yang, Shiuhkuang.

    1990-01-01

    Elastic wave propagation through structurally chiral (handed) media was studied. The primary objectives are to construct structurally chiral composites and to characterize their properties. Structurally chiral composites are constructed by stacking identical uniaxial plates, whose consecutive symmetric axes describe either a right- or a left-handed spiral. A matrix representation method is used to solve the elastic wave propagation in such layered composites. Numerical computation of the plane wave reflection and transmission characteristics for chiral arrangements are compared with those for the non-chiral one. It is concluded that the co-polarized characteristics are unaffected by the structural chirality, while the cross-polarized reflected and transmitted fields are greatly influenced by it. Numerical modeling is also applied for the real samples. The polarization ellipse of the transmitted field of each sample is calculated. To verify the form chirality, four glass-reinforced chiral and non-chiral composite samples are made from helix tape, molded, debulked, and cured individually under identical temperature and pressure histories. The spiral composites are characterized using shear and longitudinal wave transducers in ultrasonic experiments. Both the material properties and the polarization ellipse of the transmitted field of each sample are measured. It is proved conclusively that left and right handedness in the microstructures of a material rotates the plane of polarization of a propagating shear wave in the opposite directions. Thus it is now possible to say that by reducing the length scale of the handed microstructures tone more appropriate to its propagating wavelength, a medium is obtained that gives rise to effects similar to optical radar and optical dichroism.

  16. Extreme optical chirality of plasmonic nanohole arrays due to chiral Fano resonance

    NASA Astrophysics Data System (ADS)

    Kondratov, A. V.; Gorkunov, M. V.; Darinskii, A. N.; Gainutdinov, R. V.; Rogov, O. Y.; Ezhov, A. A.; Artemov, V. V.

    2016-05-01

    We study the physical origin of extreme optical chirality of subwavelength arrays of chiral holes in metal. We reconstruct the nanoscale relief of the hole arrays by the atomic-force microscopy and post-process the data to acquire an average unit-cell shape clear of noise and defects. For this shape, we perform the electromagnetic finite difference time domain simulations that reproduce all important features observed by the light-transmission experiments, including the notably strong circular dichroism and optical activity covering the whole range of possible values. To interpret the simulation results, we develop a chiral coupled-mode model which yields analytical expressions that fit accurately the numerical data in a broad wavelength range. Our conclusions undoubtedly link the extreme optical chirality to the plasmon resonances of chiral holes and the associated chiral Fano-type transmission resonance.

  17. Induced chirality through electromagnetic coupling between chiral molecular layers and plasmonic nanostructures.

    PubMed

    Abdulrahman, Nadia A; Fan, Z; Tonooka, Taishi; Kelly, Sharon M; Gadegaard, Nikolaj; Hendry, Euan; Govorov, Alexander O; Kadodwala, Malcolm

    2012-02-01

    We report a new approach for creating chiral plasmonic nanomaterials. A previously unconsidered, far-field mechanism is utilized which enables chirality to be conveyed from a surrounding chiral molecular material to a plasmonic resonance of an achiral metallic nanostructure. Our observations break a currently held preconception that optical properties of plasmonic particles can most effectively be manipulated by molecular materials through near-field effects. We show that far-field electromagnetic coupling between a localized plasmon of a nonchiral nanostructure and a surrounding chiral molecular layer can induce plasmonic chirality much more effectively (by a factor of 10(3)) than previously reported near-field phenomena. We gain insight into the mechanism by comparing our experimental results to a simple electromagnetic model which incorporates a plasmonic object coupled with a chiral molecular medium. Our work offers a new direction for the creation of hybrid molecular plasmonic nanomaterials that display significant chiroptical properties in the visible spectral region.

  18. Liquid crystal behavior induced assembling fabrication of conductive chiral MWCNTs@NCC nanopaper

    NASA Astrophysics Data System (ADS)

    Ren, Yumei; Wang, Tianjiao; Chen, Zhimin; Li, Jing; Tian, Qiuge; Yang, Hongxia; Xu, Qun

    2016-11-01

    The conductive chiral MWCNTs@NCC nanopapers obtained by the assembly of nanocrystalline cellulose liquid crystals (NCC LCs) host matrix along with one-dimensional (1-D) multi-walled carbon nanotubes (MWCNTs) have been studied in this work. Circular dichroism (CD) studies show strong signals stemming from the chiral nematic structure. Notably, the introduction of the MWCNTs has a pronounced effect on the chiral structure of the as-prepared nanopaper. Our experimental results indicate the multiple weak molecular interactions existing between MWCNTs and NCC are responsible for the effective dispersion and stabilization of MWCNTs. Moreover it also confirms the resulting nanopaper has an increased conductivity of 4.2 S/m at 1.96 wt% MWCNTs. So the co-assembly of the nanocomposite herein opens a gateway for preparing functional materials combining the photonic properties of the NCC LCs matrix with other building blocks that can supply other advantageous functions.

  19. Enhanced Chiral Recognition by Cyclodextrin Dimers

    PubMed Central

    Voskuhl, Jens; Schaepe, Kira; Ravoo, Bart Jan

    2011-01-01

    In this article we investigate the effect of multivalency in chiral recognition. To this end, we measured the host-guest interaction of a β-cyclodextrin dimer with divalent chiral guests. We report the synthesis of carbohydrate-based water soluble chiral guests functionalized with two borneol, menthol, or isopinocampheol units in either (+) or (−) configuration. We determined the interaction of these divalent guests with a β-cyclodextrin dimer using isothermal titration calorimetry. It was found that—in spite of a highly unfavorable conformation—the cyclodextrin dimer binds to guest dimers with an increased enantioselectivity, which clearly reflects the effect of multivalency. PMID:21845101

  20. Towards chirality-pure carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zhang, Yani; Zheng, Lianxi

    2010-10-01

    Current as-grown single-walled carbon nanotubes vary in diameter and chirality, which results in variations in their electronic and optical properties. Two approaches have been intensively studied to obtain chirality-pure nanotube structures and thus uniform properties for advanced applications. The first approach involves the post-synthesis separation according to the nanotubes' chiral vectors (n, m), and the second one involves direct synthes of carbon nanotubes with the same (n, m). This paper reviews the efforts along these two directions, with emphasis on the most recent progress of post-synthesis separation and the perspectives of controllable synthesis.

  1. Chiral Isotropic Liquids from Achiral Molecules

    SciTech Connect

    L Hough; M Spannuth; M Nakata; D Coleman; C Jones; G Dantlgraber; C Tschierske; J Watanabe; N Clark; et al.

    2011-12-31

    A variety of simple bent-core molecules exhibit smectic liquid crystal phases of planar fluid layers that are spontaneously both polar and chiral in the absence of crystalline order. We found that because of intralayer structural mismatch, such layers are also only marginally stable against spontaneous saddle splay deformation, which is incompatible with long-range order. This results in macroscopically isotropic fluids that possess only short-range orientational and positional order, in which the only macroscopically broken symmetry is chirality - even though the phases are formed from achiral molecules. Their conglomerate domains exhibit optical rotatory powers comparable to the highest ever found for isotropic fluids of chiral molecules.

  2. Synthesis of chiral dopants based on carbohydrates.

    PubMed

    Tsuruta, Toru; Koyama, Tetsuo; Yasutake, Mikio; Hatano, Ken; Matsuoka, Koji

    2014-07-01

    Chiral dopants based on carbohydrates for nematic liquid crystals were synthesized from D-glucose, and their helical twisting power (HTP) values were evaluated. The chiral dopants induced helices in the host nematic liquid crystals. An acetyl derivative having an ether-type glycosidic linkage between carbohydrate and a mesogenic moiety showed the highest HTP value of 10.4 μm(-1), while an acetyl derivative having an anomeric ester-type linkage did not show any HTP. It was surprising that this molecule had no HTP despite the presence of chirality in the molecule. A relationship between HTP and specific rotation was not observed in this study.

  3. A lattice chiral theory with multifermion couplings

    NASA Astrophysics Data System (ADS)

    Xue, She-Sheng

    1996-02-01

    Analyzing an SUL(2) ⊗ UR(1) chiral theory with multifermion couplings on a lattice, we find a possible region in the phase space of multifermion couplings, where no spontaneous symmetry breaking occurs, doublers are decoupled as massive Dirac fermions consistently with the SUL(2) ⊗ UR(1) chiral symmetry, the “spectator” fermion ψR( x) is free mode, whereas the normal mode of ψLi( x) is plausibly speculated to be chiral in the continuum limit. This is not in agreement with the general belief of the definite failure of theories so constructed.

  4. Undoubled Chiral Fermions on a Lattice

    NASA Astrophysics Data System (ADS)

    Xue, She-Sheng

    1997-02-01

    We analyze the dynamics of an SU L(2)⊗ U R(1) chiral theory on the lattice with a strong multifermion coupling. It is shown that no spontaneous symmetry breaking occurs; the "spectator" fermion ψR is a free mode; doublers are decoupled as massive Dirac fermions consistently with the chiral symmetries. In 1+1 dimension, we show that the right-handed three-fermion state disappears at the threshold and an undoubled left-handed chiral fermion remains in the continuum limit.

  5. The paradigm of Pseudodual Chiral Models

    SciTech Connect

    Zachos, C.K.; Curtright, T.L.

    1994-08-01

    This is a synopsis and extension of Phys. Rev. D49 5408 (1994). The Pseudodual Chiral Model illustrates 2-dimensional field theories which possess an infinite number of conservation laws but also allow particle production, at variance with naive expectations-a folk theorem of integrable models. We monitor the symmetries of the pseudodual model, both local and nonlocal, as transmutations of the symmetries of the (very different) usual Chiral Model. We refine the conventional algorithm to more efficiently produce the nonlocal symmetries of the model. We further find the canonical transformation which connects the usual chiral model to its fully equivalent dual model, thus contradistinguishing the pseudodual theory.

  6. The convoluted evolution of snail chirality

    NASA Astrophysics Data System (ADS)

    Schilthuizen, M.; Davison, A.

    2005-11-01

    The direction that a snail (Mollusca: Gastropoda) coils, whether dextral (right-handed) or sinistral (left-handed), originates in early development but is most easily observed in the shell form of the adult. Here, we review recent progress in understanding snail chirality from genetic, developmental and ecological perspectives. In the few species that have been characterized, chirality is determined by a single genetic locus with delayed inheritance, which means that the genotype is expressed in the mother's offspring. Although research lags behind the studies of asymmetry in the mouse and nematode, attempts to isolate the loci involved in snail chirality have begun, with the final aim of understanding how the axis of left-right asymmetry is established. In nature, most snail taxa (>90%) are dextral, but sinistrality is known from mutant individuals, populations within dextral species, entirely sinistral species, genera and even families. Ordinarily, it is expected that strong frequency-dependent selection should act against the establishment of new chiral types because the chiral minority have difficulty finding a suitable mating partner (their genitalia are on the ‘wrong’ side). Mixed populations should therefore not persist. Intriguingly, however, a very few land snail species, notably the subgenus Amphidromus sensu stricto, not only appear to mate randomly between different chiral types, but also have a stable, within-population chiral dimorphism, which suggests the involvement of a balancing factor. At the other end of the spectrum, in many species, different chiral types are unable to mate and so could be reproductively isolated from one another. However, while empirical data, models and simulations have indicated that chiral reversal must sometimes occur, it is rarely likely to lead to so-called ‘single-gene’ speciation. Nevertheless, chiral reversal could still be a contributing factor to speciation (or to divergence after speciation) when

  7. New chiral zinc complexes: synthesis, structure, and induction of axial chirality.

    PubMed

    Degenbeck, Helmut; Felten, Anne-Sophie; Escudero-Adán, Eduardo C; Benet-Buchholz, Jordi; Di Bari, Lorenzo; Pescitelli, Gennaro; Vidal-Ferran, Anton

    2012-08-20

    We describe an efficient methodology for the preparation of new chiral zinc complexes by assembling dynamically racemic biphenol derivatives and chiral 1,2-diamines with suitable zinc(II) precursors. Mononuclear and dinuclear zinc(II) complexes were formed from differently substituted biphenols. The solid-state and solution structural characterization of the resulting compounds allowed us to demonstrate a preferential sense of induced axial chirality for mononuclear complexes, a phenomenon that was not observed for the dinuclear ones. PMID:22862880

  8. Controlled chiral supramolecular assemblies of water soluble achiral porphyrins induced by chiral counterions.

    PubMed

    Rananaware, Anushri; La, Duong Duc; Al Kobaisi, Mohammad; Bhosale, Rajesh S; Bhosale, Sidhanath V; Bhosale, Sheshanath V

    2016-08-11

    We demonstrate a controlled chiral supramolecular assembly of achiral porphyrins induced by chiral d- and l-arginine (Arg) in water. Induction of chirality was confirmed by circular dichroism. TEM and SEM images confirm that these twisted ribbons are indeed formed by right- and left-handed helices with d- and l-Arg in water, respectively. The chiral assembly pathways described here are hierarchical, opening up the possibility that simple changes on microscopic (nm) length scales can be used to control structures on macroscopic (mm) length scales. PMID:27464524

  9. Chiral supramolecular polymers consisting of planar-chiral pillar[5]arene enantiomers.

    PubMed

    Ogoshi, Tomoki; Furuta, Takuya; Yamagishi, Tada-Aki

    2016-09-14

    Supramolecular polymers with diverse chiralities were constructed by supramolecular polymerization of planar-chiral host-guest conjugates in pS and pR forms. Hetero-chiral supramolecular polymerization using a racemic mixture of host-guest conjugates with pS and pR forms afforded a supramolecular polymer with a larger hydrodynamic radius than that obtained through homo-chiral supramolecular polymerization of host-guest conjugates with either pS or pR forms alone. PMID:27510359

  10. Scalar Mesons and Chiral States

    NASA Astrophysics Data System (ADS)

    Ishida, M.; Ishida, S.

    2004-08-01

    The essential points and physical backgrounds of the covariant level-classification scheme, based on Ū(12)SF⊗O(3, 1)L, are reviewed: This scheme is extended from the non-relativistic SU(6)SF⊗O(3)L scheme by introducing the new SU(2)-spin (ρ-spin) degree of freedom, which is necessary for covariant description of composite hadrons. Our scheme predicts the existence of new type of chiral mesons and baryons (Chiralons) out of the conventional SU(6)SF⊗O(3)L scheme. The σ nonet is a typical example of chiralons to be assigned to the (qq¯) relativistic S-wave state. The new narrow mesons Ds(2317)/Ds(2463) are naturally assigned as the ground-state scalar and axial-vector chiralons in the (cs¯) system.

  11. Chiral exceptional points in metasurfaces

    NASA Astrophysics Data System (ADS)

    Kang, Ming; Chen, Jing; Chong, Y. D.

    2016-09-01

    An exceptional point (EP) is a degeneracy occurring in a non-energy-conserving system, in which two eigenvectors of a non-Hermitian Hamiltonian coalesce. We explore how EPs can be realized in a metamaterial surface, or metasurface, consisting of a pair of lossy coupled linear antennas in each unit cell. EPs appear in the eigenvectors of the transmission matrix by tuning the frequency and the coupling and loss rates of the metasurface. Each EP is associated with the appearance of a circularly polarized transmission eigenstate; hence, within the parameter space of the system, the EPs lie along pairs of curves with distinct chirality. Our results are obtained using finite-difference time-domain simulations, as well as a fitted coupled-mode theory. The coupled-mode theory agrees well with the numerical results and is capable of accurately predicting the EP f curves.

  12. Separation mechanism of chiral impurities, ephedrine and pseudoephedrine, found in amphetamine-type substances using achiral modifiers in the gas phase.

    PubMed

    Holness, Howard K; Jamal, Adeel; Mebel, Alexander; Almirall, José R

    2012-11-01

    A new mechanism is proposed that describes the gas-phase separation of chiral molecules found in amphetamine-type substances (ATS) by the use of high-resolution ion mobility spectrometry (IMS). Straight-chain achiral alcohols of increasing carbon chain length, from methanol to n-octanol, are used as drift gas modifiers in IMS to highlight the mechanism proposed for gas-phase separations of these chiral molecules. The results suggest the possibility of using these achiral modifiers to separate the chiral molecules (R,S) and (S,R)-ephedrine and (S,S) and (R,R)-pseudoephedrine which contain an internal hydroxyl group at the first chiral center and an amino group at the other chiral center. Ionization was achieved with an electrospray source, the ions were introduced into an IMS with a resolving power of 80, and the resulting ion clusters were characterized with a coupled quadrupole mass spectrometer detector. A complementary computational study conducted at the density functional B3LYP/6-31g level of theory for the electronic structure of the analyte-modifier clusters was also performed, and showed either "bridged" or "independent" binding. The combined experimental and simulation data support the proposed mechanism for gas-phase chiral separations using achiral modifiers in the gas phase, thus enhancing the potential to conduct fast chiral separations with relative ease and efficiency.

  13. Chiral Heteroditopic Baskets Designed from Triazolated Calixarenes and Short Peptides.

    PubMed

    Gorbunov, Alexander; Sokolova, Nadezhda; Kudryashova, Elena; Nenajdenko, Valentine; Kovalev, Vladimir; Vatsouro, Ivan

    2016-08-22

    Cone calix[4]arenes and calix[6]arenes bearing two, three, and four short peptide units each having two chiral carbon atoms were prepared. The syntheses were performed by using an efficient modular approach that includes the Ugi preparation of the azido-peptide followed by its reactions with the propargylated calixarenes under CuAAC (Cu(I) -catalyzed azide-alkyne cycloaddition) conditions. The three novel multitopic hosts were probed for their ability to bind metal ions by UV titration, and showed the highest complexation efficiency towards copper(II) and lead(II). These two cations possessed quite different complexation modes with copper(II) bound predominantly by multiple-triazole sites, in contrast to lead(II), which is stabilized mainly by multiple interactions with amide groups of the peptide units. Circular dichroism data for the free chiral hosts, their equimolar mixtures with copper(II) perchlorate and lead(II) perchlorate, and for tertiary mixtures of all three compounds showed the formation of mono- and binuclear complexes, or a switching behavior, depending on the structure of the host and the addition order of the cations. PMID:27444143

  14. Instantons, chiral dynamics, and hadronic resonances

    SciTech Connect

    Cristoforetti, M.; Faccioli, P.; Traini, M.

    2007-03-01

    We use the interacting instanton liquid model (IILM) as a tool to study the role played by the chiral interactions in the lowest-lying vector and axial-vector meson resonances. We find that narrow a{sub 1} and {rho} meson resonances can be generated by instanton-induced chiral forces, even in the absence of confinement. In the IILM, these hadrons are found to have masses only about 30% larger than the experimental value and small width < or approx. 10-50 MeV. This result suggests that chiral interactions are very important in these systems and provide most of their mass. We explore the decaying patterns of the {rho} meson, in the absence of confinement. We argue that, in our model where only chiral forces are switched on, this meson decays dissociating into its quark-antiquark constituents.

  15. Personal recollections on chiral symmetry breaking

    NASA Astrophysics Data System (ADS)

    Kobayashi, Makoto

    2016-07-01

    The author's work on the mass of pseudoscalar mesons is briefly reviewed. The emergence of the study of CP violation in the renormalizable gauge theory from consideration of chiral symmetry in the quark model is discussed.

  16. Chiral Magnetic Effect in Heavy Ion Collisions

    DOE PAGESBeta

    Liao, Jinfeng

    2016-12-01

    The Chiral Magnetic Effect (CME) is a remarkable phenomenon that stems from highly nontrivial interplay of QCD chiral symmetry, axial anomaly, and gluonic topology. We show it is of fundamental importance to search for the CME in experiments. The heavy ion collisions provide a unique environment where a hot chiral-symmetric quark-gluon plasma is created, gluonic topological fluctuations generate chirality imbalance, and very strong magnetic fields |Β→|~m2π are present during the early stage of such collisions. Significant efforts have been made to look for CME signals in heavy ion collision experiments. Lastly, in this contribution we give a brief overview onmore » the status of such efforts.« less

  17. Application of cyclodextrins in chiral capillary electrophoresis.

    PubMed

    Rezanka, Pavel; Navrátilová, Klára; Rezanka, Michal; Král, Vladimír; Sýkora, David

    2014-10-01

    CE represents a very powerful separation tool in the area of chiral separations. CD-mediated chiral CE is a continuously flourishing technique within the frame of the electromigration methods. In this review, a brief overview of the synthetic procedures leading to modified CDs is provided first. Next, selected aspects related to the utilization of CDs in chiral CE are discussed specifically in the view of recently published data. Advantages of CDs and basic principles of chiral CE are remained. The topic of the determination of binding constants is touched. Particular attention is paid to the effort aiming at better understanding of the molecular level of the enantiorecognition between CDs and the analyte in the solution. Powerful approaches extensively utilized in this field are NMR, molecular modeling, and computer simulations. Then, a summary of applications of CDs in the CE enantioseparations is given, covering years 2008-2013. Finally, the general trend of modified CDs use in separation science is statistically evaluated.

  18. Chiral Pesticide Pharmacokinetics: A Range of Values

    EPA Science Inventory

    Approximately 30% of pesticides are chiral and used as mixtures of two or more stereoisomers. In biological systems, these stereoisomers can exhibit significantly different pharmacokinetics (absorption, distribution, metabolism, and elimination). In spite of these differences, th...

  19. Chirality in thiolate-protected gold clusters.

    PubMed

    Knoppe, Stefan; Bürgi, Thomas

    2014-04-15

    Over recent years, research on thiolate-protected gold clusters Au(m)(SR)n has gained significant interest. Milestones were the successful determination of a series of crystal structures (Au102(SR)44, Au25(SR)18, Au38(SR)24, Au36(SR)24, and Au28(SR)20). For Au102(SR)44, Au38(SR)24, and Au28(SR)20, intrinsic chirality was found. Strong Cotton effects (circular dichroism, CD) of gold clusters protected by chiral ligands have been reported a long time ago, indicating the transfer of chiral information from the ligand into the cluster core. Our lab has done extensive studies on chiral thiolate-protected gold clusters, including those protected with chiral ligands. We demonstrated that vibrational circular dichroism can serve as a useful tool for the determination of conformation of the ligand on the surface of the cluster. The first reports on crystal structures of Au102(SR)44 and Au38(SR)24 revealed the intrinsic chirality of these clusters. Their chirality mainly arises from the arrangement of the ligands on the surface of the cluster cores. As achiral ligands are used to stabilize the clusters, racemic mixtures are obtained. However, the separation of the enantiomers by HPLC was demonstrated which enabled the measurement of their CD spectra. Thermally induced inversion allows determination of the activation parameters for their racemization. The inversion demonstrates that the gold-thiolate interface is anything but fixed; in contrast, it is rather flexible. This result is of fundamental interest and needs to be considered in future applications. A second line of our research is the selective introduction of chiral, bidentate ligands into the ligand layer of intrinsically chiral gold clusters. The ligand exchange reaction is highly diastereoselective. The bidentate ligand connects two of the protecting units on the cluster surface and thus effectively stabilizes the cluster against thermally induced inversion. A minor (but significant) influence of chiral ligands to

  20. DH(*) in chiral smectics under electric field.

    PubMed

    Meyer, C; Rabette, C; Gisse, P; Antonova, K; Dozov, I

    2016-07-01

    The behavior of double helices (DH(*) formed in the temperature interval N(*) -SmA(*) in compounds of non-chiral liquid crystals doped with chiral molecules was investigated. Two different systems presenting left-handed and right-handed chirality were studied. A statistics of the handedness of the DH(*) revealed a correlation with the mixture chirality, as predicted theoretically in C. Meyer, Yu. A. Nastishin, M. Kleman, Phys. Rev. E 82, 031704 (2010). By applying a gradually increasing AC electric field, one can observe the shrinking of the cylinder circumscribing the DH(*) . This shrink is accompanied by a reduction of the DH(*) 's pitch. This effect was similar to the one produced by the decrease of temperature in the absence of the field. PMID:27465656

  1. Nondipole Photoemission from Chiral Enantiomers of Camphor

    NASA Astrophysics Data System (ADS)

    Bowen, K. P.; Stolte, W. C.; Young, J. A.; Demchenko, I. N.; Guillemin, R.; Hemmers, O.; Piancastelli, M. N.; Lindle, D. W.

    2010-03-01

    K-shell photoemission from the carbonyl carbon in the chiral molecule camphor has been studied in the region just above the core-shell ionization threshold. Differences between angular distributions of emitted photoelectrons from the two enantiomers are attributed to the influence of chirality combined with nondipole effects in the photoemission process, despite the fact the measurements were taken using linearly polarized x-rays. The results suggest the possibility of a new form of linear dichroism.

  2. Tests of Chiral Perturbation Theory with COMPASS

    SciTech Connect

    Friedrich, Jan

    2010-12-28

    The COMPASS experiment at CERN studies with high precision pion-photon induced reactions on nuclear targets via the Primakoff effect. This offers the possibility to test chiral perturbation theory (ChPT) in various channels: Pion Compton scattering allows to clarify the longstanding question of the pion polarisabilities, single neutral pion production is related to the chiral anomaly, and for the two-pion production cross sections exist as yet untested ChPT predictions.

  3. Chiral susceptibility in an effective interaction model

    SciTech Connect

    Min He; Yu Jiang; Sun Weimin; Zong Hongshi

    2008-04-01

    A closed integral expression for the chiral susceptibility at finite temperature is derived. The corresponding disconnected part, which proves to be of major physical relevance and free from the additive quadratic ultraviolet divergence, is identified. Then a calculation based on an effective model gluon propagator is conducted within the framework of the Dyson-Schwinger equations for two flavors in the chiral limit. A narrow, divergent peak is observed as temperature varies, and its implications are discussed.

  4. Chiral extrapolation of SU(3) amplitudes

    SciTech Connect

    Ecker, Gerhard

    2011-05-23

    Approximations of chiral SU(3) amplitudes at NNLO are proposed to facilitate the extrapolation of lattice data to the physical meson masses. Inclusion of NNLO terms is essential for investigating convergence properties of chiral SU(3) and for determining low-energy constants in a controllable fashion. The approximations are tested with recent lattice data for the ratio of decay constants F{sub K}/F{sub {pi}}.

  5. Control of normal chirality at hexagonal interfaces

    SciTech Connect

    Haraldsen, Jason T; Fishman, Randy Scott

    2010-01-01

    We study the net chirality created by the Dzyaloshinkii-Moriya interaction (DMI) at the boundary between hexagonal layers of magnetic and non-magnetic materials. It is shown that another mechanism besides elastic torsion is required to understand the change in chirality observed in Dy/Y multilayers during field-cooling. The paper shows that due to the overlap between magnetic and non-magnetic atoms, interfacial steps may produce a DMI normal to the interface in magnetic heterostructures.

  6. Analysis of rainbow scattering by a chiral sphere.

    PubMed

    Shang, Qing-Chao; Wu, Zhen-Sen; Qu, Tan; Li, Zheng-Jun; Bai, Lu; Gong, Lei

    2013-09-23

    Based on the scattering theory of a chiral sphere, rainbow phenomenon of a chiral sphere is numerically analyzed in this paper. For chiral spheres illuminated by a linearly polarized wave, there are three first-order rainbows, with whose rainbow angles varying with the chirality parameter. The spectrum of each rainbow structure is presented and the ripple frequencies are found associated with the size and refractive indices of the chiral sphere. Only two rainbow structures remain when the chiral sphere is illuminated by a circularly polarized plane wave. Finally, the rainbows of chiral spheres with slight chirality parameters are found appearing alternately in E-plane and H-plane with the variation of the chirality.

  7. Analysis of rainbow scattering by a chiral sphere.

    PubMed

    Shang, Qing-Chao; Wu, Zhen-Sen; Qu, Tan; Li, Zheng-Jun; Bai, Lu; Gong, Lei

    2013-09-23

    Based on the scattering theory of a chiral sphere, rainbow phenomenon of a chiral sphere is numerically analyzed in this paper. For chiral spheres illuminated by a linearly polarized wave, there are three first-order rainbows, with whose rainbow angles varying with the chirality parameter. The spectrum of each rainbow structure is presented and the ripple frequencies are found associated with the size and refractive indices of the chiral sphere. Only two rainbow structures remain when the chiral sphere is illuminated by a circularly polarized plane wave. Finally, the rainbows of chiral spheres with slight chirality parameters are found appearing alternately in E-plane and H-plane with the variation of the chirality. PMID:24104080

  8. A Molecular Model for Chiral Symmetry Breaking

    NASA Astrophysics Data System (ADS)

    Latinwo, Folarin; Stillinger, Frank; Debenedetti, Pablo

    In this work, we present a new class of molecular models for chiral phenomena in condensed matter systems. A key feature of these models is the ability of the four-site (tetramer) ``molecules'' to inter-convert between two distinct chiral forms (enantiomers). Given this feature, we use analytical theory and computer simulations to investigate the emergent chiral properties (including symmetry breaking) over a range of conditions. In particular, we consider the single-molecule level and condensed-phase behavior of our model system. Interestingly, we find that our liquid-phase predictions are in excellent agreement with recent experimental reports on chiral self-sorting in isotropic liquids. From this perspective, our model demonstrates accurate predictive capabilities, as well as a platform for understanding the microscopic origins of a variety of chiral phenomena. In a broader context, we anticipate that this class of models will be relevant to chirality-dominated areas such as the pharmaceutical industry and pre-biotic geochemistry.

  9. Staggered heavy baryon chiral perturbation theory

    SciTech Connect

    Bailey, Jon A.

    2008-03-01

    Although taste violations significantly affect the results of staggered calculations of pseudoscalar and heavy-light mesonic quantities, those entering staggered calculations of baryonic quantities have not been quantified. Here I develop staggered chiral perturbation theory in the light-quark baryon sector by mapping the Symanzik action into heavy baryon chiral perturbation theory. For 2+1 dynamical quark flavors, the masses of flavor-symmetric nucleons are calculated to third order in partially quenched and fully dynamical staggered chiral perturbation theory. To this order the expansion includes the leading chiral logarithms, which come from loops with virtual decuplet-like states, as well as terms of O(m{sub {pi}}{sup 3}), which come from loops with virtual octet-like states. Taste violations enter through the meson propagators in loops and tree-level terms of O(a{sup 2}). The pattern of taste symmetry breaking and the resulting degeneracies and mixings are discussed in detail. The resulting chiral forms are appropriate to lattice results obtained with operators already in use and could be used to study the restoration of taste symmetry in the continuum limit. I assume that the fourth root of the fermion determinant can be incorporated in staggered chiral perturbation theory using the replica method.

  10. Staggered heavy baryon chiral perturbation theory

    NASA Astrophysics Data System (ADS)

    Bailey, Jon A.

    2008-03-01

    Although taste violations significantly affect the results of staggered calculations of pseudoscalar and heavy-light mesonic quantities, those entering staggered calculations of baryonic quantities have not been quantified. Here I develop staggered chiral perturbation theory in the light-quark baryon sector by mapping the Symanzik action into heavy baryon chiral perturbation theory. For 2+1 dynamical quark flavors, the masses of flavor-symmetric nucleons are calculated to third order in partially quenched and fully dynamical staggered chiral perturbation theory. To this order the expansion includes the leading chiral logarithms, which come from loops with virtual decuplet-like states, as well as terms of O(mπ3), which come from loops with virtual octet-like states. Taste violations enter through the meson propagators in loops and tree-level terms of O(a2). The pattern of taste symmetry breaking and the resulting degeneracies and mixings are discussed in detail. The resulting chiral forms are appropriate to lattice results obtained with operators already in use and could be used to study the restoration of taste symmetry in the continuum limit. I assume that the fourth root of the fermion determinant can be incorporated in staggered chiral perturbation theory using the replica method.

  11. Chirality measures of α-amino acids.

    PubMed

    Jamróz, Michał H; Rode, Joanna E; Ostrowski, Sławomir; Lipiński, Piotr F J; Dobrowolski, Jan Cz

    2012-06-25

    To measure molecular chirality, the molecule is treated as a finite set of points in the Euclidean R(3) space supplemented by k properties, p(1)((i)), p(2)((i)), ..., p(k)((i)) assigned to the ith atom, which constitute a point in the Property P(k) space. Chirality measures are described as the distance between a molecule and its mirror image minimized over all its arbitrary orientation-preserving isometries in the R(3) × P(k) Cartesian product space. Following this formalism, different chirality measures can be estimated by taking into consideration different sets of atomic properties. Here, for α-amino acid zwitterionic structures taken from the Cambridge Structural Database and for all 1684 neutral conformers of 19 biogenic α-amino acid molecules, except glycine and cystine, found at the B3LYP/6-31G** level, chirality measures have been calculated by a CHIMEA program written in this project. It is demonstrated that there is a significant correlation between the measures determined for the α-amino acid zwitterions in crystals and the neutral forms in the gas phase. Performance of the studied chirality measures with changes of the basis set and computation method was also checked. An exemplary quantitative structure–activity relationship (QSAR) application of the chirality measures was presented by an introductory model for the benchmark Cramer data set of steroidal ligands of the sex-hormone binding globulin.

  12. Copper-Catalyzed Enantioselective Allyl-Allyl Coupling between Allylic Boronates and Phosphates with a Phenol/N-Heterocyclic Carbene Chiral Ligand.

    PubMed

    Yasuda, Yuto; Ohmiya, Hirohisa; Sawamura, Masaya

    2016-08-26

    Copper-catalyzed enantioselective allyl-allyl coupling between allylboronates and either Z-acyclic or cyclic allylic phosphates using a new chiral N-heterocyclic carbene ligand, bearing a phenolic hydroxy, is reported. This reaction occurs with exceptional SN 2'-type regioselectivities and high enantioselectivities to deliver chiral 1,5-diene derivatives with a tertiary stereogenic center at the allylic/homoallylic position. PMID:27467163

  13. Big, strong, neutral, twisted, and chiral π acids.

    PubMed

    Zhao, Yingjie; Huang, Guangxi; Besnard, Celine; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2015-04-13

    General synthetic access to expanded π-acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion-π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron-withdrawing substituents decreases and the high π acidity needed for strong anion-π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion-π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from -3.96 to -4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X-ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation-π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches -4.45 eV, whereas two sulfone moieties give a value of -4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion-π interactions, these conceptually innovative π-acidic surfaces are also of interest as electron transporters in conductive materials.

  14. Chiral recognition of zinc phthalocyanine on Cu(100) surface

    NASA Astrophysics Data System (ADS)

    Chen, Feng; Chen, Xiu; Liu, Lacheng; Song, Xin; Liu, Shuyi; Liu, Juan; Ouyang, Hongping; Cai, Yingxiang; Liu, Xiaoqing; Pan, Haibing; Zhu, Junfa; Wang, Li

    2012-02-01

    The windmill-like chiral nature of individual ZnPc molecules adsorbed on Cu(100) surface at room temperature has been revealed by scanning tunneling microscopy (STM) and the origin of such chirality is attributed to asymmetrical charge transfer between the molecules and the copper surface. Such chiral enantiomers do recognize each other in molecular level and spontaneously form second-level chiral supramolecular structures with the same chirality during thermally driven movements. The interactions between the ZnPc molecules during such chiral recognition process have been discussed based on the analysis of the sub-molecule-resolution STM images.

  15. Integration of inherent and induced chirality into subphthalocyanine analogue

    NASA Astrophysics Data System (ADS)

    Zhao, Luyang; Qi, Dongdong; Wang, Kang; Wang, Tianyu; Han, Bing; Tang, Zhiyong; Jiang, Jianzhuang

    2016-06-01

    Conventional conjugated systems are characteristic of only either inherent or induced chirality because of synthetic challenge in combination of chiral segment into the main chromophore. In this work, chiral binaphthyl segment is directly fused into the central chromophore of a subphthalocyanine skeleton, resulting in a novel type of chiral subphthalocyanine analogue (R/S)-1 of integrated inherent and induced chirality. Impressively, an obviously enhanced optical activity is discerned for (R/S)-1 molecules, and corresponding enhancement mechanism is elucidated in detail. The synthesis strategy based on rational molecular design will open the door towards fabrication of chiral materials with giant optical activity, which will have great potential in chiroptical devices.

  16. [Advances in polymer materials as chiral stationary phase].

    PubMed

    Dai, Rongji; Wang, Huiting; Sun, Weiwei; Deng, Yulin; Lü, Fang; Liu, Xiujie

    2016-01-01

    The applications of chiral drugs had a profound impact on human health. With the development of disciplines of chemistry, materials and life science, the research on the separation and analysis of chiral drugs became intensified. Chromatography and the selection of chiral stationary phase played important roles in resolving chiral drugs. The optimization of polymer materials and their derivatives as chiral stationary phase become the main issue in recent years. Recent studies as well as prospects in polymer materials used as chiral stationary phase are presented in this paper. PMID:27319162

  17. The asymmetric alkylation of dimethylhydrazones; intermolecular chirality transfer using sparteine as chiral ligand.

    PubMed

    McSweeney, Christina M; Foley, Vera M; McGlacken, Gerard P

    2014-12-01

    The asymmetric alkylation of ketones represents a fundamental transformation in organic chemistry. Chiral auxiliaries have been used almost exclusively for this transformation. Herein we describe a strategy for the generation of enantiomerically enriched α-alkylated ketones up to an er of 83 : 17, using a chiral ligand protocol.

  18. Salan ligands assembled around chiral bipyrrolidine: predetermination of chirality around octahedral Ti and Zr centres.

    PubMed

    Sergeeva, Ekaterina; Kopilov, Jacob; Goldberg, Israel; Kol, Moshe

    2009-06-01

    The first synthesis of Salan ligands assembled around the chiral 2,2'-bipyrrolidine backbone is described; as chelation to a metal can only occur via specific faces of the two pyrrolidine nitrogens, these ligands lead to predetermined chirality at metal centres of octahedral titanium and zirconium complexes. PMID:19462084

  19. Optical Activity Governed by Local Chiral Structures in Two-Dimensional Curved Metallic Nanostructures.

    PubMed

    Narushima, Tetsuya; Hashiyada, Shun; Okamoto, Hiromi

    2016-07-01

    Chiral nanostructures show macroscopic optical activity. Local optical activity and its handedness are not uniform in the nanostructure, and are spatially distributed depending on the shape of the nanostructure. In this study we fabricated curved chain nanostructures made of gold by connecting linearly two or more arc structures in a two-dimensional plane. Spatial features of local optical activity in the chain structures were evaluated with near-field circular dichroism (CD) imaging, and analyzed with the aid of classical electromagnetic simulation. The electromagnetic simulation predicted that local optical activity appears at inflection points where arc structures are connected. The handedness of the local optical activity was dependent on the handedness of the local chirality at the inflection point. Chiral chain structures have odd inflection points and the local optical activity distributed symmetrically with respect to structural centers. In contrast, achiral chain structures have even inflection points and showed antisymmetric distribution. In the near-field CD images of fabricated chain nanostructures, the symmetric and antisymmetric distributions of local CD were observed for chiral and achiral chain structures, respectively, consistent with the simulated results. The handedness of the local optical activity was found to be determined by the handedness of the inflection point, for the fabricated chain structures having two or more inflection points. The local optical activity was thus governed primarily by the local chirality of the inflection points for the gold chain structures. The total effect of all the inflection points in the chain structure is considered to be a predominant factor that determines the macroscopic optical activity. Chirality 28:540-544, 2016. © 2016 Wiley Periodicals, Inc.

  20. The chiral magnetic effect and chiral symmetry breaking in SU(3) quenched lattice gauge theory

    SciTech Connect

    Braguta, V. V.; Buividovich, P. V. Kalaydzhyan, T. Kuznetsov, S. V. Polikarpov, M. I.

    2012-04-15

    We study some properties of the non-Abelian vacuum induced by strong external magnetic field. We perform calculations in the quenched SU(3) lattice gauge theory with tadpole-improved Luescher-Weisz action and chirally invariant lattice Dirac operator. The following results are obtained: The chiral symmetry breaking is enhanced by the magnetic field. The chiral condensate depends on the strength of the applied field as a power function with exponent {nu} = 1.6 {+-} 0.2. There is a paramagnetic polarization of the vacuum. The corresponding susceptibility and other magnetic properties are calculated and compared with the theoretical estimations. There are nonzero local fluctuations of the chirality and electromagnetic current, which grow with the magnetic field strength. These fluctuations can be a manifestation of the Chiral Magnetic Effect.

  1. Transition State Models for Understanding the Origin of Chiral Induction in Asymmetric Catalysis.

    PubMed

    Sunoj, Raghavan B

    2016-05-17

    In asymmetric catalysis, a chiral catalyst bearing chiral center(s) is employed to impart chirality to developing stereogenic center(s). A rich and diverse set of chiral catalysts is now available in the repertoire of synthetic organic chemistry. The most recent trends point to the emergence of axially chiral catalysts based on binaphthyl motifs, in particular, BINOL-derived phosphoric acids and phosphoramidites. More fascinating ideas took shape in the form of cooperative multicatalysis wherein organo- and transition-metal catalysts are made to work in concert. At the heart of all such manifestations of asymmetric catalysis, classical or contemporary, is the stereodetermining transition state, which holds a perennial control over the stereochemical outcome of the catalytic process. Delving one step deeper, one would find that the origin of the stereoselectivity is delicately dependent on the relative stabilization of one transition state, responsible for the formation of the predominant stereoisomer, over the other transition state for the minor stereoisomer. The most frequently used working hypothesis to rationalize the experimentally observed stereoselectivity places an undue emphasis on steric factors and tends to regard the same as the origin of facial discrimination between the prochiral faces of the reacting partners. In light of the increasing number of asymmetric catalysts that rely on hydrogen bonding as well as other weak non-covalent interactions, it is important to take cognizance of the involvement of such interactions in the sterocontrolling transition states. Modern density functional theories offer a pragmatic and effective way to capture non-covalent interactions in transition states. Aided by the availability of such improved computational tools, it is quite timely that the molecular origin of stereoselectivity is subjected to more intelligible analysis. In this Account, we describe interesting molecular insights into the stereocontrolling

  2. Diastereoselective aziridination of chiral electron-deficient olefins with N-chloro-N-sodiocarbamates catalyzed by chiral quaternary ammonium salts.

    PubMed

    Murakami, Yuta; Takeda, Youhei; Minakata, Satoshi

    2011-08-01

    Chiral quaternary ammonium salt-catalyzed diastereoselective aziridination of electron-deficient olefins that possess a chiral auxiliary with N-chloro-N-sodiocarbamates was developed. The key to high stereoselectivity was found to be the employment of the "matching" stereochemical combination of chiral auxiliary/ammonium salt. For example, when 3-phenyl-(4R,7S)-4-methyl-7-isopropyl-4,5,6,7-tetrahydroindazole (L-menthopyrazole) as a chiral auxiliary and a cinchonidine-derived chiral ammonium salt as a catalyst were applied to the reaction system, perfect diastereoselectivity was realized. Furthermore, the preparation of enantiomerically pure aziridines by removal of the chiral auxiliary was demonstrated.

  3. Formation of Enhanced Uniform Chiral Fields in Symmetric Dimer Nanostructures

    PubMed Central

    Tian, Xiaorui; Fang, Yurui; Sun, Mengtao

    2015-01-01

    Chiral fields with large optical chirality are very important in chiral molecules analysis, sensing and other measurements. Plasmonic nanostructures have been proposed to realize such super chiral fields for enhancing weak chiral signals. However, most of them cannot provide uniform chiral near-fields close to the structures, which makes these nanostructures not so efficient for applications. Plasmonic helical nanostructures and blocked squares have been proved to provide uniform chiral near-fields, but structure fabrication is a challenge. In this paper, we show that very simple plasmonic dimer structures can provide uniform chiral fields in the gaps with large enhancement of both near electric fields and chiral fields under linearly polarized light illumination with polarization off the dimer axis at dipole resonance. An analytical dipole model is utilized to explain this behavior theoretically. 30 times of volume averaged chiral field enhancement is gotten in the whole gap. Chiral fields with opposite handedness can be obtained simply by changing the polarization to the other side of the dimer axis. It is especially useful in Raman optical activity measurement and chiral sensing of small quantity of chiral molecule. PMID:26621558

  4. Symmetry, Structure, and Dynamics of Monoaxial Chiral Magnets

    NASA Astrophysics Data System (ADS)

    Togawa, Yoshihiko; Kousaka, Yusuke; Inoue, Katsuya; Kishine, Jun-ichiro

    2016-11-01

    Nontrivial spin orders with magnetic chirality emerge in a particular class of magnetic materials with structural chirality, which are frequently referred to as chiral magnets. Various interesting physical properties are expected to be induced in chiral magnets through the coupling of chiral magnetic orders with conduction electrons and electromagnetic fields. One promising candidate for achieving these couplings is a chiral spin soliton lattice. Here, we review recent experimental observations mainly carried out on the monoaxial chiral magnetic crystal CrNb3S6 via magnetic imaging using electron, neutron, and X-ray beams and magnetoresistance measurements, together with the strategy for synthesizing chiral magnetic materials and underlying theoretical backgrounds. The chiral soliton lattice appears under a magnetic field perpendicular to the chiral helical axis and is very robust and stable with phase coherence on a macroscopic length scale. The tunable and topological nature of the chiral soliton lattice gives rise to nontrivial physical properties. Indeed, it is demonstrated that the interlayer magnetoresistance scales to the soliton density, which plays an essential role as an order parameter in chiral soliton lattice formation, and becomes quantized with the reduction of the system size. These interesting features arising from macroscopic phase coherence unique to the chiral soliton lattice will lead to the exploration of routes to a new paradigm for applications in spin electronics using spin phase coherence.

  5. Chiral dynamics and peripheral transverse densities

    SciTech Connect

    Granados, Carlos G.; Weiss, Christian

    2014-01-01

    In the partonic (or light-front) description of relativistic systems the electromagnetic form factors are expressed in terms of frame-independent charge and magnetization densities in transverse space. This formulation allows one to identify the chiral components of nucleon structure as the peripheral densities at transverse distances b = O(M{sub {pi}}{sup -1}) and compute them in a parametrically controlled manner. A dispersion relation connects the large-distance behavior of the transverse charge and magnetization densities to the spectral functions of the Dirac and Pauli form factors near the two--pion threshold at timelike t = 4 M{ sub {pi}}{sup 2}, which can be computed in relativistic chiral effective field theory. Using the leading-order approximation we (a) derive the asymptotic behavior (Yukawa tail) of the isovector transverse densities in the "chiral" region b = O(M{sub {pi}}{sup -1}) and the "molecular" region b = O(M{sub N}{sup 2}/M{sub {pi}}{sup 3}); (b) perform the heavy-baryon expansion of the transverse densities; (c) explain the relative magnitude of the peripheral charge and magnetization densities in a simple mechanical picture; (d) include Delta isobar intermediate states and study the peripheral transverse densities in the large-N{ sub c} limit of QCD; (e) quantify the region of transverse distances where the chiral components of the densities are numerically dominant; (f) calculate the chiral divergences of the b{sup 2}-weighted moments of the isovector transverse densities (charge and anomalous magnetic radii) in the limit M{sub {pi}} -> 0 and determine their spatial support. Our approach provides a concise formulation of the spatial structure of the nucleon's chiral component and offers new insights into basic properties of the chiral expansion. It relates the information extracted from low-t elastic form factors to the generalized parton distributions probed in peripheral high-energy scattering processes.

  6. Isospin breaking and chiral symmetry restoration

    SciTech Connect

    Gomez Nicola, A.; Torres Andres, R.

    2011-04-01

    We analyze quark condensates and chiral (scalar) susceptibilities including isospin-breaking effects at finite temperature T. These include m{sub u{ne}}m{sub d} contributions as well as electromagnetic (e{ne}0) corrections, both treated in a consistent chiral Lagrangian framework to leading order in SU(2) and SU(3) chiral perturbation theory, so that our predictions are model-independent. The chiral restoration temperature extracted from = is almost unaffected, while the isospin-breaking order parameter grows with T for the three-flavor case SU(3). We derive a sum rule relating the condensate ratio (e{ne}0)/(e=0) with the scalar susceptibility difference {chi}(T)-{chi}(0), directly measurable on the lattice. This sum rule is useful also for estimating condensate errors in staggered lattice analysis. Keeping m{sub u{ne}}m{sub d} allows one to obtain the connected and disconnected contributions to the susceptibility, even in the isospin limit, whose temperature, mass, and isospin-breaking dependence we analyze in detail. The disconnected part grows linearly, diverging in the chiral (infrared) limit as T/M{sub {pi}}, while the connected part shows a quadratic behavior, infrared regular as T{sup 2}/M{sub {eta}}{sup 2}, and coming from {pi}{sup 0{eta}} mixing terms. This smooth connected behavior suggests that isospin-breaking correlations are weaker than critical chiral ones near the transition temperature. We explore some consequences in connection with lattice data and their scaling properties, for which our present analysis for physical masses, i.e. beyond the chiral limit, provides a useful model-independent description for low and moderate temperatures.

  7. Chirality of electrodeposits grown in a magnetic field.

    PubMed

    Mhíocháin, T R Ní; Coey, J M D

    2004-06-01

    Electrodeposits grown around a point cathode in a flat, horizontal electrochemical cell have fractal form. When grown in the presence of a perpendicular applied magnetic field, the deposits develop a spiral structure with chirality which reverses on switching the field direction. These structures are modeled numerically using biased variants of the diffusion limited aggregation (DLA) model. The effects of electric and magnetic fields are modeled successfully by varying the probabilities that a random walker will move in a given direction as a result of a Coulomb force and the Lorentz force-induced flow of electrolyte past the deposit surface. By contrast, a numerical model which considers only the effect of the Lorentz force on individual ions, without reference to the surface of the growing deposit, produces spiral structures with incorrect chirality. The modified DLA model is related to the differential equations for diffusion, migration, and convection. Length scales in the problem are understood by associating the step length of the random walker with the diffusion layer thickness, the lookup radius with the hydrodynamic boundary layer thickness and a point on the numerical deposit with a nucleation center for growth of a crystallite. PMID:15244565

  8. Proton-Proton Weak Capture in Chiral Effective Field Theory

    SciTech Connect

    Marcucci, Laura Elisa; Schiavilla, Rocco; Viviani, MIchele

    2013-05-01

    The astrophysical $S$-factor for proton-proton weak capture is calculated in chiral effective field theory over the center-of-mass relative-energy range 0--100 keV. The chiral two-nucleon potential derived up to next-to-next-to-next-to leading order is augmented by the full electromagnetic interaction including, beyond Coulomb, two-photon and vacuum-polarization corrections. The low-energy constants (LEC's) entering the weak current operators are fixed so as to reproduce the $A=3$ binding energies and magnetic moments, and the Gamow-Teller matrix element in tritium $\\beta$ decay. Contributions from $S$ and $P$ partial waves in the incoming two-proton channel are retained. The $S$-factor at zero energy is found to be $S(0)=(4.030 \\pm 0.006)\\times 10^{-23}$ MeV fm$^2$, with a $P$-wave contribution of $0.020\\times 10^{-23}$ MeV fm$^2$. The theoretical uncertainty is due to the fitting procedure of the LEC's and to the cutoff dependence. It is shown that polynomial fits to parametrize the energy dependence of the $S$-factor are inherently unstable.

  9. Proton-proton weak capture in chiral effective field theory.

    PubMed

    Marcucci, L E; Schiavilla, R; Viviani, M

    2013-05-10

    The astrophysical S factor for proton-proton weak capture is calculated in chiral effective field theory over the center-of-mass relative-energy range 0-100 keV. The chiral two-nucleon potential derived up to next-to-next-to-next-to leading order is augmented by the full electromagnetic interaction including, beyond Coulomb, two-photon and vacuum-polarization corrections. The low-energy constants entering the weak current operators are fixed so as to reproduce the A=3 binding energies and magnetic moments and the Gamow-Teller matrix element in tritium β decay. Contributions from S and P partial waves in the incoming two-proton channel are retained. The S factor at zero energy is found to be S(0)=(4.030±0.006)×10(-23) MeV fm(2), with a P-wave contribution of 0.020×10(-23) MeV fm(2). The theoretical uncertainty is due to the fitting procedure of the low-energy constants and to the cutoff dependence.

  10. Proton-proton weak capture in chiral effective field theory.

    PubMed

    Marcucci, L E; Schiavilla, R; Viviani, M

    2013-05-10

    The astrophysical S factor for proton-proton weak capture is calculated in chiral effective field theory over the center-of-mass relative-energy range 0-100 keV. The chiral two-nucleon potential derived up to next-to-next-to-next-to leading order is augmented by the full electromagnetic interaction including, beyond Coulomb, two-photon and vacuum-polarization corrections. The low-energy constants entering the weak current operators are fixed so as to reproduce the A=3 binding energies and magnetic moments and the Gamow-Teller matrix element in tritium β decay. Contributions from S and P partial waves in the incoming two-proton channel are retained. The S factor at zero energy is found to be S(0)=(4.030±0.006)×10(-23) MeV fm(2), with a P-wave contribution of 0.020×10(-23) MeV fm(2). The theoretical uncertainty is due to the fitting procedure of the low-energy constants and to the cutoff dependence. PMID:23705703

  11. A novel approach to the study of conformality in the SU(3) theory with multiple flavors

    SciTech Connect

    Brower, R.; Hasenfratz, A.; Rebbi, C. Weinberg, E.; Witzel, O.

    2015-03-15

    We investigate the transition between spontaneous chiral symmetry breaking and conformal behavior in the SU(3) theory with multiple fermion flavors. We propose a new strategy for studying this transition. Instead of changing the number of flavors, we lift the mass of a subset of the fermions, keeping the rest of the fermions near the massless chiral limit in order to probe the transition.

  12. Improved Measure of Local Chirality

    SciTech Connect

    Terrence Draper; Andrei Alexandru; Ying Chen; Shao-Jing Dong; Ivan Horvath; Frank Lee; Nilmani Mathur; Harry B. Thacker; Sonali Tamhankar; Jianbo Zhang

    2004-06-01

    It is popular to probe the structure of the QCD vacuum indirectly by studying individual fermion eigenmodes, because this provides a natural way to filter out UV fluctuations. The double-peaking in the distribution of the local chiral orientation parameter (X) has been offered as evidence, by some, in support of a particular model of the vacuum. Here we caution that the X-distribution peaking varies significantly with various versions of the definition of X. Furthermore, each distribution varies little from that resulting from a random reshuffling of the left-handed (and independently the right-handed) fields, which destroys any QCD-induced left-right correlation; that is, the double-peaking is mostly a phase-space effect. We propose a new universal definition of the X parameter whose distribution is uniform for randomly reshuffled fields. Any deviations from uniformity for actual data can then be directly attributable to QCD-induced dynamics. We find that the familiar double peak disappears.

  13. The synthesis and structure of chiral enamine N-oxides.

    PubMed

    O'Neil, I A; McConville, M; Zhou, K; Brooke, C; Robertson, C M; Berry, N G

    2014-07-14

    Chiral enamine N-oxides have been synthesised by a diastereoselective intermolecular reverse-Cope cycloaddition reaction between chiral hydroxylamines and activated acetylenes. Their structures have been investigated by NMR, X-ray crystallography and computational methods.

  14. Macroscopic chirality of a liquid crystal from nonchiral molecules

    SciTech Connect

    Jakli, A.; Nair, G. G.; Lee, C. K.; Sun, R.; Chien, L. C.

    2001-06-01

    The transfer of chirality from nonchiral polymer networks to the racemic B2 phase of nonchiral banana-shaped molecules is demonstrated. This corresponds to the transfer of chirality from an achiral material to another achiral material. There are two levels of chirality transfers. (a) On a microscopic level the presence of a polymer network (chiral or nonchiral) favors a chiral state over a thermodynamically stable racemic state due to the inversion symmetry breaking at the polymer-liquid crystal interfaces. (b) A macroscopically chiral (enantimerically enriched) sample can be produced if the polymer network has a helical structure, and/or contains chemically chiral groups. The chirality transfer can be locally suppressed by exposing the liquid crystal to a strong electric field treatment.

  15. METHODS DEVELOPMENT FOR THE ANALYSIS OF CHIRAL PESTICIDES

    EPA Science Inventory

    Chiral compounds exist as a pair of nonsuperimposable mirror images called enantiomers. Enantiomers have identical physical-chemical properties, but their interactions with other chiral molecules, toxicity, biodegradation, and fate are often different. Many pharmaceutical com...

  16. Chiral heteropoly blues and controllable switching of achiral polyoxometalate clusters.

    PubMed

    Wang, Yizhan; Li, Haolong; Wu, Che; Yang, Yang; Shi, Lei; Wu, Lixin

    2013-04-22

    Managing the blues: Chiral heteropoly blues of achiral polyoxometalate clusters were created through an intermolecular interaction with a chiral organic compound. Controllable chiroptical switching of the cluster complexes was possible through reversible photochromism of the polyoxometalates (see picture).

  17. PESTICIDE EXPOSURE AND CHIRAL CHEMISTRY: THE PYRETHROID FAMILY

    EPA Science Inventory

    Advances in chiral chromatography significantly advanced the ability to analyze individual enantiomers of chiral compounds. These techniques are being employed at the U.S. EPA for human exposure and ecological research studies. Enantiomer fractions (EFs) were measured for cisp...

  18. Inter- and intramolecular annulation strategies to a cyclopentanone building block containing an all-carbon quaternary stereogenic center.

    PubMed

    Penrose, Stephen D; Stott, Andrew J; Breccia, Perla; Haughan, Alan F; Bürli, Roland W; Jarvis, Rebecca E; Dominguez, Celia

    2015-03-20

    Synthesis of (S)-2-methyl-3-fluorophenyl cyclopentanone methyl ester (1S)-1 has been achieved by both inter- and intramolecular alkylation reactions on multigram scale, using chiral pool reagents. The intramolecular variant is a novel example of a chiral bis-electrophile reacting with a carbon nucleophile to form an enantiomerically pure all-carbon quaternary center. PMID:25720587

  19. On the chiral imbalance and Weibel instabilities

    NASA Astrophysics Data System (ADS)

    Kumar, Avdhesh; Bhatt, Jitesh R.; Kaw, P. K.

    2016-06-01

    We study the chiral-imbalance and the Weibel instabilities in presence of the quantum anomaly using the Berry-curvature modified kinetic equation. We argue that in many realistic situations, e.g. relativistic heavy-ion collisions, both the instabilities can occur simultaneously. The Weibel instability depends on the momentum anisotropy parameter ξ and the angle (θn) between the propagation vector and the anisotropy direction. It has maximum growth rate at θn = 0 while θn = π / 2 corresponds to a damping. On the other hand the pure chiral-imbalance instability occurs in an isotropic plasma and depends on difference between the chiral chemical potentials of right and left-handed particles. It is shown that when θn = 0, only for a very small values of the anisotropic parameter ξ ∼ξc, growth rates of the both instabilities are comparable. For the cases ξc < ξ ≪ 1 or ξ ≳ 1 at θn = 0, the Weibel modes dominate over the chiral-imbalance instability if μ5 / T ≤ 1. However, when μ5 / T ≥ 1, it is possible to have dominance of the chiral-imbalance modes at certain values of θn for an arbitrary ξ.

  20. Chirality dependent spin polarization of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Wang, Jia; Jiang, Wanrun; Wang, Bo; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin

    2016-02-01

    The spin polarization of carbon nanotubes (CNTs) offers a tunable building block for spintronic devices and is also crucial for realizing carbon-based electronics. However, the effect of chiral CNTs is still unclear. In this paper, we use the density functional theory (DFT) method to investigate the spin polarization of a series of typical finite-length chiral CNTs (9, m). The results show that the spin density of chiral CNTs (9, m) decreases gradually with the increase in m and vanishes altogether when m is larger than or equal to 6. The armchair edge units on both ends of the (9, m) CNTs exhibit a clear inhibition of spin polarization, allowing control of the spin density of (9, m) CNTs by adjusting the number of armchair edge units on the tube end. Furthermore, analysis of the orbitals shows that the spin of the ground state for (9, m) CNTs mainly comes from the contributions of the frontier molecular orbitals (MOs), and the energy gap decreases gradually with the spin density for chiral CNTs. Our work further develops the study of the spin polarization of CNTs and provides a strategy for controlling the spin polarization of functional molecular devices through chiral vector adjustment.

  1. Ratchet transport powered by chiral active particles

    PubMed Central

    Ai, Bao-quan

    2016-01-01

    We numerically investigate the ratchet transport of mixtures of active and passive particles in a transversal asymmetric channel. A big passive particle is immersed in a ‘sea’ of active particles. Due to the chirality of active particles, the longitudinal directed transport is induced by the transversal asymmetry. For the active particles, the chirality completely determines the direction of the ratchet transport, the counterclockwise and clockwise particles move to the opposite directions and can be separated. However, for the passive particle, the transport behavior becomes complicated, the direction is determined by competitions among the chirality, the self-propulsion speed, and the packing fraction. Interestingly, within certain parameters, the passive particle moves to the left, while active particles move to the right. In addition, there exist optimal parameters (the chirality, the height of the barrier, the self-propulsion speed and the packing fraction) at which the rectified efficiency takes its maximal value. Our findings could be used for the experimental pursuit of the ratchet transport powered by chiral active particles. PMID:26795952

  2. A liquid crystalline chirality balance for vapours

    PubMed Central

    Ohzono, Takuya; Yamamoto, Takahiro; Fukuda, Jun-ichi

    2014-01-01

    Chiral discrimination of vapours plays an important role in olfactory perception of biological systems and its realization by artificial sensors has been an intriguing challenge. Here, we report a simple method that tangibly visualizes the chirality of a diverse variety of molecules dissolved from vapours with high sensitivity, by making use of a structural change in a periodic microstructure of a nematic liquid crystal confined in open microchannels. This microstructure is accompanied by a topological line defect of a zigzag form with equal lengths of ‘zig’ and ‘zag.’ We find that a tiny amount of vapour of chiral molecules injected onto the liquid crystal induces the imbalance of ‘zig’ and ‘zag’ depending on its enantiomeric excess within a few seconds. Our liquid-crystal-based ‘chirality balance’ offers a simple, quick and versatile chirality-sensing/-screening method for gas-phase analysis (for example, for odours, environmental chemicals or drugs). PMID:24781531

  3. Ratchet transport powered by chiral active particles.

    PubMed

    Ai, Bao-quan

    2016-01-01

    We numerically investigate the ratchet transport of mixtures of active and passive particles in a transversal asymmetric channel. A big passive particle is immersed in a 'sea' of active particles. Due to the chirality of active particles, the longitudinal directed transport is induced by the transversal asymmetry. For the active particles, the chirality completely determines the direction of the ratchet transport, the counterclockwise and clockwise particles move to the opposite directions and can be separated. However, for the passive particle, the transport behavior becomes complicated, the direction is determined by competitions among the chirality, the self-propulsion speed, and the packing fraction. Interestingly, within certain parameters, the passive particle moves to the left, while active particles move to the right. In addition, there exist optimal parameters (the chirality, the height of the barrier, the self-propulsion speed and the packing fraction) at which the rectified efficiency takes its maximal value. Our findings could be used for the experimental pursuit of the ratchet transport powered by chiral active particles.

  4. The Quality of Pre-hospital Circulatory Management in Patients With Multiple Trauma Referred to the Trauma Center of Shahid Beheshti Hospital in Kashan, Iran, in the First Six Months of 2013

    PubMed Central

    Maghaminejad, Farzaneh; Adib-Hajbaghery, Mohsen

    2016-01-01

    Background Circulatory management is a critical issue in pre-hospital transportation phase of multiple trauma patients. However, the quality of this important care did not receive enough attention. Objectives The aim of this study was to investigate the quality of pre-hospital circulatory management in patients with multiple trauma. Patients and Methods This was a cross-sectional study conducted in 2013. The study population consisted of all patients with multiple trauma who had been transferred by emergency medical services (EMS) to the central trauma department in Kashan Shahid Beheshti medical center, Kashan, Iran. We recruited a convenience sample of 400 patients with multiple trauma. Data were collected using the circulatory assessment questionnaire and controlling hemorrhage (CAQCH) that were designed by the researchers and were described by using frequency tabulations, central tendency measures, and variability indices. The chi-square test was used to analyze the data. Results The study sample consisted of 263 males (75.2%); 57.75% had lower levels of education and 28.75% were workers. The most common mechanism of trauma was traffic accident (85.4%). We found that the quality of circulatory management was unfavorable in 61% of the cases. A significant relationship was observed between the quality of circulatory management and type of trauma and staff’s employment status. Conclusions The quality of pre-hospital circulatory management provided to patients with multiple trauma was unfavorable. Therefore, establishment of in-service training programs on circulatory management is recommended. PMID:27556056

  5. Gauge covariant fermion propagator in quenched, chirally symmetric quantum electrodynamics

    SciTech Connect

    Roberts, C.D.; Dong, Z.; Munczek, H.J.

    1995-08-01

    The chirally symmetric solution of the massless, quenched, Dyson-Schwinger equation (DSE) for the fermion propagator in three- and four-dimensional quantum electrodynamics was obtained. The DSEs are a valuable nonperturbative tool for studying field theories. In recent years a good deal of progress was made in addressing the limitations of the DSE approach in the study of Abelian gauge theories. Key to this progress is an understanding of the role of the dressed fermion/gauge-boson vertex in ensuring gauge covariance and multiplicative renormalizability of the solution of the fermion DSE. The solutions we obtain are manifestly gauge covariant and a general gauge covariance constraint on the fermion/gauge-boson vertex is presented, which motivates a vertex Ansatz that, for the first time, both satisfies the Ward identity when the fermion self-mass is zero and ensures gauge covariance of the fermion propagator. This research facilitates gauge-invariant, nonperturbative studies of continuum quantum electrodynamics and has already been used by others in studies of the chiral phase transition.

  6. Acylation of Chiral Alcohols: A Simple Procedure for Chiral GC Analysis

    PubMed Central

    Oromí-Farrús, Mireia; Torres, Mercè; Canela, Ramon

    2012-01-01

    The use of iodine as a catalyst and either acetic or trifluoroacetic acid as a derivatizing reagent for determining the enantiomeric composition of acyclic and cyclic aliphatic chiral alcohols was investigated. Optimal conditions were selected according to the molar ratio of alcohol to acid, the reaction time, and the reaction temperature. Afterwards, chiral stability of chiral carbons was studied. Although no isomerization was observed when acetic acid was used, partial isomerization was detected with the trifluoroacetic acid. A series of chiral alcohols of a widely varying structural type were then derivatized with acetic acid using the optimal conditions. The resolution of the enantiomeric esters and the free chiral alcohols was measured using a capillary gas chromatograph equipped with a CP Chirasil-DEX CB column. The best resolutions were obtained with 2-pentyl acetates (α = 3.00) and 2-hexyl acetates (α = 1.95). This method provides a very simple and efficient experimental workup procedure for analyzing chiral alcohols by chiral-phase GC. PMID:22649749

  7. Life's First Handshake - Discovery of the Interstellar Chiral Molecule Propylene Oxide

    NASA Astrophysics Data System (ADS)

    McGuire, Brett A.; Carroll, P. Brandon; Loomis, Ryan A.; Finneran, Ian A.; Jewell, Philip R.; Remijan, Anthony J.; Blake, Geoffrey A.

    2016-06-01

    Life on Earth relies on chiral molecules, that is, species not superimposable on their mirror images. This manifests itself in the selection of a single molecular handedness, or homochirality, across the biosphere, and is perhaps most readily apparent in the large enhancement in biological activity of particular amino acid and sugar enantiomers. Yet, the ancestral origin of biological homochirality remains a mystery. The non-racemic ratios in some organics isolated from primitive meteorites hint at a primordial chiral seed, but even these samples have experienced substantial processing during planetary assembly, obscuring their complete histories. To determine the underlying origin of any enantiomeric excess, it is critical to understand the molecular gas from which these molecules originated. Here, we present the first extra-solar, astronomical detection of a chiral molecule, propylene oxide (CH3CHCH2O), in absorption toward the Galactic Center. We discuss the implications of the detection on observational searches to determine a primordial chiral excess, as well as the state of laboratory efforts in these areas.

  8. Liquid chromatographic resolution of mexiletine and its analogs on crown ether-based chiral stationary phases.

    PubMed

    Jin, Kab Bong; Kim, Hee Eun; Hyun, Myung Ho

    2014-05-01

    Mexiletine, an effective class IB antiarrhythmic agent, and its analogs were resolved on three different crown ether-based chiral stationary phases (CSPs), one (CSP 1) of which is based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid and the other two (CSP 2 and CSP 3) are based on (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6. Mexiletine was resolved with a resolution (R(S)) of greater than 1.00 on CSP 1 and CSP 3 containing residual silanol group-protecting n-octyl groups on the silica surface, but with a resolution (R(S)) of less than 1.00 on CSP 2. The chromatographic behaviors for the resolution of mexiletine analogs containing a substituted phenyl group at the chiral center on the three CSPs were quite dependent on the phenoxy group of analytes. Namely, mexiletine analogs containing 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3-methylphenoxy, 4-methylphenoxy, and a simple phenoxy group were resolved very well on the three CSPs even though the chiral recognition efficiencies vary with the CSPs. However, mexiletine analogs containing 2-methylphenoxy group were not resolved at all or only slightly resolved. Among the three CSPs, CSP 3 was found to show the highest chiral recognition efficiencies for the resolution of mexiletine and its analogs, especially in terms of resolution (R(S)).

  9. Liquid chromatographic resolution of mexiletine and its analogs on crown ether-based chiral stationary phases.

    PubMed

    Jin, Kab Bong; Kim, Hee Eun; Hyun, Myung Ho

    2014-05-01

    Mexiletine, an effective class IB antiarrhythmic agent, and its analogs were resolved on three different crown ether-based chiral stationary phases (CSPs), one (CSP 1) of which is based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid and the other two (CSP 2 and CSP 3) are based on (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6. Mexiletine was resolved with a resolution (R(S)) of greater than 1.00 on CSP 1 and CSP 3 containing residual silanol group-protecting n-octyl groups on the silica surface, but with a resolution (R(S)) of less than 1.00 on CSP 2. The chromatographic behaviors for the resolution of mexiletine analogs containing a substituted phenyl group at the chiral center on the three CSPs were quite dependent on the phenoxy group of analytes. Namely, mexiletine analogs containing 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3-methylphenoxy, 4-methylphenoxy, and a simple phenoxy group were resolved very well on the three CSPs even though the chiral recognition efficiencies vary with the CSPs. However, mexiletine analogs containing 2-methylphenoxy group were not resolved at all or only slightly resolved. Among the three CSPs, CSP 3 was found to show the highest chiral recognition efficiencies for the resolution of mexiletine and its analogs, especially in terms of resolution (R(S)). PMID:24677299

  10. Well-defined binuclear chiral spiro copper catalysts for enantioselective N-H insertion.

    PubMed

    Zhu, Shou-Fei; Xu, Bin; Wang, Guo-Peng; Zhou, Qi-Lin

    2012-01-11

    An asymmetric N-H insertion of α-diazoesters with anilines catalyzed by well-defined copper complexes of chiral spiro bisoxazoline ligands was studied in detail. The copper-catalyzed asymmetric N-H insertion of a wide range of α-alkyl-α-diazoacetates with anilines was accomplished with excellent enantioselectivity (up to 98% ee) and provided an efficient method for the preparation of optically active α-amino acid derivatives. A correlation study of the electronic properties of the substrates with the enantioselectivity of the N-H insertion reaction supports a stepwise insertion mechanism, and the significant first-order kinetic isotope effect proves that the proton transfer is most likely the rate-limiting step. A binuclear chiral spiro copper catalyst having 14-electron copper centers, a trans coordination model, a perfect C(2)-symmetric chiral pocket, and significant Cu-Cu interaction was isolated and extensively studied. The novel structure of the binuclear chiral spiro copper catalyst leads to unique reactivity as well as enantioselectivity in the N-H insertion reaction. PMID:22066865

  11. Construction and probing of multisite chiral catalysts: dendrimer fixation of c2-symmetrical diphosphinerhodium complexes.

    PubMed

    Engel, Gerald D; Gade, Lutz H

    2002-09-16

    A series of chiral phosphine-functionalized poly(propyleneimine) (PPI) dendrimers was synthesized by the reaction of carboxyl-linked C(2)-chiral pyrphos ligand (pyrphos=3,4-bis(diphenylphosphino)pyrrolidine) with zeroth-fourth generation PPI using ethyl-N,N-dimethylaminopropylcarbodiimide (EDC)/1-hydroxybenzotriazol as a coupling reagent. The dendrimers obtained were characterized by NMR spectroscopy and elemental analysis as well as FAB and MALDI-TOF mass spectrometry, which established their molecular masses of up to 20 700 amu. Metalation of the multi-site phosphines with [Rh(COD)(2)]BF(4) cleanly yielded the cationic rhododendrimers containing up to 32 metal centers (for the fourth generation species), representing the largest chiral phosphine dendrimer catalyst studied to date. The complete metalation of the chiral phosphine sites was demonstrated by (31)P NMR spectroscopy and the observation of the coordination-shifted AB part of the ABX spin system (delta(A)=33.9, delta(B)=32.9; (1)J(Rh,P)=150, 153 Hz; (2)J(P,P)=28 Hz). The relationship between the size/generation of the dendrimer and its catalytic properties was established in the asymmetric hydrogenation of Z-methyl-alpha-acetamidocinammate and dimethyl itaconate. A decrease in both activity and selectivity of the dendrimer catalysts was observed on going to the higher generations. PMID:12298024

  12. Chirality Change by Grinding Crystals in Solution

    NASA Astrophysics Data System (ADS)

    Viedma, Cristobal

    2010-07-01

    One of the greatest unsolved problems in chemistry is the origin of homochirality in the biosphere, that is, the fact that l-amino acids and d-sugars dominate in biology, while laboratory experiments with stereoselective reactions only produce racemic mixtures. Several models have been proposed to address the question of how enantiomerically pure solutions or crystalline phases could have emerged from a presumably racemic prebiotic world. Here we show that two populations of amino acid crystals of "left" and "right" hand cannot coexist in solution: one of the chiral populations disappears in an irreversible autocatalytic process that nurtures the other one. Final and complete chiral purity seems to be an inexorable fate in our systems, under grinding, in the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking has become firmly established but the underlying mechanism is being debated and we have no definitive answer.

  13. Chirality Change by Grinding Crystals in Solution

    SciTech Connect

    Viedma, Cristobal

    2010-07-22

    One of the greatest unsolved problems in chemistry is the origin of homochirality in the biosphere, that is, the fact that l-amino acids and d-sugars dominate in biology, while laboratory experiments with stereoselective reactions only produce racemic mixtures. Several models have been proposed to address the question of how enantiomerically pure solutions or crystalline phases could have emerged from a presumably racemic prebiotic world. Here we show that two populations of amino acid crystals of 'left' and 'right' hand cannot coexist in solution: one of the chiral populations disappears in an irreversible autocatalytic process that nurtures the other one. Final and complete chiral purity seems to be an inexorable fate in our systems, under grinding, in the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking has become firmly established but the underlying mechanism is being debated and we have no definitive answer.

  14. BPS pion domain walls in the supersymmetric chiral Lagrangian

    NASA Astrophysics Data System (ADS)

    Gudnason, Sven Bjarke; Nitta, Muneto; Sasaki, Shin

    2016-07-01

    We construct exact solutions of BPS pion domain walls in the four-dimensional N =1 supersymmetric S U (N ) chiral Lagrangian with pion masses introduced via linear and quadratic superpotentials. The model admits N discrete vacua in the center of S U (N ) for the linear superpotential. In addition to the latter, new vacua appear for the quadratic superpotential. We find that the domain wall solutions of pions (Nambu-Goldstone bosons) that interpolate between a pair of (pion) vacua preserve half of supersymmetry. Contrary to our expectations, we have not been able to find domain walls involving the quasi-Nambu-Goldstone bosons present in the theory, which in turn has the consequence that not all vacua of the theory are connected by a BPS domain wall solution.

  15. A semiclassical formulation of the chiral magnetic effect and chiral anomaly in even d + 1 dimensions

    NASA Astrophysics Data System (ADS)

    Dayi, Ömer F.; Elbistan, Mahmut

    2016-05-01

    In terms of the matrix valued Berry gauge field strength for the Weyl Hamiltonian in any even space-time dimensions a symplectic form whose elements are matrices in spin indices is introduced. Definition of the volume form is modified appropriately. A simple method of finding the path integral measure and the chiral current in the presence of external electromagnetic fields is presented. It is shown that within this new approach the chiral magnetic effect as well as the chiral anomaly in even d + 1 dimensions are accomplished straightforwardly.

  16. Chiral Molecules Revisited by Broadband Microwave Spectroscopy

    NASA Astrophysics Data System (ADS)

    Schnell, Melanie

    2014-06-01

    Chiral molecules have fascinated chemists for more than 150 years. While their physical properties are to a very good approximation identical, the two enantiomers of a chiral molecule can have completely different (bio)chemical activities. For example, the right-handed enantiomer of carvone smells of spearmint while the left-handed one smells of caraway. In addition, the active components of many drugs are of one specific handedness, such as in the case of ibuprofen. However, in nature as well as in pharmaceutical applications, chiral molecules often exist in mixtures with other chiral molecules. The analysis of these complex mixtures to identify the molecular components, to determine which enantiomers are present, and to measure the enantiomeric excesses (ee) remains a challenging task for analytical chemistry, despite its importance for modern drug development. We present here a new method of differentiating enantiomers of chiral molecules in the gas phase based on broadband rotational spectroscopy. The phase of the acquired signal bares the signature of the enantiomer, as it depends upon the combined quantity, μ_a μ_b μ_c, which is of opposite sign between enantiomers. It thus also provides information on the absolute configuration of the particular enantiomer. Furthermore, the signal amplitude is proportional to the ee. A significant advantage of our technique is its inherent mixture compatibility due to the fingerprint-like character of rotational spectra. In this contribution, we will introduce the technique and present our latest results on chiral molecule spectroscopy and enantiomer differentiation. D. Patterson, M. Schnell, J.M. Doyle, Nature 497 (2013) 475-477 V.A. Shubert, D. Schmitz, D. Patterson, J.M. Doyle, M. Schnell, Angewandte Chemie International Edition 53 (2014) 1152-1155

  17. Chirality: a blueprint for the future.

    PubMed

    Burke, D; Henderson, D J

    2002-04-01

    The chirality that is inherent in the enzyme systems of living organisms results in an abundance of enantiopure organic molecules in the living world. In addition to the optical properties first noticed by Pasteur, stereospecific interactions at recognition sites result in differences in both biological and toxicological effects. This fact underlies the continuing growth in chiral chemistry, rooted as it is in fundamental biochemistry. The pharmaceutical industry has undergone a strategic shift and embraced the wide spectrum of asymmetrical synthetic methods now available. The use of these processes in developmental synthesis and large-scale manufacturing has provided new challenges in drug discovery, motivated by a desire to improve industrial efficacy and decrease the time from the conception of a new drug to the market. The economic impact of the industrial production of chiral drugs is now huge--more than 50% of the 500 top-selling drugs were single-enantiomers in 1997. Sales have continued to increase by more than 20% for the past 6 yr and worldwide annual sales of enantiomeric drugs exceeded US$100 billion for the first time in the year 2000, chiral drugs representing close to one-third of all sales worldwide. While some 'chiral switches' may be of less apparent benefit, or indeed detrimental in some cases, encouragement by the regulatory agencies and the ability to extend the life cycle of a drug coming off patent promotes the trend. However, it may turn out to be the ability to provide chiral templates, and thereby attack the key targets of selectivity and specificity, that will lead to the greatest benefits. Research into new chemical entities that can interact specifically with enzyme families may potentially lead to new therapies for complex disease processes. As Richards has stated, the approach is designed to create a made to measure product, rather than one off the peg.

  18. Direct measurement of chiral structure and transport in single- and multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Cui, Taoran; Lin, Letian; Qin, Lu-Chang; Washburn, Sean

    2016-11-01

    Electrical devices based on suspended multi-wall carbon nanotubes were constructed and studied. The chiral structure of each shell in a particular nanotube was determined using nanobeam electron diffraction in a transmission electron microscope. The transport properties of the carbon nanotube were also measured. The nanotube device length was short enough that the transport was nearly ballistic, and multiple subbands contributed to the conductance. Thermal excitation of carriers significantly affected nanotube resistance at room temperature.

  19. Direct measurement of chiral structure and transport in single- and multi-walled carbon nanotubes.

    PubMed

    Cui, Taoran; Lin, Letian; Qin, Lu-Chang; Washburn, Sean

    2016-11-30

    Electrical devices based on suspended multi-wall carbon nanotubes were constructed and studied. The chiral structure of each shell in a particular nanotube was determined using nanobeam electron diffraction in a transmission electron microscope. The transport properties of the carbon nanotube were also measured. The nanotube device length was short enough that the transport was nearly ballistic, and multiple subbands contributed to the conductance. Thermal excitation of carriers significantly affected nanotube resistance at room temperature. PMID:27633072

  20. Direct measurement of chiral structure and transport in single- and multi-walled carbon nanotubes.

    PubMed

    Cui, Taoran; Lin, Letian; Qin, Lu-Chang; Washburn, Sean

    2016-11-30

    Electrical devices based on suspended multi-wall carbon nanotubes were constructed and studied. The chiral structure of each shell in a particular nanotube was determined using nanobeam electron diffraction in a transmission electron microscope. The transport properties of the carbon nanotube were also measured. The nanotube device length was short enough that the transport was nearly ballistic, and multiple subbands contributed to the conductance. Thermal excitation of carriers significantly affected nanotube resistance at room temperature.

  1. Hydroxypyridyl Imines: Enhancing Chromatographic Separation and Stereochemical Analysis of Chiral Amines via Circular Dichroism.

    PubMed

    Joyce, Leo A; Regalado, Erik L; Welch, Christopher J

    2016-09-16

    Imine-bond formation between chiral amines and commercially available 3-hydroxypyridine-2-carboxaldehyde (HCA) was exploited for rapid determination of stereochemical composition. Chiral supercritical fluid chromatography (SFC) screening of the derivatized imine compounds led to the elucidation of multiple combinations of mobile and stationary phases that gave resolution of all members of a series of chiral amines. The first eluting enantiomer was generally the derivative of the (R)-amine enantiomer across the series that was studied, indicating that the imine formed from the (S)-amine has more favorable interaction with the chiral stationary phase of the column. These conditions were then applied to more challenging compounds, namely amino alcohols and diastereomers possessing more than one stereocenter. The approach was utilized to monitor stereoselective biocatalytic transamination and assign the absolute configuration of the enantiomeric products. Finally, hydrolysis of the imine bond of the derivative was shown to generate enantiopure amine starting materials without racemization. This further highlights the value of this approach for creating readily reversed derivatives that enhance chromatographic separation and aid in the determination of absolute configuration. PMID:27529785

  2. Hydroxypyridyl Imines: Enhancing Chromatographic Separation and Stereochemical Analysis of Chiral Amines via Circular Dichroism.

    PubMed

    Joyce, Leo A; Regalado, Erik L; Welch, Christopher J

    2016-09-16

    Imine-bond formation between chiral amines and commercially available 3-hydroxypyridine-2-carboxaldehyde (HCA) was exploited for rapid determination of stereochemical composition. Chiral supercritical fluid chromatography (SFC) screening of the derivatized imine compounds led to the elucidation of multiple combinations of mobile and stationary phases that gave resolution of all members of a series of chiral amines. The first eluting enantiomer was generally the derivative of the (R)-amine enantiomer across the series that was studied, indicating that the imine formed from the (S)-amine has more favorable interaction with the chiral stationary phase of the column. These conditions were then applied to more challenging compounds, namely amino alcohols and diastereomers possessing more than one stereocenter. The approach was utilized to monitor stereoselective biocatalytic transamination and assign the absolute configuration of the enantiomeric products. Finally, hydrolysis of the imine bond of the derivative was shown to generate enantiopure amine starting materials without racemization. This further highlights the value of this approach for creating readily reversed derivatives that enhance chromatographic separation and aid in the determination of absolute configuration.

  3. Probing Chiral Interactions in Light Nuclei

    SciTech Connect

    Nogga, A; Barrett, B R; Meissner, U; Witala, H; Epelbaum, E; Kamada, H; Navratil, P; Glockle, W; Vary, J P

    2004-01-08

    Chiral two- and three-nucleon interactions are studied in a few-nucleon systems. We investigate the cut-off dependence and convergence with respect to the chiral expansion. It is pointed out that the spectra of light nuclei are sensitive to the three-nucleon force structure. As an example, we present calculations of the 1{sup +} and 3{sup +} states of {sup 6}Li using the no-core shell model approach. The results show contributions of the next-to-next-to-leading order terms to the spectra, which are not correlated to the three-nucleon binding energy prediction.

  4. Chiral thermoelectrics with quantum Hall edge states.

    PubMed

    Sánchez, Rafael; Sothmann, Björn; Jordan, Andrew N

    2015-04-10

    The thermoelectric properties of a three-terminal quantum Hall conductor are investigated. We identify a contribution to the thermoelectric response that relies on the chirality of the carrier motion rather than on spatial asymmetries. The Onsager matrix becomes maximally asymmetric with configurations where either the Seebeck or the Peltier coefficients are zero while the other one remains finite. Reversing the magnetic field direction exchanges these effects, which originate from the chiral nature of the quantum Hall edge states. The possibility to generate spin-polarized currents in quantum spin Hall samples is discussed. PMID:25910147

  5. Chiral Thermoelectrics with Quantum Hall Edge States

    NASA Astrophysics Data System (ADS)

    Sánchez, Rafael; Sothmann, Björn; Jordan, Andrew N.

    2015-04-01

    The thermoelectric properties of a three-terminal quantum Hall conductor are investigated. We identify a contribution to the thermoelectric response that relies on the chirality of the carrier motion rather than on spatial asymmetries. The Onsager matrix becomes maximally asymmetric with configurations where either the Seebeck or the Peltier coefficients are zero while the other one remains finite. Reversing the magnetic field direction exchanges these effects, which originate from the chiral nature of the quantum Hall edge states. The possibility to generate spin-polarized currents in quantum spin Hall samples is discussed.

  6. Four-modulus ``Swiss Cheese'' chiral models

    NASA Astrophysics Data System (ADS)

    Collinucci, Andrés; Kreuzer, Maximilian; Mayrhofer, Christoph; Walliser, Nils-Ole

    2009-07-01

    We study the `Large Volume Scenario' on explicit, new, compact, four-modulus Calabi-Yau manifolds. We pay special attention to the chirality problem pointed out by Blumenhagen, Moster and Plauschinn. Namely, we thoroughly analyze the possibility of generating neutral, non-perturbative superpotentials from Euclidean D3-branes in the presence of chirally intersecting D7-branes. We find that taking proper account of the Freed-Witten anomaly on non-spin cycles and of the Kähler cone conditions imposes severe constraints on the models. Nevertheless, we are able to create setups where the constraints are solved, and up to three moduli are stabilized.

  7. Asymmetric petasis reactions catalyzed by chiral biphenols.

    PubMed

    Lou, Sha; Schaus, Scott E

    2008-06-01

    Chiral biphenols catalyze the enantioselective Petasis reaction of alkenyl boronates, secondary amines, and ethyl glyoxylate. The reaction requires the use of 15 mol % of (S)-VAPOL as the catalyst, alkenyl boronates as nucleophiles, ethyl glyoxylate as the aldehyde component, and 3 A molecular sieves as an additive. The chiral alpha-amino ester products are obtained in good yields (71-92%) and high enantiomeric ratios (89:11-98:2). Mechanistic investigations indicate single ligand exchange of acyclic boronate with VAPOL and tetracoordinate boronate intermediates. PMID:18459782

  8. Consistent Two-Dimensional Chiral Gravity

    NASA Astrophysics Data System (ADS)

    Smailagic, A.; Spallucci, E.

    We study chiral induced gravity in the light-cone gauge and show that the theory is consistent for a particular choice of chiralities. The corresponding Kac-Moody central charge has no forbidden region of complex values. Generalized analysis of the critical exponents is given and their relation to the SL(2,R) vacuum states is elucidated. All the parameters containing information about the theory can be traced back to the characteristics of the residual symmetry group in the light-cone gauge.

  9. Possible chiral bands in {sup 194}Tl

    SciTech Connect

    Masiteng, P. L.; Ramashidzha, T. M.; Maliage, S. M.; Sharpey-Schafer, J. F.; Vymers, P. A.; Lawrie, E. A.; Lawrie, J. J.; Bark, R. A.; Mullins, S. M.; Murray, S. H. T.; Kau, J.; Komati, F.; Lindsay, R.; Matamba, I.; Mutshena, P.; Zhang, Y.

    2011-10-28

    High spin states in {sup 194}Tl, excited through the {sup 181}Ta({sup 18}O,5n) fusion evaporation reaction, were studied using the AFRODITE array at iThemba LABS. Candidate chiral bands built on the {pi}h{sub 9/2} x {nu}i{sub 13/2}{sup 1} configuration were found. Furthermore these bands were observed through a band crossing caused by the excitation of a {nu}i{sub 13/2} pair. Above the band crossing the excitation energies remain close, suggesting that chirality may persist for the four quasiparticle configuration too.

  10. Supernovae, neutron stars and biomolecular chirality.

    PubMed

    Bonner, W A; Rubenstein, E

    1987-01-01

    Recent theoretical and experimental investigations of the origin of biomolecular chirality are reviewed briefly. Biotic and abiotic theories are evaluated critically with the conclusion that asymmetric photochemical processes with circulary polarized light (CPL), particularly asymmetric photolyses, constitute the most viable mechanisms. Solar CPL sources appear too weak and random to be effective. We suggest an alternative CPL source, namely, the synchrotron radiation from the neutron star remnants of supernova explosions. This could asymmetrically process racemic compounds in the organic mantles of the dust grains in interstellar clouds, and the resulting chiral molecules could be transferred to Earth by cold accretion as the solar system periodically traverses these interstellar clouds.

  11. Generalized Bloch theorem and chiral transport phenomena

    NASA Astrophysics Data System (ADS)

    Yamamoto, Naoki

    2015-10-01

    Bloch theorem states the impossibility of persistent electric currents in the ground state of nonrelativistic fermion systems. We extend this theorem to generic systems based on the gauged particle number symmetry and study its consequences on the example of chiral transport phenomena. We show that the chiral magnetic effect can be understood as a generalization of the Bloch theorem to a nonequilibrium steady state, similarly to the integer quantum Hall effect. On the other hand, persistent axial currents are not prohibited by the Bloch theorem and they can be regarded as Pauli paramagnetism of relativistic matter. An application of the generalized Bloch theorem to quantum time crystals is also discussed.

  12. Chiral pesticides: Identification, description, and environmental implications

    USGS Publications Warehouse

    Ulrich, Elin M.; Morrison, Candice N.; Goldsmith, Michael R.; Foreman, William T.

    2012-01-01

    Anthropogenic chemicals, including pesticides, are a major source of contamination and pollution in the environment. Pesticides have many positive uses: increased food production, decreased damage to crops and structures, reduced disease vector populations, and more. Nevertheless, pesticide exposure can pose risks to humans and the environment, so various mitigation strategies are exercised to make them safer, minimize their use, and reduce their unintended environment effects. One strategy that may help achieve these goals relies on the unique properties of chirality or molecular asymmetry. Some common terms related to chirality are defined in Table 1.

  13. Sensitive chiral analysis by capillary electrophoresis.

    PubMed

    García-Ruiz, Carmen; Marina, María Luisa

    2006-01-01

    In this review, an updated view of the different strategies used up to now to enhance the sensitivity of detection in chiral analysis by CE will be provided to the readers. With this aim, it will include a brief description of the fundamentals and most of the recent applications performed in sensitive chiral analysis by CE using offline and online sample treatment techniques (SPE, liquid-liquid extraction, microdialysis, etc.), on-column preconcentration techniques based on electrophoretic principles (ITP, stacking, and sweeping), and alternative detection systems (spectroscopic, spectrometric, and electrochemical) to the widely used UV-Vis absorption detection.

  14. Band structure controlled by chiral imprinting

    NASA Astrophysics Data System (ADS)

    Castro-Garay, P.; Adrian Reyes, J.; Ramos-Garcia, R.

    2007-09-01

    Using the configuration of an imprinted cholesteric elastomer immersed in a racemic solvent, the authors find the solution of the boundary-value problem for the reflection and transmission of incident optical waves due to the elastomer. They show a significant width reduction of the reflection band for certain values of nematic penetration depth, which depends on the volume fraction of molecules from the solvent, whose handedness is preferably absorbed. The appearance of nested band gaps of both handednesses during the sorting mixed chiral process is also obtained. This suggests the design of chemically controlled optical filters and optically monitored chiral pumps.

  15. Band Structure Controlled by Chiral Imprinting

    NASA Astrophysics Data System (ADS)

    Reyes Cervantes, Adrian; Castro-Garay, P.; Ramos-Garcia, Ruben

    2008-03-01

    Using the configuration of an imprinted cholesteric elastomer immersed in a racemic solvent, we find the solution of the boundary--value problem for the reflection and transmission of incident optical waves due to the elastomer. We show a significant width reduction of the reflection band for certain values of nematic penetration depth, which depends on the volume fraction of molecules from the solvent, whose handedness is preferably absorbed. The appearance of nested bandgaps of both handednesses during the sorting mixed chiral process is also obtained. This suggests the design of chemically controlled optical filters and optically monitored chiral pumps.

  16. Chiral logarithms in the massless limit tamed.

    PubMed

    Kivel, Nikolai; Polyakov, Maxim V; Vladimirov, Alexei

    2008-12-31

    We derive nonlinear recursion relations for the leading chiral logarithms (LLs) in massless theories. These relations not only provide a very efficient method of computation of LLs (e.g., the 33-loop contribution is calculated in a dozen of seconds on a PC) but also equip us with a powerful tool for the summation of the LLs. Our method is not limited to chiral perturbation theory only; it is pertinent to any nonrenormalizable effective field theory such as, for instance, the theory of critical phenomena, low-energy quantum gravity, etc.

  17. Long-range interactions between chiral molecules

    SciTech Connect

    Salam, A.

    2015-01-22

    Results of molecular quantum electrodynamics calculations of discriminatory interactions between two chiral molecules undergoing resonance energy transfer, van der Waals dispersion, and optical binding are presented. A characteristic feature of the theory is that the radiation field is quantized with signals consequently propagating between centres at the speed of light. In order to correctly describe optically active chromophores, it is necessary to include magnetic as well as electric dipole coupling terms in the time-dependent perturbation theory computations. Recent work investigating the effect of an absorptive and dispersive chiral medium on the rate of migration of energy will also be discussed.

  18. Heavy-tailed chiral random matrix theory

    NASA Astrophysics Data System (ADS)

    Kanazawa, Takuya

    2016-05-01

    We study an unconventional chiral random matrix model with a heavy-tailed probabilistic weight. The model is shown to exhibit chiral symmetry breaking with no bilinear condensate, in analogy to the Stern phase of QCD. We solve the model analytically and obtain the microscopic spectral density and the smallest eigenvalue distribution for an arbitrary number of flavors and arbitrary quark masses. Exotic behaviors such as non-decoupling of heavy flavors and a power-law tail of the smallest eigenvalue distribution are illustrated.

  19. Steering Chiral Swimmers along Noisy Helical Paths

    NASA Astrophysics Data System (ADS)

    Friedrich, Benjamin M.; Jülicher, Frank

    2009-08-01

    Chemotaxis along helical paths towards a target releasing a chemoattractant is found in sperm cells and many microorganisms. We discuss the stochastic differential geometry of the noisy helical swimming path of a chiral swimmer. A chiral swimmer equipped with a simple feedback system can navigate in a concentration gradient of chemoattractant. We derive an effective equation for the alignment of helical paths with a concentration gradient which is related to the alignment of a dipole in an external field and discuss the chemotaxis index.

  20. High-resolution spectroscopy of the chiral metal complex [CpRe(CH₃)(CO)(NO)]: a potential candidate for probing parity violation.

    PubMed

    Medcraft, Chris; Wolf, Robert; Schnell, Melanie

    2014-10-20

    Heavy-metal containing chiral compounds have been suggested as promising candidates for studying parity-violation effects. We report herein the broadband rotational spectroscopy study of the chiral complex [CpRe(CH3)(CO)(NO)] in the gas phase. The spectra obtained are very rich due to the two rhenium isotopologues ((185)Re and (187)Re), hyperfine structure arising from the rhenium and nitrogen nuclei, and the asymmetry of the chiral complex. Since rhenium is located very close to the molecular center of mass, the rotational constants for the two rhenium isotopologues are very similar. However they can be differentiated by their characteristic nuclear quadrupole hyperfine splitting patterns. Comparison with calculated nuclear quadrupole coupling constants shows that all-electron relativistic basis sets are necessary for a correct description of the rhenium atom in this type of complex. The present study is an important step towards future precision studies on chiral molecules.

  1. Dispersion relations for electromagnetic wave propagation in chiral plasmas

    SciTech Connect

    Gao, M. X.; Guo, B. Peng, L.; Cai, X.

    2014-11-15

    The dispersion relations for electromagnetic wave propagation in chiral plasmas are derived using a simplified method and investigated in detail. With the help of the dispersion relations for each eignwave, we explore how the chiral plasmas exhibit negative refraction and investigate the frequency region for negative refraction. The results show that chirality can induce negative refraction in plasmas. Moreover, both the degree of chirality and the external magnetic field have a significant effect on the critical frequency and the bandwidth of the frequency for negative refraction in chiral plasmas. The parameter dependence of the effects is calculated and discussed.

  2. Chirally Symmetric but Confined Hadrons at Finite Density

    NASA Astrophysics Data System (ADS)

    Ya. Glozman, L.; Wagenbrunn, R. F.

    At a critical finite chemical potential and low temperature QCD undergoes the chiral restoration phase transition. The folklore tradition is that simultaneously hadrons are deconfined and there appears the quark matter. We demonstrate that it is possible to have confined but chirally symmetric hadrons at a finite chemical potential and hence beyond the chiral restoration point at a finite chemical potential and low temperature there could exist a chirally symmetric matter consisting of chirally symmetric but confined hadrons. If it does happen in QCD, then the QCD phase diagram should be reconsidered with obvious implications for heavy ion programs and astrophysics.

  3. Vortex Crystals with Chiral Stripes in Itinerant Magnets

    NASA Astrophysics Data System (ADS)

    Ozawa, Ryo; Hayami, Satoru; Barros, Kipton; Chern, Gia-Wei; Motome, Yukitoshi; Batista, Cristian D.

    Noncoplanar spin textures in itinerant magnets are generating increasing interest because of the associated spin Berry phase, which induces a tremendous effective magnetic field on the itinerant electrons. Such noncoplanar spin textures appear frequently in itinerant magnets, even with vanishingly small spin-orbit coupling. We explore a generic condition for noncoplanar spin ordering, with a focus on ``frustration'' in itinerant magnets, that is characterized by multiple global maxima in the magnetic susceptibility. In a simple square Kondo lattice model, we find that a noncoplanar vortex-antivortex crystal with a one-dimensional modulation of spin scalar chirality becomes stable in a wide range of electron filling fraction. The unexpected result is obtained by careful analyses of higher-order terms in the perturbative expansion in terms of the Kondo exchange coupling and the degree of noncoplanarity, as well as numerical simulation based on the Langevin and stochastic Landau-Lifshitz-Gilbert dynamics with the kernel polynomial method.

  4. When Chiral Photons Meet Chiral Fermions: Photoinduced Anomalous Hall Effects in Weyl Semimetals.

    PubMed

    Chan, Ching-Kit; Lee, Patrick A; Burch, Kenneth S; Han, Jung Hoon; Ran, Ying

    2016-01-15

    The Weyl semimetal is characterized by three-dimensional linear band touching points called Weyl nodes. These nodes come in pairs with opposite chiralities. We show that the coupling of circularly polarized photons with these chiral electrons generates a Hall conductivity without any applied magnetic field in the plane orthogonal to the light propagation. This phenomenon comes about because with all three Pauli matrices exhausted to form the three-dimensional linear dispersion, the Weyl nodes cannot be gapped. Rather, the net influence of chiral photons is to shift the positions of the Weyl nodes. Interestingly, the momentum shift is tightly correlated with the chirality of the node to produce a net anomalous Hall signal. Application of our proposal to the recently discovered TaAs family of Weyl semimetals leads to an order-of-magnitude estimate of the photoinduced Hall conductivity which is within the experimentally accessible range. PMID:26824561

  5. HPLC SEPARATION OF CHIRAL ORGANOPHOSPHORUS PESTICIDES ON POLYSACCHARIDE CHIRAL STATIONARY PHASES

    EPA Science Inventory

    High-performance liquid chromatographic separation of the individual enantiomers of 12 organophosphorus pesticides (OPs) were obtained on polysaccharide chiral HPLC columns using an alkane-alcohol mobile phase. The OP pesticides were crotoxyphos, dialifor, dyfonate, fenamiphos, ...

  6. When Chiral Photons Meet Chiral Fermions: Photoinduced Anomalous Hall Effects in Weyl Semimetals

    NASA Astrophysics Data System (ADS)

    Chan, Ching-Kit; Lee, Patrick A.; Burch, Kenneth S.; Han, Jung Hoon; Ran, Ying

    2016-01-01

    The Weyl semimetal is characterized by three-dimensional linear band touching points called Weyl nodes. These nodes come in pairs with opposite chiralities. We show that the coupling of circularly polarized photons with these chiral electrons generates a Hall conductivity without any applied magnetic field in the plane orthogonal to the light propagation. This phenomenon comes about because with all three Pauli matrices exhausted to form the three-dimensional linear dispersion, the Weyl nodes cannot be gapped. Rather, the net influence of chiral photons is to shift the positions of the Weyl nodes. Interestingly, the momentum shift is tightly correlated with the chirality of the node to produce a net anomalous Hall signal. Application of our proposal to the recently discovered TaAs family of Weyl semimetals leads to an order-of-magnitude estimate of the photoinduced Hall conductivity which is within the experimentally accessible range.

  7. Spintronics and chirality: spin selectivity in electron transport through chiral molecules.

    PubMed

    Naaman, Ron; Waldeck, David H

    2015-04-01

    Recent experiments have demonstrated that the electron transmission yield through chiral molecules depends on the electron spin orientation. This phenomenon has been termed the chiral-induced spin selectivity (CISS) effect, and it provides a challenge to theory and promise for organic molecule-based spintronic devices. This article reviews recent developments in our understanding of CISS. Different theoretical models have been used to describe the effect; however, they all presume an unusually large spin-orbit coupling in chiral molecules for the effect to display the magnitudes seen in experiments. A simplified model for an electron's transport through a chiral potential suggests that these large couplings can be manifested. Techniques for measuring spin-selective electron transport through molecules are overviewed, and some examples of recent experiments are described. Finally, we present results obtained by studying several systems, and we describe the possible application of the CISS effect for memory devices.

  8. Intelligent chiral sensing based on supramolecular and interfacial concepts.

    PubMed

    Ariga, Katsuhiko; Richards, Gary J; Ishihara, Shinsuke; Izawa, Hironori; Hill, Jonathan P

    2010-01-01

    Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.

  9. Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

    PubMed Central

    Ariga, Katsuhiko; Richards, Gary J.; Ishihara, Shinsuke; Izawa, Hironori; Hill, Jonathan P.

    2010-01-01

    Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized. PMID:22163577

  10. The sonochemical synthesis and characterization of mesoporous chiral titania using a chiral inorganic precursor.

    PubMed

    Gabashvili, Alexandra; Major, Dan T; Perkas, Nina; Gedanken, Aharon

    2010-03-01

    The paper presents a successful sonochemical attempt to synthesize mesoporous chiral titania using a chiral inorganic precursor and dodecylamine, as the surfactant template. The resulting porous structure was characterized by nitrogen sorption experiments, transmission electron microscopy, and small-angle XRD. The enantioselectivity of this mesoporous titania after the extraction of the amine was examined by selective adsorption of enantiomers and racemic aqueous solution of camphor. The selective adsorption was measured by circular dichroism (CD) spectroscopy. PMID:19942471

  11. Chiral Light-Matter Interaction in Optical Resonators.

    PubMed

    Yoo, SeokJae; Park, Q-Han

    2015-05-22

    The Purcell effect explains the modification of the spontaneous decay rate of quantum emitters in a resonant cavity. For quantum emitters such as chiral molecules, however, the cavity modification of the spontaneous decay rate has been little known. Here we extend Purcell's work to the chiral light-matter interaction in optical resonators and find the differential spontaneous decay rate of chiral molecules coupled to left and right circularly polarized resonator modes. We determine the chiral Purcell factor, which characterizes the ability of optical resonators to enhance chiroptical signals, by the quality factor and the chiral mode volume of a resonator, representing, respectively, the temporal confinement of light and the spatial confinement of the helicity of light. We show that the chiral Purcell effect can be applied to chiroptical spectroscopy. Specifically, we propose a realistic scheme to achieve resonator enhanced chiroptical spectroscopy that uses the double fishnet structure as a nanoscale cuvette supporting the chiral Purcell effect.

  12. New chiral liquid crystal with unconventional dioxane terminal unit

    NASA Astrophysics Data System (ADS)

    Perkowski, Paweł; Bubnov, Alexej; Mrukiewicz, Mateusz; Pociecha, Damian; Piecek, Wiktor; Hamplová, Věra; Kašpar, Miroslav

    2014-11-01

    While designing new chiral self-assembling materials, i.e. those possessing the liquid crystalline behaviour, special attention should be paid to the specific architecture of different molecular parts, in particular: molecular core, linkage groups, type and place of the lateral substituents, structure of the chiral centre and the chiral and non-chiral chains. For the first time a new chiral photosensitive liquid crystalline compound possessing an unconventional 1,3-dioxanylmethyl terminal unit attached to the non-chiral chain has been designed and synthesized. On cooling from the isotropic phase, the material possesses only one tilted liquid crystalline phase, namely the smectic I* phase with hexagonal ordering. The crystal phase has been detected at lower temperatures. The self-assembling and structural behaviour have been studied by different techniques and compared to that of the materials with similar molecular structure but possessing structurally different terminal units in the non-chiral chain.

  13. Insights into the Distinguishing Stress-induced Cytotoxicity of Chiral Gold Nanoclusters and the Relationship with GSTP1

    PubMed Central

    Zhang, Chunlei; Zhou, Zhijun; Zhi, Xiao; Ma, Yue; Wang, Kan; Wang, Yuxia; Zhang, Yingge; Fu, Hualin; Jin, Weilin; Pan, Fei; Cui, Daxiang

    2015-01-01

    Chiral gold nanoclusters (Au NCs) exhibit attracting properties owing to their unique physical and chemical properties. Herein we report for the first time chiral gold nanoclusters' cytotoxicity and potential molecular mechanism. The L-glutathione (i.e. L-GSH) and D-glutathione (i.e. D-GSH)-capped Au NCs were prepared and characterized by HRTEM, UV-vis, photoluminescence and circular dichroism (CD) spectroscopy. Results showed that the CD spectra of L-glutathione (i.e. L-GSH) and D-glutathione (i.e. D-GSH)-capped Au NCs exhibited multiple bands which were identically mirror-imaged, demonstrating that the chirality of GSH-capped NCs had contributions from both the metal core and the ligand. The effects of AuNCs@L-GSH and AuNCs@D-GSH on cells were similar based on the cell physiology related cytotoxicity, although the effects became more prominent in AuNCs@D-GSH treated cells, including ROS generation, mitochondrial membrane depolarization, cell cycle arrest and apoptosis. Global gene expression and pathway analysis displayed that both AuNCs@L-GSH and AuNCs@D-GSH caused the up-regulation of genes involved in cellular rescue and stress response, while AuNCs@D-GSH individually induced up-regulation of transcripts involved in some metabolic- and biosynthetic-related response. MGC-803 cells were more sensitive to the oxidative stress damage induced by chiral Au NCs than GES-1 cells, which was associated with GSTP1 hypermethylation. In conclusion, chiral gold nanoclusters exhibit this chirality-associated regulation of cytotoxicity, different gene expression profiling and epigenetic changes should be responsible for observed phenomena. Our study highlights the importance of the interplays between chiral materials and biological system at sub-nano level. PMID:25553104

  14. Chiral High-Speed Counter-Current Chromatography: Future Strategies for Chiral Selector Development.

    PubMed

    Ma, Ying; Ito, Yoichiro

    2014-01-01

    In conventional high-performance liquid chromatography, chiral separations are performed by chiral column with a chiral selector (CS) chemically boned to the solid support. In contrast, high-speed counter-current chromatography (HSCCC) performs chiral separations by dissolving CS in the liquid stationary phase. During the past two decades, several CSs were developed to successfully carry out chiral HSCCC which include N-dodecanoyl-L-proline-3,5-dimethylanilide, β-cyclodextrin derivatives, vancomycin, cinchona alkaloid derivatives, cellulose and amylose derivatives, tartaric acid derivatives, etc. Compared to HPLC which uses over hundred different kinds of CSs, the number of CSs effectively used in HSCCC is limited to several compounds. This may be due to the violent molecular movement of CS dissolved in the liquid stationary phase which reduces chiral selectivity based on steric affinity. Future development strategy of CS for HSCC proposed here is to suppress the molecular movement of the CS in the liquid stationary phase by the following three ways: 1) using viscous stationary phase such as aqueous-aqueous polymer phase system; 2) attaching a long hydrophobic chain to the asymmetric carbon, or 3) chemically bonding CS onto hydrophobic small particles such as carbon nanotubes, gold colloidal particles, and submicron silica particles.

  15. Chiral High-Speed Counter-Current Chromatography: Future Strategies for Chiral Selector Development

    PubMed Central

    Ma, Ying; Ito, Yoichiro

    2014-01-01

    In conventional high-performance liquid chromatography, chiral separations are performed by chiral column with a chiral selector (CS) chemically boned to the solid support. In contrast, high-speed counter-current chromatography (HSCCC) performs chiral separations by dissolving CS in the liquid stationary phase. During the past two decades, several CSs were developed to successfully carry out chiral HSCCC which include N-dodecanoyl-L-proline-3,5-dimethylanilide, β-cyclodextrin derivatives, vancomycin, cinchona alkaloid derivatives, cellulose and amylose derivatives, tartaric acid derivatives, etc. Compared to HPLC which uses over hundred different kinds of CSs, the number of CSs effectively used in HSCCC is limited to several compounds. This may be due to the violent molecular movement of CS dissolved in the liquid stationary phase which reduces chiral selectivity based on steric affinity. Future development strategy of CS for HSCC proposed here is to suppress the molecular movement of the CS in the liquid stationary phase by the following three ways: 1) using viscous stationary phase such as aqueous-aqueous polymer phase system; 2) attaching a long hydrophobic chain to the asymmetric carbon, or 3) chemically bonding CS onto hydrophobic small particles such as carbon nanotubes, gold colloidal particles, and submicron silica particles. PMID:24611132

  16. Separation of chiral nanotubes with an opposite handedness by chiral oligopeptide adsorption: A molecular dynamics study.

    PubMed

    Raffaini, Giuseppina; Ganazzoli, Fabio

    2015-12-18

    The separation of enantiomeric chiral nanotubes that can form non-covalent complexes with an unlike stability upon adsorption of chiral molecules is a process of potential interest in different fields and applications. Using fully atomistic molecular dynamics simulations, we report in this paper a theoretical study of the adsorption and denaturation of an oligopeptide formed by 16 chiral amino acids having a helical structure in the native state on both the inner and the outer surface of the chiral (10, 20) and (20, 10) single-walled carbon nanotubes having an opposite handedness, and of the armchair (16, 16) nanotube with a similar diameter for comparison. In the final adsorbed state, the oligopeptide loses in all cases its native helical conformation, assuming elongated geometries that maximize its contact with the surface through all the 16 amino acids. We find that the complexes formed by the two chiral nanotubes and the chosen oligopeptide have a strongly unlike stability both when adsorption takes place on the outer convex surface of the nanotube, and when it occurs on the inner concave surface. Thus, our molecular simulations indicate that separation of chiral, enantiomeric carbon nanotubes for instance by chromatographic methods can indeed be carried out using oligopeptides of a sufficient length.

  17. Chiral separation and twin-beam photonics

    NASA Astrophysics Data System (ADS)

    Bradshaw, David S.; Andrews, David L.

    2016-03-01

    It is well-known that, in a homogeneous fluid medium, most optical means that afford discrimination between molecules of opposite handedness are intrinsically weak effects. The reason is simple: the wide variety of origins for differential response commonly feature real or virtual electronic transitions that break a parity condition. Despite being electric dipole allowed, they manifest the chirality of the material in which they occur by breaking a selection rule that would otherwise preclude the simultaneous involvement of magnetic dipole or electric quadrupole forms of coupling. Although the latter are typically weaker than electric dipole effects by several orders of magnitude, it is the involvement of these weak forms of interaction that are responsible for chiral sensitivity. There have been a number of attempts to cleverly exploit novel optical configurations to enhance the relative magnitude - and hence potentially the efficiency - of chiral discrimination. The prospect of success in any such venture is enticing, because of the huge impact that such an advance might be expected to have in the health, food and medical sectors. Some of these proposals have utilized mirror reflection, and others surface plasmon coupling, or optical binding methods. Several recent works in the literature have drawn attention to a further possibility: the deployment of optical beam interference as a means to achieve chiral separations of sizeable extent. In this paper the underlying theory is fully developed to identify the true scope and limitations of such an approach.

  18. Efficient Biocatalytic Synthesis of Chiral Chemicals.

    PubMed

    Zhang, Zhi-Jun; Pan, Jiang; Ma, Bao-Di; Xu, Jian-He

    2016-01-01

    Chiral chemicals are a group of important chiral synthons for the synthesis of a series of pharmaceuticals, agrochemicals, and fine chemicals. In past decades, a number of biocatalytic approaches have been developed for the green and effective synthesis of various chiral chemicals. However, the practical application of these biocatalytic processes is still hindered by the lack of highly efficient and robust biocatalysts, which usually results in the low volumetric productivity and high cost of the bioprocesses. Further step forward of biocatalysis in industrial application strongly requires the development of versatile and highly efficient biocatalysts, aiming to increase the process efficiency and facilitate the downstream processing. Recently, the fast growth of genome sequences in the database in post-genomic era offers great opportunities for accessing numerous biocatalysts with practical application potential, and the so-called genome mining approach provides time-effective and highly specific strategy for the fast identification of target enzymes with desired properties and outperforms the traditional screening of soil samples for microbial enzyme producers of interest. A number of biocatalytic processes with industrial application potential were developed thereafter. Further development of protein engineering strategies, process optimization, and cooperative work between biologists, organic chemists, and engineers is expected to make biocatalysis technology the first choice approach for the eco-friendly, highly efficient, and cost-effective synthesis of chiral chemicals in the near future.

  19. Chiral anomaly and transport in Weyl metals.

    PubMed

    Burkov, A A

    2015-03-25

    We present an overview of our recent work on transport phenomena in Weyl metals, which may be connected to their nontrivial topological properties, particularly to chiral anomaly. We argue that there are two basic phenomena, which are related to chiral anomaly in Weyl metals: anomalous Hall effect (AHE) and chiral magnetic effect (CME). While AHE is in principle present in any ferromagnetic metal, we demonstrate that a magnetic Weyl metal is distinguished from an ordinary ferromagnetic metal by the absence of the extrinsic and the Fermi surface part of the intrinsic contributions to the AHE, as long as the Fermi energy is sufficiently close to the Weyl nodes. The AHE in a Weyl metal is thus shown to be a purely intrinsic, universal property, fully determined by the location of the Weyl nodes in the first Brillouin zone. In other words, a ferromagnetic Weyl metal may be thought of as the only example of a ferromagnetic metal with a purely intrinsic AHE. We further develop a fully microscopic theory of diffusive magnetotransport in Weyl metals. We derive coupled diffusion equations for the total and axial (i.e. node-antisymmetric) charge densities and show that chiral anomaly manifests as a magnetic-field-induced coupling between them. We demonstrate that an experimentally-observable consequence of CME in magnetotransport in Weyl metals is a quadratic negative magnetoresistance, which will dominate all other contributions to magnetoresistance under certain conditions and may be regarded as a smoking-gun transport characteristic, unique to Weyl metals.

  20. Chiral damping in magnetic domain walls dynamics

    NASA Astrophysics Data System (ADS)

    Jué, Emilie

    Domain wall (DW) motion in materials with structural inversion asymmetry (SIA) and high spin-orbit coupling has attracted much interest in the recent years due to the discovery of unexpected physical mechanisms. Especially, it has been shown that the DW dynamics in such materials can be explained by chiral DWs with (partly or fully) Néel structure, whose stability derives from an interfacial Dzyaloshinskii-Moriya interaction (DMI). In this work, we show that DMI is not the only effect inducing chiral dynamics and demonstrate the existence of a chiral damping. This result is supported by the study of the asymmetry induced by an in-plane magnetic field on field induced domain wall motion in perpendicularly magnetized asymmetric Pt/Co/Pt trilayers. Using time reversal properties, we show that this asymmetry cannot be attributed to an effective field but originates from a purely dissipative mechanism. The observation of chiral damping, not only enriches the spectrum of physical phenomena engendered by the SIA, but since it can coexist with DMI it is essential for conceiving DW and skyrmion devices

  1. Chiral damping of magnetic domain walls

    NASA Astrophysics Data System (ADS)

    Jué, Emilie; Safeer, C. K.; Drouard, Marc; Lopez, Alexandre; Balint, Paul; Buda-Prejbeanu, Liliana; Boulle, Olivier; Auffret, Stephane; Schuhl, Alain; Manchon, Aurelien; Miron, Ioan Mihai; Gaudin, Gilles

    2016-03-01

    Structural symmetry breaking in magnetic materials is responsible for the existence of multiferroics, current-induced spin-orbit torques and some topological magnetic structures. In this Letter we report that the structural inversion asymmetry (SIA) gives rise to a chiral damping mechanism, which is evidenced by measuring the field-driven domain-wall (DW) motion in perpendicularly magnetized asymmetric Pt/Co/Pt trilayers. The DW dynamics associated with the chiral damping and those with Dzyaloshinskii-Moriya interaction (DMI) exhibit identical spatial symmetry. However, both scenarios are differentiated by their time reversal properties: whereas DMI is a conservative effect that can be modelled by an effective field, the chiral damping is purely dissipative and has no influence on the equilibrium magnetic texture. When the DW motion is modulated by an in-plane magnetic field, it reveals the structure of the internal fields experienced by the DWs, allowing one to distinguish the physical mechanism. The chiral damping enriches the spectrum of physical phenomena engendered by the SIA, and is essential for conceiving DW and skyrmion devices owing to its coexistence with DMI (ref. ).

  2. Chiral anomaly and transport in Weyl metals

    NASA Astrophysics Data System (ADS)

    Burkov, A. A.

    2015-03-01

    We present an overview of our recent work on transport phenomena in Weyl metals, which may be connected to their nontrivial topological properties, particularly to chiral anomaly. We argue that there are two basic phenomena, which are related to chiral anomaly in Weyl metals: anomalous Hall effect (AHE) and chiral magnetic effect (CME). While AHE is in principle present in any ferromagnetic metal, we demonstrate that a magnetic Weyl metal is distinguished from an ordinary ferromagnetic metal by the absence of the extrinsic and the Fermi surface part of the intrinsic contributions to the AHE, as long as the Fermi energy is sufficiently close to the Weyl nodes. The AHE in a Weyl metal is thus shown to be a purely intrinsic, universal property, fully determined by the location of the Weyl nodes in the first Brillouin zone. In other words, a ferromagnetic Weyl metal may be thought of as the only example of a ferromagnetic metal with a purely intrinsic AHE. We further develop a fully microscopic theory of diffusive magnetotransport in Weyl metals. We derive coupled diffusion equations for the total and axial (i.e. node-antisymmetric) charge densities and show that chiral anomaly manifests as a magnetic-field-induced coupling between them. We demonstrate that an experimentally-observable consequence of CME in magnetotransport in Weyl metals is a quadratic negative magnetoresistance, which will dominate all other contributions to magnetoresistance under certain conditions and may be regarded as a smoking-gun transport characteristic, unique to Weyl metals.

  3. Monopoles and fractional vortices in chiral superconductors

    PubMed Central

    Volovik, G. E.

    2000-01-01

    I discuss two exotic objects that must be experimentally identified in chiral superfluids and superconductors. These are (i) the vortex with a fractional quantum number (N = 1/2 in chiral superfluids, and N = 1/2 and N = 1/4 in chiral superconductors), which plays the part of the Alice string in relativistic theories and (ii) the hedgehog in the ^l field, which is the counterpart of the Dirac magnetic monopole. These objects of different dimensions are topologically connected. They form the combined object that is called a nexus in relativistic theories. In chiral superconductors, the nexus has magnetic charge emanating radially from the hedgehog, whereas the half-quantum vortices play the part of the Dirac string. Each half-quantum vortex supplies the fractional magnetic flux to the hedgehog, representing 1/4 of the “conventional” Dirac string. I discuss the topological interaction of the superconductor's nexus with the ‘t Hooft–Polyakov magnetic monopole, which can exist in Grand Unified Theories. The monopole and the hedgehog with the same magnetic charge are topologically confined by a piece of the Abrikosov vortex. Such confinement makes the nexus a natural trap for the magnetic monopole. Other properties of half-quantum vortices and monopoles are discussed as well, including fermion zero modes. PMID:10716980

  4. Skyrme-Einstein closed cosmic chiral strings

    SciTech Connect

    Rybakov, Yu. P. Ivanova, I. S.

    2007-07-15

    Within the theory of general relativity, the configuration of a closed string (vortex) characterized by a topological charge of the degree type is described for the Skyrme-Einstein SU (2) chiral model. In the approximation of a large vortex-closure radius (a), a solution to equations of motion is obtained, along with estimates for the vortex energy and radius.

  5. Chiral anomaly and transport in Weyl metals.

    PubMed

    Burkov, A A

    2015-03-25

    We present an overview of our recent work on transport phenomena in Weyl metals, which may be connected to their nontrivial topological properties, particularly to chiral anomaly. We argue that there are two basic phenomena, which are related to chiral anomaly in Weyl metals: anomalous Hall effect (AHE) and chiral magnetic effect (CME). While AHE is in principle present in any ferromagnetic metal, we demonstrate that a magnetic Weyl metal is distinguished from an ordinary ferromagnetic metal by the absence of the extrinsic and the Fermi surface part of the intrinsic contributions to the AHE, as long as the Fermi energy is sufficiently close to the Weyl nodes. The AHE in a Weyl metal is thus shown to be a purely intrinsic, universal property, fully determined by the location of the Weyl nodes in the first Brillouin zone. In other words, a ferromagnetic Weyl metal may be thought of as the only example of a ferromagnetic metal with a purely intrinsic AHE. We further develop a fully microscopic theory of diffusive magnetotransport in Weyl metals. We derive coupled diffusion equations for the total and axial (i.e. node-antisymmetric) charge densities and show that chiral anomaly manifests as a magnetic-field-induced coupling between them. We demonstrate that an experimentally-observable consequence of CME in magnetotransport in Weyl metals is a quadratic negative magnetoresistance, which will dominate all other contributions to magnetoresistance under certain conditions and may be regarded as a smoking-gun transport characteristic, unique to Weyl metals. PMID:25712419

  6. Recent advances in SPE-chiral-HPLC methods for enantiomeric separation of chiral drugs in biological samples.

    PubMed

    Ali, Imran; Alam, Syed Dilshad; Al-Othman, Zeid A; Farooqi, Javed A

    2013-08-01

    In medical practices, the determination of enantiomeric ratio of the chiral drugs is very important for their activities, bioavailabilities and biodegradation. Only homochiral medication is safe for humans. The chiral analysis in biological samples is the first and most important step. The present article describes the technical strategies of the enantiomeric resolution of racemic drugs in biological samples. Attempts have been made to describe sample preparation by solid-phase extraction and enantiomeric resolution by chiral high-performance liquid chromatography. Various chiral stationary phases used in chiral separations of racemic drugs have been described. Efforts are also made to discuss the chiral recognition mechanism and future perspectives of chiral analyses in biological samples.

  7. A Cross-chiral RNA Polymerase Ribozyme

    PubMed Central

    Sczepanski, Jonathan T.; Joyce, Gerald F.

    2014-01-01

    Thirty years ago it was shown that the non-enzymatic, template-directed polymerization of activated mononucleotides proceeds readily in a homochiral system, but is severely inhibited by the presence of the opposing enantiomer.1 This finding poses a severe challenge for the spontaneous emergence of RNA-based life, and has led to the suggestion that either RNA was preceded by some other genetic polymer that is not subject to chiral inhibition2 or chiral symmetry was broken through chemical processes prior to the origin of RNA-based life.3,4 Once an RNA enzyme arose that could catalyze the polymerization of RNA, it would have been possible to distinguish among the two enantiomers, enabling RNA replication and RNA-based evolution to occur. It is commonly thought that the earliest RNA polymerase and its substrates would have been of the same handedness, but this is not necessarily the case. Replicating D-and L-RNA molecules may have emerged together, based on the ability of structured RNAs of one handedness to catalyze the templated polymerization of activated mononucleotides of the opposite handedness. Such a cross-chiral RNA polymerase has now been developed using in vitro evolution. The D-RNA enzyme, consisting of 83 nucleotides, catalyzes the joining of L-mono- or oligonucleotide substrates on a complementary L-RNA template, and similarly for the L-enzyme with D-substrates and a D-template. Chiral inhibition is avoided because the 106-fold rate acceleration of the enzyme only pertains to cross-chiral substrates. The enzyme's activity is sufficient to generate full-length copies of its enantiomer through the templated joining of 11 component oligonucleotides. PMID:25363769

  8. Chiral Sensitivity in Electron-Molecule Interactions

    NASA Astrophysics Data System (ADS)

    Dreiling, Joan

    2015-09-01

    All molecular forms of life possess a chiral asymmetry, with amino acids and sugars found respectively in L- and D-enantiomers only. The primordial origin of this enantiomeric excess is unknown. One possible explanation is given by the Vester- Ulbricht hypothesis, which suggests that left-handed electrons present in beta-radiation, produced by parity-violating weak decays, interacted with biological precursors and preferentially destroyed one of the two enantiomers. Experimental tests of this idea have thus far yielded inconclusive results. We show direct evidence for chirally-dependent bond breaking through a dissociative electron attachment (DEA) reaction when spin-polarized electrons are incident on gas-phase chiral molecules. This provides unambiguous evidence for a well-defined, chirally-sensitive destructive molecular process and, as such, circumstantial evidence for the Vester-Ulbricht hypothesis. I will also present the results of our systematic study of the DEA asymmetry for different chiral halocamphor molecules. Three halocamphor molecules were investigated: 3-bromocamphor (C10H15BrO), 3-iodocamphor(C10H15IO), and 10-iodocamphor. The DEA asymmetries collected for bromocamphor and iodocamphor are qualitatively different, suggesting that the atomic number of the heaviest atom in the molecule plays a crucial role in the asymmetric interactions. The DEA asymmetry data for 3- and 10-iodocamphor have the same qualitative behavior, but the 10-iodocamphor asymmetry is about twice as large at the lowest energies investigated, so the location of the heavy atom in the camphor molecule also affects the asymmetries. This work was performed at the University of Nebraska-Lincoln. This project is funded by NSF Grant PHY-1206067.

  9. Chemical synthesis of chiral conducting polymers

    SciTech Connect

    Wang, Hsing-Lin; Li, Wenguang

    2006-07-11

    An process of forming a chiral conducting polymer, e.g., polyaniline, is provided including reacting a monomer, e.g., an aniline monomer, in the presence of a chiral dopant acid to produce a first reaction mixture by addition of a solution including a first portion of an oxidizing agent, the first portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and further reacting the first reaction mixture in the presence of the chiral dopant acid by addition of a solution including a second portion of the oxidizing agent, the second portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and repeating the reaction by addition of further portions of the oxidizing agent until the monomer reaction is complete to produce a chiral conducting polymer, e.g., polyaniline. A preferred process includes addition of a catalyst during the reaction, the catalyst selected from among the group consisting of phenylene diamine, aniline oligomers and amino-capped aniline oligomers and metal salts. The processes of the present invention further provide a resultant polyaniline product having a chirality level defined by a molar ellipticity of from about 40.times.103 degree-cm2/decimole to about 700.times.103 degree-cm2/decimole. The processes of the present invention further provide a resultant polyaniline product having a nanofiber structure with a diameter of from about 30 nanometers to about 120 nanometers and from about 1 micron to about 5 microns in length.

  10. Chemical synthesis of chiral conducting polymers

    SciTech Connect

    Wang, Hsing-Lin; Li, Wenguang

    2009-01-13

    An process of forming a chiral conducting polymer, e.g., polyaniline, is provided including reacting a monomer, e.g., an aniline monomer, in the presence of a chiral dopant acid to produce a first reaction mixture by addition of a solution including a first portion of an oxidizing agent, the first portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and further reacting the first reaction mixture in the presence of the chiral dopant acid by addition of a solution including a second portion of the oxidizing agent, the second portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and repeating the reaction by addition of further portions of the oxidizing agent until the monomer reaction is complete to produce a chiral conducting polymer, e.g., polyaniline. A preferred process includes addition of a catalyst during the reaction, the catalyst selected from among the group consisting of phenylene diamine, aniline oligomers and amino-capped aniline oligomers and metal salts.The processes of the present invention further provide a resultant polyaniline product having a chirality level defined by a molar ellipticity of from about 40.times.10.sup.3 degree-cm.sup.2/decimole to about 700.times.10.sup.3 degree-cm.sup.2/decimole. The processes of the present invention further provide a resultant polyaniline product having a nanofiber structure with a diameter of from about 30 nanometers to about 120 nanometers and from about 1 micron to about 5 microns in length.

  11. Electron bubbles and Weyl fermions in chiral superfluid 3He-A

    NASA Astrophysics Data System (ADS)

    Shevtsov, Oleksii; Sauls, J. A.

    2016-08-01

    Electrons embedded in liquid 3He form mesoscopic bubbles with large radii compared to the interatomic distance between 3He atoms, voids of Nbubble≈200 3He atoms, generating a negative ion with a large effective mass that scatters thermal excitations. Electron bubbles in chiral superfluid 3He-A also provide a local probe of the ground state. We develop a scattering theory of Bogoliubov quasiparticles by negative ions embedded in 3He-A that incorporates the broken symmetries of 3He-A , particularly broken symmetries under time reversal and mirror symmetry in a plane containing the chiral axis l ̂. Multiple scattering by the ion potential, combined with branch conversion scattering by the chiral order parameter, leads to a spectrum of Weyl fermions bound to the ion that support a mass current circulating the electron bubble—a mesoscopic realization of chiral edge currents in superfluid 3He-A films. A consequence is that electron bubbles embedded in 3He-A acquire angular momentum, L ≈-(Nbubble/2 ) ℏ l ̂ , inherited from the chiral ground state. We extend the scattering theory to calculate the forces on a moving electron bubble, both the Stokes drag and a transverse force, FW=e/c v ×BW , defined by an effective magnetic field, BW∝l ̂ , generated by the scattering of thermal quasiparticles off the spectrum of Weyl fermions bound to the moving ion. The transverse force is responsible for the anomalous Hall effect for electron bubbles driven by an electric field reported by the RIKEN group. Our results for the scattering cross section, drag, and transverse forces on moving ions are compared with experiments and shown to provide a quantitative understanding of the temperature dependence of the mobility and anomalous Hall angle for electron bubbles in normal and superfluid 3He-A . We also discuss our results in relation to earlier work on the theory of negative ions in superfluid 3He.

  12. Construction, water-level, and water-quality data for multiple-well monitoring sites and test wells, Fort Irwin National Training Center, San Bernardino County, California, 2009-12

    USGS Publications Warehouse

    Kjos, Adam R.; Densmore, Jill N.; Nawikas, Joseph M.; Brown, Anthony A.

    2014-01-01

    Because of increasing water demands at the U.S. Army Fort Irwin National Training Center, the U.S. Geological Survey in cooperation with the U.S. Army carried out a study to evaluate the water quality and potential groundwater supply of undeveloped basins within the U.S. Army Fort Irwin National Training Center. In addition, work was performed in the three developed basins—Langford, Bicycle, and Irwin—proximal to or underlying cantonment to provide information in support of water-resources management and to supplement monitoring in these basins. Between 2009 and 2012, the U.S. Geological Survey installed 41 wells to expand collection of water-resource data within the U.S. Army Fort Irwin National Training Center. Thirty-four monitoring wells (2-inch diameter) were constructed at 14 single- or multiple-well monitoring sites and 7 test wells (8-inch diameter) were installed. The majority of the wells were installed in previously undeveloped or minimally developed basins (Cronise, Red Pass, the Central Corridor area, Superior, Goldstone, and Nelson Basins) proximal to cantonment (primary base housing and infrastructure). Data associated with well construction, water-level monitoring, and water-quality sampling are presented in this report.

  13. Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands.

    PubMed

    Mori, Taizo; Sharma, Anshul; Hegmann, Torsten

    2016-01-26

    Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle

  14. Geometric enantiomerism in cyclic compounds: chiral dibrominated 1,3-dioxanes.

    PubMed

    Cismaş, Crina; Vanthuyne, Nicolas; Rispaud, Hélène; Varga, Richard Attila; Bogdan, Elena; Roussel, Christian; Grosu, Ion

    2011-02-01

    The first geometric enantiomers in the cyclic compounds series are reported. The investigated compounds are 2,2-disubstituted-5-methyl-1,3-dioxane derivatives in which the substituents at position 2 bear chiral centers with identical substituents but with opposite configurations. The structure of the unlike isomers was determined from the solid state molecular structure of the compounds obtained by single crystal X-ray diffractometry and the enantiomers of these diastereoisomers were observed by chiral column HPLC base-line separation. The investigated compounds were obtained by a diastereoselective bromination reaction of the corresponding 2,2-dialkyl and 2,2-dibenzyl-5-methyl-1,3-dioxanes. PMID:20872855

  15. Zero-field Dissipationless Chiral Edge Current in Quantum Anomalous Hall State

    NASA Astrophysics Data System (ADS)

    Chang, Cui-Zu; Zhao, Weiwei; Kim, Duk Y.; Wei, Peng; Jain, J. K.; Liu, Chaoxing; Chan, Moses H. W.; Moodera, Jagadeesh S.

    The quantum anomalous Hall (QAH) state is predicted to possess, at zero magnetic field, chiral edge channels that conduct spin polarized current without dissipation, and thus holds great promise for future high-performance information processing. In this talk, we will discuss our transport experiments that probe the QAH state with gate bias and temperature dependences, by local and nonlocal magnetoresistance measurements. This allows us to unambiguously distinguish the dissipationless edge transport from transport via other dissipative channels in the QAH system. Our experiments confirm a fundamental feature of the QAH state, namely the dissipationless transport by edge channels in zero applied fields, which will be crucial for future chiral interconnected electric and spintronic applications. This research is supported by the NSF Grants (DMR-1420620, Penn State MRSEC; in MIT by DMR-1207469 and the STC Center for Integrated Quantum Materials under NSF Grant DMR-1231319) and by ONR Grant N00014-13-1-0301.

  16. Memorized chiral arrangement of gemini surfactant assemblies in nanometric hybrid organic-silica helices.

    PubMed

    Ryu, Naoya; Okazaki, Yutaka; Hirai, Kana; Takafuji, Makoto; Nagaoka, Shoji; Pouget, Emilie; Ihara, Hirotaka; Oda, Reiko

    2016-04-30

    Hybrid nanohelices were obtained from silicification of self-assemblies of gemini surfactants with tartrate counterions. The chiral arrangement of these non-chiral gemini surfactants was preserved in the silica matrix even after the counterion exchange for a non-chiral bromide, and was capable of inducing the chiral organisation of a non-chiral dye, methyl orange. PMID:26961377

  17. Outcomes of gamma knife radiosurgery, bi-modality & tri-modality treatment regimens for patients with one or multiple brain metastases: the Columbia University Medical Center experience.

    PubMed

    Wang, Tony J C; Saad, Shumaila; Qureshi, Yasir H; Jani, Ashish; Isaacson, Steven R; Sisti, Michael B; Bruce, Jeffrey N; McKhann, Guy M; Lesser, Jeraldine; Cheng, Simon K; Clifford Chao, K S; Lassman, Andrew B

    2015-04-01

    Optimal treatment of brain metastases (BMs) is debatable. However, surgery or gamma knife radiosurgery (GKRS) improves survival when combined with whole brain radiotherapy (WBRT) versus WBRT alone. We retrospectively reviewed an institutional database of patients treated with GKRS for BMs from 1998 to 2013 to explore effects of single or multi-modality therapies on survival. There were 528 patients with median age 62 years. Histologies included 257 lung, 102 breast, 62 melanoma, 40 renal cell, 29 gastrointestinal, and 38 other primary cancers. Treatments included: 206 GKRS alone, 111 GKRS plus WBRT, 109 GKRS plus neurosurgical resection (NSG), and 102 all three modalities. Median overall survival (mOS) was 16.6 months. mOS among patients with one versus multiple metastasis was 17.2 versus 16.0 months respectively (p = 0.825). For patients with one BM, mOS following GKRS alone, GKRS plus WBRT, GKRS plus NSG, and all three modalities was 9.0, 19.1, 25.5, and 25.0 months, respectively, and for patients with multiple BMs, mOS was 8.6, 20.4, 20.7, 24.5 months for the respective groups. Among all patients, multivariate analysis confirmed that tri-modality group had the longest survival (HR 0.467; 95 % CI 0.350-0.623; p < 0.001) compared to GKRS alone; however, this was not significantly different than bi-modality approaches. Uncontrolled primary extra-CNS disease, age and KPS were also independent predictors of survival. Patients treated with GKRS plus NSG, GKRS plus WBRT, or all three modalities had improved OS versus GKRS alone. In our analysis, resection and GKRS allowed avoidance of WBRT without shortening survival.

  18. Optical properties and circular dichroism of chiral metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Fan, Zhiyuan; Govorov, Alexander; OU Team

    2013-03-01

    In nature, biological systems are built up by homochiral building blocks, such as a sugar and protein. Circular dichroism (CD) is an effective tool of resolving molecular conformations. It utilizes circularly polarized light to detect differential absorption of chiral materials. In medicine, it will help us to develop new drugs and therapies, if we understand the connection between the physical or chemical properties of drug molecules and their conformations. With the rapid development of nanotechnologies, chiral nanomaterials attract lots of attention nowadays. CD signals of chiral molecules can be enhanced or shifted to the visible band in the presence of plasmonic nanocrystals. Here we present a plasmonic CD mechanism from a single chiral metal nanocrystal. The mechanism is essentially different from the dipolar plasmon-plasmon interaction in a chiral NP assembly, which mimics the CD mechanism of chiral molecules. Chiral metal nanocrystals are expected to have promising applications in biosensing. Recently a few experimental papers reported successful realizations of chiral nanocrystals in a macroscopic ensemble in solution. Particularly the paper described silver nanoparticles grown on chiral template molecules and demonstrating characteristic CD signals at a plasmonic wavelength. The plasmonic CD signals in Ref. can come from a dipolar plasmon-molecule interaction or from a chiral shape of nanocrystals. This work was supported by the NSF (project: CBET- 0933782) and by the Volkswagen Foundation.

  19. Equivalence of topological mirror superconductivity and chiral superconductivity in one dimension

    NASA Astrophysics Data System (ADS)

    Dumitrescu, Eugene; Sharma, Girish; Sau, Jay D.; Tewari, Sumanta

    2015-07-01

    Recently it has been proposed that a unitary topological mirror symmetry can stabilize multiple zero energy Majorana fermion modes in one-dimensional (1D) time-reversal (TR) invariant topological superconductors. Here we establish an exact equivalence between 1D "topological mirror superconductivity" and chiral topological superconductivity in the BDI class which can also stabilize multiple Majorana-Kramers pairs in 1D TR invariant topological superconductors. The equivalence proves that topological mirror superconductivity can be understood as chiral superconductivity in the BDI symmetry class coexisting with time-reversal symmetry. Furthermore, we show that the mirror Berry phase coincides with the chiral winding invariant of the BDI symmetry class, which is independent of the presence of the time-reversal symmetry. Thus, the time-reversal invariant topological mirror superconducting state may be viewed as a special case of the BDI symmetry class in the well-known Altland-Zirnbauer periodic table of free fermionic phases. We illustrate the results with the examples of 1D spin-orbit coupled quantum wires in the presence of nodeless s± superconductivity and the recently discussed experimental system of ferromagnetic atom (Fe) chains embedded on a lead (Pb) superconductor.

  20. Assessing the Discriminant Ability, Reliability, and Comparability of Multiple Short Forms of the Boston Naming Test in an Alzheimer’s Disease Center Cohort

    PubMed Central

    Katsumata, Yuriko; Mathews, Melissa; Abner, Erin L.; Jicha, Gregory A.; Caban-Holt, Allison; Smith, Charles D.; Nelson, Peter T.; Kryscio, Richard J.; Schmitt, Frederick A.; Fardo, David W.

    2015-01-01

    Background The Boston Naming Test (BNT) is a commonly used neuropsychological test of confrontation naming that aids in determining the presence and severity of dysnomia. Many short versions of the original 60-item test have been developed and are routinely administered in clinical/research settings. Because of the common need to translate similar measures within and across studies, it is important to evaluate the operating characteristics and agreement of different BNT versions. Methods We analyzed longitudinal data of research volunteers (n = 681) from the University of Kentucky Alzheimer’s Disease Center longitudinal cohort. Conclusions With the notable exception of the Consortium to Establish a Registry for Alzheimer’s Disease (CERAD) 15-item BNT, short forms were internally consistent and highly correlated with the full version; these measures varied by diagnosis and generally improved from normal to mild cognitive impairment (MCI) to dementia. All short forms retained the ability to discriminate between normal subjects and those with dementia. The ability to discriminate between normal and MCI subjects was less strong for the short forms than the full BNT, but they exhibited similar patterns. These results have important implications for researchers designing longitudinal studies, who must consider that the statistical properties of even closely related test forms may be quite different. PMID:25613081

  1. Analysis of Chiral Carboxylic Acids in Meteorites

    NASA Technical Reports Server (NTRS)

    Burton, A. S.; Elsila, J. E.; Hein, J. E.; Aponte, J. C.; Parker, E. T.; Glavin, D. P.; Dworkin, J. P.

    2015-01-01

    Homochirality of amino acids in proteins and sugars in DNA and RNA is a critical feature of life on Earth. In the absence of a chiral driving force, however, reactions leading to the synthesis of amino acids and sugars result in racemic mixtures. It is currently unknown whether homochirality was necessary for the origins of life or if it was a product of early life. The observation of enantiomeric excesses of certain amino acids of extraterrestrial origins in meteorites provides evidence to support the hypothesis that there was a mechanism for the preferential synthesis or destruction of a particular amino acid enantiomer [e.g., 1-3]. The cause of the observed chiral excesses is un-clear, although at least in the case of the amino acid isovaline, the degree of aqueous alteration that occurred on the meteorite parent body is correlated to the isovaline L-enantiomeric excess [3, 4]. This suggests that chiral symmetry is broken and/or amplified within the meteorite parent bodies. Besides amino acids, there have been only a few reports of other meteoritic compounds found in enantiomeric excess: sugars and sugar acids [5, 6] and the hydroxy acid lactic acid [7]. Determining whether or not additional types of molecules in meteorites are also present in enantiomeric excesses of extraterrestrial information will provide insights into mechanisms for breaking chiral symmetry. Though the previous measurements (e.g., enantiomeric composition of lactic acid [7], and chiral carboxylic acids [8]) were made by gas chromatography-mass spectrometry, the potential for increased sensitivity of liquid chromatography-mass spectrometry (LC-MS) analyses is important because for many meteorite samples, only small sample masses are available for study. Furthermore, at least in the case of amino acids, many of the largest amino acid enantiomeric excesses were observed in samples that contained lower abundances (tens of ppb) of a given amino acid enantiomer. In the present work, we describe

  2. Resonant collective dynamics of the weakly pinned soliton lattice in a monoaxial chiral helimagnet

    NASA Astrophysics Data System (ADS)

    Kishine, Jun-ichiro; Proskurin, I.; Bostrem, I. G.; Ovchinnikov, A. S.; Sinitsyn, Vl. E.

    2016-02-01

    We study the spin dynamics of a confined chiral soliton lattice whose ends are weakly held. We demonstrate that in this case the system possesses its own resonant frequency. To study features of the resonant dynamics, we analyze the collective motion of the system driven by an oscillating magnetic field directed along the chiral axis. By using the method of collective coordinates we find analytically the resonant frequency and verify the result by numerical simulation of the spin dynamics with the aid of Landau-Lifshitz-Gilbert equations. The numerical simulation shows an appearance of the asymmetric profile of the frequency response function with increasing ac field, which is typical for a nonlinear resonance. To give an explanation of this behavior, we invoke the multiple-time-scale method and predict an emergence of hysteresis phenomena. We also demonstrate that the spin-motive force is strongly amplified by the resonant oscillations.

  3. Tunable multi-band chiral metamaterials based on double-layered asymmetric split ring resonators

    NASA Astrophysics Data System (ADS)

    Jia, Xiuli; Wang, Xiaoou; Meng, Qingxin; Zhou, Zhongxiang

    2016-07-01

    We have numerically demonstrated chiral metamaterials based on double-layered asymmetric Au film with hollow out design of split ring resonators on either side of the polyimide. Multiple electric dipoles and magnetic dipoles resulted from parallel and antiparallel currents between the eight split ring resonators. Multi-band circular dichroism is found in the visible frequency regime by studying the transmission properties. Huge optical activity and the induced multi-band negative refractive index are obtained at resonance by calculating the optical activity and ellipticity of the transmitted E-fields. Chirality parameter and effective refractive index are retrieved to illustrate the tunable optical properties of the metamaterials. The underlying mechanisms for the observed circular dichroism are analyzed. These metamaterials would offer flexible electromagnetic applications in the infrared and visible regime.

  4. Circularly polarized light detection with hot electrons in chiral plasmonic metamaterials

    PubMed Central

    Li, Wei; Coppens, Zachary J.; Besteiro, Lucas V.; Wang, Wenyi; Govorov, Alexander O.; Valentine, Jason

    2015-01-01

    Circularly polarized light is utilized in various optical techniques and devices. However, using conventional optical systems to generate, analyse and detect circularly polarized light involves multiple optical elements, making it challenging to realize miniature and integrated devices. While a number of ultracompact optical elements for manipulating circularly polarized light have recently been demonstrated, the development of an efficient and highly selective circularly polarized light photodetector remains challenging. Here we report on an ultracompact circularly polarized light detector that combines large engineered chirality, realized using chiral plasmonic metamaterials, with hot electron injection. We demonstrate the detector's ability to distinguish between left and right hand circularly polarized light without the use of additional optical elements. Implementation of this photodetector could lead to enhanced security in fibre and free-space communication, as well as emission, imaging and sensing applications for circularly polarized light using a highly integrated photonic platform. PMID:26391292

  5. Circularly polarized light detection with hot electrons in chiral plasmonic metamaterials

    NASA Astrophysics Data System (ADS)

    Li, Wei; Coppens, Zachary J.; Besteiro, Lucas V.; Wang, Wenyi; Govorov, Alexander O.; Valentine, Jason

    2015-09-01

    Circularly polarized light is utilized in various optical techniques and devices. However, using conventional optical systems to generate, analyse and detect circularly polarized light involves multiple optical elements, making it challenging to realize miniature and integrated devices. While a number of ultracompact optical elements for manipulating circularly polarized light have recently been demonstrated, the development of an efficient and highly selective circularly polarized light photodetector remains challenging. Here we report on an ultracompact circularly polarized light detector that combines large engineered chirality, realized using chiral plasmonic metamaterials, with hot electron injection. We demonstrate the detector's ability to distinguish between left and right hand circularly polarized light without the use of additional optical elements. Implementation of this photodetector could lead to enhanced security in fibre and free-space communication, as well as emission, imaging and sensing applications for circularly polarized light using a highly integrated photonic platform.

  6. Attitude, Knowledge, and Practice on Evidence-Based Nursing among Registered Nurses in Traditional Chinese Medicine Hospitals: A Multiple Center Cross-Sectional Survey in China.

    PubMed

    Zhou, Fen; Hao, Yufang; Guo, Hong; Liu, Hongxia

    2016-01-01

    Objective. This study was to describe RNs' attitude, knowledge, and practice on evidence-based practice (EBP) in traditional Chinese nursing field and to estimate the related sociodemographic and professional factors. Methods. A multiple institutional cross-sectional survey design with self-reported EBP Questionnaire (EBPQ) and self-designed questionnaires were used. Results. The average scores of the total EBPQ were with a mean of 4.24 (SD = 0.79). The score of attitude was the highest one, followed by the knowledge score, and the lowest one is practice. RNs with longer experience reported stronger EBP knowledge (H = 6.64, P < 0.05). And RNs under higher working pressure reported less positive attitudes (ρ = 0.17, P < 0.001), whereas RNs holding negative professional attitude reported lower scores (Spearman's ρ: 0.12 to 0.15, P < 0.001). Significant statistics were found between RNs with research experience and without in attitude (t = -2.40, P < 0.05) and knowledge (t = -2.43, P < 0.05). Conclusions. Respondents generally viewed EBP positively and their attitudes towards EBP tended to be more positive than knowledge and practice of EBP. Data also showed that longer working experience, having administrative position, research experience, lighter working load, and better professional attitude might facilitate EBP.

  7. Attitude, Knowledge, and Practice on Evidence-Based Nursing among Registered Nurses in Traditional Chinese Medicine Hospitals: A Multiple Center Cross-Sectional Survey in China

    PubMed Central

    Hao, Yufang; Guo, Hong

    2016-01-01

    Objective. This study was to describe RNs' attitude, knowledge, and practice on evidence-based practice (EBP) in traditional Chinese nursing field and to estimate the related sociodemographic and professional factors. Methods. A multiple institutional cross-sectional survey design with self-reported EBP Questionnaire (EBPQ) and self-designed questionnaires were used. Results. The average scores of the total EBPQ were with a mean of 4.24 (SD = 0.79). The score of attitude was the highest one, followed by the knowledge score, and the lowest one is practice. RNs with longer experience reported stronger EBP knowledge (H = 6.64, P < 0.05). And RNs under higher working pressure reported less positive attitudes (ρ = 0.17, P < 0.001), whereas RNs holding negative professional attitude reported lower scores (Spearman's ρ: 0.12 to 0.15, P < 0.001). Significant statistics were found between RNs with research experience and without in attitude (t = −2.40, P < 0.05) and knowledge (t = −2.43, P < 0.05). Conclusions. Respondents generally viewed EBP positively and their attitudes towards EBP tended to be more positive than knowledge and practice of EBP. Data also showed that longer working experience, having administrative position, research experience, lighter working load, and better professional attitude might facilitate EBP. PMID:27528882

  8. Efficacy of Anastrozole in a Consecutive Series of Advanced Breast Cancer Patients Treated with Multiple Prior Chemotherapies and Endocrine Agents: M. D. Anderson Cancer Center Experience.

    PubMed

    Knoche, A. Jolynn; Michaud, Laura Boehnke; Buzdar, Aman U.

    1999-05-01

    Anastrozole is a highly selective, nonsteroidal aromatase inhibitor approved by the U.S. Food and Drug Administration (FDA) in January 1996 for the treatment of advanced breast cancer in postmenopausal women with disease progression following tamoxifen therapy. To date, information on anastrozole's use has been limited to breast cancer patients with minimal prior therapy. The purpose of this review was to determine, in clinical practice, the benefits of anastrozole in advanced breast cancer patients treated with multiple prior cytotoxic and endocrine therapies. This was a retrospective review of a consecutive series of 117 patients who received anastrozole after marketing in January 1996. As this was not a prospective study, rigorous response criteria could not be applied. Responses were categorized as improvement in disease (ID), stable disease (SD), or progressive disease (PD). One hundred eight patients were evaluable for response with a median age of 61 years and the number of prior therapies ranging from one to nine. Response, defined as improvement of disease or stable disease >/=8 weeks, was seen in 59% of patients. Patients with three or more prior endocrine therapies demonstrated a 61% response (ID + SD) and patients with ER-negative tumors demonstrated 50% response. Patients with prior aminoglutethamide therapy exhibited similar response rates to the overall group. One male patient received anastrozole without benefit. This data determines the activity of anastrozole even in heavily pretreated patients and suggests that patients who have tumors that are ER-negative may also benefit from anastrozole therapy. PMID:11348281

  9. Attitude, Knowledge, and Practice on Evidence-Based Nursing among Registered Nurses in Traditional Chinese Medicine Hospitals: A Multiple Center Cross-Sectional Survey in China.

    PubMed

    Zhou, Fen; Hao, Yufang; Guo, Hong; Liu, Hongxia

    2016-01-01

    Objective. This study was to describe RNs' attitude, knowledge, and practice on evidence-based practice (EBP) in traditional Chinese nursing field and to estimate the related sociodemographic and professional factors. Methods. A multiple institutional cross-sectional survey design with self-reported EBP Questionnaire (EBPQ) and self-designed questionnaires were used. Results. The average scores of the total EBPQ were with a mean of 4.24 (SD = 0.79). The score of attitude was the highest one, followed by the knowledge score, and the lowest one is practice. RNs with longer experience reported stronger EBP knowledge (H = 6.64, P < 0.05). And RNs under higher working pressure reported less positive attitudes (ρ = 0.17, P < 0.001), whereas RNs holding negative professional attitude reported lower scores (Spearman's ρ: 0.12 to 0.15, P < 0.001). Significant statistics were found between RNs with research experience and without in attitude (t = -2.40, P < 0.05) and knowledge (t = -2.43, P < 0.05). Conclusions. Respondents generally viewed EBP positively and their attitudes towards EBP tended to be more positive than knowledge and practice of EBP. Data also showed that longer working experience, having administrative position, research experience, lighter working load, and better professional attitude might facilitate EBP. PMID:27528882

  10. INTERACTING COSMIC RAYS WITH MOLECULAR CLOUDS: A BREMSSTRAHLUNG ORIGIN OF DIFFUSE HIGH-ENERGY EMISSION FROM THE INNER 2 Degree-Sign Multiplication-Sign 1 Degree-Sign OF THE GALACTIC CENTER

    SciTech Connect

    Yusef-Zadeh, F.; Roberts, D. A.; Royster, M.; Hewitt, J. W.; Wardle, M.; Tatischeff, V.; Uchiyama, H.; Nobukawa, M.; Tsuru, T. G.; Heinke, C.

    2013-01-01

    The high-energy activity in the inner few degrees of the Galactic center is traced by diffuse radio, X-ray, and {gamma}-ray emission. The physical relationship between different components of diffuse gas emitting at multiple wavelengths is a focus of this work. We first present radio continuum observations using the Green Bank Telescope and model the nonthermal spectrum in terms of a broken power-law distribution of {approx}GeV electrons emitting synchrotron radiation. We show that the emission detected by Fermi is primarily due to nonthermal bremsstrahlung produced by the population of synchrotron emitting electrons in the GeV energy range interacting with neutral gas. The extrapolation of the electron population measured from radio data to low and high energies can also explain the origin of Fe I 6.4 keV line and diffuse TeV emission, as observed with Suzaku, XMM-Newton, Chandra, and the H.E.S.S. observatories. The inferred physical quantities from modeling multiwavelength emission in the context of bremsstrahlung emission from the inner {approx}300 Multiplication-Sign 120 pc of the Galactic center are constrained to have the cosmic-ray ionization rate {approx}1-10 Multiplication-Sign 10{sup -15} s{sup -1}, molecular gas heating rate elevating the gas temperature to 75-200 K, fractional ionization of molecular gas 10{sup -6}-10{sup -5}, large-scale magnetic field 10-20 {mu}G, the density of diffuse and dense molecular gas {approx}100 and {approx}10{sup 3} cm{sup -3} over 300 pc and 50 pc path lengths, and the variability of Fe I K{alpha} 6.4 keV line emission on yearly timescales. Important implications of our study are that GeV electrons emitting in radio can explain the GeV {gamma}-rays detected by Fermi and that the cosmic-ray irradiation model, like the model of the X-ray irradiation triggered by past activity of Sgr A*, can also explain the origin of the variable 6.4 keV emission from Galactic center molecular clouds.

  11. Advanced dress-up chiral columns: New removable chiral stationary phases for enantioseparation of chiral carboxylic acids.

    PubMed

    Todoroki, Kenichiro; Ishii, Yasuhiro; Ide, Takafumi; Min, Jun Zhe; Inoue, Koichi; Huang, Xin; Zhang, Wei; Hamashima, Yoshitaka; Toyo'oka, Toshimasa

    2015-07-01

    This paper describes the preparation of new dress-up columns featuring reproducibly removable and replaceable chiral stationary phases. After synthesizing perfluroalkylated quinine and quinidine derivatives as chiral stationary phase compounds (F-CSPs), we adsorbed them reversibly onto a fluorous LC column through pumping of their solutions. Using this dress-up chiral column and fluorophobic elution of aqueous ammonium formate/MeOH mixtures, we could enantioseparate four racemic N-acetyl amino acids, dichlorprop, and sixteen fluorescent 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC)-derivatized amino acids. Dressing and undressing of the coated F-CSPs could be controlled by varying the fluorophilicity and fluorophobicity of the eluent. The relative standard deviations of the retention times, the retention factors, the number of theoretical plates, the enantioseparation factors, and the resolutions of each of four preparations of such dress-up columns were all less than or equal to 5.26% (from 20 repeated analyses); the reproducibilities from four different preparations were all less than or equal to 10.6%. These columns also facilitated highly sensitive and selective analyses of AQC-amino acids when detected using LC-MS/MS.

  12. Chiral separation of new designer drugs (Cathinones) on chiral ion-exchange type stationary phases.

    PubMed

    Wolrab, Denise; Frühauf, Peter; Moulisová, Alena; Kuchař, Martin; Gerner, Christopher; Lindner, Wolfgang; Kohout, Michal

    2016-02-20

    We present the enantioseparation of new designer drugs from the cathinone family on structurally different chiral ion-exchange type stationary phases. A novel strong cation-exchange type chiral stationary phase was synthesized and its performance compared with previously reported ion-exchange type chiral stationary phases. The influence of structural elements of the chiral selectors on their chromatographic performance was studied and the possibilities of tuning chromatographic parameters by varying the polarity of the employed mobile phases were determined. Evidence is provided that a change in mobile phase composition strongly influences the solvation shell of the polarized and polarizable units of the selectors and analytes, as well as ionizable mobile phase additives. Furthermore, the structural features of the selectors (e.g. the size of aromatic units and their substitution pattern) are shown to play a key role in the effective formation of diastereomeric complexes with analytes. Thus, we have achieved the enantioseparation of all test analytes with a mass spectrometry-compatible mobile phase with a chiral strong cation-exchange type stationary phase.

  13. Chiral assembly of weakly curled hard rods: Effect of steric chirality and polarity

    SciTech Connect

    Wensink, H. H. Morales-Anda, L.

    2015-10-14

    We theoretically investigate the pitch of lyotropic cholesteric phases composed of slender rods with steric chirality transmitted via a weak helical deformation of the backbone. In this limit, the model is amenable to analytical treatment within Onsager theory and a closed expression for the pitch versus concentration and helical shape can be derived. Within the same framework, we also briefly review the possibility of alternative types of chiral order, such as twist-bend or screw-like nematic phases, finding that cholesteric order dominates for weakly helical distortions. While long-ranged or “soft” chiral forces usually lead to a pitch decreasing linearly with concentration, steric chirality leads to a much steeper decrease of quadratic nature. This reveals a subtle link between the range of chiral intermolecular interaction and the pitch sensitivity with concentration. A much richer dependence on the thermodynamic state is revealed for polar helices where parallel and anti-parallel pair alignments along the local director are no longer equivalent. It is found that weak temperature variations may lead to dramatic changes in the pitch, despite the lyotropic nature of the assembly.

  14. Integration of inherent and induced chirality into subphthalocyanine analogue

    PubMed Central

    Zhao, Luyang; Qi, Dongdong; Wang, Kang; Wang, Tianyu; Han, Bing; Tang, Zhiyong; Jiang, Jianzhuang

    2016-01-01

    Conventional conjugated systems are characteristic of only either inherent or induced chirality because of synthetic challenge in combination of chiral segment into the main chromophore. In this work, chiral binaphthyl segment is directly fused into the central chromophore of a subphthalocyanine skeleton, resulting in a novel type of chiral subphthalocyanine analogue (R/S)-1 of integrated inherent and induced chirality. Impressively, an obviously enhanced optical activity is discerned for (R/S)-1 molecules, and corresponding enhancement mechanism is elucidated in detail. The synthesis strategy based on rational molecular design will open the door towards fabrication of chiral materials with giant optical activity, which will have great potential in chiroptical devices. PMID:27294871

  15. Electrical magnetochiral anisotropy in a bulk chiral molecular conductor.

    PubMed

    Pop, Flavia; Auban-Senzier, Pascale; Canadell, Enric; Rikken, Geert L J A; Avarvari, Narcis

    2014-01-01

    So far, no effect of chirality on the electrical properties of bulk chiral conductors has been observed. Introduction of chiral information in tetrathiafulvalene precursors represents a powerful strategy towards the preparation of crystalline materials in which the combination of chirality and conducting properties might allow the observation of the electrical magnetochiral anisotropy effect. Here we report the synthesis by electrocrystallization of both enantiomers of a bulk chiral organic conductor based on an enantiopure tetrathiafulvalene derivative. The enantiomeric salts crystallize in enantiomorphic hexagonal space groups. Single crystal resistivity measurements show metallic behaviour for the enantiopure salts down to 40 K, in agreement with band structure calculations. We describe here the first experimental evidence of electrical magnetochiral anisotropy in these crystals, confirming the chiral character of charge transport in our molecular materials. PMID:24796572

  16. Detecting Chirality in Molecules by Linearly Polarized Laser Fields

    NASA Astrophysics Data System (ADS)

    Yachmenev, Andrey; Yurchenko, Sergei N.

    2016-07-01

    A new scheme for enantiomer differentiation of chiral molecules using a pair of linearly polarized intense ultrashort laser pulses with skewed mutual polarization is presented. The technique relies on the fact that the off-diagonal anisotropic contributions to the electric polarizability tensor for two enantiomers have different signs. Exploiting this property, we are able to excite a coherent unidirectional rotation of two enantiomers with a π phase difference in the molecular electric dipole moment. The approach is robust and suitable for relatively high temperatures of molecular samples, making it applicable for selective chiral analysis of mixtures, and to chiral molecules with low barriers between enantiomers. As an illustration, we present nanosecond laser-driven dynamics of a tetratomic nonrigid chiral molecule with short-lived chirality. The ultrafast time scale of the proposed technique is well suited to study parity violation in molecular systems in short-lived chiral states.

  17. Progress of quartz crystal microbalance in chiral analysis.

    PubMed

    Guo, Huishi

    2014-02-01

    Chiral analysis is one of the most important/challenging analytical tasks due to the necessity for differentiation of very slight differences in the molecular configurations between chiral isomers. It consists of two processes, chiral recognition and signal transduction. Quartz crystal microbalance (QCM) holds a great promise for the next-generation sensors, due to its remarkable mass sensitivity, fast response, capable of online detection and low cost. It has been the focus of academic and practical research on chiral analysis during the last two decades. This review provides a detailed overview of recent advances made in chiral analysis based on QCM detection with regard to the recognition elements, which include synthetic macromolecules, molecular imprinting polymers (MIPs), proteins, amino acids and their derivatives, etc. The prospects of using QCM for chiral analysis are also put forward.

  18. Study of surface plasmon chirality induced by Archimedes' spiral grooves.

    PubMed

    Ohno, Tomoki; Miyanishi, Shintaro

    2006-06-26

    A chirality of surface plasmons excited on a silver film with Archimedes' spiral grooves during incidence of a circularly polarized light is analytically and numerically studied by using the finite-difference time-domain (FDTD) modeling method. We found that the surface of a plasmon has selective chirality, which is given by the sum of the chiralities of the incident light and the spiral structure. The surface plasmons with the chirality lead to zero-order, first-order, and high-order evanescent Bessel beams with electric charge distributions on the film. This selectivity could be widely applied for chiral detection of the incident light and chiral excitation of several optical modes in nanophotonics.

  19. Achiral flexible liquid crystal trimers exhibiting chiral conglomerates.

    PubMed

    Sasaki, Haruna; Takanishi, Yoichi; Yamamoto, Jun; Yoshizawa, Atsushi

    2016-04-14

    Chiral conglomerates of domains with opposite handedness have attracted much attention from researchers. We prepared a homologous series of achiral liquid crystal trimers in which two phenylpyrimidine units and one biphenyl unit were connected via flexible methylene spacers. We investigated their phase transition behaviour. Some trimers possessing odd-numbered spacers were found to exhibit a nematic phase and a dark chiral conglomerate phase possessing a layered structure. The chiral characteristics were confirmed by uncrossing the polarizers in opposite directions. The layer spacing detected using X-ray diffraction was about 80% of the molecular length. The structure-property relations indicate that intermolecular interactions cause a conformational change in the trimers possessing flexible odd-numbered methylene spacers to form helical conformers with axial chirality, which might induce chiral segregation and layer deformation to drive the chiral conglomerates.

  20. Detecting Chirality in Molecules by Linearly Polarized Laser Fields.

    PubMed

    Yachmenev, Andrey; Yurchenko, Sergei N

    2016-07-15

    A new scheme for enantiomer differentiation of chiral molecules using a pair of linearly polarized intense ultrashort laser pulses with skewed mutual polarization is presented. The technique relies on the fact that the off-diagonal anisotropic contributions to the electric polarizability tensor for two enantiomers have different signs. Exploiting this property, we are able to excite a coherent unidirectional rotation of two enantiomers with a π phase difference in the molecular electric dipole moment. The approach is robust and suitable for relatively high temperatures of molecular samples, making it applicable for selective chiral analysis of mixtures, and to chiral molecules with low barriers between enantiomers. As an illustration, we present nanosecond laser-driven dynamics of a tetratomic nonrigid chiral molecule with short-lived chirality. The ultrafast time scale of the proposed technique is well suited to study parity violation in molecular systems in short-lived chiral states. PMID:27472111

  1. Emergence of Chirality from Isotropic Interactions of Three Length Scales

    NASA Astrophysics Data System (ADS)

    Mkhonta, S. K.; Elder, K. R.; Huang, Zhi-Feng

    2016-05-01

    Chirality is known to play a pivotal role in determining material properties and functionalities. However, it remains a great challenge to understand and control the emergence of chirality and the related enantioselective process particularly when the building components of the system are achiral. Here we explore the generic mechanisms driving the formation of two-dimensional chiral structures in systems characterized by isotropic interactions and three competing length scales. We demonstrate that starting from isotropic and rotationally invariant interactions, a variety of chiral ordered patterns and superlattices with anisotropic but achiral units can self-assemble. The mechanisms for selecting specific states are related to the length-scale coupling and the selection of resonant density wave vectors. Sample phase diagrams and chiral elastic properties are identified. These findings provide a viable route for predicting chiral phases and selecting the desired handedness.

  2. Supramolecular chirality in self-assembled peptide amphiphile nanostructures.

    PubMed

    Garifullin, Ruslan; Guler, Mustafa O

    2015-08-11

    Induced supramolecular chirality was investigated in the self-assembled peptide amphiphile (PA) nanosystems. Having shown that peptide chirality can be transferred to the covalently-attached achiral pyrene moiety upon PA self-assembly, the chiral information is transferred to molecular pyrene via weak noncovalent interactions. In the first design of a supramolecular chiral system, the chromophore was covalently attached to a peptide sequence (VVAGH) via an ε-aminohexanoic acid spacer. Covalent attachment yielded a PA molecule self-assembling into nanofibers. In the second design, the chromophore was encapsulated within the hydrophobic core of self-assembled nanofibers of another PA consisting of the same peptide sequence attached to lauric acid. We observed that supramolecular chirality was induced in the chromophore by PA assembly into chiral nanostructures, whether it was covalently attached, or noncovalently bound. PMID:26146021

  3. Generation of chiral spin state by quantum simulation

    NASA Astrophysics Data System (ADS)

    Tanamoto, Tetsufumi

    2016-06-01

    Chirality of materials in nature appears when there are asymmetries in their lattice structures or interactions in a certain environment. Recent development of quantum simulation technology has enabled the manipulation of qubits. Accordingly, chirality can be realized intentionally rather than passively observed. Here we theoretically provide simple methods to create a chiral spin state in a spin-1/2 qubit system on a square lattice. First, we show that switching on and off the Heisenberg and X Y interactions produces the chiral interaction directly in the effective Hamiltonian without controlling local fields. Moreover, when initial states of spin qubits are appropriately prepared, we prove that the chirality with desirable phase is dynamically obtained. Finally, even for the case where switching on and off the interactions is infeasible and the interactions are always on, we show that, by preparing an asymmetric initial qubit state, the chirality whose phase is π /2 is dynamically generated.

  4. Self-shaping of bioinspired chiral composites

    NASA Astrophysics Data System (ADS)

    Rong, Qing-Qing; Cui, Yu-Hong; Shimada, Takahiro; Wang, Jian-Shan; Kitamura, Takayuki

    2014-08-01

    Self-shaping materials such as shape memory polymers have recently drawn considerable attention owing to their high shape-changing ability in response to changes in ambient conditions, and thereby have promising applications in the biomedical, biosensing, soft robotics and aerospace fields. Their design is a crucial issue of both theoretical and technological interest. Motivated by the shape-changing ability of Towel Gourd tendril helices during swelling/deswelling, we present a strategy for realizing self-shaping function through the deformation of micro/nanohelices. To guide the design and fabrication of self-shaping materials, the shape equations of bent configurations, twisted belts, and helices of slender chiral composite are developed using the variation method. Furthermore, it is numerically shown that the shape changes of a chiral composite can be tuned by the deformation of micro/nanohelices and the fabricated fiber directions. This work paves a new way to create self-shaping composites.

  5. New approaches in sensitive chiral CE.

    PubMed

    Sánchez-Hernández, Laura; Guijarro-Diez, Miguel; Marina, María Luisa; Crego, Antonio L

    2014-01-01

    CE has shown to have a big potential for chiral separations, with advantages such as high efficiency, high resolution, and low sample and reagents consumption. Nevertheless, when UV detection is employed, CE has some drawbacks, especially the low sensitivity obtained due to the short optical path length. Notwithstanding, sensitivity improvements can be achieved when different approaches are employed, such as sample treatment strategies (off-line or on-line), in-capillary sample preconcentration techniques, and/or alternative detection systems to UV-Vis (such as fluorescence, conductimetry, electrochemiluminiscence, MS, etc.). This article reviews the most recent methodological and instrumental advances reported from June 2011 to May 2013 for enhancing the sensitivity in chiral analysis by CE. The sensitivity achieved for the enantioseparated analytes and the applications carried out using the developed methodologies are also summarized.

  6. Active control of chirality in nonlinear metamaterials

    SciTech Connect

    Zhu, Yu; Chai, Zhen; Yang, Hong; Hu, Xiaoyong Gong, Qihuang

    2015-03-02

    An all-optical tunabe chirality is realized in a photonic metamaterial, the metamolecule of which consists of a nonlinear nano-Au:polycrystalline indium-tin oxide layer sandwiched between two L-shaped gold nano-antennas twisted 90° with each other. The maximum circular dichroism reached 30%. Under excitation of a 40 kW/cm{sup 2} weak pump light, the peak in the circular dichroism shifts 45 nm in the short-wavelength direction. An ultrafast response time of 35 ps is maintained. This work not only opens up the possibility for the realization of ultralow-power and ultrafast all-optical tunable chirality but also offers a way to construct ultrahigh-speed on-chip biochemical sensors.

  7. Nonperturbative Regulator for Chiral Gauge Theories?

    PubMed

    Grabowska, Dorota M; Kaplan, David B

    2016-05-27

    We propose a nonperturbative gauge-invariant regulator for d-dimensional chiral gauge theories on the lattice. The method involves simulating domain wall fermions in d+1 dimensions with quantum gauge fields that reside on one d-dimensional surface and are extended into the bulk via gradient flow. The result is a theory of gauged fermions plus mirror fermions, where the mirror fermions couple to the gauge fields via a form factor that becomes exponentially soft with the separation between domain walls. The resultant theory has a local d-dimensional interpretation only if the chiral fermion representation is anomaly free. A physical realization of this construction would imply the existence of mirror fermions in the standard model that are invisible except for interactions induced by vacuum topology, and which could gravitate differently than conventional matter. PMID:27284646

  8. Imprintable membranes from incomplete chiral coalescence

    NASA Astrophysics Data System (ADS)

    Zakhary, Mark J.; Gibaud, Thomas; Nadir Kaplan, C.; Barry, Edward; Oldenbourg, Rudolf; Meyer, Robert B.; Dogic, Zvonimir

    2014-01-01

    Coalescence is an essential phenomenon that governs the equilibrium behaviour in a variety of systems from intercellular transport to planetary formation. In this report, we study coalescence pathways of circularly shaped two-dimensional colloidal membranes, which are one rod-length-thick liquid-like monolayers of aligned rods. The chirality of the constituent rods leads to three atypical coalescence pathways that are not found in other simple or complex fluids. In particular, we characterize two pathways that do not proceed to completion but instead produce partially joined membranes connected by line defects—π-wall defects or alternating arrays of twisted bridges and pores. We elucidate the structure and energetics of these defects and ascribe their stability to a geometrical frustration inherently present in chiral colloidal membranes. Furthermore, we induce the coalescence process with optical forces, leading to a robust on-demand method for imprinting networks of channels and pores into colloidal membranes.

  9. On Gauge Independent Dynamical Chiral Symmetry Breaking

    SciTech Connect

    Bashir, A.; Raya, A.

    2006-09-25

    Schwinger-Dyson equations (SDEs) are an ideal framework to study nonperturbative phenomena such as dynamical chiral symmetry breaking (DCSB). Loss of gauge invariance is an obstacle to achieve fully reliable predictions from these equations. In addition to Ward-Green-Takahashi identity (WGTI), Landau-Khalatnikov-Fradkin transformations (LKFT) also play an important role in restoring the said invariance at the level of physical observables. On one hand, they impose useful constraints on the transverse part of the fermion-boson vertex and on the other, they govern the change in dynamically generated fermion propagator with a variation of gauge. We consider the latter in this article and study the gauge (in)dependence of chiral condensate in quantum electrodynamics in (2+1) space-time dimensions (QED3)

  10. Chiral patterning in Paenibacillus colonies under stress

    NASA Astrophysics Data System (ADS)

    Levine, Herbert

    2012-02-01

    One of the most striking examples of bacterial colony patterning occurs in the C-morphotype of Paenibacillus strains. Here, macroscopic chirality results from the interaction of local liquid-crystal ordering of the long bacterial cells with the self-propelled motility driven by the non-reflection-symmetric flagella. This talk will review some of the original experimental data from the Ben-Jacob lab as well as recent insight obtained via genomics. I will then discuss attempts to model and simulate the chiral patterns via solving reaction-diffusion equations on random lattices. At the end, I will introduce the challenges still to be faced in understanding transitions between these patterns and more common branching structures

  11. Optical tractor beam with chiral light

    NASA Astrophysics Data System (ADS)

    Fernandes, David E.; Silveirinha, Mário G.

    2015-06-01

    We suggest a novel mechanism to induce the motion of a chiral material body towards an optical source with no optical traps. Our solution is based on the interference between a chiral light beam and its reflection on an opaque mirror. Surprisingly, it is theoretically shown that the electromagnetic response of the material may be tailored in such a way that independent of the specific body location with respect to the mirror, it is always pulled upstream against the photon flow associated with the incoming wave. Moreover, it is proven that by controlling the handedness of the incoming light it may be possible to harness the sign of the optical force, switching from a pulling force to a pushing force.

  12. Check for chirality in {sup 102}Rh

    SciTech Connect

    Tonev, D.; Goutev, N.; Yavahchova, M. S.; Petkov, P.; Angelis, G. de; Bhowmik, R. K.; Singh, R. P.; Muralithar, S.; Madhavan, N.; Kumar, R.; Raju, M. Kumar; Kaur, J.; Mahanto, G.; Singh, A.; Kaur, N.; Garg, R.; Sukla, A.; Marinov, Ts. K.; Brant, S.

    2012-10-20

    Excited states in {sup 102}Rh, populated by the fusion-evaporation reaction {sup 94}Zr({sup 11}B,3n){sup 102}Rh at a beam energy of 36 MeV, were studied using the INGA spectrometer at IUAC, New Delhi. The angular correlations and the electromagnetic character of some of the gamma-ray transitions observed were investigated in details. A new chiral candidate sister band was found in the level-scheme of {sup 102}Rh. Lifetimes of exited states in {sup 102}Rh were measured by means of the Doppler-shift attenuation technique. The experimental results do not support the presence of static chirality in {sup 102}Rh.

  13. Chiral meta-atoms rotated by light

    SciTech Connect

    Liu Mingkai; Powell, David A.; Shadrivov, Ilya V.

    2012-07-16

    We study the opto-mechanical properties of coupled chiral meta-atoms based on a pair of twisted split-ring resonators. By using a simple analytical model in conjunction with the Maxwell stress tensor, we capture insight into the mechanism and find that this structure can be used as a general prototype of subwavelength light-driven actuators over a wide range of frequencies. This coupled structure can provide a strong and tunable torque, and can support different opto-mechanical modes, including uniform rotation, periodically variable rotation and damped oscillations. Our results suggest that chiral meta-atoms are good candidates for creating sub-wavelength motors or wrenches controlled by light.

  14. Applications of partially quenched chiral perturbation theory

    SciTech Connect

    Golterman, M.F.; Leung, K.C.

    1998-05-01

    Partially quenched theories are theories in which the valence- and sea-quark masses are different. In this paper we calculate the nonanalytic one-loop corrections of some physical quantities: the chiral condensate, weak decay constants, Goldstone boson masses, B{sub K}, and the K{sup +}{r_arrow}{pi}{sup +}{pi}{sup 0} decay amplitude, using partially quenched chiral perturbation theory. Our results for weak decay constants and masses agree with, and generalize, results of previous work by Sharpe. We compare B{sub K} and the K{sup +} decay amplitude with their real-world values in some examples. For the latter quantity, two other systematic effects that plague lattice computations, namely, finite-volume effects and unphysical values of the quark masses and pion external momenta, are also considered. We find that typical one-loop corrections can be substantial. {copyright} {ital 1998} {ital The American Physical Society}

  15. Chiral fermions as classical massless spinning particles

    NASA Astrophysics Data System (ADS)

    Duval, C.; Horváthy, P. A.

    2015-02-01

    Semiclassical chiral fermion models with Berry term are studied in a symplectic framework. In the free case, the system can be obtained from Souriau's model for a relativistic massless spinning particle by "enslaving" the spin. The Berry term is identified with the classical spin two-form of the latter model. The Souriau model carries a natural Poincaré symmetry that we highlight, but spin enslavement breaks the boost symmetry. However the relation between the models allows us to derive a Poincaré symmetry of unconventional form for chiral fermions. Then we couple our system to an external electromagnetic field. For gyromagnetic ratio g =0 we get curious superluminal Hall-type motions; for g =2 and in a pure constant magnetic field in particular, we find instead spiraling motions.

  16. Chiral perturbation theory with tensor sources

    SciTech Connect

    Cata, Oscar; Cata, Oscar; Mateu, Vicent

    2007-05-21

    We construct the most general chirally-invariant Lagrangian for mesons in the presence of external sources coupled to the tensor current \\bar psi sigma_mu nu psi. In order to have only even terms in the chiral expansion, we consider the new source of O(p2). With this choice, we build the even-parity effective Lagrangian up to the p6-order (NLO). While there are only 4 new terms at the p4-order, at p6-order we find 78 terms for n_f=2 and 113 terms for n_f=3. We provide a detailed discussion on the different mechanisms that ensure that our final set of operators is complete and non-redundant. We also examine the odd-parity sector, to conclude that the first operators appear at the p8-order (NNLO).

  17. Absence of equilibrium chiral magnetic effect

    NASA Astrophysics Data System (ADS)

    Zubkov, M. A.

    2016-05-01

    We analyze the (3 +1 )D equilibrium chiral magnetic effect (CME). We apply derivative expansion to the Wigner transform of the two-point Green function. This technique allows us to express the response of electric current to the external electromagnetic field strength through the momentum space topological invariant. We consider the wide class of the lattice regularizations of quantum field theory (that includes, in particular, the regularization with Wilson fermions) and also certain lattice models of solid state physics (including those of Dirac semimetals). It appears that in these models the mentioned topological invariant vanishes identically at nonzero chiral chemical potential. That means that the bulk equilibrium CME is absent in those systems.

  18. Oscillating chiral tensor spectrum from axionic inflation

    NASA Astrophysics Data System (ADS)

    Obata, Ippei; Soda, Jiro

    2016-08-01

    We study axionic inflation with a modulated potential and examine if the primordial tensor power spectrum exhibits oscillatory feature, which is testable with future space-based gravitational-wave experiments such as DECIGO and BBO. In the case of single-field axion monodromy inflation, it turns out that it is difficult to detect an oscillation in the spectrum due to the suppression of the sub-Planckian decay constant of the axion. On the other hand, in the case of aligned chromo-natural inflation where the axion is coupled to a SU(2) gauge field, it turns out that a sizable oscillation in the tensor spectrum can occur due to the enhancement of chiral gravitational waves sourced by the gauge field. We expect that this feature will be a new probe for axion phenomenologies in the early Universe through chiral gravitational waves.

  19. Terahertz chiral metamaterials with giant and dynamically tunable optical activity

    SciTech Connect

    Zhou, Jiangfeng; Chowdhury, Dibakar Roy; Zhao, Rongkuo; Azad, Abul K.; Chen, Hou-Tong; Soukoulis, Costas M.; Taylor, Antoinette J.; O'Hara, John F.

    2012-07-27

    We demonstrated giant optical activity using a chiral metamaterial composed of an array of conjugated bilayer metal structures. The chiral metamaterials were further integrated with photoactive inclusions to accomplish a wide tuning range of the optical activity through illumination with near-infrared light. The strong chirality observed in our metamaterials results in a negative refractive index, which can also be well controlled by the near-infrared optical excitation.

  20. Magnetotransport phenomena related to the chiral anomaly in Weyl semimetals

    NASA Astrophysics Data System (ADS)

    Spivak, B. Z.; Andreev, A. V.

    2016-02-01

    We present a theory of magnetotransport phenomena related to the chiral anomaly in Weyl semimetals. We show that conductivity, thermal conductivity, thermoelectric, and the sound absorption coefficients exhibit strong and anisotropic magnetic field dependencies. We also discuss properties of magnetoplasmons and magnetopolaritons, whose existences are entirely determined by the chiral anomaly. Finally, we discuss the conditions of applicability of the quasiclassical description of electron transport phenomena related to the chiral anomaly.

  1. Quenched QED in the chiral limit. [QED (quantum electrodynamics)

    SciTech Connect

    Vandermark, S.W.

    1993-01-01

    The main goal in this project has been to understand, through analytical methods, whether there could be a continuum limit for QED. This possibility is motivated by recent lattice simulations on quenched QED which apparently exhibit a chiral phase transition at strong coupling in the chiral limit. Another goal is to develop a novel perturbation expansion which may also be usefully applied to other theories. The author begins with the general expression for the chiral order parameter, ([bar [psi

  2. Chiral Biomarkers and Microfossils in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2010-01-01

    Homochirality of the biomolecules (D-sugars of DNA and RNA and L-amino acids of proteins) is a fundamental property of all life on Earth. Abiotic mechanisms yield racemic mixtures (D/L=1) of chiral molecules and after the death of an organism, the enantiopure chiral biomolecules slowly racemize. Several independent investigators have now established that the amino acids present in CI1 and CM2 carbonaceous meteorites have a moderate to strong excess of the L-enantiomer. Stable isotope data have established that these amino acids are both indigenous and extraterrestrial. Carbonaceous meteorites also contain many other strong chemical biomarkers including purines and pyrimidines (nitrogen heterocycles of nucleic acids); pristine and phytane (components of the chlorophyll pigment) and morphological biomarkers (microfossils of filamentous cyanobacteria). Energy dispersive X-ray Spectroscopy (EDS) analysis reveals that nitrogen is below the detectability level in most of the meteorite filaments as well as in Cambrian Trilobites and filaments of 2.7 Gya Archaean cyanobacteria from Karelia. The deficiency of nitrogen in the filaments and the total absence of sugars, of twelve of the life-critical protein amino acids, and two of the nucleobases of DNA and RNA provide clear and convincing evidence that these filaments are not modern biological contaminants. This paper reviews the chiral, chemical biomarkers morphological biomarkers and microfossils in carbonaceous meteorites. This paper reviews chiral and morphological biomarkers and discusses the missing nitrogen, sugars, protein amino acids, and nucleobases as ?bio-discriminators? that exclude modern biological contaminants as a possible explanation for the permineralized cyanobacterial filaments found in the meteorites.

  3. Hyperbolic Weyl Point in Reciprocal Chiral Metamaterials

    NASA Astrophysics Data System (ADS)

    Xiao, Meng; Lin, Qian; Fan, Shanhui

    2016-07-01

    We report the existence of Weyl points in a class of noncentral symmetric metamaterials, which has time reversal symmetry, but does not have inversion symmetry due to chiral coupling between electric and magnetic fields. This class of metamaterial exhibits either type-I or type-II Weyl points depending on its nonlocal response. We also provide a physical realization of such metamaterial consisting of an array of metal wires in the shape of elliptical helices which exhibits type-II Weyl points.

  4. Gauge cosmic chiral strings in general relativity

    SciTech Connect

    Rybakov, Yu. P.

    2009-05-15

    Cylindrically symmetric self-gravitating configurations of string (vortex) type are considered within the framework of the chiral SU(2) model with the inclusion of the Yang-Mills proper gauge field. In the approximation of the large topological charge n the solutions to the field equations are found, with the magnetic field of the vortex being longitudinal. The linear energy density of the vortex configuration is estimated.

  5. Chiral biomarkers and microfossils in carbonaceous meteorites

    NASA Astrophysics Data System (ADS)

    Hoover, Richard B.

    2010-09-01

    Homochirality of the biomolecules (D-sugars of DNA and RNA and L-amino acids of proteins) is a fundamental property of all life on Earth. Abiotic mechanisms yield racemic mixtures (D/L=1) of chiral molecules and after the death of an organism, the enantiopure chiral biomolecules slowly racemize. Several independent investigators have now established that the amino acids present in CI1 and CM2 carbonaceous meteorites have a moderate to strong excess of the L-enantiomer. Stable isotope data have established that these amino acids are both indigenous and extraterrestrial. Carbonaceous meteorites also contain many other strong chemical biomarkers including purines and pyrimidines (nitrogen heterocycles of nucleic acids); pristine and phytane (components of the chlorophyll pigment) and morphological biomarkers (microfossils of filamentous cyanobacteria). Energy dispersive X-ray Spectroscopy (EDS) analysis reveals that nitrogen is below the detectability level in most of the meteorite filaments as well as in Cambrian Trilobites and filaments of 2.7 Gya Archaean cyanobacteria from Karelia. The deficiency of nitrogen in the filaments and the total absence of sugars, of twelve of the life-critical protein amino acids, and two of the nucleobases of DNA and RNA provide clear and convincing evidence that these filaments are not modern biological contaminants. This paper reviews the chiral, chemical biomarkers morphological biomarkers and microfossils in carbonaceous meteorites. This paper reviews chiral and morphological biomarkers and discusses the missing nitrogen, sugars, protein amino acids, and nucleobases as "bio-discriminators" that exclude modern biological contaminants as a possible explanation for the permineralized cyanobacterial filaments found in the meteorites.

  6. Hyperbolic Weyl Point in Reciprocal Chiral Metamaterials.

    PubMed

    Xiao, Meng; Lin, Qian; Fan, Shanhui

    2016-07-29

    We report the existence of Weyl points in a class of noncentral symmetric metamaterials, which has time reversal symmetry, but does not have inversion symmetry due to chiral coupling between electric and magnetic fields. This class of metamaterial exhibits either type-I or type-II Weyl points depending on its nonlocal response. We also provide a physical realization of such metamaterial consisting of an array of metal wires in the shape of elliptical helices which exhibits type-II Weyl points.

  7. Circular Intensity Differential Scattering of chiral molecules

    SciTech Connect

    Bustamante, C.J.

    1980-12-01

    In this thesis a theory of the Circular Intensity Differential Scattering (CIDS) of chiral molecules as modelled by a helix oriented with respect to the direction of incidence of light is presented. It is shown that a necessary condition for the existence of CIDS is the presence of an asymmetric polarizability in the scatterer. The polarizability of the scatterer is assumed generally complex, so that both refractive and absorptive phenomena are taken into account.

  8. Investigation of a Quantitative Method for the Analysis of Chiral Monoterpenes in White Wine by HS-SPME-MDGC-MS of Different Wine Matrices.

    PubMed

    Song, Mei; Xia, Ying; Tomasino, Elizabeth

    2015-01-01

    A valid quantitative method for the analysis of chiral monoterpenes in white wine using head-space solid phase micro-extraction-MDGC-MS (HS-SPME-MDGC-MS) with stable isotope dilution analysis was established. Fifteen compounds: (S)-(-)-limonene, (R)-(+)-limonene, (+)-(2R,4S)-cis-rose oxide, (-)-(2S,4R)-cis-rose oxide, (-)-(2R,4R)-trans-rose oxide, (+)-(2S,4S)-cis-rose oxide, furanoid (+)-trans-linalool oxide, furanoid (-)-cis-linalool oxide, furanoid (-)-trans-linalool oxide, furanoid (+)-cis-linalool oxide, (-)-linalool, (+)-linalool, (-)-α-terpineol, (+)-α-terpineol and (R)-(+)-β-citronellol were quantified. Two calibration curves were plotted for different wine bases, with varying residual sugar content, and three calibration curves for each wine base were investigated during a single fiber's lifetime. This was needed as both sugar content and fiber life impacted the quantification of the chiral terpenes. The chiral monoterpene content of six Pinot Gris wines and six Riesling wines was then analyzed using the verified method. ANOVA with Tukey multiple comparisons showed significant differences for each of the detected chiral compounds in all 12 wines. PCA score plots showed a clear separation between the Riesling and Pinot Gris wines. Riesling wines had greater number of chiral terpenes in comparison to Pinot Gris wines. Beyond total terpene content it is possible that the differences in chiral terpene content may be driving the aromatic differences in white wines.

  9. Hybrid chiral metamaterials by dynamic shadowing growth

    NASA Astrophysics Data System (ADS)

    Gibbs, John; Fischer, Peer; Mark, Andrew; Eslami, Sahand; Lee, Tung-Chun

    2015-03-01

    Coupling optical and magnetic properties is possible in metamaterials and in higher-order magnetic field induced optical activities. Here, we show that these two mechanisms can be combined in nanostructures that are simultaneously ferromagnetic, chiral, and plasmonically resonant. In this talk, a short description of the fabrication of optically active helical metamaterials will first be given, followed by the highlighting of the materials' enhanced optical properties. Giant circular dichroism (CD) and optical rotatory dispersion (ORD) in the visible arise from helical plasmonic modes within the individual structures and can be tuned by altering the material composition, i.e. nanoalloys or nanocomposites, and/or by changing the structures' morphologies. By fabricating metamaterials which exhibit both strong CD and are ferromagnetic at room temperature, higher order terms in the generalized dielectric function in the presence of a B-field can be measured easily. In particular, magnetochiral dichroism (MChD) is a cross-term between chirality and an applied external B-field which has only been measured in crystals and molecules, but never in a metamaterial. We show that arrays of helical Ni nanostructures, due to the plasmonic nature of Ni, their chirality, as well as the fact they retain their ferromagnetism even at scales comparable to the average ferromagnetic domain size, exhibit an MChD signal that is much more pronounced in a metamaterial and can therefore be easily measured in the laboratory.

  10. Lagrangians for massive Dirac chiral superfields

    NASA Astrophysics Data System (ADS)

    Jiménez, Enrique; Vaquera-Araujo, C. A.

    2016-06-01

    A variant for the superspin one-half massive superparticle in 4D, N = 1, based on Dirac superfields, is offered. As opposed to the current known models that use spinor chiral superfields, the propagating fields of the supermultiplet are those of the lowest mass dimensions possible: scalar, Dirac and vector fields. Besides the supersymmetric chiral condition, the Dirac superfields are not further constrained, allowing a very straightforward implementation of the path-integral method. The corresponding superpropagators are presented. In addition, an interaction super Yukawa potential, formed by Dirac and scalar chiral superfields, is given in terms of their component fields. The model is first presented for the case of two superspin one-half superparticles related by the charged conjugation operator, but in order to treat the case of neutral superparticles, the Majorana condition on the Dirac superfields is also studied. We compare our proposal with the known models of spinor superfields for the one-half superparticle and show that it is equivalent to them.

  11. Energetic molding of chiral magnetic bubbles

    NASA Astrophysics Data System (ADS)

    Lau, Derek; Sundar, Vignesh; Zhu, Jian-Gang; Sokalski, Vincent

    2016-08-01

    Topologically protected magnetic structures such as skyrmions and domain walls (DWs) have drawn a great deal of attention recently due to their thermal stability and potential for manipulation by spin current, which is the result of chiral magnetic configurations induced by the interfacial Dzyaloshinskii-Moriya interaction (DMI). Designing devices that incorporate DMI necessitates a thorough understanding of how the interaction presents and can be measured. One approach is to measure growth asymmetry of chiral bubble domains in perpendicularly magnetized thin films, which has been described elsewhere by thermally activated DW motion. Here, we demonstrate that the anisotropic angular dependence of DW energy originating from the DMI is critical to understanding this behavior. Domains in Co/Ni multilayers are observed to preferentially grow into nonelliptical teardrop shapes, which vary with the magnitude of an applied in-plane field. We model the domain profile using energetic calculations of equilibrium shape via the Wulff construction, which serves as a new paradigm for describing chiral domains that explains both the teardrop shape and the reversal of growth symmetry at large fields.

  12. Pion scattering poles and chiral symmetry restoration

    SciTech Connect

    Fernandez-Fraile, D.; Nicola, A. Gomez; Herruzo, E. T.

    2007-10-15

    Using unitarized chiral perturbation theory methods, we perform a detailed analysis of the {pi}{pi} scattering poles f{sub 0}(600) and {rho}(770) behavior when medium effects such as temperature or density drive the system towards chiral symmetry restoration. In the analysis of real poles below threshold, we show that it is crucial to extend properly the unitarized amplitudes so that they match the perturbative Adler zeros. Our results do not show threshold enhancement effects at finite temperature in the f{sub 0}(600) channel, which remains as a pole of broad nature. We also implement T=0 finite-density effects related to chiral symmetry restoration, by varying the pole position with the pion decay constant. Although this approach takes into account only a limited class of contributions, we reproduce the expected finite-density restoration behavior, which drives the poles towards the real axis, producing threshold enhancement and {pi}{pi} bound states. We compare our results with several model approaches and discuss the experimental consequences, both in relativistic heavy ion collisions and in {pi}{yields}{pi}{pi} and {gamma}{yields}{pi}{pi} reactions in nuclei.

  13. Chiral discrimination in optical trapping and manipulation

    NASA Astrophysics Data System (ADS)

    Bradshaw, David S.; Andrews, David L.

    2014-10-01

    When circularly polarized light interacts with chiral molecules or nanoscale particles powerful symmetry principles determine the possibility of achieving chiral discrimination, and the detailed form of electrodynamic mechanisms dictate the types of interaction that can be involved. The optical trapping of molecules and nanoscale particles can be described in terms of a forward-Rayleigh scattering mechanism, with trapping forces being dependent on the positioning within the commonly non-uniform intensity beam profile. In such a scheme, nanoparticles are commonly attracted to local potential energy minima, ordinarily towards the centre of the beam. For achiral particles the pertinent material response property usually entails an electronic polarizability involving transition electric dipole moments. However, in the case of chiral molecules, additional effects arise through the engagement of magnetic counterpart transition dipoles. It emerges that, when circularly polarized light is used for the trapping, a discriminatory response can be identified between left- and right-handed polarizations. Developing a quantum framework to accurately describe this phenomenon, with a tensor formulation to correctly represent the relevant molecular properties, the theory leads to exact analytical expressions for the associated energy landscape contributions. Specific results are identified for liquids and solutions, both for isotropic media and also where partial alignment arises due to a static electric field. The paper concludes with a pragmatic analysis of the scope for achieving enantiomer separation by such methods.

  14. AkF ¯ chiral gauge theories

    NASA Astrophysics Data System (ADS)

    Shi, Yan-Liang; Shrock, Robert

    2015-11-01

    We study asymptotically free chiral gauge theories with an SU (N ) gauge group and chiral fermions transforming according to the antisymmetric rank-k tensor representation, Ak≡[k ]N , and the requisite number, nF ¯, of copies of fermions in the conjugate fundamental representation, F ¯ ≡[1] ¯ N , to render the theories anomaly-free. We denote these as AkF ¯ theories. We take N ≥2 k +1 so that nF ¯≥1 . The A2F ¯ theories form an infinite family with N ≥5 , but we show that the A3F ¯ and A4F ¯ theories are only asymptotically free for N in the respective ranges 7 ≤N ≤17 and 9 ≤N ≤11 , and that there are no asymptotically free AkF ¯ theories with k ≥5 . We investigate the types of ultraviolet to infrared evolution for these AkF ¯ theories and find that, depending on k and N , they may lead to a non-Abelian Coulomb phase, or may involve confinement with massless gauge-singlet composite fermions, bilinear fermion condensation with dynamical gauge and global symmetry breaking, or formation of multifermion condensates that preserve the gauge symmetry. We also show that there are no asymptotically free, anomaly-free SU (N ) SkF ¯ chiral gauge theories with k ≥3 , where Sk denotes the rank-k symmetric representation.

  15. Performance of Multiple Risk Assessment Tools to Predict Mortality for Adult Respiratory Distress Syndrome with Extracorporeal Membrane Oxygenation Therapy: An External Validation Study Based on Chinese Single-center Data

    PubMed Central

    Huang, Lei; Li, Tong; Xu, Lei; Hu, Xiao-Min; Duan, Da-Wei; Li, Zhi-Bo; Gao, Xin-Jing; Li, Jun; Wu, Peng; Liu, Ying-Wu; Wang, Song; Lang, Yu-Heng

    2016-01-01

    Background: There has been no external validation of survival prediction models for severe adult respiratory distress syndrome (ARDS) with extracorporeal membrane oxygenation (ECMO) therapy in China. The aim of study was to compare the performance of multiple models recently developed for patients with ARDS undergoing ECMO based on Chinese single-center data. Methods: A retrospective case study was performed, including twenty-three severe ARDS patients who received ECMO from January 2009 to July 2015. The PRESERVE (Predicting death for severe ARDS on VV-ECMO), ECMOnet, Respiratory Extracorporeal Membrane Oxygenation Survival Prediction (RESP) score, a center-specific model developed for inter-hospital transfers receiving ECMO, and the classical risk-prediction scores of Acute Physiology and Chronic Health Evaluation (APACHE) II and Sequential Organ Failure Assessment (SOFA) were calculated. In-hospital and six-month mortality were regarded as the endpoints and model performance was evaluated by comparing the area under the receiver operating characteristic curve (AUC). Results: The RESP and APACHE II scores showed excellent discriminate performance in predicting survival with AUC of 0.835 (95% confidence interval [CI], 0.659–1.010, P = 0.007) and 0.762 (95% CI, 0.558–0.965, P = 0.035), respectively. The optimal cutoff values were risk class 3.5 for RESP and 35.5 for APACHE II score, and both showed 70.0% sensitivity and 84.6% specificity. The excellent performance of these models was also evident for the pneumonia etiological subgroup, for which the SOFA score was also shown to be predictive, with an AUC of 0.790 (95% CI, 0.571–1.009, P = 0.038). However, the ECMOnet and the score developed for externally retrieved ECMO patients failed to demonstrate significant discriminate power for the overall cohort. The PRESERVE model was unable to be evaluated fully since only one patient died six months postdischarge. Conclusions: The RESP, APCHAE II, and SOFA scorings

  16. Chirality-induced magnon transport in AA-stacked bilayer honeycomb chiral magnets.

    PubMed

    Owerre, S A

    2016-11-30

    In this Letter, we study the magnetic transport in AA-stacked bilayer honeycomb chiral magnets coupled either ferromagnetically or antiferromagnetically. For both couplings, we observe chirality-induced gaps, chiral protected edge states, magnon Hall and magnon spin Nernst effects of magnetic spin excitations. For ferromagnetically coupled layers, thermal Hall and spin Nernst conductivities do not change sign as function of magnetic field or temperature similar to single-layer honeycomb ferromagnetic insulator. In contrast, for antiferromagnetically coupled layers, we observe a sign change in the thermal Hall and spin Nernst conductivities as the magnetic field is reversed. We discuss possible experimental accessible honeycomb bilayer quantum materials in which these effects can be observed. PMID:27636333

  17. Enantiomeric separations of chiral pharmaceuticals using chirally modified tetrahexahedral Au nanoparticles

    NASA Astrophysics Data System (ADS)

    Shukla, N.; Yang, D.; Gellman, A. J.

    2016-06-01

    Tetrahexahedral (THH, 24-sided) Au nanoparticles modified with D- or L-cysteine (Cys) have been used as enantioselective separators of the chiral pharmaceutical propranolol (PLL) in solution phase. Polarimetry has been used to measure the rotation of linearly polarized light by solutions containing mixtures of PLL and Cys/THH-Au NPs with varying enantiomeric excesses of each. Polarimetry yields clear evidence of enantiospecific adsorption of PLL onto the Cys/THH-Au NPs. This extends prior work using propylene oxide as a test chiral probe, by using the crystalline THH Au NPs with well-defined facets to separate a real pharmaceutical. This work suggests that chiral nanoparticles, coupled with a density separation method such as centrifugation, could be used for enantiomeric purification of real pharmaceuticals. A simple robust model developed earlier has also been used to extract the enantiospecific equilibrium constants for R- and S-PLL adsorption onto the D- and L-Cys/THH-Au NPs.

  18. Chiral light intrinsically couples to extrinsic/pseudo-chiral metasurfaces made of tilted gold nanowires

    NASA Astrophysics Data System (ADS)

    Belardini, Alessandro; Centini, Marco; Leahu, Grigore; Hooper, David C.; Li Voti, Roberto; Fazio, Eugenio; Haus, Joseph W.; Sarangan, Andrew; Valev, Ventsislav K.; Sibilia, Concita

    2016-08-01

    Extrinsic or pseudo-chiral (meta)surfaces have an achiral structure, yet they can give rise to circular dichroism when the experiment itself becomes chiral. Although these surfaces are known to yield differences in reflected and transmitted circularly polarized light, the exact mechanism of the interaction has never been directly demonstrated. Here we present a comprehensive linear and nonlinear optical investigation of a metasurface composed of tilted gold nanowires. In the linear regime, we directly demonstrate the selective absorption of circularly polarised light depending on the orientation of the metasurface. In the nonlinear regime, we demonstrate for the first time how second harmonic generation circular dichroism in such extrinsic/pseudo-chiral materials can be understood in terms of effective nonlinear susceptibility tensor elements that switch sign depending on the orientation of the metasurface. By providing fundamental understanding of the chiroptical interactions in achiral metasurfaces, our work opens up new perspectives for the optimisation of their properties.

  19. Chiral light intrinsically couples to extrinsic/pseudo-chiral metasurfaces made of tilted gold nanowires.

    PubMed

    Belardini, Alessandro; Centini, Marco; Leahu, Grigore; Hooper, David C; Li Voti, Roberto; Fazio, Eugenio; Haus, Joseph W; Sarangan, Andrew; Valev, Ventsislav K; Sibilia, Concita

    2016-01-01

    Extrinsic or pseudo-chiral (meta)surfaces have an achiral structure, yet they can give rise to circular dichroism when the experiment itself becomes chiral. Although these surfaces are known to yield differences in reflected and transmitted circularly polarized light, the exact mechanism of the interaction has never been directly demonstrated. Here we present a comprehensive linear and nonlinear optical investigation of a metasurface composed of tilted gold nanowires. In the linear regime, we directly demonstrate the selective absorption of circularly polarised light depending on the orientation of the metasurface. In the nonlinear regime, we demonstrate for the first time how second harmonic generation circular dichroism in such extrinsic/pseudo-chiral materials can be understood in terms of effective nonlinear susceptibility tensor elements that switch sign depending on the orientation of the metasurface. By providing fundamental understanding of the chiroptical interactions in achiral metasurfaces, our work opens up new perspectives for the optimisation of their properties. PMID:27553888

  20. Chirality-induced magnon transport in AA-stacked bilayer honeycomb chiral magnets.

    PubMed

    Owerre, S A

    2016-11-30

    In this Letter, we study the magnetic transport in AA-stacked bilayer honeycomb chiral magnets coupled either ferromagnetically or antiferromagnetically. For both couplings, we observe chirality-induced gaps, chiral protected edge states, magnon Hall and magnon spin Nernst effects of magnetic spin excitations. For ferromagnetically coupled layers, thermal Hall and spin Nernst conductivities do not change sign as function of magnetic field or temperature similar to single-layer honeycomb ferromagnetic insulator. In contrast, for antiferromagnetically coupled layers, we observe a sign change in the thermal Hall and spin Nernst conductivities as the magnetic field is reversed. We discuss possible experimental accessible honeycomb bilayer quantum materials in which these effects can be observed.