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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

    Koutoulogenis, Giorgos; Kaplaneris, Nikolaos; Kokotos, Christoforos G

    2016-01-01

    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. (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

  3. 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)

  4. How center vortices break chiral symmetry

    NASA Astrophysics Data System (ADS)

    Faber, Manfried; Höllwieser, Roman

    2016-01-01

    We investigate the chiral properties of near-zero modes for thick classical center vortices in SU(2) lattice gauge theory as examples of the phenomena which may arise in a vortex vacuum. In particular we analyze the creation of near-zero modes from would-be zero modes of various topological charge contributions from center vortices. We show that classical colorful spherical vortex and instanton ensembles have almost identical Dirac spectra and the low-lying eigenmodes from spherical vortices show all characteristic properties for chiral symmetry breaking. We further show that also vortex intersections are able to give rise to a finite density of near-zero modes, leading to chiral symmetry breaking via the Banks-Casher formula. We discuss the mechanism by which center vortex fluxes contribute to chiral symmetry breaking.

  5. Multiple chiral doublet bands of identical configuration in 103Rh.

    PubMed

    Kuti, I; Chen, Q B; Timár, J; Sohler, D; Zhang, S Q; Zhang, Z H; Zhao, P W; Meng, J; Starosta, K; Koike, T; Paul, E S; Fossan, D B; Vaman, C

    2014-07-18

    Three sets of chiral doublet band structures have been identified in the ^{103}Rh nucleus. The properties of the observed chiral doublet bands are in good agreement with theoretical results obtained using constrained covariant density functional theory and particle rotor model calculations. Two of them belong to an identical configuration and provide the first experimental evidence for a novel type of multiple chiral doublets, where an "excited" chiral doublet of a configuration is seen together with the "yrast" one. This observation shows that the chiral geometry in nuclei can be robust against the increase of the intrinsic excitation energy. PMID:25083635

  6. Multiple spectra of electron spin resonance in chiral molecule-based magnets networked by a single chiral ligand

    NASA Astrophysics Data System (ADS)

    Mito, M.; Nagano, T.; Tsuruta, K.; Deguchi, H.; Takagi, S.; Kishine, J.; Yoshida, Y.; Inoue, K.

    2013-10-01

    A molecule-based magnet [Cr(CN)6][Mn(R/S)-pnH(H2O)](H2O) (termed R/S-GN) is a chiral crystal without an inversion center and mirror reflection, and its structural network is constructed using a chiral ligand diaminopropane (R/S)-pn. In S-GN, multiple spectra of ESR were observed below the magnetic ordering temperature by Morgunov et al. [Phys. Rev. B 77, 184419 (2008)]. They concluded that the phenomenon at the high field side occurred because the incommensurate magnetic structure resulted in a length-controllable superlattice of domain walls (the so-called chiral soliton lattice, CSL) under a dc magnetic field H applied perpendicular to the magnetic chiral axis. However, there multiple spectra were observed even for H nearly parallel to the chiral axis, a-axis, and their interpretation is unreasonable. Thus, we conducted an X-band electron spin resonance (ESR) measurement of R-GN under conditions similar to those of their experiment and performed Fourier spectrum analyses for the data of R-GN as an approach of physical characterization. By using two Lorentz spectra, the main ESR spectra for H // a were reproduced, and furthermore two prominent periodic modes were found by spectrum analyses based on Fourier transform. Two characteristic periods, p1 and p2 (multiplicity can be physically characterized with those of p1 and p2. The unique spectra observed below the magnetic ordering temperature are due not to hyperfine structure but magnetic fine structure, and it certainly originates from the existence of plural nonequivalent magnetic sites. Thus, it is unreasonable to consider CSL to explain the multiple ESR spectra observed independently of the field direction, whereas the observed complex spectra appeal wealthy scientific potentiality in chiral crystals.

  7. Evidence for Octupole Correlations in Multiple Chiral Doublet Bands.

    PubMed

    Liu, C; Wang, S Y; Bark, R A; Zhang, S Q; Meng, J; Qi, B; Jones, P; Wyngaardt, S M; Zhao, J; Xu, C; Zhou, S-G; Wang, S; Sun, D P; Liu, L; Li, Z Q; Zhang, N B; Jia, H; Li, X Q; Hua, H; Chen, Q B; Xiao, Z G; Li, H J; Zhu, L H; Bucher, T D; Dinoko, T; Easton, J; Juhász, K; Kamblawe, A; Khaleel, E; Khumalo, N; Lawrie, E A; Lawrie, J J; Majola, S N T; Mullins, S M; Murray, S; Ndayishimye, J; Negi, D; Noncolela, S P; Ntshangase, S S; Nyakó, B M; Orce, J N; Papka, P; Sharpey-Schafer, J F; Shirinda, O; Sithole, P; Stankiewicz, M A; Wiedeking, M

    2016-03-18

    Two pairs of positive-and negative-parity doublet bands together with eight strong electric dipole transitions linking their yrast positive- and negative-parity bands have been identified in ^{78}Br. They are interpreted as multiple chiral doublet bands with octupole correlations, which is supported by the microscopic multidimensionally-constrained covariant density functional theory and triaxial particle rotor model calculations. This observation reports the first example of chiral geometry in octupole soft nuclei. PMID:27035296

  8. Evidence for Octupole Correlations in Multiple Chiral Doublet Bands

    NASA Astrophysics Data System (ADS)

    Liu, C.; Wang, S. Y.; Bark, R. A.; Zhang, S. Q.; Meng, J.; Qi, B.; Jones, P.; Wyngaardt, S. M.; Zhao, J.; Xu, C.; Zhou, S.-G.; Wang, S.; Sun, D. P.; Liu, L.; Li, Z. Q.; Zhang, N. B.; Jia, H.; Li, X. Q.; Hua, H.; Chen, Q. B.; Xiao, Z. G.; Li, H. J.; Zhu, L. H.; Bucher, T. D.; Dinoko, T.; Easton, J.; Juhász, K.; Kamblawe, A.; Khaleel, E.; Khumalo, N.; Lawrie, E. A.; Lawrie, J. J.; Majola, S. N. T.; Mullins, S. M.; Murray, S.; Ndayishimye, J.; Negi, D.; Noncolela, S. P.; Ntshangase, S. S.; Nyakó, B. M.; Orce, J. N.; Papka, P.; Sharpey-Schafer, J. F.; Shirinda, O.; Sithole, P.; Stankiewicz, M. A.; Wiedeking, M.

    2016-03-01

    Two pairs of positive-and negative-parity doublet bands together with eight strong electric dipole transitions linking their yrast positive- and negative-parity bands have been identified in 78Br. They are interpreted as multiple chiral doublet bands with octupole correlations, which is supported by the microscopic multidimensionally-constrained covariant density functional theory and triaxial particle rotor model calculations. This observation reports the first example of chiral geometry in octupole soft nuclei.

  9. Multiple Intelligences Centers and Projects.

    ERIC Educational Resources Information Center

    Chapman, Carolyn; Freeman, Lynn

    Based upon Gardner's theory of multiple intelligences, this book guides elementary school teachers through the process of using classroom learning centers and projects by providing choices for students. The guide is divided into two sections, providing the theoretical background and information on how to develop multiple intelligences learning…

  10. Indirect chiral separation and analyses in human biological fluids of the stereoisomers of a thienothiopyran-2-sulfonamide (TRUSOPT), a novel carbonic anhydrase inhibitor with two chiral centers in the molecule.

    PubMed

    Matuszewski, B K; Constanzer, M L

    1992-01-01

    The indirect chiral separation of the four stereoisomers (1)-(4) of a novel carbonic anhydrase inhibitor with two chiral centers in the molecule is reported. The method is based on chemical derivatization of the secondary amino group of the inhibitor with chiral isocyanate, formation of diastereomeric urea derivatives, each with three chiral centers in the molecule, and their separation under nonchiral HPLC conditions. The attempts to separate racemic mixture (1) + (2) from its diastereomeric counterpart (3) + (4) under nonchiral conditions, and to separate enantiomers (1) and (2) directly on a chiral stationary phase (CSP) are also reported. The indirect method was utilized for the assessment of an in vivo inversion of configuration at either one or both chiral centers of the molecule of (1). Analyses of selected whole blood and urine samples from human subjects after multiple bilateral topical ocular dosing with (1) did not reveal the presence of any of the three possible stereoisomers (2)-(4) of (1) indicating that the inversion of configuration at neither one nor two chiral centers of (1) occurs in vivo. PMID:1476862

  11. Search for multiple chiral doublets in rhodium isotopes

    SciTech Connect

    Peng, J.; Sagawa, H.; Zhang, S. Q.; Yao, J. M.; Zhang, Y.; Meng, J.

    2008-02-15

    The deformation in rhodium isotopes is investigated using adiabatic and configuration-fixed constrained triaxial relativistic mean field (RMF) approaches. The triaxial deformations are found in the ground states of {sup 102,104,106,108,110}Rh, which is consistent with triaxial Skyrme Hartree-Fock calculations. Several minima with triaxial deformation in {sup 104,106,108,110}Rh are obtained by the configuration-fixed constrained calculations. The corresponding configurations are characterized by the quantum numbers |nljm> obtained by transforming wave functions from a Cartesian basis to a spherical basis. The possible existence of multiple chiral doublets (M{chi}D) is demonstrated in {sup 104,106,108,110}Rh isotopes, based on different particle-hole configurations and triaxial deformations.

  12. 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. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26840015

  13. Multiple chiral doublet candidate nucleus {sup 105}Rh in a relativistic mean-field approach

    SciTech Connect

    Li Jian; Zhang, S. Q.; Meng, J.

    2011-03-15

    Following the reports of two pairs of chiral doublet bands observed in {sup 105}Rh, the adiabatic and configuration-fixed constrained triaxial relativistic mean-field calculations are performed to investigate their triaxial deformations with the corresponding configuration and the possible multiple chiral doublet (M{chi}D) phenomenon. The existence of the M{chi}D phenomenon in {sup 105}Rh is highly expected.

  14. Enantioselective synthesis of cyclopropanes that contain fluorinated tertiary stereogenic carbon centers: a chiral α-fluoro carbanion strategy.

    PubMed

    Shen, Xiao; Zhang, Wei; Zhang, Lei; Luo, Tao; Wan, Xiaolong; Gu, Yucheng; Hu, Jinbo

    2012-07-01

    Chiral transfer: the fluorinated sulfoximine (see scheme; Ts=p-toluenesulfonyl) was synthesized and used as the first chiral fluoromethylenation reagent for the synthesis of cyclopropanes that contain fluorinated tertiary stereogenic carbon centers in good yields, good diastereoselectivity, and excellent enantioselectivity. PMID:22689532

  15. 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

  16. Combined heterogeneous metal/chiral amine: multiple relay catalysis for versatile eco-friendly synthesis.

    PubMed

    Deiana, Luca; Jiang, Yan; Palo-Nieto, Carlos; Afewerki, Samson; Incerti-Pradillos, Celia A; Verho, Oscar; Tai, Cheuk-Wai; Johnston, Eric V; Córdova, Armando

    2014-03-24

    Herein is described a versatile and broad synergistic strategy for expansion of chemical space and the synthesis of valuable molecules (e.g. carbocycles and heterocycles), with up to three quaternary stereocenters, in a highly enantioselective fashion from simple alcohols (31 examples, 95:5 to >99.5:0.5 e.r.) using integrated heterogeneous metal/chiral amine multiple relay catalysis and air/O₂ as the terminal oxidant. A novel highly 1,4-selective heterogeneous metal/amine co-catalyzed hydrogenation of enals was also added to the relay catalysis sequences. PMID:24677482

  17. 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…

  18. 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.

  19. An In-tether Chiral Center Modulates the Helicity, Cell Permeability, and Target Binding Affinity of a Peptide.

    PubMed

    Hu, Kuan; Geng, Hao; Zhang, Qingzhou; Liu, Qisong; Xie, Mingsheng; Sun, Chengjie; Li, Wenjun; Lin, Huacan; Jiang, Fan; Wang, Tao; Wu, Yun-Dong; Li, Zigang

    2016-07-01

    The addition of a precisely positioned chiral center in the tether of a constrained peptide is reported, yielding two separable peptide diastereomers with significantly different helicity, as supported by circular dichroism (CD) and NMR spectroscopy. Single crystal X-ray diffraction analysis suggests that the absolute configuration of the in-tether chiral center in helical form is R, which is in agreement with theoretical simulations. The relationship between the secondary structure of the short peptides and their biochemical/biophysical properties remains elusive, largely because of the lack of proper controls. The present strategy provides the only method for investigating the influence of solely conformational differences upon the biochemical/biophysical properties of peptides. The significant differences in permeability and target binding affinity between the peptide diastereomers demonstrate the importance of helical conformation. PMID:27167181

  20. 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.

  1. Multiple Determinants of Caregiver Behavior in Child Care Centers

    ERIC Educational Resources Information Center

    de Schipper, Elles J.; Riksen-Walraven, J. Marianne; Geurts, Sabine A. E.

    2007-01-01

    In this study of the multiple determinants of professional caregiving, 237 caregivers (age range: 18-56 years) from 64 Dutch child care centers were extensively observed during their interactions with the children (0-4 years) in their usual care group. The choice of potential determinants of the caregiving quality was guided by Belsky's [Belsky,…

  2. Eight Biblical Interactive Learning Centers (Based on Gardner's Multiple Intelligences).

    ERIC Educational Resources Information Center

    Goldstein, Semadar

    This report describes how to implement Howard Gardner's multiple intelligences (MI) into Israel's Tanakh classrooms and includes samples of implemented materials. It also notes goals and obstacles encountered during this process and how they were overcome. To illustrate this process, the report provides an overview of Tanakh-centered activities…

  3. Phosphine-Catalyzed β,γ-Umpolung Domino Reaction of Allenic Esters: Facile Synthesis of Tetrahydrobenzofuranones Bearing a Chiral Tetrasubstituted Stereogenic Carbon Center.

    PubMed

    Takizawa, Shinobu; Kishi, Kenta; Yoshida, Yasushi; Mader, Steffen; Arteaga, Fernando Arteaga; Lee, Shoukou; Hoshino, Manabu; Rueping, Magnus; Fujita, Makoto; Sasai, Hiroaki

    2015-12-14

    An enantio-, diastereo-, regio-, and chemoselective phosphine-catalyzed β,γ-umpolung domino reaction of allenic esters with dienones has been developed for the first time. The designed sequence, involving oxy-Michael and Rauhut-Currier reactions, produced highly functionalized tetrahydrobenzofuranones, bearing a chiral tetrasubstituted stereogenic center, in up to 96 % ee. PMID:26537173

  4. Chiral four-dimensional F-theory compactifications with SU(5) and multiple U(1)-factors

    NASA Astrophysics Data System (ADS)

    Cvetič, Mirjam; Grassi, Antonella; Klevers, Denis; Piragua, Hernan

    2014-04-01

    We develop geometric techniques to determine the spectrum and the chiral indices of matter multiplets for four-dimensional F-theory compactifications on elliptic Calabi-Yau fourfolds with rank two Mordell-Weil group. The general elliptic fiber is the Calabi-Yau onefold in dP 2. We classify its resolved elliptic fibrations over a general base B. The study of singularities of these fibrations leads to explicit matter representations, that we determine both for U(1) × U(1) and SU(5) × U(1) × U(1) constructions. We determine for the first time certain matter curves and surfaces using techniques involving prime ideals. The vertical cohomology ring of these fourfolds is calculated for both cases and general formulas for the Euler numbers are derived. Explicit calculations are presented for a specific base B = ℙ3. We determine the general G 4-flux that belongs to of the resolved Calabi-Yau fourfolds. As a by-product, we derive for the first time all conditions on G 4-flux in general F-theory compactifications with a non-holomorphic zero section. These conditions have to be formulated after a circle reduction in terms of Chern-Simons terms on the 3D Coulomb branch and invoke M-theory/F-theory duality. New Chern-Simons terms are generated by Kaluza-Klein states of the circle compactification. We explicitly perform the relevant field theory computations, that yield non-vanishing results precisely for fourfolds with a non-holomorphic zero section. Taking into account the new Chern-Simons terms, all 4D matter chiralities are determined via 3D M-theory/F-theory duality. We independently check these chiralities using the subset of matter surfaces we determined. The presented techniques are general and do not rely on toric data.

  5. 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.

  6. 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.

  7. A norepinephrine coated magnetic molecularly imprinted polymer for simultaneous multiple chiral recognition.

    PubMed

    Chen, Juan; Liang, Ru-Ping; Wang, Xiao-Ni; Qiu, Jian-Ding

    2015-08-28

    A newly designed molecularly imprinted polymer (MIP) material was developed and successfully used as recognition element for enantioselective recognition by microchip electrophoresis. In this work, molecularly imprinted polymers were facilely prepared employing Fe3O4 nanoparticles (NPs) as the supporting substrate and norepinephrine as the functional monomer in the presence of template molecule in a weak alkaline solution. After extracting the embedded template molecules, the produced imprinted Fe3O4@polynorepinephrine (MIP-Fe3O4@PNE) NPs have cavities complementary to three dimensional shape of template molecules favoring high binding capacity and magnetism property for easy manipulation. The MIP-Fe3O4@PNE NPs prepared with l-tryptophan, l-valine, l-threonine, Gly-l-Phe, S-(-)-ofloxacin or S-(-)-binaphthol as template molecules were packed in the polydimethylsiloxane microchannel via magnetic field as novel stationary phase to successful enantioseparation of corresponding target analysts. The MIP-Fe3O4@PNE NPs-based microchip electrophoresis system exhibited strong recognition ability, excellent high-performance, admirable reproducibility and stability, which provided a powerful protocol for separation enantiomers within a short analytical time and opened up an avenue for multiplex chiral compound assay in various systems. PMID:26206627

  8. 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. PMID:25918365

  9. 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

  10. 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…

  11. 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

  12. Simultaneous chiral discrimination of multiple profens by cyclodextrin-modified capillary electrophoresis in normal and reversed polarity modes.

    PubMed

    La, Sookie; Kim, Jiyung; Kim, Jung-Han; Goto, Junichi; Kim, Kyoung-Rae

    2003-08-01

    Simultaneous enantioseparations of nine profens for their accurate chiral discrimination were achieved by capillary electrophoresis (CE) in the normal polarity (NP) mode with a single cyclodextrin (CD) system and in the reversed polarity (RP) mode with a dual CD system. The single CD system in the NP mode employed heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TMbetaCD) added at 75 mM-100 mM 2-(N-morpholino)ethanesulfonic acid buffer (pH 6.0) as the optimum run buffer. The dual CD system operated in the RP mode used 30 mM TMbetaCD and 1.0% anionic carboxymethyl-beta-cyclodextrin dissolved in pH 3.0, 100 mM phosphoric acid-triethanolamine buffer containing 0.01% hexadimethrine bromide added to reverse the electroosmotic flow. Fairly good enantiomeric resolutions and the opposite enantiomer migration orders were achieved in the two modes. Relative migration times to internal standard under respective optimum conditions were characteristic of each enantiomer with good precision (< 2% relative standard deviation, RSD), thereby enabling to crosscheck the chemical identification of profens and also their accurate chiralities. The method linearity in the two modes was found to be adequate (r > or = 0.9991) for the chiral assay of the profens investigated. Simultaneous enantiomeric purity test of ibuprofen, ketoprofen and flurbiprofen in a mixture was feasible in a single analysis by the present method. PMID:12900877

  13. 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. PMID:26018930

  14. 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.

  15. Chiral superconductors.

    PubMed

    Kallin, Catherine; Berlinsky, John

    2016-05-01

    Chiral superconductivity is a striking quantum phenomenon in which an unconventional superconductor spontaneously develops an angular momentum and lowers its free energy by eliminating nodes in the gap. It is a topologically non-trivial state and, as such, exhibits distinctive topological modes at surfaces and defects. In this paper we discuss the current theory and experimental results on chiral superconductors, focusing on two of the best-studied systems, Sr2RuO4, which is thought to be a chiral triplet p-wave superconductor, and UPt3, which has two low-temperature superconducting phases (in zero magnetic field), the lower of which is believed to be chiral triplet f-wave. Other systems that may exhibit chiral superconductivity are also discussed. Key signatures of chiral superconductivity are surface currents and chiral Majorana modes, Majorana states in vortex cores, and the possibility of half-flux quantum vortices in the case of triplet pairing. Experimental evidence for chiral superconductivity from μSR, NMR, strain, polar Kerr effect and Josephson tunneling experiments are discussed. PMID:27088452

  16. Chiral superconductors

    NASA Astrophysics Data System (ADS)

    Kallin, Catherine; Berlinsky, John

    2016-05-01

    Chiral superconductivity is a striking quantum phenomenon in which an unconventional superconductor spontaneously develops an angular momentum and lowers its free energy by eliminating nodes in the gap. It is a topologically non-trivial state and, as such, exhibits distinctive topological modes at surfaces and defects. In this paper we discuss the current theory and experimental results on chiral superconductors, focusing on two of the best-studied systems, Sr2RuO4, which is thought to be a chiral triplet p-wave superconductor, and UPt3, which has two low-temperature superconducting phases (in zero magnetic field), the lower of which is believed to be chiral triplet f-wave. Other systems that may exhibit chiral superconductivity are also discussed. Key signatures of chiral superconductivity are surface currents and chiral Majorana modes, Majorana states in vortex cores, and the possibility of half-flux quantum vortices in the case of triplet pairing. Experimental evidence for chiral superconductivity from μSR, NMR, strain, polar Kerr effect and Josephson tunneling experiments are discussed.

  17. The Multiple Facets of Iodine(III) Compounds in an Unprecedented Catalytic Auto-amination for Chiral Amine Synthesis.

    PubMed

    Buendia, Julien; Grelier, Gwendal; Darses, Benjamin; Jarvis, Amanda G; Taran, Frédéric; Dauban, Philippe

    2016-06-20

    Iodine(III) reagents are used in catalytic one-pot reactions, first as both oxidants and substrates, then as cross-coupling partners, to afford chiral polyfunctionalized amines. The strategy relies on an initial catalytic auto C(sp(3) )-H amination of the iodine(III) oxidant, which delivers an amine-derived iodine(I) product that is subsequently used in palladium-catalyzed cross-couplings to afford a variety of useful building blocks with high yields and excellent stereoselectivities. This study demonstrates the concept of self-amination of the hypervalent iodine reagents, which increases the value of the aryl moiety. PMID:27158802

  18. Evaluation of immunomodulatory drugs in multiple myeloma: single center experience

    PubMed Central

    Ozkan, Melda Comert; Tombuloglu, Murat; Sahin, Fahri; Saydam, Guray

    2015-01-01

    Objective: Multiple myeloma (MM) comprises 1% of all cancers and 10% of hematologic malignancies and known as an incurable disease. The introduction of immunomodulatory drugs (IMiDs) has brought a major shift in therapeutic paradigm in the treatment of newly diagnosed and relapsed/refractory MM patients. The aim of this study was to evaluate the relationship between response status and hematological parameters in patients with MM treated with thalidomide or lenalidomide. Methods: Sixty-eight patients who were treated with IMiDs in Ege University, School of Medicine, Department of Hematology, between 2005 and 2012, were evaluated, retrospectively. Results and Conclusion: We could not find any difference between the hematological parameters before and after the treatment neither with thalidomide nor lenalidomide. However, the heterogenity of our groups, the difference in treatment strategies and potential side effects would have an impact on this result. It is needed to perform prospective clinical trials to prove that whether correction of hematological parameters would reflect the response status in patients with myeloma that treated with IMiDs. PMID:27069758

  19. A Chiral Granular Gas

    NASA Astrophysics Data System (ADS)

    Tsai, J.-C.; Ye, Fangfu; Rodriguez, Juan; Gollub, J. P.; Lubensky, T. C.

    2005-05-01

    Inspired by rattleback toys, we created small chiral wires that rotate in a preferred direction on a vertically oscillating platform and quantified their motion with experiment and simulation. We demonstrate experimentally that angular momentum of rotation about particle centers of mass is converted to collective angular momentum of center-of-mass motion in a granular gas of these wires, and we introduce a continuum model that explains our observations.

  20. A chiral granular gas.

    PubMed

    Tsai, J-C; Ye, Fangfu; Rodriguez, Juan; Gollub, J P; Lubensky, T C

    2005-06-01

    Inspired by rattleback toys, we created small chiral wires that rotate in a preferred direction on a vertically oscillating platform and quantified their motion with experiment and simulation. We demonstrate experimentally that angular momentum of rotation about particle centers of mass is converted to collective angular momentum of center-of-mass motion in a granular gas of these wires, and we introduce a continuum model that explains our observations. PMID:16090323

  1. Chiral Graphene Quantum Dots.

    PubMed

    Suzuki, Nozomu; Wang, Yichun; Elvati, Paolo; Qu, Zhi-Bei; Kim, Kyoungwon; Jiang, Shuang; Baumeister, Elizabeth; Lee, Jaewook; Yeom, Bongjun; Bahng, Joong Hwan; Lee, Jaebeom; Violi, Angela; Kotov, Nicholas A

    2016-02-23

    Chiral nanostructures from metals and semiconductors attract wide interest as components for polarization-enabled optoelectronic devices. Similarly to other fields of nanotechnology, graphene-based materials can greatly enrich physical and chemical phenomena associated with optical and electronic properties of chiral nanostructures and facilitate their applications in biology as well as other areas. Here, we report that covalent attachment of l/d-cysteine moieties to the edges of graphene quantum dots (GQDs) leads to their helical buckling due to chiral interactions at the "crowded" edges. Circular dichroism (CD) spectra of the GQDs revealed bands at ca. 210-220 and 250-265 nm that changed their signs for different chirality of the cysteine edge ligands. The high-energy chiroptical peaks at 210-220 nm correspond to the hybridized molecular orbitals involving the chiral center of amino acids and atoms of graphene edges. Diverse experimental and modeling data, including density functional theory calculations of CD spectra with probabilistic distribution of GQD isomers, indicate that the band at 250-265 nm originates from the three-dimensional twisting of the graphene sheet and can be attributed to the chiral excitonic transitions. The positive and negative low-energy CD bands correspond to the left and right helicity of GQDs, respectively. Exposure of liver HepG2 cells to L/D-GQDs reveals their general biocompatibility and a noticeable difference in the toxicity of the stereoisomers. Molecular dynamics simulations demonstrated that d-GQDs have a stronger tendency to accumulate within the cellular membrane than L-GQDs. Emergence of nanoscale chirality in GQDs decorated with biomolecules is expected to be a general stereochemical phenomenon for flexible sheets of nanomaterials. PMID:26743467

  2. 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

  3. 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.

  4. Importance of the Chiral Centers of Jasmonic Acid in the Responses of Plants (Activities and Antagonism between Natural and Synthetic Analogs).

    PubMed Central

    Holbrook, L.; Tung, P.; Ward, K.; Reid, D. M.; Abrams, S.; Lamb, N.; Quail, J. W.; Moloney, M. M.

    1997-01-01

    The importance of the two chiral centers at C-3 and C-7 in the molecular structure of jasmonic acid in plant responses was investigated. We separated methyl jasmonate (MeJA) into (3R)- and (3S)-isomers with a fixed stereochemistry at C-3, but epimerization at C-7 is possible. The four isomers of the nonepimerizable analog 7-methyl MeJA were synthesized. These six esters and their corresponding acids were tested in three bioassays: (a) senescence in sunflower (Helianthus annuus) cotyledons; (b) proteinase inhibitor II gene expression in transgenic tobacco (Nicotiana tabacum) with [beta]-glucuronidase as a biochemical reporter; and (c) seed germination in Brassica napus and wheat (Triticum aestivum). The esters and acids had similar activities in the three assays, with the ester being more effective than its acid. The (3R)-stereochemistry was critical for jasmonate activity. Although activity was reduced after substituting the C-7 proton with a methyl group, the analogs with (3R,7R)- or (3R,7S)-stereochemistry were active in some of the assays. Although the four isomers of 7-methyl MeJA were inactive or only weakly active in the senescence assay, they could overcome the senescence-promoting effect of (3R)-MeJA. The strongest antagonistic effect was observed with the (3R,7S)-isomer. PMID:12223716

  5. 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...

  6. 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…

  7. Excitation of surface plasmon polariton modes with multiple nitrogen vacancy centers in single nanodiamonds

    NASA Astrophysics Data System (ADS)

    Kumar, Shailesh; Lausen, Jens L.; Garcia-Ortiz, Cesar E.; Andersen, Sebastian K. H.; Roberts, Alexander S.; Radko, Ilya P.; Smith, Cameron L. C.; Kristensen, Anders; Bozhevolnyi, Sergey I.

    2016-02-01

    Nitrogen-vacancy (NV) centers in diamonds are interesting due to their remarkable characteristics that are well suited to applications in quantum-information processing and magnetic field sensing, as well as representing stable fluorescent sources. Multiple NV centers in nanodiamonds (NDs) are especially useful as biological fluorophores due to their chemical neutrality, brightness and room-temperature photostability. Furthermore, NDs containing multiple NV centers also have potential in high-precision magnetic field and temperature sensing. Coupling NV centers to propagating surface plasmon polariton (SPP) modes gives a base for lab-on-a-chip sensing devices, allows enhanced fluorescence emission and collection which can further enhance the precision of NV-based sensors. Here, we investigate coupling of multiple NV centers in individual NDs to the SPP modes supported by silver surfaces protected by thin dielectric layers and by gold V-grooves (VGs) produced via the self-terminated silicon etching. In the first case, we concentrate on monitoring differences in fluorescence spectra obtained from a source ND, which is illuminated by a pump laser, and from a scattering ND illuminated only by the fluorescence-excited SPP radiation. In the second case, we observe changes in the average NV lifetime when the same ND is characterized outside and inside a VG. Fluorescence emission from the VG terminations is also observed, which confirms the NV coupling to the VG-supported SPP modes.

  8. Inherently Chiral Calixarenes: Synthesis, Optical Resolution, Chiral Recognition and Asymmetric Catalysis

    PubMed Central

    Li, Shao-Yong; Xu, Yao-Wei; Liu, Jun-Min; Su, Cheng-Yong

    2011-01-01

    Inherently chiral calixarenes, whose chirality is based on the absence of a planar symmetry or an inversion center in the molecules as a whole through the asymmetric array of several achiral groups upon the three-dimensional calix-skeletons, are challenging and attractive chiral molecules, because of their potential in supramolecular chemistry. The synthesis and optical resolution of all varieties of inherently chiral calixarenes are systematically discussed and classified, and their applications in chiral recognition and asymmetric catalysis are thoroughly illustrated in this review. PMID:21339996

  9. 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. PMID:24749637

  10. Punctuated Chirality

    NASA Astrophysics Data System (ADS)

    Gleiser, Marcelo; Thorarinson, Joel; Walker, Sara Imari

    2008-12-01

    Most biomolecules occur in mirror, or chiral, images of each other. However, life is homochiral: proteins contain almost exclusively L-amino acids, while only D-sugars appear in RNA and DNA. The mechanism behind this fundamental asymmetry of life remains an open problem. Coupling the spatiotemporal evolution of a general autocatalytic polymerization reaction network to external environmental effects, we show through a detailed statistical analysis that high intensity and long duration events may drive achiral initial conditions towards chirality. We argue that life’s homochirality resulted from sequential chiral symmetry breaking triggered by environmental events, thus extending the theory of punctuated equilibrium to the prebiotic realm. Applying our arguments to other potentially life-bearing planetary platforms, we predict that a statistically representative sampling will be racemic on average.

  11. Punctuated chirality.

    PubMed

    Gleiser, Marcelo; Thorarinson, Joel; Walker, Sara Imari

    2008-12-01

    Most biomolecules occur in mirror, or chiral, images of each other. However, life is homochiral: proteins contain almost exclusively L-amino acids, while only D-sugars appear in RNA and DNA. The mechanism behind this fundamental asymmetry of life remains an open problem. Coupling the spatiotemporal evolution of a general autocatalytic polymerization reaction network to external environmental effects, we show through a detailed statistical analysis that high intensity and long duration events may drive achiral initial conditions towards chirality. We argue that life's homochirality resulted from sequential chiral symmetry breaking triggered by environmental events, thus extending the theory of punctuated equilibrium to the prebiotic realm. Applying our arguments to other potentially life-bearing planetary platforms, we predict that a statistically representative sampling will be racemic on average. PMID:18841492

  12. 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

  13. 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.

  14. Chiral streamers

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

  15. 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

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

    PubMed Central

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

    2015-01-01

    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

  17. Multiplicity of europium centers in doped stoichiometric crystals of lithium niobate

    NASA Astrophysics Data System (ADS)

    Kaplyanskii, A. A.; Kapphan, S.; Kutsenko, A. B.; Polgar, K.; Skvortsov, A. P.

    2007-04-01

    The optical spectra of europium-doped stoichiometric lithium niobate (LiNbO3:Eu3+) crystals have been studied using combined excitation-luminescence spectroscopy in the range of 5D0 → 7F1, 7F0 optical transitions. Analysis of the results shows that Eu3+ ions can occupy 14 energetically nonequivalent positions in the LiNbO3 crystal lattice. This multiplicity of impurity centers is related to possible variants of the incorporation of Eu3+ ions into the LiNbO3 crystal lattice and the compensation of excess charge. Energy positions of the 5D0 level and the lowest sublevel of the 7F1 Stark multiplet are determined for Eu3+ centers of all 14 types.

  18. Worldwide phylogeography of wild boar reveals multiple centers of pig domestication.

    PubMed

    Larson, Greger; Dobney, Keith; Albarella, Umberto; Fang, Meiying; Matisoo-Smith, Elizabeth; Robins, Judith; Lowden, Stewart; Finlayson, Heather; Brand, Tina; Willerslev, Eske; Rowley-Conwy, Peter; Andersson, Leif; Cooper, Alan

    2005-03-11

    Mitochondrial DNA (mtDNA) sequences from 686 wild and domestic pig specimens place the origin of wild boar in island Southeast Asia (ISEA), where they dispersed across Eurasia. Previous morphological and genetic evidence suggested pig domestication took place in a limited number of locations (principally the Near East and Far East). In contrast, new genetic data reveal multiple centers of domestication across Eurasia and that European, rather than Near Eastern, wild boar are the principal source of modern European domestic pigs. PMID:15761152

  19. Multiple Bragg diffraction at W point in the face centered cubic photonic crystals

    NASA Astrophysics Data System (ADS)

    Nair, Rajesh V.; Jagatap, Bhagawantrao N.

    2015-01-01

    We report the experimental observation of multiple Bragg diffraction that occurs when the tip of the incident wave vector lies on a line joining the L and W points in the Brillouin zone of a face-centered cubic (FCC) photonic crystal. The multiple Bragg diffraction is analyzed for photonic crystals with different lattice constants and refractive index contrasts. Angle-dependent reflectance spectroscopy indicates strong hybridization of diffraction resonances when the tip of the incident wave vector crosses the W point and the multiple Bragg diffraction is seen to be extended over an angular range of 8 deg around the W point. We also observe a new diffraction resonance in the short-wavelength region for wave vectors shifting toward the W point in the hexagonal facet of the FCC Brillouin zone. Each diffraction resonance is fitted using the Bragg's law for different planes in the FCC photonic crystal taking into account the internal angle between the planes. The diffraction resonances in the multiple Bragg diffraction regime are assigned to FCC crystal planes with Miller indices (111), (200), (1¯11), and (220). Our results have implications for diverse kinds of wave propagations in periodic structures and applications in light emission, sensing, and structural color pigments.

  20. Chiral mirrors

    SciTech Connect

    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.

  1. Enantioselective Recognition for Many Different Kinds of Chiral Guests by One Chiral Receptor Based on Tetraphenylethylene Cyclohexylbisurea.

    PubMed

    Xiong, Jia-Bin; Xie, Wen-Zhao; Sun, Jian-Ping; Wang, Jin-Hua; Zhu, Zhi-Hua; Feng, Hai-Tao; Guo, Dong; Zhang, Hui; Zheng, Yan-Song

    2016-05-01

    A neutral chiral receptor based on TPE cyclohexylbisurea was synthesized and could discriminate the enantiomers of many different kinds of chiral reagents, including chiral acidic compounds, basic compounds, amino acids, and even neutral alcohols. The (1)H NMR spectra disclosed that the ability of chiral recognition could be ascribed to the multiple hydrogen bonds and CH-π interactions between the TPE urea receptor and the enantiomer of the chiral guest, which led to the selective aggregation of the receptor with one of the two enantiomers. This result exhibited a great potential in enantiomer discernment and high-throughput analysis of enantiomer composition of these chiral analytes by one chiral AIE molecule. PMID:27032054

  2. Chirality of Viral Capsids

    NASA Astrophysics Data System (ADS)

    Dharmavaram, Sanjay; Xie, Fangming; Bruinsma, Robijn; Klug, William; Rudnick, Joseph

    Most icosahedral viruses are classified by their T-number which identifies their capsid in terms of the number of capsomers and their relative arrangement. Certain T-numbers (T = 7 for instance) are inherently chiral (with no reflection planes) while others (e.g. T = 1) are achiral. We present a Landau-Brazovskii (LB) theory for weak crystallization in which a scalar order parameter that measures density of capsid proteins successfully predicts the various observed T-numbers and their respective chiralities. We find that chiral capsids gain stability by spontaneously breaking symmetry from an unstable chiral state. The inherently achiral LB-free energy does not preferentially select a particular chiral state from its mirror reflection. Based on the physical observation that proteins are inherently chiral molecules with directional interactions, we propose a new chiral term to the LB energy as a possible selection mechanism for chirality.

  3. 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

  4. 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

  5. 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.

  6. 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.

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

    PubMed Central

    Bryant, Dean; Seckinger, Anja; Hose, Dirk; Zojer, Niklas; Sahota, Surinder S.

    2015-01-01

    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. PMID:25929340

  8. 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

  9. Electronic circular dichroism behavior of chiral Phthiobuzone

    PubMed Central

    Li, Li; Wang, Lin; Si, Yikang

    2014-01-01

    Phthiobuzone is a bis(thiosemicarbazone) derivative with a single chiral center which has been used as a racemate in the clinical treatment of herpes and trachoma diseases. In this study, its two enantiomers were prepared from chiral amino acids and their absolute configurations were investigated by electronic circular dichroism (ECD) combined with modern quantum-chemical calculations using time-dependent density functional theory. It was found that solvation changed both the conformational distribution and the ECD spectrum of each conformer. The theoretical ECD spectra of the two enantiomers were in good agreement with the experimentally determined spectra of the corresponding isomers in dimethyl sulfoxide. The ECD behavior of the bis(thiosemicarbazone) chromophore in a chiral environment is also discussed. Our results indicate that ECD spectroscopy may be a useful tool for the stereochemical evaluation of chiral drugs. PMID:26579380

  10. Controlling and imaging chiral spin textures

    NASA Astrophysics Data System (ADS)

    Chen, Gong

    Chirality in magnetic materials is fundamentally interesting and holds potential for logic and memory applications. Using spin-polarized low-energy electron microscopy at National Center for Electron Microscopy, we recently observed chiral domain walls in thin films. We developed ways to tailor the Dzyaloshinskii-Moriya interaction, which drives the chirality, by interface engineering and by forming ternary superlattices. We find that spin-textures can be switched between left-handed, right-handed, cycloidal, helical and mixed domain wall structures by controlling uniaxial strain in magnetic films. We also demonstrate an experimental approach to stabilize skyrmions in magnetic multilayers without external magnetic field. These results exemplify the rich physics of chirality associated with interfaces of magnetic materials

  11. Asymmetric Synthesis of Chiral Atropisomeric Bis-Aryl Organophosphorus from Menthyl H-Phosphinate.

    PubMed

    Ma, Yan-Na; Yang, Shang-Dong

    2016-04-01

    This review describes new methods for the synthesis of chiral monophosphine ligands with menthyl phenylphosphinate as a chiral auxiliary through asymmetric Suzuki-Miyaura cross-coupling reactions and asymmetric C-H functionalization. The chiral menthyl phenylphosphinate as a chiral auxiliary is easy to prepare and the menthyl group can easily be transformed into other functional groups, with the chiral center synchronously remaining. These methodologies provide highly efficient and practical strategies for the synthesis of novel axially chiral biaryl monophosphine oxides and their corresponding phosphines. Meanwhile, these reactions are easy to handle and exhibit wide scope for substrates with excellent diastereomeric ratios. PMID:26991107

  12. Chirality in nonlinear optics.

    PubMed

    Haupert, Levi M; Simpson, Garth J

    2009-01-01

    The past decade has witnessed the emergence of new measurement approaches and applications for chiral thin films and materials enabled by the observations of the high sensitivity of second-order nonlinear optical measurements to chirality. In thin films, the chiral response to second harmonic generation and sum frequency generation (SFG) from a single molecular monolayer is often comparable with the achiral response. The chiral specificity also allows for symmetry-allowed SFG in isotropic chiral media, confirming predictions made approximately 50 years ago. With these experimental demonstrations in hand, an important challenge is the construction of intuitive predictive models that allow the measured chiral response to be meaningfully related back to molecular and macromolecular structure. This review defines and considers three distinct mechanisms for chiral effects in uniaxially oriented assemblies: orientational chirality, intrinsic chirality, and isotropic chirality. The role of each is discussed in experimental and computational studies of bacteriorhodopsin films, binaphthol, and collagen. Collectively, these three model systems support a remarkably simple framework for quantitatively recovering the measured chiral-specific activity. PMID:19046125

  13. Chirality in Nonlinear Optics

    NASA Astrophysics Data System (ADS)

    Haupert, Levi M.; Simpson, Garth J.

    2009-05-01

    The past decade has witnessed the emergence of new measurement approaches and applications for chiral thin films and materials enabled by the observations of the high sensitivity of second-order nonlinear optical measurements to chirality. In thin films, the chiral response to second harmonic generation and sum frequency generation (SFG) from a single molecular monolayer is often comparable with the achiral response. The chiral specificity also allows for symmetry-allowed SFG in isotropic chiral media, confirming predictions made ˜50 years ago. With these experimental demonstrations in hand, an important challenge is the construction of intuitive predictive models that allow the measured chiral response to be meaningfully related back to molecular and macromolecular structure. This review defines and considers three distinct mechanisms for chiral effects in uniaxially oriented assemblies: orientational chirality, intrinsic chirality, and isotropic chirality. The role of each is discussed in experimental and computational studies of bacteriorhodopsin films, binaphthol, and collagen. Collectively, these three model systems support a remarkably simple framework for quantitatively recovering the measured chiral-specific activity.

  14. 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,…

  15. 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)

  16. 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%.

  17. Regional gray matter atrophy in relapsing remitting multiple sclerosis: baseline analysis of multi-center data.

    PubMed

    Datta, Sushmita; Staewen, Terrell D; Cofield, Stacy S; Cutter, Gary R; Lublin, Fred D; Wolinsky, Jerry S; Narayana, Ponnada A

    2015-03-01

    Regional gray matter (GM) atrophy in multiple sclerosis (MS) at disease onset and its temporal variation can provide objective information regarding disease evolution. An automated pipeline for estimating atrophy of various GM structures was developed using tensor based morphometry (TBM) and implemented on a multi-center sub-cohort of 1008 relapsing remitting MS (RRMS) patients enrolled in a Phase 3 clinical trial. Four hundred age and gender matched healthy controls were used for comparison. Using the analysis of covariance, atrophy differences between MS patients and healthy controls were assessed on a voxel-by-voxel analysis. Regional GM atrophy was observed in a number of deep GM structures that included thalamus, caudate nucleus, putamen, and cortical GM regions. General linear regression analysis was performed to analyze the effects of age, gender, and scanner field strength, and imaging sequence on the regional atrophy. Correlations between regional GM volumes and expanded disability status scale (EDSS) scores, disease duration (DD), T2 lesion load (T2 LL), T1 lesion load (T1 LL), and normalized cerebrospinal fluid (nCSF) were analyzed using Pearson׳s correlation coefficient. Thalamic atrophy observed in MS patients compared to healthy controls remained consistent within subgroups based on gender and scanner field strength. Weak correlations between thalamic volume and EDSS (r=-0.133; p<0.001) and DD (r=-0.098; p=0.003) were observed. Of all the structures, thalamic volume moderately correlated with T2 LL (r=-0.492; P-value<0.001), T1 LL (r=-0.473; P-value<0.001) and nCSF (r=-0.367; P-value<0.001). PMID:25787188

  18. 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

  19. Regional Gray Matter Atrophy in Relapsing Remitting Multiple Sclerosis: Baseline Analysis of Multi-Center Data

    PubMed Central

    Datta, Sushmita; Staewen, Terrell D.; Cofield, Stacy S.; Cutter, Gary R.; Lublin, Fred D.; Wolinsky, Jerry S.; Narayana, Ponnada A.

    2015-01-01

    Regional gray matter (GM) atrophy in multiple sclerosis (MS) at disease onset and its temporal variation can provide objective information regarding disease evolution. An automated pipeline for estimating atrophy of various GM structures was developed using tensor based morphometry (TBM) and implemented on a multi-center sub-cohort of 1008 relapsing remitting MS (RRMS) patients enrolled in a Phase 3 clinical trial. Four hundred age and gender matched healthy controls were used for comparison. Using the analysis of covariance, atrophy differences between MS patients and healthy controls were assessed on a voxel-by-voxel analysis. Regional GM atrophy was observed in a number of deep GM structures that included thalamus, caudate nucleus, putamen, and cortical GM regions. General linear regression analysis was performed to analyze the effects of age, gender, and scanner field strength, and imaging sequence on the regional atrophy. Correlations between regional GM volumes and expanded disability status scale (EDSS) scores, disease duration (DD), T2 lesion load (T2 LL), T1 lesion load (T1 LL), and normalized cerebrospinal fluid (nCSF) were analyzed using Pearson’s correlation coefficient. Thalamic atrophy observed in MS patients compared to healthy controls remained consistent within subgroups based on gender and scanner field strength. Weak correlations between thalamic volume and EDSS (r = −0.133; p < 0.001) and DD (r = −0.098; p = 0.003) were observed. Of all the structures, thalamic volume moderately correlated with T2 LL (r = −0.492; p-value < 0.001), T1 LL (r = −0.473; p-value < 0.001) and nCSF (r = −0.367; p-value < 0.001). PMID:25787188

  20. 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. PMID:25801825

  1. 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

  2. A molecular propeller effect for chiral separation and analysis.

    PubMed

    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

  3. 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.

  4. Planar plasmonic chiral nanostructures.

    PubMed

    Zu, Shuai; Bao, Yanjun; Fang, Zheyu

    2016-02-21

    A strong chiral optical response induced at a plasmonic Fano resonance in a planar Au heptamer nanostructure was experimentally and theoretically demonstrated. The scattering spectra show the characteristic narrow-band feature of Fano resonances for both left and right circular polarized lights, with a chiral response reaching 30% at the Fano resonance. Specifically, we systematically investigate the chiral response of planar heptamers with gradually changing the inter-particle rotation angles and separation distance. The chiral spectral characteristics clearly depend on the strength of Fano resonances and the associated near-field optical distributions. Finite element method simulations together with a multipole expansion method demonstrate that the enhanced chirality is caused by the excitation of magnetic quadrupolar and electric toroidal dipolar modes. Our work provides an effective method for the design of 2D nanostructures with a strong chiral response. PMID:26818746

  5. Axially chiral BODIPYs.

    PubMed

    Lerrick, Reinner I; Winstanley, Thomas P L; Haggerty, Karen; Wills, Corinne; Clegg, William; Harrington, Ross W; Bultinck, Patrick; Herrebout, Wouter; Benniston, Andrew C; Hall, Michael J

    2014-05-11

    The synthesis and resolution of a class of chiral organic fluorophores, axially chiral 4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes (Ax*-BODIPY), is described. Ax*-BODIPYs were prepared through a modular synthesis combined with a late stage Heck functionalisation. Resolution was achieved by preparative chiral HPLC. Absolute stereochemical assignment was performed by comparison of experimental ECD spectra with TD-DFT calculations. PMID:24676233

  6. 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.

  7. Chiral atomically thin films.

    PubMed

    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. PMID:26900756

  8. Multiple-order resonant Raman scattering of the localized molecular rose center in BaF 2

    NASA Astrophysics Data System (ADS)

    Deyhimi, Farzad; Bill, Hans

    1983-11-01

    The rose center in BaF 2 is investigated by resonant Raman scattering. The spectra obtained at liquid-helium temperature show multiple order and combination bands of the internal local modes (up to the sixth order), and associated side bands of the lattice. The temperature dependence of the linewidth of the local-mode transitions has been investigated and is explained as being due to anharmonic coupling to the lattice.

  9. Religious-Centered Multiethnic Societies: Multiple Identities and Ethnopolitics in Latvia.

    ERIC Educational Resources Information Center

    Karklins, Rasma; Zepa, Brigita

    1996-01-01

    Maintains that people have multiple identities and discusses how these differential identities were realigned in Latvia during and after the collapse of the Soviet Union. Survey data suggests current ethnopolitical identity incorporates multiple dimensions and a strong contextual component. Includes graphs and tables of statistical data. (MJP)

  10. 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.

  11. Chiral Drugs: An Overview

    PubMed Central

    Nguyen, Lien Ai; He, Hua; Pham-Huy, Chuong

    2006-01-01

    About more than half of the drugs currently in use are chiral compounds and near 90% of the last ones are marketed as racemates consisting of an equimolar mixture of two enantiomers. Although they have the same chemical structure, most isomers of chiral drugs exhibit marked differences in biological activities such as pharmacology, toxicology, pharmacokinetics, metabolism etc. Some mechanisms of these properties are also explained. Therefore, it is important to promote the chiral separation and analysis of racemic drugs in pharmaceutical industry as well as in clinic in order to eliminate the unwanted isomer from the preparation and to find an optimal treatment and a right therapeutic control for the patient. In this article, we review the nomenclature, pharmacology, toxicology, pharmacokinetics, metabolism etc of some usual chiral drugs as well as their mechanisms. Different techniques used for the chiral separation in pharmaceutical industry as well as in clinical analyses are also examined. PMID:23674971

  12. A study of steric chirality: the chiral nematic phase of a system of chiral two-site HGO molecules

    NASA Astrophysics Data System (ADS)

    Varga, Szabolcs; Jackson, George

    2011-03-01

    The liquid crystalline phase behaviour of a chiral two-site hard Gaussian overlap fluid is examined using the well-known Parsons-Lee extension of the theory of Onsager. The hard-core model is constructed such that the vector connecting the centers of two hard Gaussian segments is perpendicular to the long axes of both segments. The microscopic chirality of the particle can be controlled with the dihedral angle between the long axes of the hard Gaussian segments, the distance between the two segments, and the length-to-breath ratios of each segment. In the framework of the Parsons-Lee approach three different types of phases are considered, namely, the isotropic liquid state, and the nematic and the chiral nematic (cholesteric) liquid crystalline states. For simplicity, the orientation of the particles is restricted to the plane perpendicular to the twist axis, and the particles do not have internal freedom to rotate around their main symmetry axes. The geometric condition for the formation of a chiral nematic phase, the properties of the helical structure, and the phase boundary of the ordering transition are determined by means of a free energy minimization. It is shown that steric (shape) chirality always gives rise to a helical structure in the nematic phase, and that the low density chiral systems can undergo a transition from an isotropic liquid to a twisted nematic phase on increasing the density. Analytical expressions are obtained for the twist period (pitch) in the limit of parallel stacking of the rod-like segments in layers normal to the helical axis, which are only valid for systems characterized by weak chiral strengths. A key finding of the numerical calculations is that the pitch is very sensitive to the segment separation, but not to the density or aspect ratio. It is interesting to note that the inverse of the pitch is predicted to depend linearly on the dihedral angle in all of the cases studied.

  13. Evaluation of Multiple Outcomes in the Child Parent Center Compensatory Education Program: Year II.

    ERIC Educational Resources Information Center

    Eash, Maurice J.; And Others

    Results are reported from the second year of a longitudinal evaluation of Child Parent Centers (CPC's) serving low-income urban children. Six-year-old participants and nine-year-old former participants and comparison groups were analyzed on measures including reading and mathematics achievement, internal-external control belief, and…

  14. Large-scale green chemical synthesis of adjacent quaternary chiral centers by continuous flow photodecarbonylation of aqueous suspensions of nanocrystalline ketones.

    PubMed

    Hernández-Linares, María Guadalupe; Guerrero-Luna, Gabriel; Pérez-Estrada, Salvador; Ellison, Martha; Ortin, Maria-Mar; Garcia-Garibay, Miguel A

    2015-02-01

    To demonstrate the ease of scale-up and synthetic potential of some organic solid state reactions, we report the synthesis, crystallization, and solid state photochemistry of acyclic, homochiral, hexasubstituted (+)-(2R,4S)-2-carbomethoxy-4-cyano-2,4-diphenyl-3-pentanone 1. We demonstrate that solid state photodecarbonylation of (+)-(2R,4S)-1 affords (+)-(2R,3R)-2-carbomethoxy-3-cyano-2,3-diphenyl-butane 2 with two adjacent stereogenic, all-carbon substituted quaternary centers, in quantitative chemical yield and 100% diastereoselectivity and enantiomeric excess. The efficient multigram photodecarbonylation of (+)-(2R,4S)-1 as a nanocrystalline suspension in water using a continuous flow photoreactor shows that the large-scale synthesis of synthetically challenging compounds using photochemical synthesis in the solid state can be executed in a remarkably simple manner. PMID:25578232

  15. Chiral Perturbation Theory

    NASA Astrophysics Data System (ADS)

    Tiburzi, Brian C.

    The era of high-precision lattice QCD has led to synergy between lattice computations and phenomenological input from chiral perturbation theory. We provide an introduction to chiral perturbation theory with a bent towards understanding properties of the nucleon and other low-lying baryons. Four main topics are the basis for this chapter. We begin with a discussion of broken symmetries and the procedure to construct the chiral Lagrangian. The second topic concerns specialized applications of chiral perturbation theory tailored to lattice QCD, such as partial quenching, lattice discretization, and finite-volume effects. We describe inclusion of the nucleon in chiral perturbation theory using a heavy-fermion Euclidean action. Issues of convergence are taken up as our final topic. We consider expansions in powers of the strange-quark mass, and the appearance of unphysical singularities in the heavy-particle formulation. Our aim is to guide lattice practitioners in understanding the predictions chiral perturbation theory makes for baryons, and show how the lattice will play a role in testing the rigor of the chiral expansion at physical values of the quark masses.

  16. Applications of chiral symmetry

    SciTech Connect

    Pisarski, R.D.

    1995-03-01

    The author discusses several topics in the applications of chiral symmetry at nonzero temperature. First, where does the rho go? The answer: up. The restoration of chiral symmetry at a temperature T{sub {chi}} implies that the {rho} and a{sub 1} vector mesons are degenerate in mass. In a gauged linear sigma model the {rho} mass increases with temperature, m{sub {rho}}(T{sub {chi}}) > m{sub {rho}}(0). The author conjectures that at T{sub {chi}} the thermal {rho} - a{sub 1}, peak is relatively high, at about {approximately}1 GeV, with a width approximately that at zero temperature (up to standard kinematic factors). The {omega} meson also increases in mass, nearly degenerate with the {rho}, but its width grows dramatically with temperature, increasing to at least {approximately}100 MeV by T{sub {chi}}. The author also stresses how utterly remarkable the principle of vector meson dominance is, when viewed from the modern perspective of the renormalization group. Secondly, he discusses the possible appearance of disoriented chiral condensates from {open_quotes}quenched{close_quotes} heavy ion collisions. It appears difficult to obtain large domains of disoriented chiral condensates in the standard two flavor model. This leads to the last topic, which is the phase diagram for QCD with three flavors, and its proximity to the chiral critical point. QCD may be very near this chiral critical point, and one might thereby generated large domains of disoriented chiral condensates.

  17. Chirality control in oligothiophene through chiral wrapping.

    PubMed

    Sanji, Takanobu; Kato, Nobu; Tanaka, Masato

    2006-01-19

    [structure: see text] Mixing oligothiophenes and polysaccharides, such as amylose and schizophyllan, affords novel inclusion complexes, in which oligothiophene guests adopt twisted conformation in the chiral channel created by left- or right-handed helical wrapping with the polysaccharide host polymers, leading to optical activity. PMID:16408883

  18. 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

  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. 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

  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. 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

  3. 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.

  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. Scalemic and racemic imprinting with a chiral crosslinker.

    PubMed

    Hebert, Britney; Meador, Danielle S; Spivak, David A

    2015-08-26

    The development of molecularly imprinted chiral stationary phases has traditionally been limited by the need for a chiral pure template. Paradoxically, availability of a chiral pure template largely defeats the purpose of developing a chiral stationary phase. To solve this paradox, imprinting of scalemic and racemic template mixtures was investigated using both chiral (N-α-bismethacryloyl-L-alanine) and achiral (N,O-bisacrylamide ethanolamine) crosslinkers. Imprinting of scalemic mixtures provided polymers capable of partial separation of Boc-tyrosine enantiomers with virtually the same results when using either the chiral or achiral crosslinker. However, the chiral crosslinker was required for chiral differentiation by the racemic imprinted polymers which were evaluated in both batch rebinding and chromatographic modes. Batch rebinding analysis revealed intersecting binding isotherms for the L- and D-Boc-tyrosine, indicating bias for the D or L enantiomer is concentration dependent. Partial chromatographic separation was achieved by the racemic imprinted polymers providing variable D or L bias in equal probability over multiple replicates of polymer synthesis. Correlation of enantiomer bias with the batch rebinding results and optimization of HPLC parameters are discussed. PMID:26347178

  6. Chiral plasma instabilities.

    PubMed

    Akamatsu, Yukinao; Yamamoto, Naoki

    2013-08-01

    We study the collective modes in relativistic electromagnetic or quark-gluon plasmas with an asymmetry between left- and right-handed chiral fermions, based on the recently formulated kinetic theory with Berry curvature corrections. We find that there exists an unstable mode, signaling the presence of a plasma instability. We argue the fate of this "chiral plasma instability" including the effect of collisions, and briefly discuss its relevance in heavy ion collisions and compact stars. PMID:23952387

  7. Structural reconstruction of the catalytic center of LiPDF through multiple scattering calculation with MXAN

    NASA Astrophysics Data System (ADS)

    Guo, Xiaoyun; Chu, Wangsheng; Ma, Sixuan; Gong, Weimin; Benfatto, Maurizio; Hu, Tiandou; Xie, Yaning; Wu, ZiYu

    2006-11-01

    Peptide deformylase (PDF, EC 3.5.1.27) is essential for the normal growth of eubacterium but not for mammalians. Recently, PDF has been studied as a target for new antibiotics. In this paper, X-ray absorption spectroscopy was employed to determine the local structure around the zinc ion of PDF from Leptospira Interrogans in dry powder, because it is very difficult to obtain the crystallized sample of LiPDF. We performed X-ray absorption near edge structure (XANES) calculation and reconstructed successfully the local geometry of the active center, and the results from calculations show that a water molecule (Wat1) has moved towards the zinc ion and lies in the distance range to coordinate with the zinc ion weakly. In addition, the sensitivity of theoretical spectra to the different ligand bodies was evaluated in terms of goodness-of-fit.

  8. Myelomatous pleural effusion involvement in 23 patients with multiple myeloma: A single-center clinical analysis.

    PubMed

    Zhong, Yuping; Zhang, Jiajia; Wang, Huan

    2015-05-01

    We investigated the treatment and prognosis of pleural effusion (PE) in multiple myeloma (MM) patients. From June 2005 to December 2013, 296 MM patients participated in this study. There were 23 PE patients, including 11 men and 12 women, with a median age of 56.8 years (range 37-68 years). A diagnosis of PE was based on physical examination, chest X-ray or computed tomography, and pleural fluid analysis. All patients demonstrated myeloma cells in the pleural fluid, and six patients were positive for PE M protein. PE patients received bortezomib combined with other drugs. Only one patient demonstrated a complete response; 10 patients showed partial responses, and 12 patients developed progressive disease and died. MM linked with myelomatous PE is associated with a poor prognosis. Myelomatous PE is likely a late manifestation of the natural history of MM or an expression of the aggressive behavior of the disease. PMID:26273384

  9. Chiral pesticides: identification, description, and environmental implications.

    PubMed

    Ulrich, Elin M; Morrison, Candice N; Goldsmith, Michael R; Foreman, William T

    2012-01-01

    , synthetic musks, and their degradates (Kallenborn and Hiihnerfuss 2001;Heeb et al. 2007; Hihnerfuss and Shah 2009). The stereoisomers of pesticides can have widely different efficacy, toxicity to nontarget organisms, and metabolic rates in biota. For these reasons, it is important to first be aware of likely fate and effect differences, to incorporate molecular asymmetry insights into research projects, and to study the individual stereoisomers of the applied pesticide material.With the advent of enantioselective chromatography techniques, the chirality of pesticides has been increasingly studied. While the ChirBase (Advanced ChemistryDevelopment 1997-2010) database does not include all published chiral analytical separations, it does contain more than 3,500 records for 146 of the 482 chiral pesticides (30%). The majority of the records are found in the liquid chromatography database (2,677 or 76%), followed by the gas chromatography database (652 or 18%),and the capillary electrophoresis database (203 or 6%). The finding that only 30% of the chiral pesticides covered in this review have entries in ChirBase highlights the need for expanded efforts to develop additional enantioselective chromatographic methods. Other techniques (e.g., nuclear magnetic resonance and other spectroscopy)are available for investigation of chiral compounds, but often are not utilized because of cost, complexity, or simply not recognizing that a pesticide is chiral.In this review, we have listed and have briefly described the general nature of chiral fungicides, herbicides, insecticides, and other miscellaneous classes. A data-set generated for this review contains 1,693 pesticides, the number of enantioselective separation records in ChirBase, pesticide usage class, SMILES structure string and counts of stereogenic centers. This dataset is publically available for download at the following website: http://www.epa.gov/heasd/products/products.html. With the information herein coupled to the

  10. Multiple Shh signaling centers participate in fungiform papilla and taste bud formation and maintenance

    PubMed Central

    Liu, H-X; Ermilov, A; Grachtchouk, M; Li, L; Gumucio, DL; Dlugosz, AA; Mistretta, CM

    2014-01-01

    The adult fungiform taste papilla is a complex of specialized cell types residing in the stratified squamous tongue epithelium. This unique sensory organ includes taste buds, papilla epithelium and lateral walls that extend into underlying connective tissue to surround a core of lamina propria cells. Fungiform papillae must contain long-lived, sustaining or stem cells and short-lived, maintaining or transit amplifying cells that support the papilla and specialized taste buds. Shh signaling has established roles in supporting fungiform induction, development and patterning. However, for a full understanding of how Shh transduced signals act in tongue, papilla and taste bud formation and maintenance, it is necessary to know where and when the Shh ligand and pathway components are positioned. We used immunostaining, in situ hybridization and mouse reporter strains for Shh, Ptch1, Gli1 and Gli2-expression and proliferation markers to identify cells that participate in hedgehog signaling. Whereas there is a progressive restriction in location of Shh ligand-expressing cells, from placode and apical papilla cells to taste bud cells only, a surrounding population of Ptch1 and Gli1 responding cells is maintained in signaling centers throughout papilla and taste bud development and differentiation. The Shh signaling targets are in regions of active cell proliferation. Using genetic-inducible lineage tracing for Gli1-expression, we found that Shh-responding cells contribute not only to maintenance of filiform and fungiform papillae, but also to taste buds. A requirement for normal Shh signaling in fungiform papilla, taste bud and filiform papilla maintenance was shown by Gli2 constitutive activation. We identified proliferation niches where Shh signaling is active and suggest that epithelial and mesenchymal compartments harbor potential stem and/or progenitor cell zones. In all, we report a set of hedgehog signaling centers that regulate development and maintenance of taste

  11. 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.

  12. Chiral quirkonium decays

    NASA Astrophysics Data System (ADS)

    Fok, R.; Kribs, Graham D.

    2011-08-01

    We calculate the two-body decay rates of quirkonium states formed from quirks that acquire mass solely through electroweak symmetry breaking. We consider SU(N)ic infracolor with two flavors of quirks transforming under the electroweak group (but not QCD) of the standard model. In one case, the quirks are in a chiral representation of the electroweak group, while in the other case, a vectorlike representation. The differences in the dominant decay channels between “chiral quirkonia” versus “vectorlike quirkonia” are striking. Several chiral quirkonia states can decay into the unique two-body resonance channels WH, ZH, tt¯, tb¯/bt¯, and γH, which never dominate for vectorlike quirkonia. Additionally, the channels WW, WZ, ZZ, and Wγ, are shared among both chiral and vectorlike quirkonia. Resonances of dileptons or light quarks (dijets) can dominate for some vectorlike quirkonia states throughout their mass range, while these modes never dominate for chiral quirkonia unless the decays into pairs of gauge or Higgs bosons are kinematically forbidden.

  13. Chiral Quirkonium Decays

    SciTech Connect

    Fok, R.; Kribs, Graham D.; /Fermilab

    2011-06-01

    We calculate the two-body decay rates of quirkonium states formed from quirks that acquire mass solely through electroweak symmetry breaking. We consider SU(N){sub ic} infracolor with two flavors of quirks transforming under the electroweak group (but not QCD) of the standard model. In one case, the quirks are in a chiral representation of the electroweak group, while in the other case, a vectorlike representation. The differences in the dominant decay channels between 'chiral quirkonia' versus 'vectorlike quirkonia' are striking. Several chiral quirkonia states can decay into the unique two-body resonance channels WH, ZH, t{bar t}, t{bar b}/b{bar t}, and {gamma}H, which never dominate for vectorlike quirkonia. Additionally, the channels WW, WZ, ZZ, and W{gamma}, are shared among both chiral and vectorlike quirkonia. Resonances of dileptons or light quarks (dijets) can dominate for some vectorlike quirkonia states throughout their mass range, while these modes never dominate for chiral quirkonia unless the decays into pairs of gauge or Higgs bosons are kinematically forbidden.

  14. An Aligned-Gap and Centered-Gap Rectangular Multiple Split Ring Resonator for Dielectric Sensing Applications

    PubMed Central

    Rusni, Izyani Mat; Ismail, Alyani; Alhawari, Adam Reda Hasan; Hamidon, Mohd Nizar; Yusof, Nor Azah

    2014-01-01

    This paper presents the design and development of a planar Aligned-Gap and Centered-Gap Rectangular Multiple Split Ring Resonator (SRR) for microwave sensors that operates at a resonance frequency around 5 GHz. The sensor consists of a microstrip transmission line loaded with two elements of rectangular SRR on both sides. The proposed metamaterial sensors were designed and fabricated on Rogers RT5880 substrate having dielectric constant of 2.2 and thickness of 0.787 mm. The final dimension of the proposed sensor was measured at 35 × 14 mm2. Measured results show good agreement with simulated ones as well as exhibiting high Q-factor for use in sensing application. A remarkably shift of resonance frequency is observed upon introduction of several sample with different dielectric value. PMID:25051036

  15. Spontaneous chirality in simple systems

    PubMed

    Pickett; Gross; Okuyama

    2000-10-23

    Two simple examples of spontaneous chiral symmetry breaking are presented. The first is close-packed cylindrically confined spheres. As the cylinder diameter is varied, one obtains a variety of chiral phases. The second example involves unconfined dipolar particles with an isotropic attraction, which also exhibits chiral ground states. We speculate that a dilute magnetorheological fluid film, with the addition of smaller particles to provide an attractive entropic interaction, will exhibit a chiral columnar ground state. PMID:11030973

  16. 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

  17. Rationalization of chirality induction and inversion in a zinc trisporphyrinate by a chiral monoalcohol.

    PubMed

    Li, Li; Hu, Chuanjiang; Shi, Bo; Wang, Yong

    2016-05-10

    A new host-guest system is formed between a benzene tricarboxamide linked zinc trisporphyrinate and a chiral monoalcohol (1-phenylethylalcohol). CD spectra show the chirality induction and inversion processes, which are controlled by the corresponding 1 : 1 and 1 : 2 coordination complexes. The binding constants calculated by UV-vis and CD spectral data are much larger than that for [Zn(TPP)] (TPP = tetraphenylporphyrin). The crystallographic structure of the host-guest complex reveals that multiple intramolecular hydrogen bonds and π-π interactions could contribute to its high binding affinity to 1-phenylethylalcohol. The DFT calculations suggest that the spatial orientations of porphyrin moieties change from the 1 : 1 complex to the 1 : 2 complex. The chirality induction and inversion processes are rationalized by the summation of pairwise interactions among multichromophores according to pairwise additivity. PMID:27074900

  18. 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.

  19. 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. PMID:24777209

  20. Clinical and epidemiological profile of multiple sclerosis in a reference center in the State of Bahia, Brazil.

    PubMed

    Cardoso, Eduardo; Fukuda, Thiago; Pereira, Júlio; Seixas, Jamile; Miranda, Rafael; Rodrigues, Bernardo; Saback, Thaís; Andrade, Renata; Cardoso, Grace; Martinez, Rosa; Avena, Juliane; Melo, Ailton

    2006-09-01

    Multiple sclerosis (MS) is an autoimmune, demyelinating and degenerative disease that affects the central nervous system. Its prevalence and clinical aspects vary according to the continent considered, being more frequent in Caucasians and young individuals aged 20 to 40 years. Epidemiological data from Brazil show that prevalence is variable, being more frequent in the Southern and Southeastern areas of the country, rather than in the Northern and Northeastern areas. The purpose of this paper is to describe MS clinical and epidemiological features in the State of Bahia, in the Brazilian Northeastern region. Thus, we held a cross-sectional study over the period from February to May, 2005, in the Multiple Sclerosis Patient Support Center ("Núcleo de Apoio aos Pacientes com Esclerose Múltipla") of Bahia, which included all patients with a diagnosis of MS seen over this period of time. A total of 121 patients were investigated, being 80.2% females (female:male ratio=4:1), with higher frequency in mulatto individuals (64%), and the relapsing-remitting type (91.3%). Most patients (68.7%) had mild MS, and blacks were prone to worse prognosis compared to other patients. PMID:17057875

  1. The derivation of a chiral substituent code for secondary alcohols and its application to the prediction of enantioselectivity.

    PubMed

    Suo, Jing-Jie; Zhang, Qing-You; Li, Jing-Ya; Zhou, Yan-Mei; Xu, Lu

    2013-06-01

    A chiral substituent code was proposed based on the features of secondary alcohols, in which a chiral center is attached to two substituents in addition to OH and H substituents. The new chirality code, which was generated by predefining positional information of four substituents attached to stereocenter, was applied to two datasets composed of secondary alcohols as the enantioselective products of asymmetric reactions. In the first dataset, the chemical reaction was catalyzed by a biocatalyst, lipase from Candida rugosa. The catalyst for the second dataset was (-)-diisopinocampheylchloroborane. The structure-enantioselectivity relationship models were constructed using random forests with the chiral substituent code as the input. The resulting models were assessed both in terms of single enantiomers and pairs of enantiomers. Satisfactory results were obtained for both datasets. Although the chiral substituent code was specifically developed for secondary alcohols, it can easily be extended to represent chiral compounds possessing a specific chiral center bonded to two variable substituents. PMID:23666031

  2. Quantum phenomenology for the disoriented chiral condensate

    SciTech Connect

    Amado, R.D. ); Kogan, I.I. )

    1995-01-01

    We consider the quantum state describing the disoriented chiral condensate (DCC), which may be produced in high energy collisions. We show how a mean field treatment of the quantum equations corresponding to the classical linear [sigma] model leads to a squeezed state description of the pions emerging from the DCC. We examine various squeezed and coherent state descriptions of those pions with particular attention to charge and number fluctuations. We also study the phenomenology of multiple DCC domains.

  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. Baryon chiral perturbation theory

    NASA Astrophysics Data System (ADS)

    Scherer, S.

    2012-03-01

    We provide a short introduction to the one-nucleon sector of chiral perturbation theory and address the issue of power counting and renormalization. We discuss the infrared regularization and the extended on-mass-shell scheme. Both allow for the inclusion of further degrees of freedom beyond pions and nucleons and the application to higher-loop calculations. As applications we consider the chiral expansion of the nucleon mass to order Script O(q6) and the inclusion of vector and axial-vector mesons in the calculation of nucleon form factors. Finally, we address the complex-mass scheme for describing unstable particles in effective field theory.

  5. 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

  6. Contesting the paradigm of chirality

    NASA Astrophysics Data System (ADS)

    Efrati, Efi

    2012-02-01

    In 1893 Lord Kelvin coined the term chirality, and stated what is to become the elementary paradigm of chirality: 'I call any geometrical figure, or any group of points, chiral, and say it has chirality, if its image in a plane mirror , ideally realized cannot be brought to coincide with itself'. While the notion of chirality has greatly advanced our understanding of the structures of molecules and crystals, it has been shown to be inconsistent with every pseudo-scalar quantification. In this talk I will present a tabletop demonstration of a chiral structure which is constructed through the achiral summation of identical elementary units which are symmetric under reflection. The seeming contradiction to the definition of chirality is reconciled by proposing an alternative definition, relying on the physicist interpretation of the right hand rule.

  7. 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. PMID:24079531

  8. Comparison of positively and negatively charged achiral co-monomers added to cyclodextrin monolith: improved chiral separations in capillary electrochromatography.

    PubMed

    Lu, Yang; Shamsi, Shahab A

    2014-10-01

    Cyclodextrins (CDs) and their derivatives have been one of the most popular and successful chiral additives used in electrokinetic chromatography because of the presence of multiple chiral centers, which leads to multiple chiral interactions. However, there has been relatively less published work on the use of CDs as monolithic media for capillary electrochromatography (CEC). The goal of this study was to show how the addition of achiral co-monomer to a polymerizable CD such as glycidyl methacrylate β-cyclodextrin (GMA/β-CD) can affect the enantioselective separations in monolithic CEC. To achieve this goal, polymeric monoliths columns were prepared by co-polymerizing GMA/β-CD with cationic or anionic achiral co-monomers [(2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and vinyl benzyltrimethyl-ammonium (VBTA)] in the presence of conventional crosslinker (ethylene dimethacrylate) and ternary porogen system including butanediol, propanol and water. A total of 34 negatively charged compounds, 30 positively charged compounds and 33 neutral compounds were screened to compare the enantioresolution capability on the GMA/β-CD, GMA/β-CD-VBTA and GMA/β-CD-AMPS monolithic columns. PMID:24108813

  9. Full quantum theory of the chiral anomaly transport in a Weyl semimetal

    NASA Astrophysics Data System (ADS)

    Lee, Woo-Ram; Park, Kwon; KIAS Team

    In relativistic field theory, the chiral anomaly means a violation of the number conservation of chiral fermions. In condensed matter physics, the chiral anomaly can be manifested in a Weyl semimetal as a negative magnetoresistance in the presence of parallel electric and magnetic fields. In this work, we use the Keldysh-Floquet Green's function formalism to develop a full quantum theory of the chiral anomaly transport, which can be valid in a broad range of both electric and magnetic field strengths. The authors thank KIAS Center for Advanced Computation (CAC) for providing computing resources.

  10. Prediction of enantiomeric selectivity in chromatography. Application of conformation-dependent and conformation-independent descriptors of molecular chirality.

    PubMed

    Aires-de-Sousa, João; Gasteiger, Johann

    2002-03-01

    In order to process molecular chirality by computational methods and to obtain predictions for properties that are influenced by chirality, a fixed-length conformation-dependent chirality code is introduced. The code consists of a set of molecular descriptors representing the chirality of a 3D molecular structure. It includes information about molecular geometry and atomic properties, and can distinguish between enantiomers, even if chirality does not result from chiral centers. The new molecular transform was applied to two datasets of chiral compounds, each of them containing pairs of enantiomers that had been separated by chiral chromatography. The elution order within each pair of isomers was predicted by means of Kohonen neural networks (NN) using the chirality codes as input. A previously described conformation-independent chirality code was also applied and the results were compared. In both applications clustering of the two classes of enantiomers (first eluted and last eluted enantiomers) could be successfully achieved by NN and accurate predictions could be obtained for independent test sets. The chirality code described here has a potential for a broad range of applications from stereoselective reactions to analytical chemistry and to the study of biological activity of chiral compounds. PMID:11885960

  11. Chiral electron-chiral target scattering

    SciTech Connect

    Trantham, K.W.; Gay, T.J. Johnston, M.E.

    1996-05-01

    It is possible to have an electronic counterpart to the well known effect of optical circular dichroism: electron circular dichroism (ECD) is the preferential scattering of longitudinally polarized electrons by a chiral target. Resulting essentially from a difference in total scattering cross section for different incident electron helicities, this {open_quotes}parity-violating{close_quotes} effect is allowed by symmetry because the scattering target is handed. The authors have searched for ECD in camphor by measuring the transmitted intensity of electrons with positive (negative) helicity I{sub +({minus})} through a gas cell containing stereoisomers of camphor vapor and constructing the asymmetry A = (I{sub +} {minus} I{sub {minus}}). Within their sensitivity (2x10{sup {minus}4}) the authors were not able to detect ECD at the energies investigated (10 eV). Prospects for future investigations, particularly in light of the recent positive results measured in Muenster, will be discussed.

  12. Multiple Interconversions of the E' and Oxygen-Hole Defect Centers in High-Purity Amorphous Silica during Anneal-Interrupted x Irradiation

    NASA Astrophysics Data System (ADS)

    Zhang, Lin; Mashkov, V. A.; Leisure, R. G.

    1995-02-01

    Multiple interconversions of E' centers and peroxy radicals have been observed for the first time by means of anneal-interrupted x-irradiation experiments. It is shown that each of these defects can serve as the precursor of the other; under thermal anneal an E' center can convert to a peroxy radical due to the capture of an oxygen molecule, and under irradiation the peroxy radical can covert to an E' center due to irradiation-induced release of oxygen. The results for the defect production and anneal behavior are well described in terms of simple stretched-exponential defect-reaction kinetics.

  13. 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

  14. Three-Month Test-Retest Reliability of Center of Pressure Motion During Standing Balance in Individuals with Multiple Sclerosis

    PubMed Central

    Wajda, Douglas A.; Motl, Robert W.

    2016-01-01

    Background: Balance impairment and an increased rate of falls are commonly reported in individuals with multiple sclerosis (MS). Force platform–generated center of pressure (COP) metrics have previously been recommended as an outcome measure to quantify balance deficits and distinguish between fallers and nonfallers in MS. Information is limited regarding the preservation of postural control in individuals with MS over extended time frames in the absence of an intervention. This report examines the test-retest reliability and magnitude of change of COP motion during standing balance over 3 months. Methods: Twenty individuals with MS and a history of falling underwent testing on two occasions 3 months apart in the absence of an intervention. On both occasions, participants completed two 30-second trials of three conditions: eyes open, eyes closed, and eyes open with concurrent cognitive challenge (dual task). Measures of COP area, velocity, and temporal structure were calculated and included in the reliability analysis. Results: The COP metrics displayed fair-to-excellent reliability over 3 months without an intervention. Reliability was maintained across the three commonly used balance conditions. Conclusions: These results offer insight into the reliability of COP measures over a 3-month period in MS and can inform the use of COP metrics for future study design (eg, sample size estimates) and balance outcome assessment during randomized controlled trials and fall-prevention studies in individuals with MS. PMID:27134578

  15. Increasing Retention of Adult Learners in Telecourses through the Incorporation of Learning-Centered Instructional Strategies and the Use of Multiple Modalities for Content Delivery and Interaction.

    ERIC Educational Resources Information Center

    Nelson, Lin M.

    A project was undertaken to increase retention in a health education telecourse by incorporating a competency-based orientation to distance learning and learner-centered instructional strategies into the telecourse, and by using multiple media for content delivery and interaction. A general orientation to distance learning was developed that…

  16. Separation mechanisms for palonosetron stereoisomers at different chiral selector concentrations in MEKC.

    PubMed

    Hu, Shao-Qiang; Guo, Xu-Ming; Shi, Hai-Jun; Luo, Rong-Jie

    2015-03-01

    The separation mechanisms for palonosetron (PALO) stereoisomers in MEKC using sodium cholate (SC) as surfactant and chiral selector have been studied, in a wide range of concentrations below and above the CMC. It was found that SC micelles only provide chirally selective recognition for 3a carbon chiral center in PALO molecules. The resolution of the configurations of 2 carbon chiral center is achieved by the difference of mobility in continuous phase. A schematic diagram depicting the separation mechanisms and the corresponding migration orders among all of four stereoisomers was proposed based on the measured separation parameters. A MEKC method to achieve the complete separation of four stereoisomers in very short time using a very low chiral selector concentration, instead of high concentrations generally considered, was developed based on the understanding of the mechanisms. PMID:25404138

  17. 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

  18. 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

  19. 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.

  20. Chirality and protein folding

    NASA Astrophysics Data System (ADS)

    Kwiecinska, Joanna I.; Cieplak, Marek

    2005-05-01

    There are several simple criteria of folding to a native state in model proteins. One of them involves crossing of a threshold value of the root mean square deviation distance away from the native state. Another checks whether all native contacts are established, i.e. whether the interacting amino acids come closer than some characteristic distance. We use Go-like models of proteins and show that such simple criteria may prompt one to declare folding even though fragments of the resulting conformations have a wrong sense of chirality. We propose that a better condition of folding should augment the simple criteria with the requirement that most of the local values of the chirality should be nearly native. The kinetic discrepancy between the simple and compound criteria can be substantially reduced in the Go-like models by providing the Hamiltonian with a term which favours native values of the local chirality. We study the effects of this term as a function of its amplitude and compare it to other models such as ones with side groups and ones with angle-dependent potentials.

  1. Electronic and chiroptical properties of chiral cycloiridiated complexes bearing helicenic NHC ligands.

    PubMed

    Hellou, Nora; Jahier-Diallo, Claire; Baslé, Olivier; Srebro-Hooper, Monika; Toupet, Loïc; Roisnel, Thierry; Caytan, Elsa; Roussel, Christian; Vanthuyne, Nicolas; Autschbach, Jochen; Mauduit, Marc; Crassous, Jeanne

    2016-07-28

    The first helicene-NHC-iridium complexes have been prepared in enantiopure forms. Their stereochemical, electronic, and chiroptical features were characterized experimentally and via first-principles calculations, highlighting the helical and iridium-centered chirality. PMID:27354241

  2. Chirality and equilibrium biopolymer bundles.

    PubMed

    Grason, Gregory M; Bruinsma, Robijn F

    2007-08-31

    We use continuum theory to show that chirality is a key thermodynamic control parameter for the aggregation of biopolymers: chirality produces a stable disperse phase of hexagonal bundles under moderately poor solvent conditions, as has been observed in in vitro studies of F actin [O. Pelletier et al., Phys. Rev. Lett. 91, 148102 (2003)]. The large characteristic radius of these chiral bundles is not determined by a mysterious long-range molecular interaction but by in-plane shear elastic stresses generated by the interplay between a chiral torque and an unusual, but universal, nonlinear gauge term in the strain tensor of ordered chains that is imposed by rotational invariance. PMID:17931038

  3. 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

  4. 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

  5. Diastereodivergent asymmetric sulfa-Michael additions of α-branched enones using a single chiral organic catalyst.

    PubMed

    Tian, Xu; Cassani, Carlo; Liu, Yankai; Moran, Antonio; Urakawa, Atsushi; Galzerano, Patrizia; Arceo, Elena; Melchiorre, Paolo

    2011-11-01

    A significant limitation of modern asymmetric catalysis is that, when applied to processes that generate chiral molecules with multiple stereogenic centers in a single step, researchers cannot selectively access the full matrix of all possible stereoisomeric products. Mirror image products can be discretely provided by the enantiomeric pair of a chiral catalyst. But modulating the enforced sense of diastereoselectivity using a single catalyst is a largely unmet challenge. We document here the possibility of switching the catalytic functions of a chiral organic small molecule (a quinuclidine derivative with a pendant primary amine) by applying an external chemical stimulus, in order to induce diastereodivergent pathways. The strategy can fully control the stereochemistry of the asymmetric conjugate addition of alkyl thiols to α-substituted α,β-unsaturated ketones, a class of carbonyls that has never before succumbed to a catalytic approach. The judicious choice of acidic additives and reaction media switches the sense of the catalyst's diastereoselection, thereby affording either the syn or anti product with high enantioselectivity. PMID:21936561

  6. Systems engineering and integration of control centers in support of multiple programs. [ground control for STS payloads and unmanned vehicles

    NASA Technical Reports Server (NTRS)

    Miller, David N.

    1989-01-01

    The NASA Johnson Space Center's new Multiprogram Control Center (MPCC) addresses the control requirements of complex STS payloads as well as unmanned vehicles. An account is given of the relationship of the MPCC to the STS Mission Control Center, with a view to significant difficulties that may be encountered and solutions thus far devised for generic problems. Examples of MPCC workstation applications encompass telemetry decommutation, engineering unit conversion, data-base management, trajectory processing, and flight design.

  7. 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.

  8. CHIRAL POLLUTANTS: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

    This task involves process research to determine the environmental occurrence and fate of enantiomers of selected chiral pesticides, PCBs and other chiral pollutants with an emphasis on currently-used modern pesticides expected to have short to intermediate environmental half-liv...

  9. 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 ...

  10. A search for disoriented chiral condensate at Fermilab

    SciTech Connect

    Bjorken, J.D.

    1996-10-01

    A small test/experiment at the Fermilab Collider which measures charged particle and photon multiplicities in the forward direction, {eta} {approx} 4.1, has been carried out, with the primary goal being the search for disoriented chiral condensate (DCC). The author describes the experiment and analysis methods, together with preliminary results.

  11. Mass-Selective Chiral Analysis.

    PubMed

    Boesl, Ulrich; Kartouzian, Aras

    2016-06-12

    Three ways of realizing mass-selective chiral analysis are reviewed. The first is based on the formation of diastereomers that are of homo- and hetero- type with respect to the enantiomers of involved chiral molecules. This way is quite well-established with numerous applications. The other two ways are more recent developments, both based on circular dichroism (CD). In one, conventional or nonlinear electronic CD is linked to mass spectrometry (MS) by resonance-enhanced multiphoton ionization. The other is based on CD in the angular distribution of photoelectrons, which is measured in combination with MS via photoion photoelectron coincidence. Among the many important applications of mass-selective chiral analysis, this review focuses on its use as an analytical tool for the development of heterogeneous enantioselective chemical catalysis. There exist other approaches to combine chiral analysis and mass-selective detection, such as chiral chromatography MS, which are not discussed here. PMID:27070181

  12. 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.

  13. Mass-Selective Chiral Analysis

    NASA Astrophysics Data System (ADS)

    Boesl, Ulrich; Kartouzian, Aras

    2016-06-01

    Three ways of realizing mass-selective chiral analysis are reviewed. The first is based on the formation of diastereomers that are of homo- and hetero- type with respect to the enantiomers of involved chiral molecules. This way is quite well-established with numerous applications. The other two ways are more recent developments, both based on circular dichroism (CD). In one, conventional or nonlinear electronic CD is linked to mass spectrometry (MS) by resonance-enhanced multiphoton ionization. The other is based on CD in the angular distribution of photoelectrons, which is measured in combination with MS via photoion photoelectron coincidence. Among the many important applications of mass-selective chiral analysis, this review focuses on its use as an analytical tool for the development of heterogeneous enantioselective chemical catalysis. There exist other approaches to combine chiral analysis and mass-selective detection, such as chiral chromatography MS, which are not discussed here.

  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. 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. PMID:26550743

  16. Chirality-dependent Hall Effect in Weyl Semimetals

    NASA Astrophysics Data System (ADS)

    Yang, Shengyuan; Pan, Hui; Zhang, Fan

    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 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. Journal Ref: Phys. Rev. Lett. 115 , 156603 (2015).

  17. Structural studies on the chiral selector capacity of cyclodextrin derivatives.

    PubMed

    Tokés, Béla; Ferencz, László; Buchwald, Peter; Donáth-Nagy, Gabriella; Vancea, Szende; Sánta, Nándor; Kis, Erika Lilla

    2008-04-24

    Chromatographic separation of enantiomers to assure or enhance chiral purity is of considerable importance and can be achieved by the use of selectors of great structural variety. Cyclodextrins are an important and frequently used class, and they are multimodal selectors since multiple chiral interactions are possible by very different mechanisms. Here, the results of a preliminary examination on the possible value of computational molecular modeling approaches for the predictability of cyclodextrin selector effects for compounds that possess both geometrical and optical isomerism are presented. Interactions between various cyclodextrins and pyrethroic acids are modeled, interpreted, and compared to experimental capillary electrophoresis data. PMID:18280575

  18. Chiral fiber optical isolator

    NASA Astrophysics Data System (ADS)

    Kopp, Victor I.; Zhang, Guoyin; Zhang, Sheng; Genack, Azriel Z.; Neugroschl, Dan

    2009-02-01

    We propose an in-fiber chiral optical isolator based on chiral fiber polarizer technology and calculate its performance by incorporating the magnetic field into the scattering matrix. The design will be implemented in a special preform, which is passed through a miniature heat zone as it is drawn and twisted. The birefringence of the fiber is controlled by adjusted the diameter of a dual-core optical fiber. By adjusting the twist, the fiber can convert linear to circular polarization and reject one component of circular polarization. In the novel central portion of the isolator, the fiber diameter is large. The effective birefringence of the circular central core with high Verdet constant embedded in an outer core of slightly smaller index of refraction is small. The central potion is a non-reciprocal polarization converter which passes forward traveling left circularly polarized (LCP) light as LCP, while converting backward propagating LCP to right circularly polarized (RCP) light. Both polarizations of light traveling backwards are scattered out of the isolator. Since it is an all-glass structure, we anticipate that the isolator will be able to handle several watts of power and will be environmentally robust.

  19. 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

  20. The Ridged Cross-Junction Multiple-Way Power Divider for Small Blockage and Symmetrical Slot Arrangement in the Center Feed Single-Layer Slotted Waveguide Array

    NASA Astrophysics Data System (ADS)

    Tsunemitsu, Yasuhiro; Yoshida, Goro; Goto, Naohisa; Hirokawa, Jiro; Ando, Makoto

    The center-feed in a single-layer slotted waveguide array [1]-[3] is one of the key components in polarization division duplex (PDD) wireless systems. Two center-feed arrays with orthogonal polarization and boresight beams are orthogonally arranged side-by-side for transmission and reception, simultaneously. Each antenna has extremely high XPD (almost 50dB in measurement) and a very high isolation (over 80dB in measurement) between two arrays is observed provided the symmetry of slot arrangement is preserved [4]. Unfortunately, the area blocked by the center feed causes high sidelobe levels. This paper proposes the ridged cross-junction multiple-way power divider for realizing blockage reduction and symmetrical slot arrangement at the same time.

  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. Molecular self-assemblies might discriminate the diffusion of chiral molecules.

    PubMed

    Galstian, Tigran; Allahverdyan, Karen

    2015-06-01

    Biological tissue has many self-aligned anisotropic molecular organizations, which are able to undergo reversible orientational deformations and spatially transfer them. At the same time, the majority of drugs and many biologically important molecules contain chiral centers. It is therefore important to understand the factors affecting the diffusion of chiral molecules in such elastic environments. We experimentally study the diffusion of chiral molecules in a nematic liquid crystal host representing the model of biological tissue. The analogy of Cano's quantization effect is observed (due to the gradient of the chiral dopant) and used to estimate the corresponding diffusion coefficients. It is shown that thanks to the collective orientational correlation of host molecules the diffusion of chiral dopants is noticeably reduced (by a factor of ≈1.6) for the case of rigid alignment of host molecules compared to the case when the same matrix is free to adjust that alignment. PMID:25902722

  3. 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.

  4. 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.

  5. 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.

  6. Connections between chiral Lagrangians and QCD sum-rules

    NASA Astrophysics Data System (ADS)

    Fariborz, Amir H.; Pokraka, A.; Steele, T. G.

    2016-01-01

    In this paper, it is shown how a chiral Lagrangian framework can be used to derive relationships connecting quark-level QCD correlation functions to mesonic-level two-point functions. Crucial ingredients of this connection are scale factor matrices relating each distinct quark-level substructure (e.g. quark-antiquark, four-quark) to its mesonic counterpart. The scale factors and mixing angles are combined into a projection matrix to obtain the physical (hadronic) projection of the QCD correlation function matrix. Such relationships provide a powerful bridge between chiral Lagrangians and QCD sum-rules that are particularly effective in studies of the substructure of light scalar mesons with multiple complicated resonance shapes and substantial underlying mixings. The validity of these connections is demonstrated for the example of the isotriplet a0(980)-a0(1450) system, resulting in an unambiguous determination of the scale factors from the combined inputs of QCD sum-rules and chiral Lagrangians. These scale factors lead to a remarkable agreement between the quark condensates in QCD and the mesonic vacuum expectation values that induce spontaneous chiral symmetry breaking in chiral Lagrangians. This concrete example shows a clear sensitivity to the underlying a0-system mixing angle, illustrating the value of this methodology in extensions to more complicated mesonic systems.

  7. Cellular and Nuclear Alignment Analysis for Determining Epithelial Cell Chirality.

    PubMed

    Raymond, Michael J; Ray, Poulomi; Kaur, Gurleen; Singh, Ajay V; Wan, Leo Q

    2016-05-01

    Left-right (LR) asymmetry is a biologically conserved property in living organisms that can be observed in the asymmetrical arrangement of organs and tissues and in tissue morphogenesis, such as the directional looping of the gastrointestinal tract and heart. The expression of LR asymmetry in embryonic tissues can be appreciated in biased cell alignment. Previously an in vitro chirality assay was reported by patterning multiple cells on microscale defined geometries and quantified the cell phenotype-dependent LR asymmetry, or cell chirality. However, morphology and chirality of individual cells on micropatterned surfaces has not been well characterized. Here, a Python-based algorithm was developed to identify and quantify immunofluorescence stained individual epithelial cells on multicellular patterns. This approach not only produces results similar to the image intensity gradient-based method reported previously, but also can capture properties of single cells such as area and aspect ratio. We also found that cell nuclei exhibited biased alignment. Around 35% cells were misaligned and were typically smaller and less elongated. This new imaging analysis approach is an effective tool for measuring single cell chirality inside multicellular structures and can potentially help unveil biophysical mechanisms underlying cellular chiral bias both in vitro and in vivo. PMID:26294010

  8. The management of multiple sclerosis by reference centers in south of Italy: a 2011 survey on health demands and needs in Campania region.

    PubMed

    de Waure, Chiara; Di Nardo, Francesco; Mazzucco, Walter; Nedovic, Darko; Battaglia, Mario Alberto; Busillo, Vincenzo; Di Iorio, Walter; Gallo, Antonio; Lanzillo, Roberta; Lombardi, Emilio; Maniscalco, Giorgia Teresa; Orefice, Giuseppe; Petracca, Maria; Romano, Felice; Sinisi, Leonardo; Spadera, Anna Pia; Spitaleri, Daniele; Vivo, Pasquale; Ricciardi, Walter

    2016-02-01

    This cross-sectional study has investigated the diagnostic and therapeutic management of patients suffering from multiple sclerosis (MS) in the Campania Region (Italy). A survey involving all the reference centers for MS in Campania Region was conducted from March to August 2011. Centers responded to a web-administered questionnaire on management and clinical characteristics of MS patients. In the study period, 3263 patients (mean age 37 years, 66 % females) accessed the centers. Patients received a first diagnosis of MS in 161 cases (4.9 %). About 37 % of the subjects without a previous diagnosis came to the centers on their own initiative. All patients underwent a complete neurological examination and expanded disability status scale. The other most common investigations were magnetic resonance imaging (44.0 %) and evoked potentials (22.1 %). The number of treated patients was 2797 (87.1 %). The most used drugs were interferon β and glatiramer acetate. The time between diagnosis and initiation of therapy exceeded 6 months in 32 % of cases. Second-line drugs were under-used: 16 % of patients who might benefit from them show high clinical and radiological disease activity despite treatment with immunomodulant drugs. The MS care management of the surveyed centers showed consistent margins for improvement in 2011. Even though these data do not represent the current situation, they can be used to monitor improvements in MS care. PMID:26439919

  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. 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.

  11. 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.

  12. Critical dimensions for chiral bosons

    SciTech Connect

    Mezincescu, L.; Nepomechie, R.I.

    1988-05-15

    We give the Lagrangian formulation of a Bose model in 1+1 dimensions which describes a free chiral Lie-algebra-valued current. This model is a non-Abelian generalization of the chiral scalar model of Siegel. Both the Abelian and non-Abelian actions have a gauge invariance, which becomes anomalous when the models are quantized. The condition that this anomaly be canceled coincides with the string no-ghost condition.

  13. 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.

  14. 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…

  15. 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…

  16. Treatment Verification: Multiple Analytical Methods and a Search for Causality in the Child Parent Center Compensatory Education Program.

    ERIC Educational Resources Information Center

    Conrad, Kendon J.; And Others

    Treatment verification methodology was employed in studying the Chicago Child Parent Center (CPC) compensatory education program. Established in disadvantaged areas by the Chicago public schools, CPCs are designed to break the cycle of poverty through educational intervention with children at ages 3 through 8. An element of evaluation studies that…

  17. 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.

  18. 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

  19. Characterization of the particulate methane monooxygenase metal centers in multiple redox states by X-ray absorption spectroscopy.

    PubMed

    Lieberman, Raquel L; Kondapalli, Kalyan C; Shrestha, Deepak B; Hakemian, Amanda S; Smith, Stephen M; Telser, Joshua; Kuzelka, Jane; Gupta, Rajeev; Borovik, A S; Lippard, Stephen J; Hoffman, Brian M; Rosenzweig, Amy C; Stemmler, Timothy L

    2006-10-01

    The integral membrane enzyme particulate methane monooxygenase (pMMO) converts methane, the most inert hydrocarbon, to methanol under ambient conditions. The 2.8-A resolution pMMO crystal structure revealed three metal sites: a mononuclear copper center, a dinuclear copper center, and a nonphysiological mononuclear zinc center. Although not found in the crystal structure, solution samples of pMMO also contain iron. We have used X-ray absorption spectroscopy to analyze the oxidation states and coordination environments of the pMMO metal centers in as-isolated (pMMO(iso)), chemically reduced (pMMO(red)), and chemically oxidized (pMMO(ox)) samples. X-ray absorption near-edge spectra (XANES) indicate that pMMO(iso) contains both Cu(I) and Cu(II) and that the pMMO Cu centers can undergo redox chemistry. Extended X-ray absorption fine structure (EXAFS) analysis reveals a Cu-Cu interaction in all redox forms of the enzyme. The Cu-Cu distance increases from 2.51 to 2.65 A upon reduction, concomitant with an increase in the average Cu-O/N bond lengths. Appropriate Cu2 model complexes were used to refine and validate the EXAFS fitting protocols for pMMO(iso). Analysis of Fe EXAFS data combined with electron paramagnetic resonance (EPR) spectra indicates that Fe, present as Fe(III), is consistent with heme impurities. These findings are complementary to the crystallographic data and provide new insight into the oxidation states and possible electronic structures of the pMMO Cu ions. PMID:16999437

  20. 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

  1. 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

  2. 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.

  3. 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

    2016-01-01

    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

  4. Enantioselective Synthesis of Isoquinolines: Merging Chiral-Phosphine and Gold Catalysis.

    PubMed

    Gao, Yu-Ning; Shi, Feng-Chen; Xu, Qin; Shi, Min

    2016-05-10

    The highly enantioselective synthesis of dihydroisoquinoline derivatives from aromatic sulfonated imines tethered with an alkyne moiety, through a one-pot asymmetric relay catalysis of chiral-phosphine and gold catalysts, is reported. Enantiomerically enriched dihydroisoquinoline derivatives were afforded in good yields and good-to-excellent ee values under mild conditions, based on the asymmetric aza-Morita-Baylis-Hillman reaction. Dihydroisoquinoline derivatives containing two chiral centers were also synthesized through further transformations. PMID:26990120

  5. Enhancing the ACE control center for the multiple uses of spacecraft integration and test and mission and science operations

    NASA Technical Reports Server (NTRS)

    Snow, Frank; Garrard, Thomas L.; Steck, Jane A.; Maury, Jesse L.

    1996-01-01

    In relation to the mandate to reduce space mission development and operations costs, the advanced composition explorer (ACE) will use a version of the Transportable Payload Operations Control Center (TPOCC) for its mission operations. It was determined during the phase B of the ACE project that a potential existed for substantial savings if the adaptation of the TPOCC for the ACE mission operations could include its adaptation for use as the primary component in the ground support equipment for the integration and testing of the ACE spacecraft, and for use as the basic component in the ACE science center. The implementation of this approach required the enhancement of the TPOCC requirements, changes in the development schedule and changes in the allocation and activities of the personnel responsible for the development of ACE operations. It is discussed how these issues, and the problems that arose, were addressed.

  6. Chiral symmetry in rotating systems

    NASA Astrophysics Data System (ADS)

    Malik, Sham S.

    2015-08-01

    The triaxial rotating system at critical angular momentum I ≥Iband exhibits two enatiomeric (the left- and right-handed) forms. These enatiomers are related to each other through dynamical chiral symmetry. The chiral symmetry in rotating system is defined by an operator χ ˆ =Rˆy (π) T ˆ, which involves the product of two distinct symmetries, namely, continuous and discrete. Therefore, new guidelines are required for testing its commutation with the system Hamiltonian. One of the primary objectives of this study is to lay down these guidelines. Further, the possible impact of chiral symmetry on the geometrical arrangement of angular momentum vectors and investigation of observables unique to nuclear chiral-twins is carried out. In our model, the angular momentum components (J1, J2, J3) occupy three mutually perpendicular axes of triaxial shape and represent a non-planar configuration. At certain threshold energy, the equation of motion in angular momentum develops a second order phase transition and as a result two distinct frames (i.e., the left- and right-handed) are formed. These left- and right-handed states correspond to a double well system and are related to each other through chiral operator. At this critical angular momentum, the centrifugal and Coriolis interactions lower the barrier in the double well system. The tunneling through the double well starts, which subsequently lifts the degeneracy among the rotational states. A detailed analysis of the behavior of rotational energies, spin-staggering, and the electromagnetic transition probabilities of the resulting twin-rotational bands is presented. The ensuing model results exhibit similarities with many observed features of the chiral-twins. An advantage of our formalism is that it is quite simple and it allows us to pinpoint the understanding of physical phenomenon which lead to chiral-twins in rotating systems.

  7. 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.)

  8. 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...

  9. Effects of chirality and surface stresses on the bending and buckling of chiral nanowires

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Shan; Shimada, Takahiro; Wang, Gang-Feng; Kitamura, Takayuki

    2014-01-01

    Due to their superior optical, elastic and electrical properties, chiral nanowires have many applications as sensors, probes, and building blocks of nanoelectromechanical systems. In this paper, we develop a refined Euler-Bernoulli beam model for chiral nanowires with surface effects and material chirality incorporated. This refined model is employed to investigate the bending and buckling of chiral nanowires. It is found that surface effects and material chirality significantly affect the elastic behaviour of chiral nanowires. This study is helpful not only for understanding the size-dependent behaviour of chiral nanowires, but also for characterizing their mechanical properties.

  10. Hydrogen-Regulated Chiral Nanoplasmonics.

    PubMed

    Duan, Xiaoyang; Kamin, Simon; Sterl, Florian; Giessen, Harald; Liu, Na

    2016-02-10

    Chirality is a highly important topic in modern chemistry, given the dramatically different pharmacological effects that enantiomers can have on the body. Chirality of natural molecules can be controlled by reconfiguration of molecular structures through external stimuli. Despite the rapid progress in plasmonics, active regulation of plasmonic chirality, particularly in the visible spectral range, still faces significant challenges. In this Letter, we demonstrate a new class of hybrid plasmonic metamolecules composed of magnesium and gold nanoparticles. The plasmonic chirality from such plasmonic metamolecules can be dynamically controlled by hydrogen in real time without introducing macroscopic structural reconfiguration. We experimentally investigate the switching dynamics of the hydrogen-regulated chiroptical response in the visible spectral range using circular dichroism spectroscopy. In addition, energy dispersive X-ray spectroscopy is used to examine the morphology changes of the magnesium particles through hydrogenation and dehydrogenation processes. Our study can enable plasmonic chiral platforms for a variety of gas detection schemes by exploiting the high sensitivity of circular dichroism spectroscopy. PMID:26745446

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. Repulsive Casimir force in chiral metamaterials.

    PubMed

    Zhao, R; Zhou, J; Koschny, Th; Economou, E N; Soukoulis, C M

    2009-09-01

    We demonstrate theoretically that one can obtain repulsive Casimir forces and stable nanolevitations by using chiral metamaterials. By extending the Lifshitz theory to treat chiral metamaterials, we find that a repulsive force and a minimum of the interaction energy possibly exist for strong chirality, under realistic frequency dependencies and correct limiting values (for zero and infinite frequencies) of the permittivity, permeability, and chiral coefficients. PMID:19792309

  18. Total parathyroidectomy in a large cohort of cases with hyperparathyroidism associated with multiple endocrine neoplasia type 1: experience from a single academic center

    PubMed Central

    de Menezes Montenegro, Fabio Luiz; Lourenço, Delmar Muniz; Tavares, Marcos Roberto; Arap, Sergio Samir; Nascimento, Climerio Pereira; Neto, Ledo Mazzei Massoni; D'Alessandro, André; Toledo, Rodrigo Almeida; Coutinho, Flávia Lima; Brandão, Lenine Garcia; de Britto e Silva Filho, Gilberto; Cordeiro, Anói Castro; Toledo, Sergio Pereira Almeida

    2012-01-01

    Most cases of sporadic primary hyperparathyroidism present disturbances in a single parathyroid gland and the surgery of choice is adenomectomy. Conversely, hyperparathyroidism associated with multiple endocrine neoplasia type 1 (hyperparathyroidism/multiple endocrine neoplasia type 1) is an asynchronic, asymmetrical multiglandular disease and it is surgically approached by either subtotal parathyroidectomy or total parathyroidectomy followed by parathyroid auto-implant to the forearm. In skilful hands, the efficacy of both approaches is similar and both should be complemented by prophylactic thymectomy. In a single academic center, 83 cases of hyperparathyroidism/multiple endocrine neoplasia type 1 were operated on from 1987 to 2010 and our first surgical choice was total parathyroidectomy followed by parathyroid auto-implant to the non-dominant forearm and, since 1997, associated transcervical thymectomy to prevent thymic carcinoid. Overall, 40% of patients were given calcium replacement (mean intake 1.6 g/day) during the first months after surgery, and this fell to 28% in patients with longer follow-up. These findings indicate that several months may be needed in order to achieve a proper secretion by the parathyroid auto-implant. Hyperparathyroidism recurrence was observed in up to 15% of cases several years after the initial surgery. Thus, long-term follow-up is recommended for such cases. We conclude that, despite a tendency to subtotal parathyroidectomy worldwide, total parathyroidectomy followed by parathyroid auto-implant is a valid surgical option to treat hyperparathyroidism/multiple endocrine neoplasia type 1. Larger comparative systematic studies are needed to define the best surgical approach to hyperparathyroidism/multiple endocrine neoplasia type 1. PMID:22584718

  19. 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.

  20. 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.

  1. Chiral Sensor for Enantiodiscrimination of Varied Acids.

    PubMed

    Huang, Huayin; Bian, Guangling; Zong, Hua; Wang, Yabai; Yang, Shiwei; Yue, Huifeng; Song, Ling; Fan, Hongjun

    2016-06-01

    A chiral thiophosphoroamide 4 derived from (1R,2R)-1,2-diaminocyclohexane is used as a highly effective chiral sensor for the chiral recognition of varied acids via ion-pairing and hydrogen-bonding interactions using (1)H, (19)F and (31)P NMR. PMID:27192021

  2. 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.

  3. 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

  4. 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).

  5. Microwave propagation in chiral metamaterials

    NASA Astrophysics Data System (ADS)

    Prybylski, Aida; Yon, Luis; Noginova, Natalia

    Chiral hyperbolic metamaterials are predicted to show interesting properties associated with possible topological photonic states in these materials, which present new opportunities for light control and manipulation. As prototypes, we consider two metal-dielectric systems designed for microwave range: a twisted wires array, where chirality is associated with shape of metal inclusions, and a rotated layer system, with parallel wires in each layer, and direction of the wires orientation rotated from layer to layer. Systems with different content of metal and layer-to-layer distance were fabricated and studied in the free space propagation experiment. The results were discussed in terms of effective media consideration.

  6. 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. PMID:26207458

  7. Open Repair Versus Thoracic Endovascular Aortic Repair in Multiple-Injured Patients: Observations From a Level-1 Trauma Center

    PubMed Central

    Brand, Stephan; Breitenbach, Ingo; Bolzen, Philipp; Petri, Maximilian; Krettek, Christian; Teebken, Omke

    2015-01-01

    Background: Blunt trauma of the thoracic aorta is a rare but potentially life-threatening entity. Intimal tears are a domain of non-operative management, whereas all other types of lesions should be repaired urgently. There is now a clear trend favoring minimally invasive stent grafting over open surgical repair. Objectives: The aim of the present study was to retrospectively evaluate the mortality and morbidity with either treatment option. Therefore, a retrospective observational study was performed to compare two different treatment methods at two different time periods at one trauma center. Patients and Methods: Between 1977 and 2012, all severely injured patients referred to our level 1 trauma center were screened for blunt aortic injuries. We compared baseline characteristics, 30-day and overall mortality, morbidity, duration of intensive care treatment, procedure time, and transfusion of packed red blood between patients who underwent open surgical or stent repair. Results: During the observation period, 45 blunt aortic injuries were recorded. The average Injury Severity Score (ISS) was 41.8 (range 29 - 68). Twenty-five patients underwent Open Repair (OR), and another 20 patients were scheduled to emergency stent grafting. The 30-day mortality in the surgical and stent groups were 5/25 (20%) and 2/20 (10%), respectively. The average time for open surgery was 151 minutes; the mean time for stent grafting was 67 minutes (P = 0.001). Postoperative stay on the intensive care unit was between one and 59 days (median 10) in group one and between four and 50 days in group two (median 26)(P = 0.03). Patients undergoing OR required transfusion of 6.0 units of packed red cells in median; patients undergoing stent grafting required a median of 2.0 units of packed red cells (P < 0.001). In the stent grafting group, 30-day mortality was 10% (2/20). Conclusions: Due to more sophisticated diagnostic tools and surgical approaches, mortality and morbidity of blunt aortic

  8. Mechanical chirality: A chiral catalyst with a ring to it

    NASA Astrophysics Data System (ADS)

    Goldup, Stephen M.

    2016-05-01

    A chiral [2]rotaxane in which the asymmetry is derived from the way in which the two components are mechanically interlocked -- rather than being encoded in the covalent connectivity of the components themselves -- has been shown to act as an enantioselective organocatalyst.

  9. 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.

  10. Coherent perfect absorption in chiral metamaterials.

    PubMed

    Ye, Yuqian; Hay, Darrick; Shi, Zhimin

    2016-07-15

    We study the coherent perfect absorption (CPA) of a chiral structure and derive analytically the CPA condition for transversely isotropic chiral structures in circular polarization bases. The coherent absorption of such a chiral system is generally polarization dependent and can be tuned by the relative phase between the coherent input beams. To demonstrate our theoretical predictions, a chiral metamaterial absorber operating in the terahertz frequency range is optimized. We numerically demonstrate that a coherent absorption of 99.5% can be achieved. Moreover, we show that an optimized CPA chiral structure can be used as an interferometric control of polarization state of the output beams with constant output intensity. PMID:27420535

  11. Scaling laws in chiral hydrodynamic turbulence

    NASA Astrophysics Data System (ADS)

    Yamamoto, Naoki

    2016-06-01

    We study the turbulent regime of chiral (magneto)hydrodynamics for charged and neutral matter with chirality imbalance. We find that the chiral magnetohydrodynamics for charged plasmas possesses a unique scaling symmetry, only without fluid helicity under the local charge neutrality. We also find a different type of unique scaling symmetry in the chiral hydrodynamics for neutral matter with fluid helicity in the inertial range. We show that these symmetries dictate the self-similar inverse cascade of the magnetic and kinetic energies. Our results imply the possible inverse energy cascade in core-collapse supernovae due to the chiral transport of neutrinos.

  12. 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. PMID:26148690

  13. 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

  14. Helical motion of chiral liquid crystal droplets

    NASA Astrophysics Data System (ADS)

    Yamamoto, Takaki; Sano, Masaki

    Artificial swimmers have been intensively studied to understand the mechanism of the locomotion and collective behaviors of cells and microorganisms. Among them, most of the artificial swimmers are designed to move along the straight path. However, in biological systems, chiral dynamics such as circular and helical motion are quite common because of the chirality of their bodies, which are made of chiral biomolecules. To understand the role of the chirality in the physics of microswimmers, we designed chiral artificial swimmers and the theoretical model for the chiral motion. We found that chiral liquid crystal droplets, when dispersed in surfactant solutions, swim in the helical path induced by the Marangoni effect. We will discuss the mechanism of the helical motion with our phenomenological model. This work is supported by Grant-in-Aid for JSPS Fellows (Grant No. 26.9814), and MEXT KAKENHI Grant No. 25103004.

  15. 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.

  16. On the tensorial nature of chirality

    NASA Astrophysics Data System (ADS)

    Efrati, Efi; Irvine, William

    2013-03-01

    Chirality occupies a central role in fields ranging from biological self assembly to the design of optical meta-materials. The definition of chirality, as given by lord Kelvin in 1893, associates handedness with the lack of mirror symmetry. However, the quantification of chirality based on this definition has proven to be an elusive task. The difficulty in quantifying chirality is contrasted by the ease with which one determines the handedness of objects with a well defined axis such as screws and helices. In this talk I will present table-top demonstrations that show that a single object can simultaneously be left handed and right handed when considered from different directions. The orientation dependence of handedness motivates a tensorial quantification of chirality relating directions to rotations. I will give an explicit example of such a tensorial measure of chirality for embedded surfaces, and show how the tensorial nature of chirality can be probed in experiments and exploited as a design principle.

  17. 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

  18. 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

  19. 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.

  20. Chiral phosphines in nucleophilic organocatalysis

    PubMed Central

    Xiao, Yumei; Sun, Zhanhu

    2014-01-01

    Summary This review discusses the tertiary phosphines possessing various chiral skeletons that have been used in asymmetric nucleophilic organocatalytic reactions, including annulations of allenes, alkynes, and Morita–Baylis–Hillman (MBH) acetates, carbonates, and ketenes with activated alkenes and imines, allylic substitutions of MBH acetates and carbonates, Michael additions, γ-umpolung additions, and acylations of alcohols. PMID:25246969

  1. Dynamics of the chiral transition

    SciTech Connect

    Gavin, S.

    1994-07-01

    Measurements of disoriented chiral condensates (DCC) in heavy ion collisions at RHIC can yield fundamental information on the nature of the QCD phase transition. I review theoretical efforts to understand DCC formation and present work in progress on possible experimental ramifications.

  2. Dynamics of the chiral transition

    SciTech Connect

    Gavin, S.

    1995-07-10

    Measurements of disoriented chiral condensates (DCC) in heavy ion collisions at RHIC can yield fundamental information on the nature of the QCD phase transition. I review theoretical efforts to understand DCC formation and present work in progress on their possible experimental ramifications. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  3. 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

  4. 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.

  5. 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}.

  6. Redox-Triggered Helicity Inversion in Chiral Cobalt Complexes in Combination with H(+) and NO3(-) Stimuli.

    PubMed

    Gregoliński, Janusz; Hikita, Masahiro; Sakamoto, Tatsuya; Sugimoto, Hideki; Tsukube, Hiroshi; Miyake, Hiroyuki

    2016-01-19

    Three chiral ligands with variable denticity, H2L2-H2L4, conjugated by N,N'-ethylenebis[N-methyl-(S)-alanine] and an ortho-heterosubstituted aromatic amine, were newly synthesized as analogues of previously reported H2L1. Four contracted-Λoxo cobalt(III) complexes [Co(L)](+) with left-handed helical structure of Λ4Δ2 configuration were prepared by one-electron oxidation of the corresponding contracted-Λred cobalt(II) complexes [Co(L)], which were generated from chiral ligands and Co(ClO4)2·6H2O or Co(CF3SO3)2·5.2H2O in the presence of an organic base. Although the prepared cobalt(III) complexes were very inert and kinetically stable against protonation and NO3(-) complexation, cobalt(III) reduction in the presence of CF3SO3H and/or Bu4NNO3 allowed immediate changing of their three-dimensional structures from the contracted-Λoxo form to the extended-Λ [Co(H2L)Y2](n+) (Y = solvent and/or anion, n = 0-2) form with left-handed helicity or to the extended-Δ [Co(H2L)(NO3)](+) form with right-handed helicity via N- to O-amide coordination switching. Both extended forms were contracted to the original Λoxo form by oxidation of the cobalt(II) center in the presence of an organic base. Thus, redox reactions triggered dynamic helicity inversion of the chiral cobalt complexes, via multiple molecular motions consisting of relaxation/compression, extension/contraction, and helicity inversion motions in combination with deprotonation/protonation of amide linkages and NO3(-) anion complexation. PMID:26731008

  7. 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

  8. Probing the chiral anomaly and transport in Weyl semimetals

    NASA Astrophysics Data System (ADS)

    Parameswaran, Siddharth

    2014-03-01

    The topological nature of Weyl semimetals is reflected in the Adler-Bell-Jackiw anomaly, an unusual bulk response where applying parallel electric (E) and magnetic (B) fields pumps electrons between nodes of opposite chirality at a rate proportional to E . B . We argue that this pumping is measurable via nonlocal transport experiments, in the limit of weak internode scattering. Such nonlocal transport vanishes when the injected current and magnetic field are orthogonal, and therefore serves as a test of the chiral anomaly. I will also comment on the possibility of observing similar physics in the three-dimensional Dirac semimetallic phase proposed to exist in Na3Bi and Cd3As2, which have been the subject of recent photoemission and transport experiments. We acknowledge support from the Simons Foundation, NSF Grant PHYS-1066293 (Aspen Center for Physics), DOE Contract No. DEAC02- 05CH11231, and the Gordon and Betty Moore Foundation Grant GBMF1250 (IQIM at Caltech).

  9. 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

  10. 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.

  11. 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

  12. Copper-Catalyzed Intramolecular Desymmetric Aryl C-O Coupling for the Enantioselective Construction of Chiral Dihydrobenzofurans and Dihydrobenzopyrans.

    PubMed

    Yang, Wenqiang; Liu, Yangyuan; Zhang, Shasha; Cai, Qian

    2015-07-20

    O-Heterocyclic structures such as 2,3-dihydrobenzofurans are key motifs in many natural compounds and pharmaceuticals. Enantioselective formation of chiral dihydrobenzofurans and analogues was achieved through a copper-catalyzed desymmetrization strategy with a chiral cyclic 1,2-diamine. A broad range of substrates are compatible with this Cu(I)-diamine catalytic system and afford the desired coupling products with chiral tertiary or quaternary carbon centers in high yields and good to excellent enantioselectivities under mild conditions. PMID:26060986

  13. Asymmetric Ugi 3CR on isatin-derived ketimine: synthesis of chiral 3,3-disubstituted 3-aminooxindole derivatives

    PubMed Central

    Lesma, Giordano; Meneghetti, Fiorella; Sacchetti, Alessandro; Stucchi, Mattia

    2014-01-01

    Summary An efficient Ugi three-component reaction of a preformed chiral ketimine derived from isatin with various isonitrile and acid components has been developed. The reactions proceeded smoothly and in a stereocontrolled manner with regard to the new center of the Ugi products due to the stereoinduction of the amine chiral residue. A wide variety of novel chiral 3,3-disubstituted 3-aminooxindoles were obtained, a selection of which were subjected to post-Ugi transformations, paving the way to application as peptidomimetics. PMID:24991292

  14. 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.

  15. 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

  16. 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

  17. Molecular chirality: language, history, and significance.

    PubMed

    Gal, Joseph

    2013-01-01

    In this chapter some background material concerning molecular chirality and enantiomerism is presented. First some basic chemical-molecular aspects of chirality are reviewed, after which certain relevant terminology whose use in the literature has been problematic is discussed. Then an overview is provided of some of the early discoveries that laid the foundations of the science of molecular chirality in chemistry and biology, including the discovery of the phenomenon of molecular chirality by L. Pasteur, the proposals for the asymmetric carbon atom by J.H. van 't Hoff and J.A. Lebel, Pasteur's discovery of biological enantioselectivity, the discovery of enantioselectivity at biological receptors by A. Piutti, the studies of enzymatic stereoselectivity by E. Fischer, and the work on enantioselectivity in pharmacology by A. Cushny. Finally, the role of molecular chirality in pharmacotherapy and new-drug development, arguably one of the main driving forces for the current intense interest in the phenomenon of molecular chirality, is discussed. PMID:23666078

  18. 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.

  19. 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.

  20. 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

  1. Chiral description of massive gravity

    NASA Astrophysics Data System (ADS)

    Alexandrov, Sergei; Krasnov, Kirill; Speziale, Simone

    2013-06-01

    We propose and study a new first order version of the ghost-free massive gravity. Instead of metrics or tetrads, it uses a connection together with Plebanski's chiral 2-forms as fundamental variables, rendering the phase space structure similar to that of SU(2) gauge theories. The chiral description simplifies computations of the constraint algebra, and allows us to perform the complete canonical analysis of the system. In particular, we explicitly compute the secondary constraint and carry out the stabilization procedure, thus proving that in general the theory propagates 7 degrees of freedom, consistently with previous claims. Finally, we point out that the description in terms of 2-forms opens the door to an infinite class of ghost-free massive bi-gravity actions. Our results apply directly to Euclidean signature. The reality conditions to be imposed in the Lorentzian signature appear to be more complicated than in the usual gravity case and are left as an open issue.

  2. 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.

  3. 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

  4. Microfluidic Separation of Chiral Particles

    NASA Astrophysics Data System (ADS)

    Marcos; Fu, Henry; Powers, Thomas; Stocker, Roman

    2008-11-01

    We present a combined theoretical and experimental investigation of the fluid mechanics of a helix exposed to a shear flow. In addition to classic Jeffery orbits, Resistive Force Theory predicts a drift of the helix across streamlines, perpendicular to the shear plane. The direction of the drift is determined by the direction of the shear and the chirality of the helix. We verify this prediction experimentally using microfluidics, by exposing Leptospira biflexa, a non-motile strain of helical-shaped bacteria, to a plane parabolic flow. As the shear in the top and bottom halves of the microchannel has opposite sign, we predict and observe the bacteria in these two regions to drift in opposite directions. The magnitude of the separation is in good quantitative agreement with theory. This setup can be used to separate microscale chiral objects.

  5. 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.

  6. ENANTIOMERIC RATIOS OF CHIRAL PCB ATROPISOMERS IN RADIODATED SEDIMENT CORES

    EPA Science Inventory

    Enantiomeric ratios (ERs)) of chiral polychlorinated biphenyl (PCB) atropisomers were quantified in radiodated sediment cores of Lake Hartwell SC, a reservoir heavily impacted by PCBS, to study spatial and temporal changes in chirality. A chiral analysis of cores showed accumulat...

  7. 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.

  8. Chiral particle separation by a nonchiral microlattice.

    PubMed

    Bogunovic, Lukas; Fliedner, Marc; Eichhorn, Ralf; Wegener, Sonja; Regtmeier, Jan; Anselmetti, Dario; Reimann, Peter

    2012-09-01

    We conceived a model experiment for a continuous separation strategy of chiral molecules (enantiomers) without the need of any chiral selector structure or derivatization agents: Microparticles that only differ by their chirality are shown to migrate along different directions when driven by a steady fluid flow through a square lattice of cylindrical posts. In accordance with our numerical predictions, the transport directions of the enantiomers depend very sensitively on the orientation of the lattice relative to the fluid flow. PMID:23005274

  9. Chiral Particle Separation by a Nonchiral Microlattice

    NASA Astrophysics Data System (ADS)

    Bogunovic, Lukas; Fliedner, Marc; Eichhorn, Ralf; Wegener, Sonja; Regtmeier, Jan; Anselmetti, Dario; Reimann, Peter

    2012-09-01

    We conceived a model experiment for a continuous separation strategy of chiral molecules (enantiomers) without the need of any chiral selector structure or derivatization agents: Microparticles that only differ by their chirality are shown to migrate along different directions when driven by a steady fluid flow through a square lattice of cylindrical posts. In accordance with our numerical predictions, the transport directions of the enantiomers depend very sensitively on the orientation of the lattice relative to the fluid flow.

  10. 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.

  11. 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.

  12. 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

  13. Chiral plasmons without magnetic field

    NASA Astrophysics Data System (ADS)

    Song, Justin C. W.

    2016-04-01

    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.

  14. Sperm Trajectories Form Chiral Ribbons

    PubMed Central

    Su, Ting-Wei; Choi, Inkyum; Feng, Jiawen; Huang, Kalvin; McLeod, Euan; Ozcan, Aydogan

    2013-01-01

    We report the discovery of an entirely new three-dimensional (3D) swimming pattern observed in human and horse sperms. This motion is in the form of ‘chiral ribbons’, where the planar swing of the sperm head occurs on an osculating plane creating in some cases a helical ribbon and in some others a twisted ribbon. The latter, i.e., the twisted ribbon trajectory, also defines a minimal surface, exhibiting zero mean curvature for all the points on its surface. These chiral ribbon swimming patterns cannot be represented or understood by already known patterns of sperms or other micro-swimmers. The discovery of these unique patterns is enabled by holographic on-chip imaging of >33,700 sperm trajectories at >90–140 frames/sec, which revealed that only ~1.7% of human sperms exhibit chiral ribbons, whereas it increases to ~27.3% for horse sperms. These results might shed more light onto the statistics and biophysics of various micro-swimmers' 3D motion. PMID:23588811

  15. Analytical chiral separation of the stereoisomers of a novel carbonic anhydrase inhibitor and its deethylated metabolite, and the assignment of absolute configuration of the human metabolite and chiral degradation products.

    PubMed

    Matuszewski, B K; Constanzer, M L; Kiganda, M

    1994-03-01

    Several approaches to the separation of four stereoisomers, 1-4, of a novel, topically active, carbonic anhydrase inhibitor, 1, with two chiral centers in the molecule and four isomers, 5-8, of its chiral metabolite, 5, were evaluated. These methods include nonchiral derivatization followed by separation on chiral stationary phases (CSPs) and chiral derivatization and separation on nonchiral columns and on CSPs. Baseline separation of stereoisomers 1-4 was achieved in less than 15 min after chiral derivatization with (S)-(+)-1-(1-naphthyl)ethyl isocyanate (NEIC) and chiral chromatography on a (R)-N-(3,5-dinitrobenzoyl)phenyl glycine (DNBPG) column under normal phase (NP) conditions. Similarly, isomers 5-8 were baseline separated in less than 20 min after derivatization with NEIC and chromatography on nonchiral (nitrophenyl) and chiral [(S)-(3,5-dinitrobenzoyl)leucine; DNBL] columns in series under the same NP chromatographic conditions. Only partial separation of the diastereomeric derivatives was observed on a variety of nonchiral columns. In addition, all other direct and indirect chiral separation approaches gave only partial separation of at least two stereoisomers within the group of 1-4 or 5-8. The details of chiral separations using various methods and separation (alpha) and capacity factors (k') of the derivatized isomers 1-8 on a series of chiral and nonchiral columns are presented. Using these methods, the absolute configuration of the human metabolite of 1 was established as S1S2 (5), and the heat (HD) and light (LD) degradation products of 1 as R1S2 (3) and S1S2 (5), respectively. PMID:8008715

  16. 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.

  17. Lateral chirality-sorting optical forces

    PubMed Central

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

    2015-01-01

    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

  18. 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.

  19. Chiral mass-gap in curved space.

    PubMed

    Flachi, Antonino; Fukushima, Kenji

    2014-08-29

    We discuss a new type of QCD phenomenon induced in curved space. In the QCD vacuum, a mass-gap of Dirac fermions is attributed to the spontaneous breaking of chiral symmetry. If the curvature is positive large, the chiral condensate melts but a chiral invariant mass-gap can still remain, which we name the chiral gap effect in curved space. This leads to decoupling of quark deconfinement which implies a view of black holes surrounded by a first-order QCD phase transition. PMID:25215970

  20. 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

  1. Inherently Chiral Spider-Like Oligothiophenes.

    PubMed

    Sannicolò, Francesco; Mussini, Patrizia R; Benincori, Tiziana; Martinazzo, Rocco; Arnaboldi, Serena; Appoloni, Giulio; Panigati, Monica; Quartapelle Procopio, Elsa; Marino, Valentina; Cirilli, Roberto; Casolo, Simone; Kutner, Wlodzimierz; Noworyta, Krzysztof; Pietrzyk-Le, Agnieszka; Iskierko, Zofia; Bartold, Katarzyna

    2016-07-25

    The racemate of an inherently chiral "spider-like" octathiophene monomer T83 , in which chirality is generated by torsion in its backbone, was synthesized. The racemate was resolved into configurationally stable antipodes by HPLC on a chiral stationary phase. Electrooxidation of the enantiomers resulted in materials displaying high enantiorecognition ability towards the antipodes of some chiral probes. Moreover, the T83 racemate demonstrated great aptitude to stimulate formation of 3D rigid architectures if used as a cross-linking monomer for molecular imprinting. This feature was exploited to devise a molecularly imprinted polymer-based chemosensor selective for a thymine-adenine oligonucleotide. PMID:27321902

  2. Chiral pattern formation in compact microbial colonies

    NASA Astrophysics Data System (ADS)

    Korolev, Kirill; Bino George, Ashish

    Chirality is ubiquitous in biology from single molecules to entire populations. Yet, we are still lacking a detailed understanding of how chiral patterns emerge from cell competition and growth, even in simple microbial colonies. Although many microbes grow as dense colonies with no apparent chirality, recent experiments with Escherichia coli have demonstrated that internal dynamics in such populations can be in fact chiral. We show that there is a unique way to extend the commonly-used reaction-diffusion models of colony growth to account for the emergent chirality. This new model connects microscopic and macroscopic chirality and explains the origin of logarithmic spirals separating different sub-populations in a colony. We also show that chirality is substantially enhanced by the cooperation among the cells at the expansion frontier. In heterogeneous populations composed of strains with different chiralities and growth rates, our model predicts a very rich set of possible dynamics. For example, different chiralities can result in either sharp boundaries between the strains or promote their intermixing depending on the preferred twisting directions of the strains.

  3. Opportunities Center. Concept Paper.

    ERIC Educational Resources Information Center

    Kimeldorf, Martin

    The opportunities center is a new school service concept that can help students find opportunities related to their talents and interests in work, education, leisure, small business, or community service. The opportunities center model expands the career center model into an information search center offering multiple services that link academic…

  4. 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

  5. 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

  6. Quantum theory of chiral interactions in cholesteric liquid crystals

    NASA Astrophysics Data System (ADS)

    Issaenko, S. A.; Harris, A. B.; Lubensky, T. C.

    1999-07-01

    The effective chiral interaction between molecules arising from long-range quantum interactions between fluctuating charge moments is analyzed in terms of a simple model of chiral molecules. This model is based on the approximations that (a) the dominant excited states of a molecule form a band whose width is small compared to the average energy of excitation above the ground state and (b) biaxial orientational correlation between adjacent molecules can be neglected. Previous treatments of quantum chiral interactions have been based on a multipole expansion of the effective interaction energy within second-order perturbation theory. We consider a system consisting of elongated molecules and, although we invoke the expansion in terms of coordinates transverse to the long axis of constituent molecules, we treat the longitudinal coordinate exactly. Such an approximation is plausible for molecules in real liquid crystals. The macroscopic cholesteric wave vector Q (Q=2π/P, where P is the pitch) is obtained via Q=h/K2, where K2 is the Frank elastic constant for twist and h is the torque field which we calculate from the effective chiral interaction κIJaI×aJ.RIJ, where the unit vector aI specifies the orientation of molecule I and RIJ is the displacement of molecule I relative to molecule J. We identify two distinct physical limits depending on whether one or both of the interacting molecules are excited in the virtual state. When both molecules are excited, we regain the R-8IJ dependence of κIJ on intermolecular separation found previously by Van der Meer et al. [J. Chem. Phys. 65, 3935 (1976)]. The two-molecule, unlike the one-molecule term, can be interpreted in terms of a superposition of pairwise interactions between individual atoms (or local chiral centers) on the two molecules. Contributions to κIJ when one molecule is excited in the virtual state are of order R-7IJ for helical molecules which are assumed not to have a global dipole moment, but whose atoms

  7. 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

  8. Chiral exciton in the topological insulator Bi2Se3

    NASA Astrophysics Data System (ADS)

    Kung, Hsiang-Hsi; Salehi, Maryam; Wang, Xueyun; Koirala, Nikesh; Brahlek, Matthew; Lee, Alexander; Cheong, Sang-Wook; Oh, Seongshik; Blumberg, Girsh

    Materials with novel band structures can host ``chiral excitons'', where the exciton emission preserves the helicity of the excitation photon, as recently demonstrated in transition metal dichalcogenide monolayers. Here, we report the observation of a highly polarized photoluminescence peak, which is due to chiral exciton emission in the topological insulator Bi2Se3. Surprisingly, the energy of the emission is centered at 2.26 eV, much higher than the 0.3 eV bulk band gap of Bi2Se3. The excitation profile shows maximum polarization around 2.60 eV excitation, suggesting the chiral exciton is due to interband transition between the topological surface states and a bulk band. We demonstrate that the polarization of the exciton emission is insensitive to temperature and Bi2Se3 film thickness, providing a convenient and robust platform for optoelectronic applications. Gb, HHK and AL acknowledge support from NSF Award DMR-1104884. MS, NK, MB and SO are funded by Gordon and Betty Moore Foundation's EPiQS initiative (GBMF4418) and NSF(DMR-1308142). XYW and SWC acknowledge support from NSF Award DMREF-1233349.

  9. Asymmetric α-amination of 3-substituted oxindoles using chiral bifunctional phosphine catalysts

    PubMed Central

    Jin, Qiao-Wen; Chai, Zhuo; Huang, You-Ming

    2016-01-01

    Summary A highly enantioselective α-amination of 3-substituted oxindoles with azodicarboxylates catalyzed by amino acids-derived chiral phosphine catalysts is reported. The corresponding products containing a tetrasubstituted carbon center attached to a nitrogen atom at the C-3 position of the oxindole were obtained in high yields and with up to 98% ee.

  10. Multiple-locus variable number of tandem repeats analysis of Salmonella enterica serotype paratyphi A from Yuxi and comparison with isolates from the Chinese Medical Culture Collection Center

    PubMed Central

    YAO, YINGBO; CUI, XIAOYAN; CHEN, QINGSHAN; HUANG, XINRONG; ELMORE, BRADLEY; PAN, QING; WANG, SHUKUN; LIU, JIE

    2014-01-01

    The aim of the present study was to genotype Salmonella enterica serotype paratyphi A (SPA) isolated from Yuxi, China, in a multiple-locus variable number of tandem repeats (VNTRs) analysis (MLVA) and to compare them with isolates from the Chinese Medical Culture Collection Center (CMCC). Potential VNTRs were screened from the genomes of ATCC9150 and AKU_12601 using the Tandem Repeats Finder program. Nine VNTRs were established for MLVA typing of 195 SPA isolates from Yuxi and 20 isolates from CMCC. The dendogram for MLVA profiles and minimum spanning tree (MST) were drawn using the categorical coefficient calculated by BioNumerics software. A total of 23 MLVA types were identified in 215 SPA isolates and were grouped into six distinct cluster groups A, B, C, D, E and F. A total of 195 Yuxi SPA isolates were exclusively grouped into cluster C with nine MLVA genotypes. A total of 20 CMCC isolates were grouped in clusters A B, D, E and F with the other 14 MLVA types. The MLVA with nine VNTR loci, which was exploited in the present study, represents a successful strategy for genotyping SPA. Furthermore, the 195 Yuxi isolates appear to be closely related to each other and distinct from the 20 CMCC strains. PMID:24788795

  11. Structural origin of V-defects and correlation with localized excitonic centers in InGaN/GaN multiple quantum wells

    NASA Astrophysics Data System (ADS)

    Wu, X. H.; Elsass, C. R.; Abare, A.; Mack, M.; Keller, S.; Petroff, P. M.; DenBaars, S. P.; Speck, J. S.; Rosner, S. J.

    1998-02-01

    In the growth of InGaN/GaN multiple quantum well (MQW) structures, a novel defect (called the "V-defect") initiates at threading dislocations in one of the first quantum wells in a MQW stack. This defect is common to almost all InGaN MQW heterostructures. The nature of the V-defect was evaluated using transmission electron microscopy (TEM), scanning TEM (STEM), and low-temperature cathodoluminescence (CL) on a series of In0.20Ga0.80N/GaN MQW samples. The structure of the V-defect includes buried side-wall quantum wells (on the {101¯1} planes) and an open hexagonal inverted pyramid which is defined by the six {101¯1} planes. Thus, in cross section this defect appears as an open "V". The formation of the V-defect is kinetically controlled by reduced Ga incorporation on the pyramid walls ({101¯1} planes). The V-defect is correlated with the localized excitonic recombination centers that give rise to a long-wavelength shoulder in photoluminescence (PL) and CL spectra. This long-wavelength shoulder has the following characteristics: (i) its intensity is correlated with the side-wall quantum wells; (ii) the temperature independence of the full width at half maximum strongly supports a localized exciton recombination process.

  12. Chirally-modified metal surfaces: energetics of interaction with chiral molecules.

    PubMed

    Dementyev, Petr; Peter, Matthias; Adamovsky, Sergey; Schauermann, Swetlana

    2015-09-21

    Imparting chirality to non-chiral metal surfaces by adsorption of chiral modifiers is a highly promising route to create effective heterogeneously catalyzed processes for the production of enantiopure pharmaceuticals. One of the major current challenges in heterogeneous chiral catalysis is the fundamental-level understanding of how such chirally-modified surfaces interact with chiral and prochiral molecules to induce their enantioselective transformations. Herein we report the first direct calorimetric measurement of the adsorption energy of chiral molecules onto well-defined chirally-modified surfaces. Two model modifiers 1-(1-naphthyl)ethylamine and 2-methylbutanoic acid were used to impart chirality to Pt(111) and their interaction with propylene oxide was investigated by means of single-crystal adsorption calorimetry. Differential adsorption energies and absolute surface uptakes were obtained for the R- and S-enantiomers of propylene oxide under clean ultrahigh vacuum conditions. Two types of adsorption behavior were observed for different chiral modifiers, pointing to different mechanisms of imparting chirality to metal surfaces. The results are analyzed and discussed in view of previously reported stereoselectivity of adsorption processes. PMID:26256836

  13. 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. PMID:26900920

  14. Hydrodynamics of Liquids of Chiral Molecules and Suspensions Containing Chiral Particles

    NASA Astrophysics Data System (ADS)

    Andreev, A. V.; Son, D. T.; Spivak, B.

    2010-05-01

    We obtain hydrodynamic equations describing a fluid consisting of chiral molecules or a suspension of chiral particles in a Newtonian fluid. The hydrodynamic velocity and stresses arising in a flowing chiral liquid have components that are forbidden by symmetry in a Newtonian liquid. For example, a chiral liquid in a Poiseuille flow between parallel plates exerts forces on the plates, which are perpendicular to the flow. A generic flow results in spatial separation of particles of different chirality. Thus even a racemic suspension will exhibit chiral properties in a generic flow. A suspension of particles of random shape in a Newtonian liquid is described by equations which are similar to those describing a racemic mixture of chiral particles in a liquid.

  15. 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

  16. 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. PMID:23339842

  17. A mechanism to pin skyrmions in chiral magnets

    NASA Astrophysics Data System (ADS)

    Liu, Ye-Hua; Li, You-Quan

    2013-02-01

    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 107-108 A m-2, has linear dependence on the pinning strength.

  18. Chiral plasmonic nanostructures on achiral nanopillars.

    PubMed

    Yeom, Bongjun; Zhang, Huanan; Zhang, Hui; Park, Jai Il; Kim, Kyoungwon; Govorov, Alexander O; Kotov, Nicholas A

    2013-11-13

    Chirality of plasmonic films can be strongly enhanced by three-dimensional (3D) out-of-plane geometries. The complexity of lithographic methods currently used to produce such structures and other methods utilizing chiral templates impose limitations on spectral windows of chiroptical effects, the size of substrates, and hence, further research on chiral plasmonics. Here we demonstrate 3D chiral plasmonic nanostructures (CPNs) with high optical activity in the visible spectral range based on initially achiral nanopillars from ZnO. We made asymmetric gold nanoshells on the nanopillars by vacuum evaporation at different inclination and rotation angles to achieve controlled symmetry breaking and obtained both left- and right-rotating isomers. The attribution of chiral optical effects to monolithic enantiomers made in this process was confirmed by theoretical calculations based on their geometry established from scanning electron microscope (SEM) images. The chirality of the nanoshells is retained upon the release from the substrate into a stable dispersion. Deviation of the incident angle of light from normal results in increase of polarization rotation and chiral g-factor as high as -0.3. This general approach for preparation of abiological nanoscale chiral materials can be extended to other out-of plane 3D nanostructures. The large area films made on achiral nanopillars are convenient for sensors, optical devices, and catalysis. PMID:24111695

  19. 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.

  20. 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.

  1. Partially Quenched Chiral Perturbation Theory to NNLO

    SciTech Connect

    Laehde, Timo; Bijnens, Johan; Danielsson, Niclas

    2006-07-11

    This paper summarizes the recent calculations of the masses and decay constants of the pseudoscalar mesons at the two-loop level, or NNLO, in Partially Quenched Chiral Perturbation theory (PQ{chi}PT). Possible applications include chiral extrapolations of Lattice QCD, as well as the determination of the low-energy constants (LEC:s) of QCD.

  2. 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.

  3. T864 (MiniMax): A search for disoriented chiral condensate at the Fermilab Collider

    SciTech Connect

    Bjorken, J.D.

    1996-10-01

    A small test/experiment has been performed at the Fermilab Collider to measure charged particle and photon multiplicities in the forward direction, {eta} {approximately} 4.1. The primary goal is to search for disoriented chiral condensate (DCC). The experiment and analysis methods are described, and preliminary results of the DCC search are presented.

  4. 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

  5. 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. PMID:26342164

  6. 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).

  7. Spontaneous Chiral Symmetry Breaking for Finite Systems.

    PubMed

    Boscheto, Emerson; López-Castillo, Alejandro

    2015-12-01

    Theoretical clues are desirable to help uncover the origin of bio-homochirality in life, as well as the mechanisms for the asymmetric production of functional chiral substances. Here, an open-to-matter reaction network based on a model proposed by Plasson et al. is studied. In the extended model, the statistical fluctuations lead the system to break chiral symmetry autonomously, that is, without any initial enantiomeric excess or external influence. In the stability diagrams, we observe regions of parameter space that correspond to racemic, homochiral, chiral oscillatory, and, to our knowledge, for the first time in a chiral model, chaotic regimes. The dependencies of the final concentrations of chiral substances on the parameters are determined analytically and discussed for both the racemic and homochiral regimes. PMID:26395183

  8. 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

  9. Chiral Extensions of the Mssm

    NASA Astrophysics Data System (ADS)

    Ferretti, Gabriele; Karateev, Denis

    2013-03-01

    We present a class of extensions of the MSSM characterized by a fully chiral field content (no μ-terms) and no baryon or lepton number violating term in the superpotential due to an extra U‧(1) gauge symmetry. The minimal model consists of the usual matter sector with family dependent U‧(1) charges, six Higgs weak doublets, and three singlets required to give masses to the Higgsinos and cancel anomalies. We discuss its main features such as the tree level mass spectrum and the constraints on flavor changing processes.

  10. Chirality and the Quark Model

    SciTech Connect

    Eric S. Swanson; Adam P. Szczepaniak

    2002-06-07

    The relationship of the quark model to the known chiral properties of QCD is a long-standing problem in the interpretation of low energy QCD. In particular, how can the pion be viewed as both a collective Goldstone boson quasiparticle and as a valence quark antiquark bound state? A comparison of the many-body solution of a simplified model of QCD to the constituent quark model demonstrates that the quark model is sufficiently flexible to describe meson hyperfine splitting provided proper renormalization conditions and correct degrees of freedom are employed consistently.

  11. 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.

  12. 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

  13. Clinical Features, Treatments, and Outcomes of Patients with Thymic Carcinoids and Multiple Endocrine Neoplasia Type 1 Syndrome at MD Anderson Cancer Center.

    PubMed

    Christakis, Ioannis; Qiu, Wei; Silva Figueroa, Angelica M; Hyde, Samuel; Cote, Gilbert J; Busaidy, Naifa L; Williams, Michelle; Grubbs, Elizabeth; Lee, Jeffrey E; Perrier, Nancy D

    2016-08-01

    Thymic carcinoids are rare neuroendocrine tumors that occur in 1-5 % of patients with multiple endocrine neoplasia type 1 (MEN1) and are a major cause of morbidity and mortality. The few published reports associate these tumors with male sex and smoking. Our objective was to describe cases of these tumors treated at our institution. We performed a retrospective chart review of all patients diagnosed with MEN1 at our tertiary referral center from 1980 to 2014. Patients with a histopathologic, fine-needle aspiration, or clinical diagnosis of a thymic carcinoid were included. Two hundred ninety-one patients fulfilled the criteria for a diagnosis of MEN1. Clinicopathologic characteristics, MEN1 genetic testing results, treatments, and survival rates were analyzed. Nine patients had a thymic carcinoid, six men (67 %) and three women (33 %). Six patients were non-smokers (67 %). Two patients had synchronous (22 %) and eight patients (89 %) had metachronous distant metastasis. The 10-year overall survival rate was 45 % (lower 95 % upper 95 % CI 20-100 %). The 10-year disease-free survival rate was 42 % (lower 95 % upper 95 % CI 15-100 %). Five patients had MEN1 genetic testing, and the genotypes of affected individuals were p.W341X, c.275_286delGCTTCACCGCCC, p.R98X, c.1350+(1_11)del11, and partial duplication of exons 9 and 10. A higher percentage of MEN1-related thymic carcinoids can occur in women and in non-smokers than previously reported. Both novel and known mutations were present in our cohort. Eighty nine percent of patients developed a metachronous metastasis from the thymic carcinoid. Patients with MEN1 and thymic carcinoids should be followed closely. PMID:27311764

  14. Synthesis and characterization of mixed ligand chiral nanoclusters.

    PubMed

    Guven, Zekiye P; Ustbas, Burcin; Harkness, Kellen M; Coskun, Hikmet; Joshi, Chakra P; Besong, Tabot M D; Stellacci, Francesco; Bakr, Osman M; Akbulut, Ozge

    2016-07-28

    Chiral mixed ligand silver nanoclusters were synthesized in the presence of a chiral and an achiral ligand. While the chiral ligand led mostly to the formation of nanoparticles, the presence of the achiral ligand drastically increased the yield of nanoclusters with enhanced chiral properties. PMID:27362744

  15. 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.

  16. 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.

  17. Majorana Fermions in Chiral Topological Ferromagnetic Nanowires

    NASA Astrophysics Data System (ADS)

    Dumitrescu, Eugen; Roberts, Brenden; Tewari, Sumanta; Sau, Jay D.

    2015-03-01

    Motivated by a recent experiment in which zero-bias peaks have been observed in STM experiments performed on chains of magnetic atoms on a superconductor, we show that a multichannel ferromagnetic wire deposited on a spin-orbit coupled superconducting substrate can realize a non-trivial chiral topological superconducting state with Majorana bound states localized at the wire ends. The non-trivial topological state occurs for generic parameters requiring no fine tuning, at least for very large exchange spin splitting in the wire. We theoretically obtain the signatures which appear in the presence of an arbitrary number of Majorana modes in multi-wire systems incorporating the role of finite temperature, finite potential barrier at the STM tip, and finite wire length. These signatures are presented in terms of spatial profiles of STM differential conductance which clearly reveal zero energy Majorana end modes and the prediction of a multiple Majorana based fractional Josephson effect. Co-author: S. Das Sarma. Work supported by AFOSR (FA9550-13-1-0045) at Clemson University and by LPS-CMTC and JQI-NSF-PFC at the University of Maryland.

  18. Polarization Rotation by Multilayered Chiral Metamaterial

    NASA Astrophysics Data System (ADS)

    Zhang, Yumin; Nathan Burford Collaboration

    2013-03-01

    Traditionally, negative permittivity was realized by plasma resonance of the metallic structures, and negative permeability was achieved by a resonant LC circuit. Chiral metamaterial is another route to achieve negative permittivity and permeability, and such structures were investigated at different frequency domains. Recently, it was demonstrated that a two-dimensional lattice of three-dimensional gold spirals can effectively block circular polarized light with the same handedness for a frequency range exceeding one octave. From the point of view of applications, metamaterials must be fabricated easily and cheaply, and one way to achieve this goal is planarization. We designed a multiple-layer quasi-helix PCB structure and had it fabricated. The sample was tested with automated free space microwave material measurement system at X-band. These layers of PCB can be arranged in two different configurations: left-handed or right- handed helix. We found that the polarization plane is rotated in the opposite direction for the left- and right-handed samples, and the measured S-parameters agree with the simulation result relatively well. The authors would like to acknowledge the support from GRFC grant from Southeast Missouri State University.

  19. 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

  20. Chiral phonons at high-symmetry points in monolayer hexagonal lattices.

    PubMed

    Zhang, Lifa; Niu, Qian

    2015-09-11

    In monolayer hexagonal lattices, the intravalley and intervalley scattering of electrons can involve chiral phonons at Brillouin-zone center and corners, respectively. At these high-symmetry points, there is a threefold rotational symmetry endowing phonon eigenmodes with a quantized pseudoangular momentum, which includes orbital and spin parts. Conservation of pseudoangular momentum yields selection rules for intravalley and intervalley scattering of electrons by phonons. Concrete predictions of helicity-resolved optical phenomena are made on monolayer molybdenum disulfide. The chiral phonons at Brillouin-zone corners excited by polarized photons can be detected by a valley phonon Hall effect. The chiral phonons, together with phonon circular polarization, phonon pseudoangular momentum, selection rules, and valley phonon Hall effect will extend the basis for valley-based electronics and phononics applications in the future. PMID:26406841

  1. 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

  2. Chiral Phonons at High-Symmetry Points in Monolayer Hexagonal Lattices

    NASA Astrophysics Data System (ADS)

    Zhang, Lifa; Niu, Qian

    2015-09-01

    In monolayer hexagonal lattices, the intravalley and intervalley scattering of electrons can involve chiral phonons at Brillouin-zone center and corners, respectively. At these high-symmetry points, there is a threefold rotational symmetry endowing phonon eigenmodes with a quantized pseudoangular momentum, which includes orbital and spin parts. Conservation of pseudoangular momentum yields selection rules for intravalley and intervalley scattering of electrons by phonons. Concrete predictions of helicity-resolved optical phenomena are made on monolayer molybdenum disulfide. The chiral phonons at Brillouin-zone corners excited by polarized photons can be detected by a valley phonon Hall effect. The chiral phonons, together with phonon circular polarization, phonon pseudoangular momentum, selection rules, and valley phonon Hall effect will extend the basis for valley-based electronics and phononics applications in the future.

  3. Merger of visible light induced oxidation and enantioselective alkylation with a chiral iridium catalyst.

    PubMed

    Wang, Chuanyong; Zheng, Yu; Huo, Haohua; Röse, Philipp; Zhang, Lilu; Harms, Klaus; Hilt, Gerhard; Meggers, Eric

    2015-05-11

    A single chiral octahedral iridium(III) complex is used for visible light activated asymmetric photoredox catalysis. In the presence of a conventional household lamp and under an atmosphere of air, the oxidative coupling of 2-acyl-1-phenylimidazoles with N,N-diaryl-N-(trimethylsilyl)methylamines provides aminoalkylated products in 61-93 % yields with high enantiomeric excess (90-98 % ee). Notably, the iridium center simultaneously serves three distinct functions: as the exclusive source of chirality, as the catalytically active Lewis acid, and as a central part of the photoredox sensitizer. This conceptionally simple reaction Scheme may provide new avenues for the green synthesis of non-racemic chiral molecules. PMID:25832794

  4. 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.

  5. 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

  6. Atroposelective Synthesis of Axially Chiral Thiohydantoin Derivatives.

    PubMed

    Sarigul, Sevgi; Dogan, Ilknur

    2016-07-15

    Nonracemic axially chiral thiohydantoins were synthesized atroposelectively by the reaction of o-aryl isothiocyanates with amino acid ester salts in the presence of triethylamine (TEA). The synthesis of the nonaxially chiral derivatives, however, gave thiohydantoins racemized at C-5 of the heterocyclic ring. The micropreparatively resolved enantiomers of the nonaxially chiral derivatives from the racemic products were found to be optically stable under neutral conditions. On formation of the 5-methyl-3-arylthiohydantoin ring, bulky o-aryl substituents at N3 were found to suppress the C-5 racemization and in this way enabled the transfer of chirality from the α-amino acid to the products. The corresponding 5-isopropylthiohydantoins turned out to be more prone to racemization at C-5 during the ring formation. The isomer compositions of the synthesized axially chiral thiohydantoins have been determined through HPLC analyses with chiral stationary phases. In most cases a high prevalence of the P isomers over the M isomers has been obtained. The barriers to rotation determined around the Nsp(2)-Caryl chiral axis were found to be dependent upon the size of the o-halo aryl substituents. PMID:27322739

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. A new pH and thermo-responsive chiral hydrogel for stimulated release.

    PubMed

    Shankar, B Vijai; Patnaik, Archita

    2007-08-01

    Chirality of the amphiphile to promote gelation in the given solvent medium is narrated in a new catanionic surfactant mixture from a twin-chiral, twin-tailed surfactant derived from tartaric acid and cetyltrimethylammonium bromide (CTAB). The surfactant bis(decyloxy) succinic acid (BDSA), a chiral Gemini-type surfactant with a rigid spacer, in association with CTAB formed pH and temperature responsive vesicles and hydrogels. Molecular chirality gave rise to supertwisted fibrillar hydrogels at a BDSA:CTAB molar ratio of 1:2 and in 31% water content. The hydrogels from enantiomeric BDSA were reversibly pH and irreversibly temperature responsive at pH<6.2 and at 55 degrees C, respectively, whereas the corresponding sodium succinates formed transparent clear gels reversible to both pH and temperature. The hydrogels were able to entrap and release model dye molecules, Rhodamine B, and Congo red, responding to thermal and pH stimuli. Circular dichroism unraveled the chiro-optical behavior of the assembled fibers, allowing monitoring of aggregation and packing. The presence and the relative configuration of the stereogenic centers in the structure of this low molecular weight gelator have been observed to be critical to form gels. The high curvature Gaussian gel network was modeled based on the chiral elastic membrane approach and the pitch angle of the Gaussian twist was estimated to be 45 degrees. PMID:17629325

  12. 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

  13. Hidden chirality in superficially racemic patchy silver films.

    PubMed

    Larsen, George K; He, Yizhuo; Ingram, Whitney; Zhao, Yiping

    2013-01-01

    Chiral patchy particle films where morphological enantiomers exist in equal proportion are found to have significant circular dichroism. It is determined that the rotation direction during glancing angle deposition breaks the racemic symmetry, resulting in a distribution of material which enhances the chirality of one set of enantiomers relative to the other. Microscopic analysis and geometric chirality calculations reveal that the chirality of the bulk film results from incomplete cancellations of even stronger local chiralities. PMID:24256449

  14. 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.

  15. 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.

  16. The Macromolecular Route to Chiral Amplification.

    PubMed

    Green; Park; Sato; Teramoto; Lifson; Selinger; Selinger

    1999-11-01

    Cooperative phenomena, described by one-dimensional statistical physical methods, are observed between the enantiomeric characteristics of monomeric materials and the polymers they produce. The effect of minute energies associated with this amplified chirality, although currently not interpretable, can be easily measured. Nonlinear relationships between enantiomeric excess or enantiomeric content and polymer properties may offer the possibility of developing chiral catalysts and chiral chromatographic materials in which the burden of large enantiomeric excess or content may be considerably alleviated. New approaches to information and sensor technology may become possible. PMID:10556885

  17. 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

  18. 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

  19. 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

  20. 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

  1. Characteristics of surface plasmon polaritons in a dielectrically chiral-metal-chiral waveguiding structure.

    PubMed

    Zhang, Qiang; Li, Junqing

    2016-07-15

    We demonstrate theoretically the characteristics of surface plasmon polaritons (SPPs) with an asymmetric chiral-metal-chiral (CMC) waveguide structure, under realistic frequency dependencies of the permittivity and chirality parameters. Generalized dispersion relations are derived which can be applied to the nonchiral SPPs. We find that the existence of cutoffs in different modes for the CMC structures may facilitate the design of mode-selective surface plasmon waveguides. CMC-SPPs also exhibit an interesting dependence of the polarization on the chiral strength. These novel characteristics of CMC-SPPs provide new possibilities for the design of more compact nanophotonic devices. PMID:27420505

  2. The first year follow-up after colorectal adenoma polypectomy is important: a multiple-center study in symptomatic hospital-based individuals in China.

    PubMed

    Gao, Qin-Yan; Chen, Hui-Min; Sheng, Jian-Qiu; Zheng, Ping; Yu, Cheng-Gong; Jiang, Bo; Fang, Jing-Yuan

    2010-12-01

    The recurrence of colorectal adenoma (CRA) is high. Although there are guidelines for colonoscopy surveillance after polypectomy in other countries, little is known about its recurrence rate and recurrence peak, especially in China. The aim of the present research is to investigate how long after polypectomy follow-up should take and to analyze risk factors of recurrence. 1208 patients who received polypectomies from five clinical research centers in four regions of China (Shanghai, Guangzhou, Nanjing and Beijing) were included. They were divided into 4 groups: group A (follow-up ≤ 1 year after polypectomy), group B (follow-up 2-3 years after polypectomy), group C (follow-up 4-5 years after polypectomy), and group D (follow-up > 5 years after polypectomy). The sex, age, adenoma location, size, number, and pathological characteristics were compared. On the whole, the recurrence rate was 59.46% in group A, 61.09% in group B, 78.07% in group C, and 87.12% in group D, which indicated an increased tendency with a prolonged follow-up duration. There was a significant difference between group A and C or D, and between group B and C or D (P<0.01), but there was no statistical difference between group A and B. Additionally, the recurrent patients in the first year had a recurrence rate of 97.33% in the first three years (59.46/61.09), which means that the peak of recurrence was almost entirely concentrated in the first year. The recurrence rate was higher in males and the elder. The risk factors included multiple numbers, villous feature, high-grade dysplasia of medium or smaller size and location in the distal colon. In conclusion, the peak of recurrence was almost totally concentrated in the first year; meanwhile, the first year follow-up is of critical importance in China. It may not be necessary to do the follow-up examination during the second and third years, but after three years, another colonoscopy should be undertaken. PMID:21128011

  3. Magnetohydrodynamics of chiral relativistic fluids

    NASA Astrophysics Data System (ADS)

    Boyarsky, Alexey; Fröhlich, Jürg; Ruchayskiy, Oleg

    2015-08-01

    We study the dynamics of a plasma of charged relativistic fermions at very high temperature T ≫m , where m is the fermion mass, coupled to the electromagnetic field. In particular, we derive a magnetohydrodynamical description of the evolution of such a plasma. We show that, compared to conventional magnetohydronamics (MHD) for a plasma of nonrelativistic particles, the hydrodynamical description of the relativistic plasma involves new degrees of freedom described by a pseudoscalar field originating in a local asymmetry in the densities of left-handed and right-handed fermions. This field can be interpreted as an effective axion field. Taking into account the chiral anomaly we present dynamical equations for the evolution of this field, as well as of other fields appearing in the MHD description of the plasma. Due to its nonlinear coupling to helical magnetic fields, the axion field significantly affects the dynamics of a magnetized plasma and can give rise to a novel type of inverse cascade.

  4. {Lambda}* hypernuclei with chiral dynamics

    SciTech Connect

    Uchino, Toshitaka; Hyodo, Tetsuo; Oka, Makoto

    2011-10-21

    As a strangeness S = -1 and baryon number B = 2 system, the two-body bound state of {Lambda}* = {Lambda}(1405) and a nucleon is studied. To solve the {Lambda}*N system, we construct the {Lambda}*N potential by extending the Juelich model with couplings estimated in the chiral unitary approach. We have the {Lambda}*N quasi-bound state with the mass, M{sub {Lambda}}*N{approx}2366 MeV which is shallowly bound with the binding energy B{approx}9 MeV in terms of the K-barNN system. Decay width of the fall apart process, where the {Lambda}*N resonance decays to {pi}{Sigma}N with a nucleon being as a spectator, is estimated to be {Gamma}{sub F.A}{approx}49 MeV.

  5. Deformations in chiral liquid crystals

    NASA Astrophysics Data System (ADS)

    Shibaev, Petr; Reddy, Kathryn; Bateman, Daniel; Iljin, Andrey

    2014-03-01

    Deformations and their relaxation in chiral liquid crystals are studied experimentally and theoretically in planar geometry for liquid crystalline mixtures of varying viscosities. It is shown by both methods that shear deformation in liquid crystals results in the inclination and extension of cholesteric helix in samples with high viscosity. Stretching deformation results in shrinking cholesteric helix. This leads to a possibility of detecting deformations on a nanometer scale by observing changes in selective reflection spectra. Theoretical model takes into account elastic strain of physical network formed by the entanglements between components of liquid crystalline mixture, viscosity of the matrix and elasticity of the liquid crystalline subsystem. This allows to model mechanical response of the matrix with different viscosities to stretching and shear of various amplitudes. It is shown that relaxation of the cholesteric helix takes much shorter time than mechanical relaxation of the mixtures. The model perfectly agrees with experimental data. The model is compared with theoretical model describing behavior of elastomers.

  6. 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

  7. 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...

  8. Drag suppression in anomalous chiral media

    NASA Astrophysics Data System (ADS)

    Sadofyev, Andrey V.; Yin, Yi

    2016-06-01

    We study a heavy impurity moving longitudinal with the direction of an external magnetic field in an anomalous chiral medium. Such system would carry a nondissipative current of chiral magnetic effect associated with the anomaly. We show, by generalizing Landau's criterion for superfluidity, that the "anomalous component" which gives rise to the anomalous transport will not contribute to the drag experienced by an impurity. We argue on a very general basis that those systems with a strong magnetic field would exhibit an interesting transport phenomenon—the motion of the heavy impurity is frictionless, in analogy to the case of a superfluid. We demonstrate and confirm our general results with two complementary examples: weakly coupled chiral fermion gases and strongly interacting chiral liquids.

  9. Chiral chemistry of metal-camphorate frameworks.

    PubMed

    Gu, Zhi-Gang; Zhan, Caihong; Zhang, Jian; Bu, Xianhui

    2016-06-01

    This critical review presents the various synthetic approaches and chiral chemistry of metal-camphorate frameworks (MCamFs), which are homochiral metal-organic frameworks (MOFs) constructed from a camphorate ligand. The interest in this unique subset of homochiral MOFs is derived from the many interesting chiral features for both materials and life sciences, such as asymmetrical synthesis or crystallization, homochiral structural design, chiral induction, absolute helical control and ligand handedness. Additionally, we discuss the potential applications of homochiral MCamFs. This review will be of interest to researchers attempting to design other homochiral MOFs and those engaged in the extension of MOFs for applications such as chiral recognition, enantiomer separation, asymmetric catalysis, nonlinear sensors and devices. PMID:27021070

  10. 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.

  11. Optically active particles of chiral polymers.

    PubMed

    Song, Ci; Liu, Xuan; Liu, Dong; Ren, Chonglei; Yang, Wantai; Deng, Jianping

    2013-09-01

    Particles constructed by chiral polymers (defined as PCPs) have emerged as a rapidly expanding research field in recent years because of their potentially wide-ranging applications in asymmetric catalysis, enantioselective crystallization, enantioselective release, amongst many others. The particles show considerable optical activity, due to the chirality of the corresponding polymers from which the particles are derived. This review article presents an overview on PCPs with emphasis on our group's recent achievements in the preparation of PCPs derived from optically active helical polymers and their applications. PCPs can be prepared via emulsion polymerization, precipitation polymerization, and suspension polymerization by starting from monomers. Emulsification of preformed chiral polymers and self-assembly approaches also can lead to PCPs. Chiral polymer-based core/shell particles, hollow particles, and magnetic particles are also covered because of their remarkable properties and significant potential applications. PMID:24030962

  12. 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

  13. 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}}.

  14. 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.

  15. 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.

  16. Microbial production and applications of chiral hydroxyalkanoates.

    PubMed

    Chen, Guo-Qiang; Wu, Qiong

    2005-06-01

    Polyhydroxyalkanoates (PHA) are a family of polyesters consisting of over 150 chiral hydroxyalkanoic acids (HA). This paper reviews the physiological functions of (R)-3-hydroxybutyric acid (3HB) and (R)-4-hydroxybutyric acid and summarizes the technologies developed to produce various HA [3HB, (R)-3-hydroxyoctanoic acid, (R)-3-hydroxydecanoic acid, etc.] and the applications of chiral HA. Their outlooks and perspectives are discussed. PMID:15700123

  17. 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.

  18. Interference and isospin of disoriented chiral condensates

    SciTech Connect

    Suzuki, M.

    1995-09-01

    If coherent states describe the disoriented chiral condensates (DCC`s), many states of different chiral orientations should equally contribute to a given hadronic process. However, in the classical field description, we ignore the interference between the different DCC amplitudes. It results in a disregard of isospin invariance. We examine quantitatively how good this approximation is for the DCC`s of a typical size.

  19. 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

  20. 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.

  1. 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.

  2. Enantioselectively controlled release of chiral drug (metoprolol) using chiral mesoporous silica materials

    NASA Astrophysics Data System (ADS)

    Guo, Zhen; Du, Yu; Liu, Xianbin; Ng, Siu-Choon; Chen, Yuan; Yang, Yanhui

    2010-04-01

    Chiral porous materials have attracted burgeoning attention on account of their potential applications in many areas, such as enantioseparation, chiral catalysis, chemical sensors and drug delivery. In this report, chiral mesoporous silica (CMS) materials with various pore sizes and structures were prepared using conventional achiral templates (other than chiral surfactant) and a chiral cobalt complex as co-template. The synthesized CMS materials were characterized by x-ray diffraction, nitrogen physisorption, scanning electron microscope and transmission electron microscope. These CMS materials, as carriers, were demonstrated to be able to control the enantioselective release of a representative chiral drug (metoprolol). The release kinetics, as modeled by the power law equation, suggested that the release profiles of metoprolol were remarkably dependent on the pore diameter and pore structure of CMS materials. More importantly, R- and S-enantiomers of metoprolol exhibited different release kinetics on CMS compared to the corresponding achiral mesoporous silica (ACMS), attributable to the existence of local chirality on the pore wall surface of CMS materials. The chirality of CMS materials on a molecular level was further substantiated by vibrational circular dichroism measurements.

  3. Chiral polymerization in open systems from chiral-selective reaction rates.

    PubMed

    Gleiser, Marcelo; Nelson, Bradley J; Walker, Sara Imari

    2012-08-01

    We investigate the possibility that prebiotic homochirality can be achieved exclusively through chiral-selective reaction rate parameters without any other explicit mechanism for chiral bias. Specifically, we examine an open network of polymerization reactions, where the reaction rates can have chiral-selective values. The reactions are neither autocatalytic nor do they contain explicit enantiomeric cross-inhibition terms. We are thus investigating how rare a set of chiral-selective reaction rates needs to be in order to generate a reasonable amount of chiral bias. We quantify our results adopting a statistical approach: varying both the mean value and the rms dispersion of the relevant reaction rates, we show that moderate to high levels of chiral excess can be achieved with fairly small chiral bias, below 10%. Considering the various unknowns related to prebiotic chemical networks in early Earth and the dependence of reaction rates to environmental properties such as temperature and pressure variations, we argue that homochirality could have been achieved from moderate amounts of chiral selectivity in the reaction rates. PMID:22610131

  4. 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.

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

    PubMed

    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

  6. 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

  7. 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.

  8. 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

  9. Chirality of electrodeposits grown in a magnetic field

    NASA Astrophysics Data System (ADS)

    Mhíocháin, T. R.; Coey, J. M.

    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.

  10. 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

  11. 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.

  12. Chiral Properties in ^134Pr

    NASA Astrophysics Data System (ADS)

    Starosta, K.; Chiara, C. J.; Fossan, D. B.; Koike, T.; Beausang, C. W.; Hecht, A. A.; Boston, A. J.; Chantler, H. J.; Paul, E. S.; Scraggs, H. C.; Simons, A.; Wadsworth, R.; Clark, R. M.

    2001-04-01

    The πh_11/2νh_11/2 doublet bands in ^134Pr, which represent the best evidence to date for chiral symmetry breaking in odd-odd nuclei [1], were investigated with the GAMMASPHERE array using the ^116Cd(^23Na,5n) reaction at 115 MeV. From thin-target data, the nearly degenerate ΔI=1 side band was extended from a 9^+ bandhead up to a spin of 24^+ with E2 crossovers, a total of 15 units of spin, while the main yrast band was observed from an 8^+ bandhead to 24^+. Measured γ-ray intensities suggest a staggering of the B(M1)/B(E2) ratios in the main band with the ratio smaller for even-spin initial states; these compare well with those of other N=75 isotones. Relative transition rates for γ-rays linking the doublet bands have also been extracted. Analysis of backed-target data aimed at absolute transition rates is underway. The results will be compared to calculations with particle-hole triaxial-rotor and 3-D TAC models. [1mm] [1] C.M.Petrache, et al., Nucl.Phys.A597(1996)106; V.I.Dimitrov, et al., PRL 84(2000)5732; K. Starosta, et al., PRL 86(2001).

  13. 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.

  14. Macroscopic chirality of a liquid crystal from nonchiral molecules

    NASA Astrophysics Data System (ADS)

    Jákli, 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. 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...

  17. BRAFV600E status and clinical characteristics in solitary and multiple papillary thyroid carcinoma: experience of 512 cases at a clinical center in China

    PubMed Central

    2012-01-01

    Background Papillary thyroid carcinoma (PTC) is one of the most frequent endocrine malignancies. In most cases, it often presents as multifocal tumor. It has been reported that multifocal tumors are associated with elevated risk of lymph node and distant metastases. Multifocality is also one of the factors predicting prognosis. Recent studies show that BRAFV600E mutation occurs more frequently in aggressive PTC. The purpose of this study was to evaluate BRAFV600E status and clinicopathological features in multiple and solitary PTC. Methods We performed a retrospective study to analyze 512 PTC cases who received surgery, including 376 solitary PTCs and 136 multiple PTCs. Results Multiple PTC is more related to lymph node metastasis and vascular invasion than solitary PTC. However, the distant metastasis rate and 10-year survival rate showed no difference between these two groups. BRAFV600E mutation status was more frequent in multiple PTC patients with lymph node metastasis and late stage at diagnosis. Conclusion BRAFV600E mutation is most commonly associated with extra-thyroidal extension and lymph node metastasis in PTC. Multiple PTC patients with young age, large tumors and BRAFV600E mutation should be followed carefully. Our study provides useful information for PTC patients’ followup and treatment. PMID:22681706

  18. 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.

  19. Chiral density wave in nuclear matter

    NASA Astrophysics Data System (ADS)

    Heinz, Achim; Giacosa, Francesco; Rischke, Dirk H.

    2015-01-01

    Inspired by recent work on inhomogeneous chiral condensation in cold, dense quark matter within models featuring quark degrees of freedom, we investigate the chiral density-wave solution in nuclear matter at zero temperature and nonvanishing baryon number density in the framework of the so-called extended linear sigma model (eLSM). The eLSM is an effective model for the strong interaction based on the global chiral symmetry of quantum chromodynamics (QCD). It contains scalar, pseudoscalar, vector, and axial-vector mesons as well as baryons. In the latter sector, the nucleon and its chiral partner are introduced as parity doublets in the mirror assignment. The eLSM simultaneously provides a good description of hadrons in vacuum as well as nuclear matter ground-state properties. We find that an inhomogeneous phase in the form of a chiral density wave is realized, but only for densities larger than 2.4ρ0, where ρ0 is the nuclear matter ground-state density.

  20. 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

  1. 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.

  2. Chiral effects in uniformly loaded rods

    NASA Astrophysics Data System (ADS)

    Ieşan, D.

    2010-09-01

    Examples of chiral materials include some auxetic materials, bones, some honeycomb structures, as well as composites with inclusions. The chiral effects cannot be described within classical elasticity. In the context of the linear theory of Cosserat elastic solids, we investigate the deformation of a chiral rod subjected to tractions on the lateral surface, to body loads, and to resultant forces and moments on the ends. The work is motivated by the recent interest in the using of the Cosserat elastic solid as model for auxetic composites, carbon nanotubes and bones. The three-dimensional problem is reduced to the study of some generalized plane strain problems. New chiral effects are presented. In the case of cylinders of arbitrary cross-section, the flexure produced by a transversal force, in contrast with the case of achiral materials, is accompanied by extension and bending by terminal couples. The body loads and the tractions on the lateral surface produce extension, flexure, torsion, bending by terminal couples and a plane strain. It is shown that a uniform pressure acting on the lateral surface of a chiral circular cylinder does not produce bending effects.

  3. Ratchet transport powered by chiral active particles

    NASA Astrophysics Data System (ADS)

    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. 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. PMID:26795952

  5. Corynebactin and a Serine Trilactone Based Analogue-Chirality and Molecular Modeling of ferric Complexes

    SciTech Connect

    Bluhm, Martin E.; Hay, Benjamin P.; Kim, Sangoo S.; Dertz, Emily A.; Raymond, Kenneth N.

    2002-09-14

    The chirality of ferric siderophore complexes is a determinant for their cellular recognition and transport. Corynebactin (first isolated from a Gram-positive bacterium) contains L-threonine, unlike the closely related enterobactin, which contains L-serine. Also unlike enterobactin, ferric corynebactin is preferentially L at the iron center. Experimental (circular dichroism spectra and synthesis of a corynebactin/enterobactin hybrid) and theoretical (MM3 and density functional theory calculations) results explain ferric corynebactin's properties.

  6. Deterministic photon-emitter coupling in chiral photonic circuits

    NASA Astrophysics Data System (ADS)

    Söllner, Immo; Mahmoodian, Sahand; Hansen, Sofie Lindskov; Midolo, Leonardo; Javadi, Alisa; Kiršanskė, Gabija; Pregnolato, Tommaso; El-Ella, Haitham; Lee, Eun Hye; Song, Jin Dong; Stobbe, Søren; Lodahl, Peter

    2015-09-01

    Engineering photon emission and scattering is central to modern photonics applications ranging from light harvesting to quantum-information processing. To this end, nanophotonic waveguides are well suited as they confine photons to a one-dimensional geometry and thereby increase the light-matter interaction. In a regular waveguide, a quantum emitter interacts equally with photons in either of the two propagation directions. This symmetry is violated in nanophotonic structures in which non-transversal local electric-field components imply that photon emission and scattering may become directional. Here we show that the helicity of the optical transition of a quantum emitter determines the direction of single-photon emission in a specially engineered photonic-crystal waveguide. We observe single-photon emission into the waveguide with a directionality that exceeds 90% under conditions in which practically all the emitted photons are coupled to the waveguide. The chiral light-matter interaction enables deterministic and highly directional photon emission for experimentally achievable on-chip non-reciprocal photonic elements. These may serve as key building blocks for single-photon optical diodes, transistors and deterministic quantum gates. Furthermore, chiral photonic circuits allow the dissipative preparation of entangled states of multiple emitters for experimentally achievable parameters, may lead to novel topological photon states and could be applied for directional steering of light.

  7. 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.

  8. Deterministic photon-emitter coupling in chiral photonic circuits.

    PubMed

    Söllner, Immo; Mahmoodian, Sahand; Hansen, Sofie Lindskov; Midolo, Leonardo; Javadi, Alisa; Kiršanskė, Gabija; Pregnolato, Tommaso; El-Ella, Haitham; Lee, Eun Hye; Song, Jin Dong; Stobbe, Søren; Lodahl, Peter

    2015-09-01

    Engineering photon emission and scattering is central to modern photonics applications ranging from light harvesting to quantum-information processing. To this end, nanophotonic waveguides are well suited as they confine photons to a one-dimensional geometry and thereby increase the light-matter interaction. In a regular waveguide, a quantum emitter interacts equally with photons in either of the two propagation directions. This symmetry is violated in nanophotonic structures in which non-transversal local electric-field components imply that photon emission and scattering may become directional. Here we show that the helicity of the optical transition of a quantum emitter determines the direction of single-photon emission in a specially engineered photonic-crystal waveguide. We observe single-photon emission into the waveguide with a directionality that exceeds 90% under conditions in which practically all the emitted photons are coupled to the waveguide. The chiral light-matter interaction enables deterministic and highly directional photon emission for experimentally achievable on-chip non-reciprocal photonic elements. These may serve as key building blocks for single-photon optical diodes, transistors and deterministic quantum gates. Furthermore, chiral photonic circuits allow the dissipative preparation of entangled states of multiple emitters for experimentally achievable parameters, may lead to novel topological photon states and could be applied for directional steering of light. PMID:26214251

  9. 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

  10. Assessment of Multiple Outcomes: An Evaluation Research Study of a Compensatory Early Childhood Program (Child Parent Centers and Child Parent Expansion Program).

    ERIC Educational Resources Information Center

    Eash, Maurice J.; And Others

    Child Parent Centers (CPC) have been established in selected disadvantaged areas to provide systematic educational experiences for preschool children as young as three years of age. This study provides an update on the current state of the CPC and its latest adaption, the Child Parent Expansion (CPX) Program. A three-year, longitudinal evaluation…

  11. Two-color QCD with chiral chemical potential

    NASA Astrophysics Data System (ADS)

    Braguta, V. V.; Goy, V. A.; Ilgenfritz, E.-M.; Kotov, A. Yu.; Molochkov, A. V.; Müller-Preussker, M.; Petersson, B.; Schreiber, A.

    2016-01-01

    The phase diagram of two-color QCD with a chiral chemical potential is studied on the lattice. The focus is on the confinement/deconfinement phase transition and the breaking/restoration of chiral symmetry. The simulations are carried out with dynamical staggered fermions without rooting. The dependence of the Polyakov loop, the chiral condensate and the corresponding susceptibilities on the chiral chemical potential and the temperature are presented.

  12. Inhomogeneous Polyakov loop induced by inhomogeneous chiral condensates

    NASA Astrophysics Data System (ADS)

    Hayata, Tomoya; Yamamoto, Arata

    2015-05-01

    We study the spatial inhomogeneity of the Polyakov loop induced by inhomogeneous chiral condensates. We formulate an effective model of gluons on the background fields of chiral condensates, and perform its lattice simulation. On the background of inhomogeneous chiral condensates, the Polyakov loop exhibits an in-phase spatial oscillation with the chiral condensates. We also analyze the heavy quark potential and show that the inhomogeneous Polyakov loop indicates the inhomogeneous confinement of heavy quarks.

  13. 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

  14. Asymmetric Autocatalysis Induced by Chiral Crystals of Achiral Tetraphenylethylenes

    NASA Astrophysics Data System (ADS)

    Kawasaki, Tsuneomi; Nakaoda, Mai; Kaito, Nobuhiro; Sasagawa, Taisuke; Soai, Kenso

    2010-02-01

    The achiral hydrocarbon tetraphenylethylene crystallizes in enantiomorphous forms (chiral space group: P21) to afford right- and left-handed hemihedral crystals, which can be recognized by solid-state circular dichroism spectroscopic analysis. Chiral organic crystals of tetraphenylethylene mediated enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde to give, in conjunction with asymmetric autocatalysis with amplification of chirality, almost enantiomerically pure ( S)- and ( R)-5-pyrimidyl alkanols whose absolute configurations were controlled efficiently by the crystalline chirality of the tetraphenylethylene substrate. Tetrakis( p-chlorophenyl)ethylene and tetrakis( p-bromophenyl)ethylene also show chirality in the crystalline state, which can also act as a chiral substrate and induce enantioselectivity of diisopropylzinc addition to pyrimidine-5-carbaldehyde in asymmetric autocatalysis to give enantiomerically enriched 5-pyrimidyl alkanols with the absolute configuration correlated with that of the chiral crystals. Highly enantioselective synthesis has been achieved using chiral crystals composed of achiral hydrocarbons, tetraphenylethylenes, as chiral inducers. This chemical system enables significant amplification of the amount of chirality using spontaneously formed chiral crystals of achiral organic compounds as the seed for the chirality of asymmetric autocatalysis.

  15. Chiral Separation of G-type Chemical Warfare Nerve Agents via Analytical Supercritical Fluid Chromatography

    PubMed Central

    Kasten, Shane A; Zulli, Steven; Jones, Jonathan L; Dephillipo, Thomas; Cerasoli, Douglas M

    2014-01-01

    Chemical warfare nerve agents (CWNAs) are extremely toxic organophosphorus compounds that contain a chiral phosphorus center. Undirected synthesis of G-type CWNAs produces stereoisomers of tabun, sarin, soman, and cyclosarin (GA, GB, GD, and GF, respectively). Analytical-scale methods were developed using a supercritical fluid chromatography (SFC) system in tandem with a mass spectrometer for the separation, quantitation, and isolation of individual stereoisomers of GA, GB, GD, and GF. Screening various chiral stationary phases (CSPs) for the capacity to provide full baseline separation of the CWNAs revealed that a Regis WhelkO1 (SS) column was capable of separating the enantiomers of GA, GB, and GF, with elution of the P(+) enantiomer preceding elution of the corresponding P(–) enantiomer; two WhelkO1 (SS) columns had to be connected in series to achieve complete baseline resolution. The four diastereomers of GD were also resolved using two tandem WhelkO1 (SS) columns, with complete baseline separation of the two P(+) epimers. A single WhelkO1 (RR) column with inverse stereochemistry resulted in baseline separation of the GD P(–) epimers. The analytical methods described can be scaled to allow isolation of individual stereoisomers to assist in screening and development of countermeasures to organophosphorus nerve agents. Chirality 26:817–824, 2014. © 2014 The Authors. Chirality published by John Wiley Periodicals, Inc. PMID:25298066

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. Spontaneous chiral symmetry breaking in metamaterials

    NASA Astrophysics Data System (ADS)

    Liu, Mingkai; Powell, David A.; Shadrivov, Ilya V.; Lapine, Mikhail; Kivshar, Yuri S.

    2014-07-01

    Spontaneous chiral symmetry breaking underpins a variety of areas such as subatomic physics and biochemistry, and leads to an impressive range of fundamental phenomena. Here we show that this prominent effect is now available in artificial electromagnetic systems, enabled by the advent of magnetoelastic metamaterials where a mechanical degree of freedom leads to a rich variety of strong nonlinear effects such as bistability and self-oscillations. We report spontaneous symmetry breaking in torsional chiral magnetoelastic structures where two or more meta-molecules with opposite handedness are electromagnetically coupled, modifying the system stability. Importantly, we show that chiral symmetry breaking can be found in the stationary response of the system, and the effect is successfully demonstrated in a microwave pump-probe experiment. Such symmetry breaking can lead to a giant nonlinear polarization change, energy localization and mode splitting, which provides a new possibility for creating an artificial phase transition in metamaterials, analogous to that in ferrimagnetic domains.

  1. Heterogeneous chiral catalysis: Past, present, and future

    SciTech Connect

    Brenner, J.R.

    1996-12-31

    In order to improve the scalability of the synthesis of chiral compounds, considerable effort has been devoted to the design of heterogeneous chiral catalysts. The attachment of {open_quotes}curved{close_quotes} chiral ligands, such as cinchona alkaloids, to supported metal complexes has permitted enantioselectivities approaching those in homogeneous solution. While the nature of the support has received less attention, the increased pore structure control gained during the gradual shift from polymeric supports to pillared clays, and finally to mesoporous zeolites and controlled pore glasses will hopefully allow better molecular size and shape control. Future work in this area likely will entail the use of polymeric templates as molecular imprints for protein synthesis and for antibody delivery systems.

  2. Synthesizing Information from Multiple Sources: A Descriptive Study of Elementary Students' Perceptions and Performance of Discourse Synthesis. Elementary Subjects Center Series No. 45.

    ERIC Educational Resources Information Center

    Raphael, Taffy E.; Boyd, Fenice B.

    Two studies explored the nature of fourth- and fifth-grade students' abilities to synthesize information from multiple sources of text. The studies examined the ways in which elementary students approached a synthesis activity that involved reading two well-organized and related nonfiction articles, and then drawing upon that information as they…

  3. 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.

  4. Enantioselective synthesis of chiral heterocycles containing both chroman and pyrazolone derivatives catalysed by a chiral squaramide.

    PubMed

    Li, Jun-Hua; Du, Da-Ming

    2015-05-28

    An efficient chiral squaramide-catalysed enantioselective Michael addition of pyrazolin-5-ones to 3-nitro-2H-chromenes for the synthesis of chiral heterocyclic systems containing both chroman and pyrazolone derivatives has been developed. This reaction afforded the desired products in high to excellent yields (up to 98%) with high enantioselectivities (up to 96%) and excellent diastereoselectivities (up to 99 : 1) under very low catalyst loading (0.2 mol%). This catalytic asymmetric reaction provides an efficient route toward the synthesis of chiral heterocyclic systems containing both chroman and pyrazolone derivatives, which possess potential pharmaceutical activities. PMID:25882378

  5. 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.

  6. 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

  7. Quantitative sensory testing using DFNS protocol in Europe: an evaluation of heterogeneity across multiple centers in patients with peripheral neuropathic pain and healthy subjects.

    PubMed

    Vollert, Jan; Attal, Nadine; Baron, Ralf; Freynhagen, Rainer; Haanpää, Maija; Hansson, Per; Jensen, Troels S; Rice, Andrew S C; Segerdahl, Märta; Serra, Jordi; Sindrup, Soeren H; Tölle, Thomas R; Treede, Rolf-Detlef; Maier, Christoph

    2016-03-01

    Quantitative sensory testing (QST) in accordance with the DFNS (German Research Network on Neuropathic Pain) protocol assesses the function of afferent nerve fibers on the basis of 13 parameters. Within the consortia IMI (Innovative Medicines Initiative) Europain and Neuropain, QST results from pain research units experienced in QST across Europe can be compared for the first time. Aim of this analysis was to identify possible biases in the QST assessment between 10 centers from 8 different European countries. In total, 188 healthy subjects, 217 patients with painful polyneuropathy, and 150 patients with painful peripheral nerve injury were included in the analysis. Mixed effects models were constructed for each of the 11 normally distributed QST parameters with z-value as the dependent variable, and center as the random effect. The I statistic for heterogeneity was calculated, an index ranging from 0% (no heterogeneity) to 100% (perfect heterogeneity). Data from healthy subjects were comparable with the existing reference data base. Patients with polyneuropathy mainly displayed loss of sensory function, whereas patients with peripheral nerve injury often showed sensory loss combined with mechanical hyperalgesia. Heterogeneity was overall low between different centers and parameters. There was no systematic heterogeneity for patients with painful peripheral nerve injury and painful polyneuropathy. For healthy subjects, only blunt pressure pain threshold showed a considerable heterogeneity of 42% (95% confidence interval: 0%-66%). In conclusion, QST of both healthy subjects and patients with peripheral neuropathic pain is largely homogenous within the European centers, an essential prerequisite for performing multicenter QST-based studies. PMID:26630440

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. A multichannel magneto-chiral dichroism spectrometer

    NASA Astrophysics Data System (ADS)

    Kopnov, G.; Rikken, G. L. J. A.

    2014-05-01

    In this work, we describe a multichannel magneto-chiral dichroism spectrometer for the visible and near infrared wavelength ranges. The optical signal acquisition is based on commercially available Czerny-Turner spectrograph systems equipped with solid state detector arrays. The signal analysis method is based on post-processing phase sensitive detection, where the optical properties of the sample are modulated by an alternating external magnetic field. As an illustration of the performance of this spectrometer, magneto-chiral dichroism was measured in crystals of α - NiSO4 . 6H2O and good agreement with literature results was obtained.

  13. 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.

  14. Phenomenology of chiral damping in noncentrosymmetric magnets

    NASA Astrophysics Data System (ADS)

    Akosa, Collins Ashu; Miron, Ioan Mihai; Gaudin, Gilles; Manchon, Aurélien

    2016-06-01

    A phenomenology of magnetic chiral damping is proposed in the context of magnetic materials lacking inversion symmetry. We show that the magnetic damping tensor acquires a component linear in magnetization gradient in the form of Lifshitz invariants. We propose different microscopic mechanisms that can produce such a damping in ferromagnetic metals, among which local spin pumping in the presence of an anomalous Hall effect and an effective "s-d" Dzyaloshinskii-Moriya antisymmetric exchange. The implication of this chiral damping in terms of domain-wall motion is investigated in the flow and creep regimes.

  15. 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.

  16. 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.

  17. Terahertz wave emission from plasmonic chiral metasurfaces

    NASA Astrophysics Data System (ADS)

    Matsui, Takahiro; Tomita, Satoshi; Asai, Motoki; Tadokoro, Yuzuru; Takano, Keisuke; Nakajima, Makoto; Hangyo, Masanori; Yanagi, Hisao

    2016-03-01

    Plasmonic chiral metasurfaces with pinwheel-like structures are fabricated on silver films using a focused ion-beam milling technique. In time-domain spectroscopy, we observe terahertz (THz) wave emission from metasurfaces irradiated by a near-infrared Ti:sapphire ultrashort pulsed laser. The origin of the THz wave generation is likely to be tunnelling ionization accompanied with photoelectron acceleration by ponderomotive force. Numerical simulation is carried out toward improvement of the chiral metasurfaces for better emission of circularly polarized THz waves.

  18. 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.

  19. Disoriented chiral condensate: Theory and phenomenology

    SciTech Connect

    Bjorken, J.D.

    1997-12-01

    These notes are an abbreviated version of lectures given at the 1997 Zakopane School. They contain two topics. The first is a description in elementary terms of the basic ideas underlying the speculative hypothesis that pieces of strong-interaction vacuum with a rotated chiral order parameter, disoriented chiral condensate or DCC, might be produced in high energy elementary particle collisions. The second topic is a discussion of the phenomenological techniques which may be applied to data in order to experimentally search for the existence of DCC.

  20. Topologically nontrivial time-dependent chiral condensates

    SciTech Connect

    Suzuki, M.

    1996-11-01

    Topologically nontrivial time-dependent solutions of the classical nonlinear {sigma} model are studied as candidates of the disoriented chiral condensate (DCC) in 3+1 dimensions. Unlike the analytic solutions so far discussed, these solutions cannot be transformed into isospin-uniform ones by chiral rotations. If they are produced as DCC{close_quote}s, they can be detected by a distinct pattern in the angle-rapidity distribution of the neutral-to-charged pion ratio. {copyright} {ital 1996 The American Physical Society.}

  1. 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. PMID:19437635

  2. [Value of hematopoietic stem cell autotransplantation in the treatment of multiple myeloma: initial experience at the National Bone Marrow Transplantation Center and review of the literature].

    PubMed

    Abdelkefi, A; Ladeb, S; Ben Othman, T; Torjman, L; Jeddi, R; Ben Abdeladhim, A

    2000-10-01

    Alkylating agents administered with predisone have been the standard therapy for myeloma over the lost three decades. Intensive treatment with autologous hematopoietic support has become the treatment of choice for multiple myeloma patients up to 60 years of age. From march 1999 to january 2000, seven patients with multiple myeloma (stage III) with a median age of 43 years (34-56) received an autologous stem cell transplantation. The myeloablative treatment regimen consisted of high-dose melphalan. All patients had sustained engraftment. The median duration of neutropenia (< 500/mm3) was 12 days (11-140) and the median duration of thrombocytopenia (< 20,000/mm3) was 13 days (11-110). One patient had a complete remission, one a very good partial remission, and 5 patients had a partial remission. With a median follow-up of 8 months (2-12), all patients are alive, without relapse. PMID:11190737

  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. Effect of interlayer exchange coupling on magnetic chiral structures

    SciTech Connect

    Kang, S. P.; Kwon, H. Y.; Kim, H. S.; Shim, J. H.; Won, C.

    2015-07-28

    We numerically investigated the effect of interlayer exchange coupling on magnetic chiral structures, such as a helical/cycloidal spin structure and magnetic skyrmion crystal (SkX), which are produced in a magnetic system involving the Dzyaloshinskii-Moriya interaction (DMI). We report the existence of a phase transition where the length scale of magnetic structure discontinuously changes, and that there can be a novel magnetic structure around the phase boundary that exhibits double-ordering lengths of magnetic structure. Therefore, the system has multiple ground phases determined by the ratio of interlayer exchange coupling strength and DMI strength. Furthermore, we investigated the critical condition of the external perpendicular field required for the SkX. The critical field is significantly reduced under the effect of interlayer exchange coupling, which can stabilize the SkX without the external field.

  5. 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. PMID:25195666

  6. 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.

  7. 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.

  8. Synthesis of a Chiral Crystal Form of MOF-5, CMOF-5, by Chiral Induction.

    PubMed

    Zhang, Shi-Yuan; Li, Dan; Guo, Dong; Zhang, Hui; Shi, Wei; Cheng, Peng; Wojtas, Lukasz; Zaworotko, Michael J

    2015-12-16

    Chiral variants of the prototypal metal-organic framework MOF-5, Λ-CMOF-5 and Δ-CMOF-5, have been synthesized by preparing MOF-5 in the presence of L-proline or D-proline, respectively. CMOF-5 crystallizes in chiral space group P213 instead of Fm3̅m as exhibited by MOF-5. The phase purity of CMOF-5 was validated by single-crystal and powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, N2 adsorption, microanalysis, and solid-state vibrational circular dichroism. CMOF-5 undergoes a reversible single crystal-to-single crystal phase change to MOF-5 when immersed in a variety of organic solvents, although N-methyl-2-pyrrolidone (NMP) does not induce loss of chirality. Indeed, MOF-5 undergoes chiral induction when immersed in NMP, affording racemic CMOF-5. PMID:26606156

  9. 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

  10. 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

  11. 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

  12. Chiral damping of magnetic domain walls.

    PubMed

    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. ). PMID:26689141

  13. Dispersing carbon nanotubes by chiral network surfactants.

    PubMed

    Lin, Pengcheng; Cong, Yuehua; Zhang, Baoyan

    2015-04-01

    Chiral network surfactants (CNSs) possessing miscibility with carbon nanotubes (CNTs) and chiral materials are applied to disperse CNTs. Ultraviolet-visible absorption spectroscopy is used to quantitatively determine the CNT concentration in homogeneous CNT-CNS dispersions, results indicate that CNSs with more mole fraction of polycyclic conjugated structure have better ability to load and disperse CNTs and the maximal concentration reaches 0.79 mg mL(-1). Fourier transform infrared imaging system is utilized to analyze the dispersibility of CNTs in CNT-CNS composites, and CNS with 6 mol % nonmesogens (S6) induces the best dispersibility. The CNT doped CNSs exhibit lower glass transition temperature, strengthened thermal stability, decreased the thermochromic temperature and enriched reflected colors of CNSs. Furthermore, S6 are used as a promoter to disperse CNTs in chiral host, here, a left-handed chiral liquid crystal (CLC) is selected, the miscibility between CNTs and CLCs is studied by polarized optical microscope, and CNTs can be effectively dispersed in CLCs by S6. The CNT dispersed CLCs can exhibit a faster electro-optical response process than neat CLCs. PMID:25789867

  14. Excitations in the chiral spin liquid

    NASA Astrophysics Data System (ADS)

    Schroeter, Darrell

    2009-03-01

    Recently, a spin-Hamiltonian was presented [Schroeter et al, Phys. Rev. Lett. 99, 097202 (2007)] for which the chiral spin liquid is the exact ground state. This poster will present a numerical study of the excitations of the model, including results obtained by exact diagonalization of the model on 16 and 25-site lattices.

  15. 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.

  16. Quantum group extended chiral p-models

    NASA Astrophysics Data System (ADS)

    Hadjiivanov, L. K.; Paunov, R. R.; Todorov, I. T.

    1991-06-01

    The quantum symmetry group U q of an extended chiral conformal model is determined by the requirement that symmetry transformations commute with braid group statistics operators and by the relation between fusion rules and tensor product expansions of a certain class of U 4 representations. For thermal minimal " p-models", involving no more than p - 1 unitary lowest weight representations of the Virasoro algebra Vir, U 4 is the quantum universal enveloping (QUE) algebra U 4(sl(2)) with deformation parameter q satisfying q + q-1 = 2 cos π/ p ( qp = - 1, p = 4, 5,…). To each 2-dimensional local field labelled by a pair of nonnegative integers v, v¯ (0 ⩽ v, v¯ ⩽ p - 2) we make correspond an analytic chiral field φv, of weight Δ vand q- spin I v¯. The correlation functions of φv, transform under an 1-dimensional unitary representation of the braid group. As a result we reproduce the ADE classification of 2-dimensional p models in terms of their extended chiral counterparts. It turns out that U q-extended chiral p-models always involve non-unitary and indecomposable representations of Vir.

  17. Chiral electron transport in CVD bilayer graphene

    NASA Astrophysics Data System (ADS)

    Lee, Kyunghoon; Eo, Yun Suk; Kurdak, Cagliyan; Zhong, Zhaohui

    2014-03-01

    Charge carriers in bilayer graphene have a parabolic energy spectrum. Due to this band structure they are massive quasiparticles having a finite density of state at zero energy like other non-relativistic charge carriers in conventional two dimensional materials. However, they are massive Dirac fermions which have a chiral nature similar to the case of massless Dirac fermions in single layer graphene. Coupling of pseudospin and motion of charge carrier via chirality can result in dramatic consequence for transport in bipolar regime like Klein tunneling, Fabry-Perot interference, collimation of charge carrier, Veslago lens, etc. However, little attention has been paid to chiral dependent electron transport in bilayer graphene. Here we study these properties by probing phase coherent transport behavior in CVD bilayer graphene devices with sub-200nm channel length. Complex Fabry-Perot interference patterns are observed in resonant cavities defined by local gating. By applying Fourier analysis technique, we successfully analyze and identify the origin of each individual interference pattern in bipolar and monopolar regime. Our initial results also hint at the observation of cloaking of electronic states against chiral electrons in bilayer graphene.

  18. Weighted power counting and chiral dimensional regularization

    NASA Astrophysics Data System (ADS)

    Anselmi, Damiano

    2014-06-01

    We define a modified dimensional-regularization technique that overcomes several difficulties of the ordinary technique, and is specially designed to work efficiently in chiral and parity violating quantum field theories, in arbitrary dimensions greater than 2. When the dimension of spacetime is continued to complex values, spinors, vectors and tensors keep the components they have in the physical dimension; therefore, the γ matrices are the standard ones. Propagators are regularized with the help of evanescent higher-derivative kinetic terms, which are of the Majorana type in the case of chiral fermions. If the new terms are organized in a clever way, weighted power counting provides an efficient control on the renormalization of the theory, and allows us to show that the resulting chiral dimensional regularization is consistent to all orders. The new technique considerably simplifies the proofs of properties that hold to all orders, and makes them suitable to be generalized to wider classes of models. Typical examples are the renormalizability of chiral gauge theories and the Adler-Bardeen theorem. The difficulty of explicit computations, on the other hand, may increase.

  19. Kagome antiferromagnet: a chiral topological spin liquid?

    PubMed

    Messio, Laura; Bernu, Bernard; Lhuillier, Claire

    2012-05-18

    Inspired by the recent discovery of a new instability towards a chiral phase of the classical Heisenberg model on the kagome lattice, we propose a specific chiral spin liquid that reconciles different, well-established results concerning both the classical and quantum models. This proposal is analyzed in an extended mean-field Schwinger boson framework encompassing time reversal symmetry breaking phases, which allows both a classical and a quantum phase description. At low temperatures, we find that quantum fluctuations favor this chiral phase, which is stable against small perturbations of second- and third-neighbor interactions. For spin-1/2, this phase may be, beyond the mean field, a chiral gapped spin liquid. Such a phase is consistent with the density matrix renormalization group results of Yan et al. [Science 332, 1173 (2011)]. Mysterious features of the low-lying excitations of exact diagonalization spectra also find an explanation in this framework. Moreover, thermal fluctuations compete with quantum ones and induce a transition from this flux phase to a planar zero flux phase at a nonzero value of the renormalized temperature (T/S2), reconciling these results with those obtained for the classical system. PMID:23003183

  20. 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.

  1. 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. PMID:25537446

  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. 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

  4. 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. ).

  5. Concise theory of chiral lipid membranes

    NASA Astrophysics Data System (ADS)

    Tu, Z. C.; Seifert, U.

    2007-09-01

    A theory of chiral lipid membranes is proposed on the basis of a concise free energy density which includes the contributions of the bending and the surface tension of membranes, as well as the chirality and orientational variation of tilting molecules. This theory is consistent with the previous experiments [J.M. Schnur , Science 264, 945 (1994); M.S. Spector , Langmuir 14, 3493 (1998); Y. Zhao, , Proc. Natl. Acad. Sci. USA 102, 7438 (2005)] on self-assembled chiral lipid membranes of DC8,9PC . A torus with the ratio between its two generated radii larger than 2 is predicted from the Euler-Lagrange equations. It is found that tubules with helically modulated tilting state are not admitted by the Euler-Lagrange equations and that they are less energetically favorable than helical ripples in tubules. The pitch angles of helical ripples are theoretically estimated to be about 0° and 35°, which are close to the most frequent values 5° and 28° observed in the experiment [N. Mahajan , Langmuir 22, 1973 (2006)]. Additionally, the present theory can explain twisted ribbons of achiral cationic amphiphiles interacting with chiral tartrate counterions. The ratio between the width and pitch of twisted ribbons is predicted to be proportional to the relative concentration difference of left- and right-handed enantiomers in the low relative concentration difference region, which is in good agreement with the experiment [R. Oda , Nature (London) 399, 566 (1999)].

  6. Chiral conducting surfaces via electrochemical oxidation of L-leucine-oligothiophenes.

    PubMed

    McTiernan, Christopher D; Omri, Karim; Chahma, M'hamed

    2010-09-17

    Polythiophenes bearing a specific chiral center such as L-leucine have been prepared via the electrochemical oxidation of a series of L-leucine functionalized oligothiophenes (monothiophenes and terthiophenes). These oligothiophenes have been prepared through the condensation of L-leucine methyl ester and the corresponding thiophene monomers in the presence of hydroxybenzotriazole (HOBt) and N,N'-dicyclohexylcarbodiimide (DCC) followed by hydrolysis of the esters. The electroactive polymers are electrochemically stable and exhibit excellent adhesive properties on electrode surfaces (platinum, gold, and glassy carbon) as well as interesting optical properties in both doped and undoped states. Hydrogen bonds between a free amino acid (L-leucine, D-leucine, L-alanine, D-alanine, and D/L-alanine) and the L-leucine based polythiophenes (chiral conducting surface) were probed using cyclic voltammetry. Preliminary results show that the capacitive current of a modified L-leucine-polythiophene electrode decreases as a result of the formation of a hydrogen bond barrier on the surface of the chiral conducting surface accompanied with a shift of the oxidation potential. Cyclic voltammetry responses resulting from the interaction of the chiral conducting surface with L and Dfree amino acid isomers are similar. The formation of hydrogen bonds between the chiral conducting surfaces and the free amino acids was characterized by (1)H NMR. A chemical shift was observed for the N-H group in monomer 6 as a result of the hydrogen bond formation between the L-leucine methyl ester (D-leucine methyl ester, D/L-leucine methyl ester) and monomer 6. PMID:20718451

  7. Chiral detection in high-performance liquid chromatography by vibrational circular dichroism.

    PubMed

    Tran, C D; Grishko, V I; Huang, G

    1994-09-01

    A novel chiral detector for high-performance liquid chromatography has been developed. This detector is based on the measurement of circular dichroism of chiral effluents in the infrared region, i.e., vibrational circular dichroism (VCD). In this instrument, a solid-state spectral tunable (from 2.4 to 3.5 microns) F-center laser was used as the light source. The linearly polarized laser beam was converted into left circularly polarized light (LCPL) and right circularly polarized light (RCPL) at 42 kHz by means of a photoelastic modulator. The intensity of the LCPL and RCPL transmitted through the sample was measured by a liquid nitrogen cooled indium antimonide detector. Double modulation was employed to reduce the noise associated with the laser beam. Specifically, the linearly polarized laser beam, prior to being converted to CPL, was modulated at 85 Hz by a mechanical chopper. Demodulation and amplification were accomplished with the use of two lock-in amplifiers. In its present configuration, the instrument can be used to measure the VCD of O-H groups. Its sensitivity is so high that it was able, for the first time, to detect chirally (with limits of detection of micrograms) (R)- and (S)-2,2,2-trifluoro-1-(9- anthryl)ethanol and (R)- and (S)-benzoin when these compounds were chromatographically separated from the corresponding racemic mixtures by a Chiralcel-OD column. The main advantage of this chiral detector is, however, its universality; i.e., it can be used to virtually detect any chiral compounds which has O-H group (e.g, aliphatic alcohols such as 2-octanol). PMID:7943734

  8. The development of chiral nematic mesoporous materials.

    PubMed

    Kelly, Joel A; Giese, Michael; Shopsowitz, Kevin E; Hamad, Wadood Y; MacLachlan, Mark J

    2014-04-15

    Cellulose nanocrystals (CNCs) are obtained from the sulfuric acid-catalyzed hydrolysis of bulk cellulose. The nanocrystals have diameters of ~5-15 nm and lengths of ~100-300 nm (depending on the cellulose source and hydrolysis conditions). This lightweight material has mostly been investigated to reinforce composites and polymers because it has remarkable strength that rivals carbon nanotubes. But CNCs have an additional, less explored property: they organize into a chiral nematic (historically referred to as cholesteric) liquid crystal in water. When dried into a thin solid film, the CNCs retain the helicoidal chiral nematic order and assemble into a layered structure where the CNCs have aligned orientation within each layer, and their orientation rotates through the stack with a characteristic pitch (repeating distance). The cholesteric ordering can act as a 1-D photonic structure, selectively reflecting circularly polarized light that has a wavelength nearly matching the pitch. During CNC self-assembly, it is possible to add sol-gel precursors, such as Si(OMe)4, that undergo hydrolysis and condensation as the solvent evaporates, leading to a chiral nematic silica/CNC composite material. Calcination of the material in air destroys the cellulose template, leaving a high surface area mesoporous silica film that has pore diameters of ~3-10 nm. Importantly, the silica is brilliantly iridescent because the pores in its interior replicate the chiral nematic structure. These films may be useful as optical filters, reflectors, and membranes. In this Account, we describe our recent research into mesoporous films with chiral nematic order. Taking advantage of the chiral nematic order and nanoscale of the CNC templates, new functional materials can be prepared. For example, heating the silica/CNC composites under an inert atmosphere followed by removal of the silica leaves highly ordered, mesoporous carbon films that can be used as supercapacitor electrodes. The composition

  9. Role of pseudoephedrine as chiral auxiliary in the "acetate-type" aldol reaction with chiral aldehydes; asymmetric synthesis of highly functionalized chiral building blocks.

    PubMed

    Ocejo, Marta; Carrillo, Luisa; Vicario, Jose L; Badía, Dolores; Reyes, Efraim

    2011-01-21

    We have studied in depth the aldol reaction between acetamide enolates and chiral α-heterosubstituted aldehydes using pseudoephedrine as chiral auxiliary under double stereodifferentiation conditions, showing that high diastereoselectivities can only be achieved under the matched combination of reagents and provided that the α-heteroatom-containing substituent of the chiral aldehyde is conveniently protected. Moreover, the obtained highly functionalized aldols have been employed as very useful starting materials for the stereocontrolled preparation of other interesting compounds and chiral building blocks such as pyrrolidines, indolizidines, and densely functionalized β-hydroxy and β-amino ketones using simple and high-yielding methodologies. PMID:21188970

  10. 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

  11. 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.

  12. Au nanorod helical superstructures with designed chirality.

    PubMed

    Lan, Xiang; Lu, Xuxing; Shen, Chenqi; Ke, Yonggang; Ni, Weihai; Wang, Qiangbin

    2015-01-14

    A great challenge for nanotechnology is to controllably organize anisotropic nanomaterials into well-defined three-dimensional superstructures with customized properties. Here we successfully constructed anisotropic Au nanorod (AuNR) helical superstructures (helices) with tailored chirality in a programmable manner. By designing the 'X' pattern of the arrangement of DNA capturing strands (15nt) on both sides of a two-dimensional DNA origami template, AuNRs functionalized with the complementary DNA sequences were positioned on the origami and were assembled into AuNR helices with the origami intercalated between neighboring AuNRs. Left-handed (LH) and right-handed (RH) AuNR helices were conveniently accomplished by solely tuning the mirrored-symmetric 'X' patterns of capturing strands on the origami. The inter-rod distance was precisely defined as 14 nm and inter-rod angle as 45°, thus a full helix contains 9 AuNRs with its length up to about 220 nm. By changing the AuNR/origami molar ratio in the assembly system, the average number of AuNR in the helices was tuned from 2 to 4 and 9. Intense chiroptical activities arose from the longest AuNR helices with a maximum anisotropy factor of ∼0.02, which is highly comparable to the reported macroscopic AuNR assemblies. We expect that our strategy of origami templated assembly of anisotropic chiral superstructures would inspire the bottom-up fabrication of optically active nanostructures and shed light on a variety of applications, such as chiral fluids, chiral signal amplification, and fluorescence combined chiral spectroscopy. PMID:25516475

  13. Chemical synthesis of chiral conducting polymers

    DOEpatents

    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.

  14. Chemical synthesis of chiral conducting polymers

    DOEpatents

    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.

  15. 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.

  16. 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.

  17. Tolerability and pharmacokinetics of biapenem following single and multiple intravenous administrations in healthy Chinese subjects: an open-label, randomized, single-center study.

    PubMed

    Liu, Y; Li, Z; Yang, C; Zheng, H; Lv, Y; Chen, H; Zhang, Y; Shi, S

    2013-08-01

    This study was designed to evaluate the tolerability and pharmacokinetics of biapenem after single and multiple intravenous administrations in healthy Chinese subjects. Subjects were randomly allocated to receive a single 0.15, 0.3, or 0.6 g dose of biapenem. Subjects assigned to the 0.3 g single dose group continued into the multiple-dose phase. Blood samples were collected over 6 h and plasma biapenem concentrations were determined by a validated HPLC method. Tolerability was assessed by monitoring vital signs, laboratory parameters, physical examinations, electrocardiogram, and adverse events collected by non-directive questioning/spontaneous reporting. Pharmacokinetic parameters for biapenem after intravenous administration of a single dose of 0.15, 0.3, or 0.6 g were as follows: Cmax=7.06 (1.30), 15.59 (1.33), and 29.12 (1.22) mg/L; AUC0-6 h=8.95 (1.33), 22.62 (1.25), and 42.05 (1.19) mg · h/L; t1/2=0.97 (0.13), 1.04 (0.08), and 1.12 (0.08) h; CL=15.78 (1.32), 12.91 (1.24), and 13.95 (1.19) L/h; Vd=21.87 (1.25), 19.31 (1.25), and 22.41 (1.23) L, respectively. Pharmacokinetic parameters for biapenem after intravenous administration of multiple 0.3 g doses were as follows: Cmax=18.50 (1.16) mg/L; AUC0-6 h=26.45 (1.15) mg · h/L; t1/2=1.06 (0.15) h; CL=11.06 (1.16) L/h; Vd=16.78 (1.19) L. The incidence of reported AEs was as follows: phlebitis (2/10), nausea (1/10), and diarrhea (1/10). All of the AEs were mild in intensity. The pharmacokinetic properties of biapenem were linear at dose of 0.15-0.6 g. All biapenem doses appeared to be well tolerated. PMID:23585303

  18. 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

  19. 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

  20. A Powerful Chiral Phosphoric Acid Catalyst for Enantioselective Mukaiyama-Mannich Reactions.

    PubMed

    Zhou, Fengtao; Yamamoto, Hisashi

    2016-07-25

    A new BINOL-derived chiral phosphoric acid bearing 2,4,6-trimethyl-3,5-dinitrophenyl substituents at the 3,3'-positions was developed. The utility of this chiral phosphoric acid is demonstrated by a highly enantioselective (ee up to >99 %) and diastereoselective (syn/anti up to >99:1) asymmetric Mukaiyama-Mannich reaction of imines with a wide range of ketene silyl acetals. Moreover, this method was successfully applied to the construction of vicinal tertiary and quaternary stereogenic centers with excellent diastereo- and enantioselectivity. Significantly, BINOL-derived N-triflyl phosphoramide constitutes a complementary catalyst system that allows the title reaction to be applied to more challenging imines without an N-(2-hydroxyphenyl) moiety. PMID:27265881

  1. 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

  2. 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.

  3. Chiral separation of deprenyl-N-oxide isomers by capillary electrophoresis using various cyclodextrin derivatives.

    PubMed

    Tábi, Tamás; Halász, Attila Sándor; Pálfi, Melinda; Magyar, Kálmán; Szöko, Eva

    2004-01-01

    Chiral separation of deprenyl-N-oxide isomers is presented using capillary electrophoresis in the presence of various cyclodextrin (CD) derivatives. This recently identified metabolite of R-(-)-deprenyl may possess desirable pharmacological activities. The effect of the cavity size and the substituents of the CD are examined on the enantiomer resolution of the compound having an asymmetric center on a heteroatom. The importance of hydrophilic or hydrogen bonding interaction, as well as the position of the interacting groups is demonstrated. Outstanding selectivity and resolution values are achieved using the chargeable carboxymethyl-beta-CD. 2-Hydroxypropyl-beta-CD is also suitable for the enantiomer separation of the analyte. Native beta-CD and carboxyethyl-beta-CD provide only poor enantioselectivity, whereas heptakis-(2,6-di-O-methyl)-beta-CD is capable of separating only the diastereomers. No chiral resolution can be observed in the presence of gamma-CD. PMID:14965411

  4. 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

  5. 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

  6. 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.

  7. Circularly polarized light detection with hot electrons in chiral plasmonic metamaterials.

    PubMed

    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

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. 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

  13. 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

  14. 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. PMID:26043097

  15. Chiral assembly of weakly curled hard rods: Effect of steric chirality and polarity

    NASA Astrophysics Data System (ADS)

    Wensink, H. H.; Morales-Anda, L.

    2015-10-01

    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.

  16. Chiral assembly of weakly curled hard rods: Effect of steric chirality and polarity.

    PubMed

    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. PMID:26472398

  17. 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.

  18. Enantioseparation and chiral recognition mechanism of new chiral derivatives of xanthones on macrocyclic antibiotic stationary phases.

    PubMed

    Fernandes, Carla; Tiritan, Maria Elizabeth; Cass, Quezia; Kairys, Visvaldas; Fernandes, Miguel Xavier; Pinto, Madalena

    2012-06-01

    A chiral HPLC method using four macrocyclic antibiotic chiral stationary phases (CSPs) has been investigated for determination of the enantiomeric purity of fourteen new chiral derivatives of xanthones (CDXs). The separations were performed with the CSPs Chirobiotic T, Chirobiotic TAG, Chirobiotic V and Chirobiotic R under multimodal elution conditions (normal-phase, reversed-phase and polar ionic mode). The analyses were performed at room temperature in isocratic mode and UV and CD detection at a wavelength of 254 nm. The best enantioselectivity and resolution were achieved on Chirobiotic R and Chirobiotic T CSPs, under normal elution conditions, with R(S) ranging from 1.25 to 2.50 and from 0.78 to 2.06, respectively. The optimized chromatographic conditions allowed the determination of the enantiomeric ratio of eight CDXs, always higher than 99%. In order to better understand the chromatographic behavior at a molecular level, and the structural features associated with the chiral recognition mechanism, computational studies by molecular docking were carried out using VDock. These studies shed light on the mechanisms involved in the enantioseparation for this important class of chiral compounds. PMID:22552201

  19. Chiral solitons in a coupled double Peierls chain

    NASA Astrophysics Data System (ADS)

    Cheon, Sangmo; Kim, Tae-Hwan; Lee, Sung-Hoon; Yeom, Han Woong

    2015-10-01

    Chiral edge states are the hallmark of two- and three-dimensional topological materials, but their one-dimensional (1D) analog has not yet been found. We report that the 1D topological edge states, solitons, of the charge density wave system of indium atomic wires self-assembled on a silicon surface have chirality. The system is described by a coupled double Peierls-dimerized atomic chain, where the interchain coupling induces dynamical sublattice symmetry breaking. This changes its topological symmetry from Z2×Z2 to Z4 and endows solitons with a chiral degree of freedom. Chiral solitons can produce quantized charge transport across the chain that is topologically protected and controllable by the soliton’s chirality. Individual right- and left-chiral solitons in indium wires are directly identified by scanning tunneling microscopy.

  20. Theory of Chirality Transfer in Block Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Prasad, Ishan; Grason, Gregory

    Block copolymers assemble into a rich spectrum of ordered phases, with complexity driven by asymmetry in copolymer architecture. Despite decades of study, influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has been largely instrumental in prediction of physical properties of polymeric systems. Recently, a polar orientational self-consistent field (oSCF) theory was adopted to model chiral block copolymers having a thermodynamic preference for cholesteric ordering in chiral segments, and which confirmed the equilibrium stability of a helical cylinder morphology observed for chiral diblocks. Here, I describe a newly developed oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar interactions, and focus our study on intra-domain nematic ordering in flexible block copolymer assemblies, and in particular, mechanisms of transfer of segment chirality to mesochiral symmetries of self-assembled bicontinuous network morphologies.

  1. 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. PMID:26947890

  2. Chiral solitons in a coupled double Peierls chain.

    PubMed

    Cheon, Sangmo; Kim, Tae-Hwan; Lee, Sung-Hoon; Yeom, Han Woong

    2015-10-01

    Chiral edge states are the hallmark of two- and three-dimensional topological materials, but their one-dimensional (1D) analog has not yet been found. We report that the 1D topological edge states, solitons, of the charge density wave system of indium atomic wires self-assembled on a silicon surface have chirality. The system is described by a coupled double Peierls-dimerized atomic chain, where the interchain coupling induces dynamical sublattice symmetry breaking. This changes its topological symmetry from Z₂× Z₂to Z₄ and endows solitons with a chiral degree of freedom. Chiral solitons can produce quantized charge transport across the chain that is topologically protected and controllable by the soliton's chirality. Individual right- and left-chiral solitons in indium wires are directly identified by scanning tunneling microscopy. PMID:26450206

  3. 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

  4. 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

  5. Emergence of Chirality from Isotropic Interactions of Three Length Scales.

    PubMed

    Mkhonta, S K; Elder, K R; Huang, Zhi-Feng

    2016-05-20

    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. PMID:27258877

  6. 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.

  7. Formation of chiral branched nanowires by the Eshelby Twist.

    PubMed

    Zhu, Jia; Peng, Hailin; Marshall, A F; Barnett, D M; Nix, W D; Cui, Yi

    2008-08-01

    Manipulating the morphology of inorganic nanostructures, such as their chirality and branching structure, has been actively pursued as a means of controlling their electrical, optical and mechanical properties. Notable examples of chiral inorganic nanostructures include carbon nanotubes, gold multishell nanowires, mesoporous nanowires and helical nanowires. Branched nanostructures have also been studied and been shown to have interesting properties for energy harvesting and nanoelectronics. Combining both chiral and branching motifs into nanostructures might provide new materials properties. Here we show a chiral branched PbSe nanowire structure, which is formed by a vapour-liquid-solid branching from a central nanowire with an axial screw dislocation. The chirality is caused by the elastic strain of the axial screw dislocation, which produces a corresponding Eshelby Twist in the nanowires. In addition to opening up new opportunities for tailoring the properties of nanomaterials, these chiral branched nanowires also provide a direct visualization of the Eshelby Twist. PMID:18685634

  8. 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.

  9. Transport of anisotropic chiral particles in a confined structure

    NASA Astrophysics Data System (ADS)

    Hu, Cai-tian; Ou, Ya-li; Wu, Jian-chun; Ai, Bao-quan

    2016-03-01

    Directed transport of anisotropic chiral particles is numerically investigated in the presence of the regular arrays of rigid half-circle obstacles. It is found that due to the rotational-translational coupling, the transport of anisotropic particles is considerably more complicated compared to the isotropic case. For isotropic chiral particles, the transport direction is completely determined by the chirality of particles. However, for anisotropic chiral particles, the competition between the chirality and the anisotropic degree determines the transport direction. For a given chirality, by suitably tailoring parameters (the anisotropic degree and the self-propulsion speed), particles with different anisotropic degrees (or self-propulsion speed) can move in different directions and can be separated.

  10. 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.

  11. 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

  12. Integration of inherent and induced chirality into subphthalocyanine analogue.

    PubMed

    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

  13. 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.

  14. Nonperturbative Regulator for Chiral Gauge Theories?

    NASA Astrophysics Data System (ADS)

    Grabowska, Dorota M.; Kaplan, David B.

    2016-05-01

    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.

  15. 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).

  16. Mechanically generated surface chirality at the nanoscale.

    PubMed

    Ferjani, Sameh; Choi, Yoonseuk; Pendery, Joel; Petschek, Rolfe G; Rosenblatt, Charles

    2010-06-25

    A substrate coated with an achiral polyimide alignment layer was scribed bidirectionally with the stylus of an atomic force microscope to create an easy axis for liquid crystal orientation. The resulting noncentrosymmetric topography resulted in a chiral surface that manifests itself at the molecular level. To show this unambiguously, a planar-aligned negative dielectric aniostropy achiral nematic liquid crystal was placed in contact with the surface and subjected to an electric field E. The nematic director was found to undergo an azimuthal rotation approximately linear in E. This so-called "surface electroclinic effect" is a signature of surface chirality and was not observed when the polyimide was treated for a centrosymmetric topography, and therefore was nonchiral. PMID:20867414

  17. Sensing and actuation of smart chiral honeycombs

    NASA Astrophysics Data System (ADS)

    Abramovitch, H.; Burgard, M.; Edery-Azulay, Lucy; Evans, K. E.; Hoffmeister, M.; Miller, W.; Scarpa, F.; Smith, C. W.; Tee, K. F.; Schönecker, A.; Seffner, L.

    2008-03-01

    A chiral honeycomb configuration is developed with embedded piezosensors and actuators for smart sandwich panel applications. The chiral honeycomb concept is made of repeating units of cylinders and plates (ligaments), featuring an in-plane negative Poisson's ratio. Rapid Prototyping vacuum-cast and FDM (Fusion Deposition Moulding) techniques are developed to embed micro fibres composites to be used for potential structural health monitoring (SHM) applications, and microwave absorption screens for electromagnetic compatibility. Finite Element models are also developed to prototype and simulate the response, sensing and actuation capability of the honeycombs for design purposes. Dynamic tests using scanning laser vibrometers and acoustic wave propagation are carried out to assess the feasibility of the concept.

  18. 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

  19. 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.

  20. 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.

  1. 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)

  2. 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}

  3. Chiral Hexahalogenated 4,4'-Bipyridines.

    PubMed

    Mamane, V; Peluso, P; Aubert, E; Cossu, S; Pale, P

    2016-06-01

    The preparation of 27 isomers of chiral hexahalogeno-4,4'-bipyridines by means of two complementary methods is described. The first one is convergent and based on the LDA-induced 4,4'-dimerization of trihalopyridines, whereas the second method is divergent and achieved through regioselective halogenation reactions of 4,4'-bipyridine-2,2'-diones. Iodine in 2,2'-positions of the 4,4'-bipyridines was introduced by a copper-catalyzed Finkelstein reaction (Buchwald procedure) performed on 2,2'-dibromo derivatives. Selected compounds of this new family of atropisomeric 4,4'-bipyridines were enantioseparated by high performance liquid chromatography on chiral stationary phases, and the absolute configurations of the separated enantiomers were assigned by using X-ray diffraction analysis. The latter revealed that various halogen bond types are responsible for crystal cohesion. PMID:27149320

  4. 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.

  5. Chiral fermions in asymptotically safe quantum gravity

    NASA Astrophysics Data System (ADS)

    Meibohm, J.; Pawlowski, J. M.

    2016-05-01

    We study the consistency of dynamical fermionic matter with the asymptotic safety scenario of quantum gravity using the functional renormalisation group. Since this scenario suggests strongly coupled quantum gravity in the UV, one expects gravity-induced fermion self-interactions at energies of the Planck scale. These could lead to chiral symmetry breaking at very high energies and thus to large fermion masses in the IR. The present analysis which is based on the previous works (Christiansen et al., Phys Rev D 92:121501, 2015; Meibohm et al., Phys Rev D 93:084035, 2016), concludes that gravity-induced chiral symmetry breaking at the Planck scale is avoided for a general class of NJL-type models. We find strong evidence that this feature is independent of the number of fermion fields. This finding suggests that the phase diagram for these models is topologically stable under the influence of gravitational interactions.

  6. Chiral dynamics of S -wave baryon resonances

    NASA Astrophysics Data System (ADS)

    Long, Bingwei

    2016-07-01

    As the pion mass approaches a critical value mπ⋆ from below, an S -wave resonance crosses the pion-baryon threshold and becomes a bound state with arbitrarily small binding energy, thus driving the scattering length to diverge. I explore the consequences of chiral symmetry for the values of mπ close to mπ⋆. It turns out that chiral symmetry is crucial for an S -wave resonance to be able to stand very near the threshold and in the meantime to remain narrow, provided that the mass splitting is reasonably small. The effective range of pion-baryon scattering is unexpectedly large, proportional to 4 π fπ2/mπ3 when mπ is around mπ⋆. As a result, this unexpected large length scale causes universality relations to break down much sooner than naively expected.

  7. 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.

  8. Chiral symmetries associated with angular momentum

    NASA Astrophysics Data System (ADS)

    Bhattacharya, M.; Kleinert, M.

    2014-03-01

    In quantum mechanics courses, symmetries of a physical system are usually introduced as operators which commute with the Hamiltonian. In this paper we will consider chiral symmetries which anticommute with the Hamiltonian. Typically, introductory courses at the (under)graduate level do not discuss these simple, useful and beautiful symmetries at all. The first time a student encounters them is when the Dirac equation is discussed in a course on relativistic quantum mechanics, or when particle-hole symmetry is studied in the context of superconductivity. In this paper, we will show how chiral symmetries can be simply elucidated using the theory of angular momentum, which is taught in virtually all introductory quantum mechanics courses.

  9. Chiral softballs: synthesis and molecular recognition properties.

    PubMed

    Rivera, J M; Martín, T; Rebek, J

    2001-06-01

    Studies on the different congeners of the softball were undertaken to explore structural variants for enantioselective encapsulation. Two different spacer elements in the monomeric subunit render the dimeric softball chiral although the monomer itself is achiral. The dimers represent capsules with dissymmetric cavities with volumes ranging from 190 to 390 A(3). The cavities are distorted spheres, and asymmetric guests, such as naturally occurring terpenes, generally prefer one enantiomer of the capsule to its mirror image. The selectivities are moderate (up to 4:1). The complexation studies show that the host capsules are flexible enough to arrange themselves comfortably around a guest but still maintain enough rigidity to be influenced by the occupancy of a chiral guest. The enantiomeric capsules can interconvert (racemize) by dissociation and recombination of their subunits. PMID:11457383

  10. 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.

  11. Practical chiral alcohol manufacture using ketoreductases.

    PubMed

    Huisman, Gjalt W; Liang, Jack; Krebber, Anke

    2010-04-01

    Over the past two years the application of ketoreductases in the commercial synthesis of chiral alcohols has undergone a revolution. Biocatalysts are now often the preferred catalyst for the synthesis of chiral alcohols via ketone reduction and are displacing reagents and chemocatalysts that only recently were considered break-through process solutions themselves. Tailor-made enzymes can now be generated from advanced, non-natural variants using HTP screening and modern molecular biology techniques. At the same time, global economic and environmental pressures direct industrial process development toward versatile platforms that can be applied to the different stages of product development. We will discuss the technologies that have emerged over the past years that have guided biocatalysis from the bottom of the toolbox, to the power tool of choice. PMID:20071211

  12. Analytic study of disoriented chiral condensates

    SciTech Connect

    Suzuki, M.

    1996-09-01

    By introducing a quark source in the nonlinear {sigma} model, we obtain an analytic boost-invariant solution as a candidate for the disoriented chiral condensate (DCC) in 3+1 dimensions. In order to trigger formation of the DCC, a strong transfer of axial isospin charge must occur between the expanding source and the interior in the baked Alaska scenario. An explicit chiral symmetry breaking is incorporated in the solution by connecting the decay period to the formation period. Quantitative estimates are presented with our simple solution. At least in this class of solutions, the explicit symmetry breaking masks almost completely the disorientation which would be reached asymptotically in the symmetric limit. {copyright} {ital 1996 The American Physical Society.}

  13. 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.

  14. 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.

  15. 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.

  16. Circular dichroism of planar chiral magnetic metamaterials.

    PubMed

    Decker, M; Klein, M W; Wegener, M; Linden, S

    2007-04-01

    We propose, fabricate, and study a double-layer chiral planar metamaterial that exhibits pronounced circular dichroism at near-infrared wavelengths. The antisymmetric oscillation modes of the two coupled layers allow local magnetic-dipole moments and enhanced polarization effects compared with similar single-layer systems where only electric-dipole moments occur. Experiment and rigorous theoretical calculations are in good agreement. PMID:17339960

  17. Regular Scanning Tunneling Microscope Tips can be Intrinsically Chiral

    SciTech Connect

    Tierney, Heather L.; Murphy, Colin J.; Sykes, E. Charles H.

    2011-01-07

    We report our discovery that regular scanning tunneling microscope tips can themselves be chiral. This chirality leads to differences in electron tunneling efficiencies through left- and right-handed molecules, and, when using the tip to electrically excite molecular rotation, large differences in rotation rate were observed which correlated with molecular chirality. As scanning tunneling microscopy is a widely used technique, this result may have unforeseen consequences for the measurement of asymmetric surface phenomena in a variety of important fields.

  18. 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.

  19. 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

  20. Facile Diastereoseparation of Glycosyl Sulfoxides by Chiral Stationary Phase.

    PubMed

    Taniguchi, Tohru; Asahata, Mai; Nasu, Akihito; Shichibu, Yukatsu; Konishi, Katsuaki; Monde, Kenji

    2016-07-01

    Separation of the diastereomers of glycosyl sulfoxides differing in the sulfur chirality has been difficult. This article presents a fast and scalable method for their diastereoseparation using a chiral stationary phase. The usefulness of this method was demonstrated in a 500-mg scale separation within 20 min, and in the separation of trisaccharyl sulfoxide diastereomers. Chirality 28:534-539, 2016. © 2016 Wiley Periodicals, Inc. PMID:27296702