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Sample records for multiple chiral centers

  1. Temperature-Dependent Enantio- and Diastereodivergent Synthesis of Amino Acids with One or Multiple Chiral Centers.

    PubMed

    Fan, Shiming; Liu, Shouxin; Zhu, Sufang; Feng, Juan; Zhang, Zhiwei; Huang, Jing

    2017-09-01

    A general and facile methodology for temperature-dependent enantiodivergent and diastereodivergent synthesis of amino acids with one or multiple chiral centers was developed. Camphor-based tricyclic iminolactones attack electrophiles from the endo face at low temperature (-78 to -40 °C) and from the exo face at high temperature (-10 to 25 °C).

  2. Enantio-separation of drugs with multiple chiral centers by chromatography and capillary electrophoresis.

    PubMed

    Al-Othman, Zeid A; Al-Warthan, Abdulrahman; Alam, Syed Dilshad; Ali, Imran

    2014-11-01

    Some drugs with more than one chiral center are of high medicinal values. However, the chiral resolution of such types of racemate is a challenging task for scientists. The evolution of efficient chiral selectors is a hope for the future. Some papers have described such types of chiral resolution. The different techniques used for the purpose are HPLC, micellar electrokinetic chromatography, supercritical fluid chromatography, capillary electrochromatography and capillary electrophoresis. Owing to these facts, it was necessary to review the enantiomeric resolution of racemic drugs having more than one chiral center. The present article describes the chiral resolution of labetalol, formoterol, nadolol, indenolol, nebivolol and diltiazem using above cited techniques. In addition, attempts have been made to discuss the chiral recognition mechanism and future perspectives. Copyright © 2014 John Wiley & Sons, Ltd.

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

    PubMed Central

    Koutoulogenis, Giorgos; Kaplaneris, Nikolaos

    2016-01-01

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

  4. Discrimination of Enantiomers of Dipeptide Derivatives with Two Chiral Centers by Tetraaza Macrocyclic Chiral Solvating Agents Using (1)H NMR Spectroscopy.

    PubMed

    Fang, Lixia; Lv, Caixia; Wang, Guo; Feng, Lei; Stavropoulos, Pericles; Gao, Guangpeng; Ai, Lin; Zhang, Jiaxin

    2016-12-01

    (1)H NMR spectroscopy is often used to discriminate enantiomers of chiral analytes and determine their enantiomeric excess (ee) by various chiral auxiliaries. In reported research, these studies were mainly focused on chiral discriminantion of chiral analytes with only one chiral center. However, many chiral compounds possessing two or more chiral centers are often found in natural products, chiral drugs, products of asymmetric synthesis and biological systems. Therefore, it is necessary to investigate their chiral discrimination by effective chiral auxiliaries using (1)H NMR spectroscopy. In this paper, a new class of tetraaza macrocyclic chiral solvating agents (TAMCSAs) with two amide (CONH), two amino (NH) and two phenolic hydroxyl (PhOH) groups has been designed and synthsized for chiral discrimination towards dipeptide derivatives with two chiral centers. These dipeptide derivatives are important chiral species because some of them are used as clinical drugs and special dietary supplements for treatment of human diseases, such as L-alanyl-L-glutamine and aspartame. The results show that these TAMCSAs have excellent chiral discriminating properties and offer multiple detection possibilities pertaining to (1)H NMR signals of diagnostic split protons. The nonequivalent chemical shifts (up to 0.486 ppm) of various types of protons of these dipeptide derivatives were evaluated with the assistance of well-resolved (1)H NMR signals in most cases. In addition, enantiomeric excesses (ee) of the dipeptide derivatives with different optical compositions have been calculated based on integration of well-separeted proton signals. At the same time, the possible chiral discriminating behaviors have been discussed by means of Job plots, ESI mass spectra and a proposed theoretical model of (±)-G1 with TAMCSA 1c. Additionally, the association constants of enantiomers of (±)-G5 with TAMCSA 1a were calculated by employing the nonlinear curve-fitting method.

  5. Multiple Chirality in Nuclear Rotation: A Microscopic View

    DOE PAGES

    Zhao, P. W.

    2017-10-10

    Covariant density functional theory and three-dimensional tilted axis cranking are used to investigate multiple chirality in nuclear rotation for the first time in a fully self-consistent and microscopic way. Two distinct sets of chiral solutions with negative and positive parities, respectively, are found in the nucleus 106Rh. The negative-parity solutions reproduce well the corresponding experimental spectrum as well as the B(M1)/B(E2) ratios of the transition strengths. This indicates that a predicted positive-parity chiral band should also exist. Therefore, it provides a further strong hint that multiple chirality is realized in nuclei.

  6. Multiple chirality in nuclear rotation: A microscopic view

    NASA Astrophysics Data System (ADS)

    Zhao, P. W.

    2017-10-01

    Covariant density functional theory and three-dimensional tilted axis cranking are used to investigate multiple chirality in nuclear rotation for the first time in a fully self-consistent and microscopic way. Two distinct sets of chiral solutions with negative and positive parities, respectively, are found in the nucleus 106Rh. The negative-parity solutions reproduce well the corresponding experimental spectrum as well as the B (M 1) / B (E 2) ratios of the transition strengths. This indicates that a predicted positive-parity chiral band should also exist. Therefore, it provides a further strong hint that multiple chirality is realized in nuclei.

  7. Electromagnetic transitions in multiple chiral doublet bands

    NASA Astrophysics Data System (ADS)

    Jia, Hui; Qi, Bin; Wang, Shou-Yu; Wang, Shuo; Liu, Chen

    2016-12-01

    Multiple chiral doublet bands (MχD) in the 80, 130 and 190 mass regions are studied by the model of γ = 90° triaxial rotor coupled with identical symmetric proton-neutron configurations. By selecting a suitable basis, the calculated wave functions are explicitly exhibited to be symmetric under the operator Â, which is defined as rotation by 90° about the 3-axis with the exchange of valance proton and neutron. We found that both M1 and E2 transitions are allowed between levels with different values of A, while they are forbidden between levels with same values of A. Such a selection rule holds true for MχD in different mass regions. Supported by National Natural Science Foundation of China (11675094, 11622540, 11545011, 11405096, 11461141001, U1432119), Shandong Natural Science Foundation (ZR2014AQ012), and Young Scholars Program of Shandong University, Weihai (2015WHWLJH01)

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

  9. Spontaneous transmission of chirality through multiple length scales.

    PubMed

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

    2011-06-20

    naphtho[2,3-a]pyrene molecules adsorbed in the second layer. Given its simplicity, reversibility, and rich degree of order, this system represents an ideal test bed for the investigation of symmetry breaking and the hierarchical transmission of chirality through multiple length scales.

  10. Evidence for Octupole Correlations in Multiple Chiral Doublet Bands

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  11. Possible multiple chiral doublet bands in 107Ag

    NASA Astrophysics Data System (ADS)

    Qi, B.; Jia, H.; Zhang, N. B.; Liu, C.; Wang, S. Y.

    2013-08-01

    Two pairs of nearly degenerate doublet bands in 107Ag are studied via the relativistic mean-field (RMF) theory and the multiparticle plus rotor model (PRM), which suggests these bands as two distinct sets of chiral doublet bands. For the suggested πg9/2-1⊗νh11/22 and πg9/2-1⊗νh11/2d5/2 configurations, the favorable triaxial deformation γ for nuclear chirality can be obtained from the configuration-fixed constrained triaxial RMF calculations. Adopting the PRM, the data available are reproduced very well for the two pairs of doublet bands. Chiral geometry is further conformed by analyzing the angular momentum components. We suggest that two pairs of doublet bands in 107Ag would be another example of multiple chiral doublet bands.

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

    PubMed

    Bouayad-Gervais, Samir H; Lubell, William D

    2013-11-28

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

  13. Construction of a Chiral Silicon Center by Rhodium-Catalyzed Enantioselective Intramolecular Hydrosilylation.

    PubMed

    Naganawa, Yuki; Namba, Tomoya; Kawagishi, Mayu; Nishiyama, Hisao

    2015-06-22

    Rhodium-catalyzed enantioselective desymmetrizing intramolecular hydrosilylation of symmetrically disubstituted hydrosilanes is described. The original axially chiral phenanthroline ligand (S)-BinThro (Binol-derived phenanthroline) was found to work as an effective chiral catalyst for this transformation. A chiral silicon stereogenic center is one of the chiral motifs gaining much attention in asymmetric syntheses and the present protocol provides cyclic five-membered organosilanes incorporating chiral silicon centers with high enantioselectivities (up to 91 % ee). The putative active Rh(I) catalyst takes the form of an N,N,O-tridentate coordination complex, as determined by several complementary experiments.

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

    PubMed

    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.

  15. Multiple Intelligences Centers and Projects.

    ERIC Educational Resources Information Center

    Chapman, Carolyn; Freeman, Lynn

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

  16. Multiple Intelligences Centers and Projects.

    ERIC Educational Resources Information Center

    Chapman, Carolyn; Freeman, Lynn

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

  17. Simultaneous chiral analyses of multiple analytes: case studies, implications and method development considerations.

    PubMed

    Srinivas, Nuggehally R

    2004-12-01

    The field of chiral separations had a modest beginning some two decades ago. However, due to rapid technological advancement coupled with simultaneous availability of innovative chiral stationary phases and novel chiral derivatization agents, the field of chiral separations has now totally outpaced many other separation fields. Keeping pace with rapid changes in the field of chiral separations, investigators continue to add stereoselective pharmacokinetic, pharmacodynamic, pharmacologic and toxicological data of new and/or marketed racemic compounds to the literature. Examination of the evolution of chiral separations suggests that in the beginning many investigators attempted to separate and quantify a single pair of enantiomers, adopting either direct (separation made on a chiral stationary phase) or indirect (separation made following precolumn conversion of enantiomers to corresponding diastereomers) approaches. However, more recent trends in chiral separations suggest that investigators are attempting to separate and quantify multiple pairs of enantiomers with available technologies. Added to this, some interesting trends have been observed in many of the recently reported chiral applications, including preferences regarding internal standard selection, mobile phase contents and composition, sorting out issues with mass spectrometric detection, determination of elution order, analytical manipulations of metabolite(s) without reference standards and addressing some specificity-related issues. This review mainly focuses on chiral separations involving multiple chiral analytes and attempts to justify the need for such chiral separations involving multiple analytes. In this context, several cases studies are described on the utility and applicability of such chiral separations under discrete headings to provide an account to the readership on the implications of such tasks. The topics of case studies covered in this review include: (a) therapy markers

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

    PubMed

    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.

  19. Anomalous circular dichroism in high harmonic generation of stereoisomers with two chiral centers.

    PubMed

    Zhu, Xiaosong; Liu, Xi; Lan, Pengfei; Wang, Dian; Zhang, Qingbin; Li, Wei; Lu, Peixiang

    2016-10-31

    When a molecule has more than one chiral center, it can be either a chiral molecule or a meso isomer. High harmonic generation (HHG) of stereoisomers with two chiral centers driven by circularly polarized (CP) laser pulses is investigated. Counterintuitively, it is found that the HHG exhibits prominent circular dichroism for the meso isomer, while the harmonic spectra with left and right CP laser pulses are nearly the same for the chiral isomers. We show that the anomalous circular dichroism is attributed to the characteristic recollision dynamics of HHG. This feature makes the HHG a promising tool to discriminate the meso isomer and racemic mixture, where no optical activity can be found in both cases. Similar dichroism responses are also found by applying the counter-rotating bicircular laser pulses.

  20. Chiral rotational spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  1. A Simple Method for Specifying the R/S Configuration about a Chiral Center.

    ERIC Educational Resources Information Center

    Idoux, John P.

    1982-01-01

    Describes a method for specifying R/S (clockwise/counterclockwise) configuration about a chiral center which does not require the use of a three-dimensional physical model, the mental visualization of the molecule, or the memorization of a recently reported arbitrary number system. (Author/JN)

  2. SU(3) center vortices underpin confinement and dynamical chiral symmetry breaking

    NASA Astrophysics Data System (ADS)

    O'Malley, Elyse-Ann; Kamleh, Waseem; Leinweber, Derek; Moran, Peter

    2012-09-01

    The mass function of the nonperturbative quark propagator in SU(3) gauge theory shows only a weak dependence on the vortex content of the gauge configurations. Of particular note is the survival of dynamical mass generation on vortex-free configurations having a vanishing string tension. This admits the possibility that mass generation associated with dynamical chiral symmetry breaking persists without confinement. In this paper we examine the low-lying ground state hadron spectrum of the π, ρ, N and Δ and discover that while dynamical mass generation persists in the vortex-free theory, it is not connected to dynamical chiral symmetry breaking. In this way, center vortices in SU(3) gauge theory are intimately linked to both confinement and dynamical chiral symmetry breaking.

  3. Design of Selenium-Based Chiral Chemical Probes for Simultaneous Enantio- and Chemosensing of Chiral Carboxylic Acids with Remote Stereogenic Centers by NMR Spectroscopy.

    PubMed

    Shyshkanov, Sergey A; Orlov, Nikolai V

    2016-10-17

    Selenium-based enantiopure chiral chemical probes have been designed in a modular way starting from available amino alcohols. The probes developed were found to be efficient in chemoselective interaction with carboxylic functions of chiral substrates leading to diastereomeric amide formation and in sensing α-, β-, and remote (up to seven bonds away from the carboxylic group) chiral centers by using (77) Se NMR spectroscopy. As a result, it was possible to determine the enantiomeric ratio of structurally diverse individual chiral acids including polyfunctional compounds and drugs with high accuracy. An approach to analyzing the crude reaction mixtures has been successfully developed by using bifunctional selenium- and fluorine-containing chiral probes. More importantly, it was revealed that, based on the (77) Se NMR data obtained, it is possible to obtain primary information about the location and nature of the substituents at the chiral center (chemo- and enantiosensing), which can simplify the structural elucidation of complex compounds. The derivatization procedure takes as little as 5 min and can be performed directly in an NMR tube followed by NMR measurements without any isolation and purification steps.

  4. Steering Asymmetric Lewis Acid Catalysis Exclusively with Octahedral Metal-Centered Chirality.

    PubMed

    Zhang, Lilu; Meggers, Eric

    2017-02-21

    Catalysts for asymmetric synthesis must be chiral. Metal-based asymmetric catalysts are typically constructed by assembling chiral ligands around a central metal. In this Account, a new class of effective chiral Lewis acid catalysts is introduced in which the octahedral metal center constitutes the exclusive source of chirality. Specifically, the here discussed class of catalysts are composed of configurationally stable, chiral-at-metal Λ-configured (left-handed propeller) or Δ-configured (right-handed propeller) iridium(III) or rhodium(III) complexes containing two bidentate cyclometalating 5-tert-butyl-2-phenylbenzoxazole (dubbed IrO and RhO) or 5-tert-butyl-2-phenylbenzothiazole (dubbed IrS and RhS) ligands in addition to two exchange-labile acetonitriles. They are synthetically accessible in an enantiomerically pure fashion through a convenient auxiliary-mediated synthesis. Such catalysts are of interest due to their intrinsic structural simplicity (only achiral ligands) and the prospect of an especially effective asymmetric induction due to the intimate contact between the chiral metal center and the metal-coordinated substrates or reagents. With respect to chiral Lewis acid catalysis, the bis-cyclometalated iridium and rhodium complexes provide excellent catalytic activities and asymmetric inductions for a variety of reactions including Michael additions, Friedel-Crafts reactions, cycloadditions, α-aminations, α-fluorinations, Mannich reactions, and a cross-dehydrogenative coupling. Mechanistically, substrates such as 2-acyl imidazoles are usually activated by two-point binding. Exceptions exist as for example for an efficient iridium-catalyzed enantioselective transfer hydrogenation of arylketones with ammonium formate, which putatively proceeds through an iridium-hydride intermediate. The bis-cyclometalated iridium complexes catalyze visible-light-induced asymmetric reactions by intertwining asymmetric catalysis and photoredox catalysis in a unique

  5. Stereodynamics of nitrogen chiral centers in aza-β3-cyclodipeptides.

    PubMed

    Le Grel, Philippe; Asprogenidi, Aikaterini; Huez, Philippe; Le Grel, Barbara; Salaün, Arnaud; Roisnel, Thierry; Potel, Michel; Rasti, Elham; Hocquet, Alexandre

    2013-06-01

    The present work is devoted to the synthesis, conformational analysis, and stereodynamic study of aza-β(3)-cyclodipeptides. This pseudopeptidic ring shows E/Z hydrazide bond isomerism, eight-membered ring conformation, and chirotopic nitrogen atoms, all of which are elements that are prone to modulate the ring shape. The (E,E) twist boat conformation observed in the solid state by X-ray diffraction is also the ground conformation in solution, and emerges as the lowest in energy when using quantum chemical calculations. The relative configuration associated with ring chirality and with the two nitrogen chiral centers is governed by steric crowding and adopts the (P)S(N) S(N)/(M)R(N)R(N) combination which projects side chains in equatorial position. The nitrogen pyramidal inversion (NPI) at the two chiral centers is correlated with the ring reversal. The process is significantly hindered as was shown by VT-NMR experiments run in C2D2Cl4, which did not make it possible to determine the barrier to inversion. Finally, these findings make it conceivable to resolve enantiomers of aza-β(3)-cyclodipeptides by modulating the backbone decoration appropriately. © 2013 Wiley Periodicals, Inc.

  6. Lithium Enolates in the Enantioselective Construction of Tetrasubstituted Carbon Centers with Chiral Lithium Amides as Noncovalent Stereodirecting Auxiliaries.

    PubMed

    Yu, Kai; Lu, Ping; Jackson, Jeffrey J; Nguyen, Thuy-Ai D; Alvarado, Joseph; Stivala, Craig E; Ma, Yun; Mack, Kyle A; Hayton, Trevor W; Collum, David B; Zakarian, Armen

    2017-01-11

    Lithium enolates derived from carboxylic acids are ubiquitous intermediates in organic synthesis. Asymmetric transformations with these intermediates, a central goal of organic synthesis, are typically carried out with covalently attached chiral auxiliaries. An alternative approach is to utilize chiral reagents that form discrete, well-defined aggregates with lithium enolates, providing a chiral environment conducive of asymmetric bond formation. These reagents effectively act as noncovalent, or traceless, chiral auxiliaries. Lithium amides are an obvious choice for such reagents as they are known to form mixed aggregates with lithium enolates. We demonstrate here that mixed aggregates can effect highly enantioselective transformations of lithium enolates in several classes of reactions, most notably in transformations forming tetrasubstituted and quaternary carbon centers. Easy recovery of the chiral reagent by aqueous extraction is another practical advantage of this one-step protocol. Crystallographic, spectroscopic, and computational studies of the central reactive aggregate, which provide insight into the origins of selectivity, are also reported.

  7. Calcium-catalyzed asymmetric synthesis of 3-tetrasubstituted oxindoles: efficient construction of adjacent quaternary and tertiary chiral centers.

    PubMed

    Shimizu, Shota; Tsubogo, Tetsu; Xu, Pengyu; Kobayashi, Shū

    2015-04-17

    Chiral Ca-catalyzed asymmetric addition reactions of 3-substituted oxindoles with N-Boc-imines afford 3-tetrasubstituted oxindole derivatives bearing adjacent quaternary and tertiary chiral centers, which are key structures for biological activities. Ubiquitous and nontoxic Ca catalysts (1-10 mol %) work well in this reaction, and high yields (up to 99%) and selectivities (up to >99% ee) of the products with wide substrate scope have been attained. The structures of the chiral Ca catalysts and intermediary Ca enolates are also discussed.

  8. Chiral separation of a basic drug with two chiral centers by electrokinetic chromatography for its pharmaceutical development.

    PubMed

    Martínez-Girón, Ana Belén; Marina, María Luisa; Crego, Antonio L

    2016-10-07

    A chiral method using capillary electrophoresis was developed for the separation of the four stereoisomers of a new chiral substance currently undergoing drug development as single enantiomer. After the selection of highly sulfated β-CD as chiral selector, an exhaustive study on the influence of several experimental variables on the resolution was performed, being the substitution degree of the CD a very decisive factor. Run time and resolutions were about 20min and higher than 2.0, respectively. The method was validated in terms of selectivity, linearity, accuracy, precision, and limits of detection and quantitation according to the requirements of the International Conference on Harmonisation for the determination of the chiral purity of a drug substance. The usefulness of the method was demonstrated in the control of stereoisomeric impurities in raw material as well as in the determination of the chiral stability of the drug in the solid state and in dosage forms used in safety assessment. Finally, the chiral method was used to investigate the possible in vivo inversion in biological samples.

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

    PubMed

    Laska, Matthias

    2004-02-01

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

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

    ERIC Educational Resources Information Center

    Lloyd-Williams, Paul; Giralt, Ernest

    2005-01-01

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

  11. Catalytic asymmetric synthesis of 3,3'-diaryloxindoles as triarylmethanes with a chiral all-carbon quaternary center: phase-transfer-catalyzed S(N)Ar reaction.

    PubMed

    Shirakawa, Seiji; Koga, Kenta; Tokuda, Takashi; Yamamoto, Kenichiro; Maruoka, Keiji

    2014-06-10

    Catalytic asymmetric synthesis of unsymmetrical triarylmethanes with a chiral all-carbon quaternary center was achieved by using a chiral bifunctional quaternary phosphonium bromide catalyst in the S(N)Ar reaction of 3-aryloxindoles under phase-transfer conditions. The presence of a urea moiety in the chiral phase-transfer catalyst was important for obtaining high enantioselectivity in this reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Determination of a low-level percent enantiomer of a compound with no ultraviolet chromophore using vibrational circular dichroism (VCD): enantiomeric purity by VCD of a compound with three chiral centers.

    PubMed

    Kott, Laila; Petrovic, Jelena; Phelps, Dean; Roginski, Robert; Schubert, Jared

    2014-01-01

    The chiral configuration of three of the four chiral centers in the investigational drug MLN4924 is locked by an intermediate (1S,2S,4R)-4-amino-2-(hydroxymethyl)cyclopentanol (designated as INT1a). The intermediate INT1a is a key component to the molecule, but its multiple chiral centers and lack of chromophore make it challenging to analyze for chiral purity of the desired enantiomer when it is contaminated with a small amount of its undesired enantiomer. Vibrational circular dichroism (VCD) is a technique that uses the infrared (IR) regions of the electromagnetic spectrum and as INT1a contains IR active groups, we considered using VCD to determine the chiral purity of INT1a. Since the VCD spectra of enantiomers are of equal intensity and opposite in sign, it was possible to construct calibration curves to detect the presence of low levels of this compound in the presence of its enantiomer. By normalizing the observed intensities of the VCD signals with the observed IR spectra, a partial least squares model was constructed having a root mean squared error of cross validation of 0.46% absolute over a range of 97 to 99.9% pure enantiomer (or 97-99.8% enantiomeric excess). This work demonstrates that VCD can be used for the low-level detection of a compound in the presence of its enantiomer and thus eliminates the need for an ultraviolet chromophore and chromatographic separation of the two enantiomers.

  13. Multiple scattering in turbid media containing chiral components: A Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Otsuki, Soichi

    2017-01-01

    A Monte Carlo simulation was performed for an infinite plane medium containing spherical particles as well as a chiral component. The optical activity shifts patterns in the two-dimensional map of the effective scattering Mueller matrix in the azimuthal direction. The reduced effective matrix obtained by the simulation approximately satisfies reciprocity in spite of the theoretical prediction. The pattern shifts are explained by the mixing of elements of the reduced effective Mueller matrix owing to multiplication of two rotation matrices. The reduced effective matrix was factorized using the Lu-Chipman polar decomposition affording the polarization components as a function of the distance. The functions as a retarding linear diattenuator of the medium decreases, whereas the optical rotation increases, as the distance increases. The estimated specific rotation on the medium surface is 1.6 times larger than the specific rotation in the medium used in the simulation.

  14. Copper-catalyzed asymmetric conjugate addition of trialkylaluminium reagents to trisubstituted enones: construction of chiral quaternary centers.

    PubMed

    Vuagnoux-d'Augustin, Magali; Alexakis, Alexandre

    2007-01-01

    Me3Al, Et3Al, and vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2-enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3CN)4]BF4 or [CuOTf]2C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous optimization of experimental conditions. It was shown that the main important parameter was the order of the introduction of the reagents. Then, the generated enantioenriched aluminium enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions.

  15. Asymmetric Catalytic aza-Morita-Baylis-Hillman Reaction for the Synthesis of 3-Substituted-3-Aminooxindoles with Chiral Quaternary Carbon Centers

    PubMed Central

    Hu, Fang-Le; Wei, Yin; Shi, Min; Pindi, Suresh; Li, Guigen

    2013-01-01

    Asymmetric catalytic aza-Morita-Baylis-Hillman (aza-MBH) reaction of isatin-derived ketimines with MVK has been established by using chiral amino and phosphino catalysts. The reaction resulted in biomedically important 3-substituted 3-amino-2-oxindoles in good yields (>80% for most cases) and excellent enantioselectivity (90–99%ee). Twenty-eight cases assembled with chiral quaternary stereogenic centers have been examined under convenient systems. PMID:23407608

  16. Carboxy-directed asymmetric hydrogenation of α-alkyl-α-aryl terminal olefins: highly enantioselective and chemoselective access to a chiral benzylmethyl center.

    PubMed

    Yang, Shuang; Zhu, Shou-Fei; Guo, Na; Song, Song; Zhou, Qi-Lin

    2014-04-07

    A carboxy-directed asymmetric hydrogenation of α-alkyl-α-aryl terminal olefins was developed by using a chiral spiro iridium catalyst, providing a highly efficient approach to the compounds with a chiral benzylmethyl center. The carboxy-directed hydrogenation prohibited the isomerization of the terminal olefins, and realized the chemoselective hydrogenation of various dienes. The concise enantioselective syntheses of (S)-curcudiol and (S)-curcumene were achieved by using this catalytic asymmetric hydrogenation as a key step.

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

    SciTech Connect

    Loussert, Charles; Brasselet, Etienne

    2014-02-03

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

  18. Classroom Centers for Multiple Handicapped Children 1972-1975.

    ERIC Educational Resources Information Center

    Grigsby, Camilla

    The Classroom Centers for Multiple Handicapped Children were designed to provide profoundly retarded children with instructional programs meeting individual needs. In addition to the educational and training components of the program, speech and physical therapy services were also included. Seven classroom centers served approximately 56 children…

  19. Chiral Inorganic Nanostructures.

    PubMed

    Ma, Wei; Xu, Liguang; de Moura, André F; Wu, Xiaoling; Kuang, Hua; Xu, Chuanlai; Kotov, Nicholas A

    2017-06-28

    The field of chiral inorganic nanostructures is rapidly expanding. It started from the observation of strong circular dichroism during the synthesis of individual nanoparticles (NPs) and their assemblies and expanded to sophisticated synthetic protocols involving nanostructures from metals, semiconductors, ceramics, and nanocarbons. Besides the well-established chirality transfer from bioorganic molecules, other methods to impart handedness to nanoscale matter specific to inorganic materials were discovered, including three-dimentional lithography, multiphoton chirality transfer, polarization effects in nanoscale assemblies, and others. Multiple chiral geometries were observed with characteristic scales from ångströms to microns. Uniquely high values of chiral anisotropy factors that spurred the development of the field and differentiate it from chiral structures studied before, are now well understood; they originate from strong resonances of incident electromagnetic waves with plasmonic and excitonic states typical for metals and semiconductors. At the same time, distinct similarities with chiral supramolecular and biological systems also emerged. They can be seen in the synthesis and separation methods, chemical properties of individual NPs, geometries of the nanoparticle assemblies, and interactions with biological membranes. Their analysis can help us understand in greater depth the role of chiral asymmetry in nature inclusive of both earth and space. Consideration of both differences and similarities between chiral inorganic, organic, and biological nanostructures will also accelerate the development of technologies based on chiroplasmonic and chiroexcitonic effects. This review will cover both experiment and theory of chiral nanostructures starting with the origin and multiple components of mirror asymmetry of individual NPs and their assemblies. We shall consider four different types of chirality in nanostructures and related physical, chemical, and

  20. Multiple Determinants of Caregiver Behavior in Child Care Centers

    ERIC Educational Resources Information Center

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

    2007-01-01

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

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

    ERIC Educational Resources Information Center

    Goldstein, Semadar

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  3. Photophysics and redox behavior of chiral transition metal polymers.

    PubMed

    Barron, Jason A; Glazier, Samantha; Bernhard, Stefan; Takada, Kazutake; Houston, Paul L; Abruña, Héctor D

    2003-03-10

    The absorption and emission spectra, excited-state lifetimes, quantum yields, and electrochemical measurements have been obtained for a new series of chiral complexes based on three different chiral 2,2':6',2' '-terpyridine ligands, (-)-ctpy, (-)-[ctpy-x-ctpy], and (-)-[ctpy-b-ctpy], with one, two, or multiple Ru metal centers. The room-temperature absorption and emission maxima of [[((-)-ctpy)Ru]-(-)-[ctpy-b-ctpy]-[Ru((-)-ctpy)

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    Hayami, Satoru; Ozawa, Ryo; Motome, Yukitoshi

    2016-07-01

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

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

    SciTech Connect

    Doerry, Armin W.; Bickel, Douglas L.

    2015-03-01

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

  7. Chiral Separations

    NASA Astrophysics Data System (ADS)

    Stalcup, A. M.

    2010-07-01

    The main goal of this review is to provide a brief overview of chiral separations to researchers who are versed in the area of analytical separations but unfamiliar with chiral separations. To researchers who are not familiar with this area, there is currently a bewildering array of commercially available chiral columns, chiral derivatizing reagents, and chiral selectors for approaches that span the range of analytical separation platforms (e.g., high-performance liquid chromatography, gas chromatography, supercritical-fluid chromatography, and capillary electrophoresis). This review begins with a brief discussion of chirality before examining the general strategies and commonalities among all of the chiral separation techniques. Rather than exhaustively listing all the chiral selectors and applications, this review highlights significant issues and differences between chiral and achiral separations, providing salient examples from specific classes of chiral selectors where appropriate.

  8. Chiral symmetry in quarkyonic matter

    SciTech Connect

    Kojo, T.

    2012-05-15

    The 1/N{sub c} expansion classifies nuclear matter, deconfined quark matter, and Quarkyonic matter in low temperature region. We investigate the realization of chiral symmetry in Quarkyonic matter by taking into account condensations of chiral particle-hole pairs. It is argued that chiral symmetry and parity are locally violated by the formation of chiral spirals, <{psi}-bar exp (2i{mu}{sub q} z{gamma}{sup 0} {gamma}{sup z}){psi}> . An extension to multiple chiral spirals is also briefly discussed.

  9. Chiral mixtures

    NASA Astrophysics Data System (ADS)

    Petitjean, Michel

    2002-08-01

    An index evaluating the amount of chirality of a mixture of colored random variables is defined. Properties are established. Extreme chiral mixtures are characterized and examples are given. Connections between chirality, Wasserstein distances, and least squares Procrustes methods are pointed out.

  10. Self-replication and amplification of enantiomeric excess of chiral multifunctionalized large molecules by asymmetric autocatalysis.

    PubMed

    Kawasaki, Tsuneomi; Nakaoda, Mai; Takahashi, Yutaro; Kanto, Yusuke; Kuruhara, Nanako; Hosoi, Kenji; Sato, Itaru; Matsumoto, Arimasa; Soai, Kenso

    2014-10-13

    Self-replication of large chiral molecular architectures is one of the great challenges and interests in synthetic, systems, and prebiotic chemistry. Described herein is a new chemical system in which large chiral multifunctionalized molecules possess asymmetric autocatalytic self-replicating and self-improving abilities, that is, improvement of their enantioenrichment in addition to the diastereomeric ratio. The large chiral multifunctionalized molecules catalyze the production of themselves with the same structure, including the chirality of newly formed asymmetric carbon atoms, in the reaction of the corresponding achiral aldehydes and reagent. The chirality of the large multifunctionalized molecules controlled the enantioselectivity of the reaction in a highly selective manner to construct multiple asymmetric stereogenic centers in a single reaction.

  11. Chirality and protein biosynthesis.

    PubMed

    Banik, Sindrila Dutta; Nandi, Nilashis

    2013-01-01

    Chirality is present at all levels of structural hierarchy of protein and plays a significant role in protein biosynthesis. The macromolecules involved in protein biosynthesis such as aminoacyl tRNA synthetase and ribosome have chiral subunits. Despite the omnipresence of chirality in the biosynthetic pathway, its origin, role in current pathway, and importance is far from understood. In this review we first present an introduction to biochirality and its relevance to protein biosynthesis. Major propositions about the prebiotic origin of biomolecules are presented with particular reference to proteins and nucleic acids. The problem of the origin of homochirality is unresolved at present. The chiral discrimination by enzymes involved in protein synthesis is essential for keeping the life process going. However, questions remained pertaining to the mechanism of chiral discrimination and concomitant retention of biochirality. We discuss the experimental evidence which shows that it is virtually impossible to incorporate D-amino acids in protein structures in present biosynthetic pathways via any of the two major steps of protein synthesis, namely aminoacylation and peptide bond formation reactions. Molecular level explanations of the stringent chiral specificity in each step are extended based on computational analysis. A detailed account of the current state of understanding of the mechanism of chiral discrimination during aminoacylation in the active site of aminoacyl tRNA synthetase and peptide bond formation in ribosomal peptidyl transferase center is presented. Finally, it is pointed out that the understanding of the mechanism of retention of enantiopurity has implications in developing novel enzyme mimetic systems and biocatalysts and might be useful in chiral drug design.

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

    PubMed

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

    2015-06-24

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

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

    NASA Technical Reports Server (NTRS)

    Stewart, Camiren L.

    2014-01-01

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

  14. Chiral superconductors.

    PubMed

    Kallin, Catherine; Berlinsky, John

    2016-05-01

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

  15. Pattern production through a chiral chasing mechanism

    NASA Astrophysics Data System (ADS)

    Woolley, Thomas E.

    2017-09-01

    Recent experiments on zebrafish pigmentation suggests that their typical black and white striped skin pattern is made up of a number of interacting chromatophore families. Specifically, two of these cell families have been shown to interact through a nonlocal chasing mechanism, which has previously been modeled using integro-differential equations. We extend this framework to include the experimentally observed fact that the cells often exhibit chiral movement, in that the cells chase, and run away, at angles different to the line connecting their centers. This framework is simplified through the use of multiple small limits leading to a coupled set of partial differential equations which are amenable to Fourier analysis. This analysis results in the production of dispersion relations and necessary conditions for a patterning instability to occur. Beyond the theoretical development and the production of new pattern planiforms we are able to corroborate the experimental hypothesis that the global pigmentation patterns can be dependent on the chirality of the chromatophores.

  16. Chiral Graphene Quantum Dots.

    PubMed

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

    2016-02-23

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

  17. Multiple modes of meaning-making in a science center

    NASA Astrophysics Data System (ADS)

    Rahm, Jrene

    2004-03-01

    In this paper, I address some of the unique challenges of studies of learning in museums through a microanalytic case study of meaning-making among a group of youth and a curator. Through an examination of youths' forms of participation in one exhibit, I illustrate local meaning making achieved through multiple modalities - by doing, talking, and the manipulation of the exhibit. In turn, I show how multiple on-going dialogues come to interact and constitute talk and action at the science exhibit underlining the idiosyncratic nature of meaning-making. While the dialogue examined in this paper may be considered as a rather unremarkable event in terms of learning, it underlines that the study of meaning-making entails a focus on more than mere conversations in situ in that verbal and nonverbal interactions need to be considered simultaneously. Furthermore, the analysis suggests that museums may be best seen as one among many resources for science literacy development whose impact can only be understood through an assessment of learning trajectories over time and across space. Suggestions are made for museum design and future studies of learning in consideration of the issues raised.

  18. Amino Acid Bound Surfactants: A New Synthetic Family of Polymeric Monoliths Open Up Possibilities for Chiral Separations in Capillary Electrochromatography

    PubMed Central

    He, Jun; Wang, Xiaochun; Morrill, Mike; Shamsi, Shahab A.

    2012-01-01

    By combining a novel chiral amino-acid surfactant containing acryloyl amide tail, carbamate linker and leucine head group of different chain lengths with a conventional cross linker and a polymerization technique, a new “one-pot”, synthesis for the generation of amino-acid based polymeric monolith is realized. The method promises to open up the discovery of amino-acid based polymeric monolith for chiral separations in capillary electrochromatography (CEC). Possibility of enhanced chemoselectivity for simultaneous separation of ephedrine and pseudoephedrine containing multiple chiral centers, and the potential use of this amino-acid surfactant bound column for CEC and CEC coupled to mass spectrometric detection is demonstrated. PMID:22607448

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

    PubMed Central

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

    2015-01-01

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

  20. Development of the Distinct Multiple Intelligences in Primary Students through Interest Centers

    ERIC Educational Resources Information Center

    Dueñas Macías, Fredy Alonso

    2013-01-01

    This article reports on an action research study that focused on developing the distinct multiple intelligences of an English class of fifth graders through interest centers at a Colombian school. A multiple intelligences questionnaire, an open-ended observation form, and a student mini-report sheet were used to collect data. Findings revealed…

  1. Chiral plasmonics

    PubMed Central

    Hentschel, Mario; Schäferling, Martin; Duan, Xiaoyang; Giessen, Harald; Liu, Na

    2017-01-01

    We present a comprehensive overview of chirality and its optical manifestation in plasmonic nanosystems and nanostructures. We discuss top-down fabricated structures that range from solid metallic nanostructures to groupings of metallic nanoparticles arranged in three dimensions. We also present the large variety of bottom-up synthesized structures. Using DNA, peptides, or other scaffolds, complex nanoparticle arrangements of up to hundreds of individual nanoparticles have been realized. Beyond this static picture, we also give an overview of recent demonstrations of active chiral plasmonic systems, where the chiral optical response can be controlled by an external stimulus. We discuss the prospect of using the unique properties of complex chiral plasmonic systems for enantiomeric sensing schemes. PMID:28560336

  2. Chiral plasmonics.

    PubMed

    Hentschel, Mario; Schäferling, Martin; Duan, Xiaoyang; Giessen, Harald; Liu, Na

    2017-05-01

    We present a comprehensive overview of chirality and its optical manifestation in plasmonic nanosystems and nanostructures. We discuss top-down fabricated structures that range from solid metallic nanostructures to groupings of metallic nanoparticles arranged in three dimensions. We also present the large variety of bottom-up synthesized structures. Using DNA, peptides, or other scaffolds, complex nanoparticle arrangements of up to hundreds of individual nanoparticles have been realized. Beyond this static picture, we also give an overview of recent demonstrations of active chiral plasmonic systems, where the chiral optical response can be controlled by an external stimulus. We discuss the prospect of using the unique properties of complex chiral plasmonic systems for enantiomeric sensing schemes.

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

    PubMed

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

    2016-05-06

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

  4. Multiplicity Distributions from Antiproton-Proton Collisions at 1.8 Tev Center of Mass Energy

    NASA Astrophysics Data System (ADS)

    Wang, Chi-Ho.

    Charged-particle multiplicity distributions from antiproton-proton collisions at 1800 GeV center of mass energy, obtained with the E735 detector multiplicity hodoscope, are presented and discussed. A simple iteration method is used for conversion from number of observed hodoscope hits to true charged-particle multiplicity. The first four moments of the distribution are compared with distributions from lower energies. The distributions are also fit to KNO-G and negative binomial functions.

  5. Isotopic chirality

    SciTech Connect

    Floss, H.G.

    1994-12-01

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

  6. [Comparison of diffusion tensor imaging-derived fractional anisotropy in multiple centers for identical human subjects].

    PubMed

    Saotome, Kousaku; Ishimori, Yoshiyuki; Isobe, Tomonori; Satou, Eisuke; Shinoda, Kazuya; Ookubo, Jun; Hirano, Yuuji; Oosuka, Satoru; Matsushita, Akira; Miyamoto, Katsumi; Sankai, Yoshiyuki

    2012-01-01

    The fractional anisotropy (FA) is calculated by using diffusion tensor imaging (DTI) with multiple motion probing gradients (MPG). While FA has become a widely used tool to detect moderate changes in water diffusion in brain tissue, the measured value is sensitive to scan parameters (e.g. MPG-direction, signal to noise ratio, etc.). Therefore, it is paramount to address the reproducibility of DTI measurements among multiple centers. The purpose of this study was to assess the inter-center variability of FA. We studied five healthy volunteers who underwent DTI brain scanning three times at three different centers (I-III), each with a 1.5 T scanner having a different MPG-schema. Then, we compared the FA and eigenvalue from the three centers measured in seven brain regions: splenium of corpus callosum (CCs), genu of corpus callosum (CCg), putamen, posterior limb of internal capsule, cerebral peduncle, optic radiation, and middle cerebellar peduncle. At the CCs and CCg, there was a statistical difference (p<0.05) between center Iand center IIfor the same MPG-directions. Furthermore, at CCs and CCg, there was a statistical difference (p<0.05) between center II and center III for different MPG-directions. Conversely, no statistical differences were found between center I and center III for the different MPG-directions for all regions. These results indicate that the FA value was affected by the MPG-schema as well as by the MPG-directions.

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

    PubMed

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

    2015-07-01

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

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

    PubMed

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

    2015-06-01

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

  9. Prebiotic chirality

    NASA Astrophysics Data System (ADS)

    Mekki-Berrada, Ali

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

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

    PubMed

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

    2015-09-01

    Multiple sclerosis and other demyelinating diseases in the pediatric population have received an increasing level of attention by clinicians and researchers. The low incidence of these diseases in children creates a need for the involvement of multiple clinical centers in research efforts. The Network of Pediatric Multiple Sclerosis Centers was created initially in 2006 to improve the diagnosis and care of children with demyelinating diseases. In 2010, the Network shifted its focus to multicenter research while continuing to advance the care of patients. The Network has obtained support from the National Multiple Sclerosis Society, the Guthy-Jackson Charitable Foundation, and the National Institutes of Health. The Network will continue to serve as a platform for conducting impactful research in pediatric demyelinating diseases of the central nervous system. This article provides a description of the history and development, organization, mission, research priorities, current studies, and future plans of the Network. © The Author(s) 2014.

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

    PubMed Central

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

    2014-01-01

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

  12. Chiral Polymers.

    DTIC Science & Technology

    1984-10-01

    TITLE (mid Subttlo) 񓂬-JS. TYPE OF REPORT & PERIOD COVERED CHIRAL POLYMERS /~O~~ R E~NNE 7. AUTHOR(e) 11. CONTRACT OR GRANT NUNSIER(e) J. K. Stille...acrylamide monomer containing a chiral 1,3-dioxane unit as well as both racemic and ( R )-6.-methyl ene-vi-methyl -7-butyrol actone were synthesi zed...or ( R )-propylene oxide (10)6. The key step in this synthesis is the palladium catalyzed carbonylation of 4-bromopent-4-en-2-ol. Thus, either racemic or

  13. Enhanced Stereoselectivity of a Cu(II) Complex Chiral Auxiliary in the Synthesis of Fmoc-L-γ-carboxyglutamic Acid | Center for Cancer Research

    Cancer.gov

    Bridging bioinorganic chemistry with asymmetric synthesis: a naturally occurring metalloprotein is used for the structure-based evolution of chiral auxiliaries that prove to be effective in the synthesis of Fmoc-L-γ-carboxyglutamic acid.

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

    EPA Science Inventory

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

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

    ERIC Educational Resources Information Center

    Story, Julie A.

    2014-01-01

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

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

    ERIC Educational Resources Information Center

    Story, Julie A.

    2014-01-01

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

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

    EPA Science Inventory

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    PubMed

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

    2014-08-01

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

  20. Chiral streamers

    SciTech Connect

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

    2015-10-15

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

  1. Chiral streamers

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    PubMed

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

    2005-03-11

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

  3. Phase-transfer-catalyzed asymmetric synthesis of axially chiral anilides.

    PubMed

    Liu, Kun; Wu, Xiangfei; Kan, S B Jennifer; Shirakawa, Seiji; Maruoka, Keiji

    2013-12-01

    Catalytic asymmetric synthesis of axially chiral o-iodoanilides and o-tert-butylanilides as useful chiral building blocks was achieved by means of binaphthyl-modified chiral quaternary ammonium-salt-catalyzed N-alkylations under phase-transfer conditions. The synthetic utility of axially chiral products was demonstrated in various transformations. For example, axially chiral N-allyl-o-iodoanilide was transformed to 3-methylindoline by means of radical cyclization with high chirality transfer from axial chirality to C-centered chirality. Furthermore, stereochemical information on axial chirality in o-tert-butylanilides could be used as a template to control the stereochemistry of subsequent transformations. The transition-state structure of the present phase-transfer reaction was discussed on the basis of the X-ray crystal structure of ammonium anilide, which was prepared from binaphthyl-modified chiral ammonium bromide and o-iodoanilide. The chiral tetraalkylammonium bromide as a phase-transfer catalyst recognized the steric difference between the ortho substituents on anilide to obtain high enantioselectivity. The size and structural effects of the ortho substituents on anilide were investigated, and a wide variety of axially chiral anilides that possess various functional groups could be synthesized with high enantioselectivities. This method is the only general way to access a variety of axially chiral anilides in a highly enantioselective fashion reported to date. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Disordered two-dimensional electron systems with chiral symmetry

    NASA Astrophysics Data System (ADS)

    Markoš, P.; Schweitzer, L.

    2012-10-01

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

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

    PubMed

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

    2014-01-01

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

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

    PubMed Central

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

    2015-01-01

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

  7. Chiral mirrors

    SciTech Connect

    Plum, Eric; Zheludev, Nikolay I.

    2015-06-01

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

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

    PubMed

    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.

  9. Understanding complex chiral plasmonics.

    PubMed

    Duan, Xiaoyang; Yue, Song; Liu, Na

    2015-11-07

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

  10. Advances in high-throughput and high-efficiency chiral liquid chromatographic separations.

    PubMed

    Patel, Darshan C; Wahab, M Farooq; Armstrong, Daniel W; Breitbach, Zachary S

    2016-10-07

    The need for improved liquid chromatographic chiral separations has led to the advancement of chiral screening techniques as well as the development of new, high efficiency chiral separation methods and stationary phases. This review covers these advancements, which primarily occurred over the last 15 years. High throughput techniques include multi-column screening units, multiple injection sequences, and fast gradient SFC screening. New separation methods and column technologies that aim at high efficiency chiral separations include the use of achiral UHPLC (i.e. sub-2μm) columns for separating derivatized chiral analytes or using chiral additives in the run buffer, UHPLC chiral stationary phases, and superficially porous particle based chiral stationary phases. Finally, the enhancement of chiral separations through these new technologies requires that certain instrumental considerations be made. Future directions in continuing to improve chiral separations are also discussed.

  11. The Development of Multiple Intelligence Capabilities for Early Childhood Development Center, Local Administration Organization in Chaiyaphum Province

    ERIC Educational Resources Information Center

    Siphai, Sunan; Supandee, Terdsak; Raksapuk, Chunpit; Poopayang, Piangkhae; Kratoorerk, Sangsan

    2017-01-01

    The aim of this research is to promote multiple intelligence capabilities for Early Childhood Care Center of a Sub-district Administration Organization in Chaiyaphum Province. The sample applied were 61 children aging between 3 and 5 years old at Child Development Center, Tambon Ban Kok, Amphoe Chaturus, Chaiyaphum Province, who were selected…

  12. Chiral gravitational waves from chiral fermions

    NASA Astrophysics Data System (ADS)

    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.

  13. Chirality of Viral Capsids

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed

    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.

  15. The thyroxine inactivating gene, type III deiodinase, suppresses multiple signaling centers in Dictyostelium discoideum.

    PubMed

    Singh, Shashi Prakash; Dhakshinamoorthy, Ranjani; Jaiswal, Pundrik; Schmidt, Stefanie; Thewes, Sascha; Baskar, Ramamurthy

    2014-12-15

    Thyroxine deiodinases, the enzymes that regulate thyroxine metabolism, are essential for vertebrate growth and development. In the genome of Dictyostelium discoideum, a single intronless gene (dio3) encoding type III thyroxine 5' deiodinase is present. The amino acid sequence of D. discoideum Dio3 shares 37% identity with human T4 deiodinase and is a member of the thioredoxin reductase superfamily. dio3 is expressed throughout growth and development and by generating a knockout of dio3, we have examined the role of thyroxine 5' deiodinase in D. discoideum. dio3(-) had multiple defects that affected growth, timing of development, aggregate size, cell streaming, and cell-type differentiation. A prominent phenotype of dio3(-) was the breaking of late aggregates into small signaling centers, each forming a fruiting body of its own. cAMP levels, its relay, photo- and chemo-taxis were also defective in dio3(-). Quantitative RT-PCR analyses suggested that expression levels of genes encoding adenylyl cyclase A (acaA), cAMP-receptor A (carA) and cAMP-phosphodiesterases were reduced. There was a significant reduction in the expression of CadA and CsaA, which are involved in cell-cell adhesion. The dio3(-) slugs had prestalk identity, with pronounced prestalk marker ecmA expression. Thus, Dio3 seems to have roles in mediating cAMP synthesis/relay, cell-cell adhesion and slug patterning. The phenotype of dio3(-) suggests that Dio3 may prevent the formation of multiple signaling centers during D. discoideum development. This is the first report of a gene involved in thyroxine metabolism that is also involved in growth and development in a lower eukaryote.

  16. Introduction to chiral symmetry

    SciTech Connect

    Koch, V.

    1996-01-08

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

  17. Chiral structures from achiral liquid crystals in cylindrical capillaries

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  18. Chiral structures from achiral liquid crystals in cylindrical capillaries

    PubMed Central

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    PubMed

    Ogino, Yoshiyuki; Asahi, Toru

    2015-05-21

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

  1. Controlling and imaging chiral spin textures

    NASA Astrophysics Data System (ADS)

    Chen, Gong

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

  2. Baryons and chiral symmetry

    NASA Astrophysics Data System (ADS)

    Liu, Keh-Fei

    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 πNσ 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.

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

    PubMed

    Ma, Yan-Na; Yang, Shang-Dong

    2016-04-01

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

  4. Chiral symmetry and chiral-symmetry breaking

    SciTech Connect

    Peskin, M.E.

    1982-12-01

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

  5. [Separation of chiral pharmaceutical drugs by chromatographic and electrophoretic techniques].

    PubMed

    Morin, P

    2009-07-01

    A large number of pharmaceutical drugs possess one or more centers of asymmetry giving rise to enantiomers whose pharmacological properties and toxicity are often different. At successive stages of drug discovery, the enantiomers of any chiral molecule must be isolated and analyzed and their enantiomeric purity determined. The electrophoretic and chromatographic techniques have become the most important tools to routinely determine the enantiomeric purity of pharmaceutical molecules. Liquid chromatography (LC) is the most widely used because of the large number of columns marketed, the variety of selectivities available and the ease at which analytical results can be scaled up to the preparative level. In particular, more than 80% of enantioseparations of pharmaceutical molecules are successful with polysaccharide-derivative stationary phases (cellulose, amylose) for multiple system solvents (normal phase, polar organic phase or reverse phase). Complementary selectivities can be achieved more rapidly with other types of stationary phase (glycopeptides, Pirkle, cyclodextrins) but their application is hindered by problems of stability (proteins) or transfer to the preparative scale (cyclodextrins). At the present time, glycopeptide phases offer very promising prospects for the separation of amino acids (and derivatives) and peptide enantiomers. In addition, because of its faster analysis and environmental benefits, supercritical chromatography (SFC) has given rise to renewed interest. Capillary electrophoresis (CE) is an orthogonal technique complementary to chromatographic methods. Its principle involves the formation of diastereoisomer complexes after addition of anionic (HS-beta-CD, HS-gamma-CD CM-beta-CD) or neutral (TM-beta -CD, HP-beta-CD, DM-beta-CD, HP-gamma-CD) cyclodextrins to the running buffer. Compared to LC, CE analyses are cheaper (no chiral column, no solvent, low consumption of chiral selector) and peak efficiencies are higher by one order of

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

    PubMed

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

    2012-04-16

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

  7. New approach to a novel axially chiral ligand showing spontaneous enrichment of axial chirality.

    PubMed

    Hasegawa, Tomokuni; Omote, Masaaki; Sato, Kazuyuki; Ando, Akira; Kumadaki, Itsumaro

    2003-03-01

    We have synthesized novel axially chiral ligand with two chiral centers, (R)-(R)(2)- and (S)-(S)(2)-2,2'-bis(2,2,2-trifluoro-1-hydroxyethyl)biphenyl (1), which showed a high asymmetric induction when used as ligand. Here, another new approach to 1 by kinetic and thermodynamic resolution is presented which gave these ligands in a much shorter steps, in a higher yield, and in a higher enantiomeric excess.

  8. Clinical profile of kidney involvement preceding diagnosis of multiple myeloma; a single center experience

    PubMed Central

    Balwani, Manish R; Gumber, Manoj R.; Shah, Pankaj R.; Kute, Vivek B.; Patel, Himanshu V.; Engineer, Divyesh P.; Gera, Dinesh N; Godhani, Umesh; Gautam, Rajesh Singh; Trivedi, Hargovind L.

    2016-01-01

    Introduction: The kidneys are involved in significant number of patients with multiple myeloma (MM) who can present with acute or chronic renal failure, nephritic syndrome, non-nephrotic proteinuria or tubular function defects. Objectives: To assess the clinical profile of kidney involvement preceding diagnosis of multiple myeloma Patients and Methods: Renal involvement in 29 cases with MM admitted over an 18-month period to our tertiary care center was retrospectively examined. Diagnosis of MM was confirmed by two or more of the following four features: lytic bone lesions, serum or urine monoclonal peak, Bence-Jones proteinuria, and greater than 20% plasma cells in bone marrow. Results: Renal disease was present in all patients before MM was diagnosed. Non-steroidal anti-inflammatory drugs (NSAIDs) was the most common precipitating factor for acute kidney injury (AKI). All 29 patients received combination chemotherapy of bortezomib, dexamethasone and thalidomide. More than half of the total number of patients did not complete chemotherapy because of death or lost to follow-up. Twenty-two of 29 patients required hemodialysis support. AKI was the most common renal presentation of MM. Four patients with AKI had complete renal recovery. Eleven patients who required hemodialysis support initially later on recovered to non-dialyzable range of renal failure. Seven patients became hemodialysis dependent. Twelve patients died from infection, uremia or hyperkalemia. Nine patients lost to follow up. Remission of MM was seen in 8 patients who completed chemotherapy. Conclusion: In our study AKI is the most common renal presentation preceding the diagnosis of MM. Reversal of renal function was achieved with chemotherapy and high flux hemodialysis in few cases. PMID:28197511

  9. Chiral non-Fermi liquids

    NASA Astrophysics Data System (ADS)

    Sur, Shouvik; Lee, Sung-Sik

    2014-07-01

    A non-Fermi liquid state without time-reversal and parity symmetries arises when a chiral Fermi surface is coupled with a soft collective mode in two space dimensions. The full Fermi surface is described by a direct sum of chiral patch theories, which are decoupled from each other in the low-energy limit. Each patch includes low-energy excitations near a set of points on the Fermi surface with a common tangent vector. General patch theories are classified by the local shape of the Fermi surface, the dispersion of the critical boson, and the symmetry group, which form the data for distinct universality classes. We prove that a large class of chiral non-Fermi liquid states exists as stable critical states of matter. For this, we use a renormalization group scheme where low-energy excitations of the Fermi surface are interpreted as a collection of (1+1)-dimensional chiral fermions with a continuous flavor labeling the momentum along the Fermi surface. Due to chirality, the Wilsonian effective action is strictly UV finite. This allows one to extract the exact scaling exponents although the theories flow to strongly interacting field theories at low energies. In general, the low-energy effective theory of the full Fermi surface includes patch theories of more than one universality classes. As a result, physical responses include multiple universal components at low temperatures. We also point out that, in quantum field theories with extended Fermi surface, a noncommutative structure naturally emerges between a coordinate and a momentum which are orthogonal to each other. We show that the invalidity of patch description for Fermi liquid states is tied with the presence of UV/IR mixing associated with the emergent noncommutativity. On the other hand, UV/IR mixing is suppressed in non-Fermi liquid states due to UV insensitivity, and the patch description is valid.

  10. Development of chiral sulfoxide ligands for asymmetric catalysis.

    PubMed

    Trost, Barry M; Rao, Meera

    2015-04-20

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

  11. Understanding complex chiral plasmonics

    NASA Astrophysics Data System (ADS)

    Duan, Xiaoyang; Yue, Song; Liu, Na

    2015-10-01

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

  12. Calibration of a TCCON FTS at Armstrong Flight Research Center (AFRC) Using Multiple Airborne Profiles

    NASA Astrophysics Data System (ADS)

    Hillyard, P. W.; Iraci, L. T.; Podolske, J. R.; Tanaka, T.; Yates, E. L.; Roehl, C. M.; Wunch, D.; Wennberg, P. O.; Albertson, R. T.; Blake, D. R.; Meinardi, S.; Marrero, J. E.; Yang, M. M.; Beyersdorf, A. J.; Wofsy, S. C.; Pittman, J. V.; Daube, B. C.

    2014-12-01

    Satellite missions including GOSAT, OCO-2 and ASCENDS measure column abundances of greenhouse gases. It is crucial to have calibrated ground-based measurements to which these satellite measurements can compare and refine their retrieval algorithms. To this end, a Fourier Transform Spectrometer has been deployed to the Armstrong Flight Research Center (AFRC) in Edwards, CA as a member of the Total Carbon Column Observing Network (TCCON). This location was selected due to its proximity to a highly reflective lakebed. Such surfaces have proven to be difficult for accurate satellite retrievals. This facility has been in operation since July 2013. The data collected to date at this site will be presented. In order to ensure the validity of the measurements made at this site, multiple vertical profiles have been performed using the Alpha jet, DC-8, and ER-2 as part of the AJAX (ongoing), SEAC4RS (August 2013), and SARP (July 2014) field campaigns. The integrated in-situ vertical profiles for CO2 and CH4 have been analyzed and compared with the TCCON FTS measurements, where good agreement between TCCON data and vertically-integrated aircraft in-situ data has been found.

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

    PubMed

    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.

  14. Chiral symmetry breaking from Ginsparg-Wilson fermions

    NASA Astrophysics Data System (ADS)

    Hernándes, Pilar; Jansen, Karl; Lellouch, Laurent

    We calculate the large-volume and small-mass dependences of the quark condensate in quenched QCD using Neuberger's operator. We find good agreement with the predictions of quenched chiral perturbation theory, enabling a determination of the chiral lagrangian parameter Σ, up to a multiplicative renormalization.

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

    PubMed Central

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

    2013-01-01

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

  16. Observation of Intrinsic Magnus Force and Direct Detection of Chirality in Superfluid 3He-A

    NASA Astrophysics Data System (ADS)

    Ikegami, Hiroki; Tsutsumi, Yasumasa; Kono, Kimitoshi

    2015-04-01

    We report details of the observation of the intrinsic Magnus (IM) force acting on negative and positive ions trapped just below a free surface of the A phase of superfluid 3He (3He-A). From the transport measurements of the ions along the surface, we found that the IM force acts on both the negative and positive ions. We also demonstrate that the transport measurements could distinguish whether the surface is composed of a chiral monodomain or multiple chiral domains. For multiple chiral domains, the current of the ions was found to be irreproducible and unstable, which was reasonably explained by the formation of the chiral domain structure and the dynamics of the chiral domain walls. For chiral monodomains, the appearance ratio of chirality emerging upon cooling through the superfluid transition temperature was found to depend on the direction of the external magnetic field, which implies the existence of an unknown coupling between the chirality and the magnetic field.

  17. A molecular propeller effect for chiral separation and analysis

    PubMed Central

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

    2015-01-01

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

  18. Manipulating the Lorentz force via the chirality of nanoparticles

    NASA Astrophysics Data System (ADS)

    Wang, Maoyan; Li, Hailong; Dong, Yuliang; Zhang, Xiaochuan; Du, Ming; Wang, Rui; Xu, Tong; Wu, Jian

    2016-12-01

    We demonstrate that a single plane wave pulls a chiral nanoparticle toward the light source. The nanoparticle exhibits optical gain in a particular wavelength region. The equivalence of the generalized and alternative expressions of the Lorentz force density relating to bound charges for chiral media is numerically validated. By considering the two-dimensional electromagnetic problem of incident plane waves normally impinged on active chiral cylinders, it is shown that the gradient force is mainly contributed by the bound electric and magnetic current densities of the cross-polarized waves. We also investigate how the medium parameters and impedance mismatch can be used to manipulate the pulling or pushing Lorentz forces between two chiral cylinders. This finding may provide a recipe to understand the light interaction with multiple chiral nanoparticles of arbitrary shapes (in general) with the aid of the numerical approach. It could be a promising avenue in controlling the optical micromanipulation for chiral nanoparticles with mirroring asymmetry.

  19. A molecular propeller effect for chiral separation and analysis

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

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

    PubMed

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

    2015-07-28

    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.

  1. Synthesis of complementary double-stranded helical oligomers through chiral and achiral amidinium-carboxylate salt bridges and chiral amplification in their double-helix formation.

    PubMed

    Ito, Hiroshi; Ikeda, Masato; Hasegawa, Takashi; Furusho, Yoshio; Yashima, Eiji

    2011-03-16

    A series of complementary molecular strands from 2-mer to 5-mer that are composed of m-terphenyl units bearing chiral/achiral amidine or achiral carboxyl groups linked via Pt(II) acetylide complexes were synthesized by sequential stepwise reactions, and their chiroptical properties on the double-helix formation were investigated by circular dichroism (CD) and (1)H NMR spectroscopies. In CHCl(3), the "all-chiral" amidine strands consisting of (R)- or (S)-amidine units formed preferred-handed double helices with the complementary achiral carboxylic acid strands through the amidinium-carboxylate salt bridges, resulting in characteristic induced CDs in the Pt(II) acetylide complex regions, indicating that the chiral substituents on the amidine units biased a helical sense preference. The Cotton effect patterns and intensities were highly dependent on the molecular lengths. The complementary double-helix formation was also explored using the chiral/achiral amidine strands with different sequences in which a chiral amidine unit was introduced at the center (center-chiral) or a terminus (edge-chiral) of the amidine strands. The effect of the sequences of the chiral and achiral amidine units on the amplification of chirality (the "sergeants and soldiers" effect) in the double-helix formation was investigated by comparing the CD intensities with those of the corresponding all-chiral amidine double helices with the same molecular lengths. Variable-temperature CD experiments of the all-chiral and chiral/achiral amidine duplexes demonstrated that the Pt(II)-linked complementary duplexes are dynamic and their chiroptical properties including the chirality transfer from the chiral amidine unit to the achiral amidine ones are significantly affected by the molecular lengths, sequences, and temperatures. On the basis of the above results together with molecular dynamics simulation results, key structural features of the Pt(II)-linked oligomer duplexes and the effect of the chiral

  2. Nonlinear optical spectroscopy of chiral molecules.

    PubMed

    Fischer, Peer; Hache, François

    2005-10-01

    We review nonlinear optical processes that are specific to chiral molecules in solution and on surfaces. In contrast to conventional natural optical activity phenomena, which depend linearly on the electric field strength of the optical field, we discuss how optical processes that are nonlinear (quadratic, cubic, and quartic) functions of the electromagnetic field strength may probe optically active centers and chiral vibrations. We show that nonlinear techniques open entirely new ways of exploring chirality in chemical and biological systems: The cubic processes give rise to nonlinear circular dichroism and nonlinear optical rotation and make it possible to observe dynamic chiral processes at ultrafast time scales. The quadratic second-harmonic and sum-frequency-generation phenomena and the quartic processes may arise entirely in the electric-dipole approximation and do not require the use of circularly polarized light to detect chirality. They provide surface selectivity and their observables can be relatively much larger than in linear optical activity. These processes also give rise to the generation of light at a new color, and in liquids this frequency conversion only occurs if the solution is optically active. We survey recent chiral nonlinear optical experiments and give examples of their application to problems of biophysical interest.

  3. Emerging chirality in nanoscience.

    PubMed

    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.

  4. Chiral fluctuations in achiral systems

    NASA Astrophysics Data System (ADS)

    Harris, Robert A.

    2001-12-01

    "Chiral fluctuations" are defined, and their relation to "dynamic chirality" is discussed. Simple experiments to measure chiral fluctuations are proposed. The unique aspects of these measurements for systems such as atomic clusters and gases are outlined.

  5. Persistence of multiple illnesses in World Trade Center rescue and recovery workers: a cohort study.

    PubMed

    Wisnivesky, Juan P; Teitelbaum, Susan L; Todd, Andrew C; Boffetta, Paolo; Crane, Michael; Crowley, Laura; de la Hoz, Rafael E; Dellenbaugh, Cornelia; Harrison, Denise; Herbert, Robin; Kim, Hyun; Jeon, Yunho; Kaplan, Julia; Katz, Craig; Levin, Stephen; Luft, Ben; Markowitz, Steven; Moline, Jacqueline M; Ozbay, Fatih; Pietrzak, Robert H; Shapiro, Moshe; Sharma, Vansh; Skloot, Gwen; Southwick, Steven; Stevenson, Lori A; Udasin, Iris; Wallenstein, Sylvan; Landrigan, Philip J

    2011-09-03

    More than 50,000 people participated in the rescue and recovery work that followed the Sept 11, 2001 (9/11) attacks on the World Trade Center (WTC). Multiple health problems in these workers were reported in the early years after the disaster. We report incidence and prevalence rates of physical and mental health disorders during the 9 years since the attacks, examine their associations with occupational exposures, and quantify physical and mental health comorbidities. In this longitudinal study of a large cohort of WTC rescue and recovery workers, we gathered data from 27,449 participants in the WTC Screening, Monitoring, and Treatment Program. The study population included police officers, firefighters, construction workers, and municipal workers. We used the Kaplan-Meier procedure to estimate cumulative and annual incidence of physical disorders (asthma, sinusitis, and gastro-oesophageal reflux disease), mental health disorders (depression, post-traumatic stress disorder [PTSD], and panic disorder), and spirometric abnormalities. Incidence rates were assessed also by level of exposure (days worked at the WTC site and exposure to the dust cloud). 9-year cumulative incidence of asthma was 27·6% (number at risk: 7027), sinusitis 42·3% (5870), and gastro-oesophageal reflux disease 39·3% (5650). In police officers, cumulative incidence of depression was 7·0% (number at risk: 3648), PTSD 9·3% (3761), and panic disorder 8·4% (3780). In other rescue and recovery workers, cumulative incidence of depression was 27·5% (number at risk: 4200), PTSD 31·9% (4342), and panic disorder 21·2% (4953). 9-year cumulative incidence for spirometric abnormalities was 41·8% (number at risk: 5769); three-quarters of these abnormalities were low forced vital capacity. Incidence of most disorders was highest in workers with greatest WTC exposure. Extensive comorbidity was reported within and between physical and mental health disorders. 9 years after the 9/11 WTC attacks, rescue

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

    ERIC Educational Resources Information Center

    LeClair, Daniel P.; And Others

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

  7. Periodic chiral structures

    NASA Technical Reports Server (NTRS)

    Jaggard, Dwight L.; Engheta, Nader; Pelet, Philippe; Liu, John C.; Kowarz, Marek W.; Kim, Yunjin

    1989-01-01

    The electromagnetic properties of a structure that is both chiral and periodic are investigated using coupled-mode equations. The periodicity is described by a sinusoidal perturbation of the permittivity, permeability, and chiral admittance. The coupled-mode equations are derived from physical considerations and used to examine bandgap structure and reflected and transmitted fields. Chirality is observed predominantly in transmission, whereas periodicity is present in both reflection and transmission.

  8. Planar plasmonic chiral nanostructures

    NASA Astrophysics Data System (ADS)

    Zu, Shuai; Bao, Yanjun; Fang, Zheyu

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  10. Characterizing optical chirality

    SciTech Connect

    Bliokh, Konstantin Y.; Nori, Franco

    2011-02-15

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

  11. Chiral atomically thin films.

    PubMed

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

    2016-06-01

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

  12. Chiral atomically thin films

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2015-03-01

    Regional gray matter (GM) atrophy in multiple sclerosis (MS) at disease onset and its temporal variation can provide objective information regarding disease evolution. An automated pipeline for estimating atrophy of various GM structures was developed using tensor based morphometry (TBM) and implemented on a multi-center sub-cohort of 1008 relapsing remitting MS (RRMS) patients enrolled in a Phase 3 clinical trial. Four hundred age and gender matched healthy controls were used for comparison. Using the analysis of covariance, atrophy differences between MS patients and healthy controls were assessed on a voxel-by-voxel analysis. Regional GM atrophy was observed in a number of deep GM structures that included thalamus, caudate nucleus, putamen, and cortical GM regions. General linear regression analysis was performed to analyze the effects of age, gender, and scanner field strength, and imaging sequence on the regional atrophy. Correlations between regional GM volumes and expanded disability status scale (EDSS) scores, disease duration (DD), T2 lesion load (T2 LL), T1 lesion load (T1 LL), and normalized cerebrospinal fluid (nCSF) were analyzed using Pearson׳s correlation coefficient. Thalamic atrophy observed in MS patients compared to healthy controls remained consistent within subgroups based on gender and scanner field strength. Weak correlations between thalamic volume and EDSS (r=-0.133; p<0.001) and DD (r=-0.098; p=0.003) were observed. Of all the structures, thalamic volume moderately correlated with T2 LL (r=-0.492; P-value<0.001), T1 LL (r=-0.473; P-value<0.001) and nCSF (r=-0.367; P-value<0.001). Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Multiple clinical presentations of lymphoproliferative disorders in pediatric liver transplant recipients: a single-center experience.

    PubMed

    Pinho-Apezzato, M L; Tannuri, U; Tannuri, A C A; Mello, E S; Lima, F; Gibelli, N E; Santos, M M; Ayoub, A A; Maksoud-Filho, J G; Velhote, M C; Silva, M M; Andrade, W C; Miyatani, H T

    2010-06-01

    Posttransplantation lymphoproliferative disorder (PTLD) is a serious complication following solid organ transplantation that has been linked to Epstein-Barr virus (EBV) infection. The aim of this article was to describe a single-center experience with the multiplicity of clinical presentations of PTLD. Among 350 liver transplantations performed in 303 children, 13 survivor children displayed a histological diagnosis of PTLD (13/242 survivors; 5.4%). The age at diagnosis ranged from 12 to 258 months (median, 47), and the time from transplantation ranged from 1 to 84 months (median, 13). Ten of these children (76.9%) were EBV-naïve prior to transplantation. Fever was present in all cases. The clinical signs at presentation were anemia (92.3%), diarrhea and vomiting (69.2%), recurrent upper airway infections (38.4%), Waldeyer ring lymphoid tissue hypertrophy (23.0%), abdominal mass lesions (30.7%), massive cervical and mediastinal adenopathy (15.3%), or gastrointestinal and respiratory symptoms (30.7%). One child developed fulminant hepatic allograft failure secondary to graft involvement by PTLD. Polymorphic PTLD was diagnosed in 6 patients; 7 had the diagnosis of lymphoma. Treatment consisted of stopping immunosuppression as well as starting intravenous gancyclovir and anti-CD20 monoclonal antibody therapy. The mortality rate was 53.8%. The clinical presentation of PTLD varied from fever of unknown origin to fulminant hepatic failure. The other symptoms that may be linked to the diagnosis of PTLD are pancytopenia, tonsil and adenoid hypertrophy, cervical or mediastinal lymph node enlargement, as well as abdominal masses. Despite numerous advances, the optimal treatment approach for PTLD is not completely known and the mortality rate is still high.

  16. Molecular-Level Design of Heterogeneous Chiral Catalysis

    SciTech Connect

    Francisco Zaera

    2012-03-21

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

  17. Modeling Multiple Risks During Infancy to Predict Quality of the Caregiving Environment: Contributions of a Person-Centered Approach

    PubMed Central

    Lanza, Stephanie T.; Rhoades, Brittany L.; Greenberg, Mark T.; Cox, Martha

    2011-01-01

    The primary goal of this study was to compare several variable-centered and person-centered methods for modeling multiple risk factors during infancy to predict the quality of caregiving environments at six months of age. Nine risk factors related to family demographics and maternal psychosocial risk, assessed when children were two months old, were explored in the understudied population of children born in low-income, non-urban communities in Pennsylvania and North Carolina (N = 1047). These risk factors were 1) single (unpartnered) parent status, 2) marital status, 3) mother’s age at first child birth, 4) maternal education, 5) maternal reading ability, 6) poverty status, 7) residential crowding, 8) prenatal smoking exposure, and 9) maternal depression. We compared conclusions drawn using a bivariate approach, multiple regression analysis, the cumulative risk index, and latent class analysis (LCA). The risk classes derived using LCA provided a more intuitive summary of how multiple risks were organized within individuals as compared to the other methods. The five risk classes were: married low-risk; married low-income; cohabiting multiproblem; single low-income; and single low-income/education. The LCA findings illustrated how the association between particular family configurations and the infants’ caregiving environment quality varied across race and site. Discussion focuses on the value of person-centered models of analysis to understand complexities of prediction of multiple risk factors. PMID:21477866

  18. Modeling multiple risks during infancy to predict quality of the caregiving environment: contributions of a person-centered approach.

    PubMed

    Lanza, Stephanie T; Rhoades, Brittany L; Greenberg, Mark T; Cox, Martha

    2011-06-01

    The primary goal of this study was to compare several variable-centered and person-centered methods for modeling multiple risk factors during infancy to predict the quality of caregiving environments at six months of age. Nine risk factors related to family demographics and maternal psychosocial risk, assessed when children were two months old, were explored in the understudied population of children born in low-income, non-urban communities in Pennsylvania and North Carolina (N = 1047). These risk factors were (1) single (unpartnered) parent status, (2) marital status, (3) mother's age at first child birth, (4) maternal education, (5) maternal reading ability, (6) poverty status, (7) residential crowding, (8) prenatal smoking exposure, and (9) maternal depression. We compared conclusions drawn using a bivariate approach, multiple regression analysis, the cumulative risk index, and latent class analysis (LCA). The risk classes derived using LCA provided a more intuitive summary of how multiple risks were organized within individuals as compared to the other methods. The five risk classes were: married low-risk; married low-income; cohabiting multiproblem; single low-income; and single low-income/education. The LCA findings illustrated how the association between particular family configurations and the infants' caregiving environment quality varied across race and site. Discussion focuses on the value of person-centered models of analysis to understand complexities of prediction of multiple risk factors.

  19. Chiral magnetic superconductivity

    NASA Astrophysics Data System (ADS)

    Kharzeev, Dmitri E.

    2017-03-01

    Materials with charged chiral quasiparticles in external parallel electric and magnetic fields can support an electric current that grows linearly in time, corresponding to diverging DC conductivity. From experimental viewpoint, this "Chiral Magnetic Superconductivity" (CMS) is thus analogous to conventional superconductivity. However the underlying physics is entirely different - the CMS does not require a condensate of Cooper pairs breaking the gauge degeneracy, and is thus not accompanied by Meissner effect. Instead, it owes its existence to the (temperature-independent) quantum chiral anomaly and the conservation of chirality. As a result, this phenomenon can be expected to survive to much higher temperatures. Even though the chirality of quasiparticles is not strictly conserved in real materials, the chiral magnetic superconductivity should still exhibit itself in AC measurements at frequencies larger than the chirality-flipping rate, and in microstructures of Dirac and Weyl semimetals with thickness below the mean chirality-flipping length that is about 1 - 100 μm. In nuclear physics, the CMS should contribute to the charge-dependent elliptic flow in heavy ion collisions.

  20. Superenantioselective chiral surface explosions.

    PubMed

    Gellman, Andrew J; Huang, Ye; Feng, Xu; Pushkarev, Vladimir V; Holsclaw, Brian; Mhatre, Bharat S

    2013-12-26

    Chiral inorganic materials predated life on Earth, and their enantiospecific surface chemistry may have played a role in the origins of biomolecular homochirality. However, enantiospecific differences in the interaction energies of chiral molecules with chiral surfaces are small and typically lead to modest enantioselectivities in adsorption, catalysis, and chemistry on chiral surfaces. To yield high enantioselectivities, small energy differences must be amplified by reaction mechanisms such as autocatalytic surface explosions which have nonlinear kinetics. Herein, we report the first observations of superenantiospecificity resulting from an autocatalytic surface explosion reaction of a chiral molecule on a naturally chiral surface. R,R- and S,S-tartaric acid decompose via a vacancy-mediated surface explosion mechanism on Cu single crystal surfaces. When coupled with surface chirality, this leads to decomposition rates that exhibit extraordinarily high enantiospecificity. On the enantiomorphs of naturally chiral Cu(643)(R&S), Cu(17,5,1)(R&S), Cu(531)(R&S) and Cu(651)(R&S) single crystal surfaces, R,R- and S,S-tartaric acid exhibit enantiospecific decomposition rates that differ by as much as 2 orders of magnitude, despite the fact that the effective rates constants for decomposition differ by less than a factor of 2.

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

    NASA Astrophysics Data System (ADS)

    Varga, Szabolcs; Jackson, George

    2011-03-01

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

  2. Effect of the three-center terms on the chiral superconducting d-wave pairing of the Hubbard fermions on the triangular lattice

    NASA Astrophysics Data System (ADS)

    Val'kov, V. V.; Val'kova, T. A.; Mitskan, V. A.

    2017-10-01

    Using the diagram technique for the Hubbard operators an integral equation that determines the order parameter of the superconducting phase Δ (p) was obtained in the framework of t-J-V and t-J*-V models on triangular lattice. It is shown that there are two scenarios of formation of superconducting phase with gapless spectrum at the critical concentration of carriers xc. The effect of three-center terms on implementation of this phase was also considered.

  3. Chiral-selective nonlinear optical generation and emission control with plasmonic metamaterials (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Cai, Wenshan

    2016-09-01

    Metamaterials can be designed to exhibit extraordinarily strong chiral responses. Here we present a chiral metamaterial that produces both distinguishable linear and nonlinear features in the visible to near-infrared range. In additional to the gigantic chiral effects in the linear regime, the metamaterial demonstrates a pronounced contrast between second harmonic responses from the two circular polarizations. Linear and nonlinear images probed with circularly polarized lights show strongly defined contrast. Moreover, the chiral centers of the nanometallic structures with enhanced hotspots can be purposely opened for direct access, where emitters occupying the light-confining regions produce chiral-selective enhancement of two-photon luminescence.

  4. Molecular model for chirality phenomena.

    PubMed

    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.

  5. Simultaneous Determination of Absolute Configuration and Quantity of Lipopeptides Using Chiral Liquid Chromatography/Mass Spectrometry and Diastereomeric Internal Standards.

    PubMed

    Nemati, Reza; Dietz, Christopher; Anstadt, Emily; Clark, Robert; Smith, Michael; Nichols, Frank; Yao, Xudong

    2017-02-28

    Lipopeptides promote innate immune response and are related to disease pathology. To investigate the newly emerging roles of lipopeptides, accurate measurements of stereoisomers with multiple chiral centers are essential yet challenging. This work uses (3R)- and (3S)-(15-methyl-3-((13-methyltetradecanoyl)oxy)hexadecanoyl)glycyl-l-serine, abbreviated as l-serine-(R+S)-Lipid 654, to develop a method that combines chiral liquid chromatography, a diastereomeric mixture of isotopically labeled internal standards, and multiple reaction monitoring mass spectrometry. The new method allows for simultaneously determining the absolute configuration and quantity of stereoisomers of bacteria-derived lipopeptides. Total lipid extracts of nine evaluated bacteria strains had different amounts, but only the (R)-isoform of l-serine-Lipid 654. The developed method also allowed for the first quantitative analysis of hydrolysis of a nonphospholipid as a novel substrate of honey bee venom phospholipase A2.

  6. Applications of chiral symmetry

    SciTech Connect

    Pisarski, R.D.

    1995-03-01

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

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

    PubMed

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

    2011-01-01

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

  8. RNA nucleosides as chiral sensing agents in NMR spectroscopy.

    PubMed

    Lokesh, N; Sachin, S L; Narendra, L V; Arun, K; Suryaprakash, N

    2015-07-14

    The study reports chiral sensing properties of RNA nucleosides. Adenosine, guanosine, uridine and cytidine are used as chiral derivatizing agents to differentiate chiral 1°-amines. A three component protocol has been adopted for complexation of nucleosides and amines. The chiral differentiating ability of nucleosides is examined for different amines based on the (1)H NMR chemical shift differences of diastereomers (Δδ(R,S)). Enantiomeric differentiation has been observed at multiple chemically distinct proton sites. Adenosine and guanosine exhibit large chiral differentiation (Δδ(R,S)) due to the presence of a purine ring. The diastereomeric excess (de) measured by using adenosine is in good agreement with the gravimetric values.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  10. Chirality Differentiation by Diffusion in Chiral Nematic Liquid Crystals

    NASA Astrophysics Data System (ADS)

    Jiang, Jinghua; Yang, Deng-Ke

    2017-01-01

    Chirality is of great importance in the living world. It helps differentiate biochemical reactions such as those that take place during digestion. It may also help differentiate physical processes such as diffusion. Aiming to study the latter effect, we investigate the diffusion of guest chiral molecules in chiral nematic (cholesteric) liquid-crystal hosts. We discover that the diffusion dramatically depends on the handedness of the guest and host molecules and the chiral differentiation is greatly enhanced by the proper alignment of the liquid-crystal host. The diffusion of a guest chiral molecule in a chiral host with the same handedness is much faster than in a chiral host with opposite handedness. We also observe that the differentiation of chirality depends on the diffusion direction with respect to the twisting direction (helical axis). These results might be important in understanding effects of chirality on physical processes that take place in biological organisms. In addition, this effect could be utilized for enantiomer separation.

  11. The University-Center Baccalaureate Degree in California: A Multiple Case Study

    ERIC Educational Resources Information Center

    Rhoades, Jeffrey T.

    2014-01-01

    The community college baccalaureate and the university-center baccalaureate models are gaining traction in the state of California as alternatives to addressing the need for greater access to baccalaureate degree programs and to increase the baccalaureate-educated workforce. Little is known about the characteristics and factors associated with the…

  12. The University-Center Baccalaureate Degree in California: A Multiple Case Study

    ERIC Educational Resources Information Center

    Rhoades, Jeffrey T.

    2014-01-01

    The community college baccalaureate and the university-center baccalaureate models are gaining traction in the state of California as alternatives to addressing the need for greater access to baccalaureate degree programs and to increase the baccalaureate-educated workforce. Little is known about the characteristics and factors associated with the…

  13. A Developmental, Person-Centered Approach to Exploring Multiple Motivational Pathways in Gifted Underachievement

    ERIC Educational Resources Information Center

    Snyder, Kate E.; Linnenbrink-Garcia, Lisa

    2013-01-01

    Research on underachieving gifted students has uncovered a large number of characteristics differentiating gifted underachieving and achieving students. However, less is known about the way in which underachievement develops across schooling. Using a person-centered theoretical framework and key constructs from current motivational theories, we…

  14. Observation of multiple radical pair states in photosystem 2 reaction centers.

    PubMed

    Booth, P J; Crystall, B; Ahmad, I; Barber, J; Porter, G; Klug, D R

    1991-07-30

    Charge recombination of the primary radical pair in D1/D2 reaction centers from photosystem 2 has been studied by time-resolved fluorescence and absorption spectroscopy. The kinetics of the primary radical pair are multiexponential and exhibit at least two lifetimes of 20 and 52 ns. In addition, a third lifetime of approximately 500 ps also appears to be present. These multiexponential charge-recombination kinetics reflect either different conformational states of D1/D2 reaction centers, with the different conformers exhibiting different radical pair lifetimes, or relaxations in the free energy of the radical pair state. Whichever model is invoked, the free energies of formation of the different radical pair states exhibit a linear temperature dependence from 100 to 220 K, indicating that they are dominated by entropy with negligible enthalpy contributions. These results are in agreement with previous determinations of the thermodynamics that govern primary charge separation in both D1/D2 reaction centers [Booth, P.J., Crystall, B., Giorgi, L. B., Barber, J., Klug, D.R., & Porter, G. (1990) Biochim. Biophys. Acta 1016, 141-152] and reaction centers of purple bacteria [Woodbury, N.W.T., & Parson, W.W. (1984) Biochim. Biophys. Acta 767, 345-361]. It is possible that these observations reflect structural changes that accompanying primary charge separation and assist in stabilization of the radical pair state thus optimizing the efficiency of primary electron transfer.

  15. A Developmental, Person-Centered Approach to Exploring Multiple Motivational Pathways in Gifted Underachievement

    ERIC Educational Resources Information Center

    Snyder, Kate E.; Linnenbrink-Garcia, Lisa

    2013-01-01

    Research on underachieving gifted students has uncovered a large number of characteristics differentiating gifted underachieving and achieving students. However, less is known about the way in which underachievement develops across schooling. Using a person-centered theoretical framework and key constructs from current motivational theories, we…

  16. A New Look at Multiple Goal Pursuit: The Promise of a Person-Centered Approach

    ERIC Educational Resources Information Center

    Wormington, Stephanie Virgine; Linnenbrink-Garcia, Lisa

    2017-01-01

    The current study reviewed and synthesized studies employing a person-centered approach to studying achievement goals. Towards this end, a common labeling scheme was developed for goal profiles. Ten profile types were identified across studies and compared via meta-analytic techniques in terms of academic motivation, social/emotional well-being,…

  17. Spintronics: Chiral damping

    PubMed Central

    Kim, Kyoung-Whan; Lee, Hyun-Woo

    2016-01-01

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

  18. Chiral magnetic wave

    SciTech Connect

    Kharzeev, Dmitri E.; Yee, Ho-Ung

    2011-04-15

    We consider a relativistic plasma containing charged chiral fermions in an external magnetic field, e.g. a chirally symmetric quark-gluon plasma created in relativistic heavy ion collisions. We show that triangle anomalies imply the existence of a new type of collective gapless excitation in this system that stems from the coupling between the density waves of the electric and chiral charges; we call it ''the chiral magnetic wave'' (CMW). The CMW exists even in a neutral plasma, i.e. in the absence of the axial and vector chemical potentials. We demonstrate the existence of CMW and study its properties using three different approaches: i) relativistic magnetohydrodynamics; ii) dimensional reduction to (1+1) Sine-Gordon model, appropriate in a strong magnetic field; and iii) holographic QCD (Sakai-Sugimoto model), appropriate at strong coupling. We also briefly discuss the phenomenological implications of the CMW for heavy ion collisions.

  19. Relativistic Chiral Kinetic Theory

    NASA Astrophysics Data System (ADS)

    Stephanov, Mikhail

    2016-12-01

    This very brief review of the recent progress in chiral kinetic theory is based on the results of Refs. [J.-Y. Chen, D. T. Son, M. A. Stephanov, H.-U. Yee, Y. Yin, Lorentz Invariance in Chiral Kinetic Theory, Phys. Rev. Lett. 113 (18) (2014) 182302. doi:10.1103/PhysRevLett.113.182302; J.-Y. Chen, D. T. Son, M. A. Stephanov, Collisions in Chiral Kinetic Theory, Phys. Rev. Lett. 115 (2) (2015) 021601. doi: 10.1103/PhysRevLett.115.021601; M. A. Stephanov, H.-U. Yee, The no-drag frame for anomalous chiral fluid, Phys. Rev. Lett. 116 (12) (2016) 122302. doi: 10.1103/PhysRevLett.116.122302].

  20. Chiral Hypervalent, Pentacoordinated Phosphoranes.

    PubMed

    Krasowska, Dorota; Chrzanowski, Jacek; Kiełbasiński, Piotr; Drabowicz, Józef

    2016-11-21

    This review presents synthetic procedures applied to the preparation of chiral (mainly optically active) pentacoordinated, hypervalent mono and bicyclic phosphoranes. The mechanisms of their stereoisomerization and their selected interconversions are also presented.

  1. Biocatalysis: Chiral cascades

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Bo; Reetz, Manfred T.

    2015-12-01

    Racemic or enantiomerically pure alcohols can be converted with high yield into enantiopure chiral amines in a one-pot redox-neutral cascade process by the clever combination of an alcohol dehydrogenase and an appropriate amine dehydrogenase.

  2. Regulation of the chiral twist and supramolecular chirality in co-assemblies of amphiphilic L-glutamic acid with bipyridines.

    PubMed

    Zhu, Xuefeng; Duan, Pengfei; Zhang, Li; Liu, Minghua

    2011-03-14

    A series of amphiphilic L-glutamic acid derivatives with various saturated alkyl chains has been designed and their co-assembly with 4,4'-bipyridine in aqueous media has been investigated. While the individual amphiphiles formed hydrogels with water and self-assembled into fine fiber networks, the addition of 4,4'-bipyridine caused significant changes in the co-assembled nanostructures such that twisted chiral ribbons were formed. In these supramolecular systems, either fine structural changes or adjustment of the stoichiometric ratio of the two components had crucial effects on the formation of the chiral twists. Based on detailed investigations by SEM and XRD analyses, FTIR, CD, and UV/Vis spectroscopies, and molecular simulation, it is considered that a delicate synergistic balance between π-π stacking, hydrophobic, and chiral interactions is responsible for the formation of the chiral twists. An interesting sandwich structure, in which an excess of 4,4'-bipyridine is inserted into the space of primary cages constructed from the amphiphile and 4,4'-bipyridine, is proposed. Remarkably, the handedness of these chiral twists is related not only to the chiral center of the glutamic unit, but also the chain length of the alkyl tails. This work provides a deeper understanding of the formation mechanism of chiral twists, and exemplifies a feasible shortcut to the rational design of chiral structures from basic molecular structures to supramolecular systems.

  3. Scalemic and racemic imprinting with a chiral crosslinker.

    PubMed

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

    2015-08-26

    The development of molecularly imprinted chiral stationary phases has traditionally been limited by the need for a chiral pure template. Paradoxically, availability of a chiral pure template largely defeats the purpose of developing a chiral stationary phase. To solve this paradox, imprinting of scalemic and racemic template mixtures was investigated using both chiral (N-α-bismethacryloyl-L-alanine) and achiral (N,O-bisacrylamide ethanolamine) crosslinkers. Imprinting of scalemic mixtures provided polymers capable of partial separation of Boc-tyrosine enantiomers with virtually the same results when using either the chiral or achiral crosslinker. However, the chiral crosslinker was required for chiral differentiation by the racemic imprinted polymers which were evaluated in both batch rebinding and chromatographic modes. Batch rebinding analysis revealed intersecting binding isotherms for the L- and D-Boc-tyrosine, indicating bias for the D or L enantiomer is concentration dependent. Partial chromatographic separation was achieved by the racemic imprinted polymers providing variable D or L bias in equal probability over multiple replicates of polymer synthesis. Correlation of enantiomer bias with the batch rebinding results and optimization of HPLC parameters are discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    PubMed Central

    Muller, Gilles

    2009-01-01

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

  5. The quest for chirality

    SciTech Connect

    Bonner, W.A.

    1996-07-01

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

  6. Electrodynamics of chiral matter

    NASA Astrophysics Data System (ADS)

    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.

  7. Induced circular dichroism of polyoxometalates via electrostatic encapsulation with chiral organic cations.

    PubMed

    Wang, Yizhan; Shi, Lei; Yang, Yang; Li, Bao; Wu, Lixin

    2014-09-21

    To explore the principle of chiral induction in inorganic clusters, chiral organic cations with two stereocenters, R- and S-BPEA, are used to encapsulate a series of polyoxometalates (POMs) bearing different structures and transition absorption bands in aqueous solution, constructing a series of chiral supramolecular complexes. Due to the induction of chiral organic cations, POMs possessing both chiral and achiral structures show an induced circular dichroism (ICD) effect. ICD signals in the absorption bands corresponding to ligand to metal charge transfer (LMCT) transitions, d-d transitions and intervalence charge transfer (IVCT) transitions are observed for different complexes. Moreover, the ICD of the POMs exhibits a direct correlation with the degree of POM distortion and the distance between the chiral center and the POM surface. The encapsulation of POMs with chiral organic cations via electrostatic interactions provides a facile and effective method for constructing optically pure POM-based materials.

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

    PubMed

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

    2012-01-01

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

  9. The effect of multiple antireflective coatings and center thickness on resistance of polycarbonate spectacle lenses to penetration by pointed missiles.

    PubMed

    Chou, B Ralph; Gupta, Alina; Hovis, Jeffery K

    2005-11-01

    Previous work has shown that the impact resistance to blunt missiles is affected by coatings applied to either CR-39 or polycarbonate lenses. We investigated the effects of multiple antireflection (minimum angle of resolution [MAR]) coatings on the resistance of polycarbonate lenses to puncture on impact by sharp, high-speed missiles. Four groups of surfaced plano polycarbonate lenses were investigated. Two groups had a scratch-resistant (SR) coating applied to both surfaces. One of these groups had a 2-mm center thickness and the other had a 3-mm center thickness. The other two groups of 2-mm and 3-mm thick lenses had a MAR coating applied over the SR coating. The lenses were impacted by a missile consisting of an industrial sewing machine needle mounted in a cylindrical aluminum carrier. The sharp missiles were able to pierce the lenses at speeds between 29.6 m/s and 46.2 m/s. Impact resistance was lowest for the thinner lenses and lenses with a MAR coating. The effect of the MAR and lens thickness was subadditive. We have confirmed previous observations that polycarbonate lenses are more susceptible to penetration by sharp, high-speed missiles than blunt missiles. We have also found that reducing lens center thickness and applying a MAR coating further reduces the penetration resistance. Therefore, the use of 2-mm center thickness and MAR-coated polycarbonate lenses should be discouraged for industrial eye protectors where sharp missile hazards are possible.

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

    SciTech Connect

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

    2014-10-16

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

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

    PubMed

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

    2014-10-16

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

  12. Chiral nihility effects on energy flow in chiral materials.

    PubMed

    Qiu, Cheng-Wei; Burokur, Nawaz; Zouhd, Saïd; Li, Le-Wei

    2008-01-01

    The propagation of electromagnetic plane waves in an isotropic chiral medium is characterized, and a special interest is shown in chiral nihility and the effects of chirality on energy transmission. In particular, the wave impedance is matched to that of free space. Moreover, the refractive index n is also matched in impedance to that of free space when an appropriate value of the chirality is chosen. A "chiral nihility" medium is explored in which both the permittivity and the permeability tend to zero. Some specific case studies of chiral nihility are presented, and Brewster angles are found to cover an extremely wide range. The E-field distributions in these different cases where the chiral slab is placed in free space are analyzed by using the appropriate constitutive relations. It is shown from numerical calculations that one can obtain some critical characteristics of the effects of chirality on energy transmission and reflection, such as transparency and power tunneling.

  13. Enantioselective synthesis of chiral sulfinates using chiral diamines.

    PubMed

    Nakamura, Shuichi; Tateyama, Motoaki; Sugimoto, Hideki; Nakagawa, Masaya; Watanabe, Yoshihiko; Shibata, Norio; Toru, Takeshi

    2005-02-01

    The reaction of p-toluenesulfinyl chloride with alcohols in the presence of chiral diamines was examined. Chiral sulfinates were obtained in good yields with enantioselectivity up to 76% ee. Copyright 2005 Wiley-Liss, Inc.

  14. Chirality of light and its interaction with chiral matter

    NASA Astrophysics Data System (ADS)

    Tang, Yiqiao

    This thesis conducts a systematic study on the chirality of light and its interaction with chiral matter. In the theory section, we introduce a measure of local density of chirality, applying to arbitrary electromagnetic fields. This optical chirality suggests the existence of superchiral modes, which are more selective than circularly polarized light (CPL) in preferentially exciting single enantiomers in certain regions of space. Experimentally, we demonstrate an 11-fold enhancement over CPL in discriminating chiral fluorophores of single handedness in a precisely sculpted superchiral field. This result agrees to within 15% with theoretical predictions. Any chiral configuration of point charges is beyond the scope of our theory on optical chirality. To address chiroptical excitations at nanoscale, we develop a model of twisted dipolar oscillators. We design a simple tunable chiral nanostructure and observe localized chiroptical "hot spots" with dramatically enhanced circular differential scattering. Our work on superchiral light and 3D chiral metamaterials establishes optical chirality as a fundamental and tunable property of light, with implications ranging from plasmonic sensors, absolute asymmetric synthesis to new strategies for fabricating three-dimensional chiral metamaterials. This thesis is organized as such: Chapter 1 provides a background on previous studies of chiroptical phenomena, and recent efforts in preparing chiral metamaterials. Chapter 2 derives theory on optical chirality, superchiral modes and coupled-dipolar oscillators at nanoscale. Chapter 3 introduces material, apparatus, and pitfalls in chiroptical experiments. Chapter 4 is an overview of the experimental procedure and results on generating and observing superchiral enhancement. Chapter 5 describes the experiments on using spectroscopic polarization microscopy to study chiral 3D chiral metamaterials. Finally in Chapter 6, I discuss quantization of optical chirality and perspectives on

  15. Superconductivity in a chiral nanotube

    NASA Astrophysics Data System (ADS)

    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.

  16. Chiral anomalies and differential geometry

    SciTech Connect

    Zumino, B.

    1983-10-01

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

  17. Superconductivity in a chiral nanotube

    PubMed Central

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

    2017-01-01

    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. PMID:28205518

  18. Superconductivity in a chiral nanotube.

    PubMed

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

    2017-02-16

    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.

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

    PubMed

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

    2013-04-01

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

  20. Regio- and Stereoselective Modification of Chiral α-Amino Ketones by Pd-Catalyzed Allylic Alkylation.

    PubMed

    Huwig, Kai; Schultz, Katharina; Kazmaier, Uli

    2015-07-27

    Chiral α-amino ketones are excellent nucleophiles for stereoselective palladium-catalyzed allylic alkylations. Both chiral as well as achiral allylic substrates can be applied, while the stereochemical outcome of the reaction is controlled by the chiral ketone enolate. The substituted amino ketones formed can be reduced stereoselectively, and up to five consecutive stereogenic centers can be obtained. This approach can be used for the synthesis of highly substituted piperidine derivatives.

  1. Simulations of Simple Nanomachines in Carbon Nanotude Bundles Based on Chirality

    DTIC Science & Technology

    2008-12-01

    BUNDLES BASED ON CHIRALITY D. L. Majure*, R. W. Haskins, N. J. Lee, C. R. Welch U.S. Army Engineer Research and Development Center, 3909 Halls Ferry...using the LAMMPS program. Each chirality type and diameter produced a different force function as the van der Waals forces “rubbed” against each other...One property discovered through the simulations is that certain chirality combinations produce useful behavior during the pullout process. One

  2. Cancer in World Trade Center responders: Findings from multiple cohorts and options for future study.

    PubMed

    Boffetta, Paolo; Zeig-Owens, Rachel; Wallenstein, Sylvan; Li, Jiehui; Brackbill, Robert; Cone, James; Farfel, Mark; Holden, William; Lucchini, Roberto; Webber, Mayris P; Prezant, David; Stellman, Steven D

    2016-02-01

    Three longitudinal studies of cancer incidence in varied populations of World Trade Center responders have been conducted. We compared the design and results of the three studies. Separate analyses of these cohorts revealed excess cancer incidence in responders for all cancers combined and for cancers of the thyroid and prostate. Methodological dissimilarities included recruitment strategies, source of cohort members, demographic characteristics, overlap between cohorts, assessment of WTC and other occupational exposures and confounders, methods and duration of follow-up, approaches for statistical analysis, and latency analyses. The presence of three cohorts strengthens the effort of identifying and quantifying the cancer risk; the heterogeneity in design might increase sensitivity to the identification of cancers potentially associated with exposure. The presence and magnitude of an increased cancer risk remains to be fully elucidated. Continued long-term follow up with minimal longitudinal dropout is crucial to achieve this goal. © 2016 Wiley Periodicals, Inc.

  3. Estimation Method of Center of Inertia Frequency based on Multiple Synchronized Phasor Measurement Data

    NASA Astrophysics Data System (ADS)

    Hashiguchi, Takuhei; Watanabe, Masayuki; Goda, Tadahiro; Mitani, Yasunori; Saeki, Osamu; Hojo, Masahide; Ukai, Hiroyuki

    Open access and deregulation have been introduced into Japan and some independent power producers (IPP) and power producer and suppliers (PPS) are participating in the power generation business, which is possible to makes power system dynamics more complex. To maintain power system condition under various situations, it is essential that a real time measurement system over wide area is available. Therefore we started a project to construct an original measurement system by the use of phasor measurement units (PMU) in Japan. This paper describes the estimation method of a center of inertia frequency by applying actual measurement data. The application of this method enables us to extract power system oscillations from measurement data appropriately. Moreover, the analysis of power system dynamics for power system oscillations occurring in western Japan 60Hz system is shown. These results will lead to the clarification of power system dynamics and may make it possible to realize the monitoring of power system oscillations associated with power system stability.

  4. Patient-Centered Care of Older Adults with Cardiovascular Disease and Multiple Chronic Conditions

    PubMed Central

    Kim, Dae Hyun; Rich, Michael W.

    2016-01-01

    Multimorbidity, defined as the presence of 2 or more chronic conditions, is common among older adults with cardiovascular disease. These individuals are at increased risk for poor health outcomes and account for a large proportion of healthcare utilization. Clinicians are challenged with the heterogeneity of this population, the complexity of the treatment regimen, limited high-quality evidence, and fragmented healthcare systems. Each treatment recommended by a clinical practice guideline for a single cardiovascular disease may be rational, but the combination of all evidence-based recommendations can be impractical or even harmful to individuals with multimorbidity. These challenges can be overcome with a patient-centered approach that incorporates the individual’s preferences, relevant evidence, the overall and condition-specific prognosis, clinical feasibility of treatments, and interactions with other treatments and coexisting chronic conditions. The ultimate goal is to maximize benefits and minimize harms by optimizing adherence to the most essential treatments, while acknowledging trade-offs between treatments for different health conditions. It may be necessary to discontinue therapies that are not essential or potentially harmful to decrease the risk of drug-drug and drug-disease interactions from polypharmacy. A decision to initiate, withhold, or stop a treatment should be based on the time horizon to benefits vs. the individual’s prognosis. In this review, we illustrate how cardiologists and general practitioners can adopt a patient-centered approach to focus on the aspects of cardiovascular and non-cardiovascular health that have the greatest impact on functioning and quality of life in older adults with cardiovascular disease and multimorbidity. PMID:27378591

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

    NASA Astrophysics Data System (ADS)

    Dreiling, Joan

    2016-05-01

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

  6. Chiral electroweak currents in nuclei

    DOE PAGES

    Riska, D. O.; Schiavilla, R.

    2017-01-10

    Here, the development of the chiral dynamics based description of nuclear electroweak currents is reviewed. Gerald E. (Gerry) Brown’s role in basing theoretical nuclear physics on chiral Lagrangians is emphasized. Illustrative examples of the successful description of electroweak observables of light nuclei obtained from chiral effective field theory are presented.

  7. Chirality, quantum mechanics, and biological determinism

    NASA Astrophysics Data System (ADS)

    Davies, P. C. W.

    2006-08-01

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

  8. Supramolecular chirality in self-assembled soft materials: regulation of chiral nanostructures and chiral functions.

    PubMed

    Zhang, Li; Qin, Long; Wang, Xiufeng; Cao, Hai; Liu, Minghua

    2014-10-29

    Supramolecular chirality, which arises from the nonsymmetric spatial arrangement of components in the self-assembly systems, has gained great attention owing to its relation to the natural biological structures and the possible new functions in advanced materials. During the self-assembling process, both chiral and achiral components are possible to form chiral nanostructures. Therefore, it becomes an important issue how to fabricate these molecular components into chiral nanostructures. Furthermore, once the chiral nanostructure is obtained, will it show new functions that simple component molecule could not? In this research news, we report our recent development in the regulation of chiral nanostructures in soft gels or vesicle materials. We have further developed several new functions pertaining to the soft gel materials, which single chiral molecules could not perform, such as the chiroptical switch, chiral recognition and the asymmetry catalysis.

  9. The Impact of Age upon Contingency Planning for Multiple-casualty Incidents Based on a Single Center's Experience.

    PubMed

    Ashkenazi, Itamar; Einav, Sharon; Olsha, Oded; Turegano-Fuentes, Fernando; Krausz, Michael M; Alfici, Ricardo

    2016-10-01

    Introduction Trauma patients in the extremes of age may require a specialized approach during a multiple-casualty incident (MCI). Problem The aim of this study was to examine the type of injuries encountered in children and elderly patients and the implications of these injuries for treatment and organization. A review of medical record files of patients admitted in MCIs in one Level II trauma center was conducted. Patients were classified according to age: children (≤12 years), adults (between 12-65 years), and elders (≥65 years). The files of 534 were screened: 31 (5.8%) children and 54 (10.1%) elderly patients. One-third of the elderly patients were either moderately or severely injured, compared to only 6.5% of the children and 11.1% of the adults (P<.001). Elderly patients required more blood transfusions (P=.0001), more computed tomography imaging (P=.0001), and underwent more surgery (P=.0004). Elders were hospitalized longer (P=.0003). There was no mortality among injured children, compared to nine (2.0%) of the adults and seven (13.0%) of the elderly patients (P<.0001). All the adult deaths occurred early and directly related to their injuries, whereas most of the deaths among the elderly patients (four out of seven) occurred late and were due to complications and multiple organ failure. Injury at an older age confers an increased risk of complications and death in victims of MCIs. Ashkenazi I , Einav S , Olsha O , Turegano-Fuentes F , Krausz MM , Alfici R . The impact of age upon contingency planning for multiple-casualty incidents based on a single center's experience. Prehosp Disaster Med. 2016;31(5):492-497.

  10. Doped Chiral Polymer Metamaterials

    NASA Technical Reports Server (NTRS)

    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.

  11. Creating chiral anomalies

    NASA Astrophysics Data System (ADS)

    Bradlyn, Barry; Cano, Jennifer; Wang, Zhijun; Hirschberger, Max; Ong, N. Phuan; Bernevig, B. Andrei

    Materials with intrinsic Weyl points should present exotic magnetotransport phenomena due to spectral flow between Weyl nodes of opposite chirality - the so-called ``chiral anomaly''. However, to date, the most definitive transport data showing the presence of a chiral anomaly comes from Dirac (not Weyl) materials. These semimetals develop Weyl fermions only in the presence of an externally applied magnetic field, when the four-fold degeneracy is lifted. In this talk we examine Berry phase effects on transport due to the emergence of these field-induced Weyl point and (in some cases) line nodes. We pay particular attention to the differences between intrinsic and field-induced Weyl fermions, from the point of view of kinetic theory. Finally, we apply our analysis to a particular material relevant to current experiments performed at Princeton.

  12. [Chirality and drugs].

    PubMed

    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.

  13. Numerical descriptors for the characterization of chiral compounds and their applications in modeling biological and toxicological activities.

    PubMed

    Natarajan, Ramanathan; Basak, Subhash C

    2011-01-01

    Due to the advancement in chiral synthesis and separation technology and the new regulatory policies for chiral pharmaceuticals several manufacturers are replacing the previously marketed racemate chemicals with single enantiomeric products, the so called chiral switch. Though 25% of agrochemicals are chiral in nature, most of them are sold as racemates or enantiomer enriched products. Chiral pesticides and some of the pharmaceuticals reach the human food chain as pollutants. Stereoisomers (enantiomers and diastereoisomers) not only differ from one another in their medicinal effects, but also in their phramacokinectic (adsorption, distribution, biotransformation and excretion) profiles and toxicological properties. Several recent attempts have been reported in the literature on developing mathematical models to predict the properties of chiral molecules from structure and such methods utilized numerical characterization. A comparison of different mathematical approaches on the numerical characterization of molecules with chiral center(s) and a brief background on the importance of stereochemistry in pharmacology, agrochemistry and environmental toxicology is presented.

  14. Chiral discrimination of α-hydroxy acids and N-Ts-α-amino acids induced by tetraaza macrocyclic chiral solvating agents by using (1)H NMR spectroscopy.

    PubMed

    Lv, Caixia; Feng, Lei; Zhao, Hongmei; Wang, Guo; Stavropoulos, Pericles; Ai, Lin

    2017-02-21

    In the field of chiral recognition, reported chiral discrimination by (1)H NMR spectroscopy has mainly focused on various chiral analytes with a single chiral center, regarded as standard chiral substrates to evaluate the chiral discriminating abilities of a chiral auxiliary. Among them, chiral α-hydroxy acids, α-amino acids and their derivatives are chiral organic molecules involved in a wide variety of biological processes, and also play an important role in the area of preparation of pharmaceuticals, as they are part of the synthetic process in the production of chiral drug intermediates and protein-based drugs. In this paper, several α-hydroxy acids and N-Ts-α-amino acids were used to evaluate the chiral discriminating abilities of tetraaza macrocyclic chiral solvating agents (TAMCSAs) 1a-1d by (1)H NMR spectroscopy. The results indicate that α-hydroxy acids and N-Ts-α-amino acids were successfully discriminated in the presence of TAMCSAs 1a-1d by (1)H NMR spectroscopy in most cases. The enantiomers of the α-hydroxy acids and N-Ts-α-amino acids were assigned based on the change of integration of the (1)H NMR signals of the corresponding protons. The enantiomeric excesses (ee) of N-Ts-α-amino acids 11 with different optical compositions were calculated based on the integration of the (1)H NMR signals of the CH3 protons (Ts group) of the enantiomers of (R)- and (S)-11 in the presence of TAMCSA 1b. At the same time, the possible chiral discriminating behaviors have been discussed by means of the Job plots of (±)-2 with TAMCSAs 1b and proposed theoretical models of the enantiomers of 2 and 6 with TAMCSA 1a, respectively.

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

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

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

  16. Diabetes Attitude Scale: validation in type-2 diabetes patients in multiple centers in China.

    PubMed

    Lou, Qingqing; Chen, Yufeng; Guo, Xiaohui; Yuan, Li; Chen, Tao; Wang, Chun; Shen, Li; Sun, Zilin; Zhao, Fang; Dai, Xia; Huang, Jin; Yang, Huiying

    2014-01-01

    The aim of the paper is to report the development and psychometric testing of Diabetes Attitude Scale. A prospective study was performed. The cultural equivalency and content validity of the Diabetes Attitude Scale were determined by panels of endocrinologists, physiologists, nurses and dieticians. An accurate and usable translation was obtained for each of five subscales examining attitudes on need for special training, the seriousness of type-2 diabetes, the need for controlling the condition, its psychosocial impact and the degree of autonomy given to patients in decision making. The validation was derived from 5961 patients with type-2 diabetes, recruited from 50 centers in 29 provinces throughout China between March 1st and September 30th, 2010. The modified Diabetes Attitude Scale showed an acceptable level of internal consistency. The strength of the inter-correlations among the domains of five subscales suggests that the instrument measures related but separate domains of patients' attitudes toward diabetes. Moreover, the test-retest intraclass correlation coefficients were high enough to support the stability of the Chinese version of the third version of the scale. The psychometric properties of the Chinese version of Diabetes Attitude Scale demonstrated satisfactory validity and reliability and appeared to effectively evaluate attitudes toward diabetes in patients with type-2 diabetes.

  17. Sparse matrix multiplications for linear scaling electronic structure calculations in an atom-centered basis set using multiatom blocks.

    PubMed

    Saravanan, Chandra; Shao, Yihan; Baer, Roi; Ross, Philip N; Head-Gordon, Martin

    2003-04-15

    A sparse matrix multiplication scheme with multiatom blocks is reported, a tool that can be very useful for developing linear-scaling methods with atom-centered basis functions. Compared to conventional element-by-element sparse matrix multiplication schemes, efficiency is gained by the use of the highly optimized basic linear algebra subroutines (BLAS). However, some sparsity is lost in the multiatom blocking scheme because these matrix blocks will in general contain negligible elements. As a result, an optimal block size that minimizes the CPU time by balancing these two effects is recovered. In calculations on linear alkanes, polyglycines, estane polymers, and water clusters the optimal block size is found to be between 40 and 100 basis functions, where about 55-75% of the machine peak performance was achieved on an IBM RS6000 workstation. In these calculations, the blocked sparse matrix multiplications can be 10 times faster than a standard element-by-element sparse matrix package. Copyright 2003 Wiley Periodicals, Inc. J Comput Chem 24: 618-622, 2003

  18. Chiral d-wave superconductivity in doped graphene.

    PubMed

    Black-Schaffer, Annica M; Honerkamp, Carsten

    2014-10-22

    A highly unconventional superconducting state with a spin-singlet dx2-y2+/-idxy-wave, or chiral d-wave symmetry has recently been suggested to emerge from electron-electron interactions in doped graphene. It has been argued that graphene doped to the van Hove singularity at 1/4 doping, where the density of states diverge, is particularly likely to be a chiral d-wave superconductor. In this review we summarize the currently mounting theoretical evidence for the existence of a chiral d-wave superconducting state in graphene, obtained with methods ranging from mean-field studies of effective Hamiltonians to angle-resolved renormalization group calculations. We further discuss the multiple distinctive properties of the chiral d-wave superconducting state in graphene, as well as its stability in the presence of disorder. We also review the means of enhancing the chiral d-wave state using proximity-induced superconductivity. The appearance of chiral d-wave superconductivity is intimately linked to the hexagonal crystal lattice and we also offer a brief overview of other materials which have also been proposed to be chiral d-wave superconductors.

  19. Chiral Liouville gravity

    NASA Astrophysics Data System (ADS)

    Compère, Geoffrey; Song, Wei; Strominger, Andrew

    2013-05-01

    Classical two-dimensional Liouville gravity is often considered in conformal gauge which has a residual left and right Virasoro symmetry algebra. We consider an alternate, chiral, gauge which has a residual right Virasoro Kac-Moody algebra, and no left Virasoro algebra. The Kac-Moody zero mode is the left-moving energy. Dirac brackets of the constrained Hamiltonian theory are derived, and the residual symmetries are shown to be generated by integrals of the conserved chiral currents. The central charge and Kac-Moody level are computed. The possible existence of a corresponding quantum theory is discussed.

  20. Polar Superhelices in Ferroelectric Chiral Nanosprings

    PubMed Central

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

    2016-01-01

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

  1. Polar Superhelices in Ferroelectric Chiral Nanosprings

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  2. Generalized Stern-Gerlach Effect for Chiral Molecules

    NASA Astrophysics Data System (ADS)

    Li, Yong; Bruder, C.; Sun, C. P.

    2007-09-01

    The Stern-Gerlach effect is well known as spin-dependent splitting of a beam of atoms with magnetic moments by a magnetic-field gradient. Here, we show that an induced gauge potential may lead to a similar effect for chiral molecules. In the presence of three inhomogeneous light fields, the center of mass of a three-level chiral molecule is subject to an optically induced gauge potential, and the internal dynamics of the molecule can be described as an adiabatic evolution in the reduced pseudospin subspace of the two lowest energy levels. We demonstrate numerically that such an induced gauge potential can lead to observable pseudospin-dependent and chirality-dependent generalized Stern-Gerlach effects for mixed left- and right-handed chiral molecules under realistic conditions.

  3. Generalized Stern-Gerlach effect for chiral molecules.

    PubMed

    Li, Yong; Bruder, C; Sun, C P

    2007-09-28

    The Stern-Gerlach effect is well known as spin-dependent splitting of a beam of atoms with magnetic moments by a magnetic-field gradient. Here, we show that an induced gauge potential may lead to a similar effect for chiral molecules. In the presence of three inhomogeneous light fields, the center of mass of a three-level chiral molecule is subject to an optically induced gauge potential, and the internal dynamics of the molecule can be described as an adiabatic evolution in the reduced pseudospin subspace of the two lowest energy levels. We demonstrate numerically that such an induced gauge potential can lead to observable pseudospin-dependent and chirality-dependent generalized Stern-Gerlach effects for mixed left- and right-handed chiral molecules under realistic conditions.

  4. Quantitative determination of free D-Asp, L-Asp and N-methyl-D-aspartate in mouse brain tissues by chiral separation and Multiple Reaction Monitoring tandem mass spectrometry.

    PubMed

    Fontanarosa, Carolina; Pane, Francesca; Sepe, Nunzio; Pinto, Gabriella; Trifuoggi, Marco; Squillace, Marta; Errico, Francesco; Usiello, Alessandro; Pucci, Piero; Amoresano, Angela

    2017-01-01

    Several studies have suggested that free d-Asp has a crucial role in N-methyl d-Asp receptor-mediated neurotransmission playing very important functions in physiological and pathological processes. This paper describes the development of an analytical procedure for the direct and simultaneous determination of free d-Asp, l-Asp and N-methyl d-Asp in specimens of different mouse brain tissues using chiral LC-MS/MS in Multiple Reaction Monitoring scan mode. After comparing three procedures and different buffers and extraction solvents, a simple preparation procedure was selected the analytes of extraction. The method was validated by analyzing l-Asp, d-Asp and N-methyl d-Asp recovery at different spiked concentrations (50, 100 and 200 pg/μl) yielding satisfactory recoveries (75-110%), and good repeatability. Limits of detection (LOD) resulted to be 0.52 pg/μl for d-Asp, 0.46 pg/μl for l-Asp and 0.54 pg/μl for NMDA, respectively. Limits of quantification (LOQ) were 1.57 pg/μl for d-Asp, 1.41 pg/μl for l-Asp and 1.64 pg/μl for NMDA, respectively. Different concentration levels were used for constructing the calibration curves which showed good linearity. The validated method was then successfully applied to the simultaneous detection of d-Asp, l-Asp and NMDA in mouse brain tissues. The concurrent, sensitive, fast, and reproducible measurement of these metabolites in brain tissues will be useful to correlate the amount of free d-Asp with relevant neurological processes, making the LC-MS/MS MRM method well suited, not only for research work but also for clinical analyses.

  5. Quantitative determination of free D-Asp, L-Asp and N-methyl-D-aspartate in mouse brain tissues by chiral separation and Multiple Reaction Monitoring tandem mass spectrometry

    PubMed Central

    Fontanarosa, Carolina; Pane, Francesca; Sepe, Nunzio; Pinto, Gabriella; Trifuoggi, Marco; Squillace, Marta; Errico, Francesco; Usiello, Alessandro; Pucci, Piero; Amoresano, Angela

    2017-01-01

    Several studies have suggested that free d-Asp has a crucial role in N-methyl d-Asp receptor-mediated neurotransmission playing very important functions in physiological and pathological processes. This paper describes the development of an analytical procedure for the direct and simultaneous determination of free d-Asp, l-Asp and N-methyl d-Asp in specimens of different mouse brain tissues using chiral LC-MS/MS in Multiple Reaction Monitoring scan mode. After comparing three procedures and different buffers and extraction solvents, a simple preparation procedure was selected the analytes of extraction. The method was validated by analyzing l-Asp, d-Asp and N-methyl d-Asp recovery at different spiked concentrations (50, 100 and 200 pg/μl) yielding satisfactory recoveries (75–110%), and good repeatability. Limits of detection (LOD) resulted to be 0.52 pg/μl for d-Asp, 0.46 pg/μl for l-Asp and 0.54 pg/μl for NMDA, respectively. Limits of quantification (LOQ) were 1.57 pg/μl for d-Asp, 1.41 pg/μl for l-Asp and 1.64 pg/μl for NMDA, respectively. Different concentration levels were used for constructing the calibration curves which showed good linearity. The validated method was then successfully applied to the simultaneous detection of d-Asp, l-Asp and NMDA in mouse brain tissues. The concurrent, sensitive, fast, and reproducible measurement of these metabolites in brain tissues will be useful to correlate the amount of free d-Asp with relevant neurological processes, making the LC-MS/MS MRM method well suited, not only for research work but also for clinical analyses. PMID:28662080

  6. Enantiomeric separation and determination of absolute stereochemistry of asymmetric molecules in drug discovery: building chiral technology toolboxes.

    PubMed

    McConnell, Oliver; Bach, Alvin; Balibar, Carl; Byrne, Neal; Cai, Yanxuan; Carter, Guy; Chlenov, Michael; Di, Li; Fan, Kristi; Goljer, Igor; He, Yanan; Herold, Don; Kagan, Michael; Kerns, Edward; Koehn, Frank; Kraml, Christina; Marathias, Vasilios; Marquez, Brian; McDonald, Leonard; Nogle, Lisa; Petucci, Christopher; Schlingmann, Gerhard; Tawa, Gregory; Tischler, Mark; Williamson, R Thomas; Sutherland, Alan; Watts, William; Young, Mairead; Zhang, Mei-Yi; Zhang, Yingru; Zhou, Dahui; Ho, Douglas

    2007-09-01

    The application of Chiral Technology, or the (extensive) use of techniques or tools for the determination of absolute stereochemistry and the enantiomeric or chiral separation of racemic small molecule potential lead compounds, has been critical to successfully discovering and developing chiral drugs in the pharmaceutical industry. This has been due to the rapid increase over the past 10-15 years in potential drug candidates containing one or more asymmetric centers. Based on the experiences of one pharmaceutical company, a summary of the establishment of a Chiral Technology toolbox, including the implementation of known tools as well as the design, development, and implementation of new Chiral Technology tools, is provided.

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

    PubMed

    Wernisch, Stefanie; Pell, Reinhard; Lindner, Wolfgang

    2012-07-01

    The intramolecular distances of anion and cation exchanger sites of zwitterionic chiral stationary phases represent potential tuning sites for enantiomer selectivity. In this contribution, we investigate the influence of alkanesulfonic acid chain length and flexibility on enantiomer separations of chiral acids, bases, and amphoteric molecules for six Cinchona alkaloid-based chiral stationary phases in comparison with structurally related anion and cation exchangers. Employing polar-organic elution conditions, we observed an intramolecular counterion effect for acidic analytes which led to reduced retention times but did not impair enantiomer selectivities. Retention of amphoteric analytes is based on simultaneous double ion pairing of their charged functional groups with the acidic and basic sites of the zwitterionic selectors. A chiral center in the vicinity of the strong cation exchanger site is vital for chiral separations of bases. Sterically demanding side chains are beneficial for separations of free amino acids. Enantioseparations of free (un-derivatized) peptides were particularly successful in stationary phases with straight-chain alkanesulfonic acid sites, pointing to a beneficial influence of more flexible moieties. In addition, we observed pseudo-enantiomeric behavior of quinine and quinidine-derived chiral stationary phases facilitating reversal of elution orders for all analytes. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Chiral Recognition Mechanisms of four β-Blockers by HPLC with Amylose Chiral Stationary Phase

    PubMed Central

    Wang, Dongmei; Li, Fang; Jiang, Zhen; Yu, Li; Guo, Xingjie

    2014-01-01

    The high performance liquid chromatography (HPLC) enantioseparation of four β-blocking agents metoprolol, bisoprolol, propranolol and atenolol was performed on amylose tris-(3,5-dimethylphenylcarbamate) chiral stationary phase using n-hexane-ethanol-diethylamine (DEA) as the mobile phase and related chiral recognition mechanisms were discussed. Enantiomeric separation of the four β-blockers was a result of more than one type of interaction between solutes and CSP. Besides hydrogen bonding, there was another type interaction that was independent of solvent polarity and responsible for enantiomeric selectivity, such as - interactions. Both the groups close to the chiral centers and the substituent groups on the phenyl rings, which were far away from the chiral centers, could contribute to the good separation. The separations of the four β-blocker enantiomers were all enthalpy driven process. In the range of 293–308K (20–35 ℃), as the temperature increased, the retention as well as the resolution decreased. The molecular size rather than concentration of the alcohol modifiers affected the resolution and retention. PMID:25237340

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

    PubMed

    Harada, Shinji; Morikawa, Takahiro; Nishida, Atsushi

    2013-10-18

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

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

    PubMed Central

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

    2014-01-01

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

  11. An Aligned-Gap and Centered-Gap Rectangular Multiple Split Ring Resonator for dielectric sensing applications.

    PubMed

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

    2014-07-21

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

  12. Chiral fiber sensors

    NASA Astrophysics Data System (ADS)

    Kopp, Victor I.; Churikov, Victor M.; Singer, Jonathan; Neugroschl, Daniel; Genack, Azriel Z.

    2010-04-01

    We have fabricated a variety of chiral fiber sensors by twisting one or more standard or custom optical fibers with noncircular or nonconcentric core as they pass though a miniature oven. The resulting structures are as stable as the glass material and can be produced with helical pitch ranging from microns to hundreds of microns. The polarization selectivity of the chiral gratings is determined by the geometry of the fiber cross section. Single helix structures are polarization insensitive, while double helix gratings interact only with a single optical polarization component. Both single and double helix gratings may function as a fiber long period grating, coupling core and cladding modes or as a diffraction grating scattering light from the fiber core out of the fiber. The resulting dips in the transmission spectrum are sensitive to fiber elongation, twist and temperature, and (in the case of the long period gratings) to the refractive index of the surrounding medium. The suitability of chiral gratings for sensing temperature, elongation, twist and liquid levels will be discussed. Gratings made of radiation sensitive glass can be used to measure the cumulative radiation dose, while gratings made of radiation-hardened glass are suitable for stable sensing of the environment in nuclear power plants. Excellent temperature stability up to 900°C is found in pure silica chiral diffraction grating sensors.

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

    NASA Astrophysics Data System (ADS)

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

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

  14. Tuning spontaneous radiation of chiral molecules by asymmetric chiral nanoparticles.

    PubMed

    Guzatov, Dmitry V; Klimov, Vasily V; Chan, Hsun-Chi; Guo, Guang-Yu

    2017-03-20

    We have obtained analytical expressions for the radiative decay rate of the spontaneous emission of a chiral molecule located near a dielectric spherical particle with a chiral nonconcentric spherical shell made of a bi-isotropic material. Our numerical and graphical analyses show that material composition, thickness and degree of non-concentricity of the shell can influence significantly the spontaneous radiation of the chiral molecule. In particular, the radiative decay rates can differ in orders of magnitude for a chiral molecule located near the thin and thick parts of a nonconcentric shell as well as near a concentric shell made of chiral metamaterial. We also find that the radiative decay rates of the "right" and "left" chiral molecule enantiomers located near a nanoparticle with a chiral metamaterial shell can differ pronouncedly from each other. Our findings therefore suggest a way to tune the spontaneous emission of chiral molecules by varying the material composition, thickness and degree of non-concentricity of the shell in the nearby composite nanoparticle and also to enhance the chirality selection of chiral molecules in racemic mixtures.

  15. Bottom-Up Hierarchical Self-Assembly of Chiral Porphyrins through Coordination and Hydrogen Bonds.

    PubMed

    Oliveras-González, Cristina; Di Meo, Florent; González-Campo, Arántzazu; Beljonne, David; Norman, Patrick; Simón-Sorbed, Maite; Linares, Mathieu; Amabilino, David B

    2015-12-23

    A series of chiral synthetic compounds is reported that shows intricate but specific hierarchical assembly because of varying positions of coordination and hydrogen bonds. The evolution of the aggregates (followed by absorption spectroscopy and temperature-dependent circular dichroism studies in solution) reveal the influence of the proportion of stereogenic centers in the side groups connected to the chromophore ring in their optical activity and the important role of pyridyl groups in the self-assembly of these chiral macrocycles. The optical activity spans 2 orders of magnitude depending on composition and constitution. Two of the aggregates show very high optical activity even though the isolated chromophores barely give a circular dichroism signal. Molecular modeling of the aggregates, starting from the pyridine-zinc(II) porphyrin interaction and working up, and calculation of the circular dichroism signal confirm the origin of this optical activity as the chiral supramolecular organization of the molecules. The aggregates show a broad absorption range, between approximately 390 and 475 nm for the transitions associated with the Soret region alone, that spans wavelengths far more than the isolated chromophore. The supramolecular assemblies of the metalloporphyrins in solution were deposited onto highly oriented pyrolitic graphite in order to study their hierarchy in assembly by atomic force microscopy. Zero and one-dimensional aggregates were observed, and a clear dependence on deposition temperature was shown, indicating that the hierarchical assembly took place largely in solution. Moreover, scanning electron microscopy images of porphyrins and metalloporphyrins precipitated under out-of-equilibrium conditions showed the dependence of the number and position of chiral amide groups in the formation of a fibrillar nanomaterial. The combination of coordination and hydrogen bonding in the complicated assembly of these molecules-where there is a clear hierarchy

  16. Interweaving chiral spirals

    NASA Astrophysics Data System (ADS)

    Kojo, Toru; Hidaka, Yoshimasa; Fukushima, Kenji; McLerran, Larry D.; Pisarski, Robert D.

    2012-02-01

    We elaborate how to construct interweaving chiral spirals in (2+1) dimensions, defined as a superposition of chiral spirals oriented in different directions. We divide a two-dimensional Fermi sea into distinct wedges, characterized by the opening angle 2 Θ and depth Q≃p, where p is the Fermi momentum. In each wedge, the energy is lowered by forming a single chiral spiral. The optimal values for Θ and Q are chosen by balancing this gain in energy versus the cost of deforming the Fermi surface (which dominates at large Θ) and patch-patch interactions (dominant at small Θ). Using a non-local four-Fermi interaction model, we estimate the gain and cost in energy by expanding in terms of 1/N (where N is the number of colors), Λ/Q, and Θ. Due to a form factor in our non-local model, at small 1/N the mass gap (chiral condensate) is large, and the interaction among quarks and the condensate local in momentum space. Consequently, interactions between different patches are localized near their boundaries, and it is simple to embed many chiral spirals. We identify the dominant and subdominant terms at high density and categorize formulate an expansion in terms of Λ/Q or Θ. The kinetic term in the transverse directions is subdominant, so that techniques from (1+1)-dimensional systems can be utilized. To leading order in 1/N and Λ/Q, the total gain in energy is ˜pΛQCD2 with Θ˜(. Since Θ decreases with increasing p, there should be phase transitions associated with the change in the wedge number. We also argue the effects of subdominant terms at lower density where the large- N approximation is more reliable.

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

    PubMed

    2014-05-01

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

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

    PubMed

    Lu, Yang; Shamsi, Shahab A

    2014-10-01

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

  19. Comparison of Positively and Negatively Charged Achiral Co-Monomers Added to Cyclodextrin Monolith: Improved Chiral Separations in Capillary Electrochromatography

    PubMed Central

    Lu, Yang; Shamsi, Shahab A.

    2014-01-01

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

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

    PubMed

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

    2006-09-01

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

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2014-09-01

    The aim of this study was to describe contextual events, abuse experiences, and disclosure processes of adolescents who presented to a hospital-based Child Advocacy Center for medical evaluation and evidentiary collection as indicated after experiencing multiple perpetrator rape during a single event (n=32) and to compare these findings to a group of single perpetrator sexual assaults (n=534). This study used a retrospective mixed-methods design with in-depth, forensic interviews and complete physical examinations of gang-raped adolescents. Patients ranged from 12 to 17 years (M=14 years). Girls who experienced multiple perpetrator rape during a single event were more likely to have run away, to have drunk alcohol in the past month, and to have participated in binge drinking in the past 2 weeks. Acute presentation of these victims were rare but 30% had hymenal transections and 38% had sexually transmitted infections (STIs). Forensic interviews revealed alcohol was a common weapon used by offenders, and its use resulted in victims experiencing difficulty in remembering and reporting details for police investigation or physical and mental health care. Most victims were raped at parties they attended with people they thought they could trust, and they felt let down by witnesses who could have helped but did not intervene. Although relatively rare, multiple perpetrator rape during a single event is a type of severe sexual assault experience and has significant risks for deleterious health outcomes. These victims require health care by trained providers to diagnose physical findings, treat STIs, screen for trauma, and support victims. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

  3. Core-Scaffold-Inspired Asymmetric Synthesis of Polysubstituted Chiral Hexahydropyridazines that Potently Inhibit Breast Cancer Cell Proliferation by Inducing Apoptosis.

    PubMed

    Leng, Hai-Jun; Peng, Fu; Zingales, Sarah; Huang, Wei; Wang, Biao; Zhao, Qian; Zhou, Rui; He, Gu; Peng, Cheng; Han, Bo

    2015-12-07

    The highly enantioselective preparation of pharmacologically interesting hexahydropyridazine derivatives based on a multicomponent cascade reaction is described. This one-pot approach utilizes an organocatalytic Michael reaction followed by intermolecular α-amination and intramolecular hemiaminalization to yield a chiral pyridazine backbone with contiguous stereogenic centers and multiple functional groups in good yield and with high stereoselectivity. Compounds synthesized by this method potently inhibited proliferation of MCF-7 breast cancer cells. Mechanistic studies suggest that compound 5 c exerts these anticancer effects by inducing apoptosis through extracellular signal related kinase (ERK)- and poly(adenosine diphosphate ribose) polymerase (PARP)-regulated pathways, as well as mitochondrial pathways.

  4. Complex [Cd(dafo) 2(tphpo)(CH 3COO)]ClO 4 (dafo=4,5-diazafluoren-9-one, tphpo=triphenylphosphine oxide) with chiral metal centers. Helical packing induced by π-π stacking interactions of dafo rings

    NASA Astrophysics Data System (ADS)

    Wu, B.-L.; Zhang, H.-Y.; Wu, Q.-A.; Hou, H.-W.; Zh, Y.

    2003-08-01

    The first complex of 4,5-diazafluoren-9-one (dafo) and cadmium: [Cd(dafo) 2(tphpo)(CH 3COO)]ClO 4 (triphenylphosphine oxide=tphpo) is a quaternary complex with chiral metal centers and crystallizes in a monoclinic cell with space group P2(1)/ n. Cadmium centers with 7-fold coordination adopt a distorted monocapped trigonal prismatic geometry. Two oxygen atoms of acetate and one oxygen atom of triphenylphosphine oxide form the top triangle of the trigonal prism, while three nitrogen atoms from two dafo groups construct the bigger bottom triangle. The last nitrogen atom of dafo groups occupies the monocapped position. Here, dafo molecules display two different coordination patterns, namely unsymmetric and symmetric chelation. Moreover, the interesting linking of screw related cations is fabricated by inter-molecular π-π stacking interactions in the complex.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. An Introduction to the Theory of the Chiral Magnetic Effect

    NASA Astrophysics Data System (ADS)

    Liao, Jinfeng

    2016-09-01

    Anomalous chiral transport processes, with the notable example of the Chiral Magnetic Effect (CME), are remarkable phenomena that manifest microscopic quantum anomaly of chiral fermions in a macroscopic many-body setting. Significant progress has been achieved both in their theoretical understanding and in their experimental search. In this talk, an elementary introduction will be given for the CME as well as other anomalous chiral effects such as the Chiral Magnetic Wave (CMW) and the vorticity-driven effects. The theoretical foundation for describing them is rapidly emerging, including the anomalous hydrodynamics framework for (nearly) equilibrated systems while the chiral kinetic theory for out-of-equilibrium systems. The most recent results along these lines will be highlighted, with an emphasis on their applications to heavy ion collision experiments. Finally the currently pressing issues and anticipated future developments, in the context of recently formed Beam Energy Scan Theory (BEST) Collaboration, will be envisioned. The speaker acknowledges partial support from NSF, DOE, and RIKEN BNL Research Center.

  7. Optical properties of chiral nanotubes

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

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

  8. Modes of structurally chiral lasers

    NASA Astrophysics Data System (ADS)

    Topf, René D. M.; McCall, Martin W.

    2014-11-01

    We employ coupled wave theory to enumerate the lasing modes of structurally chiral lasers. The elliptical modes are shown to be fundamentally distinct from those of a scalar distributed feedback laser. High threshold modes are shown to lase with the opposite chirality as the active medium, in contrast to their low-threshold counterparts that lase with the same chirality as the active medium. The lasing mode structure suggests the intriguing possibility of dynamically changing the polarization handedness of a chiral laser, as well as the possibility of lasing within the forbidden band-gap region. These observations arise from the fundamental interplay between the distributed chirality-preserving reflections within the active medium and the localized chirality-reversing reflections at the medium's boundaries.

  9. ENANTIOMER-SPECIFIC EFFECTS OF CHIRAL POLLUTANTS

    EPA Science Inventory

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

  10. Doubly charged trimeric cluster ions: effective in mutual chiral recognition of tadalafil and three proton pump inhibitors.

    PubMed

    Wang, Lu; Chai, Yunfeng; Zhu, Wenquan; Pan, Yuanjiang; Sun, Cuirong; Zeng, Su

    2017-02-27

    Mutual chiral recognition of four stereoisomers of tadalafil and three pairs of enantiomers of proton pump inhibitors (PPIs) including pantoprazole, lansoprazole, and omeprazole, as well as quantitative analysis of enantiomeric excess is achieved on the basis of the competitive fragmentation of doubly charged trimeric Ni(II) cluster ions. Compared with a singly charged trimeric cluster ion, a doubly charged trimeric cluster ion was proved efficient in the recognition of chiral drugs with one or multiple chiral centers, due to its rich fragmentation ions. Upon collision-induced dissociation (CID), the cluster ion [Ni(II)(PPIs)(tadalafil)2](2+) yielded two diagnostic ions [tadalafil + H](+) and [tadalafil - benzo[d][1,3]dixoloe](+) through electrospray ionization quadrupole time-of-flight mass spectrometry. The abundance ratio of the two fragment ions relied mainly on the configuration of PPIs and tadalafil, and therefore the chiral selectivity (Rchiral) of one enantiomer relative to the others is different. The chiral recognition of all four stereoisomers of tadalafil was achieved by using S configuration PPIs as references, and S-omeprazole showed the best selectivity. The Rchiral values for R,R/S,S, R,S/S,R, R,R/R,S and R,R/S,R-tadalafils were 1.47, 1.17, 2.37, and 2.10, respectively. In a reciprocal process, the Rchiral was 1.36 and 1.31 for R/S-pantoprazole and R/S-lansoprazole, respectively, by using R,R-tadalafil as a reference. Although omeprazole is a racemic drug, it can also be discriminated with S-omeprazole. Calibration curves were constructed with favorable correlation coefficients (r(2) > 0.991) by relating the ln(Rchiral) values to the isomeric composition in a mixture. The sensitivity of the methodology allows mixtures to be analyzed for the enantiomeric excess (ee) by recording the ratios of fragment ion abundances in a mass spectrum. The sensitivity of the methodology allowed the determination of enantiomeric impurities of 5% molar composition in

  11. Chiral conical diffraction

    NASA Astrophysics Data System (ADS)

    Berry, M. V.; Jeffrey, M. R.

    2006-05-01

    The geometrical and wave optics are explored for light emerging from a slab of transparent biaxial crystal with optical activity (chirality), for an incident beam directed along the optic axis. The geometrical optics, here derived from Hamilton's principle, is dominated by a circularly symmetric cusped caustic surface ('spun cusp') threaded by an axial focal line. In wave optics, formulated exactly in the paraxial approximation in terms of integrals previously obtained by Belsky and Stepanov and here derived using a unitary evolution operator, the field is determined by two dimensionless parameters. The geometrical features are decorated by interference, here explored in the focal image plane (where the Poggendorff rings of the non-chiral case are in sharpest focus) and along the axis. Asymptotic approximations are derived in terms of the geometrical optics rays (including interference and evanescent waves), near the spun cusp, and uniformly across the caustic surface far from the cusp.

  12. Chiral symmetry and pentaquarks

    SciTech Connect

    Dmitri Diakonov

    2004-07-01

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

  13. Chiral Dynamics 2006

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

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

  14. [Chirality and drugs].

    PubMed

    Husson, H P

    1997-01-01

    Following a brief historical review of the notion of chirality, the importance of the relationship between pharmacological activity and the enantiomeric forms of drugs is indicated. Different approaches for the preparation of optically-pure molecules are discussed, and an original strategy, known as the "CN(R,S) method", is described. To conclude, an application of this method in the synthesis of a pharmacologically-active molecule is presented.

  15. Chiral Biomarkers in Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2010-01-01

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

  16. Long-term results of thulium laser resection of the prostate: a prospective study at multiple centers.

    PubMed

    Sun, Feng; Han, Bangmin; Cui, Di; Zhao, Fujun; Sun, Xiaowen; Zhuo, Jian; Jing, Yifeng; Liu, Haitao; Xia, Shujie; Yang, Yong; Luo, Guangheng; Guo, Fengfu

    2015-04-01

    To evaluate the long-term durability and complication rates after thulium laser resection of prostate (TmLRP) through a prospective multiple-center study. From November 2004 to December 2011, we prospectively studied 2,216 patients with symptomatic benign prostatic hyperplasia (BPH) treated with thulium laser resection of the prostate at four medical centers. Patients were assessed on International Prostate Symptom Score (IPSS), quality of life (QoL), maximum urinary flow rate (Qmax), and postvoid residual urine (PVR). Perioperative complications were classified according to the modified Clavien classification system. Of 2,216 patients treated with TmLRP, 1,353 (61.1 %), 1,129 (50.9 %), 847 (38.2 %), and 541 (24.4 %) patients were followed at 5, 6, 7, and 8 years, respectively. Postoperatively, IPSS, QoL, Qmax, and PVR showed a significant improvement from 3 month after surgery and remained significantly improved during the entire follow-up period (p < 0.01). Minor complications occurred in 526 (23.7 %) of the 2,216 patients (Clavien 1: 21.5 %; Clavien 2: 2.3 %). Major complications requiring re-interventions occurred in 48 (2.2 %) of the 2,216 patients (Clavien 3: 2.2 %). No Clavien 4 or Clavien 5 complication had occurred. Urethral stricture and bladder neck contracture occurred in 2.6 % (58) and 1.6 % (35) patients, respectively. Persistent stress incontinence was found in 0.1 % (2) of the patients. Re-operation as a result of BPH recurrence was required in 1.2 % (27) patients. Thulium laser resection of the prostate is a safe and effective procedure with excellent durability in the treatment of symptomatic BPH.

  17. Generalized simplicial chiral models

    NASA Astrophysics Data System (ADS)

    Alimohammadi, Masoud

    2000-02-01

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

  18. Chiral magnetohydrodynamic turbulence

    NASA Astrophysics Data System (ADS)

    Pavlović, Petar; Leite, Natacha; Sigl, Günter

    2017-07-01

    In this work the influence of the chiral anomaly effect on the evolution of magnetohydrodynamic turbulence was studied. We argue that before the electroweak symmetry breaking and for temperatures high enough such that the electron mass can be ignored, the description of a charged plasma in general needs to take into account the interplay between turbulence and the anomaly effects. It was demonstrated that this generalization can have important consequences on the evolution of turbulence, leading to the creation of maximally-helical fields from initially nonhelical ones. Therefore, chiral effects can strongly support turbulent inverse cascade, and lead to a slower decrease of the magnetic field with time, and also to a faster growth of the correlation length, when compared to the evolution predicted by the standard magnetohydrodynamics description. Using the weak anomaly approximation, and treating the anomaly contributions to magnetic energy and helicity as a small perturbation, we derive the specific solutions for the inverse cascade regime that demonstrate how chiral effects support the inverse cascade.

  19. Collective Hamiltonian for chiral modes

    NASA Astrophysics Data System (ADS)

    Chen, Q. B.; Zhang, S. Q.; Zhao, P. W.; Jolos, R. V.; Meng, J.

    2013-02-01

    A collective model is proposed to describe the chiral rotation and vibration and applied to a system with one h11/2 proton particle and one h11/2 neutron hole coupled to a triaxial rigid rotor. The collective Hamiltonian is constructed from the potential energy and mass parameter obtained in the tilted axis cranking approach. By diagonalizing the collective Hamiltonian with a box boundary condition, it is found that for the chiral rotation, the partner states become more degenerate with the increase of the cranking frequency, and for the chiral vibrations, their important roles for the collective excitation are revealed at the beginning of the chiral rotation region.

  20. Microchip electrophoresis for chiral separations.

    PubMed

    Belder, Detlev; Ludwig, Martin

    2003-08-01

    Microchip electrophoresis (MCE) is a promising new technique for the separation of enantiomers. This recently introduced technique enables chiral separations to be performed in seconds on tiny micromachined devices. This review is intended to give a brief introduction into the principles of chiral separations with MCE with regard to methodology and instrumentation. Different approaches to realize chiral separations in microfluidic devices are described and discussed. This review gives an overview of original work done in this field with emphasis on approaches to improve detection and resolution in chiral MCE.

  1. Free-standing chiral plasmonics

    NASA Astrophysics Data System (ADS)

    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.

  2. Multiplicity

    DTIC Science & Technology

    1991-04-01

    practice as a "[descent] into that inner circle of the Inferno where the damned endlessly degate multiplicity for sentencing." United States v. Barnard...select the charges to be brought in a particular case"). 19 Brown v. Ohio, 432 U.S. 161, 165 (1977). 20 Whalen v. United States, 445 U.S. at 689. 21...parte Lange, 8-5 U.S. (19 Wall.) 163 (1874). Cf. Brown v. Ohio, 432 U.S. at 165 ("once the legislature has acted courts may not impose more than one

  3. High-performance liquid chromatographic separations of stereoisomers of chiral basic agrochemicals with polysaccharide-based chiral columns and polar organic mobile phases.

    PubMed

    Matarashvili, Iza; Shvangiradze, Iamze; Chankvetadze, Lali; Sidamonidze, Shota; Takaishvili, Nino; Farkas, Tivadar; Chankvetadze, Bezhan

    2015-12-01

    The separation of the stereoisomers of 23 chiral basic agrochemicals was studied on six different polysaccharide-based chiral columns in high-performance liquid chromatography with various polar organic mobile phases. Along with the successful separation of analyte stereoisomers, emphasis was placed on the effect of the chiral selector and mobile phase composition on the elution order of stereoisomers. The interesting phenomenon of reversal of enantiomer/stereoisomer elution order function of the polysaccharide backbone (cellulose or amylose), type of derivative (carbamate or benzoate), nature, and position of the substituent(s) in the phenylcarbamate moiety (methyl or chloro) and the nature of the mobile phase was observed. For several of the analytes containing two chiral centers all four stereoisomers were resolved with at least one chiral selector/mobile phase combination.

  4. Optimization of the LC enantioseparation of chiral pharmaceuticals using cellulose tris(4-chloro-3-methylphenylcarbamate) as chiral selector and polar non-aqueous mobile phases.

    PubMed

    Dossou, Katina S S; Chiap, Patrice; Chankvetadze, Bezhan; Servais, Anne-Catherine; Fillet, Marianne; Crommen, Jacques

    2010-06-01

    The resolving power of a new commercial polysaccharide-based chiral stationary phase, Sepapak-4, with cellulose tris(4-chloro-3-methylphenylcarbamate) coated on silica microparticles as chiral selector, was evaluated toward the enantioseparation of ten basic drugs with widely different structures and hydrophobic properties, using ACN as the main component of the mobile phase. A multivariate approach (experimental design) was used to screen the factors (temperature, n-hexane content, acidic and basic additives) likely to influence enantioresolution. Then, the optimization was performed using a face-centered central composite design. Complete enantioseparation could be obtained for almost all tested chiral compounds, demonstrating the high chiral discrimination ability of this chiral stationary phase using polar organic mobile phases made up of ACN and containing an acidic additive (TFA or formic acid), 0.1% diethylamine and n-hexane. These results clearly illustrate the key role of the nature of the acidic additive in the mobile phase.

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

    ERIC Educational Resources Information Center

    Meyer, Edgar F., Jr.

    1978-01-01

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

  6. Chiral drag force

    NASA Astrophysics Data System (ADS)

    Rajagopal, Krishna; Sadofyev, Andrey V.

    2015-10-01

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

  7. Chiral-auxiliary-mediated asymmetric synthesis of ruthenium polypyridyl complexes.

    PubMed

    Gong, Lei; Wenzel, Marianne; Meggers, Eric

    2013-11-19

    An octahedral metal complex with 6 different monodentate ligands can form 15 diastereomers as pairs of enantiomers. As a result, the elaborate stereochemistry of octahedral coordination geometries provides tremendous opportunities in the fields of catalysis, the materials sciences, and the life sciences. The demand for enantiomerically pure coordination complexes for tasks related to the selective molecular recognition of biomacromolecules led us to develop synthetic methods to control the absolute stereochemistry at octahedral metal centers. A few years ago our laboratory therefore embarked on a project exploring new and general synthetic strategies for the asymmetric synthesis of inert octahedral transition metal complexes. We initially used the example of thermally inert ruthenium polypyridyl complexes and developed a family of chiral bidentate ligands, including salicyloxazolines, (mercaptophenyl)oxazolines, sulfinylphenols, N-acetylsulfinamides, a phosphinohydroxybinaphthyl, and even the amino acid proline to serve as chiral auxiliaries for asymmetric coordination chemistry. All these chiral auxiliaries strongly coordinate to ruthenium(II) in a bidentate, deprotonated fashion, allowing them to control the absolute metal-centered configuration in the course of subsequent ligand exchange reactions. Finally, we can remove them from the metal without any loss of chiral information and without leaving a chemical trace. A key feature of these chiral auxiliary ligands is their switchable binding strength. A chelate effect ensures that the chiral ligands coordinate very tightly to the metal center, placing their carbon-based, sulfur-based, or axial chirality in a well-defined position close to the metal center to efficiently establish the absolute metal-centered configuration. At the same time a coordinating phenolate, carboximidate, carboxylate, or thiophenolate moiety makes the coordination reversible by weakening the binding strength through protonation or

  8. Isothermal Titration Calorimetry of Chiral Polymeric Nanoparticles.

    PubMed

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

    2015-09-01

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

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

    PubMed

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

    2015-07-20

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

  10. Rooting Prebiotic Chirality in Spinomeric Chemistry?

    NASA Astrophysics Data System (ADS)

    Popa, Radu; Cimpoiašu, Vily Marius; Scorei, Romulus Ion

    2009-10-01

    Spinomeric chemistry is a domain of physical chemistry that explores the role of spin-isomery in chemical reactivity. In large magnetic fields (B), chemical structures with three adjacent nuclear spins (such as H217O, H233O,-NH2 and 13CH2) form complex spinomers. Known departure from a 1:1 ratio between various types of spinomers opens interesting research avenues in their potential role in asymmetric hydration processes. Recent time domain 1H nuclear magnetic resonance (TD-1HNMR) findings revealed the existence of small, yet consistent, H217O-controlled enantio-different proton exchange reactivity in sugars. The mechanisms behind this effect are unclear and may involve spinomer/enantiocenter (e.g. H217O/*C) interactions or spinomer/spinomer (e.g. H217O-NH2) interactions. We developed an experimental model that allows for the verification and study of such effects. We used TD-1HNMR at 0.589T to study and compare proton exchange enantio-differences in asparagine (Asn) and mandelic acid in response to titration with at constant pH. Unlike Asn, mandelic acid has no complex spinomer group (such as -NH2) in its chiral center. We report finding enantio-differences regarding ΔpK and 1/T2(0) correlated with H217/O, and linear changes in ΔM2 indicating differences in the affinity of enantiomers for H217O surface hydration. These results stress the importance of H217O-based spinomeric chemistry in chiral reactivity and open windows toward a novel interpretation of the origin of prebiotic chiral reactivity in the presence of moderately large B (such as on magnetic mineral surfaces or on satellites of gaseous giants), as well as toward abiotic isotopic fractionation of H217O in the presence of chiral organic molecules.

  11. Chiral Crystallization of Ethylenediamine Sulfate

    ERIC Educational Resources Information Center

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

    2005-01-01

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

  12. Chiral Crystallization of Ethylenediamine Sulfate

    ERIC Educational Resources Information Center

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

    2005-01-01

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

  13. CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

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

  14. CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

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

  15. Empirical description of chiral autocatalysis.

    PubMed

    Micskei, Karoly; Póta, György; Caglioti, Luciano; Palyi, Gyula

    2006-05-11

    The only known example of chiral autocatalysis is the alkylation of N-heterocyclic aldehydes with iPr(2)Zn (Soai reaction). The mechanism and some details of this reaction are not yet clear. An empirical formula is proposed here for the description of this chiral autocatalytic reaction. This formula allows the calculation of some very informative parameters.

  16. Mass-Selective Chiral Analysis

    NASA Astrophysics Data System (ADS)

    Boesl, Ulrich; Kartouzian, Aras

    2016-06-01

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

  17. Quark structure of chiral solitons

    SciTech Connect

    Dmitri Diakonov

    2004-05-01

    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+.

  18. Controlling Chirality of Entropic Crystals.

    PubMed

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

    2015-10-09

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

  19. Chiral models: Geometrical aspects

    NASA Astrophysics Data System (ADS)

    Perelomov, A. M.

    1987-02-01

    Two-dimensional classical chiral models of field theory are considered, the main attention being paid on geometrical aspects of such theories. A characteristic feature of these models is that the interaction is inserted not by adding the interaction Lagrangian to the free field Lagrangian, but has a purely geometrical origin and is related to the inner curvature of the manifold. These models are in many respects analogous to non-Abelian gauge theories and as became clear recently, they are also important for the superstring theory which nowadays is the most probable candidate for a truly unified theory of all interactions including gravitation.

  20. Adaptation to Survival in Germinal Center is the Initial Step in Onset of Indolent Stage of Multiple Myeloma

    PubMed Central

    Silva, Ariosto S.; Gatenby, Robert A.

    2011-01-01

    Aberrant mutations of centrocytes in germinal centers (GC) can generate two completely different diseases: B-cell lymphomas and monoclonal gammopathy of undetermined significance (MGUS). In this article we use computational models to examine the evolutionary dynamics by which initial adaptation to survival in the GC allows naïve MGUS cells to proliferate in the bone marrow and initiate the evolutionary process that will lead to aggressive multiple myeloma (MM). Our simulations show that MGUS cells may generate bone marrow tumors ranging from indolent to aggressive, depending on the original adaptation in the GC. All these tumors, however, are limited to approximately 15% of the marrow cellularity due to hypoxia-induced quiescence (this correlates with the cellularity that separates MGUS and MM, ~10%). Resistance to hypoxia-induced quiescence and cell death was one of the two major bone marrow adaptations that allowed continued tumor growth and establishment of paracrine cytokine loops, known to increase MM cell replication and de novo multidrug resistance. The second major adaptation was an increase in IL-6-independent growth rate, which correlates with the mutations observed in advanced stage patients. Even though there was an increase in the microvessel density in all simulations, the “angiogenic switch” was not due to a MM angiogenic phenotype, but rather the response of MM cells to the regional hypoxia caused by the increased tumor burden. These results indicate that treatments targeting the adaptation to survival and proliferation in hypoxia, in conjunction with currently available therapies, may have synergistic effects, by delaying tumor growth and reducing cytokine paracrine loops mediated by angiogenic factors. PMID:21958215

  1. Manufacturing Differences Affect Human Bone Marrow Stromal Cell Characteristics and Function: Comparison of Production Methods and Products from Multiple Centers

    PubMed Central

    Liu, Shutong; de Castro, Luis F.; Jin, Ping; Civini, Sara; Ren, Jiaqiang; Reems, Jo-Anna; Cancelas, Jose; Nayak, Ramesh; Shaw, Georgina; O’Brien, Timothy; McKenna, David H.; Armant, Myriam; Silberstein, Leslie; Gee, Adrian P.; Hei, Derek J.; Hematti, Peiman; Kuznetsov, Sergei A.; Robey, Pamela G.; Stroncek, David F.

    2017-01-01

    Human bone marrow stromal cells (BMSCs, also known as bone marrow-derived mesenchymal stem cells) are manufactured using many different methods, but little is known about the spectrum of manufacturing methods used and their effects on BMSC characteristics and function. Seven centers using, and one developing, Good Manufacturing Practices (GMP) processes were surveyed as to their production methods. Among the seven centers, all used marrow aspirates as the starting material, but no two centers used the same manufacturing methods. Two to four BMSC lots from each center were compared using global gene expression. Among the twenty-four BMSC lots from the eight centers intra-center transcriptome variability was low and similar among centers. Principal component analysis and unsupervised hierarchical clustering analysis separated all the lots from five centers into five distinct clusters. BMSCs from six of the eight centers were tested for their ability to form bone and support hematopoiesis by in vivo transplantation (defining features of BMSCs). Those from all six centers tested formed bone, but the quantity formed was highly variable and BMSCs from only three centers supported hematopoiesis. These results show that differences in manufacturing resulted in variable BMSC characteristics including their ability to form bone and support hematopoiesis. PMID:28447618

  2. Manufacturing Differences Affect Human Bone Marrow Stromal Cell Characteristics and Function: Comparison of Production Methods and Products from Multiple Centers.

    PubMed

    Liu, Shutong; de Castro, Luis F; Jin, Ping; Civini, Sara; Ren, Jiaqiang; Reems, Jo-Anna; Cancelas, Jose; Nayak, Ramesh; Shaw, Georgina; O'Brien, Timothy; McKenna, David H; Armant, Myriam; Silberstein, Leslie; Gee, Adrian P; Hei, Derek J; Hematti, Peiman; Kuznetsov, Sergei A; Robey, Pamela G; Stroncek, David F

    2017-04-27

    Human bone marrow stromal cells (BMSCs, also known as bone marrow-derived mesenchymal stem cells) are manufactured using many different methods, but little is known about the spectrum of manufacturing methods used and their effects on BMSC characteristics and function. Seven centers using, and one developing, Good Manufacturing Practices (GMP) processes were surveyed as to their production methods. Among the seven centers, all used marrow aspirates as the starting material, but no two centers used the same manufacturing methods. Two to four BMSC lots from each center were compared using global gene expression. Among the twenty-four BMSC lots from the eight centers intra-center transcriptome variability was low and similar among centers. Principal component analysis and unsupervised hierarchical clustering analysis separated all the lots from five centers into five distinct clusters. BMSCs from six of the eight centers were tested for their ability to form bone and support hematopoiesis by in vivo transplantation (defining features of BMSCs). Those from all six centers tested formed bone, but the quantity formed was highly variable and BMSCs from only three centers supported hematopoiesis. These results show that differences in manufacturing resulted in variable BMSC characteristics including their ability to form bone and support hematopoiesis.

  3. Extended surface chirality from supramolecular assemblies of adsorbed chiral molecules

    NASA Astrophysics Data System (ADS)

    Ortega Lorenzo, M.; Baddeley, C. J.; Muryn, C.; Raval, R.

    2000-03-01

    The increasing demand of the chemical and pharmaceutical industries for enantiomerically pure compounds has spurred the development of a range of so-called `chiral technologies' (ref. 1), which aim to exert the ultimate control over a chemical reaction by directing its enantioselectivity. Heterogeneous enantioselective catalysis is particularly attractive because it allows the production and ready separation of large quantities of chiral product while using only small quantities of catalyst. Heterogeneous enantioselectivity is usually induced by adsorbing chiral molecules onto catalytically active surfaces. A mimic of one such catalyst is formed by adsorbing (R,R)-tartaric acid molecules on Cu(110) surfaces: this generates a variety of surface phases, of which only one is potentially catalytically active, and leaves the question of how adsorbed chiral molecules give rise to enantioselectivity. Here we show that the active phase consists of extended supramolecular assemblies of adsorbed (R,R)-tartaric acid, which destroy existing symmetry elements of the underlying metal and directly bestow chirality to the modified surface. The adsorbed assemblies create chiral `channels' exposing bare metal atoms, and it is these chiral spaces that we believe to be responsible for imparting enantioselectivity, by forcing the orientation of reactant molecules docking onto catalytically active metal sites. Our findings demonstrate that it is possible to sustain a single chiral domain across an extended surface-provided that reflection domains of opposite handedness are removed by a rigid and chiral local adsorption geometry, and that inequivalent rotation domains are removed by successful matching of the rotational symmetry of the adsorbed molecule with that of the underlying metal surface.

  4. Nanoscale chirality in metal and semiconductor nanoparticles.

    PubMed

    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.

  5. Nanoscale chirality in metal and semiconductor nanoparticles

    PubMed Central

    Thomas, K. George

    2016-01-01

    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. PMID:27752651

  6. From chiral vibration to static chirality in ^135Nd

    NASA Astrophysics Data System (ADS)

    Mukhopadhyay, S.; Almehed, D.; Garg, U.; Frauendorf, S.; Li, T.; Madhusudhana Rao, P. V.; Wang, X.; Ghugre, S. S.; Carpenter, M. P.; Gros, S.; Hecht, A.; Janssens, R. V. F.; Kondev, F. G.; Lauritsen, T.; Seweryniak, D.; Zhu, S.

    2007-10-01

    Lifetimes were obtained in a DSAM measurement at Gammasphere, using the ^100Mo(^40Ar, 5n)^135Nd reaction. Electromagnetic transition probabilities have been measured for the intra- and inter-band transitions in the two sequences in the nucleus ^135Nd that were previously identified as a composite chiral bands [1]. The measurements are in good agreement with results of a new combination of TAC and RPA calculations. The chiral character of the bands is affirmed and it is observed that their behavior is associated with a transition from a vibrational into a static chiral regime. [1] S. Zhu et al., Phys. Rev. Lett.91, 132501 (2003).

  7. Chiral limit of QCD

    SciTech Connect

    Gupta, R.

    1994-12-31

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

  8. Chiral quantum optics

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

    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. Chiral Conjugated Corrals.

    PubMed

    Ball, Melissa; Fowler, Brandon; Li, Panpan; Joyce, Leo A; Li, Fang; Liu, Taifeng; Paley, Daniel; Zhong, Yu; Li, Hexing; Xiao, Shengxiong; Ng, Fay; Steigerwald, Michael L; Nuckolls, Colin

    2015-08-12

    We present here a new design motif for strained, conjugated macrocycles that incorporates two different aromatics into the cycle with an -A-B-A-B- pattern. In this study, we demonstrate the concept by alternating electron donors and acceptors in a conjugated cycle. The donor is a bithiophene, and the acceptor is a perylene diimide derivative. The macrocycle formed has a persistent elliptiform cavity that is lined with the sulfur atoms of the thiophenes and the π-faces of the perylene diimide. Due to the linkage of the perylene diimide subunits, the macrocycles exist in both chiral and achiral forms. We separate the three stereoisomers using chiral high-performance liquid chromatography and study their interconversion. The mechanism for interconversion involves an "intramolecular somersault" in which one of the PDIs rotates around its transverse axis, thereby moving one of its diimide heads through the plane of the cavity. These unusual macrocycles are black in color with an absorption spectrum that spans the visible range. Density functional theory calculations reveal a photoinduced electron transfer from the bithiophene to the perylene diimide.

  10. The hierarchy of chirality.

    PubMed

    Schulgasser, Kalman; Witztum, Allan

    2004-09-21

    Twisting is a prevalent feature of long, thin vertical leaves; it has been shown that this twist contributes to the mechanical integrity of the leaf. We address the question as to how this twist comes about, and posit that it is a reflection of twist at a lower structural (geometric) level. The stiffness required for maintaining verticality in leaves is due to turgescent parenchyma cells, sometimes thickened epidermis, cuticle, and is generally most significantly contributed to by vascular bundles and fibers. These contain cellulose in the cell walls. Such cellulose chains spiral upward within the cell wall layers which are of a characteristic handedness. This results in an isolated cell behaving mechanically in a chiral manner; specifically elongation (contraction) of a single cell will result in rotation of the cell about its axis of particular handedness. We propose a mathematical model that shows that when cells are mechanically associated in groups, the chiral behavior of the cell will be expressed at larger scales, albeit to a mitigated degree. Thus cell extension during leaf development may explain the characteristic twist of such leaves.

  11. Chiral quantum optics.

    PubMed

    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.

  12. Candidates for Twin Chiral Bands in Rh102

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    Excited states in Rh102, populated in the fusion-evaporation reaction Zr94(B11,3n)Rh102 at a beam energy of 36 MeV, were studied using the Indian National Gamma Array spectrometer at Inter University Accelerator Center, New Delhi. The angular correlations and the electromagnetic character of some of the gamma-ray transitions observed were investigated in detail. A new chiral candidate sister band was found. Lifetimes of exited states in both chiral candidate bands of Rh102 were measured for the first time in the A ˜100 mass region by means of the Doppler-shift attenuation technique. The derived reduced transition probabilities are compared to the predictions of the two quasiparticles plus triaxial rotor model. Both experimental results and calculations do not support the presence of static chirality in Rh102.

  13. Candidates for twin chiral bands in 102Rh.

    PubMed

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

    2014-02-07

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

  14. VCD study of alpha-methylbenzyl amine derivatives: detection of the unchanged chiral motif.

    PubMed

    Merten, Christian; Amkreutz, Marc; Hartwig, Andreas

    2010-08-01

    Chiral alpha-methylbenzyl amine is a well known and often used chiral auxiliary, e.g., in the resolution of racemates or asymmetric catalysis. In this work, alpha-methylbenzyl amine and its derivatives N,alpha-dimethylbenzyl amine, N,N,alpha-trimethylbenzyl amine, and bis[alpha-methylbenzyl] amine were investigated by vibrational circular dichroism (VCD) spectroscopy and density functional theory (DFT). For all compounds, stable low energy conformers were obtained by the DFT calculations and based on those, the theoretical vibrational absorption (VA) and VCD spectra were calculated and compared with experimental spectra. Hence, the absolute configurations and conformational preferences were determined. A qualitative comparison of all the experimental VCD spectra of the investigated chiral molecules supported by the calculated ones is given which clearly shows similarities between the spectra of the different chiral amines. These can be assigned to vibrations of the unchanged chiral center.

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

    PubMed

    Galstian, Tigran; Allahverdyan, Karen

    2015-06-07

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

  16. Chiral perturbation theory with nucleons

    SciTech Connect

    Meissner, U.G.

    1991-09-01

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

  17. Chiral quantum dot based materials

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  18. A new approach to 3-hydroxyprolinol derivatives by samarium diiodide-mediated reductive coupling of chiral nitrone with carbonyl compounds.

    PubMed

    Wu, Shao-Feng; Zheng, Xiao; Ruan, Yuan-Ping; Huang, Pei-Qiang

    2009-07-21

    A flexible diastereoselective approach to trans-(3S)-hydroxyprolinol derivatives is described, which is based on the samarium diiodide-mediated reductive coupling of the chiral 1-pyrroline N-oxide (nitrone)(S)-10 with carbonyl compounds. The reductive hydroxyalkylation of nitrone 10 with ketones and aromatic aldehydes is highly diastereoselective in establishing the C-2 chiral center of the pyrrolidine ring.

  19. [A comment on chiral thin layer chromatography].

    PubMed

    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.

  20. Palladium(II)-catalyzed enantioselective C(sp³)-H activation using a chiral hydroxamic acid ligand.

    PubMed

    Xiao, Kai-Jiong; Lin, David W; Miura, Motofumi; Zhu, Ru-Yi; Gong, Wei; Wasa, Masayuki; Yu, Jin-Quan

    2014-06-04

    An enantioselective method for Pd(II)-catalyzed cross-coupling of methylene β-C(sp(3))-H bonds in cyclobutanecarboxylic acid derivatives with arylboron reagents is described. High yields and enantioselectivities were achieved through the development of chiral mono-N-protected α-amino-O-methylhydroxamic acid (MPAHA) ligands, which form a chiral complex with the Pd(II) center. This reaction provides an alternative approach to the enantioselective synthesis of cyclobutanecarboxylates containing α-chiral quaternary stereocenters. This new class of chiral catalysts also show promises for enantioselective β-C(sp(3))-H activation of acyclic amides.

  1. Regio- and Enantioselective Synthesis of Chiral Pyrimidine Acyclic Nucleosides via Rhodium-Catalyzed Asymmetric Allylation of Pyrimidines.

    PubMed

    Liang, Lei; Xie, Ming-Sheng; Qin, Tao; Zhu, Man; Qu, Gui-Rong; Guo, Hai-Ming

    2017-10-06

    A direct route to branched N-allylpyrimidine analogues is herein reported via the highly regio- and enantioselective asymmetric allylation of pyrimidines with racemic allylic carbonates. With [Rh(COD)Cl]2/chiral diphosphine as the catalyst, a range of chiral pyrimidine acyclic nucleosides could be obtained under neutral conditions in good yields (up to 95% yield) with high levels of regio- and enantioselectivities (15:1 to >40:1 B/L and up to 99% ee). Furthermore, chiral pyrimidine acyclic nucleoside bearing two adjacent chiral centers has been successfully synthesized by asymmetric dihydroxylation.

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

    NASA Astrophysics Data System (ADS)

    Meng, Jie; Zhao, Pengwei

    2016-05-01

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

  3. Epitaxial Electrodeposition of Chiral Metal Oxide Films

    NASA Astrophysics Data System (ADS)

    Switzer, Jay

    2006-03-01

    Chirality is ubiquitous in Nature. One enantiomer of a molecule is often physiologically active, while the other enantiomer may be either inactive or toxic. Chiral surfaces offer the possibility of developing heterogeneous enantiospecific catalysts that can more readily be separated from the products and reused. Chiral surfaces might also serve as electrochemical sensors for chiral molecules- perhaps even implantable chiral sensors that could be used to monitor drug levels in the body. Our trick to produce chiral surfaces is to electrodeposit low symmetry metal oxide films with chiral orientations on achiral substrates (see, Nature 425, 490, 2003). The relationship between three-dimensional and two-dimensional chirality will be discussed. Chiral surfaces lack mirror or glide plane symmetry. It is possible to produce chiral surfaces of materials which do not crystallize in chiral space groups. We have deposited chiral orientations of achiral CuO onto single-crystal Au and Cu using both tartaric acid and the amino acids alanine and valine to control the handedness of the electrodeposited films. We will present results on the chiral recognition of molecules such as tartaric or malic acid and L-dopa on the chiral electrodeposited CuO. Initial work on the electrochemical biomineralization of chiral nanostructures of calcite will also be discussed.

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

    PubMed

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

    2016-05-01

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

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

    PubMed Central

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

    2015-01-01

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

  6. Ultrafast Chiral Chromatography as the Second Dimension in Two-Dimensional Liquid Chromatography Experiments.

    PubMed

    Barhate, Chandan L; Regalado, Erik L; Contrella, Nathan D; Lee, Joon; Jo, Junyong; Makarov, Alexey A; Armstrong, Daniel W; Welch, Christopher J

    2017-03-21

    Chromatographic separation and analysis of complex mixtures of closely related species is one of the most challenging tasks in modern pharmaceutical analysis. In recent years, two-dimensional liquid chromatography (2D-LC) has become a valuable tool for improving peak capacity and selectivity. However, the relatively slow speed of chiral separations has limited the use of chiral stationary phases (CSPs) as the second dimension in 2D-LC, especially in the comprehensive mode. Realizing that the recent revolution in the field of ultrafast enantioselective chromatography could now provide significantly faster separations, we herein report an investigation into the use of ultrafast chiral chromatography as a second dimension for 2D chromatographic separations. In this study, excellent selectivity, peak shape, and repeatability were achieved by combining achiral and chiral narrow-bore columns (2.1 mm × 100 mm and 2.1 mm × 150 mm, sub-2 and 3 μm) in the first dimension with 4.6 mm × 30 mm and 4.6 mm × 50 mm columns packed with highly efficient chiral selectors (sub-2 μm fully porous and 2.7 μm fused-core particles) in the second dimension, together with the use of 0.1% phosphoric acid/acetonitrile eluents in both dimensions. Multiple achiral × chiral and chiral × chiral 2D-LC examples (single and multiple heart-cutting, high-resolution sampling, and comprehensive) using ultrafast chiral chromatography in the second dimension are successfully applied to the separation and analysis of complex mixtures of closely related pharmaceuticals and synthetic intermediates, including chiral and achiral drugs and metabolites, constitutional isomers, stereoisomers, and organohalogenated species.

  7. Chiral higher spin gravity

    NASA Astrophysics Data System (ADS)

    Krishnan, Chethan; Raju, Avinash

    2017-06-01

    We construct a candidate for the most general chiral higher spin theory with AdS3 boundary conditions. In the Chern-Simons language, on the left it has the Drinfeld-Sokolov reduced form, but on the right all charges and chemical potentials are turned on. Altogether (for the spin-3 case) these are 19 functions. Despite this, we show that the resulting metric has the form of the "most general" AdS3 boundary conditions discussed by Grumiller and Riegler. The asymptotic symmetry algebra is a product of a W3 algebra on the left and an affine s l (3 )k current algebra on the right, as desired. The metric and higher spin fields depend on all the 19 functions. We compare our work with previous results in the literature.

  8. Amino Acids and Chirality

    NASA Technical Reports Server (NTRS)

    Cook, Jamie E.

    2012-01-01

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

  9. Chiral electroweak gauge interactions

    NASA Astrophysics Data System (ADS)

    Rajpoot, Subhash

    1990-10-01

    The hypercharge U(1)Y of the standard electroweak model is split into chiral hypercharges U(1)L×U(1)R. Under the new gauge symmetry SU(2)L×U(1)L×U(1)R, quarks and leptons are left-handed doublets transforming only under SU(2)L×U(1)L and right-handed singlets transforming only under U(1)R. Consistent with the measurements of the mass of the standard massive neutral boson Z0 at the SLAC and CERN colliders and the neutral-current couplings involving neutrino beams and electron beams, the additional massive neutral gauge boson can be as light as a few hundred GeV. The model utilizes the generalized see saw mechanism of Gell-Mann, Ramond, and Slansky to give masses to all the fermions of the theory.

  10. Deformed chiral nucleons

    NASA Astrophysics Data System (ADS)

    Price, C. E.; Shepard, J. R.

    1991-04-01

    We compute properties of the nucleon in a hybrid chiral model based on the linear σ-model with quark degrees of freedom treated explicity. In contrast to previous calculations, we do not use the hedgehog ansatz. Instead we solve self-consistently for a state with well defined spin and isospin projections. We allow this state to be deformed and find that, although d- and g-state admixtures in the predominantly s-state single quark wave functions are not large, they have profound effects on many nucleon properties including magnetic moments and gA. Our best fit parameters provide excellent agreement with experiment but are much different from those determined in hedgehog calculations.

  11. Chiral Bosonization of Superconformal Ghosts

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

  12. Chiral discrimination in optical binding

    NASA Astrophysics Data System (ADS)

    Forbes, Kayn A.; Andrews, David L.

    2015-05-01

    The laser-induced intermolecular force that exists between two or more particles in the presence of an electromagnetic field is commonly termed "optical binding." Distinct from the single-particle forces that are at play in optical trapping at the molecular level, the phenomenon of optical binding is a manifestation of the coupling between optically induced dipole moments in neutral particles. In other, more widely known areas of optics, there are many examples of chiral discrimination—signifying the different response a chiral material has to the handedness of an optical input. In the present analysis, extending previous work on chiral discrimination in optical binding, a mechanism is identified using a quantum electrodynamical approach. It is shown that the optical binding force between a pair of chiral molecules can be significantly discriminatory in nature, depending upon both the handedness of the interacting particles and the polarization of the incident light, and it is typically several orders of magnitude larger than previously reported.

  13. Spontaneous compactification and chiral fermions

    NASA Astrophysics Data System (ADS)

    Frampton, Paul H.; Yamamoto, Katsuji

    The question is addressed of which chiral fermions survive in spontaneously compactified solutions of the generalized Einstein-Yang-Mills field equations for higher even space-time dimensions. First, we study the allowed fermion representations of SU( N) which have no gauge or gravitational chiral anomalies in arbitrary even dimension and show how to find all such representations for the case of totally antisymmetric SU( N) tensors. Second, we look explicitly at monopole-induced spontaneous compactification in six dimensions; here, interesting chiral fermions in four dimensions do not occur easily but instead require highly artificial assignments of quantum numbers under the U(1) gauge group associated with the monopole. Finally, we consider instanton-induced spontaneous compactification in eight dimensions; for this case, we may readily obtain acceptable chiral fermions in four dimensions, including Georgi's three-family SU(11) model.

  14. Chirally motivated K - nuclear potentials

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2014-08-20

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

  16. Meta-Chirality: Fundamentals, Construction and Applications

    PubMed Central

    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

  17. Meta-Chirality: Fundamentals, Construction and Applications.

    PubMed

    Ma, Xiaoliang; Pu, Mingbo; Li, Xiong; Guo, Yinghui; Gao, Ping; Luo, Xiangang

    2017-05-17

    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.

  18. Chiral selectivity of amino acid adsorption on chiral surfaces--the case of alanine on Pt.

    PubMed

    Franke, J-H; Kosov, D S

    2015-02-07

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

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

    PubMed

    Dolan, James G

    2010-01-01

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

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

    PubMed Central

    Dolan, James G.

    2010-01-01

    Current models of healthcare quality recommend that patient management decisions be evidence-based and patient-centered. Evidence-based decisions require a thorough understanding of current information regarding the natural history of disease and the anticipated outcomes of different management options. Patient-centered decisions incorporate patient preferences, values, and unique personal circumstances into the decision making process and actively involve both patients along with health care providers as much as possible. Fundamentally, therefore, evidence-based, patient-centered decisions are multi-dimensional and typically involve multiple decision makers. Advances in the decision sciences have led to the development of a number of multiple criteria decision making methods. These multi-criteria methods are designed to help people make better choices when faced with complex decisions involving several dimensions. They are especially helpful when there is a need to combine “hard data” with subjective preferences, to make trade-offs between desired outcomes, and to involve multiple decision makers. Evidence-based, patient-centered clinical decision making has all of these characteristics. This close match suggests that clinical decision support systems based on multi-criteria decision making techniques have the potential to enable patients and providers to carry out the tasks required to implement evidence-based, patient-centered care effectively and efficiently in clinical settings. The goal of this paper is to give readers a general introduction to the range of multi-criteria methods available and show how they could be used to support clinical decision-making. Methods discussed include the balance sheet, the even swap method, ordinal ranking methods, direct weighting methods, multi-attribute decision analysis, and the analytic hierarchy process (AHP) PMID:21394218

  1. Application of chiral critical clusters to assymetric synthesis

    DOEpatents

    Ferrieri, Richard A.

    2002-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    DOE PAGES

    Zhang, Yu; Rouxel, Jeremy; Autschbach, Jochen; ...

    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.

  4. Understanding Rate Acceleration and Stereoinduction of an Asymmetric Giese Reaction Mediated by a Chiral Rhodium Catalyst.

    PubMed

    Tutkowski, Brandon; Meggers, Eric; Wiest, Olaf

    2017-06-21

    The surprising acceleration of the addition of electron-rich radicals to α,β-unsaturated 2-acyl imidazoles by a chiral-at-metal rhodium catalyst is investigated. M06/Lanl2DZ (Rh),6-31G(d) calculations reproduce the observed rate acceleration and shed light on a catalyst design where a rigid chiral pocket with a steric interaction >5 Å from the chiral metal center leads to the observed high stereoinduction. Analysis of the molecular orbitals of two key addition transition states emphasize the role of the catalyst as a Lewis acid without significant charge transfer.

  5. Macdonald index and chiral algebra

    NASA Astrophysics Data System (ADS)

    Song, Jaewon

    2017-08-01

    For any 4d N = 2 SCFT, there is a subsector described by a 2d chiral algebra. The vacuum character of the chiral algebra reproduces the Schur index of the corresponding 4d theory. The Macdonald index counts the same set of operators as the Schur index, but the former has one more fugacity than the latter. We conjecture a prescription to obtain the Macdonald index from the chiral algebra. The vacuum module admits a filtration, from which we construct an associated graded vector space. From this grading, we conjecture a notion of refined character for the vacuum module of a chiral algebra, which reproduces the Macdonald index. We test this prescription for the Argyres-Douglas theories of type ( A 1 , A 2 n ) and ( A 1 , D 2 n+1) where the chiral algebras are given by Virasoro and \\widehat{su}(2) affine Kac-Moody algebra. When the chiral algebra has more than one family of generators, our prescription requires a knowledge of the generators from the 4d.

  6. Optical properties of chiral nanostructures

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

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

  7. Gain properties of an uncoated and chiral coated slotted sphere embedded in a chiral background.

    PubMed

    Awan, Z A

    2016-10-10

    The gain properties of an uncoated and a chiral coated slotted sphere embedded in a chiral background have been investigated using numerical simulations. In this paper, it is found that a chiral background medium enhances the gain of an uncoated slotted sphere in the forward direction as compared to the free space background. It is shown that the forward direction gain of a chiral coated slotted sphere embedded in a chiral background increases with the increase in the background chirality. It is further determined that the maximum gain moves away from the polar direction toward the forward direction as the chirality of the coating increases for a fixed background chirality. Also, this maximum gain gradually decreases as the chirality of the coating increases. An interesting feature of an angular window is introduced for a chiral coated slotted sphere embedded in a chiral background where the gain is nearly constant for a specific range of angles.

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

    PubMed

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

    2016-07-12

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

  9. Improvement of chiral stationary phases based on cinchona alkaloids bonded to crown ethers by chiral modification.

    PubMed

    Zhao, Jianchao; Wu, Haixia; Wang, Dongqiang; Wu, Haibo; Cheng, Lingping; Jin, Yu; Ke, Yanxiong; Liang, Xinmiao

    2015-09-17

    To improve the chiral recognition capability of a cinchona alkaloid crown ether chiral stationary phase, the crown ether moiety was modified by the chiral group of (1S, 2S)-2-aminocyclohexyl phenylcarbamate. Both quinine and quinidine-based stationary phases were evaluated by chiral acids, chiral primary amines and amino acids. The quinine/quinidine and crown ether provided ion-exchange sites and complex interaction site for carboxyl group and primary amine group in amino acids, respectively, which were necessary for the chiral discrimination of amino acid enantiomers. The introduction of the chiral group greatly improved the chiral recognition for chiral primary amines. The structure of crown ether moiety was proved to play a dominant role in the chiral recognitions for chiral primary amines and amino acids.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  11. Coffee and Green Tea Consumption and Subsequent Risk of Malignant Lymphoma and Multiple Myeloma in Japan: The Japan Public Health Center-based Prospective Study.

    PubMed

    Ugai, Tomotaka; Matsuo, Keitaro; Sawada, Norie; Iwasaki, Motoki; Yamaji, Taiki; Shimazu, Taichi; Sasazuki, Shizuka; Inoue, Manami; Kanda, Yoshinobu; Tsugane, Shoichiro

    2017-08-01

    Background: The aim of this study was to investigate the association of coffee and green tea consumption and the risk of malignant lymphoma and multiple myeloma in a large-scale population-based cohort study in Japan.Methods: In this analysis, a total of 95,807 Japanese subjects (45,937 men and 49,870 women; ages 40-69 years at baseline) of the Japan Public Health Center-based Prospective Study who completed a questionnaire about their coffee and green tea consumption were followed up until December 31, 2012, for an average of 18 years. HRs and 95% confidence intervals were estimated using a Cox regression model adjusted for potential confounders as a measure of association between the risk of malignant lymphoma and multiple myeloma associated with coffee and green tea consumption at baseline.Results: During the follow-up period, a total of 411 malignant lymphoma cases and 138 multiple myeloma cases were identified. Overall, our findings showed no significant association between coffee or green tea consumption and the risk of malignant lymphoma or multiple myeloma for both sexes.Conclusions: In this study, we observed no significant association between coffee or green tea consumption and the risk of malignant lymphoma or multiple myeloma.Impact: Our results do not support an association between coffee or green tea consumption and the risk of malignant lymphoma or multiple myeloma. Cancer Epidemiol Biomarkers Prev; 26(8); 1352-6. ©2017 AACR. ©2017 American Association for Cancer Research.

  12. AID-dependent activation of a MYC transgene induces multiple myeloma in a conditional mouse model of post-germinal center malignancies.

    PubMed

    Chesi, Marta; Robbiani, Davide F; Sebag, Michael; Chng, Wee Joo; Affer, Maurizio; Tiedemann, Rodger; Valdez, Riccardo; Palmer, Stephen E; Haas, Stephanie S; Stewart, A Keith; Fonseca, Rafael; Kremer, Richard; Cattoretti, Giorgio; Bergsagel, P Leif

    2008-02-01

    By misdirecting the activity of Activation-Induced Deaminase (AID) to a conditional MYC transgene, we have achieved sporadic, AID-dependent MYC activation in germinal center B cells of Vk*MYC mice. Whereas control C57BL/6 mice develop benign monoclonal gammopathy with age, all Vk*MYC mice progress to an indolent multiple myeloma associated with the biological and clinical features highly characteristic of the human disease. Furthermore, antigen-dependent myeloma could be induced by immunization with a T-dependent antigen. Consistent with these findings in mice, more frequent MYC rearrangements, elevated levels of MYC mRNA, and MYC target genes distinguish human patients with multiple myeloma from individuals with monoclonal gammopathy, implicating a causal role for MYC in the progression of monoclonal gammopathy to multiple myeloma.

  13. Consistent Chiral Kinetic Theory in Weyl Materials: Chiral Magnetic Plasmons.

    PubMed

    Gorbar, E V; Miransky, V A; Shovkovy, I A; Sukhachov, P O

    2017-03-24

    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.

  14. Consistent Chiral Kinetic Theory in Weyl Materials: Chiral Magnetic Plasmons

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2016-02-01

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

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

    ERIC Educational Resources Information Center

    LeMarechal, Jean Francois

    2008-01-01

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

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

    ERIC Educational Resources Information Center

    LeMarechal, Jean Francois

    2008-01-01

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

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

    ERIC Educational Resources Information Center

    Teixeira de Melo, Ana; Alarcao, Madalena

    2012-01-01

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

  19. Physician Provider Profiling in Brooke Army Medical Center’s Internal Medicine Clinic: A Multiple Regression and Process Control Model

    DTIC Science & Technology

    1999-12-01

    in Brooke Army Medical Center’s Internal Medicine Clinic during the 3rd & 4th quarter of FY 1998. Data regarding 26,502 individual patient-provider...accomplished by selecting internists and internal medicine residents and a single primary diagnosis. Second level case mix adjustment accounted for other

  20. Possible formation of chiral polarons in graphene.

    PubMed

    Kandemir, B S

    2013-01-16

    A theoretical investigation of the possible existence of chiral polaron formation in graphene is reported. We present an analytical method to calculate the ground-state of the electron-phonon system within the framework of the Lee-Low-Pines theory. On the basis of our model, the influence of electron-optical phonon interaction on the graphene electronic spectrum is investigated. We considered only the doubly degenerate optical phonon modes of E(2g) symmetry near the zone center Γ. It is analytically shown that the energy dispersions of both valence and conduction bands of the pristine graphene differ significantly from those obtained through the standard electron self-energy calculations arising from the electron-optical phonon interactions. In this paper, we also show for the first time that the degenerate band structure of the graphene promotes the chiral polaron formation. Furthermore, due to the k-dependent nature of the polaronic self-energy, in analogy with quantum chromodynamics, we also propose a running electron-phonon coupling constant as a function of energy.

  1. Chirality dependence of nanoscale ferromagnetic NOT gates

    NASA Astrophysics Data System (ADS)

    Lewis, E. R.; Petit, D.; O'Brien, L.; Zeng, H. T.; Read, D. E.; Cowburn, R. P.

    2011-03-01

    The behavior of a transverse domain wall (DW) interacting with a ferromagnetic NOT gate is studied with specific emphasis on the role of the DW chirality (sense of rotation of magnetization crossing the DW). We examine both the effect of the incoming DW chirality on the operation of the NOT gate and the effect of the gate on the DW chirality. We find that the chirality of the incoming DW does not affect the range of fields over which the NOT gate operates correctly. The effect of the NOT gate on the DW chirality depends on the chirality of the incoming DW: when the DW is incident on the NOT gate with the wide side of the DW on the inside of the V-shape formed by the gate, the chirality is conserved, but when the DW is incident on the gate with its wide side on the outside of the V-shape, the chirality may reverse.

  2. Chiral Chlordane Components in Environmental Matrices

    EPA Science Inventory

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

  3. Enantioselective Recognition by Chiral Supramolecular Gels.

    PubMed

    Zhang, Li; Jin, Qingxian; Liu, Minghua

    2016-10-06

    Chiral supramolecular gels, in which small organic molecules self-assemble into chiral nanostructures and entangle each other to immobilize solvents through various noncovalent interactions, can work as a matrix for enantioselective recognition on chiral analytes. Through gelation and the formation of well-defined nanostructures, the chiral sense of the component molecules can be accumulated or amplified, and thus, the enantioselective recognition ability can be enhanced. Furthermore, a chiral microenvironment formed in the gel networks could provide additional stereochemical recognition geometry and attribute to efficient recognition. In this focus review, enantioselective recognition on chiral analytes through chiral supramolecular gels, with either amplified signals or the gel-sol phase transition, is discussed. This review is expected to provide useful insights into the design and fabrication of supramolecular gel systems with chiral features and high enantioselectivity.

  4. ENZYME DEGRADATION OF CHIRAL ORGANIC PHOSPHORUS INSECTICIDES

    EPA Science Inventory

    Chiral organic phosphorus pesticides (OPs) are expected to be biologically degraded enantioselectively by endogenous enzymes. Various chiral Ops were treated with the enzyme phosphotriesterase (PTE) obtained from partially purified extracts of Escherichia coli strain DH-5- carryi...

  5. Chiral Chlordane Components in Environmental Matrices

    EPA Science Inventory

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

  6. ENZYME DEGRADATION OF CHIRAL ORGANIC PHOSPHORUS INSECTICIDES

    EPA Science Inventory

    Chiral organic phosphorus pesticides (OPs) are expected to be biologically degraded enantioselectively by endogenous enzymes. Various chiral Ops were treated with the enzyme phosphotriesterase (PTE) obtained from partially purified extracts of Escherichia coli strain DH-5- carryi...

  7. Chiral symmetry breaking by monopole condensation

    NASA Astrophysics Data System (ADS)

    Iwazaki, Aiichi

    2017-08-01

    Under the assumption of Abelian dominance in QCD, we have shown that chiral condensate is locally present around each QCD monopole. The essence is that either charge or chirality of a quark is not conserved, when the low energy massless quark collides with QCD monopole. In reality, the charge is conserved so that the chirality is not conserved. Reviewing the presence of the local chiral condensate, we show by using chiral anomaly that chiral nonsymmetric quark pair production takes place when a color charge is putted in a vacuum with monopole condensation, while chiral symmetric pair production takes place in a vacuum with no monopole condensation. Our results strongly indicate that the chiral symmetry is broken by the monopole condensation.

  8. Phase diagram of chirally imbalanced QCD matter

    SciTech Connect

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

    2011-05-15

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

  9. Chiral multi-electron emission

    NASA Astrophysics Data System (ADS)

    Berakdar, Jamal; Klar, Hubert

    2001-01-01

    In this report we review recent progress in the understanding of the role of chirality in the multi-electron emission. A brief account of the chiral single-electron photoemission is given. In this case the chirality of the experimental set-up is brought about by an initial orientation of the target or/and by specifying a certain projection of the photoelectron spin. The dependence of the photoelectron spectrum on the chirality of the experiment is probed by changing the initial orientation of the target or by inverting the photoelectron spin projection. In a further section we envisage the direct transition of chiral electron pairs from an isotropic bound initial state into a double-continuum state following the absorption of a circularly polarised photon. We work out the necessary conditions under which the spectrum of the correlated photoelectron pair shows a chiral character, i.e. a dependence on the chirality of the exciting photon. The magnitude and the general behaviour of the chiral effects are estimated from simple analytical models and more elaborate numerical methods are presented for a more quantitative predictions. As a further example for the chiral multi-electron emission we study the photoelectron Auger-electron coincidence spectrum. The Auger hole is created by ionising a randomly oriented target by a circular polarised photon. We investigate how the helicity the photon is transferred to the emitted photoelectron pair. The theoretical findings are analysed and interpreted in light of recent experiments. In a final section we focus on the emission of correlated electrons where the initial state is already oriented, e.g. via optical pumping by circularly polarised light. The initial orientation of the atom is transferred to the continuum states following the ionisation of the target by low-energy electrons. We formulate and analyse the theoretical concepts for the transition of the screw sense of the initially bound atomic electron to the continuum

  10. Enantioselective control of lattice and shape chirality in inorganic nanostructures using chiral biomolecules.

    PubMed

    Ben-Moshe, Assaf; Wolf, Sharon Grayer; Bar Sadan, Maya; Houben, Lothar; Fan, Zhiyuan; Govorov, Alexander O; Markovich, Gil

    2014-07-08

    A large number of inorganic materials form crystals with chiral symmetry groups. Enantioselectively synthesizing nanostructures of such materials should lead to interesting optical activity effects. Here we report the synthesis of colloidal tellurium and selenium nanostructures using thiolated chiral biomolecules. The synthesis conditions are tuned to obtain tellurium nanostructures with chiral shapes and large optical activity. These nanostructures exhibit visible optical and chiroptical responses that shift with size and are successfully simulated by an electromagnetic model. The model shows that they behave as chiral optical resonators. The chiral tellurium nanostructures are transformed into chiral gold and silver telluride nanostructures with very large chiroptical activity, demonstrating a simple colloidal chemistry path to chiral plasmonic and semiconductor metamaterials. These materials are natural candidates for studies related to interactions of chiral (bio)molecules with chiral inorganic surfaces, with relevance to asymmetric catalysis, chiral crystallization and the evolution of homochirality in biomolecules.

  11. Chiral Thirring–Wess model

    SciTech Connect

    Rahaman, Anisur

    2015-10-15

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

  12. Hydrogen-regulated chiral nanoplasmonics

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  13. Controlling Chirality of Entropic Crystals

    NASA Astrophysics Data System (ADS)

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

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

  14. Tactoids of chiral liquid crystals

    NASA Astrophysics Data System (ADS)

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

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

  15. Brønsted acid catalyzed phosphoramidic acid additions to alkenes: diastereo- and enantioselective halogenative cyclizations for the synthesis of C- and P-chiral phosphoramidates.

    PubMed

    Toda, Yasunori; Pink, Maren; Johnston, Jeffrey N

    2014-10-22

    The first highly diastereo- and enantioselective additions of a halogen and phosphoramidic acid to unactivated alkenes have been developed, catalyzed by a chiral Brønsted acid. A unique feature of these additions is the opportunity for stereocontrol at two noncontiguous chiral centers, carbon and phosphorus, leading to cyclic P-chiral phosphoramidates. In addition to their inherent value, the phosphoramidates are precursors to enantioenriched epoxy allylamines.

  16. Chiral vibrations in the A=135 region

    SciTech Connect

    Almehed, Daniel; Doenau, Friedrich; Frauendorf, Stefan

    2011-05-15

    Chiral vibrations in the A=135 region are studied in the framework of a RPA plus self-consistent tilted axis cranking formalism. In this model chiral vibrations appear as a precursor toward the static chiral regime. The properties of the RPA phonons are discussed and compared to experimental data. We discuss the limits of the chiral region and the transition to the nonharmonic regime.

  17. Bifurcated, modular syntheses of chiral annulet triazacyclononanes.

    PubMed

    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.

  18. Extreme chirality in Swiss roll metamaterials.

    PubMed

    Demetriadou, A; Pendry, J B

    2009-09-16

    The chiral Swiss roll metamaterial is a resonant, magnetic medium that exhibits a negative refractive band for one-wave polarization. Its unique structure facilitates huge chiral effects: a plane polarized wave propagating through this system can change its polarization by 90° in less than a wavelength. Such chirality is at least 100 times greater than previous structures have achieved. In this paper, we discuss this extreme chiral behaviour with both numerical and analytical results.

  19. Chirality: a relational geometric-physical property.

    PubMed

    Gerlach, Hans

    2013-11-01

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

  20. A Prolonged Outbreak of KPC-3-Producing Enterobacter cloacae and Klebsiella pneumoniae Driven by Multiple Mechanisms of Resistance Transmission at a Large Academic Burn Center.

    PubMed

    Kanamori, Hajime; Parobek, Christian M; Juliano, Jonathan J; van Duin, David; Cairns, Bruce A; Weber, David J; Rutala, William A

    2017-02-01

    Klebsiella pneumoniae carbapenemase (KPC)-producing Enterobacter cloacae has been recently recognized in the United States. Whole-genome sequencing (WGS) has become a useful tool for analysis of outbreaks and for determining transmission networks of multidrug-resistant organisms in health care settings, including carbapenem-resistant Enterobacteriaceae (CRE). We experienced a prolonged outbreak of CRE E. cloacae and K. pneumoniae over a 3-year period at a large academic burn center despite rigorous infection control measures. To understand the molecular mechanisms that sustained this outbreak, we investigated the CRE outbreak isolates by using WGS. Twenty-two clinical isolates of CRE, including E. cloacae (n = 15) and K. pneumoniae (n = 7), were sequenced and analyzed genetically. WGS revealed that this outbreak, which seemed epidemiologically unlinked, was in fact genetically linked over a prolonged period. Multiple mechanisms were found to account for the ongoing outbreak of KPC-3-producing E. cloacae and K. pneumoniae This outbreak was primarily maintained by a clonal expansion of E. cloacae sequence type 114 (ST114) with distribution of multiple resistance determinants. Plasmid and transposon analyses suggested that the majority of blaKPC-3 was transmitted via an identical Tn4401b element on part of a common plasmid. WGS analysis demonstrated complex transmission dynamics within the burn center at levels of the strain and/or plasmid in association with a transposon, highlighting the versatility of KPC-producing Enterobacteriaceae in their ability to utilize multiple modes to resistance gene propagation. Copyright © 2017 American Society for Microbiology.

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

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-06-01

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

  3. Chiral scalars from an extended system

    SciTech Connect

    Kim, W.; Kim, J. ); Park, Y. )

    1991-07-15

    We propose a new action with a modified linear chiral constraint, which contains a chiral boson (a single self-dual theory) or left-right chiral bosons (free scalar field theory) according to the parameter {alpha}, and discuss the constraint algebra between the two theories.

  4. Chiral Block Copolymer Structures for Metamaterial Applications

    DTIC Science & Technology

    2015-01-27

    transformation. 15. SUBJECT TERMS Block Copolymers, Chiral Metamaterials, Gyroids, Nanotechnology, Nanoporous Materials , Networks...Chiral Metamaterials, Gyroids, Nanotechnology, Nanoporous Materials , Networks 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT Same as... nanoporous materials for templating, in particular with network morphologies, as templates could be developed. BCPs comprising chiral entities were

  5. Self-Assembly of Chiral Plasmonic Nanostructures.

    PubMed

    Lan, Xiang; Wang, Qiangbin

    2016-12-01

    Plasmonic chiroptical effects have attracted significant attention for their widespread potential applications in negative-refractive-index materials, advanced light-polarization filters, and ultrasensitive sensing devices, etc. As compared to top-down fabrication methods, the bottom-up self-assembly strategy provides nanoscale resolution, parallel production, and isotropic optical response, and therefore plays an indispensable role in the fabrication of chiral plasmonic nanostructures. The optical properties of these chiral structures can be predicted based on the near-field coupling of localized surface plasmons in structural components, which offers a route to tune or enhance optical activity by selecting building blocks and designing structural configurations. To date, three main types of chiral plasmonic nanostructures, i.e., chiral "plasmonic molecules", chiral superstructures, and chiral-molecule-metal hybrid complexes, are usually assembled, in which metal nanoparticles with various sizes, shapes, and compositions, and/or chiral molecules are employed as building blocks. Here, recent achievements in the self-assembly of chiral plasmonic nanostructures are highlighted and perspectives on the future directions of chiral plasmonics integrated with bottom-up self-assembly are presented, showing three typical examples, including chiral plasmonic switches, chiral nanoparticles, and chiral metamaterials.

  6. Metabolism studies of chiral pesticides: A critical review.

    PubMed

    de Albuquerque, Nayara Cristina Perez; Carrão, Daniel Blascke; Habenschus, Maísa Daniela; de Oliveira, Anderson Rodrigo Moraes

    2017-08-11

    The consumption of pesticides worldwide has been growing in recent decades, and consequently the exposure of humans and other animals to them as well. However, even though it is known that chiral pesticides can behave stereoselectively, the knowledge about the risks to human health and the environment is scarce. Among the pesticides registered to date, approximately 30% have at least one center of asymmetry, and just 7% of them are currently marketed as a pure stereoisomer or as an enriched mixture of the active stereoisomer. There are several in vitro, in vivo, and in silico models available to evaluate the enantioselective metabolism of chiral pesticides aiming ecotoxicological and risk assessment. Therefore, this paper intends to provide a critical view of the metabolism of chiral pesticides in non-target species, including humans, and discuss their implications, as well as, conduct a review of the analytical techniques employed for in vitro and in vivo metabolism studies of chiral pesticides. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. A disoriented chiral condensate search at the Fermilab Tevatron

    SciTech Connect

    Convery, Mary Elizabeth

    1997-05-01

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

  8. Chiral separation of agricultural fungicides.

    PubMed

    Pérez-Fernández, Virginia; García, Maria Ángeles; Marina, Maria Luisa

    2011-09-23

    Fungicides are very important and diverse environmental and agricultural concern species. Their determination in commercial formulations or environmental matrices, requires highly efficient, selective and sensitive methods. A significant number of these chemicals are chiral with the activity residing usually in one of the enantiomers. The different toxicological and degradation behavior observed in many cases for fungicide enantiomers, results in the need to investigate them separately. For this purpose, separation techniques such as GC, HPLC, supercritical fluid chromatography (SFC) and CE have widely been employed although, at present, HPLC still dominates chromatographic chiral analysis of fungicides. This review covers the literature concerning the enantiomeric separation of fungicides usually employed in agriculture grouping the chiral separation methodologies developed for their analysis in environmental, biological, and food samples.

  9. Chiral bag with vector mesons

    NASA Astrophysics Data System (ADS)

    Hosaka, A.; Toki, H.; Weise, W.

    1990-01-01

    We investigate nucleon structure in a (non-linear) chiral bag model with vector mesons. The model incorporates two different degrees of freedom: mesons outside the bag at long and intermediate ranges, and quarks inside the bag at short distances. The ρ, a 1 and ω mesons outside the bag are included in a chiral effective lagrangian based on the non-linear sigma model. The classical solution is obtained using the hedgehog ansatz, and the cranking method is applied to construct the physical nucleon states. Static properties of the nucleon such as its mass, axial vector coupling constant, magnetic moments and charge radii are studied in detail as functions of the bag radius. Quark and meson contributions to these quantities are calculated separately. In particular, we discuss the extent to which the vector-meson dominance picture holds in the chiral bag.

  10. Chirality and gravitational parity violation.

    PubMed

    Bargueño, Pedro

    2015-06-01

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

  11. B-side electron transfer promoted by absorbance of multiple photons in Rhodobacter sphaeroides R-26 reaction centers

    SciTech Connect

    Lin, S.; Jackson, J.A.; Taguchi, A.K.W.; Woodbury, N.W.

    1999-06-03

    Femtosecond transient absorbance spectra of quinone-depleted Rhodobacter sphaeroides R-26 reaction centers in the Q{sub X} transition region have been measured at 15 K under various excitation conditions. This study focuses on the excitation wavelength dependence and excitation intensity dependence of the formation of charge-separated states on the A- and B-side of the reaction center, judging from the bleaching of the 533 nm (B-side) and 544 nm (A-side) ground-state transitions of the reaction center bacteriopheophytins (H{sub A} and H{sub B}). Upon low-intensity selective excitation directly into the bacteriopheophytin Q{sub Y} transitions (near 760 nm), bleaching of both ground-state bacteriopheophytin Q{sub X} transitions appeared immediately, showing that initially either the A- or B-side bacteriopheophytin could be excited. However, both excited states ultimately resulted in P{sup +}H{sub A}{sup {minus}} formation under these conditions. Low-intensity excitation at any of the various wavelengths showed no difference in the kinetics of the A-side charge separation forming P{sup +}H{sub A}{sup {minus}} and no substantial formation of the B-side charge-separated state, P{sup +}H{sub B}{sup {minus}}. In contrast, high-intensity 595 nm excitation resulted in substantial long-lived bleaching of the B-side bacteriopheophytin ground-state transition at 533 nm. This 533 nm bleaching was formed with essentially the same time constant as the bleaching at 544 nm due to A-side charge separation. Both bleaching bands persisted at the longest times measured in quinone-removed reaction centers. The long-lived bleaching at 533 nm using high-intensity excitation most likely represents the formation of P{sup +}H{sub B}{sup {minus}} with a relative yield of nearly 40%. One possible mechanism for B-side electron transfer is that two-photon excitation of the reaction center resulting in the state P{sup *}B{sub B}{sup *} makes P{sup +}B{sub B}{sup {minus}} thermodynamically

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

    PubMed

    Rintell, David; Melito, Richard

    2013-01-01

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

  13. Reexamination of Coccidioides spp. reserved in the Research Center for Pathogenic Fungi and Microbial Toxicoses, Chiba University, based on a multiple gene analysis.

    PubMed

    Sano, Ayako; Miyaji, Makoto; Kamei, Katsuhiko; Mikami, Yuzuru; Nishimura, Kazuko

    2006-01-01

    The Research Center for Pathogenic Fungi and Microbial Toxicoses, Chiba University is the only organization in Japan to possess a series isolates of Coccidioides spp., which are the most virulent pathogenic fungi and which are treated as biosafety level 3 microorganisms. Recently, the genus Coccidioides has been classified into two species, C. immitis and C. posadasii, based on their endemic areas and genotyping; the former species is endemic to the state of California, and the latter is endemic to other parts of North and South America. We reevaluated 19 isolates of Coccidioides immitis stored in our center using a multiple gene analysis. Five isolates were identified as C. immitis and 14 as C. posadasii. Their sequence information in GenBank will help to identify the two genospecies of Coccidioides spp.

  14. The Predictive Role of the Neutrophil/Lymphocyte Ratio in Survival with Multiple Myeloma: A Single Center Experience.

    PubMed

    Onec, Birgul; Okutan, Harika; Albayrak, Murat; Saribacak Can, Esra; Aslan, Vedat; Unver Koluman, Basak; Soyer Kosemehmetoglu, Ozge; Albayrak, Aynur; Kos, Durdu Mehmet

    2017-03-01

    Recent studies have shown a positive correlation between tumor-related immune response markers and the poor outcome in solid tumors. In this study, we aimed to investigate the neutrophil/lymphocyte ratio (NLR) in multiple myeloma. To the best of our knowledge, this would be the second report concerning this topic. We retrospectively reviewed the data for 52 multiple myeloma patients. The patients were grouped using the baseline NLR as NLR ≤ 1.72 and NLR > 1.72 using receiver operating characteristic analysis to determine a cut off. We compared the two groups in terms of both the known prognostic factors of the myeloma and the overall survival (OS). Our study showed that NLR is associated with C-reactive protein and β2 microglobulin (P = 0.02 and P = 0.001, respectively). The patients with NLR > 1.72 had significantly worse stages, performance status, and kidney functions. The whole group's OS was estimated as 35.1 months while the patients with lower NLR had better OS when compared with those with NLR > 1.72 (42.75 and 26.14 months, respectively, P: 0.04). Neutrophil/lymphocyte ratio, which is associated with stage, performance status, and kidney functions, can be used in daily practice as a predictor for survival in multiple myeloma. Simply adding NLR to the routine charts may enrich our data for larger studies. © 2016 Wiley Periodicals, Inc.

  15. Chiral symmetry on the lattice

    SciTech Connect

    Creutz, M.

    1994-11-01

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

  16. Topological responses from chiral anomaly in multi-Weyl semimetals

    NASA Astrophysics Data System (ADS)

    Huang, Ze-Min; Zhou, Jianhui; Shen, Shun-Qing

    2017-08-01

    Multi-Weyl semimetals are a kind of topological phase of matter with discrete Weyl nodes characterized by multiple monopole charges, in which the chiral anomaly, the anomalous nonconservation of an axial current, occurs in the presence of electric and magnetic fields. Electronic transport properties related to the chiral anomaly in the presence of both electromagnetic fields and axial electromagnetic fields in multi-Weyl semimetals are systematically studied. It has been found that the anomalous Hall conductivity has a modification linear in the axial vector potential from inhomogeneous strains. The axial electric field leads to an axial Hall current that is proportional to the distance of Weyl nodes in momentum space. This axial current may generate chirality accumulation of Weyl fermions through delicately engineering the axial electromagnetic fields even in the absence of external electromagnetic fields. Therefore this work provides a nonmagnetic mechanism of generation of chirality accumulation in Weyl semimetals and might shed new light on the application of Weyl semimetals in the emerging field of valleytronics.

  17. Chiral salicyloxazolines as auxiliaries for the asymmetric synthesis of ruthenium polypyridyl complexes.

    PubMed

    Gong, Lei; Mulcahy, Seann P; Devarajan, Deepa; Harms, Klaus; Frenking, Gernot; Meggers, Eric

    2010-09-06

    Chiral auxiliaries are promising emerging tools for the asymmetric synthesis of octahedral metal complexes. We recently introduced chiral salicyloxazolines as coordinating bidentate chiral ligands which provide excellent control over the metal-centered configuration in the course of ligand substitution reactions and can be removed afterward in an acid-induced fashion under complete retention of configuration (J. Am. Chem. Soc. 2009, 131, 9602-9603). Here reported is our detailed investigation of this sequence of reactions, affording virtually enantiopure ruthenium polypyridyl complexes. The control of the metal-centered chirality by the coordinated chiral salicyloxazolinate ligand was evaluated as a function of reaction conditions, the employed bidentate 2,2'-bipyridine and 1,10-phenanthroline ligands, and the substituent at the asymmetric 5-position of the oxazoline heterocycle. Most striking was the strong influence of the reaction solvent, with aprotic solvents of lower polarity providing the most favorable diastereoselectivities. Through a combination of computational and experimental results, it was revealed that the observed stereoselectivities are under thermodynamic control. The removal of the chiral salicyloxazoline auxiliary under retention of the configuration requires acidic conditions and a coordinating solvent such as MeCN or THF in order to prevent partial racemization. This method represents the first general strategy for the asymmetric synthesis of enantiopure heteroleptic ruthenium polypyridyl complexes.

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

    PubMed

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

    1999-09-14

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

  19. Chiral Sulfur Functional Groups as Definers of the Chirality at the Metal in Ir and Rh Half-Sandwich Complexes: A Combined CD/X-ray Study.

    PubMed

    Avello, Marta G; Frutos, María; de la Torre, María C; Viso, Alma; Velado, Marina; de la Pradilla, Roberto Fernández; Sierra, Miguel A; Gornitzka, Heinz; Hemmert, Catherine

    2017-07-27

    Mesoionic carbenes (MICs) derived from triazolium salts that contain chiral sulfoxide or sulfoximine functional groups were used to construct enantiopure chiral-at-metal Ir(III) and Rh(III) half-sandwich complexes through the synthetic sequence of MIC complexation/C-H aromatic activation. The process was efficient and diastereoselective for the formation of enantiopure five-membered metallacycles. The use of the enantiomers of the chiral sulfur groups allowed us to prepare complexes that had opposite configurations at the metal center. Complete retention of the configuration at the metal center was observed during the formation of cationic Ir(III) complexes and upon insertion of alkynes into the Ir(III) -C bond, as demonstrated by a combined circular dichroism/X-ray study. These results point to a vicinal-assisted SN 1-like mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    NASA Astrophysics Data System (ADS)

    Goldup, Stephen M.

    2016-05-01

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

  1. Chiral HPLC for a study of the optical purity of new liquid crystalline materials derived from lactic acid

    NASA Astrophysics Data System (ADS)

    Vojtylová, T.; Kašpar, M.; Hamplová, V.; Novotná, V.; Sýkora, D.

    2014-08-01

    New liquid crystalline (LC) materials were prepared by derivatization of lactic acid. First compound possesses the lactic acid unit as the only chiral center and the second group of LC materials contains two chiral centers. Mesomorphic properties of both the newly synthesized LC materials were studied and the presence of the SmA*-SmC* or exhibit the twist grain boundary (TGB) phases, namely TGBA and TGBC, in a wide range of temperatures down to the room temperature was established. The potential of high-performance liquid chromatography (HPLC) applying chiral stationary phases to separate enantiomers or diastereoisomers of the synthesized LC compounds was evaluated. Two different brands of commercial chiral sorbents, Lux Amylose-2 and Chiralpak AD-3, both based on modified silica with derivatized polysaccharide, were employed in the development of separation procedures. The optimized chiral HPLC method provided a baseline separation of the individual enantiomers for the LC material containing one chiral center. In the case of the more complex compound with two asymmetric carbon atoms, where four isomers exist, partial separation was reached only using the current chiral HPLC.

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

    SciTech Connect

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

    2006-07-10

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

  3. Brilliant Sm, Eu, Tb, and Dy Chiral Lanthanide Complexes with Strong Circularly Polarized Luminescence

    PubMed Central

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

    2009-01-01

    The synthesis, characterization, and luminescent behavior of trivalent Sm, Eu, Dy, and Tb complexes of two enantiomeric, octadentate, chiral, 2-hydroxyisophthalamide ligands are reported. These complexes are highly luminescent in solution. Functionalization of the achiral parent ligand with a chiral 1-phenylethylamine substituent on the open face of the complex in close proximity to the metal center yields complexes with strong circularly polarized luminescence (CPL) activity. This appears to be the first example of a system utilizing the same ligand architecture to sensitize four different lanthanide cations and display CPL activity. The luminescence dissymmetry factor, glum, recorded for the Eu(III) complex is one of the highest values reported, and this is the first time the CPL effect has been demonstrated for a Sm(III) complex with a chiral ligand. The combination of high luminescence intensity with CPL activity should enable new bioanalytical applications of macromolecules in chiral environments. PMID:17199285

  4. Chiral magnetic effect in condensed matter systems

    SciTech Connect

    Li, Qiang; Kharzeev, Dmitri E.

    2016-12-01

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

  5. Chiral xenobiotics bioaccumulations and environmental health prospectives.

    PubMed

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

    2015-08-01

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

  6. Kinetic therapy in multiple trauma patients with severe blunt chest trauma: an analysis at a level-1 trauma center.

    PubMed

    Zeckey, C; Wendt, K; Mommsen, P; Winkelmann, M; Frömke, C; Weidemann, J; Stübig, T; Krettek, C; Hildebrand, F

    2015-01-01

    Chest trauma is a relevant risk factor for mortality after multiple trauma. Kinetic therapy (KT) represents a potential treatment option in order to restore pulmonary function. Decision criteria for performing kinetic therapy are not fully elucidated. The purpose of this study was to investigate the decision making process to initiate kinetic therapy in a well defined multiple trauma cohort. A retrospective analysis (2000-2009) of polytrauma patients (age > 16 years, ISS ⩾ 16) with severe chest trauma (AIS(Chest) ⩾ 3) was performed. Patients with AIS(Head) ⩾ 3 were excluded. Patients receiving either kinetic (KT+) or lung protective ventilation strategy (KT-) were compared. Chest trauma was classified according to the AIS(Chest), Pulmonary Contusion Score (PCS), Wagner Jamieson Score and Thoracic Trauma Severity Score (TTS). There were multiple outcome parameters investigated included mortality, posttraumatic complications and clinical data. A multivariate regression analysis was performed. Two hundred and eighty-three patients were included (KT+: n=160; KT-: n=123). AIS(Chest), age and gender were comparable in both groups. There were significant higher values of the ISS, PCS, Wagner Jamieson Score and TTS in group KT+. The incidence of posttraumatic complications and mortality was increased compared to group KT- (p< 0.05). Despite that, kinetic therapy failed to be an independent risk factor for mortality in multivariate logistic regression analysis. Kinetic therapy is an option in severely injured patients with severe chest trauma. Decision making is not only based on anatomical aspects such as the AIS(Chest), but on overall injury severity, pulmonary contusions and physiological deterioration. It could be assumed that the increased mortality in patients receiving KT is primarily caused by these factors and does not reflect an independent adverse effect of KT. Furthermore, KT was not shown to be an independent risk factor for mortality.

  7. Selective control of reconfigurable chiral plasmonic metamolecules

    PubMed Central

    Kuzyk, Anton; Urban, Maximilian J.; Idili, Andrea; Ricci, Francesco; Liu, Na

    2017-01-01

    Selective configuration control of plasmonic nanostructures using either top-down or bottom-up approaches has remained challenging in the field of active plasmonics. We demonstrate the realization of DNA-assembled reconfigurable plasmonic metamolecules, which can respond to a wide range of pH changes in a programmable manner. This programmability allows for selective reconfiguration of different plasmonic metamolecule species coexisting in solution through simple pH tuning. This approach enables discrimination of chiral plasmonic quasi-enantiomers and arbitrary tuning of chiroptical effects with unprecedented degrees of freedom. Our work outlines a new blueprint for implementation of advanced active plasmonic systems, in which individual structural species can be programmed to perform multiple tasks and functions in response to independent external stimuli. PMID:28439556

  8. Chiral Nanoarchitectonics: Towards the Design, Self-Assembly, and Function of Nanoscale Chiral Twists and Helices.

    PubMed

    Zhang, Li; Wang, Tianyu; Shen, Zhaocun; Liu, Minghua

    2016-02-10

    Helical structures such as double helical DNA and the α-helical proteins found in biological systems are among the most beautiful natural structures. Chiral nanoarchitectonics, which is used here to describe the hierarchical formation and fabrication of chiral nanoarchitectures that can be observed by atomic force microscopy (AFM), scanning tunneling microscopy (STM), scanning electron microscopy (SEM), or transmission electron microscopy (TEM), is one of the most effective ways to mimic those natural chiral nanostructures. This article focuses on the formation, structure, and function of the most common chiral nanoarchitectures: nanoscale chiral twists and helices. The types of molecules that can be designed and how they can form hierarchical chiral nanoarchitectures are explored. In addition, new and unique functions such as amplified chiral sensing, chiral separation, biological effects, and circularly polarized luminescence associated with the chiral nanoarchitectures are discussed.

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

    PubMed

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

    2017-04-13

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  11. Is there a "most chiral tetrahedron"?

    PubMed

    Rassat, André; Fowler, Patrick W

    2004-12-03

    A degree of chirality is a function that purports to measure the amount of chirality of an object: it is equal for enantiomers, vanishes only for achiral or degenerate objects and is similarity invariant, dimensionless and normalisable to the interval [0,1]. For a tetrahedron of non-zero three-dimensional volume, achirality is synonymous with the presence of a mirror plane containing one edge and bisecting its opposite, and hence it is easy to design degree-of-chirality functions based on edge length that incorporate all constraints. It is shown that such functions can have largest maxima at widely different points in the tetrahedral shape space, and by incorporation of appropriate factors, the maxima can be pushed to any point in the space. Thus the phrase "most chiral tetrahedron" has no general meaning: any chiral tetrahedron is the most chiral for some legitimate choice of degree of chirality.

  12. Chiral magnetic plasmons in anomalous relativistic matter

    NASA Astrophysics Data System (ADS)

    Gorbar, E. V.; Miransky, V. A.; Shovkovy, I. A.; Sukhachov, P. O.

    2017-03-01

    The chiral plasmon modes of relativistic matter in background magnetic and strain-induced pseudomagnetic fields are studied in detail using the consistent chiral kinetic theory. The results reveal a number of anomalous features of these chiral magnetic and pseudomagnetic plasmons that could be used to identify them in experiment. In a system with nonzero electric (chiral) chemical potential, the background magnetic (pseudomagnetic) fields not only modify the values of the plasmon frequencies in the long-wavelength limit, but also affect the qualitative dependence on the wave vector. Similar modifications can be also induced by the chiral shift parameter in Weyl materials. Interestingly, even in the absence of the chiral shift and external fields, the chiral chemical potential alone leads to a splitting of plasmon energies at linear order in the wave vector.

  13. Helical motion of chiral liquid crystal droplets

    NASA Astrophysics Data System (ADS)

    Yamamoto, Takaki; Sano, Masaki

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

  14. No chiral truncation of quantum log gravity?

    NASA Astrophysics Data System (ADS)

    Andrade, Tomás; Marolf, Donald

    2010-03-01

    At the classical level, chiral gravity may be constructed as a consistent truncation of a larger theory called log gravity by requiring that left-moving charges vanish. In turn, log gravity is the limit of topologically massive gravity (TMG) at a special value of the coupling (the chiral point). We study the situation at the level of linearized quantum fields, focussing on a unitary quantization. While the TMG Hilbert space is continuous at the chiral point, the left-moving Virasoro generators become ill-defined and cannot be used to define a chiral truncation. In a sense, the left-moving asymptotic symmetries are spontaneously broken at the chiral point. In contrast, in a non-unitary quantization of TMG, both the Hilbert space and charges are continuous at the chiral point and define a unitary theory of chiral gravity at the linearized level.

  15. Chirality effect in disordered graphene ribbon junctions

    NASA Astrophysics Data System (ADS)

    Long, Wen

    2012-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

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

    PubMed

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

    2008-12-28

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

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

    PubMed Central

    Jiang, Wei; Fang, Baishan

    2016-01-01

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

  19. Baryon and chiral symmetry breaking

    SciTech Connect

    Gorsky, A.; Krikun, A.

    2014-07-23

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

  20. Flow methods in chiral analysis.

    PubMed

    Trojanowicz, Marek; Kaniewska, Marzena

    2013-11-01

    The methods used for the separation and analytical determination of individual isomers are based on interactions with substances exhibiting optical activity. The currently used methods for the analysis of optically active compounds are primarily high-performance separation methods, such as gas and liquid chromatography using chiral stationary phases or chiral selectors in the mobile phase, and highly efficient electromigration techniques, such as capillary electrophoresis using chiral selectors. Chemical sensors and biosensors may also be designed for the analysis of optically active compounds. As enantiomers of the same compound are characterised by almost identical physico-chemical properties, their differentiation/separation in one-step unit operation in steady-state or dynamic flow systems requires the use of highly effective chiral selectors. Examples of such determinations are reviewed in this paper, based on 105 references. The greatest successes for isomer determination involve immunochemical interactions, enantioselectivity of the enzymatic biocatalytic processes, and interactions with ion-channel receptors or molecularly imprinted polymers. Conducting such processes under dynamic flow conditions may significantly enhance the differences in the kinetics of such processes, leading to greater differences in the signals recorded for enantiomers. Such determinations in flow conditions are effectively performed using surface-plasmon resonance and piezoelectric detections, as well as using common spectroscopic and electrochemical detections.

  1. Chiral phosphines in nucleophilic organocatalysis

    PubMed Central

    Xiao, Yumei; Sun, Zhanhu

    2014-01-01

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

  2. Synthesis and characterization of conformationally rigid chiral pyridine-N-heterocyclic carbene-based palladacycles with an unexpected Pd-N bond cleavage.

    PubMed

    Ng, Kim Hong; Li, Yongxin; Tan, Wei Xian; Chiang, Minyi; Pullarkat, Sumod A

    2013-03-01

    The versatility of a previously developed method for the synthesis of chiral carbene-based palladacycles is demonstrated through the synthesis of two new chiral pyridine-functionalized N-heterocyclic carbene palladacycles with different wingtip groups. The efficiency in their resolution with different counter anions and different chiral amino acid salt auxiliaries has been studied. The absolute stereochemistries of all the chiral compounds were confirmed by single crystal X-ray crystallography. An unexpected Pd-N bond cleavage that resulted in the racemization of the α-carbon center in these complexes has also been investigated.

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

    PubMed Central

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

    2012-01-01

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

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

    SciTech Connect

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

    2015-02-07

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

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2004-05-26

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

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

    PubMed

    Lloyd, David; Dykes, Jason

    2011-12-01

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

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

    PubMed

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

    2016-01-19

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

  9. Chiral NH-Controlled Supramolecular Metallacycles.

    PubMed

    Dong, Jinqiao; Tan, Chunxia; Zhang, Kang; Liu, Yan; Low, Paul J; Jiang, Jianwen; Cui, Yong

    2017-02-01

    Chiral NH functionalities-based discrimination is a key feature of Nature's chemical armory, yet selective binding of biologically active molecules in synthetic systems with high enantioselectivity poses significant challenges. Here we report the assembly of three chiral fluorescent Zn6L6 metallacycles from pyridyl-functionalized Zn(salalen) or Zn(salen) complexes. Each of these metallacycles has a nanoscale hydrophobic cavity decorated with six, three, or zero chiral NH functionalities and packs into a three-dimensional supramolecular porous framework. The binding affinity and enantioselectivity of the metallacycles toward α-hydroxycarboxylic acids, amino acids, small molecule pharamaceuticals (l-dopa, d-penicillamine), and chiral amines increase with the number of chiral NH moieties in the cyclic structure. From single-crystal X-ray diffraction, molecular simulations, and quantum chemical calculations, the chiral recognition and discrimination are attributed to the specific binding of enantiomers in the chiral pockets of the metallacycles. The parent metallacycles are fluorescent with the intensity of emission being linearly related to the enantiomeric composition of the chiral biorelevant guests, which allow them to be utilized in chiral sensing. The fact that manipulation of chiral NH functionalities in metallacycles can control the enantiorecognition of biomolecular complexes would facilitate the design of more effective supramolecular assemblies for enantioselective processes.

  10. Prognostic factors and outcome in relapsed multiple myeloma after nonmyeloablative allo-SCT: a single center experience.

    PubMed

    Minnema, M C; van Dorp, S; van de Donk, N W C J; Schouten, F; Kersten, M J; Coenen, J L L M; Schouten, H; Zweegman, S; Schaafsma, R; Lokhorst, H M

    2011-02-01

    For relapsed multiple myeloma (MM) patients, allo-SCT is a possible treatment option, but recent data obtained using a nonmyeloablative (NMA) conditioning regimen are scarce. We retrospectively collected data from 38 relapsed MM patients who received a NMA allo-SCT from October 2001 to January 2008. In total, 18 patients (48%) were transplanted using a matched unrelated donor. The median follow-up is 2.3 years. In 16 patients (42%) the response improved and eight patients (21%) were rapidly progressive within 6 months after allo-SCT. In total, 15 patients (39%) were in CR after allo-SCT. The median PFS was 1.4 years (range, 0.1-4.9), and having a CR after allo-SCT or having chronic GVHD resulted in longer PFS. Median OS was 3.1 years (range, 0.2-7.2) and again having a CR after allo-SCT or chronic GVHD was associated with a better OS. Six patients (16%) have died from treatment-related diseases. These results indicate that NMA allo-SCT is a treatment option in relapsed MM patients and that results may be improved by strategies that enhance the CR rate after allo-SCT.

  11. Implementing a multiple-isolator unit for centralized preparation of cytotoxic drugs in a cancer center pharmacy.

    PubMed

    Cazin, J L; Gosselin, P

    1999-08-01

    Due to numerous reasons: assuring safety (technicians, patients, nurses, environment), preventing medication errors, cost, maintaining pharmaceutical quality, rules and regulations, it was decided to create a dedicated room within the pharmacy for the preparation of intravenous cytotoxic drugs. After a preliminary study, the following choices were made: isolator unit instead of a vertical laminar air-flow hood, rigid surface instead of flexible film, a multiple-unit structure (one half suit unit for storage and one isolator unit for passthrough, two preparation units, each with four double-gloving portals) instead of a single-unit structure. After the equipment was installed, the physical and microbiological processes were validated and a medical/pharmaceutical catalog of protocols was created. Then the technicians were trained and the standard operating procedures were written. Updated every six months, they describe the general organization, gaseous sterilization of the isolators, the drugs and the medical devices, prescription analysis and circuit, preparation of nominative forms and labels, double checking the preparations delivery, cleaning and maintenance, documentation and reports, waste disposal, safety and protection and instructions for emergency. The pharmacists, pharmacy staff, physicians and nurses were all included in a work group responsible for the isolator unit project. The unit was opened in January 1997.

  12. Fibrous networks with incorporated macrocycles: a chiral stimuli-responsive supramolecular supergelator and its application to biocatalysis in organic media.

    PubMed

    Qi, Zhenhui; Wu, Changzhu; Malo de Molina, Paula; Sun, Han; Schulz, Andrea; Griesinger, Christian; Gradzielski, Michael; Haag, Rainer; Ansorge-Schumacher, Marion B; Schalley, Christoph A

    2013-07-29

    A new and versatile, crown ether appended, chiral supergelator has been designed and synthesized based on the bis-urea motif. The introduction of a stereogenic center improved its gelation ability significantly relative to its achiral analogue. This low-molecular-weight gelator forms supramolecular gels in a variety of organic solvents. It is sensitive to multiple chemical stimuli and the sol-gel phase transitions can be reversibly triggered by host-guest interactions. The gel can be used to trap enzymes and release them on demand by chemical stimuli. It stabilizes the microparticles in Pickering emulsions so that enzyme-catalyzed organic reactions can take place in the polar phase inside the microparticles, the organic reactants diffusing through the biphasic interface from the surrounding organic phase. Because of the higher interface area between the organic and polar phases, enzyme activity is enhanced in comparison with simple biphasic systems.

  13. Multiple Myeloma Symptoms

    MedlinePlus

    ... Treatment Center Finder Home » About Multiple Myeloma » Symptoms Multiple Myeloma Symptoms Multiple myeloma symptoms may vary by patient, ... to be managed or prevented. The most common multiple myeloma symptoms may include: Bone pain or bone fractures ...

  14. Octahedral Chiral-at-Metal Iridium Catalysts: Versatile Chiral Lewis Acids for Asymmetric Conjugate Additions.

    PubMed

    Shen, Xiaodong; Huo, Haohua; Wang, Chuanyong; Zhang, Bo; Harms, Klaus; Meggers, Eric

    2015-06-26

    Octahedral iridium(III) complexes containing two bidentate cyclometalating 5-tert-butyl-2-phenylbenzoxazole (IrO) or 5-tert-butyl-2-phenylbenzothiazole (IrS) ligands in addition to two labile acetonitrile ligands are demonstrated to constitute a highly versatile class of asymmetric Lewis acid catalysts. These complexes feature the metal center as the exclusive source of chirality and serve as effective asymmetric catalysts (0.5-5.0 mol % catalyst loading) for a variety of reactions with α,β-unsaturated carbonyl compounds, namely Friedel-Crafts alkylations (94-99% ee), Michael additions with CH-acidic compounds (81-97% ee), and a variety of cycloadditions (92-99% ee with high d.r.). Mechanistic investigations and crystal structures of an iridium-coordinated substrates and iridium-coordinated products are consistent with a mechanistic picture in which the α,β-unsaturated carbonyl compounds are activated by two-point binding (bidentate coordination) to the chiral Lewis acid.

  15. Chiral logarithms in quenched QCD

    SciTech Connect

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

    2004-08-01

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

  16. Chiral supramolecular organization from a sheet-like achiral gel: a study of chiral photoinduction.

    PubMed

    Royes, Jorge; Polo, Víctor; Uriel, Santiago; Oriol, Luis; Piñol, Milagros; Tejedor, Rosa M

    2017-05-31

    Chiral photoinduction in a photoresponsive gel based on an achiral 2D architecture with high geometric anisotropy and low roughness has been investigated. Circularly polarized light (CPL) was used as a chiral source and an azobenzene chromophore was employed as a chiral trigger. The chiral photoinduction was studied by evaluating the preferential excitation of enantiomeric conformers of the azobenzene units. Crystallographic data and density functional theory (DFT) calculations show how chirality is transferred to the achiral azomaterials as a result of the combination of chiral photochemistry and supramolecular interactions. This procedure could be applied to predict and estimate chirality transfer from a chiral physical source to a supramolecular organization using different light-responsive units.

  17. Increasing frequency and fatality of poison control center reported exposures involving medication and multiple substances: data from reports of the American Association of Poison Control Centers 1984-2013.

    PubMed

    Greenwald, Peter W; Farmer, Brenna M; O'Neill, Matthew; Essner, Rachel A; Flomenbaum, Neal E

    2016-08-01

    Medication use has become increasingly prevalent in the United States, with up trending use of both prescription and over the counter medication. The increasing use and availability of medication may be changing the nature of poisoning fatality. To evaluate changes in fatal poisoning over time, with respect to fatalities involving one or more medications, using annual reports published by the American Association of Poison Control Centers (AAPCC). AAPCC annual reports were reviewed from 1984 to 2013. Data from tables in each annual report titled Number of Substances Involved in Human Exposure Cases and Summary of Fatal Exposures were abstracted. Fatality rates and changes in these rates over time were calculated for exposures to 1, 2, or ≥ 3 substances. All substances detailed in Summary of Fatal Exposures tables were then coded as medication or non-medication. The percentage of fatalities involving 1, 2, or ≥ 3 medications was calculated and trended over time. Subset analysis was performed to compare the periods 1984-2005 and 2006-2013 in order to limit confounding from changes in reporting. Secondary analysis linking the number of substances cases were exposed to and the fatality rate was performed for data from 2006-2013. There were 59,866,357 human exposures and 29,659 fatalities reported from 1984 to 2013. There were 49.5 fatalities per 100,000 exposures. The majority of fatalities (52.2%) involved more than one substance, although multiple substances were involved in only 8.3% of exposures. Fatality rates increased over time and were higher for cases involving multiple substances. Medications were involved in 79.2% of fatalities, a percentage that increased from 70% in the 1980s to nearly 90% after 2010. In recent years, the majority of fatalities have involved multiple medications. For data from 2006-2013 there was a strong association between fatality rate and number of substances involved in an exposure (221 additional fatalities per 100

  18. New Developments in Chiral Cooperative Ion Pairing Organocatalysis by Means of Ammonium Oxyanions and Fluorides: From Protonation to Deprotonation Reactions.

    PubMed

    Legros, Fabien; Oudeyer, Sylvain; Levacher, Vincent

    2016-10-13

    This personal account summarizes our contribution to the ion pairing organocatalysis mainly by use of chiral quaternary or tertiary ammonium fluorides, aryloxides and carboxylates. Starting from an experimental observation, we were able to develop several approaches for the enantioselective protonation of silyl enolates and enol esters giving rise to chiral carbonyl compounds bearing a stereogenic center at the α-position. Moving from protonation to deprotonation reactions, chiral ammonium ion pair catalysts were successfully applied to several asymmetric transformations such as an Henry reaction or a direct vinylogous aldol reaction to cite a few. An outlook of further possible developments in this field of research will also be discussed.

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

    PubMed Central

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

    2014-01-01

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

  20. Chiral crystal in cold QCD matter at intermediate densities?

    SciTech Connect

    Rapp, Ralf; Shuryak, Edward; Zahed, Ismail

    2001-02-01

    The analogue of Overhauser (particle-hole) pairing in electronic systems (spin-density waves with non-zero total momentum Q) is analyzed in finite-density QCD for 3 colors and 2 flavors, and compared to the color-superconducting BCS ground state (particle-particle pairing, Q=0). The calculations are based on effective nonperturbative four-fermion interactions acting in both the scalar diquark as well as the scalar-isoscalar quark-hole (''{sigma}'') channel. Within the Nambu-Gorkov formalism we set up the coupled channel problem, including multiple chiral density wave formation, and evaluate the resulting gaps and free energies. Employing medium-modified instanton-induced 't Hooft interactions, as applicable around {mu}{sub q}{approx_equal}0.4GeV (or 4 times nuclear saturation density), we find the ''chiral crystal phase'' to be competitive with the color superconductor.

  1. Quantum Networks with Chiral-Light-Matter Interaction in Waveguides.

    PubMed

    Mahmoodian, Sahand; Lodahl, Peter; Sørensen, Anders S

    2016-12-09

    We propose a scalable architecture for a quantum network based on a simple on-chip photonic circuit that performs loss-tolerant two-qubit measurements. The circuit consists of two quantum emitters positioned in the arms of an on-chip Mach-Zehnder interferometer composed of waveguides with chiral-light-matter interfaces. The efficient chiral-light-matter interaction allows the emitters to perform high-fidelity intranode two-qubit parity measurements within a single chip and to emit photons to generate internode entanglement, without any need for reconfiguration. We show that, by connecting multiple circuits of this kind into a quantum network, it is possible to perform universal quantum computation with heralded two-qubit gate fidelities F∼0.998 achievable in state-of-the-art quantum dot systems.

  2. Quantum Networks with Chiral-Light-Matter Interaction in Waveguides

    NASA Astrophysics Data System (ADS)

    Mahmoodian, Sahand; Lodahl, Peter; Sørensen, Anders S.

    2016-12-01

    We propose a scalable architecture for a quantum network based on a simple on-chip photonic circuit that performs loss-tolerant two-qubit measurements. The circuit consists of two quantum emitters positioned in the arms of an on-chip Mach-Zehnder interferometer composed of waveguides with chiral-light-matter interfaces. The efficient chiral-light-matter interaction allows the emitters to perform high-fidelity intranode two-qubit parity measurements within a single chip and to emit photons to generate internode entanglement, without any need for reconfiguration. We show that, by connecting multiple circuits of this kind into a quantum network, it is possible to perform universal quantum computation with heralded two-qubit gate fidelities F ˜0.998 achievable in state-of-the-art quantum dot systems.

  3. Chiral nanoparticles in singular light fields

    PubMed Central

    Vovk, Ilia A.; Baimuratov, Anvar S.; Zhu, Weiren; Shalkovskiy, Alexey G.; Baranov, Alexander V.; Fedorov, Anatoly V.; Rukhlenko, Ivan D.

    2017-01-01

    The studying of how twisted light interacts with chiral matter on the nanoscale is paramount for tackling the challenging task of optomechanical separation of nanoparticle enantiomers, whose solution can revolutionize the entire pharmaceutical industry. Here we calculate optical forces and torques exerted on chiral nanoparticles by Laguerre–Gaussian beams carrying a topological charge. We show that regardless of the beam polarization, the nanoparticles are exposed to both chiral and achiral forces with nonzero reactive and dissipative components. Longitudinally polarized beams are found to produce chirality densities that can be 109 times higher than those of transversely polarized beams and that are comparable to the chirality densities of beams polarized circularly. Our results and analytical expressions prove useful in designing new strategies for mechanical separation of chiral nanoobjects with the help of highly focussed beams. PMID:28378842

  4. Completely Chiral Optical Force for Enantioseparation

    NASA Astrophysics Data System (ADS)

    Rukhlenko, Ivan D.; Tepliakov, Nikita V.; Baimuratov, Anvar S.; Andronaki, Semen A.; Gun’Ko, Yurii K.; Baranov, Alexander V.; Fedorov, Anatoly V.

    2016-11-01

    Fast and reliable separation of enantiomers of chiral nanoparticles requires elimination of all the forces that are independent of the nanoparticle handedness and creation of a sufficiently strong force that either pushes different enantiomers in opposite directions or delays the diffusion of one of them with respect to the other. Here we show how to construct such a completely chiral optical force using two counterpropagating circularly polarized plane waves of opposite helicities. We then explore capabilities of the related enantioseparation method by analytically solving the problem of the force-induced diffusion of chiral nanoparticles in a confined region, and reveal that it results in exponential spatial dependencies of the quantities measuring the purity of chiral substances. The proposed concept of a completely chiral optical force can potentially advance enantioseparation and enantiopurification techniques for all kinds of chiral nanoparticles that strongly interact with light.

  5. Stable pentaquarks from strange chiral multiplets

    SciTech Connect

    Beane, Silas R.

    2004-12-01

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

  6. Stable Pentaquarks from Strange Chiral Multiplets

    SciTech Connect

    Silas Beane

    2004-12-01

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

  7. Asymmetric synthesis using chiral-encoded metal

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    PubMed

    Gal, Joseph

    2013-01-01

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

  9. Asymmetric synthesis using chiral-encoded metal

    PubMed Central

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

    2016-01-01

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

  10. Chiral nanoparticles in singular light fields

    NASA Astrophysics Data System (ADS)

    Vovk, Ilia A.; Baimuratov, Anvar S.; Zhu, Weiren; Shalkovskiy, Alexey G.; Baranov, Alexander V.; Fedorov, Anatoly V.; Rukhlenko, Ivan D.

    2017-04-01

    The studying of how twisted light interacts with chiral matter on the nanoscale is paramount for tackling the challenging task of optomechanical separation of nanoparticle enantiomers, whose solution can revolutionize the entire pharmaceutical industry. Here we calculate optical forces and torques exerted on chiral nanoparticles by Laguerre-Gaussian beams carrying a topological charge. We show that regardless of the beam polarization, the nanoparticles are exposed to both chiral and achiral forces with nonzero reactive and dissipative components. Longitudinally polarized beams are found to produce chirality densities that can be 109 times higher than those of transversely polarized beams and that are comparable to the chirality densities of beams polarized circularly. Our results and analytical expressions prove useful in designing new strategies for mechanical separation of chiral nanoobjects with the help of highly focussed beams.

  11. Completely Chiral Optical Force for Enantioseparation

    PubMed Central

    Rukhlenko, Ivan D.; Tepliakov, Nikita V.; Baimuratov, Anvar S.; Andronaki, Semen A.; Gun’ko, Yurii K.; Baranov, Alexander V.; Fedorov, Anatoly V.

    2016-01-01

    Fast and reliable separation of enantiomers of chiral nanoparticles requires elimination of all the forces that are independent of the nanoparticle handedness and creation of a sufficiently strong force that either pushes different enantiomers in opposite directions or delays the diffusion of one of them with respect to the other. Here we show how to construct such a completely chiral optical force using two counterpropagating circularly polarized plane waves of opposite helicities. We then explore capabilities of the related enantioseparation method by analytically solving the problem of the force-induced diffusion of chiral nanoparticles in a confined region, and reveal that it results in exponential spatial dependencies of the quantities measuring the purity of chiral substances. The proposed concept of a completely chiral optical force can potentially advance enantioseparation and enantiopurification techniques for all kinds of chiral nanoparticles that strongly interact with light. PMID:27827437

  12. Spatial control of chirality in supramolecular aggregates.

    PubMed

    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.

  13. Spatial control of chirality in supramolecular aggregates

    PubMed Central

    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

  14. Spatial control of chirality in supramolecular aggregates

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    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.

  15. Enantioselective recognition at mesoporous chiral metal surfaces

    PubMed Central

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

    2014-01-01

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

  16. Enantioselective recognition at mesoporous chiral metal surfaces

    NASA Astrophysics Data System (ADS)

    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.

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

    EPA Science Inventory

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

  18. On chirality of slime mould.

    PubMed

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

    2016-02-01

    Left-right patterning and lateralised behaviour is an ubiquitous aspect of plants and animals. The mechanisms linking cellular chirality to the large-scale asymmetry of multicellular structures are incompletely understood, and it has been suggested that the chirality of living cells is hardwired in their cytoskeleton. We examined the question of biased asymmetry in a unique organism: the slime mould Physarum polycephalum, which is unicellular yet possesses macroscopic, complex structure and behaviour. In laboratory experiment using a T-shape, we found that Physarum turns right in more than 74% of trials. The results are in agreement with previously published studies on asymmetric movement of muscle cells, neutrophils, liver cells and growing neural filaments, and for the first time reveal the presence of consistently-biased laterality in the fungi kingdom. Exact mechanisms of the slime mould's direction preference remain unknown. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  19. On lattice chiral gauge theories

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  20. Chiral vortical effect for bosons

    NASA Astrophysics Data System (ADS)

    Avkhadiev, Artur; Sadofyev, Andrey V.

    2017-08-01

    The thermal contribution to the chiral vortical effect is believed to be related to the axial anomaly in external gravitational fields. We use the universality of the spin-gravity interaction to extend this idea to a wider set of phenomena. We consider the Kubo formula at weak coupling for the spin current of a vector field and derive a novel anomalous effect caused by the medium rotation: the chiral vortical effect for bosons. The effect consists in a spin current of vector bosons along the angular velocity of the medium. We argue that it has the same anomalous nature as in the fermionic case and show that this effect provides a mechanism for helicity transfer, from flow helicity to magnetic helicity.

  1. Surface defects and chiral algebras

    DOE PAGES

    Córdova, Clay; Gaiotto, Davide; Shao, Shu-Heng

    2017-05-26

    Here, we investigate superconformal surface defects in four-dimensional N = 2 superconformal theories. Each such defect gives rise to a module of the associated chiral algebra and the surface defect Schur index is the character of this module. Various natural chiral algebra operations such as Drinfield-Sokolov reduction and spectral flow can be interpreted as constructions involving four-dimensional surface defects. We compute the index of these defects in the free hypermultiplet theory and Argyres-Douglas theories, using both infrared techniques involving BPS states, as well as renormalization group flows onto Higgs branches. We find perfect agreement with the predicted characters, in eachmore » case.« less

  2. Chirality and the angular momentum of light.

    PubMed

    Cameron, Robert P; Götte, Jörg B; Barnett, Stephen M; Yao, Alison M

    2017-02-28

    Chirality is exhibited by objects that cannot be rotated into their mirror images. It is far from obvious that this has anything to do with the angular momentum of light, which owes its existence to rotational symmetries. There is nevertheless a subtle connection between chirality and the angular momentum of light. We demonstrate this connection and, in particular, its significance in the context of chiral light-matter interactions.This article is part of the themed issue 'Optical orbital angular momentum'.

  3. Chiral phases of fundamental and adjoint quarks

    SciTech Connect

    Natale, A. A.

    2016-01-22

    We consider a QCD chiral symmetry breaking model where the gap equation contains an effective confining propagator and a dressed gluon propagator with a dynamically generated mass. This model is able to explain the ratios between the chiral transition and deconfinement temperatures in the case of fundamental and adjoint quarks. It also predicts the recovery of the chiral symmetry for a large number of quarks (n{sub f} ≈ 11 – 13) in agreement with lattice data.

  4. Chiral Plasmonic Nanostructures on Achiral Nanopillars

    DTIC Science & Technology

    2013-10-10

    0704-0188 3. DATES COVERED (From - To) - UU UU UU UU Approved for public release; distribution is unlimited. Chiral Plasmonic Nanostructures on Achiral...Nanopillars Chirality of plasmonic films can be strongly enhanced by threedimensional (3D) out-of-plane geometries. The complexity of lithographic...methods currently used to produce such structures and other methods utilizing chiral templates impose limitations on spectral windows of chiroptical

  5. Chiral phases of fundamental and adjoint quarks

    NASA Astrophysics Data System (ADS)

    Natale, A. A.

    2016-01-01

    We consider a QCD chiral symmetry breaking model where the gap equation contains an effective confining propagator and a dressed gluon propagator with a dynamically generated mass. This model is able to explain the ratios between the chiral transition and deconfinement temperatures in the case of fundamental and adjoint quarks. It also predicts the recovery of the chiral symmetry for a large number of quarks (nf ≈ 11 - 13) in agreement with lattice data.

  6. Chirality and the angular momentum of light

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    Chirality is exhibited by objects that cannot be rotated into their mirror images. It is far from obvious that this has anything to do with the angular momentum of light, which owes its existence to rotational symmetries. There is nevertheless a subtle connection between chirality and the angular momentum of light. We demonstrate this connection and, in particular, its significance in the context of chiral light-matter interactions. This article is part of the themed issue 'Optical orbital angular momentum'.

  7. Enantioselective Biotransformation of Chiral Persistent Organic Pollutants.

    PubMed

    Zhang, Ying; Ye, Jing; Liu, Min

    2017-01-01

    Enantiomers of chiral compounds commonly undergo enantioselective transformation in most biologically mediated processes. As chiral persistent organic pollutants (POPs) are extensively distributed in the environment, differences between enantiomers in biotransformation should be carefully considered to obtain exact enrichment and specific health risks. This review provides an overview of in vivo biotransformation of chiral POPs currently indicated in the Stockholm Convention and their chiral metabolites. Peer-reviewed journal articles focused on the research question were thoroughly searched. A set of inclusion and exclusion criteria were developed to identify relevant studies. We mainly compared the results from different animal models under controlled laboratory conditions to show the difference between enantiomers in terms of distinct transformation potential. Interactions with enzymes involved in enantioselective biotransformation, especially cytochrome P450 (CYP), were discussed. Further research areas regarding this issue were proposed. Limited evidence for a few POPs has been found in 30 studies. Enantioselective biotransformation of α-hexachlorocyclohexane (α-HCH), chlordane, dichlorodiphenyltrichloroethane (DDT), heptachlor, hexabromocyclododecane (HBCD), polychlorinated biphenyls (PCBs), and toxaphene, has been investigated using laboratory mammal, fish, bird, and worm models. Tissue and excreta distributions, as well as bioaccumulation and elimination kinetics after administration of racemate and pure enantiomers, have been analyzed in these studies. Changes in enantiomeric fractions have been considered as an indicator of enantioselective biotransformation of chiral POPs in most studies. Results of different laboratory animal models revealed that chiral POP biotransformation is seriously affected by chirality. Pronounced results of species-, tissue-, gender-, and individual-dependent differences are observed in in vivo biotransformation of chiral POPs

  8. Chiral anomaly, bosonization, and fractional charge

    SciTech Connect

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

    1985-06-15

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

  9. Spatial Symmetry Breaking Determines Spiral Wave Chirality

    NASA Astrophysics Data System (ADS)

    Quail, Thomas; Shrier, Alvin; Glass, Leon

    2014-10-01

    Chirality represents a fundamental property of spiral waves. Introducing obstacles into cardiac monolayers leads to the initiation of clockwise-rotating, counterclockwise-rotating, and pairs of spiral waves. Simulations show that the precise location of the obstacle and the pacing frequency determine spiral wave chirality. Instabilities predicted by curves relating the action potential duration and the pacing frequency at different spatial locations predict sites of wave break initiation and, hence, spiral wave chirality.

  10. Chiral gold phosphate catalyzed tandem hydroamination/asymmetric transfer hydrogenation enables access to chiral tetrahydroquinolines.

    PubMed

    Du, Yu-Liu; Hu, Yue; Zhu, Yi-Fan; Tu, Xi-Feng; Han, Zhi-Yong; Gong, Liu-Zhu

    2015-05-01

    A highly efficient chiral gold phosphate-catalyzed tandem hydroamination/asymmetric transfer hydrogenation reaction is described. A series of chiral tetrahydroquinolines were obtained in excellent yields and enantioselectivities. In this reaction, the gold catalyst enables both the hydroamination step as a π-Lewis acid and the asymmetric hydrogen-transfer process as an effective chiral Lewis acid.

  11. Chiral Crystalline Sponges for the Absolute Structure Determination of Chiral Guests.

    PubMed

    Yan, KaKing; Dubey, Ritesh; Arai, Tatsuhiko; Inokuma, Yasuhide; Fujita, Makoto

    2017-08-23

    Chiral crystalline sponges with preinstalled chiral references were synthesized. On the basis of the known configurations of the chiral references, the absolute structures of guest compounds absorbed in the pores of the crystalline sponges can be reliably determined without crystallization or chemical modification.

  12. Enantioselective Cyclopropanation with α-Alkyl-α-diazoesters Catalyzed by Chiral Oxazaborolidinium Ion: Total Synthesis of (+)-Hamavellone B.

    PubMed

    Shim, Su Yong; Kim, Jae Yeon; Nam, Miso; Hwang, Geum-Sook; Ryu, Do Hyun

    2016-01-15

    Chiral oxazaborolidinium ion-catalyzed asymmetric cyclopropanation of α- or α,β-substituted acroleins with α-alkyl-α-diazoesters has been developed. With this methodology, chiral functionalized cyclopropanes containing a quaternary stereogenic center were obtained with high to excellent enantioselectivities (up to >99% ee). The synthetic utility of optically enriched functionalized cyclopropane was demonstrated in the first total synthesis of (+)-hamavellone B, which establishes the absolute configuration of natural (+)-hamavellone B.

  13. Staggered chiral random matrix theory

    SciTech Connect

    Osborn, James C.

    2011-02-01

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

  14. Flat-space chiral gravity.

    PubMed

    Bagchi, Arjun; Detournay, Stéphane; Grumiller, Daniel

    2012-10-12

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

  15. Observation of Charge-Dependent Azimuthal Correlations in p-Pb Collisions and Its Implication for the Search for the Chiral Magnetic Effect.

    PubMed

    Khachatryan, V; Sirunyan, A M; Tumasyan, A; Adam, W; Asilar, E; Bergauer, T; Brandstetter, J; Brondolin, E; Dragicevic, M; Erö, J; Flechl, M; Friedl, M; Frühwirth, R; Ghete, V M; Hartl, C; Hörmann, N; Hrubec, J; Jeitler, M; König, A; Krätschmer, I; Liko, D; Matsushita, T; Mikulec, I; Rabady, D; Rad, N; Rahbaran, B; Rohringer, H; Schieck, J; Strauss, J; Waltenberger, W; Wulz, C-E; Dvornikov, O; Makarenko, V; Zykunov, V; Mossolov, V; Shumeiko, N; Suarez Gonzalez, J; Alderweireldt, S; De Wolf, E A; Janssen, X; Lauwers, J; Van De Klundert, M; Van Haevermaet, H; Van Mechelen, P; Van Remortel, N; Van Spilbeeck, A; Abu Zeid, S; Blekman, F; D'Hondt, J; Daci, N; De Bruyn, I; Deroover, K; Lowette, S; Moortgat, S; Moreels, L; Olbrechts, A; Python, Q; Tavernier, S; Van Doninck, W; Van Mulders, P; Van Parijs, I; Brun, H; Clerbaux, B; De Lentdecker, G; Delannoy, H; Fasanella, G; Favart, L; Goldouzian, R; Grebenyuk, A; Karapostoli, G; Lenzi, T; Léonard, A; Luetic, J; Maerschalk, T; Marinov, A; Randle-Conde, A; Seva, T; Vander Velde, C; Vanlaer, P; Vannerom, D; Yonamine, R; Zenoni, F; Zhang, F; Cimmino, A; Cornelis, T; Dobur, D; Fagot, A; Garcia, G; Gul, M; Khvastunov, I; Poyraz, D; Salva, S; Schöfbeck, R; Sharma, A; Tytgat, M; Van Driessche, W; Yazgan, E; Zaganidis, N; Bakhshiansohi, H; Beluffi, C; Bondu, O; Brochet, S; Bruno, G; Caudron, A; De Visscher, S; Delaere, C; Delcourt, M; Francois, B; Giammanco, A; Jafari, A; Jez, P; Komm, M; Krintiras, G; Lemaitre, V; Magitteri, A; Mertens, A; Musich, M; Nuttens, C; Piotrzkowski, K; Quertenmont, L; Selvaggi, M; Vidal Marono, M; Wertz, S; Beliy, N; Aldá Júnior, W L; Alves, F L; Alves, G A; Brito, L; Hensel, C; Moraes, A; Pol, M E; Rebello Teles, P; Belchior Batista Das Chagas, E; Carvalho, W; Chinellato, J; Custódio, A; Da Costa, E M; Da Silveira, G G; De Jesus Damiao, D; De Oliveira Martins, C; Fonseca De Souza, S; Huertas Guativa, L M; Malbouisson, H; Matos Figueiredo, D; Mora Herrera, C; Mundim, L; Nogima, H; Prado Da Silva, W L; Santoro, A; Sznajder, A; Tonelli Manganote, E J; Vilela Pereira, A; Ahuja, S; Bernardes, C A; Dogra, S; Fernandez Perez Tomei, T R; Gregores, E M; Mercadante, P G; Moon, C S; Novaes, S F; Padula, Sandra S; Romero Abad, D; Ruiz Vargas, J C; Aleksandrov, A; Hadjiiska, R; Iaydjiev, P; Rodozov, M; Stoykova, S; Sultanov, G; Vutova, M; Dimitrov, A; Glushkov, I; Litov, L; Pavlov, B; Petkov, P; Fang, W; Ahmad, M; Bian, J G; Chen, G M; Chen, H S; Chen, M; Chen, Y; Cheng, T; Jiang, C H; Leggat, D; Liu, Z; Romeo, F; Shaheen, S M; Spiezia, A; Tao, J; Wang, C; Wang, Z; Zhang, H; Zhao, J; Ban, Y; Chen, G; Li, Q; Liu, S; Mao, Y; Qian, S J; Wang, D; Xu, Z; Avila, C; Cabrera, A; Chaparro Sierra, L F; Florez, C; Gomez, J P; González Hernández, C F; Ruiz Alvarez, J D; Sanabria, J C; Godinovic, N; Lelas, D; Puljak, I; Ribeiro Cipriano, P M; Sculac, T; Antunovic, Z; Kovac, M; Brigljevic, V; Ferencek, D; Kadija, K; Mesic, B; Micanovic, S; Sudic, L; Susa, T; Attikis, A; Mavromanolakis, G; Mousa, J; Nicolaou, C; Ptochos, F; Razis, P A; Rykaczewski, H; Tsiakkouri, D; Finger, M; Finger, M; Carrera Jarrin, E; Abdelalim, A A; Mohammed, Y; Salama, E; Kadastik, M; Perrini, L; Raidal, M; Tiko, A; Veelken, C; Eerola, P; Pekkanen, J; Voutilainen, M; Härkönen, J; Järvinen, T; Karimäki, V; Kinnunen, R; Lampén, T; Lassila-Perini, K; Lehti, S; Lindén, T; Luukka, P; Tuominiemi, J; Tuovinen, E; Wendland, L; Talvitie, J; Tuuva, T; Besancon, M; Couderc, F; Dejardin, M; Denegri, D; Fabbro, B; Faure, J L; Favaro, C; Ferri, F; Ganjour, S; Ghosh, S; Givernaud, A; Gras, P; Hamel de Monchenault, G; Jarry, P; Kucher, I; Locci, E; Machet, M; Malcles, J; Rander, J; Rosowsky, A; Titov, M; Zghiche, A; Abdulsalam, A; Antropov, I; Baffioni, S; Beaudette, F; Busson, P; Cadamuro, L; Chapon, E; Charlot, C; Davignon, O; Granier de Cassagnac, R; Jo, M; Lisniak, S; Miné, P; Nguyen, M; Ochando, C; Ortona, G; Paganini, P; Pigard, P; Regnard, S; Salerno, R; Sirois, Y; Strebler, T; Yilmaz, Y; Zabi, A; Agram, J-L; Andrea, J; Aubin, A; Bloch, D; Brom, J-M; Buttignol, M; Chabert, E C; Chanon, N; Collard, C; Conte, E; Coubez, X; Fontaine, J-C; Gelé, D; Goerlach, U; Le Bihan, A-C; Skovpen, K; Van Hove, P; Gadrat, S; Beauceron, S; Bernet, C; Boudoul, G; Bouvier, E; Carrillo Montoya, C A; Chierici, R; Contardo, D; Courbon, B; Depasse, P; El Mamouni, H; Fan, J; Fay, J; Gascon, S; Gouzevitch, M; Grenier, G; Ille, B; Lagarde, F; Laktineh, I B; Lethuillier, M; Mirabito, L; Pequegnot, A L; Perries, S; Popov, A; Sabes, D; Sordini, V; Vander Donckt, M; Verdier, P; Viret, S; Toriashvili, T; Tsamalaidze, Z; Autermann, C; Beranek, S; Feld, L; Heister, A; Kiesel, M K; Klein, K; Lipinski, M; Ostapchuk, A; Preuten, M; Raupach, F; Schael, S; Schomakers, C; Schulz, J; Verlage, T; Weber, H; Zhukov, V; Albert, A; Brodski, M; Dietz-Laursonn, E; Duchardt, D; Endres, M; Erdmann, M; Erdweg, S; Esch, T; Fischer, R; Güth, A; Hamer, M; Hebbeker, T; Heidemann, C; Hoepfner, K; Knutzen, S; Merschmeyer, M; Meyer, A; Millet, P; Mukherjee, S; Olschewski, M; Padeken, K; Pook, T; Radziej, M; Reithler, H; Rieger, M; Scheuch, F; Sonnenschein, L; Teyssier, D; Thüer, S; Cherepanov, V; Flügge, G; Kargoll, B; Kress, T; Künsken, A; Lingemann, J; Müller, T; Nehrkorn, A; Nowack, A; Pistone, C; Pooth, O; Stahl, A; Aldaya Martin, M; Arndt, T; Asawatangtrakuldee, C; Beernaert, K; Behnke, O; Behrens, U; Bin Anuar, A A; Borras, K; Campbell, A; Connor, P; Contreras-Campana, C; Costanza, F; Diez Pardos, C; Dolinska, G; Eckerlin, G; Eckstein, D; Eichhorn, T; Eren, E; Gallo, E; Garay Garcia, J; Geiser, A; Gizhko, A; Grados Luyando, J M; Gunnellini, P; Harb, A; Hauk, J; Hempel, M; Jung, H; Kalogeropoulos, A; Karacheban, O; Kasemann, M; Keaveney, J; Kleinwort, C; Korol, I; Krücker, D; Lange, W; Lelek, A; Leonard, J; Lipka, K; Lobanov, A; Lohmann, W; Mankel, R; Melzer-Pellmann, I-A; Meyer, A B; Mittag, G; Mnich, J; Mussgiller, A; Ntomari, E; Pitzl, D; Placakyte, R; Raspereza, A; Roland, B; Sahin, M Ö; Saxena, P; Schoerner-Sadenius, T; Seitz, C; Spannagel, S; Stefaniuk, N; Van Onsem, G P; Walsh, R; Wissing, C; Blobel, V; Centis Vignali, M; Draeger, A R; Dreyer, T; Garutti, E; Gonzalez, D; Haller, J; Hoffmann, M; Junkes, A; Klanner, R; Kogler, R; Kovalchuk, N; Lapsien, T; Lenz, T; Marchesini, I; Marconi, D; Meyer, M; Niedziela, M; Nowatschin, D; Pantaleo, F; Peiffer, T; Perieanu, A; Poehlsen, J; Sander, C; Scharf, C; Schleper, P; Schmidt, A; Schumann, S; Schwandt, J; Stadie, H; Steinbrück, G; Stober, F M; Stöver, M; Tholen, H; Troendle, D; Usai, E; Vanelderen, L; Vanhoefer, A; Vormwald, B; Akbiyik, M; Barth, C; Baur, S; Baus, C; Berger, J; Butz, E; Caspart, R; Chwalek, T; Colombo, F; De Boer, W; Dierlamm, A; Fink, S; Freund, B; Friese, R; Giffels, M; Gilbert, A; Goldenzweig, P; Haitz, D; Hartmann, F; Heindl, S M; Husemann, U; Katkov, I; Kudella, S; Lobelle Pardo, P; Mildner, H; Mozer, M U; Müller, Th; Plagge, M; Quast, G; Rabbertz, K; Röcker, S; Roscher, F; Schröder, M; Shvetsov, I; Sieber, G; Simonis, H J; Ulrich, R; Wagner-Kuhr, J; Wayand, S; Weber, M; Weiler, T; Williamson, S; Wöhrmann, C; Wolf, R; Anagnostou, G; Daskalakis, G; Geralis, T; Giakoumopoulou, V A; Kyriakis, A; Loukas, D; Topsis-Giotis, I; Kesisoglou, S; Panagiotou, A; Saoulidou, N; Tziaferi, E; Evangelou, I; Flouris, G; Foudas, C; Kokkas, P; Loukas, N; Manthos, N; Papadopoulos, I; Paradas, E; Filipovic, N; Bencze, G; Hajdu, C; Horvath, D; Sikler, F; Veszpremi, V; Vesztergombi, G; Zsigmond, A J; Beni, N; Czellar, S; Karancsi, J; Makovec, A; Molnar, J; Szillasi, Z; Bartók, M; Raics, P; Trocsanyi, Z L; Ujvari, B; Bahinipati, S; Choudhury, S; Mal, P; Mandal, K; Nayak, A; Sahoo, D K; Sahoo, N; Swain, S K; Bansal, S; Beri, S B; Bhatnagar, V; Chawla, R; Bhawandeep, U; Kalsi, A K; Kaur, A; Kaur, M; Kumar, R; Kumari, P; Mehta, A; Mittal, M; Singh, J B; Walia, G; Kumar, Ashok; Bhardwaj, A; Choudhary, B C; Garg, R B; Keshri, S; Malhotra, S; Naimuddin, M; Nishu, N; Ranjan, K; Sharma, R; Sharma, V; Bhattacharya, R; Bhattacharya, S; Chatterjee, K; Dey, S; Dutt, S; Dutta, S; Ghosh, S; Majumdar, N; Modak, A; Mondal, K; Mukhopadhyay, S; Nandan, S; Purohit, A; Roy, A; Roy, D; Roy Chowdhury, S; Sarkar, S; Sharan, M; Thakur, S; Behera, P K; Chudasama, R; Dutta, D; Jha, V; Kumar, V; Mohanty, A K; Netrakanti, P K; Pant, L M; Shukla, P; Topkar, A; Aziz, T; Dugad, S; Kole, G; Mahakud, B; Mitra, S; Mohanty, G B; Parida, B; Sur, N; Sutar, B; Banerjee, S; Bhowmik, S; Dewanjee, R K; Ganguly, S; Guchait, M; Jain, Sa; Kumar, S; Maity, M; Majumder, G; Mazumdar, K; Sarkar, T; Wickramage, N; Chauhan, S; Dube, S; Hegde, V; Kapoor, A; Kothekar, K; Pandey, S; Rane, A; Sharma, S; Behnamian, H; Chenarani, S; Eskandari Tadavani, E; Etesami, S M; Fahim, A; Khakzad, M; Mohammadi Najafabadi, M; Naseri, M; Paktinat Mehdiabadi, S; Rezaei Hosseinabadi, F; Safarzadeh, B; Zeinali, M; Felcini, M; Grunewald, M; Abbrescia, M; Calabria, C; Caputo, C; Colaleo, A; Creanza, D; Cristella, L; De Filippis, N; De Palma, M; Fiore, L; Iaselli, G; Maggi, G; Maggi, M; Miniello, G; My, S; Nuzzo, S; Pompili, A; Pugliese, G; Radogna, R; Ranieri, A; Selvaggi, G; Silvestris, L; Venditti, R; Verwilligen, P; Abbiendi, G; Battilana, C; Bonacorsi, D; Braibant-Giacomelli, S; Brigliadori, L; Campanini, R; Capiluppi, P; Castro, A; Cavallo, F R; Chhibra, S S; Codispoti, G; Cuffiani, M; Dallavalle, G M; Fabbri, F; Fanfani, A; Fasanella, D; Giacomelli, P; Grandi, C; Guiducci, L; Marcellini, S; Masetti, G; Montanari, A; Navarria, F L; Perrotta, A; Rossi, A M; Rovelli, T; Siroli, G P; Tosi, N; Albergo, S; Costa, S; Di Mattia, A; Giordano, F; Potenza, R; Tricomi, A; Tuve, C; Barbagli, G; Ciulli, V; Civinini, C; D'Alessandro, R; Focardi, E; Lenzi, P; Meschini, M; Paoletti, S; Sguazzoni, G; Viliani, L; Benussi, L; Bianco, S; Fabbri, F; Piccolo, D; Primavera, F; Calvelli, V; Ferro, F; Lo Vetere, M; Monge, M R; Robutti, E; Tosi, S; Brianza, L; Dinardo, M E; Fiorendi, S; Gennai, S; Ghezzi, A; Govoni, P; Malberti, M; Malvezzi, S; Manzoni, R A; Menasce, D; Moroni, L; Paganoni, M; Pedrini, D; Pigazzini, S; Ragazzi, S; Tabarelli de Fatis, T; Buontempo, S; Cavallo, N; De Nardo, G; Di Guida, S; Esposito, M; Fabozzi, F; Fienga, F; Iorio, A O M; Lanza, G; Lista, L; Meola, S; Paolucci, P; Sciacca, C; Thyssen, F; Azzi, P; Bacchetta, N; Benato, L; Bisello, D; Boletti, A; Carlin, R; Carvalho Antunes De Oliveira, A; Checchia, P; Dall'Osso, M; De Castro Manzano, P; Dorigo, T; Dosselli, U; Gasparini, F; Gasparini, U; Gozzelino, A; Lacaprara, S; Margoni, M; Meneguzzo, A T; Pazzini, J; Pozzobon, N; Ronchese, P; Simonetto, F; Torassa, E; Zanetti, M; Zotto, P; Zumerle, G; Braghieri, A; Magnani, A; Montagna, P; Ratti, S P; Re, V; Riccardi, C; Salvini, P; Vai, I; Vitulo, P; Alunni Solestizi, L; Bilei, G M; Ciangottini, D; Fanò, L; Lariccia, P; Leonardi, R; Mantovani, G; Menichelli, M; Saha, A; Santocchia, A; Androsov, K; Azzurri, P; Bagliesi, G; Bernardini, J; Boccali, T; Castaldi, R; Ciocci, M A; Dell'Orso, R; Donato, S; Fedi, G; Giassi, A; Grippo, M T; Ligabue, F; Lomtadze, T; Martini, L; Messineo, A; Palla, F; Rizzi, A; Savoy-Navarro, A; Spagnolo, P; Tenchini, R; Tonelli, G; Venturi, A; Verdini, P G; Barone, L; Cavallari, F; Cipriani, M; Del Re, D; Diemoz, M; Gelli, S; Longo, E; Margaroli, F; Marzocchi, B; Meridiani, P; Organtini, G; Paramatti, R; Preiato, F; Rahatlou, S; Rovelli, C; Santanastasio, F; Amapane, N; Arcidiacono, R; Argiro, S; Arneodo, M; Bartosik, N; Bellan, R; Biino, C; Cartiglia, N; Cenna, F; Costa, M; Covarelli, R; Degano, A; Demaria, N; Finco, L; Kiani, B; Mariotti, C; Maselli, S; Migliore, E; Monaco, V; Monteil, E; Monteno, M; Obertino, M M; Pacher, L; Pastrone, N; Pelliccioni, M; Pinna Angioni, G L; Ravera, F; Romero, A; Ruspa, M; Sacchi, R; Shchelina, K; Sola, V; Solano, A; Staiano, A; Traczyk, P; Belforte, S; Casarsa, M; Cossutti, F; Della Ricca, G; Zanetti, A; Kim, D H; Kim, G N; Kim, M S; Lee, S; Lee, S W; Oh, Y D; Sekmen, S; Son, D C; Yang, Y C; Lee, A; Kim, H; Brochero Cifuentes, J A; Kim, T J; Cho, S; Choi, S; Go, Y; Gyun, D; Ha, S; Hong, B; Jo, Y; Kim, Y; Lee, B; Lee, K; Lee, K S; Lee, S; Lim, J; Park, S K; Roh, Y; Almond, J; Kim, J; Lee, H; Oh, S B; Radburn-Smith, B C; Seo, S H; Yang, U K; Yoo, H D; Yu, G B; Choi, M; Kim, H; Kim, J H; Lee, J S H; Park, I C; Ryu, G; Ryu, M S; Choi, Y; Goh, J; Hwang, C; Lee, J; Yu, I; Dudenas, V; Juodagalvis, A; Vaitkus, J; Ahmed, I; Ibrahim, Z A; Komaragiri, J R; Md Ali, M A B; Mohamad Idris, F; Wan Abdullah, W A T; Yusli, M N; Zolkapli, Z; Castilla-Valdez, H; De La Cruz-Burelo, E; Heredia-De La Cruz, I; Hernandez-Almada, A; Lopez-Fernandez, R; Magaña Villalba, R; Mejia Guisao, J; Sanchez-Hernandez, A; Carrillo Moreno, S; Oropeza Barrera, C; Vazquez Valencia, F; Carpinteyro, S; Pedraza, I; Salazar Ibarguen, H A; Uribe Estrada, C; Morelos Pineda, A; Krofcheck, D; Butler, P H; Ahmad, A; Ahmad, M; Hassan, Q; Hoorani, H R; Khan, W A; Saddique, A; Shah, M A; Shoaib, M; Waqas, M; Bialkowska, H; Bluj, M; Boimska, B; Frueboes, T; Górski, M; Kazana, M; Nawrocki, K; Romanowska-Rybinska, K; Szleper, M; Zalewski, P; Bunkowski, K; Byszuk, A; Doroba, K; Kalinowski, A; Konecki, M; Krolikowski, J; Misiura, M; Olszewski, M; Walczak, M; Bargassa, P; Beirão Da Cruz E Silva, C; Calpas, B; Di Francesco, A; Faccioli, P; Ferreira Parracho, P G; Gallinaro, M; Hollar, J; Leonardo, N; Lloret Iglesias, L; Nemallapudi, M V; Rodrigues Antunes, J; Seixas, J; Toldaiev, O; Vadruccio, D; Varela, J; Vischia, P; Afanasiev, S; Bunin, P; Gavrilenko, M; Golutvin, I; Gorbunov, I; Kamenev, A; Karjavin, V; Lanev, A; Malakhov, A; Matveev, V; Palichik, V; Perelygin, V; Shmatov, S; Shulha, S; Skatchkov, N; Smirnov, V; Voytishin, N; Zarubin, A; Chtchipounov, L; Golovtsov, V; Ivanov, Y; Kim, V; Kuznetsova, E; Murzin, V; Oreshkin, V; Sulimov, V; Vorobyev, A; Andreev, Yu; Dermenev, A; Gninenko, S; Golubev, N; Karneyeu, A; Kirsanov, M; Krasnikov, N; Pashenkov, A; Tlisov, D; Toropin, A; Epshteyn, V; Gavrilov, V; Lychkovskaya, N; Popov, V; Pozdnyakov, I; Safronov, G; Spiridonov, A; Toms, M; Vlasov, E; Zhokin, A; Bylinkin, A; Markin, O; Tarkovskii, E; Andreev, V; Azarkin, M; Dremin, I; Kirakosyan, M; Leonidov, A; Terkulov, A; Baskakov, A; Belyaev, A; Boos, E; Ershov, A; Gribushin, A; Kaminskiy, A; Kodolova, O; Korotkikh, V; Lokhtin, I; Miagkov, I; Obraztsov, S; Petrushanko, S; Savrin, V; Snigirev, A; Vardanyan, I; Blinov, V; Skovpen, Y; Shtol, D; Azhgirey, I; Bayshev, I; Bitioukov, S; Elumakhov, D; Kachanov, V; Kalinin, A; Konstantinov, D; Krychkine, V; Petrov, V; Ryutin, R; Sobol, A; Troshin, S; Tyurin, N; Uzunian, A; Volkov, A; Adzic, P; Cirkovic, P; Devetak, D; Dordevic, M; Milosevic, J; Rekovic, V; Alcaraz Maestre, J; Barrio Luna, M; Calvo, E; Cerrada, M; Chamizo Llatas, M; Colino, N; De La Cruz, B; Delgado Peris, A; Escalante Del Valle, A; Fernandez Bedoya, C; Fernández Ramos, J P; Flix, J; Fouz, M C; Garcia-Abia, P; Gonzalez Lopez, O; Goy Lopez, S; Hernandez, J M; Josa, M I; Navarro De Martino, E; Pérez-Calero Yzquierdo, A; Puerta Pelayo, J; Quintario Olmeda, A; Redondo, I; Romero, L; Soares, M S; de Trocóniz, J F; Missiroli, M; Moran, D; Cuevas, J; Fernandez Menendez, J; Gonzalez Caballero, I; González Fernández, J R; Palencia Cortezon, E; Sanchez Cruz, S; Suárez Andrés, I; Vizan Garcia, J M; Cabrillo, I J; Calderon, A; Castiñeiras De Saa, J R; Curras, E; Fernandez, M; Garcia-Ferrero, J; Gomez, G; Lopez Virto, A; Marco, J; Martinez Rivero, C; Matorras, F; Piedra Gomez, J; Rodrigo, T; Ruiz-Jimeno, A; Scodellaro, L; Trevisani, N; Vila, I; Vilar Cortabitarte, R; Abbaneo, D; Auffray, E; Auzinger, G; Bachtis, M; Baillon, P; Ball, A H; Barney, D; Bloch, P; Bocci, A; Bonato, A; Botta, C; Camporesi, T; Castello, R; Cepeda, M; Cerminara, G; D'Alfonso, M; d'Enterria, D; Dabrowski, A; Daponte, V; David, A; De Gruttola, M; De Roeck, A; Di Marco, E; Dobson, M; Dorney, B; du Pree, T; Duggan, D; Dünser, M; Dupont, N; Elliott-Peisert, A; Fartoukh, S; Franzoni, G; Fulcher, J; Funk, W; Gigi, D; Gill, K; Girone, M; Glege, F; Gulhan, D; Gundacker, S; Guthoff, M; Hammer, J; Harris, P; Hegeman, J; Innocente, V; Janot, P; Kieseler, J; Kirschenmann, H; Knünz, V; Kornmayer, A; Kortelainen, M J; Kousouris, K; Krammer, M; Lange, C; Lecoq, P; Lourenço, C; Lucchini, M T; Malgeri, L; Mannelli, M; Martelli, A; Meijers, F; Merlin, J A; Mersi, S; Meschi, E; Milenovic, P; Moortgat, F; Morovic, S; Mulders, M; Neugebauer, H; Orfanelli, S; Orsini, L; Pape, L; Perez, E; Peruzzi, M; Petrilli, A; Petrucciani, G; Pfeiffer, A; Pierini, M; Racz, A; Reis, T; Rolandi, G; Rovere, M; Ruan, M; Sakulin, H; Sauvan, J B; Schäfer, C; Schwick, C; Seidel, M; Sharma, A; Silva, P; Sphicas, P; Steggemann, J; Stoye, M; Takahashi, Y; Tosi, M; Treille, D; Triossi, A; Tsirou, A; Veckalns, V; Veres, G I; Verweij, M; Wardle, N; Wöhri, H K; Zagozdzinska, A; Zeuner, W D; Bertl, W; Deiters, K; Erdmann, W; Horisberger, R; Ingram, Q; Kaestli, H C; Kotlinski, D; Langenegger, U; Rohe, T; Bachmair, F; Bäni, L; Bianchini, L; Casal, B; Dissertori, G; Dittmar, M; Donegà, M; Grab, C; Heidegger, C; Hits, D; Hoss, J; Kasieczka, G; Lecomte, P; Lustermann, W; Mangano, B; Marionneau, M; Martinez Ruiz Del Arbol, P; Masciovecchio, M; Meinhard, M T; Meister, D; Micheli, F; Musella, P; Nessi-Tedaldi, F; Pandolfi, F; Pata, J; Pauss, F; Perrin, G; Perrozzi, L; Quittnat, M; Rossini, M; Schönenberger, M; Starodumov, A; Tavolaro, V R; Theofilatos, K; Wallny, R; Aarrestad, T K; Amsler, C; Caminada, L; Canelli, M F; De Cosa, A; Galloni, C; Hinzmann, A; Hreus, T; Kilminster, B; Ngadiuba, J; Pinna, D; Rauco, G; Robmann, P; Salerno, D; Yang, Y; Zucchetta, A; Candelise, V; Doan, T H; Jain, Sh; Khurana, R; Konyushikhin, M; Kuo, C M; Lin, W; Lu, Y J; Pozdnyakov, A; Yu, S S; Kumar, Arun; Chang, P; Chang, Y H; Chang, Y W; Chao, Y; Chen, K F; Chen, P H; Dietz, C; Fiori, F; Hou, W-S; Hsiung, Y; Liu, Y F; Lu, R-S; Miñano Moya, M; Paganis, E; Psallidas, A; Tsai, J F; Tzeng, Y M; Asavapibhop, B; Singh, G; Srimanobhas, N; Suwonjandee, N; Adiguzel, A; Cerci, S; Damarseckin, S; Demiroglu, Z S; Dozen, C; Dumanoglu, I; Girgis, S; Gokbulut, G; Guler, Y; Hos, I; Kangal, E E; Kara, O; Kayis Topaksu, A; Kiminsu, U; Oglakci, M; Onengut, G; Ozdemir, K; Sunar Cerci, D; Tali, B; Turkcapar, S; Zorbakir, I S; Zorbilmez, C; Bilin, B; Bilmis, S; Isildak, B; Karapinar, G; Yalvac, M; Zeyrek, M; Gülmez, E; Kaya, M; Kaya, O; Yetkin, E A; Yetkin, T; Cakir, A; Cankocak, K; Sen, S; Grynyov, B; Levchuk, L; Sorokin, P; Aggleton, R; Ball, F; Beck, L; Brooke, J J; Burns, D; Clement, E; Cussans, D; Flacher, H; Goldstein, J; Grimes, M; Heath, G P; Heath, H F; Jacob, J; Kreczko, L; Lucas, C; Newbold, D M; Paramesvaran, S; Poll, A; Sakuma, T; Seif El Nasr-Storey, S; Smith, D; Smith, V J; Belyaev, A; Brew, C; Brown, R M; Calligaris, L; Cieri, D; Cockerill, D J A; Coughlan, J A; Harder, K; Harper, S; Olaiya, E; Petyt, D; Shepherd-Themistocleous, C H; Thea, A; Tomalin, I R; Williams, T; Baber, M; Bainbridge, R; Buchmuller, O; Bundock, A; Burton, D; Casasso, S; Citron, M; Colling, D; Corpe, L; Dauncey, P; Davies, G; De Wit, A; Della Negra, M; Di Maria, R; Dunne, P; Elwood, A; Futyan, D; Haddad, Y; Hall, G; Iles, G; James, T; Lane, R; Laner, C; Lucas, R; Lyons, L; Magnan, A-M; Malik, S; Mastrolorenzo, L; Nash, J; Nikitenko, A; Pela, J; Penning, B; Pesaresi, M; Raymond, D M; Richards, A; Rose, A; Seez, C; Summers, S; Tapper, A; Uchida, K; Vazquez Acosta, M; Virdee, T; Wright, J; Zenz, S C; Cole, J E; Hobson, P R; Khan, A; Kyberd, P; Leslie, D; Reid, I D; Symonds, P; Teodorescu, L; Turner, M; Borzou, A; Call, K; Dittmann, J; Hatakeyama, K; Liu, H; Pastika, N; Cooper, S I; Henderson, C; Rumerio, P; West, C; Arcaro, D; Avetisyan, A; Bose, T; Gastler, D; Rankin, D; Richardson, C; Rohlf, J; Sulak, L; Zou, D; Benelli, G; Berry, E; Cutts, D; Garabedian, A; Hakala, J; Heintz, U; Hogan, J M; Jesus, O; Kwok, K H M; Laird, E; Landsberg, G; Mao, Z; Narain, M; Piperov, S; Sagir, S; Spencer, E; Syarif, R; Breedon, R; Breto, G; Burns, D; Calderon De La Barca Sanchez, M; Chauhan, S; Chertok, M; Conway, J; Conway, R; Cox, P T; Erbacher, R; Flores, C; Funk, G; Gardner, M; Ko, W; Lander, R; Mclean, C; Mulhearn, M; Pellett, D; Pilot, J; Shalhout, S; Smith, J; Squires, M; Stolp, D; Tripathi, M; Bravo, C; Cousins, R; Dasgupta, A; Everaerts, P; Florent, A; Hauser, J; Ignatenko, M; Mccoll, N; Saltzberg, D; Schnaible, C; Takasugi, E; Valuev, V; Weber, M; Burt, K; Clare, R; Ellison, J; Gary, J W; Ghiasi Shirazi, S M A; Hanson, G; Heilman, J; Jandir, P; Kennedy, E; Lacroix, F; Long, O R; Olmedo Negrete, M; Paneva, M I; Shrinivas, A; Si, W; Wei, H; Wimpenny, S; Yates, B R; Branson, J G; Cerati, G B; Cittolin, S; Derdzinski, M; Holzner, A; Klein, D; Krutelyov, V; Letts, J; Macneill, I; Olivito, D; Padhi, S; Pieri, M; Sani, M; Sharma, V; Simon, S; Tadel, M; Vartak, A; Wasserbaech, S; Welke, C; Wood, J; Würthwein, F; Yagil, A; Zevi Della Porta, G; Amin, N; Bhandari, R; Bradmiller-Feld, J; Campagnari, C; Dishaw, A; Dutta, V; Franco Sevilla, M; George, C; Golf, F; Gouskos, L; Gran, J; Heller, R; Incandela, J; Mullin, S D; Ovcharova, A; Qu, H; Richman, J; Stuart, D; Suarez, I; Yoo, J; Anderson, D; Apresyan, A; Bendavid, J; Bornheim, A; Bunn, J; Chen, Y; Duarte, J; Lawhorn, J M; Mott, A; Newman, H B; Pena, C; Spiropulu, M; Vlimant, J R; Xie, S; Zhu, R Y; Andrews, M B; Azzolini, V; Ferguson, T; Paulini, M; Russ, J; Sun, M; Vogel, H; Vorobiev, I; Weinberg, M; Cumalat, J P; Ford, W T; Jensen, F; Johnson, A; Krohn, M; Mulholland, T; Stenson, K; Wagner, S R; Alexander, J; Chaves, J; Chu, J; Dittmer, S; Mcdermott, K; Mirman, N; Nicolas Kaufman, G; Patterson, J R; Rinkevicius, A; Ryd, A; Skinnari, L; Soffi, L; Tan, S M; Tao, Z; Thom, J; Tucker, J; Wittich, P; Zientek, M; Winn, D; Abdullin, S; Albrow, M; Apollinari, G; Banerjee, S; Bauerdick, L A T; Beretvas, A; Berryhill, J; Bhat, P C; Bolla, G; Burkett, K; Butler, J N; Cheung, H W K; Chlebana, F; Cihangir, S; Cremonesi, M; Elvira, V D; Fisk, I; Freeman, J; Gottschalk, E; Gray, L; Green, D; Grünendahl, S; Gutsche, O; Hare, D; Harris, R M; Hasegawa, S; Hirschauer, J; Hu, Z; Jayatilaka, B; Jindariani, S; Johnson, M; Joshi, U; Klima, B; Kreis, B; Lammel, S; Linacre, J; Lincoln, D; Lipton, R; Liu, T; Lopes De Sá, R; Lykken, J; Maeshima, K; Magini, N; Marraffino, J M; Maruyama, S; Mason, D; McBride, P; Merkel, P; Mrenna, S; Nahn, S; Newman-Holmes, C; O'Dell, V; Pedro, K; Prokofyev, O; Rakness, G; Ristori, L; Sexton-Kennedy, E; Soha, A; Spalding, W J; Spiegel, L; Stoynev, S; Strobbe, N; Taylor, L; Tkaczyk, S; Tran, N V; Uplegger, L; Vaandering, E W; Vernieri, C; Verzocchi, M; Vidal, R; Wang, M; Weber, H A; Whitbeck, A; Wu, Y; Acosta, D; Avery, P; Bortignon, P; Bourilkov, D; Brinkerhoff, A; Carnes, A; Carver, M; Curry, D; Das, S; Field, R D; Furic, I K; Konigsberg, J; Korytov, A; Low, J F; Ma, P; Matchev, K; Mei, H; Mitselmakher, G; Rank, D; Shchutska, L; Sperka, D; Thomas, L; Wang, J; Wang, S; Yelton, J; Linn, S; Markowitz, P; Martinez, G; Rodriguez, J L; Ackert, A; Adams, J R; Adams, T; Askew, A; Bein, S; Diamond, B; Hagopian, S; Hagopian, V; Johnson, K F; Khatiwada, A; Prosper, H; Santra, A; Yohay, R; Baarmand, M M; Bhopatkar, V; Colafranceschi, S; Hohlmann, M; Noonan, D; Roy, T; Yumiceva, F; Adams, M R; Apanasevich, L; Berry, D; Betts, R R; Bucinskaite, I; Cavanaugh, R; Evdokimov, O; Gauthier, L; Gerber, C E; Hofman, D J; Jung, K; Kurt, P; O'Brien, C; Sandoval Gonzalez, I D; Turner, P; Varelas, N; Wang, H; Wu, Z; Zakaria, M; Zhang, J; Bilki, B; Clarida, W; Dilsiz, K; Durgut, S; Gandrajula, R P; Haytmyradov, M; Khristenko, V; Merlo, J-P; Mermerkaya, H; Mestvirishvili, A; Moeller, A; Nachtman, J; Ogul, H; Onel, Y; Ozok, F; Penzo, A; Snyder, C; Tiras, E; Wetzel, J; Yi, K; Anderson, I; Blumenfeld, B; Cocoros, A; Eminizer, N; Fehling, D; Feng, L; Gritsan, A V; Maksimovic, P; Martin, C; Osherson, M; Roskes, J; Sarica, U; Swartz, M; Xiao, M; Xin, Y; You, C; Al-Bataineh, A; Baringer, P; Bean, A; Boren, S; Bowen, J; Bruner, C; Castle, J; Forthomme, L; Kenny, R P; Khalil, S; Kropivnitskaya, A; Majumder, D; Mcbrayer, W; Murray, M; Sanders, S; Stringer, R; Tapia Takaki, J D; Wang, Q; Ivanov, A; Kaadze, K; Maravin, Y; Mohammadi, A; Saini, L K; Skhirtladze, N; Toda, S; Rebassoo, F; Wright, D; Anelli, C; Baden, A; Baron, O; Belloni, A; Calvert, B; Eno, S C; Ferraioli, C; Gomez, J A; Hadley, N J; Jabeen, S; Kellogg, R G; Kolberg, T; Kunkle, J; Lu, Y; Mignerey, A C; Ricci-Tam, F; Shin, Y H; Skuja, A; Tonjes, M B; Tonwar, S C; Abercrombie, D; Allen, B; Apyan, A; Barbieri, R; Baty, A; Bi, R; Bierwagen, K; Brandt, S; Busza, W; Cali, I A; Demiragli, Z; Di Matteo, L; Gomez Ceballos, G; Goncharov, M; Hsu, D; Iiyama, Y; Innocenti, G M; Klute, M; Kovalskyi, D; Krajczar, K; Lai, Y S; Lee, Y-J; Levin, A; Luckey, P D; Maier, B; Marini, A C; Mcginn, C; Mironov, C; Narayanan, S; Niu, X; Paus, C; Roland, C; Roland, G; Salfeld-Nebgen, J; Stephans, G S F; Sumorok, K; Tatar, K; Varma, M; Velicanu, D; Veverka, J; Wang, J; Wang, T W; Wyslouch, B; Yang, M; Zhukova, V; Benvenuti, A C; Chatterjee, R M; Evans, A; Finkel, A; Gude, A; Hansen, P; Kalafut, S; Kao, S C; Kubota, Y; Lesko, Z; Mans, J; Nourbakhsh, S; Ruckstuhl, N; Rusack, R; Tambe, N; Turkewitz, J; Acosta, J G; Oliveros, S; Avdeeva, E; Bartek, R; Bloom, K; Claes, D R; Dominguez, A; Fangmeier, C; Gonzalez Suarez, R; Kamalieddin, R; Kravchenko, I; Malta Rodrigues, A; Meier, F; Monroy, J; Siado, J E; Snow, G R; Stieger, B; Alyari, M; Dolen, J; George, J; Godshalk, A; Harrington, C; Iashvili, I; Kaisen, J; Kharchilava, A; Kumar, A; Parker, A; Rappoccio, S; Roozbahani, B; Alverson, G; Barberis, E; Hortiangtham, A; Massironi, A; Morse, D M; Nash, D; Orimoto, T; Teixeira De Lima, R; Trocino, D; Wang, R-J; Wood, D; Bhattacharya, S; Charaf, O; Hahn, K A; Kubik, A; Kumar, A; Mucia, N; Odell, N; Pollack, B; Schmitt, M H; Sung, K; Trovato, M; Velasco, M; Dev, N; Hildreth, M; Hurtado Anampa, K; Jessop, C; Karmgard, D J; Kellams, N; Lannon, K; Marinelli, N; Meng, F; Mueller, C; Musienko, Y; Planer, M; Reinsvold, A; Ruchti, R; Smith, G; Taroni, S; Wayne, M; Wolf, M; Woodard, A; Alimena, J; Antonelli, L; Bylsma, B; Durkin, L S; Flowers, S; Francis, B; Hart, A; Hill, C; Hughes, R; Ji, W; Liu, B; Luo, W; Puigh, D; Winer, B L; Wulsin, H W; Cooperstein, S; Driga, O; Elmer, P; Hardenbrook, J; Hebda, P; Lange, D; Luo, J; Marlow, D; Mc Donald, J; Medvedeva, T; Mei, K; Mooney, M; Olsen, J; Palmer, C; Piroué, P; Stickland, D; Svyatkovskiy, A; Tully, C; Zuranski, A; Malik, S; Barker, A; Barnes, V E; Folgueras, S; Gutay, L; Jha, M K; Jones, M; Jung, A W; Miller, D H; Neumeister, N; Schulte, J F; Shi, X; Sun, J; Wang, F; Xie, W; Parashar, N; Stupak, J; Adair, A; Akgun, B; Chen, Z; Ecklund, K M; Geurts, F J M; Guilbaud, M; Li, W; Michlin, B; Northup, M; Padley, B P; Redjimi, R; Roberts, J; Rorie, J; Tu, Z; Zabel, J; Betchart, B; Bodek, A; de Barbaro, P; Demina, R; Duh, Y T; Ferbel, T; Galanti, M; Garcia-Bellido, A; Han, J; Hindrichs, O; Khukhunaishvili, A; Lo, K H; Tan, P; Verzetti, M; Agapitos, A; Chou, J P; Contreras-Campana, E; Gershtein, Y; Gómez Espinosa, T A; Halkiadakis, E; Heindl, M; Hidas, D; Hughes, E; Kaplan, S; Kunnawalkam Elayavalli, R; Kyriacou, S; Lath, A; Nash, K; Saka, H; Salur, S; Schnetzer, S; Sheffield, D; Somalwar, S; Stone, R; Thomas, S; Thomassen, P; Walker, M; Delannoy, A G; Foerster, M; Heideman, J; Riley, G; Rose, K; Spanier, S; Thapa, K; Bouhali, O; Celik, A; Dalchenko, M; De Mattia, M; Delgado, A; Dildick, S; Eusebi, R; Gilmore, J; Huang, T; Juska, E; Kamon, T; Mueller, R; Pakhotin, Y; Patel, R; Perloff, A; Perniè, L; Rathjens, D; Rose, A; Safonov, A; Tatarinov, A; Ulmer, K A; Akchurin, N; Cowden, C; Damgov, J; De Guio, F; Dragoiu, C; Dudero, P R; Faulkner, J; Gurpinar, E; Kunori, S; Lamichhane, K; Lee, S W; Libeiro, T; Peltola, T; Undleeb, S; Volobouev, I; Wang, Z; Greene, S; Gurrola, A; Janjam, R; Johns, W; Maguire, C; Melo, A; Ni, H; Sheldon, P; Tuo, S; Velkovska, J; Xu, Q; Arenton, M W; Barria, P; Cox, B; Goodell, J; Hirosky, R; Ledovskoy, A; Li, H; Neu, C; Sinthuprasith, T; Sun, X; Wang, Y; Wolfe, E; Xia, F; Clarke, C; Harr, R; Karchin, P E; Sturdy, J; Belknap, D A; Buchanan, J; Caillol, C; Dasu, S; Dodd, L; Duric, S; Gomber, B; Grothe, M; Herndon, M; Hervé, A; Klabbers, P; Lanaro, A; Levine, A; Long, K; Loveless, R; Ojalvo, I; Perry, T; Pierro, G A; Polese, G; Ruggles, T; Savin, A; Smith, N; Smith, W H; Taylor, D; Woods, N

    2017-03-24

    Charge-dependent azimuthal particle correlations with respect to the second-order event plane in p-Pb and PbPb collisions at a nucleon-nucleon center-of-mass energy of 5.02 TeV have been studied with the CMS experiment at the LHC. The measurement is performed with a three-particle correlation technique, using two particles with the same or opposite charge within the pseudorapidity range |η|<2.4, and a third particle measured in the hadron forward calorimeters (4.4<|η|<5). The observed differences between the same and opposite sign correlations, as functions of multiplicity and η gap between the two charged particles, are of similar magnitude in p-Pb and PbPb collisions at the same multiplicities. These results pose a challenge for the interpretation of charge-dependent azimuthal correlations in heavy ion collisions in terms of the chiral magnetic effect.

  16. Observation of charge-dependent azimuthal correlations in pPb collisions and its implication for the search for the chiral magnetic effect

    SciTech Connect

    Khachatryan, Vardan; et al.

    2016-10-02

    Charge-dependent azimuthal particle correlations with respect to the second-order event plane in pPb and PbPb collisions at a nucleon-nucleon center-of-mass energy of 5.02 TeV have been studied with the CMS experiment at the LHC. The measurement is performed with a three-particle correlation technique, using two particles with the same or opposite charge within the pseudorapidity range abs(eta)<2.4, and a third particle measured in the hadron forward calorimeters (4.4< abs(eta)<5). The observed differences between the same and opposite sign correlations, as functions of multiplicity and eta gap between the two charged particles, are of similar magnitude in pPb and PbPb collisions at the same multiplicities. These results pose a challenge for the interpretation of charge-dependent azimuthal correlations in heavy ion collisions in terms of the chiral magnetic effect.

  17. Observation of Charge-Dependent Azimuthal Correlations in p -Pb Collisions and Its Implication for the Search for the Chiral Magnetic Effect

    NASA Astrophysics Data System (ADS)

    Khachatryan, V.; Sirunyan, A. M.; Tumasyan, A.; Adam, W.; Asilar, E.; Bergauer, T.; Brandstetter, J.; Brondolin, E.; Dragicevic, M.; Erö, J.; Flechl, M.; Friedl, M.; Frühwirth, R.; Ghete, V. M.; Hartl, C.; Hörmann, N.; Hrubec, J.; Jeitler, M.; König, A.; Krätschmer, I.; Liko, D.; Matsushita, T.; Mikulec, I.; Rabady, D.; Rad, N.; Rahbaran, B.; Rohringer, H.; Schieck, J.; Strauss, J.; Waltenberger, W.; Wulz, C.-E.; Dvornikov, O.; Makarenko, V.; Zykunov, V.; Mossolov, V.; Shumeiko, N.; Suarez Gonzalez, J.; Alderweireldt, S.; De Wolf, E. A.; Janssen, X.; Lauwers, J.; Van De Klundert, M.; Van Haevermaet, H.; Van Mechelen, P.; Van Remortel, N.; Van Spilbeeck, A.; Abu Zeid, S.; Blekman, F.; D'Hondt, J.; Daci, N.; De Bruyn, I.; Deroover, K.; Lowette, S.; Moortgat, S.; Moreels, L.; Olbrechts, A.; Python, Q.; Tavernier, S.; Van Doninck, W.; Van Mulders, P.; Van Parijs, I.; Brun, H.; Clerbaux, B.; De Lentdecker, G.; Delannoy, H.; Fasanella, G.; Favart, L.; Goldouzian, R.; Grebenyuk, A.; Karapostoli, G.; Lenzi, T.; Léonard, A.; Luetic, J.; Maerschalk, T.; Marinov, A.; Randle-conde, A.; Seva, T.; Vander Velde, C.; Vanlaer, P.; Vannerom, D.; Yonamine, R.; Zenoni, F.; Zhang, F.; Cimmino, A.; Cornelis, T.; Dobur, D.; Fagot, A.; Garcia, G.; Gul, M.; Khvastunov, I.; Poyraz, D.; Salva, S.; Schöfbeck, R.; Sharma, A.; Tytgat, M.; Van Driessche, W.; Yazgan, E.; Zaganidis, N.; Bakhshiansohi, H.; Beluffi, C.; Bondu, O.; Brochet, S.; Bruno, G.; Caudron, A.; De Visscher, S.; Delaere, C.; Delcourt, M.; Francois, B.; Giammanco, A.; Jafari, A.; Jez, P.; Komm, M.; Krintiras, G.; Lemaitre, V.; Magitteri, A.; Mertens, A.; Musich, M.; Nuttens, C.; Piotrzkowski, K.; Quertenmont, L.; Selvaggi, M.; Vidal Marono, M.; Wertz, S.; Beliy, N.; Aldá Júnior, W. L.; Alves, F. L.; Alves, G. A.; Brito, L.; Hensel, C.; Moraes, A.; Pol, M. E.; Rebello Teles, P.; Belchior Batista Das Chagas, E.; Carvalho, W.; Chinellato, J.; Custódio, A.; Da Costa, E. M.; Da Silveira, G. G.; De Jesus Damiao, D.; De Oliveira Martins, C.; Fonseca De Souza, S.; Huertas Guativa, L. M.; Malbouisson, H.; Matos Figueiredo, D.; Mora Herrera, C.; Mundim, L.; Nogima, H.; Prado Da Silva, W. L.; Santoro, A.; Sznajder, A.; Tonelli Manganote, E. J.; Vilela Pereira, A.; Ahuja, S.; Bernardes, C. A.; Dogra, S.; Fernandez Perez Tomei, T. R.; Gregores, E. M.; Mercadante, P. G.; Moon, C. S.; Novaes, S. F.; Padula, Sandra S.; Romero Abad, D.; Ruiz Vargas, J. C.; Aleksandrov, A.; Hadjiiska, R.; Iaydjiev, P.; Rodozov, M.; Stoykova, S.; Sultanov, G.; Vutova, M.; Dimitrov, A.; Glushkov, I.; Litov, L.; Pavlov, B.; Petkov, P.; Fang, W.; Ahmad, M.; Bian, J. G.; Chen, G. M.; Chen, H. S.; Chen, M.; Chen, Y.; Cheng, T.; Jiang, C. H.; Leggat, D.; Liu, Z.; Romeo, F.; Shaheen, S. M.; Spiezia, A.; Tao, J.; Wang, C.; Wang, Z.; Zhang, H.; Zhao, J.; Ban, Y.; Chen, G.; Li, Q.; Liu, S.; Mao, Y.; Qian, S. J.; Wang, D.; Xu, Z.; Avila, C.; Cabrera, A.; Chaparro Sierra, L. F.; Florez, C.; Gomez, J. P.; González Hernández, C. F.; Ruiz Alvarez, J. D.; Sanabria, J. C.; Godinovic, N.; Lelas, D.; Puljak, I.; Ribeiro Cipriano, P. M.; Sculac, T.; Antunovic, Z.; Kovac, M.; Brigljevic, V.; Ferencek, D.; Kadija, K.; Mesic, B.; Micanovic, S.; Sudic, L.; Susa, T.; Attikis, A.; Mavromanolakis, G.; Mousa, J.; Nicolaou, C.; Ptochos, F.; Razis, P. A.; Rykaczewski, H.; Tsiakkouri, D.; Finger, M.; Finger, M.; Carrera Jarrin, E.; Abdelalim, A. A.; Mohammed, Y.; Salama, E.; Kadastik, M.; Perrini, L.; Raidal, M.; Tiko, A.; Veelken, C.; Eerola, P.; Pekkanen, J.; Voutilainen, M.; Härkönen, J.; Järvinen, T.; Karimäki, V.; Kinnunen, R.; Lampén, T.; Lassila-Perini, K.; Lehti, S.; Lindén, T.; Luukka, P.; Tuominiemi, J.; Tuovinen, E.; Wendland, L.; Talvitie, J.; Tuuva, T.; Besancon, M.; Couderc, F.; Dejardin, M.; Denegri, D.; Fabbro, B.; Faure, J. L.; Favaro, C.; Ferri, F.; Ganjour, S.; Ghosh, S.; Givernaud, A.; Gras, P.; Hamel de Monchenault, G.; Jarry, P.; Kucher, I.; Locci, E.; Machet, M.; Malcles, J.; Rander, J.; Rosowsky, A.; Titov, M.; Zghiche, A.; Abdulsalam, A.; Antropov, I.; Baffioni, S.; Beaudette, F.; Busson, P.; Cadamuro, L.; Chapon, E.; Charlot, C.; Davignon, O.; Granier de Cassagnac, R.; Jo, M.; Lisniak, S.; Miné, P.; Nguyen, M.; Ochando, C.; Ortona, G.; Paganini, P.; Pigard, P.; Regnard, S.; Salerno, R.; Sirois, Y.; Strebler, T.; Yilmaz, Y.; Zabi, A.; Agram, J.-L.; Andrea, J.; Aubin, A.; Bloch, D.; Brom, J.-M.; Buttignol, M.; Chabert, E. C.; Chanon, N.; Collard, C.; Conte, E.; Coubez, X.; Fontaine, J.-C.; Gelé, D.; Goerlach, U.; Le Bihan, A.-C.; Skovpen, K.; Van Hove, P.; Gadrat, S.; Beauceron, S.; Bernet, C.; Boudoul, G.; Bouvier, E.; Carrillo Montoya, C. A.; Chierici, R.; Contardo, D.; Courbon, B.; Depasse, P.; El Mamouni, H.; Fan, J.; Fay, J.; Gascon, S.; Gouzevitch, M.; Grenier, G.; Ille, B.; Lagarde, F.; Laktineh, I. B.; Lethuillier, M.; Mirabito, L.; Pequegnot, A. L.; Perries, S.; Popov, A.; Sabes, D.; Sordini, V.; Vander Donckt, M.; Verdier, P.; Viret, S.; Toriashvili, T.; Tsamalaidze, Z.; Autermann, C.; Beranek, S.; Feld, L.; Heister, A.; Kiesel, M. K.; Klein, K.; Lipinski, M.; Ostapchuk, A.; Preuten, M.; Raupach, F.; Schael, S.; Schomakers, C.; Schulz, J.; Verlage, T.; Weber, H.; Zhukov, V.; Albert, A.; Brodski, M.; Dietz-Laursonn, E.; Duchardt, D.; Endres, M.; Erdmann, M.; Erdweg, S.; Esch, T.; Fischer, R.; Güth, A.; Hamer, M.; Hebbeker, T.; Heidemann, C.; Hoepfner, K.; Knutzen, S.; Merschmeyer, M.; Meyer, A.; Millet, P.; Mukherjee, S.; Olschewski, M.; Padeken, K.; Pook, T.; Radziej, M.; Reithler, H.; Rieger, M.; Scheuch, F.; Sonnenschein, L.; Teyssier, D.; Thüer, S.; Cherepanov, V.; Flügge, G.; Kargoll, B.; Kress, T.; Künsken, A.; Lingemann, J.; Müller, T.; Nehrkorn, A.; Nowack, A.; Pistone, C.; Pooth, O.; Stahl, A.; Aldaya Martin, M.; Arndt, T.; Asawatangtrakuldee, C.; Beernaert, K.; Behnke, O.; Behrens, U.; Bin Anuar, A. A.; Borras, K.; Campbell, A.; Connor, P.; Contreras-Campana, C.; Costanza, F.; Diez Pardos, C.; Dolinska, G.; Eckerlin, G.; Eckstein, D.; Eichhorn, T.; Eren, E.; Gallo, E.; Garay Garcia, J.; Geiser, A.; Gizhko, A.; Grados Luyando, J. M.; Gunnellini, P.; Harb, A.; Hauk, J.; Hempel, M.; Jung, H.; Kalogeropoulos, A.; Karacheban, O.; Kasemann, M.; Keaveney, J.; Kleinwort, C.; Korol, I.; Krücker, D.; Lange, W.; Lelek, A.; Leonard, J.; Lipka, K.; Lobanov, A.; Lohmann, W.; Mankel, R.; Melzer-Pellmann, I.-A.; Meyer, A. B.; Mittag, G.; Mnich, J.; Mussgiller, A.; Ntomari, E.; Pitzl, D.; Placakyte, R.; Raspereza, A.; Roland, B.; Sahin, M. Ö.; Saxena, P.; Schoerner-Sadenius, T.; Seitz, C.; Spannagel, S.; Stefaniuk, N.; Van Onsem, G. P.; Walsh, R.; Wissing, C.; Blobel, V.; Centis Vignali, M.; Draeger, A. R.; Dreyer, T.; Garutti, E.; Gonzalez, D.; Haller, J.; Hoffmann, M.; Junkes, A.; Klanner, R.; Kogler, R.; Kovalchuk, N.; Lapsien, T.; Lenz, T.; Marchesini, I.; Marconi, D.; Meyer, M.; Niedziela, M.; Nowatschin, D.; Pantaleo, F.; Peiffer, T.; Perieanu, A.; Poehlsen, J.; Sander, C.; Scharf, C.; Schleper, P.; Schmidt, A.; Schumann, S.; Schwandt, J.; Stadie, H.; Steinbrück, G.; Stober, F. M.; Stöver, M.; Tholen, H.; Troendle, D.; Usai, E.; Vanelderen, L.; Vanhoefer, A.; Vormwald, B.; Akbiyik, M.; Barth, C.; Baur, S.; Baus, C.; Berger, J.; Butz, E.; Caspart, R.; Chwalek, T.; Colombo, F.; De Boer, W.; Dierlamm, A.; Fink, S.; Freund, B.; Friese, R.; Giffels, M.; Gilbert, A.; Goldenzweig, P.; Haitz, D.; Hartmann, F.; Heindl, S. M.; Husemann, U.; Katkov, I.; Kudella, S.; Lobelle Pardo, P.; Mildner, H.; Mozer, M. U.; Müller, Th.; Plagge, M.; Quast, G.; Rabbertz, K.; Röcker, S.; Roscher, F.; Schröder, M.; Shvetsov, I.; Sieber, G.; Simonis, H. J.; Ulrich, R.; Wagner-Kuhr, J.; Wayand, S.; Weber, M.; Weiler, T.; Williamson, S.; Wöhrmann, C.; Wolf, R.; Anagnostou, G.; Daskalakis, G.; Geralis, T.; Giakoumopoulou, V. A.; Kyriakis, A.; Loukas, D.; Topsis-Giotis, I.; Kesisoglou, S.; Panagiotou, A.; Saoulidou, N.; Tziaferi, E.; Evangelou, I.; Flouris, G.; Foudas, C.; Kokkas, P.; Loukas, N.; Manthos, N.; Papadopoulos, I.; Paradas, E.; Filipovic, N.; Bencze, G.; Hajdu, C.; Horvath, D.; Sikler, F.; Veszpremi, V.; Vesztergombi, G.; Zsigmond, A. J.; Beni, N.; Czellar, S.; Karancsi, J.; Makovec, A.; Molnar, J.; Szillasi, Z.; Bartók, M.; Raics, P.; Trocsanyi, Z. L.; Ujvari, B.; Bahinipati, S.; Choudhury, S.; Mal, P.; Mandal, K.; Nayak, A.; Sahoo, D. K.; Sahoo, N.; Swain, S. K.; Bansal, S.; Beri, S. B.; Bhatnagar, V.; Chawla, R.; Bhawandeep, U.; Kalsi, A. K.; Kaur, A.; Kaur, M.; Kumar, R.; Kumari, P.; Mehta, A.; Mittal, M.; Singh, J. B.; Walia, G.; Kumar, Ashok; Bhardwaj, A.; Choudhary, B. C.; Garg, R. B.; Keshri, S.; Malhotra, S.; Naimuddin, M.; Nishu, N.; Ranjan, K.; Sharma, R.; Sharma, V.; Bhattacharya, R.; Bhattacharya, S.; Chatterjee, K.; Dey, S.; Dutt, S.; Dutta, S.; Ghosh, S.; Majumdar, N.; Modak, A.; Mondal, K.; Mukhopadhyay, S.; Nandan, S.; Purohit, A.; Roy, A.; Roy, D.; Roy Chowdhury, S.; Sarkar, S.; Sharan, M.; Thakur, S.; Behera, P. K.; Chudasama, R.; Dutta, D.; Jha, V.; Kumar, V.; Mohanty, A. K.; Netrakanti, P. K.; Pant, L. M.; Shukla, P.; Topkar, A.; Aziz, T.; Dugad, S.; Kole, G.; Mahakud, B.; Mitra, S.; Mohanty, G. B.; Parida, B.; Sur, N.; Sutar, B.; Banerjee, S.; Bhowmik, S.; Dewanjee, R. K.; Ganguly, S.; Guchait, M.; Jain, Sa.; Kumar, S.; Maity, M.; Majumder, G.; Mazumdar, K.; Sarkar, T.; Wickramage, N.; Chauhan, S.; Dube, S.; Hegde, V.; Kapoor, A.; Kothekar, K.; Pandey, S.; Rane, A.; Sharma, S.; Behnamian, H.; Chenarani, S.; Eskandari Tadavani, E.; Etesami, S. M.; Fahim, A.; Khakzad, M.; Mohammadi Najafabadi, M.; Naseri, M.; Paktinat Mehdiabadi, S.; Rezaei Hosseinabadi, F.; Safarzadeh, B.; Zeinali, M.; Felcini, M.; Grunewald, M.; Abbrescia, M.; Calabria, C.; Caputo, C.; Colaleo, A.; Creanza, D.; Cristella, L.; De Filippis, N.; De Palma, M.; Fiore, L.; Iaselli, G.; Maggi, G.; Maggi, M.; Miniello, G.; My, S.; Nuzzo, S.; Pompili, A.; Pugliese, G.; Radogna, R.; Ranieri, A.; Selvaggi, G.; Silvestris, L.; Venditti, R.; Verwilligen, P.; Abbiendi, G.; Battilana, C.; Bonacorsi, D.; Braibant-Giacomelli, S.; Brigliadori, L.; Campanini, R.; Capiluppi, P.; Castro, A.; Cavallo, F. R.; Chhibra, S. S.; Codispoti, G.; Cuffiani, M.; Dallavalle, G. M.; Fabbri, F.; Fanfani, A.; Fasanella, D.; Giacomelli, P.; Grandi, C.; Guiducci, L.; Marcellini, S.; Masetti, G.; Montanari, A.; Navarria, F. L.; Perrotta, A.; Rossi, A. M.; Rovelli, T.; Siroli, G. P.; Tosi, N.; Albergo, S.; Costa, S.; Di Mattia, A.; Giordano, F.; Potenza, R.; Tricomi, A.; Tuve, C.; Barbagli, G.; Ciulli, V.; Civinini, C.; D'Alessandro, R.; Focardi, E.; Lenzi, P.; Meschini, M.; Paoletti, S.; Sguazzoni, G.; Viliani, L.; Benussi, L.; Bianco, S.; Fabbri, F.; Piccolo, D.; Primavera, F.; Calvelli, V.; Ferro, F.; Lo Vetere, M.; Monge, M. R.; Robutti, E.; Tosi, S.; Brianza, L.; Dinardo, M. E.; Fiorendi, S.; Gennai, S.; Ghezzi, A.; Govoni, P.; Malberti, M.; Malvezzi, S.; Manzoni, R. A.; Menasce, D.; Moroni, L.; Paganoni, M.; Pedrini, D.; Pigazzini, S.; Ragazzi, S.; Tabarelli de Fatis, T.; Buontempo, S.; Cavallo, N.; De Nardo, G.; Di Guida, S.; Esposito, M.; Fabozzi, F.; Fienga, F.; Iorio, A. O. M.; Lanza, G.; Lista, L.; Meola, S.; Paolucci, P.; Sciacca, C.; Thyssen, F.; Azzi, P.; Bacchetta, N.; Benato, L.; Bisello, D.; Boletti, A.; Carlin, R.; Carvalho Antunes De Oliveira, A.; Checchia, P.; Dall'Osso, M.; De Castro Manzano, P.; Dorigo, T.; Dosselli, U.; Gasparini, F.; Gasparini, U.; Gozzelino, A.; Lacaprara, S.; Margoni, M.; Meneguzzo, A. T.; Pazzini, J.; Pozzobon, N.; Ronchese, P.; Simonetto, F.; Torassa, E.; Zanetti, M.; Zotto, P.; Zumerle, G.; Braghieri, A.; Magnani, A.; Montagna, P.; Ratti, S. P.; Re, V.; Riccardi, C.; Salvini, P.; Vai, I.; Vitulo, P.; Alunni Solestizi, L.; Bilei, G. M.; Ciangottini, D.; Fanò, L.; Lariccia, P.; Leonardi, R.; Mantovani, G.; Menichelli, M.; Saha, A.; Santocchia, A.; Androsov, K.; Azzurri, P.; Bagliesi, G.; Bernardini, J.; Boccali, T.; Castaldi, R.; Ciocci, M. A.; Dell'Orso, R.; Donato, S.; Fedi, G.; Giassi, A.; Grippo, M. T.; Ligabue, F.; Lomtadze, T.; Martini, L.; Messineo, A.; Palla, F.; Rizzi, A.; Savoy-Navarro, A.; Spagnolo, P.; Tenchini, R.; Tonelli, G.; Venturi, A.; Verdini, P. G.; Barone, L.; Cavallari, F.; Cipriani, M.; Del Re, D.; Diemoz, M.; Gelli, S.; Longo, E.; Margaroli, F.; Marzocchi, B.; Meridiani, P.; Organtini, G.; Paramatti, R.; Preiato, F.; Rahatlou, S.; Rovelli, C.; Santanastasio, F.; Amapane, N.; Arcidiacono, R.; Argiro, S.; Arneodo, M.; Bartosik, N.; Bellan, R.; Biino, C.; Cartiglia, N.; Cenna, F.; Costa, M.; Covarelli, R.; Degano, A.; Demaria, N.; Finco, L.; Kiani, B.; Mariotti, C.; Maselli, S.; Migliore, E.; Monaco, V.; Monteil, E.; Monteno, M.; Obertino, M. M.; Pacher, L.; Pastrone, N.; Pelliccioni, M.; Pinna Angioni, G. L.; Ravera, F.; Romero, A.; Ruspa, M.; Sacchi, R.; Shchelina, K.; Sola, V.; Solano, A.; Staiano, A.; Traczyk, P.; Belforte, S.; Casarsa, M.; Cossutti, F.; Della Ricca, G.; Zanetti, A.; Kim, D. H.; Kim, G. N.; Kim, M. S.; Lee, S.; Lee, S. W.; Oh, Y. D.; Sekmen, S.; Son, D. C.; Yang, Y. C.; Lee, A.; Kim, H.; Brochero Cifuentes, J. A.; Kim, T. J.; Cho, S.; Choi, S.; Go, Y.; Gyun, D.; Ha, S.; Hong, B.; Jo, Y.; Kim, Y.; Lee, B.; Lee, K.; Lee, K. S.; Lee, S.; Lim, J.; Park, S. K.; Roh, Y.; Almond, J.; Kim, J.; Lee, H.; Oh, S. B.; Radburn-Smith, B. C.; Seo, S. h.; Yang, U. K.; Yoo, H. D.; Yu, G. B.; Choi, M.; Kim, H.; Kim, J. H.; Lee, J. S. H.; Park, I. C.; Ryu, G.; Ryu, M. S.; Choi, Y.; Goh, J.; Hwang, C.; Lee, J.; Yu, I.; Dudenas, V.; Juodagalvis, A.; Vaitkus, J.; Ahmed, I.; Ibrahim, Z. A.; Komaragiri, J. R.; Md Ali, M. A. B.; Mohamad Idris, F.; Wan Abdullah, W. A. T.; Yusli, M. N.; Zolkapli, Z.; Castilla-Valdez, H.; De La Cruz-Burelo, E.; Heredia-De La Cruz, I.; Hernandez-Almada, A.; Lopez-Fernandez, R.; Magaña Villalba, R.; Mejia Guisao, J.; Sanchez-Hernandez, A.; Carrillo Moreno, S.; Oropeza Barrera, C.; Vazquez Valencia, F.; Carpinteyro, S.; Pedraza, I.; Salazar Ibarguen, H. A.; Uribe Estrada, C.; Morelos Pineda, A.; Krofcheck, D.; Butler, P. H.; Ahmad, A.; Ahmad, M.; Hassan, Q.; Hoorani, H. R.; Khan, W. A.; Saddique, A.; Shah, M. A.; Shoaib, M.; Waqas, M.; Bialkowska, H.; Bluj, M.; Boimska, B.; Frueboes, T.; Górski, M.; Kazana, M.; Nawrocki, K.; Romanowska-Rybinska, K.; Szleper, M.; Zalewski, P.; Bunkowski, K.; Byszuk, A.; Doroba, K.; Kalinowski, A.; Konecki, M.; Krolikowski, J.; Misiura, M.; Olszewski, M.; Walczak, M.; Bargassa, P.; Beirão Da Cruz E Silva, C.; Calpas, B.; Di Francesco, A.; Faccioli, P.; Ferreira Parracho, P. G.; Gallinaro, M.; Hollar, J.; Leonardo, N.; Lloret Iglesias, L.; Nemallapudi, M. V.; Rodrigues Antunes, J.; Seixas, J.; Toldaiev, O.; Vadruccio, D.; Varela, J.; Vischia, P.; Afanasiev, S.; Bunin, P.; Gavrilenko, M.; Golutvin, I.; Gorbunov, I.; Kamenev, A.; Karjavin, V.; Lanev, A.; Malakhov, A.; Matveev, V.; Palichik, V.; Perelygin, V.; Shmatov, S.; Shulha, S.; Skatchkov, N.; Smirnov, V.; Voytishin, N.; Zarubin, A.; Chtchipounov, L.; Golovtsov, V.; Ivanov, Y.; Kim, V.; Kuznetsova, E.; Murzin, V.; Oreshkin, V.; Sulimov, V.; Vorobyev, A.; Andreev, Yu.; Dermenev, A.; Gninenko, S.; Golubev, N.; Karneyeu, A.; Kirsanov, M.; Krasnikov, N.; Pashenkov, A.; Tlisov, D.; Toropin, A.; Epshteyn, V.; Gavrilov, V.; Lychkovskaya, N.; Popov, V.; Pozdnyakov, I.; Safronov, G.; Spiridonov, A.; Toms, M.; Vlasov, E.; Zhokin, A.; Bylinkin, A.; Markin, O.; Tarkovskii, E.; Andreev, V.; Azarkin, M.; Dremin, I.; Kirakosyan, M.; Leonidov, A.; Terkulov, A.; Baskakov, A.; Belyaev, A.; Boos, E.; Ershov, A.; Gribushin, A.; Kaminskiy, A.; Kodolova, O.; Korotkikh, V.; Lokhtin, I.; Miagkov, I.; Obraztsov, S.; Petrushanko, S.; Savrin, V.; Snigirev, A.; Vardanyan, I.; Blinov, V.; Skovpen, Y.; Shtol, D.; Azhgirey, I.; Bayshev, I.; Bitioukov, S.; Elumakhov, D.; Kachanov, V.; Kalinin, A.; Konstantinov, D.; Krychkine, V.; Petrov, V.; Ryutin, R.; Sobol, A.; Troshin, S.; Tyurin, N.; Uzunian, A.; Volkov, A.; Adzic, P.; Cirkovic, P.; Devetak, D.; Dordevic, M.; Milosevic, J.; Rekovic, V.; Alcaraz Maestre, J.; Barrio Luna, M.; Calvo, E.; Cerrada, M.; Chamizo Llatas, M.; Colino, N.; De La Cruz, B.; Delgado Peris, A.; Escalante Del Valle, A.; Fernandez Bedoya, C.; Fernández Ramos, J. P.; Flix, J.; Fouz, M. C.; Garcia-Abia, P.; Gonzalez Lopez, O.; Goy Lopez, S.; Hernandez, J. M.; Josa, M. I.; Navarro De Martino, E.; Pérez-Calero Yzquierdo, A.; Puerta Pelayo, J.; Quintario Olmeda, A.; Redondo, I.; Romero, L.; Soares, M. S.; de Trocóniz, J. F.; Missiroli, M.; Moran, D.; Cuevas, J.; Fernandez Menendez, J.; Gonzalez Caballero, I.; González Fernández, J. R.; Palencia Cortezon, E.; Sanchez Cruz, S.; Suárez Andrés, I.; Vizan Garcia, J. M.; Cabrillo, I. J.; Calderon, A.; Castiñeiras De Saa, J. R.; Curras, E.; Fernandez, M.; Garcia-Ferrero, J.; Gomez, G.; Lopez Virto, A.; Marco, J.; Martinez Rivero, C.; Matorras, F.; Piedra Gomez, J.; Rodrigo, T.; Ruiz-Jimeno, A.; Scodellaro, L.; Trevisani, N.; Vila, I.; Vilar Cortabitarte, R.; Abbaneo, D.; Auffray, E.; Auzinger, G.; Bachtis, M.; Baillon, P.; Ball, A. H.; Barney, D.; Bloch, P.; Bocci, A.; Bonato, A.; Botta, C.; Camporesi, T.; Castello, R.; Cepeda, M.; Cerminara, G.; D'Alfonso, M.; d'Enterria, D.; Dabrowski, A.; Daponte, V.; David, A.; De Gruttola, M.; De Roeck, A.; Di Marco, E.; Dobson, M.; Dorney, B.; du Pree, T.; Duggan, D.; Dünser, M.; Dupont, N.; Elliott-Peisert, A.; Fartoukh, S.; Franzoni, G.; Fulcher, J.; Funk, W.; Gigi, D.; Gill, K.; Girone, M.; Glege, F.; Gulhan, D.; Gundacker, S.; Guthoff, M.; Hammer, J.; Harris, P.; Hegeman, J.; Innocente, V.; Janot, P.; Kieseler, J.; Kirschenmann, H.; Knünz, V.; Kornmayer, A.; Kortelainen, M. J.; Kousouris, K.; Krammer, M.; Lange, C.; Lecoq, P.; Lourenço, C.; Lucchini, M. T.; Malgeri, L.; Mannelli, M.; Martelli, A.; Meijers, F.; Merlin, J. A.; Mersi, S.; Meschi, E.; Milenovic, P.; Moortgat, F.; Morovic, S.; Mulders, M.; Neugebauer, H.; Orfanelli, S.; Orsini, L.; Pape, L.; Perez, E.; Peruzzi, M.; Petrilli, A.; Petrucciani, G.; Pfeiffer, A.; Pierini, M.; Racz, A.; Reis, T.; Rolandi, G.; Rovere, M.; Ruan, M.; Sakulin, H.; Sauvan, J. B.; Schäfer, C.; Schwick, C.; Seidel, M.; Sharma, A.; Silva, P.; Sphicas, P.; Steggemann, J.; Stoye, M.; Takahashi, Y.; Tosi, M.; Treille, D.; Triossi, A.; Tsirou, A.; Veckalns, V.; Veres, G. I.; Verweij, M.; Wardle, N.; Wöhri, H. K.; Zagozdzinska, A.; Zeuner, W. D.; Bertl, W.; Deiters, K.; Erdmann, W.; Horisberger, R.; Ingram, Q.; Kaestli, H. C.; Kotlinski, D.; Langenegger, U.; Rohe, T.; Bachmair, F.; Bäni, L.; Bianchini, L.; Casal, B.; Dissertori, G.; Dittmar, M.; Donegà, M.; Grab, C.; Heidegger, C.; Hits, D.; Hoss, J.; Kasieczka, G.; Lecomte, P.; Lustermann, W.; Mangano, B.; Marionneau, M.; Martinez Ruiz del Arbol, P.; Masciovecchio, M.; Meinhard, M. T.; Meister, D.; Micheli, F.; Musella, P.; Nessi-Tedaldi, F.; Pandolfi, F.; Pata, J.; Pauss, F.; Perrin, G.; Perrozzi, L.; Quittnat, M.; Rossini, M.; Schönenberger, M.; Starodumov, A.; Tavolaro, V. R.; Theofilatos, K.; Wallny, R.; Aarrestad, T. K.; Amsler, C.; Caminada, L.; Canelli, M. F.; De Cosa, A.; Galloni, C.; Hinzmann, A.; Hreus, T.; Kilminster, B.; Ngadiuba, J.; Pinna, D.; Rauco, G.; Robmann, P.; Salerno, D.; Yang, Y.; Zucchetta, A.; Candelise, V.; Doan, T. H.; Jain, Sh.; Khurana, R.; Konyushikhin, M.; Kuo, C. M.; Lin, W.; Lu, Y. J.; Pozdnyakov, A.; Yu, S. S.; Kumar, Arun; Chang, P.; Chang, Y. H.; Chang, Y. W.; Chao, Y.; Chen, K. F.; Chen, P. H.; Dietz, C.; Fiori, F.; Hou, W.-S.; Hsiung, Y.; Liu, Y. F.; Lu, R.-S.; Miñano Moya, M.; Paganis, E.; Psallidas, A.; Tsai, J. f.; Tzeng, Y. M.; Asavapibhop, B.; Singh, G.; Srimanobhas, N.; Suwonjandee, N.; Adiguzel, A.; Cerci, S.; Damarseckin, S.; Demiroglu, Z. S.; Dozen, C.; Dumanoglu, I.; Girgis, S.; Gokbulut, G.; Guler, Y.; Hos, I.; Kangal, E. E.; Kara, O.; Kayis Topaksu, A.; Kiminsu, U.; Oglakci, M.; Onengut, G.; Ozdemir, K.; Sunar Cerci, D.; Tali, B.; Turkcapar, S.; Zorbakir, I. S.; Zorbilmez, C.; Bilin, B.; Bilmis, S.; Isildak, B.; Karapinar, G.; Yalvac, M.; Zeyrek, M.; Gülmez, E.; Kaya, M.; Kaya, O.; Yetkin, E. A.; Yetkin, T.; Cakir, A.; Cankocak, K.; Sen, S.; Grynyov, B.; Levchuk, L.; Sorokin, P.; Aggleton, R.; Ball, F.; Beck, L.; Brooke, J. J.; Burns, D.; Clement, E.; Cussans, D.; Flacher, H.; Goldstein, J.; Grimes, M.; Heath, G. P.; Heath, H. F.; Jacob, J.; Kreczko, L.; Lucas, C.; Newbold, D. M.; Paramesvaran, S.; Poll, A.; Sakuma, T.; Seif El Nasr-storey, S.; Smith, D.; Smith, V. J.; Belyaev, A.; Brew, C.; Brown, R. M.; Calligaris, L.; Cieri, D.; Cockerill, D. J. A.; Coughlan, J. A.; Harder, K.; Harper, S.; Olaiya, E.; Petyt, D.; Shepherd-Themistocleous, C. H.; Thea, A.; Tomalin, I. R.; Williams, T.; Baber, M.; Bainbridge, R.; Buchmuller, O.; Bundock, A.; Burton, D.; Casasso, S.; Citron, M.; Colling, D.; Corpe, L.; Dauncey, P.; Davies, G.; De Wit, A.; Della Negra, M.; Di Maria, R.; Dunne, P.; Elwood, A.; Futyan, D.; Haddad, Y.; Hall, G.; Iles, G.; James, T.; Lane, R.; Laner, C.; Lucas, R.; Lyons, L.; Magnan, A.-M.; Malik, S.; Mastrolorenzo, L.; Nash, J.; Nikitenko, A.; Pela, J.; Penning, B.; Pesaresi, M.; Raymond, D. M.; Richards, A.; Rose, A.; Seez, C.; Summers, S.; Tapper, A.; Uchida, K.; Vazquez Acosta, M.; Virdee, T.; Wright, J.; Zenz, S. C.; Cole, J. E.; Hobson, P. R.; Khan, A.; Kyberd, P.; Leslie, D.; Reid, I. D.; Symonds, P.; Teodorescu, L.; Turner, M.; Borzou, A.; Call, K.; Dittmann, J.; Hatakeyama, K.; Liu, H.; Pastika, N.; Cooper, S. I.; Henderson, C.; Rumerio, P.; West, C.; Arcaro, D.; Avetisyan, A.; Bose, T.; Gastler, D.; Rankin, D.; Richardson, C.; Rohlf, J.; Sulak, L.; Zou, D.; Benelli, G.; Berry, E.; Cutts, D.; Garabedian, A.; Hakala, J.; Heintz, U.; Hogan, J. M.; Jesus, O.; Kwok, K. H. M.; Laird, E.; Landsberg, G.; Mao, Z.; Narain, M.; Piperov, S.; Sagir, S.; Spencer, E.; Syarif, R.; Breedon, R.; Breto, G.; Burns, D.; Calderon De La Barca Sanchez, M.; Chauhan, S.; Chertok, M.; Conway, J.; Conway, R.; Cox, P. T.; Erbacher, R.; Flores, C.; Funk, G.; Gardner, M.; Ko, W.; Lander, R.; Mclean, C.; Mulhearn, M.; Pellett, D.; Pilot, J.; Shalhout, S.; Smith, J.; Squires, M.; Stolp, D.; Tripathi, M.; Bravo, C.; Cousins, R.; Dasgupta, A.; Everaerts, P.; Florent, A.; Hauser, J.; Ignatenko, M.; Mccoll, N.; Saltzberg, D.; Schnaible, C.; Takasugi, E.; Valuev, V.; Weber, M.; Burt, K.; Clare, R.; Ellison, J.; Gary, J. W.; Ghiasi Shirazi, S. M. A.; Hanson, G.; Heilman, J.; Jandir, P.; Kennedy, E.; Lacroix, F.; Long, O. R.; Olmedo Negrete, M.; Paneva, M. I.; Shrinivas, A.; Si, W.; Wei, H.; Wimpenny, S.; Yates, B. R.; Branson, J. G.; Cerati, G. B.; Cittolin, S.; Derdzinski, M.; Holzner, A.; Klein, D.; Krutelyov, V.; Letts, J.; Macneill, I.; Olivito, D.; Padhi, S.; Pieri, M.; Sani, M.; Sharma, V.; Simon, S.; Tadel, M.; Vartak, A.; Wasserbaech, S.; Welke, C.; Wood, J.; Würthwein, F.; Yagil, A.; Zevi Della Porta, G.; Amin, N.; Bhandari, R.; Bradmiller-Feld, J.; Campagnari, C.; Dishaw, A.; Dutta, V.; Franco Sevilla, M.; George, C.; Golf, F.; Gouskos, L.; Gran, J.; Heller, R.; Incandela, J.; Mullin, S. D.; Ovcharova, A.; Qu, H.; Richman, J.; Stuart, D.; Suarez, I.; Yoo, J.; Anderson, D.; Apresyan, A.; Bendavid, J.; Bornheim, A.; Bunn, J.; Chen, Y.; Duarte, J.; Lawhorn, J. M.; Mott, A.; Newman, H. B.; Pena, C.; Spiropulu, M.; Vlimant, J. R.; Xie, S.; Zhu, R. Y.; Andrews, M. B.; Azzolini, V.; Ferguson, T.; Paulini, M.; Russ, J.; Sun, M.; Vogel, H.; Vorobiev, I.; Weinberg, M.; Cumalat, J. P.; Ford, W. T.; Jensen, F.; Johnson, A.; Krohn, M.; Mulholland, T.; Stenson, K.; Wagner, S. R.; Alexander, J.; Chaves, J.; Chu, J.; Dittmer, S.; Mcdermott, K.; Mirman, N.; Nicolas Kaufman, G.; Patterson, J. R.; Rinkevicius, A.; Ryd, A.; Skinnari, L.; Soffi, L.; Tan, S. M.; Tao, Z.; Thom, J.; Tucker, J.; Wittich, P.; Zientek, M.; Winn, D.; Abdullin, S.; Albrow, M.; Apollinari, G.; Banerjee, S.; Bauerdick, L. A. T.; Beretvas, A.; Berryhill, J.; Bhat, P. C.; Bolla, G.; Burkett, K.; Butler, J. N.; Cheung, H. W. K.; Chlebana, F.; Cihangir, S.; Cremonesi, M.; Elvira, V. D.; Fisk, I.; Freeman, J.; Gottschalk, E.; Gray, L.; Green, D.; Grünendahl, S.; Gutsche, O.; Hare, D.; Harris, R. M.; Hasegawa, S.; Hirschauer, J.; Hu, Z.; Jayatilaka, B.; Jindariani, S.; Johnson, M.; Joshi, U.; Klima, B.; Kreis, B.; Lammel, S.; Linacre, J.; Lincoln, D.; Lipton, R.; Liu, T.; Lopes De Sá, R.; Lykken, J.; Maeshima, K.; Magini, N.; Marraffino, J. M.; Maruyama, S.; Mason, D.; McBride, P.; Merkel, P.; Mrenna, S.; Nahn, S.; Newman-Holmes, C.; O'Dell, V.; Pedro, K.; Prokofyev, O.; Rakness, G.; Ristori, L.; Sexton-Kennedy, E.; Soha, A.; Spalding, W. J.; Spiegel, L.; Stoynev, S.; Strobbe, N.; Taylor, L.; Tkaczyk, S.; Tran, N. V.; Uplegger, L.; Vaandering, E. W.; Vernieri, C.; Verzocchi, M.; Vidal, R.; Wang, M.; Weber, H. A.; Whitbeck, A.; Wu, Y.; Acosta, D.; Avery, P.; Bortignon, P.; Bourilkov, D.; Brinkerhoff, A.; Carnes, A.; Carver, M.; Curry, D.; Das, S.; Field, R. D.; Furic, I. K.; Konigsberg, J.; Korytov, A.; Low, J. F.; Ma, P.; Matchev, K.; Mei, H.; Mitselmakher, G.; Rank, D.; Shchutska, L.; Sperka, D.; Thomas, L.; Wang, J.; Wang, S.; Yelton, J.; Linn, S.; Markowitz, P.; Martinez, G.; Rodriguez, J. L.; Ackert, A.; Adams, J. R.; Adams, T.; Askew, A.; Bein, S.; Diamond, B.; Hagopian, S.; Hagopian, V.; Johnson, K. F.; Khatiwada, A.; Prosper, H.; Santra, A.; Yohay, R.; Baarmand, M. M.; Bhopatkar, V.; Colafranceschi, S.; Hohlmann, M.; Noonan, D.; Roy, T.; Yumiceva, F.; Adams, M. R.; Apanasevich, L.; Berry, D.; Betts, R. R.; Bucinskaite, I.; Cavanaugh, R.; Evdokimov, O.; Gauthier, L.; Gerber, C. E.; Hofman, D. J.; Jung, K.; Kurt, P.; O'Brien, C.; Sandoval Gonzalez, I. D.; Turner, P.; Varelas, N.; Wang, H.; Wu, Z.; Zakaria, M.; Zhang, J.; Bilki, B.; Clarida, W.; Dilsiz, K.; Durgut, S.; Gandrajula, R. P.; Haytmyradov, M.; Khristenko, V.; Merlo, J.-P.; Mermerkaya, H.; Mestvirishvili, A.; Moeller, A.; Nachtman, J.; Ogul, H.; Onel, Y.; Ozok, F.; Penzo, A.; Snyder, C.; Tiras, E.; Wetzel, J.; Yi, K.; Anderson, I.; Blumenfeld, B.; Cocoros, A.; Eminizer, N.; Fehling, D.; Feng, L.; Gritsan, A. V.; Maksimovic, P.; Martin, C.; Osherson, M.; Roskes, J.; Sarica, U.; Swartz, M.; Xiao, M.; Xin, Y.; You, C.; Al-bataineh, A.; Baringer, P.; Bean, A.; Boren, S.; Bowen, J.; Bruner, C.; Castle, J.; Forthomme, L.; Kenny, R. P.; Khalil, S.; Kropivnitskaya, A.; Majumder, D.; Mcbrayer, W.; Murray, M.; Sanders, S.; Stringer, R.; Tapia Takaki, J. D.; Wang, Q.; Ivanov, A.; Kaadze, K.; Maravin, Y.; Mohammadi, A.; Saini, L. K.; Skhirtladze, N.; Toda, S.; Rebassoo, F.; Wright, D.; Anelli, C.; Baden, A.; Baron, O.; Belloni, A.; Calvert, B.; Eno, S. C.; Ferraioli, C.; Gomez, J. A.; Hadley, N. J.; Jabeen, S.; Kellogg, R. G.; Kolberg, T.; Kunkle, J.; Lu, Y.; Mignerey, A. C.; Ricci-Tam, F.; Shin, Y. H.; Skuja, A.; Tonjes, M. B.; Tonwar, S. C.; Abercrombie, D.; Allen, B.; Apyan, A.; Barbieri, R.; Baty, A.; Bi, R.; Bierwagen, K.; Brandt, S.; Busza, W.; Cali, I. A.; Demiragli, Z.; Di Matteo, L.; Gomez Ceballos, G.; Goncharov, M.; Hsu, D.; Iiyama, Y.; Innocenti, G. M.; Klute, M.; Kovalskyi, D.; Krajczar, K.; Lai, Y. S.; Lee, Y.-J.; Levin, A.; Luckey, P. D.; Maier, B.; Marini, A. C.; Mcginn, C.; Mironov, C.; Narayanan, S.; Niu, X.; Paus, C.; Roland, C.; Roland, G.; Salfeld-Nebgen, J.; Stephans, G. S. F.; Sumorok, K.; Tatar, K.; Varma, M.; Velicanu, D.; Veverka, J.; Wang, J.; Wang, T. W.; Wyslouch, B.; Yang, M.; Zhukova, V.; Benvenuti, A. C.; Chatterjee, R. M.; Evans, A.; Finkel, A.; Gude, A.; Hansen, P.; Kalafut, S.; Kao, S. C.; Kubota, Y.; Lesko, Z.; Mans, J.; Nourbakhsh, S.; Ruckstuhl, N.; Rusack, R.; Tambe, N.; Turkewitz, J.; Acosta, J. G.; Oliveros, S.; Avdeeva, E.; Bartek, R.; Bloom, K.; Claes, D. R.; Dominguez, A.; Fangmeier, C.; Gonzalez Suarez, R.; Kamalieddin, R.; Kravchenko, I.; Malta Rodrigues, A.; Meier, F.; Monroy, J.; Siado, J. E.; Snow, G. R.; Stieger, B.; Alyari, M.; Dolen, J.; George, J.; Godshalk, A.; Harrington, C.; Iashvili, I.; Kaisen, J.; Kharchilava, A.; Kumar, A.; Parker, A.; Rappoccio, S.; Roozbahani, B.; Alverson, G.; Barberis, E.; Hortiangtham, A.; Massironi, A.; Morse, D. M.; Nash, D.; Orimoto, T.; Teixeira De Lima, R.; Trocino, D.; Wang, R.-J.; Wood, D.; Bhattacharya, S.; Charaf, O.; Hahn, K. A.; Kubik, A.; Kumar, A.; Mucia, N.; Odell, N.; Pollack, B.; Schmitt, M. H.; Sung, K.; Trovato, M.; Velasco, M.; Dev, N.; Hildreth, M.; Hurtado Anampa, K.; Jessop, C.; Karmgard, D. J.; Kellams, N.; Lannon, K.; Marinelli, N.; Meng, F.; Mueller, C.; Musienko, Y.; Planer, M.; Reinsvold, A.; Ruchti, R.; Smith, G.; Taroni, S.; Wayne, M.; Wolf, M.; Woodard, A.; Alimena, J.; Antonelli, L.; Bylsma, B.; Durkin, L. S.; Flowers, S.; Francis, B.; Hart, A.; Hill, C.; Hughes, R.; Ji, W.; Liu, B.; Luo, W.; Puigh, D.; Winer, B. L.; Wulsin, H. W.; Cooperstein, S.; Driga, O.; Elmer, P.; Hardenbrook, J.; Hebda, P.; Lange, D.; Luo, J.; Marlow, D.; Mc Donald, J.; Medvedeva, T.; Mei, K.; Mooney, M.; Olsen, J.; Palmer, C.; Piroué, P.; Stickland, D.; Svyatkovskiy, A.; Tully, C.; Zuranski, A.; Malik, S.; Barker, A.; Barnes, V. E.; Folgueras, S.; Gutay, L.; Jha, M. K.; Jones, M.; Jung, A. W.; Miller, D. H.; Neumeister, N.; Schulte, J. F.; Shi, X.; Sun, J.; Wang, F.; Xie, W.; Parashar, N.; Stupak, J.; Adair, A.; Akgun, B.; Chen, Z.; Ecklund, K. M.; Geurts, F. J. M.; Guilbaud, M.; Li, W.; Michlin, B.; Northup, M.; Padley, B. P.; Redjimi, R.; Roberts, J.; Rorie, J.; Tu, Z.; Zabel, J.; Betchart, B.; Bodek, A.; de Barbaro, P.; Demina, R.; Duh, Y. t.; Ferbel, T.; Galanti, M.; Garcia-Bellido, A.; Han, J.; Hindrichs, O.; Khukhunaishvili, A.; Lo, K. H.; Tan, P.; Verzetti, M.; Agapitos, A.; Chou, J. P.; Contreras-Campana, E.; Gershtein, Y.; Gómez Espinosa, T. A.; Halkiadakis, E.; Heindl, M.; Hidas, D.; Hughes, E.; Kaplan, S.; Kunnawalkam Elayavalli, R.; Kyriacou, S.; Lath, A.; Nash, K.; Saka, H.; Salur, S.; Schnetzer, S.; Sheffield, D.; Somalwar, S.; Stone, R.; Thomas, S.; Thomassen, P.; Walker, M.; Delannoy, A. G.; Foerster, M.; Heideman, J.; Riley, G.; Rose, K.; Spanier, S.; Thapa, K.; Bouhali, O.; Celik, A.; Dalchenko, M.; De Mattia, M.; Delgado, A.; Dildick, S.; Eusebi, R.; Gilmore, J.; Huang, T.; Juska, E.; Kamon, T.; Mueller, R.; Pakhotin, Y.; Patel, R.; Perloff, A.; Perniè, L.; Rathjens, D.; Rose, A.; Safonov, A.; Tatarinov, A.; Ulmer, K. A.; Akchurin, N.; Cowden, C.; Damgov, J.; De Guio, F.; Dragoiu, C.; Dudero, P. R.; Faulkner, J.; Gurpinar, E.; Kunori, S.; Lamichhane, K.; Lee, S. W.; Libeiro, T.; Peltola, T.; Undleeb, S.; Volobouev, I.; Wang, Z.; Greene, S.; Gurrola, A.; Janjam, R.; Johns, W.; Maguire, C.; Melo, A.; Ni, H.; Sheldon, P.; Tuo, S.; Velkovska, J.; Xu, Q.; Arenton, M. W.; Barria, P.; Cox, B.; Goodell, J.; Hirosky, R.; Ledovskoy, A.; Li, H.; Neu, C.; Sinthuprasith, T.; Sun, X.; Wang, Y.; Wolfe, E.; Xia, F.; Clarke, C.; Harr, R.; Karchin, P. E.; Sturdy, J.; Belknap, D. A.; Buchanan, J.; Caillol, C.; Dasu, S.; Dodd, L.; Duric, S.; Gomber, B.; Grothe, M.; Herndon, M.; Hervé, A.; Klabbers, P.; Lanaro, A.; Levine, A.; Long, K.; Loveless, R.; Ojalvo, I.; Perry, T.; Pierro, G. A.; Polese, G.; Ruggles, T.; Savin, A.; Smith, N.; Smith, W. H.; Taylor, D.; Woods, N.; CMS Collaboration

    2017-03-01

    Charge-dependent azimuthal particle correlations with respect to the second-order event plane in p -Pb and PbPb collisions at a nucleon-nucleon center-of-mass energy of 5.02 TeV have been studied with the CMS experiment at the LHC. The measurement is performed with a three-particle correlation technique, using two particles with the same or opposite charge within the pseudorapidity range |η | <2.4 , and a third particle measured in the hadron forward calorimeters (4.4 <|η | <5 ). The observed differences between the same and opposite sign correlations, as functions of multiplicity and η gap between the two charged particles, are of similar magnitude in p -Pb and PbPb collisions at the same multiplicities. These results pose a challenge for the interpretation of charge-dependent azimuthal correlations in heavy ion collisions in terms of the chiral magnetic effect.

  18. Chiral plasmons without magnetic field

    PubMed Central

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

    2016-01-01

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

  19. Chiral plasmons without magnetic field

    NASA Astrophysics Data System (ADS)

    Song, Justin C. W.

    2016-04-01

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

  20. Dimer crystallization of chiral proteoids.

    PubMed

    Wang, Po-Yuan; Mason, Thomas G

    2017-03-08

    Proteins can self-assemble into a variety of exquisitely organized structures through hierarchical reaction pathways. To examine how different core shapes of proteins and entropy combine to influence self-assembly, we create systems of lithographically fabricated proteomimetic colloids, or 'proteoids', and explore how Brownian monolayers of mobile proteoids, which have hard interactions, self-assemble as they are slowly crowded. Remarkably, chiral C-shaped proteoids having circular heads on only one side form enantiopure lock-and-key chiral dimers; these dimers have corrugated, shape-complementary perimeters, so they, in turn, form lock-and-key arrangements into chiral dimer crystals. Time-lapse video microscopy reveals the expulsion of monomers from the growing dimer crystals through tautomerization translocation reactions which expedite the crystallization kinetics. By lithographically mutating proteoids, we also tune the types and structures of the resulting dimer crystals. Thus, rational design of sub-particle features in hard-core colloidal shapes can be used to sterically select desired self-assembly pathways without introducing any site-specific attractions, thereby generating a striking degree of hierarchical self-ordering, reminiscent of protein crystallization.

  1. Chiral methyl-branched pheromones.

    PubMed

    Ando, Tetsu; Yamakawa, Rei

    2015-07-01

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

  2. Coupled wire construction of chiral spin liquids

    NASA Astrophysics Data System (ADS)

    Thomale, Ronny; Meng, Tobias; Neupert, Titus; Greiter, Martin

    We develop a coupled wire construction of chiral spin liquids. The starting point are individual wires of electrons in the Mott regime that are subject to a Zeeman field and Rashba spin-orbit coupling. Suitable spin-flip couplings between the wires yield an Abelian chiral spin liquid state which supports spinon excitations above a bulk gap, and chiral edge states. The approach generalizes to non-Abelian chiral spin liquids at level k with parafermionic edge states. RT is supported by the European Research Council through ERC-StG-336012-TOPOLECTRICS. MG and RT are supported by DFG-SFB 1170.

  3. Chiral selection on inorganic crystalline surfaces

    NASA Technical Reports Server (NTRS)

    Hazen, Robert M.; Sholl, David S.

    2003-01-01

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

  4. Chiral selection on inorganic crystalline surfaces

    NASA Technical Reports Server (NTRS)

    Hazen, Robert M.; Sholl, David S.

    2003-01-01

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

  5. Lateral chirality-sorting optical forces

    PubMed Central

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

    2015-01-01

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

  6. Asymmetric catalysis with chiral ferrocene ligands.

    PubMed

    Dai, Li-Xin; Tu, Tao; You, Shu-Li; Deng, Wei-Ping; Hou, Xue-Long

    2003-09-01

    Chiral ferrocene ligands have been widely used in asymmetric catalysis. The advantages of using ferrocene as a scaffold for chiral ligands are described, particularly those regarding planar chirality, rigid bulkiness, and ease of derivatization. The role of planar chirality in 1,2- and 1,1'-disubstituted ferrocene systems is discussed. By using a bulky ferrocene fragment, novel ferrocene ligands were designed, and high enantioselectivity and regioselectivity were achieved in the allylic substitution reaction of monosubstituted allyl substrates. Using the tunable electronic properties of a diphosphine-oxazoline ferrocenyl ligand, the regioselectivity of the intermolecular asymmetric Heck reaction was also examined.

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

    PubMed

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

    2014-07-30

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    PubMed

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

    2016-03-07

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

  10. Electron-Hole Asymmetric Chiral Breakdown of Reentrant Quantum Hall States

    NASA Astrophysics Data System (ADS)

    Rossokhaty, A. V.; Baum, Y.; Folk, J. A.; Watson, J. D.; Gardner, G. C.; Manfra, M. J.

    2016-10-01

    Reentrant integer quantum Hall (RIQH) states are believed to be correlated electron solid phases, although their microscopic description remains unclear. As bias current increases, longitudinal and Hall resistivities measured for these states exhibit multiple sharp breakdown transitions, a signature unique to RIQH states. A comparison of RIQH breakdown characteristics at multiple voltage probes indicates that these signatures can be ascribed to a phase boundary between broken-down and unbroken regions, spreading chirally from source and drain contacts as a function of bias current and passing voltage probes one by one. The chiral sense of the spreading is not set by the chirality of the edge state itself, instead depending on electron- or holelike character of the RIQH state.

  11. Chiral molecules in the ISM: the best candidates

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  12. Spontaneous emission of a chiral molecule near a cluster of two chiral spherical particles

    SciTech Connect

    Guzatov, D V; Klimov, V V

    2015-03-31

    We have obtained and investigated analytical expressions for the radiative spontaneous decay rate of a chiral (optically active) molecule located near a cluster of two identical chiral (biisotropic) spherical particles. It is found that the composition of the particles, their location and size have a significant effect on the spontaneous emission of chiral molecules. In particular, it is shown that in the case of nanoparticles of chiral metamaterials, the radiative spontaneous decay rate for the 'right-' and 'left-handed' enantiomers of chiral molecules located in the gap of the cluster are significantly different. (metamaterials)

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

    PubMed

    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.

  14. A Robust, Recyclable Resin for Decagram Scale Resolution of (±)-Mefloquine and Other Chiral N-Heterocycles.

    PubMed

    Kreituss, Imants; Chen, Kuang-Yen; Eitel, Simon H; Adam, Jean-Michel; Wuitschik, Georg; Fettes, Alec; Bode, Jeffrey W

    2016-01-22

    Decagram quantities of enantiopure (+)-mefloquine have been produced via kinetic resolution of racemic mefloquine using a ROMP-gel supported chiral acyl hydroxamic acid resolving agent. The requisite monomer was prepared in a few synthetic steps without chromatography and polymerization was safely performed on a >30 gram scale under ambient conditions. The reagent was readily regenerated and reused multiple times for the resolution of 150 grams of (±)-mefloquine and other chiral N-heterocylces.

  15. Chiral Process Monitoring Using Fourier Transform Microwave Spectroscopy

    NASA Astrophysics Data System (ADS)

    Neill, Justin L.; Muckle, Matt; Pate, Brooks

    2017-06-01

    We present the application of Fourier transform microwave (FTMW) spectroscopy in monitoring the chiral purity of components in a reaction mixture. This is of particular interest due to the increasing use of continuous pharmaceutical manufacturing processes, in which a number of attributes (including the chiral purity of the product) can change on short time scales. Therefore, new techniques that can accomplish this measurement rapidly are desired. The excellent specificity of FTMW spectroscopy, coupled with newly developed techniques for measuring enantiomeric excess in a mixture, have motivated this work. In collaboration with B. Frank Gupton (Virginia Commonwealth University), we are testing this application first with the synthesis of artemisinin. Artemisinin, a common drug for malaria treatment, is of high global health interest and subject to supply shortages, and therefore a strong candidate for continuous manufacturing. It also has moderately high molecular weight (282 amu) and seven chiral centers, making it a good candidate to test the capabilities of FTMW spectroscopy. Using a miniature cavity-enhanced FTMW spectrometer design, we aim to demonstrate selective component quantification in the reaction mixture. Future work that will be needed to fully realize this application will be discussed. R.D. Suenram, J.U. Grabow, A.Zuban, and I.Leonov, Rev. Sci. Instrum. 70, 2127 (1999).

  16. Chiral exciton in the topological insulator Bi2Se3

    NASA Astrophysics Data System (ADS)

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

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

  17. Chiral magnetic wave in an expanding QCD fluid

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    PubMed Central

    Torii, Masahiro; Kato, Kohsuke; Uraguchi, Daisuke

    2016-01-01

    Summary 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. PMID:27829916

  20. Chiral Inhibition of Rivaroxaban Derivatives Towards UDP-Glucuronosyltransferase (UGT) Isoforms.

    PubMed

    Yao, Zhuhua; Liu, Yong-Zhe; Ma, Ai-Lun; Wang, Shu-Fen; Lu, Dan; Hu, Cui-Min; Zhang, Yan-Yan; Wang, Haina; Hu, Lingyun; Deng, Jun; Yang, Kun; Fang, Zhong-Ze

    2015-12-01

    Rivaroxaban is an oral direct factor Xa (FXa) inhibitor clinically used to prevent and treat thromboembolic disorders. Drug-drug interaction (DDI) exist for rivaroxaban and the inhibitors of CYP3A4/5. This study aims to investigate the inhibition of rivaroxaban and its derivatives with a chiral center towards UDP-glucuronosyltransferases (UGTs). Chemical synthesis was performed to obtain rivaroxaban derivatives with different chiral centers. UGTs supersomes-catalyzed 4-methylumbelliferone (4-MU) glucuronidation was employed to evaluate the inhibition potential towards various UGT isoforms. A significant influence of rivaroxaban derivatives towards UGT1A3 was observed. Chiral centers produce different effects towards the effect of four pairs of rivaroxaban derivatives towards UGT1A3 activity, with stronger inhibition potential of S1 than R1, but stronger inhibition capability of R2, R3, R4 than S2, S3, and S4. Competitive inhibition of R3 and R4 towards UGT1A3 was demonstrated by Dixon and Lineweaver-Burk plots. In conclusion, the significant influence of rivaroxaban derivatives towards UGT1A3's activity was demonstrated in the present study. The chirality centers highly affected the inhibition behavior of rivaroxaban derivatives towards UGT1A3.

  1. Synthesis, structure, and properties of a series of chiral tweezer-diamine complexes consisting of an achiral zinc(II) bisporphyrin host and chiral diamine guest: induction and rationalization of supramolecular chirality.

    PubMed

    Brahma, Sanfaori; Ikbal, Sk Asif; Rath, Sankar Prasad

    2014-01-06

    We report here the synthesis, structure, and spectroscopic properties of a series of supramolecular chiral 1:1 tweezer-diamine complexes consisting of an achiral Zn(II) bisporphyrin (Zn2DPO) host and five different chiral diamine guests, namely, (R)-diaminopropane (DAP), (1S,2S)-diaminocyclohexane (CHDA), (S)-phenylpropane diamine (PPDA), (S)-phenyl ethylenediamine (PEDA), and (1R,2R)-diphenylethylene diamine (DPEA). The solid-state structures are preserved in solution, as reflected in their (1)H NMR spectra, which also revealed the remarkably large upfield shifts of the NH2 guest protons with the order Zn2DPO·DAP > Zn2DPO·CHDA > Zn2DPO·PPDA> Zn2DPO·PEDA ≫ Zn2DPO·DPEA, which happens to be the order of binding constants of the respective diamines with Zn2DPO. As the bulk of the substituent at the chiral center of the guest ligand increases, the Zn-Nax distance of the tweezer-diamine complex also increases, which eventually lowers the binding of the guest ligand toward the host. Also, the angle between the two porphyrin rings gradually increases with increasing bulk of the guest in order to accommodate the guest within the bisporphyrin cavity with minimal steric clash. The notably high amplitude bisignate CD signal response by Zn2DPO·DAP, Zn2DPO·CHDA, and Zn2DPO·PPDA can be ascribed to the complex's high stability and the formation of a unidirectional screw as observed in the X-ray structures of the complexes. A relatively lower value of CD amplitude shown by Zn2DPO·PEDA is due to the lower stability of the complex. The projection of the diamine binding sites of the chiral guest would make the two porphyrin macrocycles oriented in either a clockwise or anticlockwise direction in order to minimize host-guest steric clash. In sharp contrast, Zn2DPO·DPEA shows a very low amplitude bisignate CD signal due to the presence of both left- (dictated by the pre-existing chirality of (1R,2R)-DPEA) and right-handed screws (dictated by the steric differentiation at

  2. New generation planar chiral metamaterials with small and constant chirality over a certain frequency band

    NASA Astrophysics Data System (ADS)

    Dincer, Furkan; Karaaslan, Muharrrem; Akgol, Oguzhan; Unal, Emin; Demirel, Ekrem; Sabah, Cumali

    2015-01-01

    Chiral metamaterial (MTM) researchers generally concentrate and aim to obtain large chirality with optical activity in certain frequencies. However, new generation planar chiral MTM which have small and constant/flat chirality over a certain frequency band have not queried by this time in literature. In fact, this area is mostly ignored by researchers. This study, first one according to best of our knowledge in the literature, is investigating the small and constant/fixed chirality and focuses on the new generation planar chiral MTM based on circular split ring resonators (SRRs), in details. It can be seen from the results that the proposed model can provide small and constant/flat chirality over a certain frequency band and thus it can be used to design myriad novel devices such as polarization rotators, and electromagnetic transmission and antireflection filters for several frequency regions.

  3. Large-Nc gauge theory and chiral random matrix theory

    NASA Astrophysics Data System (ADS)

    Hanada, Masanori; Lee, Jong-Wan; Yamada, Norikazu

    2013-07-01

    We discuss how the 1/Nc expansion and the chiral random matrix theory (χRMT) can be used in the study of large-Nc gauge theories. We first clarify the parameter region in which each of these two approaches is valid. While the fermion mass m is fixed in the standard large-Nc arguments (’t Hooft large-Nc limit), m must be scaled appropriately with a certain negative power of Nc in order for the gauge theories to be described by the χRMT. Then, although these two limits are not compatible in general, we show that the breakdown of chiral symmetry can be detected by combining the large-Nc argument and the χRMT with some care. As a concrete example, we numerically study the four-dimensional SU(Nc) gauge theory with Nf=2 heavy adjoint fermions, introduced as the center symmetry preserver keeping the infrared physics intact, on a 24 lattice. By looking at the low-lying eigenvalues of the overlap-Dirac operator for a massless probe fermion in the adjoint representation, we find that the chiral symmetry is indeed broken with the expected breaking pattern. This result reproduces a well-known fact that the chiral symmetry is spontaneously broken in the pure SU(Nc) gauge theory in the large-Nc and the large-volume limit and therefore supports the validity of the combined approach. We also provide an interpretation of the gap and unexpected Nc scaling, both of which are observed in the Dirac spectrum.

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

    PubMed

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

    2016-03-22

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

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

    PubMed

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

    2015-01-01

    Chiral molecular crystals built up by chiral molecules without inversion centers have attracted much interest owing to their versatile functionalities related to optical, magnetic, and electrical properties. However, there is a difficulty in chiral crystal growth due to the lack of symmetry. Therefore, we made the molecular design to introduce intermolecular hydrogen bonds in chiral crystals. Racemic and enantiopure bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) derivatives possessing hydroxymethyl groups as the source of hydrogen bonds were designed. The novel racemic trans-vic-(hydroxymethyl)(methyl)-BEDT-TTF 1, and racemic and enantiopure trans-vic-bis(hydroxymethyl)-BEDT-TTF 2 were synthesized. Moreover, the preparations, crystal structure analyses, and electrical resistivity measurements of the novel achiral charge transfer salt θ(21)-[(S,S)-2]3[(R,R)-2]3(ClO4)2 and the chiral salt α'-[(R,R)-2]ClO4(H2O) were carried out. In the former θ(21)-[(S,S)-2]3[(R,R)-2]3(ClO4)2, there are two sets of three crystallographically independent donor molecules [(S,S)-2]2[(R,R)-2] in a unit cell, where the two sets are related by an inversion center. The latter α'-[(R,R)-2]ClO4(H2O) is the chiral salt with included solvent H2O, which is not isostructural with the reported chiral salt α'-[(S,S)-2]ClO4 without H2O, but has a similar donor arrangement. According to the molecular design by introduction of hydroxy groups and a ClO4 (-) anion, many intermediate-strength intermolecular hydrogen bonds (2.6-3.0 Å) were observed in these crystals between electron donor molecules, anions, and included H2O solvent, which improve the crystallinity and facilitate the extraction of physical properties. Both salts are semiconductors with relatively low resistivities at room temperature and activation energies of 1.2 ohm cm with E a = 86 meV for θ(21)-[(S,S)-2]3[(R,R)-2]3(ClO4)2 and 0.6 ohm cm with E a = 140 meV for α'-[(R,R)-2]2ClO4(H2O), respectively. The variety of donor

  6. Collective Hamiltonian for Chiral and Wobbling Modes

    NASA Astrophysics Data System (ADS)

    Chen, Q. B.; Zhang, S. Q.; Zhao, P. W.; Jolos, R. V.; Meng, J.

    The recent progresses of the collective Hamiltonian for chiral and wobbling modes are briefly introduced. The collective Hamiltonian is constructed from the collective potential and mass parameter obtained in the tilted axis cranking approach. The collective Hamiltonian can reproduce the exact solutions by the particle rotor model very well for both chiral and wobbling modes.

  7. Chiral magnetic effect in condensed matter systems

    NASA Astrophysics Data System (ADS)

    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].

  8. PROBING THE ENANTIOSELECTIVITY OF CHIRAL PESTICIDES

    EPA Science Inventory

    Up to 25% of all pesticides are chiral; that is, they exist as two mirror image isomers called enantiomers. It is known that enantiomers usually differ in their biological properties through their differential interaction with enzymes or other naturally occurring chiral molecule...

  9. Immobilization of enzyme on chiral polyelectrolyte surface.

    PubMed

    Ding, Chao; Sun, Hanjun; Ren, Jinsong; Qu, Xiaogang

    2017-02-01

    Chiral D- and L-N-acryloyl aspartic acid (NAsp) polyelectrolyte (PE) surfaces with similar chemical compositions and physical properties but opposite chirality are designed for enzyme immobilization. Enzymes immobilized onto the chiral PE surfaces present high chiral preference, namely L-NAsp PE surface can keep most of the catalytic activity of the immobilized enzymes, however, for enzymes immobilized on D-NAsp PE surface a large decrease in catalytic activity occurred which was 11 times lower compared with L-NAsp PE surface. This phenomenon of chiral effect on enzymes immobilization can be explained by attenuated total reflectance (ATR) and circular dichroism (CD) results. The results exhibited that L-NAsp PE surface could preserve most of the secondary structures of immobilized enzymes while on D-NAsp PE surface with a large conformation alteration. These chiral surface induced differences after enzyme immobilization can be further used for logic operation. These results imply a novel strategy for the design of new enzymes immobilization materials based on the chiral effect and expand the applications of enzymes in biochips, chemical transformations and chiral biodevices.

  10. Chiral gravity, log gravity, and extremal CFT

    SciTech Connect

    Maloney, Alexander; Song Wei; Strominger, Andrew

    2010-03-15

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

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

    PubMed

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

    2015-10-01

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

  12. Chiral THz metamaterial with tunable optical activity

    SciTech Connect

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

    2010-01-01

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

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

    PubMed Central

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

    2016-01-01

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

  14. Poor outcomes for IgD multiple myeloma patients following high-dose melphalan and autologous stem cell transplantation: a single center experience.

    PubMed

    Chong, Yong Pil; Kim, Shin; Ko, Ok Bae; Koo, Ja Eun; Lee, Danbi; Park, Sang Hyoung; Park, Soo Jung; Lee, Daeho; Kim, Sang We; Suh, Cheolwon

    2008-10-01

    Immunoglobulin (Ig) D multiple myeloma (MM) accounts for 2% of all MM cases and has been reported to be associated with poor prognosis compared with other MM subtypes. The aim of the present study was to compare the effects of high-dose melphalan treatment and autologous stem cell transplantation (ASCT) on the survival of patients with IgD MM and patients with other MM subtypes. Between November 1998 and January 2005, a total of 77 patients with MM who underwent ASCT at the Asan Medical Center were enrolled in this study. High-dose melphalan (total 200 mg/m2) was used as high-dose chemotherapy. The study population was divided into two groups based on MM subtype: those with IgD MM; and those with other MM subtypes. A total of 8 patients with IgD MM were identified, accounting for about 10% of the study population. Thirty-six patients (47%) had IgG MM, 17 patients (22%) had IgA MM, and 16 patients (20%) had free light-chain MM. The two groups were similar in baseline characteristics. The median follow-up was 17 months and the median overall survival (OS) was 39 months. In the IgD MM group, median eventfree survival (EFS) and OS were 6.9 and 12 months, respectively. In the patients with other MM subtypes, median EFS and OS were 11.5 and 55.5 months (p=0.01, p<0.01), respectively. Multivariate analysis of all patients identified IgD subtype (p=0.002) and Southwest Oncology Group (SWOG) stage 2 or greater at the time of ASCT (p=0.01) as adverse prognostic factors for survival. In this small study at a single center in Korea, patients with IgD MM had poorer outcomes after ASCT than did patients with other MM subtypes.

  15. Chirally-sensitive electron-molecule interactions

    NASA Astrophysics Data System (ADS)

    Dreiling, J. M.; Gay, T. J.

    2015-09-01

    All molecular forms of life have chemically-specific handedness. However, the origin of these asymmetries is not understood. A possible explanation was suggested by Vester and Ulbricht immediately following the discovery of parity violation in 1957: chiral beta radiation in cosmic rays may have preferentially destroyed one enantiomeric form of various biological precursors. In the experiments reported here, we observed chiral specificity in two electron- molecule interactions: quasi-elastic scattering and dissociative electron attachment. Using low- energy longitudinally spin-polarized (chiral) electrons as substitutes for beta rays, we found that chiral bromocamphor molecules exhibited both a transmission and dissociative electron attachment rate that depended on their handedness for a given direction of incident electron spin. Consequently, these results, especially those with dissociative electron attachment, connect the universal chiral asymmetry of the weak force with a molecular breakup process, thereby demonstrating the viability of the Vester-Ulbricht hypothesis.

  16. Enantioselective environmental toxicology of chiral pesticides.

    PubMed

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

    2015-03-16

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

  17. Radiation pressure of active dispersive chiral slabs.

    PubMed

    Wang, Maoyan; Li, Hailong; Gao, Dongliang; Gao, Lei; Xu, Jun; Qiu, Cheng-Wei

    2015-06-29

    We report a mechanism to obtain optical pulling or pushing forces exerted on the active dispersive chiral media. Electromagnetic wave equations for the pure chiral media using constitutive relations containing dispersive Drude models are numerically solved by means of Auxiliary Differential Equation Finite Difference Time Domain (ADE-FDTD) method. This method allows us to access the time averaged Lorentz force densities exerted on the magnetoelectric coupling chiral slabs via the derivation of bound electric and magnetic charge densities, as well as bound electric and magnetic current densities. Due to the continuously coupled cross-polarized electromagnetic waves, we find that the pressure gradient force is engendered on the active chiral slabs under a plane wave incidence. By changing the material parameters of the slabs, the total radiation pressure exerted on a single slab can be directed either along the propagation direction or in the opposite direction. This finding provides a promising avenue for detecting the chirality of materials by optical forces.

  18. A liquid crystalline chirality balance for vapours

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  19. A liquid crystalline chirality balance for vapours.

    PubMed

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

    2014-04-30

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

  20. Cosmic chirality both true and false.

    PubMed

    Barron, Laurence D

    2012-12-01

    The discrete symmetries of parity P, time reversal T, and charge conjugation C may be used to characterize the properties of chiral systems. It is well known that parity violation infiltrates into ordinary matter via an interaction between the nucleons and electrons, mediated by the Z(0) particle, that lifts the degeneracy of the mirror-image enantiomers of a chiral molecule. Being odd under P but even under T, this P-violating interaction exhibits true chirality and so may induce absolute enantioselection under all circumstances. It has been suggested that CP violation may also infiltrate into ordinary matter via a P-odd, T-odd interaction mediated by the (as yet undetected) axion. This CP-violating interaction exhibits false chirality and so may induce absolute enantioselection in processes far from equilibrium. Both true and false cosmic chirality should be considered together as possible sources of homochirality in the molecules of life.

  1. Chiral organic compounds in induced cholesteric mesophases

    NASA Astrophysics Data System (ADS)

    Kutulya, Lidiya A.

    1998-09-01

    The results of original investigations being in touch with regularities of the chiral components molecular structure effect on the properties of induced cholesteric mesophases were generalized. It was shown that presence of an elongate (pi) -electron fragment in the chiral dopants molecules is general requirement of high helical twisting power ((beta) ). (beta) values and the character of temperature dependences of induced helical pitch are significantly effected by molecular shape of chiral dopants. Variation of the extent of (pi) -electron fragment anisometry, and also incorporation and variation of terminal alkyl or alkoxyl groups at chiral dopants molecules are useful approach to a regulation of temperature dependences of induced cholesteric helix pitch. Influence on thermal stability of mesophases of different types of chiral dopants was analyzed.

  2. Large Chiroptical Effects in Planar Chiral Metamaterials

    NASA Astrophysics Data System (ADS)

    Ye, Weimin; Yuan, Xiaodong; Guo, Chucai; Zhang, Jianfa; Yang, Biao; Zhang, Shuang

    2017-05-01

    Chiroptical effects characterized by different optical responses for left- (LCP) and right-handed circularly polarized light (RCP) are powerful and valuable tools in optics with wide applications in polarization-resolved imaging and sensing. Previously observed strong chiroptical effects are limited to metamaterials with complex three-dimensional chiral structures at the subwavelength scale. Although asymmetrical transmission of LCP and RCP have been investigated in planar chiral metasurfaces, the observed weak chiroptical effects result from anisotropic Ohmic dissipation of the metal constituents. Here, we demonstrate by theory and proof-of-concept experiments that a large difference in transmittances of LCP and RCP can be attained in a single-layer planar chiral metamaterial with a subwavelength thickness. Without violating the reciprocity and mirror symmetry, the strong chiroptical effect, independent of dielectric loss, arises from a mechanism of multimode interference. The described effect may lead to a gateway towards chiral manipulations of light and chiral optical devices.

  3. Chiral magnetic effect in condensed matter systems

    DOE PAGES

    Li, Qiang; Kharzeev, Dmitri E.

    2016-12-01

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

  4. Microwave chirality discrimination in enantiomeric liquids

    NASA Astrophysics Data System (ADS)

    Hollander, E.; Kamenetskii, E. O.; Shavit, R.

    2017-07-01

    Chirality discrimination is of fundamental interest in biology, chemistry, and metamaterial studies. In optics, near-field plasmon-resonance spectroscopy with superchiral probing fields is effectively applicable for analyses of large biomolecules with chiral properties. We show possibility for microwave near-field chirality discrimination analysis based on magnon-resonance spectroscopy. Newly developed capabilities in microwave sensing using magnetoelectric (ME) probing fields originated from multiresonance magnetic-dipolar-mode oscillations in quasi-2D yttrium-iron-garnet disks provide potential for unprecedented measurements of chemical and biological objects. We report on microwave near-field chirality discrimination for aqueous D- and L-glucose solutions. The shown ME-field sensing is addressed to deepen our understanding of microwave-biosystem interactions. It can also be important for an analysis and design of microwave chiral metamaterials.

  5. Environmental behavior of the chiral triazole fungicide fenbuconazole and its chiral metabolites: enantioselective transformation and degradation in soils.

    PubMed

    Li, Yuanbo; Dong, Fengshou; Liu, Xingang; Xu, Jun; Li, Jing; Kong, Zhiqiang; Chen, Xiu; Zheng, Yongquan

    2012-03-06

    Fenbuconazole is a widely used systemic agricultural fungicide of the triazole class with one chiral center. In the present study, the enantioselective degradation of fenbuconazole and its chiral metabolites, RH-9129 and RH-9130, in two soils under aerobic and anaerobic conditions were investigated using a chiral OD-RH column on a reversed-phase liquid chromatography-tandem mass spectrometry system. Under aerobic or anaerobic conditions, the results showed the occurrence of enantioselectivity with (-)-fenbuconazole preferentially degraded in both soils. Further enantioselective analysis of converted products showed that the concentrations of four RH-9129 and RH-9130 stereoisomers were different from each other under both aerobic and anaerobic conditions. The four stereoisomer concentrations followed the order (-)-RH-9129 > (+)-RH-9129 > (-)-RH-9130 > (+)-RH-9130 in Langfang alkaline soil. However, in the case of Changsha acidic soil, different RH-9129 and RH-9130 stereoisomer patterns were produced in the order (-)-RH-9129 > (+)-RH-9129 > (+)-RH-9130 > (-)-RH-9130. The (-)-RH-9129 stereoisomer had the highest concentration formed by transformation of fenbuconazole in both soils. The degradation of RH-9129 and RH-9130 in the two soils is also stereoselective under both aerobic and anaerobic conditions, the results indicating that the (+)-RH-9130 enantiomer degraded faster than the (-)-RH-9130 enantiomer and the (+)-RH-9129 enantiomer degraded faster than the (-)-RH-9129 enantiomer. In addition, the (-)-RH-9129 isomer exhibited the slowest degradation rate in both soils. This study provides the first experimental evidence of stereoselective degradation and transformation of fenbuconazole as well as its chiral metabolites in the environment.

  6. A mechanism to pin skyrmions in chiral magnets.

    PubMed

    Liu, Ye-Hua; Li, You-Quan

    2013-02-20

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

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

    PubMed

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

    2016-05-10

    The highly enantioselective synthesis of dihydroisoquinoline derivatives from aromatic sulfonated imines tethered with an alkyne moiety, through a one-pot asymmetric relay catalysis of chiral-phosphine and gold catalysts, is reported. Enantiomerically enriched dihydroisoquinoline derivatives were afforded in good yields and good-to-excellent ee values under mild conditions, based on the asymmetric aza-Morita-Baylis-Hillman reaction. Dihydroisoquinoline derivatives containing two chiral centers were also synthesized through further transformations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Supersymmetric chiral models: Geometrical aspects

    NASA Astrophysics Data System (ADS)

    Perelomov, A. M.

    1989-03-01

    We consider classical supersymmetric chiral models of field theory and focus our attention on the geometrical aspects of such theories. A characteristic feature of such models is that the interaction is not introduced by adding the interaction Lagrangian to the free field Lagrangian, but has a purely geometrical origin and is related to the inner curvature of the target manifold. In many aspects these models are analogous to gauge theories and, as became clear recently, they are also important for superstring theory, which nowadays is the most probable candidate for a truly unified theory of all interactions including gravitation.

  9. Status of chiral meson physics

    SciTech Connect

    Bijnens, Johan

    2016-01-22

    This talk includes a short introduction to Chiral Perturbation Theory in the meson sector concentrating on a number of recent developments. I discuss the latest fit of the low-energy constants. Finite volume corrections are discussed for the case with twisted boundary conditions for form-factors and first results at two-loops for three flavours for masses. The last part discusses the extension to other symmetry breaking patterns relevant for technicolour and related theories as well as the calculation of leading logarithms to high loop orders.

  10. Chiral Supersymmetric Gepner Model Orientifolds

    NASA Astrophysics Data System (ADS)

    Blumenhagen, Ralph; Weigand, Timo

    2004-02-01

    We explicitly construct A-type orientifolds of supersymmetric Gepner models. In order to reduce the tadpole cancellation conditions to a treatable number we explicitly work out the generic form of the one-loop Klein bottle, annulus and Möbius strip amplitudes for simple current extensions of Gepner models. Equipped with these formulas, we discuss two examples in detail to provide evidence that in this setting certain features of the MSSM like unitary gauge groups with large enough rank, chirality and family replication can be achieved.

  11. Supramolecular chirality induction in bis(zinc porphyrin) by amino acid derivatives: rationalization and applications of the ligand bulkiness effect.

    PubMed

    Borovkov, V V; Yamamoto, N; Lintuluoto, J M; Tanaka, T; Inoue, Y

    2001-06-01

    The achiral syn conformer (face-to-face) of the ethane-bridged bis(zinc porphyrin) (syn-ZnD) transforms into the corresponding chiral extended anti bis-ligated species (anti-ZnD.L2) in the presence of enantiopure ligands (L: amino acid derivatives). The mechanism of the supramolecular chirality induction is based on chiral ligand binding to zinc porphyrins and subsequent formation of either right- or left-handed screw structures in anti-ZnD.L2. The screw structure formation arises from steric interactions between the bulkiest substituent at the asymmetric carbon of the ligand and the peripheral ethyl groups of the neighboring porphyrin ring directed towards the covalent bridge. The sign and amplitude of the induced circular dichroism (CD) are dependent on the steric bulk of the substituents at the chiral center. The greater difference in size between the chiral center's substituents gives the stronger induced CD signal. Rationalization of the ligand bulkiness effect on chirality induction by amino acid derivatives, application of this supramolecular system for the determination of ligand absolute configuration, and relative bulkiness of the substituents at the asymmetric carbon are discussed. Copyright 2001 Wiley-Liss, Inc.

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

    PubMed

    Çağlar, Tolga; Berker, A Nihat

    2016-09-01

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

  13. FATE AND EFFECTS OF THE ENANTIOMERS OF CHIRAL ENVIRONMENTAL POLLUTANTS

    EPA Science Inventory

    Enantiomers, the mirror image isomers of chiral compounds, are known to be selective in their interaction with other chiral molecules, including enzymes and other biochemicals. This holds true for pesticides, about 25% of which are chiral molecules, and other chiral environmental...

  14. Proteomic Characterization of the World Trade Center dust-activated mdig and c-myc signaling circuit linked to multiple myeloma.

    PubMed

    Wu, Kai; Li, Lingzhi; Thakur, Chitra; Lu, Yongju; Zhang, Xiangmin; Yi, Zhengping; Chen, Fei

    2016-11-11

    Several epidemiological studies suggested an increased incidence rate of multiple myeloma (MM) among first responders and other individuals who exposed to World Trade Center (WTC) dust. In this report, we provided evidence showing that WTC dust is potent in inducing mdig protein and/or mRNA in bronchial epithelial cells, B cells and MM cell lines. An increased mdig expression in MM bone marrow was observed, which is associated with the disease progression and prognosis of the MM patients. Through integrative genomics and proteomics approaches, we further demonstrated that mdig directly interacts with c-myc and JAK1 in MM cell lines, which contributes to hyperactivation of the IL-6-JAK-STAT3 signaling important for the pathogenesis of MM. Genetic silencing of mdig reduced activity of the major downstream effectors in the IL-6-JAK-STAT3 pathway. Taken together, these data suggest that WTC dust may be one of the key etiological factors for those who had been exposed for the development of MM by activating mdig and c-myc signaling circuit linked to the IL-6-JAK-STAT3 pathway essential for the tumorigenesis of the malignant plasma cells.

  15. Proteomic Characterization of the World Trade Center dust-activated mdig and c-myc signaling circuit linked to multiple myeloma

    PubMed Central

    Wu, Kai; Li, Lingzhi; Thakur, Chitra; Lu, Yongju; Zhang, Xiangmin; Yi, Zhengping; Chen, Fei

    2016-01-01

    Several epidemiological studies suggested an increased incidence rate of multiple myeloma (MM) among first responders and other individuals who exposed to World Trade Center (WTC) dust. In this report, we provided evidence showing that WTC dust is potent in inducing mdig protein and/or mRNA in bronchial epithelial cells, B cells and MM cell lines. An increased mdig expression in MM bone marrow was observed, which is associated with the disease progression and prognosis of the MM patients. Through integrative genomics and proteomics approaches, we further demonstrated that mdig directly interacts with c-myc and JAK1 in MM cell lines, which contributes to hyperactivation of the IL-6-JAK-STAT3 signaling important for the pathogenesis of MM. Genetic silencing of mdig reduced activity of the major downstream effectors in the IL-6-JAK-STAT3 pathway. Taken together, these data suggest that WTC dust may be one of the key etiological factors for those who had been exposed for the development of MM by activating mdig and c-myc signaling circuit linked to the IL-6-JAK-STAT3 pathway essential for the tumorigenesis of the malignant plasma cells. PMID:27833099

  16. Clinical practice and risk factors for immediate complications of endotracheal intubation in the intensive care unit: a prospective, multiple-center study.

    PubMed

    Jaber, Samir; Amraoui, Jibba; Lefrant, Jean-Yves; Arich, Charles; Cohendy, Robert; Landreau, Liliane; Calvet, Yves; Capdevila, Xavier; Mahamat, Aba; Eledjam, Jean-Jacques

    2006-09-01

    To describe the current practice of physicians, to report complications associated with endotracheal intubation (ETI) performed in THE intensive care unit (ICU), and to isolate predictive factors of immediate life-threatening complications. Multiple-center observational study. Seven intensive care units of two university hospitals. : We evaluated 253 occurrences of ETI in 220 patients. From January 1 to June 30, 2003, data related to all ETI performed in ICU were collected. Information regarding patient descriptors, procedures, and immediate complications were analyzed. The main indications to intubate the trachea were acute respiratory failure, shock, and coma. Some 148 ETIs (59%) were performed by residents. At least one severe complication occurred in 71 ETIs (28%): severe hypoxemia (26%), hemodynamic collapse (25%), and cardiac arrest (2%). The other complications were difficult intubation (12%), cardiac arrhythmia (10%), esophageal intubation (5%), and aspiration (2%). Presence of acute respiratory failure and the presence of shock as an indication for ETI were identified as independent risk factors for occurrence of complications, and ETI performed by a junior physician supervised by a senior (i.e., two operators) was identified as a protective factor for the occurrence of complications. ETI in ICU patients is associated with a high rate of immediate and severe life-threatening complications. Independent risk factors of complication occurrence were presence of acute respiratory failure and presence of shock as an indication for ETI. Further studies should aim to better define protocols for intubation in critically ill patients to make this procedure safer.

  17. Chiral Resolution of Racemic Environmental Pollutants by Capillary Electrophoresis.

    PubMed

    Ali, Imran; Gupta, Vinod K; Aboul-Enein, Hassan Y

    2008-01-01

    The chiral resolution of environmental pollutants is an urgent need of today. Therefore, the chiral resolution of the environmental pollutants by capillary electrophoresis was reviewed. Various aspects of the chiral resolution by capillary electrophoresis such as chiral selectors, optimization of capillary electrophoresis conditions [composition of the back ground electrolyte (BGE), pH of the BGE, ionic strength of the BGE, structures and types of the chiral selectors, applied voltage, temperature, structures of the chiral pollutants, use of organic modifiers and other parameters, optimization by dependent variables], detection, sample treatment, validation of the methods and the chiral recognition mechanisms have been discussed.

  18. Nucleic acids, proteins, and chirality

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

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

  19. The chirality of ciliary beats.

    PubMed

    Hilfinger, A; Jülicher, F

    2008-03-19

    Many eukaryotic cells possess cilia which are motile, whip-like appendages that can oscillate and thereby induce motion and fluid flows. These organelles contain a highly conserved structure called the axoneme, whose characteristic architecture is based on a cylindrical arrangement of nine doublets of microtubules. Complex bending waves emerge from the interplay of active internal forces generated by dynein motor proteins within the structure. These bending waves are typically chiral and often exhibit a sense of rotation. In order to study how the shape of the beat emerges from the axonemal structure, we present a three-dimensional description of ciliary dynamics based on the self-organization of dynein motors and microtubules. Taking into account both bending and twisting of the cilium, we determine self-organized beating patterns and find that modes with both a clockwise and anticlockwise sense of rotation exist. Because of the axonemal chirality, only one of these modes is selected dynamically for given parameter values and properties of dynein motors. This physical mechanism, which underlies the selection of a beating pattern with specific sense of rotation, triggers the breaking of the left-right symmetry of developing embryos which is induced by asymmetric fluid flows that are generated by rotating cilia.

  20. Chiral magnetism at oxide interfaces

    NASA Astrophysics Data System (ADS)

    Randeria, Mohit

    2014-03-01

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