WorldWideScience

Sample records for axial chiral molecular

  1. Effects of Wavenumber and Chirality on the Axial Compressive Behavior of Wavy Carbon Nanotubes: A Molecular Mechanics Study

    Directory of Open Access Journals (Sweden)

    Masaki Kawachi

    2014-01-01

    Full Text Available The effects of wavenumber and chirality on the axial compressive behavior and properties of wavy carbon nanotubes (CNTs with multiple Stone-Wales defects are investigated using molecular mechanics simulations with the adaptive intermolecular reactive empirical bond-order potential. The wavy CNTs are assumed to be point-symmetric with respect to their axial centers. It is found that the wavy CNT models, respectively, exhibit a buckling point and long wavelength buckling mode regardless of the wavenumbers and chiralities examined. It is also found that the wavy CNTs have nearly the same buckling stresses as their pristine straight counterparts.

  2. Organocatalytic atroposelective synthesis of axially chiral styrenes

    Science.gov (United States)

    Zheng, Sheng-Cai; Wu, San; Zhou, Qinghai; Chung, Lung Wa; Ye, Liu; Tan, Bin

    2017-05-01

    Axially chiral compounds are widespread in biologically active compounds and are useful chiral ligands or organocatalysts in asymmetric catalysis. It is well-known that styrenes are one of the most abundant and principal feedstocks and thus represent excellent prospective building blocks for chemical synthesis. Driven by the development of atroposelective synthesis of axially chiral styrene derivatives, we discovered herein the asymmetric organocatalytic approach via direct Michael addition reaction of substituted diones/ketone esters/malononitrile to alkynals. The axially chiral styrene compounds were produced with good chemical yields, enantioselectivities and almost complete E/Z-selectivities through a secondary amine-catalysed iminium activation strategy under mild conditions. Such structural motifs are important precursors for further transformations into biologically active compounds and synthetic useful intermediates and may have potential applications in asymmetric synthesis as olefin ligands or organocatalysts.

  3. Molecular chirality at surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ernst, Karl-Heinz [Empa, Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse 129, 8600 Duebendorf (Switzerland); Organic Chemistry Institute, University Zurich, 8057 Zuerich (Switzerland)

    2012-11-15

    With the adsorption of larger molecules being increasingly tackled by surface scientists, the aspect of chirality often plays a role. This paper gives a topical review of molecular chirality at surfaces and gives a phenomenological overview of different aspects of adsorption and self-assembly of chiral and prochiral molecules and the principles of mirror-symmetry breaking at a surface. After a brief introduction into the history of molecular chirality and the important role it played for understanding the spatial structure of molecules, definitions of chirality are presented. Topics treated here are principle ways to create single chiral adsorbates, chiral ensembles, and monolayers by achiral molecules, adsorption of intrinsically chiral molecules at achiral and chiral surfaces, long-range symmetry breaking in two-dimensional (2D) crystals due to additional chiral bias, chiral restructuring of solid surfaces under the influence of chiral molecules, switching the handedness of adsorbates, and chirality at the liquid/air interface. An outlook onto further potential research directions and recommendations for further reading, including nonsurface-related sources of chiral topics completes this paper. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Influence of Axial and Point Chirality in the Chiral Self-Assembly of Twin N-Annulated Perylenecarboxamides.

    Science.gov (United States)

    Buendía, Julia; Greciano, Elisa E; Sánchez, Luis

    2015-12-18

    The synthesis of three bis(N-annulated perylenecarboxamides) endowed with achiral or chiral side chains is reported. The restricted rotation of the perylene moieties yields atropisomers that can be separated by chiral HPLC. The CD spectra of the six stereoisomers show a dichroic pattern in a good solvent that changes drastically upon adding a poor solvent that favors the aggregation. The cooperative character of the supramolecular polymerization mechanism of 1-3 has been determined by denaturation experiments, which reveal that the formation of homochiral aggregates is favored over the formation of heterochiral aggregates. A complete set of amplification of chirality experiments have been carried out, revealing the preponderance of axial chirality over point chirality. The results presented herein shed relevant light on the structural conditions exhibited by molecular units endowed with different elements of asymmetry to generate chiral supramolecular structures and the supremacy of axial chirality over point chirality in the origin of homochirality.

  5. Revealing atropisomer axial chirality in drug discovery.

    Science.gov (United States)

    LaPlante, Steven R; Edwards, Paul J; Fader, Lee D; Jakalian, Araz; Hucke, Oliver

    2011-03-07

    An often overlooked source of chirality is atropisomerism, which results from slow rotation along a bond axis due to steric hindrance and/or electronic factors. If undetected or not managed properly, this time-dependent chirality has the potential to lead to serious consequences, because atropisomers can be present as distinct enantiomers or diastereoisomers with their attendant different properties. Herein we introduce a strategy to reveal and classify compounds that have atropisomeric chirality. Energy barriers to axial rotation were calculated using quantum mechanics, from which predicted high barriers could be experimentally validated. A calculated rotational energy barrier of 20 kcal mol(-1) was established as a suitable threshold to distinguish between atropisomers and non-atropisomers with a prediction accuracy of 86%. This methodology was applied to subsets of drug databases in the course of which atropisomeric drugs were identified. In addition, some drugs were exposed that were not yet known to have this chiral attribute. The most valuable utility of this tool will be to predict atropisomerism along the drug discovery pathway. When used in concert with our compound classification scheme, decisions can be made during early discovery stages such as "hit-to-lead" and "lead optimization," to foresee and validate the presence of atropisomers and to exercise options of removing, further stabilizing, or rendering the chiral axis of interest more freely rotatable via SAR design, thereby decreasing this potential liability within a compound series. The strategy can also improve drug development plans, such as determining whether a drug or series should be developed as a racemic mixture or as an isolated single compound. Moreover, the work described herein can be extended to other chemical fields that require the assessment of potential chiral axes.

  6. Deracemization of Axially Chiral Nicotinamides by Dynamic Salt Formation with Enantiopure Dibenzoyltartaric Acid (DBTA

    Directory of Open Access Journals (Sweden)

    Fumitoshi Yagishita

    2013-11-01

    Full Text Available Dynamic atroposelective resolution of chiral salts derived from oily racemic nicotinamides and enantiopure dibenzoyltartaric acid (DBTA was achieved by crystallization. The absolute structures of the axial chiral nicotinamides were determined by X-ray structural analysis. The chirality could be controlled by the selection of enantiopure DBTA as a chiral auxiliary. The axial chirality generated by dynamic salt formation was retained for a long period after dissolving the chiral salt in solution even after removal of the chiral acid. The rate of racemization of nicotinamides could be controlled based on the temperature and solvent properties, and that of the salts was prolonged compared to free nicotinamides, as the molecular structure of the pyridinium ion in the salts was different from that of acid-free nicotinamides.

  7. Molecular model for chirality phenomena.

    Science.gov (United States)

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

    2016-10-21

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

  8. Vector and Axial Currents in Wilson Chiral Perturbation Theory

    CERN Document Server

    Aoki, Sinya; Sharpe, Stephen R

    2009-01-01

    We reconsider the construction of the vector and axial-vector currents in Wilson Chiral Perturbation Theory (WChPT), the low-energy effective theory for lattice QCD with Wilson fermions. We discuss in detail the finite renormalization of the currents that has to be taken into account in order to properly match the currents. We explicitly show that imposing the chiral Ward identities on the currents does, in general, affect the axial-vector current at O(a). As an application of our results we compute the pion decay constant to one loop in the two flavor theory. Our result differs from previously published ones.

  9. Induced axial chirality in biocatalytic asymmetric ketone reduction.

    Science.gov (United States)

    Agudo, Rubén; Roiban, Gheorghe-Doru; Reetz, Manfred T

    2013-02-06

    Catalytic asymmetric reduction of prochiral ketones of type 4-alkylidene cyclohexanone with formation of the corresponding axially chiral R-configurated alcohols (up to 99% ee) was achieved using alcohol dehydrogenases, whereas chiral transition-metal catalysts fail. Reversal of enantioselectivity proved to be possible by directed evolution based on saturation mutagenesis (up to 98% ee (S)). Utilization of ketone with a vinyl bromide moiety allows respective R- and S-alcohols to be exploited as key compounds in Pd-catalyzed cascade reactions.

  10. Atropisomerism: the effect of the axial chirality in bioactive compounds; Atropoisomerismo: o efeito da quiralidade axial em substancias bioativas

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Anderson Rouge dos; Pinheiro, Alessandra Campbell; Sodero, Ana Carolina Renno; Cunha, Andrea Sousa da; Padilha, Monica Costa; Sousa, Priscila Mesquita de; Fontes, Silvia Paredes [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Organica; Veloso, Marcia Paranho [Universidade Federal de Alfenas, MG (Brazil); Fraga, Carlos Alberto Manssour [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Faculdade de Farmacia. Lab. de Avaliacao e Sintese de Substancias Bioativas (LASSBio)]. E-mail: cmfraga@pharma.ufrj.br

    2007-01-15

    Atropisomerism is a special kind of stereoisomeric relationship that arises from the freezing of a certain conformation of an organic molecule, associated with a high rotational barrier about a single covalent bond. Atropisomerism has been originally described in orto-functionalized biphenyl derivatives, but a lot of other organic functionalities can present this structural phenomenon, characterized by the presence of chiral properties in compounds that do not present classical stereogenic centers. Atropisomeric compounds, intermediates and catalysts have well-know importance in organic synthesis, but the influence of the axial chirality in substances able to modulate biological systems is still not very exploited in drug design and development. In this context, the present account describes the importance of this structural property in the medicinal chemistry of different classes of bioactive compounds or therapeutic agents, emphasizing how atropisomerism could affect the molecular recognition of a ligand or a prototype by the target bioreceptor. (author)

  11. Design and Enantioselective Construction of Axially Chiral Naphthyl-Indole Skeletons.

    Science.gov (United States)

    Zhang, Hong-Hao; Wang, Cong-Shuai; Li, Can; Mei, Guang-Jian; Li, Yuxue; Shi, Feng

    2017-01-02

    The first enantioselective construction of a new class of axially chiral naphthyl-indole skeletons has been established by organocatalytic asymmetric coupling reactions of 2-naphthols with 2-indolylmethanols (up to 99 % yield, 97:3 e.r.). This approach not only affords a new type of axially chiral heterobiaryl backbone, but also provides a new catalytic enantioselective strategy for constructing axially chiral biaryl scaffolds by making use of the C3-electrophilicity of 2-indolylmethanols.

  12. Monitoring molecular chirality exchange by photon echoes

    Directory of Open Access Journals (Sweden)

    Mukamel Shaul

    2013-03-01

    Full Text Available We construct pulse polarization configurations in heterodyne four wave mixing for monitoring ultrafast(picosecondexchange rates between optical isomers with axial chirality.This information is not available from linear circular dichroism,since enantiomers may not be isolated and racemate shows no chiral signal.

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

    Science.gov (United States)

    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.

  14. Determination of the absolute configurations at stereogenic centers in the presence of axial chirality.

    Science.gov (United States)

    Polavarapu, Prasad L; Jeirath, Neha; Kurtán, Tibor; Pescitelli, Gennaro; Krohn, Karsten

    2009-01-01

    Cephalochromin, a homodimeric naphthpyranone natural product, contains both axial chirality due to the hindered rotation along the biaryl axis and central chirality due to the C-2, C-2' stereogenic centers of the fused pyranone ring. For determining the absolute configurations (ACs) of central chirality elements, different chiroptical spectroscopic methods, namely vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotation (OR), have been used. From these experimental data, in conjunction with corresponding quantum chemical predictions at B3LYP/6-311G* level, it is found that the ECD spectra of cephalochromin are dominated by its axial chirality and are not suitable to distinguish the (aS,2S,2'S) and (aS,2R,2'R) diastereomers and hence to determine the ACs of the central chirality elements. OR signs also did not distinguish the (aS,2S,2'S) and (aS,2R,2'R) diastereomers. On other hand, VCD spectrum of cephalochromin exhibited separate spectral features attributable to axial chirality and stereogenic centers, thereby allowing the determination of both types of chirality elements. This is the first investigation demonstrating that, because of vibrations specific to the studied stereogenic centers, VCD spectroscopy can be used to simultaneously determine the ACs of axial and central chirality elements whenever other chiroptical methods (ECD and OR) fail to report on them.

  15. Axial form factor of the nucleon in the perturbative chiral quark model

    CERN Document Server

    Khosonthongkee, K; Faessler, Amand; Gutsche, T; Lyubovitskij, V E; Pumsa-ard, K; Yan, Y

    2004-01-01

    We apply the perturbative chiral quark model (PCQM) at one loop to analyze the axial form factor of the nucleon. This chiral quark model is based on an effective Lagrangian, where baryons are described by relativistic valence quarks and a perturbative cloud of Goldstone bosons as dictated by chiral symmetry. We apply the formalism to obtain analytical expressions for the axial form factor of the nucleon, which is given in terms of fundamental parameters of low-energy pion-nucleon physics (weak pion decay constant, strong pion-nucleon form factor) and of only one model parameter (radius of the nucleonic three-quark core).

  16. Unusual dimeric tetrahydroxanthone derivatives from Aspergillus lentulus and the determination of their axial chiralities

    Science.gov (United States)

    Li, Tian-Xiao; Yang, Ming-Hua; Wang, Ying; Wang, Xiao-Bing; Luo, Jun; Luo, Jian-Guang; Kong, Ling-Yi

    2016-12-01

    The research on secondary metabolites of Aspergillus lentulus afforded eight unusual heterodimeric tetrahydroxanthone derivatives, lentulins A-H (2-9), along with the known compound neosartorin (1). Compounds 1-6 exhibited potent antimicrobial activities especially against methicillin-resistant Staphylococci. Their absolute configurations, particularly the axial chiralities, were unambiguously demonstrated by a combination of electronic circular dichroism (ECD), Rh2(OCOCF3)4-induced ECD experiments, modified Mosher methods, and chemical conversions. Interestingly, compounds 1-4 were the first samples of atropisomers within the dimeric tetrahydroxanthone class. Further investigation of the relationships between their axial chiralities and ECD Cotton effects led to the proposal of a specific CD Exciton Chirality rule to determine the axial chiralities in dimeric tetrahydroxanthones and their derivatives.

  17. Discovery and enantiocontrol of axially chiral urazoles via organocatalytic tyrosine click reaction.

    Science.gov (United States)

    Zhang, Ji-Wei; Xu, Jin-Hui; Cheng, Dao-Juan; Shi, Chuan; Liu, Xin-Yuan; Tan, Bin

    2016-02-11

    Axially chiral compounds play an important role in areas such as asymmetric catalysis. The tyrosine click-like reaction is an efficient approach for synthesis of urazoles with potential applications in pharmaceutical and asymmetric catalysis. Here we discover a class of urazole with axial chirality by restricted rotation around an N-Ar bond. By using bifunctional organocatalyst, we successfully develop an organocatalytic asymmetric tyrosine click-like reaction in high yields with excellent enantioselectivity under mild reaction conditions. The excellent remote enantiocontrol of the strategy originates from the efficient discrimination of the two reactive sites in the triazoledione and transferring the stereochemical information of the catalyst into the axial chirality of urazoles at the remote position far from the reactive site.

  18. Atropoisomerismo: o efeito da quiralidade axial em substâncias bioativas Atropisomerism: the effect of the axial chirality in bioactive compounds

    Directory of Open Access Journals (Sweden)

    Anderson Rouge dos Santos

    2007-02-01

    Full Text Available Atropisomerism is a special kind of stereoisomeric relationship that arises from the freezing of a certain conformation of an organic molecule, associated with a high rotational barrier about a single covalent bond. Atropisomerism has been originally described in orto-functionalyzed biphenyl derivatives, but a lot of other organic functionalities can present this structural phenomenon, characterized by the presence of chiral properties in compounds that don't present classical stereogenic centers. Atropisomeric compounds, intermediates and catalysts have well-know importance in organic synthesis, but the influence of the axial chirality in substances able to modulate biological systems is still not very exploited in drug design and development. In this context, the present account describes the importance of this structural property in the medicinal chemistry of different classes of bioactive compounds or therapeutic agents, emphasizing how atropisomerism could affect the molecular recognition of a ligand or a prototype by the target bioreceptor.

  19. A Molecular Model for Chiral Symmetry Breaking

    Science.gov (United States)

    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.

  20. Chiral perturbation theory study of the axial $N\\to\\Delta(1232)$ transition

    CERN Document Server

    Geng, L S; Alvarez-Ruso, L; Vacas, M J Vicente

    2008-01-01

    We have performed a theoretical study of the axial Nucleon to Delta(1232) ($N\\to\\Delta$) transition form factors up to one-loop order in covariant baryon chiral perturbation theory within a formalism in which the unphysical spin-1/2 components of the $\\Delta$ fields are decoupled.

  1. Geometrical approach to central molecular chirality: a chirality selection rule

    OpenAIRE

    Capozziello, S.; Lattanzi, A

    2004-01-01

    Chirality is of primary importance in many areas of chemistry and has been extensively investigated since its discovery. We introduce here the description of central chirality for tetrahedral molecules using a geometrical approach based on complex numbers. According to this representation, for a molecule having n chiral centres, it is possible to define an index of chirality. Consequently a chirality selection rule has been derived which allows the characterization of a molecule as achiral, e...

  2. Atropselective syntheses of (-) and (+) rugulotrosin A utilizing point-to-axial chirality transfer

    Science.gov (United States)

    Qin, Tian; Skraba-Joiner, Sarah L.; Khalil, Zeinab G.; Johnson, Richard P.; Capon, Robert J.; Porco, John A.

    2015-03-01

    Chiral, dimeric natural products containing complex structures and interesting biological properties have inspired chemists and biologists for decades. A seven-step total synthesis of the axially chiral, dimeric tetrahydroxanthone natural product rugulotrosin A is described. The synthesis employs a one-pot Suzuki coupling/dimerization to generate the requisite 2,2‧-biaryl linkage. Highly selective point-to-axial chirality transfer was achieved using palladium catalysis with achiral phosphine ligands. Single X-ray crystal diffraction data were obtained to confirm both the atropisomeric configuration and absolute stereochemistry of rugulotrosin A. Computational studies are described to rationalize the atropselectivity observed in the key dimerization step. Comparison of the crude fungal extract with synthetic rugulotrosin A and its atropisomer verified that nature generates a single atropisomer of the natural product.

  3. Vector and axial vector mesons in a nonlocal chiral quark model

    Science.gov (United States)

    Izzo Villafañe, M. F.; Gómez Dumm, D.; Scoccola, N. N.

    2016-09-01

    Basic features of nonstrange vector and axial vector mesons are analyzed in the framework of a chiral quark model that includes nonlocal four-fermion couplings. Unknown model parameters are determined from some input values of masses and decay constants, while nonlocal form factors are taken from a fit to lattice QCD results for effective quark propagators. Numerical results show a good agreement with the observed meson phenomenology.

  4. Vortex solutions in axial or chiral coupled non-relativistic spinor- Chern-Simons theory

    CERN Document Server

    Németh, Z A

    1997-01-01

    The interaction of a spin 1/2 particle (described by the non-relativistic "Dirac" equation of Lévy-Leblond) with Chern-Simons gauge fields is studied. It is shown, that similarly to the four dimensional spinor models, there is a consistent possibility of coupling them also by axial or chiral type currents. Static self dual vortex solutions together with a vortex-lattice are found with the new couplings.

  5. Nucleon-to-Delta axial transition form factors in relativistic baryon chiral perturbation theory

    CERN Document Server

    Geng, L S; Alvarez-Ruso, L; Vacas, M J Vicente

    2008-01-01

    We report a theoretical study of the axial Nucleon to Delta(1232) ($N\\to\\Delta$) transition form factors up to one-loop order in relativistic baryon chiral perturbation theory. We adopt a formalism in which the $\\Delta$ couplings obey the spin-3/2 gauge symmetry and, therefore, decouple the unphysical spin-1/2 fields. We compare the results with phenomenological form factors obtained from neutrino bubble chamber data and in quark models.

  6. Nuclear axial current operators to fourth order in chiral effective field theory

    OpenAIRE

    Krebs, H; Epelbaum, E.; Meißner, U.-G

    2016-01-01

    We present the complete derivation of the nuclear axial charge and current operators as well as the pseudoscalar operators to fourth order in the chiral expansion relative to the dominant one-body contribution using the method of unitary transformation. We demonstrate that the unitary ambiguity in the resulting operators can be eliminated by the requirement of renormalizability and by matching of the pion-pole contributions to the nuclear forces. We give expressions for the renormalized singl...

  7. Vector and axial vector mesons in a nonlocal chiral quark model

    CERN Document Server

    Villafañe, M F Izzo; Scoccola, N N

    2016-01-01

    Basic features of nonstrange vector and axial vector mesons are analyzed in the framework of a chiral quark model that includes nonlocal four fermion couplings. Unknown model parameters are determined from some input values of masses and decay constants, while nonlocal form factors are taken from a fit to lattice QCD results for effective quark propagators. Numerical results show a good agreement with the observed meson phenomenology.

  8. Spectral Remittances of Chiral Sculptured Zirconia Thin Films in Non-axial propagation

    CERN Document Server

    Babaei, Ferydon; 10.1080/09500340802130597

    2010-01-01

    The transmission and reflection spectra from a right-handed chiral sculptured zirconia thin film are calculated using the piecewise homogeneity approximation method and the Bruggeman homogenization formalism and considering that the dispersion of dielectric function happens in non-axial propagation state. First and second Bragg peaks were observed in cross-poloraized reflectances and it became clear that increasing the azimutal angle affects the spectra of linearly polarized state significantly. This is opposite to circularly polarized state.

  9. Chiral and U(1) axial symmetry restoration in linear sigma models with two quark flavors

    CERN Document Server

    Michalski, S

    2006-01-01

    We study the restoration of chiral symmetry in linear sigma models with two quark flavors. The models taken into consideration have a U(2) x U(2) and an O(N) internal symmetry. The physical mesons of these models are sigma, pion, \\eta and a_0 where the latter two are not present in the O(N) model. Including two-loop contributions through sunset graphs we calculate the temperature behavior of the order parameter and the masses for explicit chiral symmetry breaking with and without a U(1) axial anomaly. Decay threshold effects introduced by the sunset graphs alter the temperature dependence of the condensate and consequently that of the masses as well. Chiral symmetry tends to be restored at higher temperatures in the two-loop approximation than in the Hartree-Fock approximation. To model a dynamical restoration of the U(1) axial symmetry we imply a temperature-dependent anomaly parameter that sharply drops at about 175 MeV. This triggers the restoration of chiral symmetry before the full symmetry is restored a...

  10. Chiroptical studies on supramolecular chirality of molecular aggregates.

    Science.gov (United States)

    Sato, Hisako; Yajima, Tomoko; Yamagishi, Akihiko

    2015-10-01

    The attempts of applying chiroptical spectroscopy to supramolecular chirality are reviewed with a focus on vibrational circular dichroism (VCD). Examples were taken from gels, solids, and monolayers formed by low-molecular mass weight chiral gelators. Particular attention was paid to a group of gelators with perfluoroalkyl chains. The effects of the helical conformation of the perfluoroalkyl chains on the formation of chiral architectures are reported. It is described how the conformation of a chiral gelator was determined by comparing the experimental and theoretical VCD spectra together with a model proposed for the molecular aggregation in fibrils. The results demonstrate the potential utility of the chiroptical method in analyzing organized chiral aggregates.

  11. The baryon axial current in large $N_c$ chiral perturbation theory

    CERN Document Server

    Hernandez-Ruiz, Maria A

    2014-01-01

    In this thesis we calculate the baryon axial current within the combined framework of the $1/N_c$ expansion and chiral perturbation theory, where $N_c$ is the number of colors. This calculation shall consider Feynman diagrams to order of one-loop, octet and decuplet intermediaries states. We obtain corrections due to one-loop and perturbative SU(3) symmetry breaking. The first corrections come from Feynman diagrams, then talk about a broken chiral symmetry in the implicit limit $m_q \\rightarrow 0$, where $m_q$ is the quark mass and the second corrections are obtained by ignoring isospin breaking and in that case the SU(3) symmetry breaking a first-order perturbation is included, leading an explicit break symmetry. The matrix elements of the spatial components of the axial operator between the states of the spin flavor symmetry, give the typical values of the axial vector coupling. For the baryon octet, links axial vector are $g_A$, just as they are defined in experiments of baryon semileptonic decays, where $...

  12. Chiral extrapolation of nucleon axial charge gA in effective field theory

    Science.gov (United States)

    Li, Hong-na; Wang, P.

    2016-12-01

    The extrapolation of nucleon axial charge gA is investigated within the framework of heavy baryon chiral effective field theory. The intermediate octet and decuplet baryons are included in the one loop calculation. Finite range regularization is applied to improve the convergence in the quark-mass expansion. The lattice data from three different groups are used for the extrapolation. At physical pion mass, the extrapolated gA are all smaller than the experimental value. Supported by National Natural Science Foundation of China (11475186) and Sino-German CRC 110 (NSFC 11621131001)

  13. Nuclear axial current operators to fourth order in chiral effective field theory

    CERN Document Server

    Krebs, H; Meißner, U -G

    2016-01-01

    We present the complete derivation of the nuclear axial charge and current operators as well as the pseudoscalar operators to fourth order in the chiral expansion relative to the dominant one-body contribution using the method of unitary transformation. We demonstrate that the unitary ambiguity in the resulting operators can be eliminated by the requirement of renormalizability and by matching of the pion-pole contributions to the nuclear forces. We give expressions for the renormalized single-, two- and three-nucleon contributions to the charge and current operators and pseudoscalar operators including the relevant relativistic corrections. We also verify explicitly the validity of the continuity equation.

  14. A molecular propeller effect for chiral separation and analysis

    Science.gov (United States)

    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.

  15. Simultaneous Chiral SeparationUsing a Combinatorial Molecular Imprinting Phase

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Molecular imprinting chiral stationary phase against Cbz-L-Serine (Cbz-L-Ser) and Cbz-L-Alaine (Cbz-L-Ala) were prepared utilizing acrylamide + 2-vinylpyridine as combined basic functional monomers.Cross-selectivity was used to obtain simultaneous chiral separations of Cbz-DL-Ser and Cbz-DL-Ala by connecting two columns packed with Cbz-L-Ser and Cbz-L-Ala imprinted chiral stationary phase, respectively.

  16. Simultaneous Adjustment of Size and Helical Sense of Chiral Nanospheres and Nanotubes Derived from an Axially Racemic Poly(phenylacetylene).

    Science.gov (United States)

    Arias, Sandra; Núñez-Martínez, Manuel; Quiñoá, Emilio; Riguera, Ricardo; Freire, Félix

    2017-01-01

    Nanospheres and nanotubes with full control of their size and helical sense are obtained in chloroform from the axially racemic chiral poly(phenylacetylene) poly-(R)-1 using either Ag(+) as both chiral inducer and cross-linking agent or Na(+) as chiral inducer and Ag(+) as cross-linking agent. The size is tuned by the polymer/ion ratio while the helical sense is modulated by the polymer/cosolvent (i.e., MeCN) ratio. In this way, the helicity and the size of the nanoparticles can be easily interconverted by very simple experimental changes.

  17. Molecular-Level Design of Heterogeneous Chiral Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    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.

  18. Asymmetric Synthesis of Multisubstituted Dihydrobenzofurans by Intramolecular Conjugate Addition of Short-Lived C-O Axially Chiral Enolates.

    Science.gov (United States)

    Tomohara, Keisuke; Kasamatsu, Koji; Yoshimura, Tomoyuki; Furuta, Takumi; Kawabata, Takeo

    2016-07-01

    Enantioselective intramolecular conjugate addition reactions of short-lived C-O axially chiral enolates have been developed. The reactions proceeded with inversion of the configuration and provided dihydrobenzofurans with contiguous tetra- and trisubstituted carbon centers in up to 96% enantiomeric excess (ee).

  19. Discrete nanocubes as plasmonic reporters of molecular chirality.

    Science.gov (United States)

    Lu, Fang; Tian, Ye; Liu, Mingzhao; Su, Dong; Zhang, Hui; Govorov, Alexander O; Gang, Oleg

    2013-07-10

    One of the most intriguing structural properties, chirality, is often exhibited by organic and bio-organic molecular constructs. Chiral spectral signatures, typically appearing in the UV range for organic materials and known as circular dichroism (CD), are widely used to probe a molecular stereometry. Such probing has an increasingly broad importance for biomedical and pharmacological fields due to synthesis/separation/detection of homochiral species, biological role of chiral organization, and structural response to environmental conditions and enantiomeric drugs. Recent theoretical and experimental works demonstrated that the CD signal from chiral organic molecules could appear in the plasmonic (typically, visible) band when they coupled with plasmonic particles. However, the magnitude of this CD signal, induced by discrete nonchiral plasmonic particles, and its native molecular analog were found to be comparable. Here we show that shaped nonchiral nanoparticles, namely, gold/silver core/shell nanocubes, can act as plasmonic reporters of chirality for attached molecules by providing a giant, 2 orders of magnitude CD enhancement in a near-visible region. Through the experimental and theoretical comparison with nanoparticles of other shapes and materials, we demonstrate a uniqueness of silver nanocube geometry for the CD enhancement. The discovered phenomenon opens novel opportunities in ultrasensitive probing of chiral molecules and for novel optical nanomaterials based on the chiral elements.

  20. Relevance of the axial anomaly at the finite-temperature chiral transition in QCD

    CERN Document Server

    Pelissetto, Andrea

    2013-01-01

    We address the issue of the relevance of the suppression of the U(1)_A symmetry breaking, induced by the axial anomaly, at the finite-temperature chiral QCD transition with two light flavors. If the U(1)_A breaking is substantially suppressed at the transition, the effective symmetry breaking that determines the universality class is U(2)_L X U(2)_R -> U(2)_V. We perform a high-order perturbative study of the renormalization-group (RG) flow of the corresponding three-dimensional (3D) multiparameter Phi theory that has the same order parameter and symmetry-breaking pattern. We confirm the existence of a stable fixed point (FP), and determine its attraction domain in the space of the bare quartic parameters. Therefore, the chiral QCD transition might be continuous also if the U(1)_A symmetry is effectively restored at Tc. However, the corresponding universality class differs from the O(4) vector universality class which would describe a continuous transition in the presence of a substantial U(1)_A symmetry brea...

  1. Molecular-level Design of Heterogeneous Chiral Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gellman, Andrew John [Carnegie Mellon University; Sholl, David S. [Georgia Institute of Technology; Tysoe, Wilfred T. [University of Wisconsin - Milwaukee; Zaera, Francisco [University of California at Riverside

    2013-04-28

    Understanding and controlling selectivity is one of the key challenges in heterogeneous catalysis. Among problems in catalytic selectivity enantioselectivity is perhaps the most the most challenging. The primary goal of the project on “Molecular-level Design of Heterogeneous Chiral Catalysts” is to understand the origins of enantioselectivity on chiral heterogeneous surfaces and catalysts. The efforts of the project team include preparation of chiral surfaces, characterization of chiral surfaces, experimental detection of enantioselectivity on such surfaces and computational modeling of the interactions of chiral probe molecules with chiral surfaces. Over the course of the project period the team of PI’s has made some of the most detailed and insightful studies of enantioselective chemistry on chiral surfaces. This includes the measurement of fundamental interactions and reaction mechanisms of chiral molecules on chiral surfaces and leads all the way to rationale design and synthesis of chiral surfaces and materials for enantioselective surface chemistry. The PI’s have designed and prepared new materials for enantioselective adsorption and catalysis. Naturally Chiral Surfaces • Completion of a systematic study of the enantiospecific desorption kinetics of R-3-methylcyclohexanone (R-3-MCHO) on 9 achiral and 7 enantiomeric pairs of chiral Cu surfaces with orientations that span the stereographic triangle. • Discovery of super-enantioselective tartaric acid (TA) and aspartic acid (Asp) decomposition as a result of a surface explosion mechanism on Cu(643)R&S. Systematic study of super-enantiospecific TA and Asp decomposition on five enantiomeric pairs of chiral Cu surfaces. • Initial observation of the enantiospecific desorption of R- and S-propylene oxide (PO) from Cu(100) imprinted with {3,1,17} facets by L-lysine adsorption. Templated Chiral Surfaces • Initial observation of the enantiospecific desorption of R- and S-PO from Pt(111) and Pd(111

  2. Development of Ar-BINMOL-Derived Atropisomeric Ligands with Matched Axial and sp(3) Central Chirality for Catalytic Asymmetric Transformations.

    Science.gov (United States)

    Xu, Zheng; Xu, Li-Wen

    2015-10-01

    Recently, academic chemists have renewed their interest in the development of 1,1'-binaphthalene-2,2'-diol (BINOL)-derived chiral ligands. Six years ago, a working hypothesis, that the chirality matching of hybrid chirality on a ligand could probably lead to high levels of stereoselective induction, prompted us to use the axial chirality of BINOL derivatives to generate new stereogenic centers within the same molecule with high stereoselectivity, obtaining as a result sterically favorable ligands for applications in asymmetric catalysis. This Personal Account describes our laboratory's efforts toward the development of a novel class of BINOL-derived atropisomers bearing both axial and sp(3) central chirality, the so-called Ar-BINMOLs, for asymmetric synthesis. Furthermore, on the basis of the successful application of Ar-BINMOLs and their derivatives in asymmetric catalysis, the search for highly efficient and enantioselective processes also compelled us to give special attention to the BINOL-derived multifunctional ligands with multiple stereogenic centers for use in catalytic asymmetric reactions.

  3. Incommensurate Chirality Density Wave Transition in a Hybrid Molecular Framework

    Science.gov (United States)

    Hill, Joshua A.; Christensen, Kirsten E.; Goodwin, Andrew L.

    2017-09-01

    Using single-crystal x-ray diffraction we characterize the 235 K incommensurate phase transition in the hybrid molecular framework tetraethylammonium silver(I) dicyanoargentate, [NEt4]Ag3(CN )4 . We demonstrate the transition to involve spontaneous resolution of chiral [NEt4]+ conformations, giving rise to a state in which molecular chirality is incommensurately modulated throughout the crystal lattice. We refer to this state as an incommensurate chirality density wave (XDW) phase, which represents a fundamentally new type of chiral symmetry breaking in the solid state. Drawing on parallels to the incommensurate ferroelectric transition of NaNO2 , we suggest the XDW state arises through coupling between acoustic (shear) and molecular rotoinversion modes. Such coupling is symmetry forbidden at the Brillouin zone center but symmetry allowed for small but finite modulation vectors q =[0 ,0 ,qz]* . The importance of long-wavelength chirality modulations in the physics of this hybrid framework may have implications for the generation of mesoscale chiral textures, as required for advanced photonic materials.

  4. Development of an accurate molecular mechanics model for buckling behavior of multi-walled carbon nanotubes under axial compression.

    Science.gov (United States)

    Safaei, B; Naseradinmousavi, P; Rahmani, A

    2016-04-01

    In the present paper, an analytical solution based on a molecular mechanics model is developed to evaluate the elastic critical axial buckling strain of chiral multi-walled carbon nanotubes (MWCNTs). To this end, the total potential energy of the system is calculated with the consideration of the both bond stretching and bond angular variations. Density functional theory (DFT) in the form of generalized gradient approximation (GGA) is implemented to evaluate force constants used in the molecular mechanics model. After that, based on the principle of molecular mechanics, explicit expressions are proposed to obtain elastic surface Young's modulus and Poisson's ratio of the single-walled carbon nanotubes corresponding to different types of chirality. Selected numerical results are presented to indicate the influence of the type of chirality, tube diameter, and number of tube walls in detailed. An excellent agreement is found between the present numerical results and those found in the literature which confirms the validity as well as the accuracy of the present closed-form solution. It is found that the value of critical axial buckling strain exhibit significant dependency on the type of chirality and number of tube walls. Copyright © 2016. Published by Elsevier Inc.

  5. Preparation of Chiral 1,4-Phenylene-silicas via Chiral Low-molecular-weight Amphiphiles

    Institute of Scientific and Technical Information of China (English)

    XIAO Min; LIU Xiao-juan; HU Kai; WU Li-min; LI Yi; LI Bao-zong; YANG Yong-gang

    2012-01-01

    Chiral organic-inorganic hybrid silicas can be prepared via the self-assemblies of chiral surfactants and gelators as templates.However,the relationship between the chirality of the hybrid silica and the structure of the surfactant/gelator has not been systemically studied.Herein,a series of chiral low-molecular-weight amphiphiles(LMWAs) derived from L-valine was synthesized.Their alkyl chains were n-butadecyl,n-hexadecyl and n-octadecyl,respectively.They can form viscous liquids in pure water,and physical gels in tetrahydrofuran,cyclohexanone,acetonitrile,acetone,chlorobenzene and nitrobenzenc.Chiral 1,4-phenylene-silicas were prepared via the self-assemblies of these LMWAs as templates.With increasing the alkyl chain length,the 1,4-phenylene-silicas changed from short mesoporous nanorods to long nanotubcs. The circular dichroism spectra of the 1,4-phenylene-silicas indicated that the long nanotubes exhibit the strongest chirality.

  6. Axial-vector form factors of the nucleon within the chiral quark-soliton model and their strange components

    CERN Document Server

    Silva, A; Urbano, D; Göke, K; Silva, Antonio; Kim, Hyun-CHul; Urbano, Diana; Goeke, Klaus

    2005-01-01

    We investigate three different axial-vector form factors of the nucleon, $G_A^{0}$, $G_A^3$, $G_A^8$, within the framework of the SU(3) chiral quark-soliton model, emphasizing their strangeness content. We take into account the rotational $1/N_c$ and linear strange quark ($m_s$) contributions using the symmetry-conserving SU(3) quantization and assuming isospin symmetry. The strange axial-vector form factor is also obtained and they all are discussed in the context of the parity-violating scattering of polarized electrons off the nucleon and its relevance to the strange vector form factors.

  7. Nucleon and Delta axial-vector couplings in 1/N{sub c}-Baryon Chiral Perturbation Theory

    Energy Technology Data Exchange (ETDEWEB)

    Goity, Jose Luis [JLAB; Calle Cordon, Alvaro [JLAB

    2013-08-01

    In this contribution, baryon axial-vector couplings are studied in the framework of the combined 1/N{sub c} and chiral expansions. This framework is implemented on the basis of the emergent spin-flavor symmetry in baryons at large N{sub c} and HBChPT, and linking both expansions ({xi}-expansion), where 1/N{sub c} is taken to be a quantity order p. The study is carried out including one-loop contributions, which corresponds to order xi to the third for baryon masses and order {xi} square for the axial couplings.

  8. Aldol Reactions of Axially Chiral 5-Methyl-2-(o-arylimino-3-(o-aryl-thiazolidine-4-ones

    Directory of Open Access Journals (Sweden)

    Sule Erol Gunal

    2016-06-01

    Full Text Available Axially chiral 5-methyl-2-(o-arylimino-3-(o-aryl-thiazolidine-4-ones have been subjected to aldol reactions with benzaldehyde to produce secondary carbinols which have been found to be separable by HPLC on a chiral stationary phase. Based on the reaction done on a single enantiomer resolved via a chromatographic separation from a racemic mixture of 5-methyl-2-(α-naphthylimino-3-(α-naphthyl-thiazolidine-4-one by HPLC on a chiral stationary phase, the aldol reaction was shown to proceed via an enolate intermediate. The axially chiral enolate of the thiazolidine-4-one was found to shield one face of the heterocyclic ring rendering face selectivity with respect to the enolate. The selectivities observed at C-5 of the ring varied from none to 11.5:1 depending on the size of the ortho substituent. Although the aldol reaction proceeded with a lack of face selectivity with respect to benzaldehyde, recrystallization returned highly diastereomerically enriched products.

  9. Supramolecular Chirality: Solvent Chirality Transfer in Molecular Chemistry and Polymer Chemistry

    Directory of Open Access Journals (Sweden)

    Michiya Fujiki

    2014-08-01

    Full Text Available Controlled mirror symmetry breaking arising from chemical and physical origin is currently one of the hottest issues in the field of supramolecular chirality. The dynamic twisting abilities of solvent molecules are often ignored and unknown, although the targeted molecules and polymers in a fluid solution are surrounded by solvent molecules. We should pay more attention to the facts that mostly all of the chemical and physical properties of these molecules and polymers in the ground and photoexcited states are significantly influenced by the surrounding solvent molecules with much conformational freedom through non-covalent supramolecular interactions between these substances and solvent molecules. This review highlights a series of studies that include: (i historical background, covering chiral NaClO3 crystallization in the presence of d-sugars in the late 19th century; (ii early solvent chirality effects for optically inactive chromophores/fluorophores in the 1960s–1980s; and (iii the recent development of mirror symmetry breaking from the corresponding achiral or optically inactive molecules and polymers with the help of molecular chirality as the solvent use quantity.

  10. Design and synthesis of novel chiral molecular tweezers based on deoxycholic acid

    Institute of Scientific and Technical Information of China (English)

    Zhi Gang Zhao; Xing Li Liu; Yi Zhong

    2008-01-01

    A novel type of chiral molecular tweezers has been designed and synthesized by using deoxycholic acid as backbone and ethanoyl and the chiral unsymmetrical urea unit as arms. Their structures were characterized by 1H NMR, IR, MS spectra and elemental analysis. These molecular tweezers showed good binding ability for neutral molecules and chiral molecules.

  11. Axially chiral imidodiphosphoric Acid catalyst for asymmetric sulfoxidation reaction: insights on asymmetric induction.

    Science.gov (United States)

    Jindal, Garima; Sunoj, Raghavan B

    2014-04-22

    Insights into chiral induction for an asymmetric sulfoxidation reaction involving a single oxygen atom transfer are gained through analyzing the stereocontrolling transition states. The fitting of the substrate into the chiral cavity of a new class of imidodiphosphoric Brønsted acids, as well as weak CH⋅⋅⋅π and CH⋅⋅⋅O noncovalent interactions, are identified as responsible for the observed chiral induction.

  12. A complex-polarization-propagator protocol for magneto-chiral axial dichroism and birefringence dispersion

    DEFF Research Database (Denmark)

    Cukras, Janusz; Kauczor, Joanna; Norman, Patrick

    2016-01-01

    A computational protocol for magneto-chiral dichroism and magneto-chiral birefringence dispersion is presented within the framework of damped response theory, also known as complex polarization propagator theory, at the level of time-dependent Hartree–Fock and time-dependent density functional...... theory. Magneto-chiral dichroism and magneto-chiral birefringence spectra in the (resonant) frequency region below the first ionization threshold of R-methyloxirane and L-alanine are presented and compared with the corresponding results obtained for both the electronic circular dichroism and the magnetic...

  13. A complex-polarization-propagator protocol for magneto-chiral axial dichroism and birefringence dispersion.

    Science.gov (United States)

    Cukras, Janusz; Kauczor, Joanna; Norman, Patrick; Rizzo, Antonio; Rikken, Geert L J A; Coriani, Sonia

    2016-05-21

    A computational protocol for magneto-chiral dichroism and magneto-chiral birefringence dispersion is presented within the framework of damped response theory, also known as complex polarization propagator theory, at the level of time-dependent Hartree-Fock and time-dependent density functional theory. Magneto-chiral dichroism and magneto-chiral birefringence spectra in the (resonant) frequency region below the first ionization threshold of R-methyloxirane and l-alanine are presented and compared with the corresponding results obtained for both the electronic circular dichroism and the magnetic circular dichroism. The additional information content yielded by the magneto-chiral phenomena, as well as their potential experimental detectability for the selected species, is discussed.

  14. Syntheses and molecular self-assembly of chiral phosphorami dates

    Institute of Scientific and Technical Information of China (English)

    DU, Da-Ming; HUA, Wen-Ting; WANG, Jian-Wu

    2000-01-01

    Two chiral phosphoramidates, ( R )-( - )-1, 1′-binaphthyl-2, 2′-dihydroxy-N-[ α-( S)-methylbenzyl] phosphoramidate and (-)-l,1′-biphenyl-2,2′-dihydroxy-N-[ α-( S)-methylbenzyl]- phosphoramidate were synthesized. Their crystal structures were determined by X-ray single crystal diffraction analysis. The phoshorramidate molecules are self-associated by inter molecular N-H…… O = P hydrogen bonds and aromatic edge to face interactions.

  15. Axially chiral macrocyclic E-alkene bearing bisazole component formed by sequential C-H homocoupling and ring-closing metathesis.

    Science.gov (United States)

    Nishio, Shotaro; Somete, Takashi; Sugie, Atsushi; Kobayashi, Tohru; Yaita, Tsuyoshi; Mori, Atsunori

    2012-05-18

    Clipping by ring-closing metathesis freezes rotation of a C-C bond to result in forming axial chirality. Treatment of bisbenzimidazole bearing an N-(3-butenyl) substituent with a Grubbs' catalyst undergoes ring-closing metathesis, in which the stereochemistry of the thus formed olefin was exclusively E-form. Analysis by HPLC with a chiral stationary column confirmed clear baseline separation of each enantiomer.

  16. Louis Pasteur, language, and molecular chirality. I. Background and dissymmetry.

    Science.gov (United States)

    Gal, Joseph

    2011-01-01

    Louis Pasteur resolved sodium ammonium (±)-tartrate in 1848, thereby discovering molecular chirality. Although hindered by the primitive state of organic chemistry, he introduced new terminology and nomenclature for his new science of molecular and crystal chirality. He was well prepared for this task by his rigorous education and innate abilities, and his linguistic achievements eventually earned him membership in the supreme institution for the French language, the Académie française. Dissymmetry had been in use in French from the early 1820s for disruption or absence of symmetry or for dissimilarity or difference in appearance between two objects, and Pasteur initially used it in the latter connotation, without any reference to handedness or enantiomorphism. Soon, however, he adopted it in the meaning of chirality. Asymmetry had been in use in French since 1691 but Pasteur ignored it in favor of dissymmetry. The two terms are not synonymous but it is not clear whether Pasteur recognized this difference in choosing the former over the latter. However, much of the literature mistranslates his dissymmetry as asymmetry. Twenty years before Pasteur the British polymath John Herschel proposed that optical rotation in the noncrystalline state is due to the "unsymmetrical" [his term] nature of the molecules and later used dissymmetrical for handed. Chirality, coined by Lord Kelvin in 1894 and introduced into chemistry by Mislow in 1962, has nearly completely replaced dissymmetry in the meaning of handedness, but the use of dissymmetry continues today in other contexts for lack of symmetry, reduction of symmetry, or dissimilarity.

  17. Design and Synthesis of Chiral Molecular Tweezers Based on Deoxycholic Acid

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A series of new chiral molecular tweezers have been designed and synthesized by using deoxycholic acid as spacer and aromatic amines as arms.Instead of using toxic phosgene,the triphosgene was employed in synthesis of the molecular tweezers receptors.These chiral molecular tweezers showed good enantioselectivity for D-amino acid methyl esters.

  18. Synthetic studies on axial chiral biaryls and functional materials utilizing arene-metal complexes; aren kinzokusakutai no tokusei wo riyo shita jikufusai biariru, oyobi shinki kinosei zairyo no gosei kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    Uemura, Motokazu [Osaka Prefecture University, Osaka (Japan). Faculty of Integrated Arts and Sceinces

    1999-12-16

    Axially chiral biaryls compounds are of importance not only as chiral ligands for asymmetric reactions but also as biologically active natural products, e. g., korupensamine, michellamine and vancomycin. (Arene) chromium complex exists in two enantiomeric forms based on a planar chirality. Axially chiral biaryls were stereoselectively prepared by palladium(0)-catalyzed cross-coupling of (aryl halide)Cr(CO){sub 3} complexes with arylboronic acids. This method was applied for the total synthesis of antimaralial agent korupensamine A, naphthyltetrahydro-isoquinoline alkaloid. Furthermore, chiral 1,2-diols and diamines are important compounds for asymmetric reactions. These enantionerically pure 1,2-diols and 1,2-diamines were stereoselectively prepared by pinacol coupling of planar chiral chromium complexes of benzaldehydes and benzaldimines with samarium iodide. Moreover, non-biaryl axial compounds, N,N-dialkyl 2,6-disubstituted benzamides were synthesized in enantiomerically pure form utilizing planar chiral arene chromium complex. (author)

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

    Science.gov (United States)

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

    2016-06-01

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

  20. Synthesis of axially chiral oxazoline-carbene ligands with an N-naphthyl framework and a study of their coordination with AuCl·SMe(2).

    Science.gov (United States)

    Wang, Feijun; Li, Shengke; Qu, Mingliang; Zhao, Mei-Xin; Liu, Lian-Jun; Shi, Min

    2012-01-01

    Axially chiral oxazoline-carbene ligands with an N-naphthyl framework were successfully prepared, and their coordination behavior with AuCl·SMe(2) was also investigated, affording the corresponding Au(I) complexes in moderate to high yields.

  1. Numerical study of The Remittances of Axially Excited Chiral Sculptured Zirconia Thin Films

    CERN Document Server

    Babaei, Ferydon; 10.1080/09500340701836997

    2009-01-01

    The transmission and reflection spectra from a right-handed chiral sculptured zirconia thin film are calculated using the coupled wave theory and the Bruggeman homogenization formalism in conjunction with the experimental data for the relative dielectric constant of zirconia thin film. The dielectric dispersion function effect on these spectra appeared in wavelengths shorter than the Bragg wavelength. In wavelengths larger than the Bragg wavelength, the dispersion of the dielectric function can be ignored. The results achieved in this work are consistent with the experimental data (Wu et al. (2000)). A shift towards shorter wavelengths is observed for the Bragg peak with increasing the void fraction, which is in agreement with the theoretical work of Lakhtakia (2000). Sorge et al. (2006) also found this effect in their experimental results on TiO2 chiral thin films, while they also found that unlike our results the intensity of the reflectance of the Bragg peak decreases with increasing the void fraction. Thi...

  2. Molecular dynamics study of nanojoining between axially positioned Ag nanowires

    Science.gov (United States)

    Cui, Jianlei; Theogene, Barayavuga; Wang, Xuewen; Mei, Xuesong; Wang, Wenjun; Wang, Kedian

    2016-08-01

    The miniaturization of electronics devices into nanometer scale is indispensable for next-generation semiconductor technology. Ag nanowires (Ag NWs) are considered to be the promising candidates for future electronic circuit owing to the excellent electrical and thermal properties. The nanojoining of axially positioned Ag NWs was performed by molecular dynamics simulation. Through the detailed atomic evolution during the nanojoining, the results indicate that the temperature and the distance between Ag NWs in axial direction have a great impact on nanojoining effect. When the nanojoining temperature is relatively high, the atoms are disordered and the atomic queues become to distort with strong thermodynamic properties and weak effect of metal bonds. At the relatively low temperature, the Ag NWs can be well connected with good junction quality and their own morphology, which is similar to the cold welding without fusion, while the distance between Ag NWs should be controlled for interaction and diffusion of interfacial atoms at nanowires head. When the Ag NWs are placed on Si and SiO2 substrate, because the atomic species and lattice structure of substrate material can differently affect the motions of Ag atoms through the interactive force between the atoms, the nanojoining quality of Ag NWs on Si substrate is better than that on the SiO2 substrate. So, for getting effective and reliable nanojoining without nanosolders and other materials, the temperature, distance and substrate surface should be reasonably controlled and selected, providing helpful theoretical guidance for experiment and application of nanojoining.

  3. Chiral separation of racemic drugs using molecular imprinting

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Molecularly imprinted polymers (MIPs) of (S)-ketoprofen and (S)-naproxen are prepared using non-covalent imprinting in the presence of template molecules. The prepared MIPs are used as the chiral stationary phase to separate ramemic naproxen and ketoprofen. The results show that racemic naproxen and ketoprofen are efficiently resolved on MIPs. The effect of concentration of acetic acid in the mobile phase is studied, and the data are analyzed using the affinity chromatography model, and the close agreement is achieved between the simulated and experimental curves. The results suggest that the affinity chromatography mechanism controls the retention in this system. Moreover, the affinity chromatography equilibrium constants on (S)-naproxen and (S)-ketoprofen are estimated.

  4. Discrimination of Axial and Central Stereogenic Elements in Chiral Bis(oxazolines) Based on Atropisomeric 3,3'-Bithiophene Scaffolds Through Chiroptical Spectroscopies.

    Science.gov (United States)

    Gabrieli, Sara; Mazzeo, Giuseppe; Longhi, Giovanna; Abbate, Sergio; Benincori, Tiziana

    2016-10-01

    Two diastereoisomeric pairs of bis-oxazolines, provided with a stereogenic center at carbon 4 and based on the 3,3'-bithiophene atropisomeric scaffold, were synthesized and structurally characterized. They differ in the substituents at positions 2 and 5 of the thiophene rings, which are functionalized with methyl (1) or phenyl (2) groups, respectively. In vibrational circular dichroism (VCD) spectra, recorded in CCl4 solutions, it is possible to distinctly recognize the characteristic features of axial and central stereogenic elements. In tandem with Density Functional Theory (DFT) calculations, the absolute configuration (AC) of the diastereoisomers was safely established. In this case, VCD was shown to be superior to ECD (electronic circular dichroism) in the assignment of AC. The normal modes, evaluated from DFT calculations, show that the VCD signals in correspondence with the stereogenic axis of the bithiophene unit are different for 1 and 2. The VCD spectra of a molecular analog of 1, the (S)-2,2',5,5'-tetramethyl-4,4'-bis-(diphenylphosphino)-3,3'-bithiophene oxide (3), characterized by the same 3,3'-bithiophene scaffold, but devoid of stereogenic centers, exhibits signals similar to those observed in the case of diastereoisomer (aS,R,R)-1a, associated with almost identical normal modes. Chirality 28:686-695, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  5. X-ray Circular Dichroism Signals: A Unique Probe of Local Molecular Chirality

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yu; Rouxel, Jeremy; Autschbach, Jochen; Govind, Niranjan; Mukamel, Shaul

    2017-09-01

    Core-resonant circular dichroism (CD) signals are induced by molecular chirality and vanish for achiral molecules and racemic mixtures. The highly localized nature of core excitations makes them ideal probes of local chirality within molecules. Simulations of circular dichroism spectra of several molecular families illustrate how these signals vary with the electronic coupling to substitution groups, the distance between the X-ray chromophore and the chiral center, geometry, and chemical structure. Clear insights on the molecular structure are obtained through analysis of the X-ray CD spectra.

  6. Measuring the optical chirality of molecular aggregates at liquid-liquid interfaces.

    Science.gov (United States)

    Watarai, Hitoshi; Adachi, Kenta

    2009-10-01

    Some new experimental methods for measuring the optical chirality of molecular aggregates formed at liquid-liquid interfaces have been reviewed. Chirality measurements of interfacial aggregates are highly important not only in analytical spectroscopy but also in biochemistry and surface nanochemistry. Among these methods, a centrifugal liquid membrane method was shown to be a highly versatile method for measuring the optical chirality of the liquid-liquid interface when used in combination with a commercially available circular dichroism (CD) spectropolarimeter, provided that the interfacial aggregate exhibited a large molar absorptivity. Therefore, porphyrin and phthalocyanine were used as chromophoric probes of the chirality of itself or guest molecules at the interface. A microscopic CD method was also demonstrated for the measurement of a small region of a film or a sheet sample. In addition, second-harmonic generation and Raman scattering methods were reviewed as promising methods for detecting interfacial optical molecules and measuring bond distortions of chiral molecules, respectively.

  7. Chiral Nanoscience and Nanotechnology

    OpenAIRE

    Dibyendu S. Bag; T.C. Shami; K.U. Bhasker Rao

    2008-01-01

    The paper reviews nanoscale science and technology of chiral molecules/macromolecules-under twosubtopics-chiral nanotechnology and nano-chiral technology. Chiral nanotechnology discusses thenanotechnology, where molecular chirality plays a role in the properties of materials, including molecularswitches, molecular motors, and other molecular devices; chiral supramolecules and self-assembled nanotubesand their functions are also highlighted. Nano-chiral technology  describes the nanoscale appr...

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

    Science.gov (United States)

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

    2012-05-18

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

  9. Molecular modeling study of chiral drug crystals: lattice energy calculations.

    Science.gov (United States)

    Li, Z J; Ojala, W H; Grant, D J

    2001-10-01

    The lattice energies of a number of chiral drugs with known crystal structures were calculated using Dreiding II force field. The lattice energies, including van der Waals, Coulombic, and hydrogen-bonding energies, of homochiral and racemic crystals of some ephedrine derivatives and of several other chiral drugs, are compared. The calculated energies are correlated with experimental data to probe the underlying intermolecular forces responsible for the formation of racemic species, racemic conglomerates, or racemic compounds, termed chiral discrimination. Comparison of the calculated energies among ephedrine derivatives reveals that a greater Coulombic energy corresponds to a higher melting temperature, while a greater van der Waals energy corresponds to a larger enthalpy of fusion. For seven pairs of homochiral and racemic compounds, correlation of the differences between the two forms in the calculated energies and experimental enthalpy of fusion suggests that the van der Waals interactions play a key role in the chiral discrimination in the crystalline state. For salts of the chiral drugs, the counter ions diminish chiral discrimination by increasing the Coulombic interactions. This result may explain why salt forms favor the formation of racemic conglomerates, thereby facilitating the resolution of racemates.

  10. Molecular dynamics simulation and NMR investigation of the association of the β-blockers atenolol and propranolol with a chiral molecular micelle

    Science.gov (United States)

    Morris, Kevin F.; Billiot, Eugene J.; Billiot, Fereshteh H.; Hoffman, Charlene B.; Gladis, Ashley A.; Lipkowitz, Kenny B.; Southerland, William M.; Fang, Yayin

    2015-08-01

    Molecular dynamics simulations and NMR spectroscopy were used to compare the binding of two β-blocker drugs to the chiral molecular micelle poly-(sodium undecyl-(L)-leucine-valine). The molecular micelle is used as a chiral selector in capillary electrophoresis. This study is part of a larger effort to understand the mechanism of chiral recognition in capillary electrophoresis by characterizing the molecular micelle binding of chiral compounds with different geometries and charges. Propranolol and atenolol were chosen because their structures are similar, but their chiral interactions with the molecular micelle are different. Molecular dynamics simulations showed both propranolol enantiomers inserted their aromatic rings into the molecular micelle core and that (S)-propranolol associated more strongly with the molecular micelle than (R)-propranolol. This difference was attributed to stronger molecular micelle hydrogen bonding interactions experienced by (S)-propranolol. Atenolol enantiomers were found to bind near the molecular micelle surface and to have similar molecular micelle binding free energies.

  11. Resonant second-harmonic-generation circular-dichroism microscopy reveals molecular chirality in native biological tissues

    CERN Document Server

    Chen, Mei-Yu; Kan, Che-Wei; Lin, Yen-Yin; Ye, Cin-Wei; Wu, Meng-Jer; Liu, Hsiang-Lin; Chu, Shi-Wei

    2016-01-01

    Conventional linear optical activity effects are widely used for studying chiral materials. However, poor contrast and artifacts due to sample anisotropy limit the applicability of these methods. Here we demonstrate that nonlinear second-harmonic-generation circular dichroism spectral microscopy can overcome these limits. In intact collagenous tissues, clear spectral resonance is observed with sub-micrometer spatial resolution. By performing gradual protein denaturation studies, we show that the resonant responses are dominantly due to the molecular chirality.

  12. Enantiopure Functional Molecular Motors Obtained by a Switchable Chiral-Resolution Process.

    Science.gov (United States)

    van Leeuwen, Thomas; Gan, Jefri; Kistemaker, Jos C M; Pizzolato, Stefano F; Chang, Mu-Chieh; Feringa, Ben L

    2016-05-17

    Molecular switches, rotors, and motors play an important role in the development of nano-machines and devices, as well as responsive and adaptive functional materials. For unidirectional rotors based on chiral overcrowded alkenes, their stereochemical homogeneity is of crucial importance. Herein, a method to obtain new and functionalizable overcrowded alkenes in enantiopure form is presented. The procedure involves a short synthesis of three steps and a solvent-switchable chiral resolution by using a readily available resolving agent. X-ray crystallography revealed the mode of binding of the motor with the resolving agent, as well as the absolute configuration of the motor. (1) H NMR and UV/Vis spectroscopy techniques were used to determine the dynamic behavior of this molecular motor. This method provides rapid access to ample amounts of enantiopure molecular motors, which will greatly facilitate the further development of responsive molecular systems based on chiral overcrowded alkenes.

  13. Liquid Crystal Phases of Molecular Bananas: Polarity and Chirality as Broken Symmetries

    Science.gov (United States)

    Clark, Noel

    2006-03-01

    The study of the interplay of chirality and polarity has been a particularly rich theme of soft matter science since Meyer's seminal discovery that tilted smectics of chiral molecules are macroscopically polar. This event, and the subsequent realization of polar domains and high-speed electro-optic switching in chiral smectics, engaged the liquid crystal community in a worldwide pursuit of novel smectics for applications, featured by the synthesis of more than 50,000 new liquid crystal compounds, and by a consequent broad diversification of the palette of liquid crystal phases and possibilities for supermolecular ordering. A current important activity in this scenario is the study of polar order in synthetically achiral molecules, for example, in molecular bananas, which, as their shape suggests, might be expected to organize in a polar way. Indeed they do, but beyond this, almost everything learned about them has been surprising, including their persistent tendency to exhibit chirality as a spontaneously broken symmetry. I will discuss some of these new phases and phenomena, including the discovery of fluid conglomerates (Pasteur's experiment in a fluid), triclinic fluid order, chiral twist grain boundary phases of achiral molecules, chirality flipping and field-induced deracemization, ferroelectric and antiferroelectric phases with supermolecular- scale polarization modulation, and chiral thermotropic sponge phases.

  14. Effect of axial ligands on the molecular configurations, stability, reactivity, and photodynamic activities of silicon phthalocyanines.

    Science.gov (United States)

    Luan, Liqiang; Ding, Lanlan; Shi, Jiawei; Fang, Wenjuan; Ni, Yuxing; Liu, Wei

    2014-12-01

    To demonstrate the effect of axial ligands on the structure-activity relationship, a series of axially substituted silicon phthalocyanines (SiPcs) have been synthesized with changes to the axial ligands. The reactivity of the axial ligand upon shielding by the phthalocyanine ring current, along with their stability, photophysical, and photodynamic therapy (PDT) activities were compared and evaluated for the first time. As revealed by single-crystal XRD analysis, rotation of the axial -OMe ligands was observed in SiPc 3, which resulted in two molecular configurations coexisting synchronously in both the solid and solution states and causing a split of the phthalocyanine α protons in the (1)H NMR spectra that is significantly different from all SiPcs reported so far. The remarkable photostability, good singlet oxygen quantum yield, and efficient in vitro photodynamic activity synergistically show that compound 3 is one of the most promising photosensitizers for PDT.

  15. Absolute configuration of an axially chiral sulfonate determined from its optical rotatory dispersion, electronic circular dichroism, and vibrational circular dichroism spectra.

    Science.gov (United States)

    Covington, Cody L; Raghavan, Vijay; Smuts, Jonathan P; Armstrong, Daniel W; Polavarapu, Prasad L

    2017-11-01

    The absolute configuration (AC) of an axially chiral sulfonate (aCSO), 3,5-dimethyl-2-(naphthalen-1-yl)-6-(naphthalen-1-yl)benzenesulfonate (labeled as aCSO5), was investigated using optical rotatory dispersion (ORD), electronic circular dichroism (ECD), and vibrational circular dichroism (VCD) spectroscopies. All three methods led to the same conclusion and the AC of aCSO5 is reliably determined to be (-)-(aR, aR), or conversely (+)-(aS, aS). © 2017 Wiley Periodicals, Inc.

  16. a Chiral Tagging Strategy for Determining Absolute Configuration and Enantiomeric Excess by Molecular Rotational Spectroscopy

    Science.gov (United States)

    Evangelisti, Luca; Caminati, Walther; Patterson, David; Thomas, Javix; Xu, Yunjie; West, Channing; Pate, Brooks

    2017-06-01

    The introduction of three wave mixing rotational spectroscopy by Patterson, Schnell, and Doyle [1,2] has expanded applications of molecular rotational spectroscopy into the field of chiral analysis. Chiral analysis of a molecule is the quantitative measurement of the relative abundances of all stereoisomers of the molecule and these include both diastereomers (with distinct molecular rotational spectra) and enantiomers (with equivalent molecular rotational spectra). This work adapts a common strategy in chiral analysis of enantiomers to molecular rotational spectroscopy. A "chiral tag" is attached to the molecule of interest by making a weakly bound complex in a pulsed jet expansion. When this tag molecule is enantiopure, it will create diastereomeric complexes with the two enantiomers of the molecule being analyzed and these can be differentiated by molecule rotational spectroscopy. Identifying the structure of this complex, with knowledge of the absolute configuration of the tag, establishes the absolute configuration of the molecule of interest. Furthermore, the diastereomer complex spectra can be used to determine the enantiomeric excess of the sample. The ability to perform chiral analysis will be illustrated by a study of solketal using propylene oxide as the tag. The possibility of using current methods of quantum chemistry to assign a specific structure to the chiral tag complex will be discussed. Finally, chiral tag rotational spectroscopy offers a "gold standard" method for determining the absolute configuration of the molecule through determination of the substitution structure of the complex. When this measurement is possible, rotational spectroscopy can deliver a quantitative three dimensional structure of the molecule with correct stereochemistry as the analysis output. [1] David Patterson, Melanie Schnell, John M. Doyle, Nature 497, 475 (2013). [2] David Patterson, John M. Doyle, Phys. Rev. Lett. 111, 023008 (2013).

  17. A Tethered Ru-S Complex with an Axial Chiral Thiolate Ligand for Cooperative Si-H Bond Activation: Application to Enantioselective Imine Reduction.

    Science.gov (United States)

    Wübbolt, Simon; Maji, Modhu Sudan; Irran, Elisabeth; Oestreich, Martin

    2017-02-13

    An axial chiral version of the 2,6-dimesitylphenyl group attached to sulfur is reported. Its multistep preparation starts from (S)-binol, and the thiol group is established by a racemization-free thermal Newman-Kwart rearrangement. The new chiral thiolate ligand decorated with one mesityl group is used in the synthesis of a tethered ruthenium chloride complex. Its spectroscopic characterization revealed solvent-dependent epimerization at the ruthenium center. The major diastereomer is crystallographically characterized. Chloride abstraction with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF4) yields the corresponding coordinatively unsaturated ruthenium complex with the Ru-S bond exposed. Si-H bond activation at this Ru-S bond proceeds in syn fashion but with moderate facial selectivity (d.r. = 70:30), generating diastereomeric chiral-at-ruthenium hydrosilane adducts. Their application to catalytic imine hydrosilylation led to promising enantioinduction (40% ee), thereby providing proof of concept for asymmetric catalysis involving cooperative Si-H bond activation.

  18. Dynamic control and amplification of molecular chirality by circular polarized light

    NARCIS (Netherlands)

    Huck, N.P.M.; Jager, W.F.; de Lange, B.; Feringa, B.L.

    1996-01-01

    The enantiomers of a racemic photoresponsive material represent two distinct states that can be modulated with irradiation at a single wavelength by changing the handedness of the light, Dynamic control over molecular chirality was obtained by the interconversion of enantiomers of helically shaped m

  19. Photoinduced Reorganization of Motor-Doped Chiral Liquid Crystals : Bridging Molecular Isomerization and Texture Rotation

    NARCIS (Netherlands)

    Bosco, Alessandro; Jongejan, Mahthild G. M.; Eelkema, Rienk; Katsonis, Nathalie; Lacaze, Ernmanuelle; Ferrarini, Alberta; Feringa, Ben L.; Lacaze, Emmanuelle

    2008-01-01

    We recently reported that the photoisomerization of molecular motors used as chiral dopants in a cholesteric liquid crystal film induces a rotational reorganization which can be observed by optical microscopy and produces the motion of microscopic objects placed on top of the film (Feringa, B. L.;

  20. Dynamic control and amplification of molecular chirality by circular polarized light

    NARCIS (Netherlands)

    Huck, N.P.M.; Jager, W.F.; de Lange, B.; Feringa, B.L.

    1996-01-01

    The enantiomers of a racemic photoresponsive material represent two distinct states that can be modulated with irradiation at a single wavelength by changing the handedness of the light, Dynamic control over molecular chirality was obtained by the interconversion of enantiomers of helically shaped

  1. Effects of surface molecular chirality on adhesion and differentiation of stem cells.

    Science.gov (United States)

    Yao, Xiang; Hu, Yiwen; Cao, Bin; Peng, Rong; Ding, Jiandong

    2013-12-01

    Chirality is one of the most fascinating and ubiquitous cues in nature, especially in life. The effects of chiral surfaces on stem cells have, however, not yet been revealed. Herein we examined the molecular chirality effect on stem cell behaviors. Self assembly monolayers of L- or D-cysteine (Cys) were formed on a glass surface coated with gold. Mesenchymal stem cells (MSCs) derived from bone marrow of rats exhibited more adhering preference and thus less cell spreading on the L surface than on the d one at the confluent condition. More protein adsorption was observed on the L surface after immersed in cell culture medium with fetal bovine serum. After osteogenic and adipogenic co-induction at the confluent condition, a larger proportion of cells became osteoblasts on the d surface, while the adipogenic fraction on the L surface was found to be higher than on the D surface. In order to interpret how this chirality effect worked, we fabricated Cys microislands of two sizes on the non-fouling poly(ethylene glycol) hydrogel to pre-define the spreading areas of single cells. Then the differentiation extents did not exhibit a significant difference between L and D surfaces under a given area of microislands, yet very significant differences of osteogenesis and adipogenesis were found between different areas. So, the molecular chirality influenced stem cells, probably via favored adsorption of natural proteins on the L surface, which led to more cell adhesion; and the larger cell spreading area with higher cell tension in turn favored osteogenesis rather than adipogenesis. As a result, this study reveals the molecular chirality on material surfaces as an indirect regulator of stem cells.

  2. Molecular dynamics studies and quantification of the effect of chirality on the formation of liquid crystal mesophases

    Energy Technology Data Exchange (ETDEWEB)

    Solymosi, Miklos

    2002-07-01

    Results are presented from theoretical studies and from a series of molecular dynamics simulations undertaken to quantify the effect of chirality on the formation of liquid crystal mesophases. In the theoretical studies we have proposed a scaled chiral index with a formulation which allows comparison to be made between molecules comprising different numbers of atoms. We have undertaken chirality calculations utilizing the proposed scaled chiral index, G{sub 0S}, for one optimized static molecular geometry for a range of liquid crystal chiral dopants and ferroelectric liquid crystal molecules. The scaled chiral index, G{sub 0S}, allows a rapid calculation to be made of a pseudoscalar quantity which shows a good correlation with the helical twisting power of liquid crystal chiral dopants in a nematic liquid crystal solvent. This could prove a powerful aid in the design of novel dopant molecules where the dopant is rigid and the helical twisting is predominantly a steric effect. The same scaled chirality index, G{sub 0S}, calculation for ferroelectric liquid crystal molecules hints at an inverse correlation with spontaneous polarization agreeing with some experimental results. The scaled chiral index is a chemically useful index that can also be decomposed into atomic or functional group contributions, thereby creating a new measure of the asymmetric potential of functional groups and their different possible substitution positions. In the molecular dynamics simulation studies we have investigated two three-site Gay-Berne models, one chiral and the other achiral, each with a rotated central site forming a zigzag shape. In the chiral model one of the end site was additionally rotated out of the plane of the other two sites by a chiral angle {theta}{sub c}. Results from the achiral phase simulations support the theory that steric molecular shape can be associated with a driving force that leads to the smectic A - smectic C phase transition since such a transition was

  3. Chiral Hydrogen Bond Environment Providing Unidirectional Rotation in Photoactive Molecular Motors.

    Science.gov (United States)

    García-Iriepa, Cristina; Marazzi, Marco; Zapata, Felipe; Valentini, Alessio; Sampedro, Diego; Frutos, Luis Manuel

    2013-05-02

    Generation of a chiral hydrogen bond environment in efficient molecular photoswitches is proposed as a novel strategy for the design of photoactive molecular motors. Here, the following strategy is used to design a retinal-based motor presenting singular properties: (i) a single excitation wavelength is needed to complete the unidirectional rotation process (360°); (ii) the absence of any thermal step permits the process to take place at low temperatures; and (iii) the ultrafast process permits high rotational frequencies.

  4. Molecular Recognition of Biomolecules by Chiral CdSe Quantum Dots

    Science.gov (United States)

    Mukhina, Maria V.; Korsakov, Ivan V.; Maslov, Vladimir G.; Purcell-Milton, Finn; Govan, Joseph; Baranov, Alexander V.; Fedorov, Anatoly V.; Gun’Ko, Yurii K.

    2016-04-01

    Molecular recognition is one of the most important phenomena in Chemistry and Biology. Here we present a new way of enantiomeric molecular recognition using intrinsically chiral semiconductor nanocrystals as assays. Real-time confocal microscopy studies supported by circular dichroism spectroscopy data and theoretical modelling indicate an ability of left-handed molecules of cysteine and, to a smaller extent, histidine and arginine to discriminate between surfaces of left- and right-handed nanocrystals.

  5. Molecular chirality in meteorites and interstellar ices, and the chirality experiment on board the ESA cometary Rosetta mission.

    Science.gov (United States)

    Myrgorodska, Iuliia; Meinert, Cornelia; Martins, Zita; Le Sergeant d'Hendecourt, Louis; Meierhenrich, Uwe J

    2015-01-26

    Life, as it is known to us, uses exclusively L-amino acid and D-sugar enantiomers for the molecular architecture of proteins and nucleic acids. This Minireview explores current models of the original symmetry-breaking influence that led to the exogenic delivery to Earth of prebiotic molecules with a slight enantiomeric excess. We provide a short overview of enantiomeric enhancements detected in bodies of extraterrestrial origin, such as meteorites, and interstellar ices simulated in the laboratory. Data are interpreted from different points of view, namely, photochirogenesis, parity violation in the weak nuclear interaction, and enantioenrichment through phase transitions. Photochemically induced enantiomeric imbalances are discussed more specifically in the topical context of the "chirality module" on board the cometary Rosetta spacecraft of the ESA. This device will perform the first enantioselective in situ analyses of samples taken from a cometary nucleus. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Chiral induction in phenanthroline-derived oligoamide foldamers: an acid- and base-controllable switch in helical molecular strands.

    Science.gov (United States)

    Hu, Hai-Yu; Xiang, Jun-Feng; Yang, Yong; Chen, Chuan-Feng

    2008-03-20

    A series of phenanthroline-derived oligoamides bearing a chiral (R)-phenethylamino end group were synthesized that displayed chiral helical induction and subsequently formed one-hand helical foldamers in solution. Moreover, an acid- and base-controllable switch in the helical molecular strands was observed, which has been demonstrated by NMR, UV-vis, and circular dichroism spectroscopy.

  7. Synthesis of Hymecromone Derivatives Containing Chiral 1,1'-Bi-2-naphthyl Moiety for Dual-mode Molecular Switch

    Institute of Scientific and Technical Information of China (English)

    Zi Xing SHAN; Chun Guang XIAO

    2004-01-01

    Some hymecromone derivatives containing chiral 1,1(-bi-2-naphthyl moiety were synthesized and their photodimerizations were investigated.It was found that fluorescence intensity and optical rotation of the new chiral hymecromone derivatives could be regulated by light.This property has potential significance for developing a new type of dual-mode molecular switch.

  8. Electrical and mechanical anharmonicities from NIR-VCD spectra of compounds exhibiting axial and planar chirality: the cases of (S)-2,3-pentadiene and methyl-d(3) (R)- and (S)-[2.2]paracyclophane-4-carboxylate.

    Science.gov (United States)

    Abbate, Sergio; Longhi, Giovanna; Gangemi, Fabrizio; Gangemi, Roberto; Superchi, Stefano; Caporusso, Anna Maria; Ruzziconi, Renzo

    2011-10-01

    The IR and Near infrared (NIR) vibrational circular dichroism (VCD) spectra of molecules endowed with noncentral chirality have been investigated. Data for fundamental, first, and second overtone regions of (S)-2,3-pentadiene, exhibiting axial chirality, and methyl-d(3) (R)- and (S)-[2.2]paracyclophane-4-carboxylate, exhibiting planar chirality have been measured and analyzed. The analysis of NIR and IR VCD spectra was based on the local-mode model and the use of density functional theory (DFT), providing mechanical and electrical anharmonic terms for all CH-bonds. The comparison of experimental and calculated spectra is satisfactory and allows one to monitor fine details in the asymmetric charge distribution in the molecules: these details consist in the harmonic frequencies, in the principal anharmonicity constants, in both the atomic polar and axial tensors and in their first and second derivatives with respect to the CH-stretching coordinates.

  9. New studies on molecular chirality in the gas phase: enantiomer differentiation and determination of enantiomeric excess.

    Science.gov (United States)

    Patterson, David; Schnell, Melanie

    2014-06-21

    Chirality plays a fundamental role in the activity of biological molecules and broad classes of chemical reactions. The chemistry of life is built almost exclusively on left-handed amino acids and right-handed sugars, a phenomenon known as "homochirality of life". Furthermore, most drugs developed in the last decade are of specified chirality. Thus, fast and reliable methods that can differentiate molecules of different handedness, determine the enantiomeric excess of even molecular mixtures, and allow for an unambiguous determination of molecular handedness are of great interest, in particular with respect to complex mixtures. In this perspective article, we discuss the recent developments, with an emphasis on modern spectroscopic methods using gas-phase samples, such as photoelectron circular dichroism, Coulomb explosion imaging, and microwave three-wave mixing.

  10. CD Spectroscopic Study on the Molecular Recognition of Chiral Salen-Metal Complexes

    Institute of Scientific and Technical Information of China (English)

    刘涛; 阮文娟; 南晶; 朱志昂

    2003-01-01

    The molecular recognition behavior of the chiral salen-metal complexes towards guest molecules, such as imidazole derivatives and amino-acid ester, was systematically investigated by means of circular dichroism (CD) spectra. The coordination numbers of the host-guest complexes as well as the recognition capability of the salen-metal complexes were explained by character and intensity analyses of the CD spectra.

  11. Toward efficient asymmetric hydrogenation: architectural and functional engineering of chiral molecular catalysts.

    Science.gov (United States)

    Noyori, Ryoji; Kitamura, Masato; Ohkuma, Takeshi

    2004-04-13

    Asymmetric hydrogenation uses inexpensive, clean hydrogen gas and a very small amount of a chiral molecular catalyst, providing the most powerful way to produce a wide array of enantio-enriched compounds in a large quantity without forming any waste. The recent revolutionary advances in this field have entirely changed the synthetic approach to producing performance chemicals that require a high degree of structural precision. The means of developing efficient asymmetric hydrogenations is discussed from a mechanistic point of view.

  12. Strong magneto-chiral dichroism in a paramagnetic molecular helix observed by hard X-ray

    Science.gov (United States)

    Sessoli, Roberta; Boulon, Marie-Emmanuelle; Caneschi, Andrea; Mannini, Matteo; Poggini, Lorenzo; Wilhelm, Fabrice; Rogalev, Andrei

    2014-01-01

    Magneto-chiral dichroism (MχD) is a non-reciprocal, i. e. directional, effect observed in magnetised chiral systems featuring an unbalanced absorption of unpolarised light depending on the direction of the magnetisation. Despite the fundamental interest in a phenomenon breaking both parity and time reversal symmetries, MχD is one of the least investigated aspects of light-matter interaction because of the weakness of the effect in most reported experiments. Here we have exploited the element selectivity of hard X-ray radiation to investigate the magneto-chiral properties of enentiopure crsytals of two isostructural molecular helicoidal chains comprising Cobalt(II) and Manganese (II) ions, respectively. A strong magneto-chiral dichroism, with Kuhn asymmetry of the order of a few percent, has been observed in the Cobalt chain system, while it is practically absent for the Manganese derivative. The spectral features of the XMχD signal differ significantly from the natural and magnetic dichroic contributions and have been here rationalized using the simple multipolar expansion of matter-radiation interaction. PMID:25729401

  13. Axial level-dependent molecular and cellular mechanisms underlying the genesis of the embryonic neural plate.

    Science.gov (United States)

    Kondoh, Hisato; Takada, Shinji; Takemoto, Tatsuya

    2016-06-01

    The transcription factor gene Sox2, centrally involved in neural primordial regulation, is activated by many enhancers. During the early stages of embryonic development, Sox2 is regulated by the enhancers N2 and N1 in the anterior neural plate (ANP) and posterior neural plate (PNP), respectively. This differential use of the enhancers reflects distinct regulatory mechanisms underlying the genesis of ANP and PNP. The ANP develops directly from the epiblast, triggered by nodal signal inhibition, and via the combined action of TFs SOX2, OTX2, POU3F1, and ZIC2, which promotes the the ANP development and inhibits other cell lineages. In contrast, the PNP is derived from neuromesodermal bipotential axial stem cells that develop into the neural plate when Sox2 is activated by the N1 enhancer, whereas they develop into the paraxial mesoderm when the N1 enhancer is repressed by the action of TBX6. The axial stem cells are maintained by the activity of WNT3a and T (Brachyury). However, at axial levels more anterior to the 8th somites (cervical levels), the development of both the neural plate and somite proceeds in the absence of WNT3a, T, or TBX6. These observations indicate that distinct molecular and cellular mechanisms determine neural plate genesis based on the axial level, and contradict the classical concept of the term "neural induction," which assumes a pan-neural plate mechanism.

  14. Chiral Nanoscience and Nanotechnology

    Directory of Open Access Journals (Sweden)

    Dibyendu S. Bag

    2008-09-01

    Full Text Available The paper reviews nanoscale science and technology of chiral molecules/macromolecules-under twosubtopics-chiral nanotechnology and nano-chiral technology. Chiral nanotechnology discusses thenanotechnology, where molecular chirality plays a role in the properties of materials, including molecularswitches, molecular motors, and other molecular devices; chiral supramolecules and self-assembled nanotubesand their functions are also highlighted. Nano-chiral technology  describes the nanoscale approaches to chiraltechnology such as asymmetric synthesis and catalysis, chiral separation and detection, and enantiomericanalysis. Chiral sensors have also been included. The state-of-the-art chiral research at DMSRDE,Kanpur isalso presented.Defence Science Journal, 2008, 58(5, pp.626-635, DOI:http://dx.doi.org/10.14429/dsj.58.1685

  15. Synthesis and characterization of sugar based low molecular weight gelators and the preparation of chiral sulfinamides

    Science.gov (United States)

    Mangunuru, Hari Prasad Reddy

    Low molecular weight gelators (LMWGs) have received considerable attention in the field of chemistry from last few decades. These compounds form self-assembled fibrous networks like micelles, cylindrical, sheets, fibers, layers and so on. The fibrous network entraps the solvent and forms gel, because of the self-assembly phenomenon and their demonstrated potential uses in a variety of areas, ranging from environmental to medicinal applications. Sugars are good starting materials to synthesize the new class of LMWG's, because these are different from some expensive materials, these are natural products. We have synthesized and characterized the LMGS's based on D-glucose and D-glucosamine. D-glucosamine is the versatile starting material to make different peptoids and triazoles. Several series of compounds were synthesized using compounds 1-3 as starting material and studied the gelation behavior all the compounds. We have studied the self-assembling properties of a new class of tripeptoids, synthesized by one-pot Ugi reaction from simple starting materials. Among the focused library of tripeptoids synthesized, we found that several efficient low molecular weight organogelators were obtained for aqueous DMSO and ethanol mixtures. We have also synthesized and characterized a series of monosaccharide triazole derivatives. These compounds were synthesized from N-acetyl glucosamine and D-glucose via a Cu(I) catalyzed azide/alkyne cycloaddition reaction (CuAAc). The compounds have been screened for their gelation properties and several efficient low molecular weight organo/hydro gelators were obtained, among these compounds, five per-acetyl glucosamine derivatives and one peracetyl glucose derivative were able to form gels in water. These new molecules are expected to be useful in drug delivery and tissue engineering.*. Asymmetric synthesis of chiral amines is a challenging in synthetic organic chemistry. The development of new catalysts for asymmetric organic

  16. Design Molecular Recognition Materials for Chiral Sensors, Separtations and Catalytic Materials

    Energy Technology Data Exchange (ETDEWEB)

    Jia, S.; Nenoff, T.M.; Provencio, P.; Qiu, Y.; Shelnutt, J.A.; Thoma, S.G.; Zhang, J.

    1998-11-01

    The goal is the development of materials that are highly sensitive and selective for chid chemicals and biochemical (such as insecticides, herbicides, proteins, and nerve agents) to be used as sensors, catalysts and separations membranes. Molecular modeling methods are being used to tailor chiral molecular recognition sites with high affinity and selectivity for specified agents. The work focuses on both silicate and non-silicate materials modified with chirally-pure fictional groups for the catalysis or separations of enantiomerically-pure molecules. Surfactant and quaternary amine templating is being used to synthesize porous frameworks, containing mesopores of 30 to 100 angstroms. Computer molecukw modeling methods are being used in the design of these materials, especially in the chid surface- modi~ing agents. Molecular modeling is also being used to predict the catalytic and separations selectivities of the modified mesoporous materials. The ability to design and synthesize tailored asymmetric molecular recognition sites for sensor coatings allows a broader range of chemicals to be sensed with the desired high sensitivity and selectivity. Initial experiments target the selective sensing of small molecule gases and non-toxic model neural compounds. Further efforts will address designing sensors that greatly extend the variety of resolvable chemical species and forming a predictive, model-based method for developing advanced sensors.

  17. Axially chiral benzimidazolium based silver(I) and gold(I) bis-NHC complexes of R-BINOL scaffold: synthesis, characterization and DFT studies

    Indian Academy of Sciences (India)

    SONALI RAMGOPAL MAHULE

    2017-09-01

    The axially chiral ligand of R-BINOL scaffold was synthesized by a series of manipulations which involved different chemical reactions to obtain the desired sliver(I) and gold(I) {[L(L' -NHC) ₂]M}Cl (L = 3,3' -dimethyl-2,2' -dimethoxy-1,1' -binaphthyl, L' = i-propyl-benzo[d]imidazole) (M =Ag and Au)complexes. Enantiopure R-BINOL was employed as a basic unit to synthesize a benzimidazole based bis- NHC ligand 1g which was obtained through the formation of different intermediate 1(a-f) compounds. The newly synthesized bis-NHC ligand precursor (1g) and its corresponding {[L(L' -NHC) ₂]Ag}Cl (1h) and {[L(L' _-NHC) ₂]Au}Cl (1i) complexes were characterized by different spectroscopic techniques. The geometries of the optimized structure of the complexes 1h and 1i were computed at the B3LYP/SDD, 6-31G(d) level. Lowtemperature fluorescence spectroscopic studies did not show any evidence for the weak metal-metal interaction in these complexes.

  18. Rare π5^6Pb Interactions in a Two-dimensional Rare Metal-organic Coordination Polymer with Two Distinct Kinds of Axially Chiral Units

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    A new metal-organic coordination polymer [Pb(mfpdc)(CH3OH)]n (1, mfpdc = 2,6-dimethyl-4-(2-furanyl) pyridine-3,5-dicarboxylate) was synthesized and characterized by single-crystal X-ray analyses. The crystal is orthorhombic, space group Pbca, a = 15.6297(18), b = 9.4803(11), c = 18.598(2) A, V= 2755.8(6) A3, Z = 8, Mr= 498.44, Dc= 2.403 Mg/m3, F(000) = 1872, the final R = 0.0275 and wR = 0.0726 (1 〉 2σ(I)). There are interesting polynuclear zigzag (PbOs)n chains in the structure of 1, and there have interesting axially chiral S- and R-unit Pb4L units constructed from prochiral organic ligands through C-H...O bonding. The (R/S)-Pb4L units by sharing Pb centers generate a 2-D coordination network, in which there exist rare n65Pb (3.2610 A) interactions. The solid-state photoluminescent emission of compound 1 appears at 487 nm.

  19. Final Technical Report for DOE Grant DE-FG02-03ER15473 “Molecular Level Design of Heterogeneous Chiral Catalysis”

    Energy Technology Data Exchange (ETDEWEB)

    David Sholl; Andrew Gellman

    2007-03-15

    The production of enantiomerically pure chiral compounds is of great importance in the pharmaceutical industry. Although processes involving chiral catalysis and separations involving solid surfaces are known, the molecular-scale details of these processes are not well understood. This lack of understanding strongly limits the development of new chiral processes. Our collaborative research effort examines several intertwined aspects of chirality and enantioselectivity at catalytically active metal surfaces. At Carnegie Mellon, our efforts focus on the development of chirally imprinted metal powders as materials for chiral columns and the experimental and theoretical study of small chiral molecules adsorbed on well-characterized metal surfaces, both achiral and chiral. These efforts are being performed in close collaboration with our team members at the University of California Riverside and the University of Wisconsin Milwaukee.

  20. Absolute structure determination of compounds with axial and planar chirality using the crystalline sponge method† †Electronic supplementary information (ESI) available: Details of sample preparation and crystallographic analysis. CCDC 1051799, 1051800, 1051618, 1051619, 1043948 and 1043949. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01681a Click here for additional data file. Click here for additional data file.

    Science.gov (United States)

    Yoshioka, Shota; Inokuma, Yasuhide; Hoshino, Manabu; Sato, Takashi

    2015-01-01

    The absolute stereochemistry of compounds with axial and planar chirality is successfully determined by the crystalline sponge method without crystallization or derivatization of the compounds. This method is applied to absolute structure determination in the asymmetric synthesis of unique compounds with axial and planar chirality. PMID:28706719

  1. Light-driven rotary molecular motors without point chirality: a minimal design.

    Science.gov (United States)

    Wang, Jun; Oruganti, Baswanth; Durbeej, Bo

    2017-03-08

    A fundamental requirement for achieving photoinduced unidirectional rotary motion about an olefinic bond in a molecular motor is that the potential energy surface of the excited state is asymmetric with respect to clockwise and counterclockwise rotations. In most available light-driven rotary molecular motors, such asymmetry is guaranteed by the presence of a stereocenter. Here, we present non-adiabatic molecular dynamics simulations based on multiconfigurational quantum chemistry to demonstrate that this chiral feature is not essential for inducing unidirectional rotary motion in molecules that incorporate a cyclohexenylidene moiety into a protonated Schiff-base framework. Rather, the simulations show that it is possible to exploit the intrinsic asymmetry of the puckered cyclohexenylidene to control the direction of photoinduced rotation.

  2. Chiral liquids

    Directory of Open Access Journals (Sweden)

    Zakharov V.I.

    2015-01-01

    Full Text Available We review briefly properties of chiral liquids, or liquids with massless fermionic constituents. We concentrate on three effects, namely, the low ratio of viscosity η to entropy density s, chiral magnetic and vortical effects. We sketch standard derivations of these effects in the hydrodynamic approximation and then concentrate on possibile unifying approach which is based on consideration of the (anomalously conserved axial current. The point is that the conservation of chirality is specific for the microscopic, field-theoretic description of massless fermions and their interactions. On the macroscopic side, the standard hydrodynamic equations are not consistent, generally speaking, with conservation of a helical macroscopic motion. Imposing extra constraints on the hydrodynamics might resolve this “clash-of-symmetries” paradox.

  3. Supramolecular tilt chirality in crystals of steroids and alkaloids.

    Science.gov (United States)

    Hisaki, Ichiro; Tohnai, Norimitsu; Miyata, Mikiji

    2008-03-01

    The concept of supramolecular chirality has assumed increasing importance in association with the development of supramolecular chemistry over the last two decades. In chiral crystals, 2 1 helical molecular assemblies are frequently observed as key motifs. Helical handedness of the 2 1 assemblies, however, has not been determined from the mathematical or crystallographical viewpoints. In this context, we have proposed two new concepts, three-axial chirality and tilt chirality. On the basis of the concepts, we describe supramolecular chirality and determine the handedness of 2 1 assemblies that are composed of relatively complicated molecules with multiple stereogenic centers such as brucine, bile acids, and cinchona alkaloids as well as those of simple molecules.

  4. Chiral lactic hydrazone derivatives as potential bioactive antibacterial agents: Synthesis, spectroscopic, structural and molecular docking studies

    Science.gov (United States)

    Noshiranzadeh, Nader; Heidari, Azam; Haghi, Fakhri; Bikas, Rahman; Lis, Tadeusz

    2017-01-01

    A series of novel chiral lactic-hydrazone derivatives were synthesized by condensation of (S)-lactic acid hydrazide with salicylaldehyde derivatives and characterized by elemental analysis and spectroscopic studies (FT-IR, 1H NMR and 13C NMR spectroscopy). The structure of one compound was determined by single crystal X-ray analysis. Antibacterial activity of the synthesized compounds was studied against Staphylococcus aureus, Streptococcus pneumonia, Escherichia coli and Pseudomonas aeruginosa as bacterial cultures by broth microdilution method. All of the synthesized compounds showed good antibacterial activity with MIC range of 64-512 μg/mL. Compounds (S,E)-2-hydroxy-N-(2-hydroxy-5-nitrobenzylidene)propanehydrazide (5) and (S,E)-2-hydroxy-N-((3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl)propanehydrazide (7) were the most effective antibacterial derivatives against S. aureus and E. coli respectively with a MIC value of 64 μg/mL. Bacterial biofilm formation assay showed that these compounds significantly inhibited biofilm formation of P. aeruginosa. Also, in silico molecular docking studies were performed to show lipoteichoic acid synthase (LtaS) inhibitory effect of lactic hydrazone derivatives. The association between electronic and structural effects of some substituents on the benzylidene moiety and the biological activity of these chiral compounds were studied. Structural studies show that compound with higher hydrogen bonding interactions show higher antibacterial activity. The results show chiral hydrazone derivatives based on lactic acid hydrazide could be used as potential lead compounds for developing novel antibacterial agents.

  5. Molecularly Imprinted Polymers for the Identification and Separation of Chiral Drugs and Biomolecules

    Directory of Open Access Journals (Sweden)

    Sha Yang

    2016-06-01

    Full Text Available Molecularly imprinting polymers (MIPs have been extensively applied in chromatography for the separation of chiral drugs. In this review, we mainly summarize recent developments of various MIPs used as chiral stationary phases (CSPs in high performance liquid chromatography (HPLC, capillary electrochromatography (CEC, and supercritical fluid chromatography (SFC. Among them, HPLC has the advantages of straightforward operation and high selectivity. However, the low separation efficiency, due to slow interaction kinetics and heavy peak broadening, is the main challenge for the application of MIPs in HPLC. On the other hand, CEC possesses both the high selectivity of HPLC and the high efficiency of capillary electrophoresis. In CEC, electroosmotic flow is formed across the entire column and reduces the heavy peak broadening observed in HPLC mode. SFC can modify the low interaction kinetics in HPLC when supercritical fluids are utilized as mobile phases. If SFC and MIP-based CSPs can be well combined, better separation performance can be achieved. Particles, monoliths and membrane are typical formats of MIPs. Traditional MIP particles produced by bulk polymerization have been replaced by MIP particles by surface imprinting technology, which are highly consistent in size and shape. Monolithic MIPs are prepared by in situ method in a column, greatly shortening the pre-preparation time. Some novel materials, such as magnetic nanoparticles, are integrated into the MIPs to enhance the controllability and efficiency of the polymerization. This review will be helpful to guide the preparation, development, and application of MIPs in chromatographic and electrophoretic enantioseparation.

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

    Science.gov (United States)

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

    2014-06-01

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

  7. Rapid and efficient synthesis of new chiral aromatic amide molecular tweezers under solvent-free conditions using microwave

    Institute of Scientific and Technical Information of China (English)

    Xiao Xiang Zhao; Zhi Gang Zhao; Xing Li Liu; Xiu Ming Wu

    2009-01-01

    An efficient and simple method for the synthesis of new chiral aromatic amide molecular tweezers by irradiation with microwave under solvent-free conditions has been developed.Its main advantages are short reaction times.good conversions and the environmentally friendly nature of the process.

  8. C sub 6 sub 0 fullerene and its molecular complexes under axial and shear deformation

    CERN Document Server

    Spitsina, N G; Bashkin, I V; Meletov, K P

    2002-01-01

    We have studied the pristine C sub 6 sub 0 and its molecular complexes with the organic donors bis(ethylenedithio) tetrathiafulvalene (BEDT-TTF or ET) and tetramethyltetraselenafulvalene (TMTSF) by means of ESR and Raman spectroscopy at high pressure. The important changes in the ESR signal of C sub 6 sub 0 were observed under axial pressure combined with shear deformation. It is shown that the treatment at a anisotropic pressure of 4 GPa results in a reduction in the symmetry of the C sub 6 sub 0 molecule and the formation of radicals. Treatment of the molecular complex of (ET) sub 2 centre dot C sub 6 sub 0 at a pressure of approx 4.5 GPa and a temperature of 150 deg. C leads to the formation of C sub 6 sub 0 dimers. The Raman spectra of the molecular complex C sub 6 sub 0 centre dot TMTSF centre dot 2(CS sub 2) were measured in situ at ambient temperature and pressures up to 9.5 GPa. The pressure behaviour of the Raman peaks reveals singularity at 5.0 +- 0.5 GPa related to the softening and splitting of so...

  9. Nanoscale soldering of axially positioned single-walled carbon nanotubes: a molecular dynamics simulation study.

    Science.gov (United States)

    Cui, Jianlei; Yang, Lijun; Zhou, Liang; Wang, Yang

    2014-02-12

    The miniaturization of electronics devices into the nanometer scale is indispensable for next-generation semi-conductor technology. Carbon nanotubes (CNTs) are considered to be the promising candidates for future interconnection wires. To study the carbon nanotubes interconnection during nanosoldering, the melting process of nanosolder and nanosoldering process between single-walled carbon nanotubes are simulated with molecular dynamics method. As the simulation results, the melting point of 2 nm silver solder is about 605 K because of high surface energy, which is below the melting temperature of Ag bulk material. In the nanosoldering process simulations, Ag atoms may be dragged into the nanotubes to form different connection configuration, which has no apparent relationship with chirality of SWNTs. The length of core filling nanowires structure has the relationship with the diameter, and it does not become longer with the increasing diameter of SWNT. Subsequently, the dominant mechanism of was analyzed. In addition, as the heating temperature and time, respectively, increases, more Ag atoms can enter the SWNTs with longer length of Ag nanowires. And because of the strong metal bonds, less Ag atoms can remain with the tight atomic structures in the gap between SWNT and SWNT. The preferred interconnection configurations can be achieved between SWNT and SWNT in this paper.

  10. Crystal structure of (2R-1-[(methylsulfonyloxy]propan-2-aminium chloride: a chiral molecular salt

    Directory of Open Access Journals (Sweden)

    H. R. Rajegowda

    2015-10-01

    Full Text Available In the title chiral molecular salt, C4H12NO3S+·Cl−, the cation is protonated at the N atom, producing [RNH3]+, where R is CH3SO2OCH2C(HCH3. The N atom in the cation is sp3-hybridized. In the crystal, cations and anions are connected by strong N—H...Cl hydrogen bonds to generate edge-shared 12-membered rings of the form {...Cl...HNH}3. This pattern of hydrogen bonding gives rise to zigzag supramolecular layers in the ab plane. The layers are connected into a three-dimensional architecture by C—H...O hydrogen bonds. The structure was refined as an inversion twin.

  11. Assembled molecular face-rotating polyhedra to transfer chirality from two to three dimensions.

    Science.gov (United States)

    Wang, Xinchang; Wang, Yu; Yang, Huayan; Fang, Hongxun; Chen, Ruixue; Sun, Yibin; Zheng, Nanfeng; Tan, Kai; Lu, Xin; Tian, Zhongqun; Cao, Xiaoyu

    2016-08-24

    In nature, protein subunits on the capsids of many icosahedral viruses form rotational patterns, and mathematicians also incorporate asymmetric patterns into faces of polyhedra. Chemists have constructed molecular polyhedra with vacant or highly symmetric faces, but very little is known about constructing polyhedra with asymmetric faces. Here we report a strategy to embellish a C3h truxene unit with rotational patterns into the faces of an octahedron, forming chiral octahedra that exhibit the largest molar ellipticity ever reported, to the best of our knowledge. The directionalities of the facial rotations can be controlled by vertices to achieve identical rotational directionality on each face, resembling the homo-directionality of virus capsids. Investigations of the kinetics and mechanism reveal that non-covalent interaction among the faces is essential to the facial homo-directionality.

  12. Short-range interactions within molecular complexes formed in supersonic beams: structural effects and chiral discrimination

    Science.gov (United States)

    Latini; Satta; Guidoni; Piccirillo; Speranza

    2000-03-17

    One- and two-color, mass-selected R2PI spectra of the S13-pentanol, were recorded after a supersonic molecular beam expansion. Spectral analysis, coupled with theoretical calculations, indicate that several hydrogen-bonded [R.solv] conformers are present in the beam. The R2PI excitation spectra of [R.solv] are characterized by significant shifts of their band origin relative to that of bare R. The extent and direction of these spectral shifts depend on the structure and configuration of solv and are attributed to different short-range interactions in the ground and excited [R.solv] complexes. Measurement of the binding energies of [R.solv] in their neutral and ionic states points to a subtle balance between attractive (electrostatic and dispersive) and repulsive (steric) forces, which control the spectral features of the complexes and allow enantiomeric discrimination of chiral solv molecules.

  13. Molecular Modeling Study of Chiral Separation and Recognition Mechanism of β-Adrenergic Antagonists by Capillary Electrophoresis

    Directory of Open Access Journals (Sweden)

    Yifeng Chai

    2012-01-01

    Full Text Available Chiral separations of five β-adrenergic antagonists (propranolol, esmolol, atenolol, metoprolol, and bisoprolol were studied by capillary electrophoresis using six cyclodextrins (CDs as the chiral selectors. Carboxymethylated-β-cyclodextrin (CM-β-CD exhibited a higher enantioselectivity power compared to the other tested CDs. The influences of the concentration of CM-β-CD, buffer pH, buffer concentration, temperature, and applied voltage were investigated. The good chiral separation of five β-adrenergic antagonists was achieved using 50 mM Tris buffer at pH 4.0 containing 8 mM CM-β-CD with an applied voltage of 24 kV at 20 °C. In order to understand possible chiral recognition mechanisms of these racemates with CM-β-CD, host-guest binding procedures of CM-β-CD and these racemates were studied using the molecular docking software Autodock. The binding free energy was calculated using the Autodock semi-empirical binding free energy function. The results showed that the phenyl or naphthyl ring inserted in the hydrophobic cavity of CM-β-CD and the side chain was found to point out of the cyclodextrin rim. Hydrogen bonding between CM-β-CD and these racemates played an important role in the process of enantionseparation and a model of the hydrogen bonding interaction positions was constructed. The difference in hydrogen bonding formed with the –OH next to the chiral center of the analytes may help to increase chiral discrimination and gave rise to a bigger separation factor. In addition, the longer side chain in the hydrophobic phenyl ring of the enantiomer was not beneficial for enantioseparation and the chiral selectivity factor was found to correspond to the difference in binding free energy.

  14. Study on the mechanism of chiral recognition with molecularly imprinted polymers

    Energy Technology Data Exchange (ETDEWEB)

    Lu Yan; Li Chenxi; Zhang Hesheng; Liu Xiaohang

    2003-08-11

    This study aimed at elucidating the chiral recognition mechanism with molecularly imprinted polymers (MIPs) in aqueous environment. The system used ethylene glycol dimethacrylate (EGDMA), methacrylic acid (MAA), and 4-L-phenylalanylamino-pyridine (4-L-PheNHPy) as the cross-linking monomer, functional monomer and template, respectively, to assemble the imprinted polymer. A self-assembly mechanism, which includes the pre-organizing functional monomers around template before polymerization process, was proposed. This mechanism was supported by {sup 1}H NMR titration test. Interactions between functional monomer and template were observed using UV-Vis spectroscopy of solutions of these components as well. These studies indicated a 1:2 molecular complex dominantly formed between 4-L-PheNHPy and MAA. Association constant was estimated to be 97,000 M{sup -2}. Based on these results, a model mainly involving two-spot interaction was proposed evolving from our reported concept of exact placement of functional group. Ionic interaction between the primary amino group of 4-L-PheNHPy and carboxylic acid group inside the microcavity on MIPs was believed to play a predominate role in the enantioselectivity as supported by the observation of the relationship between the retention factor of 4-L-PheNHPy and the pH of mobile phase. While thermodynamic study at different pH revealed that, the interaction between the pyridyl group of 4-L-PheNHPy and the carboxylic acid group on the MIPs is also strong, implying that it also plays a profound role in determining the highly chiral selectivity of MIPs.

  15. Gelation induced supramolecular chirality: chirality transfer, amplification and application.

    Science.gov (United States)

    Duan, Pengfei; Cao, Hai; Zhang, Li; Liu, Minghua

    2014-08-14

    Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.

  16. Effects of molecular chirality on self-assembly and switching in liquid crystals at the cross-over between rod-like and bent shapes.

    Science.gov (United States)

    Ocak, Hale; Poppe, Marco; Bilgin-Eran, Belkız; Karanlık, Gürkan; Prehm, Marko; Tschierske, Carsten

    2016-09-21

    A bent-core compound derived from a 4-cyanoresorcinol core unit with two terephthalate based rod-like wings and carrying chiral 3,7-dimethyloctyloxy side chains has been synthesized in racemic and enantiomerically pure form and characterized by polarizing microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical investigations to study the influence of molecular chirality on the superstructural chirality and polar order in lamellar liquid crystalline phases. Herein we demonstrate that the coupling of molecular chirality with superstructural layer chirality in SmCsPF domain phases (forming energetically distinct diastereomeric pairs) can fix the tilt direction and thus stabilize synpolar order, leading to bistable ferroelectric switching in the SmC* phases of the (S)-enantiomer, whereas tristable modes determine the switching of the racemate. Moreover, the mechanism of electric field induced molecular reorganization changes from a rotation around the molecular long axis in the racemate to a rotation on the tilt-cone for the (S)-enantiomer. At high temperature the enantiomer behaves like a rod-like molecule with a chirality induced ferroelectric SmC* phase and an electroclinic effect in the SmA'* phase. At reduced temperature sterically induced polarization, due to the bent molecular shape, becomes dominating, leading to much higher polarization values, thus providing access to high polarization ferroelectric materials with weakly bent compounds having only "weakly chiral" stereogenic units. Moreover, the field induced alignment of the SmCsPF(()*()) domains gives rise to a special kind of electroclinic effect appearing even in the absence of molecular chirality. Comparison with related compounds indicates that the strongest effects of chirality appear for weakly bent molecules with a relatively short coherence length of polar order, whereas for smectic phases with long range polar order the effects of the interlayer interfaces can override

  17. Central-to-axial chirality transfer revealed by liquid crystals: a combined experimental and computational approach for the determination of absolute configuration of carboxylic acids with an α chirality centre.

    Science.gov (United States)

    Ferrarini, Alberta; Ferroni, Fiammetta; Pieraccini, Silvia; Rosini, Carlo; Superchi, Stefano; Spada, Gian Piero

    2011-10-01

    The conversion into 6,7-dihydro-5H-dibenz[c,e]azepine (DAZ) N-protected amides is a viable route for the determination of the absolute configuration of chiral 2-substituted carboxylic acids. The biphenyl moiety of DAZ, besides being a probe of chirality for the electronic circular dichroism (ECD) spectroscopy, makes these systems suitable for configuration assignment by exploiting the chirality amplification which occurs in nematic liquid crystals. To assess the reliability of the liquid crystal method in detecting the absolute stereochemistry of chiral amides bound to a biphenyl group, we measured the helical twisting power of a series of DAZ-N-protected amides and compared these data with the results obtained from ECD measurements. We will show that the liquid crystal method, corroborated by HTP predictions, is trustworthy with our biphenyl derivatives, even when ECD spectra are ambiguous for the presence of aryl moieties displaying strong UV absorptions in the same range of the biphenyl chromophore.

  18. Enantiodifferentiation of chiral baclofen by β-cyclodextrin using capillary electrophoresis: A molecular modeling approach

    Science.gov (United States)

    Suliman, FakhrEldin O.; Elbashir, Abdalla A.

    2012-07-01

    Using capillary electrophoresis baclofen (BF) enantiomers were separated only in the presence of β-cyclodextrin (βCD) as a chiral selector when added to the background electrolyte. Proton nuclear magnetic resonance and electrospray ionization mass spectrometry (ESI-MS) techniques were used to determine the structure of the BF-βCD inclusion complexes. From the MS data BF was found to form a 1:1 complex with α- and βCD, while the NMR data suggest location of the aromatic ring of BF into the cyclodextrin cavity. A molecular modeling study, using the semiempirical PM6 calculations was used to investigate the mechanism of enantiodifferentiation of BF with cyclodextrins. Optimization of the structures of the complexes by PM6 method indicated that separation is obtained in the presence of β-CD due to a large binding energy difference (ΔΔE) of 46.8 kJ mol-1 between S-BF-βCD and R-BF-βCD complexes. In the case of αCD complexes ΔΔE was 1.3 kJ mol-1 indicating poor resolution between the two enantiomers. Furthermore, molecular dynamic simulations show that the formation of more stable S-BF-βCD complex compared to R-BF-β-CD complex is primarily due to differences in intermolecular hydrogen bonding.

  19. Molecular Dynamics Modeling of the Effect of Axial and Transverse Compression on the Residual Tensile Properties of Ballistic Fiber

    Directory of Open Access Journals (Sweden)

    Sanjib C. Chowdhury

    2017-02-01

    Full Text Available Ballistic impact induces multiaxial loading on Kevlar® and polyethylene fibers used in protective armor systems. The influence of multiaxial loading on fiber failure is not well understood. Experiments show reduction in the tensile strength of these fibers after axial and transverse compression. In this paper, we use molecular dynamics (MD simulations to explain and develop a fundamental understanding of this experimental observation since the property reduction mechanism evolves from the atomistic level. An all-atom MD method is used where bonded and non-bonded atomic interactions are described through a state-of-the-art reactive force field. Monotonic tension simulations in three principal directions of the models are conducted to determine the anisotropic elastic and strength properties. Then the models are subjected to multi-axial loads—axial compression, followed by axial tension and transverse compression, followed by axial tension. MD simulation results indicate that pre-compression distorts the crystal structure, inducing preloading of the covalent bonds and resulting in lower tensile properties.

  20. The Question of Absolute Space and Time Directions in Relation to Molecular Chirality, Parity Violation, and Biomolecular Homochirality

    Energy Technology Data Exchange (ETDEWEB)

    Quack, Martin (ETH - Zurich)

    2001-03-21

    The questions of the absolute directions of space and time or the “observability” of absolute time direction as well as absolute handedness-left or right- are related to the fundamental symmetries of physics C, P, T as well as their combinations, in particular CPT, and their violations, such as parity violation. At the same time there is a relation to certain still open questions in chemistry concerning the fundamental physical- chemical principles of molecular chirality and in biochemistry concerning the selection of homochirality in evolution. In the lecture we shall introduce the concepts and then report new theoretical results from our work on parity violation in chiral molecules, showing order of magnitude increases with respect to previously accepted values. We discus as well our current experimental efforts. We shall briefly mention the construction of an absolute molecular clock.

  1. The Question of Absolute Space and Time Directions in Relation to Molecular Chirality, Parity Violation, and Biomolecular Homochirality

    Energy Technology Data Exchange (ETDEWEB)

    Quack, Martin (ETH - Zurich)

    2001-03-21

    The questions of the absolute directions of space and time or the 'observability' of absolute time direction as well as absolute handedness - left or right - are related to the fundamental symmetries of physics C, P, T as well as their combinations, in particular CPT, and their violations, such as parity violation. At the same time there is a relation to certain still open questions in chemistry concerning the fundamental physical-chemical principles of molecular chirality and in biochemistry concerning the selection of homochirality in evolution. In the lecture we shall introduce the concepts and then report new theoretical results from our work on parity violation in chiral molecules, showing order of magnitude increases with respect to previously accepted values. We discuss as well our current experimental efforts. We shall briefly mention the construction of an absolute molecular clock.

  2. Visualizing Molecular Chirality in the Organic Chemistry Laboratory Using Cholesteric Liquid Crystals

    Science.gov (United States)

    Popova, Maia; Bretz, Stacey Lowery; Hartley, C. Scott

    2016-01-01

    Although stereochemistry is an important topic in second-year undergraduate organic chemistry, there are limited options for laboratory activities that allow direct visualization of macroscopic chiral phenomena. A novel, guided-inquiry experiment was developed that allows students to explore chirality in the context of cholesteric liquid crystals.…

  3. Molecular and Merrifield supported chiral diamines for enantioselective addition of ZnR2 (R = Me, Et) to ketones.

    Science.gov (United States)

    Calvillo-Barahona, Mercedes; Cordovilla, Carlos; Genov, Miroslav N; Martínez-Ilarduya, Jesús M; Espinet, Pablo

    2013-10-28

    Chiral 1,2-ethylenediamines have been previously reported as active catalysts in the enantioselective addition reactions of ZnR2 to either methyl- or trifluoromethyl-ketones. Subtle changes in the molecular structure of different catalysts are described herein and lead to a dramatic effect in their catalytic activity. From these findings, we demonstrate the selective reactivity of the ligands used in the addition of ZnR2 (R = Me, Et) to methyl- and trifluoromethyl-ketones offering an enantioselective access either to chiral non-fluorinated alcohols or to chiral fluorinated tertiary alcohols. Considering the importance of the chiral trifluoromethyl carbinol fragment in several biologically active compounds, we have extended the scope of the addition reaction of ZnEt2 to several trifluoromethylketones catalyzed by (R,R)-1,2-diphenylethylenediamine derivatives. This work explores a homogeneous approach that provides excellent yields and very high ee and the use of a heterogenized tail-tied ligand affording moderate ee, high yields and allowing an easier handling and recycling.

  4. Control and femtosecond time-resolved imaging of torsion in a chiral molecule

    DEFF Research Database (Denmark)

    Hansen, Jonas Lerche; Nielsen, Jens Hedegaard; Madsen, Christian Bruun;

    2012-01-01

    We study how the combination of long and short laser pulses can be used to induce torsion in an axially chiral biphenyl derivative (3,5-difluoro-3′,5′-dibromo-4′-cyanobiphenyl). A long, with respect to the molecular rotational periods, elliptically polarized laser pulse produces 3D alignment of t...

  5. Control and femtosecond time-resolved imaging of torsion in a chiral molecule

    DEFF Research Database (Denmark)

    Hansen, Jonas Lerche; Nielsen, Jens Hedegaard; Madsen, Christian Bruun

    2012-01-01

    We study how the combination of long and short laser pulses can be used to induce torsion in an axially chiral biphenyl derivative (3,5-difluoro-3′,5′-dibromo-4′-cyanobiphenyl). A long, with respect to the molecular rotational periods, elliptically polarized laser pulse produces 3D alignment of t...

  6. Chiral ammonium betaine-catalyzed asymmetric Mannich-type reaction of oxindoles

    Directory of Open Access Journals (Sweden)

    Masahiro Torii

    2016-09-01

    Full Text Available A highly diastereo- and enantioselective Mannich-type reaction of 3-aryloxindoles with N-Boc aldimines was achieved under the catalysis of axially chiral ammonium betaines. This catalytic method provides a new tool for the construction of consecutive quaternary and tertiary stereogenic carbon centers on biologically intriguing molecular frameworks with high fidelity.

  7. Bulky melamine-based Zn-porphyrin tweezer as a CD probe of molecular chirality.

    Science.gov (United States)

    Petrovic, Ana G; Vantomme, Ghislaine; Negrón-Abril, Yashira L; Lubian, Elisa; Saielli, Giacomo; Menegazzo, Ileana; Cordero, Roselynn; Proni, Gloria; Nakanishi, Koji; Carofiglio, Tommaso; Berova, Nina

    2011-10-01

    The transfer of chirality from a guest molecule to an achiral host is the subject of significant interest especially when, upon chiral induction, the chiroptical response of the host/guest complex can effectively report the absolute configuration (AC) of the guest. For more than a decade, dimeric metalloporphyrin hosts (tweezers) have been successfully applied as chirality probes for determination of the AC for a wide variety of chiral synthetic compounds and natural products. The objective of this study is to investigate the utility of a new class of melamine-bridged Zn-porphyrin tweezers as sensitive AC reporters. A combined approach based on an experimental CD analysis and a theoretical prediction of the prevailing interporphyrin helicity demonstrates that these tweezers display favorable properties for chiral recognition. Herein, we discuss the application of the melamine-bridged tweezer to the chiral recognition of a diverse set of chiral guests, such as 1,2-diamines, α-amino-esters and amides, secondary alcohols, and 1,2-amino-alcohols. The bulky periphery and the presence of a rigid porphyrin linkage lead, in some cases, to a more enhanced CD sensitivity than that reported earlier with other tweezers.

  8. Axially Chiral C2-Symmetric N-Heterocyclic Carbene (NHC) Palladium Complex-Catalyzed Asymmetric Fluorination and Amination of Oxindoles

    Institute of Scientific and Technical Information of China (English)

    张睿; 王德; 徐琴; 姜佳俊; 施敏

    2012-01-01

    Chiral C2-symmetric N-heterocyclic carbene (NHC) palladium diaquo complex 5b prepared from (S)-BINAM was found to be a fairly effective catalyst for the enantioselective asymmetric fluorination of oxindoles to give the corresponding products in moderate enantioselectivities along with good to excellent yields.

  9. Chiral supergravity and anomalies

    CERN Document Server

    Mielke, E W; Macias, Alfredo; Mielke, Eckehard W.

    1999-01-01

    Similarily as in the Ashtekar approach, the translational Chern-Simons term is, as a generating function, instrumental for a chiral reformulation of simple (N=1) supergravity. After applying the algebraic Cartan relation between spin and torsion, the resulting canonical transformation induces not only decomposition of the gravitational fields into selfdual and antiselfdual modes, but also a splitting of the Rarita-Schwinger fields into their chiral parts in a natural way. In some detail, we also analyze the consequences for axial and chiral anomalies.

  10. Spiral Galaxies as Chiral Objects?

    CERN Document Server

    Capozziello, S; Capozziello, Salvatore; Lattanzi, Alessandra

    2005-01-01

    Spiral galaxies show axial symmetry and an intrinsic 2D-chirality. Environmental effects can influence the chirality of originally isolated stellar systems and a progressive loss of chirality can be recognised in the Hubble sequence. We point out a preferential modality for genetic galaxies as in microscopic systems like aminoacids, sugars or neutrinos. This feature could be the remnant of a primordial symmetry breaking characterizing systems at all scales.

  11. Direct Observation of Molecular Preorganization for Chirality Transfer on a Catalyst Surface

    DEFF Research Database (Denmark)

    Demers-Carpentier, Vincent; Goubert,, Guillaume; Masini, Federico

    2011-01-01

    The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex that conti......The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex...... functional theory calculations reveals the stereodirecting forces governing preorganization into precise chiral modifier-substrate bimolecular surface complexes. The study shows that the chiral modifier induces prochiral switching on the surface and that different prochiral ratios prevail at different...

  12. Direct Observation of Molecular Preorganization for Chirality Transfer on a Catalyst Surface

    DEFF Research Database (Denmark)

    Demers-Carpentier, Vincent; Goubert,, Guillaume; Masini, Federico

    2011-01-01

    The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex that conti...

  13. Chiral Rotational Spectroscopy

    CERN Document Server

    Cameron, Robert P; Barnett, Stephen M

    2015-01-01

    We introduce chiral rotational spectroscopy: a new technique that enables the determination of the individual optical activity polarisability components $G_{XX}'$, $G_{YY}'$, $G_{ZZ}'$, $A_{X,YZ}$, $A_{Y,ZX}$ and $A_{Z,XY}$ of chiral molecules, in a manner that reveals the enantiomeric constitution of a sample whilst yielding an incisive signal even for a racemate. Chiral rotational spectroscopy could find particular use in the analysis of molecules that are chiral by virtue of their isotopic constitution and molecules with multiple chiral centres. The principles that underpin chiral rotational spectroscopy can also be exploited in the search for molecular chirality in space, which, if found, may add weight to hypotheses that biological homochirality and indeed life itself are of cosmic origin.

  14. Development of simulation approach for two-dimensional chiral molecular self-assembly driven by hydrogen bond at the liquid/solid interface

    Science.gov (United States)

    Qin, Yuan; Yao, Man; Hao, Ce; Wan, Lijun; Wang, Yunhe; Chen, Ting; Wang, Dong; Wang, Xudong; Chen, Yonggang

    2017-09-01

    Two-dimensional (2D) chiral self-assembly system of 5-(benzyloxy)-isophthalic acid derivative/(S)-(+)-2-octanol/highly oriented pyrolytic graphite was studied. A combined density functional theory/molecular mechanics/molecular dynamics (DFT/MM/MD) approach for system of 2D chiral molecular self-assembly driven by hydrogen bond at the liquid/solid interface was thus proposed. Structural models of the chiral assembly were built on the basis of scanning tunneling microscopy (STM) images and simplified for DFT geometry optimization. Merck Molecular Force Field (MMFF) was singled out as the suitable force field by comparing the optimized configurations of MM and DFT. MM and MD simulations for hexagonal unit model which better represented the 2D assemble network were then preformed with MMFF. The adhesion energy, evolution of self-assembly process and characteristic parameters of hydrogen bond were obtained and analyzed. According to the above simulation, the stabilities of the clockwise and counterclockwise enantiomorphous networks were evaluated. The calculational results were supported by STM observations and the feasibility of the simulation method was confirmed by two other systems in the presence of chiral co-absorbers (R)-(-)-2-octanol and achiral co-absorbers 1-octanol. This theoretical simulation method assesses the stability trend of 2D enantiomorphous assemblies with atomic scale and can be applied to the similar hydrogen bond driven 2D chirality of molecular self-assembly system.

  15. The chiral phase transition in a random matrix model with molecular correlations

    CERN Document Server

    Wettig, T; Weidenmüller, H A; Wettig, Tilo

    1995-01-01

    The chiral phase transition of QCD is analyzed in a model combining random matrix elements of the Dirac operator with specially chosen non-random ones. The special form of the latter is motivated by the assumption that the fermionic quasi-zero modes associated with instanton and anti-instanton configurations determine the chiral properties of QCD. Our results show that the degree of correlation between these modes plays the decisive role. To reduce the value of the chiral condensate by more than a factor of 2 about 95 percent of the instantons and anti-instantons must form so-called molecules. This conclusion agrees with numerical results of the Stony Brook group.

  16. Application of Homochiral Alkylated Organic Cages as Chiral Stationary Phases for Molecular Separations by Capillary Gas Chromatography

    Directory of Open Access Journals (Sweden)

    Shengming Xie

    2016-11-01

    Full Text Available Molecular organic cage compounds have attracted considerable attention due to their potential applications in gas storage, catalysis, chemical sensing, molecular separations, etc. In this study, a homochiral pentyl cage compound was synthesized from a condensation reaction of (S,S-1,2-pentyl-1,2-diaminoethane and 1,3,5-triformylbenzene. The imine-linked pentyl cage diluted with a polysiloxane (OV-1701 was explored as a novel stationary phase for high-resolution gas chromatographic separation of organic compounds. Some positional isomers were baseline separated on the pentyl cage-coated capillary column. In particular, various types of enantiomers including chiral alcohols, esters, ethers and epoxides can be resolved without derivatization on the pentyl cage-coated capillary column. The reproducibility of the pentyl cage-coated capillary column for separation was investigated using nitrochlorobenzene and styrene oxide as analytes. The results indicate that the column has good stability and separation reproducibility after being repeatedly used. This work demonstrates that molecular organic cage compounds could become a novel class of chiral separation media in the near future.

  17. Application of Homochiral Alkylated Organic Cages as Chiral Stationary Phases for Molecular Separations by Capillary Gas Chromatography.

    Science.gov (United States)

    Xie, Shengming; Zhang, Junhui; Fu, Nan; Wang, Bangjin; Hu, Cong; Yuan, Liming

    2016-11-08

    Molecular organic cage compounds have attracted considerable attention due to their potential applications in gas storage, catalysis, chemical sensing, molecular separations, etc. In this study, a homochiral pentyl cage compound was synthesized from a condensation reaction of (S,S)-1,2-pentyl-1,2-diaminoethane and 1,3,5-triformylbenzene. The imine-linked pentyl cage diluted with a polysiloxane (OV-1701) was explored as a novel stationary phase for high-resolution gas chromatographic separation of organic compounds. Some positional isomers were baseline separated on the pentyl cage-coated capillary column. In particular, various types of enantiomers including chiral alcohols, esters, ethers and epoxides can be resolved without derivatization on the pentyl cage-coated capillary column. The reproducibility of the pentyl cage-coated capillary column for separation was investigated using nitrochlorobenzene and styrene oxide as analytes. The results indicate that the column has good stability and separation reproducibility after being repeatedly used. This work demonstrates that molecular organic cage compounds could become a novel class of chiral separation media in the near future.

  18. Emerging chirality in nanoscience.

    Science.gov (United States)

    Wang, Yong; Xu, Jun; Wang, Yawen; Chen, Hongyu

    2013-04-07

    Chirality in nanoscience may offer new opportunities for applications beyond the traditional fields of chirality, such as the asymmetric catalysts in the molecular world and the chiral propellers in the macroscopic world. In the last two decades, there has been an amazing array of chiral nanostructures reported in the literature. This review aims to explore and categorize the common mechanisms underlying these systems. We start by analyzing the origin of chirality in simple systems such as the helical spring and hair vortex. Then, the chiral nanostructures in the literature were categorized according to their material composition and underlying mechanism. Special attention is paid to highlight systems with original discoveries, exceptional structural characteristics, or unique mechanisms.

  19. Photoinduced molecular chirality probed by ultrafast resonant X-ray spectroscopy

    Directory of Open Access Journals (Sweden)

    Jérémy R. Rouxel

    2017-07-01

    Full Text Available Recently developed circularly polarized X-ray light sources can probe the ultrafast chiral electronic and nuclear dynamics through spatially localized resonant core transitions. We present simulations of time-resolved circular dichroism signals given by the difference of left and right circularly polarized X-ray probe transmission following an excitation by a circularly polarized optical pump with the variable time delay. Application is made to formamide which is achiral in the ground state and assumes two chiral geometries upon optical excitation to the first valence excited state. Probes resonant with various K-edges (C, N, and O provide different local windows onto the parity breaking geometry change thus revealing the enantiomer asymmetry.

  20. A molecular view of the role of chirality in charge-driven polypeptide complexation

    Energy Technology Data Exchange (ETDEWEB)

    Hoffmann, K. Q.; Perry, S. L.; Leon, L.; Priftis, D.; Tirrell, M.; de Pablo, J. J.

    2015-01-01

    Polyelectrolyte molecules of opposite charge are known to form stable complexes in solution. Depending on the system conditions, such complexes can be solid or liquid. The latter are known as complex coacervates, and they appear as a second liquid phase in equilibrium with a polymer-dilute aqueous phase. This work considers the complexation between poly(glutamic acid) and poly(lysine), which is of particular interest because it enables examination of the role of chirality in ionic complexation, without changes to the overall chemical composition. Systematic atomic-level simulations are carried out for chains of poly(glutamic acid) and poly(lysine) with varying combinations of chirality along the backbone. Achiral chains form unstructured complexes. In contrast, homochiral chains lead to formation of stable beta-sheets between molecules of opposite charge, and experiments indicate that beta-sheet formation is correlated with the formation of solid precipitates. Changes in chirality along the peptide backbone are found to cause "kinks" in the beta-sheets. These are energetically unfavorable and result in irregular structures that are more difficult to pack together. Taken together, these results provide new insights that may be of use for the development of simple yet strong bioinspired materials consisting of beta-rich domains and amorphous regions.

  1. Synthesis of Ruthenium(III Phthalocyanine with Di-axial Bromo Ligands - A Promising Molecular Conductor with Giant Negative Magnetoresistance

    Directory of Open Access Journals (Sweden)

    Mario A.V. Gamboa

    2015-01-01

    Full Text Available The electron transport of Phthalocyanines (Pc with central metal and di-axial ligands (such as FeIII(PcL2; where L = CN, Cl, Br originates from its intermolecular Pc π-π orbital overlap while its giant negative magnetoresistance (GNMR arises from its intramolecular Pc-π(HOMO and Fe-d (s=1/2 interaction. However, the π-d interaction tends to localize itinerant electrons resulting in the decrease in the conductivity of the FeIII(PcL2 series compared to the non-magnetic CoIII(PcL2 where π-d interaction is absent. More so, the axial ligand field energy of the FeIII(PcL2 system is found to have the ability to proportionally modulate the π-d interaction. In reference thereof, theoretical calculations point that isostructural RuIII(PcBr2 would provide the best balance of π-d orbital energy interplay. That is, RuIII(PcBr2 is expected to be a molecule with high electrical conductivity and GNMR which would make it an ideal magnetic molecular conductor. This paper reports on the synthesis of RuIII(PcBr2.

  2. The liquid surface of chiral ionic liquids as seen from molecular dynamics simulations combined with intrinsic analysis

    Energy Technology Data Exchange (ETDEWEB)

    Lísal, Martin, E-mail: lisal@icpf.cas.cz [E. Hála Laboratory of Thermodynamics, Institute of Chemical Process Fundamentals of the ASCR, v. v. i., 165 02 Prague 6-Suchdol, Czech Republic and Department of Physics, Faculty of Science, J. E. Purkinje University, 400 96 Ústí n. Lab. (Czech Republic)

    2013-12-07

    We present molecular-level insight into the liquid/gas interface of two chiral room-temperature ionic liquids (RTILs) derived from 1-n-butyl-3-methylimidazolium bromide ([bmim][Br]); namely, (R)-1-butyl-3-(3-hydroxy-2-methylpropyl)imidazolium bromide (hydroxypropyl) and 1-butyl-3-[(1R)-nopyl]imidazolium bromide (nopyl). We use our currently developed force field which was validated against the experimental bulk density, heat of vaporization, and surface tension of [bmim][Br]. The force field for the RTILs adopts the Chemistry at Harvard Molecular Mechanics (CHARMM) parameters for the intramolecular and repulsion-dispersion interactions along with the reduced partial atomic charges based on ab initio calculations. The net charges of the ions are around ±0.8e, which mimic the anion to cation charge transfer and many-body effects. Molecular dynamics simulations in the slab geometry combined with the intrinsic interface analysis are employed to provide a detailed description of the RTIL/gas interface in terms of the structural and dynamic properties of the interfacial, sub-interfacial, and central layers at a temperature of 300 K. The focus is on the comparison of the liquid/gas interface for the chiral RTILs with the interface for parent [bmim][Br]. The structure of the interface is elucidated by evaluating the surface roughness, intrinsic atomic density profiles, and orientation ordering of the cations. The dynamics of the ions at the interfacial region is characterized by computing the survival probability, and normal and lateral self-diffusion coefficients in the layers.

  3. The liquid surface of chiral ionic liquids as seen from molecular dynamics simulations combined with intrinsic analysis

    Science.gov (United States)

    Lísal, Martin

    2013-12-01

    We present molecular-level insight into the liquid/gas interface of two chiral room-temperature ionic liquids (RTILs) derived from 1-n-butyl-3-methylimidazolium bromide ([bmim][Br]); namely, (R)-1-butyl-3-(3-hydroxy-2-methylpropyl)imidazolium bromide (hydroxypropyl) and 1-butyl-3-[(1R)-nopyl]imidazolium bromide (nopyl). We use our currently developed force field which was validated against the experimental bulk density, heat of vaporization, and surface tension of [bmim][Br]. The force field for the RTILs adopts the Chemistry at Harvard Molecular Mechanics (CHARMM) parameters for the intramolecular and repulsion-dispersion interactions along with the reduced partial atomic charges based on ab initio calculations. The net charges of the ions are around ±0.8e, which mimic the anion to cation charge transfer and many-body effects. Molecular dynamics simulations in the slab geometry combined with the intrinsic interface analysis are employed to provide a detailed description of the RTIL/gas interface in terms of the structural and dynamic properties of the interfacial, sub-interfacial, and central layers at a temperature of 300 K. The focus is on the comparison of the liquid/gas interface for the chiral RTILs with the interface for parent [bmim][Br]. The structure of the interface is elucidated by evaluating the surface roughness, intrinsic atomic density profiles, and orientation ordering of the cations. The dynamics of the ions at the interfacial region is characterized by computing the survival probability, and normal and lateral self-diffusion coefficients in the layers.

  4. Cooperativity of axial and centre chirality in the biaryl disulfoxide/Rh(i)-catalysed asymmetric 1,4-addition of arylboronic aids to 2-cyclohexenone: a DFT study.

    Science.gov (United States)

    Zha, Gao-Feng; Qin, Hua-Li; Kantchev, Eric Assen B

    2017-03-08

    Atropisomeric biaryl disulfoxides contain two independent chiral elements. Previously, the (M,S,S)-diastereomer showed very high catalytic activity and selectivity in the Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-enones whereas the (M,R,R) counterpart - none. Herein, DFT computations on the key transmetallation (turnover-determining) and carborhodation (enantioselectivity-determining) steps of the catalytic cycle show that the (M,S,S)-ligand gives rise to lower reaction barriers for these elementary steps. However, the barriers for the (M,R,R)-ligand are not sufficiently high to explain the lack of reactivity. Hence, this phenomenon is most likely due to the failure of catalyst formation from the ligand and the dimeric Rh precatalyst complex. The hitherto unknown (M,S,R)-ligand shows predicted enantioselectivity similar to the (M,S,S)-ligand as a consequence of lower reaction barriers associated with those isomers whose key features resemble the (M,S,S)-ligand.

  5. The molecular mechanism studies of chirality effect of PHA-739358 on Aurora kinase A by molecular dynamics simulation and free energy calculations

    Science.gov (United States)

    Cheng, Yuanhua; Cui, Wei; Chen, Quan; Tung, Chen-Ho; Ji, Mingjuan; Zhang, Fushi

    2011-02-01

    Aurora kinase family is one of the emerging targets in oncology drug discovery and several small molecules targeting aurora kinases have been discovered and evaluated under early phase I/II trials. Among them, PHA-739358 (compound 1r) is a 3-aminopyrazole derivative with strong activity against Aurora A under early phase II trial. Inhibitory potency of compound 1r (the benzylic substituent at the pro-R position) is 30 times over that of compound 1s (the benzylic substituent at the pro-S position). In present study, the mechanism of how different configurations influence the binding affinity was investigated using molecular dynamics (MD) simulations, free energy calculations and free energy decomposition analysis. The predicted binding free energies of these two complexes are consistent with the experimental data. The analysis of the individual energy terms indicates that although the van der Waals contribution is important for distinguishing the binding affinities of these two inhibitors, the electrostatic contribution plays a more crucial role in that. Moreover, it is observed that different configurations of the benzylic substituent could form different binding patterns with protein, thus leading to variant inhibitory potency of compounds 1r and 1s. The combination of different molecular modeling techniques is an efficient way to interpret the chirality effects of inhibitors and our work gives valuable information for the chiral drug design in the near future.

  6. Chiral Quark Model of Mesons

    CERN Document Server

    Wang, X J; Wang, Xiao-Jun; Yan, Mu-Lin

    1999-01-01

    We study SU(3)$_L\\timesSU(3)_R$ chiral quark model of mesons up to next leading order of $1/N_c$ expansion. Composite vector and axial-vector mesons resonances are introduced via non-linear realization of chiral SU(3) and vector meson dominant. Effects of one-loop graphs of pseudoscalar, vector and axial-vector mesons is calculated systematically and the significant results are obtained. Correction of effective gluon interaction is studied too. The light quark masses are introduced via new mechanism which agree with phenomenology and the requirement of chiral symmetry. Up to powers four of derivatives, chiral effective lagrangian of mesons is derived and evaluated to next leading order of $1/N_c$. Low energy limit of the model is examined. Ten low energy coupling constants $L_i(i=1,2,...,10)$ in ChPT are obtained and agree with ChPT well.

  7. Study of axial magnetic effect

    Energy Technology Data Exchange (ETDEWEB)

    Braguta, Victor [IHEP, Protvino, Moscow region, 142284 Russia ITEP, B. Cheremushkinskaya street 25, Moscow, 117218 (Russian Federation); School of Biomedicine, Far Eastern Federal University, Ajax 10 Building 25, Russian island, Vladivostok, 690922 (Russian Federation); Chernodub, M. N. [CNRS, Laboratoire de Mathématiques et Physique Théorique, Université François-Rabelais Tours, Fédération Denis Poisson, Parc de Grandmont, 37200 Tours, France Department of Physics and Astronomy, University of Gent, Krijgslaan 281, S9, B-9000 Gent (Belgium); School of Biomedicine, Far Eastern Federal University, Ajax 10 Building 25, Russian island, Vladivostok, 690922 (Russian Federation); Goy, V. A. [School of Natural Sciences, Far Eastern Federal University, Sukhanova street 8, Vladivostok, 690950 (Russian Federation); Landsteiner, K. [Instituto de Física Teórica UAM/CSIC, C/ Nicolás Cabrera 13-15, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Molochkov, A. V. [School of Biomedicine, Far Eastern Federal University, Ajax 10 Building 25, Russian island, Vladivostok, 690922 (Russian Federation); Ulybyshev, M. [ITEP, B. Cheremushkinskaya street 25, Moscow, 117218 Russia Institute for Theoretical Problems of Microphysics, Moscow State University, Moscow, 119899 (Russian Federation)

    2016-01-22

    The Axial Magnetic Effect manifests itself as an equilibrium energy flow of massless fermions induced by the axial (chiral) magnetic field. Here we study the Axial Magnetic Effect in the quenched SU(2) lattice gauge theory with massless overlap fermions at finite temperature. We numerically observe that in the low-temperature hadron phase the effect is absent due to the quark confinement. In the high-temperature deconfinement phase the energy flow is an increasing function of the temperature which reaches the predicted asymptotic T{sup 2} behavior at high temperatures. We find, however, that energy flow is about one order of magnitude lower compared to a theoretical prediction.

  8. The anomalous transport of axial charge: topological vs non-topological fluctuations

    CERN Document Server

    Iatrakis, Ioannis; Yin, Yi

    2015-01-01

    Axial charge imbalance is an essential ingredient in novel effects associated with chiral anomaly such as chiral magnetic effects (CME). In a non-Abelian plasma with chiral fermions, local axial charge can be generated a) by topological fluctuations which would create domains with non-zero winding number b) by conventional non-topological thermal fluctuations. We provide a holographic evaluations of medium's response to dynamically generated axial charge density in hydrodynamic limit and examine if medium's response depends on the microscopic origins of axial charge imbalance. We show a local domain with non-zero winding number would induce a non-dissipative axial current due to chiral anomaly. We illustrate holographically that a local axial charge imbalance would be damped out with the damping rate related to Chern-Simon diffusive constant. By computing chiral magnetic current in the presence of dynamically generated axial charge density, we found that the ratio of CME current over the axial charge density ...

  9. Chiral memory via chiral amplification and selective depolymerization of porphyrin aggregates.

    Science.gov (United States)

    Helmich, Floris; Lee, Cameron C; Schenning, Albertus P H J; Meijer, E W

    2010-12-01

    Chiral memory at the supramolecular level is obtained via a new approach using chiral Zn porphrins and achiral Cu porphyrins. In a "sergeant-and-soldiers" experiment, the Zn "sergeant" transfers its own chirality to Cu "soldiers" and, after chiral amplification, the "sergeant" is removed from the coaggregates by axial ligation with a Lewis base. After this extraction, the preferred helicity observed for the aggregates containing achiral Cu porphyrins reveals a chiral memory effect that is stable and can be erased and partially restored upon subsequent heating and cooling.

  10. Chiral heat wave and mixing of magnetic, vortical and heat waves in chiral media

    Energy Technology Data Exchange (ETDEWEB)

    Chernodub, M.N. [CNRS, Laboratoire de Mathématiques et Physique Théorique,Université de Tours, 37200 (France); Soft Matter Physics Laboratory, Far Eastern Federal University,Sukhanova 8, Vladivostok (Russian Federation); Department of Physics and Astronomy, University of Gent,Krijgslaan 281, S9, Gent (Belgium)

    2016-01-18

    We show that a hot rotating fluid of relativistic chiral fermions possesses a new gapless collective mode associated with coherent propagation of energy density and chiral density waves along the axis of rotation. This mode, which we call the Chiral Heat Wave, emerges due to a mixed gauge-gravitational anomaly. At finite density the Chiral Heat Wave couples to the Chiral Vortical Wave while in the presence of an external magnetic field it mixes with the Chiral Magnetic Wave. The coupling of the Chiral Magnetic and Chiral Vortical Waves is also demonstrated. We find that the coupled waves — which are coherent fluctuations of the vector, axial and energy currents — have generally different velocities compared to the velocities of the individual waves.

  11. Chiral Ionic Liquids in Chromatographic Separation and Spectroscopic Discrimination

    Science.gov (United States)

    Li, Min; Bwambok, David K.; Fakayode, Sayo O.; Warner, Isiah M.

    Chiral ionic liquids (CILs) are a subclass of ionic liquids (ILs) in which the cation, anion, or both may be chiral. The chirality can be central, axial, or planar. CILs possess a number of unique advantageous properties which are inherited from ionic liquids including negligible vapor pressure, wide liquidus temperature range, high thermal stability, and high tunability. Due to their dual functionalities as chiral selectors and chiral solvents simultaneously, CILs recently have been widely used both in enantiomeric chromatographic separation and in chiral spectroscopic discrimination. In this chapter, the various applications of CILs in chiral chromatographic separations such as GC, HPLC, CE, and MEKC are reviewed. The applications of CILs in enantiomeric spectroscopic discrimination using techniques such as NMR, fluorescence, and NIR are described. In addition, chiral recognition and separation mechanism using the CILs as chiral selectors or chiral solvents is also discussed.

  12. Axial distortion as a sensor of supercoil changes: a molecular model for the homeostatic regulation of DNA gyrase

    Indian Academy of Sciences (India)

    Shyam Unniraman; Valakunja Nagaraja

    2001-12-01

    Negative supercoiling stimulates transcription of many genes. In contrast, transcription of the genes coding for DNA gyrase is subject to a novel mechanism of autoregulation, wherein relaxation of the template DNA stimulates their transcription. Since DNA gyrase is the sole supercoiling activity in the eubacterial cell, relaxation-stimulated transcription (RST) could reflect an autoregulatory mechanism to maintain supercoil levels within the cell. Extensive deletion and mutational analyses of Escherichia coli gyrA promoter have shown that the $-10$ region is essential for RST; however, a molecular model has proved to be elusive. We find a strong bend centre immediately downstream of the $-10$ region in the gyrA promoter. On the basis of analysis of various mutants in the $-10$ region, we propose a model where axial distortion acts as a sensor of topological changes in DNA. Our model is consistent with earlier data with E. coli gyrA and gyrB promoters. We also extrapolate the model to explain the phenomenon of RST of gyr promoters in other organisms and contrast it with promoters induced by supercoiling.

  13. Dual chirality control of palladium(II) complexes bearing tropos biphenyl diamine ligands.

    Science.gov (United States)

    Aikawa, Kohsuke; Mikami, Koichi

    2005-12-14

    Axial and center chirality of Pd complexes with tropos biphenyl secondary diamine ligands is shown to be controlled by chiral amide (R)-DABNTf, which can efficiently discriminate between two enantiomeric Pd complexes.

  14. Design of chiral dimesogens containing cholesteryl groups; formation of new molecular organizations and their application to molecular photonics.

    Science.gov (United States)

    Mallia, V Ajay; Tamaoki, Nobuyuki

    2004-02-20

    Photoresponsive liquid crystals and organogels are finding increasing application in information technology and photonics. In this tutorial review, the authors describe how weak intermolecular interactions facilitate molecular organization of cholesterol-containing dimesogens to form such materials. Design considerations and photoresponsive properties of both organogels and glassy liquid crystals are discussed and their applications to molecular photonics highlighted. The review will be of value to readers interested in the development of new materials which respond to the different properties of light.

  15. C3 -Symmetric Boron Lewis Acid with a Cage-Shape for Chiral Molecular Recognition and Asymmetric Catalysis.

    Science.gov (United States)

    Konishi, Akihito; Nakaoka, Koichi; Maruyama, Hikaru; Nakajima, Hideto; Eguchi, Tomohiro; Baba, Akio; Yasuda, Makoto

    2017-01-26

    Chiral Lewis acids play an important role in the precise construction of various types of chiral molecules. Here, a cage-shaped borate 2 was designed and synthesized as a chiral Lewis acid that possesses a unique C3 -symmetric structure composed of three homochiral binaphthyl moieties. The highly symmetrical structure of 2 with homochirality was clearly elucidated by X-ray crystallographic analysis. The peculiar chiral environment of 2⋅THF exhibited chiral recognition of some simple amines and a sulfoxide. Moreover, the application of 2⋅THF to hetero-Diels-Alder reactions as a chiral Lewis-acid catalyst afforded the enantioselective products, which were obtained through an entropy-controlled pathway according to the analysis of the relationship between optical yield and reaction temperature. In particular, the robust chiral reaction field of 2⋅THF allowed the first example of an asymmetric hetero-Diels-Alder reaction with a simple diene despite the requirement of high temperature. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Foreign-catalyst-free growth of InAs/InSb axial heterostructure nanowires on Si (111) by molecular-beam epitaxy.

    Science.gov (United States)

    So, Hyok; Pan, Dong; Li, Lixia; Zhao, Jianhua

    2017-03-01

    Epitaxial high-quality InAs/InSb axial heterostructure nanowires are of great interest due to their distinct advantages in fundamental research as well as applications in semiconductor electronic and quantum devices. Currently, nearly all the growth of InAs/InSb axial heterostructure nanowires is assisted with foreign catalysts such as Au, and work on foreign-catalyst-free growth of InAs/InSb axial heterostructure nanowires is lacking. Here we report on the growth of InAs/InSb axial heterostructure nanowires on Si (111) substrates by molecular-beam epitaxy without using any foreign catalysts. The Sb/In beam equivalent pressure (BEP) ratio is found to have important influence on the heterostructure nanowire morphology, and InSb nanowires can be epitaxially grown on InAs nanowire stems with a hexagonal prism and nanosheet-like shapes when the Sb/In BEP ratio varies from 10 to 20. Transmission electron microscopy studies reveal that the InAs nanowire stems have a mixture of zincblende (ZB) and wurtzite (WZ) crystal structures, while InSb nanowire parts have a pure ZB crystal structure free of stacking faults. Composition analysis of axial heterostructure nanowires provides clear evidence that the InSb nanowires are epitaxially grown on InAs nanowires in an In self-assisted vapor-liquid-solid manner. This study paves a new route for growing narrow-gap semiconductor heterostructures with strong spin-orbit interaction for the study of topological states, and the growth manner presented here is expected to be used to grow other In-based axial heterostructure nanowires.

  17. Axial myopathy

    DEFF Research Database (Denmark)

    Witting, Nanna; Andersen, Linda K; Vissing, John

    2016-01-01

    musculature involvement in the majority of myopathies in which paraspinal musculature was examined. Even in diseases named after a certain pattern of non-axial muscle affection, such as facioscapulohumeral and limb girdle muscular dystrophies, affection of the axial musculature was often severe and early...

  18. Establishment and molecular modeling study of maltodextrin-based synergistic enantioseparation systems with two new hydroxy acid chiral ionic liquids as additives in capillary electrophoresis.

    Science.gov (United States)

    Yang, Xuan; Du, Yingxiang; Feng, Zijie; Liu, Zongran; Li, Jingtang

    2017-06-02

    Discovering more superior performance of ionic liquids for the separation science has triggered increasing interest. In this work, two new Hydroxy acid-based chiral ionic liquids (CILs) (tertramethylammonium-d-pantothenate (TMA-d-PAN), tertramethylammonium-d-quinate (TMA-d-QUI)) were designed and first used as additives to establish the maltodextrin-based synergistic systems for enantioseparation in capillary electrophoresis (CE). Compared to traditional single maltodextrin chiral separation system, significantly improved separations of all tested drugs in the CIL/Maltodextrin synergistic systems were obtained. Some parameters (CIL concentration, maltodextrin concentration, buffer pH, and applied voltage) in the TMA-d-PAN/Maltodextrin synergistic system have been examined and optimized for analytes. The molecular docking software AutoDock was applied to simulate the recognition process and surmise feasible resolution mechanism in the Maltodextrin/CILs synergistic systems, which has certain guiding value. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Chiral recognition of metalaxyl enantiomers by human serum albumin: evidence from molecular modeling and photophysical approach.

    Science.gov (United States)

    Ding, Fei; Li, Xiu-Nan; Diao, Jian-Xiong; Sun, Ye; Zhang, Li; Sun, Ying

    2012-06-01

    Metalaxyl is an acylamine fungicide, belonging to the most widely known member of the amide group. This task is aimed to scrutinize binding region and spatial structural change of principal vector human serum albumin (HSA) complex with (R)-/(S)-metalaxyl by exploiting molecular modeling, steady-state and time-resolved fluorescence, and circular dichroism (CD) approaches. According to molecular modeling, (R)-metalaxyl is situated within subdomains IIA and IIIA and the affinity of site I with (R)-metalaxyl is greater than site II, whereas (S)-metalaxyl is only located at subdomain IIA and the affinity of (S)-metalaxyl with site I is superior compared with that with (R)-metalaxyl. This coincides with the competitive ligand binding, guanidine hydrochloride-induced unfolding of protein, and hydrophobic 8-anilino-1-naphthalenesulfonic acid experiments; the acting forces between (R)-/(S)-metalaxyl and HSA are hydrophobic, π-π interactions, and hydrogen bonds, as derived from molecular modeling. Fluorescence emission manifested that the complex of (R)-/(S)-metalaxyl to HSA is the formation of adduct with an affinity of 10(4) M(-1), which corroborates the time-resolved fluorescence that the static type was operated. Furthermore, the changes of far-UV CD spectra evidence the polypeptide chain of HSA partially unfolded after conjugation with (R)-/(S)-metalaxyl. Through this work, we envisage that it can offer central clues on the biodistribution, absorption, and bioaccumulation of (R)-/(S)-metalaxyl. Copyright © 2012 Wiley Periodicals, Inc.

  20. Chiral photochemistry

    CERN Document Server

    Inoue, Yoshihisa

    2004-01-01

    Direct Asymmetric Photochemistry with Circularly Polarized Light, H. RauCoherent Laser Control of the Handedness of Chiral Molecules, P. Brumer and M. ShapiroMagnetochiral Anisotropy in Asymmetric Photochemistry, G.L.J.A.RikkenEnantiodifferentiating Photosensitized Reactions, Y. InoueDiastereodifferentiating Photoreactions, N. Hoffmann and J.-P. PeteChirality in Photochromism, Y. Yokoyama and M. SaitoChiral Photochemistry with Transition Metal Complexes, S. Sakaki and T. HamadaTemplate-Induced Enantioselective Photochemical Reactions in S

  1. Chiral algebras

    CERN Document Server

    Beilinson, Alexander

    2004-01-01

    Chiral algebras form the primary algebraic structure of modern conformal field theory. Each chiral algebra lives on an algebraic curve, and in the special case where this curve is the affine line, chiral algebras invariant under translations are the same as well-known and widely used vertex algebras. The exposition of this book covers the following topics: the "classical" counterpart of the theory, which is an algebraic theory of non-linear differential equations and their symmetries; the local aspects of the theory of chiral algebras, including the study of some basic examples, such as the ch

  2. Chiral Graphene Quantum Dots.

    Science.gov (United States)

    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.

  3. Liquid chromatography with mass spectrometry enantioseparation of pomalidomide on cyclodextrin-bonded chiral stationary phases and the elucidation of the chiral recognition mechanisms by NMR spectroscopy and molecular modeling.

    Science.gov (United States)

    Szabó, Zoltán-István; Szőcs, Levente; Horváth, Péter; Komjáti, Balázs; Nagy, József; Jánoska, Ádám; Muntean, Daniela-Lucia; Noszál, Béla; Tóth, Gergő

    2016-08-01

    A sensitive and validated liquid chromatography with mass spectrometry method was developed for the enantioseparation of the racemic mixture of pomalidomide, a novel, second-generation immunomodulatory drug, using β-cyclodextrin-bonded stationary phases. Four cyclodextrin columns (β-, hydroxypropyl-β-, carboxymethyl-β-, and sulfobutyl-β-cyclodextrin) were screened and the effects of eluent composition, flow rate, temperature, and organic modifier on enantioseparation were studied. Optimized parameters, offering baseline separation (resolution = 2.70 ± 0.02) were the following: β-cyclodextrin stationary phase, thermostatted at 15°C, and mobile phase consisting of methanol/0.1% acetic acid 10:90 v/v, delivered with 0.8 mL/min flow rate. For the optimized parameter at multiple reaction monitoring mode 274.1-201.0 transition with 20 eV collision energy and 100 V fragmentor voltage the limit of detection and limit of quantitation were 0.75 and 2.00 ng/mL, respectively. Since enantiopure standards were not available, elution order was determined upon comparison of the circular dichroism signals of the separated pomalidomide enantiomers with that of enantiopure thalidomide. The mechanisms underlying the chiral discrimination between the enantiomers were also investigated. Pomalidomide-β-cyclodextrin inclusion complex was characterized using nuclear magnetic resonance spectroscopy and molecular modeling. The thermodynamic aspects of chiral separation were also studied.

  4. Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate

    Science.gov (United States)

    Jiang, Wenge; Pacella, Michael S.; Athanasiadou, Dimitra; Nelea, Valentin; Vali, Hojatollah; Hazen, Robert M.; Gray, Jeffrey J.; McKee, Marc D.

    2017-04-01

    Chirality is ubiquitous in biology, including in biomineralization, where it is found in many hardened structures of invertebrate marine and terrestrial organisms (for example, spiralling gastropod shells). Here we show that chiral, hierarchically organized architectures for calcium carbonate (vaterite) can be controlled simply by adding chiral acidic amino acids (Asp and Glu). Chiral, vaterite toroidal suprastructure having a `right-handed' (counterclockwise) spiralling morphology is induced by L-enantiomers of Asp and Glu, whereas `left-handed' (clockwise) morphology is induced by D-enantiomers, and sequentially switching between amino-acid enantiomers causes a switch in chirality. Nanoparticle tilting after binding of chiral amino acids is proposed as a chiral growth mechanism, where a `mother' subunit nanoparticle spawns a slightly tilted, consequential `daughter' nanoparticle, which by amplification over various length scales creates oriented mineral platelets and chiral vaterite suprastructures. These findings suggest a molecular mechanism for how biomineralization-related enantiomers might exert hierarchical control to form extended chiral suprastructures.

  5. Chiral superconductors.

    Science.gov (United States)

    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.

  6. Axial Vector $Z'$ and Anomaly Cancellation

    CERN Document Server

    Ismail, Ahmed; Tsao, Kuo-Hsing; Unwin, James

    2016-01-01

    Whilst the prospect of new $Z'$ gauge bosons with only axial couplings to the Standard Model (SM) fermions is widely discussed, examples of anomaly-free renormalisable models are lacking in the literature. We look to remedy this by constructing several motivated examples. Specifically, we consider axial vectors which couple universally to all SM fermions, as well as those which are generation-specific, leptophilic, and leptophobic. Anomaly cancellation typically requires the presence of new coloured and charged chiral fermions, and we argue that the masses of these new states must generally be comparable to that of the axial vector. Finally, an axial vector mediator could provide a portal between SM and hidden sector states, and we also consider the possibility that the axial vector couples to dark matter. If the dark matter relic density is set due to freeze-out via the axial vector, this strongly constrains the parameter space.

  7. Axial vector Z‧ and anomaly cancellation

    Science.gov (United States)

    Ismail, Ahmed; Keung, Wai-Yee; Tsao, Kuo-Hsing; Unwin, James

    2017-05-01

    Whilst the prospect of new Z‧ gauge bosons with only axial couplings to the Standard Model (SM) fermions is widely discussed, examples of anomaly-free renormalisable models are lacking in the literature. We look to remedy this by constructing several motivated examples. Specifically, we consider axial vectors which couple universally to all SM fermions, as well as those which are generation-specific, leptophilic, and leptophobic. Anomaly cancellation typically requires the presence of new coloured and charged chiral fermions, and we argue that in a large class of models masses of these new states are expected to be comparable to that of the axial vector. Finally, an axial vector mediator could provide a portal between SM and hidden sector states, and we also consider the possibility that the axial vector couples to dark matter. If the dark matter relic density is set due to freeze-out via the axial vector, this strongly constrains the parameter space.

  8. Chiral molecular assemblies from a novel achiral amphiphilic 2-(heptadecyl) naphtha[2,3]imidazole through interfacial coordination.

    Science.gov (United States)

    Yuan, Jing; Liu, Minghua

    2003-04-30

    A novel amphiphilic compound 2-(heptadecyl) naphtha[2,3]imidazole (NpImC17) was synthesized, and its coordination with AgNO(3) in situ in the monolayer at the air/water interface and ex situ in the Langmuir-Blodgett (LB) film on solid substrate has been investigated. It has been found that interfacial coordination between NpImC17 and Ag(I) ion occurred both in the monolayer and in the LB film. It is interesting to note that the Ag(I)-coordinated ultrathin film became chiral although the ligand itself is achiral. It was suggested that the chirality of the Ag(I)-coordinated LB film was developed due to the formation of a helical coordination polymer through the interfacial coordination. To the best of our knowledge, this is the first report on the formation of chiral monolayer and LB films from an achiral molecule through interfacial coordination.

  9. Stereodirection of an α-ketoester at sub-molecular sites on chirally modified Pt(111): Heterogeneous asymmetric catalysis

    DEFF Research Database (Denmark)

    Demers-Carpentier, V.; Rasmussen, A.M.H.; Goubert, G.

    2013-01-01

    Chirally modified Pt catalysts are used in the heterogeneous asymmetric hydrogenation of α-ketoesters. Stereoinduction is believed to occur through the formation of chemisorbed modifier–substrate complexes. In this study, the formation of diastereomeric complexes by coadsorbed methyl 3,3,3-triflu......Chirally modified Pt catalysts are used in the heterogeneous asymmetric hydrogenation of α-ketoesters. Stereoinduction is believed to occur through the formation of chemisorbed modifier–substrate complexes. In this study, the formation of diastereomeric complexes by coadsorbed methyl 3...

  10. Communication: Structural locking mediated by a water wire: A high-resolution rotational spectroscopy study on hydrated forms of a chiral biphenyl derivative.

    Science.gov (United States)

    Domingos, Sérgio R; Pérez, Cristóbal; Schnell, Melanie

    2016-10-28

    We report the observation of structural changes in an axially chiral molecule, biphenyl-2-carboxaldehyde, due to aggregation with water. Using high-resolution broadband rotational spectroscopy we find that two water molecules link opposite sides of the molecule, resembling a water wire. We show that this effect can be explained by a cooperative rearrangement of both molecule and a water dimer. Hydrogen bonding interactions are shown to change the original structure upon aggregation of water. This phenomenon is insightful on the role of microsolvation in assisting structural morphing of stereo-selective chiral molecular systems.

  11. Enantioseparation Using Cellulose Tris(3,5-dimethylphenylcarbamate as Chiral Stationary Phase for HPLC: Influence of Molecular Weight of Cellulose

    Directory of Open Access Journals (Sweden)

    Yuji Okada

    2016-11-01

    Full Text Available The cellulose oligomers with different degrees of polymerization (DP, 7, 11, 18, 24, 26, 40 and 52, were prepared by hydrolysis of microcrystalline cellulose with phosphoric acid. These oligomers including the starting microcrystalline cellulose (DP 124 were converted to tris(3,5-dimethylphenylcarbamate (CDMPC derivatives by the reaction with an excess of 3,5-dimethylphenyl isocyanate to be used as the chiral stationary phase (CSP in high-performance liquid chromatography (HPLC. The structures of the CDMPC derivatives were investigated by infrared spectroscopy (IR, 1H-NMR, circular dichroism (CD and size exclusion chromatography (SEC, and the DPs of the derivatives estimated by SEC agreed with those estimated by 1H-NMR. After coating the derivatives on silica gel, their chiral recognition abilities were evaluated using eight racemates under a normal phase condition with a hexane-2-propanol (99/1 mixture as an eluent. The chiral recognition abilities of 7- and 11-mers, particularly the former, were lower than those of the higher oligomers from DP 18 to 52, which had rather similar abilities to that of 124-mer, although the abilities depended on the racemates. DP 18 seems to be sufficient for CDMPC to exhibit chiral recognition similar to that of the CDMPC with larger DPs.

  12. On the temperature dependence of the chiral vortical effects

    CERN Document Server

    Kalaydzhyan, Tigran

    2014-01-01

    We discuss the origins of temperature dependence of the axial vortical effect (AVE), i.e. generation of an axial current in a rotating chiral medium along the rotation axis. We show that the corresponding transport coefficient depends on the number of light weakly interacting degrees of freedom, rather than on the gravitational anomaly. We also comment on the role of low-dimensional defects in the rotating medium, and appearance of the chiral vortical effect due to them.

  13. When did Louis Pasteur present his memoir on the discovery of molecular chirality to the Académie des sciences? Analysis of a discrepancy.

    Science.gov (United States)

    Gal, Joseph

    2008-11-01

    Louis Pasteur presented his historic memoir on the discovery of molecular chirality to the Académie des sciences in Paris on May 22nd, 1848. The literature, however, nearly completely ignores this date, widely claiming instead May 15th, 1848, which first surfaced in 1922 in Pasteur's collected works edited by his grandson Louis Pasteur Vallery-Radot. On May 21st, 1848, i.e., one day before Pasteur's presentation in Paris, his mother died in Arbois, eastern France. Informed at an unknown point in time that she was "very ill," Pasteur left for Arbois only after his presentation. Biographies of Pasteur by his son-in-law René Vallery-Radot or the grandson, and Pasteur's collected correspondence edited by the grandson are incomprehensibly laconic or silent about the historic presentation. While no definite conclusions are possible, the evidence strongly suggests a deliberate alteration of the record by the biographer relatives, presumably for fear of adverse public judgment of Pasteur for a real or perceived insensitivity to a grave family medical emergency. Such fear would have been in accord with their hagiographic portrayal of Pasteur, and the findings raise questions concerning the extent of their zeal in protecting his "demigod" image. Universal recognition of the true date of Pasteur's announcement of molecular chirality is long overdue.

  14. Isotopic chirality

    Energy Technology Data Exchange (ETDEWEB)

    Floss, H.G. [Univ. of Washington, Seattle, WA (United States)

    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.

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

    Science.gov (United States)

    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.

  16. Possible $D\\bar{D}$ and $B\\bar{B}$ Molecular states in a chiral quark model

    CERN Document Server

    Li, M T; Dong, Y B; Zhang, Z Y

    2012-01-01

    We perform a systematic study of the bound state problem of $D\\bar{D}$ and $B\\bar{B}$ systems by using effective interaction in our chiral quark model. Our results show that both the interactions of $D\\bar{D}$ and $B\\bar{B}$ states are attractive, which consequently result in $I^G(J^{PC})=0^+(0^{++})$ $D\\bar{D}$ and $B\\bar{B}$ bound states.

  17. Influence of Chirality of Crizotinib on Its MTH1 Protein Inhibitory Activity: Insight from Molecular Dynamics Simulations and Binding Free Energy Calculations.

    Directory of Open Access Journals (Sweden)

    Yuzhen Niu

    Full Text Available As a promising target for the treatment of lung cancer, the MutT Homolog 1 (MTH1 protein can be inhibited by crizotinib. A recent work shows that the inhibitory potency of (S-crizotinib against MTH1 is about 20 times over that of (R-crizotinib. But the detailed molecular mechanism remains unclear. In this study, molecular dynamics (MD simulations and free energy calculations were used to elucidate the mechanism about the effect of chirality of crizotinib on the inhibitory activity against MTH1. The binding free energy of (S-crizotinib predicted by the Molecular Mechanics/Generalized Born Surface Area (MM/GBSA and Adaptive biasing force (ABF methodologies is much lower than that of (R-crizotinib, which is consistent with the experimental data. The analysis of the individual energy terms suggests that the van der Waals interactions are important for distinguishing the binding of (S-crizotinib and (R-crizotinib. The binding free energy decomposition analysis illustrated that residues Tyr7, Phe27, Phe72 and Trp117 were important for the selective binding of (S-crizotinib to MTH1. The adaptive biasing force (ABF method was further employed to elucidate the unbinding process of (S-crizotinib and (R-crizotinib from the binding pocket of MTH1. ABF simulation results suggest that the reaction coordinates of the (S-crizotinib from the binding pocket is different from (R-crizotinib. The results from our study can reveal the details about the effect of chirality on the inhibition activity of crizotinib to MTH1 and provide valuable information for the design of more potent inhibitors.

  18. Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II–O and Ni(II–N coordination bonds

    Directory of Open Access Journals (Sweden)

    Vadim A. Soloshonok

    2012-11-01

    Full Text Available We describe herein the design and synthesis of asymmetric, pentadentate ligands, which are able to coordinate to Ni(II cations leading to quasi-diastereomeric complexes displaying two new elements of chirality: stereogenic axis and helix along with configurational stabilization of the stereogenic center on the nitrogen. Due to the stereocongested structural characteristics of the corresponding Ni(II complexes, the formation of quasi-diastereomeric products is highly stereoselective providing formation of only two, (Ra*,Mh*,Rc* and (Ra*,Ph*,Rc*, out of the four possible stereochemical combinations. The reversible quasi-diastereomeric transformation between the products (Ra*,Mh*,Rc* and (Ra*,Ph*,Rc* occurs by intramolecular trans-coordination of Ni–NH and Ni–O bonds providing a basis for a chiral switch model.

  19. Chiral magnetic effect in condensed matter systems

    Science.gov (United States)

    Li, Qiang; Kharzeev, Dmitri E.

    2016-12-01

    The chiral magnetic effect (CME) is the generation of electrical current induced by chirality imbalance in the presence of magnetic field. It is a macroscopic manifestation of the quantum chiral anomaly [S. L. Adler. Axial-vector vertex in spinor electrodynamics. Physical Review, 177, 2426 (1969), J. S. Bell and R. Jackiw. A PCAC puzzle: π 0 γγin the σ-model. Il Nuovo Cimento A, 60, 47-61 (1969)] in systems possessing charged chiral fermions. In quark-gluon plasma containing nearly massless quarks, the chirality imbalance is sourced by the topological transitions. In condensed matter systems, the chiral quasiparticles emerge in gapless semiconductors with two energy bands having pointlike degeneracies opening the path to the study of chiral anomaly [H. B. Nielsen and M. Ninomiya. The Adler-Bell-Jackiw anomaly and Weyl fermions in a crystal. Physics Letters B, 130, 389-396 (1983)]. Recently, these novel materials - so-called Dirac and Weyl semimetals have been discovered experimentally, are suitable for the investigation of the CME in condensed matter experiments. Here we report on the first experimental observation of the CME in a 3D Dirac semimetal ZrTe5 [Q. Li, D. E. Kharzeev, C. Zhang, Y. Huang, I. Pletikosić, A. V. Fedorov, R. D. Zhong, J. A. Schneeloch, G. D. Gu, and T. Valla. Chiral magnetic effect in ZrTe5. Nature Physics (2016) doi:10.1038/nphys3648].

  20. Laser Writing of Multiscale Chiral Polymer Metamaterials

    Directory of Open Access Journals (Sweden)

    E. P. Furlani

    2012-01-01

    Full Text Available A new approach to metamaterials is presented that involves laser-based patterning of novel chiral polymer media, wherein chirality is realized at two distinct length scales, intrinsically at the molecular level and geometrically at a length scale on the order of the wavelength of the incident field. In this approach, femtosecond-pulsed laser-induced two-photon lithography (TPL is used to pattern a photoresist-chiral polymer mixture into planar chiral shapes. Enhanced bulk chirality can be realized by tuning the wavelength-dependent chiral response at both the molecular and geometric level to ensure an overlap of their respective spectra. The approach is demonstrated via the fabrication of a metamaterial consisting of a two-dimensional array of chiral polymer-based L-structures. The fabrication process is described and modeling is performed to demonstrate the distinction between molecular and planar geometric-based chirality and the effects of the enhanced multiscale chirality on the optical response of such media. This new approach to metamaterials holds promise for the development of tunable, polymer-based optical metamaterials with low loss.

  1. 3-(1H-Indol-3-yl)-2-[3-(4-nitrophenyl)ureido]propanamide Enantiomers With Human Formyl-Peptide Receptor Agonist Activity: Molecular Modeling of Chiral Recognition by FPR2

    Science.gov (United States)

    Schepetkin, Igor A.; Kirpotina, Liliya N.; Khlebnikov, Andrei I.; Leopoldo, Marcello; Lucente, Ermelinda; Lacivita, Enza; De Giorgio, Paola; Quinn, Mark T.

    2012-01-01

    N-formyl peptide receptors (FPRs) are G protein-coupled receptors (GPCRs) that play critical roles in inflammatory reactions, and FPR-specific interactions can possibly be used to facilitate the resolution of pathological inflammatory reactions. Recent studies indicated that FPRs have stereo-selective preference for chiral ligands. Here, we investigated the structure-activity relationship of 24 chiral ureidopropanamides, including previously reported compounds PD168368/PD176252 and their close analogs, and used molecular modeling to define chiral recognition by FPR2. Unlike previously reported 6-methyl-2,4-disubstituted pyridazin-3(2H)-ones, whose R-forms preferentially activated FPR1/FPR2, we found that four S-enantiomers in the seven ureidopropanamide pairs tested preferentially activated intracellular Ca2+ flux in FPR2-transfected cells, while the R-counterpart was more active in two enantiomer pairs. Thus, active enantiomers of FPR2 agonists can be in either R- or S- configurations, depending on the molecular scaffold and specific substituents at the chiral center. Using molecular modeling approaches, including field point methodology, homology modeling, and docking studies, we propose a model that can explain stereoselective activity of chiral FPR2 agonists. Importantly, our docking studies of FPR2 chiral agonists correlated well with the FPR2 pharmacophore model derived previously. We conclude that the ability of FPR2 to discriminate between the enantiomers is the consequence of the arrangement of the three asymmetric hydrophobic subpockets at the main orthosteric FPR2 binding site with specific orientation of charged regions in the subpockets. PMID:23219934

  2. Natural and magnetic optical activity of 2-D chiral cyanido-bridged Mn(II)-Nb(IV) molecular ferrimagnets.

    Science.gov (United States)

    Chorazy, Szymon; Podgajny, Robert; Nitek, Wojciech; Fic, Tomasz; Görlich, Edward; Rams, Michał; Sieklucka, Barbara

    2013-08-04

    Unique two dimensional enantiopure cyanido-bridged {[Mn(II)(R-mpm)2]2[Nb(IV)(CN)8]}·4H2O and {[Mn(II)(S-mpm)2]2[Nb(IV)(CN)8]}·4H2O (-S) (mpm = α-methyl-2-pyridine-methanol) ferrimagnets with TC = 23.5 K were synthesized and characterized. They reveal natural optical activity (NOA) due to the chiral crystal structure, and magnetic optical activity (MOA) in the presence of an external magnetic field, with the strong enhancement in the magnetically ordered phase below TC.

  3. Large Enhancement of Circular Dichroism Using an Embossed Chiral Metamaterial

    CERN Document Server

    Mousavi, S Hamed Shams; El-Sayed, Mostafa A; Eftekhar, Ali A; Adibi, Ali

    2016-01-01

    In the close vicinity of a chiral nanostructure, the circular dichroism of a biomolecule could be greatly enhanced, due to the interaction with the local superchiral fields. Modest enhancement of optical activity using a planar metamaterial, with some chiral properties, and achiral nanoparticles has been previously reported. A more substantial chirality enhancement can be achieved in the local filed of a chiral nanostructure with a three-dimensional arrangement. Using an embossed chiral nanostructure designed for chiroptical sensing, we measure the circular dichroism spectra of two biomolecules, Chlorophylls A and B, at the molecular level, using a simple polarization resolved reflection measurement. This experiment is the first realization of the on-resonance surface-enhanced circular dichroism, achieved by matching the chiral resonances of a strongly chiral metamaterial with that of a chiral molecule, resulting in an unprecedentedly large differential CD spectrum from a monolayer of a chiral material.

  4. Heavy-Light Mesons in Chiral AdS/QCD

    CERN Document Server

    Liu, Yizhuang

    2016-01-01

    We discuss a minimal holographic model for the description of heavy-light and light mesons with chiral symmetry, defined in a slab of AdS space. The model consists of a pair of chiral Yang-Mills and tachyon fields with specific boundary conditions that break spontaneously chiral symmetry in the infrared. The heavy-light spectrum and decay constants are evaluated explicitly. In the heavy mass limit the model exhibits both heavy-quark and chiral symmetry and allows for the explicit derivation of the one-pion axial couplings to the heavy-light mesons.

  5. Is the Chiral Vortical Effect Vanishing in Heavy Ion Collisions?

    CERN Document Server

    Landsteiner, Karl; Pena-Benitez, Francisco

    2013-01-01

    We study the frequency dependence of all the chiral vortical and magnetic conductivities for a relativistic chiral gas of free fermions and for a strongly coupled CFT with holographic dual in four dimensions. Both systems present gauge and gravitational anomalies and we compute their contribution to the conductivities. The chiral vortical conductivities and the chiral magnetic conductivity in the energy current show an unexpected frequency dependence in the form of a delta centered at zero frequency. We argue that this makes the CVE practically unobservable in heavy ion collisions. In the appendix we discuss why the CME seems to vanish in the consistent current for a particular implementation of the axial chemical potential.

  6. Chirality on Surfaces: Modeling and Behaviour.

    Energy Technology Data Exchange (ETDEWEB)

    Paci, Irina; Szleifer, Igal; Ratner, Mark A.

    2007-09-01

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Chirality has been a fascinating topic in chemistry, ever since its first observation by Biot in 1815. Its molecular basis was first understood by Pasteur in 1848. Enantiomers, identical in every way but mirror-images of each other, have similar physical properties, behave identically in chemical reactions with achiral molecules, but have very different interactions with chiral molecules. In recent decades, chirality has become an important direction in pharmaceutical research, as many drugs have stereoselective activity. This review focuses on a new aspect of chiral resolution on solid surfaces, and relationships between molecular structure, thermodynamic effects, and the result of chiral surface self-organization.

  7. On Chiral Space Groups and Chiral Molecules

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    This note explains the relationship (as well as the absence of a relationship) between chiral space groups and chiral molecules (which have absolute configurations). For a chiral molecule, which must crystallize in a chiral space group, the outcome of the absolute configuration determination must be linked to some other properties of the chiral crystal such as its optical activity for the observation to the relevant.

  8. On Chiral Space Groups and Chiral Molecules

    Institute of Scientific and Technical Information of China (English)

    NgSeikWng; HUSheng-Zhi

    2003-01-01

    This note explains the relationship (as well as the absence of a relationship) between chiral space groups and chiral molecules (which have absolute configurations).For a chiral molecule,which must crystallize in a chiral space group,the outcome of the absolute configuration determination must be linked to some other properties of the chiral crystal such as its optical activity for the observation to the relevant.

  9. PHYLOGENY AND SYSTEMATICS OF EUGLENA (EUGLENACEAE) SPECIES WITH AXIAL, STELLATE CHLOROPLASTS BASED ON MORPHOLOGICAL AND MOLECULAR DATA-NEW TAXA, EMENDED DIAGNOSES, AND EPITYPIFICATIONS(1).

    Science.gov (United States)

    Kosmala, Sylwia; Karnkowska-Ishikawa, Anna; Milanowski, Rafał; Kwiatowski, Jan; Zakryś, Bożena

    2009-04-01

    Morphological and molecular studies, as well as original literature reexamination, necessitate establishment of five Euglena species with a single axial, stellate chloroplast [Euglena viridis (O. F. Müller) Ehrenberg 1830, Euglena pseudoviridis Chadefaud 1937, Euglena stellata Mainx 1926, Euglena pseudostellata sp. nov., and Euglena cantabrica Pringsheim 1956], three species with two chloroplasts (Euglena geniculata Dujardin ex Schmitz 1884, Euglena chadefaudii Bourrelly 1951, and Euglena pseudochadefaudii sp. nov.), and one species with three chloroplasts (Euglena tristella Chu 1946). The primary morphological features, allowing distinction of the considered species are the presence and the shape of mucocysts, as well as the number of chloroplasts. Spherical mucocysts occur in E. cantabrica and E. geniculata, while spindle-shaped mucocysts are present in E. stellata, E. pseudostellata, E. chadefaudii, E. pseudochadefaudii, and E. tristella. No mucocysts are observed in E. viridis and E. pseudoviridis. Two new species (E. pseudochadefaudii sp. nov. and E. pseudostellata sp. nov.) differ from the respective species, E. chadefaudii and E. stellata, only at the molecular level. Molecular signatures and characteristic sequences are designated for nine distinguished species. Emended diagnoses for all and delimitation of epitypes for seven species (except E. viridis and E. tristella) are proposed.

  10. Supramolecular Chirality in Dynamic Coordination Chemistry

    Directory of Open Access Journals (Sweden)

    Hiroyuki Miyake

    2014-10-01

    Full Text Available Labile metal complexes have a useful coordination bond; which is weaker than a covalent C–C bond and is reversibly and dynamically formed and dissociated. Such labile metal complexes also can be used to construct chiral shapes and offer dynamic conversion of chiral molecular shapes in response to external stimuli. This review provides recent examples of chirality induction and describes the dynamic conversion systems produced by chiral metal complexes including labile metal centers, most of which respond to external stimuli by exhibiting sophisticated conversion phenomena.

  11. Enantioselective recognition at mesoporous chiral metal surfaces

    Science.gov (United States)

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

    2014-02-01

    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.

  12. Spatial control of chirality in supramolecular aggregates

    Science.gov (United States)

    Castriciano, Maria A.; Gentili, Denis; Romeo, Andrea; Cavallini, Massimiliano; Scolaro, Luigi Monsù

    2017-01-01

    Chirality is one of the most intriguing properties of matter related to a molecule’s lack of mirror symmetry. The transmission of chirality from the molecular level up to the macroscopic scale has major implications in life sciences but it is also relevant for many chemical applications ranging from catalysis to spintronic. These technological applications require an accurate control of morphology, homogeneity and chiral handedness of thin films and nanostructures. We demonstrate a simple approach to specifically transfer chirality to the model supramolecular system of J aggregates of the protonated form of tetrakis(4-sulfonatophenyl)-porphyrin by utilizing a soft lithography technique. This approach successfully allows the fabrication of an ordered distribution of sub-micrometric structures in precise and controllable positions with programmed chirality, providing a fundamental breakthrough toward the exploitation of chiral supramolecular aggregates in technological applications, such as sensors, non-linear optics and spintronic. PMID:28275239

  13. Spatial control of chirality in supramolecular aggregates.

    Science.gov (United States)

    Castriciano, Maria A; Gentili, Denis; Romeo, Andrea; Cavallini, Massimiliano; Scolaro, Luigi Monsù

    2017-03-09

    Chirality is one of the most intriguing properties of matter related to a molecule's lack of mirror symmetry. The transmission of chirality from the molecular level up to the macroscopic scale has major implications in life sciences but it is also relevant for many chemical applications ranging from catalysis to spintronic. These technological applications require an accurate control of morphology, homogeneity and chiral handedness of thin films and nanostructures. We demonstrate a simple approach to specifically transfer chirality to the model supramolecular system of J aggregates of the protonated form of tetrakis(4-sulfonatophenyl)-porphyrin by utilizing a soft lithography technique. This approach successfully allows the fabrication of an ordered distribution of sub-micrometric structures in precise and controllable positions with programmed chirality, providing a fundamental breakthrough toward the exploitation of chiral supramolecular aggregates in technological applications, such as sensors, non-linear optics and spintronic.

  14. Notes on conservation laws in chiral hydrodynamics

    CERN Document Server

    Zakharov, V I

    2016-01-01

    We consider chiral fluids within the standard framework of a chiral-invariant underlying field theory, anomalous in presence of electromagnetic fields. Apart from the Noether axial current of the underlying theory, in the limit of ideal fluid there exist extra conserved currents, corresponding to classical helical motions. The extra conservation laws are known to break down once viscosity is non-vanishing. Which looks puzzling, as if introduction of viscosity were inconsistent with chiral invariance. As a resolution of the puzzle, we argue that locally one can introduce an inertial frame where an extra conservation law still holds. In other words, the extra currents are covariantly conserved. The emergent gravitational field is determined by dynamics of the viscous fluid. We turn then to instabilities of chiral plasma against decays into helical magnetic or vortical configurations. We emphasise similarity between the two cases in the far infrared region, responsible for the decays. This similarity is not appa...

  15. Chiral Magnetic Effect in Heavy Ion Collisions

    CERN Document Server

    Liao, Jinfeng

    2016-01-01

    The Chiral Magnetic Effect (CME) is a remarkable phenomenon that stems from highly nontrivial interplay of QCD chiral symmetry, axial anomaly, and gluonic topology. It is of fundamental importance to search for the CME in experiments. The heavy ion collisions provide a unique environment where a hot chiral-symmetric quark-gluon plasma is created, gluonic topological fluctuations generate chirality imbalance, and very strong magnetic fields $|\\vec{\\bf B}|\\sim m_\\pi^2$ are present during the early stage of such collisions. Significant efforts have been made to look for CME signals in heavy ion collision experiments. In this contribution we give a brief overview on the status of such efforts.

  16. Chiral imbalance in QCD

    Directory of Open Access Journals (Sweden)

    Andrianov Alexander

    2017-01-01

    Full Text Available The chiral imbalance (ChI is given by a difference between the numbers of RH and LH quarks which may occur in the fireball after heavy ion collision. To characterize it adiabatically a quark chiral (axial chemical potential must be introduced taking into account emergence of a ChI in such a phase. In this report the phenomenology of formation of Local spatial Parity Breaking (LPB in the hot and dense baryon matter is discussed and its simulation within a number of QCD-inspired models is outlined. The appearance of new states in the spectra of scalar, pseudoscalar and vector particles in such a matter is elucidated. In particular, from the effective vector meson theory in the presence of Chern-Simons interaction it is demonstrated that the spectrum of massive vector mesons splits into three polarization components with different effective masses. The asymmetry in production of longitudinally and transversely polarized states of ρ and ω mesons for various values of the dilepton invariant mass can serve as a characteristic indication of the LPB in PHENIX, STAR and ALICE experiments.

  17. In vitro DNA binding, pBR322 plasmid cleavage and molecular modeling study of chiral benzothiazole Schiff-base-valine Cu(II) and Zn(II) complexes to evaluate their enantiomeric biological disposition for molecular target DNA.

    Science.gov (United States)

    Alizadeh, Rahman; Afzal, Mohd; Arjmand, Farukh

    2014-10-15

    Bicyclic heterocyclic compounds viz. benzothiazoles are key components of deoxyribonucleic acid (DNA) molecules and participate directly in the encoding of genetic information. Benzothiazoles, therefore, represent a potent and selective class of antitumor compounds. The design and synthesis of chiral antitumor chemotherapeutic agents of Cu(II) and Zn(II), L- and -D benzothiazole Schiff base-valine complexes 1a &b and 2a &b, respectively were carried out and thoroughly characterized by spectroscopic and analytical techniques. Interaction of 1a and b and 2a and b with CT DNA by employing UV-vis, florescence, circular dichroic methods and cleavage studies of 1a with pBR322 plasmid, molecular docking were done in order to demonstrate their enantiomeric disposition toward the molecular drug target DNA. Interestingly, these studies unambiguously demonstrated the greater potency of L-enantiomer in comparison to D-enantiomer.

  18. In vitro DNA binding, pBR322 plasmid cleavage and molecular modeling study of chiral benzothiazole Schiff-base-valine Cu(II) and Zn(II) complexes to evaluate their enantiomeric biological disposition for molecular target DNA

    Science.gov (United States)

    Alizadeh, Rahman; Afzal, Mohd; Arjmand, Farukh

    2014-10-01

    Bicyclic heterocyclic compounds viz. benzothiazoles are key components of deoxyribonucleic acid (DNA) molecules and participate directly in the encoding of genetic information. Benzothiazoles, therefore, represent a potent and selective class of antitumor compounds. The design and synthesis of chiral antitumor chemotherapeutic agents of Cu(II) and Zn(II), L- and -D benzothiazole Schiff base-valine complexes 1a &b and 2a &b, respectively were carried out and thoroughly characterized by spectroscopic and analytical techniques. Interaction of 1a and b and 2a and b with CT DNA by employing UV-vis, florescence, circular dichroic methods and cleavage studies of 1a with pBR322 plasmid, molecular docking were done in order to demonstrate their enantiomeric disposition toward the molecular drug target DNA. Interestingly, these studies unambiguously demonstrated the greater potency of L-enantiomer in comparison to D-enantiomer.

  19. Axial Nucleon form factors from lattice QCD

    CERN Document Server

    Alexandrou, C; Carbonell, J; Constantinou, M; Harraud, P A; Guichon, P; Jansen, K; Korzec, T; Papinutto, M

    2010-01-01

    We present results on the nucleon axial form factors within lattice QCD using two flavors of degenerate twisted mass fermions. Volume effects are examined using simulations at two volumes of spatial length $L=2.1$ fm and $L=2.8$ fm. Cut-off effects are investigated using three different values of the lattice spacings, namely $a=0.089$ fm, $a=0.070$ fm and $a=0.056$ fm. The nucleon axial charge is obtained in the continuum limit and chirally extrapolated to the physical pion mass enabling comparison with experiment.

  20. Bandgap tuning in GaAs1‑xSbx axial nanowires grown by Ga-assisted molecular beam epitaxy

    Science.gov (United States)

    Ahmad, Estiak; Ojha, S. K.; Kasanaboina, P. K.; Reynolds, C. L., Jr.; Liu, Y.; Iyer, S.

    2017-03-01

    In this work we present a comprehensive study on the effects of Sb incorporation on the composition modulation, structural and optical properties of self-assisted axial GaAs1‑xSbx nanowires of 2–6 μm in length grown on (111) Si substrate by molecular beam epitaxy. The Sb composition in the GaAs1‑xSbx axial nanowire (NW) was varied from 2.8–16 at.%, as determined from energy dispersive x-ray spectroscopy. Lower Sb composition leads to thinner nanowires and inhomogeneous Sb composition distribution radially with a depleted Sb surface region inducing weak type-II optical emission, the presence of an additional peak at higher Bragg angle in the x-ray diffraction spectra and an electric-field-induced strong Raman LO mode. Higher Sb composition of 16 at.% leads to a more uniform Sb compositional distribution radially leading to type-I optical transitions exhibiting the lowest PL peak energy occurring at 1.13 eV. In addition, the high quality of these nanowires exhibiting pure zinc blende crystal structure, largely free of any planar defects, is borne out by high resolution transmission electron microscopy and selected area diffraction patterns. The shift and broadening of the Raman LO and TO modes reveal evidence of increased Sb incorporation in the nanowires. Significant improvement in optical characteristics was achieved by the incorporation of a Al0.2Ga0.8As passivating shell. The results are very promising and reveal the potential to further red shift the optical emission wavelength by fine tuning of the fluxes during growth.

  1. Stegosaurus chirality

    OpenAIRE

    Cameron, R.P.; Cameron, J. A.; Barnett, S. M.

    2016-01-01

    We explain that Stegosaurus exhibited exterior chirality and observe that the largest plate in particular of USNM 4394, USNM 4714, DMNS 2818 and NHMUK R36730 appears to have tilted to the right rather than to the left in each case. Several instances in which Stegosaurus specimens have been confused with their distinct, hypothetical mirror-image forms are highlighted. We believe our findings to be consistent with the hypothesis that Stegosaurus's plates acted primarily as display structures. A...

  2. Dynamic chirality, chirality transfer and aggregation behaviour of dithienylethene switches

    NARCIS (Netherlands)

    de Jong, Jaap J. D.; van Rijn, Patrick; Tiemersma-Wegeman, Theodora D.; Lucas, Linda N.; Browne, Wesley R.; Kellogg, Richard M.; Uchida, Kingo; Van Esch, Jan H.; Feringa, Ben L.

    2008-01-01

    The synthesis and characterisation of a series of chiral and achiral low molecular weight organogelators (LMWGs) based on bis-amide substituted dithienylethene photochromic switches is reported. The LMWGs gelate a range of solvents depending on the specific functionalisation of the hydrogen bonding

  3. Enantioselective Biotransformation of Chiral Persistent Organic Pollutants.

    Science.gov (United States)

    Zhang, Ying; Ye, Jing; Liu, Min

    2017-01-01

    . Enantioselective biotransformation of chiral POPs is dependent on enzyme amounts and activities. However, the role of cytochrome P450 in enantioselective biotransformation has not yet been confirmed. Currently available data on biotransformation of chiral POPs provide a preliminary understanding of the fate of chiral compounds in organisms. Further detailed studies of species-dependent biotransformation pathway and molecular mechanism in various animal models should be performed to comprehensively understand chiral POP biotransformation.

  4. Supramolecular helices: chirality transfer from conjugated molecules to structures.

    Science.gov (United States)

    Yang, Yang; Zhang, Yajie; Wei, Zhixiang

    2013-11-13

    Different scales of chirality endow a material with many excellent properties and potential applications. In this review, using π-conjugated molecules as functional building blocks, recent progress on supramolecular helices inspired by biological helicity is summarized. First, induced chirality on conjugated polymers and small molecules is introduced. Molecular chirality can be amplified to nanostructures, superstructures, and even macroscopic structures by a self-assembly process. Then, the principles for tuning the helicity of supramolecular chirality, as well as formation of helical heterojunctions, are summarized. Finally, the potential applications of chiral structures in chiral sensing and organic electronic devices are critically reviewed. Due to recent progress in chiral structures, an interdisciplinary area called "chiral electronics" is expected to gain wide popularity in the near future.

  5. Direct chromatographic enantioresolution of fully constrained β-amino acids: exploring the use of high-molecular weight chiral selectors.

    Science.gov (United States)

    Sardella, Roccaldo; Ianni, Federica; Lisanti, Antonella; Scorzoni, Stefania; Marini, Francesca; Sternativo, Silvia; Natalini, Benedetto

    2014-05-01

    To the best of our knowledge enantioselective chromatographic protocols on β-amino acids with polysaccharide-based chiral stationary phases (CSPs) have not yet appeared in the literature. Therefore, the primary objective of this work was the development of chromatographic methods based on the use of an amylose derivative CSP (Lux Amylose-2), enabling the direct normal-phase (NP) enantioresolution of four fully constrained β-amino acids. Also, the results obtained with the glycopeptide-type Chirobiotic T column employed in the usual polar-ionic (PI) mode of elution are compared with those achieved with the polysaccharide-based phase. The Lux Amylose-2 column, in combination with alkyl sulfonic acid containing NP eluent systems, prevailed over the Chirobiotic T one, when used under the PI mode of elution, and hence can be considered as the elective choice for the enantioseparation of this class of rigid β-amino acids. Moreover, the extraordinarily high α (up to 4.60) and R S (up to 10.60) values provided by the polysaccharidic polymer, especially when used with camphor sulfonic acid containing eluent systems, make it also suitable for preparative-scale enantioisolations.

  6. Microwave assisted one-pot synthesis of novel molecular clefts with only one chiral arm based on deoxycholic acid

    Institute of Scientific and Technical Information of China (English)

    Bi Tao Zeng; Zhi Gang Zhao; Xing Li Liu; Yun Shi

    2008-01-01

    A rapid, safe, and efficient method for the synthesis of novel molecular clefts based" on deoxycholic acid was reported. Sevennew molecular clefts have been synthesized in good yields (89-98%). This method proved to be extremely simple and highlyefficient. The structures of these receptors were confirmed by 1H NMR, IR, MS spectra and elemental analysis.

  7. Chiral Anomaly in Contorted Spacetimes

    CERN Document Server

    Mielke, E W

    1999-01-01

    The Dirac equation in Riemann-Cartan spacetimes with torsion is reconsidered. As is well-known, only the axial covector torsion $A$, a one-form, couples to massive Dirac fields. Using diagrammatic techniques, we show that besides the familiar Riemannian term only the Pontrjagin type four-form $dA\\wedge dA$ does arise additionally in the chiral anomaly, but not the Nieh-Yan term $d ^* A$, as has been claimed recently. Implications for cosmic strings in Einstein-Cartan theory as well as for Ashtekar's canonical approach to quantum gravity are discussed.

  8. Chiral corrections to the Adler-Weisberger sum rule

    Science.gov (United States)

    Beane, Silas R.; Klco, Natalie

    2016-12-01

    The Adler-Weisberger sum rule for the nucleon axial-vector charge, gA , offers a unique signature of chiral symmetry and its breaking in QCD. Its derivation relies on both algebraic aspects of chiral symmetry, which guarantee the convergence of the sum rule, and dynamical aspects of chiral symmetry breaking—as exploited using chiral perturbation theory—which allow the rigorous inclusion of explicit chiral symmetry breaking effects due to light-quark masses. The original derivations obtained the sum rule in the chiral limit and, without the benefit of chiral perturbation theory, made various attempts at extrapolating to nonvanishing pion masses. In this paper, the leading, universal, chiral corrections to the chiral-limit sum rule are obtained. Using PDG data, a recent parametrization of the pion-nucleon total cross sections in the resonance region given by the SAID group, as well as recent Roy-Steiner equation determinations of subthreshold amplitudes, threshold parameters, and correlated low-energy constants, the Adler-Weisberger sum rule is confronted with experimental data. With uncertainty estimates associated with the cross-section parametrization, the Goldberger-Treimann discrepancy, and the truncation of the sum rule at O (Mπ4) in the chiral expansion, this work finds gA=1.248 ±0.010 ±0.007 ±0.013 .

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

    Science.gov (United States)

    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

  10. Radiation and chemical crosslinking promote strain hardening behavior and molecular alignment in ultra high molecular weight polyethylene during multi-axial loading conditions.

    Science.gov (United States)

    Kurtz, S M; Pruitt, L A; Jewett, C W; Foulds, J R; Edidin, A A

    1999-08-01

    The mechanical behavior and evolution of crystalline morphology during large deformation of eight types of virgin and crosslinked ultra high molecular weight polyethylene (UHMWPE) were studied using the small punch test and transmission electron microscopy (TEM). We investigated the hypothesis that both radiation and chemical crosslinking hinder molecular mobility at large deformations, and hence promote strain hardening and molecular alignment during the multiaxial loading of the small punch test. Chemical crosslinking of UHMWPE was performed using 0.25% dicumyl peroxide (GHR 8110, GUR 1020 and 1050), and radiation crosslinking was performed using 150 kGy of electron beam radiation (GUR 1150). Crosslinking increased the ultimate load at failure and decreased the ultimate displacement of the polyethylenes during the small punch test. Crosslinking also increased the near-ultimate hardening behavior of the polyethylenes. Transmission electron microscopy was used to characterize the crystalline morphology of the bulk material, undeformed regions of the small punch test specimens, and deformed regions of the specimens oriented perpendicular and parallel to the punch direction. In contrast with the virgin polyethylenes, which showed only subtle evidence of lamellar alignment, the crosslinked polyethylenes exhibited enhanced crystalline lamellae orientation after the small punch test, predominantly in the direction parallel to the punch direction or deformation axis. Thus, the results of this study support the hypothesis that crosslinking promotes strain hardening during multiaxial loading because of increased resistance to molecular mobility at large deformations effected by molecular alignment. The data also illustrate the sensitivity of large deformation mechanical behavior and crystalline morphology to the method of crosslinking and resin of polyethylene.

  11. Chirality study inside biological tissue by second harmonic generation circular dichroism

    Science.gov (United States)

    Hsu, Kuo-Jen; Lee, Hsuan; Zhuo, Guan-Yu; Chao, Pen-Hsiu; Chu, Shi-Wei

    2013-02-01

    Many biological systems are composed of chiral molecules and their functions depend strongly on their chirality. For example, most amino acids are of left-handed chirality while most polysaccharides are of right-handed chirality. Both of them are vital for human life, so it is important to perform chiral detection inside bio-tissues. Here we demonstrated second harmonic generation circular dichroism (SHG-CD) as a novel chiral imaging contrast in thick biotissue. Compared with conventional chiral detection, SHG-CD provides at least three orders higher contrast. In addition, due to the nonlinear nature of SHG, this technique provides optical sectioning capability, so the axial contrast is much better. The advantages of nonlinear optical microscopy are optical sectioning and deep penetration capabilities. The SHG-CD achieved 100% signal contrast with sub-micrometer spatial resolution. This method is expected to offer a novel contrast mechanism of imaging chirality inside complex bio-tissues.

  12. Chirality and gravitational parity violation.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2015-06-01

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

  14. Molecular modeling on the recognition of DNA sequence and conformational repair of sheared DNA by novel chiral metal complex D, L-[Co(phen)2hpip]3+

    Institute of Scientific and Technical Information of China (English)

    WU; Yanbo; ZHANG; Cuiping

    2006-01-01

    A study on the recognition of DNA sequence and conformational repair of sheared DNA by Novel Chiral Metal complex D,L-[Co(phen)2hpip]3+ (phen=1,10 phenanthroline, hpip=2-[2-hydroxyphenyl] imidazole [4,5-f][1,10] phenanthroline) is carried out with molecular simulations. The results reveal that two isomers of the complex could both recognize the normal DNA in the minor groove orientation, while recognize the sheared DNA in the major groove orientation and both isomers could convert the conformation of mismatched bases from sheared form to parallel form. Further analysis shows that the steric details of complex's intercalation to base stack determine the results of recognition, which is induced by the steric collision among ancillary ligand phen, bases and DNA backbone, and by the steric crowding occurring in the process of structural expansion of bases and DNA backbone. Detailed analysis reveals that the conformational repair of mismatched bases relates not only to the steric interactions, but also to the π-π stack among normal bases, mismatched bases and hpip ligand.

  15. Detecting chirality in molecules by linearly polarized laser fields

    CERN Document Server

    Yachmenev, Andrey

    2016-01-01

    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 {\\pi} 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 non-rigid 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.

  16. Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

    Directory of Open Access Journals (Sweden)

    Hironori Izawa

    2010-07-01

    Full Text Available 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.

  17. Chiral mirrors

    Energy Technology Data Exchange (ETDEWEB)

    Plum, Eric, E-mail: erp@orc.soton.ac.uk [Optoelectronics Research Centre and Centre for Photonic Metamaterials, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom); Zheludev, Nikolay I., E-mail: niz@orc.soton.ac.uk [Optoelectronics Research Centre and Centre for Photonic Metamaterials, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom); The Photonics Institute and Centre for Disruptive Photonic Technologies, Nanyang Technological University, Singapore 637378 (Singapore)

    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.

  18. Radiative neutron-proton capture in effective chiral lagrangians

    CERN Document Server

    Park, T S; Rho, M; Park, Tae Sun; Min, Dong Pil; Rho, Mannque

    1994-01-01

    We calculate the cross-section for the thermal n+p\\rightarrow d+\\gamma process in chiral perturbation theory to next-to-next-to-leading order using heavy-fermion formalism. The exchange current correction is found to be (4.5\\pm 0.3)~\\% in amplitude and the chiral perturbation at one-loop order gives the cross section \\sigma_{th}^{np}=(334\\pm 2)\\ {\\mbox mb} which is in agreement with the experimental value (334.2\\pm 0.5)\\ {\\mbox mb}. Together with the axial charge transitions, this provides a strong support for the power of chiral Lagrangians for nuclear physics.

  19. Chiral recognition of Propranolol enantiomers by β-Cyclodextrin: Quantum chemical calculation and molecular dynamics simulation studies

    Energy Technology Data Exchange (ETDEWEB)

    Ghatee, Mohammad Hadi, E-mail: ghatee@susc.ac.ir; Sedghamiz, Tahereh

    2014-12-05

    Highlights: • Enantiomeric recognition of Propranolol studied by β-Cyclodextrin complexations. • Complexes characterized by PM3 and molecular dynamics (MD) simulation methods. • Results support more stability of R-enantiomer complex in gas and in aqueous solution phases. • Gas phase complexes are unlikely free-energy-wise, though solution phase’s are more likely. • Higher molecular diffusion in aqueous solution phase is inherent to S-enantiomer. - Abstract: Enantiomeric recognition of Propranolol by complexation with β-Cyclodextrin was studied by PM3 method and molecular dynamics (MD) simulation. Gas phase results show that the R-enantiomer complex is more stable than the S-enantiomer complex by 8.54 kJ/mol (Hartree–Fock energy). Using polarized continuum model, solution phase of R-enantiomer complex was found to be more stable than S-enantiomer complex by 25.95 kJ/mol. Both complexes hardly occur at room temperature free-energy-wise, though, complexation with R-enantiomer is more favorable than with S-enantiomer enthalpy-wise. Also, complexes were studied by molecular dynamics simulation in gas and solution phases. More stability of R-enantiomer complex in gas phase is confirmed by MD van der Waals energy (5.04 kJ/mol) and closely by the counterpart PM3 binding energy (8.54 kJ/mol). Simulation in solution phase indicates more stability of R-enantiomer complex. Finally, simulated transport property provides insight into the high anisotropic atoms motion according to which S-Propranolol found possessing significantly higher dynamics.

  20. Non-centrosymmetric behavior of a clay film ion-exchanged with chiral metal complexes.

    Science.gov (United States)

    Suzuki, Yasutaka; Matsunaga, Ryoya; Sato, Hisako; Kogure, Toshihiro; Yamagishi, Akihiko; Kawamata, Jun

    2009-12-07

    SHG measurements on a highly transparent clay film ion-exchanged with chiral metal complexes revealed that the mono-molecular layer of the chiral complexes in an interlayer space acquired a non-centrosymmetric character.

  1. The axial charges of the hidden-charm pentaquark states

    CERN Document Server

    Wang, Guang-Juan; Zhu, Shi-Lin

    2016-01-01

    With the chiral quark model, we have calculated the axial charges of the pentaquark states with $(I,I_3)=(\\frac{1}{2},\\frac{1}{2})$ and $J^{P}=\\frac{1}{2}^{\\pm},\\frac{3}{2}^{\\pm},\\frac{5}{2}^{\\pm}$. The $P_c$ states with the same $J^P$ quantum numbers but different color-spin-flavor configurations have very different axial charges, which encode important information on their underlying structures. For some of the $J^{P}=\\frac{3}{2}^{\\pm}$ or $\\frac{5}{2}^{\\pm}$ pentaquark states, their axial charges are much smaller than that of the proton.

  2. Controlling stereochemical outcomes of asymmetric processes by catalyst remote molecular functionalizations: chiral diamino-oligothiophenes (DATs) as ligands in asymmetric catalysis.

    Science.gov (United States)

    Albano, Vincenzo Giulio; Bandini, Marco; Barbarella, Giovanna; Melucci, Manuela; Monari, Magda; Piccinelli, Fabio; Tommasi, Simona; Umani-Ronchi, Achille

    2006-01-11

    The synthesis, characterization, and structure-guided application of a new class of highly versatile chiral C(2)-symmetric diamine-oligothiophene ligands in Pd-catalyzed asymmetric transformations are presented. Experimental investigations of the intimate role of pendant pi-conjugate oligothiophenes in determining the catalytic activity of the corresponding chiral Pd complexes are described. Their unusual behavior opens up new routes toward the logical design of finely tuned organometallic catalysts by remote structural functionalizations.

  3. Chiral conducting polymers.

    Science.gov (United States)

    Kane-Maguire, Leon A P; Wallace, Gordon G

    2010-07-01

    This critical review describes the preparation and properties of a relatively new class of chiral macromolecules, namely chiral conducting polymers. It focuses in particular on examples based on polypyrrole, polythiophene and polyaniline. They possess remarkable properties, combining not only chirality with electrical conductivity but also the ability to undergo facile redox and pH switching. These unique properties have opened up a range of exciting new potential applications, including as chiral sensors, as novel stationary phases for chiral separations, and as chiral electrodes for electrochemical asymmetric synthesis (153 references).

  4. Chirality detection of enantiomers using twisted optical metamaterials

    Science.gov (United States)

    Zhao, Yang; Askarpour, Amir N.; Sun, Liuyang; Shi, Jinwei; Li, Xiaoqin; Alù, Andrea

    2017-01-01

    Many naturally occurring biomolecules, such as amino acids, sugars and nucleotides, are inherently chiral. Enantiomers, a pair of chiral isomers with opposite handedness, often exhibit similar physical and chemical properties due to their identical functional groups and composition, yet show different toxicity to cells. Detecting enantiomers in small quantities has an essential role in drug development to eliminate their unwanted side effects. Here we exploit strong chiral interactions with plasmonic metamaterials with specifically designed optical response to sense chiral molecules down to zeptomole levels, several orders of magnitude smaller than what is typically detectable with conventional circular dichroism spectroscopy. In particular, the measured spectra reveal opposite signs in the spectral regime directly associated with different chiral responses, providing a way to univocally assess molecular chirality. Our work introduces an ultrathin, planarized nanophotonic interface to sense chiral molecules with inherently weak circular dichroism at visible and near-infrared frequencies. PMID:28120825

  5. Cooperative expression of atomic chirality in inorganic nanostructures

    Science.gov (United States)

    Wang, Peng-Peng; Yu, Shang-Jie; Govorov, Alexander O.; Ouyang, Min

    2017-02-01

    Cooperative chirality phenomena extensively exist in biomolecular and organic systems via intra- and inter-molecular interactions, but study of inorganic materials has been lacking. Here we report, experimentally and theoretically, cooperative chirality in colloidal cinnabar mercury sulfide nanocrystals that originates from chirality interplay between the crystallographic lattice and geometric morphology at different length scales. A two-step synthetic scheme is developed to allow control of critical parameters of these two types of handedness, resulting in different chiral interplays expressed as observables through materials engineering. Furthermore, we adopt an electromagnetic model with the finite element method to elucidate cooperative chirality in inorganic systems, showing excellent agreement with experimental results. Our study enables an emerging class of nanostructures with tailored cooperative chirality that is vital for fundamental understanding of nanoscale chirality as well as technology applications based on new chiroptical building blocks.

  6. Chirality detection of enantiomers using twisted optical metamaterials

    Science.gov (United States)

    Zhao, Yang; Askarpour, Amir N.; Sun, Liuyang; Shi, Jinwei; Li, Xiaoqin; Alù, Andrea

    2017-01-01

    Many naturally occurring biomolecules, such as amino acids, sugars and nucleotides, are inherently chiral. Enantiomers, a pair of chiral isomers with opposite handedness, often exhibit similar physical and chemical properties due to their identical functional groups and composition, yet show different toxicity to cells. Detecting enantiomers in small quantities has an essential role in drug development to eliminate their unwanted side effects. Here we exploit strong chiral interactions with plasmonic metamaterials with specifically designed optical response to sense chiral molecules down to zeptomole levels, several orders of magnitude smaller than what is typically detectable with conventional circular dichroism spectroscopy. In particular, the measured spectra reveal opposite signs in the spectral regime directly associated with different chiral responses, providing a way to univocally assess molecular chirality. Our work introduces an ultrathin, planarized nanophotonic interface to sense chiral molecules with inherently weak circular dichroism at visible and near-infrared frequencies.

  7. Computational Design of a Family of Light-Driven Rotary Molecular Motors with Improved Quantum Efficiency.

    Science.gov (United States)

    Nikiforov, Alexander; Gamez, Jose A; Thiel, Walter; Filatov, Michael

    2016-01-07

    Two new light-driven molecular rotary motors based on the N-alkylated indanylidene benzopyrrole frameworks are proposed and studied using quantum chemical calculations and nonadiabatic molecular dynamics simulations. These new motors perform pure axial rotation, and the photochemical steps of the rotary cycle are dominated by the fast bond-length-alternation motion that enables ultrafast access to the S1/S0 intersection. The new motors are predicted to display a quantum efficiency higher than that of the currently available synthetic all-hydrocarbon motors. Remarkably, the quantum efficiency is not governed by the topography (peaked versus sloped) of the minimum-energy conical intersection, whereas the S1 decay time depends on the topography as well as on the energy of the intersection relative to the S1 minimum. It is the axial chirality (helicity), rather than the point chirality, that controls the sense of rotation of the motor.

  8. Chiral Selectivity in Inter-reactant Recognition and Electron Transfer of the Oxidation of Horse Heart Cytochrome c by Trioxalatocobaltate(III).

    Science.gov (United States)

    Nazmutdinov, Renat R; Bronshtein, Michael D; Zinkicheva, Tamara T; Hansen, Niels Sthen; Zhang, Jingdong; Ulstrup, Jens

    2016-09-19

    Outer-sphere electron transfer (ET) between optically active transition-metal complexes and either other transition-metal complexes or metalloproteins is a prototype reaction for kinetic chirality. Chirality as the ratio between bimolecular rate constants of two enantiomers mostly amounts to 1.05-1.2 with either the Λ or Δ form the more reactive, but the origin of chirality in ET parameters such as work terms, electronic transmission coefficient, and nuclear reorganization free energy has not been addressed. We report a study of ET between the Λ-/Δ-[Co(Ox)3](3-) pair (Ox = oxalate) and horse heart cytochrome c (cyt c). This choice is prompted by strong ion-pair formation that enables separation into inter-reactant interaction (chiral "recognition") and ET within the ion pair ("stereoselectivity"). Chiral selectivity was first addressed experimentally. Λ-[Co(Ox)3](3-) was found to be both the more strongly bound and faster reacting enantiomer expressed respectively by the ion-pair formation constant KX and ET rate constant kET(X) (X = Λ and Δ), with KΛ/KΔ and kET(Λ)/kET(Δ) both ≈1.1-1.2. rac-[Co(Ox)3](3-) behavior is intermediate between those of Λ- and Δ-[Co(Ox)3](3-). Chirality was next analyzed by quantum-mechanical ET theory combined with density functional theory and statistical mechanical computations. We also modeled the ion pair K(+)·[Co(Ox)3](3-) in order to address the influence of the solution ionic strength. The complex structure of cyt c meant that this reactant was represented solely by the heme group including the chiral axial ligands L-His and L-Met. Both singlet and triplet hemes as well as hemes with partially deprotonated propionic acid side groups were addressed. The computations showed that the most favorable inter-reactant configuration involved a narrow distance and orientation space very close to the contact distance, substantiating the notion of a reaction complex and the equivalence of the binding constant to a bimolecular

  9. Chiral resolution of derivatized amino acids using uniformly sized molecularly imprinted polymers in hydro-organic mobile phases.

    Science.gov (United States)

    Haginaka, Jun; Kagawa, Chino

    2004-04-01

    Uniformly sized molecularly imprinted polymers (MIPs) for Boc-L-Trp were prepared using ethylene glycol dimethacrylate (EDMA) as the cross-linker, and methacylic acid (MAA) and/or 4-vinylpyridine (4-VPY) as the functional monomers or without use of a functional monomer. The MIPs prepared were evaluated using acetonitrile or a mixture of phosphate buffer and acetonitrile as the mobile phase. The Boc-L-Trp-imprinted EDMA polymers can recognize Boc-L-Trp by its molecular shape, and can thus afford the enantioseparation of Boc-Trp. Besides the molecular shape recognition, the hydrophobic interactions with the polymer backbones as well as the hydrogen-bonding interactions of Boc-L-Trp with carboxyl and pyridyl groups in the polymers should work for the retention and recognition of Boc-L-Trp on the imprinted MAA- co-EDMA and 4-VPY- co-EDMA polymers, respectively, in the hydro-organic mobile phase. The hydrogen-bonding interactions seem to become dominant when only acetonitrile is used as the mobile phase. The Boc-L-Trp-imprinted 4-VPY- co-EDMA polymers gave the highest retentivity and enantioselectivity for Boc-Trp among the MIPs prepared. However, the simultaneous use of MAA and 4-VPY was not effective for the enantioseparation of Boc-Trp in a hydro-organic mobile phase. Furthermore, the baseline separation of Boc-Trp enantiomers was attained within 10 min on the Boc-L-Trp-imprinted 4-VPY- co-EDMA polymers under the optimized HPLC conditions.

  10. Laminar and Turbulent Dynamos in Chiral Magnetohydrodynamics. I. Theory

    Science.gov (United States)

    Rogachevskii, Igor; Ruchayskiy, Oleg; Boyarsky, Alexey; Fröhlich, Jürg; Kleeorin, Nathan; Brandenburg, Axel; Schober, Jennifer

    2017-09-01

    The magnetohydrodynamic (MHD) description of plasmas with relativistic particles necessarily includes an additional new field, the chiral chemical potential associated with the axial charge (i.e., the number difference between right- and left-handed relativistic fermions). This chiral chemical potential gives rise to a contribution to the electric current density of the plasma (chiral magnetic effect). We present a self-consistent treatment of the chiral MHD equations, which include the back-reaction of the magnetic field on a chiral chemical potential and its interaction with the plasma velocity field. A number of novel phenomena are exhibited. First, we show that the chiral magnetic effect decreases the frequency of the Alfvén wave for incompressible flows, increases the frequencies of the Alfvén wave and of the fast magnetosonic wave for compressible flows, and decreases the frequency of the slow magnetosonic wave. Second, we show that, in addition to the well-known laminar chiral dynamo effect, which is not related to fluid motions, there is a dynamo caused by the joint action of velocity shear and chiral magnetic effect. In the presence of turbulence with vanishing mean kinetic helicity, the derived mean-field chiral MHD equations describe turbulent large-scale dynamos caused by the chiral alpha effect, which is dominant for large fluid and magnetic Reynolds numbers. The chiral alpha effect is due to an interaction of the chiral magnetic effect and fluctuations of the small-scale current produced by tangling magnetic fluctuations (which are generated by tangling of the large-scale magnetic field by sheared velocity fluctuations). These dynamo effects may have interesting consequences in the dynamics of the early universe, neutron stars, and the quark–gluon plasma.

  11. The Chiral Dipolar Hard Sphere Model.

    OpenAIRE

    Mazars, Martial

    2009-01-01

    Abstract A simple molecular model of chiral molecules is presented in this paper : the chiral dipolar hard sphere model. The discriminatory interaction between enantiomers is represented by electrostatic (or magnetic) dipoles-dipoles interactions : short ranged steric repulsion are represented by hard sphere potential and, in each molecule, two point dipoles are located inside the sphere. The model is described in detail and some of its elementary properties are given ; in particul...

  12. Chiral Gravitational Waves from Chiral Fermions

    CERN Document Server

    Anber, Mohamed M

    2016-01-01

    We report on a new mechanism that leads to the generation of primordial chiral gravitational waves, and hence, the violation of the parity symmetry in the Universe. We show that nonperturbative production of fermions with a definite helicity is accompanied by the generation of chiral gravitational waves. This is a generic and model-independent phenomenon that can occur during inflation, reheating and radiation eras, and can leave imprints in the cosmic microwave background polarization and may be observed in future ground- and space-based interferometers. We also discuss a specific model where chiral gravitational waves are generated via the production of light chiral fermions during pseudoscalar inflation.

  13. Chiral gravitational waves from chiral fermions

    Science.gov (United States)

    Anber, Mohamed M.; Sabancilar, Eray

    2017-07-01

    We report on a new mechanism that leads to the generation of primordial chiral gravitational waves, and hence, the violation of the parity symmetry in the Universe. We show that nonperturbative production of fermions with a definite helicity is accompanied by the generation of chiral gravitational waves. This is a generic and model-independent phenomenon that can occur during inflation, reheating and radiation eras, and can leave imprints in the cosmic microwave background polarization and may be observed in future ground- and space-based interferometers. We also discuss a specific model where chiral gravitational waves are generated via the production of light chiral fermions during pseudoscalar inflation.

  14. Molecular modeling and spectroscopic studies on the interaction of the chiral drug venlafaxine hydrochloride with bovine serum albumin

    Science.gov (United States)

    Shahabadi, Nahid; Hadidi, Saba

    2014-03-01

    This study was designed to examine the interaction of racemic antidepressant drug "S,R-venlafaxine hydrochloride (VEN)" with bovine serum albumin (BSA) under physiological conditions. The mechanism of interaction was studied by spectroscopic techniques combination with molecular modeling. Stern-Volmer analysis of fluorescence quenching data shows the presence of the static quenching mechanism. The thermodynamic parameters indicated that the hydrogen bonding and weak van der Waals interactions are the predominant intermolecular forces stabilizing the complex. The number of binding sites (n) was calculated. Through the site marker competitive experiment, VEN was confirmed to be located in subdomain IIIA of BSA. The binding distance (r = 4.93 nm) between the donor BSA and acceptor VEN was obtained according to Förster's non-radiative energy transfer theory. According to UV-vis spectra and CD data binding of VEN leaded to conformational changes of BSA. Molecular docking simulations of S and R-VEN revealed that both isomers have similar interaction and the same binding sites, from this point of view S and R isomers are equal.

  15. Chiral recognition of Propranolol enantiomers by β-Cyclodextrin: Quantum chemical calculation and molecular dynamics simulation studies

    Science.gov (United States)

    Ghatee, Mohammad Hadi; Sedghamiz, Tahereh

    2014-12-01

    Enantiomeric recognition of Propranolol by complexation with β-Cyclodextrin was studied by PM3 method and molecular dynamics (MD) simulation. Gas phase results show that the R-enantiomer complex is more stable than the S-enantiomer complex by 8.54 kJ/mol (Hartree-Fock energy). Using polarized continuum model, solution phase of R-enantiomer complex was found to be more stable than S-enantiomer complex by 25.95 kJ/mol. Both complexes hardly occur at room temperature free-energy-wise, though, complexation with R-enantiomer is more favorable than with S-enantiomer enthalpy-wise. Also, complexes were studied by molecular dynamics simulation in gas and solution phases. More stability of R-enantiomer complex in gas phase is confirmed by MD van der Waals energy (5.04 kJ/mol) and closely by the counterpart PM3 binding energy (8.54 kJ/mol). Simulation in solution phase indicates more stability of R-enantiomer complex. Finally, simulated transport property provides insight into the high anisotropic atoms motion according to which S-Propranolol found possessing significantly higher dynamics.

  16. Axial couplings of heavy hadrons from domain-wall lattice QCD

    CERN Document Server

    Detmold, William; Meinel, Stefan

    2012-01-01

    We calculate matrix elements of the axial current for static-light mesons and baryons in lattice QCD with dynamical domain wall fermions. We use partially quenched heavy hadron chiral perturbation theory in a finite volume to extract the axial couplings g_1, g_2, and g_3 from the data. These axial couplings allow the prediction of strong decay rates and enter chiral extrapolations of most lattice results in the b sector. Our calculations are performed with two lattice spacings and with pion masses down to 227 MeV.

  17. Light axial vector mesons

    CERN Document Server

    Chen, Kan; Liu, Xiang; Matsuki, Takayuki

    2015-01-01

    Inspired by the abundant experimental observation of axial vector states, we study whether the observed axial vector states can be categorized into the conventional axial vector meson family. In this paper we carry out analysis based on the mass spectra and two-body Okubo-Zweig-Iizuka-allowed decays. Besides testing the possible axial vector meson assignments, we also predict abundant information for their decays and the properties of some missing axial vector mesons, which are valuable to further experimental exploration of the observed and predicted axial vector mesons.

  18. Chiral THz metamaterial with tunable optical activity

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Jiangfeng [Los Alamos National Laboratory; Taylor, Antoinette [Los Alamos National Laboratory; O' Hara, John [Los Alamos National Laboratory; Chowdhury, Roy [Los Alamos National Laboratory; Zhao, Rongkuo [IOWA STATE UNIV; Soukoullis, Costas M [IOWA STATE UNIV

    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

  19. Synthesis of Chiral 2,5-Bis(oxazolinyl)thiophenes and Their Application as Chiral Shift Reagents for 1, 1'-Bi-2-naphthol

    Institute of Scientific and Technical Information of China (English)

    GAO,Ming-Zhang(高明章); WANG,Bo(汪波); LIU,Han-Biao(刘汉标); XU,Zun-Le(许遵乐)

    2002-01-01

    A series of C2-symmetrical chiral 2,5-bis(4'-alkyloxazolin-2-yl) thiophenes (thiobox) have been synthesized from thiophene-2, 5-dicarboxylic acid by sequential amidation with a chiral ethanolamine, conversion of hydroxyl to chloro group,and base-promoted oxazoline ring formation. As demonstrated by ( - )-2, 5-bis [ 4'-( S)-isopropyloxazolin-2'-yl] thiophene,these thiobox systems exhibited remarkable chirality recognition of 1, 1'-bi-2-naphthol giving rise to pronounced shifts in the 1H NMR signals of the latter axial chiral compound at the positions of C-3, C-4, C-5, and C-8.

  20. Generation of Supramolecular Chirality around Twofold Rotational or Helical Axes in Crystalline Assemblies of Achiral Components

    Directory of Open Access Journals (Sweden)

    Mikiji Miyata

    2015-10-01

    Full Text Available A multi-point approximation method clarifies supramolecular chirality of twofold rotational or helical assemblies as well as bundles of the one-dimensional (1D assemblies. While one-point approximation of materials claims no chirality generation of such assemblies, multi-point approximations do claim possible generation in the 1D assemblies of bars and plates. Such chirality derives from deformations toward three-axial directions around the helical axes. The chiral columns are bundled in chiral ways through symmetry operations. The preferable right- or left-handed columns are bundled together to yield chiral crystals with right- or left-handedness, respectively, indicating that twofold helix symmetry operations cause chiral crystals composed of achiral components via a three-stepwise and three-directional process.

  1. Numerical study of chiral plasma instability within the classical statistical field theory approach

    CERN Document Server

    Buividovich, P V

    2015-01-01

    We report on a numerical study of the real-time dynamics of chirally imbalanced lattice Dirac fermions coupled to dynamical electromagnetic field. To this end we use the classical statistical field theory approach, in which the quantum evolution of fermions is simulated exactly, and electromagnetic fields are treated as classical. Motivated by recent experiments on chirally imbalanced Dirac semimetals, we use the Wilson-Dirac lattice Hamiltonian for fermions in order to model the emergent nature of chiral symmetry at low energies. In general, we observe that the backreaction of fermions on the electromagnetic field prevents the system from acquiring large chirality imbalance. In the case of chirality pumping in parallel electric and magnetic fields, electric field is screened by the produced on-shell fermions and the accumulation of chirality is hence stopped. In the case of evolution with initially present chirality imbalance, axial charge tends to decay at the expense of nonzero helicity of electromagnetic ...

  2. Nanoconfinement-Induced Structures in Chiral Liquid Crystals

    OpenAIRE

    2013-01-01

    We employ Monte Carlo simulations in a specialized isothermal-isobaric and in the grand canonical ensemble to study structure formation in chiral liquid crystals as a function of molecular chirality. Our model potential consists of a simple Lennard-Jones potential, where the attractive contribution has been modified to represent the orientation dependence of the interaction between a pair of chiral liquid-crystal molecules. The liquid crystal is confined between a pair of planar and atomicall...

  3. Optical Spectra of Graded Nanostructured TiO2 Chiral Thin Films

    CERN Document Server

    Babaei, F; Savaloni, H; 10.1016/j.optcom.2010.03.005

    2010-01-01

    The rigorous coupled wave analysis method (RCWA) is applied to the graded chiral TiO2 thin films in axial and non-axial excited states using the Bruggeman homogenization formalism. The dependence of the filtering frequency and polarization selectivity as a function of different structural parameters, are investigated. A good agreement with experimental results reported by other researchers is achieved.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Guo Zhen; Liu Xianbin; Ng, Siu-Choon; Chen Yuan; Yang Yanhui [School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 637459 (Singapore); Du Yu, E-mail: du_yu@jlu.edu.cn, E-mail: yhyang@ntu.edu.sg [College of Electronic Science and Engineering, Jilin University, Changchun 130012 (China)

    2010-04-23

    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.

  6. Baryons and Chiral Symmetry

    CERN Document Server

    Liu, Keh-Fei

    2016-01-01

    The relevance of chiral symmetry in baryons is highlighted in three examples in the nucleon spectroscopy and structure. The first one is the importance of chiral dynamics in understanding the Roper resonance. The second one is the role of chiral symmetry in the lattice calculation of $\\pi N \\sigma$ term and strangeness. The third one is the role of chiral $U(1)$ anomaly in the anomalous Ward identity in evaluating the quark spin and the quark orbital angular momentum. Finally, the chiral effective theory for baryons is discussed.

  7. Nuclear chirality, a model and the data

    Science.gov (United States)

    Starosta, K.; Koike, T.

    2017-09-01

    In the last decade, the manifestation of chirality in atomic nuclei has become the subject of numerous experimental and theoretical studies. The common feature of current model calculations is that the chiral geometry of angular momentum coupling is extracted from expectation values of orientation operators, rather than being a starting point in construction of a model. However, using the particle-hole coupling model for triaxial odd-odd nuclei it is possible to construct a basis which contains right-handed, left-handed and planar states of angular momentum coupling. If this basis is used, the chirality is an explicit rather than an extracted feature as in any other models with non-chiral bases. The time-reversal symmetry, which relates the basis states of opposite handedness, can be used to reduce the dimension of matrices for diagonalization of the model Hamiltonian, proving the effectiveness of this approach. Moreover, the final model eigenstate wave functions show a concentration of amplitudes among a relatively small number (˜1%) of components compared to the full model space. In that sense, the ‘chiral’ basis provides a useful tool to examine model predictions providing direct insight into the structure of doublet states. In this work, similarities and differences between the rotational behaviour of an axial and triaxial body provide a starting point for derivation of the basis optimal for valence nucleon coupling to an axial and a triaxial core. The derived ‘chiral’ basis is optimal for coupling of a valence particle and hole to the triaxial core. Model predictions are presented and discussed. A comprehensive review of current experimental data on observed chiral band candidates is also provided.

  8. Electromagnetic Response of the Chiral Magnetic Effect in Weyl Semimetals

    CERN Document Server

    Barnes, Edwin; Minic, Djordje

    2016-01-01

    Weyl semimetals are predicted to realize the three-dimensional axial anomaly first discussed in particle physics. The anomaly leads to unusual transport phenomena such as the chiral magnetic effect in which an applied magnetic field induces a current parallel to the field. Here we investigate diagnostics of the axial anomaly based on the fundamental equations of axion electrodynamics. We find that materials with Weyl nodes of opposite chirality and finite energy separation immersed in a uniform magnetic field exhibit an anomaly-induced oscillatory magnetic field with a period set by the chemical potential difference of the nodes. In the case where a chemical potential imbalance is created by applying parallel electric and magnetic fields, we find a suppression of the magnetic field component parallel to the electric field inside the material for rectangular samples, suggesting that the chiral magnetic current opposes this imbalance. For cylindrical geometries, we instead find an enhancement of this magnetic f...

  9. On chiral and non chiral 1D supermultiplets

    Energy Technology Data Exchange (ETDEWEB)

    Toppan, Francesco, E-mail: toppan@cbpf.b [Centro Brasileiro de Pesquisas Fisicas (TEO/CBPF), Rio de Janeiro, RJ (Brazil). Coordenacao de Fisica Teorica

    2011-07-01

    In this talk I discuss and clarify some issues concerning chiral and non chiral properties of the one-dimensional supermultiplets of the N-extended supersymmetry. Quaternionic chirality can be defined for N = 4, 5, 6, 7, 8. Octonionic chirality for N = 8 and beyond. Inequivalent chiralities only arise when considering several copies of N = 4 or N = 8 supermultiplets. (author)

  10. From helical to planar chirality by on-surface chemistry.

    Science.gov (United States)

    Stetsovych, Oleksandr; Švec, Martin; Vacek, Jaroslav; Chocholoušová, Jana Vacek; Jančařík, Andrej; Rybáček, Jiří; Kosmider, Krzysztof; Stará, Irena G; Jelínek, Pavel; Starý, Ivo

    2017-03-01

    The chirality of molecular structures is paramount in many phenomena, including enantioselective reactions, molecular self-assembly, biological processes and light or electron-spin polarization. Flat prochiral molecules, which are achiral in the gas phase or solution, can exhibit adsorption-induced chirality when deposited on surfaces. The whole array of such molecular adsorbates is naturally racemic as spontaneous global mirror-symmetry breaking is disfavoured. Here we demonstrate a chemical method of obtaining flat prochiral molecules adsorbed on the solid achiral surface in such a way that a specific adsorbate handedness globally dominates. An optically pure helical precursor is flattened in a cascade of on-surface reactions, which enables chirality transfer. The individual reaction products are identified by high-resolution scanning-probe microscopy. The ultimate formation of globally non-racemic assemblies of flat molecules through stereocontrolled on-surface synthesis allows for chirality to be expressed in as yet unexplored types of organic-inorganic chiral interfaces.

  11. From helical to planar chirality by on-surface chemistry

    Science.gov (United States)

    Stetsovych, Oleksandr; Švec, Martin; Vacek, Jaroslav; Chocholoušová, Jana Vacek; Jančařík, Andrej; Rybáček, Jiří; Kosmider, Krzysztof; Stará, Irena G.; Jelínek, Pavel; Starý, Ivo

    2016-11-01

    The chirality of molecular structures is paramount in many phenomena, including enantioselective reactions, molecular self-assembly, biological processes and light or electron-spin polarization. Flat prochiral molecules, which are achiral in the gas phase or solution, can exhibit adsorption-induced chirality when deposited on surfaces. The whole array of such molecular adsorbates is naturally racemic as spontaneous global mirror-symmetry breaking is disfavoured. Here we demonstrate a chemical method of obtaining flat prochiral molecules adsorbed on the solid achiral surface in such a way that a specific adsorbate handedness globally dominates. An optically pure helical precursor is flattened in a cascade of on-surface reactions, which enables chirality transfer. The individual reaction products are identified by high-resolution scanning-probe microscopy. The ultimate formation of globally non-racemic assemblies of flat molecules through stereocontrolled on-surface synthesis allows for chirality to be expressed in as yet unexplored types of organic-inorganic chiral interfaces.

  12. Rayleigh-Ritz axial buckling analysis of single-walled carbon nanotubes with different boundary conditions

    Energy Technology Data Exchange (ETDEWEB)

    Ansari, R., E-mail: r_ansari@guilan.ac.i [Department of Mechanical Engineering, University of Guilan, P.O. Box 3756, Rasht (Iran, Islamic Republic of); Sahmani, S.; Rouhi, H. [Department of Mechanical Engineering, University of Guilan, P.O. Box 3756, Rasht (Iran, Islamic Republic of)

    2011-02-28

    Eringen's nonlocality is incorporated into the shell theory to include the small-scale effects on the axial buckling of single-walled carbon nanotubes (SWCNTs) with arbitrary boundary conditions. To this end, the Rayleigh-Ritz solution technique is implemented in conjunction with the set of beam functions as modal displacement functions. Then, molecular dynamics simulations are employed to obtain the critical buckling loads of armchair and zigzag SWCNTs, the results of which are matched with those of nonlocal shell model to extract the appropriate values of nonlocal parameter. It is found that in contrast to the chirality, boundary conditions have a considerable influence on the proper values of nonlocal parameter.

  13. Chiral symmetry and chiral-symmetry breaking

    Energy Technology Data Exchange (ETDEWEB)

    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)

  14. Optical properties and circular dichroism of chiral metal nanoparticles

    Science.gov (United States)

    Fan, Zhiyuan; Govorov, Alexander; OU Team

    2013-03-01

    In nature, biological systems are built up by homochiral building blocks, such as a sugar and protein. Circular dichroism (CD) is an effective tool of resolving molecular conformations. It utilizes circularly polarized light to detect differential absorption of chiral materials. In medicine, it will help us to develop new drugs and therapies, if we understand the connection between the physical or chemical properties of drug molecules and their conformations. With the rapid development of nanotechnologies, chiral nanomaterials attract lots of attention nowadays. CD signals of chiral molecules can be enhanced or shifted to the visible band in the presence of plasmonic nanocrystals. Here we present a plasmonic CD mechanism from a single chiral metal nanocrystal. The mechanism is essentially different from the dipolar plasmon-plasmon interaction in a chiral NP assembly, which mimics the CD mechanism of chiral molecules. Chiral metal nanocrystals are expected to have promising applications in biosensing. Recently a few experimental papers reported successful realizations of chiral nanocrystals in a macroscopic ensemble in solution. Particularly the paper described silver nanoparticles grown on chiral template molecules and demonstrating characteristic CD signals at a plasmonic wavelength. The plasmonic CD signals in Ref. can come from a dipolar plasmon-molecule interaction or from a chiral shape of nanocrystals. This work was supported by the NSF (project: CBET- 0933782) and by the Volkswagen Foundation.

  15. Extrinsic electromagnetic chirality in metamaterials

    OpenAIRE

    Plum, E.; Fedotov, V. A.; Zheludev, N. I.

    2009-01-01

    Three- and two-dimensional chirality arising from the mutual orientation of non-chiral planar metamaterial structures and the incident electromagnetic wave (extrinsic chirality) lead to pronounced optical activity, circular dichroism and asymmetric transmission indistinguishable from those seen in media consisting of three- and two-dimensionally chiral molecules (intrinsic chirality).

  16. Preparation and Properties of Carbon Fiber Chiral Materials

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ping; HUANG Zhixin; WANG Guoqing

    2008-01-01

    The chiral materials were prepared by using the carbon fiber helices as chiral inclusions,and the composite of Fe3O4 and polyaniline as matrix.The electromagnetic properties,including the rotation angles,the axial ratios and the complex chirality parameters,were measured by using a circular waveguide method in the 8.5-11.0 GHz frequency range.The dependence of these electromagnetic properties on the frequency and the concentration of the Fe3O4 in the composite matrix were analyzed.The results show that an appropriate concentration of Fe3O4 in the matrix is useful in improving the electromagnetic properties of the chiral material.

  17. Chiral current generation in QED by longitudinal photons

    CERN Document Server

    Avalo, J L Acosta

    2016-01-01

    We report the generation of a pseudovector electric current having imbalanced chirality in an electron-positron strongly magnetized gas in QED. It propagates along the external applied magnetic field B as a chiral magnetic effect in QED. It is triggered by a perturbative electric field parallel to B, associated to a pseudovector longitudinal mode propagating along B. An electromagnetic chemical potential was introduced, but our results remain valid even for vanishing chemical potential. A nonzero fermion mass was assumed, which is usually considered vanishing in the literature. In the quantum field theory formalism at finite temperature and density, an anomaly relation for the axial current was found for a medium of massive fermions. It bears some analogy to the Adler-Bell-Jackiw anomaly. From the expression for the chiral current in terms of the photon self-energy tensor in a medium, it is obtained that electrons and positrons scattered by longitudinal photons (inside the light cone) contribute to the chiral...

  18. Spontaneous transmission of chirality through multiple length scales.

    Science.gov (United States)

    Iski, Erin V; Tierney, Heather L; Jewell, April D; Sykes, E Charles H

    2011-06-20

    The hierarchical transfer of chirality in nature, from the nano-, to meso-, to macroscopic length scales, is very complex, and as of yet, not well understood. The advent of scanning probes has allowed chirality to be monitored at the single molecule or monolayer level and has opened up the possibility to track enantiospecific interactions and chiral self-assembly with molecular-scale detail. This paper describes the self-assembly of a simple, model molecule (naphtho[2,3-a]pyrene) that is achiral in the gas phase, but becomes chiral when adsorbed on a surface. This polyaromatic hydrocarbon forms a stable and reversibly ordered system on Cu(111) in which the transmission of chirality from single surface-bound molecules to complex 2D chiral architectures can be monitored as a function of molecular packing density and surface temperature. In addition to the point chirality of the surface-bound molecule, the unit cell of the molecular domains was also found to be chiral due to the incommensurate alignment of the molecular rows with respect to the underlying metal lattice. These molecular domains always aggregated in groups of three, all of the same chirality, but with different rotational orientations, forming homochiral "tri-lobe" ensembles. At a larger length scale, these tri-lobe ensembles associated with nearest-neighbor tri-lobe units of opposite chirality at lower packing densities before forming an extended array of homochiral tri-lobe ensembles at higher converges. This system displayed chirality at a variety of size scales from the molecular (≈1 nm) and domain (≈5 nm) to the tri-lobe ensemble (≈10 nm) and extended array (>25 nm) levels. The chirality of the tri-lobe ensembles dictated how the overall surface packing occurred and both homo- and heterochiral arrays could be reproducibly and reversibly formed and interchanged as a function of surface coverage. Finally, these chirally templated surfaces displayed remarkable enantiospecificity for

  19. Axial Stringy System of the Kerr Spinning Particle

    CERN Document Server

    Burinskii, A

    2004-01-01

    The structure of classical spinning particle based on the Kerr-Newman black hole (BH) solution is investigated. For large angular momentum, $|a|>>m$, the BH horizons disappear exposing a naked ringlike source which is a circular relativistic string. It was shown recently that electromagnetic excitations of this string lead to the appearance of an extra axial stringy system which consists of two half-infinite strings of opposite chirality. In this paper we consider the relation of this stringy system to the Dirac equation. We also show that the axial strings are the Witten superconducting strings and describe their structure by the Higgs field model where the Higgs condensate is used to regularize axial singularity. We argue that this axial stringy system may play the role of a classical carrier of the wave function.

  20. Chiral rotational spectroscopy

    Science.gov (United States)

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

    2016-09-01

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

  1. Chiral Superfluidity for QCD

    CERN Document Server

    Kalaydzhyan, Tigran

    2014-01-01

    We argue that the strongly coupled quark-gluon plasma formed at LHC and RHIC can be considered as a chiral superfluid. The "normal" component of the fluid is the thermalized matter in common sense, while the "superfluid" part consists of long wavelength (chiral) fermionic states moving independently. We use the bosonization procedure with a finite cut-off and obtain a dynamical axion-like field out of the chiral fermionic modes. Then we use relativistic hydrodynamics for macroscopic description of the effective theory obtained after the bosonization. Finally, solving the hydrodynamic equations in gradient expansion, we find that in the presence of external electromagnetic fields or rotation the motion of the "superfluid" component gives rise to the chiral magnetic, chiral vortical, chiral electric and dipole wave effects. Latter two effects are specific for a two-component fluid, which provides us with crucial experimental tests of the model.

  2. Mechanical separation of chiral dipoles by chiral light

    CERN Document Server

    Canaguier-Durand, Antoine; Genet, Cyriaque; Ebbesen, Thomas W

    2013-01-01

    Optical forces take on a specific form when involving chiral light fields interacting with chiral objects. We show that optical chirality density and flow can have mechanical effects through reactive and dissipative components of chiral forces exerted on chiral dipoles. Remarkably, these force components are directly related to standard observables: optical rotation and circular dichroism, respectively. As a consequence, resulting forces and torques are dependent on the enantiomeric form of the chiral dipole. This leads to promising strategies for the mechanical separation of chiral objects using chiral light forces.

  3. Chirality and chiroptical properties of amyloid fibrils.

    Science.gov (United States)

    Dzwolak, Wojciech

    2014-09-01

    Chirality of amyloid fibrils-linear beta-sheet-rich aggregates of misfolded protein chains-often manifests in morphological traits such as helical twist visible in atomic force microscopy and in chiroptical properties accessible to vibrational circular dichroism (VCD). According to recent studies the relationship between molecular chirality of polypeptide building blocks and superstructural chirality of amyloid fibrils may be more intricate and less deterministic than previously assumed. Several puzzling experimental findings have put into question earlier intuitive ideas on: 1) the bottom-up chirality transfer upon amyloidogenic self-assembly, and 2) the structural origins of chiroptical properties of protein aggregates. For example, removal of a single amino acid residue from an amyloidogenic all-L peptide was shown to reverse handedness of fibrils. On the other hand, certain types of amyloid aggregates revealed surprisingly strong VCD spectra with the sign and shape dependent on the conditions of fibrillation. Hence, microscopic and chiroptical studies have highlighted chirality as one more aspect of polymorphism of amyloid fibrils. This brief review is intended to outline the current state of research on amyloid-like fibrils from the perspective of their structural and superstructural chirality and chiroptical properties.

  4. Chiral anomaly and transport in Weyl metals

    Science.gov (United States)

    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.

  5. Chiral atomically thin films

    Science.gov (United States)

    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.

  6. Chiral Shock Waves

    CERN Document Server

    Sen, Srimoyee

    2016-01-01

    We study shock waves in relativistic chiral matter. We argue that the conventional Rankine- Hugoinot relations are modified due to the presence of chiral transport phenomena. We show that the entropy discontinuity in a weak shock wave is linearly proportional to the pressure discontinuity when the effect of chiral transport becomes sufficiently large. We also show that rarefaction shock waves, which do not exist in usual nonchiral fluids, can appear in chiral matter. These features are exemplified by shock propagation in dense neutrino matter in the hydrodynamic regime.

  7. Anomalous chiral superfluidity

    Energy Technology Data Exchange (ETDEWEB)

    Lublinsky, Michael, E-mail: lublinsky@phys.uconn.ed [Department of Physics and Astronomy, Stony Brook University, Stony Brook, NY 11794 (United States); Physics Department, Ben-Gurion University, Beer Sheva 84105 (Israel); Zahed, Ismail [Department of Physics and Astronomy, Stony Brook University, Stony Brook, NY 11794 (United States)

    2010-02-08

    We discuss both the anomalous Cartan currents and the energy-momentum tensor in a left chiral theory with flavor anomalies as an effective theory for flavored chiral phonons in a chiral superfluid with the gauged Wess-Zumino-Witten term. In the mean-field (leading tadpole) approximation the anomalous Cartan currents and the energy-momentum tensor take the form of constitutive currents in the chiral superfluid state. The pertinence of higher order corrections and the Adler-Bardeen theorem is briefly noted.

  8. Quark matter in a parallel electric and magnetic field background: Chiral phase transition and equilibration of chiral density

    Science.gov (United States)

    Ruggieri, M.; Peng, G. X.

    2016-05-01

    In this article, we study spontaneous chiral symmetry breaking for quark matter in the background of static and homogeneous parallel electric field E and magnetic field B . We use a Nambu-Jona-Lasinio model with a local kernel interaction to compute the relevant quantities to describe chiral symmetry breaking at a finite temperature for a wide range of E and B . We study the effect of this background on the inverse catalysis of chiral symmetry breaking for E and B of the same order of magnitude. We then focus on the effect of the equilibration of chiral density n5 , produced dynamically by an axial anomaly on the critical temperature. The equilibration of n5 , a consequence of chirality-flipping processes in the thermal bath, allows for the introduction of the chiral chemical potential μ5, which is computed self-consistently as a function of the temperature and field strength by coupling the number equation to the gap equation and solving the two within an expansion in E /T2 , B /T2 , and μ52/T2 . We find that even if chirality is produced and equilibrates within a relaxation time τM , it does not change drastically the thermodynamics, with particular reference to the inverse catalysis induced by the external fields, as long as the average μ5 at equilibrium is not too large.

  9. Doped Chiral Polymer Metamaterials Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Doped Chiral Polymer Metamaterials (DCPM) with tunable resonance frequencies have been developed by adding plasmonic inclusions into chiral polymers with variable...

  10. Can circular dichroism in core-level photoemission provide a spectral fingerprint of adsorbed chiral molecules?

    Energy Technology Data Exchange (ETDEWEB)

    Allegretti, F [Physics Department, University of Warwick, Coventry CV4 7AL (United Kingdom); Polcik, M [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D 14195 Berlin (Germany); Sayago, D I [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D 14195 Berlin (Germany); Demirors, F [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D 14195 Berlin (Germany); O' Brien, S [Physics Department, University of Warwick, Coventry CV4 7AL (United Kingdom); Nisbet, G [Centre for Applied Catalysis, Department of Chemical and Biological Sciences, University of Huddersfield, Queensgate, Huddersfield HD1 3DH (United Kingdom); Lamont, C L A [Centre for Applied Catalysis, Department of Chemical and Biological Sciences, University of Huddersfield, Queensgate, Huddersfield HD1 3DH (United Kingdom); Woodruff, D P [Physics Department, University of Warwick, Coventry CV4 7AL (United Kingdom)

    2005-04-01

    The results of experimental measurements and theoretical simulations of circular dichroism in the angular distribution (CDAD) of photoemission from atomic core levels of each of the enantiomers of a chiral molecule, alanine, adsorbed on Cu(1 1 0) are presented. Measurements in, and out of, substrate mirror planes allow one to distinguish the CDAD due to the chirality of the sample from that due to a chiral experimental geometry. For these studies of oriented chiral molecules, the CDAD is seen not only in photoemission from the molecular chiral centre, but also from other atoms which have chiral geometries as a result of the adsorption. The magnitude of the CDAD due to the sample chirality differs for different adsorption phases of alanine, and for different emission angles and energies, but is generally small compared with CDAD out of the substrate mirror planes which is largely unrelated to the molecular chirality. While similar measurements of other molecules may reveal larger CDAD due to molecular chirality, the fact that the results for one chiral molecule show weak effects means that such CDAD is unlikely to provide a simple and routine general spectral fingerprint of adsorbed molecular chirality.

  11. Reconfigurable self-assembly through chiral control of interfacial tension.

    Science.gov (United States)

    Gibaud, Thomas; Barry, Edward; Zakhary, Mark J; Henglin, Mir; Ward, Andrew; Yang, Yasheng; Berciu, Cristina; Oldenbourg, Rudolf; Hagan, Michael F; Nicastro, Daniela; Meyer, Robert B; Dogic, Zvonimir

    2012-01-04

    From determining the optical properties of simple molecular crystals to establishing the preferred handedness in highly complex vertebrates, molecular chirality profoundly influences the structural, mechanical and optical properties of both synthetic and biological matter on macroscopic length scales. In soft materials such as amphiphilic lipids and liquid crystals, the competition between local chiral interactions and global constraints imposed by the geometry of the self-assembled structures leads to frustration and the assembly of unique materials. An example of particular interest is smectic liquid crystals, where the two-dimensional layered geometry cannot support twist and chirality is consequently expelled to the edges in a manner analogous to the expulsion of a magnetic field from superconductors. Here we demonstrate a consequence of this geometric frustration that leads to a new design principle for the assembly of chiral molecules. Using a model system of colloidal membranes, we show that molecular chirality can control the interfacial tension, an important property of multi-component mixtures. This suggests an analogy between chiral twist, which is expelled to the edges of two-dimensional membranes, and amphiphilic surfactants, which are expelled to oil-water interfaces. As with surfactants, chiral control of interfacial tension drives the formation of many polymorphic assemblages such as twisted ribbons with linear and circular topologies, starfish membranes, and double and triple helices. Tuning molecular chirality in situ allows dynamical control of line tension, which powers polymorphic transitions between various chiral structures. These findings outline a general strategy for the assembly of reconfigurable chiral materials that can easily be moved, stretched, attached to one another and transformed between multiple conformational states, thus allowing precise assembly and nanosculpting of highly dynamical and designable materials with complex

  12. Control and femtosecond time-resolved imaging of torsion in a chiral molecule

    CERN Document Server

    Hansen, Jonas L; Madsen, Christian Bruun; Lindhardt, Anders Thyboe; Johansson, Mikael P; Skrydstrup, Troels; Madsen, Lars Bojer; Stapelfeldt, Henrik

    2012-01-01

    We study how the combination of long and short laser pulses, can be used to induce torsion in an axially chiral biphenyl derivative (3,5-difluoro-3',5'-dibromo-4'-cyanobiphenyl). A long, with respect to the molecular rotational periods, elliptically polarized laser pulse produces 3D alignment of the molecules, and a linearly polarized short pulse initiates torsion about the stereogenic axis. The torsional motion is monitored in real-time by measuring the dihedral angle using femtosecond time-resolved Coulomb explosion imaging. Within the first 4 picoseconds, torsion occurs with a period of 1.25 picoseconds and an amplitude of 3 degrees in excellent agreement with theoretical calculations. At larger times the quantum states of the molecules describing the torsional motion dephase and an almost isotropic distribution of the dihedral angle is measured. We demonstrate an original application of covariance analysis of two-dimensional ion images to reveal strong correlations between specific ejected ionic fragments...

  13. Realisation of chiral symmetry in the domain model of QCD

    CERN Document Server

    Kalloniatis, Alexander C

    2003-01-01

    The domain model for the QCD vacuum has previously been developed and shown to exhibit confinement of quarks and strong correlation of the local chirality of quark modes and duality of the background domain-like gluon field. Quark fluctuations satisfy a chirality violating boundary conditions parametrized by a random chiral angle $\\alpha_j$ on the $j-th$ domain. The free energy of an ensemble of $N\\to\\infty$ domains depends on $\\{\\alpha_j, j=1... N\\}$ through the logarithm of the quark determinant. Its parity odd part is given by the axial anomaly. The anomaly contribution to the free energy suppresses continuous axial U(1) degeneracy in the ground state, leaving only a residual axial Z(2) symmetry. This discrete symmetry and flavour $SU(N_f)_L\\times SU(N_f)_R$ chiral symmetry in turn are spontaneously broken with a quark condensate arising due to the asymmetry of the spectrum of Dirac operator. In order to illustrate the splitting between the $\\eta'$ from octet pseudoscalar mesons realised in the domain mode...

  14. Helical Ordering in Chiral Block Copolymers

    Science.gov (United States)

    Zhao, Wei; Hong, Sung Woo; Chen, Dian; Grason, Gregory; Russell, Thomas

    2012-02-01

    Introducing molecular chirality into the segments of block copolymers can influence the nature of the resultant morphology. Such an effect was found for poly(styrene-b-L-lactide) (PS-b-PLLA) diblock copolymers where hexagonally packed PLLA helical microdomains (H* phase) form in a PS matrix. However, molecular ordering of PLLA within the helical microdomains and the transfer of chirality from the segmental level to the mesoscale is still not well understood. We developed a field theoretic model to describe the interactions between segments of chiral blocks, which have the tendency to form a ``cholesteric'' texture. Based on the model, we calculated the bulk morphologies of chiral AB diblock copolymers using self-consistent field theory (SCFT). Experiments show that the H* phase only forms when microphase separation between PS and PLLA block happens first and crystallization of PLLA block is suppressed or happens within confined microdomain. Hence, crystalline ordering is not necessary for H* phase formation. The SCFT offers the chance to explore the range of thermodynamic stability of helical structures in the phase diagram of chiral block copolymer melts, by tuning parameters not only like the block segregation strength and composition, but also new parameters such as the ratio between preferred helical pitch to the radius of gyration and the Frank elastic constant for inter-segment distortions.

  15. Applications of chiral symmetry

    CERN Document Server

    Pisarski, R D

    1995-01-01

    I discuss several topics in the applications of chiral symmetry at nonzero temperature, including: where the rho goes, disoriented chiral condensates, and the phase diagram for QCD with 2+1 flavors. (Based upon talks presented at the "Workshop on Finite Temperature QCD", Wuhan, P.R.C., April, 1994.)

  16. Cell chirality: its origin and roles in left-right asymmetric development.

    Science.gov (United States)

    Inaki, Mikiko; Liu, Jingyang; Matsuno, Kenji

    2016-12-19

    An item is chiral if it cannot be superimposed on its mirror image. Most biological molecules are chiral. The homochirality of amino acids ensures that proteins are chiral, which is essential for their functions. Chirality also occurs at the whole-cell level, which was first studied mostly in ciliates, single-celled protozoans. Ciliates show chirality in their cortical structures, which is not determined by genetics, but by 'cortical inheritance'. These studies suggested that molecular chirality directs whole-cell chirality. Intriguingly, chirality in cellular structures and functions is also found in metazoans. In Drosophila, intrinsic cell chirality is observed in various left-right (LR) asymmetric tissues, and appears to be responsible for their LR asymmetric morphogenesis. In other invertebrates, such as snails and Caenorhabditis elegans, blastomere chirality is responsible for subsequent LR asymmetric development. Various cultured cells of vertebrates also show intrinsic chirality in their cellular behaviours and intracellular structural dynamics. Thus, cell chirality may be a general property of eukaryotic cells. In Drosophila, cell chirality drives the LR asymmetric development of individual organs, without establishing the LR axis of the whole embryo. Considering that organ-intrinsic LR asymmetry is also reported in vertebrates, this mechanism may contribute to LR asymmetric development across phyla.This article is part of the themed issue 'Provocative questions in left-right asymmetry'.

  17. Chirality-Controlled Synthesis and Applications of Single-Wall Carbon Nanotubes.

    Science.gov (United States)

    Liu, Bilu; Wu, Fanqi; Gui, Hui; Zheng, Ming; Zhou, Chongwu

    2017-01-24

    Preparation of chirality-defined single-wall carbon nanotubes (SWCNTs) is the top challenge in the nanotube field. In recent years, great progress has been made toward preparing single-chirality SWCNTs through both direct controlled synthesis and postsynthesis separation approaches. Accordingly, the uses of single-chirality-dominated SWCNTs for various applications have emerged as a new front in nanotube research. In this Review, we review recent progress made in the chirality-controlled synthesis of SWCNTs, including metal-catalyst-free SWCNT cloning by vapor-phase epitaxy elongation of purified single-chirality nanotube seeds, chirality-specific growth of SWCNTs on bimetallic solid alloy catalysts, chirality-controlled synthesis of SWCNTs using bottom-up synthetic strategy from carbonaceous molecular end-cap precursors, etc. Recent major progresses in postsynthesis separation of single-chirality SWCNT species, as well as methods for chirality characterization of SWCNTs, are also highlighted. Moreover, we discuss some examples where single-chirality SWCNTs have shown clear advantages over SWCNTs with broad chirality distributions. We hope this review could inspire more research on the chirality-controlled preparation of SWCNTs and equally important inspire the use of single-chirality SWCNT samples for more fundamental studies and practical applications.

  18. Cell chirality: its origin and roles in left–right asymmetric development

    Science.gov (United States)

    Inaki, Mikiko; Liu, Jingyang

    2016-01-01

    An item is chiral if it cannot be superimposed on its mirror image. Most biological molecules are chiral. The homochirality of amino acids ensures that proteins are chiral, which is essential for their functions. Chirality also occurs at the whole-cell level, which was first studied mostly in ciliates, single-celled protozoans. Ciliates show chirality in their cortical structures, which is not determined by genetics, but by ‘cortical inheritance’. These studies suggested that molecular chirality directs whole-cell chirality. Intriguingly, chirality in cellular structures and functions is also found in metazoans. In Drosophila, intrinsic cell chirality is observed in various left–right (LR) asymmetric tissues, and appears to be responsible for their LR asymmetric morphogenesis. In other invertebrates, such as snails and Caenorhabditis elegans, blastomere chirality is responsible for subsequent LR asymmetric development. Various cultured cells of vertebrates also show intrinsic chirality in their cellular behaviours and intracellular structural dynamics. Thus, cell chirality may be a general property of eukaryotic cells. In Drosophila, cell chirality drives the LR asymmetric development of individual organs, without establishing the LR axis of the whole embryo. Considering that organ-intrinsic LR asymmetry is also reported in vertebrates, this mechanism may contribute to LR asymmetric development across phyla. This article is part of the themed issue ‘Provocative questions in left–right asymmetry’. PMID:27821533

  19. Chiral Symmetry in Light-Cone Field Theory

    CERN Document Server

    Lenz, F; Thies, M; Yazaki, K

    2004-01-01

    An analysis of spontaneously broken chiral symmetry in light-cone field theory is presented. The non-locality inherent to light-cone field theory requires revision of the standard procedure in the derivation of Ward-Takahashi identities. We derive the general structure of chiral Ward-Takahashi identities and construct them explicitly for various model field theories. Gell-Mann-Oakes-Renner relations and relations between fermion propagators and the structure functions of Nambu-Goldstone bosons are discussed and the necessary modifications of the Ward-Takahashi identities due to the axial anomaly are indicated.

  20. BWR AXIAL PROFILE

    Energy Technology Data Exchange (ETDEWEB)

    J. Huffer

    2004-09-28

    The purpose of this calculation is to develop axial profiles for estimating the axial variation in burnup of a boiling water reactor (BWR) assembly spent nuclear fuel (SNF) given the average burnup of an assembly. A discharged fuel assembly typically exhibits higher burnup in the center and lower burnup at the ends of the assembly. Criticality safety analyses taking credit for SNF burnup must account for axially varying burnup relative to calculations based on uniformly distributed assembly average burnup due to the under-burned tips. Thus, accounting for axially varying burnup in criticality analyses is also referred to as accounting for the ''end effect'' reactivity. The magnitude of the reactivity change due to ''end effect'' is dependent on the initial assembly enrichment, the assembly average burnup, and the particular axial profile characterizing the burnup distribution. The set of bounding axial profiles should incorporate multiple BWR core designs and provide statistical confidence (95 percent confidence that 95 percent of the population is bound by the profile) that end nodes are conservatively represented. The profiles should also conserve the overall burnup of the fuel assembly. More background on BWR axial profiles is provided in Attachment I.

  1. Chiral pesticides: Identification, description, and environmental implications

    Science.gov (United States)

    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.

  2. [Management of axial spondyloarthritis].

    Science.gov (United States)

    Kiltz, U; Baraliakos, X; Braun, J

    2016-11-01

    The term spondyloarthritis (SpA) is now increasingly used to classify and diagnose patients who are characterized by inflammation in the axial skeleton and peripheral manifestations (arthritis and enthesitis). The management of SpA should be tailored according to the current manifestations of the disease, the disease activity and functional impairment. The current article focuses on diagnosis and therapy in patients with axial SpA. Diagnostic procedures are discussed in light of diagnostic utility and feasibility in daily routine care. Cornerstones of treatment in patients with axial SpA are a combination of regular exercise and pharmacological treatment options aiming at anti-inflammatory strategies.

  3. Hyperpolarizabilities of Chiral Molecules Based on Three-Coupled-Oscillator Model

    Institute of Scientific and Technical Information of China (English)

    WANG Xiao-Ou; LI Jun-Qing; LI Chun-Fei

    2004-01-01

    @@ A chiral molecular model of three coupled oscillators is established. A set of coupling equations and hyperpolarizabilities for the chiral molecules with the tripod structure are presented. The expression of second-order nonlinear susceptibility is derived for an isotropic molecular system. The calculated hyperpolarizabilities of NPAN and NPP chiral molecules are consistent with the experimental results and the applicability of this model is validated.

  4. Chiral dynamics and peripheral transverse densities

    Energy Technology Data Exchange (ETDEWEB)

    Granados, Carlos G. [Uppsala University (Sweden); Weiss, Christian [JLAB, Newport News, VA (United States)

    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.

  5. Molecular Modeling on the Recognition of Wobble DNA Including G:T Mismatched Pairs by Two Structures of Chiral Metal Complex △,∧-[Ru(phen)2hpip]2+

    Institute of Scientific and Technical Information of China (English)

    ZHANG Cui-Ping; WU Yan-Bo; YANG Pin

    2006-01-01

    In this work, the recognition of DNA including G:T mismatched pairs by the two different structures of[Ru(phen)2hpip]2+ was firstly studied with molecular modeling respectively. The results revealed that all of the four chiral isomers of the two structures could recognize the mismatched DNA from the minor groove orientation especially and the interaction was enantioselective and sitespecific. The two left isomers were more preferential than the right ones. Especially, the structure Ⅱ which had much lower energy after interacting with DNA was the advantaged structure. Detailed energy analysis indicated that the steric interaction in the process of the complex inserting base stack determined the recognition results and the electrostatic interaction made an effect to some extent.

  6. 现代有机分析在中药检测食物分析和手性识别的应用%Application of Modern Organic Analysis in Traditional Chinese Medicine Test, Food Analysis and Chiral Molecular Recognition

    Institute of Scientific and Technical Information of China (English)

    张来新; 赵卫星

    2011-01-01

    Conception, application and prospect of organic analytical chemistry were briefly introduced. Application of new modern organic analysis technologies in traditional Chinese medicine test, food analysis and chiral molecular recognition was mainly discussed. At last, future development of the organic analysis was prospected.%简要介绍了有机分析化学的概念、应用与发展前景,重点综述了利用现代有机分析的新技术新方法测定中药材中药用成分研究;现代有机分析新方法新技术对食物中有关成分测定;现代有机分析在手性识别方面的应用.并对有机分析的发展进行了展望.

  7. Evidence for chiral logarithms in the baryon spectrum

    CERN Document Server

    Walker-Loud, Andre

    2011-01-01

    Using precise lattice QCD computations of the baryon spectrum, we present the first direct evidence for the presence of contributions to the baryon masses which are non-analytic in the light quark masses; contributions which are often denoted "chiral logarithms". We isolate the poor convergence of SU(3) baryon chiral perturbation theory to the flavor-singlet mass combination. The flavor-octet baryon mass splittings, which are corrected by chiral logarithms at next to leading order in SU(3) chiral perturbation theory, yield baryon-pion axial coupling constants D, F, C and H consistent with QCD values; the first evidence of chiral logarithms in the baryon spectrum. The Gell-Mann--Okubo relation, a flavor-27 baryon mass splitting, which is dominated by chiral corrections from light quark masses, provides further evidence for the presence of non-analytic light quark mass dependence in the baryon spectrum; we simultaneously find the GMO relation to be inconsistent with the first few terms in a taylor expansion in ...

  8. Chiral Liquid Crystals: Structures, Phases, Effects

    Directory of Open Access Journals (Sweden)

    Ingo Dierking

    2014-06-01

    Full Text Available The introduction of chirality, i.e., the lack of mirror symmetry, has a profound effect on liquid crystals, not only on the molecular scale but also on the supermolecular scale and phase. I review these effects, which are related to the formation of supermolecular helicity, the occurrence of novel thermodynamic phases, as well as electro-optic effects which can only be observed in chiral liquid crystalline materials. In particular, I will discuss the formation of helical superstructures in cholesteric, Twist Grain Boundary and ferroelectric phases. As examples for the occurrence of novel phases the Blue Phases and Twist Grain Boundary phases are introduced. Chirality related effects are demonstrated through the occurrence of ferroelectricity in both thermotropic as well as lyotropic liquid crystals. Lack of mirror symmetry is also discussed briefly for some biopolymers such as cellulose and DNA, together with its influence on liquid crystalline behavior.

  9. Applications of chiral symmetry

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Axial Halbach Magnetic Bearings

    Science.gov (United States)

    Eichenberg, Dennis J.; Gallo, Christopher A.; Thompson, William K.

    2008-01-01

    Axial Halbach magnetic bearings have been investigated as part of an effort to develop increasingly reliable noncontact bearings for future high-speed rotary machines that may be used in such applications as aircraft, industrial, and land-vehicle power systems and in some medical and scientific instrumentation systems. Axial Halbach magnetic bearings are passive in the sense that unlike most other magnetic bearings that have been developed in recent years, they effect stable magnetic levitation without need for complex active control.

  11. Derivative expansion for the effective action of chiral gauge fermions. The normal parity component

    Energy Technology Data Exchange (ETDEWEB)

    Salcedo, L.L. [Dept. de Fisica Moderna, Universidad de Granada (Spain)

    2001-04-01

    Explicit exact formulas are presented, up to fourth order in a strict chiral covariant derivative expansion, for the normal parity component of the Euclidean effective action of even-dimensional Dirac fermions. The bosonic background fields considered are scalar, pseudo-scalar, vector and axial vector. No assumptions are made on the internal symmetry group and, in particular, the scalar and pseudo-scalar fields need not be on the chiral circle. (orig.)

  12. Derivative expansion for the effective action of chiral gauge fermions. The abnormal parity component

    Energy Technology Data Exchange (ETDEWEB)

    Salcedo, L.L. [Dept. de Fisica Moderna, Universidad de Granada (Spain)

    2001-04-01

    Explicit exact formulas are presented, for the leading order term in a strict chiral covariant derivative expansion, for the abnormal parity component of the effective action of two- and four-dimensional Dirac fermions in the presence of scalar, pseudo-scalar, vector and axial vector background fields. The formulas hold for completely general internal symmetry groups and general configurations. In particular, the scalar and pseudo-scalar fields need not be on the chiral circle. (orig.)

  13. Rotating pigment cells exhibit an intrinsic chirality.

    Science.gov (United States)

    Yamanaka, Hiroaki; Kondo, Shigeru

    2015-01-01

    In multicellular organisms, cell properties, such as shape, size and function are important in morphogenesis and physiological functions. Recently, 'cellular chirality' has attracted attention as a cellular property because it can cause asymmetry in the bodies of animals. In recent in vitro studies, the left-right bias of cellular migration and of autonomous arrangement of cells under some specific culture conditions were discovered. However, it is difficult to identify the molecular mechanism underlying their intrinsic chirality because the left-right bias observed to date is subtle or is manifested in the stable orientation of cells. Here, we report that zebrafish (Danio rerio) melanophores exhibit clear cellular chirality by unidirectional counterclockwise rotational movement under isolated conditions without any special settings. The chirality is intrinsic to melanophores because the direction of the cellular rotation was not affected by the type of extracellular matrix. We further found that the cellular rotation was generated as a counter action of the clockwise movement of actin cytoskeleton. It suggested that the mechanism that directs actin cytoskeleton in the clockwise direction is pivotal for determining cellular chirality.

  14. Quark Matter in a Parallel Electric and Magnetic Field Background: Equilibrated Chiral Density Effect on Chiral Phase Transition

    CERN Document Server

    Ruggieri, M

    2016-01-01

    In this article we study spontaneous chiral symmetry breaking for quark matter in the background of an electric-magnetic flux tube with static, homogeneous and parallel electric field $\\bm E$ and magnetic field $\\bm B$. We use a Nambu-Jona-Lasinio model with a local kernel interaction to compute the relevant quantities to describe chiral symmetry breaking at finite temperature for a wide range of $E$ and $B$. We study the effect of the flux tube background on inverse catalysis of chiral symmetry breaking for $E$ and $B$ of the same order of magnitude. We then focus on the effect of equilibration of chiral density, $n_5$, produced dynamically by axial anomaly on the critical temperature. The equilibration of $n_5$, a consequence of chirality flipping processes in the thermal bath, allows for the introduction of the chiral chemical potential, $\\mu_5$, which is computed self-consistently as a function of temperature and field strength by coupling the number equation to the gap equation. We find that even if chir...

  15. Chirality Relay in 2,2'-Substituted 1,1'-Binaphthyl: Access to Propeller Chirality of the Tricoordinate Boron Center.

    Science.gov (United States)

    Wang, Chen; Sun, Zuo-Bang; Xu, Qing-Wen; Zhao, Cui-Hua

    2016-11-14

    It is a challenging issue to achieve propeller chirality for triarylboranes owing to the low transition barrier between the P and M forms of the boron center. Herein, we report a new strategy to achieve propeller chirality of triarylboranes. It was found that the chirality relay from axially chiral 1,1'-binaphthyl to propeller chirality of the trivalent boron center can be realized when a Me2 N and a Mes2 B group (Mes=mesityl) are introduced at the 2,2'-positions of the 1,1'-binaphthyl skeleton (BN-BNaph) owing to the strong π-π interaction between the Me2 N-bonded naphthyl ring and the phenyl ring of one adjacent Mes group, which not only exerts great steric hindrance on the rotation of the two Mes groups but also gives unequal stability to the two configurations of the boron center for a given configuration of the binaphthyl moiety. The stereostructures of the boron center were fully characterized through (1) H NMR spectroscopy, X-ray crystal analyses, and theoretical calculations. Detailed comparisons with the analog BN-Ph-BNaph, in which the Mes2 B group is separated from 1,1'-binaphthyl by a para-phenylene spacer, confirmed the essential role of π-π interaction for the successful chirality relay in BN-BNaph.

  16. Spectral signatures of chirality

    DEFF Research Database (Denmark)

    Pedersen, Jesper Goor; Mortensen, Asger

    2009-01-01

    We present a new way of measuring chirality, via the spectral shift of photonic band gaps in one-dimensional structures. We derive an explicit mapping of the problem of oblique incidence of circularly polarized light on a chiral one-dimensional photonic crystal with negligible index contrast...... to the formally equivalent problem of linearly polarized light incident on-axis on a non-chiral structure with index contrast. We derive analytical expressions for the first-order shifts of the band gaps for negligible index contrast. These are modified to give good approximations to the band gap shifts also...

  17. Catalysis of Dynamical Chiral Symmetry Breaking by Chiral Chemical Potential

    CERN Document Server

    Braguta, V V

    2016-01-01

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

  18. Enantiospecific adsorption of cysteine on a chiral Au34 cluster

    Science.gov (United States)

    Pelayo, José de Jesús; Valencia, Israel; Díaz, Gabriela; López-Lozano, Xóchitl; Garzón, Ignacio L.

    2015-12-01

    The interaction of biological molecules like chiral amino acids with chiral metal clusters is becoming an interesting and active field of research because of its potential impact in, for example, chiral molecular recognition phenomena. In particular, the enantiospecific adsorption (EA) of cysteine (Cys) on a chiral Au55 cluster was theoretically predicted a few years ago. In this work, we present theoretical results, based on density functional theory, of the EA of non-zwitterionic cysteine interacting with the C3-Au34 chiral cluster, which has been experimentally detected in gas phase, using trapped ion electron diffraction. Our results show that, indeed, the adsorption energy of the amino acid depends on which enantiomers participate in the formation Cys-Au34 chiral complex. EA was obtained in the adsorption modes where both the thiol, and the thiol-amino functional groups of Cys are adsorbed on low-coordinated sites of the metal cluster surface. Similarly to what was obtained for the Cys-Au55 chiral complex, in the present work, it is found that the EA is originated from the different strength and location of the bond between the COOH functional group and surface Au atoms of the Au34 chiral cluster. Calculations of the vibrational spectrum for the different Cys-Au34 diastereomeric complexes predict the existence of a vibro-enantiospecific effect, indicating that the vibrational frequencies of the adsorbed amino acid depend on its handedness.

  19. Scalemic and racemic imprinting with a chiral crosslinker.

    Science.gov (United States)

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Soft Matrix Elements in Non-local Chiral Quark Model

    CERN Document Server

    Kotko, Piotr

    2009-01-01

    Using non-local chiral quark model and currents satisfying Ward-Takahashi identities we analyze Distribution Amplitudes (DA) of photon and pion-to-photon Transition Distribution Amplitudes (TDA) in the low energy regime. Photon DA's are calculated analytically up to twist-4 and reveal several interesting features of photon structure. TDA's calculated in the present model satisfy polynomiality condition. Normalization of vector TDA is fixed by the axial anomaly. We also compute relevant form factors and compare them with existing data. Axial form factor turns out to be much lower then the vector one, what indeed is seen in the experimental data.

  1. Chiral vibrational structures of proteins at interfaces probed by sum frequency generation spectroscopy.

    Science.gov (United States)

    Fu, Li; Wang, Zhuguang; Yan, Elsa C Y

    2011-01-01

    We review the recent development of chiral sum frequency generation (SFG) spectroscopy and its applications to study chiral vibrational structures at interfaces. This review summarizes observations of chiral SFG signals from various molecular systems and describes the molecular origins of chiral SFG response. It focuses on the chiral vibrational structures of proteins and presents the chiral SFG spectra of proteins at interfaces in the C-H stretch, amide I, and N-H stretch regions. In particular, a combination of chiral amide I and N-H stretches of the peptide backbone provides highly characteristic vibrational signatures, unique to various secondary structures, which demonstrate the capacity of chiral SFG spectroscopy to distinguish protein secondary structures at interfaces. On the basis of these recent developments, we further discuss the advantages of chiral SFG spectroscopy and its potential application in various fields of science and technology. We conclude that chiral SFG spectroscopy can be a new approach to probe chiral vibrational structures of protein at interfaces, providing structural and dynamic information to study in situ and in real time protein structures and dynamics at interfaces.

  2. The effect of "on/off" molecular switching on the photophysical and photochemical properties of axially calixarene substituted activatable silicon(iv)phthalocyanine photosensitizers.

    Science.gov (United States)

    Güngör, Ömer; Altınbaş Özpınar, Gül; Durmuş, Mahmut; Ahsen, Vefa

    2016-05-04

    Silicon(iv) phthalocyanines ( and ) bearing two calixarene groups as axial ligands were synthesized. Surprisingly, both phthalocyanines were obtained as two different isomers ( and ) depending on the distance between calixarene benzene groups and the phthalocyanine ring. DFT and TD-DFT computations were performed to model plausible structures of these isomers and to simulate electronic absorption spectra. These isomers converted into each other depending on the polarity of the used solvent, temperature and light irradiation. The photophysical and photochemical properties of each isomer were investigated in dimethylsulfoxide (DMSO) for the determination of photodynamic therapy (PDT) activities of these compounds. The more blue-shifted isomers ( and ) showed higher fluorescence quantum yields and singlet oxygen generation compared to more red-shifted counterparts ( and ). This behavior is extremely important for developing activatable photosensitizers for cancer treatment by PDT. Although these photosensitizers produce lower singlet oxygen in normal cells, they produce higher singlet oxygen (six times higher for ) in cancer cells since these photosensitizers converted to more blue-shifted isomers by using light irradiation.

  3. On the chiral separation effect in a slab

    CERN Document Server

    Sitenko, Yu A

    2016-01-01

    We study an influence of boundaries on chiral effects in hot dense relativistic spinor matter in a strong magnetic field which is transverse to bounding planes. The most general set of boundary conditions ensuring the confinement of matter within the bounding planes is considered. We find that, in thermal equilibrium, the nondissipative axial current along the magnetic field is induced, depending on chemical potential and temperature, as well as on a choice of boundary conditions. As temperature increases from zero to large values, a stepwise behaviour of the axial current density as a function of chemical potential is changed to a smooth one; the choice of a boundary condition can facilitate either amplification or diminution of the chiral separation effect. This points at a significant role of boundaries for physical systems with hot dense magnetized relativistic spinor matter, e.g., compact stars, heavy-ion collisions, novel materials known as Dirac and Weyl semimetals.

  4. Color chiral solitons

    CERN Document Server

    Novozhilov, V Yu; Novozhilov, Victor; Novozhilov, Yuri

    2002-01-01

    We discuss specific features of color chiral solitons (asymptotics, possibility of confainment, quantization) at example of isolated SU(2) color skyrmions, i.e. skyrmions in a background field which is the vacuum field forming the gluon condensate.

  5. Chiral brownian heat pump.

    Science.gov (United States)

    van den Broek, M; Van den Broeck, C

    2008-04-04

    We present the exact analysis of a chiral Brownian motor and heat pump. Optimization of the construction predicts, for a nanoscale device, frequencies of the order of kHz and cooling rates of the order of femtojoule per second.

  6. Chiral Brownian heat pump

    OpenAIRE

    Van Den Broek, Martijn; Van Den Broeck, Christian

    2007-01-01

    We present the exact analysis of a chiral Brownian motor and heat pump. Optimization of the construction predicts, for a nanoscale device, frequencies of the order of kHz and cooling rates of the order of femtojoule per second.

  7. Chiral lagrangian approach to exchange vector currents in nuclei

    CERN Document Server

    Park, T S; Rho, M; Park, Tae Sun; Min, Dong Pil; Rho, Mannque

    1995-01-01

    Exchange vector currents are calculated up to one-loop order (corresponding to next-to-next-to-leading order) in chiral perturbation theory. As an illustration of the power of the approach, we apply the formalism to the classic nuclear process n+p\\rightarrow d +\\gamma at thermal energy. The exchange current correction comes out to be (4.5 \\pm 0.3) \\% in amplitude giving a predicted cross section \\sigma= (334\\pm 3)\\ {\\mbox mb} in excellent agreement with the experimental value (334.2\\pm 0.5)\\ {\\mbox mb}. Together with the axial charge transitions computed previously, this result provides a strong support for the power of chiral Lagrangians in nuclear physics. As a by-product of our results, we suggest an open problem in the application of chiral Lagrangian approach to nuclear processes that has to do with giving a physical meaning to the short-range correlations that play an important role in nuclei.

  8. Chiral magnetic effect and anomalous transport from real-time lattice simulations

    CERN Document Server

    Mueller, Niklas; Sharma, Sayantan

    2016-01-01

    We present a first-principle study of anomaly induced transport phenomena by performing real-time lattice simulations with dynamical fermions coupled simultaneously to non-Abelian $SU(N_c)$ and Abelian $U(1)$ gauge fields. Investigating the behavior of vector and axial currents during a sphaleron transition in the presence of an external magnetic field, we demonstrate how the interplay of the Chiral magnetic (CME) and Chiral separation effect (CSE) lead to the formation of a propagating wave. We further analyze the dependence of the magnitude of the induced vector current and the propagation of the wave on the amount of explicit chiral symmetry breaking due to finite quark mass.

  9. Electrodynamics of chiral matter

    Science.gov (United States)

    Qiu, Zebin; Cao, Gaoqing; Huang, Xu-Guang

    2017-02-01

    Many-body systems with chiral fermions can exhibit novel transport phenomena that violate parity and time-reversal symmetries, such as the chiral magnetic effect, the anomalous Hall effect, and the anomalous generation of charge. Based on the Maxwell-Chern-Simons electrodynamics, we examine some electromagnetic and optical properties of such systems including the electrostatics, the magnetostatics, the propagation of electromagnetic waves, the novel optical effects, etc.

  10. Chiral Odd GPDs

    Directory of Open Access Journals (Sweden)

    Goldstein Gary R.

    2015-01-01

    Full Text Available Nucleon spin structure, transversity and the tensor charge are of central importance to understanding the role of QCD in hadronic physics. A new approach to measuring orbital angular momenta of quarks in the proton via twist 3 GPDs is shown. The “flexible parametrization” of chiral even GPDs is reviewed and its transformation into the chiral odd sector is discussed. The resulting parametrization is applied to recent data on π0 and η electroproduction.

  11. Synergistic effects on enantioselectivity of zwitterionic chiral stationary phases for separations of chiral acids, bases, and amino acids by HPLC.

    Science.gov (United States)

    Hoffmann, Christian V; Pell, Reinhard; Lämmerhofer, Michael; Lindner, Wolfgang

    2008-11-15

    In an attempt to overcome the limited applicability scope of earlier proposed Cinchona alkaloid-based chiral weak anion exchangers (WAX) and recently reported aminosulfonic acid-based chiral strong cation exchangers (SCX), which are conceptionally restricted to oppositely charged solutes, their individual chiral selector (SO) subunits have been fused in a combinatorial synthesis approach into single, now zwitterionic, chiral SO motifs. The corresponding zwitterionic ion-exchange-type chiral stationary phases (CSPs) in fact combined the applicability spectra of the parent chiral ion exchangers allowing for enantioseparations of chiral acids and amine-type solutes in liquid chromatography using polar organic mode with largely rivaling separation factors as compared to the parent WAX and SCX CSPs. Furthermore, the application spectrum could be remarkably expanded to various zwitterionic analytes such as alpha- and beta-amino acids and peptides. A set of structurally related yet different CSPs consisting of either a quinine or quinidine alkaloid moiety as anion-exchange subunit and various chiral or achiral amino acids as cation-exchange subunits enabled us to derive structure-enantioselectivity relationships, which clearly provided strong unequivocal evidence for synergistic effects of the two oppositely charged ion-exchange subunits being involved in molecular recognition of zwitterionic analytes by zwitterionic SOs driven by double ionic coordination.

  12. Atom-Specific Identification of Adsorbed Chiral Molecules by Photoemission

    Science.gov (United States)

    Kim, J. W.; Carbone, M.; Dil, J. H.; Tallarida, M.; Flammini, R.; Casaletto, M. P.; Horn, K.; Piancastelli, M. N.

    2005-09-01

    The study of chiral adsorbed molecules is important for an analysis of enantioselectivity in heterogeneous catalysis. Here we show that such molecules can be identified through circular dichroism in core-level photoemission arising from the chiral carbon atoms in stereoisomers of 2,3-butanediol molecules adsorbed on Si(100), using circularly polarized x rays. The asymmetry in the carbon 1s intensity excited by right and left circularly polarized light is readily observed, and changes sign with the helicity of the radiation or handedness of the enantiomers; it is absent in the achiral form of the molecule. This observation demonstrates the possibility of determining molecular chirality in the adsorbed phase.

  13. Chirality as a physical aspect of structure formation in biological macromolecular systems

    Science.gov (United States)

    Malyshko, E. V.; Tverdislov, V. A.

    2016-08-01

    A novel regularity of hierarchical structures is found in the formation of chiral biological macromolecular systems. The formation of structures with alternating chirality (helical structures) serves as an instrument of stratification. The ability of a carbon atom to form chiral compounds is an important factor that determined the carbon basis of living systems on the Earth as well as their development through a series of chiral bifurcations. In the course of biological evolution, the helical structures became basic elements of the molecular machines in the cell. The discreteness of structural levels allowed the mechanical degrees of freedom formation in the molecular machines in the cell.

  14. Electromagnetic Signatures of the Chiral Anomaly in Weyl Semimetals

    Science.gov (United States)

    Barnes, Edwin; Heremans, J. J.; Minic, Djordje

    2016-11-01

    Weyl semimetals are predicted to realize the three-dimensional axial anomaly first discussed in particle physics. The anomaly leads to unusual transport phenomena such as the chiral magnetic effect in which an applied magnetic field induces a current parallel to the field. Here we investigate diagnostics of the axial anomaly based on the fundamental equations of axion electrodynamics. We find that materials with Weyl nodes of opposite chirality and finite energy separation immersed in a uniform magnetic field exhibit an anomaly-induced oscillatory magnetic field with a period set by the chemical potential difference of the nodes. In the case where a chemical potential imbalance is created by applying parallel electric and magnetic fields, we find a suppression of the magnetic-field component parallel to the electric field inside the material for rectangular samples, suggesting that the chiral magnetic current opposes this imbalance. For cylindrical geometries, we instead find an enhancement of this magnetic-field component along with an anomaly-induced azimuthal component. We propose experiments to detect such magnetic signatures of the axial anomaly.

  15. Evaluating chiral symmetry restoration through the use of sum rules

    Directory of Open Access Journals (Sweden)

    Rapp Ralf

    2012-11-01

    Full Text Available We pursue the idea of assessing chiral restoration via in-medium modifications of hadronic spectral functions of chiral partners. The usefulness of sum rules in this endeavor is illustrated, focusing on the vector/axial-vector channel. We first present an update on obtaining quantitative results for pertinent vacuum spectral functions. These serve as a basis upon which the in-medium spectral functions can be constructed. A novel feature of our analysis of the vacuum spectral functions is the need to include excited resonances, dictated by satisfying the Weinberg-type sum rules. This includes excited states in both the vector and axial-vector channels.We also analyze the QCD sum rule for the finite temperature vector spectral function, based on a ρ spectral function tested in dilepton data which develops a shoulder at low energies.We find that the ρ′ peak flattens off which may be a sign of chiral restoration, though a study of the finite temperature axial-vector spectral function remains to be carried out.

  16. Chiral Molecules Revisited by Broadband Microwave Spectroscopy

    Science.gov (United States)

    Schnell, Melanie

    2014-06-01

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

  17. Thermal Conductivity of Nanotubes: Effects of Chirality and Isotope Impurity

    OpenAIRE

    Gang, Zhang; Li, Baowen

    2005-01-01

    We study the dependence of thermal conductivity of single walled nanotubes (SWNT) on chirality and isotope impurity by nonequilibrium molecular dynamics method with accurate potentials. It is found that, contrary to electronic conductivity, the thermal conductivity is insensitive to the chirality. The isotope impurity, however, can reduce the thermal conductivity up to 60% and change the temperature dependence behavior. We also study the dependence of thermal conductivity on tube length for t...

  18. Synthesis of Stable and Soluble One-Handed Helical Homopoly(substituted acetylenes without the Coexistence of Any Other Chiral Moieties via Two-Step Polymer Reactions in Membrane State: Molecular Design of the Starting Monomer

    Directory of Open Access Journals (Sweden)

    Takashi Kaneko

    2012-01-01

    Full Text Available A soluble and stable one-handed helical poly(substituted phenylacetylene without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer followed by two-step polymer reactions in membrane state: (1 removing the chiral groups (desubstitution; and (2 introduction of achiral long alkyl groups at the same position as the desubstitution to enhance the solubility of the resulting one-handed helical polymer (resubstitution. The starting chiral monomer should have four characteristic substituents: (i a chiral group bonded to an easily hydrolyzed spacer group; (ii two hydroxyl groups; (iii a long rigid hydrophobic spacer between the chiral group and the polymerizing group; (iv a long achiral group near the chiral group. As spacer group a carbonate ester was selected. The two hydroxyl groups formed intramolecular hydrogen bonds stabilizing a one-handed helical structure in solution before and after the two-step polymer reactions in membrane state. The rigid long hydrophobic spacer, a phenylethynylphenyl group, enhanced the solubility of the starting polymer, and realized effective chiral induction from the chiral side groups to the main chain in the asymmetric-induced polymerization. The long alkyl group near the chiral group avoided shrinkage of the membrane and kept the reactivity of resubstitution in membrane state after removing the chiral groups. The g value (g = ([θ]/3,300/ε for the CD signal assigned to the main chain in the obtained final polymer was almost the same as that of the starting polymer in spite of the absence of any other chiral moieties. Moreover, since the one-handed helical structure was maintained by the intramolecular hydrogen bonds in a solution, direct observation of the one-handed helicity of the final homopolymer has been realized in CD for the solution for the first time.

  19. Synthesis of stable and soluble one-handed helical homopoly(substituted acetylene)s without the coexistence of any other chiral moieties via two-step polymer reactions in membrane state: molecular design of the starting monomer.

    Science.gov (United States)

    Abe, Yunosuke; Aoki, Toshiki; Jia, Hongge; Hadano, Shingo; Namikoshi, Takeshi; Kakihana, Yuriko; Liu, Lijia; Zang, Yu; Teraguchi, Masahiro; Kaneko, Takashi

    2012-01-04

    A soluble and stable one-handed helical poly(substituted phenylacetylene) without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer followed by two-step polymer reactions in membrane state: (1) removing the chiral groups (desubstitution); and (2) introduction of achiral long alkyl groups at the same position as the desubstitution to enhance the solubility of the resulting one-handed helical polymer (resubstitution). The starting chiral monomer should have four characteristic substituents: (i) a chiral group bonded to an easily hydrolyzed spacer group; (ii) two hydroxyl groups; (iii) a long rigid hydrophobic spacer between the chiral group and the polymerizing group; (iv) a long achiral group near the chiral group. As spacer group a carbonate ester was selected. The two hydroxyl groups formed intramolecular hydrogen bonds stabilizing a one-handed helical structure in solution before and after the two-step polymer reactions in membrane state. The rigid long hydrophobic spacer, a phenylethynylphenyl group, enhanced the solubility of the starting polymer, and realized effective chiral induction from the chiral side groups to the main chain in the asymmetric-induced polymerization. The long alkyl group near the chiral group avoided shrinkage of the membrane and kept the reactivity of resubstitution in membrane state after removing the chiral groups. The g value (g = ([θ]/3,300)/ε) for the CD signal assigned to the main chain in the obtained final polymer was almost the same as that of the starting polymer in spite of the absence of any other chiral moieties. Moreover, since the one-handed helical structure was maintained by the intramolecular hydrogen bonds in a solution, direct observation of the one-handed helicity of the final homopolymer has been realized in CD for the solution for the first time.

  20. Chiral Random Matrix Theory and Chiral Perturbation Theory

    CERN Document Server

    Damgaard, P H

    2011-01-01

    Spontaneous breaking of chiral symmetry in QCD has traditionally been inferred indirectly through low-energy theorems and comparison with experiments. Thanks to the understanding of an unexpected connection between chiral Random Matrix Theory and chiral Perturbation Theory, the spontaneous breaking of chiral symmetry in QCD can now be shown unequivocally from first principles and lattice simulations. In these lectures I give an introduction to the subject, starting with an elementary discussion of spontaneous breaking of global symmetries.

  1. Chiral Random Matrix Theory and Chiral Perturbation Theory

    Energy Technology Data Exchange (ETDEWEB)

    Damgaard, Poul H, E-mail: phdamg@nbi.dk [Niels Bohr International Academy and Discovery Center, The Niels Bohr Institute, Blegdamsvej 17, DK-2100 Copenhagen (Denmark)

    2011-04-01

    Spontaneous breaking of chiral symmetry in QCD has traditionally been inferred indirectly through low-energy theorems and comparison with experiments. Thanks to the understanding of an unexpected connection between chiral Random Matrix Theory and chiral Perturbation Theory, the spontaneous breaking of chiral symmetry in QCD can now be shown unequivocally from first principles and lattice simulations. In these lectures I give an introduction to the subject, starting with an elementary discussion of spontaneous breaking of global symmetries.

  2. Light-Directed Dynamic Chirality Inversion in Functional Self-Organized Helical Superstructures.

    Science.gov (United States)

    Bisoyi, Hari Krishna; Li, Quan

    2016-02-24

    Helical superstructures are widely observed in nature, in synthetic polymers, and in supramolecular assemblies. Controlling the chirality (the handedness) of dynamic helical superstructures of molecular and macromolecular systems by external stimuli is a challenging task, but is of great fundamental significance with appealing morphology-dependent applications. Light-driven chirality inversion in self-organized helical superstructures (i.e. cholesteric, chiral nematic liquid crystals) is currently in the limelight because inversion of the handedness alters the chirality of the circularly polarized light that they selectively reflect, which has wide potential for application. Here we discuss the recent developments toward inversion of the handedness of cholesteric liquid crystals enabled by photoisomerizable chiral molecular switches or motors. Different classes of chiral photoresponsive dopants (guests) capable of conferring light-driven reversible chirality inversion of helical superstructures fabricated from different nematic hosts are discussed. Rational molecular designs of chiral molecular switches toward endowing handedness inversion to the induced helical superstructures of cholesteric liquid crystals are highlighted. This Review is concluded by throwing light on the challenges and opportunities in this emerging frontier, and it is expected to provide useful guidelines toward the development of self-organized soft materials with stimuli-directed chirality inversion capability and multifunctional host-guest systems.

  3. Studies of chirality effect of 4-(phenylamino)-pyrrolo[2,1-f][1,2,4]triazine on p38α by molecular dynamics simulations and free energy calculations

    Science.gov (United States)

    Chen, Quan; Cui, Wei; Ji, Mingjuan

    2009-10-01

    4-(Phenylamino)-pyrrolo[2,1-f][1,2,4]triazines have been discovered as inhibitors of p38α. Experimental assays have proven that the configuration of α-Me-benzyl connected with amide at C6 is essential for the binding affinity. The S-configured inhibitor (11j) displays 80 times more potency than the R-configured one (11k). Here we investigated the mechanism how different configurations influence the binding affinity using molecular dynamics simulations, free energy calculations and free energy decomposition analysis. We found that the van der Waals interactions play the most important role in differentiating the activities between 11j and 11k with p38α. The difference of the van der Waals interactions is primarily determined by two residues, LEU108 and LEU167. Consequently stabilization of pyrrolo[2,1-f][1,2,4]triazine ring is important for the activities of inhibitors. Meanwhile we observed that the different configuration of the α-Me-benzyl group leads to the difference of binding between 11j and 11k. In conclusion, our work shows that it is feasible to analyze the chirality effect of inhibitors with different configurations by molecular dynamics simulations and free energy calculations, and provides useful information for drug design.

  4. Can the chirality of the ISM be measured

    Science.gov (United States)

    Pendleton, Y.; Sandford, S. A.; Werner, Michael W.; Lauer, J.; Chang, Sherwood

    1990-04-01

    Many moderately complex carbon-based molecules of the type associated with biological systems can exist in one of two mirror-image forms (left-handed and right-handed), which can be distinguished on the basis of their influence on the state of polarization of a light beam. Both forms are possible in nature; yet in living organisms it is invariably the rule that one of these two species predominates. This gives rise to a net chirality. One possible explanation for the net chirality is that the early earth was somehow seeded from the ISM with an excess of chiral organic compounds which led to the development of life forms which are based on left-handed amino acids and right-handed sugars. Molecular spectroscopy of the interstellar medium (ISM) has revealed a complex variety of molecular species similar to those thought to have been available in the oceans and atmospheres of the earth at the time life formed. The detection of such molecules demonstrates the generality of the chemical processes occurring in both environments. If this generality extends to the processes which produce chirality, it may be possible to detect a net chirality in the ISM. This is of particular interest because determining whether or not net chirality exists elsewhere in the universe is an essential aspect of understanding how life developed on earth and how widely distributed it might be. Researchers report preliminary results of a feasibility study to determine whether or not a net chirality in the ISM can be measured. If laboratory results identify candidate chiral molecules that might exist in the ISM, the next step in this feasibility study will be to estimate the detectability of the chiral signature in astrophysical environments.

  5. Can the chirality of the ISM be measured

    Science.gov (United States)

    Pendleton, Y.; Sandford, S. A.; Werner, Michael W.; Lauer, J.; Chang, Sherwood

    1990-01-01

    Many moderately complex carbon-based molecules of the type associated with biological systems can exist in one of two mirror-image forms (left-handed and right-handed), which can be distinguished on the basis of their influence on the state of polarization of a light beam. Both forms are possible in nature; yet in living organisms it is invariably the rule that one of these two species predominates. This gives rise to a net chirality. One possible explanation for the net chirality is that the early earth was somehow seeded from the ISM with an excess of chiral organic compounds which led to the development of life forms which are based on left-handed amino acids and right-handed sugars. Molecular spectroscopy of the interstellar medium (ISM) has revealed a complex variety of molecular species similar to those thought to have been available in the oceans and atmospheres of the earth at the time life formed. The detection of such molecules demonstrates the generality of the chemical processes occurring in both environments. If this generality extends to the processes which produce chirality, it may be possible to detect a net chirality in the ISM. This is of particular interest because determining whether or not net chirality exists elsewhere in the universe is an essential aspect of understanding how life developed on earth and how widely distributed it might be. Researchers report preliminary results of a feasibility study to determine whether or not a net chirality in the ISM can be measured. If laboratory results identify candidate chiral molecules that might exist in the ISM, the next step in this feasibility study will be to estimate the detectability of the chiral signature in astrophysical environments.

  6. Altered Axial Skeletal Development

    Science.gov (United States)

    The axial skeleton is routinely examined in standard developmental toxicity bioassays and has proven to be sensitive to a wide variety of chemical agents. Dysmorphogenesis in the skull, vertebral column and ribs has been described in both human populations and in laboratory anima...

  7. Chiral anomalies and differential geometry

    Energy Technology Data Exchange (ETDEWEB)

    Zumino, B.

    1983-10-01

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

  8. Superconductivity in a chiral nanotube

    Science.gov (United States)

    Qin, F.; Shi, W.; Ideue, T.; Yoshida, M.; Zak, A.; Tenne, R.; Kikitsu, T.; Inoue, D.; Hashizume, D.; Iwasa, Y.

    2017-02-01

    Chirality of materials are known to affect optical, magnetic and electric properties, causing a variety of nontrivial phenomena such as circular dichiroism for chiral molecules, magnetic Skyrmions in chiral magnets and nonreciprocal carrier transport in chiral conductors. On the other hand, effect of chirality on superconducting transport has not been known. Here we report the nonreciprocity of superconductivity--unambiguous evidence of superconductivity reflecting chiral structure in which the forward and backward supercurrent flows are not equivalent because of inversion symmetry breaking. Such superconductivity is realized via ionic gating in individual chiral nanotubes of tungsten disulfide. The nonreciprocal signal is significantly enhanced in the superconducting state, being associated with unprecedented quantum Little-Parks oscillations originating from the interference of supercurrent along the circumference of the nanotube. The present results indicate that the nonreciprocity is a viable approach toward the superconductors with chiral or noncentrosymmetric structures.

  9. Quarkyonic Chiral Spirals

    CERN Document Server

    Kojo, Toru; McLerran, Larry; Pisarski, Robert D

    2009-01-01

    We consider the formation of chiral density waves in Quarkyonic matter, which is a phase where cold, dense quarks experience confining forces. We model confinement following Gribov and Zwanziger, taking the gluon propagator, in Coulomb gauge and momentum space, as 1/(p^2)^2. We assume that the number of colors, N, is large, and that the quark chemical potential, mu, is much larger than renormalization mass scale, Lambda_QCD. To leading order in 1/N and Lambda_QCD, a gauge theory with Nf flavors of massless quarks in 3+1 dimensions naturally reduces to a gauge theory in 1+1 dimensions, with an enlarged flavor symmetry of SU(2Nf). Through an anomalous chiral rotation, in two dimensions a Fermi sea of massless quarks maps directly onto the corresponding theory in vacuum. A chiral condensate forms locally, and varies with the spatial position, z, as . Following Schon and Thies, we term this two dimensional pion condensate a (Quarkyonic) chiral spiral. Massive quarks also exhibit chiral spirals, with the magnitude...

  10. An Introduction to Chiral Symmetry on the Lattice

    CERN Document Server

    Chandrasekharan, S

    2004-01-01

    The $SU(N_f)_L \\otimes SU(N_f)_R$ chiral symmetry of QCD is of central importance for the nonperturbative low-energy dynamics of light quarks and gluons. Lattice field theory provides a theoretical framework in which these dynamics can be studied from first principles. The implementation of chiral symmetry on the lattice is a nontrivial issue. In particular, local lattice fermion actions with the chiral symmetry of the continuum theory suffer from the fermion doubling problem. The Ginsparg-Wilson relation implies L\\"uscher's lattice variant of chiral symmetry which agrees with the usual one in the continuum limit. Local lattice fermion actions that obey the Ginsparg-Wilson relation have an exact chiral symmetry, the correct axial anomaly, they obey a lattice version of the Atiyah-Singer index theorem, and still they do not suffer from the notorious doubling problem. The Ginsparg-Wilson relation is satisfied exactly by Neuberger's overlap fermions which are a limit of Kaplan's domain wall fermions, as well as ...

  11. Chiral Sensitivity in Electron-Molecule Interactions

    Science.gov (United States)

    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. Molecular recognition on supramolecular systems (XXXV)-- Synthesis of novel b-cyclodextrin derivative bearing pyridinio group and its chiral discrimination of amino acids

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A novel b-cyclodextrin derivative 4 bearing a pyridinio group on the primary side was synthesized by the reaction of 2-aminopyridine with 6-b-cyclodextrin monoaldehyde 3, and its complexation stability constants with several aliphatic amino acids have been determined in phosphate buffer solution ( pH = 7.2, 0.1 mol·L-1) at 25 ℃ by using spectrofluormetric titrations. The stoichiometry is 1︰1 for the inclusion complexation of amino acids with compound 4. Circular dichroism study indicates that the aromatic moiety was embedded shallowly into the cyclodextrin cavity. As a spectral probe, the pyridinio group in the modified cyclodextrin can recognize not only differences of the size and shape of amino acid molecules, but also the L/D-amino acid chiral isomer. As com-pared with mono-[6-(1-pyridinio)-6-deoxy]-b-cyclodextrin 5, compound 4 switched the enantiomer preference for L- to D-isomer, and showed the highest enantioselectivity of 5.4 for D/L-serine. The-se results are discussed from the viewpoints of geometric compensation, induced-fit concept and cooperation of several weak interactions.

  13. Molecular recognition on supramolecular systems (XXXV)——Synthesis of novel β-cyclodextrin derivative bearing pyridinio group and its chiral discrimination of amino acids

    Institute of Scientific and Technical Information of China (English)

    刘育; 康诗钊

    2001-01-01

    A novel p-cyclodextrin derivative 4 bearing a pyridinio group on the primary side was synthesized by the reaction of 2-aminopyridine with 6-p-cyclodextrin monoaldehyde 3, and its complexation stability constants with several aliphatic amino acids have been determined in phosphate buffer solution ( pH = 7.2, 0.1 mol ?L-1) at 25℃by using spectrofluorometric titrations. The stoichiometry is 1 : 1 for the inclusion complexation of amino acids with compound 4. Circular dichroism study indicates that the aromatic moiety was embedded shallowly into the cyclodextrin cavity. As a spectral probe, the pyridinio group in the modified cyclodextrin can recognize not only differences of the size and shape of amino acid molecules, but also the L/D-amino acid chiral iso-mer. As compared with mono-[6-(1-pyridinio)-6-deoxy]-p-cyclodextrin 5, compound 4 switched the enantiomer preference for L- to D-isomer, and showed the highest enantioselectivity of 5.4 for D/L-serine. These results are discussed from the viewpoints of ge

  14. Octet-baryon axial-vector charges and SU(3)-breaking effects in the semileptonic hyperon decays

    CERN Document Server

    Ledwig, T; Geng, L S; Vacas, M J Vicente

    2014-01-01

    The octet-baryon axial-vector charges and the g1/f1 ratios measured in the semileptonic hyperon decays are studied up to O(p^3) using the covariant baryon chiral perturbation theory with explicit decuplet contributions. We clarify the role of different low-energy constants and find a good convergence for the chiral expansion of the axial-vector charges of the baryon octet, g1(0), with O(p^3) corrections typically around 20% of the leading ones. This is a consequence of strong cancellations between different next-to-leading order terms. We show that considering only non-analytic terms is not enough and that analytic terms appearing at the same chiral order play an important role in this description. The same effects still hold for the chiral extrapolation of the axial-vector charges and result in a rather mild quark-mass dependence. As a result, we report a determination of the leading order chiral couplings, D=0.623(61)(17) and F=0.441(47)(2), as obtained from a completely consistent chiral analysis up to O(p...

  15. Chiral Synthons in Pesticide Syntheses

    NARCIS (Netherlands)

    Feringa, Bernard

    1988-01-01

    The use of chiral synthons in the preparation of enantiomerically pure pesticides is described in this chapter. Several routes to chiral synthons based on asymmetric synthesis or on natural products are illustrated. Important sources of chiral building blocks are reviewed. Furthermore the implicatio

  16. Chiral fermions on the lattice

    CERN Document Server

    Jahn, O; Jahn, Oliver; Pawlowski, Jan M.

    2002-01-01

    We discuss topological obstructions to putting chiral fermions on an even dimensional lattice. The setting includes Ginsparg-Wilson fermions, but is more general. We prove a theorem which relates the total chirality to the difference of generalised winding numbers of chiral projection operators. For an odd number of Weyl fermions this implies that particles and anti-particles live in topologically different spaces.

  17. On the axial $U(1)$ symmetry at finite temperature

    CERN Document Server

    Cossu, Guido; Hashimoto, Shoji; Noaki, Jun-ichi; Tomiya, Akio

    2015-01-01

    We study the $U(1)_A$ anomaly in two-flavor lattice QCD at finite temperature with the M\\"obius domain-wall Dirac operator. We generate gauge configurations in the temperature range $(0.9, 1.2) T_c$ on different physical volumes, $L=$ 2--4 fm, and lattice spacings. We measure the difference of the susceptibilities of the flavor non-singlet scalar ($\\chi_\\delta$) and pseudoscalar ($\\chi_\\pi$) mesons. They are related by an axial $U(1)$ transformation and the difference vanishes if the axial $U(1)$ symmetry is respected. We identify the source of axial $U(1)$ symmetry breaking at finite temperature in the lowest eigenmodes, for the observable $\\chi_\\pi - \\chi_\\delta$. We then reweight the M\\"obius domain-wall fermion partition function to that of the overlap-Dirac operator to fully recover chiral symmetry. Our data show a significant discrepancy in the results coming from the M\\"obius domain-wall valence quarks, the overlap valence quarks on our DWF configurations and the reweighted ones that have full chiral s...

  18. Mechanistic insights on cooperative asymmetric multicatalysis using chiral counterions.

    Science.gov (United States)

    Jindal, Garima; Sunoj, Raghavan B

    2014-08-15

    Cooperative multicatalytic methods are steadily gaining popularity in asymmetric catalysis. The use of chiral Brønsted acids such as phosphoric acids in conjunction with a range of transition metals has been proven to be effective in asymmetric synthesis. However, the lack of molecular-level understanding and the accompanying ambiguity on the role of the chiral species in stereoinduction continues to remain an unresolved puzzle. Herein, we intend to disclose some novel transition state models obtained through DFT(B3LYP and M06) computations for a quintessential reaction in this family, namely, palladium-catalyzed asymmetric Tsuji-Trost allylation of aldehydes. The aldehyde is activated as an enamine by the action of a secondary amine (organocatalysis), which then adds to an activated Pd-allylic species (transition metal catalysis) generated through the protonation of allyic alcohol by chiral BINOL-phosphoric acid (Brønsted acid catalysis). We aim to decipher the nature of chiral BINOL-phosphates and their role in creating a quaternary chiral carbon atom in this triple catalytic system. The study reports the first transition state model capable of rationalizing chiral counterion-induced enantioselectivity. It is found that the chiral phosphate acts as a counterion in the stereocontrolling event rather than the conventional ligand mode.

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

    Science.gov (United States)

    Dreiling, Joan

    2016-05-01

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

  20. Sum-Frequency Generation from Chiral Media and Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Na [Univ. of California, Berkeley, CA (United States)

    2006-02-13

    Sum frequency generation (SFG), a second-order nonlinear optical process, is electric-dipole forbidden in systems with inversion symmetry. As a result, it has been used to study chiral media and interfaces, systems intrinsically lacking inversion symmetry. This thesis describes recent progresses in the applications of and new insights into SFG from chiral media and interfaces. SFG from solutions of chiral amino acids is investigated, and a theoretical model explaining the origin and the strength of the chiral signal in electronic-resonance SFG spectroscopy is discussed. An interference scheme that allows us to distinguish enantiomers by measuring both the magnitude and the phase of the chiral SFG response is described, as well as a chiral SFG microscope producing chirality-sensitive images with sub-micron resolution. Exploiting atomic and molecular parity nonconservation, the SFG process is also used to solve the Ozma problems. Sum frequency vibrational spectroscopy is used to obtain the adsorption behavior of leucine molecules at air-water interfaces. With poly(tetrafluoroethylene) as a model system, we extend the application of this surface-sensitive vibrational spectroscopy to fluorine-containing polymers.

  1. Chiral Quantum Optics

    CERN Document Server

    Lodahl, Peter; Stobbe, Søren; Schneeweiss, Philipp; Volz, Jürgen; Rauschenbeutel, Arno; Pichler, Hannes; Zoller, Peter

    2016-01-01

    At the most fundamental level, the interaction between light and matter is manifested by the emission and absorption of single photons by single quantum emitters. Controlling light--matter interaction is the basis for diverse applications ranging from light technology to quantum--information processing. Many of these applications are nowadays based on photonic nanostructures strongly benefitting from their scalability and integrability. The confinement of light in such nanostructures imposes an inherent link between the local polarization and propagation direction of light. This leads to {\\em chiral light--matter interaction}, i.e., the emission and absorption of photons depend on the propagation direction and local polarization of light as well as the polarization of the emitter transition. The burgeoning research field of {\\em chiral quantum optics} offers fundamentally new functionalities and applications both for single emitters and ensembles thereof. For instance, a chiral light--matter interface enables...

  2. Doped Chiral Polymer Metamaterials

    Science.gov (United States)

    Park, Cheol (Inventor); Kang, Jin Ho (Inventor); Gordon, Keith L. (Inventor); Sauti, Godfrey (Inventor); Lowther, Sharon E. (Inventor); Bryant, Robert G. (Inventor)

    2017-01-01

    Some implementations provide a composite material that includes a first material and a second material. In some implementations, the composite material is a metamaterial. The first material includes a chiral polymer (e.g., crystalline chiral helical polymer, poly-.gamma.-benzyl-L-glutamate (PBLG), poly-L-lactic acid (PLA), polypeptide, and/or polyacetylene). The second material is within the chiral polymer. The first material and the second material are configured to provide an effective index of refraction value for the composite material of 1 or less. In some implementations, the effective index of refraction value for the composite material is negative. In some implementations, the effective index of refraction value for the composite material of 1 or less is at least in a wavelength of one of at least a visible spectrum, an infrared spectrum, a microwave spectrum, and/or an ultraviolet spectrum.

  3. [Chirality and drugs].

    Science.gov (United States)

    Testa, B; Reist, M; Carrupt, P A

    2000-07-01

    The two enantiomers of a chiral drug may have vastly different pharmacodynamic and pharmacokinetic properties. As a result, the research and development of chiral drugs raises specific problems some of which are discussed here. Thus, various pharmacokinetic interactions may involve two enantiomers, as seen for example when one enantiomer inhibits the metabolism of the other and modifies its effects. A different situation occurs when a third compound stereoselectively inhibits the metabolism of one of the two enantiomers. Another problem examined here results from the lack of configurational stability of some chiral drugs, a little known phenomenon whose consequences can be of pharmacological or pharmaceutical significance depending on the rate of the reaction of racemization or epimerisation. In-depth investigations are needed before choosing between a eutomer or a racemate.

  4. Chiral quark model

    Indian Academy of Sciences (India)

    H Weigel

    2003-11-01

    In this talk I review studies of hadron properties in bosonized chiral quark models for the quark flavor dynamics. Mesons are constructed from Bethe–Salpeter equations and baryons emerge as chiral solitons. Such models require regularization and I show that the two-fold Pauli–Villars regularization scheme not only fully regularizes the effective action but also leads the scaling laws for structure functions. For the nucleon structure functions the present approach serves to determine the regularization prescription for structure functions whose leading moments are not given by matrix elements of local operators. Some numerical results are presented for the spin structure functions.

  5. Binary mixtures of chiral gases

    CERN Document Server

    Presilla, Carlo

    2015-01-01

    A possible solution of the well known paradox of chiral molecules is based on the idea of spontaneous symmetry breaking. At low pressure the molecules are delocalized between the two minima of a given molecular potential while at higher pressure they become localized in one minimum due to the intermolecular dipole-dipole interactions. Evidence for such a phase transition is provided by measurements of the inversion spectrum of ammonia and deuterated ammonia at different pressures. In particular, at pressure greater than a critical value no inversion line is observed. These data are well accounted for by a model previously developed and recently extended to mixtures. In the present paper, we discuss the variation of the critical pressure in binary mixtures as a function of the fractions of the constituents.

  6. Surface nanoscale axial photonics

    CERN Document Server

    Sumetsky, M

    2011-01-01

    Dense photonic integration promises to revolutionize optical computing and communications. However, efforts towards this goal face unacceptable attenuation of light caused by surface roughness in microscopic devices. Here we address this problem by introducing Surface Nanoscale Axial Photonics (SNAP). The SNAP platform is based on whispering gallery modes circulating around the optical fiber surface and undergoing slow axial propagation readily described by the one-dimensional Schr\\"odinger equation. These modes can be steered with dramatically small nanoscale variation of the fiber radius, which is quite simple to introduce in practice. The extremely low loss of SNAP devices is achieved due to the fantastically low surface roughness inherent in a drawn fiber surface. In excellent agreement with the developed theory, we experimentally demonstrate localization of light in quantum wells, halting light by a point source, tunneling through potential barriers, dark states, etc. This demonstration, prototyping basi...

  7. A numerical study of non-perturbative corrections to the Chiral Separation Effect in quenched finite-density QCD

    CERN Document Server

    Puhr, M

    2016-01-01

    We use exactly chiral overlap lattice fermions to investigate the Chiral Separation Effect in quenched QCD at finite density. We employ a recently developed numerical method which allows, for the first time, to address the transport properties of exactly chiral lattice fermions with non-zero chemical potential. Studying the axial current along the external magnetic field, we find a linear dependence consistent with the free fermion result for topologically trivial gauge field configurations. However, for configurations with nontrivial topology in the confinement regime the axial current is strongly suppressed due to contributions of topological modes of the Dirac operator, which suggests that non-perturbative corrections to the Chiral Separation Effect have topological origin.

  8. Nanoconfinement-induced structures in chiral liquid crystals.

    Science.gov (United States)

    Melle, Michael; Theile, Madlona; Hall, Carol K; Schoen, Martin

    2013-08-28

    We employ Monte Carlo simulations in a specialized isothermal-isobaric and in the grand canonical ensemble to study structure formation in chiral liquid crystals as a function of molecular chirality. Our model potential consists of a simple Lennard-Jones potential, where the attractive contribution has been modified to represent the orientation dependence of the interaction between a pair of chiral liquid-crystal molecules. The liquid crystal is confined between a pair of planar and atomically smooth substrates onto which molecules are anchored in a hybrid fashion. Hybrid anchoring allows for the formation of helical structures in the direction perpendicular to the substrate plane without exposing the helix to spurious strains. At low chirality, we observe a cholesteric phase, which is transformed into a blue phase at higher chirality. More specifically, by studying the unit cell and the spatial arrangement of disclination lines, this blue phase can be established as blue phase II. If the distance between the confining substrates and molecular chirality are chosen properly, we see a third structure, which may be thought of as a hybrid, exhibiting mixed features of a cholesteric and a blue phase.

  9. Nanoconfinement-Induced Structures in Chiral Liquid Crystals

    Directory of Open Access Journals (Sweden)

    Carol K. Hall

    2013-08-01

    Full Text Available We employ Monte Carlo simulations in a specialized isothermal-isobaric and in the grand canonical ensemble to study structure formation in chiral liquid crystals as a function of molecular chirality. Our model potential consists of a simple Lennard-Jones potential, where the attractive contribution has been modified to represent the orientation dependence of the interaction between a pair of chiral liquid-crystal molecules. The liquid crystal is confined between a pair of planar and atomically smooth substrates onto which molecules are anchored in a hybrid fashion. Hybrid anchoring allows for the formation of helical structures in the direction perpendicular to the substrate plane without exposing the helix to spurious strains. At low chirality, we observe a cholesteric phase, which is transformed into a blue phase at higher chirality. More specifically, by studying the unit cell and the spatial arrangement of disclination lines, this blue phase can be established as blue phase II. If the distance between the confining substrates and molecular chirality are chosen properly, we see a third structure, which may be thought of as a hybrid, exhibiting mixed features of a cholesteric and a blue phase.

  10. Synthesis and Catalytic Asymmetric Reaction of Chiral Pyridine Prolinol Derivatives

    Institute of Scientific and Technical Information of China (English)

    CHEN Xiao; ZHANG Yong-Xin; DU Da-Ming; HUA Wen-Ting

    2003-01-01

    @@ The enantioselective reduction of prochiral ketones with borane in the presence of a chiral ligand leading to enantiomerically pure secondary alcohols has received considerable attention in recent years. [1] Enantiomerically pure secondary alcohols are important intermediates for the synthesis of various other organic compounds such as halides, esters, ethers, ketones and amines. To the best of our knowledge, the use of pyridine prolinol derivatives in the reduction of ketones has not been reported so far. Thus, it should be of interest to investigate the catalytic a bility of such ligands. We have an ongoing project in the synthesis and application of chiral pyridine derivatives in chiral molecular recognition[2] and we want to evaluate the effect resulting from the introduction of a pyridinyl moiety onto the catalysts. We expect that the cooperation of pyridine unit and chiral prolinol unit in new ligands may result in unique properties for catalytic reaction.

  11. Dimers of cyclic carbonates: chirality recognition in battery solvents and energy storage.

    Science.gov (United States)

    Kollipost, Franz; Hesse, Susanne; Lee, Juhyon J; Suhm, Martin A

    2011-08-21

    Dimers of ethylene carbonate and propylene carbonate are created in supersonic jet expansions and characterized by FTIR spectroscopy. Fermi resonances are switched on and off by dimerization. There is a unique centrosymmetric dimer of ethylene carbonate in a pronounced case of complementary chirality synchronization, contributing to its energy storage capacity at melting. Two chiral propylene carbonate molecules combine in more intricate ways. If they have the same handedness, one of them is forced into an axial conformation and the binding partner stays in the more stable equatorial structure. If they have opposite handedness, centrosymmetric dimers of either axial or equatorial conformations are formed. This suggests the usefulness of chirality control in elucidating ionic transport mechanisms in battery solvents and asymmetric catalysis in such solvents.

  12. Interweaving Chiral Spirals

    CERN Document Server

    Kojo, Toru; Fukushima, Kenji; McLerran, Larry; Pisarski, Robert D

    2011-01-01

    We elaborate how to construct the interweaving chiral spirals in (2+1) dimensions, that is defined as a superposition of differently oriented chiral spirals. We divide the two-dimensional Fermi sea into distinct wedges characterized by the opening angle 2 Theta and the depth Q \\simeq pF, where pF is the Fermi momentum. Each wedge earns an energy gain by forming a single chiral spiral. The optimal values for Theta and Q are chosen by the balance between this energy gain and the energy costs from the deformed Fermi surface (dominant at large Theta) and patch-patch interactions (dominant at small Theta). We estimate these energy gains and costs by means of the expansions in terms of 1/Nc, Lambda_QCD/Q, and Theta using a non-local four-Fermi interaction model: At small 1/Nc the mass gap (chiral condensate) is large enough and the interaction among quarks and the condensate is local in momentum space thanks to the form factor in our non-local model. The fact that patch-patch interactions lie only near the patch bo...

  13. Simplicial chiral models

    CERN Document Server

    Rossi, P; Rossi, Paolo; Tan, Chung I

    1995-01-01

    Principal chiral models on a d-1 dimensional simplex are introduced and studied analytically in the large N limit. The d = 0 , 2, 4 and \\infty models are explicitly solved. Relationship with standard lattice models and with few-matrix systems in the double scaling limit are discussed.

  14. Evidence of effective axial U (1 ) symmetry restoration at high temperature QCD

    Science.gov (United States)

    Tomiya, A.; Cossu, G.; Aoki, S.; Fukaya, H.; Hashimoto, S.; Kaneko, T.; Noaki, J.; Jlqcd Collaboration

    2017-08-01

    We study the axial U (1 ) symmetry at a finite temperature in two-flavor lattice QCD. Employing the Möbius domain-wall fermions, we generate gauge configurations slightly above the critical temperature Tc with different lattice sizes L =2 - 4 fm . Our action allows frequent topology tunneling while keeping good chiral symmetry close enough to that of overlap fermions. This allows us to recover full chiral symmetry by an overlap/domain-wall reweighting. Above the phase transition, a strong suppression of the low-lying modes is observed in both overlap and domain-wall Dirac spectra. We, however, find a sizable violation of the Ginsparg-Wilson relation in the Möbius domain-wall Dirac eigenmodes, which dominates the signals of the axial U (1 ) symmetry breaking near the chiral limit. We also find that the use of the overlap fermion only in the valence sector is dangerous since it suffers from the artifacts due to partial quenching. Reweighting the Möbius domain-wall fermion determinant to that of the overlap fermion, we observe the axial U(1) breaking to vanish in the chiral limit, which is stable against the changes of the lattice volume and lattice spacing.

  15. One-loop corrections to the baryon axial vector current

    Indian Academy of Sciences (India)

    M A Hernández-Ruíz

    2012-10-01

    The symmetry breaking corrections to the pion–baryon couplings vanish to first order in $1/N_{c}$, where $N_{c}$ is the number of colours. Loop graphs with octet and decuplet intermediate states cancel to various orders in $N_{c}$ as a consequence of the large-$N_{c}$ spin-flavour symmetry of QCD baryons. The baryon axial vector current is computed at one-loop order in heavy baryon chiral perturbation theory in the large Nc limit. $1/N_{c}$ corrections in the case of $g_{A}$ in QCD are presented here.

  16. Chiral magnetic effect without chirality source in asymmetric Weyl semimetals

    CERN Document Server

    Kharzeev, Dmitri; Meyer, Rene

    2016-01-01

    We describe a new type of the Chiral Magnetic Effect (CME) that should occur in Weyl semimetals with an asymmetry in the dispersion relations of the left- and right-handed chiral Weyl fermions. In such materials, time-dependent pumping of electrons from a non-chiral external source generates a non-vanishing chiral chemical potential. This is due to the different capacities of the left- and right-handed (LH and RH) chiral Weyl cones arising from the difference in the density of states in the LH and RH cones. The chiral chemical potential then generates, via the chiral anomaly, a current along the direction of an applied magnetic field even in the absence of an external electric field. The source of chirality imbalance in this new setup is thus due to the band structure of the system and the presence of (non-chiral) electron source, and not due to the parallel electric and magnetic fields. We illustrate the effect by an argument based on the effective field theory, and by the chiral kinetic theory calculation f...

  17. Relaxation Dynamics in Photoexcited Chiral Molecules Studied by Time-Resolved Photoelectron Circular Dichroism: Toward Chiral Femtochemistry

    CERN Document Server

    Comby, Antoine; Boggio-Pasqua, Martial; Descamps, Dominique; Légaré, Francois; Nahon, Laurent; Petit, Stéphane; Pons, Bernard; Fabre, Baptiste; Mairesse, Yann; Blanchet, Valérie

    2016-01-01

    Unravelling the main initial dynamics responsible for chiral recognition is a key stepin the understanding of many biological processes. However this challenging task requires a sensitive enantiospecic probe to investigate molecular dynamics on their natural femtosecond timescale. Here we show that, in the gas phase, the ultrafast relaxationdynamics of photoexcited chiral molecules can be tracked by recording Time-ResolvedPhotoElectron Circular Dichroism (TR-PECD) resulting from the photoionisation bya circularly polarized probe pulse. A large forward/backward asymmetry along theprobe propagation axis is observed in the photoelectron angular distribution. Its evolution with pump-probe delay reveals ultrafast dynamics that are inaccessible in theangle-integrated photoelectron spectrum nor via the usual electron emission anisotropyparameter ($\\beta$). PECD, which originates from the electron scattering in the chiral molecular potential, appears as a new sensitive observable for ultrafast molecular dynamicsin ch...

  18. Experimental signatures of the mixed axial-gravitational anomaly in the Weyl semimetal NbP

    Science.gov (United States)

    Gooth, Johannes; Niemann, Anna C.; Meng, Tobias; Grushin, Adolfo G.; Landsteiner, Karl; Gotsmann, Bernd; Menges, Fabian; Schmidt, Marcus; Shekhar, Chandra; Süß, Vicky; Hühne, Ruben; Rellinghaus, Bernd; Felser, Claudia; Yan, Binghai; Nielsch, Kornelius

    2017-07-01

    The conservation laws, such as those of charge, energy and momentum, have a central role in physics. In some special cases, classical conservation laws are broken at the quantum level by quantum fluctuations, in which case the theory is said to have quantum anomalies. One of the most prominent examples is the chiral anomaly, which involves massless chiral fermions. These particles have their spin, or internal angular momentum, aligned either parallel or antiparallel with their linear momentum, labelled as left and right chirality, respectively. In three spatial dimensions, the chiral anomaly is the breakdown (as a result of externally applied parallel electric and magnetic fields) of the classical conservation law that dictates that the number of massless fermions of each chirality are separately conserved. The current that measures the difference between left- and right-handed particles is called the axial current and is not conserved at the quantum level. In addition, an underlying curved space-time provides a distinct contribution to a chiral imbalance, an effect known as the mixed axial-gravitational anomaly, but this anomaly has yet to be confirmed experimentally. However, the presence of a mixed gauge-gravitational anomaly has recently been tied to thermoelectrical transport in a magnetic field, even in flat space-time, suggesting that such types of mixed anomaly could be experimentally probed in condensed matter systems known as Weyl semimetals. Here, using a temperature gradient, we observe experimentally a positive magneto-thermoelectric conductance in the Weyl semimetal niobium phosphide (NbP) for collinear temperature gradients and magnetic fields that vanishes in the ultra-quantum limit, when only a single Landau level is occupied. This observation is consistent with the presence of a mixed axial-gravitational anomaly, providing clear evidence for a theoretical concept that has so far eluded experimental detection.

  19. Detecting the chirality for coupled quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Cao Huijuan [Institute for Condensed Matter Physics, School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou 510631 (China); Hu Lian [Institute for Condensed Matter Physics, School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou 510631 (China)], E-mail: huliancaohj@yahoo.com

    2008-04-21

    We propose a scheme to detect the chirality for a system consisting of three coupled quantum dots. The chirality is found to be determined by the frequency of the transition between chiral states under the chiral symmetry broken perturbation. The results are important to construct quantum gates and to demonstrate chiral entangle states in the triangle spin dots.

  20. Kaon Thresholds and Two-Flavor Chiral Expansions for Hyperons

    Energy Technology Data Exchange (ETDEWEB)

    Fu-Jiun Jiang, Brian C. Tiburzi, Andre Walker-Loud

    2011-01-01

    Two-flavor chiral expansions provide a useful perturbative framework to study hadron properties. Such expansions should exhibit marked improvement over the conventional three-flavor chiral expansion. Although one can theoretically formulate two-flavor theories for the various hyperon multiplets, the nearness of kaon thresholds can seriously undermine the effectiveness of the perturbative expansion in practice. We investigate the importance of virtual kaon thresholds on hyperon properties, specifically their masses and isovector axial charges. Using a three-flavor expansion that includes SU(3) breaking effects, we uncover the underlying expansion parameter governing the description of virtual kaon thresholds. For spin-half hyperons, this expansion parameter is quite small. Consequently virtual kaon contributions are well described in the two-flavor theory by terms analytic in the pion mass-squared. For spin three-half hyperons, however, one is closer to the kaon production threshold, and the expansion parameter is not as small. Breakdown of SU(2) chiral perturbation theory is shown to arise from a pole in the expansion parameter associated with the kaon threshold. Estimating higher-order corrections to the expansion parameter is necessary to ascertain whether the two-flavor theory of spin three-half hyperons remains perturbative. We find that, despite higher-order corrections, there is a useful perturbative expansion for the masses and isovector axial charges of both spin-half and spin three-half hyperons.

  1. Critical Axial Load

    Directory of Open Access Journals (Sweden)

    Walt Wells

    2008-01-01

    Full Text Available Our objective in this paper is to solve a second order differential equation for a long, simply supported column member subjected to a lateral axial load using Heun's numerical method. We will use the solution to find the critical load at which the column member will fail due to buckling. We will calculate this load using Euler's derived analytical approach for an exact solution, as well as Euler's Numerical Method. We will then compare the three calculated values to see how much they deviate from one another. During the critical load calculation, it will be necessary to calculate the moment of inertia for the column member.

  2. Renormalization of the baryon axial vector current in large-N{sub c}

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez-Ruiz, Maria de los Angeles [University Aut. de San Luis Potosi, Av. V. Carranza 2405, 78216, San Luis Potosi (Mexico)

    2010-07-01

    The baryon axial vector current is computed at one-loop order in heavy baryon chiral perturbation theory in the large-N{sub c} limit, where N{sub c} is the number of colors. Loop graphs with octet and decuplet intermediate states cancel to various orders in N{sub c} as a consequence of the large-N{sub c} spin-flavor symmetry of QCD baryons. We present a preliminary study of the convergence of the chiral expansion with 1/N{sub c} corrections in the case of g{sub A} = N{sub c} = 3. (author)

  3. Structural determination of molecular stereochemistry using VCD spectroscopy and a conformational code: absolute configuration and solution conformation of a chiral liquid pesticide, (R)-(+)-malathion.

    Science.gov (United States)

    Izumi, Hiroshi; Ogata, Atsushi; Nafie, Laurence A; Dukor, Rina K

    2009-01-01

    The absolute configuration and solution conformation of (R)-(+)-malathion were determined by using vibrational circular dichroism spectroscopy and a fragment-conformational search with a recently published conformational code. The determination of molecular stereochemistry was carried out without a conformational search using molecular mechanics calculations. Density functional theory calculations of the fragments of (R)-malathion, ethyl propionate, (R)-ethyl 2-(methylthio)propanoate, (R)-diethyl 2-(methylthio)succinate, and O,O,S-trimethyl phosphorodithioate were carried out, and the principal conformational features of the fragments were profiled. This fragment-conformational search reduces the time needed for the selection of the predominant conformations for (R)-malathion and significantly improves the accuracy of the determination of absolute configuration.

  4. Soldering Chiralities; 2, Non-Abelian Case

    CERN Document Server

    Wotzasek, C

    1996-01-01

    We study the non-abelian extension of the soldering process of two chiral WZW models of opposite chiralities, resulting in a (non-chiral) WZW model living in a 2D space-time with non trivial Riemanian curvature.

  5. Chiral current generation in QED by longitudinal photons

    Directory of Open Access Journals (Sweden)

    J.L. Acosta Avalo

    2016-08-01

    Full Text Available We report the generation of a pseudovector electric current having imbalanced chirality in an electron–positron strongly magnetized gas in QED. It propagates along the external applied magnetic field B as a chiral magnetic effect in QED. It is triggered by a perturbative electric field parallel to B, associated to a pseudovector longitudinal mode propagating along B. An electromagnetic chemical potential was introduced, but our results remain valid even when it vanishes. A nonzero fermion mass was assumed, which is usually considered vanishing in the literature. In the quantum field theory formalism at finite temperature and density, an anomaly relation for the axial current was found for a medium of massive fermions. It bears some analogy to the Adler–Bell–Jackiw anomaly. From the expression for the chiral current in terms of the photon self-energy tensor in a medium, it is obtained that electrons and positrons scattered by longitudinal photons (inside the light cone contribute to the chiral current, as well as the to pair creation due to longitudinal photons (out of light cone. In the static limit, an electric pseudovector current is obtained in the lowest Landau level.

  6. Chiral current generation in QED by longitudinal photons

    Energy Technology Data Exchange (ETDEWEB)

    Acosta Avalo, J.L., E-mail: jlacosta@instec.cu [Instituto Superior de Tecnologías y Ciencias Aplicadas (INSTEC), Ave Salvador Allende, No. 1110, Vedado, La Habana 10400 (Cuba); Pérez Rojas, H., E-mail: hugo@icimaf.cu [Instituto de Cibernética, Matemática y Física (ICIMAF), Calle E esq 15, No. 309, Vedado, La Habana 10400 (Cuba)

    2016-08-15

    We report the generation of a pseudovector electric current having imbalanced chirality in an electron–positron strongly magnetized gas in QED. It propagates along the external applied magnetic field B as a chiral magnetic effect in QED. It is triggered by a perturbative electric field parallel to B, associated to a pseudovector longitudinal mode propagating along B. An electromagnetic chemical potential was introduced, but our results remain valid even when it vanishes. A nonzero fermion mass was assumed, which is usually considered vanishing in the literature. In the quantum field theory formalism at finite temperature and density, an anomaly relation for the axial current was found for a medium of massive fermions. It bears some analogy to the Adler–Bell–Jackiw anomaly. From the expression for the chiral current in terms of the photon self-energy tensor in a medium, it is obtained that electrons and positrons scattered by longitudinal photons (inside the light cone) contribute to the chiral current, as well as the to pair creation due to longitudinal photons (out of light cone). In the static limit, an electric pseudovector current is obtained in the lowest Landau level.

  7. Chiral current generation in QED by longitudinal photons

    Science.gov (United States)

    Acosta Avalo, J. L.; Pérez Rojas, H.

    2016-08-01

    We report the generation of a pseudovector electric current having imbalanced chirality in an electron-positron strongly magnetized gas in QED. It propagates along the external applied magnetic field B as a chiral magnetic effect in QED. It is triggered by a perturbative electric field parallel to B, associated to a pseudovector longitudinal mode propagating along B. An electromagnetic chemical potential was introduced, but our results remain valid even when it vanishes. A nonzero fermion mass was assumed, which is usually considered vanishing in the literature. In the quantum field theory formalism at finite temperature and density, an anomaly relation for the axial current was found for a medium of massive fermions. It bears some analogy to the Adler-Bell-Jackiw anomaly. From the expression for the chiral current in terms of the photon self-energy tensor in a medium, it is obtained that electrons and positrons scattered by longitudinal photons (inside the light cone) contribute to the chiral current, as well as the to pair creation due to longitudinal photons (out of light cone). In the static limit, an electric pseudovector current is obtained in the lowest Landau level.

  8. Out-of-Equilibrium Chiral Magnetic Effect at Strong Coupling

    CERN Document Server

    Lin, Shu

    2013-01-01

    We study the charge transports originating from triangle anomaly in out-of-equilibrium conditions in the framework of AdS/CFT correspondence at strong coupling, to gain useful insights on possible charge separation effects that may happen in the very early stages of heavy-ion collisions. We first construct a gravity background of a homogeneous mass shell with a finite (axial) charge density gravitationally collapsing to a charged blackhole, which serves as a dual model for out-of-equilibrium charged plasma undergoing thermalization. We find that a finite charge density in the plasma slows down the thermalization. We then study the out-of-equilibrium properties of Chiral Magnetic Effect and Chiral Magnetic Wave in this background. As the medium thermalizes, the magnitude of chiral magnetic conductivity and the response time delay grow. We find a dynamical peak in the spectral function of retarded current correlator, which we identify as an out-of-equilibrium chiral magnetic wave. The group velocity of the out-...

  9. Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study.

    Science.gov (United States)

    Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

    2015-09-21

    Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au-allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive.

  10. Chiral Dynamics 2006

    Science.gov (United States)

    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

  11. Chiral Biomarkers in Meteorites

    Science.gov (United States)

    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

  12. Enantiospecific adsorption of cysteine on a chiral Au34 cluster

    Science.gov (United States)

    de Jesús Pelayo, José; Valencia, Israel; Díaz, Gabriela; López-Lozano, Xóchitl; Garzón, Ignacio L.

    2015-12-01

    The interaction of biological molecules like chiral amino acids with chiral metal clusters is becoming an interesting and active field of research because of its potential impact in, for example, chiral molecular recognition phenomena. In particular, the enantiospecific adsorption (EA) of cysteine (Cys) on a chiral Au55 cluster was theoretically predicted a few years ago. In this work, we present theoretical results, based on density functional theory, of the EA of non-zwitterionic cysteine interacting with the C3-Au34 chiral cluster, which has been experimentally detected in gas phase, using trapped ion electron diffraction. Our results show that, indeed, the adsorption energy of the amino acid depends on which enantiomers participate in the formation Cys-Au34 chiral complex. EA was obtained in the adsorption modes where both the thiol, and the thiol-amino functional groups of Cys are adsorbed on low-coordinated sites of the metal cluster surface. Similarly to what was obtained for the Cys-Au55 chiral complex, in the present work, it is found that the EA is originated from the different strength and location of the bond between the COOH functional group and surface Au atoms of the Au34 chiral cluster. Calculations of the vibrational spectrum for the different Cys-Au34 diastereomeric complexes predict the existence of a vibro-enantiospecific effect, indicating that the vibrational frequencies of the adsorbed amino acid depend on its handedness. Contribution to the Topical Issue "Atomic Cluster Collisions (7th International Symposium)", edited by G. Delgado Barrio, A. Solov'Yov, P. Villarreal, R. Prosmiti.

  13. Generalized simplicial chiral models

    CERN Document Server

    Alimohammadi, M

    2000-01-01

    Using the auxiliary field representation of the simplicial chiral models on a (d-1)-dimensional simplex, we generalize the simplicial chiral models by replacing the term Tr$(AA^{\\d})$ in the Lagrangian of these models, by an arbitrary class function of $AA^{\\d}; V(AA^{\\d})$. This is the same method that has been used in defining the generalized two-dimensional Yang-Mills theories (gYM_2) from ordinary YM_2. We call these models, the " generalized simplicial chiral models ". With the help of the results of one-link integral over a U(N) matrix, we compute the large-N saddle-point equations for eigenvalue density function $\\ro (z)$ in the weak ($\\b >\\b_c$) and strong ($\\b <\\b_c$) regions. In d=2, where the model somehow relates to gYM_2 theory, we solve the saddle-point equations and find $\\ro (z)$ in two region, and calculate the explicit value of critical point $\\b_c$ for $V(B)=TrB^n (B=AA^{\\d})$. For $V(B)=Tr B^2,Tr B^3$ and Tr$B^4$, we study the critical behaviour of the model at d=2, and by calculating t...

  14. Chiral nuclear thermodynamics

    CERN Document Server

    Fiorilla, Salvatore; Weise, Wolfram

    2011-01-01

    We calculate the equation of state of nuclear matter for arbitrary isospin-asymmetry up to three loop order in the free energy density in the framework of in-medium chiral perturbation theory. In our approach 1\\pi- and 2\\pi-exchange dynamics with the inclusion of the \\Delta-isobar excitation as an explicit degree of freedom, corresponding to the long- and intermediate-range correlations, are treated explicitly. Few contact terms fixed to reproduce selected known properties of nuclear matter encode the short-distance physics. Two-body as well as three-body forces are systematically included. We find a critical temperature of about 15 MeV for symmetric nuclear matter. We investigate the dependence of the liquid-gas first-order phase transition on isospin-asymmetry. In the same chiral framework we calculate the chiral condensate of isospin-symmetric nuclear matter at finite temperatures. The contribution of the \\Delta-isobar excitation is essential for stabilizing the condensate. As a result, we find no indicati...

  15. Free-standing chiral plasmonics

    Science.gov (United States)

    Leong, Eunice Sok Ping; Deng, Jie; Wu, Siji; Khoo, Eng Huat; Liu, Yan Jun

    2014-11-01

    Chiral plasmonic nanostructures offer the ability to achieve strong optical circular dichroism (CD) activity over a broad spectral range, which has been challenging for chiral molecules. Chiral plasmonic nanostructures have been extensively studied based on top-down and bottom-up fabrication techniques. Particularly, in the top-down electron-beam lithography, 3D plasmonic nanostructure fabrication involves layer-by-layer patterning and complex alignment, which is time-consuming and causes many defects in the structures. Here, we present a free-standing 3D chiral plamonic nanostructures using the electron-beam lithography technique with much simplified fabrication processes. The 3D chiral plasmonic nanostructures consist of a free-standing ultrathin silicon nitride membrane with well-aligned L-shape metal nanostructures on one side and disk-shape ones on the other side. The free-standing membrane provides an ultra-smooth metal/dielectric interface and uniformly defines the gap between the upper and lower layers in an array of chiral nanostructures. Such free-standing chiral plasmonic nanostructures exhibit strong CD at optical frequencies, which can be engineered by simply changing the disk size on one side of the membrane. Experimental results are in good agreement with the finite-difference time-domain simulations. Such free-standing chiral plasmonics holds great potential for chirality analysis of biomolecules, drugs, and chemicals.

  16. Strain induced Chiral Magnetic Effect in Weyl semimetals

    CERN Document Server

    Cortijo, Alberto; Landsteiner, Karl; Vozmediano, María A H

    2016-01-01

    We argue that strain applied to a time-reversal and inversion breaking Weyl semi-metal in a magnetic field can induce an electric current via the chiral magnetic effect. A tight binding model is used to show that strain generically changes the locations in the Brillouin zone but also the energies of the band touching points (tips of the Weyl cones). Since axial charge in a Weyl semi-metal can relax via inter-valley scattering processes the induced current will decay with a timescale given by the lifetime of a chiral quasiparticle. We estimate the strength and lifetime of the current for typical material parameters and find that it should be experimentally observable.

  17. Ftmw Study of the Chirality Recognition Between Two Different Chiral Molecules: the Glycidol-Propylene Oxide Complex

    Science.gov (United States)

    Thomas, Javix; Sunahori, Fumie X.; Borho, Nicole; Xu, Yunjie

    2010-06-01

    The chirality recognition effect between the prototype chiral molecular systems, i.e. glycidol and propylene oxide has been studied using rotational spectroscopy and high level ab initio calculations. Extensive ab initio calculations have been performed to locate all possible low energy conformers of the diastereomeric pair and twenty eight minima have been found. The four most sable hetero and four homo chiral dimers, formed from the two lowest energy monomer conformations G+g- and G-g+ of the glycidol, were predicted to be close in their stability. Jet-cooled rotational spectra of some of them have been detected using a pulsed molecular beam Fourier transform microwave spectrometer and been assigned for the first time. All the low energy binary conformers observed show one primary intermolecular O-H- - -O hydrogen bond and two secondary intermolecular C-H- - -O hydrogen bonds. The induced fit phenomenon detectedwill be discussed.

  18. Enantiomeric in vitro DNA binding, pBR322 DNA cleavage and molecular docking studies of chiral L- and D-ternary copper(II) complexes of histidine and picolinic acid.

    Science.gov (United States)

    Parveen, Shazia; Arjmand, Farukh; Ahmad, Iqbal

    2014-01-05

    Novel chiral ternary Cu(II) and Ni(II) complexes of l/d-histidine and picolinic acid, 1 and 2(a and b) were synthesized and characterized by elemental analysis, molar conductance and spectroscopic data (IR, NMR, EPR, UV-vis). In vitro DNA binding profile of both Cu(II) and Ni(II) complexes have been investigated by UV-vis titrations, while fluorescence spectroscopy, circular dichroism and viscosity measurements were carried out for Cu(II) complexes 1(a and b). Both the enantiomers of 1 and 2(a and b) bind to CT DNA via electrostatic interactions and the intrinsic binding constant, Kb values for complexes 1 and 2(a and b) were found to be 5.6×10(4), 9.8×10(3), 8.2×10(3) and 6.7×10(3)M(-1), respectively suggesting greater binding propensity of l-form of Cu(II) complex 1a. The DNA cleavage activity of complexes 1(a and b), investigated by agarose gel electrophoresis suggested an oxidative pathway for DNA cleavage. Further, the molecular docking studies of complexes 1(a and b) were carried out with B-DNA revealing that the complexes bind to the adenine-thymine residues in the minor groove of the DNA. The resulting binding energies of docked metal complexes 1(a and b) were found to be -265.1 and -218.9KJmol(-1), respectively. Furthermore, enantiomeric complexes 1 and 2(a and b) were screened for in vitro antimicrobial activity.

  19. Chiral Imbalance in QCD and its consequences

    Directory of Open Access Journals (Sweden)

    Andrianov Alexander

    2016-01-01

    Full Text Available Under extreme conditions of high temperature and/or large quark (baryon density, the vacuum of QCD changes its properties, and deconfinement, chiral symmetry restoration as well as chiral symmetry breaking take place. These transitions (phases are accompanied by the rapid change in the rate and nature of topological transitions connecting different topological sectors. The heavy ion collisions (HIC program opens a possibility to study these phenomena in so-called non-Abelian Quark-gluon plasma (QGP. In these phases the currents of light quarks (vector and axial-vector can be independently examined for right-handed (RH and left-handed (LH quarks. To describe such a quark matter chiral chemical potential can be introduced to quantify the presence of chirality imbalance (ChI i.e. the difference between the average numbers of RH and LH quarks in the fireball after HIC. In this review talk we will focus our attention on the discussion of the ChI related developments in heavy ion physics at central collisions and the plans for the future experiments aimed at establishing (or falsifying the presence of Local spacial Parity Breaking (LPB in heavy ion data. We describe some of experimental observables in detecting the signal of LPB. A number of measurements is proposed that allow to reach a definite conclusion on the occurrence of LPB effects in non-Abelian QGP produced in central heavy ion collisions and its simulation within a number of QCD-inspired models is outlined. Based on the effective meson theory in the presence of Chern-Simons interaction it is found that the spectrum of massive vector mesons splits into three polarization components with different effective masses. Moreover a resonance broadening occurs that leads to an increase of spectral contribution to the dilepton production as compared to the vacuum state. The asymmetry in production of longitudinally and transversely polarized states of ρ and ω mesons for various values of the

  20. Chiral Imbalance in QCD and its consequences

    Science.gov (United States)

    Andrianov, Alexander; Andrianov, Vladimir; Espriu, Domenec

    2016-10-01

    Under extreme conditions of high temperature and/or large quark (baryon) density, the vacuum of QCD changes its properties, and deconfinement, chiral symmetry restoration as well as chiral symmetry breaking take place. These transitions (phases) are accompanied by the rapid change in the rate and nature of topological transitions connecting different topological sectors. The heavy ion collisions (HIC) program opens a possibility to study these phenomena in so-called non-Abelian Quark-gluon plasma (QGP). In these phases the currents of light quarks (vector and axial-vector) can be independently examined for right-handed (RH) and left-handed (LH) quarks. To describe such a quark matter chiral chemical potential can be introduced to quantify the presence of chirality imbalance (ChI) i.e. the difference between the average numbers of RH and LH quarks in the fireball after HIC. In this review talk we will focus our attention on the discussion of the ChI related developments in heavy ion physics at central collisions and the plans for the future experiments aimed at establishing (or falsifying) the presence of Local spacial Parity Breaking (LPB) in heavy ion data. We describe some of experimental observables in detecting the signal of LPB. A number of measurements is proposed that allow to reach a definite conclusion on the occurrence of LPB effects in non-Abelian QGP produced in central heavy ion collisions and its simulation within a number of QCD-inspired models is outlined. Based on the effective meson theory in the presence of Chern-Simons interaction it is found that the spectrum of massive vector mesons splits into three polarization components with different effective masses. Moreover a resonance broadening occurs that leads to an increase of spectral contribution to the dilepton production as compared to the vacuum state. The asymmetry in production of longitudinally and transversely polarized states of ρ and ω mesons for various values of the dilepton

  1. Chiral discrimination in optical trapping and manipulation

    Science.gov (United States)

    Bradshaw, David S.; Andrews, David L.

    2014-10-01

    When circularly polarized light interacts with chiral molecules or nanoscale particles powerful symmetry principles determine the possibility of achieving chiral discrimination, and the detailed form of electrodynamic mechanisms dictate the types of interaction that can be involved. The optical trapping of molecules and nanoscale particles can be described in terms of a forward-Rayleigh scattering mechanism, with trapping forces being dependent on the positioning within the commonly non-uniform intensity beam profile. In such a scheme, nanoparticles are commonly attracted to local potential energy minima, ordinarily towards the centre of the beam. For achiral particles the pertinent material response property usually entails an electronic polarizability involving transition electric dipole moments. However, in the case of chiral molecules, additional effects arise through the engagement of magnetic counterpart transition dipoles. It emerges that, when circularly polarized light is used for the trapping, a discriminatory response can be identified between left- and right-handed polarizations. Developing a quantum framework to accurately describe this phenomenon, with a tensor formulation to correctly represent the relevant molecular properties, the theory leads to exact analytical expressions for the associated energy landscape contributions. Specific results are identified for liquids and solutions, both for isotropic media and also where partial alignment arises due to a static electric field. The paper concludes with a pragmatic analysis of the scope for achieving enantiomer separation by such methods.

  2. Chiral nanophotonics chiral optical properties of plasmonic systems

    CERN Document Server

    Schäferling, Martin

    2017-01-01

    This book describes the physics behind the optical properties of plasmonic nanostructures focusing on chiral aspects. It explains in detail how the geometry determines chiral near-fields and how to tailor their shape and strength. Electromagnetic fields with strong optical chirality interact strongly with chiral molecules and, therefore, can be used for enhancing the sensitivity of chiroptical spectroscopy techniques. Besides a short review of the latest results in the field of plasmonically enhanced enantiomer discrimination, this book introduces the concept of chiral plasmonic near-field sources for enhanced chiroptical spectroscopy. The discussion of the fundamental properties of these light sources provides the theoretical basis for further optimizations and is of interest for researchers at the intersection of nano-optics, plasmonics and stereochemistry. .

  3. Isothermal Titration Calorimetry of Chiral Polymeric Nanoparticles.

    Science.gov (United States)

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

    2015-09-01

    Chiral polymeric nanoparticles are of prime importance, mainly due to their enantioselective potential, for many applications such as catalysis and chiral separation in chromatography. In this article we report on the preparation of chiral polymeric nanoparticles by miniemulsion polymerization. In addition, we describe the use of isothermal titration calorimetry (ITC) to measure the chiral interactions and the energetics of the adsorption of enantiomers from aqueous solutions onto chiral polymeric nanoparticles. The characterization of chirality in nano-systems is a very challenging task; here, we demonstrate that ITC can be used to accurately determine the thermodynamic parameters associated with the chiral interactions of nanoparticles. The use of ITC to measure the energetics of chiral interactions and recognition at the surfaces of chiral nanoparticles can be applied to other nanoscale chiral systems and can provide further insight into the chiral discrimination processes of nanomaterials. © 2015 Wiley Periodicals, Inc.

  4. Discovery of the Interstellar Chiral Molecule Propylene Oxide (CH$_3$CHCH$_2$O)

    CERN Document Server

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

    2016-01-01

    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 (CH$_3$CHCH$_2$O), 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.

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

    Science.gov (United States)

    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.

  6. Use of peak sharpening effects to improve the separation of chiral compounds with molecularly imprinted porous polymer layer open-tubular capillaries.

    Science.gov (United States)

    Kulsing, Chadin; Yang, Yuanzhong; Chowdhury, Jamil M; Boysen, Reinhard I; Hearn, Milton T W

    2017-02-17

    This investigation demonstrates the application of a new peak sharpening technique to improve the separation of difficult-to-resolve racemic mixtures in capillary electro-chromatography. Molecularly imprinted porous layer open tubular (MIP-PLOT) capillaries, prepared by a layer-on-layer polymerization approach with Z-l-Asp-OH as the template, were selected to validate the approach. SEM revealed that the polymer film thickness can be varied by changes in both the polymer composition and the layer-on-layer regime. Capillaries made with methacrylic acid as the functional monomer could not separate the Z-Asp-OH racemate, due to weak interactions between the MIP-PLOT material and the target analytes. In contrast, MIP-PLOT capillaries prepared with 4-vinylpyridine as the functional monomer resulted in increased ionic interactions with the target analytes. Separation of the enantiomers could be enhanced when a peak zone sharpening effect was exploited through the use of specific BGE compositions and by taking advantage of eigenpeak phenomena. In this manner, the position of a sharpening zone and the peak shape of the sample analytes could be fine-tuned, so that when the sharpening zone and the target analyte co-migrated the separation of the Z-l-Asp-OH enantiomer from its d-enantiomer in a racemic mixture could be achieved under overloading conditions.

  7. Chiromers: conformation-driven mirror-image supramolecular chirality isomerism identified in a new class of helical rosette nanotubes

    Science.gov (United States)

    Hemraz, Usha D.; El-Bakkari, Mounir; Yamazaki, Takeshi; Cho, Jae-Young; Beingessner, Rachel L.; Fenniri, Hicham

    2014-07-01

    Rosette nanotubes are biologically inspired nanostructures, formed through the hierarchical organization of a hybrid DNA base analogue (G∧C), which features hydrogen-bonding arrays of guanine and cytosine. Several twin-G∧C motifs functionalized with chiral moieties, which undergo a self-assembly process under methanolic and aqueous conditions to produce helical rosette nanotubes (RNTs), were synthesized and characterized. The built-in molecular chirality in the twin-G∧C building blocks led to the supramolecular chirality exhibited by the RNTs, as evidenced by the CD activity. Depending on the motifs and environmental conditions, mirror-image supramolecular chirality due to absolute molecular chirality, solvent-induced and structure-dependent supramolecular chirality inversion, and pH-controlled chiroptical switching were observed.Rosette nanotubes are biologically inspired nanostructures, formed through the hierarchical organization of a hybrid DNA base analogue (G∧C), which features hydrogen-bonding arrays of guanine and cytosine. Several twin-G∧C motifs functionalized with chiral moieties, which undergo a self-assembly process under methanolic and aqueous conditions to produce helical rosette nanotubes (RNTs), were synthesized and characterized. The built-in molecular chirality in the twin-G∧C building blocks led to the supramolecular chirality exhibited by the RNTs, as evidenced by the CD activity. Depending on the motifs and environmental conditions, mirror-image supramolecular chirality due to absolute molecular chirality, solvent-induced and structure-dependent supramolecular chirality inversion, and pH-controlled chiroptical switching were observed. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00340c

  8. Maxwell-Chern-Simons Hydrodynamics for the Chiral Magnetic Effect

    CERN Document Server

    Ozonder, Sener

    2010-01-01

    The rate of vacuum changing topological solutions of the gluon field, sphalerons, is estimated to be large at the typical temperatures of heavy-ion collisions, particularly at the Relativistic Heavy Ion Collider. Such windings in the gluon field are expected to produce parity-odd bubbles, which cause separation of positively and negatively charged quarks along the axis of the external magnetic field. This Chiral Magnetic Effect can be mimicked by Chern-Simons modified electromagnetism. Here we present a model of relativistic hydrodynamics including the effects of axial anomalies via the Chern-Simons term.

  9. Simulating net particle production and chiral magnetic current in a CP-odd domain

    CERN Document Server

    Fukushima, Kenji

    2015-01-01

    We elucidate the numerical formulation to simulate net production of particles and anomalous currents with CP-breaking background fields which cause an imbalance of particles over anti-particles. For a concrete demonstration we numerically impose pulsed electric and magnetic fields to observe that the dynamical chiral magnetic current follows together with the net particle production. The produced particle density is quantitatively consistent with the axial anomaly, while the chiral magnetic current is suppressed by a delay before the the onset of the current generation.

  10. Numerical Study of Nonperturbative Corrections to the Chiral Separation Effect in Quenched Finite-Density QCD

    Science.gov (United States)

    Puhr, Matthias; Buividovich, P. V.

    2017-05-01

    We demonstrate the nonrenormalization of the chiral separation effect (CSE) in quenched finite-density QCD in both confinement and deconfinement phases using a recently developed numerical method which allows us, for the first time, to address the transport properties of exactly chiral, dense lattice fermions. This finding suggests that CSE can be used to fix renormalization constants for axial current density. Explaining the suppression of the CSE which we observe for topologically nontrivial gauge field configurations on small lattices, we also argue that CSE vanishes for self-dual non-Abelian fields inside instanton cores.

  11. Quark structure of chiral solitons

    CERN Document Server

    Diakonov, D

    2004-01-01

    There is a prejudice that the chiral soliton model of baryons is something orthogonal to the good old constituent quark models. In fact, it is the opposite: the spontaneous chiral symmetry breaking in strong interactions explains the appearance of massive constituent quarks of small size thus justifying the constituent quark models, in the first place. Chiral symmetry ensures that constituent quarks interact very strongly with the pseudoscalar fields. The ``chiral soliton'' is another word for the chiral field binding constituent quarks. We show how the old SU(6) quark wave functions follow from the ``soliton'', however, with computable relativistic corrections and additional quark-antiquark pairs. We also find the 5-quark wave function of the exotic baryon Theta+.

  12. Applications Of Chiral Perturbation Theory

    CERN Document Server

    Mohta, V

    2005-01-01

    Effective field theory techniques are used to describe the spectrum and interactions of hadrons. The mathematics of classical field theory and perturbative quantum field theory are reviewed. The physics of effective field theory and, in particular, of chiral perturbation theory and heavy baryon chiral perturbation theory are also reviewed. The geometry underlying heavy baryon chiral perturbation theory is described in detail. Results by Coleman et. al. in the physics literature are stated precisely and proven. A chiral perturbation theory is developed for a multiplet containing the recently- observed exotic baryons. A small coupling expansion is identified that allows the calculation of self-energy corrections to the exotic baryon masses. Opportunities in lattice calculations are discussed. Chiral perturbation theory is used to study the possibility of two multiplets of exotic baryons mixed by quark masses. A new symmetry constraint on reduced partial widths is identified. Predictions in the literature based ...

  13. Dileptons and Chiral Symmetry Restoration

    CERN Document Server

    Hohler, P M

    2015-01-01

    We report on recent work relating the medium effects observed in dilepton spectra in heavy-ion collisions to potential signals of chiral symmetry restoration. The key connection remains the approach to spectral function degeneracy between the vector-isovector channel with its chiral partner, the axialvector-isovector channel. Several approaches are discussed to elaborate this connection, namely QCD and Weinberg sum rules with input for chiral order parameters from lattice QCD, and chiral hadronic theory to directly evaluate the medium effects of the axialvector channel and the pertinent pion decay constant as function of temperature. A pattern emerges where the chiral mass splitting between rho and a_1 burns off and is accompanied by a strong broadening of the spectral distributions.

  14. Divergence of the axial current and fermion density in Gross-Neveu models

    CERN Document Server

    Karbstein, Felix

    2007-01-01

    The divergence of the axial current is used to relate the spatial derivative of the fermion density to the bare fermion mass and scalar/pseudoscalar condensates in 1+1 dimensional Gross-Neveu models. This serves as a novel test of known results, to explain simple features of the continuous chiral model and to resolve a conflict concerning the assignment of baryon number to certain multi-fermion bound states.

  15. Build Axial Gradient Field by Using Axial Magnetized Permanent Rings

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Axial magnetic field produced by an axial magnetized permanent ring was studied. For two permanent rings, if they are magnetized in the same directions, a nearly uniform axial field can be produced. If they are magnetized in opposite direction,an axial gradient magnetic field can be generated, with the field range changing from -B0 to B0. A permanent magnet with a high axial gradient field was fabricated, the measured results agree with the PANDIRA calculation very well. For wider usage,it is desirable for the field gradient to be changed. Some methods to produce the variable gradient field are presented. These kinds of axial gradient magnetic field can also be used as a beam focusing for linear accelerator if the periodic field can be produced along the beam trajectory. The axial magnetic field is something like a solenoid, large stray field will leak to the outside environment if no method is taken to control them. In this paper, one method is illustrated to shield off the outside leakage field.

  16. Chiral Nuclear Dynamics II

    CERN Document Server

    Rho, Mannque

    2008-01-01

    This is the sequel to the first volume to treat in one effective field theory framework the physics of strongly interacting matter under extreme conditions. This is vital for understanding the high temperature phenomena taking place in relativistic heavy ion collisions and in the early Universe, as well as the high-density matter predicted to be present in compact stars. The underlying thesis is that what governs hadronic properties in a heat bath and/or a dense medium is hidden local symmetry which emerges from chiral dynamics of light quark systems and from the duality between QCD in 4D and

  17. Observing Disoriented Chiral Condensates

    CERN Document Server

    Bjorken, James D; Taylor, C C

    1993-01-01

    We speculate that, in very high energy hadronic collisions, large fireballs may be produced with interiors which have anomalous chiral order parameters. Such a process would result in radiation of pions with distinctive momentum and isospin distributions, and may provide an explanation of Centauro and related phenomena in cosmic-ray events. The phenomenology of such events is reviewed, with emphasis on the possibility of observing such phenomena at Fermilab experiment T-864 (MiniMax), or at a Full Acceptance Detector (FAD) at the SSC.

  18. Dissipative Axial Inflation

    CERN Document Server

    Notari, Alessio

    2016-01-01

    We analyze in detail the background cosmological evolution of a scalar field coupled to a massless abelian gauge field through an axial term $\\frac{\\phi}{f_\\gamma} F \\tilde{F}$, such as in the case of an axion. Gauge fields in this case are known to experience tachyonic growth and therefore can backreact on the background as an effective dissipation into radiation energy density $\\rho_R$, which which can lead to inflation without the need of a flat potential. We analyze the system, for momenta $k$ smaller than the cutoff $f_\\gamma$, including numerically the backreaction. We consider the evolution from a given static initial condition and explicitly show that, if $f_\\gamma$ is smaller than the field excursion $\\phi_0$ by about a factor of at least ${\\cal O} (20)$, there is a friction effect which turns on before that the field can fall down and which can then lead to a very long stage of inflation with a generic potential. In addition we find superimposed oscillations, which would get imprinted on any kind of...

  19. Room temperature chiral discrimination in paramagnetic NMR spectroscopy

    CERN Document Server

    Soncini, Alessandro

    2016-01-01

    A recently proposed theory of chiral discrimination in NMR spectroscopy based on the detection of a molecular electric polarization $\\mathbf{P}$ rotating in a plane perpendicular to the NMR magnetic field [A. D. Buckingham, J. Chem. Phys. $\\mathbf{140}$, 011103 (2014)], is here generalized to paramagnetic systems. Our theory predicts new contributions to $\\mathbf{P}$, varying as the square of the inverse temperature. Ab initio calculations for ten Dy$^{3+}$ complexes, at 293K, show that in strongly anisotropic paramagnetic molecules $\\mathbf{P}$ can be more than 1000 times larger than in diamagnetic molecules, making paramagnetic NMR chiral discrimination amenable to room temperature detection.

  20. Baryon resonances as dynamically generated states in chiral dynamics

    CERN Document Server

    Jido, Dasiuke

    2012-01-01

    We discuss baryon resonances which are dynamically generated in hadron dynamics based on chiral coupled channels approach. With the dynamical description of the baryon resonance, we discuss the origin of the resonance pole, finding that for the description of N(1535) some other components than meson and baryon are necessary. Since the chiral unitary model provides a microscopic description in terms of constituent hadrons, it is straightforward to calculate transition amplitudes and form factors of resonances without introducing further parameters. Finally we briefly discuss few-body nuclear kaonic systems as hadronic molecular states.

  1. Spontaneous Chiral Symmetry Breaking as Condensation of Dynamical Chirality

    CERN Document Server

    Alexandru, Andrei

    2012-01-01

    The occurrence of spontaneous chiral symmetry breaking (SChSB) is equivalent to sufficient abundance of Dirac near-zeromodes. However, dynamical mechanism leading to breakdown of chiral symmetry should be naturally reflected in chiral properties of the modes. Here we offer such connection, presenting evidence that SChSB in QCD proceeds via the appearance of modes exhibiting dynamical tendency for local chiral polarization. These modes form a band of finite width Lambda_ch (chiral polarization scale) around the surface of otherwise anti--polarized Dirac sea, and condense. Lambda_ch characterizes the dynamics of the breaking phenomenon and can be converted to a quark mass scale, thus offering conceptual means to determine which quarks of nature are governed by broken chiral dynamics. It is proposed that, within the context of SU(3) gauge theories with fundamental Dirac quarks, mode condensation is equivalent to chiral polarization, making Lambda_ch an "order parameter" of SChSB. Several uses of these features, ...

  2. Repulsive Casimir Force in Chiral Metamaterials

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-09-04

    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.

  3. Repulsive Casimir Force in Chiral Metamaterials

    OpenAIRE

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

    2009-01-01

    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 exist for strong chirality, under realistic frequency dependencies and correct limiting values (for zero and infinite frequencies) of the permittivity, permeability, and chiral coefficients.

  4. Repulsive Casimir Force in Chiral Metamaterials

    Science.gov (United States)

    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.

  5. Action-derived molecular dynamics simulations for the migration and coalescence of vacancies in graphene and carbon nanotubes.

    Science.gov (United States)

    Lee, Alex Taekyung; Ryu, Byungki; Lee, In-Ho; Chang, K J

    2014-03-19

    We report the results of action-derived molecular dynamics simulations for the migration and coalescence processes of monovacancies in graphene and carbon nanotubes with different chiralities. In carbon nanotubes, the migration pathways and barriers of a monovacancy depend on the tube chirality, while there is no preferential pathway in graphene due to the lattice symmetry and the absence of the curvature effect. The probable pathway changes from the axial to circumferential direction as the chirality varies from armchair to zigzag. The chirality dependence is attributed to the preferential orientation of the reconstructed bond formed around each vacancy site. It is energetically more favourable for two monovacancies to coalesce into a divacancy via alternative movements rather than simultaneous movements. The energy barriers for coalescence are generally determined by the migration barrier for the monovacancy, although there are some variations due to interactions between two diffusing vacancies. In graphene and armchair nanotubes, two monovacancies prefer to migrate along different zigzag atomic chains rather than a single atomic chain connecting these vacancies. On the other hand, in zigzag tubes, the energy barrier for coalescence increases significantly unless monovacancies lie on the same circumference.

  6. Nanoscale chirality in metal and semiconductor nanoparticles.

    Science.gov (United States)

    Kumar, Jatish; Thomas, K George; Liz-Marzán, Luis M

    2016-10-18

    The field of chirality has recently seen a rejuvenation due to the observation of chirality in inorganic nanomaterials. The advancements in understanding the origin of nanoscale chirality and the potential applications of chiroptical nanomaterials in the areas of optics, catalysis and biosensing, among others, have opened up new avenues toward new concepts and design of novel materials. In this article, we review the concept of nanoscale chirality in metal nanoclusters and semiconductor quantum dots, then focus on recent experimental and theoretical advances in chiral metal nanoparticles and plasmonic chirality. Selected examples of potential applications and an outlook on the research on chiral nanomaterials are additionally provided.

  7. Nonequilibrium chiral perturbation theory and disoriented chiral condensates

    CERN Document Server

    Nicola, A G

    1999-01-01

    We analyse the extension of Chiral Perturbation Theory to describe a meson gas out of thermal equilibrium. For that purpose, we let the pion decay constant be a time-dependent function and work within the Schwinger-Keldysh contour technique. A useful connection with curved space-time QFT allows to consistently renormalise the model, introducing two new low-energy constants in the chiral limit. We discuss the applicability of our approach within a Relativistic Heavy-Ion Collision environment. In particular, we investigate the formation of Disoriented Chiral Condensate domains in this model, via the parametric resonance mechanism.

  8. Chiral quantum optics.

    Science.gov (United States)

    Lodahl, Peter; Mahmoodian, Sahand; Stobbe, Søren; Rauschenbeutel, Arno; Schneeweiss, Philipp; Volz, Jürgen; Pichler, Hannes; Zoller, Peter

    2017-01-25

    Advanced photonic nanostructures are currently revolutionizing the optics and photonics that underpin applications ranging from light technology to quantum-information processing. The strong light confinement in these structures can lock the local polarization of the light to its propagation direction, leading to propagation-direction-dependent emission, scattering and absorption of photons by quantum emitters. The possibility of such a propagation-direction-dependent, or chiral, light-matter interaction is not accounted for in standard quantum optics and its recent discovery brought about the research field of chiral quantum optics. The latter offers fundamentally new functionalities and applications: it enables the assembly of non-reciprocal single-photon devices that can be operated in a quantum superposition of two or more of their operational states and the realization of deterministic spin-photon interfaces. Moreover, engineered directional photonic reservoirs could lead to the development of complex quantum networks that, for example, could simulate novel classes of quantum many-body systems.

  9. Chirally extended quantum chromodynamics

    CERN Document Server

    Brower, R C; Tan, C I; Richard C Brower; Yue Shen; Chung-I Tan

    1994-01-01

    We propose an extended Quantum Chromodynamics (XQCD) Lagrangian in which the fermions are coupled to elementary scalar %\\sigma and \\pi fields through a Yukawa coupling which preserves chiral invariance. Our principle motivation is to find a new lattice formulation for QCD which avoids the source of critical slowing down usually encountered as the bare quark mass is tuned to the chiral limit. The phase diagram and the weak coupling limit for XQCD are studied. They suggest a conjecture that the continuum limit of XQCD is the same as the continuum limit of conventional lattice formulation of QCD. As examples of such universality, we present the large N solutions of two prototype models for XQCD, in which the mass of the spurious pion and sigma resonance go to infinity with the cut-off. Even if the universality conjecture turns out to be false, we believe that XQCD will still be useful as a low energy effective action for QCD phenomenology on the lattice. Numerical simulations are recommended to further investiga...

  10. The Development of Chiral Catalysis in Asymmetric Synthesis%手性催化在不对称合成中的发展

    Institute of Scientific and Technical Information of China (English)

    杨晓刚; 黄蓓

    2012-01-01

    介绍了手性化合物的重要性及其发展情况,从手性分子的制备、手性有机小分子催化的应用等方面总结了手性分子的研究进展,指出了手性分子的发展方向。%The importance and devopment of chiral compounds are introduced, from the preparation of chiral molecule, the application of chiral organic small molecular catalyst, the research progress of chiral molealle are summarized, the development direction of chiral molecule are pointed out.

  11. Stimuli-Directed Helical Chirality Inversion and Bio-Applications

    Directory of Open Access Journals (Sweden)

    Ziyu Lv

    2016-08-01

    Full Text Available Helical structure is a sophisticated ubiquitous motif found in nature, in artificial polymers, and in supramolecular assemblies from microscopic to macroscopic points of view. Significant progress has been made in the synthesis and structural elucidation of helical polymers, nevertheless, a new direction for helical polymeric materials, is how to design smart systems with controllable helical chirality, and further use them to develop chiral functional materials and promote their applications in biology, biochemistry, medicine, and nanotechnology fields. This review summarizes the recent progress in the development of high-performance systems with tunable helical chirality on receiving external stimuli and discusses advances in their applications as drug delivery vesicles, sensors, molecular switches, and liquid crystals. Challenges and opportunities in this emerging area are also presented in the conclusion.

  12. Supernovae, Neutrinos and the Chirality of Amino Acids

    Directory of Open Access Journals (Sweden)

    Toshitaka Kajino

    2011-05-01

    Full Text Available A mechanism for creating an enantioenrichment in the amino acids, the building blocks of the proteins, that involves global selection of one handedness by interactions between the amino acids and neutrinos from core-collapse supernovae is defined. The chiral selection involves the dependence of the interaction cross sections on the orientations of the spins of the neutrinos and the 14N nuclei in the amino acids, or in precursor molecules, which in turn couple to the molecular chirality. It also requires an asymmetric distribution of neutrinos emitted from the supernova. The subsequent chemical evolution and galactic mixing would ultimately populate the Galaxy with the selected species. The resulting amino acids could either be the source thereof on Earth, or could have triggered the chirality that was ultimately achieved for Earth’s proteinaceous amino acids.

  13. Stardust, Supernovae and the Chirality of the Amino Acids

    Energy Technology Data Exchange (ETDEWEB)

    Boyd, R N; Kajino, T; Onaka, T

    2011-03-09

    A mechanism for creating enantiomerism in the amino acids, the building blocks of the proteins, that involves global selection of one chirality by interactions between the amino acids and neutrinos from core-collapse supernovae is described. The selection involves the dependence of the interaction cross sections on the orientations of the spins of the neutrinos and the 14N nuclei in the amino acids, or in precursor molecules, which in turn couple to the molecular chirality. The subsequent chemical evolution and galactic mixing would ultimately populate the Galaxy with the selected species. The resulting amino acids could either be the source thereof on Earth, or could have triggered the chirality that was ultimately achieved for Earth's amino acids.

  14. Supernovae, Neutrinos, and the Chirality of the Amino Acids

    CERN Document Server

    Boyd, R N; Onaka, T

    2011-01-01

    A mechanism for creating an enantioenrichment in the amino acids, the building blocks of the proteins, that involves global selection of one handedness by interactions between the amino acids and neutrinos from core-collapse supernovae is described. The chiral selection involves the dependence of the interaction cross sections on the orientations of the spins of the neutrinos and the 14N nuclei in the amino acids, or in precursor molecules, which in turn couple to the molecular chirality. It also requires an asymmetric distribution of neutrinos emitted from the supernova. The subsequent chemical evolution and galactic mixing would ultimately populate the Galaxy with the selected species. The resulting amino acids could either be the source thereof on Earth, or could have triggered the chirality that was ultimately achieved for Earth's proteinaceous amino acids.

  15. Baryons in the chiral regime

    Energy Technology Data Exchange (ETDEWEB)

    Knippschild, Bastian

    2012-03-05

    Quantum Chromodynamics (QCD) is the theory of strong interactions, one of the four fundamental forces in our Universe. It describes the interaction of gluons and quarks which build up hadrons like protons and neutrons. Most of the visible matter in our universe is made of protons and neutrons. Hence, we are interested in their fundamental properties like their masses, their distribution of charge and their shape. The only known theoretical, non-perturbative and ab initio method to investigate hadron properties at low energies is lattice Quantum Chromodynamics (lattice QCD). However, up-to-date simulations (especially for baryonic quantities) do not achieve the accuracy of experiments. In fact, current simulations do not even reproduce the experimental values for the form factors. The question arises wether these deviations can be explained by systematic effects in lattice QCD simulations. This thesis is about the computation of nucleon form factors and other hadronic quantities from lattice QCD. So called Wilson fermions are used and the u- and d-quarks are treated fully dynamically. The simulations were performed using gauge ensembles with a range of lattice spacings, volumes and pion masses. First of all, the lattice spacing was set to be able to make contact between the lattice results and their experimental complement and to be able to perform a continuum extrapolation. The light quark mass has been computed and found to be m{sub ud}{sup MS}(2 GeV)=3.03(17)(38) MeV. This value is in good agreement with values from experiments and other lattice determinations. Electro-magnetic and axial form factors of the nucleon have been calculated. From these form factors the nucleon radii and the coupling constants were computed. The different ensembles enabled us to investigate systematically the dependence of these quantities on the volume, the lattice spacing and the pion mass. Finally we perform a continuum extrapolation and chiral extrapolations to the physical point

  16. Chiral quantum dot based materials

    Science.gov (United States)

    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.

  17. Spontaneous chiral resolution in two-dimensional systems of patchy particles

    Energy Technology Data Exchange (ETDEWEB)

    Martínez-González, J. A.; Chapela, G. A. [Departamento de Física, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Col. Vicentina, 09340 México D.F. (Mexico); Quintana-H, J., E-mail: jaq@unam.mx [Instituto de Química, Universidad Nacional Autónoma de México - Apdo. Postal 70213, 04510 Coyoacán, México D.F. (Mexico)

    2014-05-21

    Short ranged potentials and their anisotropy produce spontaneous chiral resolution in a two dimensional model of patchy particles introduced in this paper. This model could represent an equimolar binary mixture (racemic mixture) of two kinds of chiral molecules (enantiomers) adsorbed to a bi-dimensional domain where only lateral short ranged interactions are present. Most racemic mixtures undergo chiral resolution due to their spatial anisotropy, the combined effect of long range forces and the thermodynamic conditions. The patchy particles are modeled as a hard disk and four different bonding sites located to produce chirality. Phase behavior and structural properties are analysed using Discontinuous Molecular Dynamics in the canonical ensemble. When the four patchy particles are separated by the angles (60°, 120°, 60°, 120°), spontaneous chiral resolution is produced, given by the formation of homochiral clusters, if started from the corresponding racemic mixture. Gel behavior is also obtained in all the systems for low temperatures and low densities.

  18. Understanding Internal Chirality Induction of Triarylsilyl Ethers Formed from Enantiopure Alcohols.

    Science.gov (United States)

    Wang, Li; Zhang, Tian; Redden, Brandon K; Sheppard, Cody I; Clark, Robert W; Smith, Mark D; Wiskur, Sheryl L

    2016-09-16

    Chirality transmission from point chirality to helical chirality was explored using triarylsilyl ethers. Circular dichroism (CD) spectroscopy was employed to show that the alcohol stereocenter of silylated, enantiopure secondary alcohols can transmit chirality to the aryl groups on the silicon resulting in a higher population of one helical conformation over another. Cotton effects characteristic of the aryl groups organized into one preferred conformation were observed for all of the compounds examined, which included both triphenyl- and trinaphthylsilyl groups. Alcohols with an R configuration typically induced a PMP helical twist, while an S configuration induced a MPM helical twist. Molecular modeling combined with solid-state structures also gave evidence signifying that point chirality adjacent to triphenylsilyl groups could bias the conformation of the phenyl groups. This work helps in our understanding of the origin of selectivity in our silylation-based kinetic resolutions and a role the phenyl groups play in that selectivity.

  19. Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity.

    Science.gov (United States)

    Oulevey, Patric; Luber, Sandra; Varnholt, Birte; Bürgi, Thomas

    2016-09-19

    Ionic liquids (ILs) are receiving increasing interest for their use in synthetic laboratories and industry. Being composed of charged entities, they show a complex and widely unexplored dynamic behavior. Chiral ionic liquids (CILs) have a high potential as solvents for use in asymmetric synthesis. Chiroptical methods, owing to their sensitivity towards molecular conformation, offer unique possibilities to study the structure of these chiral ionic liquids. Raman optical activity proved particularly useful to study ionic liquids composed of amino acids and the achiral 1-ethyl-3-methylimidazolium counterion. We could substantiate, supported by selected theoretical methods, that the achiral counterion adopts an overall chiral conformation in the presence of chiral amino acid ions. These findings suggest that in the design of chiral ionic liquids for asymmetric synthesis, the structure of the achiral counter ion also has to be carefully considered. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. [A comment on chiral thin layer chromatography].

    Science.gov (United States)

    Chen, Xuexian; Yuan, Liming

    2016-01-01

    In recent eight years, authors' group has repeated a lot of experiments of chiral thin layer chromatography coming from literature. From the practical opinion, we summarized that there are nine characteristics for chiral thin layer chromatography. Some progresses of chiral thin layer chromatography are reviewed, and the enantioselectivity of a commercial chiral thin layer plate is introduced. The study of vancomycin as the chiral selector in thin layer chromatography is also reported.

  1. Magnetic and axial-vector transitions of the baryon antidecuplet

    CERN Document Server

    Kim, H -Ch; Göke, K

    2007-01-01

    We report the recent results of the magnetic transitions and axial-vector transitions of the baryon antidecuplet within the framework of the chiral quark-soliton model. The dynamical model parameters are fixed by experimental data for the magnetic moments of the baryon octet, for the hyperon semileptonic decay constants, and for the singlet axial-vector constant. The transition magnetic moments $\\mu_{\\Lambda\\Sigma}$ and $\\mu_{N\\Delta}$ are well reproduced and other octet-decuplet and octet-antidecuplet transitions are predicted. In particular, the present calculation of $\\mu_{\\Sigma\\Sigma^*}$ is found to be below the upper bound $0.82\\mu_N$ that the SELEX collaboration measured very recently. The results explains consistently the recent findings of a new $N^*$ resonance from the GRAAL and Tohoku LNS group. We also obtain the transition axial-vector constants for the $\\Theta^+\\to KN$ from which the decay width of the $\\Theta^{+}$ pentaquark baryon is determined as a function of the pion-nucleon sigma term $\\Si...

  2. Chiral Fermions on the Lattice

    CERN Document Server

    Bietenholz, Wolfgang

    2010-01-01

    In the last century the non-perturbative regularization of chiral fermions was a long-standing problem. We review how this problem was finally overcome by the formulation of a modified but exact form of chiral symmetry on the lattice. This also provides a sound definition of the topological charge of lattice gauge configurations. We illustrate a variety of applications to QCD in the p-, the epsilon- and the delta-regime, where simulation results can now be related to Random Matrix Theory and Chiral Perturbation Theory. The latter contains Low Energy Constants as free parameters, and we comment on their evaluation from first principles of QCD.

  3. Coupling chiral bosons to gravity

    CERN Document Server

    Braga, N R F; Braga, N R F; Wotzasek, C

    1995-01-01

    chiral boson actions of Floreanini and Jackiw (FJ), and of McClain,Wu and Yu (MWY) have been recently shown to be different representations of the same chiral boson theory. MWY displays manifest covariance and also a (gauge) symmetry that is hidden in the FJ side, which, on the other hand, displays the physical spectrum in a simple manner. We make use of the covariance of the MWY representation for the chiral boson to couple it to background gravity showing explicitly the equivalence with the previous results for the FJ representation

  4. Chiral gravity in higher dimensions

    CERN Document Server

    Ootsuka, T; Ura, K; Ootsuka, Takayoshi; Tanaka, Erico; Ura, Kousuke

    2003-01-01

    We construct a chiral theory of gravity in 7 and 8 dimensions, which are equivalent to Einstein-Cartan theory using less variables. In these dimensions, we can construct such higher dimensional chiral gravity because of the existence of gravitational instanton. The octonionic-valued variables in the theory represent the deviation from the gravitational instanton, and from their non-associativity, prevents the theory to be SO(n) gauge invariant. Still the chiral gravity holds G_2 (7-D), and Spin(7) (8-D) gauge symmetry.

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

    Science.gov (United States)

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

    2008-09-01

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

  6. Chiral Relaxation Time at the Chiral Crossover of Quantum Chromodynamics

    CERN Document Server

    Ruggieri, M; Chernodub, M

    2016-01-01

    We study microscopic processes responsible for chirality flips in the thermal bath of Quantum Chromodynamics at finite temperature and zero baryon chemical potential. We focus on the temperature range where the crossover from chirally broken phase to quark-gluon plasma takes place, namely $T \\simeq (150, 200)$ MeV. The processes we consider are quark-quark scatterings mediated by collective excitations with the quantum number of pions and $\\sigma$-meson, hence we refer to these processes simply as \\sugg{to} one-pion (one-$\\sigma$) exchange\\sugg{s}. We use a Nambu-Jona-Lasinio model to compute equilibrium properties of the thermal bath, as well as the relevant scattering kernel to be used in the collision integral to estimate the chiral relaxation time $\\tau$. We find $\\tau\\simeq 0.1 \\div 1$ fm/c around the chiral crossover.

  7. Consistent chiral kinetic theory in Weyl materials: chiral magnetic plasmons

    CERN Document Server

    Gorbar, E V; Shovkovy, I A; Sukhachov, P O

    2016-01-01

    We argue that the correct definition of the electric current in the chiral kinetic theory for Weyl materials should include the Chern--Simons contribution that makes the theory consistent with the local conservation of the electric charge in electromagnetic and strain-induced pseudoelectromagnetic fields. By making use of such a kinetic theory, we study the plasma frequencies of collective modes in Weyl materials in constant magnetic and pseudomagnetic fields taking into account the effects of dynamical electromagnetism. We show that the collective modes are chiral plasmons. While the plasma frequency of the longitudinal collective mode coincides with the Langmuir one, this mode is unusual because it is characterized not only by oscillations of the electric current density, but also oscillations of the chiral current density. The latter are triggered by a dynamical version of the chiral electric separation effect. We also find that the plasma frequencies of the transverse modes split up in a magnetic field. T...

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

    Energy Technology Data Exchange (ETDEWEB)

    Tartakovskaya, Elena V., E-mail: elena_tartakovskaya@yahoo.com [Institute of Magnetism NAS of Ukraine, Vernadsky blvd 36b, 03142 Kiev (Ukraine); Institute of High Technologies, Taras Shevchenko National University of Kiev, 03022 Kiev (Ukraine)

    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. - Highlights: • Field-induced spin chirality in magnetic multilayers is explained. • The roles of the RKKY, the DM and the Zeeman interactions are clarified. • Theoretical analysis of the chirality factor is in agreement with experimental data.

  9. Three chiral ionic liquids as additives for enantioseparation in capillary electrophoresis and their comparison with conventional modifiers.

    Science.gov (United States)

    Zhang, Qi; Qi, Xueyong; Feng, Chunlai; Tong, Shanshan; Rui, Mengjie

    2016-09-02

    The combined use of chiral ionic liquids (ILs) and conventional chiral selectors in CE to establish synergistic system has proven to be a convenient and effective approach for enantioseparation. In this work, three amino acid chiral ILs, tetramethylammonium-l-arginine (TMA-l-Arg), tetramethylammonium-l-hydroxyproline (TMA-l-Hyp) and tetramethylammonium-l-isoleucine (TMA-l-Ile), were first applied in CE enantioseparation to investigate their potential synergistic effect with hydroxypropyl-β-cyclodextrin (HP-β-CD). Markedly improved separations were obtained in the chiral ILs/HP-β-CD synergistic systems compared with single HP-β-CD system. Parameters, such as the chiral ILs concentration, HP-β-CD concentration, buffer pH, applied voltage and capillary temperature, were optimized. A systematic comparison of chiral ILs with conventional (commonly used) modifiers was also performed, including the use of achiral ILs, conventional salts and molecular organic solvents. In addition, the chiral configuration of ILs was investigated to demonstrate the existence of synergistic effect between chiral ILs and HP-β-CD. All these results indicate that chiral ILs, as additives for CE chiral separation, has significant superiority over conventional modifiers in certain cases.

  10. Dissipative axial inflation

    Science.gov (United States)

    Notari, Alessio; Tywoniuk, Konrad

    2016-12-01

    We analyze in detail the background cosmological evolution of a scalar field coupled to a massless abelian gauge field through an axial term phi/fγ F ~F, such as in the case of an axion. Gauge fields in this case are known to experience tachyonic growth and therefore can backreact on the background as an effective dissipation into radiation energy density ρR, which can lead to inflation without the need of a flat potential. We analyze the system, for momenta k smaller than the cutoff fγ, including the backreaction numerically. We consider the evolution from a given static initial condition and explicitly show that, if fγ is smaller than the field excursion phi0 by about a factor of at least Script O (20), there is a friction effect which turns on before the field can fall down and which can then lead to a very long stage of inflation with a generic potential. In addition we find superimposed oscillations, which would get imprinted on any kind of perturbations, scalars and tensors. Such oscillations have a period of 4-5 efolds and an amplitude which is typically less than a few percent and decreases linearly with fγ. We also stress that the curvature perturbation on uniform density slices should be sensitive to slow-roll parameters related to ρR rather than dot phi2/2 and we discuss the existence of friction terms acting on the perturbations, although we postpone a calculation of the power spectrum and of non-gaussianity to future work and we simply define and compute suitable slow roll parameters. Finally we stress that this scenario may be realized in the axion case, if the coupling 1/fγ to U(1) (photons) is much larger than the coupling 1/fG to non-abelian gauge fields (gluons), since the latter sets the range of the potential and therefore the maximal allowed phi0~ fG.

  11. Interlocked chiral/polar domain walls and large optical rotation in Ni3TeO6

    Directory of Open Access Journals (Sweden)

    Xueyun Wang

    2015-07-01

    Full Text Available Chirality, i.e., handedness, pervades much of modern science from elementary particles, DNA-based biology to molecular chemistry; however, most of the chirality-relevant materials have been based on complex molecules. Here, we report inorganic single-crystalline Ni3TeO6, forming in a corundum-related R3 structure with both chirality and polarity. These chiral Ni3TeO6 single crystals exhibit a large optical specific rotation (α—1355° dm−1 cm3 g−1. We demonstrate, for the first time, that in Ni3TeO6, chiral and polar domains form an intriguing domain pattern, resembling a radiation warning sign, which stems from interlocked chiral and polar domain walls through lowering of the wall energy.

  12. Interlocked chiral/polar domain walls and large optical rotation in Ni{sub 3}TeO{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xueyun; Huang, Fei-Ting [Rutgers Center for Emergent Materials and Department of Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08854 (United States); Yang, Junjie [Laboratory for Pohang Emergent Materials and Max Plank POSTECH Center for Complex Phase Materials, Pohang University of Science and Technology, Pohang 790-784 (Korea, Republic of); Oh, Yoon Seok [Rutgers Center for Emergent Materials and Department of Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08854 (United States); Department of Physics, Ulsan National Institute of Science and Technology (UNIST), Ulsan 689-798 (Korea, Republic of); Cheong, Sang-Wook, E-mail: sangc@physics.rutgers.edu [Rutgers Center for Emergent Materials and Department of Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08854 (United States); Laboratory for Pohang Emergent Materials and Max Plank POSTECH Center for Complex Phase Materials, Pohang University of Science and Technology, Pohang 790-784 (Korea, Republic of)

    2015-07-01

    Chirality, i.e., handedness, pervades much of modern science from elementary particles, DNA-based biology to molecular chemistry; however, most of the chirality-relevant materials have been based on complex molecules. Here, we report inorganic single-crystalline Ni{sub 3}TeO{sub 6}, forming in a corundum-related R3 structure with both chirality and polarity. These chiral Ni{sub 3}TeO{sub 6} single crystals exhibit a large optical specific rotation (α)—1355° dm{sup −1} cm{sup 3} g{sup −1}. We demonstrate, for the first time, that in Ni{sub 3}TeO{sub 6}, chiral and polar domains form an intriguing domain pattern, resembling a radiation warning sign, which stems from interlocked chiral and polar domain walls through lowering of the wall energy.

  13. Reducible chiral metamaterials

    CERN Document Server

    Ciattoni, Alessandro; Rizza, Carlo

    2016-01-01

    We introduce the concept of 3D reducible metamaterials whose constituent permittivity can be modelled by a factorized profile. The separated cartesian coordinates dependence, easily achieved in all-optical reconfigurable materials, allows to physically regard a reducible metamaterial as a superposition of three fictitious 1D generating media. We prove that, in the long-wavelength limit, the electromagnetic response of reducible metamaterials can be reconstructed from the properties of the 1D generating media whose interplay provides large freedom to control the electromagnetic chirality. Our approach introduces an unprecedented decomposition strategy in metamaterial science which allows the full ab-initio and flexible design of a complex 3D bianisotropic response by using 1D metamaterials as basic building blocks.

  14. Chirality in photonic systems

    Science.gov (United States)

    Solnyshkov, Dmitry; Malpuech, Guillaume

    2016-10-01

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

  15. Amino Acids and Chirality

    Science.gov (United States)

    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.

  16. Nonequilibrium study of the chiral magnetic effect from real-time simulations with dynamical fermions

    Science.gov (United States)

    Mace, Mark; Mueller, Niklas; Schlichting, Sören; Sharma, Sayantan

    2017-02-01

    We present a real-time lattice approach to study the nonequilibrium dynamics of vector and axial charges in S U (N )×U (1 ) gauge theories. Based on a classical description of the non-Abelian and Abelian gauge fields, we include dynamical fermions and develop operator definitions for (improved) Wilson and overlap fermions that allow us to study real-time manifestations of the axial anomaly from first principles. We present a first application of this approach to anomalous transport phenomena such as the chiral magnetic effect (CME) and the chiral separation effect (CSE) by studying the dynamics of fermions during and after a S U (N ) sphaleron transition in the presence of a U (1 ) magnetic field. We investigate the fermion mass and magnetic field dependence of the suggested signatures of the CME and the CSE and point out some important aspects which need to be accounted for in the macroscopic description of anomalous transport phenomena.

  17. Chiral symmetry and pi-pi scattering in the Covariant Spectator Theory

    CERN Document Server

    Biernat, Elmar P; Ribeiro, J E; Stadler, Alfred; Gross, Franz

    2014-01-01

    The pi-pi scattering amplitude calculated with a model for the quark-antiquark interaction in the framework of the Covariant Spectator Theory (CST) is shown to satisfy the Adler zero constraint imposed by chiral symmetry. The CST formalism is established in Minkowski space and our calculations are performed in momentum space. We prove that the axial-vector Ward-Takahashi identity is satisfied by our model. Then we show that, similarly to what happens within the Bethe-Salpeter formalism, application of the axial-vector Ward-Takahashi identity to the CST pi-pi scattering amplitude allows us to sum the intermediate quark-quark interactions to all orders. The Adler self-consistency zero for pi-pi scattering in the chiral limit emerges as the result for this sum.

  18. Chiral Dynamics With Wilson Fermions

    CERN Document Server

    Splittorff, K

    2012-01-01

    Close to the continuum the lattice spacing affects the smallest eigenvalues of the Wilson Dirac operator in a very specific manner determined by the way in which the discretization breaks chiral symmetry. These effects can be computed analytically by means of Wilson chiral perturbation theory and Wilson random matrix theory. A number of insights on chiral Dynamics with Wilson fermions can be obtained from the computation of the microscopic spectrum of the Wilson Dirac operator. For example, the unusual volume scaling of the smallest eigenvalues observed in lattice simulations has a natural explanation. The dynamics of the eigenvalues of the Wilson Dirac operator also allow us to determine the additional low energy constants of Wilson chiral perturbation theory and to understand why the Sharpe-Singleton scenario is only realized in unquenched simulations.

  19. Domains of Disoriented Chiral Condensate

    CERN Document Server

    Amado, R D; Lu, Yang

    1996-01-01

    The probability distribution of neutral pion fraction from independent domains of disoriented chiral condensate is characterized. The signal for the condensate is clear for a small number of domains but is greatly reduced for more than three.

  20. Chirally motivated K - nuclear potentials

    Science.gov (United States)

    Cieplý, A.; Friedman, E.; Gal, A.; Gazda, D.; Mareš, J.

    2011-08-01

    In-medium subthreshold Kbar N scattering amplitudes calculated within a chirally motivated meson-baryon coupled-channel model are used self consistently to confront K- atom data across the periodic table. Substantially deeper K- nuclear potentials are obtained compared to the shallow potentials derived in some approaches from threshold Kbar N amplitudes, with Re VK-chiral = - (85 ± 5) MeV at nuclear matter density. When Kbar NN contributions are incorporated phenomenologically, a very deep K- nuclear potential results, Re VK-chiral + phen . = - (180 ± 5) MeV, in agreement with density dependent potentials obtained in purely phenomenological fits to the data. Self consistent dynamical calculations of K--nuclear quasibound states generated by VK-chiral are reported and discussed.

  1. Review of chiral perturbation theory

    Indian Academy of Sciences (India)

    B Ananthanarayan

    2003-11-01

    A review of chiral perturbation theory and recent developments on the comparison of its predictions with experiment is presented. Some interesting topics with scope for further elaboration are touched upon.

  2. Chiral magnetic wave in an expanding QCD fluid

    Science.gov (United States)

    Taghavi, Seyed Farid; Wiedemann, Urs Achim

    2015-02-01

    As a consequence of the chiral anomaly, the hydrodynamics of hot quantum chromodynamics (QCD) matter coupled to quantum electrodynamics allows for a long-wavelength mode of chiral charge density, the chiral magnetic wave (CMW), that provides for a mechanism of electric charge separation along the direction of an external magnetic field. Here, we investigate the efficiency of this mechanism for values of the time-dependent magnetic field and of the energy density attained in the hot QCD matter of ultrarelativistic heavy-ion collisions. To this end, we derive the CMW equations of motion for expanding systems by treating the CMW as a charge perturbation on top of an expanding Bjorken-type background field in the limit μ /T ≪1 . Both, approximate analytical and full numerical solutions to these equations of motion, indicate that for the lifetime and thermodynamic conditions of ultrarelativistic heavy-ion collisions, the efficiency of CMW-induced electric charge separation decreases with increasing center-of-mass energy and that the effect is numerically very small. We note, however, that if sizable oriented asymmetries in the axial charge distribution (that are not induced by the CMW) are present in the early fluid dynamic evolution, then the mechanism of CMW-induced electric charge separation can be much more efficient.

  3. Worldline construction of a covariant chiral kinetic theory

    Science.gov (United States)

    Mueller, Niklas; Venugopalan, Raju

    2017-07-01

    We discuss a novel worldline framework for computations of the chiral magnetic effect (CME) in ultrarelativistic heavy-ion collisions. Starting from the fermion determinant in the QCD effective action, we show explicitly how its real part can be expressed as a supersymmetric worldline action of spinning, colored, Grassmannian particles in background fields. Restricting ourselves for simplicity to spinning particles, we demonstrate how their constrained Hamiltonian dynamics arises for both massless and massive particles. In a semiclassical limit, this gives rise to the covariant generalization of the Bargmann-Michel-Telegdi equation; the derivation of the corresponding Wong equations for colored particles is straightforward. In a previous paper [N. Mueller and R. Venugopalan, arXiv:1701.03331.], we outlined how Berry's phase arises in a nonrelativistic adiabatic limit for massive particles. We extend the discussion here to systems with a finite chemical potential. We discuss a path integral formulation of the relative phase in the fermion determinant that places it on the same footing as the real part. We construct the corresponding anomalous worldline axial-vector current and show in detail how the chiral anomaly appears. Our work provides a systematic framework for a relativistic kinetic theory of chiral fermions in the fluctuating topological backgrounds that generate the CME in a deconfined quark-gluon plasma. We outline some further applications of this framework in many-body systems.

  4. Chiral Corrections to Nucleon Two- and Three-Point Correlation Functions

    CERN Document Server

    Tiburzi, Brian C

    2015-01-01

    We consider multi-particle contributions to nucleon two- and three-point functions from the perspective of chiral dynamics. Lattice nucleon interpolating operators, which have definite chiral transformation properties, can be mapped into chiral perturbation theory. Using the most common of such operators, we determine pion-nucleon and pion-delta couplings to nucleon two- and three-point correlation functions at leading order in the low-energy expansion. The couplings of pions to nucleons and deltas in two-point functions are consistent with simple phase-space considerations, in accordance with the Lehmann spectral representation. An argument based on available phase space on a torus is utilized to derive the scaling of multiple-pion couplings. While multi-pion states are indeed suppressed, this suppression scales differently with particle number compared to that in infinite volume. For nucleon three-point correlation functions, we investigate the axial-vector current at vanishing momentum transfer. The effect...

  5. Berry curvature and four-dimensional monopoles in the relativistic chiral kinetic equation.

    Science.gov (United States)

    Chen, Jiunn-Wei; Pu, Shi; Wang, Qun; Wang, Xin-Nian

    2013-06-28

    We derive a relativistic chiral kinetic equation with manifest Lorentz covariance from Wigner functions of spin-1/2 massless fermions in a constant background electromagnetic field. It contains vorticity terms and a four-dimensional Euclidean Berry monopole which gives an axial anomaly. By integrating out the zeroth component of the 4-momentum p, we reproduce the previous three-dimensional results derived from the Hamiltonian approach, together with the newly derived vorticity terms. The phase space continuity equation has an anomalous source term proportional to the product of electric and magnetic fields (FσρF[over ˜]σρ∼EσBσ). This provides a unified interpretation of the chiral magnetic and vortical effects, chiral anomaly, Berry curvature, and the Berry monopole in the framework of Wigner functions.

  6. Meta-Chirality: Fundamentals, Construction and Applications

    Directory of Open Access Journals (Sweden)

    Xiaoliang Ma

    2017-05-01

    Full Text Available Chiral metamaterials represent a special type of artificial structures that cannot be superposed to their mirror images. Due to the lack of mirror symmetry, cross-coupling between electric and magnetic fields exist in chiral mediums and present unique electromagnetic characters of circular dichroism and optical activity, which provide a new opportunity to tune polarization and realize negative refractive index. Chiral metamaterials have attracted great attentions in recent years and have given rise to a series of applications in polarization manipulation, imaging, chemical and biological detection, and nonlinear optics. Here we review the fundamental theory of chiral media and analyze the construction principles of some typical chiral metamaterials. Then, the progress in extrinsic chiral metamaterials, absorbing chiral metamaterials, and reconfigurable chiral metamaterials are summarized. In the last section, future trends in chiral metamaterials and application in nonlinear optics are introduced.

  7. Meta-Chirality: Fundamentals, Construction and Applications

    Science.gov (United States)

    Ma, Xiaoliang; Pu, Mingbo; Li, Xiong; Guo, Yinghui; Gao, Ping; Luo, Xiangang

    2017-01-01

    Chiral metamaterials represent a special type of artificial structures that cannot be superposed to their mirror images. Due to the lack of mirror symmetry, cross-coupling between electric and magnetic fields exist in chiral mediums and present unique electromagnetic characters of circular dichroism and optical activity, which provide a new opportunity to tune polarization and realize negative refractive index. Chiral metamaterials have attracted great attentions in recent years and have given rise to a series of applications in polarization manipulation, imaging, chemical and biological detection, and nonlinear optics. Here we review the fundamental theory of chiral media and analyze the construction principles of some typical chiral metamaterials. Then, the progress in extrinsic chiral metamaterials, absorbing chiral metamaterials, and reconfigurable chiral metamaterials are summarized. In the last section, future trends in chiral metamaterials and application in nonlinear optics are introduced. PMID:28513560

  8. Homogenization of resonant chiral metamaterials

    DEFF Research Database (Denmark)

    Andryieuski, Andrei; Menzel, C.; Rockstuhl, Carsten

    2010-01-01

    Homogenization of metamaterials is a crucial issue as it allows to describe their optical response in terms of effective wave parameters as, e.g., propagation constants. In this paper we consider the possible homogenization of chiral metamaterials. We show that for meta-atoms of a certain size...... an analytical criterion for performing the homogenization and a tool to predict the homogenization limit. We show that strong coupling between meta-atoms of chiral metamaterials may prevent their homogenization at all....

  9. Homogenization of resonant chiral metamaterials

    DEFF Research Database (Denmark)

    Andryieuski, Andrei; Menzel, C.; Rockstuhl, Carsten

    2010-01-01

    Homogenization of metamaterials is a crucial issue as it allows to describe their optical response in terms of effective wave parameters as, e.g., propagation constants. In this paper we consider the possible homogenization of chiral metamaterials. We show that for meta-atoms of a certain size...... an analytical criterion for performing the homogenization and a tool to predict the homogenization limit. We show that strong coupling between meta-atoms of chiral metamaterials may prevent their homogenization at all....

  10. Chiral thermodynamics of nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Fiorilla, Salvatore

    2012-10-23

    The equation of state of nuclear matter is calculated at finite temperature in the framework of in-medium chiral perturbation theory up to three-loop order. The dependence of its thermodynamic properties on the isospin-asymmetry is investigated. The chiral quark condensate is evaluated for symmetric nuclear matter. Its behaviour as a function of density and temperature sets important nuclear physics constraints for the QCD phase diagram.

  11. Baryon spectrum and chiral dynamics

    CERN Document Server

    Glozman, L Ya

    1995-01-01

    New results on baryon structure and spectrum developed in collaboration with Dan Riska [1-4] are reported. The main idea is that beyond the chiral symmetry spontaneous breaking scale light and strange baryons should be considered as systems of three constituent quarks with an effective confining interaction and a chiral interaction that is mediated by the octet of Goldstone bosons (pseudoscalar mesons) between the constituent quarks.

  12. Chiral symmetry breaking by spatial confinement in tactoidal droplets of lyotropic chromonic liquid crystals.

    Science.gov (United States)

    Tortora, Luana; Lavrentovich, Oleg D

    2011-03-29

    In many colloidal systems, an orientationally ordered nematic (N) phase emerges from the isotropic (I) melt in the form of spindle-like birefringent tactoids. In cases studied so far, the tactoids always reveal a mirror-symmetric nonchiral structure, sometimes even when the building units are chiral. We report on chiral symmetry breaking in the nematic tactoids formed in molecularly nonchiral polymer-crowded aqueous solutions of low-molecular weight disodium cromoglycate. The parity is broken by twisted packing of self-assembled molecular aggregates within the tactoids as manifested by the observed optical activity. Fluorescent confocal microscopy reveals that the chiral N tactoids are located at the boundaries of cells. We explain the chirality induction as a replacement of energetically costly splay packing of the aggregates within the curved bipolar tactoidal shape with twisted packing. The effect represents a simple pathway of macroscopic chirality induction in an organic system with no molecular chirality, as the only requirements are orientational order and curved shape of confinement.

  13. Chiral symmetry breaking by spatial confinement in tactoidal droplets of lyotropic chromonic liquid crystals

    Science.gov (United States)

    Tortora, Luana; Lavrentovich, Oleg D.

    2011-01-01

    In many colloidal systems, an orientationally ordered nematic (N) phase emerges from the isotropic (I) melt in the form of spindle-like birefringent tactoids. In cases studied so far, the tactoids always reveal a mirror-symmetric nonchiral structure, sometimes even when the building units are chiral. We report on chiral symmetry breaking in the nematic tactoids formed in molecularly nonchiral polymer-crowded aqueous solutions of low-molecular weight disodium cromoglycate. The parity is broken by twisted packing of self-assembled molecular aggregates within the tactoids as manifested by the observed optical activity. Fluorescent confocal microscopy reveals that the chiral N tactoids are located at the boundaries of cells. We explain the chirality induction as a replacement of energetically costly splay packing of the aggregates within the curved bipolar tactoidal shape with twisted packing. The effect represents a simple pathway of macroscopic chirality induction in an organic system with no molecular chirality, as the only requirements are orientational order and curved shape of confinement. PMID:21402929

  14. Comment on topological Invariants, instantons, and the chiral anomaly on spaces with torsion

    CERN Document Server

    Kreimer, D; Kreimer, Dirk; Mielke, Eckehard W.

    2001-01-01

    In Riemann-Cartan spacetimes with torsion only its axial covector piece $A$ couples to massive Dirac fields. Using renormalization group arguments, we show that besides the familiar Riemannian term only the Pontrjagin type four-form $dA\\wedge dA$ does arise additionally in the chiral anomaly, but not the Nieh-Yan term $d^\\star A$, as has been claimed in a recent paper [PRD 55, 7580 (1997)].

  15. Quark model with chiral-symmetry breaking and confinement in the Covariant Spectator Theory

    Energy Technology Data Exchange (ETDEWEB)

    Biernat, Elmer P. [CFTP, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal; Pena, Maria Teresa [CFTP, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal; Departamento de Física, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal; Ribiero, Jose' Emilio F. [CeFEMA, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal; Stadler, Alfred [Departamento de Física, Universidade de Évora, 7000-671 Évora, Portugal; Gross, Franz L. [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States)

    2016-03-01

    We propose a model for the quark-antiquark interaction in Minkowski space using the Covariant Spectator Theory. We show that with an equal-weighted scalar-pseudoscalar structure for the confining part of our interaction kernel the axial-vector Ward-Takahashi identity is preserved and our model complies with the Adler-zero constraint for pi-pi-scattering imposed by chiral symmetry.

  16. Electromagnetic form factors of the baryon octet in the perturbative chiral quark model

    CERN Document Server

    Cheedket, S; Gutsche, T; Faessler, A; Pumsa-ard, K; Yan, Y; Gutsche, Th.; Faessler, Amand

    2002-01-01

    We apply the perturbative chiral quark model at one loop to analyze the electromagnetic form factors of the baryon octet. The analytic expressions for baryon form factors, which are given in terms of fundamental parameters of low-energy pion-nucleon physics(weak pion decay constant, axial nucleon coupling, strong pion-nucleon form factor), and the numerical results for baryon magnetic moments, charge and magnetic radii are presented. Our results are in good agreement with experimental data.

  17. Modulated nematic structures induced by chirality and steric polarization

    Science.gov (United States)

    Longa, Lech; PajÄ k, Grzegorz

    2016-04-01

    What kind of one-dimensional modulated nematic structures (ODMNS) can form nonchiral and chiral bent-core and dimeric materials? Here, using the Landau-de Gennes theory of nematics, extended to account for molecular steric polarization, we study a possibility of formation of ODMNS, both in nonchiral and intrinsically chiral liquid crystalline materials. Besides nematic and cholesteric phases, we find four bulk ODMNS for nonchiral materials, two of which, to the best of our knowledge, have not been reported so far. These two structures are longitudinal (NLP) and transverse (NTP) periodic waves where the polarization field being periodic in one dimension stays parallel and perpendicular, respectively, to the wave vector. The other two phases are the twist-bend nematic phase (NTB) and the splay-bend nematic phase (NSB), but their fine structure appears more complex than that considered so far. The presence of molecular chirality converts nonchiral NTP and NSB into new NTB phases. Surprisingly, the nonchiral NLP phase can stay stable even in the presence of intrinsic chirality.

  18. Analytical solutions for elastic binary nanotubes of arbitrary chirality

    Science.gov (United States)

    Jiang, Lai; Guo, Wanlin

    2016-12-01

    Analytical solutions for the elastic properties of a variety of binary nanotubes with arbitrary chirality are obtained through the study of systematic molecular mechanics. This molecular mechanics model is first extended to chiral binary nanotubes by introducing an additional out-of-plane inversion term into the so-called stick-spiral model, which results from the polar bonds and the buckling of binary graphitic crystals. The closed-form expressions for the longitudinal and circumferential Young's modulus and Poisson's ratio of chiral binary nanotubes are derived as functions of the tube diameter. The obtained inversion force constants are negative for all types of binary nanotubes, and the predicted tube stiffness is lower than that by the former stick-spiral model without consideration of the inversion term, reflecting the softening effect of the buckling on the elastic properties of binary nanotubes. The obtained properties are shown to be comparable to available density functional theory calculated results and to be chirality and size sensitive. The developed model and explicit solutions provide a systematic understanding of the mechanical performance of binary nanotubes consisting of III-V and II-VI group elements.

  19. Analytical solutions for elastic binary nanotubes of arbitrary chirality

    Science.gov (United States)

    Jiang, Lai; Guo, Wanlin

    2016-09-01

    Analytical solutions for the elastic properties of a variety of binary nanotubes with arbitrary chirality are obtained through the study of systematic molecular mechanics. This molecular mechanics model is first extended to chiral binary nanotubes by introducing an additional out-of-plane inversion term into the so-called stick-spiral model, which results from the polar bonds and the buckling of binary graphitic crystals. The closed-form expressions for the longitudinal and circumferential Young's modulus and Poisson's ratio of chiral binary nanotubes are derived as functions of the tube diameter. The obtained inversion force constants are negative for all types of binary nanotubes, and the predicted tube stiffness is lower than that by the former stick-spiral model without consideration of the inversion term, reflecting the softening effect of the buckling on the elastic properties of binary nanotubes. The obtained properties are shown to be comparable to available density functional theory calculated results and to be chirality and size sensitive. The developed model and explicit solutions provide a systematic understanding of the mechanical performance of binary nanotubes consisting of III-V and II-VI group elements.

  20. Chiral switching by spontaneous conformational change in adsorbed organic molecules.

    Science.gov (United States)

    Weigelt, Sigrid; Busse, Carsten; Petersen, Lars; Rauls, Eva; Hammer, Bjørk; Gothelf, Kurt V; Besenbacher, Flemming; Linderoth, Trolle R

    2006-02-01

    Self-assembly of adsorbed organic molecules is a promising route towards functional surface nano-architectures, and our understanding of associated dynamic processes has been significantly advanced by several scanning tunnelling microscopy (STM) investigations. Intramolecular degrees of freedom are widely accepted to influence ordering of complex adsorbates, but although molecular conformation has been identified and even manipulated by STM, the detailed dynamics of spontaneous conformational change in adsorbed molecules has hitherto not been addressed. Molecular surface structures often show important stereochemical effects as, aside from truly chiral molecules, a large class of so-called prochiral molecules become chiral once confined on a surface with an associated loss of symmetry. Here, we investigate a model system in which adsorbed molecules surprisingly switch between enantiomeric forms as they undergo thermally induced conformational changes. The associated kinetic parameters are quantified from time-resolved STM data whereas mechanistic insight is obtained from theoretical modelling. The chiral switching is demonstrated to enable an efficient channel towards formation of extended homochiral surface domains. Our results imply that appropriate prochiral molecules may be induced (for example, by seeding) to assume only one enantiomeric form in surface assemblies, which is of relevance for chiral amplification and asymmetric heterogenous catalysis.

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

    Science.gov (United States)

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

    2016-07-12

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

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

    Science.gov (United States)

    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. Spin-Dependent Transport through Chiral Molecules Studied by Spin-Dependent Electrochemistry

    Science.gov (United States)

    2016-01-01

    Conspectus Molecular spintronics (spin + electronics), which aims to exploit both the spin degree of freedom and the electron charge in molecular devices, has recently received massive attention. Our recent experiments on molecular spintronics employ chiral molecules which have the unexpected property of acting as spin filters, by way of an effect we call “chiral-induced spin selectivity” (CISS). In this Account, we discuss new types of spin-dependent electrochemistry measurements and their use to probe the spin-dependent charge transport properties of nonmagnetic chiral conductive polymers and biomolecules, such as oligopeptides, L/D cysteine, cytochrome c, bacteriorhodopsin (bR), and oligopeptide-CdSe nanoparticles (NPs) hybrid structures. Spin-dependent electrochemical measurements were carried out by employing ferromagnetic electrodes modified with chiral molecules used as the working electrode. Redox probes were used either in solution or when directly attached to the ferromagnetic electrodes. During the electrochemical measurements, the ferromagnetic electrode was magnetized either with its magnetic moment pointing “UP” or “DOWN” using a permanent magnet (H = 0.5 T), placed underneath the chemically modified ferromagnetic electrodes. The spin polarization of the current was found to be in the range of 5–30%, even in the case of small chiral molecules. Chiral films of the l- and d-cysteine tethered with a redox-active dye, toludin blue O, show spin polarizarion that depends on the chirality. Because the nickel electrodes are susceptible to corrosion, we explored the effect of coating them with a thin gold overlayer. The effect of the gold layer on the spin polarization of the electrons ejected from the electrode was investigated. In addition, the role of the structure of the protein on the spin selective transport was also studied as a function of bias voltage and the effect of protein denaturation was revealed. In addition to

  4. Chirality in Bare and Passivated Gold Nanoclusters

    CERN Document Server

    Garzon, I L; Rodrigues-Hernandez, J I; Sigal, I; Beltran, M R; Michaelian, K

    2002-01-01

    Chiral structures have been found as the lowest-energy isomers of bare (Au$_{28}$ and Au$_{55}) and thiol-passivated (Au$_{28}(SCH$_{3})$_{16}$ and Au$_{38}$(SCH$_{3}$)$_{24}) gold nanoclusters. The degree of chirality existing in the chiral clusters was calculated using the Hausdorff chirality measure. We found that the index of chirality is higher in the passivated clusters and decreases with the cluster size. These results are consistent with the observed chiroptical activity recently reported for glutahione-passivated gold nanoclusters, and provide theoretical support for the existence of chirality in these novel compounds.

  5. Using the Chiral Organophosphorus Derivatizing Agents for Determination of the Enantiomeric Composition of Chiral Carboxylic Acids by 31PNMR Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    Chao CHE; Zhong Ning ZHANG; Gui Lan HUANG; Xin Xing WANG; Zhao Hai QIN

    2004-01-01

    The use of chiral organophosphorus derivatizing agents prepared in situ from chiral tartrate or chiral diamine for the 31PNMR determination of the enantiomeric composition of chiral carboxylic acids is described. The method is accurate, reliable and convenient.

  6. Spectral Density Functions and Their Sum Rules in an Effective Chiral Field Theory

    CERN Document Server

    Klevansky, S P

    1997-01-01

    The validity of Weinberg's two sum rules for massless QCD, as well as the six additional sum rules introduced into chiral perturbation theory by Gasser and Leutwyler, are investigated for the extended Nambu-Jona-Lasinio chiral model that includes vector and axial vector degrees of freedom. A detailed analysis of the vector, axial vector and coupled pion plus longitudinal axial vector modes is given. We show that, under Pauli-Villars regularization of the meson polarization amplitudes that determine the spectral density functions, all of the sum rules involving inverse moments higher than zero are automatically obeyed by the model spectral densities. By contrast, the zero moment sum rules acquire a non-vanishing right hand side that is proportional to the quark condensate density of the non-perturbative groundstate. We use selected sum rules in conjunction with other calculations to obtain explicit expressions for the scale-independent coupling constants $\\bar l_i$ of chiral perturbation theory in the combinat...

  7. Electrical Property Analytical Prediction on Archimedes Chiral Carbon Nanoscrolls

    Science.gov (United States)

    Hassanzadazar, M.; Ahmadi, M. T.; Ismail, Razali; Goudarzi, Hadi

    2016-10-01

    Carbon nanoscrolls (CNS) with flexible exterior areas and interesting electrical and mechanical properties have gained interest in recent years, both experimentally and theoretically. These structures have been employed as ion channels, tunable water channels, molecular sensors, and gene and drug distribution systems. In this study, electrical behaviour of all types of CNS containing armchair, zigzag, and chiral CNSs band structure is investigated. In armchair CNSs, the small band gap among valence and the conduction band as a pseudo-gap are reported, which reveals a semimetallic property for some of these CNSs. This small band gap, as a result of layer interaction, has been confirmed. Also, in many other types of armchair CNSs at the Fermi level, related levels cross each other, illustrating metallic characteristics. On the other hand, our numerical results show small band gaps for zigzag types of CNSs, which means that they are semiconductors. However, it cannot be considered as a general occurrence because only in rare circumstances is a very small band gap observed that gives rise to semimetallic CNSs. In addition, the electrical properties of chiral CNSs are explored. Small band gaps between the associated valence and the conduction band reveals that chiral CNSs mainly exhibit semiconducting behaviour. Finally, all the numerical results are tabulated in the form of a CNS periodic table and a symmetric arrangement with respect to the armchair nanoscrolls and as a table diagonal data for the chiral CNSs is noticed. In addition, this investigation highlights the variations of the energy structure of chiral CNSs with respect to their length. Presented results offer significant potential for chiral CNSs as an alternative to silicon-based sensors in nanotechnology. Therefore, the band gap variations in the presence of attached materials as a sensor platform need to be explored.

  8. Thermal Conductivity of Nanotubes Revisited: Effects of Chirality, Isotope Impurity, Tube Length, and Temperature

    OpenAIRE

    Zhang, Gang; Li, Baowen

    2004-01-01

    We study the dependence of thermal conductivity of single walled nanotubes (SWNT) on chirality, isotope impurity, tube length and temperature by nonequilibrium molecular dynamics method with accurate potentials. It is found that, contrary to electronic conductivity, the thermal conductivity is insensitive to the chirality. The isotope impurity, however, can reduce the thermal conductivity up to 60% and change the temperature dependence behavior. We also found that the tube length dependence o...

  9. Bottom-up graphene-nanoribbon fabrication reveals chiral edges and enantioselectivity.

    Science.gov (United States)

    Han, Patrick; Akagi, Kazuto; Federici Canova, Filippo; Mutoh, Hirotaka; Shiraki, Susumu; Iwaya, Katsuya; Weiss, Paul S; Asao, Naoki; Hitosugi, Taro

    2014-09-23

    We produce precise chiral-edge graphene nanoribbons on Cu{111} using self-assembly and surface-directed chemical reactions. We show that, using specific properties of the substrate, we can change the edge conformation of the nanoribbons, segregate their adsorption chiralities, and restrict their growth directions at low surface coverage. By elucidating the molecular-assembly mechanism, we demonstrate that our method constitutes an alternative bottom-up strategy toward synthesizing defect-free zigzag-edge graphene nanoribbons.

  10. Consistent Chiral Kinetic Theory in Weyl Materials: Chiral Magnetic Plasmons

    Science.gov (United States)

    Gorbar, E. V.; Miransky, V. A.; Shovkovy, I. A.; Sukhachov, P. O.

    2017-03-01

    We argue that the correct definition of the electric current in the chiral kinetic theory for Weyl materials should include the Chern-Simons contribution that makes the theory consistent with the local conservation of the electric charge in electromagnetic and strain-induced pseudoelectromagnetic fields. By making use of such a kinetic theory, we study the plasma frequencies of collective modes in Weyl materials in constant magnetic and pseudomagnetic fields, taking into account the effects of dynamical electromagnetism. We show that the collective modes are chiral plasmons. While the plasma frequency of the longitudinal collective mode coincides with the Langmuir one, this mode is unusual because it is characterized not only by oscillations of the electric current density, but also by oscillations of the chiral current density. The latter are triggered by a dynamical version of the chiral electric separation effect. We also find that the plasma frequencies of the transverse modes split up in a magnetic field. This finding suggests an efficient means of extracting the chiral shift parameter from the measurement of the plasma frequencies in Weyl materials.

  11. Spin Helicity in Chiral Lanthanide Chains.

    Science.gov (United States)

    Mihalcea, Ionut; Perfetti, Mauro; Pineider, Francesco; Tesi, Lorenzo; Mereacre, Valeriu; Wilhelm, Fabrice; Rogalev, Andrei; Anson, Christopher E; Powell, Annie K; Sessoli, Roberta

    2016-10-17

    We report here the determination of the helical spin structure of three Ln-based chiral chains of the formula [Ln(Hnic)(nic)2(NO3)]n (Hnic = nicotinic acid; Ln = Tb, Dy, and Er) by means of cantilever torque magnetometry. While the Dy and Er derivatives are strongly axial (easy-axis and easy-plane anisotropy, respectively), the Tb derivative is characterized by a remarkable rhombicity. In agreement with these findings, alternating-current susceptibility reveals slow magnetic relaxation only in the Dy derivative. Dilution of Dy(III) ions in the diamagnetic Y-based analogue shows that the weak ferromagnetic intrachain interactions do not contribute significantly to the energy barrier for the reversal of magnetization, which is better described as a single-ion process. Single crystals of the two enantiomers of the Dy derivative have also been investigated using hard X-ray synchrotron radiation at the L-edge of the metal revealing optical activity although with negligible involvement of the 4f electrons of the Dy(III) ion.

  12. An Inherent Chiral Calix[4]arene Bearing Chiral Groups without Forming Sub-ring

    Institute of Scientific and Technical Information of China (English)

    Xian Xian LIU; Yan Song ZHENG; Wan Ling MO

    2006-01-01

    The NMR spectra revealed that the calixarene frame of 1, 3-disubstituted calix[4]arenes bearing optically active groups is asymmetric, even without the formation of a sub-ring. This inherent chirality arises from the interaction of the two chiral groups, which hinder the substituents' free rotation. Thus, these chiral calix[4]arenes display good chiral recognition ability.

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

    Science.gov (United States)

    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.)

  14. Relativistic RPA in axial symmetry

    CERN Document Server

    Arteaga, D Pena; 10.1103/PhysRevC.77.034317

    2009-01-01

    Covariant density functional theory, in the framework of self-consistent Relativistic Mean Field (RMF) and Relativistic Random Phase approximation (RPA), is for the first time applied to axially deformed nuclei. The fully self-consistent RMF+RRPA equations are posed for the case of axial symmetry and non-linear energy functionals, and solved with the help of a new parallel code. Formal properties of RPA theory are studied and special care is taken in order to validate the proper decoupling of spurious modes and their influence on the physical response. Sample applications to the magnetic and electric dipole transitions in $^{20}$Ne are presented and analyzed.

  15. Axial Current and Noether Charge

    CERN Document Server

    Mahato, Prasanta

    2012-01-01

    A decade ago, a Lagrangian density has been proposed by the author where only the local symmetries of the Lorentz subgroup of (A)ds group is retained. This formalism has been found to produce some results encompassing that of standard Einstein-Hilbert formalism. In the present article, the conserved axial vector matter currents, constructed in some earlier paper, have been found to be a result of Noether's theorem. PACS: 04.20.Fy, 04.20.Cv, 11.40.-q Keywords: Torsion, Axial Current, Noether's Theorem

  16. Chaos of chiral condensate

    CERN Document Server

    Hashimoto, Koji; Yoshida, Kentaroh

    2016-01-01

    Assigning a chaos index for vacua of generic quantum field theories is a challenging problem. We find chaotic behavior of chiral condensates of a quantum gauge theory at strong coupling limit, by using the AdS/CFT correspondence. We evaluate the time evolution of homogeneous quark condensates and in an N=2 supersymmetric QCD with the SU(N_c) gauge group at large N_c and at large 't Hooft coupling lambda. At an equivalent classical gravity picture, a Lyapunov exponent is readily defined. We show that the condensates exhibit chaotic behavior for energy density E > (6x10^2) (N_c/lambda^2) (m_q)^4 where m_q is the quark mass. The energy region of the chaotic vacua of the N=2 supersymmetric QCD increases for smaller N_c or larger lambda. The Lyapunov exponent is calculated as a function of the theory (N_c,lambda,E), showing that the N=2 supersymmetric QCD is more chaotic for smaller N_c.

  17. Chiral Thirring–Wess model

    Energy Technology Data Exchange (ETDEWEB)

    Rahaman, Anisur, E-mail: anisur.rahman@saha.ac.in

    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.

  18. Chiral Logs in Quenched QCD

    CERN Document Server

    Dong, S J; Horváth, I; Lee, F X; Liu, K F; Mathur, N; Zhang, J B

    2003-01-01

    The quenched chiral logs are examined on a $16^3 \\times 28$ lattice with Iwasaki gauge action and overlap fermions. The pion decay constant $f_{\\pi}$ is used to set the lattice spacing, $a = 0.200(3)$ fm. With pion mass as low as $\\sim 180 {\\rm MeV}$, we see the quenched chiral logs clearly in $m_{\\pi}^2/m$ and $f_P$, the pseudoscalar decay constant. We analyze the data to determine how low the pion mass needs to be in order for the quenched one-loop chiral perturbation theory ($\\chi$PT) to apply. With the constrained curve fitting, we are able to extract the quenched chiral log parameter $\\delta$ together with the chiral cutoff $\\Lambda_{\\chi}$ and other parameters. Only for $m_{\\pi} \\leq 300 {\\rm MeV}$ do we obtain a consistent and stable fit with a constant $\\delta$ which we determine to be 0.23(2). By comparing to the $12^3 \\times 28$ lattice, we estimate the finite volume effect to be about 1.8% for the smallest pion mass. We also study the quenched non-analytic terms in the nucleon and the $\\rho$ masses...

  19. Surface second harmonic generation of chiral molecules using three-coupled-oscillator model

    Institute of Scientific and Technical Information of China (English)

    Wang Xiao-Ou; Li Chun-Fei; Li Jun-Qing

    2006-01-01

    Based on the three-coupled-oscillator molecular model we proposed, the relation between the second-order susceptibilities of a chiral film and the molecular hyperpolarizabilities is given. The effect of microscopic parameters on the second-order susceptibilities is simulated numerically and the difference between the efficiencies of s-polarized second-harmonic fields induced by the left- and the right-handed circularly-polarized fundamental beams is discussed. The theoretical basis for studying second-order nonlinear optical properties of the chiral molecular media with a tripod-like structure is provided in this paper.

  20. Orientation-dependent handedness and chiral design

    OpenAIRE

    Efrati, Efi; Irvine, William T. M.

    2013-01-01

    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 ...

  1. Chiral gap effect in curved space

    CERN Document Server

    Flachi, Antonino

    2014-01-01

    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.

  2. Chirality: a relational geometric-physical property.

    Science.gov (United States)

    Gerlach, Hans

    2013-11-01

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

  3. Bifurcated, modular syntheses of chiral annulet triazacyclononanes.

    Science.gov (United States)

    Argouarch, Gilles; Stones, Graham; Gibson, Colin L; Kennedy, Alan R; Sherrington, David C

    2003-12-21

    Three chiral 2,6-disubstituted tri-N-methyl azamacrocycles have been prepared by modular methods. These macrocycles were accessed from three chiral 1,4,7-triazaheptanes intermediates that were prepared by two independent routes. The first of these routes involved the benzylamine opening of chiral tosyl aziridines followed by debenzylation but was problematic on solubility grounds. A second, more effective, route was developed which avoided debenzylation by using ammonia in the nucleophilic opening of chiral tosyl aziridines.

  4. Chiral Decomposition For Non-Abelian Bosons

    CERN Document Server

    Braga, N R F; Braga, Nelson R. F.; Wotzasek, Clovis

    1996-01-01

    We study the non-abelian extension for the splitting of a scalar field into chiral components. Using this procedure we find a non ambiguous way of coupling a non abelian chiral scalar field to gravity. We start with a (non-chiral) WZW model covariantly coupled to a background metric and, after the splitting, arrive at two chiral Wess-Zumino-Witten (WZW) models coupled to gravity.

  5. On the Biological Advantage of Chirality

    OpenAIRE

    1999-01-01

    The presence of chirality in the main molecules of life may well be not just a structural artifact, but of pure biological advantage. The possibility of the existence of a phenomenon of a special mode of interaction, labeled as "chiral interaction" (CI), for which structural chirality is a necessary condition, is the main reason for such an advantage. In order to demonstrate such a possibility, macroscopic chiral devices are introduced and presented as analogies for such an interaction. For t...

  6. Application of computational chemistry methods to the prediction of chirality and helical twisting power in liquid crystal systems

    Science.gov (United States)

    Noto, Anthony G.; Marshall, Kenneth L.

    2005-08-01

    Until recently, it has not been possible to determine, with any real certainty, a complete picture of "chirality" (absolute configuration, optical rotation direction, and helical twisting power) for new chiral compounds without first synthesizing, purifying, characterizing, and testing every new material. Recent advances in computational chemistry now allow the prediction of certain key chiral molecular properties prior to synthesis, which opens the possibility of predetermining the "chiroptical" properties of new liquid crystal dopants and mixtures for advanced optical and photonics applications. A key element to this activity was the development of both the chirality index (G0) by Osipov et al., and the scaled chirality index (G0S) by Solymosi et al., that can be used as a "figure of merit" for molecular chirality. Promising correlations between G0S and both circular dichroism (CD) and the helical twisting power (HTP) of a chiral dopant in a liquid crystal host have been shown by Neal et al., Osipov, and Kuball. Our work improves the predictive capabilities of G0S by taking into account the actual mass of each atom in the molecule in the calculations; in previous studies the mass of each atom was assumed to be equal. This "weighted" scaled chirality index (G0SW) was calculated and correlated to existing experimental HTP data for each member of a series of existing, well-known chiral compounds. The computed HTP using G0SW for these model systems correlated to the experimental data with remarkable accuracy. Weighted, scaled chiral indices were also calculated for the first time for a series of novel chiral transition metal dithiolene dyes for near-IR liquid crystal device applications.

  7. Chiral dynamics of baryons in the perturbative chiral quark model

    Energy Technology Data Exchange (ETDEWEB)

    Pumsa-ard, K.

    2006-07-01

    In this work we develop and apply variants of a perturbative chiral quark model (PCQM) to the study of baryonic properties dominantly in the low-energy region. In a first step we consider a noncovariant form of the PCQM, where confinement is modelled by a static, effective potential and chiral corrections are treated to second order, in line with similar chiral quark models. We apply the PCQM to the study of the electromagnetic form factors of the baryon octet. We focus in particular on the low-energy observables such as the magnetic moments, the charge and magnetic radii. In addition, the electromagnetic N-delta transition is also studied in the framework of the PCQM. In the chiral loop calculations we consider a quark propagator, which is restricted to the quark ground state, or in hadronic language to nucleon and delta intermediate states, for simplicity. We furthermore include the low-lying excited states to the quark propagator. In particular, the charge radius of the neutron and the transverse helicity amplitudes of the N-delta transition are considerably improved by this additional effect. In a next step we develop a manifestly Lorentz covariant version of the PCQM, where in addition higher order chiral corrections are included. The full chiral quark Lagrangian is motivated by and in analogy to the one of Chiral Perturbation Theory (ChPT). This Lagrangian contains a set of low energy constants (LECs), which are parameters encoding short distance effects and heavy degrees of freedom. We evaluate the chiral Lagrangian to order O(p{sup 4}) and to one loop to generate the dressing of the bare quark operators by pseudoscalar mesons. In addition we include the vector meson degrees of freedom in our study. Projection of the dressed quark operators on the baryonic level serves to calculate the relevant matrix elements. In a first application of this scheme, we resort to a parameterization of the valence quark form factors in the electromagnetic sector. Constraints

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

    Science.gov (United States)

    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.

  9. Origin of Stereodivergence in Cooperative Asymmetric Catalysis with Simultaneous Involvement of Two Chiral Catalysts.

    Science.gov (United States)

    Bhaskararao, Bangaru; Sunoj, Raghavan B

    2015-12-23

    Accomplishing high diastereo- and enantioselectivities simultaneously is a persistent challenge in asymmetric catalysis. The use of two chiral catalysts in one-pot conditions might offer new avenues to this end. Chirality transfer from a catalyst to product gets increasingly complex due to potential chiral match-mismatch issues. The origin of high enantio- and diastereoselectivities in the reaction between a racemic aldehyde and an allyl alcohol, catalyzed by using axially chiral iridium phosphoramidites PR/S-Ir and cinchona amine is established through transition-state modeling. The multipoint contact analysis of the stereocontrolling transition state revealed how the stereodivergence could be achieved by inverting the configuration of the chiral catalysts that are involved in the activation of the reacting partners. While the enantiocontrol is identified as being decided in the generation of PR/S-Ir-π-allyl intermediate from the allyl alcohol, the diastereocontrol arises due to the differential stabilizations in the C-C bond formation transition states. The analysis of the weak interactions in the transition states responsible for chiral induction revealed that the geometric disposition of the quinoline ring at the C8 chiral carbon of cinchona-enamine plays an anchoring role. The quinolone ring is noted as participating in a π-stacking interaction with the phenyl ring of the Ir-π-allyl moiety in the case of PR with the (8R,9R)-cinchona catalyst combination, whereas a series of C-H···π interactions is identified as vital to the relative stabilization of the stereocontrolling transition states when PR is used with (8S,9S)-cinchona.

  10. Use of chiral cell shape to ensure highly directional swimming in trypanosomes.

    Science.gov (United States)

    Wheeler, Richard John

    2017-01-01

    Swimming cells typically move along a helical path or undergo longitudinal rotation as they swim, arising from chiral asymmetry in hydrodynamic drag or propulsion bending the swimming path into a helix. Helical paths are beneficial for some forms of chemotaxis, but why asymmetric shape is so prevalent when a symmetric shape would also allow highly directional swimming is unclear. Here, I analyse the swimming of the insect life cycle stages of two human parasites; Trypanosoma brucei and Leishmania mexicana. This showed quantitatively how chirality in T. brucei cell shape confers highly directional swimming. High speed videomicrographs showed that T. brucei, L. mexicana and a T. brucei RNAi morphology mutant have a range of shape asymmetries, from wild-type T. brucei (highly chiral) to L. mexicana (near-axial symmetry). The chiral cells underwent longitudinal rotation while swimming, with more rapid longitudinal rotation correlating with swimming path directionality. Simulation indicated hydrodynamic drag on the chiral cell shape caused rotation, and the predicted geometry of the resulting swimming path matched the directionality of the observed swimming paths. This simulation of swimming path geometry showed that highly chiral cell shape is a robust mechanism through which microscale swimmers can achieve highly directional swimming at low Reynolds number. It is insensitive to random variation in shape or propulsion (biological noise). Highly symmetric cell shape can give highly directional swimming but is at risk of giving futile circular swimming paths in the presence of biological noise. This suggests the chiral T. brucei cell shape (associated with the lateral attachment of the flagellum) may be an adaptation associated with the bloodstream-inhabiting lifestyle of this parasite for robust highly directional swimming. It also provides a plausible general explanation for why swimming cells tend to have strong asymmetries in cell shape or propulsion.

  11. Neutrino Oscillation Induced by Chiral Phase Transition

    Institute of Scientific and Technical Information of China (English)

    MU Cheng-Fu; SUN Gao-Feng; ZHUANG Peng-Fei

    2009-01-01

    Electric charge neutrality provides a relationship between chiral dynamics and neutrino propagation in compact stars.Due to the sudden drop of the electron density at the first-order chiral phase transition,the oscillation for low energy neutrinos is significant and can be regarded as a signature of chiral symmetry restoration in the core of compact stars.

  12. Quenched Chiral Perturbation Theory to one loop

    NARCIS (Netherlands)

    Colangelo, G.; Pallante, E.

    1998-01-01

    The divergences of the generating functional of quenched Chiral Perturbation theory (qCHPT) to one loop are computed in closed form. We show how the quenched chiral logarithms can be reabsorbed in the renormalization of the B0 parameter of the leading order Lagrangian. Finally, we do the chiral powe

  13. Shear Viscosity of Turbulent Chiral Plasma

    CERN Document Server

    Kumar, Avdhesh; Das, Amita; Kaw, P K

    2016-01-01

    It is well known that the difference between the chemical potentials of left-handed and right-handed particles in a parity violating (chiral) plasma can lead to an instability. We show that the chiral instability may drive turbulent transport. Further we estimate the anomalous viscosity of chiral plasma arising from the enhanced collisionality due to turbulence.

  14. Exact Chiral Symmetry on the Lattice

    CERN Document Server

    Neuberger, H

    2001-01-01

    Developments during the last eight years have refuted the folklore that chiral symmetries cannot be preserved on the lattice. The mechanism that permits chiral symmetry to coexist with the lattice is quite general and may work in Nature as well. The reconciliation between chiral symmetry and the lattice is likely to revolutionize the field of numerical QCD.

  15. Axially Symmetric, Spatially Homothetic Spacetimes

    CERN Document Server

    Wagh, S M; Wagh, Sanjay M.; Govinder, Keshlan S.

    2002-01-01

    We show that the existence of appropriate spatial homothetic Killing vectors is directly related to the separability of the metric functions for axially symmetric spacetimes. The density profile for such spacetimes is (spatially) arbitrary and admits any equation of state for the matter in the spacetime. When used for studying axisymmetric gravitational collapse, such solutions do not result in a locally naked singularity.

  16. Thermophoresis of Axially Symmetric Bodies

    Science.gov (United States)

    2007-11-02

    Sweden Abstract. Thermophoresis of axially symmetric bodies is investigated to first order in the Knudsen-mimber, Kn. The study is made in the limit...derived. Asymptotic solutions are studied. INTRODUCTION Thermophoresis as a phenomenon has been known for a long time, and several authors have approached

  17. Axial structure of the nucleon

    Energy Technology Data Exchange (ETDEWEB)

    Veronique Bernard; Latifa Elouadrhiri; Ulf-G Meissner

    2002-01-01

    We review the current status of experimental and theoretical understanding of the axial nucleon structure at low and moderate energies. Topics considered include (quasi)elastic (anti)neutrino-nucleon scattering, charged pion electroproduction off nucleons and ordinary as well as radiative muon capture on the proton.

  18. Intrinsic chirality and prochirality at Air/R-(+)- and S-(-)-limonene interfaces: spectral signatures with interference chiral sum-frequency generation vibrational spectroscopy.

    Science.gov (United States)

    Fu, Li; Zhang, Yun; Wei, Zhe-Hao; Wang, Hong-Fei

    2014-09-01

    We report in this work detailed measurements of the chiral and achiral sum-frequency vibrational spectra in the C-H stretching vibration region (2800-3050 cm(-1)) of the air/liquid interfaces of R-(+)-limonene and S-(-)-limonene, using the recently developed high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The achiral SFG spectra of R-limonene and S-limonene, as well as the RS racemic mixture (50/50 equal amount mixture), show that the corresponding molecular groups of the R and S enantiomers are with the same interfacial orientations. The interference chiral SFG spectra of the limonene enantiomers exhibit a spectral signature from the chiral response of the Cα-H stretching mode, and a spectral signature from the prochiral response of the CH(2) asymmetric stretching mode, respectively. The chiral spectral feature of the Cα-H stretching mode changes sign from R-(+)-limonene to S-(-)-limonene surfaces, and disappears for the RS racemic mixture surface. While the prochiral spectral feature of the CH(2) asymmetric stretching mode is the same for R-(+)-limonene and S-(-)-limonene surfaces, and also surprisingly remains the same for the RS racemic mixture surface. Therefore, the structures of the R-(+)-limonene and the S-(-)-limonene at the liquid interfaces are nevertheless not mirror images to each other, even though the corresponding groups have the same tilt angle from the interfacial normal, i.e., the R-(+)-limonene and the S-(-)-limonene at the surface are diastereomeric instead of enantiomeric. These results provide detailed information in understanding the structure and chirality of molecular interfaces and demonstrate the sensitivity and potential of SFG-VS as a unique spectroscopic tool for chirality characterization and chiral recognition at the molecular interface.

  19. Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds

    Directory of Open Access Journals (Sweden)

    Márcio S. Silva

    2017-02-01

    Full Text Available Nuclear magnetic resonance (NMR is a powerful tool for the elucidation of chemical structure and chiral recognition. In the last decade, the number of probes, media, and experiments to analyze chiral environments has rapidly increased. The evaluation of chiral molecules and systems has become a routine task in almost all NMR laboratories, allowing for the determination of molecular connectivities and the construction of spatial relationships. Among the features that improve the chiral recognition abilities by NMR is the application of different nuclei. The simplicity of the multinuclear NMR spectra relative to 1H, the minimal influence of the experimental conditions, and the larger shift dispersion make these nuclei especially suitable for NMR analysis. Herein, the recent advances in multinuclear (19F, 31P, 13C, and 77Se NMR spectroscopy for chiral recognition of organic compounds are presented. The review describes new chiral derivatizing agents and chiral solvating agents used for stereodiscrimination and the assignment of the absolute configuration of small organic compounds.

  20. Chiral resolution of basic drugs by capillary electrophoresis with new glycosaminoglycans.

    Science.gov (United States)

    Tsukamoto, T; Ushio, T; Haginaka, J

    1999-12-09

    New glycosaminoglycans, fucose-containing glycosaminoglycan (FGAG) and depolymerized holothurian glycosaminoglycan (DHG), were investigated as chiral additives for the separation of drug enantiomers by capillary electrophoresis. The average molecular masses of FGAG and DHG were estimated to be about 59,000 and 14,000, respectively. A variety of basic drug enantiomers were resolved using 10 mM phosphate buffer, pH 5.0, containing 3% FGAG or DHG. Since chiral recognition properties of FGAG and DHG are different, some drug enantiomers were only separated by using FGAG or DHG. With regard to comparison of chiral recognition abilities of FGAG and DHG with other chiral selectors, tolperisone and eperisone enantiomers were not separated with alpha- or beta-cyclodextrin, or heparin as the chiral additives, but were separated with FGAG and DHG. The results obtained reveal that FGAG and DHG are useful as the chiral selectors for separations of drug enantiomers by CE, and that they could be complementarily used with other chiral additives.