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Sample records for chiral aromatic imines

  1. Stereoselective Reduction of Imines with Trichlorosilane Using Solid-Supported Chiral Picolinamides

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    Sílvia D. Fernandes

    2016-09-01

    Full Text Available The stereoselective reduction of imines with trichlorosilane catalyzed by chiral Lewis bases is a well-established procedure for the synthesis of enantio-enriched amines. Five supported cinchona-based picolinamides have been prepared and their activity tested in a model reaction. The comparison of different supporting materials revealed that polystyrene gave better results than silica in terms of stereoselectivity. The applicability of the solid-supported catalyst of choice to the reduction of different imines was also demonstrated. Additionally, for the first time, a catalytic reactor containing a polymer-immobilized chiral picolinamide has been employed for the stereoselective reduction of imines with trichlorosilane under continuous flow conditions.

  2. Stereodivergent Mannich reaction of bis(trimethylsilyl)ketene acetals with N-tert-butanesulfinyl imines by Lewis acid or Lewis base activation, a one-pot protocol to obtain chiral β-amino acids.

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    Cantú-Reyes, Margarita; Alvarado-Beltrán, Isabel; Ballinas-Indilí, Ricardo; Álvarez-Toledano, Cecilio; Hernández-Rodríguez, Marcos

    2017-09-20

    We report a one-pot synthesis of chiral β 2,2,3 -amino acids by the Mannich addition of bistrimethylsilyl ketene acetals to N-tert-butanesulfinyl imines followed by the removal of the chiral auxiliary. The synthesis and isolation of pure β-amino acid hydrochlorides were conducted under mild conditions, without strong bases and this method is operationally simple. The stereoselective reaction was promoted by two different activation methods that lead to different stereoisomers: (1) Lewis Acid (LA) catalysis with boron trifluoride diethyl etherate and (2) Lewis Base (LB) catalysis with tetrabutylammonium difluorotriphenylsilicate. The reaction presented good diastereoselectivity with LB activation and moderate to good dr with LA catalysis. The exceptions in both protocols were imines with electron donating groups in the aromatic ring.

  3. Asymmetric aza-Diels-Alder reaction of Danishefsky's diene with imines in a chiral reaction medium

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    Pégot Bruce

    2006-09-01

    Full Text Available Abstract The asymmetric aza-Diels-Alder reaction of chiral imines with Danishefsky's diene in chiral ionic liquids provides the corresponding cycloadduct with moderate to high diastereoselectivity. The reaction has proved to perform better at room temperature in ionic liquids without either Lewis acid catalyst or organic solvent. Chiral ionic liquids are recycled while their efficiency is preserved.

  4. An entry to a chiral dihydropyrazole scaffold: enantioselective [3 + 2] cycloaddition of nitrile imines.

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    Sibi, Mukund P; Stanley, Levi M; Jasperse, Craig P

    2005-06-15

    We have developed a versatile strategy to access dihydropyrazoles in highly enantioenriched form. Dipolar cycloaddition of electron-deficient acceptors and in situ-generated nitrile imines proceeds with high regio- and enantioselectivity using 10 mol % chiral Lewis acid catalyst. A variety of dihydropyrazoles that incorporate functionality for further manipulation have been prepared.

  5. Chiral Organic Cages with a Triple-Stranded Helical Structure Derived from Helicene.

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    Malik, Abaid Ullah; Gan, Fuwei; Shen, Chengshuo; Yu, Na; Wang, Ruibin; Crassous, Jeanne; Shu, Mouhai; Qiu, Huibin

    2018-02-28

    We report the use of helicene with an intrinsic helical molecular structure to prepare covalent organic cages via imine condensation. The organic cages revealed a [3+2]-type architecture containing a triple-stranded helical structure with three helicene units arranged in a propeller-like fashion with the framework integrally twisted. Such structural chirality was retained upon dissolution in organic solvents, as indicated by a strong diastereotopy effect in proton NMR and unique Cotton effects in circular dichroism spectra. Further study on chiral adsorption showed that the chiral organic cages possess considerable enantioselectivity toward a series of aromatic racemates.

  6. Enantioselective Synthesis of α-Mercapto-β-amino Esters via Rh(II)/Chiral Phosphoric Acid-Cocatalyzed Three-Component Reaction of Diazo Compounds, Thiols, and Imines.

    Science.gov (United States)

    Xiao, Guolan; Ma, Chaoqun; Xing, Dong; Hu, Wenhao

    2016-12-02

    An enantioselective method for the synthesis of α-mercapto-β-amino esters has been developed via a rhodium(II)/chiral phosphoric acid-cocatalyzed three-component reaction of diazo compounds, thiols, and imines. This transformation is proposed to proceed through enantioselective trapping of the sulfonium ylide intermediate generated in situ from the diazo compound and thiol by the phosphoric acid-activated imine. With this method, a series of α-mercapto-β-amino esters were obtained in good yields with moderate to good stereoselectivities.

  7. Asymmetric Synthesis via Chiral Aziridines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Harden, Adrian; Wyatt, Paul

    1996-01-01

    A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines)]. In the b......A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines...

  8. Photocatalytic organic transformation by layered double hydroxides: highly efficient and selective oxidation of primary aromatic amines to their imines under ambient aerobic conditions.

    Science.gov (United States)

    Yang, Xiu-Jie; Chen, Bin; Li, Xu-Bing; Zheng, Li-Qiang; Wu, Li-Zhu; Tung, Chen-Ho

    2014-06-25

    We report the first application of layered double hydroxide as a photocatalyst in the transformation of primary aromatic amines to their corresponding imines with high efficiency and selectivity by using oxygen in an air atmosphere as a terminal oxidant under light irradiation.

  9. Control of π-Electron Rotations in Chiral Aromatic Molecules Using Intense Laser Pulses

    Science.gov (United States)

    Kanno, Manabu; Kono, Hirohiko; Fujimura, Yuichi

    Our recent theoretical studies on laser-induced π-electron rotations in chiral aromatic molecules are reviewed. π electrons of a chiral aromatic molecule can be rotated along its aromatic ring by a nonhelical, linearly polarized laser pulse. An ansa aromatic molecule with a six-membered ring, 2,5-dichloro[n](3,6) pyrazinophane, which belongs to a planar-chiral molecule group, and its simplified molecule 2,5-dichloropyrazine are taken as model molecules. Electron wavepacket simulations in the frozen-molecular-vibration approximation show that the initial direction of π-electron rotation depends on the polarization direction of a linearly polarized laser pulse applied. Consecutive unidirectional rotation can be achieved by applying a sequence of linearly polarized pump and dump pulses to prevent reverse rotation. Optimal control simulations of π-electron rotation show that another controlling factor for unidirectional rotation is the relative optical phase between the different frequency components of an incident pulse in addition to photon polarization direction. Effects of nonadiabatic coupling between π-electron rotation and molecular vibrations are also presented, where the constraints of the frozen approximation are removed. The angular momentum gradually decays mainly owing to nonadiabatic coupling, while the vibrational amplitudes greatly depend on their rotation direction. This suggests that the direction of π-electron rotation on an attosecond timescale can be identified by detecting femtosecond molecular vibrations.

  10. Rhodium-catalyzed asymmetric hydrogenation of unprotected NH imines assisted by a thiourea.

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    Zhao, Qingyang; Wen, Jialin; Tan, Renchang; Huang, Kexuan; Metola, Pedro; Wang, Rui; Anslyn, Eric V; Zhang, Xumu

    2014-08-04

    Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)-thiourea provided chiral amines with up to 97% yield and 95% ee. (1)H NMR studies, coupled with control experiments, implied that catalytic chloride-bound intermediates were involved in the mechanism through a dual hydrogen-bonding interaction. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Thermal, structural and electrochemical properties of new aliphatic-aromatic imine with piperazine moieties blended with titanium dioxide

    Science.gov (United States)

    Różycka, Anna; Fryń, Patryk; Iwan, Agnieszka; Bogdanowicz, Krzysztof Artur; Filapek, Michal; Górska, Natalia; Dąbczyński, Paweł; Rysz, Jakub; Pociecha, Damian; Hreniak, Agnieszka; Marzec, Monika

    2018-02-01

    A new piperazine imine, (7E)-N-((4-((E)-(4-hexadecylphenylimino)methyl)piperazin-1-yl)methylene)-4-dodecylbenzenamine, has been synthesized by the condensation of 1,4-piperazinedicarboxaldehyde with 4-hexadecylaniline. The imine was characterized by cyclic voltammetry, Fourier transform middle-infrared absorption spectroscopy and X-ray diffraction. Thermal properties of imine was analyzed by differential scanning calorimetry method during first and second heating scan at 10 and 20 °C/min. Texture of imine was investigated by polarized optical microscopy and atomic force microscopy. Furthermore, imine was blended with titanium dioxide in anatase form and fully characterized by the same methods. Piperazine imine and its mixture with titanium dioxide exhibited only a transition from crystal to isotropic state. Imine exhibits two-step reduction wave attributed to one-electron transfer in each step as was found by cyclic voltammetry. Both titanium dioxide and poly(3-hexylthiophene) change the electrochemical properties of piperazine imine, however, in different ways. Studied imine blended with titanium dioxide exhibited higher value of energy band gap than pure piperazine imine and lower Eg than pure poly(3-hexylthiophene).

  12. Chiral multichromic single crystals for optical devices (LDRD 99406).

    Energy Technology Data Exchange (ETDEWEB)

    Kemp, Richard Alan; Felix, Ana M. (University of New Mexico, Albuquerque, NM)

    2006-12-01

    This report summarizes our findings during the study of a novel system that yields multi-colored materials as products. This system is quite unusual as it leads to multi-chromic behavior in single crystals, where one would expect that only a single color would exist. We have speculated that these novel solids might play a role in materials applications such as non-linear optics, liquid crystal displays, piezoelectric devices, and other similar applications. The system examined consisted of a main-group alkyl compound (a p block element such as gallium or aluminum) complexed with various organic di-imines. The di-imines had substituents of two types--either alkyl or aromatic groups attached to the nitrogen atoms. We observed that single crystals, characterized by X-ray crystallography, were obtained in most cases. Our research during January-July, 2006, was geared towards understanding the factors leading to the multi-chromic nature of the complexes. The main possibilities put forth initially considered (a) the chiral nature of the main group metal, (b) possible reduction of the metal to a lower-valent, radical state, (c) the nature of the ligand(s) attached to the main group metal, and (d) possible degradation products of the ligand leading to highly-colored products. The work carried out indicates that the most likely explanation considered involves degradation of the aromatic ligands (a combination of (c) and (d)), as the experiments performed can clearly rule out (a) and (b).

  13. Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents

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    Gennari Cesare

    1998-01-01

    Full Text Available We have recently described the development of a quantitative transition state model for the prediction of stereoselectivity in the boron-mediated aldol reaction. This model provides qualitative insights into the factors contributing to the stereochemical outcome of a variety of reactions of synthetic importance. The force field model was used to assist the design and preparation of new chiral boron ligands derived from menthone. The chiral boron enolates were employed in various stereoselective processes, including the addition to chiral aldehydes and the reagent-controlled total synthesis of (3S,4S-statine. The chiral enolates derived from alpha-halo and alpha-oxysubstituted thioacetates were added to aldehydes and imines. Addition to imines leads to the enantioselective synthesis of chiral aziridines, a formal total synthesis of (+-thiamphenicol, and a new highly efficient synthesis of the paclitaxel (taxol® C-13 side-chain and taxol semisynthesis from baccatin III. The stereochemical outcome of the addition to imines was rationalised with the aid of computational studies. Enantioselective addition reactions of the chiral boron enolate derived from thioacetate have successfully been applied to solid phase bound aldehydes to give aldol products in comparable yields and enantioselectivities to the usual solution conditions.

  14. Frozen Chirality of Tertiary Aromatic Amides: Access to Enantioenriched Tertiary α-Amino Acid or Amino Alcohol without Chiral Reagent.

    Science.gov (United States)

    Mai, Thi Thoa; Viswambharan, Baby; Gori, Didier; Guillot, Régis; Naubron, Jean-Valère; Kouklovsky, Cyrille; Alezra, Valérie

    2017-04-27

    One of the fundamental and intriguing aspects of life is the homochirality of the essential molecules. In this field, the absolute asymmetric synthesis of α-amino acids is a major challenge. Herein, we report access, by chemical means, to tertiary α-amino acid derivatives in up to 96 % ee without using any chiral reagent. In our strategy, the dynamic axial chirality of tertiary aromatic amides is frozen in a crystal and is responsible for the stereoselectivity of the subsequent steps. Furthermore, we could control the configuration of the final product by manually sorting and selecting the initial crystals. Based on vibrational circular dichroism studies, we could rationalize the observed stereoselectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Catalytic asymmetric diels-alder reaction of quinone imine ketals: a site-divergent approach.

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    Hashimoto, Takuya; Nakatsu, Hiroki; Maruoka, Keiji

    2015-04-07

    The catalytic asymmetric Diels-Alder reaction of quinone imine ketals with diene carbamates catalyzed by axially chiral dicarboxylic acids is reported herein. A variety of primary and secondary alkyl-substituted quinone derivatives which have not been applied in previous asymmetric quinone Diels-Alder reactions could be employed using this method. More importantly, we succeeded in developing a strategy to divert the reaction site in unsymmetrical 3-alkyl quinone imine ketals from the inherently favored unsubstituted C=C bond to the disfavored alkyl-substituted C=C bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Poly-Cross-Linked PEI Through Aromatically Conjugated Imine Linkages as a New Class of pH-Responsive Nucleic Acids Packing Cationic Polymers

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    Chen, Shun; Jin, Tuo

    2016-01-01

    Cationic polyimines polymerized through aromatically conjugated bis-imine linkages and intra-molecular cross-linking were found to be a new class of effective transfection materials for their flexibility in structural optimization, responsiveness to intracellular environment, the ability to facilitate endosome escape and cytosol release of the nucleic acids, as well as self-metabolism. When three phthalaldehydes of different substitution positions were used to polymerize highly branched low-molecular weight polyethylenimine (PEI 1.8K), the product through ortho-phthalimines (named PPOP) showed significantly higher transfection activity than its two tere- and iso-analogs (named PPTP and PPIP). Physicochemical characterization confirmed the similarity of three polyimines in pH-responded degradability, buffer capacity, as well as the size and Zeta potential of the polyplexes formed from the polymers. A mechanistic speculation may be that the ortho-positioned bis-imine linkage of PPOP may only lead to the straight trans-configuration due to steric hindrance, resulting in larger loops of intra-polymer cross-linking and more flexible backbone. PMID:26869931

  17. A chiroptical switch based on supramolecular chirality transfer through alkyl chain entanglement and dynamic covalent bonding.

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    Lv, Kai; Qin, Long; Wang, Xiufeng; Zhang, Li; Liu, Minghua

    2013-12-14

    Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.

  18. The isomerization of allylrhodium intermediates in the rhodium-catalyzed nucleophilic allylation of cyclic imines.

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    Hepburn, Hamish B; Lam, Hon Wai

    2014-10-20

    Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene-rhodium complexes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Nonadiabatic Response Model of Laser-Induced Ultrafast π-Electron Rotations in Chiral Aromatic Molecules

    International Nuclear Information System (INIS)

    Kanno, Manabu; Kono, Hirohiko; Fujimura, Yuichi; Lin, Sheng H.

    2010-01-01

    We theoretically investigated the nonadiabatic couplings between optically induced π-electron rotations and molecular vibrations in a chiral aromatic molecule irradiated by a nonhelical, linearly polarized laser pulse. The results of wave packet dynamics simulation show that the vibrational amplitudes strongly depend on the initial rotation direction, clockwise or counterclockwise, which is controlled by the polarization direction of the incident pulse. This suggests that attosecond π-electron rotations can be observed by spectroscopic detection of femtosecond molecular vibrations.

  20. Chiral 1,3,2-oxazaborolidines in asymmetric synthesis: recent advances

    International Nuclear Information System (INIS)

    Glushkov, Vladimir A; Tolstikov, Alexander G

    2004-01-01

    The use of chiral 1,3,2-oxazaborolidines in asymmetric organic synthesis, particularly, in enantioselective reduction of ketones, imines and oxime ethers, asymmetric Diels-Alder reactions, aldol condensation and atroposelective reduction of lactones is reviewed. Reactions of immobilised 1,3,2-oxazaborolidines are also considered.

  1. Anion-π Catalysts with Axial Chirality.

    Science.gov (United States)

    Wang, Chao; Matile, Stefan

    2017-09-04

    The idea of anion-π catalysis is to stabilize anionic transition states by anion-π interactions on aromatic surfaces. For asymmetric anion-π catalysis, π-acidic surfaces have been surrounded with stereogenic centers. This manuscript introduces the first anion-π catalysts that operate with axial chirality. Bifunctional catalysts with tertiary amine bases next to π-acidic naphthalenediimide planes are equipped with a bulky aromatic substituent in the imide position to produce separable atropisomers. The addition of malonic acid half thioesters to enolate acceptors is used for evaluation. In the presence of a chiral axis, the selective acceleration of the disfavored but relevant enolate addition was much better than with point chirality, and enantioselectivity could be observed for the first time for this reaction with small-molecule anion-π catalysts. Enantioselectivity increased with the π acidity of the π surface, whereas the addition of stereogenic centers around the aromatic plane did not cause further improvements. These results identify axial chirality of the active aromatic plane generated by atropisomerism as an attractive strategy for asymmetric anion-π catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Highly efficient induction of chirality in intramolecular

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    Cossio; Arrieta; Lecea; Alajarin; Vidal; Tovar

    2000-06-16

    Highly stereocontrolled, intramolecular [2 + 2] cycloadditions between ketenimines and imines leading to 1,2-dihydroazeto[2, 1-b]quinazolines have been achieved. The source of stereocontrol is a chiral carbon atom adjacent either to the iminic carbon or nitrogen atom. In the first case, the stereocontrol stems from the preference for the axial conformer in the first transition structure. In the second case, the origin of the stereocontrol lies on the two-electron stabilizing interaction between the C-C bond being formed and the sigma orbital corresponding to the polar C-X bond, X being an electronegative atom. These models can be extended to other related systems for predicting the stereochemical outcome in this intramolecular reaction.

  3. Electric-field triggered controlled release of bioactive volatiles from imine-based liquid crystalline phases.

    Science.gov (United States)

    Herrmann, Andreas; Giuseppone, Nicolas; Lehn, Jean-Marie

    2009-01-01

    Application of an electric field to liquid crystalline film forming imines with negative dielectric anisotropy, such as N-(4-methoxybenzylidene)-4-butylaniline (MBBA, 1), results in the expulsion of compounds that do not participate in the formation of the liquid crystalline phase. Furthermore, amines and aromatic aldehydes undergo component exchange with the imine by generating constitutional dynamic libraries. The strength of the electric field and the duration of its application to the liquid crystalline film influence the release rate of the expelled compounds and, at the same time, modulate the equilibration of the dynamic libraries. The controlled release of volatile organic molecules with different chemical functionalities from the film was quantified by dynamic headspace analysis. In all cases, higher headspace concentrations were detected in the presence of an electric field. These results point to the possibility of using imine-based liquid crystalline films to build devices for the controlled release of a broad variety of bioactive volatiles as a direct response to an external electric signal.

  4. EVALUATION OF ANTIOXIDANT ACTIVITY OF SOME IMINES DERIVATIVES OF L-ARGININE.

    Science.gov (United States)

    Iacob, Andreea-Teodora; Drăgan, Maria; Constantin, Sandra; Lupaşcu, Florentina; Confederat, Luminiţa; Buron, F; Routier, S; Profire, Lenuţa

    2016-01-01

    L-Arginine is an a-amino acid which plays important roles in different diseases or processes, such as Alzheimer disease, inflammatory process, healing and tissue regeneration and it also could be useful as an anti-atherosclerotic agent. Considering the large amount of studies on the beneficial effects of different antioxidants, this paper is focused on the evaluation of the antioxidant potential of some imine derivatives, synthesized by the authors and described in a previous article. The evaluation of the antioxidant power was performed using phosphomolydenum-reducing antioxidant power (PRAP) and ferric reducing antioxidant power (FRAP) assays, tests described in the literature and which are used with some minor modifications. It was found that most of the imine derivatives are more active than the L-Arginine in the PPAP and FRAP assays. The most active derivative was the compound obtained by condensation of L-arginine with 2,3-dihydroxybenzaldehyde (2k) and 2-nitrobenzaldehyde (2g). Following the described protocol, some imine derivatives of L-arginine were evaluated in terms of antioxidant potential using in vitro methods. The most favorable influence was obtained by the aromatic substitution with nitro and hydroxyl, the corresponding derivatives being the most active derivatives compared to L-arginine.

  5. Asymmetric Baylis-Hillman Reaction between Chiral Activated Alkenes and Aromatic Aldehydes in Me3N/H2O/Solvent Medium

    Institute of Scientific and Technical Information of China (English)

    Ke HE; Zheng Hong ZHOU; Hong Ying TANG; Guo Feng ZHAO; Chu Chi TANG

    2005-01-01

    Chiral activated alkene, L-menthyl acrylate and (+)-N-α-phenylethyl acrylamide,induced asymmetric Baylis-Hillman reaction of aromatic aldehydes was realized at 25℃ for 7 days in Me3N/H2O/solvent homogeneous medium. The corresponding Baylis-Hillman adducts were obtained in good chemical yield with moderate to excellent diastereoselectivity (up to 99% de).

  6. Deracemization of Racemic Amino Acids Using (R)- and (S)-Alanine Racemase Chiral Analogues as Chiral Converters

    International Nuclear Information System (INIS)

    Paik, Manjeong; Jeon, So Hee; Lee, Wonjae; Kang, Jong Seong; Kim, Kwan Mook

    2014-01-01

    Our findings show that both (R)- and (S)-ARCA can be practical chiral converters for L- and D-amino acids, respectively, in the deracemization of racemic amino acids. The overall stereoselectivities of both chiral converters are generally greater than 90%. In addition, we developed chiral and achiral HPLC methods for the analysis of stereoselectivity determination. This chromatographic method proved much more accurate and convenient at determining both enantiomer and diastereomer purity than did those previously reported. Deracemization is the stereoselective process of converting a racemate into either a pure enantiomer or a mixture in which one enantiomer is present in excess.1 Previous studies have shown that (S)-alanine racemase chiral analogue (ARCA) [(S)-2-hydroxy-2'-(3-phenyluryl-benzyl)-1,1'-binaphthyl-3-carboxaldehyde], developed as a chiral convertor compound that imitates the function of alanine racemase, plays an essential role in the stereoselective conversion of amino acid. Since (S)-ARCA showed a higher stability with D-amino acids than with L-amino acids, several L-amino acids were preferentially converted to D-amino acids via (S)-ARCA/D-amino acid imine diastereomer formation. For the deracemization process undertaken in this study, we utilized both (R)-ARCA and (S)-ARCA as chiral converters, which were expected to generate L- and D-amino acids, respectively, from the starting racemic mixtures

  7. Inversion of Supramolecular Chirality by Sonication-Induced Organogelation

    Science.gov (United States)

    Maity, Sibaprasad; Das, Priyadip; Reches, Meital

    2015-01-01

    Natural helical structures have inspired the formation of well-ordered peptide-based chiral nanostructures in vitro. These structures have drawn much attention owing to their diverse applications in the area of asymmetric catalysts, chiral photonic materials, and nanoplasmonics. The self-assembly of two enantiomeric fluorinated aromatic dipeptides into ordered chiral fibrillar nanostructures upon sonication is described. These fibrils form organogels. Our results clearly indicate that fluorine-fluorine interactions play an important role in self-assembly. Circular dichroism analysis revealed that both peptides (peptides 1 and 2), containing two fluorines, depicted opposite cotton effects in their monomeric form compared with their aggregated form. This shows that supramolecular chirality inversion took place during the stimuli-responsive self-aggregation process. Conversely, peptide 3, containing one fluorine, did not exhibit chirality inversion in sonication-induced organogelation. Therefore, our results clearly indicate that fluorination plays an important role in the organogelation process of these aromatic dipeptides. Our findings may have broad implications regarding the design of chiral nanostructures for possible applications such as chiroptical switches, asymmetric catalysis, and chiral recognitions. PMID:26553508

  8. Preparation of poly (imine imine ketone) s microshells

    International Nuclear Information System (INIS)

    Cui Yi; Luo Xuan; Fan Yongheng; Zhang Lin; Liu Lei; Lin Runxiong

    2010-01-01

    Large diameter (0.6 ∼ 2.0 mm) microshells of poly (imine imine ketone) s (PIIKs) were prepared by micro-liquid technique and double-layer latex technique. A double T-channel droplet generator was designed and developed for the fabrication of PIIKs microshells of controlled size continuously. Manipulative conditions of the diameter and thickness of shells were studied, and the effect of density mismatch on shell quality was discussed. Phase separation during the preparation process affects the morphology of shells. Spinodal phase separation tends to occur at the outer surface of the shells, while binodal phase separation at the inner surface. The diameters of PIIKs shells were measured, 88% of which vary in ± 5% of the average diameter. The sphericity is better than 99%. (authors)

  9. Formation of enamines by alkylation of imines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1966-01-01

    cf. CA 64, 12473c. With ice-cooling, 1 equiv. alkylating agent was added to one equiv. of the imine in 1M soln. in a solvent in the presence of NaH to give both N- and C-alkylated products. The following summarizes the date (imine, solvent, alkylating agent, % unreacted imine, % N-alkylated product,

  10. The alkylation of imine anions formation of enamines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The ambident anions derived from imines were alkylated using a variety of solvents and alkylating agents. Under reactive conditions enamines (N-alkylation) are formed as the main products instead of the usually obsd. homologous imines (C-alkylation). The influence of the type of imine, solvent, and

  11. Pyridine group assisted addition of diazo-compounds to imines in the 3-CC reaction of 2-aminopyridines, aldehydes, and diazo-compounds.

    Science.gov (United States)

    Gulevich, Anton V; Helan, Victoria; Wink, Donald J; Gevorgyan, Vladimir

    2013-02-15

    A novel three-component coupling (3-CC) reaction of 2-aminoazines, aromatic aldehydes, and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles as well as β-amino acid derivatives.

  12. Bifunctional organocatalysts for the asymmetric synthesis of axially chiral benzamides

    Directory of Open Access Journals (Sweden)

    Ryota Miyaji

    2017-08-01

    Full Text Available Bifunctional organocatalysts bearing amino and urea functional groups in a chiral molecular skeleton were applied to the enantioselective synthesis of axially chiral benzamides via aromatic electrophilic bromination. The results demonstrate the versatility of bifunctional organocatalysts for the enantioselective construction of axially chiral compounds. Moderate to good enantioselectivities were afforded with a range of benzamide substrates. Mechanistic investigations were also carried out.

  13. Pyridine Group-Assisted Addition of Diazo-Compounds to Imines in the 3-CC Reaction of 2-Aminopyridines, Aldehydes, and Diazo-Compounds

    Science.gov (United States)

    Gulevich, Anton V.; Helan, Victoria; Wink, Donald J.

    2013-01-01

    A novel three-component (3-CC) coupling reaction of 2-aminoazines, aromatic aldehydes and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles, as well as to β-amino acid derivatives. PMID:23373731

  14. Hydride, hydrogen, proton, and electron affinities of imines and their reaction intermediates in acetonitrile and construction of thermodynamic characteristic graphs (TCGs) of imines as a "molecule ID card".

    Science.gov (United States)

    Zhu, Xiao-Qing; Liu, Qiao-Yun; Chen, Qiang; Mei, Lian-Rui

    2010-02-05

    A series of 61 imines with various typical structures were synthesized, and the thermodynamic affinities (defined as enthalpy changes or redox potentials in this work) of the imines to abstract hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the imines to abstract hydrogen atoms and protons, and the thermodynamic affinities of the hydrogen adducts of the imines to abstract electrons in acetonitrile were determined by using titration calorimetry and electrochemical methods. The pure heterolytic and homolytic dissociation energies of the C=N pi-bond in the imines were estimated. The polarity of the C=N double bond in the imines was examined using a linear free-energy relationship. The idea of a thermodynamic characteristic graph (TCG) of imines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose and predict the characteristic chemical properties of imines and their various reaction intermediates as well as the reduction mechanism of the imines. The information disclosed in this work could not only supply a gap of thermodynamics for the chemistry of imines but also strongly promote the fast development of the applications of imines.

  15. Enhanced reactivities toward amines by introducing an imine arm to the pincer ligand: Direct coupling of two amines to form an imine without oxidant

    KAUST Repository

    He, Lipeng

    2012-07-23

    Dehydrogenative homocoupling of primary alcohols to form esters and coupling of amines to form imines was accomplished using a class of novel pincer ruthenium complexes. The reactivities of the ruthenium pincer complexes for the direct coupling of amines to form imines were enhanced by introducing an imine arm to the pincer ligand. Selective oxidation of benzylamines to imines was achieved using aniline derivatives as the substrate and solvent. © 2012 American Chemical Society.

  16. Enhanced reactivities toward amines by introducing an imine arm to the pincer ligand: Direct coupling of two amines to form an imine without oxidant

    KAUST Repository

    He, Lipeng; Chen, Tao; Gong, Dirong; Lai, Zhiping; Huang, Kuo-Wei

    2012-01-01

    Dehydrogenative homocoupling of primary alcohols to form esters and coupling of amines to form imines was accomplished using a class of novel pincer ruthenium complexes. The reactivities of the ruthenium pincer complexes for the direct coupling of amines to form imines were enhanced by introducing an imine arm to the pincer ligand. Selective oxidation of benzylamines to imines was achieved using aniline derivatives as the substrate and solvent. © 2012 American Chemical Society.

  17. Chiral ligand exchange high-speed countercurrent chromatography: mechanism, application and comparison with conventional liquid chromatography in enantioseparation of aromatic α-hydroxyl acids

    Science.gov (United States)

    Tong, Shengqiang; Shen, Mangmang; Cheng, Dongping; Ito, Yoichiro; Yan, Jizhong

    2014-01-01

    This work concentrates on the separation mechanism and application of chiral ligand exchange high-speed countercurrent chromatography (HSCCC) in enantioseparations, and comparison with traditional chiral ligand exchange high performance liquid chromatography (HPLC). The enantioseparation of ten aromatic α-hydroxyl acids were performed by these two chromatographic methods. Results showed that five of the racemates were successfully enantioseparated by HSCCC while only three of the racemates could be enantioseparated by HPLC using a suitable chiral ligand mobile phase additive. For HSCCC, the two-phase solvent system was composed of butanol-water (1:1, v/v), to which N-n-dodecyl-L-proline was added in the organic phase as chiral ligand and cupric acetate was added in the aqueous phase as a transition metal ion. Various operation parameters in HSCCC were optimized by enantioselective liquid-liquid extraction. Based on the results of the present studies the separation mechanism for HSCCC was proposed. For HPLC, the optimized mobile phase composed of aqueous solution containing 6 mmol L−1 L-phenylalanine and 3 mmol L−1 cupric sulfate and methanol was used for enantioseparation. Among three ligands tested on a conventional reverse stationary phase column, only one was found to be effective. In the present studies HSCCC presented unique advantages due to its high versatility of two-phase solvent systems and it could be used as an alternative method for enantioseparations. PMID:25087742

  18. Influence of Endo- and Exocyclic Heteroatoms on Stabilities and 1,3-Dipolar Cycloaddition Reactivities of Mesoionic Azomethine Ylides and Imines.

    Science.gov (United States)

    Champagne, Pier Alexandre; Houk, K N

    2017-10-20

    The geometries, stabilities, and 1,3-dipolar cycloaddition reactivities of 24 mesoionic azomethine ylides and imines were investigated using density functional theory calculations at the M06-2X/6-311+G-(d,p)/M06-2X/6-31G-(d) level. The computed structures highlight how the commonly used "aromatic" resonance form should be replaced by two more accurate resonance structures. Stabilities of the dipoles were assessed by various homodesmotic schemes and are consistent with these compounds being nonaromatic. The activation free energies with ethylene or acetylene range from 11.8 to 36.6 kcal/mol. Within each dipole type, the predicted cycloaddition reactivities correlate with the reaction energies and the resonance stabilization energies provided by the various substituents. Endocyclic (X) heteroatoms increase the reactivity of the 1,3-dipoles in the order of O > NH ≅ S, whereas exocyclic (Y) substituents increase it in the order of CH 2 > NH > O > S. Distortion/interaction analysis indicated that the difference in reactivity between differently substituted 1,3-dipoles is driven by distortion, whereas the difference between azomethine ylides and imines is related to lower interaction energies of imines with the dipolarophiles.

  19. Construction of an Asymmetric Quaternary Carbon Center via Allylation of Hydrazones

    International Nuclear Information System (INIS)

    Kim, Jin Bum; Satyender, Apuri; Jang, Doo Ok

    2013-01-01

    Asymmetric indium-mediated allylation of imine derivatives bearing a chiral auxiliary is a reliable strategy for the synthesis of chiral homoallylic amines. Various techniques for indium-mediated stereoselective allylation of imines bearing a chiral auxiliary have been reported. In 1997 Loh and co-workers reported indium-mediated allylation with imines derived from L-valine methyl ester. Since then, many forms of indium-mediated allylation bearing a chiral auxiliary have been reported, including imines derived from (S)-valinol, (R)-phenylglycinol, uracil, (R)-phenylglycinol methyl ester, N-tert-butanesufinamide, and (1R,2S)-1-amino-2-indanol. However, the synthesis of chiral auxiliaries often involves a laborious multi-step synthesis with expensive reagents. Therefore, the development of readily accessible chiral auxiliaries for asymmetric indium-mediated all-ylation is in high demand

  20. Well-defined silica-supported zirconium–imido complexes mediated heterogeneous imine metathesis

    KAUST Repository

    Hamzaoui, Bilel

    2016-02-15

    Upon prolonged thermal exposure under vacuum, a well-defined single-site surface species [(≡Si-O-)Zr(NEt2)3] (1) evolves into an ethylimido complex [(≡Si-O-)Zr(=NEt)NEt2] (2). Reactions of 2 with an imine substrate result in imido/imine (=NRi, R: Et, Ph) exchange (metathesis) with the formation of [(≡Si-O-)Zr(=NPh)NEt2] (3). Compounds 2 and 3 effectively catalyze imine/imine cross-metathesis and are thus considered as the first heterogeneous catalysts active for imine metathesis. © The Royal Society of Chemistry 2016.

  1. Well-defined silica-supported zirconium–imido complexes mediated heterogeneous imine metathesis

    KAUST Repository

    Hamzaoui, Bilel; Pelletier, Jeremie; Abou-Hamad, Edy; Basset, Jean-Marie

    2016-01-01

    Upon prolonged thermal exposure under vacuum, a well-defined single-site surface species [(≡Si-O-)Zr(NEt2)3] (1) evolves into an ethylimido complex [(≡Si-O-)Zr(=NEt)NEt2] (2). Reactions of 2 with an imine substrate result in imido/imine (=NRi, R: Et, Ph) exchange (metathesis) with the formation of [(≡Si-O-)Zr(=NPh)NEt2] (3). Compounds 2 and 3 effectively catalyze imine/imine cross-metathesis and are thus considered as the first heterogeneous catalysts active for imine metathesis. © The Royal Society of Chemistry 2016.

  2. 1,4-Bis{(+-(S-[1-(1-naphthylethyl]iminomethyl}benzene

    Directory of Open Access Journals (Sweden)

    Armando Espinosa Leija

    2009-10-01

    Full Text Available The title compound, C32H28N2, is a chiral bis-imine in which both imine groups display the common E configuration. The naphthyl groups present different orientations with respect to the central core, as reflected in the dihedral angles of 21.4 (2 and 78.83 (14° between the benzene and naphthyl mean planes, thus the highest possible C2 local molecular symmetry is not attained. This C1 molecular conformation allows multiple C—H...π intermolecular contacts involving all aromatic rings, while no π–π interactions are available for the stabilization of the crystal structure. The resulting packing structure is based on molecules stacked along [100].

  3. Catalytic oxidation of 2-aminophenols and ortho hydroxylation of aromatic amines by tyrosinase

    International Nuclear Information System (INIS)

    Toussaint, O.; Lerch, K.

    1987-01-01

    The usual substrates of tyrosinase, a copper-containing monooxygenase (EC 1.14.18.1), are monophenols and o-diphenols which are both converted to o-quinones. In this paper, the authors studied the reaction of this enzyme with two new classes of substrates: aromatic amines and o-aminophenols, structural analogues of monophenols and o-diphenols, respectively. They undergo the same catalytic reactions (ortho hydroxylation and oxidation), as documented by product analysis and kinetic studies. In the presence of tyrosinase, arylamines and o-aminophenols are converted to o-quinone imines, which are isolated as quinone anils or phenoxazones. As an example, in the presence of tyrosinase, 2-amino-3-hydroxybenzoic acid (an o-aminophenol) is converted to cinnabarinic acid, a well-known phenoxazone, while p-aminotoluene (an aromatic amine) gives rise to the formation of 5-amino-2-methyl-1,4-benzoquinone 1-(4-methylanil). Kinetic studies using an oxygen electrode show that arylamines and the corresponding monophenols exhibit similar Michaelis constants. In contrast, the reaction rates observed for aromatic amines are relatively slow as compared to monophenols. The enzymatic conversion of arylamines by tryosinase is different from the typical ones: N-oxidation and ring hydroxylation without further oxidation. This difference originates from the regiospecific hydroxylation (ortho position) and subsequent oxidation of the intermediate o-aminophenol to the corresponding o-quinone imine. Finally, the well-know monooxygenase activity of tyrosinase was also confirmed for the aromatic amine p-aminotoluene, with 18 O 2

  4. High Pressure Diels Alder Reactions of 1-Vinyl-2,2,6-trimethylcyclohexene Catalyzed by Chiral Lewis Acids; An Enantioselective Route to a Drimane Sesquiterpene Precursor.

    NARCIS (Netherlands)

    Knol, Joop; Meetsma, Auke; Feringa, Bernard

    1995-01-01

    The Diels Alder reaction of 1-vinyl-2,2,6-trimethylcyclohexene and 3-((E)-3-(methoxycarbonyl)propenoyl)-1,3-oxazolidin-2-one under high pressure, catalyzed by a chiral bis-imine copper(II) complex, yields a drimane sesquiterpene precursor in a highly regio- and diastereoselective manner with

  5. Three-dimensional aromatic networks.

    Science.gov (United States)

    Toyota, Shinji; Iwanaga, Tetsuo

    2014-01-01

    Three-dimensional (3D) networks consisting of aromatic units and linkers are reviewed from various aspects. To understand principles for the construction of such compounds, we generalize the roles of building units, the synthetic approaches, and the classification of networks. As fundamental compounds, cyclophanes with large aromatic units and aromatic macrocycles with linear acetylene linkers are highlighted in terms of transannular interactions between aromatic units, conformational preference, and resolution of chiral derivatives. Polycyclic cage compounds are constructed from building units by linkages via covalent bonds, metal-coordination bonds, or hydrogen bonds. Large cage networks often include a wide range of guest species in their cavity to afford novel inclusion compounds. Topological isomers consisting of two or more macrocycles are formed by cyclization of preorganized species. Some complicated topological networks are constructed by self-assembly of simple building units.

  6. Convergent Synthesis of Piperidines by the Union of Conjugated Alkynes with Imines: A Unique Regioselective Bond Construction for Heterocycle Synthesis

    Science.gov (United States)

    Chen, Ming Z.; Micalizio, Glenn C.

    2009-01-01

    A two-step process is described for the union of aromatic imines, conjugated alkynes and aldehydes that results in a stereoselective synthesis of highly substituted piperidines. This synthetic process has been made possible by defining a unique regioselective functionalization of conjugated alkynes that establishes a suitably functionalized substrate for subsequent heterocycle-forming cationic annulation. Given the flexibility of the coupling process, heterocycles can be accessed through a process that establishes up to four stereogenic centers and four fused rings. PMID:19817447

  7. Imine-based [2]catenanes in water.

    Science.gov (United States)

    Caprice, Kenji; Pupier, Marion; Kruve, Anneli; Schalley, Christoph A; Cougnon, Fabien B L

    2018-02-07

    We report the efficient condensation of imine-based macrocycles from dialdehyde A and aliphatic diamines B n in pure water. Within the libraries, we identified a family of homologous amphiphilic [2]catenanes, whose self-assembly is primarily driven by the hydrophobic effect. The length and odd-even character of the diamine alkyl linker dictate both the yield and the conformation of the [2]catenanes, whose particular thermodynamic stability further shifts the overall equilibrium in favour of imine condensation. These findings highlight the role played by solvophobic effects in the self-assembly of complex architectures.

  8. Fluorescence recognition of chiral amino alcohols by using a novel ionic liquid sensor.

    Science.gov (United States)

    Cai, Pengfei; Wu, Datong; Zhao, Xiaoyong; Pan, Yuanjiang

    2017-08-07

    A novel task-specific ionic liquid derived from l-phenylalaninol was prepared as an enantioselective fluorescent sensor for the first time. Fluorescent chiral ionic liquid 1 (FCIL1) is found to exhibit highly enantioselective fluorescence enhancements toward both aromatic and non-aromatic chiral amino alcohols. When (S)-FCIL1 was treated with the enantiomers of phenylalaninol, a great fluorescence enhancement at 349 nm could be observed and the value of the enantiomeric fluorescence difference (ef) is 5.92. This demonstrated that the chiral sensor (S)-FCIL1 exhibited an excellent enantioselective response behaviour to d-phenylalaninol. Besides that, both the fluorescence intensity at 349 nm (I 349 ) and the ratio of I 349 to I 282 depend linearly on the concentration of amino alcohols. Both the concentration and the enantiomeric composition could be determined by using the chiral ionic liquid. Differently, the sensor treated with the enantiomers of 2-amino-1-butanol showed an opposite result: the fluorescence intensity of the S-enantiomer is higher than that of the R-enantiomer. Furthermore, the size of the substituents on the chiral carbon might be important for the enantioselective fluorescent response.

  9. Asymmetric and symmetric bolaform supra-amphiphiles: formation of imine bond influenced by aggregation.

    Science.gov (United States)

    Wang, Guangtong; Wu, Guanglu; Wang, Zhiqiang; Zhang, Xi

    2014-02-18

    A series of bolaform supra-amphilphiles with different symmetries were fabricated through dynamic benzoic imine bond formation. The pH dependence of imine formations of these supra-amphiphiles were characterazied. We found that the extent of the imine formation of these supra-amphiphies were different. The supra-amphiphiles with a poorer symmetry always exhibited a lower imine formation at a given pH. Therefore, the varied extent of imine bond formation indicate the different aggregations of these supra-amphilphiles, which are controlled by the molecular symmetry of the supra-amphiphiles.

  10. Semi-catalytic reduction of secondary amides to imines and aldehydes.

    Science.gov (United States)

    Lee, Sun-Hwa; Nikonov, Georgii I

    2014-06-21

    Secondary amides can be reduced by silane HSiMe2Ph into imines and aldehydes by a two-stage process involving prior conversion of amides into iminoyl chlorides followed by catalytic reduction mediated by the ruthenium complex [Cp(i-Pr3P)Ru(NCCH3)2]PF6 (1). Alkyl and aryl amides bearing halogen, ketone, and ester groups were converted with moderate to good yields under mild reaction conditions to the corresponding imines and aldehydes. This procedure does not work for substrates bearing the nitro-group and fails for heteroaromatic amides. In the case of cyano substituted amides, the cyano group is reduced to imine.

  11. Concise methods for the synthesis of chiral polyoxazolines and their application in asymmetric hydrosilylation

    Directory of Open Access Journals (Sweden)

    Wei Jie Li

    2010-03-01

    Full Text Available Seven polyoxazoline ligands were synthesized in high yield in a one-pot reaction by heating polycarboxylic acids or their esters and chiral β-amino alcohols under reflux with concomitant removal of water or the alcohol produced in the reaction. The method is much simpler and more efficient in comparison to those methods reported in the literature.The compounds were used as chiral ligands in the rhodium-catalyzed asymmetric hydrosilylation of aromatic ketones, and the effects of the linkers and the substituents present on the oxazoline rings on the yield and enantioselectivity investigated. Compound 2 was identified as the best ligand of this family for the hydrosilylation of aromatic ketones.

  12. o-Naphthoquinone-Catalyzed Aerobic Oxidation of Amines to (Ket)imines: A Modular Catalyst Approach.

    Science.gov (United States)

    Goriya, Yogesh; Kim, Hun Young; Oh, Kyungsoo

    2016-10-07

    A modular aerobic oxidation of amines to imines has been achieved using an ortho-naphthoquinone (o-NQ) catalyst. The cooperative catalyst system of o-NQ and Cu(OAc) 2 enabled the formation of homocoupled imines from benzylamines, while the presence of TFA helped the formation of cross-coupled imines in excellent yields. The current mild aerobic oxidation protocol could also be applied to the oxidation of secondary amines to imines or ketimines with the help of cocatalyst, Ag 2 CO 3 , with excellent yields.

  13. Analyses of polycyclic aromatic hydrocarbon (PAH) and chiral-PAH analogues-methyl-β-cyclodextrin guest-host inclusion complexes by fluorescence spectrophotometry and multivariate regression analysis.

    Science.gov (United States)

    Greene, LaVana; Elzey, Brianda; Franklin, Mariah; Fakayode, Sayo O

    2017-03-05

    The negative health impact of polycyclic aromatic hydrocarbons (PAHs) and differences in pharmacological activity of enantiomers of chiral molecules in humans highlights the need for analysis of PAHs and their chiral analogue molecules in humans. Herein, the first use of cyclodextrin guest-host inclusion complexation, fluorescence spectrophotometry, and chemometric approach to PAH (anthracene) and chiral-PAH analogue derivatives (1-(9-anthryl)-2,2,2-triflouroethanol (TFE)) analyses are reported. The binding constants (K b ), stoichiometry (n), and thermodynamic properties (Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS)) of anthracene and enantiomers of TFE-methyl-β-cyclodextrin (Me-β-CD) guest-host complexes were also determined. Chemometric partial-least-square (PLS) regression analysis of emission spectra data of Me-β-CD-guest-host inclusion complexes was used for the determination of anthracene and TFE enantiomer concentrations in Me-β-CD-guest-host inclusion complex samples. The values of calculated K b and negative ΔG suggest the thermodynamic favorability of anthracene-Me-β-CD and enantiomeric of TFE-Me-β-CD inclusion complexation reactions. However, anthracene-Me-β-CD and enantiomer TFE-Me-β-CD inclusion complexations showed notable differences in the binding affinity behaviors and thermodynamic properties. The PLS regression analysis resulted in square-correlation-coefficients of 0.997530 or better and a low LOD of 3.81×10 -7 M for anthracene and 3.48×10 -8 M for TFE enantiomers at physiological conditions. Most importantly, PLS regression accurately determined the anthracene and TFE enantiomer concentrations with an average low error of 2.31% for anthracene, 4.44% for R-TFE and 3.60% for S-TFE. The results of the study are highly significant because of its high sensitivity and accuracy for analysis of PAH and chiral PAH analogue derivatives without the need of an expensive chiral column, enantiomeric resolution, or use of a polarized

  14. A High-Resolution Magic Angle Spinning NMR Study of the Enantiodiscrimination of 3,4-Methylenedioxymethamphetamine (MDMA by an Immobilized Polysaccharide-Based Chiral Phase.

    Directory of Open Access Journals (Sweden)

    Juliana C Barreiro

    Full Text Available This paper reports the investigation of the chiral interaction between 3,4-methylenedioxy-methamphetamine (MDMA enantiomers and an immobilized polysaccharide-based chiral phase. For that, suspended-state high-resolution magic angle spinning nuclear magnetic resonance spectroscopy (1H HR-MAS NMR was used. 1H HR-MAS longitudinal relaxation time and Saturation Transfer Difference (STD NMR titration experiments were carried out yielding information at the molecular level of the transient diastereoisomeric complexes of MDMA enantiomers and the chiral stationary phase. The interaction of the enantiomers takes place through the aromatic moiety of MDMA and the aromatic group of the chiral selector by π-π stacking for both enantiomers; however, a stronger interaction was observed for the (R-enantiomer, which is the second one to elute at the chromatographic conditions.

  15. Chemoselective organocatalytic aerobic oxidation of primary amines to secondary imines.

    Science.gov (United States)

    Wendlandt, Alison E; Stahl, Shannon S

    2012-06-01

    Biomimetic aerobic oxidation of primary benzylic amines has been achieved by using a quinone catalyst. Excellent selectivity is observed for primary, unbranched benzylic amines relative to secondary/tertiary amines, branched benzylic amines, and aliphatic amines. The exquisite selectivity for benzylic amines enables oxidative self-sorting within dynamic mixtures of amines and imines to afford high yields of cross-coupled imine products.

  16. Identification of quinone imine containing glutathione conjugates of diclofenac in rat bile.

    Science.gov (United States)

    Waldon, Daniel J; Teffera, Yohannes; Colletti, Adria E; Liu, Jingzhou; Zurcher, Danielle; Copeland, Katrina W; Zhao, Zhiyang

    2010-12-20

    High-resolution accurate MS with an LTQ-Orbitrap was used to identify quinone imine metabolites derived from the 5-hydroxy (5-OH) and 4 prime-hydroxy (4'-OH) glutathione conjugates of diclofenac in rat bile. The initial quinone imine metabolites formed by oxidation of diclofenac have been postulated to be reactive intermediates potentially involved in diclofenac-mediated hepatotoxicity; while these metabolites could be formed using in vitro systems, they have never been detected in vivo. This report describes the identification of secondary quinone imine metabolites derived from 5-OH and 4'-OH diclofenac glutathione conjugates in rat bile. To verify the proposed structures, the diclofenac quinone imine GSH conjugate standards were prepared synthetically and enzymatically. The novel metabolite peaks displayed the identical retention times, accurate mass MS/MS spectra, and the fragmentation patterns as the corresponding authentic standards. The formation of these secondary quinone metabolites occurs only under conditions where bile salt homeostasis was experimentally altered. Standard practice in biliary excretion experiments using bile duct-cannulated rats includes infusion of taurocholic acid and/or other bile acids to replace those lost due to continuous collection of bile; for this experiment, the rats received no replacement bile acid infusion. High-resolution accurate mass spectrometry data and comparison with chemically and enzymatically prepared quinone imines of diclofenac glutathione conjugates support the identification of these metabolites. A mechanism for the formation of these reactive quinone imine containing glutathione conjugates of diclofenac is proposed.

  17. Syntheses of Azo-Imine Derivatives from Vanillin as an Acid Base Indicator

    Directory of Open Access Journals (Sweden)

    Bambang Purwono

    2013-05-01

    Full Text Available Preparations of azo, imine and azo-imine derivatives from vanillin as an indicator of acid-base titration have been carried out. The azo derivative of 4-hydroxy-3-methoxy-5-(phenylazobenzaldehyde 2 was produced by diazotitation reaction of vanillin in 37.04% yield. The azo product was then refluxed with aniline in ethanol to yield azo-imine derivatives, 2-methoxy-6-(phenylazo-4-((phenyliminomethylphenol 1 in 82.21% yield. The imine derivative, 2-methoxy-4-((phenyliminomethyl-phenol 3 was obtained by refluxing of vanillin and aniline mixture in ethanol solvent and produced 82.17% yield. The imine product was then reacted with benzenediazonium chloride salt. However, the products indicated hydrolyzed product of 4-hydroxy-3-methoxy-5-(phenylazobenzaldehyde 2 in 22.15% yield. The 2-methoxy-4-((phenyliminomethylphenol 2 could be used as an indicator for titration of NaOH by H2C2O4 with maximum concentration of H2C2O4 0.1 M while the target compound 1 could be used as titration indicator for titration of NaOH with H2C2O4 with same result using phenolphthalein indicator.

  18. Occurrence of cyclic imines in European commercial seafood and consumers risk assessment

    DEFF Research Database (Denmark)

    Rambla-Alegre, Maria; Miles, Christopher O.; de la Iglesia, Pablo

    2018-01-01

    Cyclic imines constitute a quite recently discovered group of marine biotoxins that act on neural receptors and that bioaccumulate in seafood. They are grouped together due to the imino group functioning as their common pharmacore, responsible for acute neurotoxicity in mice. Cyclic imines (CIs...... countries (Italy, Portugal, Slovenia, Spain, Ireland, Norway, The Netherlands and Denmark) were obtained over 2 years. Emerging cyclic imine concentrations in all the samples were analysed on a LC-3200QTRAP and LC-HRMS QExactive mass spectrometer. In shellfish, two CIs, pinnatoxin G (PnTX-G) and 13...

  19. Extremely long aromatics: diastereomerically pure [19]helicene

    Czech Academy of Sciences Publication Activity Database

    Nejedlý, Jindřich; Rybáček, Jiří; Stará, Irena G.; Starý, Ivo

    2016-01-01

    Roč. 14, č. 2 (2016), s. 78-79 ISSN 2336-7202. [Mezioborové setkání mladých biologů, biochemiků a chemiků /16./. 10.05.2016-13.05.2016, Milovy] R&D Projects: GA ČR(CZ) GA16-08294S Institutional support: RVO:61388963 Keywords : long helicene * long aromatics * chiral molecules Subject RIV: CC - Organic Chemistry

  20. Non-Markovian response of ultrafast coherent electronic ring currents in chiral aromatic molecules in a condensed phase

    International Nuclear Information System (INIS)

    Mineo, H.; Lin, S. H.; Fujimura, Y.; Xu, J.; Xu, R. X.; Yan, Y. J.

    2013-01-01

    Results of a theoretical study on non-Markov response for femtosecond laser-driven coherent ring currents in chiral aromatic molecules embedded in a condensed phase are presented. Coherent ring currents are generated by coherent excitation of a pair of quasi-degenerated π-electronic excited states. The coherent electronic dynamical behaviors are strongly influenced by interactions between the electronic system and phonon bath in a condensed phase. Here, the bath correlation time is not instantaneous but should be taken to be a finite time in ultrashort time-resolved experiments. In such a case, Markov approximation breaks down. A hierarchical master equation approach for an improved semiclassical Drude dissipation model was adopted to examine the non-Markov effects on ultrafast coherent electronic ring currents of (P)-2,2 ′ -biphenol in a condensed phase. Time evolution of the coherent ring current derived in the hierarchical master equation approach was calculated and compared with those in the Drude model in the Markov approximation and in the static limit. The results show how non-Markovian behaviors in quantum beat signals of ring currents depend on the Drude bath damping constant. Effects of temperatures on ultrafast coherent electronic ring currents are also clarified

  1. Metal-free, mild, nonepimerizing, chemo- and enantio- or diastereoselective N-alkylation of amines by alcohols via oxidation/imine-iminium formation/reductive amination: a pragmatic synthesis of octahydropyrazinopyridoindoles and higher ring analogues.

    Science.gov (United States)

    Khan, Imran A; Saxena, Anil K

    2013-12-06

    A mild step and atom-economical nonepimerizing chemo- and enantioselective N-alkylating procedure has been developed via oxidation/imine-iminium formation/reduction cascade using TEMPO-BAIB-HEH-Brønsted acid catalysis in DMPU as solvent and a stoichiometric amount of amine. The optimized conditions were further extended for the nonenzymatic kinetic resolution of the chiral amine thus formed under nonenzymatic in situ hydrogen-transfer conditions using VAPOL-derived phosphoric acid (VAPOL-PA) as the Brønsted acid catalyst. The enantioselective cascade of the presented reaction was successfully utilized in the synthesis of octahydropyrazinopyridoindole and its higher ring analogues.

  2. Examination of new chiral smectics with four aromatic rings

    Science.gov (United States)

    Żurowska, Magdalena; Czerwiński, Michał; Dziaduszek, Jerzy; Filipowicz, Marek

    2018-05-01

    This paper presents the results of the study of four chiral mesogens with the acronym (4X1X2). The investigated compounds might be of interest for use as components of multicomponent mixtures useful in technical devices. The compounds have high chemical stability. Their mesomorphic properties were tested by means of polarizing optical microscopy and differential scanning calorimetry. The helical pitch of the prepared compounds and mixtures was estimated using the selective reflection method. Their phase smectic layer structure and usefulness for formulation of multicomponent antiferroelectric mixtures were then reported.

  3. Reversal of diastereofacial selectivity in hydride reductions of N-tert-butanesulfinyl imines.

    Science.gov (United States)

    Colyer, John T; Andersen, Neil G; Tedrow, Jason S; Soukup, Troy S; Faul, Margaret M

    2006-09-01

    A variety of N-tert-butanesulfinyl imines were reduced with NaBH4 in THF containing 2% water to provide the corresponding secondary sulfinamides in high yield and diastereoselectivity. By using the same sulfinyl imine starting materials and changing the reductant to L-Selectride, the stereoselectivity could be efficiently reversed to afford the opposite product diastereomer in high yield and selectivity.

  4. Chiral near-fields around chiral dolmen nanostructure

    International Nuclear Information System (INIS)

    Fu, Tong; Wang, Tiankun; Chen, Yuyan; Wang, Yongkai; Qu, Yu; Zhang, Zhongyue

    2017-01-01

    Discriminating the handedness of the chiral molecule is of great importance in the field of pharmacology and biomedicine. Enhancing the chiral near-field is one way to increase the chiral signal of chiral molecules. In this paper, the chiral dolmen nanostructure (CDN) is proposed to enhance the chiral near-field. Numerical results show that the CDN can increase the optical chirality of the near-field by almost two orders of magnitude compared to that of a circularly polarized incident wave. In addition, the optical chirality of the near-field of the bonding mode is enhanced more than that of the antibonding mode. These results provide an effective method for tailoring the chiral near-field for biophotonics sensors. (paper)

  5. Mechanical separation of chiral dipoles by chiral light

    International Nuclear Information System (INIS)

    Canaguier-Durand, Antoine; Hutchison, James A; Genet, Cyriaque; Ebbesen, Thomas W

    2013-01-01

    We calculate optical forces and torques exerted on a chiral dipole by chiral light fields and reveal genuine chiral forces in combining the chiral contents of both light field and dipolar matter. Here, the optical chirality is characterized in a general way through the definition of optical chirality density and chirality flow. We show, in particular, that both terms have mechanical effects associated, respectively, with reactive and dissipative components of the chiral forces. Remarkably, these chiral force components are directly related to standard observables: optical rotation for the reactive component and circular dichroism for the dissipative one. As a consequence, the resulting forces and torques are dependent on the enantiomeric form of the chiral dipole. This suggests promising strategies for using chiral light forces to mechanically separate chiral objects according to their enantiomeric form. (paper)

  6. Visible Light Induced Green Transformation of Primary Amines to Imines Using a Silicate Supported Anatase Photocatalyst

    Directory of Open Access Journals (Sweden)

    Sifani Zavahir

    2015-01-01

    Full Text Available Catalytic oxidation of amine to imine is of intense present interest since imines are important intermediates for the synthesis of fine chemicals, pharmaceuticals, and agricultural chemicals. However, considerable efforts have been made to develop efficient methods for the oxidation of secondary amines to imines, while little attention has until recently been given to the oxidation of primary amines, presumably owing to the high reactivity of generated imines of primary amines that are easily dehydrogenated to nitriles. Herein, we report the oxidative coupling of a series of primary benzylic amines into corresponding imines with dioxygen as the benign oxidant over composite catalysts of TiO2 (anatase-silicate under visible light irradiation of λ > 460 nm. Visible light response of this system is believed to be as a result of high population of defects and contacts between silicate and anatase crystals in the composite and the strong interaction between benzylic amine and the catalyst. It is found that tuning the intensity and wavelength of the light irradiation and the reaction temperature can remarkably enhance the reaction activity. Water can also act as a green medium for the reaction with an excellent selectivity. This report contributes to the use of readily synthesized, environmentally benign, TiO2 based composite photocatalyst and solar energy to realize the transformation of primary amines to imine compounds.

  7. Visible light induced green transformation of primary amines to imines using a silicate supported anatase photocatalyst.

    Science.gov (United States)

    Zavahir, Sifani; Zhu, Huaiyong

    2015-01-26

    Catalytic oxidation of amine to imine is of intense present interest since imines are important intermediates for the synthesis of fine chemicals, pharmaceuticals, and agricultural chemicals. However, considerable efforts have been made to develop efficient methods for the oxidation of secondary amines to imines, while little attention has until recently been given to the oxidation of primary amines, presumably owing to the high reactivity of generated imines of primary amines that are easily dehydrogenated to nitriles. Herein, we report the oxidative coupling of a series of primary benzylic amines into corresponding imines with dioxygen as the benign oxidant over composite catalysts of TiO2 (anatase)-silicate under visible light irradiation of λ > 460 nm. Visible light response of this system is believed to be as a result of high population of defects and contacts between silicate and anatase crystals in the composite and the strong interaction between benzylic amine and the catalyst. It is found that tuning the intensity and wavelength of the light irradiation and the reaction temperature can remarkably enhance the reaction activity. Water can also act as a green medium for the reaction with an excellent selectivity. This report contributes to the use of readily synthesized, environmentally benign, TiO2 based composite photocatalyst and solar energy to realize the transformation of primary amines to imine compounds.

  8. The Brønsted Acid-Catalyzed, Enantioselective Aza-Diels-Alder Reaction for the Direct Synthesis of Chiral Piperidones.

    Science.gov (United States)

    Weilbeer, Claudia; Sickert, Marcel; Naumov, Sergei; Schneider, Christoph

    2017-01-12

    We disclose herein the first enantioselective aza-Diels-Alder reaction of β-alkyl-substituted vinylketene silyl-O,O-acetals and imines furnishing a broad range of optically highly enriched 4-alkyl-substituted 2-piperidones. As a catalyst for this one-pot reaction we employed a chiral phosphoric acid which effects a vinylogous Mannich reaction directly followed by ring-closure to the lactam. Subsequent fully diastereoselective transformations including hydrogenation, enolate alkylation, and lactam alkylation/reduction processes converted the cycloadducts into various highly substituted piperidines of great utility for the synthesis of natural products and medicinally active compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Thermally Induced Denitrogenative Annulation for the Synthesis of Dihydroquinolinimines and Chroman-4-imines.

    Science.gov (United States)

    Chou, Chih-Hung; Chen, Ying-Yu; Rajagopal, Basker; Tu, Hsiu-Chung; Chen, Kuan-Lin; Wang, Sheng-Fu; Liang, Chien-Fu; Tyan, Yu-Chang; Lin, Po-Chiao

    2016-03-04

    A rapid growth in synthetic methods for the preparation of diverse organic molecules using N-sulfonyl-1,2,3-triazoles is of great interest in organic synthesis. Transition metals are generally used to activate the α-imino diazo intermediates. Metal-free methods have not been studied in detail, but can be a good complement to transition metal catalysis in the mild reaction conditions. We herein report a novel method for the preparation of 2,3-dihydroquinolin-4-imine and chroman-4-imine analogs from their corresponding N-sulfonyl-1,2,3-triazoles in the absence of metal catalysts. To achieve intramolecular annulation, the introduction of an electron-donating group is required at the meta position of N-sulfonyl-1,2,3-triazole methyl anilines. The inclusion of tailored substituents on the aniline moieties and nitrogen atoms enhances the nucleophilicity of the phenyl π-electrons, thus allowing them to undergo a Friedel-Crafts-type reaction with the highly electrophilic ketenimines. This metal-free method was carefully optimized to generate a variety of dihydroquinolin-4-imines and chroman-4-imines in moderate-to-good yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Diastereoselective Addition of α-Metalated Sulfoxides to Imines Revisited: Mechanism, Computational Studies, and the Effect of External Chiral Ligands

    DEFF Research Database (Denmark)

    Pedersen, Brian; Rein, Tobias; Søtofte, Inger

    2003-01-01

    six-membered "flat chair") was probed by quantum mechanical calculations, which underpinned the idea of using external chiral ligands to enhance the diastereoselectivity of otherwise moderately selective reactions. In this way, the diastereomeric ratio of the product 3a could be raised from (84 : 16...

  11. Competitive chiral induction in a 2D molecular assembly: Intrinsic chirality versus coadsorber-induced chirality.

    Science.gov (United States)

    Chen, Ting; Li, Shu-Ying; Wang, Dong; Wan, Li-Jun

    2017-11-01

    Noncovalently introducing stereogenic information is a promising approach to embed chirality in achiral molecular systems. However, the interplay of the noncovalently introduced chirality with the intrinsic chirality of molecules or molecular aggregations has rarely been addressed. We report a competitive chiral expression of the noncovalent interaction-mediated chirality induction and the intrinsic stereogenic center-controlled chirality induction in a two-dimensional (2D) molecular assembly at the liquid/solid interface. Two enantiomorphous honeycomb networks are formed by the coassembly of an achiral 5-(benzyloxy)isophthalic acid (BIC) derivative and 1-octanol at the liquid/solid interface. The preferential formation of the globally homochiral assembly can be achieved either by using the chiral analog of 1-octanol, ( S )-6-methyl-1-octanol, as a chiral coadsorber to induce chirality to the BIC assembly via noncovalent hydrogen bonding or by covalently linking a chiral center in the side chain of BIC. Both the chiral coadsorber and the intrinsically chiral BIC derivative can act as a chiral seeds to induce a preferred handedness in the assembly of the achiral BIC derivatives. Furthermore, the noncovalent interaction-mediated chirality induction can restrain or even overrule the manifestation of the intrinsic chirality of the BIC molecule and dominate the handedness of the 2D molecular coassembly. This study provides insight into the interplay of intrinsically chiral centers and external chiral coadsorbers in the chiral induction, transfer, and amplification processes of 2D molecular assembly.

  12. Chiral Gold Nanoclusters: Atomic Level Origins of Chirality.

    Science.gov (United States)

    Zeng, Chenjie; Jin, Rongchao

    2017-08-04

    Chiral nanomaterials have received wide interest in many areas, but the exact origin of chirality at the atomic level remains elusive in many cases. With recent significant progress in atomically precise gold nanoclusters (e.g., thiolate-protected Au n (SR) m ), several origins of chirality have been unveiled based upon atomic structures determined by using single-crystal X-ray crystallography. The reported chiral Au n (SR) m structures explicitly reveal a predominant origin of chirality that arises from the Au-S chiral patterns at the metal-ligand interface, as opposed to the chiral arrangement of metal atoms in the inner core (i.e. kernel). In addition, chirality can also be introduced by a chiral ligand, manifested in the circular dichroism response from metal-based electronic transitions other than the ligand's own transition(s). Lastly, the chiral arrangement of carbon tails of the ligands has also been discovered in a very recent work on chiral Au 133 (SR) 52 and Au 246 (SR) 80 nanoclusters. Overall, the origins of chirality discovered in Au n (SR) m nanoclusters may provide models for the understanding of chirality origins in other types of nanomaterials and also constitute the basis for the development of various applications of chiral nanoparticles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2016-11-08

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

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

    Directory of Open Access Journals (Sweden)

    Shengming Xie

    2016-11-01

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

  15. Chiral 1,2- and 1,3-diol-functionalized chromophores as Lego building blocks for coupled structures.

    Science.gov (United States)

    Spange, Stefan; Hofmann, Katja; Walfort, Bernhard; Rüffer, Tobias; Lang, Heinrich

    2005-10-14

    Chiral nitroanilines containing 1,2- or 1,3-diol functionalities have been synthesized by nucleophilic aromatic substitution of fluoronitroanilines with 1-aminopropane-2,3-diols and 2-aminopropane-1,3-diol in the melt. X-ray structure analyses confirm retention of the configuration of the chiral center. The novel chromophores are suitable to link reversibly to various substituted arylboronic acids which allows the construction of new solvatochromic sensor molecules suitable to response to solvent and anion coordination by fluoride. The solvatochromism of the new compounds has been studied using the Kamlet-Taft LSE relationship.

  16. Highly selective formation of imines catalyzed by silver nanoparticles supported on alumina

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen; Poreddy, Raju; Engelbrekt, Christian

    2014-01-01

    The oxidative dehydrogenation of alcohols to aldehydes catalyzed by Ag nanoparticles supported on Al2O3 was studied. The catalyst promoted the direct formation of imines by tandem oxidative dehydrogenation and condensation of alcohols and amines. The reactions were performed under mild conditions......-2 in the gas phase. The use of an efficient and selective Ag catalyst for the oxidative dehydrogenation of alcohol in the presence of amines gives a new green reaction protocol for imine synthesis. (C) 2014, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B...... and afforded the imines in high yield (up to 99%) without any byproducts other than H2O. The highest activity was obtained over 5 wt% Ag/Al2O3 in toluene with air as oxidant. The reactions were also performed under oxidant-free conditions where the reaction was driven to the product side by the production of H...

  17. Chiral symmetry and chiral-symmetry breaking

    International Nuclear Information System (INIS)

    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

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

    Science.gov (United States)

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

    2014-08-14

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

  19. Developing chiral technologies. Optical division by liquid chromatography; Hattensuru kiraru technology. Ekitai chromatography ni yoru kogaku bunkatsu

    Energy Technology Data Exchange (ETDEWEB)

    Onishi, a. [Daicel Chemical Industries, Ltd., Osaka (Japan)

    1998-05-01

    Optical division using chiral fixing phase for polysaccharide derivative based HPLC has been exhibiting superior capability as an analysis means. It now has transcended the framework of analysis as a result of the encounter with the SMB process, and is completing itself as an optically active body manufacturing means. This paper introduces the following examples of applying the chiral fixing phase for HPLC using polysaccharide derivatives as an unconformity identifier to the unconformity identifying mechanism and mass synthesis: 1) aromatic groups and carbamate groups as substitution groups are arranged regularly along a polysaccharide main chain having a regular and unconformable stereostructure, and a certain `unconformity identification field` is formed: 2) hydrogen bonding and dipole-to-dipole interactions take place between solutes in the ester groups and carbamate groups, and such an interaction act as stacking of aromatic rings among those having aromatic rings; and as a result, interactions in 2) occur in the `unconformity identification field` in 1), where the unconformity identification is executed. This paper describes the pseudo migration bed (SMB) process developed by UOP Corporation as a method for mass-synthesizing fillers for the polysaccharide derivative based HPLC. 6 refs., 3 figs.

  20. An Efficient Synthesis of Substituted Quinolines via Indium(III) Chloride Catalyzed Reaction of Imines with Alkynes

    International Nuclear Information System (INIS)

    Zhu, Mei; Fu, Weijun; Xun, Chen; Zou, Guanglong

    2012-01-01

    An efficient synthetic method for the preparation of quinolines through indium(III) chloride-catalyzed tandem addition-cyclization-oxidation reactions of imines with alkynes was developed. The processes can provide a diverse range of quinoline derivatives in good yields from simple imines and alkynes

  1. Enhanced Ionic Conductivity of Poly(Ethylene Imine) Phosphate

    DEFF Research Database (Denmark)

    Senadeera, G.K.R.; Careem, M.A.; Skaarup, Steen

    1996-01-01

    The conductivity of mixtures of phosphoric acid with poly(ethylene imine) has been studied, and it was found that the conductivity of such mixtures with high acid content can be enhanced by the addition of highly dispersed silica (fumed silica). At the same time, silica addition increases the sti...

  2. Computational Prediction and Rationalization, and Experimental Validation of Handedness Induction in Helical Aromatic Oligoamide Foldamers.

    Science.gov (United States)

    Liu, Zhiwei; Hu, Xiaobo; Abramyan, Ara M; Mészáros, Ádám; Csékei, Márton; Kotschy, András; Huc, Ivan; Pophristic, Vojislava

    2017-03-13

    Metadynamics simulations were used to describe the conformational energy landscapes of several helically folded aromatic quinoline carboxamide oligomers bearing a single chiral group at either the C or N terminus. The calculations allowed the prediction of whether a helix handedness bias occurs under the influence of the chiral group and gave insight into the interactions (sterics, electrostatics, hydrogen bonds) responsible for a particular helix sense preference. In the case of camphanyl-based and morpholine-based chiral groups, experimental data confirming the validity of the calculations were already available. New chiral groups with a proline residue were also investigated and were predicted to induce handedness. This prediction was verified experimentally through the synthesis of proline-containing monomers, their incorporation into an oligoamide sequence by solid phase synthesis and the investigation of handedness induction by NMR spectroscopy and circular dichroism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. On chiral and non chiral 1D supermultiplets

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

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

  4. On chiral and non chiral 1D supermultiplets

    International Nuclear Information System (INIS)

    Toppan, Francesco

    2011-01-01

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

  5. [2++2+2] Cycloisomerisation of Aromatic Cyanodiynes in the Synthesis of Pyridohelicenes and Their Analogues

    Czech Academy of Sciences Publication Activity Database

    Klívar, Jiří; Jančařík, Andrej; Šaman, David; Pohl, Radek; Fiedler, Pavel; Bednárová, Lucie; Starý, Ivo; Stará, Irena G.

    2016-01-01

    Roč. 22, č. 40 (2016), s. 14401-14405 ISSN 0947-6539 R&D Projects: GA ČR(CZ) GA14-29667S Institutional support: RVO:61388963 Keywords : aromatic compounds * chiral ity * helical structures * helicenes * heterocycles Subject RIV: CC - Organic Chemistry Impact factor: 5.317, year: 2016

  6. Synthesis and reactions of imines of α,β-ethylenic silicon-containing aldehydes with complex metal hydrides

    International Nuclear Information System (INIS)

    Surnin, V.A.; Stadnichuk, M.D.

    1986-01-01

    Imines of 3-trimethylsilyl-2-propenal or its hydrocarbon analog are reduced chemoselectively at the C=N double bond by sodium borohydride. The direction of lithium aluminum hydride reduction of these imines is not influenced by the nature of the element attached to the C=C bond silicon versus carbon, but rather is determined by the nature of the radical group attached to the nitrogen atom; N-arylimines undergo addition with lithium aluminum hydride at the C=N bond exclusively, whereas for N-alkylimines the addition reactions occur either partially or in full in the 1,4-position, depending on the reaction conditions, to give imines of saturated aldehydes after demetallation

  7. Synthesis and characterization of two new TiO2-containing benzothiazole-based imine composites for organic device applications.

    Science.gov (United States)

    Różycka, Anna; Iwan, Agnieszka; Bogdanowicz, Krzysztof Artur; Filapek, Michal; Górska, Natalia; Pociecha, Damian; Malinowski, Marek; Fryń, Patryk; Hreniak, Agnieszka; Rysz, Jakub; Dąbczyński, Paweł; Marzec, Monika

    2018-01-01

    The effect of the presence of titanium dioxide in two new imines, ( E , E )-(butane-1,4-diyl)bis(oxybutane-4,1-diyl) bis(4-{[(benzo[ d ][1,3]thiazol-2-yl)methylidene]amino}benzoate) (SP1) and ( E )- N -[(benzo[ d ][1,3]thiazol-2-yl)methylidene]-4-dodecylaniline (SP2), on the properties and stability of imine:TiO 2 composites for organic device applications were examined. The investigated titanium dioxide (in anatase form, obtained via the sol-gel method) exhibited a surface area of 59.5 m 2 /g according to Brunauer-Emmett-Teller theory, and its structure is a combination of both meso- and microporous. The average pore diameter calculated by the Barrett-Joyner-Halenda method was 6.2 nm and the cumulative volume of pores was 0.117 m 3 /g. The imine SP1 exhibited columnar organization (Col), while SP2 revealed a hexagonal columnar crystalline phase (Col hk ). The imine:TiO 2 mixtures in various weight ratio (3:0, 3:1, 3:2, 3:3) showed a lower energy gap and HOMO-LUMO energy levels compared to pure TiO 2 . This implies that TiO 2 provides not only a larger surface area for sensitizer adsorption and good electron collection, but also causes a shift of the imine energy levels resulting from intermolecular interaction. Also the temperature of the phase transition was slightly affected with the increase of TiO 2 concentration in imine-based composites. The changes observed in the Fourier transform middle-infrared absorption (FT-MIR) spectra confirmed the significant influence of TiO 2 on structural properties of both investigated imines. Similar interactions of oxygen vacancies existing on the TiO 2 surface with SP1 and SP2 were observed. The imine:TiO 2 mixtures showed good air stability and reusability, which demonstrates its potential for organic device applications.

  8. Synthesis and characterization of two new TiO2-containing benzothiazole-based imine composites for organic device applications

    Science.gov (United States)

    Różycka, Anna; Bogdanowicz, Krzysztof Artur; Filapek, Michal; Górska, Natalia; Pociecha, Damian; Malinowski, Marek; Fryń, Patryk; Hreniak, Agnieszka; Rysz, Jakub; Dąbczyński, Paweł

    2018-01-01

    The effect of the presence of titanium dioxide in two new imines, (E,E)-(butane-1,4-diyl)bis(oxybutane-4,1-diyl) bis(4-{[(benzo[d][1,3]thiazol-2-yl)methylidene]amino}benzoate) (SP1) and (E)-N-[(benzo[d][1,3]thiazol-2-yl)methylidene]-4-dodecylaniline (SP2), on the properties and stability of imine:TiO2 composites for organic device applications were examined. The investigated titanium dioxide (in anatase form, obtained via the sol–gel method) exhibited a surface area of 59.5 m2/g according to Brunauer–Emmett–Teller theory, and its structure is a combination of both meso- and microporous. The average pore diameter calculated by the Barrett–Joyner–Halenda method was 6.2 nm and the cumulative volume of pores was 0.117 m3/g. The imine SP1 exhibited columnar organization (Col), while SP2 revealed a hexagonal columnar crystalline phase (Colhk). The imine:TiO2 mixtures in various weight ratio (3:0, 3:1, 3:2, 3:3) showed a lower energy gap and HOMO–LUMO energy levels compared to pure TiO2. This implies that TiO2 provides not only a larger surface area for sensitizer adsorption and good electron collection, but also causes a shift of the imine energy levels resulting from intermolecular interaction. Also the temperature of the phase transition was slightly affected with the increase of TiO2 concentration in imine-based composites. The changes observed in the Fourier transform middle-infrared absorption (FT-MIR) spectra confirmed the significant influence of TiO2 on structural properties of both investigated imines. Similar interactions of oxygen vacancies existing on the TiO2 surface with SP1 and SP2 were observed. The imine:TiO2 mixtures showed good air stability and reusability, which demonstrates its potential for organic device applications. PMID:29600135

  9. Toxicity of Aromatic Ketone to Yeast Cell and Improvement of the Asymmetric Reduction of Aromatic Ketone Catalyzed by Yeast Cell with the Introduction of Resin Adsorption

    Directory of Open Access Journals (Sweden)

    Zhong-Hua Yang

    2008-01-01

    Full Text Available Asymmetric reduction of the prochiral aromatic ketone catalyzed by yeast cells is one of the most promising routes to produce its corresponding enantiopure aromatic alcohol, but the space-time yield does not meet people’s expectations. Therefore, the toxicity of aromatic ketone and aromatic alcohol to the yeast cell is investigated in this work. It has been found that the aromatic compounds are poisonous to the yeast cell. The activity of yeast cell decreases steeply when the concentration of acetophenone (ACP is higher than 30.0 mmol/L. Asymmetric reduction of acetophenone to chiral S-α-phenylethyl alcohol (PEA catalyzed by the yeast cell was chosen as the model reaction to study in detail the promotion effect of the introduction of the resin adsorption on the asymmetric reduction reaction. The resin acts as the substrate reservoir and product extraction agent in situ. It has been shown that this reaction could be remarkably improved with this technique when the appropriate kind of resin is applied. The enantioselectivity and yield are acceptable even though the initial ACP concentration reaches 72.2 mmol/L.

  10. Lipase-catalyzed highly enantioselective kinetic resolution of boron-containing chiral alcohols.

    Science.gov (United States)

    Andrade, Leandro H; Barcellos, Thiago

    2009-07-16

    The first application of enzymes as catalysts to obtain optically pure boron compounds is described. The kinetic resolution of boron-containing chiral alcohols via enantioselective transesterification catalyzed by lipases was studied. Aromatic, allylic, and aliphatic secondary alcohols containing a boronate ester or boronic acid group were resolved by lipase from Candida antartica (CALB), and excellent E values (E > 200) and high enantiomeric excesses (up to >99%) of both remaining substrates and acetylated product were obtained.

  11. Siegel's chiral boson and the chiral Schwinger model

    International Nuclear Information System (INIS)

    Berger, T.

    1992-01-01

    In this paper Siegel's proposal for a Lagrangian formulation of a chiral boson is analyzed by applying recent results on 2d chiral quantum gravity. A model is derived whose solution consists of a massive scalar and two massless chiral scalars. Therefore it is a minimally bosonized two-fermion chiral Schwinger model

  12. Two-chiral component microemulsion EKC - chiral surfactant and chiral oil. Part 2: diethyl tartrate.

    Science.gov (United States)

    Kahle, Kimberly A; Foley, Joe P

    2007-08-01

    In this second study on dual-chirality microemulsions containing a chiral surfactant and a chiral oil, a less hydrophobic and lower interfacial tension chiral oil, diethyl tartrate, is employed (Part 1, Foley, J. P. et al.., Electrophoresis, DOI: 10.1002/elps.200600551). Six stereochemical combinations of dodecoxycarbonylvaline (DDCV: R, S, or racemic, 2.00% w/v), racemic 2-hexanol (1.65% v/v), and diethyl tartrate (D, L, or racemic, 0.88% v/v) were examined as pseudostationary phases (PSPs) for the enantioseparation of six chiral pharmaceutical compounds: pseudoephedrine, ephedrine, N-methyl ephedrine, metoprolol, synephrine, and atenolol. Average efficiencies increased with the addition of a chiral oil to R-DDCV PSP formulations. Modest improvements in resolution and enantioselectivity (alpha(enant)) were achieved with two-chiral-component systems over the one-chiral-component microemulsion. Slight enantioselective synergies were confirmed using a thermodynamic model. Results obtained in this study are compared to those obtained in Part 1 as well as those obtained with chiral MEEKC using an achiral, low-interfacial-tension oil (ethyl acetate). Dual-chirality microemulsions with the more hydrophobic oil dibutyl tartrate yielded, relative to diethyl tartrate, higher efficiencies (100,000-134,000 vs. 80,800-94,300), but lower resolution (1.64-1.91 vs. 2.08-2.21) due to lower enantioselectivities (1.060-1.067 vs. 1.078-1.081). Atenolol enantiomers could not be separated with the dibutyl tartrate-based microemulsions but were partially resolved using diethyl tartrate microemulsions. A comparable single-chirality microemulsion based on the achiral oil ethyl acetate yielded, relative to diethyl tartrate, lower efficiency (78 300 vs. 91 600), higher resolution (1.99 vs. 1.83), and similar enantioselectivities.

  13. Two-chiral-component microemulsion electrokinetic chromatography-chiral surfactant and chiral oil: part 1. dibutyl tartrate.

    Science.gov (United States)

    Kahle, Kimberly A; Foley, Joe P

    2007-06-01

    The first simultaneous use of a chiral surfactant and a chiral oil for microemulsion EKC (MEEKC) is reported. Six stereochemical combinations of dodecoxycarbonylvaline (DDCV: R, S, or racemic, 2.00% w/v), racemic 2-hexanol (1.65% v/v), and dibutyl tartrate (D, L, or racemic, 1.23% v/v) were examined as chiral pseudostationary phases (PSPs) for the separation of six pairs of pharmaceutical enantiomers: pseudoephedrine, ephedrine, N-methyl ephedrine, metoprolol, synephrine, and atenolol. Subtle differences were observed for three chromatographic figures of merit (alpha(enant), alpha(meth), k) among the chiral microemulsions; a moderate difference was observed for efficiency (N) and elution range. Dual-chirality microemulsions provided both the largest and smallest enantioselectivities, due to small positive and negative synergies between the chiral microemulsion components. For the ephedrine family of compounds, dual-chiral microemulsions with surfactant and oil in opposite stereochemical configurations provided higher enantioselectivities than the single-chiral component microemulsion (RXX), whereas dual-chiral microemulsions with surfactant and oil in the same stereochemical configurations provided lower enantioselectivities than RXX. Slight to moderate enantioselective synergies were confirmed using a thermodynamic model. Efficiencies observed with microemulsions comprised of racemic dibutyl tartrate or dibutyl-D-tartrate were significantly higher than those obtained with dibutyl-L-tartrate, with an average difference in plate count of about 25 000. Finally, one two-chiral-component microemulsion (RXS) provided significantly better resolution than the remaining one- and two-chiral-component microemulsions for the ephedrine-based compounds, but only slightly better or equivalent resolution for non-ephedrine compounds.

  14. Copper(II)-catalyzed exo and enantioselective cycloadditions of azomethine imines.

    Science.gov (United States)

    Sibi, Mukund P; Rane, Digamber; Stanley, Levi M; Soeta, Takahiro

    2008-07-17

    A strategy for exo and enantioselective 1,3-dipolar cycloaddition of azomethine imines to 2-acryloyl-3-pyrazolidinone is described. The corresponding cycloadducts are isolated with high diastereoselectivities (up to >96:4 exo/endo) and enantioselectivities (up to 98% ee).

  15. Chiral superconductors.

    Science.gov (United States)

    Kallin, Catherine; Berlinsky, John

    2016-05-01

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

  16. Chiral Recognition and Separation by Chirality-Enriched Metal-Organic Frameworks.

    Science.gov (United States)

    Das, Saikat; Xu, Shixian; Ben, Teng; Qiu, Shilun

    2018-05-16

    Endowed with chiral channels and pores, chiral metal-organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality-enriched MOFs with accessible pores. The ability of the materials to form host-guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed-matrix membranes (MMMs) composed of chirality-enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Combined Experimental and Theoretical Investigations on Optical Activities of Möbius Aromatic and Möbius Antiaromatic Hexaphyrin Phosphorus Complexes.

    Science.gov (United States)

    Mori, Tadashi; Tanaka, Takayuki; Higashino, Tomohiro; Yoshida, Kota; Osuka, Atsuhiro

    2016-06-23

    Intrinsically chiral Möbius aromatic [28]hexaphyrin monophosphorus(V) and Möbius antiaromatic [30]hexaphyrin bisphosphorus(V) complexes have been optically resolved and their absolute configurations (ACs) were determined by combined experimental and theoretical investigations on their circular dichroisms (CDs). First elutes in chiral HPLC exhibited strong positive Cotton effects (CEs) at the B-band, characteristic for the ML configurations in their Möbius strips. Weak CEs at the Q-band, if attainable, complemented their AC assignment. The whole CD pattern and intensity were well reproduced by time-dependent approximate coupled cluster theory using model systems that omit five outward meso-aryl substituents (inward-meso-retained model), providing a solid basis for AC assignment. The cost efficient TD-DFT method with appropriate functionals for fully substituted (nontruncated) complexes well reproduced CEs around the B-band (but less satisfactory at the Q-band), also allows the rapid AC estimation for their Möbius strips. Observed difference in CDs between aromatic and antiaromatic hexaphyrins were better interpreted by their shifts in energy levels and altered interactions of relevant molecular orbitals, rather than small differences in Möbius geometries nor aromatic/antiaromatic character, despite the correlations recently claimed in planar π-systems.

  18. Chiral Magnetic Spirals

    International Nuclear Information System (INIS)

    Basar, Goekce; Dunne, Gerald V.; Kharzeev, Dmitri E.

    2010-01-01

    We argue that the presence of a very strong magnetic field in the chirally broken phase induces inhomogeneous expectation values, of a spiral nature along the magnetic field axis, for the currents of charge and chirality, when there is finite baryon density or an imbalance between left and right chiralities. This 'chiral magnetic spiral' is a gapless excitation transporting the currents of (i) charge (at finite chirality), and (ii) chirality (at finite baryon density) along the direction of the magnetic field. In both cases it also induces in the transverse directions oscillating currents of charge and chirality. In heavy ion collisions, the chiral magnetic spiral possibly provides contributions both to the out-of-plane and the in-plane dynamical charge fluctuations recently observed at BNL RHIC.

  19. Tuning peptide self-assembly by an in-tether chiral center

    Science.gov (United States)

    Hu, Kuan; Xiong, Wei; Li, Hu; Zhang, Pei-Yu; Yin, Feng; Zhang, Qianling; Jiang, Fan; Li, Zigang

    2018-01-01

    The self-assembly of peptides into ordered nanostructures is important for understanding both peptide molecular interactions and nanotechnological applications. However, because of the complexity and various self-assembling pathways of peptide molecules, design of self-assembling helical peptides with high controllability and tunability is challenging. We report a new self-assembling mode that uses in-tether chiral center-induced helical peptides as a platform for tunable peptide self-assembly with good controllability. It was found that self-assembling behavior was governed by in-tether substitutional groups, where chirality determined the formation of helical structures and aromaticity provided the driving force for self-assembly. Both factors were essential for peptide self-assembly to occur. Experiments and theoretical calculations indicate long-range crystal-like packing in the self-assembly, which was stabilized by a synergy of interpeptide π-π and π-sulfur interactions and hydrogen bond networks. In addition, the self-assembled peptide nanomaterials were demonstrated to be promising candidate materials for applications in biocompatible electrochemical supercapacitors.

  20. Chiral Spirals from Discontinuous Chiral Symmetry

    Science.gov (United States)

    Kojo, Toru

    2014-09-01

    Recently phases of the inhomongeneous chiral condensates (IChC) attract renewed attentions in quark matter context. A number of theoretical studies have suggested that in some domain of moderate quark density the IChC phases are energetically more favored than the normal, chiral symmetric phase. In particular, the NJL-type model studies indicate that the phase of IChCs may mask the usual 1st order chiral phase transition line and its critical end point, and might change the conventional wisdom. In this talk, I will discuss characteristic features of the IChC phases and their potential impacts on the compact star physics. In particular, some of the IChC phases open gaps near the quark Fermi surface, suppressing back-reaction from the quark to gluon sectors. This mechanism delays the chiral restoration in the strange quark sector, forbids the emergence of the large bag constant, and as a consequence, makes the quark matter EOS very stiff. Recently phases of the inhomongeneous chiral condensates (IChC) attract renewed attentions in quark matter context. A number of theoretical studies have suggested that in some domain of moderate quark density the IChC phases are energetically more favored than the normal, chiral symmetric phase. In particular, the NJL-type model studies indicate that the phase of IChCs may mask the usual 1st order chiral phase transition line and its critical end point, and might change the conventional wisdom. In this talk, I will discuss characteristic features of the IChC phases and their potential impacts on the compact star physics. In particular, some of the IChC phases open gaps near the quark Fermi surface, suppressing back-reaction from the quark to gluon sectors. This mechanism delays the chiral restoration in the strange quark sector, forbids the emergence of the large bag constant, and as a consequence, makes the quark matter EOS very stiff. NSF Grants PHY09-69790, PHY13-05891.

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

    OpenAIRE

    Capozziello, S.; Lattanzi, A.

    2004-01-01

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

  2. Chiral nanophotonics chiral optical properties of plasmonic systems

    CERN Document Server

    Schäferling, Martin

    2017-01-01

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

  3. Quantum coherent π-electron rotations in a non-planar chiral molecule induced by using a linearly polarized UV laser pulse

    Science.gov (United States)

    Mineo, Hirobumi; Fujimura, Yuichi

    2015-06-01

    We propose an ultrafast quantum switching method of π-electron rotations, which are switched among four rotational patterns in a nonplanar chiral aromatic molecule (P)-2,2’- biphenol and perform the sequential switching among four rotational patterns which are performed by the overlapped pump-dump laser pulses. Coherent π-electron dynamics are generated by applying the linearly polarized UV pulse laser to create a pair of coherent quasidegenerated excited states. We also plot the time-dependent π-electron ring current, and discussed ring current transfer between two aromatic rings.

  4. RuO4-mediated oxidation of secondary amines 2. imines as main reaction intermediates

    Directory of Open Access Journals (Sweden)

    Florea Cristina A.

    2017-01-01

    Full Text Available Oxidation by RuO4 (generated in situ from RuO2 and NaIO4 of secondary amines such as Bn–NH–CH2R (1; R=H, Me gave complex reaction mixtures, but mainly amides. In the presence of cyanide, the leading products were α-aminonitriles. Comparison of the oxidation products of 1 with those from the corresponding imines PhCH=N–CH2R and Bn–N=CH–R showed that formation of the indicated imines is the first main step in the oxidation of 1. A detailed mechanism is proposed.

  5. Synthetic approaches to aromatic belts: building up strain in macrocyclic polyarenes.

    Science.gov (United States)

    Eisenberg, David; Shenhar, Roy; Rabinovitz, Mordecai

    2010-08-01

    This tutorial review discusses synthetic strategies towards aromatic belts, defined here as double-stranded conjugated macrocycles, such as [n]cyclacenes, [n]cyclophenacenes, Schlüter belt, and Vögtle belt. Their appeal stems, firstly, from the unique nature of their conjugation, having p orbitals oriented radially rather than perpendicular to the plane of the macrocycle. Secondly, as aromatic belts are model compounds of carbon nanotubes of different chiralities, a synthetic strategy towards the buildup of structural strain in these compounds could finally open a route towards rational chemical synthesis of carbon nanotubes. The elusiveness of these compounds has stimulated fascinating and ingenious synthetic strategies over the last decades. The various strategies are classified here by their approach to the buildup of structural strain, which is the main obstacle in the preparation of these curved polyarenes.

  6. Docking, synthesis and bioassay studies of imine derivatives as potential inhibitors for dengue NS2B/ NS3 serine protease

    Directory of Open Access Journals (Sweden)

    Neni Frimayanti

    2017-11-01

    Full Text Available Objective: To search imine derivatives as new active agents against dengue type 2 NS2B/NS3 using molecular docking, since there is no effective vaccine against flaviviral infections. Methods: In this research, molecular docking was performed for a series of imine derivatives and the information obtained from the docking studies was used to explore the binding modes of these imine derivatives with dengue type 2 NS2B/NS3 serine protease. A set of imine were synthesized and bioassay study of the inhibitory activities of these compounds was then performed. Results: The results indicated that MY8 and MY4 have the ability to inhibit DEN2 NS2B/NS3 proteolytic activity. Conclusions: These two compounds were chosen as the reference for the next stage in drug design as new inhibitor agents against NS2B/NS3.

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

    NARCIS (Netherlands)

    Helmich, F.A.; Lee, C.C.; Schenning, A.P.H.J.; Meijer, E.W.

    2010-01-01

    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

  8. Stereospecific synthesis of specifically deuterated metoprolol enantiomers from chiral starting materials

    Energy Technology Data Exchange (ETDEWEB)

    Shetty, H.U.; Murthy, S.S.; Nelson, W.L. (Washington Univ., Seattle, WA (USA). Dept. of Medicinal Chemistry)

    1989-10-01

    Enantiomers of metoprolol (1) containing six deuterium atoms in the isopropyl methyl groups ((2R)), two deuterium atoms at C-2 and C-6 of the aromatic ring ((2S)), and two deuterium atoms at C-3 of the propanolamine side chain ((2S)) were prepared. Chiral 2,2-dimethyl-1,3-dioxolane-4-methanols ((4R) and (4S)) were key synthons. Sources of deuterium were ({sup 2}H{sub 6})-isopropyl-amine, 4-(2-methoxyethyl)-2,6-({sup 2}H{sub 2})-phenol, prepared by {sup 2}HCl/{sup 2}H{sub 2}O exchange, and (4S)-2,2-dimethyl-1,3-dioxolane-4-({sup 2}H{sub 2})-4-methanol, prepared by LiAl{sup 2}H{sub 4} reduction of (4S)-methyl 2,2-dimethyl-1,3-dioxolane-4-carboxylate. Enantiomeric excess was greater than 94% for each of the prepared enantiomers, as determined independently by {sup 1}H NMR spectroscopy on diastereomeric derivatives and by chiral column HPLC. (author).

  9. Chiral Cliffs: Investigating the Influence of Chirality on Binding Affinity.

    Science.gov (United States)

    Schneider, Nadine; Lewis, Richard A; Fechner, Nikolas; Ertl, Peter

    2018-05-11

    Chirality is understood by many as a binary concept: a molecule is either chiral or it is not. In terms of the action of a structure on polarized light, this is indeed true. When examined through the prism of molecular recognition, the answer becomes more nuanced. In this work, we investigated chiral behavior on protein-ligand binding: when does chirality make a difference in binding activity? Chirality is a property of the 3D structure, so recognition also requires an appreciation of the conformation. In many situations, the bioactive conformation is undefined. We set out to address this by defining and using several novel 2D descriptors to capture general characteristic features of the chiral center. Using machine-learning methods, we built different predictive models to estimate if a chiral pair (a set of two enantiomers) might exhibit a chiral cliff in a binding assay. A set of about 3800 chiral pairs extracted from the ChEMBL23 database was used to train and test our models. By achieving an accuracy of up to 75 %, our models provide good performance in discriminating chiral cliffs from non-cliffs. More importantly, we were able to derive some simple guidelines for when one can reasonably use a racemate and when an enantiopure compound is needed in an assay. We critically discuss our results and show detailed examples of using our guidelines. Along with this publication we provide our dataset, our novel descriptors, and the Python code to rebuild the predictive models. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Extreme halophilic alcohol dehydrogenase mediated highly efficient syntheses of enantiopure aromatic alcohols.

    Science.gov (United States)

    Alsafadi, Diya; Alsalman, Safaa; Paradisi, Francesca

    2017-11-07

    Enzymatic synthesis of enantiopure aromatic secondary alcohols (including substituted, hetero-aromatic and bicyclic structures) was carried out using halophilic alcohol dehydrogenase ADH2 from Haloferax volcanii (HvADH2). This enzyme showed an unprecedented substrate scope and absolute enatioselectivity. The cofactor NADPH was used catalytically and regenerated in situ by the biocatalyst, in the presence of 5% ethanol. The efficiency of HvADH2 for the conversion of aromatic ketones was markedly influenced by the steric and electronic factors as well as the solubility of ketones in the reaction medium. Furthermore, carbonyl stretching band frequencies ν (C[double bond, length as m-dash]O) have been measured for different ketones to understand the effect of electron withdrawing or donating properties of the ketone substituents on the reaction rate catalyzed by HvADH2. Good correlation was observed between ν (C[double bond, length as m-dash]O) of methyl aryl-ketones and the reaction rate catalyzed by HvADH2. The enzyme catalyzed the reductions of ketone substrates on the preparative scale, demonstrating that HvADH2 would be a valuable biocatalyst for the preparation of chiral aromatic alcohols of pharmaceutical interest.

  11. Thermal chiral vortical and magnetic waves: New excitation modes in chiral fluids

    Energy Technology Data Exchange (ETDEWEB)

    Kalaydzhyan, Tigran, E-mail: tigran@caltech.edu [Department of Physics, University of Illinois, 845 W Taylor Street, Chicago, IL 60607 (United States); Jet Propulsion Laboratory, 4800 Oak Grove Dr, M/S 298, Pasadena, CA 91109 (United States); Murchikova, Elena [TAPIR, California Institute of Technology, MC 350-17, Pasadena, CA 91125 (United States)

    2017-06-15

    In certain circumstances, chiral (parity-violating) medium can be described hydrodynamically as a chiral fluid with microscopic quantum anomalies. Possible examples of such systems include strongly coupled quark–gluon plasma, liquid helium {sup 3}He-A, neutron stars and the Early Universe. We study first-order hydrodynamics of a chiral fluid on a vortex background and in an external magnetic field. We show that there are two previously undiscovered modes describing heat waves propagating along the vortex and magnetic field. We call them the Thermal Chiral Vortical Wave and Thermal Chiral Magnetic Wave. We also identify known gapless excitations of density (chiral vortical and chiral magnetic waves) and transverse velocity (chiral Alfvén wave). We demonstrate that the velocity of the chiral vortical wave is zero, when the full hydrodynamic framework is applied, and hence the wave is absent and the excitation reduces to the charge diffusion mode. We also comment on the frame-dependent contributions to the obtained propagation velocities.

  12. Thermal chiral vortical and magnetic waves: New excitation modes in chiral fluids

    International Nuclear Information System (INIS)

    Kalaydzhyan, Tigran; Murchikova, Elena

    2017-01-01

    In certain circumstances, chiral (parity-violating) medium can be described hydrodynamically as a chiral fluid with microscopic quantum anomalies. Possible examples of such systems include strongly coupled quark–gluon plasma, liquid helium "3He-A, neutron stars and the Early Universe. We study first-order hydrodynamics of a chiral fluid on a vortex background and in an external magnetic field. We show that there are two previously undiscovered modes describing heat waves propagating along the vortex and magnetic field. We call them the Thermal Chiral Vortical Wave and Thermal Chiral Magnetic Wave. We also identify known gapless excitations of density (chiral vortical and chiral magnetic waves) and transverse velocity (chiral Alfvén wave). We demonstrate that the velocity of the chiral vortical wave is zero, when the full hydrodynamic framework is applied, and hence the wave is absent and the excitation reduces to the charge diffusion mode. We also comment on the frame-dependent contributions to the obtained propagation velocities.

  13. Thermal chiral vortical and magnetic waves: New excitation modes in chiral fluids

    Directory of Open Access Journals (Sweden)

    Tigran Kalaydzhyan

    2017-06-01

    Full Text Available In certain circumstances, chiral (parity-violating medium can be described hydrodynamically as a chiral fluid with microscopic quantum anomalies. Possible examples of such systems include strongly coupled quark–gluon plasma, liquid helium 3He-A, neutron stars and the Early Universe. We study first-order hydrodynamics of a chiral fluid on a vortex background and in an external magnetic field. We show that there are two previously undiscovered modes describing heat waves propagating along the vortex and magnetic field. We call them the Thermal Chiral Vortical Wave and Thermal Chiral Magnetic Wave. We also identify known gapless excitations of density (chiral vortical and chiral magnetic waves and transverse velocity (chiral Alfvén wave. We demonstrate that the velocity of the chiral vortical wave is zero, when the full hydrodynamic framework is applied, and hence the wave is absent and the excitation reduces to the charge diffusion mode. We also comment on the frame-dependent contributions to the obtained propagation velocities.

  14. Non-uniform chiral phase in effective chiral quark models

    International Nuclear Information System (INIS)

    Sadzikowski, M.; Broniowski, W.

    2000-01-01

    We analyze the phase diagram in effective chiral quark models (the Nambu-Jona-Lasinio model, the σ-model with quarks) and show that at the mean-field level a phase with a periodically-modulated chiral fields separates the usual phases with broken and restored chiral symmetry. A possible signal of such a phase is the production of multipion jets travelling in opposite directions, with individual pions having momenta of the order of several hundred MeV. This signal can be interpreted in terms of disoriented chiral condensates. (author)

  15. Insight into the chiral induction in supramolecular stacks through preferential chiral salvation

    NARCIS (Netherlands)

    George, S.J.; Tomovic, Z.; Schenning, A.P.H.J.; Meijer, E.W.

    2011-01-01

    Preferred handedness in the supramolecular chirality of self-assembled achiral oligo(p-phenylenevinylene) (OPV) derivatives is induced by chiral solvents and spectroscopic probing provides insight into the mechanistic aspects of this chiral induction through chiral solvation

  16. Electron induced conformational changes of an imine-based molecular switch on a Au(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Lotze, Christian; Henningsen, Nils; Franke, Katharina; Schulze, Gunnar; Pascual, Jose Ignacio [Inst. f. Experimentalphysik, Freie Universitaet Berlin (Germany); Luo, Ying; Haag, Rainer [Inst. f. Organische Chemie, Freie Universitaet Berlin (Germany)

    2009-07-01

    Azobenzene-based molecules exhibit a cis-trans configurational photoisomerisation in solution. Recently, the adsorption properties of azobenzene derivatives have been investigated on different metal surfaces in order to explore the possible changes in the film properties induced by external stimuli. In azobenzene, the diazo-bridge is a key group for the isomerization process. Its interaction with a metal surface is dominated through the N lone-pair electrons, which reduces the efficiency of the conformational change. In order to reduce the molecule-surface interaction, we explore an alternative molecular architecture by substituting the diazo-bridge (-N=N-) of azobenzene by an imine-group (-N=CH-). We have investigated the imine-based compound para-carboxyl-di-benzene-imine (PCI) adsorbed on a Au(111) surface. The carboxylic terminations mediates the formation of strongly bonded molecular dimers, which align in ordered rows preferentially following the fcc regions of the Au(111) herringbone reconstruction. Low temperature scanning tunneling microscopy was used to induce conformational changes between trans and cis state of individual molecules in a molecular monolayer.

  17. Autoamplification of molecular chirality through the induction of supramolecular chirality

    NARCIS (Netherlands)

    van Dijken, Derk Jan; Beierle, John M.; Stuart, Marc C. A.; Szymanski, Wiktor; Browne, Wesley R.; Feringa, Ben L.

    2014-01-01

    The novel concept for the autoamplification of molecular chirality, wherein the amplification proceeds through the induction of supramolecular chirality, is presented. A solution of prochiral, ring-open diarylethenes is doped with a small amount of their chiral, ring-closed counterpart. The

  18. Active chiral fluids.

    Science.gov (United States)

    Fürthauer, S; Strempel, M; Grill, S W; Jülicher, F

    2012-09-01

    Active processes in biological systems often exhibit chiral asymmetries. Examples are the chirality of cytoskeletal filaments which interact with motor proteins, the chirality of the beat of cilia and flagella as well as the helical trajectories of many biological microswimmers. Here, we derive constitutive material equations for active fluids which account for the effects of active chiral processes. We identify active contributions to the antisymmetric part of the stress as well as active angular momentum fluxes. We discuss four types of elementary chiral motors and their effects on a surrounding fluid. We show that large-scale chiral flows can result from the collective behavior of such motors even in cases where isolated motors do not create a hydrodynamic far field.

  19. Electronic structure and UV spectra of N-arylthio-1,4-benzoquinone imines

    International Nuclear Information System (INIS)

    Pirozhenko, V.V.; Boldeskul, I.E.; Kolesnikov, V.T.; Vid, L.V.; Kuz'menko, L.O.

    1986-01-01

    The electronic structure of N-arylthio-1,4-benzoquinone imines (II) was studied by quantum-chemical methods (CNDO/2). It was shown that the special characteristics of the reactivity of the compounds in reaction with chlorine compared with sulfenylketimines R 2 C=N-S-Ar not containing a quinonoid ring may be due to the different nature of the lowest unoccupied molecular orbitals (LUMO). The UV spectra of compounds (II) were investigated. In the visible region the spectra of all the compounds contain strong absorption (R 1 = R 2 = R 3 = R 4 = R 5 = H, λ/sub m/ = 433 nm, epsilon/sub m/ = 2.12 x 10 4 liters/mole x cm), due to intramolecular charge transfer from the sulfur atom to the quinonoid fragment of the molecule. It was established that there is a linear relation between the energy of the transition and the σ + constants of the substituents in the aryl fragment. The assignment of the transitions was confirmed by calculations of the UV spectra of N-arylthio-1,4-benzoquinone imines by the PPP method. Comparison of the UV spectra of these compounds with the UV spectra of N-arylsulfonyl-1,4-benzoquinone imines makes it possible to conclude that the sulfur atom of the SO 2 group, unlike the divalent sulfur atom, is not capable of transmitting the electronic effects of the substituents from one part of the molecule to the other

  20. In(OTf)3 catalyzed allylation reaction of imines with tetraallyltin

    Institute of Scientific and Technical Information of China (English)

    Xiao Ning Wei; Ling Yan Liu; Bing Wang; Wei Xing Chang; Jing Li

    2009-01-01

    In the presence of catalytic amount of In(OTf)3 (10 mol%), a series of aldimines reacted with tetraallyltin in a 2:1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom efficiency was achieved under mild reaction conditions and a new protocol (allyl)4Sn/In(OTf)3 for simple imines was developed.

  1. Novel Chiral Bis-Phosphoramides as Organocatalysts for Tetrachlorosilane-Mediated Reactions

    Directory of Open Access Journals (Sweden)

    Sergio Rossi

    2017-12-01

    Full Text Available The formation of novel chiral bidentate phosphoroamides structures able to promote Lewis base-catalyzed Lewis acid-mediated reactions was investigated. Two different classes of phosphoroamides were synthetized: the first class presents a phthalic acid/primary diamine moiety, designed with the aim to perform a self-assembly recognition process through hydrogen bonds; the second one is characterized by the presence of two phosphoroamides as side arms connected to a central pyridine unit, able to chelate SiCl4 in a 2:1 adduct. These species were tested as organocatalysts in the stereoselective allylation of benzaldehyde and a few other aromatic aldehydes with allyl tributyltin in the presence of SiCl4 with good results. NMR studies confirm that only pyridine-based phosphoroamides effectively coordinate tetrachlorosilane and may lead to the generation of a self-assembled entity that would act as a promoter of the reaction. Although further work is necessary to clarify and confirm the formation of the hypothesized adduct, the study lays the foundation for the design and the synthesis of chiral supramolecular organocatalysts.

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

    Directory of Open Access Journals (Sweden)

    Mireia Oromí-Farrús

    2012-01-01

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

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

    Science.gov (United States)

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

    2012-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-04-23

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

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

    International Nuclear Information System (INIS)

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

    2010-01-01

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

  6. Chiral discotics; expression and amplification of chirality

    NARCIS (Netherlands)

    Brunsveld, L.; Meijer, E.W.; Rowan, A.E.; Nolte, R.J.M.; Denmark, S.E.; Nolte, R.J.M.; Meijer, E.W.

    2003-01-01

    In this contribution, chirality and discotic liquid crystals are discussed as a tool for studying the self-assembly of these molecules, both in solution and in the solid state. Therefore, the objective of this chapter is to summarize and elucidate how molecular chirality can be expressed in discotic

  7. Static and dynamical anomalies caused by chiral soliton lattice in molecular-based chiral magnets

    International Nuclear Information System (INIS)

    Kishine, Jun-ichiro; Inoue, Katsuya; Kikuchi, Koichi

    2007-01-01

    Interplay of crystallographic chirality and magnetic chirality has been of great interest in both chemist's and physicist's viewpoints. Crystals belonging to chiral space groups are eligible to stabilize macroscopic chiral magnetic order. This class of magnetic order is described by the chiral XY model, where the transverse magnetic field perpendicular to the chiral axis causes the chiral soliton lattice (CSL) formation. As a clear evidence of the chiral magnetic order, the temperature dependence of the transverse magnetization exhibits sharp cusp just below the mean field ferrimagnetic transition temperature, indicating the formation of the CSL. In addition to the static anomaly, we expect the CSL formation also causes dynamical anomalies such as induction of the spin supercurrent

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

    Science.gov (United States)

    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.

  9. Bis-Indole Derivatives for Polysaccharide Compositional Analysis and Chiral Resolution of D-, L-Monosaccharides by Ligand Exchange Capillary Electrophoresis Using Borate-Cyclodextrin as a Chiral Selector

    Directory of Open Access Journals (Sweden)

    Wen-Bin Yang

    2011-02-01

    Full Text Available A series of aldo-bis-indole derivatives (aldo-BINs was prepared by aromatic C-alkylation reactions of aldoses and indole in acetic acid solution. Common monosaccharides such as glucose, mannose, galactose, fucose, xylose, rhamnose, ribose, arabinose and N-acetylglucosamine were smoothly derivatized to form the UV absorbing aldo-BINs. The use of a capillary electrophoretic method to separate these novel aldo-BIN derivatives was established. The capillary electrophoresis conditions were set by using borate buffer (100 mM at high pH (pH 9.0. The limit of determination was assessed to be 25 nM. The enantioseparation of D, L-pairs of aldo-BINs based on chiral ligand-exchange capillary electrophoresis technology was also achieved by using modified hydroxypropyl-β-cyclodextrin as the chiral selector in the presence of borate buffer. This aldose labeling method was applied successfully to the compositional and configurational analysis of saccharides, exemplified by a rapid and efficient method to simultaneously analyze the composition and configuration of saccharides from the medicinal herbs Cordyceps sinensis and Dendrobium huoshanense.

  10. Chirality invariance and 'chiral' fields

    International Nuclear Information System (INIS)

    Ziino, G.

    1978-01-01

    The new field model derived in the present paper actually gives a definite answer to three fundamental questions concerning elementary-particle physics: 1) The phenomenological dualism between parity and chirality invariance: it would be only an apparent display of a general 'duality' principle underlying the intrinsic nature itself of (spin 1/2) fermions and expressed by the anticommutativity property between scalar and pseudoscalar charges. 2) The real physical meaning of V - A current structure: it would exclusively be connected to the one (just pointed out) of chiral fields themselves. 3) The unjustified apparent oddness shown by Nature in weak interactions, for the fact of picking out only one of the two (left- and right-handed) fermion 'chiral' projections: the key to such a 'mystery' would just be provided by the consequences of the dual and partial character of the two fermion-antifermion field bases. (Auth.)

  11. Chiral measurements with the Fixed-Point Dirac operator and construction of chiral currents

    International Nuclear Information System (INIS)

    Hasenfratz, P.; Hauswirth, S.; Holland, K.; Joerg, T.; Niedermayer, F.

    2002-01-01

    In this preliminary study, we examine the chiral properties of the parametrized Fixed-Point Dirac operator D FP , see how to improve its chirality via the Overlap construction, measure the renormalized quark condensate Σ-circumflex and the topological susceptibility χ t , and investigate local chirality of near zero modes of the Dirac operator. We also give a general construction of chiral currents and densities for chiral lattice actions

  12. Rh(III)-catalyzed olefination of N-sulfonyl imines: synthesis of ortho-olefinated benzaldehydes.

    Science.gov (United States)

    Zhang, Tao; Wu, Lamei; Li, Xingwei

    2013-12-20

    Rh(III)-catalyzed olefination of N-sulfonyl imines using acrylates and styrenes has been achieved for the synthesis of ortho-olefinated benaldehydes. This reaction proceeds via a chelation assisted C-H olefination/in situ hydrolysis process.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  14. Influence of microemulsion chirality on chromatographic figures of merit in EKC: results with novel three-chiral-component microemulsions and comparison with one- and two-chiral-component microemulsions.

    Science.gov (United States)

    Kahle, Kimberly A; Foley, Joe P

    2007-08-01

    Novel microemulsion formulations containing all chiral components are described for the enantioseparation of six pairs of pharmaceutical enantiomers (atenolol, ephedrine, metoprolol, N-methyl ephedrine, pseudoephedrine, and synephrine). The chiral surfactant dodecoxycarbonylvaline (DDCV, R- and S-), the chiral cosurfactant S-2-hexanol, and the chiral oil diethyl tartrate (R- and S-) were combined to create four different chiral microemulsions, three of which were stable. Results obtained for enantioselectivity, efficiency, and resolution were compared for the triple-chirality systems and the single-chirality system that contained chiral surfactant only. Improvements in enantioselectivity and resolution were achieved by simultaneously incorporating three chiral components into the aggregate. The one-chiral-component microemulsion provided better efficiencies. Enantioselective synergies were identified for the three-chiral-component nanodroplets using a thermodynamic model. Additionally, two types of dual-chirality systems, chiral surfactant/chiral cosurfactant and chiral surfactant/chiral oil, were examined in terms of chromatographic figures of merit, with the former providing much better resolution. The two varieties of two-chiral-component microemulsions gave similar values for enantioselectivity and efficiency. Lastly, the microemulsion formulations were divided into categories based on the number of chiral microemulsion reagents and the average results for each pair of enantiomers were analyzed for trends. In general, enantioselectivity and resolution were enhanced while efficiency was decreased as more chiral components were used to create the pseudostationary phase (PSP).

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

    International Nuclear Information System (INIS)

    Chernodub, M.N.

    2016-01-01

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

  16. Sensitive criterion for chirality; Chiral doublet bands in 104Rh59

    International Nuclear Information System (INIS)

    Koike, T.; Starosta, K.; Vaman, C.; Ahn, T.; Fossan, D.B.; Clark, R.M.; Cromaz, M.; Lee, I.Y.; Macchiavelli, A.O.

    2003-01-01

    A particle plus triaxial rotor model was applied to odd-odd nuclei in the A ∼ 130 region in order to study the unique parity πh11/2xνh11/2 rotational bands. With maximum triaxiality assumed and the intermediate axis chosen as the quantization axis for the model calculations, the two lowest energy eigenstates of a given spin have chiral properties. The independence of the quantity S(I) on spin can be used as a new criterion for chirality. In addition, a diminishing staggering amplitude of S(I) with increasing spin implies triaxiality in neighboring odd-A nuclei. Chiral quartet bases were constructed specifically to examine electromagnetic properties for chiral structures. A set of selection rules unique to chirality was derived. Doublet bands built on the πg9/2xνh11/2 configuration have been discovered in odd-odd 104Rh using the 96Zr(11B, 3n) reaction. Based on the discussed criteria for chirality, it is concluded that the doublet bands observed in 104Rh exhibit characteristic chiral properties suggesting a new region of chirality around A ∼110. In addition, magnetic moment measurements have been performed to test the πh11/2xνh11/2 configuration in 128Cs and the πg9/2xνh11/2 configuration in 104Rh

  17. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    International Nuclear Information System (INIS)

    Montalvo-Gonzalez, Ruben; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy

    2010-01-01

    Two C 2 -symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh III (Cp * ) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  18. Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Maggi, Agnese; Madsen, Robert

    2012-01-01

    A new method for the direct synthesis of imines from alcohols and amines is described where hydrogen gas is liberated. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex [RuCl2(IiPr)(p-cymene)] in the presence of the ligand DABCO and molecular sieves. The imination can...... be applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol...

  19. Chiral polarization scale of QCD vacuum and spontaneous chiral symmetry breaking

    International Nuclear Information System (INIS)

    Alexandru, Andrei; Horv, Ivan

    2013-01-01

    It has recently been found that dynamics of pure glue QCD supports the low energy band of Dirac modes with local chiral properties qualitatively different from that of a bulk: while bulk modes suppress chirality relative to statistical independence between left and right, the band modes enhance it. The width of such chirally polarized zone – chiral polarization scale bigwedge ch – has been shown to be finite in the continuum limit at fixed physical volume. Here we present evidence that bigwedge ch remains non-zero also in the infinite volume, and is therefore a dynamical scale in the theory. Our experiments in N f = 2+1 QCD support the proposition that the same holds in the massless limit, connecting bigwedge ch to spontaneous chiral symmetry breaking. In addition, our results suggest that thermal agitation in quenched QCD destroys both chiral polarization and condensation of Dirac modes at the same temperature T ch > T c .

  20. Chiral Induction with Chiral Conformational Switches in the Limit of Low "Sergeants to Soldiers" Ratio

    DEFF Research Database (Denmark)

    Nuermaimaiti, Ajiguli; Bombis, Christian; Knudsen, Martin Markvard

    2014-01-01

    Molecular-level insights into chiral adsorption phenomena are highly relevant within the fields of asymmetric heterogeneous catalysis or chiral separation and may contribute to understand the origins of homochirality in nature. Here, we investigate chiral induction by the "sergeants and soldiers......" mechanism for an oligo(phenylene ethynylene) based chiral conformational switch by coadsorbing it with an intrinsically chiral seed on Au(111). Through statistical analysis of scanning tunneling microscopy (STM) data we demonstrate successful chiral induction with a very low concentration of seeding...... molecules down to 3%. The microscopic mechanism for the observed chiral induction is suggested to involve nucleation of the intrinsically chiral seeds, allowing for effective transfer and amplification of chirality to large numbers of soldier target molecules....

  1. α,β-Unsaturated imines via Ru-catalyzed coupling of allylic alcohols and amines.

    Science.gov (United States)

    Rigoli, Jared W; Moyer, Sara A; Pearce, Simon D; Schomaker, Jennifer M

    2012-03-07

    A convenient synthesis of α,β-unsaturated imines requiring only an allylic alcohol, an amine and a Ru catalyst has been developed. The use of large excesses of oxidant and the purification of sensitive intermediates can be avoided.

  2. Interactions of helquats with chiral acidic aromatic analytes investigated by partial-filling affinity capillary electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Růžička, Martin; Koval, Dušan; Vávra, Jan; Reyes Gutierrez, Paul Eduardo; Teplý, Filip; Kašička, Václav

    2016-01-01

    Roč. 1467, Oct 7 (2016), s. 417-426 ISSN 0021-9673 R&D Projects: GA ČR(CZ) GA15-01948S; GA ČR GA13-32974S; GA ČR GA13-19213S Institutional support: RVO:61388963 Keywords : affinity capillary electrophoresis * binding constant * chiral separation * helquats * noncovalent interactions * partial filling Subject RIV: CB - Analytical Chemistry , Separation Impact factor: 3.981, year: 2016

  3. Quenched chiral logarithms

    International Nuclear Information System (INIS)

    Sharpe, S.R.

    1992-04-01

    I develop a diagrammatic method for calculating chiral logarithms in the quenched approximation. While not rigorous, the method is based on physically reasonable assumptions, which can be tested by numerical simulations. The main results are that, at leading order in the chiral expansion, (a) there are no chiral logarithms in quenched f π m u = m d ; (b) the chiral logarithms in B K and related kaon B-parameters are, for m d = m s the same in the quenched approximation as in the full theory (c) for m π and the condensate, there are extra chiral logarithms due to loops containing the η', which lead to a peculiar non-analytic dependence of these quantities on the bare quark mass. Following the work of Gasser and Leutwyler, I discuss how there is a predictable finite volume dependence associated with each chiral logarithm. I compare the resulting predictions with numerical results: for most quantities the expected volume dependence is smaller than the errors. but for B V and B A there is an observed dependence which is consistent with the predictions

  4. Nonlinear spectroscopic studies of chiral media

    International Nuclear Information System (INIS)

    Belkin, Mikhail Alexandrovich

    2004-01-01

    Molecular chirality plays an important role in chemistry, biology, and medicine. Traditional optical techniques for probing chirality, such as circular dichroism and Raman optical activity rely on electric-dipole forbidden transitions. As a result, their intrinsic low sensitivity limits their use to probe bulk chirality rather than chiral surfaces, monolayers or thin films often important for chemical or biological systems. Contrary to the traditional chirality probes, chiral signal in sum-frequency generation (SFG) is electric-dipole allowed both on chiral surface and in chiral bulk making it a much more promising tool for probing molecular chirality. SFG from a chiral medium was first proposed in 1965, but had never been experimentally confirmed until this thesis work was performed. This thesis describes a set of experiments successfully demonstrating that chiral SFG responses from chiral monolayers and liquids are observable. It shows that, with tunable inputs, SFG can be used as a sensitive spectroscopic tool to probe chirality in both electronic and vibrational resonances of chiral molecules. The monolayer sensitivity is feasible in both cases. It also discusses the relevant theoretical models explaining the origin and the strength of the chiral signal in vibrational and electronic SFG spectroscopies

  5. Arabidopsis and Maize RidA Proteins Preempt Reactive Enamine/Imine Damage to Branched-Chain Amino Acid Biosynthesis in Plastids[C][W][OPEN

    Science.gov (United States)

    Niehaus, Thomas D.; Nguyen, Thuy N.D.; Gidda, Satinder K.; ElBadawi-Sidhu, Mona; Lambrecht, Jennifer A.; McCarty, Donald R.; Downs, Diana M.; Cooper, Arthur J.L.; Fiehn, Oliver; Mullen, Robert T.; Hanson, Andrew D.

    2014-01-01

    RidA (for Reactive Intermediate Deaminase A) proteins are ubiquitous, yet their function in eukaryotes is unclear. It is known that deleting Salmonella enterica ridA causes Ser sensitivity and that S. enterica RidA and its homologs from other organisms hydrolyze the enamine/imine intermediates that Thr dehydratase forms from Ser or Thr. In S. enterica, the Ser-derived enamine/imine inactivates a branched-chain aminotransferase; RidA prevents this damage. Arabidopsis thaliana and maize (Zea mays) have a RidA homolog that is predicted to be plastidial. Expression of either homolog complemented the Ser sensitivity of the S. enterica ridA mutant. The purified proteins hydrolyzed the enamines/imines formed by Thr dehydratase from Ser or Thr and protected the Arabidopsis plastidial branched-chain aminotransferase BCAT3 from inactivation by the Ser-derived enamine/imine. In vitro chloroplast import assays and in vivo localization of green fluorescent protein fusions showed that Arabidopsis RidA and Thr dehydratase are chloroplast targeted. Disrupting Arabidopsis RidA reduced root growth and raised the root and shoot levels of the branched-chain amino acid biosynthesis intermediate 2-oxobutanoate; Ser treatment exacerbated these effects in roots. Supplying Ile reversed the root growth defect. These results indicate that plastidial RidA proteins can preempt damage to BCAT3 and Ile biosynthesis by hydrolyzing the Ser-derived enamine/imine product of Thr dehydratase. PMID:25070638

  6. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    Energy Technology Data Exchange (ETDEWEB)

    Montalvo-Gonzalez, Ruben [Universidad Autonoma de Nayarit, Tepic, Nay (Mexico). Unidad Academica de Ciencias Quimico Biologicas y Farmaceuticas; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy, E-mail: somanatha@sundown.sdsu.ed [Instituto Tecnologico de Tijuana, B.C. (Mexico). Centro de Graduados e Investigacion

    2010-07-01

    Two C{sub 2}-symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh{sup III}(Cp{sup *}) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  7. New stereoselective intramolecular

    Science.gov (United States)

    Alajarin; Vidal; Tovar; Ramirez De Arellano MC; Cossio; Arrieta; Lecea

    2000-11-03

    Efficient 1,4-asymmetric induction has been achieved in the highly stereocontrolled intramolecular [2 + 2] cycloadditions between ketenimines and imines, leading to 1,2-dihydroazeto[2, 1-b]quinazolines. The chiral methine carbon adjacent to the iminic nitrogen controls the exclusive formation of the cycloadducts with relative trans configuration at C2 and C8. The stepwise mechanistic model, based on theoretical calculations, fully supports the stereochemical outcome of these cycloadditions.

  8. Silver Films with Hierarchical Chirality.

    Science.gov (United States)

    Ma, Liguo; Cao, Yuanyuan; Duan, Yingying; Han, Lu; Che, Shunai

    2017-07-17

    Physical fabrication of chiral metallic films usually results in singular or large-sized chirality, restricting the optical asymmetric responses to long electromagnetic wavelengths. The chiral molecule-induced formation of silver films prepared chemically on a copper substrate through a redox reaction is presented. Three levels of chirality were identified: primary twisted nanoflakes with atomic crystal lattices, secondary helical stacking of these nanoflakes to form nanoplates, and tertiary micrometer-sized circinates consisting of chiral arranged nanoplates. The chiral Ag films exhibited multiple plasmonic absorption- and scattering-based optical activities at UV/Vis wavelengths based on their hierarchical chirality. The Ag films showed chiral selectivity for amino acids in catalytic electrochemical reactions, which originated from their primary atomic crystal lattices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Induction of Chirality in Two-Dimensional Nanomaterials: Chiral 2D MoS2 Nanostructures.

    Science.gov (United States)

    Purcell-Milton, Finn; McKenna, Robert; Brennan, Lorcan J; Cullen, Conor P; Guillemeney, Lilian; Tepliakov, Nikita V; Baimuratov, Anvar S; Rukhlenko, Ivan D; Perova, Tatiana S; Duesberg, Georg S; Baranov, Alexander V; Fedorov, Anatoly V; Gun'ko, Yurii K

    2018-02-27

    Two-dimensional (2D) nanomaterials have been intensively investigated due to their interesting properties and range of potential applications. Although most research has focused on graphene, atomic layered transition metal dichalcogenides (TMDs) and particularly MoS 2 have gathered much deserved attention recently. Here, we report the induction of chirality into 2D chiral nanomaterials by carrying out liquid exfoliation of MoS 2 in the presence of chiral ligands (cysteine and penicillamine) in water. This processing resulted in exfoliated chiral 2D MoS 2 nanosheets showing strong circular dichroism signals, which were far past the onset of the original chiral ligand signals. Using theoretical modeling, we demonstrated that the chiral nature of MoS 2 nanosheets is related to the presence of chiral ligands causing preferential folding of the MoS 2 sheets. There was an excellent match between the theoretically calculated and experimental spectra. We believe that, due to their high aspect ratio planar morphology, chiral 2D nanomaterials could offer great opportunities for the development of chiroptical sensors, materials, and devices for valleytronics and other potential applications. In addition, chirality plays a key role in many chemical and biological systems, with chiral molecules and materials critical for the further development of biopharmaceuticals and fine chemicals, and this research therefore should have a strong impact on relevant areas of science and technology such as nanobiotechnology, nanomedicine, and nanotoxicology.

  10. Chiral ward-Takahashi identities at finite temperature and chiral phase transition in (2+1) dimensional chiral Gross-Neveu model

    International Nuclear Information System (INIS)

    Shen Kun; Qiu Zhongping

    1993-01-01

    Chiral Ward-Takahashi identities at finite temperature are derived in (2+1) dimensional chiral Gross-Neveu model. In terms of these identities, fermion mass generation and the mass spectra of bound states are investigate at finite temperature. Taking the fermion mass as an order parameter, the authors discuss the phase structure and chiral phase transition and obtain the critical temperature

  11. Synthetic studies toward chiral aromatic triynes as key substrates for the asymmetric synthesis of helicene-like molecules

    Czech Academy of Sciences Publication Activity Database

    Alexandrová, Zuzana; Stará, Irena G.; Sehnal, Petr; Teplý, Filip; Starý, Ivo; Šaman, David; Fiedler, Pavel

    2004-01-01

    Roč. 69, č. 12 (2004), s. 2193-2211 ISSN 0010-0765 R&D Projects: GA ČR GA203/02/0248 Institutional research plan: CEZ:AV0Z4055905 Keywords : alkynes * chirality * helical structures Subject RIV: CC - Organic Chemistry Impact factor: 1.062, year: 2004

  12. Chirality: from QCD to condensed matter

    International Nuclear Information System (INIS)

    Kharzeev, D.

    2015-01-01

    This lecture is about chirality and consists of 4 parts. In the first part a general introduction of chirality is given and its implementation in nuclear and particle physics, in particular the chiral magnetic effect, as well as Chirality in quantum materials (CME, optoelectronics, photonics) are discussed. The 2nd lecture is about the chiral magnetic effect. The 3rd lecture deals with the chiral magnetic effect and hydrodynamics and the last part with chirality and light. (nowak)

  13. Oxidative N-Heterocyclic Carbene-Catalyzed γ-Carbon Addition of Enals to Imines: Mechanistic Studies and Access to Antimicrobial Compounds.

    Science.gov (United States)

    Zheng, Peng-Cheng; Cheng, Jiajia; Su, Shihu; Jin, Zhichao; Wang, Yu-Huang; Yang, Song; Jin, Lin-Hong; Song, Bao-An; Chi, Yonggui Robin

    2015-07-06

    The reaction mechanism of the γ-carbon addition of enal to imine under oxidative N-heterocyclic carbene catalysis is studied experimentally. The oxidation, γ-carbon deprotonation, and nucleophilic addition of γ-carbon to imine were found to be facile steps. The results of our study also provide highly enantioselective access to tricyclic sulfonyl amides that exhibit interesting antimicrobial activities against X. oryzae, a bacterium that causes bacterial disease in rice growing. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Chirality in adsorption on solid surfaces.

    Science.gov (United States)

    Zaera, Francisco

    2017-12-07

    In the present review we survey the main advances made in recent years on the understanding of chemical chirality at solid surfaces. Chirality is an important topic, made particularly relevant by the homochiral nature of the biochemistry of life on Earth, and many chiral chemical reactions involve solid surfaces. Here we start our discussion with a description of surface chirality and of the different ways that chirality can be bestowed on solid surfaces. We then expand on the studies carried out to date to understand the adsorption of chiral compounds at a molecular level. We summarize the work published on the adsorption of pure enantiomers, of enantiomeric mixtures, and of prochiral molecules on chiral and achiral model surfaces, especially on well-defined metal single crystals but also on other flat substrates such as highly ordered pyrolytic graphite. Several phenomena are identified, including surface reconstruction and chiral imprinting upon adsorption of chiral agents, and the enhancement or suppression of enantioselectivity seen in some cases upon adsorption of enantiomixtures of chiral compounds. The possibility of enhancing the enantiopurity of adsorbed layers upon the addition of chiral seeds and the so-called "sergeants and soldiers" phenomenon are presented. Examples are provided where the chiral behavior has been associated with either thermodynamic or kinetic driving forces. Two main approaches to the creation of enantioselective surface sites are discussed, namely, via the formation of supramolecular chiral ensembles made out of small chiral adsorbates, and by adsorption of more complex chiral molecules capable of providing suitable chiral environments for reactants by themselves, via the formation of individual adsorbate:modifier adducts on the surface. Finally, a discussion is offered on the additional effects generated by the presence of the liquid phase often required in practical applications such as enantioselective crystallization, chiral

  15. A metalloenzyme-like catalytic system for the chemoselective oxidative cross-coupling of primary amines to imines under ambient conditions.

    Science.gov (United States)

    Largeron, Martine; Fleury, Maurice-Bernard

    2015-02-23

    The direct oxidative cross-coupling of primary amines is a challenging transformation as homocoupling is usually preferred. We report herein the chemoselective preparation of cross-coupled imines through the synergistic combination of low loadings of Cu(II) metal-catalyst and o-iminoquinone organocatalyst under ambient conditions. This homogeneous cooperative catalytic system has been inspired by the reaction of copper amine oxidases, a family of metalloenzymes with quinone organic cofactors that mediate the selective oxidation of primary amines to aldehydes. After optimization, the desired cross-coupled imines are obtained in high yields with broad substrate scope through a transamination process that leads to the homocoupled imine intermediate, followed by dynamic transimination. The ability to carry out the reactions at room temperature and with ambient air, rather than molecular oxygen as the oxidant, and equimolar amounts of each coupling partner is particularly attractive from an environmentally viewpoint. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Chirality in molecular collision dynamics

    Science.gov (United States)

    Lombardi, Andrea; Palazzetti, Federico

    2018-02-01

    Chirality is a phenomenon that permeates the natural world, with implications for atomic and molecular physics, for fundamental forces and for the mechanisms at the origin of the early evolution of life and biomolecular homochirality. The manifestations of chirality in chemistry and biochemistry are numerous, the striking ones being chiral recognition and asymmetric synthesis with important applications in molecular sciences and in industrial and pharmaceutical chemistry. Chiral discrimination phenomena, due to the existence of two enantiomeric forms, very well known in the case of interaction with light, but still nearly disregarded in molecular collision studies. Here we review some ideas and recent advances about the role of chirality in molecular collisions, designing and illustrating molecular beam experiments for the demonstration of chiral effects and suggesting a scenario for a stereo-directional origin of chiral selection.

  17. Fluxionally chiral DMAP catalysts: kinetic resolution of axially chiral biaryl compounds.

    Science.gov (United States)

    Ma, Gaoyuan; Deng, Jun; Sibi, Mukund P

    2014-10-27

    Can organocatalysts that incorporate fluxional groups provide enhanced selectivity in asymmetric transformations? To address this issue, we have designed chiral 4-dimethylaminopyridine (DMAP) catalysts with fluxional chirality. These catalysts were found to be efficient in promoting the acylative kinetic resolution of secondary alcohols and axially chiral biaryl compounds with selectivity factors of up to 37 and 51, respectively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Photoexcitation circular dichroism in chiral molecules

    Science.gov (United States)

    Beaulieu, S.; Comby, A.; Descamps, D.; Fabre, B.; Garcia, G. A.; Géneaux, R.; Harvey, A. G.; Légaré, F.; Mašín, Z.; Nahon, L.; Ordonez, A. F.; Petit, S.; Pons, B.; Mairesse, Y.; Smirnova, O.; Blanchet, V.

    2018-05-01

    Chiral effects appear in a wide variety of natural phenomena and are of fundamental importance in science, from particle physics to metamaterials. The standard technique of chiral discrimination—photoabsorption circular dichroism—relies on the magnetic properties of a chiral medium and yields an extremely weak chiral response. Here, we propose and demonstrate an orders of magnitude more sensitive type of circular dichroism in neutral molecules: photoexcitation circular dichroism. This technique does not rely on weak magnetic effects, but takes advantage of the coherent helical motion of bound electrons excited by ultrashort circularly polarized light. It results in an ultrafast chiral response and the efficient excitation of a macroscopic chiral density in an initially isotropic ensemble of randomly oriented chiral molecules. We probe this excitation using linearly polarized laser pulses, without the aid of further chiral interactions. Our time-resolved study of vibronic chiral dynamics opens a way to the efficient initiation, control and monitoring of chiral chemical change in neutral molecules at the level of electrons.

  19. Observation of chiral phonons

    KAUST Repository

    Zhu, Hanyu; Yi, Jun; Li, Ming-yang; Xiao, Jun; Zhang, Lifa; Yang, Chih-Wen; Kaindl, Robert A.; Li, Lain-Jong; Wang, Yuan; Zhang, Xiang

    2018-01-01

    Chirality reveals symmetry breaking of the fundamental interaction of elementary particles. In condensed matter, for example, the chirality of electrons governs many unconventional transport phenomena such as the quantum Hall effect. Here we show that phonons can exhibit intrinsic chirality in monolayer tungsten diselenide. The broken inversion symmetry of the lattice lifts the degeneracy of clockwise and counterclockwise phonon modes at the corners of the Brillouin zone. We identified the phonons by the intervalley transfer of holes through hole-phonon interactions during the indirect infrared absorption, and we confirmed their chirality by the infrared circular dichroism arising from pseudoangular momentum conservation. The chiral phonons are important for electron-phonon coupling in solids, phonon-driven topological states, and energy-efficient information processing.

  20. Observation of chiral phonons

    KAUST Repository

    Zhu, Hanyu

    2018-02-01

    Chirality reveals symmetry breaking of the fundamental interaction of elementary particles. In condensed matter, for example, the chirality of electrons governs many unconventional transport phenomena such as the quantum Hall effect. Here we show that phonons can exhibit intrinsic chirality in monolayer tungsten diselenide. The broken inversion symmetry of the lattice lifts the degeneracy of clockwise and counterclockwise phonon modes at the corners of the Brillouin zone. We identified the phonons by the intervalley transfer of holes through hole-phonon interactions during the indirect infrared absorption, and we confirmed their chirality by the infrared circular dichroism arising from pseudoangular momentum conservation. The chiral phonons are important for electron-phonon coupling in solids, phonon-driven topological states, and energy-efficient information processing.

  1. On the synthesis of 11C-labelled aromatic amino acids

    International Nuclear Information System (INIS)

    Halldin, C.

    1984-01-01

    The use of 11 C-labelled aromatic amino acids in positron emission tomography (PET) and their importance in physiological studies, especially cerebral protein synthesis or their role as precursors of neurotransmitters, is discussed. The synthesis of 11 -C-labelled aromatic amino acids by various routes is presented and new 11 C-labelled precursors, aromatic and aliphatic 11 C-aldehydes, are reported. The 11 C-aldehydes were obtained in 60-95% radiochemical yield and reaction times were of the order of 5 min. The 11 C-aldehydes have been used in condensation reactions with 2-aryl-5-oxazolones in the presence of a tertiary amine, diazabicyclooctane (DABCO), to produce the corresponding [α- 11 C]-4-arylene-2-aryl-5-oxazolones. Ring opening, hydrogenation and removal of protecting groups were carried out in one step to produce the racemic [3- 11 C]-labelled aromatic amino acids in 8-30% radiochemical yield. The total reaction time was 52-60 min. L-[3- 11 C]Phenylalanine was obtained by a seven-step synthesis in 80% e.e. (enantiomeric excess) and 60% e.e., respectively, in 10-15% radiochemical yield within 60 min, by use of the chiral rhodium complex of (R)-1,2-bis(diphenylphosphino)propane ((R)-PROPHOS) or (+)-2,3-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane ((+)-DIOP) in the hydrogenation reaction. Racemic [2- 11 C]-labelled aromatic amino acids were produced by a high-pressure, high-temperature modification of the Buechere-Strecker synthesis. [2- 11 C]Phenylglycine was obtained in 20% radiochemical yield within 50 min. [3- 11 C]Phenylpyruvic acid was prepared via the aldehyde-oxyzolone condensation reaction in 40% radiochemical yield within 40 min (not including LC separation). Its use in the synthesis of [3- 11 C]-phenylalanine by enzymatic transamination is also discussed. With 32 refs.(Author)

  2. Identifying chiral bands in real nuclei

    International Nuclear Information System (INIS)

    Shirinda, O.; Lawrie, E.A.

    2012-01-01

    The application of the presently used fingerprints of chiral bands (originally derived for strongly broken chirality) is investigated for real chiral systems. In particular the chiral fingerprints concerning the B(M1) staggering patterns and the energy staggering are studied. It is found that both fingerprints show considerable changes for real chiral systems, a behaviour that creates a significant risk for misinterpretation of the experimental data and can lead to a failure to identify real chiral systems. (orig.)

  3. Functionalized Poly(propylene imine) Dendrimers as Novel Phase Transfer Catalyst in Supercritical Cabon Dioxide

    NARCIS (Netherlands)

    Goetheer, E.L.V.; Baars, M.W.P.L.; Broeke, van den L.J.P.; Meijer, E.W.; Keurentjes, J.T.F.

    2000-01-01

    Perfluoro-functionalized poly(propylene imine) dendrimers have been used as reactive extractants for anionic species and as phase transfer catalysts for two types of reactions. Different generations of dendrimers have been used for applications in carbon dioxide. First, the reactive extraction of

  4. Chirality-controlled crystallization via screw dislocations.

    Science.gov (United States)

    Sung, Baeckkyoung; de la Cotte, Alexis; Grelet, Eric

    2018-04-11

    Chirality plays an important role in science from enantiomeric separation in chemistry to chiral plasmonics in nanotechnology. However, the understanding of chirality amplification from chiral building blocks to ordered helical superstructures remains a challenge. Here, we demonstrate that topological defects, such as screw dislocations, can drive the chirality transfer from particle to supramolecular structure level during the crystallization process. By using a model system of chiral particles, which enables direct imaging of single particle incorporation into growing crystals, we show that the crystallization kinetic pathway is the key parameter for monitoring, via the defects, the chirality amplification of the crystalline structures from racemic to predominantly homohelical. We provide an explanation based on the interplay between geometrical frustration, racemization induced by thermal fluctuations, and particle chirality. Our results demonstrate that screw dislocations not only promote the growth, but also control the chiral morphology and therefore the functionality of crystalline states.

  5. Spin Chirality of Cu3 and V3 Nanomagnets. 1. Rotation Behavior of Vector Chirality, Scalar Chirality, and Magnetization in the Rotating Magnetic Field, Magnetochiral Correlations.

    Science.gov (United States)

    Belinsky, Moisey I

    2016-05-02

    The rotation behavior of the vector chirality κ, scalar chirality χ, and magnetization M in the rotating magnetic field H1 is considered for the V3 and Cu3 nanomagnets, in which the Dzialoshinsky-Moriya coupling is active. The polar rotation of the field H1 of the given strength H1 results in the energy spectrum characterized by different vector and scalar chiralities in the ground and excited states. The magnetochiral correlations between the vector and scalar chiralities, energy, and magnetization in the rotating field were considered. Under the uniform polar rotation of the field H1, the ground-state chirality vector κI performs sawtooth oscillations and the magnetization vector MI performs the sawtooth oscillating rotation that is accompanied by the correlated transformation of the scalar chirality χI. This demonstrates the magnetochiral effect of the joint rotation behavior and simultaneous frustrations of the spin chiralities and magnetization in the rotating field, which are governed by the correlation between the chiralities and magnetization.

  6. Chiral forces and molecular dissymmetry

    International Nuclear Information System (INIS)

    Mohan, R.

    1992-01-01

    Chiral molecules leading to helical macromolecules seem to preserve information and extend it better. In the biological world RNA is the very paradigm for self-replication, elongation and autocatalytic editing. The nucleic acid itself is not chiral. It acquires its chirality by association with D-sugars. Although the chiral information or selectivity put in by the unit monomer is no longer of much interest to the biologists - they tend to leave it to the Darwinian selection principle to take care of it as illustrated by Frank's model - it is vital to understand the origin of chirality. There are three different approaches for the chiral origin of life: (1) Phenomenological, (2) Electromagnetic molecular and Coriolis forces and (3) Atomic or nuclear force, the neutral weak current. The phenomenological approach involves spontaneous symmetry breaking fluctuations in far for equilibrium systems or nucleation and crystallization. Chance plays a major role in the chiral molecule selected

  7. Introduction to Chiral Symmetry

    Energy Technology Data Exchange (ETDEWEB)

    Koch, Volker [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2017-05-09

    These lectures are an attempt to a pedagogical introduction into the elementary concepts of chiral symmetry in nuclear physics. We will also discuss some effective chiral models such as the linear and nonlinear sigma model as well as the essential ideas of chiral perturbation theory. We will present some applications to the physics of ultrarelativistic heavy ion collisionsd.

  8. Introduction to chiral symmetry

    International Nuclear Information System (INIS)

    Koch, V.

    1996-01-01

    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

  9. Chiral algebras for trinion theories

    International Nuclear Information System (INIS)

    Lemos, Madalena; Peelaers, Wolfger

    2015-01-01

    It was recently understood that one can identify a chiral algebra in any four-dimensional N=2 superconformal theory. In this note, we conjecture the full set of generators of the chiral algebras associated with the T n theories. The conjecture is motivated by making manifest the critical affine module structure in the graded partition function of the chiral algebras, which is computed by the Schur limit of the superconformal index for T n theories. We also explicitly construct the chiral algebra arising from the T 4 theory. Its null relations give rise to new T 4 Higgs branch chiral ring relations.

  10. Simplified chiral superfield propagators for chiral constant mass superfields

    International Nuclear Information System (INIS)

    Srivastava, P.P.

    1983-01-01

    Unconstrained superfield potentials are introduced to derive Feynman rules for chiral superfields following conventional procedure which is easy and instructive. Propagators for the case when the mass parameters are constant chiral superfields are derived. The propagators reported here are very simple compared to those available in literature and allow a manageable calculation of higher loops. (Author) [pt

  11. Role of Achiral Nucleobases in Multicomponent Chiral Self-Assembly: Purine-Triggered Helix and Chirality Transfer.

    Science.gov (United States)

    Deng, Ming; Zhang, Li; Jiang, Yuqian; Liu, Minghua

    2016-11-21

    Chiral self-assembly is a basic process in biological systems, where many chiral biomolecules such as amino acids and sugars play important roles. Achiral nucleobases usually covalently bond to saccharides and play a significant role in the formation of the double helix structure. However, it remains unclear how the achiral nucleobases can function in chiral self-assembly without the sugar modification. Herein, we have clarified that purine nucleobases could trigger N-(9-fluorenylmethox-ycarbonyl) (Fmoc)-protected glutamic acid to self-assemble into helical nanostructures. Moreover, the helical nanostructure could serve as a matrix and transfer the chirality to an achiral fluorescence probe, thioflavin T (ThT). Upon chirality transfer, the ThT showed not only supramolecular chirality but also circular polarized fluorescence (CPL). Without the nucleobase, the self-assembly processes cannot happen, thus providing an example where achiral molecules played an essential role in the expression and transfer of the chirality. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Timoshenko beam model for chiral materials

    Science.gov (United States)

    Ma, T. Y.; Wang, Y. N.; Yuan, L.; Wang, J. S.; Qin, Q. H.

    2018-06-01

    Natural and artificial chiral materials such as deoxyribonucleic acid (DNA), chromatin fibers, flagellar filaments, chiral nanotubes, and chiral lattice materials widely exist. Due to the chirality of intricately helical or twisted microstructures, such materials hold great promise for use in diverse applications in smart sensors and actuators, force probes in biomedical engineering, structural elements for absorption of microwaves and elastic waves, etc. In this paper, a Timoshenko beam model for chiral materials is developed based on noncentrosymmetric micropolar elasticity theory. The governing equations and boundary conditions for a chiral beam problem are derived using the variational method and Hamilton's principle. The static bending and free vibration problem of a chiral beam are investigated using the proposed model. It is found that chirality can significantly affect the mechanical behavior of beams, making materials more flexible compared with nonchiral counterparts, inducing coupled twisting deformation, relatively larger deflection, and lower natural frequency. This study is helpful not only for understanding the mechanical behavior of chiral materials such as DNA and chromatin fibers and characterizing their mechanical properties, but also for the design of hierarchically structured chiral materials.

  13. Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality.

    Science.gov (United States)

    Arthurs, Ross A; Ismail, Muhammad; Prior, Christopher C; Oganesyan, Vasily S; Horton, Peter N; Coles, Simon J; Richards, Christopher J

    2016-02-24

    Reaction of [IrCp*Cl2 ]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6 H4 ) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp *,RIr *. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc ,Sp ,RIr . Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Investigation of a Quantitative Method for the Analysis of Chiral Monoterpenes in White Wine by HS-SPME-MDGC-MS of Different Wine Matrices

    Directory of Open Access Journals (Sweden)

    Mei Song

    2015-04-01

    Full Text Available A valid quantitative method for the analysis of chiral monoterpenes in white wine using head-space solid phase micro-extraction-MDGC-MS (HS-SPME-MDGC-MS with stable isotope dilution analysis was established. Fifteen compounds: (S-(−-limonene, (R-(+-limonene, (+-(2R,4S-cis-rose oxide, (−-(2S,4R-cis-rose oxide, (−-(2R,4R-trans-rose oxide, (+-(2S,4S-cis-rose oxide, furanoid (+-trans-linalool oxide, furanoid (−-cis-linalool oxide, furanoid (−-trans-linalool oxide, furanoid (+-cis-linalool oxide, (−-linalool, (+-linalool, (−-α-terpineol, (+-α-terpineol and (R-(+-β-citronellol were quantified. Two calibration curves were plotted for different wine bases, with varying residual sugar content, and three calibration curves for each wine base were investigated during a single fiber’s lifetime. This was needed as both sugar content and fiber life impacted the quantification of the chiral terpenes. The chiral monoterpene content of six Pinot Gris wines and six Riesling wines was then analyzed using the verified method. ANOVA with Tukey multiple comparisons showed significant differences for each of the detected chiral compounds in all 12 wines. PCA score plots showed a clear separation between the Riesling and Pinot Gris wines. Riesling wines had greater number of chiral terpenes in comparison to Pinot Gris wines. Beyond total terpene content it is possible that the differences in chiral terpene content may be driving the aromatic differences in white wines.

  15. Merging constitutional and motional covalent dynamics in reversible imine formation and exchange processes.

    Science.gov (United States)

    Kovaříček, Petr; Lehn, Jean-Marie

    2012-06-06

    The formation and exchange processes of imines of salicylaldehyde, pyridine-2-carboxaldehyde, and benzaldehyde have been studied, showing that the former has features of particular interest for dynamic covalent chemistry, displaying high efficiency and fast rates. The monoimines formed with aliphatic α,ω-diamines display an internal exchange process of self-transimination type, inducing a local motion of either "stepping-in-place" or "single-step" type by bond interchange, whose rate decreases rapidly with the distance of the terminal amino groups. Control of the speed of the process over a wide range may be achieved by substituents, solvent composition, and temperature. These monoimines also undergo intermolecular exchange, thus merging motional and constitutional covalent behavior within the same molecule. With polyamines, the monoimines formed execute internal motions that have been characterized by extensive one-dimensional, two-dimensional, and EXSY proton NMR studies. In particular, with linear polyamines, nondirectional displacement occurs by shifting of the aldehyde residue along the polyamine chain serving as molecular track. Imines thus behave as simple prototypes of systems displaying relative motions of molecular moieties, a subject of high current interest in the investigation of synthetic and biological molecular motors. The motional processes described are of dynamic covalent nature and take place without change in molecular constitution. They thus represent a category of dynamic covalent motions, resulting from reversible covalent bond formation and dissociation. They extend dynamic covalent chemistry into the area of molecular motions. A major further step will be to achieve control of directionality. The results reported here for imines open wide perspectives, together with other chemical groups, for the implementation of such features in multifunctional molecules toward the design of molecular devices presenting a complex combination of

  16. Chiral Responsive Liquid Quantum Dots.

    Science.gov (United States)

    Zhang, Jin; Ma, Junkai; Shi, Fangdan; Tian, Demei; Li, Haibing

    2017-08-01

    How to convert the weak chiral-interaction into the macroscopic properties of materials remains a huge challenge. Here, this study develops highly fluorescent, selectively chiral-responsive liquid quantum dots (liquid QDs) based on the hydrophobic interaction between the chiral chains and the oleic acid-stabilized QDs, which have been designated as (S)-1810-QDs. The fluorescence spectrum and liquidity of thermal control demonstrate the fluorescence properties and the fluidic behavior of (S)-1810-QDs in the solvent-free state. Especially, (S)-1810-QDs exhibit a highly chiral-selective response toward (1R, 2S)-2-amino-1,2-diphenyl ethanol. It is anticipated that this study will facilitate the construction of smart chiral fluidic sensors. More importantly, (S)-1810-QDs can become an attractive material for chiral separation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. A catalyst-free addition reaction of zinc amide enolates to N-sulfonyle imines

    Energy Technology Data Exchange (ETDEWEB)

    Joo, Seong Ryu; Im, Pyeong Won; Kim, Jong Sung; Kim, Seung Hoi [Dept. of Chemistry, Dankook University, Cheonan (Korea, Republic of); Park Soo Youl [Interface Chemistry and Engineering Research Team, Korea Research Institute of Chemical Technology, Daejon (Korea, Republic of)

    2016-12-15

    Despite the remarkable expansion of the imino-Reformatsky reaction, one interesting aspect is that, to the best of our knowledge, zinc enolates derived solely from α-halo esters have been mainly used in the recent progress. In contrast, a few limited examples have been reported concerning the application of zinc enolates derived from α-halo amide to the imino-Reformatsky reaction. In recent years, Rodriguez-Solla and co-workers reported the addition reaction of samarium enolates derived from both α-halo esters and amides to imines, resulting in the synthe- sis of β-amino esters or amides. In conclusion, we established a potential synthetic proto- col for the preparation of β-amino amides. This work was accomplished by the direct addition of zinc amide enolates to N-sulfonyl imines in the absence of any metal-catalyst under mild conditions. Due to the operational simplicity of the proposed method, it can be further utilized in synthetic organic chemistry. Further studies to elucidate the scope of this approach are currently underway in our laboratory.

  18. A catalyst-free addition reaction of zinc amide enolates to N-sulfonyle imines

    International Nuclear Information System (INIS)

    Joo, Seong Ryu; Im, Pyeong Won; Kim, Jong Sung; Kim, Seung Hoi; Park Soo Youl

    2016-01-01

    Despite the remarkable expansion of the imino-Reformatsky reaction, one interesting aspect is that, to the best of our knowledge, zinc enolates derived solely from α-halo esters have been mainly used in the recent progress. In contrast, a few limited examples have been reported concerning the application of zinc enolates derived from α-halo amide to the imino-Reformatsky reaction. In recent years, Rodriguez-Solla and co-workers reported the addition reaction of samarium enolates derived from both α-halo esters and amides to imines, resulting in the synthe- sis of β-amino esters or amides. In conclusion, we established a potential synthetic proto- col for the preparation of β-amino amides. This work was accomplished by the direct addition of zinc amide enolates to N-sulfonyl imines in the absence of any metal-catalyst under mild conditions. Due to the operational simplicity of the proposed method, it can be further utilized in synthetic organic chemistry. Further studies to elucidate the scope of this approach are currently underway in our laboratory

  19. Applications of chiral symmetry

    International Nuclear Information System (INIS)

    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 χ implies that the ρ and a 1 vector mesons are degenerate in mass. In a gauged linear sigma model the ρ mass increases with temperature, m ρ (T χ ) > m ρ (0). The author conjectures that at T χ the thermal ρ - a 1 , peak is relatively high, at about ∼1 GeV, with a width approximately that at zero temperature (up to standard kinematic factors). The ω meson also increases in mass, nearly degenerate with the ρ, but its width grows dramatically with temperature, increasing to at least ∼100 MeV by T χ . 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 quenchedclose 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

  20. Helical Polyacetylenes Induced via Noncovalent Chiral Interactions and Their Applications as Chiral Materials.

    Science.gov (United States)

    Maeda, Katsuhiro; Yashima, Eiji

    2017-08-01

    Construction of predominantly one-handed helical polyacetylenes with a desired helix sense utilizing noncovalent chiral interactions with nonracemic chiral guest compounds based on a supramolecular approach is described. As with the conventional dynamic helical polymers possessing optically active pendant groups covalently bonded to the polymer chains, this noncovalent helicity induction system can show significant chiral amplification phenomena, in which the chiral information of the nonracemic guests can transfer with high cooperativity through noncovalent bonding interactions to induce an almost single-handed helical conformation in the polymer backbone. An intriguing "memory effect" of the induced macromolecular helicity is observed for some polyacetylenes, which means that the helical conformations induced in dynamic helical polyacetylene can be transformed into metastable static ones by tuning their helix-inversion barriers. Potential applications of helical polyacetylenes with controlled helix sense constructed by the "noncovalent helicity induction and/or memory effect" as chiral materials are also described.

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

    Science.gov (United States)

    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.

  2. Chiral Synthons in Pesticide Syntheses

    NARCIS (Netherlands)

    Feringa, Bernard

    1988-01-01

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

  3. Nucleation Mechanisms of Aromatic Polyesters, PET, PBT, and PEN, on Single-Wall Carbon Nanotubes: Early Nucleation Stages

    Directory of Open Access Journals (Sweden)

    Adriana Espinoza-Martínez

    2012-01-01

    Full Text Available Nucleation mechanisms of poly(ethylene terephthalate (PET, poly(butylene terephthalate (PBT, and poly(ethylene naphthalate (PEN on single-wall carbon nanotubes (SWNTs are proposed, based on experimental evidence, theoretical epitaxy analysis, and semiempirical quantum chemical calculations. In order to elucidate early nucleation stages polyester-coated nanotubes were obtained from highly diluted solutions. High-resolution transmission electron microscopy (HRTEM revealed helical morphologies for PET/SWNTs and PEN/SWNTs and the formation of lobules with different orientations for PBT/SWNTs. To explain the morphological behavior one model was proposed based on crystallographic interactions, that is, epitaxy. Theoretical epitaxy calculations indicated that epitaxy is not possible from the strict epitaxy point of view. Instead, aromatic self-assembly mechanism was proposed based on π-π interactions and the chirality of the nanotube. It was proposed that the mechanism implies two steps to produce helical or lobular morphologies with different orientations. In the first step polymer chains were approached, aligned parallel to the nanotube axis and adsorbed due to electrostatic interactions and the flexibility of the molecule. However, due to π-π interactions between the aromatic rings of the polymer and the nanotube, in the second step chains reoriented on the nanotube surface depending on the chirality of the nanotube. The mechanism was supported by semi-empirical calculations.

  4. Chiral bag model

    International Nuclear Information System (INIS)

    Musakhanov, M.M.

    1980-01-01

    The chiral bag model is considered. It is suggested that pions interact only with the surface of a quark ''bag'' and do not penetrate inside. In the case of a large bag the pion field is rather weak and goes to the linearized chiral bag model. Within that model the baryon mass spectrum, β decay axial constant, magnetic moments of baryons, pion-baryon coupling constants and their form factors are calculated. It is shown that pion corrections to the calculations according to the chiral bag model is essential. The obtained results are found to be in a reasonable agreement with the experimental data

  5. Cell Chirality Drives Left-Right Asymmetric Morphogenesis.

    Science.gov (United States)

    Inaki, Mikiko; Sasamura, Takeshi; Matsuno, Kenji

    2018-01-01

    Most macromolecules found in cells are chiral, meaning that they cannot be superimposed onto their mirror image. However, cells themselves can also be chiral, a subject that has received little attention until very recently. In our studies on the mechanisms of left-right (LR) asymmetric development in Drosophila , we discovered that cells can have an intrinsic chirality to their structure, and that this "cell chirality" is generally responsible for the LR asymmetric development of certain organs in this species. The actin cytoskeleton plays important roles in the formation of cell chirality. In addition, Myosin31DF ( Myo31DF ), which encodes Drosophila Myosin ID, was identified as a molecular switch for cell chirality. In other invertebrate species, including snails and Caenorhabditis elegans , chirality of the blastomeres, another type of cell chirality, determines the LR asymmetry of structures in the body. Thus, chirality at the cellular level may broadly contribute to LR asymmetric development in various invertebrate species. Recently, cell chirality was also reported for various vertebrate cultured cells, and studies suggested that cell chirality is evolutionarily conserved, including the essential role of the actin cytoskeleton. Although the biological roles of cell chirality in vertebrates remain unknown, it may control LR asymmetric development or other morphogenetic events. The investigation of cell chirality has just begun, and this new field should provide valuable new insights in biology and medicine.

  6. Isotopic chirality

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-12-01

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

  7. Relativistic Chiral Kinetic Theory

    International Nuclear Information System (INIS)

    Stephanov, Mikhail

    2016-01-01

    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)].

  8. Relativistic Chiral Kinetic Theory

    Energy Technology Data Exchange (ETDEWEB)

    Stephanov, Mikhail

    2016-12-15

    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)].

  9. Pure chiral optical fibres.

    Science.gov (United States)

    Poladian, L; Straton, M; Docherty, A; Argyros, A

    2011-01-17

    We investigate the properties of optical fibres made from chiral materials, in which a contrast in optical activity forms the waveguide, rather than a contrast in the refractive index; we refer to such structures as pure chiral fibres. We present a mathematical formulation for solving the modes of circularly symmetric examples of such fibres and examine the guidance and polarisation properties of pure chiral step-index, Bragg and photonic crystal fibre designs. Their behaviour is shown to differ for left- and right-hand circular polarisation, allowing circular polarisations to be isolated and/or guided by different mechanisms, as well as differing from equivalent non-chiral fibres. The strength of optical activity required in each case is quantified.

  10. Towards chiral distributions of dopants in microporous frameworks: helicoidal supramolecular arrangement of (1R,2S)-ephedrine and transfer of chirality.

    Science.gov (United States)

    Gómez-Hortigüela, Luis; Álvaro-Muñoz, Teresa; Bernardo-Maestro, Beatriz; Pérez-Pariente, Joaquín

    2015-01-07

    A molecular-mechanics computational study is performed in order to analyze the arrangement of (1R,2S)-(-)-ephedrine molecules within the 12-MR channels of the AFI aluminophosphate microporous framework and the influence on the spatial distribution of dopants embedded in the tetrahedral network. Results showed that ephedrine molecules arrange exclusively as dimers by π-π stacking of the aromatic rings within the AFI channels. Interestingly, the asymmetric nature of ephedrine and the presence of H-bond-forming groups (NH2 and OH) involve a preferential orientation where consecutive dimers within the channels are rotated by an angle of +30°; this is driven by the establishment of inter-dimer H-bonds. This preferential orientation leads to the development of a supramolecular enantiomerically-pure helicoidal (chiral) arrangement of ephedrine dimers. In addition, the computational results demonstrate that the particular molecular structure of ephedrine imparts a strong trend to attract negative charges to the vicinity of the NH2(+) positively-charged groups. Hence divalent dopants such as Mg, whose replacement by trivalent Al in the aluminophosphate network involves the generation of a negative charge, will tend to locate close to the NH2(+) molecular groups, suggesting that an imprinting of the organic arrangement to the spatial distribution of dopants would be feasible. Combined with the trend of ephedrine to arrange in a helicoidal fashion, an enantiomerically-pure helicoidal distribution of dopants would be expected, thus inducing a new type of chirality in microporous materials.

  11. Chiral perturbation theory with nucleons

    International Nuclear Information System (INIS)

    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, πN scattering and the σ-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

  12. Chiral magnetic effect of light

    Science.gov (United States)

    Hayata, Tomoya

    2018-05-01

    We study a photonic analog of the chiral magnetic (vortical) effect. We discuss that the vector component of magnetoelectric tensors plays a role of "vector potential," and its rotation is understood as "magnetic field" of a light. Using the geometrical optics approximation, we show that "magnetic fields" cause an anomalous shift of a wave packet of a light through an interplay with the Berry curvature of photons. The mechanism is the same as that of the chiral magnetic (vortical) effect of a chiral fermion, so that we term the anomalous shift "chiral magnetic effect of a light." We further study the chiral magnetic effect of a light beyond geometric optics by directly solving the transmission problem of a wave packet at a surface of a magnetoelectric material. We show that the experimental signal of the chiral magnetic effect of a light is the nonvanishing of transverse displacements for the beam normally incident to a magnetoelectric material.

  13. QCD and the chiral critical point

    International Nuclear Information System (INIS)

    Gavin, S.; Gocksch, A.; Pisarski, R.D.

    1994-01-01

    As an extension of QCD, consider a theory with ''2+1'' flavors, where the current quark masses are held in a fixed ratio as the overall scale of the quark masses is varied. At nonzero temperature and baryon density it is expected that in the chiral limit the chiral phase transition is of first order. Increasing the quark mass from zero, the chiral transition becomes more weakly first order, and can end in a chiral critical point. We show that the only massless field at the chiral critical point is a σ meson, with the universality class that of the Ising model. Present day lattice simulations indicate that QCD is (relatively) near to the chiral critical point

  14. Chirality-dependent cellular uptake of chiral nanocarriers and intracellular delivery of different amounts of guest molecules

    Science.gov (United States)

    Kehr, Nermin Seda; Jose, Joachim

    2017-12-01

    We demonstrate the organic molecules loaded and chiral polymers coated periodic mesoporous organosilica (PMO) to generate chiral nanocarriers that we used to study chirality-dependent cellular uptake in serum and serum-free media and the subsequent delivery of different amounts of organic molecules into cells. Our results show that the amount of internalized PMO and thus the transported amount of organic molecules by nanocarrier PMO into cells was chirality dependent and controlled by hard/soft protein corona formation on the PMO surfaces. Therefore, this study demonstrate that chiral porous nanocarriers could potentially be used as advanced drug delivery systems which are able to use the specific chiral surface-protein interactions to influence/control the amount of (bio)active molecules delivered to cells in drug delivery and/or imaging applications.

  15. Hydrogenation of imines catalysed by ruthenium(II) complexes based on lutidine-derived CNC pincer ligands.

    Science.gov (United States)

    Hernández-Juárez, Martín; Vaquero, Mónica; Álvarez, Eleuterio; Salazar, Verónica; Suárez, Andrés

    2013-01-14

    The preparation of new Ru(II) complexes incorporating fac-coordinated lutidine-derived CNC ligands is reported. These derivatives are selectively deprotonated by (t)BuOK at one of the methylene arms of the pincer, leading to catalytically active species in the hydrogenation of imines.

  16. Chiral dynamics of baryons in the perturbative chiral quark model

    Energy Technology Data Exchange (ETDEWEB)

    Pumsa-ard, K.

    2006-07-01

    In this work we develop and apply variants of a perturbative chiral quark model (PCQM) to the study of baryonic properties dominantly in the low-energy region. In a first step we consider a noncovariant form of the PCQM, where confinement is modelled by a static, effective potential and chiral corrections are treated to second order, in line with similar chiral quark models. We apply the PCQM to the study of the electromagnetic form factors of the baryon octet. We focus in particular on the low-energy observables such as the magnetic moments, the charge and magnetic radii. In addition, the electromagnetic N-delta transition is also studied in the framework of the PCQM. In the chiral loop calculations we consider a quark propagator, which is restricted to the quark ground state, or in hadronic language to nucleon and delta intermediate states, for simplicity. We furthermore include the low-lying excited states to the quark propagator. In particular, the charge radius of the neutron and the transverse helicity amplitudes of the N-delta transition are considerably improved by this additional effect. In a next step we develop a manifestly Lorentz covariant version of the PCQM, where in addition higher order chiral corrections are included. The full chiral quark Lagrangian is motivated by and in analogy to the one of Chiral Perturbation Theory (ChPT). This Lagrangian contains a set of low energy constants (LECs), which are parameters encoding short distance effects and heavy degrees of freedom. We evaluate the chiral Lagrangian to order O(p{sup 4}) and to one loop to generate the dressing of the bare quark operators by pseudoscalar mesons. In addition we include the vector meson degrees of freedom in our study. Projection of the dressed quark operators on the baryonic level serves to calculate the relevant matrix elements. In a first application of this scheme, we resort to a parameterization of the valence quark form factors in the electromagnetic sector. Constraints

  17. Detecting the chirality for coupled quantum dots

    International Nuclear Information System (INIS)

    Cao Huijuan; Hu Lian

    2008-01-01

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

  18. Oscillation damping of chiral string loops

    International Nuclear Information System (INIS)

    Babichev, Eugeny; Dokuchaev, Vyacheslav

    2002-01-01

    Chiral cosmic string loops tend to the stationary (vorton) configuration due to energy loss into gravitational and electromagnetic radiation. We describe the asymptotic behavior of near stationary chiral loops and their fading to vortons. General limits on the gravitational and electromagnetic energy losses by near stationary chiral loops are found. For these loops we estimate the oscillation damping time. We present solvable examples of gravitational radiation energy loss by some chiral loop configurations. The analytical dependence of string energy with time is found in the case of the chiral ring with small amplitude radial oscillations

  19. Chiral algebras of class S

    CERN Document Server

    Beem, Christopher; Rastelli, Leonardo; van Rees, Balt C.

    2015-01-01

    Four-dimensional N=2 superconformal field theories have families of protected correlation functions that possess the structure of two-dimensional chiral algebras. In this paper, we explore the chiral algebras that arise in this manner in the context of theories of class S. The class S duality web implies nontrivial associativity properties for the corresponding chiral algebras, the structure of which is best summarized in the language of generalized topological quantum field theory. We make a number of conjectures regarding the chiral algebras associated to various strongly coupled fixed points.

  20. Nanoscale chirality in metal and semiconductor nanoparticles.

    Science.gov (United States)

    Kumar, Jatish; Thomas, K George; Liz-Marzán, Luis M

    2016-10-18

    The field of chirality has recently seen a rejuvenation due to the observation of chirality in inorganic nanomaterials. The advancements in understanding the origin of nanoscale chirality and the potential applications of chiroptical nanomaterials in the areas of optics, catalysis and biosensing, among others, have opened up new avenues toward new concepts and design of novel materials. In this article, we review the concept of nanoscale chirality in metal nanoclusters and semiconductor quantum dots, then focus on recent experimental and theoretical advances in chiral metal nanoparticles and plasmonic chirality. Selected examples of potential applications and an outlook on the research on chiral nanomaterials are additionally provided.

  1. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    Science.gov (United States)

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Chiral Thirring–Wess model

    Energy Technology Data Exchange (ETDEWEB)

    Rahaman, Anisur, E-mail: anisur.rahman@saha.ac.in

    2015-10-15

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

  3. Chiral Thirring–Wess model

    International Nuclear Information System (INIS)

    Rahaman, Anisur

    2015-01-01

    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

  4. Multivalent contrast agents based on Gd-DTPA-terminated poly (propylene imine) dendrimers for Magnetic Resonance Imaging

    NARCIS (Netherlands)

    Langereis, S.; Lussanet, de Q.G; Genderen, van M.H.P.; Backes, W.H.; Meijer, E.W.

    2004-01-01

    A convenient methodol. has been developed for the synthesis of gadolinium-diethylenetriaminepentaacetic acid (Gd-DTPA)-terminated poly(propylene imine) dendrimers as contrast agents for magnetic resonance imaging (MRI). In our strategy, isocyanate-activated, tert-butyl-protected DTPA analogs were

  5. Broadband reflection of polymer-stabilized chiral nematic liquid crystals induced by a chiral azobenzene compound.

    Science.gov (United States)

    Chen, Xingwu; Wang, Ling; Chen, Yinjie; Li, Chenyue; Hou, Guoyan; Liu, Xin; Zhang, Xiaoguang; He, Wanli; Yang, Huai

    2014-01-21

    A chiral nematic liquid crystal-photopolymerizable monomer-chiral azobenzene compound composite was prepared and then polymerized under UV irradiation. The reflection wavelength of the composite can be extended to cover the 1000-2400 nm range and also be adjusted to the visible light region by controlling the concentration of chiral compounds.

  6. Orientation-Dependent Handedness and Chiral Design

    Directory of Open Access Journals (Sweden)

    Efi Efrati

    2014-01-01

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

  7. Removal of some organic pollutants in water employing ceramic membranes impregnated with cross-linked silylated dendritic and cyclodextrin polymers.

    Science.gov (United States)

    Allabashi, Roza; Arkas, Michael; Hörmann, Gerold; Tsiourvas, Dimitris

    2007-01-01

    Triethoxysilylated derivatives of poly(propylene imine) dendrimer, polyethylene imine and polyglycerol hyperbranched polymers and beta-cyclodextrin have been synthesized and characterized. These compounds impregnated ceramic membranes made from Al(2)O(3), SiC and TiO(2) and subsequently sol-gel reaction led to their polymerization and chemical bond formation with the ceramic substrates. The resulting organic-inorganic filters were tested for the removal of a variety of organic pollutants from water. They were found to remove of polycyclic aromatic hydrocarbons (up to 99%), of monocyclic aromatic hydrocarbons (up to 93%), trihalogen methanes (up to 81%), pesticides (up to 43%) and methyl-tert-butyl ether (up to 46%).

  8. Macdonald index and chiral algebra

    Science.gov (United States)

    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.

  9. An N = 2 worldsheet approach to D-branes in bihermitian geometries: I. Chiral and twisted chiral fields

    International Nuclear Information System (INIS)

    Sevrin, Alexander; Staessens, Wieland; Wijns, Alexander

    2008-01-01

    We investigate N = (2, 2) supersymmetric nonlinear σ-models in the presence of a boundary. We restrict our attention to the case where the bulk geometry is described by chiral and twisted chiral superfields corresponding to a bihermitian bulk geometry with two commuting complex structures. The D-brane configurations preserving an N = 2 worldsheet supersymmetry are identified. Duality transformations interchanging chiral for twisted chiral fields and vice versa while preserving all supersymmetries are explicitly constructed. We illustrate our results with various explicit examples such as the WZW-model on the Hopf surface S 3 x S 1 . The duality transformations provide e.g new examples of coisotropic A-branes on Kaehler manifolds (which are not necessarily hyper-Kaehler). Finally, by dualizing a chiral and a twisted chiral field to a semi-chiral multiplet, we initiate the study of D-branes in bihermitian geometries where the cokernel of the commutator of the complex structures is non-empty.

  10. Laser Writing of Multiscale Chiral Polymer Metamaterials

    Directory of Open Access Journals (Sweden)

    E. P. Furlani

    2012-01-01

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

  11. The covariant chiral ring

    Energy Technology Data Exchange (ETDEWEB)

    Bourget, Antoine; Troost, Jan [Laboratoire de Physique Théorique, École Normale Supérieure, 24 rue Lhomond, 75005 Paris (France)

    2016-03-23

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

  12. Novel electrochemical method for the characterization of the degree of chirality in chiral polyaniline.

    Science.gov (United States)

    Feng, Zhang; Li, Ma; Yan, Yang; Jihai, Tang; Xiao, Li; Wanglin, Li

    2013-01-01

    A novel method to indicate the degree of chirality in polyaniline (PANI) was developed. The (D-camphorsulfonic acid)- and (HCl)-PANI-based electrodes exhibited significantly different electrochemical performances in D- and L-Alanine (Ala) aqueous solution, respectively, which can be used for the characterization the optical activity of chiral PANI. Cyclic voltammogram, tafel, and open circuit potential of PANI-based electrodes were measured within D- and L-Ala electrolyte solution, respectively. The open circuit potentials under different reacting conditions were analyzed by Doblhofer model formula, in which [C(+)](poly1)/[C(+)](poly2) was used as a parameter to characterize the degree of chirality in chiral PANI. The results showed that [C(+)](poly1)/[C(+)](poly2) can be increased with increasing concentrations of (1S)-(+)- and (1R)-(-)-10-camphorsulfonic acid. In addition, we detected that appropriate response time and lower temperature are necessary to improve the degree of chirality. Copyright © 2012 Wiley Periodicals, Inc.

  13. Molecular-Level Design of Heterogeneous Chiral Catalysis

    International Nuclear Information System (INIS)

    Zaera, Francisco

    2012-01-01

    The following is a proposal to continue our multi-institutional research on heterogeneous chiral catalysis. Our team combines the use of surface-sensitive analytical techniques for the characterization of model systems with quantum and statistical mechanical calculations to interpret experimental data and guide the design of future research. Our investigation focuses on the interrelation among the three main mechanisms by which enantioselectivity can be bestowed to heterogeneous catalysts, namely: (1) by templating chirality via the adsorption of chiral supramolecular assemblies, (2) by using chiral modifiers capable of forming chiral complexes with the reactant and force enantioselective surface reactions, and (3) by forming naturally chiral surfaces using imprinting chiral agents. Individually, the members of our team are leaders in these various aspects of chiral catalysis, but the present program provides the vehicle to generate and exploit the synergies necessary to address the problem in a comprehensive manner. Our initial work has advanced the methodology needed for these studies, including an enantioselective titration procedure to identify surface chiral sites, infrared spectroscopy in situ at the interface between gases or liquids and solids to mimic realistic catalytic conditions, and DFT and Monte Carlo algorithms to simulate and understand chirality on surfaces. The next step, to be funded by the monies requested in this proposal, is to apply those methods to specific problems in chiral catalysis, including the identification of the requirements for the formation of supramolecular surface structures with enantioselective behavior, the search for better molecules to probe the chiral nature of the modified surfaces, the exploration of the transition from supramolecular to one-to-one chiral modification, the correlation of the adsorption characteristics of one-to-one chiral modifiers with their physical properties, in particular with their configuration

  14. Molecular-level Design of Heterogeneous Chiral Catalysts

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-04-28

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

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

    Directory of Open Access Journals (Sweden)

    Michiya Fujiki

    2014-08-01

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

  16. Synthesis of N-substituted a,a-difluoro-b-aminophosphonates by addition of diethyl lithiodifluoromethylphosphonate to imines

    Czech Academy of Sciences Publication Activity Database

    Cherkupally, Prabhakar; Beier, Petr

    2012-01-01

    Roč. 141, Sep (2012), s. 76-82 ISSN 0022-1139 R&D Projects: GA ČR GP203/08/P310 Institutional support: RVO:61388963 Keywords : nucleophilic addition * difluorophosphonate * aminophosphonate * imines Subject RIV: CC - Organic Chemistry Impact factor: 1.939, year: 2012

  17. Azeotropic Preparation of a "C"-Phenyl "N"-Aryl Imine: An Introductory Undergraduate Organic Chemistry Laboratory Experiment

    Science.gov (United States)

    Silverberg, Lee J.; Coyle, David J.; Cannon, Kevin C.; Mathers, Robert T.; Richards, Jeffrey A.; Tierney, John

    2016-01-01

    Imines are important in biological chemistry and as intermediates in organic synthesis. An experiment for introductory undergraduate organic chemistry is presented in which benzaldehyde was condensed with "p"-methoxyaniline in toluene to give 4-methoxy-"N"-(phenylmethylene)benzenamine. Water was removed by azeotropic…

  18. Chirality-induced magnon transport in AA-stacked bilayer honeycomb chiral magnets.

    Science.gov (United States)

    Owerre, S A

    2016-11-30

    In this Letter, we study the magnetic transport in AA-stacked bilayer honeycomb chiral magnets coupled either ferromagnetically or antiferromagnetically. For both couplings, we observe chirality-induced gaps, chiral protected edge states, magnon Hall and magnon spin Nernst effects of magnetic spin excitations. For ferromagnetically coupled layers, thermal Hall and spin Nernst conductivities do not change sign as function of magnetic field or temperature similar to single-layer honeycomb ferromagnetic insulator. In contrast, for antiferromagnetically coupled layers, we observe a sign change in the thermal Hall and spin Nernst conductivities as the magnetic field is reversed. We discuss possible experimental accessible honeycomb bilayer quantum materials in which these effects can be observed.

  19. Asymmetric synthesis using chiral-encoded metal

    Science.gov (United States)

    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.

  20. Chiral relay: a novel strategy for the control and amplification of enantioselectivity in chiral Lewis acid promoted reactions.

    Science.gov (United States)

    Corminboeuf, Olivier; Quaranta, Laura; Renaud, Philippe; Liu, Mei; Jasperse, Craig P; Sibi, Mukund P

    2003-01-03

    Chiral Lewis acid catalysis has emerged as one of the premiere method to control stereochemistry. Much effort has gone into the design of superior ligands with increasing steric extension to shield distant reactive sites. We report here an alternative and complementary approach based on a "chiral relay". This strategy focuses on the improved design of achiral templates which may relay and amplify the stereochemistry from ligands. The essence of this strategy is that the chiral Lewis acid would effectively convert an achiral template into a chiral non-racemic template. This approach combines the advantages of enantioselective catalysis (substoichiometric amount of the chiral inducer) with the ones of chiral auxiliary control (efficient and predictable stereocontrol).

  1. Extreme chirality in Swiss roll metamaterials

    International Nuclear Information System (INIS)

    Demetriadou, A; Pendry, J B

    2009-01-01

    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 deg. 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.

  2. Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands.

    Science.gov (United States)

    Mori, Taizo; Sharma, Anshul; Hegmann, Torsten

    2016-01-26

    Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle

  3. Symmetry, structure, and dynamics of monoaxial chiral magnets

    International Nuclear Information System (INIS)

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

    2016-01-01

    Nontrivial spin orders with magnetic chirality emerge in a particular class of magnetic materials with structural chirality, which are frequently referred to as chiral magnets. Various interesting physical properties are expected to be induced in chiral magnets through the coupling of chiral magnetic orders with conduction electrons and electromagnetic fields. One promising candidate for achieving these couplings is a chiral spin soliton lattice. Here, we review recent experimental observations mainly carried out on the monoaxial chiral magnetic crystal CrNb_3S_6 via magnetic imaging using electron, neutron, and X-ray beams and magnetoresistance measurements, together with the strategy for synthesizing chiral magnetic materials and underlying theoretical backgrounds. The chiral soliton lattice appears under a magnetic field perpendicular to the chiral helical axis and is very robust and stable with phase coherence on a macroscopic length scale. The tunable and topological nature of the chiral soliton lattice gives rise to nontrivial physical properties. Indeed, it is demonstrated that the interlayer magnetoresistance scales to the soliton density, which plays an essential role as an order parameter in chiral soliton lattice formation, and becomes quantized with the reduction of the system size. These interesting features arising from macroscopic phase coherence unique to the chiral soliton lattice will lead to the exploration of routes to a new paradigm for applications in spin electronics using spin phase coherence. (author)

  4. Chirality: a relational geometric-physical property.

    Science.gov (United States)

    Gerlach, Hans

    2013-11-01

    The definition of the term chirality by Lord Kelvin in 1893 and 1904 is analyzed by taking crystallography at that time into account. This shows clearly that chirality is a relational geometric-physical property, i.e., two relations between isometric objects are possible: homochiral or heterochiral. In scientific articles the relational term chirality is often mistaken for the two valued measure for the individual (absolute) sense of chirality, an arbitrary attributive term. © 2013 Wiley Periodicals, Inc.

  5. Light-front realization of chiral symmetry breaking

    International Nuclear Information System (INIS)

    Itakura, Kazunori; Maedan, Shinji

    2001-01-01

    We discuss a description of chiral symmetry breaking in the light-front (LF) formalism. Based on careful analyses of several modes, we give clear answers to the following three fundamental questions: (i) What is the difference between the LF chiral transformation and the ordinary chiral transformation? (ii) How does a gap equation for the chiral condensate emerge? (iii) What is the consequence of the coexistence of a nonzero chiral condensate and the trivial Fock vacuum? The answer to Question (i) is given through a classical analysis of each model. Question (ii) is answered based on our recognition of the importance of characteristic constraints, such as the zero-mode and fermionic constraints. Question (iii) is intimately related to another important problem, reconciliation of the nonzero chiral condensate ≠ 0 and the invariance of the vacuum under the LF chiral transformation Q 5 LF | 0> = 0. This and Question (iii) are understood in terms of the modified chiral transformation laws of the dependent variables. The characteristic ways in which the chiral symmetry breaking is realized are that the chiral charge Q 5 LF is no longer conserved and that the transformation of the scalar and pseudoscalar fields is modified. We also discuss other outcomes, such as the light-cone wave function of the pseudoscalar meson in the Nambu-Jona-Lasinio model. (author)

  6. Chiral stationary phase optimized selectivity liquid chromatography: A strategy for the separation of chiral isomers.

    Science.gov (United States)

    Hegade, Ravindra Suryakant; De Beer, Maarten; Lynen, Frederic

    2017-09-15

    Chiral Stationary-Phase Optimized Selectivity Liquid Chromatography (SOSLC) is proposed as a tool to optimally separate mixtures of enantiomers on a set of commercially available coupled chiral columns. This approach allows for the prediction of the separation profiles on any possible combination of the chiral stationary phases based on a limited number of preliminary analyses, followed by automated selection of the optimal column combination. Both the isocratic and gradient SOSLC approach were implemented for prediction of the retention times for a mixture of 4 chiral pairs on all possible combinations of the 5 commercial chiral columns. Predictions in isocratic and gradient mode were performed with a commercially available and with an in-house developed Microsoft visual basic algorithm, respectively. Optimal predictions in the isocratic mode required the coupling of 4 columns whereby relative deviations between the predicted and experimental retention times ranged between 2 and 7%. Gradient predictions led to the coupling of 3 chiral columns allowing baseline separation of all solutes, whereby differences between predictions and experiments ranged between 0 and 12%. The methodology is a novel tool allowing optimizing the separation of mixtures of optical isomers. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Highly Enantioselective Production of Chiral Secondary Alcohols Using Lactobacillus paracasei BD101 as a New Whole Cell Biocatalyst and Evaluation of Their Antimicrobial Effects.

    Science.gov (United States)

    Yılmaz, Durmuşhan; Şahin, Engin; Dertli, Enes

    2017-11-01

    Chiral secondary alcohols are valuable intermediates for many important enantiopure pharmaceuticals and biologically active molecules. In this work, we studied asymmetric reduction of aromatic ketones to produce the corresponding chiral secondary alcohols using lactic acid bacteria (LAB) as new biocatalysts. Seven LAB strains were screened for their ability to reduce acetophenones to their corresponding alcohols. Among these strains, Lactobacillus paracasei BD101 was found to be the most successful at reducing the ketones to the corresponding alcohols. The reaction conditions were further systematically optimized for this strain and high enantioselectivity (99%) and very good yields were obtained. These secondary alcohols were further tested for their antimicrobial activities against important pathogens and significant levels of antimicrobial activities were observed although these activities were altered depending on the secondary alcohols as well as their enantiomeric properties. The current methodology demonstrates a promising and alternative green approach for the synthesis of chiral secondary alcohols of biological importance in a cheap, mild, and environmentally useful process. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

  8. Hadron properties in chiral sigma model

    International Nuclear Information System (INIS)

    Shen Hong

    2005-01-01

    The modification of hadron masses in nuclear medium is studied by using the chiral sigma model, which is extended to generate the omega meson mass by the sigma condensation in the vacuum in the same way as the nucleon mass. The chiral sigma model provides proper equilibrium properties of nuclear matter. It is shown that the effective masses of both nucleons and omega mesons decrease in nuclear medium, while the effective mass of sigma mesons increases oat finite density in the chiral sigma model. The results obtained in the chiral sigma model are compared with those obtained in the Walecka model, which includes sigma and omega mesons in a non-chiral fashion. (author)

  9. Chiral recognition in separation science: an overview.

    Science.gov (United States)

    Scriba, Gerhard K E

    2013-01-01

    Chiral recognition phenomena play an important role in nature as well as analytical separation sciences. In separation sciences such as chromatography and capillary electrophoresis, enantiospecific interactions between the enantiomers of an analyte and the chiral selector are required in order to observe enantioseparations. Due to the large structural variety of chiral selectors applied, different mechanisms and structural features contribute to the chiral recognition process. This chapter briefly illustrates the current models of the enantiospecific recognition on the structural basics of various chiral selectors.

  10. No chiral truncation of quantum log gravity?

    Science.gov (United States)

    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.

  11. Direct Detection of Hardly Detectable Hidden Chirality of Hydrocarbons and Deuterated Isotopomers by a Helical Polyacetylene through Chiral Amplification and Memory.

    Science.gov (United States)

    Maeda, Katsuhiro; Hirose, Daisuke; Okoshi, Natsuki; Shimomura, Kouhei; Wada, Yuya; Ikai, Tomoyuki; Kanoh, Shigeyoshi; Yashima, Eiji

    2018-03-07

    We report the first direct chirality sensing of a series of chiral hydrocarbons and isotopically chiral compounds (deuterated isotopomers), which are almost impossible to detect by conventional optical spectroscopic methods, by a stereoregular polyacetylene bearing 2,2'-biphenol-derived pendants. The polyacetylene showed a circular dichroism due to a preferred-handed helix formation in response to the hardly detectable hidden chirality of saturated tertiary or chiroptical quaternary hydrocarbons, and deuterated isotopomers. In sharp contrast to the previously reported sensory systems, the chirality detection by the polyacetylene relies on an excess one-handed helix formation induced by the chiral hydrocarbons and deuterated isotopomers via significant amplification of the chirality followed by its static memory, through which chiral information on the minute and hidden chirality can be stored as an excess of a single-handed helix memory for a long time.

  12. Effect of aluminum alkyls on a homogeneous and silica-supported phenoxy-imine titanium catalyst for ethylene trimerization

    NARCIS (Netherlands)

    Karbach, Fabian F.; Severn, John R.; Duchateau, Robbert

    A phenoxy-imine titanium catalyst (FI-catalyst) for selective ethylene trimerization was immobilized on methyl aluminoxane (MAO) pretreated silica and its activity and selectivity was compared with that of the corresponding homogeneous catalyst system. The homogeneous and heterogeneous ethylene

  13. Harvesting Covert Networks: The Case Study of the iMiner Database

    DEFF Research Database (Denmark)

    Memon, Nasrullah; Wiil, Uffe Kock; Alhajj, Reda

    2011-01-01

    was incorporated in the iMiner prototype tool, which makes use of investigative data mining techniques to analyse data. This paper will present the developed framework along with the form and structure of the terrorist data in the database. Selected cases will be referenced to highlight the effectiveness of the i...... collected by intelligence agencies and government organisations is inaccessible to researchers. To counter the information scarcity, we designed and built a database of terrorist-related data and information by harvesting such data from publicly available authenticated websites. The database...

  14. Chiral anomaly, Berry phase, and chiral kinetic theory from worldlines in quantum field theory

    Science.gov (United States)

    Mueller, Niklas; Venugopalan, Raju

    2018-03-01

    In previous work, we outlined a worldline framework that can be used for systematic computations of the chiral magnetic effect (CME) in ultrarelativistic heavy-ion collisions. Towards this end, we first expressed the real part of the fermion determinant in the QCD effective action as a supersymmetric worldline action of spinning, colored, Grassmanian point particles in background gauge fields, with equations of motion that are covariant generalizations of the Bargmann-Michel-Telegdi and Wong equations. The chiral anomaly, in contrast, arises from the phase of the fermion determinant. Remarkably, the latter too can be expressed as a point particle worldline path integral, which can be employed to derive the anomalous axial vector current. We will show here how Berry's phase can be obtained in a consistent nonrelativistic adiabatic limit of the real part of the fermion determinant. Our work provides a general first principles demonstration that the topology of Berry's phase is distinct from that of the chiral anomaly confirming prior arguments by Fujikawa in specific contexts. This suggests that chiral kinetic treatments of the CME in heavy-ion collisions that include Berry's phase alone are incomplete. We outline the elements of a worldline covariant relativistic chiral kinetic theory that captures the physics of how the chiral current is modified by many-body scattering and topological fluctuations.

  15. Chiral dynamics with (nonstrange quarks

    Directory of Open Access Journals (Sweden)

    Kubis Bastian

    2017-01-01

    Full Text Available We review the results and achievements of the project B.3. Topics addressed include pion photoproduction off the proton and off deuterium, three-flavor chiral perturbation theory studies, chiral symmetry tests in Goldstone boson decays, the development of unitarized chiral perturbation theory to next-to-leading order, the two-pole structure of the Λ(1405, the dynamical generation of the lowest S11 resonances, the theory of hadronic atoms and its application to various systems, precision studies in light-meson decays based on dispersion theory, the Roy–Steiner analysis of pion–nucleon scattering, a high-precision extraction of the elusive pion–nucleon σ-term, and aspects of chiral dynamics in few-nucleon systems.

  16. Enantiomeric Separation of 1-(Benzofuran-2-yl)alkylamines on Chiral Stationary Phases Based on Chiral Crown Ethers

    International Nuclear Information System (INIS)

    Park, Soohyun; Kim, Sang Jun; Hyun, Myung Ho

    2012-01-01

    Optically active chiral amines are important as building blocks for pharmaceuticals and as scaffolds for chiral ligands and, consequently, many efforts have been devoted to the development of efficient methods for their preparation. For example, reduction of amine precursors with chiral catalysts, enzymatic kinetic resolution or dynamic kinetic resolution of racemic amines and the direct amination of ketones with transaminases have been developed as the efficient methods for the preparation of optically active chiral amines. During the process of developing or utilizing optically active chiral amines, the methods for the determination of their enantiomeric composition are essential. Among various methods, liquid chromatographic resolution of enantiomers on chiral stationary phases (CSPs) have been known to be one of the most accurate and economic means for the determination of the enantiomeric composition of optically active chiral compounds. Especially, CSPs based on chiral crown ethers have been successfully used for the resolution of racemic primary amines. For example, CSPs based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid (CSP 1, Figure 1) or (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6 (CSP 2 and CSP 3, Figure 1) have been known to be quite effective for the resolution of cyclic and non-cyclic amines, various fluoroquinolone antibacterials containing a primary amino group, tocainide (antiarrhythmic agent) and its analogues, aryl-a-amino ketones and 3-amino-1,4-benzodiazepin-2-ones

  17. Spectral signatures of chirality

    DEFF Research Database (Denmark)

    Pedersen, Jesper Goor; Mortensen, Asger

    2009-01-01

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

  18. Preparation and Use of Aziridino Alcohols as Promoters for the Enantioselective Addition of Dialkylzinc Reagents to N-(Diphenylphosphinoyl) IminesImines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Guijarro, David; Andersson, Pher G.

    1997-01-01

    A set of chiral aziridino alcohols has been synthesised, either from amino acids (serine, threonine or allo-threonine) or via Sharpless asymmetric aminohydroxylation/dihydroxylation of simple prochiral olefins. The ligands mediate the addition of diethylzinc to N-phosphinoylimines, with up to 94...

  19. Profuse and Selective Growth in vitro of Rat Spinal Axons on a Micro-Patterned Poly (ethylene imine) Grid

    National Research Council Canada - National Science Library

    Mouveroux, J

    2001-01-01

    To distribute neurites (axons) along a surface and to guide them towards specific point targets we cultured spinal cord explants on coverslips printed with a micro-patterned grid of poly (ethylene imine) (PEI) lanes...

  20. Is there chirality in atomic nuclei?

    International Nuclear Information System (INIS)

    Meng Jie

    2009-01-01

    Static chiral symmetries are common in nature, for example, the macroscopic spirals of snail shells, the microscopic handedness of certain molecules, and human hands. The concept of chirality in atomic nuclei was first proposed in 1997, and since then many efforts have been made to understand chiral symmetry and its spontaneous breaking in atomic nuclei. Recent theoretical and experimental progress in the verification of chirality in atomic nuclei will be reviewed, together with a discussion of the problems that await to be solved in the future. (authors)

  1. Influence of Chirality in Ordered Block Copolymer Phases

    Science.gov (United States)

    Prasad, Ishan; Grason, Gregory

    2015-03-01

    Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.

  2. Chiral four-membered cyclic nitrones; asymmetric induction in the (4+2)-cycloaddition reaction of chiral ynamines and nitroalkenes

    NARCIS (Netherlands)

    van Elburg, P.A.; Honig, G.W.N.; Reinhoudt, David

    1987-01-01

    Chiral four-membered cyclic nitrones were synthesized by the asymmetric (4+2)-cycloaddition of nitroalkenes 1 and chiral ynamines 2. The subsequent stereoselective addition of nucleophiles to these nitrones enabled the synthesis of chiral N-hydroxyazetidines.

  3. Search for the characters of chiral rotation in excited bands for the idea chiral nuclei with A ∼ 130

    International Nuclear Information System (INIS)

    Chen Qibo; Yao Jiangming; Meng Jie; Zhang Shuangquan; Qi Bin

    2010-01-01

    Since the occurrence of chirality was originally suggested in 1997 by Frauendorf and Meng [1] and experimentally observed in 2001 [2] , the investigation of chiral symmetry in atomic nuclei becomes one of the most important topics in nuclear physics. More and more chiral doublet bands [3-7] in atomic nuclei [8] have been reported. There are also many discussions about the fingerprints of chirality. In the pioneer paper [1] , the two lowest near degenerate bands given by the particle-rotor model (PRM) are interpreted as chiral doublet bands. If the nucleus has chiral geometry with proper configuration, the character of chiral rotation may appear not only in the two lowest bands, but also in the other bands. Therefore, it is interesting to search for the character of chiral rotation, Based on the PRM model with configuration corresponding to A ∼ 130 mass region, we examine the theoretical spectroscopy of higher excited bands (band3, band4, band5 and band6) beyond the two lowest bands (bandl and band2), including energies, spin-alignments, projection of total angular momentum and electromagnetic transition probabilities. The results show that band3 and band4 have characters of chirality in some spin region. (authors)

  4. Variational approach to chiral quark models

    Energy Technology Data Exchange (ETDEWEB)

    Futami, Yasuhiko; Odajima, Yasuhiko; Suzuki, Akira

    1987-03-01

    A variational approach is applied to a chiral quark model to test the validity of the perturbative treatment of the pion-quark interaction based on the chiral symmetry principle. It is indispensably related to the chiral symmetry breaking radius if the pion-quark interaction can be regarded as a perturbation.

  5. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen

    Directory of Open Access Journals (Sweden)

    Bashir Ahmad Dar

    2012-06-01

    Full Text Available The present work is intended to determine the catalytic activity of Mixed Oxide supported gold for aerobic oxidative dehydrogenation of amines to imines using Ceria as a main constituent of the each support. The model catalysts Au/CeO2:TiO2 Au/CeO2:SiO2, Au/CeO2:ZrO2 and Au/CeO2:Al2Os were prepared by deposition co-precipitation method and deposition of gold was determined by EDEX analysis. The supported nano-gold catalyzes the dehydrogenation of secondary amines to imines without loss of activity. On recycling good amount of product yield is obtained. Oxidation of secondary amines to imines is carried at 100˚C and almost 90 % conversion was obtained with >99% selectivity. © 2012 BCREC UNDIP. All rights reservedReceived: 26th December 2011; Revised: 7th June 2012; Accepted: 13rd June 2012[How to Cite: B.A. Dar, M. Sharma, B. Singh. (2012. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen. Bulletin of Chemical Reaction Engineering & Catalysis, 7(1: 79-84.  doi:10.9767/bcrec.7.1.1257.79-84][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1257.79-84 ] | View in 

  6. Some aspects of chirality: Fermion masses and chiral p-forms

    Energy Technology Data Exchange (ETDEWEB)

    Kleppe, A

    1997-05-01

    The properties of fermion mass matrices are investigated from different points of view, both within the minimal Standard Model and in extensions of the model. It is shown how mass matrix invariants are used to define the measurables of the quark mixing matrix as invariant functions of the mass matrices. One model is presented where the family pattern is suggested to originate from a kind of mass scaling. A Lagrangian density is defined for an entire charge sector, such that the existence of a Dirac field with mass m{sub 0} implies the existence of other Dirac fields where the corresponding quanta have masses Rm{sub 0}, R{sup 2}m{sub 0}, .. which are obtained by a discrete scale transformation. This suggests a certain type of democratic fermion mass matrices. Also extensions of the minimal Standard Model are investigated, obtained by including right-handed neutrinos in the model. The Standard Model extended by two right-handed neutrinos gives rise to a mass spectrum with two massive and three massless neutrinos. The phenomenological consequences of this model are discussed. The neutrino mass matrix in such a scheme has what is defined as a democratic texture. They are studied for the cases with two and three right-handed neutrinos, resp. The chiral fields that we find in the Standard Model have certain similarities with self-dual fields. Among other things, both chiral and self-dual fields suffer species doubling on the lattice. Chiral p-forms are self-dual fields that appear in twice odd dimensions. Chiral p-forms violate manifest covariance, in the same sense as manifest covariance is violated by non-covariant gauges in electrodynamics. It is shown that a covariant action can nevertheless be formulated for chiral p-forms, by introducing an infinite set of gauge fields in a carefully controlled way.

  7. Some aspects of chirality: Fermion masses and chiral p-forms

    International Nuclear Information System (INIS)

    Kleppe, A.

    1997-05-01

    The properties of fermion mass matrices are investigated from different points of view, both within the minimal Standard Model and in extensions of the model. It is shown how mass matrix invariants are used to define the measurables of the quark mixing matrix as invariant functions of the mass matrices. One model is presented where the family pattern is suggested to originate from a kind of mass scaling. A Lagrangian density is defined for an entire charge sector, such that the existence of a Dirac field with mass m 0 implies the existence of other Dirac fields where the corresponding quanta have masses Rm 0 , R 2 m 0 , .. which are obtained by a discrete scale transformation. This suggests a certain type of democratic fermion mass matrices. Also extensions of the minimal Standard Model are investigated, obtained by including right-handed neutrinos in the model. The Standard Model extended by two right-handed neutrinos gives rise to a mass spectrum with two massive and three massless neutrinos. The phenomenological consequences of this model are discussed. The neutrino mass matrix in such a scheme has what is defined as a democratic texture. They are studied for the cases with two and three right-handed neutrinos, resp. The chiral fields that we find in the Standard Model have certain similarities with self-dual fields. Among other things, both chiral and self-dual fields suffer species doubling on the lattice. Chiral p-forms are self-dual fields that appear in twice odd dimensions. Chiral p-forms violate manifest covariance, in the same sense as manifest covariance is violated by non-covariant gauges in electrodynamics. It is shown that a covariant action can nevertheless be formulated for chiral p-forms, by introducing an infinite set of gauge fields in a carefully controlled way

  8. Polyethylene imine modified hydrochar adsorption for chromium (VI) and nickel (II) removal from aqueous solution.

    Science.gov (United States)

    Shi, Yuanji; Zhang, Tao; Ren, Hongqiang; Kruse, Andrea; Cui, Ruofan

    2018-01-01

    An adsorbent hydrochar was synthesized from corn cobs and modified with polyethylene imine (PEI). The hydrochars before and after modification were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis. FTIR and XPS revealed that the PEI was grafted onto the hydrochar via ether and imine bonds formed with glutaraldehyde. The maximum adsorption capacities for Cr(VI) (33.663mg/g) and Ni(II) (29.059mg/g) on the modified hydrochars were 365% and 43.7% higher, respectively, than those on the unmodified hydrochar. A pseudo-second-order model described the adsorption of Ni(II) and Cr(VI) on all the adsorbents. The adsorption of Cr(VI) was endothermic, spontaneous, increased disorder, and obeyed the Langmuir model. By contrast, the adsorption of Ni(II) was exothermic, spontaneous, decreased disorder, and obeyed the Freundlich model. XPS confirmed that the adsorption sites and mechanisms for Ni(II) and Cr(VI) on the modified hydrochars were different. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Chirality effect in disordered graphene ribbon junctions

    International Nuclear Information System (INIS)

    Long Wen

    2012-01-01

    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. (paper)

  10. Chiral topological insulator of magnons

    Science.gov (United States)

    Li, Bo; Kovalev, Alexey A.

    2018-05-01

    We propose a magnon realization of 3D topological insulator in the AIII (chiral symmetry) topological class. The topological magnon gap opens due to the presence of Dzyaloshinskii-Moriya interactions. The existence of the topological invariant is established by calculating the bulk winding number of the system. Within our model, the surface magnon Dirac cone is protected by the sublattice chiral symmetry. By analyzing the magnon surface modes, we confirm that the backscattering is prohibited. By weakly breaking the chiral symmetry, we observe the magnon Hall response on the surface due to opening of the gap. Finally, we show that by changing certain parameters, the system can be tuned between the chiral topological insulator, three-dimensional magnon anomalous Hall, and Weyl magnon phases.

  11. Chiralities of spiral waves and their transitions.

    Science.gov (United States)

    Pan, Jun-ting; Cai, Mei-chun; Li, Bing-wei; Zhang, Hong

    2013-06-01

    The chiralities of spiral waves usually refer to their rotation directions (the turning orientations of the spiral temporal movements as time elapses) and their curl directions (the winding orientations of the spiral spatial geometrical structures themselves). Traditionally, they are the same as each other. Namely, they are both clockwise or both counterclockwise. Moreover, the chiralities are determined by the topological charges of spiral waves, and thus they are conserved quantities. After the inwardly propagating spirals were experimentally observed, the relationship between the chiralities and the one between the chiralities and the topological charges are no longer preserved. The chiralities thus become more complex than ever before. As a result, there is now a desire to further study them. In this paper, the chiralities and their transition properties for all kinds of spiral waves are systemically studied in the framework of the complex Ginzburg-Landau equation, and the general relationships both between the chiralities and between the chiralities and the topological charges are obtained. The investigation of some other models, such as the FitzHugh-Nagumo model, the nonuniform Oregonator model, the modified standard model, etc., is also discussed for comparison.

  12. Enantioselective Biotransformation of Chiral Persistent Organic Pollutants.

    Science.gov (United States)

    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

  13. Symmetries of Ginsparg-Wilson chiral fermions

    International Nuclear Information System (INIS)

    Mandula, Jeffrey E.

    2009-01-01

    The group structure of the variant chiral symmetry discovered by Luescher in the Ginsparg-Wilson description of lattice chiral fermions is analyzed. It is shown that the group contains an infinite number of linearly independent symmetry generators, and the Lie algebra is given explicitly. CP is an automorphism of this extended chiral group, and the CP transformation properties of the symmetry generators are found. The group has an infinite-parameter invariant subgroup, and the factor group, whose elements are its cosets, is isomorphic to the continuum chiral symmetry group. Features of the currents associated with these symmetries are discussed, including the fact that some different, noncommuting symmetry generators lead to the same Noether current. These are universal features of lattice chiral fermions based on the Ginsparg-Wilson relation; they occur in the overlap, domain-wall, and perfect-action formulations. In a solvable example, free overlap fermions, these noncanonical elements of lattice chiral symmetry are related to complex energy singularities that violate reflection positivity and impede continuation to Minkowski space.

  14. Chiral ionic liquids in chromatographic and electrophoretic separations.

    Science.gov (United States)

    Kapnissi-Christodoulou, Constantina P; Stavrou, Ioannis J; Mavroudi, Maria C

    2014-10-10

    This report provides an overview of the application of chiral ionic liquids (CILs) in separation technology, and particularly in capillary electrophoresis and both gas and liquid chromatography. There is a large number of CILs that have been synthesized and designed as chiral agents. However, only a few have successfully been applied in separation technology. Even though this application of CILs is still in its early stages, the scientific interest is increasing dramatically. This article is focused on the use of CILs as chiral selectors, background electrolyte additives, chiral ligands and chiral stationary phases in electrophoretic and chromatographic techniques. Different examples of CILs, which contain either a chiral cation, a chiral anion or both, are presented in this review article, and their major advantages along with their potential applications in chiral electrophoretic and chromatographic recognition are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Vector mesons and chiral symmetry

    International Nuclear Information System (INIS)

    Ecker, G.

    1989-01-01

    The ambiguities in the off-shell behaviour of spin-1 exchange can be resolved to O(p 4 ) in the chiral low-energy expansion if the asymptotic behaviour of QCD is properly incorporated. As a consequence, the chiral version of vector (and axial-vector) meson dominance is model independent. Additional high-energy constraints motivated by QCD determine the V,A resonance couplings uniquely. In particular, QCD in its effective chiral realization sucessfully predicts Γ(ρ→2π). 10 refs. (Author)

  16. Magnetoelectronic properties of chiral carbon nanotubes and tori

    International Nuclear Information System (INIS)

    Shyu, F L; Tsai, C C; Lee, C H; Lin, M F

    2006-01-01

    Magnetoelectronic properties of chiral carbon nanotubes and toroids are studied for any magnetic field. They are sensitive to the changes in the magnitude and the direction of the magnetic field, as well as the chirality. The important differences between chiral and achiral carbon nanotubes include band symmetry, band curvature, band crossing, band-edge state, state degeneracy, band spacing, energy gap, and semiconductor-metal transition. Carbon tori also exhibit the strong chirality dependence on the field modulation of discrete states. Chiral carbon tori might differ from chiral carbon nanotubes in energy-gap modulation, density of states, and state degeneracy

  17. Chiral corrections to the Adler-Weisberger sum rule

    Science.gov (United States)

    Beane, Silas R.; Klco, Natalie

    2016-12-01

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

  18. Chiral discrimination in nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Lazzeretti, Paolo

    2017-11-01

    Chirality is a fundamental property of molecules whose spatial symmetry is characterized by the absence of improper rotations, making them not superimposable to their mirror image. Chiral molecules constitute the elementary building blocks of living species and one enantiomer is favoured in general (e.g. L-aminoacids and D-sugars pervade terrestrial homochiral biochemistry) because most chemical reactions producing natural substances are enantioselective. Since the effect of chiral chemicals and drugs on living beings can be markedly different between enantiomers, the quest for practical spectroscopical methods to scrutinize chirality is an issue of great importance and interest. Nuclear magnetic resonance (NMR) is a topmost analytical technique, but spectrometers currently used are ‘blind’ to chirality, i.e. unable to discriminate the two mirror-image forms of a chiral molecule, because, in the absence of a chiral solvent, the spectral parameters, chemical shifts and spin-spin coupling constants are identical for enantiomers. Therefore, the development of new procedures for routine chiral recognition would offer basic support to scientists. However, in the presence of magnetic fields, a distinction between true and false chirality is mandatory. The former epitomizes natural optical activity, which is rationalized by a time-even pseudoscalar, i.e. the trace of a second-rank tensor, the mixed electric dipole/magnetic dipole polarizability. The Faraday effect, magnetic circular dichroism and magnetic optical activity are instead related to a time-odd axial vector. The present review summarizes recent theoretical and experimental efforts to discriminate enantiomers via NMR spectroscopy, with the focus on the deep connection between chirality and symmetry properties under the combined set of fundamental discrete operations, namely charge conjugation, parity (space inversion) and time (motion) reversal.

  19. Algebraic study of chiral anomalies

    Indian Academy of Sciences (India)

    Chiral anomalies; gauge theories; bundles; connections; quantum field ... The algebraic structure of chiral anomalies is made globally valid on non-trivial bundles by the introduction of a fixed background connection. ... Current Issue : Vol.

  20. Supersymmetric chiral electrodynamics as a renormalized theory

    International Nuclear Information System (INIS)

    Ansel'm, A.A.; Iogansen, A.A.

    1991-01-01

    It is well know that the QED of chiral fermions is a nonrenormalizable theory, inasmuch as the gauge current in it is not conserved because of the presence of an anomaly. It is evident that in this theory unitarity is also violated. The principal object of investigation in the present paper is supersymmetric chiral QED, supersymmetric QED is a renormalizable theory. This happens because the radiative corrections generate here a charged current of a chiral fermion that appears in the chiral (i.e., longitudinal) part of the vector supermultiplet. At first sight, the chiral part of the vector multiplet is unphysical and contains only supergauge degrees of freedom. However, this is valid only at the classical level, whereas, because of the anomaly, the radiative corrections lead to nonconservation of the gauge current, as a result of which the degrees of freedom associated with the chiral part of the vector multiplet become physical. On the other hand, owing to the nonconservation of the gauge charge, the apparently neutral fermion appearing int he chiral (longitudinal) part of the vector superfield becomes charged

  1. Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

    KAUST Repository

    Barman, Samir

    2017-04-06

    Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

  2. Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

    KAUST Repository

    Barman, Samir; Merle, Nicolas; Minenkov, Yury; De Mallmann, Aimery; Samantaray, Manoja; Le Qué mé ner, Fré dé ric; Szeto, Kai C.; Abou-Hamad, Edy; Cavallo, Luigi; Taoufik, Mostafa; Basset, Jean-Marie

    2017-01-01

    Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

  3. An efficient protocol for the synthesis of highly sensitive indole imines utilizing green chemistry: optimization of reaction conditions.

    Science.gov (United States)

    Nisar, Bushra; Rubab, Syeda Laila; Raza, Abdul Rauf; Tariq, Sobia; Sultan, Ayesha; Tahir, Muhammad Nawaz

    2018-04-11

    Novel and highly sensitive indole-based imines have been synthesized. Their synthesis has been compared employing a variety of protocols. Ultimately, a convenient, economical and high yielding set of conditions employing green chemistry have been designed for their synthesis.

  4. Chirality plays important roles in radiopharmaceuticals

    International Nuclear Information System (INIS)

    Shen Yumei

    2006-01-01

    The paper introduces the basic concept of chirality, target specific selectivity and their relationship in radiopharmaceuticals. If the ligands labeled by radionuclides have chiral center, the enantiomers must be separated, or the target specific selectivity will not be good. Chirality is one of the most important factors which must be considered in the study of the structure-activity relationship of radiopharmaceuticals. (authors)

  5. Chiral perturbation theory

    International Nuclear Information System (INIS)

    Ecker, G.

    1996-06-01

    After a general introduction to the structure of effective field theories, the main ingredients of chiral perturbation theory are reviewed. Applications include the light quark mass ratios and pion-pion scattering to two-loop accuracy. In the pion-nucleon system, the linear σ model is contrasted with chiral perturbation theory. The heavy-nucleon expansion is used to construct the effective pion-nucleon Lagrangian to third order in the low-energy expansion, with applications to nucleon Compton scattering. (author)

  6. Holographic Chiral Magnetic Spiral

    International Nuclear Information System (INIS)

    Kim, Keun-Young; Sahoo, Bindusar; Yee, Ho-Ung

    2010-06-01

    We study the ground state of baryonic/axial matter at zero temperature chiral-symmetry broken phase under a large magnetic field, in the framework of holographic QCD by Sakai-Sugimoto. Our study is motivated by a recent proposal of chiral magnetic spiral phase that has been argued to be favored against previously studied phase of homogeneous distribution of axial/baryonic currents in terms of meson super-currents dictated by triangle anomalies in QCD. Our results provide an existence proof of chiral magnetic spiral in strong coupling regime via holography, at least for large axial chemical potentials, whereas we don't find the phenomenon in the case of purely baryonic chemical potential. (author)

  7. Synthesis and characterization of mixed ligand chiral nanoclusters

    KAUST Repository

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

    2016-01-01

    Chiral mixed ligand silver nanoclusters were synthesized in the presence of a chiral and an achiral ligand. While the chiral ligand led mostly to the formation of nanoparticles, the presence of the achiral ligand drastically increased the yield of nanoclusters with enhanced chiral properties. © 2016 The Royal Society of Chemistry.

  8. Synthesis and characterization of mixed ligand chiral nanoclusters

    KAUST Repository

    Guven, Zekiye P.

    2016-06-22

    Chiral mixed ligand silver nanoclusters were synthesized in the presence of a chiral and an achiral ligand. While the chiral ligand led mostly to the formation of nanoparticles, the presence of the achiral ligand drastically increased the yield of nanoclusters with enhanced chiral properties. © 2016 The Royal Society of Chemistry.

  9. Illuminating the chirality of Weyl fermions

    Science.gov (United States)

    Ma, Qiong; Xu, Su-Yang; Chan, Ching-Kit; Zhang, Cheng-Long; Chang, Guoqing; Lin, Hsin; Jia, Shuang; Lee, Patrick; Gedik, Nuh; Jarillo-Herrero, Pablo

    In particle physics, Weyl fermions (WF) are elementary particles that travel at the speed of light and have a definite chirality. In condensed matter, it has been recently realized that WFs can arise as magnetic monopoles in the momentum space of a novel topological metal, the Weyl semimetal (WSM). Their chirality, given by the sign of the monopole charge, is the defining property of a WSM, since it directly serves as the topological number and gives rise to exotic properties such as Fermi arcs and the chiral anomaly. Moreover, the two chiralities, analogous to the two valleys in 2D materials, lead to a new degree of freedom in a 3D crystal, suggesting novel pathways to store and carry information. By shining circularly polarized light on the WSM TaAs, we illuminate the chirality of the WFs and achieve an electrical current that is highly controllable based on the WFs' chirality. Our results open up a wide range of new possibilities for experimentally studying and controlling the WFs and their associated quantum anomalies by optical and electrical means, which suggest the exciting prospect of ``Weyltronics''.

  10. New chiral zwitterionic phosphorus heterocycles: synthesis, structure, properties and application as chiral solvating agents.

    Science.gov (United States)

    Sheshenev, Andrey E; Boltukhina, Ekaterina V; Grishina, Anastasiya A; Cisařova, Ivana; Lyapkalo, Ilya M; Hii, King Kuok Mimi

    2013-06-17

    A family of new chiral zwitterionic phosphorus-containing heterocycles (zPHC) have been derived from methylene-bridged bis(imidazolines). These structures were unambiguously determined, including single-crystal XRD analysis for two compounds. The stability, acid/base and electronic properties of these dipolar phosphorus heterocycles were subsequently investigated. zPHCs can be successfully employed as a new class of chiral solvating agents for the enantiodifferentiation of chiral carboxylic and sulfonic acids by NMR spectroscopy. The stoichiometry and binding constants for the donor-acceptor complexes formed were established by NMR titration methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Chiral anomalies and differential geometry

    International Nuclear Information System (INIS)

    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

  12. What's wrong with anomalous chiral gauge theory?

    International Nuclear Information System (INIS)

    Kieu, T.D.

    1994-05-01

    It is argued on general ground and demonstrated in the particular example of the Chiral Schwinger Model that there is nothing wrong with apparently anomalous chiral gauge theory. If quantised correctly, there should be no gauge anomaly and chiral gauge theory should be renormalisable and unitary, even in higher dimensions and with non-Abelian gauge groups. Furthermore, it is claimed that mass terms for gauge bosons and chiral fermions can be generated without spoiling the gauge invariance. 19 refs

  13. Self-inductance of chiral conducting nanotubes

    International Nuclear Information System (INIS)

    Miyamoto, Yoshiyuki; Rubio, Angel; Louie, Steven G.; Cohen, Marvin L.

    1998-01-01

    Chiral conductivity in nanotubes has recently been predicted theoretically. The realization and application of chiral conducting nanotubes can be of great interest from both fundamental and technological viewpoints. These chiral currents, if they are realized, can be detected by measuring the self-inductance. We have treated Maxwell's equations for chiral conducting nanotubes (nanocoils) and find that the self-inductance and the resistivity of nanocoils should depend on the frequency of the alternating current even when the capacitance of the nanocoils is not taken into account. This is in contrast to elementary treatment of ordinary coils. This fact is useful to distinguish nanocoils by electrical measurements

  14. Macroscopic chirality of a liquid crystal from nonchiral molecules

    International Nuclear Information System (INIS)

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

    2001-01-01

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

  15. Chiral symmetry breaking is permitted in supersymmetric QED

    International Nuclear Information System (INIS)

    Walker, M.

    2000-01-01

    Full text: A chirally symmetric theory will generally have a chirally symmetric and a chirally asymmetric solution for the dressed fermionic propagator. It has been claimed that no chirally asymmetric solution for the fermionic propagator exists in supersymmetric QED. This result in the superfield formalism uses a gauge dependent argument whose validity has since been questioned. We present an analogous analysis using the component formalism which demonstrates that chiral symmetry breaking is permitted in this theory. We open the presentation with a brief introduction to supersymmetry, supersymmetric QED, and the superfield formalism. We describe chiral symmetry breaking and the Dyson-Schwinger equation used to analyse it. The derivation of the erroneous theorem claiming the lack of an a chiral propagator is outlined and its flaws discussed. We finish with the equivalent derivation in component fields and our contradictory result

  16. Chiral spiral induced by a strong magnetic field

    Directory of Open Access Journals (Sweden)

    Abuki Hiroaki

    2016-01-01

    Full Text Available We study the modification of the chiral phase structure of QCD due to an external magnetic field. We first demonstrate how the effect of magnetic field can systematically be incorporated into a generalized Ginzburg-Landau framework. We then analyze the phase structure in the vicinity of the chiral critical point. In the chiral limit, the effect is found to be so drastic that it brings a “continent” of chiral spiral in the phase diagram, by which the chiral tricritical point is totally washed out. This is the case no matter how small the intensity of magnetic field is. On the other hand, the current quark mass protects the chiral critical point from a weak magnetic field. However, the critical point will eventually be covered by the chiral spiral phase as the magnetic field grows.

  17. Broken chiral symmetry and the structure of hadrons

    International Nuclear Information System (INIS)

    Spence, W.L.

    1982-01-01

    The spontaneous breaking of chiral symmetry plays a decisive role in the structure of hadrons composed of light quarks. The formalism by which the dynamics of chiral symmetry breaking and its implications for hadronic structure can be explored in a simplified world in which fully relativistic zero-bare-mass quarks interact through a chirally symmetric instantaneous confining potential is presented. By thus modeling the essentials of the chiral limit-N/sub c/ infinity limit of QCD contact is made with the successes of existent semiphenomenological models of hadrons but post assumptions which explicitly violate chiral symetry are avoided. This revised approach then makes possible a unification of the dynamics of hadron structure with the mechanism of spontaneous chiral breaking and guarantees the appearance of the correct Goldstone excitations. The chiral breaking order parameter (absolute value anti psi psi), effective quark mass, and Goldstone boson wave function are obtainable by solving a single non-linear integral equation once a potential has been prescribed. The stability of the chiral asymmetric vacuum must then be established by studying the linear eigenvalue problem which determines the spectrum of states with vacuum quantum numbers. The nature of the instability of the chiral symmetric vacuum that leads to spontaneous symmetry breaking is explained and its apparent contingency on details of the dynamics is emphasized. It is argued that a single massless fermion in a chirally symmetric potential does form bound states for which a semi-classical description is given. Coupling to vacuum pairs of such bound states occasions the possibility of chiral symmetry breakdown

  18. Lanthanide(III) complexes of bis-semicarbazone and bis-imine-substituted phenanthroline ligands: solid-state structures, photophysical properties, and anion sensing.

    Science.gov (United States)

    Nadella, Sandeep; Selvakumar, Paulraj M; Suresh, Eringathodi; Subramanian, Palani S; Albrecht, Markus; Giese, Michael; Fröhlich, Roland

    2012-12-21

    Phenanthroline-based hexadentate ligands L(1) and L(2) bearing two achiral semicarbazone or two chiral imine moieties as well as the respective mononuclear complexes incorporating various lanthanide ions, such as La(III), Eu(III), Tb(III), Lu(III), and Y(III) metal ions, were synthesized, and the crystal structures of [ML(1)Cl(3)] (M=La(III), Eu(III), Tb(III), Lu(III), or Y(III)) complexes were determined. Solvent or water molecules act as coligands for the rare-earth metals in addition to halide anions. The big Ln(III) ion exhibits a coordination number (CN) of 10, whereas the corresponding Eu(III), Tb(III), Lu(III), and Y(III) centers with smaller ionic radii show CN=9. Complexes of L(2), namely [ML(2)Cl(3)] (M=Eu(III), Tb(III), Lu(III), or Y(III)) ions could also be prepared. Only the complex of Eu(III) showed red luminescence, whereas all the others were nonluminescent. The emission properties of the Eu derivative can be applied as a photophysical signal for sensing various anions. The addition of phosphate anions leads to a unique change in the luminescence behavior. As a case study, the quenching behavior of adenosine-5'-triphosphate (ATP) was investigated at physiological pH value in an aqueous solvent. A specificity of the sensor for ATP relative to adenosine-5'-diphosphate (ADP) and adenosine-5'-monophosphate (AMP) was found. (31)P NMR spectroscopic studies revealed the formation of a [EuL(2)(ATP)] coordination species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Speciation and gene flow between snails of opposite chirality.

    Directory of Open Access Journals (Sweden)

    Angus Davison

    2005-09-01

    Full Text Available Left-right asymmetry in snails is intriguing because individuals of opposite chirality are either unable to mate or can only mate with difficulty, so could be reproductively isolated from each other. We have therefore investigated chiral evolution in the Japanese land snail genus Euhadra to understand whether changes in chirality have promoted speciation. In particular, we aimed to understand the effect of the maternal inheritance of chirality on reproductive isolation and gene flow. We found that the mitochondrial DNA phylogeny of Euhadra is consistent with a single, relatively ancient evolution of sinistral species and suggests either recent "single-gene speciation" or gene flow between chiral morphs that are unable to mate. To clarify the conditions under which new chiral morphs might evolve and whether single-gene speciation can occur, we developed a mathematical model that is relevant to any maternal-effect gene. The model shows that reproductive character displacement can promote the evolution of new chiral morphs, tending to counteract the positive frequency-dependent selection that would otherwise drive the more common chiral morph to fixation. This therefore suggests a general mechanism as to how chiral variation arises in snails. In populations that contain both chiral morphs, two different situations are then possible. In the first, gene flow is substantial between morphs even without interchiral mating, because of the maternal inheritance of chirality. In the second, reproductive isolation is possible but unstable, and will also lead to gene flow if intrachiral matings occasionally produce offspring with the opposite chirality. Together, the results imply that speciation by chiral reversal is only meaningful in the context of a complex biogeographical process, and so must usually involve other factors. In order to understand the roles of reproductive character displacement and gene flow in the chiral evolution of Euhadra, it will be

  20. Higher derivative regularization and chiral anomaly

    International Nuclear Information System (INIS)

    Nagahama, Yoshinori.

    1985-02-01

    A higher derivative regularization which automatically leads to the consistent chiral anomaly is analyzed in detail. It explicitly breaks all the local gauge symmetry but preserves global chiral symmetry and leads to the chirally symmetric consistent anomaly. This regularization thus clarifies the physics content contained in the consistent anomaly. We also briefly comment on the application of this higher derivative regularization to massless QED. (author)

  1. New remarks on chiral bosonization

    International Nuclear Information System (INIS)

    Souza Dutra, A. de

    1992-01-01

    We discuss a certain duality between the constraints appearing in ordinary Lagrangian density and its first order counterpart for the gauged Siegel chiral boson. It is demonstrated the equivalence, at the classical level, of the two versions of the gauged Siegel chiral boson to its corresponding gauged Floreanini-Jackiw chiral bosons. It is also argued that the most general constrained Lagrangian density, that leads to a bosonic field obeying a first order differential equation of motion and preserve simultaneously Lorentz invariance, is just the Floreanini-Jackiw one. (author)

  2. Chiral Dynamics 2006

    Science.gov (United States)

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

    2007-10-01

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

  3. Chiral gravity, log gravity, and extremal CFT

    International Nuclear Information System (INIS)

    Maloney, Alexander; Song Wei; Strominger, Andrew

    2010-01-01

    We show that the linearization of all exact solutions of classical chiral gravity around the AdS 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.

  4. Confining but chirally symmetric dense and cold matter

    International Nuclear Information System (INIS)

    Glozman, L. Ya.

    2012-01-01

    The possibility for existence of cold, dense chirally symmetric matter with confinement is reviewed. The answer to this question crucially depends on the mechanism of mass generation in QCD and interconnection of confinement and chiral symmetry breaking. This question can be clarified from spectroscopy of hadrons and their axial properties. Almost systematical parity doubling of highly excited hadrons suggests that their mass is not related to chiral symmetry breaking in the vacuum and is approximately chirally symmetric. Then there is a possibility for existence of confining but chirally symmetric matter. We clarify a possible mechanism underlying such a phase at low temperatures and large density. Namely, at large density the Pauli blocking prevents the gap equation to generate a solution with broken chiral symmetry. However, the chirally symmetric part of the quark Green function as well as all color non-singlet quantities are still infrared divergent, meaning that the system is with confinement. A possible phase transition to such a matter is most probably of the first order. This is because there are no chiral partners to the lowest lying hadrons.

  5. Nickel(0)-catalyzed enantioselective annulations of alkynes and arylenoates enabled by a chiral NHC ligand: efficient access to cyclopentenones.

    Science.gov (United States)

    Ahlin, Joachim S E; Donets, Pavel A; Cramer, Nicolai

    2014-11-24

    Cyclopentenones are versatile structural motifs of natural products as well as reactive synthetic intermediates. The nickel-catalyzed reductive [3+2] cycloaddition of α,β-unsaturated aromatic esters and alkynes constitutes an efficient method for their synthesis. Here, nickel(0) catalysts comprising a chiral bulky C1-symmetric N-heterocyclic carbene ligand were shown to enable an efficient asymmetric synthesis of cyclopentenones from mesityl enoates and internal alkynes under mild conditions. The bulky NHC ligand provided the cyclopentenone products in very high enantioselectivity and led to a regioselective incorporation of unsymmetrically substituted alkynes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2017-01-24

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

  7. Chirality detection of enantiomers using twisted optical metamaterials

    Science.gov (United States)

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

    2017-01-01

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

  8. A Highly Stable Microporous Covalent Imine Network Adsorbent for Natural Gas Upgrading and Flue Gas CO2 Capture

    KAUST Repository

    Das, Swapan Kumar; Wang, Xinbo; Ostwal, Mayur; Lai, Zhiping

    2016-01-01

    The feasible capture and separation of CO2 and N2 from CH4 is an important task for natural gas upgrading and the control of greenhouse gas emissions. Here, we studied the microporous covalent imine networks (CIN) material prepared through Schiff

  9. Nucleon parton distributions in chiral perturbation theory

    International Nuclear Information System (INIS)

    Moiseeva, Alena

    2013-01-01

    Properties of the chiral expansion of nucleon light-cone operators have been studied. In the framework of the chiral perturbation theory we have demonstrated that convergency of the chiral expansion of nucleon parton distributions strongly depends on the value of the variable x. Three regions in x with essentially different analytical properties of the resulting chiral expansion for parton distributions were found. For each of the regions we have elaborated special power counting rules corresponding to the partial resummation of the chiral series. The nonlocal effective operators for the vector and the axial nucleon parton distributions have been constructed at the zeroth and the first chiral order. Using the derived nonlocal operators and the derived power counting rules we have obtained the second order expressions for the nucleon GPDs H(x,ξ,Δ 2 ), H(x,ξ,Δ 2 ),E(x,ξ,Δ 2 ) valid in the region x>or similar a 2 χ .

  10. Cosmic chirality both true and false.

    Science.gov (United States)

    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. Copyright © 2012 Wiley Periodicals, Inc.

  11. Supramolecular Influence on Keto-Enol Tautomerism and Thermochromic Properties of o-Hydroxy Schiff Bases

    Directory of Open Access Journals (Sweden)

    Marija Zbačnik

    2016-06-01

    Full Text Available This work presents a study on thermo-optical properties of three Schiff bases (imines in the solid state. The Schiff bases were obtained by means of mechanochemical synthesis using monosubstituted o-hydroxy aromatic aldehydes and monosubstituted aromatic amines. The keto-enol tautomerism and proton transfer via intramolecular O∙∙∙N hydrogen bond of the reported compounds was found to be influenced more by supramolecular interactions than by a temperature change. All products were characterised by powder X-ray diffraction (PXRD, FT-IR spectroscopy, thermogravimetric (TG analysis and differential scanning calorimetry (DSC. Molecular and crystal structures of compounds 1, 2 and 3 were determined by single crystal X-ray diffraction (SCXRD. The molecules of 1 appear to be present as the enol-imine, the molecules of 2 as the keto-amine tautomer and the molecules of 3 exhibit keto-enol tautomeric equilibrium in the solid state. An analysis of Cambridge structural database (CSD data on similar imines has been used for structural comparison. This work is licensed under a Creative Commons Attribution 4.0 International License.

  12. Chiral fermions on the lattice

    International Nuclear Information System (INIS)

    Randjbar Daemi, S.; Strathdee, J.

    1995-01-01

    The overlap approach to chiral gauge theories on arbitrary D-dimensional lattices is studied. The doubling problem and its relation to chiral anomalies for D = 2 and 4 is examined. In each case it is shown that the doublers can be eliminated and the well known perturbative results for chiral anomalies can be recovered. We also consider the multi-flavour case and give the general criteria for the construction of anomaly free chiral gauge theories on arbitrary lattices. We calculate the second order terms in a continuum approximation to the overlap formula in D dimensions and show that they coincide with the bilinear part of the effective action of D-dimensional Weyl fermions coupled to a background gauge field. Finally, using the same formalism we reproduce the correct Lorentz, diffeomorphism and gauge anomalies in the coupling of a Weyl fermion to 2-dimensional gravitation and Maxwell fields. (author). 15 refs

  13. Quenched Chiral Perturbation Theory to one loop

    NARCIS (Netherlands)

    Colangelo, G.; Pallante, E.

    The divergences of the generating functional of quenched Chiral Perturbation theory (qCHPT) to one loop are computed in closed form. We show how the quenched chiral logarithms can be reabsorbed in the renormalization of the B0 parameter of the leading order Lagrangian. Finally, we do the chiral

  14. Chiral dynamics with (non)strange quarks

    International Nuclear Information System (INIS)

    Kubis, Bastian; Meißner, Ulf-G.

    2017-01-01

    We review the results and achievements of the project B.3. Topics addressed include pion photoproduction off the proton and off deuterium, three-flavor chiral perturbation theory studies, chiral symmetry tests in Goldstone boson decays, the development of unitarized chiral perturbation theory to next-to-leading order, the two-pole structure of the Λ(1405), the dynamical generation of the lowest S_1_1 resonances, the theory of hadronic atoms and its application to various systems, precision studies in light-meson decays based on dispersion theory, the Roy–Steiner analysis of pion–nucleon scattering, a high-precision extraction of the elusive pion–nucleon σ-term, and aspects of chiral dynamics in few-nucleon systems.

  15. Chiral dynamics with (non)strange quarks

    Science.gov (United States)

    Kubis, Bastian; Meißner, Ulf-G.

    2017-01-01

    We review the results and achievements of the project B.3. Topics addressed include pion photoproduction off the proton and off deuterium, three-flavor chiral perturbation theory studies, chiral symmetry tests in Goldstone boson decays, the development of unitarized chiral perturbation theory to next-to-leading order, the two-pole structure of the Λ(1405), the dynamical generation of the lowest S11 resonances, the theory of hadronic atoms and its application to various systems, precision studies in light-meson decays based on dispersion theory, the Roy-Steiner analysis of pion-nucleon scattering, a high-precision extraction of the elusive pion-nucleon σ-term, and aspects of chiral dynamics in few-nucleon systems.

  16. Chiral symmetry breaking and cooling in lattice QCD

    International Nuclear Information System (INIS)

    Woloshyn, R.M.; Lee, F.X.

    1995-08-01

    Chiral symmetry breaking is calculated as a function of cooling in quenched lattice QCD. A non-zero signal is found for the chiral condensate beyond one hundred cooling steps, suggesting that there is chiral symmetry breaking associated with instantons. Quantitatively, the chiral condensate in cooled gauge field configurations is small compared to the value without cooling. (author) 7 refs., 1 tab., 3 figs

  17. A web site for calculating the degree of chirality.

    Science.gov (United States)

    Zayit, Amir; Pinsky, Mark; Elgavi, Hadassah; Dryzun, Chaim; Avnir, David

    2011-01-01

    The web site, http://www.csm.huji.ac.il/, uses the Continuous Chirality Measure to evaluate quantitatively the degree of chirality of a molecule, a structure, a fragment. The value of this measure ranges from zero, the molecule is achiral, to higher values (the upper limit is 100); the higher the chirality value, the more chiral the molecule is. The measure is based on the distance between the chiral molecule and the nearest structure that is achiral. Questions such as the following can be addressed: by how much is one molecule more chiral than the other? how does chirality change along conformational motions? is there a correlation between chirality and enantioselectivity in a series of molecules? Both elementary and advanced features are offered. Related calculation options are the symmetry measures and shape measures. Copyright © 2009 Wiley-Liss, Inc.

  18. Two-color QCD with non-zero chiral chemical potential

    Energy Technology Data Exchange (ETDEWEB)

    Braguta, V.V. [Institute for High Energy Physics NRC “Kurchatov Institute' ,142281 Protvino (Russian Federation); Far Eastern Federal University, School of Biomedicine,690950 Vladivostok (Russian Federation); Goy, V.A. [Far Eastern Federal University, School of Natural Sciences,690950 Vladivostok (Russian Federation); Ilgenfritz, E.M. [Joint Institute for Nuclear Research,BLTP, 141980 Dubna (Russian Federation); Kotov, A.Yu. [Institute of Theoretical and Experimental Physics,117259 Moscow (Russian Federation); Molochkov, A.V. [Far Eastern Federal University, School of Biomedicine,690950 Vladivostok (Russian Federation); Müller-Preussker, M.; Petersson, B. [Humboldt-Universität zu Berlin, Institut für Physik,12489 Berlin (Germany)

    2015-06-16

    The phase diagram of two-color QCD with non-zero chiral chemical potential is studied by means of lattice simulation. We focus on the influence of a chiral chemical potential on the confinement/deconfinement phase transition and the breaking/restoration of chiral symmetry. The simulation is carried out with dynamical staggered fermions without rooting. The dependences of the Polyakov loop, the chiral condensate and the corresponding susceptibilities on the chiral chemical potential and the temperature are presented. The critical temperature is observed to increase with increasing chiral chemical potential.

  19. A variational approach to chiral quark models

    International Nuclear Information System (INIS)

    Futami, Yasuhiko; Odajima, Yasuhiko; Suzuki, Akira.

    1987-01-01

    A variational approach is applied to a chiral quark model to test the validity of the perturbative treatment of the pion-quark interaction based on the chiral symmetry principle. It is indispensably related to the chiral symmetry breaking radius if the pion-quark interaction can be regarded as a perturbation. (author)

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

    Science.gov (United States)

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

    2008-11-15

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

  1. Transfer of chirality from adsorbed chiral molecules to the substrates highlighted by circular dichroism in angle-resolved valence photoelectron spectroscopy

    DEFF Research Database (Denmark)

    Contini, G.; Turchini, S.; Sanna, Simone

    2012-01-01

    Studies of self-assembled chiral molecules on achiral metallic surfaces have mostly focused on the determination of the geometry of adsorbates and their electronic structure. The aim of this paper is to provide direct information on the chirality character of the system and on the chirality...... transfer from molecules to substrate by means of circular dichroism in the angular distribution of valence photoelectrons for the extended domain of the chiral self-assembled molecular structure, formed by alaninol adsorbed on Cu(100). We show, by the dichroic behavior of a mixed molecule–copper valence...... state, that the presence of molecular chiral domains induces asymmetry in the interaction with the substrate and locally transfers the chiral character to the underlying metal atoms participating in the adsorption process; combined information related to the asymmetry of the initial electronic state...

  2. Multiaxial Polarity Determines Individual Cellular and Nuclear Chirality.

    Science.gov (United States)

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

    2017-02-01

    Intrinsic cell chirality has been implicated in the left-right (LR) asymmetry of embryonic development. Impaired cell chirality could lead to severe birth defects in laterality. Previously, we detected cell chirality with an in vitro micropatterning system. Here, we demonstrate for the first time that chirality can be quantified as the coordination of multiaxial polarization of individual cells and nuclei. Using an object labeling, connected component based method, we characterized cell chirality based on cell and nuclear shape polarization and nuclear positioning of each cell in multicellular patterns of epithelial cells. We found that the cells adopted a LR bias the boundaries by positioning the sharp end towards the leading edge and leaving the nucleus at the rear. This behavior is consistent with the directional migration observed previously on the boundary of micropatterns. Although the nucleus is chirally aligned, it is not strongly biased towards or away from the boundary. As the result of the rear positioning of nuclei, the nuclear positioning has an opposite chirality to that of cell alignment. Overall, our results have revealed deep insights of chiral morphogenesis as the coordination of multiaxial polarization at the cellular and subcellular levels.

  3. Chiral anomaly, bosonization, and fractional charge

    International Nuclear Information System (INIS)

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

    1985-01-01

    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 ν = 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

  4. A spectral route to determining chirality

    DEFF Research Database (Denmark)

    Pedersen, Jesper Goor; Mortensen, Asger

    2009-01-01

    We show how one-dimensional structured media can be used to measure chirality, via the spectral shift of the photonic band gap edges. Analytically, we show that a chiral contrast can, in some cases, be mapped unto an index contrast, thereby greatly simplifying the analysis of such structures. Using...... this mapping, we derive a first-order shift of the band gap edges with chirality. Potentially, this effect could be used for measuring enantiomeric excess....

  5. Chiral properties of baryon interpolating fields

    International Nuclear Information System (INIS)

    Nagata, Keitaro; Hosaka, Atsushi; Dmitrasinovic, V.

    2008-01-01

    We study the chiral transformation properties of all possible local (non-derivative) interpolating field operators for baryons consisting of three quarks with two flavors, assuming good isospin symmetry. We derive and use the relations/identities among the baryon operators with identical quantum numbers that follow from the combined color, Dirac and isospin Fierz transformations. These relations reduce the number of independent baryon operators with any given spin and isospin. The Fierz identities also effectively restrict the allowed baryon chiral multiplets. It turns out that the non-derivative baryons' chiral multiplets have the same dimensionality as their Lorentz representations. For the two independent nucleon operators the only permissible chiral multiplet is the fundamental one, ((1)/(2),0)+(0,(1)/(2)). For the Δ, admissible Lorentz representations are (1,(1)/(2))+((1)/(2),1) and ((3)/(2),0)+(0,(3)/(2)). In the case of the (1,(1)/(2))+((1)/(2),1) chiral multiplet, the I(J)=(3)/(2)((3)/(2)) Δ field has one I(J)=(1)/(2)((3)/(2)) chiral partner; otherwise it has none. We also consider the Abelian (U A (1)) chiral transformation properties of the fields and show that each baryon comes in two varieties: (1) with Abelian axial charge +3; and (2) with Abelian axial charge -1. In case of the nucleon these are the two Ioffe fields; in case of the Δ, the (1,(1)/(2))+((1)/(2),1) multiplet has an Abelian axial charge -1 and the ((3)/(2),0)+(0,(3)/(2)) multiplet has an Abelian axial charge +3. (orig.)

  6. Search for chirality in 109Ag

    International Nuclear Information System (INIS)

    Timar, J.; Nyako, B.M.; Berek, G.; Gal, J.; Kalinka, G.; Krasznahorkay, A.; Molnar, J.; Zolnai, L.

    2007-01-01

    Complete text of publication follows. The existence of nuclear chirality is one of the most intriguing questions of contemporary high-spin nuclear structure studies. Rotational doublet-band candidates for chiral structures have been observed mostly in two regions of the nuclear chart: around 134 Pr, and around 104 Rh. In this second region chirality in the Rh isotopes are rather well studied, chiral doubling have also been observed in 100 Tc, however, results obtained for chirality in the studied Ag nuclei ( 105 Ag and 106 Ag) look rather contradictory. Thus, it is interesting to study these doublet bands in the nearby higher-mass Ag nuclei. In order to search for a chiral-candidate partner band to the yrast πg 9/2 v(h 11/2 ) 2 band in 109 Ag, high-spin states of this nucleus have been studied using the 96 Zr( 18 O,p4n) reaction. The experiment was performed at iThemba LABS using 8 Clover detectors of the AFRODITE array and the DIAMANT charged-particle array to detect the γ-rays and the charged particles, respectively. Altogether ∼140 million γγ-coincidence events were collected. Approximately 10 million events of them correspond to the reaction channel producing 109 Ag. No chiral candidate partner band has been found to the πg 9/2 v(h 11/2 ) 2 band with this statistics, however, the level scheme could be extended by several new levels and γ-transitions. A preliminary level scheme of 109 Ag obtained from the ongoing data analysis is shown in Fig. 1

  7. Generalized chiral membrane dynamics

    International Nuclear Information System (INIS)

    Cordero, R.; Rojas, E.

    2003-01-01

    We develop the dynamics of the chiral superconducting membranes (with null current) in an alternative geometrical approach. Besides of this, we show the equivalence of the resulting description with the one known Dirac-Nambu-Goto (DNG) case. Integrability for chiral string model is obtained using a proposed light-cone gauge. In a similar way, domain walls are integrated by means of a simple Ansatz. (Author)

  8. Rhodium(III)-catalyzed three-component reaction of imines, alkynes, and aldehydes through C-H activation.

    Science.gov (United States)

    Huang, Ji-Rong; Song, Qiang; Zhu, Yu-Qin; Qin, Liu; Qian, Zhi-Yong; Dong, Lin

    2014-12-15

    An efficient rhodium(III)-catalyzed tandem three-component reaction of imines, alkynes and aldehydes through CH activation has been developed. High stereo- and regioselectivity, as well as good yields were obtained in most cases. The simple and atom-economical approach offers a broad scope of substrates, providing polycyclic skeletons with potential biological properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Structural and electrochemical studies of TiO2 complexes with (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivative bases towards organic devices.

    Science.gov (United States)

    Rozycka, Anna; Iwan, Agnieszka; Bogdanowicz, Krzysztof Artur; Filapek, Michal; Górska, Natalia; Hreniak, Agnieszka; Marzec, Monika

    2018-06-12

    Three (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivatives were synthesized via a condensation reaction with p-toluenesulfonic acid as a catalyst. The effects of the end groups and vinylene (-HC[double bond, length as m-dash]CH-) moieties on the structural, thermal, optical, electrochemical and photovoltaic properties of imines were investigated to check the influence of TiO2 on the imine properties. The thermal behavior of imines and their complexes with TiO2 was widely investigated using FT-IR, XRD, DSC and POM methods in order to determine the order type in the imine structure. All imines present the highest occupied molecular orbital (HOMO) levels of about -5.39 eV (SAI1 and SAI2) and -5.27 eV (SAI3) and the lowest unoccupied molecular orbital (LUMO) levels at about -3.17 eV. The difference of the end groups in the imines in each case did not affect redox properties. Generally, both oxidation and reduction are easier after TiO2 addition and it also changes the HOMO-LUMO levels of imines. Moreover, changes in the characteristic bands for imines in the region 1500-1700 cm-1 observed as a drastic decrease of intensity or even disappearance of bands in the imine : TiO2 mixture suggest the formation of a complex (C[double bond, length as m-dash]N)-TiO2. Organic devices with the configuration of ITO/TiO2/SAIx (or SAIx : TiO2)/Au were fabricated and investigated in the presence and absence of visible light irradiation with an intensity of 93 mW cm-2. In all imines and complexes with TiO2, the generation of the photocurrent indicates their use as photodiodes and the best result was observed for SAI3 : TiO2 complexes.

  10. The ''closed'' chiral symmetry and its application to tetraquark

    International Nuclear Information System (INIS)

    Chen, Hua-Xing

    2012-01-01

    We investigate the chiral (flavor) structure of tetraquarks, and study chiral transformation properties of the ''non-exotic'' [(anti 3, 3)+(3, anti 3)] and [(8,1)+(1,8)] tetraquark chiral multiplets. We find that as long as this kind of tetraquark states contains one quark and one antiquark having the same chirality, such as q L q L anti q L anti q R + q R q R anti q R anti q L , they transform in the same way as the lowest level anti q q chiral multiplets under chiral transformations. There is only one [(anti 3, 3)+(3, anti 3)] chiral multiplet whose quark-antiquark pairs all have the opposite chirality (q L q L anti q R anti q R + q R q R anti q L anti q L ), and it transforms differently from others. Based on these studies, we construct local tetraquark currents belonging to the ''non-exotic'' chiral multiplet [(anti 3, 3)+(3, anti 3)] and having quantum numbers J PC =1 -+ . (orig.)

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

    Science.gov (United States)

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

    2013-01-01

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

  12. Chiral Rayleigh particles discrimination in dynamic dual optical traps

    International Nuclear Information System (INIS)

    Carretero, Luis; Acebal, Pablo; Blaya, Salvador

    2017-01-01

    Highlights: • A chiral optical conveyor belt for enantiomeric separation of nanopar-ticles is numerically demonstrated. • Chiral resolution has been theoretically analyzed for chiral spheres immersed in water. • Electromagnetic fields have been designed for obtaining Chiral selective optical tweezers to separate enantiomers in different spatial regions. - Abstract: A chiral optical conveyor belt for enantiomeric separation of nanoparticles is numerically demonstrated by using different types of counter propagating elliptical Laguerre Gaussian beams with different beam waist and topological charge. The analysis of chiral resolution has been made for particles immersed in water demonstrating that in the analyzed conditions one type of enantiomer is trapped in a deep potential and the others are transported by the chiral conveyor toward another trap located in a different geometrical region.

  13. Chiral anomaly, bosonization and fractional charge

    International Nuclear Information System (INIS)

    Mignaco, J.A.; Rego Monteiro, M.A. do.

    1984-01-01

    A method to evaluate the Jacobian of chiral rotations, regulating determinants through the proper time method and using Seeley's asymptotic expansion is presented. With this method the chiral anomaly ofr ν=4,6 dimensions is computed easily, bosonization of some massless two-dimensional models is discussed and the problem of charge fractionization is handled. Besides, the general validity of Fujikawa's approach to regulate the Jacobian of chiral rotations with non-hermitean operators is commented. (Author) [pt

  14. Supersymmetry and the chiral Schwinger model

    International Nuclear Information System (INIS)

    Amorim, R.; Das, A.

    1998-01-01

    We have constructed the N= (1) /(2) supersymmetric general Abelian model with asymmetric chiral couplings. This leads to a N= (1) /(2) supersymmetrization of the Schwinger model. We show that the supersymmetric general model is plagued with problems of infrared divergence. Only the supersymmetric chiral Schwinger model is free from such problems and is dynamically equivalent to the chiral Schwinger model because of the peculiar structure of the N= (1) /(2) multiplets. copyright 1998 The American Physical Society

  15. Chiral Tunnelling in Twisted Graphene Bilayer

    OpenAIRE

    He, Wen-Yu; Chu, Zhao-Dong; He, Lin

    2013-01-01

    The perfect transmission in graphene monolayer and the perfect reflection in Bernal graphene bilayer for electrons incident in the normal direction of a potential barrier are viewed as two incarnations of the Klein paradox. Here we show a new and unique incarnation of the Klein paradox. Owing to the different chiralities of the quasiparticles involved, the chiral fermions in twisted graphene bilayer shows adjustable probability of chiral tunnelling for normal incidence: they can be changed fr...

  16. Electromagnetic couplings of the chiral perturbation theory Lagrangian from the perturbative chiral quark model

    International Nuclear Information System (INIS)

    Lyubovitskij, V.E.; Gutsche, Th.; Faessler, Amand; Mau, R. Vinh

    2002-01-01

    We apply the perturbative chiral quark model to the study of the low-energy πN interaction. Using an effective chiral Lagrangian we reproduce the Weinberg-Tomozawa result for the S-wave πN scattering lengths. After inclusion of the photon field we give predictions for the electromagnetic O(p 2 ) low-energy couplings of the chiral perturbation theory effective Lagrangian that define the electromagnetic mass shifts of nucleons and first-order (e 2 ) radiative corrections to the πN scattering amplitude. Finally, we estimate the leading isospin-breaking correction to the strong energy shift of the π - p atom in the 1s state, which is relevant for the experiment 'pionic hydrogen' at PSI

  17. Pion polarizability in a chiral quark model

    International Nuclear Information System (INIS)

    Volkov, M.K.; Ehbert, D.

    1980-01-01

    The pion polarizability is calculated in a chiral meson-quark model at the one-loop level. The results are in complete agreement with earlier ones obtained within a chiral meson-baryon theory. A critical discussion of a recent paper by Lanta and Tarrach is given. The results of the paper give evidence to the nonlinear chiral Lagrangian favour

  18. Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

    Directory of Open Access Journals (Sweden)

    Hironori Izawa

    2010-07-01

    Full Text Available Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.

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

    Science.gov (United States)

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

    2012-06-08

    A chiral HPLC method using four macrocyclic antibiotic chiral stationary phases (CSPs) has been investigated for determination of the enantiomeric purity of fourteen new chiral derivatives of xanthones (CDXs). The separations were performed with the CSPs Chirobiotic T, Chirobiotic TAG, Chirobiotic V and Chirobiotic R under multimodal elution conditions (normal-phase, reversed-phase and polar ionic mode). The analyses were performed at room temperature in isocratic mode and UV and CD detection at a wavelength of 254 nm. The best enantioselectivity and resolution were achieved on Chirobiotic R and Chirobiotic T CSPs, under normal elution conditions, with R(S) ranging from 1.25 to 2.50 and from 0.78 to 2.06, respectively. The optimized chromatographic conditions allowed the determination of the enantiomeric ratio of eight CDXs, always higher than 99%. In order to better understand the chromatographic behavior at a molecular level, and the structural features associated with the chiral recognition mechanism, computational studies by molecular docking were carried out using VDock. These studies shed light on the mechanisms involved in the enantioseparation for this important class of chiral compounds. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Chiral symmetry breaking and confinement - solutions of relativistic wave equations

    International Nuclear Information System (INIS)

    Murugesan, P.

    1983-01-01

    In this thesis, an attempt is made to explore the question whether confinement automatically leads to chiral symmetry breaking. While it should be accepted that chiral symmetry breaking manifests in nature in the absence of scalar partners of pseudoscalar mesons, it does not necessarily follow that confinement should lead to chiral symmetry breaking. If chiral conserving forces give rise to observed spectrum of hadrons, then the conjuncture that confinement is responsible for chiral symmetry breaking is not valid. The method employed to answer the question whether confinement leads to chiral symmetry breaking or not is to solve relativistic wave equations by introducing chiral conserving as well as chiral breaking confining potentials and compare the results with experimental observations. It is concluded that even though chiral symmetry is broken in nature, confinement of quarks need not be the cause of it

  1. Topological chiral phonons in center-stacked bilayer triangle lattices

    Science.gov (United States)

    Xu, Xifang; Zhang, Wei; Wang, Jiaojiao; Zhang, Lifa

    2018-06-01

    Since chiral phonons were found in an asymmetric two-dimensional hexagonal lattice, there has been growing interest in the study of phonon chirality, which were experimentally verified very recently in monolayer tungsten diselenide (2018 Science 359 579). In this work, we find chiral phonons with nontrivial topology in center-stacked bilayer triangle lattices. At the Brillouin-zone corners, (), circularly polarized phonons and nonzero phonon Berry curvature are observed. Moreover, we find that the phonon chirality remain robust with changing sublattice mass ratio and interlayer coupling. The chiral phonons at the valleys are demonstrated in doubler-layer sodium chloride along the [1 1 1] direction. We believe that the findings on topological chiral phonons in triangle lattices will give guidance in the study of chiral phonons in real materials and promote the phononic applications.

  2. Minimally doubled fermions and spontaneous chiral symmetry breaking

    Directory of Open Access Journals (Sweden)

    Osmanaj (Zeqirllari Rudina

    2018-01-01

    Full Text Available Chiral symmetry breaking in massless QCD is a very important feature in the current understanding of low energy physics. Low - lying Dirac modes are suitable to help us understand the spontaneous chiral symmetry breaking, since the formation of a non zero chiral condensate is an effect of their accumulation near zero. The Banks – Casher relation links the spectral density of the Dirac operator to the condensate with an identity that can be read in both directions. In this work we propose a spectral method to achieve a reliable determination of the density of eigenvalues of Dirac operator near zero using the Gauss – Lanczos quadrature. In order to understand better the dynamical chiral symmetry breaking and use the method we propose, we have chosen to work with minimally doubled fermions. These kind of fermions have been proposed as a strictly local discretization of the QCD fermions action, which preserves chiral symmetry at finite cut-off. Being chiral fermions, is easier to work with them and their low - lying Dirac modes and to understand the dynamical spontaneous chiral symmetry breaking.

  3. Minimally doubled fermions and spontaneous chiral symmetry breaking

    Science.gov (United States)

    Osmanaj (Zeqirllari), Rudina; Hyka (Xhako), Dafina

    2018-03-01

    Chiral symmetry breaking in massless QCD is a very important feature in the current understanding of low energy physics. Low - lying Dirac modes are suitable to help us understand the spontaneous chiral symmetry breaking, since the formation of a non zero chiral condensate is an effect of their accumulation near zero. The Banks - Casher relation links the spectral density of the Dirac operator to the condensate with an identity that can be read in both directions. In this work we propose a spectral method to achieve a reliable determination of the density of eigenvalues of Dirac operator near zero using the Gauss - Lanczos quadrature. In order to understand better the dynamical chiral symmetry breaking and use the method we propose, we have chosen to work with minimally doubled fermions. These kind of fermions have been proposed as a strictly local discretization of the QCD fermions action, which preserves chiral symmetry at finite cut-off. Being chiral fermions, is easier to work with them and their low - lying Dirac modes and to understand the dynamical spontaneous chiral symmetry breaking.

  4. Sum-Frequency Generation from Chiral Media and Interfaces

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-02-13

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

  5. Sum-Frequency Generation from Chiral Media and Interfaces

    International Nuclear Information System (INIS)

    Ji, Na

    2006-01-01

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

  6. Aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Roder, M.

    1985-01-01

    Papers dealing with radiolysis of aromatic hydrocarbons of different composition (from benzene to terphenyls and hydrocarbons with condensed rings) as well as their mixtures (with alkanes, alkenes, other aromatic hydrocarbons) are reviewed. High radiation stability of aromatic hydrocarbons in condensed phases associated with peculiarities of molecular structure of compounds is underlined. Mechanisms of radiolytic processes, vaues of product yields are considered

  7. Asymmetric Michael Addition Mediated by Chiral Ionic Liquids.

    Science.gov (United States)

    Suzuki, Yumiko

    2018-06-01

    Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines.

  8. Probing molecular chirality by coherent optical absorption spectra

    Energy Technology Data Exchange (ETDEWEB)

    Jia, W. Z. [Quantum Optoelectronics Laboratory, School of Physics and Technology, Southwest Jiaotong University, Chengdu 610031 (China); Wei, L. F. [Quantum Optoelectronics Laboratory, School of Physics and Technology, Southwest Jiaotong University, Chengdu 610031 (China); State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China)

    2011-11-15

    We propose an approach to sensitively probe the chirality of molecules by measuring their coherent optical-absorption spectra. It is shown that quantum dynamics of the cyclic three-level chiral molecules driven by appropriately designed external fields is total-phase dependent. This will result in chirality-dependent absorption spectra for the probe field. As a consequence, the charality-dependent information in the spectra (such as the locations and relative heights of the characteristic absorption peaks) can be utilized to identify molecular chirality and determinate enantiomer excess (i.e., the percentages of different enantiomers). The feasibility of the proposal with chiral molecules confined in hollow-core photonic crystal fiber is also discussed.

  9. Lattice regularized chiral perturbation theory

    International Nuclear Information System (INIS)

    Borasoy, Bugra; Lewis, Randy; Ouimet, Pierre-Philippe A.

    2004-01-01

    Chiral perturbation theory can be defined and regularized on a spacetime lattice. A few motivations are discussed here, and an explicit lattice Lagrangian is reviewed. A particular aspect of the connection between lattice chiral perturbation theory and lattice QCD is explored through a study of the Wess-Zumino-Witten term

  10. Chiral tunneling in a twisted graphene bilayer.

    Science.gov (United States)

    He, Wen-Yu; Chu, Zhao-Dong; He, Lin

    2013-08-09

    The perfect transmission in a graphene monolayer and the perfect reflection in a Bernal graphene bilayer for electrons incident in the normal direction of a potential barrier are viewed as two incarnations of the Klein paradox. Here we show a new and unique incarnation of the Klein paradox. Owing to the different chiralities of the quasiparticles involved, the chiral fermions in a twisted graphene bilayer show an adjustable probability of chiral tunneling for normal incidence: they can be changed from perfect tunneling to partial or perfect reflection, or vice versa, by controlling either the height of the barrier or the incident energy. As well as addressing basic physics about how the chiral fermions with different chiralities tunnel through a barrier, our results provide a facile route to tune the electronic properties of the twisted graphene bilayer.

  11. SU(3) chiral symmetry for baryons

    International Nuclear Information System (INIS)

    Dmitrasinovic, V.

    2011-01-01

    Three-quark nucleon interpolating fields in QCD have well-defined SU L (3)xSU R (3) and U A (1) chiral transformation properties, viz. [(6,3)+(3,6)], [(3,3-bar)+(3-bar,3)], [(8,1)+(1,8)] and their 'mirror' images. It has been shown (phenomenologically) in Ref. [2] that mixing of the [(6,3)+(3,6)] chiral multiplet with one ordinary ('naive') and one 'mirror' field belonging to the [(3,3-bar)+(3-bar,3)], [(8,1)+(1,8)] multiplets can be used to fit the values of the isovector (g A (3) ) and the flavor-singlet (isoscalar) axial coupling (g A (0) ) of the nucleon and then predict the axial F and D coefficients, or vice versa, in reasonable agreement with experiment. In an attempt to derive such mixing from an effective Lagrangian, we construct all SU L (3)xSU R (3) chirally invariant non-derivative one-meson-baryon interactions and then calculate the mixing angles in terms of baryons' masses. It turns out that there are (strong) selection rules: for example, there is only one non-derivative chirally symmetric interaction between J 1/2 fields belonging to the [(6,3)+(3,6)] and the [(3,3-bar)+(3-bar,3)] chiral multiplets, that is also U A (1) symmetric. We also study the chiral interactions of the [(3,3-bar)+(3-bar,3)] and [(8,1)+(1,8)] nucleon fields. Again, there are selection rules that allow only one off-diagonal non-derivative chiral SU L (3)xSU R (3) interaction of this type, that also explicitly breaks the U A (1) symmetry. We use this interaction to calculate the corresponding mixing angles in terms of baryon masses and fit two lowest lying observed nucleon (resonance) masses, thus predicting the third (J = 1/2, I = 3/2)Δ resonance, as well as one or two flavor-singlet Λ hyperon(s), depending on the type of mixing. The effective chiral Lagrangians derived here may be applied to high density matter calculations.

  12. The synthesis and characterization of novel brush-type chiral stationary phase based on terpenoid selector for resolution of chiral drugs

    Directory of Open Access Journals (Sweden)

    Wang Dao-Cai

    2016-01-01

    Full Text Available In the light of the chiral resolution mechanism and structures of brush-type CSP, a new chiral selector 4′-carboxyl-1′-ursolic methyl ester-3β-yl-benzoate has been prepared. Then the terpenoid chiral selector was covalently linked to 3-aminopropyl silica gel. Its structure identification data are provided by 1H NMR, MS and elementary analysis. The enantiodiscriminating capability of the brush-type CSP was evaluated by static adsorption experiment with methyl mandelate, aniline derivative of mandelic acid, benzoin and ibuprofen. Experimental results demonstrated that the chiral selector has selectivity, and the enantiomers of methyl mandelate and ibuprofen could be separated on the CSP, which indicated that the novel brush-type CSP possess a bright prospects for chiral separation potentially.

  13. Chiral charge erasure via thermal fluctuations of magnetic helicity

    International Nuclear Information System (INIS)

    Long, Andrew J.; Sabancilar, Eray

    2016-01-01

    We consider a relativistic plasma of fermions coupled to an Abelian gauge field and carrying a chiral charge asymmetry, which might arise in the early Universe through baryogenesis. It is known that on large length scales, λ≳1/(αμ_5), the chiral anomaly opens an instability toward the erasure of chiral charge and growth of magnetic helicity. Here the chemical potential μ_5 parametrizes the chiral asymmetry and α is the fine-structure constant. We study the process of chiral charge erasure through the thermal fluctuations of magnetic helicity and contrast with the well-studied phenomenon of Chern-Simons number diffusion. Through the fluctuation-dissipation theorem we estimate the amplitude and time scale of helicity fluctuations on the length scale λ, finding δ H∼λT and τ∼αλ"3T"2 for a relativistic plasma at temperature T. We argue that the presence of a chiral asymmetry allows the helicity to grow diffusively for a time t∼T"3/(α"5μ_5"4) until it reaches an equilibrium value H∼μ_5T"2/α, and the chiral asymmetry is partially erased. If the chiral asymmetry is small, μ_5< T/α, this avenue for chiral charge erasure is found to be slower than the chiral magnetic effect for which t∼T/(α"3μ_5"2). This mechanism for chiral charge erasure can be important for the hypercharge sector of the Standard Model as well as extensions including U(1) gauge interactions, such as asymmetric dark matter models.

  14. A chiral aluminum solvating agent (CASA) for 1H NMR chiral analysis of alcohols at low temperature.

    Science.gov (United States)

    Seo, Min-Seob; Jang, Sumin; Kim, Hyunwoo

    2018-03-16

    A chiral aluminum solvating agent (CASA) was demonstrated to be a general and efficient reagent for 1H NMR chiral analysis of alcohols. The sodium salt of the CASA (CASA-Na) showed a complete baseline peak separation of the hydroxyl group for various chiral alcohols including primary, secondary, and tertiary alcohols with alkyl and aryl substituents in CD3CN. Due to the weak intermolecular interaction, 1H NMR measurement at low temperature (-40 to 10 °C) was required.

  15. Generalized chiral perturbation theory

    International Nuclear Information System (INIS)

    Knecht, M.; Stern, J.

    1994-01-01

    The Generalized Chiral Perturbation Theory enlarges the framework of the standard χPT (Chiral Perturbation Theory), relaxing certain assumptions which do not necessarily follow from QCD or from experiment, and which are crucial for the usual formulation of the low energy expansion. In this way, experimental tests of the foundations of the standard χPT become possible. Emphasis is put on physical aspects rather than on formal developments of GχPT. (author). 31 refs

  16. Chiral separation of substituted phenylalanine analogues using chiral palladium phosphine complexes with enantioselective liquid-liquid extraction

    NARCIS (Netherlands)

    Verkuijl, B.J.V.; Schuur, B.; Minnaard, A.J.; Vries, de J.G.; Feringa, B.L.

    2010-01-01

    Chiral palladium phosphine complexes have been employed in the chiral separation of amino acids and phenylalanine analogues in particular. The use of (S)-xylyl-BINAP as a ligand for the palladium complex in enantioselective liquid–liquid extraction allowed the separation of the phenylalanine

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

    Energy Technology Data Exchange (ETDEWEB)

    Rogachevskii, Igor; Kleeorin, Nathan [Department of Mechanical Engineering, Ben-Gurion University of the Negev, P.O. Box 653, Beer-Sheva 84105 (Israel); Ruchayskiy, Oleg [Discovery Center, Niels Bohr Institute, Blegdamsvej 17, DK-2100 Copenhagen (Denmark); Boyarsky, Alexey [Instituut-Lorentz for Theoretical Physics, Universiteit Leiden, Niels Bohrweg 2, 2333 CA Leiden (Netherlands); Fröhlich, Jürg [Institute of Theoretical Physics, ETH Hönggerberg, CH-8093 Zurich (Switzerland); Brandenburg, Axel; Schober, Jennifer, E-mail: gary@bgu.ac.il [Nordita, KTH Royal Institute of Technology and Stockholm University, Roslagstullsbacken 23, SE-10691 Stockholm (Sweden)

    2017-09-10

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

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

  19. A nonlocal model of chiral dynamics

    International Nuclear Information System (INIS)

    Holdom, B.; Terning, J.; Verbeek, K.

    1989-01-01

    We consider a nonlocal generalization of the nonlinear σ model. Our chirally symmetric model couples quarks with self-energy Σ(p) to Goldstone bosons (GBs). By integrating out the quarks we obtain a chiral lagrangian, the parameters of which are finite integrals of Σ(p). We find that chiral symmetry is not sufficient to derive the well-known Pagels-Stokar formula for the GB decay constant. We reproduce the Wess-Zumino term and we illustrate the dependence of other four derivative coefficients on Σ(p). (orig.)

  20. Chirality and chiroptical properties of amyloid fibrils.

    Science.gov (United States)

    Dzwolak, Wojciech

    2014-09-01

    Chirality of amyloid fibrils-linear beta-sheet-rich aggregates of misfolded protein chains-often manifests in morphological traits such as helical twist visible in atomic force microscopy and in chiroptical properties accessible to vibrational circular dichroism (VCD). According to recent studies the relationship between molecular chirality of polypeptide building blocks and superstructural chirality of amyloid fibrils may be more intricate and less deterministic than previously assumed. Several puzzling experimental findings have put into question earlier intuitive ideas on: 1) the bottom-up chirality transfer upon amyloidogenic self-assembly, and 2) the structural origins of chiroptical properties of protein aggregates. For example, removal of a single amino acid residue from an amyloidogenic all-L peptide was shown to reverse handedness of fibrils. On the other hand, certain types of amyloid aggregates revealed surprisingly strong VCD spectra with the sign and shape dependent on the conditions of fibrillation. Hence, microscopic and chiroptical studies have highlighted chirality as one more aspect of polymorphism of amyloid fibrils. This brief review is intended to outline the current state of research on amyloid-like fibrils from the perspective of their structural and superstructural chirality and chiroptical properties. © 2014 Wiley Periodicals, Inc.

  1. Homochiral Evolution in Self-Assembled Chiral Polymers and Block Copolymers.

    Science.gov (United States)

    Wen, Tao; Wang, Hsiao-Fang; Li, Ming-Chia; Ho, Rong-Ming

    2017-04-18

    The significance of chirality transfer is not only involved in biological systems, such as the origin of homochiral structures in life but also in man-made chemicals and materials. How the chiral bias transfers from molecular level (molecular chirality) to helical chain (conformational chirality) and then to helical superstructure or phase (hierarchical chirality) from self-assembly is vital for the chemical and biological processes in nature, such as communication, replication, and enzyme catalysis. In this Account, we summarize the methodologies for the examination of homochiral evolution at different length scales based on our recent studies with respect to the self-assembly of chiral polymers and chiral block copolymers (BCPs*). A helical (H*) phase to distinguish its P622 symmetry from that of normal hexagonally packed cylinder phase was discovered in the self-assembly of BCPs* due to the chirality effect on BCP self-assembly. Enantiomeric polylactide-containing BCPs*, polystyrene-b-poly(l-lactide) (PS-PLLA) and polystyrene-b-poly(d-lactide) (PS-PDLA), were synthesized for the examination of homochiral evolution. The optical activity (molecular chirality) of constituted chiral repeating unit in the chiral polylactide is detected by electronic circular dichroism (ECD) whereas the conformational chirality of helical polylactide chain can be explicitly determined by vibrational circular dichroism (VCD). The H* phases of the self-assembled polylactide-containing BCPs* can be directly visualized by 3D transmission electron microscopy (3D TEM) technique at which the handedness (hierarchical chirality) of the helical nanostructure is thus determined. The results from the ECD, VCD, and 3D TEM for the investigated chirality at different length scales suggest the homochiral evolution in the self-assembly of the BCPs*. For chiral polylactides, twisted lamellae in crystalline banded spherulite can be formed by dense packing scheme and effective interactions upon helical

  2. Asymmetric Michael Addition Mediated by Chiral Ionic Liquids

    Science.gov (United States)

    Suzuki, Yumiko

    2018-01-01

    Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines. PMID:29861702

  3. Chiroptical studies on supramolecular chirality of molecular aggregates.

    Science.gov (United States)

    Sato, Hisako; Yajima, Tomoko; Yamagishi, Akihiko

    2015-10-01

    The attempts of applying chiroptical spectroscopy to supramolecular chirality are reviewed with a focus on vibrational circular dichroism (VCD). Examples were taken from gels, solids, and monolayers formed by low-molecular mass weight chiral gelators. Particular attention was paid to a group of gelators with perfluoroalkyl chains. The effects of the helical conformation of the perfluoroalkyl chains on the formation of chiral architectures are reported. It is described how the conformation of a chiral gelator was determined by comparing the experimental and theoretical VCD spectra together with a model proposed for the molecular aggregation in fibrils. The results demonstrate the potential utility of the chiroptical method in analyzing organized chiral aggregates. © 2015 Wiley Periodicals, Inc.

  4. Solid-phase receptor-based assay for the detection of cyclic imines by chemiluminescence, fluorescence, or colorimetry.

    Science.gov (United States)

    Rodríguez, Laura P; Vilariño, Natalia; Molgó, Jordi; Aráoz, Rómulo; Antelo, Alvaro; Vieytes, Mercedes R; Botana, Luis M

    2011-08-01

    The spirolides and gymnodimines are marine phycotoxins included in the group of cyclic imines. The toxicity of these compounds to humans is still unknown, although their toxicity by intraperitoneal injection in rodents is very high. A receptor-based method was developed using the competition of the 13-desmethyl spirolide C with biotin-labeled α-bungarotoxin for binding to nicotinic acetylcholine receptors and the immobilization of the α-bungarotoxin-receptor complex on streptavidin-coated surfaces. The quantification of the immobilized receptor can be achieved using a specific antibody. Finally, after the addition of a secondary antibody labeled with horseradish peroxidase, three alternative substrates of this enzyme generate a chemiluminescent, fluorescent, or colorimetric signal. The assay performs well in shellfish extracts and the detection range is 5-150 nM of 13-desmethyl spirolide C in shellfish extracts, which is at least 5 times more sensitive than the existing fluorescence polarization assay. This assay can also detect gymnodimine, although with 10 times lower sensitivity than the spirolide. The detection of cyclic imines with microplate assays would be useful for screening purposes in order to reduce the number of samples to be processed by bioassays or analytical methods.

  5. Chiral dynamics and peripheral transverse densities

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-01

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

  6. Intrinsic Chirality Origination in Carbon Nanotubes.

    Science.gov (United States)

    Pierce, Neal; Chen, Gugang; P Rajukumar, Lakshmy; Chou, Nam Hawn; Koh, Ai Leen; Sinclair, Robert; Maruyama, Shigeo; Terrones, Mauricio; Harutyunyan, Avetik R

    2017-10-24

    Elucidating the origin of carbon nanotube chirality is key for realizing their untapped potential. Currently, prevalent theories suggest that catalyst structure originates chirality via an epitaxial relationship. Here we studied chirality abundances of carbon nanotubes grown on floating liquid Ga droplets, which excludes the influence of catalyst features, and compared them with abundances grown on solid Ru nanoparticles. Results of growth on liquid droplets bolsters the intrinsic preference of carbon nuclei toward certain chiralities. Specifically, the abundance of the (11,1)/χ = 4.31° tube can reach up to 95% relative to (9,4)/χ = 17.48°, although they have exactly the same diameter, (9.156 Å). However, the comparative abundances for the pair, (19,3)/χ = 7.2° and (17,6)/χ = 14.5°, with bigger diameter, (16.405 Å), fluctuate depending on synthesis temperature. The abundances of the same pairs of tubes grown on floating solid polyhedral Ru nanoparticles show completely different trends. Analysis of abundances in relation to nucleation probability, represented by a product of the Zeldovich factor and the deviation interval of a growing nuclei from equilibrium critical size, explain the findings. We suggest that the chirality in the nanotube in general is a result of interplay between intrinsic preference of carbon cluster and induction by catalyst structure. This finding can help to build the comprehensive theory of nanotube growth and offers a prospect for chirality-preferential synthesis of carbon nanotubes by the exploitation of liquid catalyst droplets.

  7. Chiral filtration-induced spin/valley polarization in silicene line defects

    Science.gov (United States)

    Ren, Chongdan; Zhou, Benhu; Sun, Minglei; Wang, Sake; Li, Yunfang; Tian, Hongyu; Lu, Weitao

    2018-06-01

    The spin/valley polarization in silicene with extended line defects is investigated according to the chiral filtration mechanism. It is shown that the inner-built quantum Hall pseudo-edge states with identical chirality can serve as a chiral filter with a weak magnetic field and that the transmission process is restrained/strengthened for chiral states with reversed/identical chirality. With two parallel line defects, which act as natural chiral filtration, the filter effect is greatly enhanced, and 100% spin/valley polarization can be achieved.

  8. Reactions of ethyl diazoacetate catalyzed by methylrhenium trioxide

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Z.; Espenson, H. [Iowa State Univ., Ames, IA (United States)

    1995-11-03

    Methylrhenium trioxide (CH{sub 3}ReO{sub 3} or MTO) has found wise use in catalysis, including the epoxidation and metathesis of olefins, aldehyde olefination, and oxygen transfer. Extensive reports have now appeared in the area of MTO-catalyzed substrate oxidations with hydrogen peroxide. Certain catalytic applications of MTO for organic reactions that do not utilize peroxide have now been realized. In particular, a catalytic amount of MTO with ethyl diazoacetate (EDA) will convert aromatic imines to aziridines and convert aldehydes and ketones to epoxides. The aziridine preparation proceeds in high yields under anaerobic conditions more conveniently than with existing methods. Compounds with a three-membered heterocyclic ring can be obtained with the EDA/MTO catalytic system. Aromatic imines undergo cycloaddition reactions to give aziridines under mild conditions.

  9. Physics of chiral symmetry breaking

    International Nuclear Information System (INIS)

    Shuryak, E.V.

    1991-01-01

    This subsection of the 'Modeling QCD' Workshop has included five talks. E. Shuryak spoke on 'Recent Progress in Understanding Chiral Symmetry Breaking'; below it is split into two parts: (i) a mini-review of the field and (ii) a brief presentation of the status of the theory of interacting instantons. The next sections correspond to the following talks: (iii) K. Goeke et al., 'Chiral Restoration and Medium Corrections to Nucleon in the NJL Model'; (iv) M. Takizawa and K. Kubodera, 'Study of Meson Properties and Quark Condensates in the NJL Model with Instanton Effects'; (v) G. Klein and A. G. Williams, 'Dynamical Chiral Symmetry Breaking in Dual QCD'; and (vi) R. D. Ball, 'Skyrmions and Baryons.' (orig.)

  10. Cell chirality: emergence of asymmetry from cell culture.

    Science.gov (United States)

    Wan, Leo Q; Chin, Amanda S; Worley, Kathryn E; Ray, Poulomi

    2016-12-19

    Increasing evidence suggests that intrinsic cell chirality significantly contributes to the left-right (LR) asymmetry in embryonic development, which is a well-conserved characteristic of living organisms. With animal embryos, several theories have been established, but there are still controversies regarding mechanisms associated with embryonic LR symmetry breaking and the formation of asymmetric internal organs. Recently, in vitro systems have been developed to determine cell chirality and to recapitulate multicellular chiral morphogenesis on a chip. These studies demonstrate that chirality is indeed a universal property of the cell that can be observed with well-controlled experiments such as micropatterning. In this paper, we discuss the possible benefits of these in vitro systems to research in LR asymmetry, categorize available platforms for single-cell chirality and multicellular chiral morphogenesis, and review mathematical models used for in vitro cell chirality and its applications in in vivo embryonic development. These recent developments enable the interrogation of the intracellular machinery in LR axis establishment and accelerate research in birth defects in laterality.This article is part of the themed issue 'Provocative questions in left-right asymmetry'. © 2016 The Author(s).

  11. Compositional analysis of nitrile terminated poly(propylene imine) dendrimers by high-performance liquid chromatography combined with electrospray mass spectrometry

    NARCIS (Netherlands)

    van der Wal, S; Mengerink, Y; Brackman, JC; de Brabander, EMM; Jeronimus-Stratingh, CM; Bruins, AP

    1998-01-01

    Separation methods for nitrile terminated poly(propylene imine) dendrimers were developed to monitor and optimize their large scale production. Detailed analyses of defects within a dendrimer generation were performed by HPLC at alkaline pH (sodium hydroxide) on a polymer-based column or at neutral

  12. Nanomechanical properties of hydroxyapatite (HAP) with DAB dendrimers (poly-propylene imine) coatings onto titanium surfaces

    International Nuclear Information System (INIS)

    Charitidis, Costas A.; Skarmoutsou, Amalia; Tsetsekou, Athena; Brasinika, Despina; Tsiourvas, Dimitris

    2013-01-01

    Highlights: ► The synthesis of hydroxyapatite (HAP) nanoparticles in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB). ► The nanomechanical properties of different HAP-DAB coatings onto titanium surfaces. ► Wear resistance and adhesion properties of the synthesized coatings quantified by nanoindentation data analysis. -- Abstract: Coatings of hydroxyapatite (HAP) nanorods onto titanium surfaces were synthesized with the aim to improve coatings’ mechanical properties and adhesion to the substrate. The coatings are consisting of HAP nanorods synthesized in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB) bearing 32 amine end groups employing varying calcium: dendrimer ratios and varying hydrothermal treatments. The quality, surface morphology and structure of the coatings were characterized with X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and energy dispersive microanalysis. Wear resistance and adhesion properties of the coatings onto titanium substrates were studied through nanoindentation analysis. The experimental conditions, namely the calcium: dendrimer molar ratio and the hydrothermal treatment temperature were carefully selected; thus, it was possible to produce coatings of high hardness and elastic modulus values (ranging between 1–4.5 GPa and 40–150 GPa, respectively) and/or high wear resistance and plastic deformation values

  13. Nanomechanical properties of hydroxyapatite (HAP) with DAB dendrimers (poly-propylene imine) coatings onto titanium surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Charitidis, Costas A., E-mail: charitidis@chemeng.ntua.gr [School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou, Zografou, 15780 Athens (Greece); Skarmoutsou, Amalia [School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou, Zografou, 15780 Athens (Greece); Tsetsekou, Athena; Brasinika, Despina [School of Mining Engineering and Metallurgy, National Technical University of Athens, Iroon Polytechniou, Zografou, 15780 Athens (Greece); Tsiourvas, Dimitris [National Centre for Scientific Research “Demokritos”, Institute of Physical Chemistry, Agia Paraskevi, 15310 Athens (Greece)

    2013-04-20

    Highlights: ► The synthesis of hydroxyapatite (HAP) nanoparticles in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB). ► The nanomechanical properties of different HAP-DAB coatings onto titanium surfaces. ► Wear resistance and adhesion properties of the synthesized coatings quantified by nanoindentation data analysis. -- Abstract: Coatings of hydroxyapatite (HAP) nanorods onto titanium surfaces were synthesized with the aim to improve coatings’ mechanical properties and adhesion to the substrate. The coatings are consisting of HAP nanorods synthesized in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB) bearing 32 amine end groups employing varying calcium: dendrimer ratios and varying hydrothermal treatments. The quality, surface morphology and structure of the coatings were characterized with X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and energy dispersive microanalysis. Wear resistance and adhesion properties of the coatings onto titanium substrates were studied through nanoindentation analysis. The experimental conditions, namely the calcium: dendrimer molar ratio and the hydrothermal treatment temperature were carefully selected; thus, it was possible to produce coatings of high hardness and elastic modulus values (ranging between 1–4.5 GPa and 40–150 GPa, respectively) and/or high wear resistance and plastic deformation values.

  14. Massive states in chiral perturbation theory

    Energy Technology Data Exchange (ETDEWEB)

    Mallik, S [Saha Inst. of Nuclear Physics, Calcutta (India)

    1995-08-01

    It is shown that the chiral nonanalytic terms generated by {Delta}{sub 33} resonance in the nucleon self-energy is reproduced in chiral perturbation theory by perturbing appropriate local operators contained in the pion-nucleon effective Lagrangian itself. (orig.)

  15. Enantiomeric Profiling of Chiral Pharmacologically Active Compounds in the Environment with the Usage of Chiral Liquid Chromatography 
Coupled with Tandem Mass Spectrometry

    Science.gov (United States)

    Camacho-Muñoz, Dolores; Petrie, Bruce; Castrignanò, Erika; Kasprzyk-Hordern, Barbara

    2016-01-01

    The issue of drug chirality is attracting increasing attention among the scientific community. The phenomenon of chirality has been overlooked in environmental research (environmental occurrence, fate and toxicity) despite the great impact that chiral pharmacologically active compounds (cPACs) can provoke on ecosystems. The aim of this paper is to introduce the topic of chirality and its implications in environmental contamination. Special attention has been paid to the most recent advances in chiral analysis based on liquid chromatography coupled with mass spectrometry and the most popular protein based chiral stationary phases. Several groups of cPACs of environmental relevance, such as illicit drugs, human and veterinary medicines were discussed. The increase in the number of papers published in the area of chiral environmental analysis indicates that researchers are actively pursuing new opportunities to provide better understanding of environmental impacts resulting from the enantiomerism of cPACs. PMID:27713682

  16. Lateral shifting in one dimensional chiral photonic crystal

    Energy Technology Data Exchange (ETDEWEB)

    You Yuan, E-mail: yctcyouyuan@163.com [School of Physics and Electronics, Yancheng Teachers University, Yancheng, 224002 Jiangsu (China); Chen Changyuan [School of Physics and Electronics, Yancheng Teachers University, Yancheng, 224002 Jiangsu (China)

    2012-07-01

    We report the lateral shifts of the transmitted waves in a one dimensional chiral photonic crystal by using the stationary-phase approach. It is revealed that two kinds of lateral shifts are observed due to the existence of cross coupling in chiral materials, which is different from what has been observed in previous non-chiral photonic crystals. Unlike the chiral slab, the positions of lateral shift peaks are closely related to the band edges of band gap characteristics of periodic structure and lateral shifts can be positive as well as negative. Besides, the lateral shifts show a strong dependence on the chiral factor, which varies the lateral shift peaks in both magnitudes and positions. These features are desirable for future device applications.

  17. Lateral shifting in one dimensional chiral photonic crystal

    International Nuclear Information System (INIS)

    You Yuan; Chen Changyuan

    2012-01-01

    We report the lateral shifts of the transmitted waves in a one dimensional chiral photonic crystal by using the stationary-phase approach. It is revealed that two kinds of lateral shifts are observed due to the existence of cross coupling in chiral materials, which is different from what has been observed in previous non-chiral photonic crystals. Unlike the chiral slab, the positions of lateral shift peaks are closely related to the band edges of band gap characteristics of periodic structure and lateral shifts can be positive as well as negative. Besides, the lateral shifts show a strong dependence on the chiral factor, which varies the lateral shift peaks in both magnitudes and positions. These features are desirable for future device applications.

  18. Chiral Plasmonic Nanostructures Fabricated by Circularly Polarized Light.

    Science.gov (United States)

    Saito, Koichiro; Tatsuma, Tetsu

    2018-05-09

    The chirality of materials results in a wide variety of advanced technologies including image display, data storage, light management including negative refraction, and enantioselective catalysis and sensing. Here, we introduce chirality to plasmonic nanostructures by using circularly polarized light as the sole chiral source for the first time. Gold nanocuboids as precursors on a semiconductor were irradiated with circularly polarized light to localize electric fields at specific corners of the cuboids depending on the handedness of light and deposited dielectric moieties as electron oscillation boosters by the localized electric field. Thus, plasmonic nanostructures with high chirality were developed. The present bottom-up method would allow the large-scale and cost-effective fabrication of chiral materials and further applications to functional materials and devices.

  19. Spectroscopic Diagnosis of Excited-State Aromaticity: Capturing Electronic Structures and Conformations upon Aromaticity Reversal.

    Science.gov (United States)

    Oh, Juwon; Sung, Young Mo; Hong, Yongseok; Kim, Dongho

    2018-03-06

    Aromaticity, the special energetic stability derived from cyclic [4 n + 2]π-conjugated electronic structures, has been the topic of intense interest in chemistry because it plays a critical role in rationalizing molecular stability, reactivity, and physical/chemical properties. Recently, the pioneering work by Colin Baird on aromaticity reversal, postulating that aromatic (antiaromatic) character in the ground state reverses to antiaromatic (aromatic) character in the lowest excited triplet state, has attracted much scientific attention. The completely reversed aromaticity in the excited state provides direct insight into understanding the photophysical/chemical properties of photoactive materials. In turn, the application of aromatic molecules to photoactive materials has led to numerous studies revealing this aromaticity reversal. However, most studies of excited-state aromaticity have been based on the theoretical point of view. The experimental evaluation of aromaticity in the excited state is still challenging and strenuous because the assessment of (anti)aromaticity with conventional magnetic, energetic, and geometric indices is difficult in the excited state, which practically restricts the extension and application of the concept of excited-state aromaticity. Time-resolved optical spectroscopies can provide a new and alternative avenue to evaluate excited-state aromaticity experimentally while observing changes in the molecular features in the excited states. Time-resolved optical spectroscopies take advantage of ultrafast laser pulses to achieve high time resolution, making them suitable for monitoring ultrafast changes in the excited states of molecular systems. This can provide valuable information for understanding the aromaticity reversal. This Account presents recent breakthroughs in the experimental assessment of excited-state aromaticity and the verification of aromaticity reversal with time-resolved optical spectroscopic measurements. To

  20. A stereoselective, catalytic strategy for the in-flow synthesis of advanced precursors of rasagiline and tamsulosin.

    Science.gov (United States)

    Brenna, Davide; Pirola, Margherita; Raimondi, Laura; Burke, Anthony J; Benaglia, Maurizio

    2017-12-01

    The diastereoselective, trichlorosilane-mediate reduction of imines, bearing different and removable chiral auxiliaries, in combination either with achiral bases or catalytic amounts of chiral Lewis bases, was investigated to afford immediate precursors of chiral APIs (Active Pharmaceutical Ingredients). The carbon-nitrogen double bond reduction was successfully performed in batch and in flow mode, in high yields and almost complete stereocontrol. By this metal-free approach, the formal synthesis of rasagiline and tamsulosin was successfully accomplished in micro(meso) flow reactors, under continuous flow conditions. The results of these explorative studies represent a new, important step towards the development of automated processes for the preparation of enantiopure biologically active compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Spin-Selective Transmission and Devisable Chirality in Two-Layer Metasurfaces.

    Science.gov (United States)

    Li, Zhancheng; Liu, Wenwei; Cheng, Hua; Chen, Shuqi; Tian, Jianguo

    2017-08-15

    Chirality is a nearly ubiquitous natural phenomenon. Its minute presence in most naturally occurring materials makes it incredibly difficult to detect. Recent advances in metasurfaces indicate that they exhibit devisable chirality in novel forms; this finding offers an effective opening for studying chirality and its features in such nanostructures. These metasurfaces display vast possibilities for highly sensitive chirality discrimination in biological and chemical systems. Here, we show that two-layer metasurfaces based on twisted nanorods can generate giant spin-selective transmission and support engineered chirality in the near-infrared region. Two designed metasurfaces with opposite spin-selective transmission are proposed for treatment as enantiomers and can be used widely for spin selection and enhanced chiral sensing. Specifically, we demonstrate that the chirality in these proposed metasurfaces can be adjusted effectively by simply changing the orientation angle between the twisted nanorods. Our results offer simple and straightforward rules for chirality engineering in metasurfaces and suggest intriguing possibilities for the applications of such metasurfaces in spin optics and chiral sensing.

  2. Non-perturbative chiral corrections for lattice QCD

    International Nuclear Information System (INIS)

    Thomas, A.W.; Leinweber, D.B.; Lu, D.H.

    2002-01-01

    We explore the chiral aspects of extrapolation of observables calculated within lattice QCD, using the nucleon magnetic moments as an example. Our analysis shows that the biggest effects of chiral dynamics occur for quark masses corresponding to a pion mass below 600 MeV. In this limited range chiral perturbation theory is not rapidly convergent, but we can develop some understanding of the behaviour through chiral quark models. This model dependent analysis leads us to a simple Pade approximant which builds in both the limits m π → 0 and m π → ∞ correctly and permits a consistent, model independent extrapolation to the physical pion mass which should be extremely reliable. (author)

  3. Modification of the twist angle in chiral nematic polymer films by photoisomerization of the chiral dopant

    NARCIS (Netherlands)

    Witte, van de P.; Neuteboom, E.E.; Brehmer, M.; Lub, Johan

    1999-01-01

    A method for the production of polarization sensitive recordings in liquid crystalline polymers is presented. The system is based on local modification of the twist angle of chiral nematic polymer films. The twist angle of the polymer film is varied by modifying the chemical structure of the chiral

  4. DEVELOPMENT AND REGISTRATION OF CHIRAL DRUGS

    NARCIS (Netherlands)

    WITTE, DT; ENSING, K; FRANKE, JP; DEZEEUW, RA

    1993-01-01

    In this review we describe the impact of chirality on drug development and registration in the United States, Japan and the European Community. Enantiomers may have differences in their pharmacological profiles, and, therefore, chiral drugs ask for special analytical and pharmacological attention

  5. LINEARLY POLARIZED PROBES OF SURFACE CHIRALITY

    NARCIS (Netherlands)

    VERBIEST, T; KAURANEN, M; MAKI, JJ; TEERENSTRA, MN; SCHOUTEN, AJ; NOLTE, RJM; PERSOONS, A

    1995-01-01

    We present a new nonlinear optical technique to study surface chirality. We demonstrate experimentally that the efficiency of second-harmonic generation from isotropic chiral surfaces is different for excitation with fundamental light that is +45 degrees and -45 degrees linearly polarized with

  6. Chiral doublet bands in odd-A nuclei 103,105Rh

    International Nuclear Information System (INIS)

    Qi Bin; Wang Shouyu; Zhang Shuangquan; Meng Jie

    2010-01-01

    Spontaneous chiral symmetry breaking is a phenomenon of general interest in chemistry, biology and particle physics. Since the pioneering work of nuclear chirality in 1997 [1] , much effort has been devoted to further explore this interesting phenomenon. Following the observation of chiral doublet bands in N = 75 isotones [2] more candidates have been reported over more than 20 nuclei experimentally in A∼100, 130 and 190 mass regions including odd-odd, odd-A and even-even nuclei. However, the identification and the intrinsic mechanism of candidate chiral doublet bands are still under debate. Although various versions of particle rotor model (PRM) and titled axis cranking model (TAC) had been applied to study chiral bands, the essential starting point for understanding their properties is based on the ideal picture, i.e. one particle and one hole coupled with a γ = 30 rigid triaxial rotor. On the other hand, from the investigation of semiclassical TAC based on the mean field, it is shown that the chiral doublet bands in the real nuclei are not always consistent with the static chirality, but mixed with the character of dynamic chirality. Thus it is necessary to construct a fully quantal model for the description of chiral doublet bands in the real nuclei, which is aimed to understand the properties of chiral doublet bands in real nuclei, and to present clearly the picture and character of chiral motion [3] . Recently, we have developed the multi-particle multi-hole coupled with the triaxial rotor model, which is able to describe the nuclear rotation related to many valence nucleons. Adopting this model, chirality in odd-A nuclei 103,105 Rh with πg 9/2 -1 ⊗νh 11/2 2 configuration and in odd-A nucleus 135 Nd with πh 11/2 2 ⊗νh 11/2 1 configuration [4] are studied in a fully quantal approach. For the chiral doublet bands, the observed energies and the B(M1) and B(E2) values are reproduced very well. Root mean square values of the angular momentum components

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

    Science.gov (United States)

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

    2016-11-14

    It is a challenging issue to achieve propeller chirality for triarylboranes owing to the low transition barrier between the P and M forms of the boron center. Herein, we report a new strategy to achieve propeller chirality of triarylboranes. It was found that the chirality relay from axially chiral 1,1'-binaphthyl to propeller chirality of the trivalent boron center can be realized when a Me 2 N and a Mes 2 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 Me 2 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 Mes 2 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. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. The three dimensional dual of 4D chirality

    International Nuclear Information System (INIS)

    Porrati, M.; Girardello, L.

    2009-01-01

    Chiral gauge theories can be defined in four-dimensional Anti de Sitter space, but AdS boundary conditions explicitly break the chiral symmetry in a specific, well defined manner, which in turns results in an anomalous Ward identity. When the 4D theory admits a dual description in terms of a 3D CFT, the 3D dual of the broken chiral symmetry is a certain double-trace deformation of the CFT, which produces the same anomalous chiral Ward identities that obtains in the 4D bulk theory.

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

    Science.gov (United States)

    Inaki, Mikiko; Liu, Jingyang; Matsuno, Kenji

    2016-12-19

    An item is chiral if it cannot be superimposed on its mirror image. Most biological molecules are chiral. The homochirality of amino acids ensures that proteins are chiral, which is essential for their functions. Chirality also occurs at the whole-cell level, which was first studied mostly in ciliates, single-celled protozoans. Ciliates show chirality in their cortical structures, which is not determined by genetics, but by 'cortical inheritance'. These studies suggested that molecular chirality directs whole-cell chirality. Intriguingly, chirality in cellular structures and functions is also found in metazoans. In Drosophila, intrinsic cell chirality is observed in various left-right (LR) asymmetric tissues, and appears to be responsible for their LR asymmetric morphogenesis. In other invertebrates, such as snails and Caenorhabditis elegans, blastomere chirality is responsible for subsequent LR asymmetric development. Various cultured cells of vertebrates also show intrinsic chirality in their cellular behaviours and intracellular structural dynamics. Thus, cell chirality may be a general property of eukaryotic cells. In Drosophila, cell chirality drives the LR asymmetric development of individual organs, without establishing the LR axis of the whole embryo. Considering that organ-intrinsic LR asymmetry is also reported in vertebrates, this mechanism may contribute to LR asymmetric development across phyla.This article is part of the themed issue 'Provocative questions in left-right asymmetry'. © 2016 The Authors.

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

    Science.gov (United States)

    Inaki, Mikiko; Liu, Jingyang

    2016-01-01

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

  11. Asymmetric chiral colour

    International Nuclear Information System (INIS)

    Cuypers, F.

    1990-01-01

    Chiral colour is considered in a general framework where the coupling constants associated with each SU(3) component are allowed to be different. To reproduce QCD at low energy, gluons and axigluons cannot then be maximally mixed. Present data form e + e - colliders contrains the axigluon mass to values between 50 GeV and 375 GeV whilst the mixing angle is bounded by 13deg and 45deg. The lower limit of the axigluon mass is a definite bound at 90% C.L., whereas the upper limit only applies if chiral colour is to explain the anomalously high rates of hadron production at TRISTAN. (orig.)

  12. Chiral-glass transition in a diluted dipolar-interaction Heisenberg system

    International Nuclear Information System (INIS)

    Zhang Kaicheng; Liu Guibin; Zhu Yan

    2011-01-01

    Recently, numerical simulations reveal that a spin-glass transition can occur in the three-dimensional diluted dipolar system. By defining the chirality of triple spins in a diluted dipolar Heisenberg spin glass, we study the chiral ordering in the system using parallel tempering algorithm and heat bath method. The finite-size scaling analysis reveals that the system undergoes a chiral-glass transition at finite temperature. - Highlights: → We define the chirality in a diluted dipolar Heisenberg system. → The system undergoes a chiral-glass transition at finite temperature. → We extract the critical exponents of the chiral-glass transition.

  13. Chiral interaction and biomolecular evolution

    International Nuclear Information System (INIS)

    Gilat, G.

    1992-01-01

    Recent developments in the concept of chiral interaction open now new options and dynamical possibilities for biomolecules which have so far been overlooked. A few of these possibilities are mentioned, such as the control mechanism of enzymatic activity and the role played by non-ergodicity in evolutionary processes. It is shown that chiral interaction, being a surface phenomenon, does not obey Barron's symmetry constraints, which are suitable for force fields present in bulk interactions. In particular, the situation at the ocean-air surface in the prebiotic era is described, as well as the possible role played by chiral interaction in conjunction with the terrestrial magnetic field normal to the ocean surface, which could have lead to a process of deracernization at the ocean-air interface. (author)

  14. Fusion rules of chiral algebras

    International Nuclear Information System (INIS)

    Gaberdiel, M.

    1994-01-01

    Recently we showed that for the case of the WZW and the minimal models fusion can be understood as a certain ring-like tensor product of the symmetry algebra. In this paper we generalize this analysis to arbitrary chiral algebras. We define the tensor product of conformal field theory in the general case and prove that it is associative and symmetric up to equivalence. We also determine explicitly the action of the chiral algebra on this tensor product. In the second part of the paper we demonstrate that this framework provides a powerful tool for calculating restrictions for the fusion rules of chiral algebras. We exhibit this for the case of the W 3 algebra and the N=1 and N=2 NS superconformal algebras. (orig.)

  15. Probing chirality with a femtosecond reaction microscope

    Directory of Open Access Journals (Sweden)

    Janssen M. H. M.

    2013-03-01

    Full Text Available Detection of molecular chirality with high sensitivity and selectivity is important for many analytical and practical applications. Photoionization has emerged as a very sensitive probe of chirality in molecules. We show here that a table top setup with a femtosecond laser and a single imaging detector for both photoelectrons and photoions enables detection of chirality up to 3 orders of magnitude better than the existing conventional absorption based techniques.

  16. The role of resonances in chiral perturbation theory

    International Nuclear Information System (INIS)

    Ecker, G.; Rafael, E. de

    1988-09-01

    The strong interactions of low-lying meson resonances (spin ≤ 1) with the octet of pseudoscalar mesons (π,Κ,η) are considered to lowest order in the derivative expansion of chiral SU(3). The resonance contributions to the coupling constants of the O(p 4 ) effective chiral lagrangian involving pseudoscalar fields only are determined. These low-energy coupling constants are found to be dominated by the resonance contributions. Although we do not treat the vector and axial-vector mesons as gauge bosons of local chiral symmetry, vector meson dominance emerges as a prominent result of our analysis. As a further application of chiral resonance couplings, we calculate the electromagnetic pion mass difference to lowest order in chiral perturbation theory with explicit resonance fields. 29 refs., 2 figs., 5 tabs. (Author)

  17. Can the chirality of the ISM be measured

    Science.gov (United States)

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

    1990-01-01

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

  18. Can the chirality of the ISM be measured

    International Nuclear Information System (INIS)

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

    1990-01-01

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

  19. Total synthesis of fluoxetine and duloxetine through an in situ imine formation/borylation/transimination and reduction approach.

    Science.gov (United States)

    Calow, Adam D J; Fernández, Elena; Whiting, Andrew

    2014-08-28

    We report efficient, catalytic, asymmetric total syntheses of both (R)-fluoxetine and (S)-duloxetine from α,β-unsaturated aldehydes conducting five sequential one-pot steps (imine formation/copper mediated β-borylation/transimination/reduction/oxidation) followed by the specific ether group formation which deliver the desired products (R)-fluoxetine in 45% yield (96% ee) and (S)-duloxetine in 47% yield (94% ee).

  20. Intrinsic Chirality and Prochirality at Air/R-(+)- and S-(-)-Limonene Interfaces: Spectral Signatures with Interference Chiral Sum-Frequency Generation Vibrational Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Li; Zhang, Yun; Wei, Zhehao; Wang, Hongfei

    2014-06-04

    We report in this work detailed measurements on the chiral and achiral sum-frequency vibrational spectra in the C-H stretching vibration region (2800-3050cm-1) of the air/liquid interfaces of R-limonene and S-limonene, using the recently developed high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The achiral SFG spectra of R-limonene and S-limonene, as well as the equal amount (50/50) racemic mixture show that the enantiomers are with the same interfacial orientations. The interference chiral SFG spectra of the limonene enantiomers exhibit spectral signature from chiral response of the Cα-H stretching mode, and spectral signature from prochiral response of the CH2 asymmetric stretching mode, respectively. The chiral spectral feature of the Cα-H stretching mode changes sign from R-limonene to S-limonene, and disappears for the 50/50 racemic mixture. While the prochiral spectral feature of the CH2 asymmetric stretching mode is the same for R-limonene and S-limonene, and also surprisingly remains the same for the 50/50 racemic mixture. These results provided detail information in understanding the structure and chirality of molecular interfaces, and demonstrated the sensitivity and potential of SFG-VS as unique spectroscopic tool for chirality characterization and chiral recognition at the molecular interface.

  1. Chiral metamaterials: from optical activity and negative refractive index to asymmetric transmission

    International Nuclear Information System (INIS)

    Li, Zhaofeng; Mutlu, Mehmet; Ozbay, Ekmel

    2013-01-01

    We summarize the progress in the development and application of chiral metamaterials. After a brief review of the salient features of chiral metamaterials, such as giant optical activity, circular dichroism, and negative refractive index, the common method for the retrieval of effective parameters for chiral metamaterials is surveyed. Then, we introduce some typical chiral structures, e.g., chiral metamaterial consisting of split ring resonators, complementary chiral metamaterial, and composite chiral metamaterial, on the basis of the studies of the authors’ group. The coupling effect during the construction of bulk chiral metamaterials is mentioned and discussed. We introduce the application of bianisotropic chiral structures in the field of asymmetric transmission. Finally, we mention a few directions for future research on chiral metamaterials. (review article)

  2. Access to Optically Pure β-Hydroxy Esters via Non-Enzymatic Kinetic Resolution by a Planar-Chiral DMAP Catalyst

    Directory of Open Access Journals (Sweden)

    Alba E. Díazlvarez

    2014-09-01

    Full Text Available The development of new approaches to obtain optically pure β-hydroxy esters is an important area in synthetic organic chemistry since they are precursors of other high value compounds. Herein, the kinetic resolution of racemic β-hydroxy esters using a planar-chiral DMAP derivative catalyst is presented. Following this procedure, a range of aromatic β-hydroxy esters was obtained in excellent selectivities (up to s = 107 and high enantiomeric excess (up to 99% ee. Furthermore, the utility of the present method was demonstrated in the synthesis of (S-3-hydroxy-N-methyl-3-phenylpropanamide, a key intermediate for bioactive molecules such as fluoxetine, tomoxetine or nisoxetine, in its enantiomerically pure form.

  3. Quark matter in a chiral chromodielectric model

    International Nuclear Information System (INIS)

    Broniowski, W.; Kutschera, M.; Cibej, M.; Rosina, M.

    1989-03-01

    Zero and finite temperature quark matter is studied in a chiral chromodielectric model with quark, meson and chromodielectric degrees of freedom. Mean field approximation is used. Two cases are considered: two-flavor and three-flavor quark matter. It is found that at sufficiently low densities and temperatures the system is in a chirally broken phase, with quarks acquiring effective masses of the order of 100 MeV. At higher densities and temperatures a chiral phase transition occurs and the quarks become massless. A comparison to traditional nuclear physics suggests that the chirally broken phase with massive quark gas may be the ground state of matter at densities of the order of a few nuclear saturation densities. 24 refs., 5 figs. (author)

  4. Laminar and Turbulent Dynamos in Chiral Magnetohydrodynamics. II. Simulations

    Science.gov (United States)

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

    2018-05-01

    Using direct numerical simulations (DNS), we study laminar and turbulent dynamos in chiral magnetohydrodynamics with an extended set of equations that accounts for an additional contribution to the electric current due to the chiral magnetic effect (CME). This quantum phenomenon originates from an asymmetry between left- and right-handed relativistic fermions in the presence of a magnetic field and gives rise to a chiral dynamo. We show that the magnetic field evolution proceeds in three stages: (1) a small-scale chiral dynamo instability, (2) production of chiral magnetically driven turbulence and excitation of a large-scale dynamo instability due to a new chiral effect (α μ effect), and (3) saturation of magnetic helicity and magnetic field growth controlled by a conservation law for the total chirality. The α μ effect becomes dominant at large fluid and magnetic Reynolds numbers and is not related to kinetic helicity. The growth rate of the large-scale magnetic field and its characteristic scale measured in the numerical simulations agree well with theoretical predictions based on mean-field theory. The previously discussed two-stage chiral magnetic scenario did not include stage (2), during which the characteristic scale of magnetic field variations can increase by many orders of magnitude. Based on the findings from numerical simulations, the relevance of the CME and the chiral effects revealed in the relativistic plasma of the early universe and of proto-neutron stars are discussed.

  5. Chiral Recognition by Fluorescence: One Measurement for Two Parameters

    Directory of Open Access Journals (Sweden)

    Shanshan Yu

    2014-01-01

    Full Text Available This outlook describes two strategies to simultaneously determine the enantiomeric composition and concentration of a chiral substrate by a single fluorescent measurement. One strategy utilizes a pseudoenantiomeric sensor pair that is composed of a 1,1′-bi-2-naphthol-based amino alcohol and a partially hydrogenated 1,1′-bi-2-naphthol-based amino alcohol. These two molecules have the opposite chiral configuration with fluorescent enhancement at two different emitting wavelengths when treated with the enantiomers of mandelic acid. Using the sum and difference of the fluorescent intensity at the two wavelengths allows simultaneous determination of both concentration and enantiomeric composition of the chiral acid. The other strategy employs a 1,1′-bi-2-naphthol-based trifluoromethyl ketone that exhibits fluorescent enhancement at two emission wavelengths upon interaction with a chiral diamine. One emission responds mostly to the concentration of the chiral diamine and the ratio of the two emissions depends on the chiral configuration of the enantiomer but independent of the concentration, allowing both the concentration and enantiomeric composition of the chiral diamine to be simultaneously determined. These strategies would significantly simplify the practical application of the enantioselective fluorescent sensors in high-throughput chiral assay.

  6. From cosmic chirality to protein structure: Lord Kelvin's legacy.

    Science.gov (United States)

    Barron, Laurence D

    2012-11-01

    A selection of my work on chirality is sketched in two distinct parts of this lecture. Symmetry and Chirality explains how the discrete symmetries of parity P, time reversal T, and charge conjugation C may be used to characterize the properties of chiral systems. The concepts of true chirality (time-invariant enantiomorphism) and false chirality (time-noninvariant enantiomorphism) that emerge provide an extension of Lord Kelvin's original definition of chirality to situations where motion is an essential ingredient thereby clarifying, inter alia, the nature of physical influences able to induce absolute enantioselection. Consideration of symmetry violations reveals that strict enantiomers (exactly degenerate) are interconverted by the combined CP operation. Raman optical activity surveys work, from first observation to current applications, on a new chiroptical spectroscopy that measures vibrational optical activity via Raman scattering of circularly polarized light. Raman optical activity provides incisive information ranging from absolute configuration and complete solution structure of smaller chiral molecules and oligomers to protein and nucleic acid structure of intact viruses. Copyright © 2012 Wiley Periodicals, Inc., A Wiley Company.

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

    Science.gov (United States)

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

    2016-05-10

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

  8. The chirality operators for Heisenberg spin systems

    International Nuclear Information System (INIS)

    Subrahmanyam, V.

    1994-01-01

    The ground state of closed Heisenberg spin chains with an odd number of sites has a chiral degeneracy, in addition to a two-fold Kramers degeneracy. A non-zero chirality implies that the spins are not coplanar, and is a measure of handedness. The chirality operator, which can be treated as a spin-1/2 operator, is explicitly constructed in terms of the spin operators, and is given as commutator of permutation operators. (author). 3 refs

  9. A Review on Chiral Chromatography and its Application to the ...

    African Journals Online (AJOL)

    MoZarD

    amounts of material and is for measuring the relative proportions of ... the stationary phase must themselves be made chiral, giving differing ... electrophoretic medium that change it to chiral mobile phase (Eliel, et ... column containing a chiral stationary phase is also called a chiral ... densitometry, and a TLC method for the.

  10. Chiral thermodynamics of nuclear matter

    International Nuclear Information System (INIS)

    Fiorilla, Salvatore

    2012-01-01

    The equation of state of nuclear matter is calculated at finite temperature in the framework of in-medium chiral perturbation theory up to three-loop order. The dependence of its thermodynamic properties on the isospin-asymmetry is investigated. The chiral quark condensate is evaluated for symmetric nuclear matter. Its behaviour as a function of density and temperature sets important nuclear physics constraints for the QCD phase diagram.

  11. Chiral thermodynamics of nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Fiorilla, Salvatore

    2012-10-23

    The equation of state of nuclear matter is calculated at finite temperature in the framework of in-medium chiral perturbation theory up to three-loop order. The dependence of its thermodynamic properties on the isospin-asymmetry is investigated. The chiral quark condensate is evaluated for symmetric nuclear matter. Its behaviour as a function of density and temperature sets important nuclear physics constraints for the QCD phase diagram.

  12. Inexpensive chirality on the lattice

    International Nuclear Information System (INIS)

    Kamleh, W.; Williams, A.G.; Adams, D.

    2000-01-01

    Full text: Implementing lattice fermions that resemble as closely as possible continuum fermions is one of the main goals of the theoretical physics community. Aside from a lack of infinitely powerful computers, one of the main impediments to this is the Nielsen-Ninomiya No-Go theorem for chirality on the lattice. One of the consequences of this theorem is that exact chiral symmetry and a lack of fermion doublers cannot be simultaneously satisfied for fermions on the lattice. In the commonly used Wilson fermion formulation, chiral symmetry is explicitly sacrificed on the lattice to avoid fermion doubling. Recently, an alternative has come forward, namely, the Ginsparg-Wilson relation and one of its solutions, the Overlap fermion. The Ginsparg-Wilson relation is a statement of lattice-deformed chirality. The Overlap-Dirac operator is a member of the family of solutions of the Ginsparg-Wilson relation. In recent times, Overlap fermions have been of great interest to the community due to their excellent chiral properties. However, they are significantly more expensive to implement than Wilson fermions. This expense is primarily due to the fact that the Overlap implementation requires an evaluation of the sign function for the Wilson-Dirac operator. The sign function is approximated by a high order rational polynomial function, but this approximation is poor close to the origin. The less near-zero modes that the Wilson- Dirac operator possesses, the cheaper the Overlap operator will be to implement. A means of improving the eigenvalue properties of the Wilson-Dirac operator by the addition of a so-called 'Clover' term is put forward. Numerical results are given that demonstrate this improvement. The Nielsen-Ninomiya no-go theorem and chirality on the lattice are reviewed. The general form of solutions of the Ginsparg-Wilson relation are given, and the Overlap solution is discussed. Properties of the Overlap-Dirac operator are given, including locality and analytic

  13. Patterns of symmetry breaking in chiral QCD

    Science.gov (United States)

    Bolognesi, Stefano; Konishi, Kenichi; Shifman, Mikhail

    2018-05-01

    We consider S U (N ) Yang-Mills theory with massless chiral fermions in a complex representation of the gauge group. The main emphasis is on the so-called hybrid ψ χ η model. The possible patterns of realization of the continuous chiral flavor symmetry are discussed. We argue that the chiral symmetry is broken in conjunction with a dynamical Higgsing of the gauge group (complete or partial) by bifermion condensates. As a result a color-flavor locked symmetry is preserved. The 't Hooft anomaly matching proceeds via saturation of triangles by massless composite fermions or, in a mixed mode, i.e. also by the "weakly" coupled fermions associated with dynamical Abelianization, supplemented by a number of Nambu-Goldstone mesons. Gauge-singlet condensates are of the multifermion type and, though it cannot be excluded, the chiral symmetry realization via such gauge invariant condensates is more contrived (requires a number of four-fermion condensates simultaneously and, even so, problems remain) and less plausible. We conclude that in the model at hand, chiral flavor symmetry implies dynamical Higgsing by bifermion condensates.

  14. Chiral superfluidity of the quark-gluon plasma

    International Nuclear Information System (INIS)

    Kalaydzhyan, Tigran

    2012-08-01

    In this paper we argue that the strongly coupled quark-gluon plasma can be considered as a chiral superfluid. The ''normal'' component of the fluid is the thermalized matter in common sense, while the ''superfluid'' part consists of long wavelength (chiral) fermionic states moving independently. We use several nonperturbative techniques to demonstrate that. First, we analyze the fermionic spectrum in the deconfinement phase (T c c ) using lattice (overlap) fermions and observe a gap between near-zero modes and the bulk of the spectrum. Second, we use the bosonization procedure with a finite cut-off and obtain a dynamical axion-like field out of the chiral fermionic modes. Third, we use relativistic hydrodynamics for macroscopic description of the effective theory obtained after the bosonization. Finally, solving the hydrodynamic equations in gradient expansion, we find that in the presence of external electromagnetic fields the motion of the ''superfluid'' component gives rise to the chiral magnetic, chiral electric and dipole wave effects. Latter two effects are specific for a two-component fluid, which provides us with crucial experimental tests of the model.

  15. Chiral Drug Analysis in Forensic Chemistry: An Overview

    Directory of Open Access Journals (Sweden)

    Cláudia Ribeiro

    2018-01-01

    Full Text Available Many substances of forensic interest are chiral and available either as racemates or pure enantiomers. Application of chiral analysis in biological samples can be useful for the determination of legal or illicit drugs consumption or interpretation of unexpected toxicological effects. Chiral substances can also be found in environmental samples and revealed to be useful for determination of community drug usage (sewage epidemiology, identification of illicit drug manufacturing locations, illegal discharge of sewage and in environmental risk assessment. Thus, the purpose of this paper is to provide an overview of the application of chiral analysis in biological and environmental samples and their relevance in the forensic field. Most frequently analytical methods used to quantify the enantiomers are liquid and gas chromatography using both indirect, with enantiomerically pure derivatizing reagents, and direct methods recurring to chiral stationary phases.

  16. Chiral recognition with enantioselective ion exchangers based on carbamoylated cinchonan derivatives as chiral selectors for the HPLC enantioseparation

    International Nuclear Information System (INIS)

    Laemmerhofer, M.

    1996-11-01

    The high-performance liquid chromatographic (HPLC) separation of enantiomers is preferentially performed using chiral stationary phases (CSPs). If the chiral auxiliary (selector, SO) contains charged or ionizable groups one gets ion exchanger type CSPs which may bind and retain oppositely charged analytes (selectands, SAs). We prepared anion exchanger type CSPs with various quinine and quinidine carbarnates as chiral SOs immobilized either on porous or non-porous silica. These CSPs are able to resolve the enantiomers of a wide spectrum of chiral carboxylic, sulfonic, phosphonic, phosphoric acids and of many other chiral acidic solutes (e.g. N-derivatized alpha-, beta- , gamma-amino acids as 2,4-dinitrophenyl, 3,5-dinitrobenzoyl, benzoyl, acetyl, formyl, t.-butoxycarbonyl, benzyloxycarbonyl, 9-fluorenylmethoxycarbonyl, dansyl amino acids and peptides, alpha-arylalkylcarboxylic acids as profens, alpha-aryloxyalkylcarboxylic acids, alpha-arylthioalkylcarboxylic acids and acidic drugs like etodolac, proglumide, acenocournarol, leucovorin, omeprazole, pantoprazole) employing buffered aqueous mobile phases or non-aqueous mobile phases with buffer dissolved in the organic solvent. The influence of mobile phase parameters and other experimental conditions on retention and enantioselectivity has been evaluated for isocratic and gradient elution techniques, aided by the commercial method development computer software DryLab. Several 'Quantitative Structure-Retention Relationships' (QSRR) have been derived, which allowed prediction of enantioselectivity of new analytes and moreover the optimization of the SO-structure. Spectroscopic investigations as H-NMR, FTIR of certain SO-SA-complexes have been exerted to unveil the mechanism of chiral recognition. (author)

  17. Chirality and gravitational parity violation.

    Science.gov (United States)

    Bargueño, Pedro

    2015-06-01

    In this review, parity-violating gravitational potentials are presented as possible sources of both true and false chirality. In particular, whereas phenomenological long-range spin-dependent gravitational potentials contain both truly and falsely chiral terms, it is shown that there are models that extend general relativity including also coupling of fermionic degrees of freedom to gravity in the presence of torsion, which give place to short-range truly chiral interactions similar to that usually considered in molecular physics. Physical mechanisms which give place to gravitational parity violation together with the expected size of the effects and their experimental constraints are discussed. Finally, the possible role of parity-violating gravity in the origin of homochirality and a road map for future research works in quantum chemistry is presented. © 2015 Wiley Periodicals, Inc.

  18. Amino-acid- and peptide-directed synthesis of chiral plasmonic gold nanoparticles.

    Science.gov (United States)

    Lee, Hye-Eun; Ahn, Hyo-Yong; Mun, Jungho; Lee, Yoon Young; Kim, Minkyung; Cho, Nam Heon; Chang, Kiseok; Kim, Wook Sung; Rho, Junsuk; Nam, Ki Tae

    2018-04-01

    Understanding chirality, or handedness, in molecules is important because of the enantioselectivity that is observed in many biochemical reactions 1 , and because of the recent development of chiral metamaterials with exceptional light-manipulating capabilities, such as polarization control 2-4 , a negative refractive index 5 and chiral sensing 6 . Chiral nanostructures have been produced using nanofabrication techniques such as lithography 7 and molecular self-assembly 8-11 , but large-scale and simple fabrication methods for three-dimensional chiral structures remain a challenge. In this regard, chirality transfer represents a simpler and more efficient method for controlling chiral morphology 12-18 . Although a few studies 18,19 have described the transfer of molecular chirality into micrometre-sized helical ceramic crystals, this technique has yet to be implemented for metal nanoparticles with sizes of hundreds of nanometres. Here we develop a strategy for synthesizing chiral gold nanoparticles that involves using amino acids and peptides to control the optical activity, handedness and chiral plasmonic resonance of the nanoparticles. The key requirement for achieving such chiral structures is the formation of high-Miller-index surfaces ({hkl}, h ≠ k ≠ l ≠ 0) that are intrinsically chiral, owing to the presence of 'kink' sites 20-22 in the nanoparticles during growth. The presence of chiral components at the inorganic surface of the nanoparticles and in the amino acids and peptides results in enantioselective interactions at the interface between these elements; these interactions lead to asymmetric evolution of the nanoparticles and the formation of helicoid morphologies that consist of highly twisted chiral elements. The gold nanoparticles that we grow display strong chiral plasmonic optical activity (a dis-symmetry factor of 0.2), even when dispersed randomly in solution; this observation is supported by theoretical calculations and direct

  19. Single-Handed Helical Polybissilsesquioxane Nanotubes and Mesoporous Nanofibers Prepared by an External Templating Approach Using Low-Molecular-Weight Gelators

    Directory of Open Access Journals (Sweden)

    Jing Hu

    2017-01-01

    Full Text Available Chiral low-molecular-weight gelators (LMWGs derived from amino acids can self-assemble into helical fibers and twisted/coiled nanoribbons by H-bonding and π–π interaction. Silica nanotubes with single-handed helices have been prepared using chiral LMWGs through sol–gel transcription. Molecular-scale chirality exists at the inner surfaces. Here, we discuss single-handed helical aromatic ring-bridged polybissilsesquioxane nanotubes and mesoporous nanofibers prepared using chiral LMWGs. This review aims at describing the formation mechanisms of the helical nanostructures, the origination of optical activity, and the applications for other helical nanomaterial preparation, mainly based on our group’s results. The morphology and handedness can be controlled by changing the chirality and kinds of LMWGs and tuning the reaction conditions. The aromatic rings arrange in a partially crystalline structure. The optical activity of the polybissilsesquioxane nanotubes and mesoporous nanofibers originates from chiral defects, including stacking and twisting of aromatic groups, on the inner surfaces. They can be used as the starting materials for preparation of silica, silicon, carbonaceous, silica/carbon, and silicon carbide nanotubes.

  20. The chiral bosonization in non-Abelian gauge theories

    International Nuclear Information System (INIS)

    Andrianov, A.A.; Novozhilov, Y.

    1985-01-01

    The chiral bosonization in non-Abelian gauge theories is described starting directly from the QCD functional. For a given mass scale Λ, the QCD may be equivalently represented by colour chiral fields, gauge fields and high energy fermions. The effective action for colour chiral fields may admit the existence of a colour Skyrmion-boson with the baryon number 2/3. (author)

  1. Chirality - The forthcoming 160th Anniversary of Pasteur's Discovery

    OpenAIRE

    Molčanov, K.; Kojić-Prodić., B.

    2007-01-01

    The presented review on chirality is dedicated to the centennial birth anniversary of Nobel laureate Vladimir Prelog and 160 years of Pasteur's discovery of chirality on tartrates. Chirality has been recognized in nature by artists and architects, who have used it for decorations and basic constructions, as shown in the Introduction. The progress of science through history has enabled the gathering of knowledge on chirality and its many ways of application. The key historical discoveries abou...

  2. Chiral symmetry restoration and quasi-elastic electron-nucleus scattering

    International Nuclear Information System (INIS)

    Henley, E.M.; Krein, G.

    1989-01-01

    Chiral symmetry is known to be an important concept in hadronic interactions. It holds in QCD, but is known to be broken at low energies. It is therefore useful to study chiral symmetry and its breaking together with its consequences in nuclear physics. It is the latter phenomena we consider here. It is difficult to study nonperturbative QCD at low energies and models are needed. The Nambu-Jona-Lasinio (NJL) model fits this category; it incorporates chiral symmetry and its breaking, and allows one to study its effects in nucleons and nuclei. In particular, the constituent quark mass varies with density (ρ) and temperature (T). At high ρ and T chiral symmetry is restored. It is the ρ dependence which yields important effects in electron scattering due to partial restoration of chiral symmetry in nuclei. We begin with the NJL model with a small chiral symmetry breaking

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

    Science.gov (United States)

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The paradigm of Pseudodual Chiral Models

    International Nuclear Information System (INIS)

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

    1994-01-01

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

  5. Diels-Alder cycloaddition strategy for kinetic resolution of chiral pyrazolidinones.

    Science.gov (United States)

    Sibi, Mukund P; Kawashima, Keisuke; Stanley, Levi M

    2009-09-03

    A rare example of the application of a catalytic, enantioselective Diels-Alder cycloaddition to affect a kinetic resolution has been developed. Chiral pyrazolidinones are resolved with high selectivity through a process that utilizes a relay of stereochemical information from a permanent chiral center to a fluxional chiral center to enhance the inherent selectivity of the chiral Lewis acid catalyst.

  6. Reversible optical transcription of supramolecular chirality into molecular chirality

    NARCIS (Netherlands)

    Jong, Jaap J.D. de; Lucas, Linda N.; Kellogg, Richard M.; Esch, Jan H. van; Feringa, Bernard

    2004-01-01

    In nature, key molecular processes such as communication, replication, and enzyme catalysis all rely on a delicate balance between molecular and supramolecular chirality. Here we report the design, synthesis, and operation of a reversible, photoresponsive, self-assembling molecular system in which

  7. Tailoring the chirality of light emission with spherical Si-based antennas.

    Science.gov (United States)

    Zambrana-Puyalto, Xavier; Bonod, Nicolas

    2016-05-21

    Chirality of light is of fundamental importance in several enabling technologies with growing applications in life sciences, chemistry and photodetection. Recently, some attention has been focused on chiral quantum emitters. Consequently, optical antennas which are able to tailor the chirality of light emission are needed. Spherical nanoresonators such as colloids are of particular interest to design optical antennas since they can be synthesized at a large scale and they exhibit good optical properties. Here, we show that these colloids can be used to tailor the chirality of a chiral emitter. To this purpose, we derive an analytic formalism to model the interaction between a chiral emitter and a spherical resonator. We then compare the performances of metallic and dielectric spherical antennas to tailor the chirality of light emission. It is seen that, due to their strong electric dipolar response, metallic spherical nanoparticles spoil the chirality of light emission by yielding achiral fields. In contrast, thanks to the combined excitation of electric and magnetic modes, dielectric Si-based particles feature the ability to inhibit or to boost the chirality of light emission. Finally, it is shown that dual modes in dielectric antennas preserve the chirality of light emission.

  8. Chiral Floquet Phases of Many-Body Localized Bosons

    Directory of Open Access Journals (Sweden)

    Hoi Chun Po

    2016-12-01

    Full Text Available We construct and classify chiral topological phases in driven (Floquet systems of strongly interacting bosons, with finite-dimensional site Hilbert spaces, in two spatial dimensions. The construction proceeds by introducing exactly soluble models with chiral edges, which in the presence of many-body localization (MBL in the bulk are argued to lead to stable chiral phases. These chiral phases do not require any symmetry and in fact owe their existence to the absence of energy conservation in driven systems. Surprisingly, we show that they are classified by a quantized many-body index, which is well defined for any MBL Floquet system. The value of this index, which is always the logarithm of a positive rational number, can be interpreted as the entropy per Floquet cycle pumped along the edge, formalizing the notion of quantum-information flow. We explicitly compute this index for specific models and show that the nontrivial topology leads to edge thermalization, which provides an interesting link between bulk topology and chaos at the edge. We also discuss chiral Floquet phases in interacting fermionic systems and their relation to chiral bosonic phases.

  9. Controllable rotational inversion in nanostructures with dual chirality.

    Science.gov (United States)

    Dai, Lu; Zhu, Ka-Di; Shen, Wenzhong; Huang, Xiaojiang; Zhang, Li; Goriely, Alain

    2018-04-05

    Chiral structures play an important role in natural sciences due to their great variety and potential applications. A perversion connecting two helices with opposite chirality creates a dual-chirality helical structure. In this paper, we develop a novel model to explore quantitatively the mechanical behavior of normal, binormal and transversely isotropic helical structures with dual chirality and apply these ideas to known nanostructures. It is found that both direction and amplitude of rotation can be finely controlled by designing the cross-sectional shape. A peculiar rotational inversion of overwinding followed by unwinding, observed in some gourd and cucumber tendril perversions, not only exists in transversely isotropic dual-chirality helical nanobelts, but also in the binormal/normal ones when the cross-sectional aspect ratio is close to 1. Beyond this rotational inversion region, the binormal and normal dual-chirality helical nanobelts exhibit a fixed directional rotation of unwinding and overwinding, respectively. Moreover, in the binormal case, the rotation of these helical nanobelts is nearly linear, which is promising as a possible design for linear-to-rotary motion converters. The present work suggests new designs for nanoscale devices.

  10. Chiral rings and anomalies in supersymmetric gauge theory

    International Nuclear Information System (INIS)

    Cachazo, Freddy; Witten, Edward; Seiberg, Nathan; Douglas, Michael R.

    2002-01-01

    Motivated by recent work of Dijkgraaf and Vafa, we study anomalies and the chiral ring structure in a supersymmetric U(N) gauge theory with an adjoint chiral superfield and an arbitrary superpotential. A certain generalization of the Konishi anomaly leads to an equation which is identical to the loop equation of a bosonic matrix model. This allows us to solve for the expectation values of the chiral operators as functions of a finite number of 'integration constants'. From this, we can derive the Dijkgraaf-Vafa relation of the effective superpotential to a matrix model. Some of our results are applicable to more general theories. For example, we determine the classical relations and quantum deformations of the chiral ring of N=1 super Yang-Mills theory with SU(N) gauge group, showing, as one consequence, that all supersymmetric vacua of this theory have a nonzero chiral condensate. (author)

  11. Highly efficient oxidation of amines to imines by singlet oxygen and its application in Ugi-type reactions.

    Science.gov (United States)

    Jiang, Gaoxi; Chen, Jian; Huang, Jie-Sheng; Che, Chi-Ming

    2009-10-15

    A variety of secondary benzylic amines were oxidized to imines in 90% to >99% yields by singlet oxygen generated from oxygen and a porphyrin photosensitizer. On the basis of these reactions, a protocol was developed for oxidative Ugi-type reactions with singlet oxygen as the oxidant. This protocol has been used to synthesize C1- and N-functionalized benzylic amines in up to 96% yields.

  12. Assembling optically active and nonactive metamaterials with chiral units

    Directory of Open Access Journals (Sweden)

    Xiang Xiong

    2012-12-01

    Full Text Available Metamaterials constructed with chiral units can be either optically active or nonactive depending on the spatial configuration of the building blocks. For a class of chiral units, their effective induced electric and magnetic dipoles, which originate from the induced surface electric current upon illumination of incident light, can be collinear at the resonant frequency. This feature provides significant advantage in designing metamaterials. In this paper we concentrate on several examples. In one scenario, chiral units with opposite chiralities are used to construct the optically nonactive metamaterial structure. It turns out that with linearly polarized incident light, the pure electric or magnetic resonance (and accordingly negative permittivity or negative permeability can be selectively realized by tuning the polarization of incident light for 90°. Alternatively, units with the same chirality can be assembled as a chiral metamaterial by taking the advantage of the collinear induced electric and magnetic dipoles. It follows that for the circularly polarized incident light, negative refractive index can be realized. These examples demonstrate the unique approach to achieve certain optical properties by assembling chiral building blocks, which could be enlightening in designing metamaterials.

  13. Chiral recognition and determination of enantiomeric excess by mass spectrometry: A review

    International Nuclear Information System (INIS)

    Yu, Xiangying; Yao, Zhong-Ping

    2017-01-01

    Chiral analysis is of great importance to fundamental and applied research in chemical, biological and pharmaceutical sciences. Due to the superiority of mass spectrometry (MS) over other analytical methods in terms of speed, specificity and sensitivity, chiral analysis by MS has attracted much interest in recent years. Chiral analysis by MS typically involves introduction of a chiral selector to form diastereomers with analyte enantiomers, and comparison of the behaviors of diastereomers in MS. Chiral differentiation can be achieved by comparing the relative abundances of diastereomers, the thermodynamic or kinetic constants of ion-molecule reactions of diastereomers in the gas phase, the dissociation of diastereomers in MS/MS, or the mobility of diastereomers in ion mobility mass spectrometry. In this review, chiral recognition and determination of enantiomeric excess by these chiral MS methods were summarized, and the prospects of chiral analysis by MS were discussed. - Highlights: • Both chiral recognition and determination of enantiomeric excess by mass spectrometry are systematically reviewed. • Classification is based on the behavioral differences of diastereomers formed between chiral analytes and chiral selectors. • Development of ion mobility mass spectrometry for chiral differentiation is covered. • Various methods are highlighted and compared.

  14. Chiral recognition and determination of enantiomeric excess by mass spectrometry: A review

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xiangying [College of Pharmacy, Jinan University, Guangzhou 510632, Guangdong (China); State Key Laboratory of Chinese Medicine and Molecular Pharmacology (Incubation) and Shenzhen Key Laboratory of Food Biological Safety Control, Shenzhen Research Institute of Hong Kong Polytechnic University, Shenzhen 518057 (China); Yao, Zhong-Ping, E-mail: zhongping.yao@polyu.edu.hk [State Key Laboratory of Chinese Medicine and Molecular Pharmacology (Incubation) and Shenzhen Key Laboratory of Food Biological Safety Control, Shenzhen Research Institute of Hong Kong Polytechnic University, Shenzhen 518057 (China); Key Laboratory of Natural Resources of Changbai Mountain and Functional Molecules (Yanbian University), Ministry of Education, Yanji 133002, Jilin (China); State Key Laboratory of Chirosciences, Food Safety and Technology Research Centre and Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong Special Administrative Region (China)

    2017-05-22

    Chiral analysis is of great importance to fundamental and applied research in chemical, biological and pharmaceutical sciences. Due to the superiority of mass spectrometry (MS) over other analytical methods in terms of speed, specificity and sensitivity, chiral analysis by MS has attracted much interest in recent years. Chiral analysis by MS typically involves introduction of a chiral selector to form diastereomers with analyte enantiomers, and comparison of the behaviors of diastereomers in MS. Chiral differentiation can be achieved by comparing the relative abundances of diastereomers, the thermodynamic or kinetic constants of ion-molecule reactions of diastereomers in the gas phase, the dissociation of diastereomers in MS/MS, or the mobility of diastereomers in ion mobility mass spectrometry. In this review, chiral recognition and determination of enantiomeric excess by these chiral MS methods were summarized, and the prospects of chiral analysis by MS were discussed. - Highlights: • Both chiral recognition and determination of enantiomeric excess by mass spectrometry are systematically reviewed. • Classification is based on the behavioral differences of diastereomers formed between chiral analytes and chiral selectors. • Development of ion mobility mass spectrometry for chiral differentiation is covered. • Various methods are highlighted and compared.

  15. Chiral nucleon-nucleon forces in nuclear structure calculations

    Directory of Open Access Journals (Sweden)

    Coraggio L.

    2016-01-01

    Full Text Available Realistic nuclear potentials, derived within chiral perturbation theory, are a major breakthrough in modern nuclear structure theory, since they provide a direct link between nuclear physics and its underlying theory, namely the QCD. As a matter of fact, chiral potentials are tailored on the low-energy regime of nuclear structure physics, and chiral perturbation theory provides on the same footing two-nucleon forces as well as many-body ones. This feature fits well with modern advances in ab-initio methods and realistic shell-model. Here, we will review recent nuclear structure calculations, based on realistic chiral potentials, for both finite nuclei and infinite nuclear matter.

  16. Recent status of the chiral bag model

    International Nuclear Information System (INIS)

    Hosaka, Atsushi; Toki, Hiroshi.

    1995-01-01

    In this note, recent status of the chiral bag model is presented. As it combines the MIT quark bag model and the Skyrme model, the chiral bag model interpolates the two models smoothly as a function of the chiral bag radius R. The correct limit of R → ∞ is reproduced by including the higher order terms in the Ω expansion of the cranking method. It resolves the so-called small g A problem in a class of models where the semiclassical method is used. (author)

  17. On infinite regular and chiral maps

    OpenAIRE

    Arredondo, John A.; Valdez, Camilo Ramírez y Ferrán

    2015-01-01

    We prove that infinite regular and chiral maps take place on surfaces with at most one end. Moreover, we prove that an infinite regular or chiral map on an orientable surface with genus can only be realized on the Loch Ness monster, that is, the topological surface of infinite genus with one end.

  18. Insights on some chiral smectic phases

    Indian Academy of Sciences (India)

    journal of. August 2003 physics pp. 285–295. Insights on some chiral ... Liquid crystals; smectics; chirality; frustrated phases; twist grain boundary phases. ... molecules are more or less packed in layers and smectic phases can be seen ..... (imaging plate or CCD camera) which was located at about 300 mm from the sample.

  19. Mass generation and chiral symmetry breaking by pseudoparticles

    International Nuclear Information System (INIS)

    Hietarinta, J.; Palmer, W.F.; Pinsky, S.S.

    1978-01-01

    Massless QCD is studied with regard to mass generation and chiral SU(N/sub f/) symmetry breaking from pseudoparticle effects. While mass is generated when there is only one massless quark, and chiral U(1) is always broken, no rigorous indication of the breaking of chiral SU(N/sub f/) and mass generation is seen when there are more than one massless quarks in the original theory

  20. Nitrile ylides: diastereoselective cycloadditions using chiral oxazolidinones without Lewis acid.

    Science.gov (United States)

    Sibi, Mukund P; Soeta, Takahiro; Jasperse, Craig P

    2009-12-03

    Lewis acid complexation is generally required for chiral-auxiliary-controlled stereoselectivity, and chiral Lewis acid catalysis is frequently optimal for introducing asymmetry. In this work, we show that nitrile ylide cycloadditions to electron-poor acceptors attached to chiral auxiliaries proceed in high yield and stereoselectivity in the absence of Lewis acids. In contrast, chiral Lewis acids are inferior in these cycloadditions.

  1. N-Aryl-oxazolidin-2-imine Muscle Selective Androgen Receptor Modulators Enhance Potency through Pharmacophore Reorientation

    Energy Technology Data Exchange (ETDEWEB)

    Nirschl, Alexandra A.; Zou, Yan; Krystek, Jr., Stanley R.; Sutton, James C.; Simpkins, Ligaya M.; Lupisella, John A.; Kuhns, Joyce E.; Seethala, Ramakrishna; Golla, Rajasree; Sleph, Paul G.; Beehler, Blake C.; Grover, Gary J.; Egan, Donald; Fura, Aberra; Vyas, Viral P.; Li, Yi-Xin; Sack, John S.; Kish, Kevin F.; An, Yongmi; Bryson, James A.; Gougoutas, Jack Z.; DiMarco, John; Zahler, Robert; Ostrowski, Jacek; Hamann, Lawrence G.; (BMS)

    2010-11-09

    A novel selective androgen receptor modulator (SARM) scaffold was discovered as a byproduct obtained during synthesis of our earlier series of imidazolidin-2-ones. The resulting oxazolidin-2-imines are among the most potent SARMs known, with many analogues exhibiting sub-nM in vitro potency in binding and functional assays. Despite the potential for hydrolytic instability at gut pH, compounds of the present class showed good oral bioavailability and were highly active in a standard rodent pharmacological model.

  2. Pions and the chiral bag

    International Nuclear Information System (INIS)

    Rho, M.

    1982-01-01

    As an aid to discussing the structure of nucleons and nuclei conceptual framework, heuristic arguments are presented which indicate that a hadron can be considered as a bag consisting of two different phases. The chiral structure of the phase outside the bag is discussed in terms of effective field theories and it is shown to what extent experiments in nuclei can constrain the structure of such theories. Results thus obtained are then combined to set up a set of equations for the bag structure of u and d hadrons, incorporating asymptotic freedom in the phase inside of the bag confinement of quarks and gluons by boundary conditions and spontaneously broken chiral symmetry in the outside. This set of equations which represent a chirally invariant generalization of the M.I.T. bag model is then solved. (U.K.)

  3. Chirality conservation in the lattice gauge theory

    International Nuclear Information System (INIS)

    Peskin, M.E.

    1978-01-01

    The derivation of conservation laws corresponding to chiral invariance in quantum field theories of interacting quarks and gluons are studied. In particular there is interest in observing how these conservation laws are constrained by the requirement that the field theory be locally gauge invariant. To examine this question, a manifestly gauge-invariant definition of local operators in a quantum field theory is introduced, a definition which relies in an essential way on the use of the formulation of gauge fields on a lattice due to Wilson and Polyakov to regulate ultraviolet divergences. The conceptual basis of the formalism is set out and applied to a long-standing puzzle in the phenomenology of quark-gluon theories: the fact that elementary particle interactions reflect the conservation of isospin-carrying chiral currents but not of the isospin-singlet chiral current. It is well known that the equation for the isospin-singlet current contains an extra term, the operator F/sub mu neu/F/sup mu neu/, not present in the other chirality conservation laws; however, this term conventionally has the form of a total divergence and so still allows the definition of a conserved chiral current. It is found that, when the effects of maintaining gauge invariance are properly taken into account, the structure of this operator is altered by renormalization effects, so that it provides an explicit breaking of the unwanted chiral invariance. The relation between this argument, based on renormaliztion, is traced to a set of more heuristic arguments based on gauge field topology given by 't Hooft; it is shown that the discussion provides a validation, through short-distance analysis, of the picture 'Hooft has proposed. The formal derivation of conservation laws for chiral currents are set out in detail

  4. Chiral superfluidity of the quark-gluon plasma

    Energy Technology Data Exchange (ETDEWEB)

    Kalaydzhyan, Tigran [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Institute for Theoretical and Experimental Physics ITEP, Moscow (Russian Federation)

    2012-08-15

    In this paper we argue that the strongly coupled quark-gluon plasma can be considered as a chiral superfluid. The ''normal'' component of the fluid is the thermalized matter in common sense, while the ''superfluid'' part consists of long wavelength (chiral) fermionic states moving independently. We use several nonperturbative techniques to demonstrate that. First, we analyze the fermionic spectrum in the deconfinement phase (T{sub c}chiral fermionic modes. Third, we use relativistic hydrodynamics for macroscopic description of the effective theory obtained after the bosonization. Finally, solving the hydrodynamic equations in gradient expansion, we find that in the presence of external electromagnetic fields the motion of the ''superfluid'' component gives rise to the chiral magnetic, chiral electric and dipole wave effects. Latter two effects are specific for a two-component fluid, which provides us with crucial experimental tests of the model.

  5. Chirality, Metallicity, and Transition Dependent Asymmetries in Resonance Raman Excitation Profiles of Chirality-Enriched Carbon Nanotubes

    Science.gov (United States)

    Doorn, Stephen; Duque, Juan; Telg, Hagen; Haroz, Erik; Tu, Xiaomin; Zheng, Ming

    2014-03-01

    Access to carbon nanotube samples enriched in single chiralities allows the observation of new photophysical behaviors obscured or difficult to demonstrate in mixed-chirality ensembles. Recent examples include the observation of strongly asymmetric G-band excitation profiles resulting from non-Condon effects1 and the unambiguous demonstration of Raman interference effects.2 We present here our most recent results demonstrating the generality of the non-Condon behavior to include metallic species (specifically several armchair chiralities). Additionally, the Eii dependence in non-Condon behavior with excitations from E11 thru E44 for both RBM and G modes will be discussed. 1. J.G. Duque, et. al., ACS Nano, 5, 5233 (2011). 2. J.G. Duque, et. al., Phys. Rev. Lett. 108, 117404 (2012).

  6. A quantitative measure of chirality inside nucleic acid databank.

    Science.gov (United States)

    Pietropaolo, Adriana; Parrinello, Michele

    2011-08-01

    We show the capability of a chirality index (Pietropaolo et al., Proteins 2008;70:667-677) to investigate nucleic acid structures because of its high sensitivity to helical conformations. By analyzing selected structures of DNA and RNA, we have found that sequences rich in cytosine and guanine have a tendency to left-handed chirality, in contrast to regions rich in adenine or thymine which show strong negative, right-handed, chirality values. We also analyze RNA structures, where specific loops and hairpin motifs are characterized by a well-defined chirality value. We find that in nucleosome the chirality is exalted, whereas in ribosome it is reduced. Our results illustrate the sensitivity of this descriptor for nucleic acid conformations. Copyright © 2011 Wiley-Liss, Inc.

  7. Chirality and energy transfer amplified circularly polarized luminescence in composite nanohelix

    Science.gov (United States)

    Yang, Dong; Duan, Pengfei; Zhang, Li; Liu, Minghua

    2017-01-01

    Transfer of both chirality and energy information plays an important role in biological systems. Here we show a chiral donor π-gelator and assembled it with an achiral π-acceptor to see how chirality and energy can be transferred in a composite donor–acceptor system. It is found that the individual chiral gelator can self-assemble into nanohelix. In the presence of the achiral acceptor, the self-assembly can also proceed and lead to the formation of the composite nanohelix. In the composite nanohelix, an energy transfer is realized. Interestingly, in the composite nanohelix, the achiral acceptor can both capture the supramolecular chirality and collect the circularly polarized energy from the chiral donor, showing both supramolecular chirality and energy transfer amplified circularly polarized luminescence (ETACPL). PMID:28585538

  8. Magnetic fields and chiral asymmetry in the early hot universe

    Energy Technology Data Exchange (ETDEWEB)

    Sydorenko, Maksym; Shtanov, Yuri [Bogolyubov Institute for Theoretical Physics, 03680 Kiev (Ukraine); Tomalak, Oleksandr, E-mail: maxsydorenko@gmail.com, E-mail: tomalak@uni-mainz.de, E-mail: shtanov@bitp.kiev.ua [Institut für Kernphysik, Johannes Gutenberg Universität, 55128 Mainz (Germany)

    2016-10-01

    In this paper, we study analytically the process of external generation and subsequent free evolution of the lepton chiral asymmetry and helical magnetic fields in the early hot universe. This process is known to be affected by the Abelian anomaly of the electroweak gauge interactions. As a consequence, chiral asymmetry in the fermion distribution generates magnetic fields of non-zero helicity, and vice versa. We take into account the presence of thermal bath, which serves as a seed for the development of instability in magnetic field in the presence of externally generated lepton chiral asymmetry. The developed helical magnetic field and lepton chiral asymmetry support each other, considerably prolonging their mutual existence, in the process of 'inverse cascade' transferring magnetic-field power from small to large spatial scales. For cosmologically interesting initial conditions, the chiral asymmetry and the energy density of helical magnetic field are shown to evolve by scaling laws, effectively depending on a single combined variable. In this case, the late-time asymptotics of the conformal chiral chemical potential reproduces the universal scaling law previously found in the literature for the system under consideration. This regime is terminated at lower temperatures because of scattering of electrons with chirality change, which exponentially washes out chiral asymmetry. We derive an expression for the termination temperature as a function of the chiral asymmetry and energy density of helical magnetic field.

  9. Chirality in distorted square planar Pd(O,N)2 compounds.

    Science.gov (United States)

    Brunner, Henri; Bodensteiner, Michael; Tsuno, Takashi

    2013-10-01

    Salicylidenimine palladium(II) complexes trans-Pd(O,N)2 adopt step and bowl arrangements. A stereochemical analysis subdivides 52 compounds into 41 step and 11 bowl types. Step complexes with chiral N-substituents and all the bowl complexes induce chiral distortions in the square planar system, resulting in Δ/Λ configuration of the Pd(O,N)2 unit. In complexes with enantiomerically pure N-substituents ligand chirality entails a specific square chirality and only one diastereomer assembles in the lattice. Dimeric Pd(O,N)2 complexes with bridging N-substituents in trans-arrangement are inherently chiral. For dimers different chirality patterns for the Pd(O,N)2 square are observed. The crystals contain racemates of enantiomers. In complex two independent molecules form a tight pair. The (RC) configuration of the ligand induces the same Δ chirality in the Pd(O,N)2 units of both molecules with varying square chirality due to the different crystallographic location of the independent molecules. In complexes and atrop isomerism induces specific configurations in the Pd(O,N)2 bowl systems. The square chirality is largest for complex [(Diop)Rh(PPh3 )Cl)], a catalyst for enantioselective hydrogenation. In the lattice of two diastereomers with the same (RC ,RC) configuration in the ligand Diop but opposite Δ and Λ square configurations co-crystallize, a rare phenomenon in stereochemistry. © 2013 Wiley Periodicals, Inc.

  10. Magnetic fields and chiral asymmetry in the early hot universe

    International Nuclear Information System (INIS)

    Sydorenko, Maksym; Shtanov, Yuri; Tomalak, Oleksandr

    2016-01-01

    In this paper, we study analytically the process of external generation and subsequent free evolution of the lepton chiral asymmetry and helical magnetic fields in the early hot universe. This process is known to be affected by the Abelian anomaly of the electroweak gauge interactions. As a consequence, chiral asymmetry in the fermion distribution generates magnetic fields of non-zero helicity, and vice versa. We take into account the presence of thermal bath, which serves as a seed for the development of instability in magnetic field in the presence of externally generated lepton chiral asymmetry. The developed helical magnetic field and lepton chiral asymmetry support each other, considerably prolonging their mutual existence, in the process of 'inverse cascade' transferring magnetic-field power from small to large spatial scales. For cosmologically interesting initial conditions, the chiral asymmetry and the energy density of helical magnetic field are shown to evolve by scaling laws, effectively depending on a single combined variable. In this case, the late-time asymptotics of the conformal chiral chemical potential reproduces the universal scaling law previously found in the literature for the system under consideration. This regime is terminated at lower temperatures because of scattering of electrons with chirality change, which exponentially washes out chiral asymmetry. We derive an expression for the termination temperature as a function of the chiral asymmetry and energy density of helical magnetic field.

  11. Synthesis and characterization of mesoporous silica modified with chiral auxiliaries for their potential application as chiral stationary phase.

    Science.gov (United States)

    Mayani, Vishal J; Abdi, S H R; Kureshy, R I; Khan, N H; Agrawal, Santosh; Jasra, R V

    2008-05-16

    Novel chiral stationary phase (CSP) based on chiral aminoalcohol immobilized on ordered mesoporous silica SBA-15 1a and standard silica 1b and their copper complexes 1a' and 1b', respectively, was synthesized as potential material for chiral ligand exchange chromatography (CLEC). Microanalysis, inductively coupled plasma spectroscopy (ICP), thermo-gravimetric analysis (TGA), cross polarized magic angle spinning (CP-MAS) (13)C NMR, Powder X-ray diffraction (PXRD), FTIR, N(2) adsorption isotherm, scanning electron microscopy (SEM), transmitted electron microscope (TEM) and solid reflectance UV-vis spectroscopy were used to characterize these materials. All the chiral stationary phases thus synthesized were used for the separation of different racemic compounds such as mandelic acid, 2,2'-dihydroxy-1,1'-binaphthalene BINOL) and diethyl tartrate by simple medium-pressure column chromatography. Successful enantio-separation of racemic mandelic acid was achieved with all the stationary phases but 1a and 1b gave slightly better resolution than their copper complexes 1a' and 1b'. Remarkably these materials are stable under the given experimental conditions and can be used repeatedly for several cycles of enantioresolution. It was observed that the porosity and surface area of the stationary phase play an important role in the chiral separation.

  12. Phosphoric acids as amplifiers of molecular chirality in liquid crystalline media

    NARCIS (Netherlands)

    Eelkema, R; Feringa, BL

    2006-01-01

    A new system for the double amplification of the molecular chirality of simple chiral amines in achiral liquid crystalline media is described. It involves a conformationally flexible phosphoric acid based receptor that by binding to chiral amines induces chirality in the liquid crystalline matrix.

  13. On the Mechanical Properties of Chiral Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Mahnaz Zakeri

    2013-12-01

    Full Text Available Carbon nanotubes (CNTs are specific structures with valuable characteristics. In general, the structure of each nanotube is defined by a unique chiral vector. In this paper, different structures of short single-walled CNTs are simulated and their mechanical properties are determined using finite element method. For this aim, a simple algorithm is presented which is able to model the geometry of single-walled CNTs with any desired structure based on nano-scale continuum mechanics approach. By changing the chiral angle from 0 to 30 degree for constant length to radius ratio, the effect of nanotube chirality on its mechanical properties is evaluated. It is observed that the tensile modulus of CNTs changes between 0.93-1.02 TPa for different structures, and it can be higher for chiral structures than zigzag and armchair ones. Also, for different chiral angles, the bending modulus changes between 0.76-0.82 TPa, while the torsional modulus varies in the range of 0.283-0.301TPa.

  14. Self-assembly of chiral molecular polygons.

    Science.gov (United States)

    Jiang, Hua; Lin, Wenbin

    2003-07-09

    Treatment of 2,2'-diacetyl-1,1'-binaphthyl-6,6'-bis(ethyne), L-H2, with 1 equiv of trans-Pt(PEt3)2Cl2 led to a mixture of different sizes of chiral metallocycles [trans-(PEt3)2Pt(L)]n (n = 3-8, 1-6). Each of the chiral molecular polygons 1-6 was purified by silica gel column chromatography and characterized by 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, MS, IR, UV-vis, and circular dichroism spectroscopies, and microanalysis. The presence of tunable cavities (1.4-4.3 nm) and chiral functionalities in these molecular polygons promises to make them excellent receptors for a variety of guests.

  15. Chiral Drug Analysis in Forensic Chemistry: An Overview

    OpenAIRE

    Cláudia Ribeiro; Cristiana Santos; Valter Gonçalves; Ana Ramos; Carlos Afonso; Maria Elizabeth Tiritan

    2018-01-01

    Many substances of forensic interest are chiral and available either as racemates or pure enantiomers. Application of chiral analysis in biological samples can be useful for the determination of legal or illicit drugs consumption or interpretation of unexpected toxicological effects. Chiral substances can also be found in environmental samples and revealed to be useful for determination of community drug usage (sewage epidemiology), identification of illicit drug manufacturing locations, ille...

  16. Pion polarizability in a chiral quark model

    International Nuclear Information System (INIS)

    Volkov, M.K.; Ebert, D.

    1981-01-01

    It is shown that the pion polarizability calculated in a chiral model with quark loops agrees exactly with the analogous quantity found in a chiral meson-baryon model. The results of a paper by Llanta and Tarrach are discussed critically

  17. Specific Noncovalent Association of Chiral Large-Ring Hexaimines: Ion Mobility Mass Spectrometry and PM7 Study.

    Science.gov (United States)

    Troć, Anna; Gajewy, Jadwiga; Danikiewicz, Witold; Kwit, Marcin

    2016-09-05

    Ion mobility mass spectrometry and PM7 semiempirical calculations are effective complementary methods to study gas phase formation of noncovalent complexes from vaselike macrocycles. The specific association of large-ring chiral hexaimines, derived from enantiomerically pure trans-1,2-diaminocyclohexane and various isophthaldehydes, is driven mostly by CH-π and π-π stacking interactions. The isotrianglimine macrocycles are prone to form two types of aggregates: tail-to-tail and head-to-head (capsule) dimers. The stability of the tail-to-tail dimers is affected by the size and electronic properties of the substituents at the C-5 position of the aromatic ring. Electron-withdrawing groups stabilize the aggregate, whereas bulky or electron-donating groups destabilize the complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Chiral bosonization on a Riemann surface

    International Nuclear Information System (INIS)

    Eguchi, Tohru; Ooguri, Hirosi

    1987-01-01

    We point out that the basic addition theorem of θ-functions, Fay's identity, implies an equivalence between bosons and chiral fermions on Riemann surfaces with arbitrary genus. We present a rule for a bosonized calculation of correlation functions. We also discuss ghost systems of n and (1-n) tensors and derive formulas for their chiral determinants. (orig.)

  19. Self-organized internal architectures of chiral micro-particles

    International Nuclear Information System (INIS)

    Provenzano, Clementina; Mazzulla, Alfredo; Desiderio, Giovanni; Pagliusi, Pasquale; De Santo, Maria P.; Cipparrone, Gabriella; Perrotta, Ida

    2014-01-01

    The internal architecture of polymeric self-assembled chiral micro-particles is studied by exploring the effect of the chirality, of the particle sizes, and of the interface/surface properties in the ordering of the helicoidal planes. The experimental investigations, performed by means of different microscopy techniques, show that the polymeric beads, resulting from light induced polymerization of cholesteric liquid crystal droplets, preserve both the spherical shape and the internal self-organized structures. The method used to create the micro-particles with controlled internal chiral architectures presents great flexibility providing several advantages connected to the acquired optical and photonics capabilities and allowing to envisage novel strategies for the development of chiral colloidal systems and materials

  20. Aromatic chemical feedstocks from coal

    Energy Technology Data Exchange (ETDEWEB)

    Collin, G

    1982-06-01

    Liquid byproducts of coal carbonization meet some 25% of the world demand for aromatic chemicals, currently at approx. 30 million t/a, in particular 15% of the demand for benzene and over 95% of the demand for condensed aromatics and heteroaromatics. Industrial processing of the aromatic byproducts of coal pressure gasification is carried out to only a minor extent. Other methods that may be employed in future to obtain carbochemical aromatic compounds are solvolysis and supercritical gas extraction, the catalytic liquid-phase hydrogenation and hydropyrolysis of coal, which also permit recovery of benzene and homologues, phenols, and condensed and partially hydrogenated aromatics, and the synthesis of aromatics using methanol as the key compound. As with the present means of obtaining aromatic chemicals from coal, the processes that may in the future be applied on an industrial scale to obtain pure aromatics will only be economically feasible if linked with the manufacture of other mass products and combined with the present production of carbochemical aromatics.

  1. Aromatic raw materials from coal

    Energy Technology Data Exchange (ETDEWEB)

    Collin, G

    1982-06-01

    Liquid byproducts of coal carbonization meet some 25% of the world demand for aromatic chemicals, currently at approx. 30 million t/a, in particular 15% of the demand for benzene and over 95% of the demand for condensed aromatics and heteroaromatics. Industrial processing of the aromatic byproducts of coal pressure gasification is carried out to only a minor extent. Other methods that may be employed in future to obtain carbochemical aromatic compounds are solvolysis and supercritical gas extraction, the catalytic liquid-phase hydrogenation and hydropyrolysis of coal, which also permit recovery of benzene and homologues, phenols, and condensed and partially hydrogenated aromatics, and the synthesis of aromatics using methanol as the key compound. As with the present means of obtaining aromatic chemicals from coal, the processes that may in future be applied on an industrial scale to obtain pure aromatics will only be economically feasible if linked with the manufacture of other mass products and combined with the present production of carbochemical aromatics. (In German)

  2. Chiral ferrocenes in asymmetric catalysis: synthesis and applications

    National Research Council Canada - National Science Library

    Dai, Li-Xin; Hou, Xue-Long

    2010-01-01

    .... It provides a thorough overview of the synthesis and characterization of different types of chiral ferrocene ligands, their application to various catalytic asymmetric reactions, and versatile chiral...

  3. Prenatal exposure to polycyclic aromatic hydrocarbons/aromatics, BDNF and child development

    International Nuclear Information System (INIS)

    Perera, Frederica; Phillips, David H.; Wang, Ya; Roen, Emily; Herbstman, Julie; Rauh, Virginia; Wang, Shuang; Tang, Deliang

    2015-01-01

    Objectives: Within a New York City (NYC) birth cohort, we assessed the associations between polycyclic aromatic hydrocarbon (PAH) and other aromatic DNA adducts and brain derived neurotrophic factor (BDNF) concentrations in umbilical cord blood, and neurodevelopment at age 2 years and whether BDNF is a mediator of the associations between PAH/aromatic-DNA adducts and neurodevelopment. Methods: PAH/aromatic-DNA adduct concentrations in cord blood were measured in 505 children born to nonsmoking African-American and Dominican women residing in NYC, and a subset was assessed for neurodevelopment at 2 years using the Bayley Scales of Infant Development Mental Development Index (MDI). A spectrum of PAH/aromatic-DNA adducts was measured using the 32 P-postlabeling assay; DNA adducts formed by benzo[a]pyrene (B[a]P), a representative PAH, were measured by High Performance Liquid Chromatography (HPLC)/fluorescence. BDNF mature protein in cord blood plasma was quantified by an ELISA. Multivariate regression analysis, adjusting for potential confounders, was conducted. Results: PAH/aromatic-DNA adduct concentration measured by postlabeling was inversely associated with BDNF concentration (p=0.02) and with MDI scores at 2 years (p=0.04). BDNF level was positively associated with MDI scores (p=0.003). Restricting to subjects having all three measures (PAH/aromatic-DNA adducts by postlabeling, MDI, and BDNF), results were similar but attenuated (p=0.13, p=0.05, p=0.01, respectively). Associations between B[a]P-DNA adducts and BDNF and B[a]P-DNA adducts and MDI at age 2 years were not significant. At age 3 years, the positive association of BDNF with MDI was not observed. Conclusions: The results at age 2 suggest that prenatal exposure to a spectrum of PAH/aromatic pollutants may adversely affect early neurodevelopment, in part by reducing BDNF levels during the fetal period. However, the same relationship was not seen at age 3. - Highlights: • Cord blood Polycyclic Aromatic

  4. Prenatal exposure to polycyclic aromatic hydrocarbons/aromatics, BDNF and child development

    Energy Technology Data Exchange (ETDEWEB)

    Perera, Frederica, E-mail: fpp1@columbia.edu [Department of Environmental Health Sciences, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Phillips, David H. [Analytical and Environmental Sciences Division, MRC-PHE Centre for Environment and Health, King' s College London, Franklin-Wilkins Building, London SE1 9NH (United Kingdom); Wang, Ya [Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Department of Biostatistics, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Roen, Emily; Herbstman, Julie [Department of Environmental Health Sciences, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Rauh, Virginia [Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); The Heilbrunn Department of Population and Family Health, Columbia University, 60 Haven Avenue, New York, NY 10032 (United States); Wang, Shuang [Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Department of Biostatistics, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Tang, Deliang [Department of Environmental Health Sciences, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States)

    2015-10-15

    Objectives: Within a New York City (NYC) birth cohort, we assessed the associations between polycyclic aromatic hydrocarbon (PAH) and other aromatic DNA adducts and brain derived neurotrophic factor (BDNF) concentrations in umbilical cord blood, and neurodevelopment at age 2 years and whether BDNF is a mediator of the associations between PAH/aromatic-DNA adducts and neurodevelopment. Methods: PAH/aromatic-DNA adduct concentrations in cord blood were measured in 505 children born to nonsmoking African-American and Dominican women residing in NYC, and a subset was assessed for neurodevelopment at 2 years using the Bayley Scales of Infant Development Mental Development Index (MDI). A spectrum of PAH/aromatic-DNA adducts was measured using the {sup 32}P-postlabeling assay; DNA adducts formed by benzo[a]pyrene (B[a]P), a representative PAH, were measured by High Performance Liquid Chromatography (HPLC)/fluorescence. BDNF mature protein in cord blood plasma was quantified by an ELISA. Multivariate regression analysis, adjusting for potential confounders, was conducted. Results: PAH/aromatic-DNA adduct concentration measured by postlabeling was inversely associated with BDNF concentration (p=0.02) and with MDI scores at 2 years (p=0.04). BDNF level was positively associated with MDI scores (p=0.003). Restricting to subjects having all three measures (PAH/aromatic-DNA adducts by postlabeling, MDI, and BDNF), results were similar but attenuated (p=0.13, p=0.05, p=0.01, respectively). Associations between B[a]P-DNA adducts and BDNF and B[a]P-DNA adducts and MDI at age 2 years were not significant. At age 3 years, the positive association of BDNF with MDI was not observed. Conclusions: The results at age 2 suggest that prenatal exposure to a spectrum of PAH/aromatic pollutants may adversely affect early neurodevelopment, in part by reducing BDNF levels during the fetal period. However, the same relationship was not seen at age 3. - Highlights: • Cord blood Polycyclic

  5. Homogenization of resonant chiral metamaterials

    DEFF Research Database (Denmark)

    Andryieuski, Andrei; Menzel, C.; Rockstuhl, Carsten

    2010-01-01

    Homogenization of metamaterials is a crucial issue as it allows to describe their optical response in terms of effective wave parameters as, e.g., propagation constants. In this paper we consider the possible homogenization of chiral metamaterials. We show that for meta-atoms of a certain size...... an analytical criterion for performing the homogenization and a tool to predict the homogenization limit. We show that strong coupling between meta-atoms of chiral metamaterials may prevent their homogenization at all....

  6. Deep-Subwavelength Resolving and Manipulating of Hidden Chirality in Achiral Nanostructures.

    Science.gov (United States)

    Zu, Shuai; Han, Tianyang; Jiang, Meiling; Lin, Feng; Zhu, Xing; Fang, Zheyu

    2018-04-24

    The chiral state of light plays a vital role in light-matter interactions and the consequent revolution of nanophotonic devices and advanced modern chiroptics. As the light-matter interaction goes into the nano- and quantum world, numerous chiroptical technologies and quantum devices require precise knowledge of chiral electromagnetic modes and chiral radiative local density of states (LDOS) distributions in detail, which directly determine the chiral light-matter interaction for applications such as chiral light detection and emission. With classical optical techniques failing to directly measure the chiral radiative LDOS, deep-subwavelength imaging and control of circular polarization (CP) light associated phenomena are introduced into the agenda. Here, we simultaneously reveal the hidden chiral electromagnetic mode and acquire its chiral radiative LDOS distribution of a single symmetric nanostructure at the deep-subwavelength scale by using CP-resolved cathodoluminescence (CL) microscopy. The chirality of the symmetric nanostructure under normally incident light excitation, resulting from the interference between the symmetric and antisymmetric modes of the V-shaped nanoantenna, is hidden in the near field with a giant chiral distribution (∼99%) at the arm-ends, which enables the circularly polarized CL emission from the radiative LDOS hot-spot and the following active helicity control at the deep-subwavelength scale. The proposed V-shaped nanostructure as a functional unit is further applied to the helicity-dependent binary encoding and the two-dimensional display applications. The proposed physical principle and experimental configuration can promote the future chiral characterization and manipulation at the deep-subwavelength scale and provide direct guidelines for the optimization of chiral light-matter interactions for future quantum studies.

  7. Nuclear chiral dynamics and thermodynamics

    Science.gov (United States)

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

    2013-11-01

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

  8. Chiral perturbation theory for nucleon generalized parton distributions

    Energy Technology Data Exchange (ETDEWEB)

    Diehl, M. [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Manashov, A. [Regensburg Univ. (Germany). Inst. fuer Physik 1 - Theoretische Physik]|[Sankt-Petersburg State Univ. (Russian Federation). Dept. of Theoretical Physics; Schaefer, A. [Regensburg Univ. (Germany). Inst. fuer Physik 1 - Theoretische Physik

    2006-08-15

    We analyze the moments of the isosinglet generalized parton distributions H, E, H, E of the nucleon in one-loop order of heavy-baryon chiral perturbation theory. We discuss in detail the construction of the operators in the effective theory that are required to obtain all corrections to a given order in the chiral power counting. The results will serve to improve the extrapolation of lattice results to the chiral limit. (orig.)

  9. Bose-Einstein condensation and chiral phase transition in linear sigma model

    International Nuclear Information System (INIS)

    Shu Song; Li Jiarong

    2005-01-01

    With the linear sigma model, we have studied Bose-Einstein condensation and the chiral phase transition in the chiral limit for an interacting pion system. A μ-T phase diagram including these two phenomena is presented. It is found that the phase plane has been divided into three areas: the Bose-Einstein condensation area, the chiral symmetry broken phase area and the chiral symmetry restored phase area. Bose-Einstein condensation can occur either from the chiral symmetry broken phase or from the restored phase. We show that the onset of the chiral phase transition is restricted in the area where there is no Bose-Einstein condensation

  10. Parity doublers in chiral potential quark models

    International Nuclear Information System (INIS)

    Kalashnikova, Yu. S.; Nefediev, A. V.; Ribeiro, J. E. F. T.

    2007-01-01

    The effect of spontaneous breaking of chiral symmetry over the spectrum of highly excited hadrons is addressed in the framework of a microscopic chiral potential quark model (Generalised Nambu-Jona-Lasinio model) with a vectorial instantaneous quark kernel of a generic form. A heavy-light quark-antiquark bound system is considered, as an example, and the Lorentz nature of the effective light-quark potential is identified to be a pure Lorentz-scalar, for low-lying states in the spectrum, and to become a pure spatial Lorentz vector, for highly excited states. Consequently, the splitting between the partners in chiral doublets is demonstrated to decrease fast in the upper part of the spectrum so that neighboring states of an opposite parity become almost degenerate. A detailed microscopic picture of such a 'chiral symmetry restoration' in the spectrum of highly excited hadrons is drawn and the corresponding scale of restoration is estimated

  11. Leading order relativistic chiral nucleon-nucleon interaction

    Science.gov (United States)

    Ren, Xiu-Lei; Li, Kai-Wen; Geng, Li-Sheng; Long, Bingwei; Ring, Peter; Meng, Jie

    2018-01-01

    Motivated by the successes of relativistic theories in studies of atomic/molecular and nuclear systems and the need for a relativistic chiral force in relativistic nuclear structure studies, we explore a new relativistic scheme to construct the nucleon-nucleon interaction in the framework of covariant chiral effective field theory. The chiral interaction is formulated up to leading order with covariant power counting and a Lorentz invariant chiral Lagrangian. We find that the relativistic scheme induces all six spin operators needed to describe the nuclear force. A detailed investigation of the partial wave potentials shows a better description of the {}1S0 and {}3P0 phase shifts than the leading order Weinberg approach, and similar to that of the next-to-leading order Weinberg approach. For the other partial waves with angular momenta J≥slant 1, the relativistic results are almost the same as their leading order non-relativistic counterparts. )

  12. Interwoven Patterns of Chirality Among Solar Structures: a Review

    Science.gov (United States)

    Martin, Sara F.

    2009-05-01

    Chirality is the handedness of solar magnetic structures as recognized in two dimensional solar images or in other solar data revealing distinct magnetic patterns. This review covers the historical succession of discoveries of the chirality of solar magnetic structures, beginning with left and right-handed helical magnetic clouds detected in many interplanetary coronal mass ejections. This led to the recognition of corresponding chiralities in coronal loop systems. Separately, chiral patterns in filaments, filament channels, sunspots, sigmoidal structures, and flare loop systems were established, interrelated, and linked to the chirality of coronal loop systems. The result was the finding that all solar chiral patterns fall into two and only two larger chiral systems with one system more prevalent in the northern hemisphere and the other in the southern hemisphere. From chiral characteristics, along with knowledge or assumptions about the magnetic field topology, we have the ability to better deduce the helicities characteristic of many solar structures. Traditionally, helicity is a property of magnetic fields with strict mathematical definitions in two well-known forms: twist and writhe. Application of the principle of the conservation of helicity to chiral systems now leads to more mature interpretations of the helicity of whole solar magnetic field systems as well as their components, which together must contain equivalent amounts of both left and right-handed helicity. From this broadened perspective, comes a better understanding of why right-handed coronal loops necessarily exist above filaments with left-handed barbs that always overly left-handed filament channels and vice versa. Along with this greater understanding, we are collectively at the point of learning to better recognize and predict the senses of roll, twist, and writhe in the axial fields of erupting prominences. These, in turn, confirm the signs of helicity in associated CMEs and magnetic clouds

  13. A series of intrinsically chiral gold nanocage structures.

    Science.gov (United States)

    Liu, X J; Hamilton, I P

    2017-07-27

    We present a series of intrinsically chiral gold nanocage structures, Au 9n+6 , which are stable for n ≥ 2. These structures consist of an Au 9n tube which is capped with Au 3 units at each end. Removing the Au 3 caps, we obtain a series of intrinsically chiral gold nanotube structures, Au 9n , which are stable for n ≥ 4. The intrinsic chirality of these structures results from the helicity of the gold strands which form the tube and not because an individual Au atom is a chiral center. The symmetry of these structures is C 3 and substructures of gold hexagons with a gold atom in the middle are particularly prominent. We focus on the properties of Au 42 (C 3 ) and Au 105 (C 3 ) which are the two smallest gold nanocage structures to be completely tiled by these Au 7 "golden-eye" substructures. Our main focus is on Au 42 (C 3 ) since gold clusters in the 40-50 atom regime are currently being investigated in gas phase experiments. We show that the intrinsically chiral Au 42 cage structure is energetically comparable with previously reported achiral cage and compact Au 42 structures. Cage structures are of particular interest because species can be encapsulated (and stabilized) inside the cage and we provide strong evidence that Au 6 @Au 42 (C 3 ) is the global minimum Au 48 structure. The intrinsically chiral gold nanocage structures, which exhibit a range of size-related properties, have potential applications in chiral catalysis and as components in nanostructured devices.

  14. Lock-in of a Chiral Soliton Lattice by Itinerant Electrons

    Science.gov (United States)

    Okumura, Shun; Kato, Yasuyuki; Motome, Yukitoshi

    2018-03-01

    Chiral magnets often show intriguing magnetic and transport properties associated with their peculiar spin textures. A typical example is a chiral soliton lattice, which is found in monoaxial chiral magnets, such as CrNb3S6 and Yb(Ni1-xCux)3Al9 in an external magnetic field perpendicular to the chiral axis. Here, we theoretically investigate the electronic and magnetic properties in the chiral soliton lattice by a minimal itinerant electron model. Using variational calculations, we find that the period of the chiral soliton lattice can be locked at particular values dictated by the Fermi wave number, in stark contrast to spin-only models. We discuss this behavior caused by the spin-charge coupling as a possible mechanism for the lock-in discovered in Yb(Ni1-xCux)3Al9 [T. Matsumura et al., https://doi.org/10.7566/JPSJ.86.124702" xlink:type="simple">J. Phys. Soc. Jpn. 86, 124702 (2017)]. We also show that the same mechanism leads to the spontaneous formation of the chiral soliton lattice even in the absence of the magnetic field.

  15. Substrate specific hydrolysis of aromatic and aromatic-aliphatic esters in orchid tissue cultures

    Directory of Open Access Journals (Sweden)

    Agnieszka Mironowicz

    2014-01-01

    Full Text Available We found that tissue cultures of higher plants were able, similarly as microorganisms, to transform low-molecular-weight chemical compounds. In tissue cultures of orchids (Cymbidium 'Saint Pierre' and Dendrobium phalaenopsis acetates of phenols and aromatic-aliphatic alcohols were hydrolyzed, whereas methyl esters of aromatic and aromatic-aliphatic acids did not undergo this reaction. Acetates of racemic aromatic-aliphatic alcohols were hydrolyzed with distinct enantiospecificity.

  16. Pentaquarks in chiral color dielectric model

    Indian Academy of Sciences (India)

    Recent experiments indicate that a narrow baryonic state having strangeness +1 and mass of about 1540 MeV may be existing. Such a state was predicted in chiral model by Diakonov et al. In this work I compute the mass and width of this state in chiral color dielectric model. I show that the computed width is about 30 MeV.

  17. Chiral symmetry breaking from Ginsparg-Wilson fermions

    CERN Document Server

    Hernández, Pilar; Lellouch, L P; Hernandez, Pilar; Jansen, Karl; Lellouch, Laurent

    2000-01-01

    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 \\Sigma, up to a multiplicative renormalization.

  18. Preface to the Special Issue: Chiral Symmetry in Hadrons and Nuclei

    International Nuclear Information System (INIS)

    Geng, Lisheng; Meng, Jie; Zhao, Qiang; Zou, Bingsong

    2014-01-01

    The recent past years have seen a remarkable progress towards a unified description of nonperturbative strong interaction phenomena based on the fundamental theory of the strong interaction, quantum chromodynamics, and effective field theories. The papers collected in this special issue focus on the recent progress in hadron and nuclear physics related to the chiral symmetry. They are written based on presentations at the Seventh International Symposium on Chiral Symmetry in Hadron and Nuclei which took place at Beihang University, Beijing, 27-30 October 2013. The sub-topics discussed in these papers include chiral and heavy-quark spin symmetry; chiral dynamics of few-body hadron systems; chiral symmetry and hadrons in a nuclear medium; chiral dynamics in nucleon-nucleon interaction and atomic nuclei; chiral symmetry in rotating nuclei; hadron structure and interactions; exotic hadrons, heavy flavor hadrons and nuclei; mesonic atoms and nuclei

  19. Design, preparation and application of a Pirkle-type chiral stationary phase for enantioseparation of some racemic organic acids and molecular dynamics studies

    Directory of Open Access Journals (Sweden)

    Reşit Çakmak

    2017-08-01

    Full Text Available This study consists of two parts. In the first part of the study; a Pirkle-type chiral stationary phase was prepared by synthesizing an aromatic amine derivative of (R-2-amino-1-butanol as a chiral selectorand binding to L- tyrosine -modified cyanogen bromide (CNBr-activated Sepharose 4B and then, packed into the separation column. T he chromatographic performance of the separation column was evaluated w ith racemic mandelic acid and 2-phenylpropionic acid by using phosphate buffers at three different pHs as mobile phase. In the resolution processes, t he prepared solutions were loaded onto the separation column at two different concentrations and at three different pHs for each racemic organic acid, separately. Enantiomeric excess (ee % of the eluates was determined on CHIRALPAK AD-H chiral analytical column by HPLC. The maximum ee% for mandelic acid and 2-phenylpropionic acid was determined to be 60.84 and 27.4, respectively. Separation factors (k 1 ’, k 2 ’, α, and Rs were calculated for each acid. The structures of the obtained compounds were characterized using the spectroscopic methods (NMR, and elemental analysis. In the second part of the study; enantioselective interactions between the prepared CSP and the analytes have been widely studied by docking, molecular dynamics simulation and quantum mechanical computation methods. The reason of column eluation of rac-2-phenylpropionic acid with lower enantiomeric yield was explained by these techniques.

  20. Recent progress of chiral stationary phases for separation of enantiomers in gas chromatography.

    Science.gov (United States)

    Xie, Sheng-Ming; Yuan, Li-Ming

    2017-01-01

    Chromatography techniques based on chiral stationary phases are widely used for the separation of enantiomers. In particular, gas chromatography has developed rapidly in recent years due to its merits such as fast analysis speed, lower consumption of stationary phases and analytes, higher column efficiency, making it a better choice for chiral separation in diverse industries. This article summarizes recent progress of novel chiral stationary phases based on cyclofructan derivatives and chiral porous materials including chiral metal-organic frameworks, chiral porous organic frameworks, chiral inorganic mesoporous materials, and chiral porous organic cages in gas chromatography, covering original research papers published since 2010. The chiral recognition properties and mechanisms of separation toward enantiomers are also introduced. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Alternative Experimental Evidence for Chiral Restoration in Excited Baryons

    International Nuclear Information System (INIS)

    Glozman, L. Ya.

    2007-01-01

    It has been suggested that chiral symmetry is approximately restored in excited hadrons at zero temperature and density (effective symmetry restoration). Using very general chiral symmetry arguments, it is shown that those excited nucleons that are assumed from the spectroscopic patterns to be in approximate chiral multiplets must only weakly decay into the Nπ channel (f N*Nπ /f NNπ ) 2 NNπ . It turns out that for all those well-established excited nucleons which can be classified into chiral doublets the ratio is (f N*Nπ /f NNπ ) 2 ∼0.1 or much smaller for the high-spin states. In contrast, the only well-established excited nucleon for which the chiral partner cannot be identified from the spectroscopic data, N(1520), has a decay constant into the Nπ channel that is comparable with f NNπ

  2. Finite nuclei in relativistic models with a light chiral scalar meson

    International Nuclear Information System (INIS)

    Serot, B.D.; Furnstahl, R.J.

    1993-01-01

    Relativistic chiral models with a light scalar, meson appear to provide an economical marriage of successful relativistic mean-field theories and chiral symmetry. In these models, the scalar meson serves as both the chiral partner of the pion and the mediator of the intermediate-range nucleon-nucleon (NN) attraction. However, while some of these models can reproduce the empirical nuclear matter saturation point, they fail to reproduce observed properties of finite nuclei, such as spin-orbit splittings, shell structure, charge densities, and surface energetics. There deficiencies imply that this realization of chiral symmetry is incorrect. An alternative scenario for chiral hadronic models, which features a heavy chiral scalar and dynamical generation of the NN attraction, is discussed

  3. Pion polarizability in a chiral quark model

    International Nuclear Information System (INIS)

    Ebert, D.; Volkov, M.K.

    1981-01-01

    The pion polarizability is calculated in a chiral meson-quark model at the one-loop level. The results are in complete agreement with earlier ones obtained within a chiral meson-baryon theory. A critical discussion of a recent paper by Llanta and Tarrach is given. (orig.)

  4. Pion polarizability in a chiral quark model

    International Nuclear Information System (INIS)

    Volkov, M.K.; Ehbert, D.

    1981-01-01

    The pion polarizability is calculated in a chiral meson- quark model at the one-loop level. The results are in complete agreement with earlier ones obtained within a chiral meson-baryon theory. A critical discussion of a recent paper by Llanta and Tarrach is given [ru

  5. Chirality in nonlinear optics and optical switching

    NARCIS (Netherlands)

    Meijer, E.W.; Feringa, B.L.

    1993-01-01

    Chirality in molecular opto-electronics is limited sofar to the use of optically active liquid crystals and a number of optical phenomena are related to the helical macroscopic structure obtained by using one enantiomer, only. In this paper, the use of chirality in nonlinear optics and optical

  6. Chiral damping of magnetic domain walls

    KAUST Repository

    Jué, Emilie

    2015-12-21

    Structural symmetry breaking in magnetic materials is responsible for the existence of multiferroics1, current-induced spin–orbit torques2, 3, 4, 5, 6, 7 and some topological magnetic structures8, 9, 10, 11, 12. In this Letter we report that the structural inversion asymmetry (SIA) gives rise to a chiral damping mechanism, which is evidenced by measuring the field-driven domain-wall (DW) motion in perpendicularly magnetized asymmetric Pt/Co/Pt trilayers. The DW dynamics associated with the chiral damping and those with Dzyaloshinskii–Moriya interaction (DMI) exhibit identical spatial symmetry13, 14, 15, 16, 17, 18, 19. However, both scenarios are differentiated by their time reversal properties: whereas DMI is a conservative effect that can be modelled by an effective field, the chiral damping is purely dissipative and has no influence on the equilibrium magnetic texture. When the DW motion is modulated by an in-plane magnetic field, it reveals the structure of the internal fields experienced by the DWs, allowing one to distinguish the physical mechanism. The chiral damping enriches the spectrum of physical phenomena engendered by the SIA, and is essential for conceiving DW and skyrmion devices owing to its coexistence with DMI (ref. 20).

  7. Chiral damping of magnetic domain walls

    KAUST Repository

    Jué , Emilie; Safeer, C.  K.; Drouard, Marc; Lopez, Alexandre; Balint, Paul; Buda-Prejbeanu, Liliana; Boulle, Olivier; Auffret, Stephane; Schuhl, Alain; Manchon, Aurelien; Miron, Ioan Mihai; Gaudin, Gilles

    2015-01-01

    Structural symmetry breaking in magnetic materials is responsible for the existence of multiferroics1, current-induced spin–orbit torques2, 3, 4, 5, 6, 7 and some topological magnetic structures8, 9, 10, 11, 12. In this Letter we report that the structural inversion asymmetry (SIA) gives rise to a chiral damping mechanism, which is evidenced by measuring the field-driven domain-wall (DW) motion in perpendicularly magnetized asymmetric Pt/Co/Pt trilayers. The DW dynamics associated with the chiral damping and those with Dzyaloshinskii–Moriya interaction (DMI) exhibit identical spatial symmetry13, 14, 15, 16, 17, 18, 19. However, both scenarios are differentiated by their time reversal properties: whereas DMI is a conservative effect that can be modelled by an effective field, the chiral damping is purely dissipative and has no influence on the equilibrium magnetic texture. When the DW motion is modulated by an in-plane magnetic field, it reveals the structure of the internal fields experienced by the DWs, allowing one to distinguish the physical mechanism. The chiral damping enriches the spectrum of physical phenomena engendered by the SIA, and is essential for conceiving DW and skyrmion devices owing to its coexistence with DMI (ref. 20).

  8. Theory of conductivity of chiral particles

    International Nuclear Information System (INIS)

    Kailasvuori, Janik; Šopík, Břetislav; Trushin, Maxim

    2013-01-01

    In this methodology focused paper we scrutinize the application of the band-coherent Boltzmann equation approach to calculating the conductivity of chiral particles. As the ideal testing ground we use the two-band kinetic Hamiltonian with an N-fold chiral twist that arises in a low-energy description of charge carriers in rhombohedrally stacked multilayer graphene. To understand the role of chirality in the conductivity of such particles we also consider the artificial model with the chiral winding number decoupled from the power of the dispersion. We first utilize the approximate but analytically solvable band-coherent Boltzmann approach including the ill-understood principal value terms that are a byproduct of several quantum many-body theory derivations of Boltzmann collision integrals. Further on, we employ the finite-size Kubo formula with the exact diagonalization of the total Hamiltonian perturbed by disorder. Finally, we compare several choices of Ansatz in the derivation of the Boltzmann equation according to the qualitative agreement between the Boltzmann and Kubo conductivities. We find that the best agreement can be reached in the approach where the principal value terms in the collision integral are absent. (paper)

  9. Parsing of the free energy of aromatic-aromatic stacking interactions in solution

    Energy Technology Data Exchange (ETDEWEB)

    Kostjukov, Viktor V.; Khomytova, Nina M. [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine); Hernandez Santiago, Adrian A.; Tavera, Anna-Maria Cervantes; Alvarado, Julieta Salas [Faculty of Chemical Sciences, Autonomous University of Puebla, Puebla (Mexico); Evstigneev, Maxim P., E-mail: max_evstigneev@mail.ru [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine)

    2011-10-15

    Graphical abstract: Highlights: > A protocol for decomposition of the free energy of aromatic stacking is developed. > The factors stabilizing/destabilizing stacking of aromatic molecules are defined. > Hydrophobic contribution is found to be dominant. - Abstract: We report an analysis of the energetics of aromatic-aromatic stacking interactions for 39 non-covalent reactions of self- and hetero-association of 12 aromatic molecules with different structures and charge states. A protocol for computation of the contributions to the total energy from various energetic terms has been developed and the results are consistent with experiment in 92% of all the systems studied. It is found that the contributions from hydrogen bonds and entropic factors are always unfavorable, whereas contributions from van-der-Waals, electrostatic and/or hydrophobic effects may lead to stabilizing or destabilizing factors depending on the system studied. The analysis carried out in this work provides an answer to the questions 'What forces stabilize/destabilize the stacking of aromatic molecules in aqueous-salt solution and what are their relative importance?'

  10. Parsing of the free energy of aromatic-aromatic stacking interactions in solution

    International Nuclear Information System (INIS)

    Kostjukov, Viktor V.; Khomytova, Nina M.; Hernandez Santiago, Adrian A.; Tavera, Anna-Maria Cervantes; Alvarado, Julieta Salas; Evstigneev, Maxim P.

    2011-01-01

    Graphical abstract: Highlights: → A protocol for decomposition of the free energy of aromatic stacking is developed. → The factors stabilizing/destabilizing stacking of aromatic molecules are defined. → Hydrophobic contribution is found to be dominant. - Abstract: We report an analysis of the energetics of aromatic-aromatic stacking interactions for 39 non-covalent reactions of self- and hetero-association of 12 aromatic molecules with different structures and charge states. A protocol for computation of the contributions to the total energy from various energetic terms has been developed and the results are consistent with experiment in 92% of all the systems studied. It is found that the contributions from hydrogen bonds and entropic factors are always unfavorable, whereas contributions from van-der-Waals, electrostatic and/or hydrophobic effects may lead to stabilizing or destabilizing factors depending on the system studied. The analysis carried out in this work provides an answer to the questions 'What forces stabilize/destabilize the stacking of aromatic molecules in aqueous-salt solution and what are their relative importance?'

  11. ζ-function regularization of chiral Jacobians for singular Dirac operators

    International Nuclear Information System (INIS)

    Carneiro, C.E.I.; Dias, S.A.; Thomaz, M.T.

    1989-01-01

    We propose a definition of the chiral Jacobian which uses the invariance of the generating functional under chiral rotations. This definition takes into account the contributions of all terms which, after rotation, depend on the chiral parameter α. We show that when the Dirac operator has zero eigenvalues the presence of fermionic sources gives an additional dependence on α. Our definition, by considering this α dependence, reconciles the ζ-function method of calculating chiral Jacobians with Fujikawa's

  12. Chirality-dependent friction of bulk molecular solids.

    Science.gov (United States)

    Yang, Dian; Cohen, Adam E

    2014-08-26

    We show that the solid-solid friction between bulk chiral molecular solids can depend on the relative chirality of the two materials. In menthol and 1-phenyl-1-butanol, heterochiral friction is smaller than homochiral friction, while in ibuprofen, heterochiral friction is larger. Chiral asymmetries in the coefficient of sliding friction vary with temperature and can be as large as 30%. In the three compounds tested, the sign of the difference between heterochiral and homochiral friction correlated with the sign of the difference in melting point between racemate (compound or conglomerate) and pure enantiomer. Menthol and ibuprofen each form a stable racemic compound, while 1-phenyl-1-butanol forms a racemic conglomerate. Thus, a difference between heterochiral and homochiral friction does not require the formation of a stable interfacial racemic compound. Measurements of chirality-dependent friction provide a unique means to distinguish the role of short-range intermolecular forces from all other sources of dissipation in the friction of bulk molecular solids.

  13. Chirality-Discriminated Conductivity of Metal-Amino Acid Biocoordination Polymer Nanowires.

    Science.gov (United States)

    Zheng, Jianzhong; Wu, Yijin; Deng, Ke; He, Meng; He, Liangcan; Cao, Jing; Zhang, Xugang; Liu, Yaling; Li, Shunxing; Tang, Zhiyong

    2016-09-27

    Biocoordination polymer (BCP) nanowires are successfully constructed through self-assembly of chiral cysteine amino acids and Cd cations in solution. The varied chirality of cysteine is explored to demonstrate the difference of BCP nanowires in both morphology and structure. More interestingly and surprisingly, the electrical property measurement reveals that, although all Cd(II)/cysteine BCP nanowires behave as semiconductors, the conductivity of the Cd(II)/dl-cysteine nanowires is 4 times higher than that of the Cd(II)/l-cysteine or Cd(II)/d-cysteine ones. The origin of such chirality-discriminated characteristics registered in BCP nanowires is further elucidated by theoretical calculation. These findings demonstrate that the morphology, structure, and property of BCP nanostructures could be tuned by the chirality of the bridging ligands, which will shed light on the comprehension of chirality transcription as well as construction of chirality-regulated functional materials.

  14. Rediscovering Chirality - Role of S-Metoprolol in Cardiovascular Disease Management.

    Science.gov (United States)

    Mohan, Jagdish C; Shah, Siddharth N; Chinchansurkar, Sunny; Dey, Arindam; Jain, Rishi

    2017-06-01

    The process of drug discovery and development today encompass a myriad of paths for bringing a new therapeutic molecule that has minimal adverse effects and of optimal use to the patient. Chirality was proposed in the direction of providing a purer and safer form of drug [Ex- cetrizine and levocetrizine]. Decades have passed since the introduction of this concept and numerous chiral molecules are in existence in therapeutics, yet somehow this concept has been ignored. This review aims to rediscover the ignored facts about chirality, its benefits and clear some common myths considering the example of S-Metoprolol in the management of Hypertension and other cardiovascular diseases. Relevant articles from Pubmed, Embase, Medline and Google Scholar were searched using the terms "Chiral", "Chirality", "Enantiomers", "Isomers", "Isomerism", "Stereo-chemistry", and "S-Metoprolol". Out of 103 articles found 17 articles mentioning in general about the concept of chirality and articles on study of S-metoprolol in various cardiovascular diseases were then reviewed. Many articles mention about the importance of chirality yet the concept has not been highlighted much. Clear benefits with chiral molecules have been documented for various drug molecules few amongst them being anaesthetics, antihypertensives, antidepressants. Benefits of S-metoprolol over racemate are also clear in terms of responder rates, dose of administration and adverse effects profile in various cardiovascular diseases. Chirality is a good way forward in providing a new drug molecule which is safe with lesser pharmacokinetic and pharmacodynamics variability, lesser side effects and more potent action. S-metoprolol is chirally pure form of racemate metoprolol and has lesser side effects, is safer in patients of COPD and Diabetes who also have hypertension and comparable responder rates at half the doses when compared to racemate.

  15. 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.

    Science.gov (United States)

    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

  16. Visualization of Stereoselective Supramolecular Polymers by Chirality-Controlled Energy Transfer.

    Science.gov (United States)

    Sarkar, Aritra; Dhiman, Shikha; Chalishazar, Aditya; George, Subi J

    2017-10-23

    Chirality-driven self-sorting is envisaged to efficiently control functional properties in supramolecular materials. However, the challenge arises because of a lack of analytical methods to directly monitor the enantioselectivity of the resulting supramolecular assemblies. Presented herein are two fluorescent core-substituted naphthalene-diimide-based donor and acceptor molecules with minimal structural mismatch and they comprise strong self-recognizing chiral motifs to determine the self-sorting process. As a consequence, stereoselective supramolecular polymerization with an unprecedented chirality control over energy transfer has been achieved. This chirality-controlled energy transfer has been further exploited as an efficient probe to visualize microscopically the chirality driven self-sorting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Metal-Ion-Mediated Supramolecular Chirality of l-Phenylalanine Based Hydrogels.

    Science.gov (United States)

    Wang, Fang; Feng, Chuan-Liang

    2018-05-14

    For chiral hydrogels and related applications, one of the critical issues is how to control the chirality of supramolecular systems in an efficient way, including easy operation, efficient transfer of chirality, and so on. Herein, supramolecular chirality of l-phenylalanine based hydrogels can be effectively controlled by using a broad range of metal ions. The degree of twisting (twist pitch) and the diameter of the chiral nanostructures can also be efficiently regulated. These are ascribed to the synergic effect of hydrogen bonding and metal ion coordination. This study may develop a method to design a new class of electronically, optically, and biologically active materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Engineering Aromatic-Aromatic Interactions To Nucleate Folding in Intrinsically Disordered Regions of Proteins.

    Science.gov (United States)

    Balakrishnan, Swati; Sarma, Siddhartha P

    2017-08-22

    Aromatic interactions are an important force in protein folding as they combine the stability of a hydrophobic interaction with the selectivity of a hydrogen bond. Much of our understanding of aromatic interactions comes from "bioinformatics" based analyses of protein structures and from the contribution of these interactions to stabilizing secondary structure motifs in model peptides. In this study, the structural consequences of aromatic interactions on protein folding have been explored in engineered mutants of the molten globule protein apo-cytochrome b 5 . Structural changes from disorder to order due to aromatic interactions in two variants of the protein, viz., WF-cytb5 and FF-cytb5, result in significant long-range secondary and tertiary structure. The results show that 54 and 52% of the residues in WF-cytb5 and FF-cytb5, respectively, occupy ordered regions versus 26% in apo-cytochrome b 5 . The interactions between the aromatic groups are offset-stacked and edge-to-face for the Trp-Phe and Phe-Phe mutants, respectively. Urea denaturation studies indicate that both mutants have a C m higher than that of apo-cytochrome b 5 and are more stable to chaotropic agents than apo-cytochrome b 5 . The introduction of these aromatic residues also results in "trimer" interactions with existing aromatic groups, reaffirming the selectivity of the aromatic interactions. These studies provide insights into the aromatic interactions that drive disorder-to-order transitions in intrinsically disordered regions of proteins and will aid in de novo protein design beyond small peptide scaffolds.

  19. Decay patterns of multi-quasiparticle bands—a model independent test of chiral symmetry

    International Nuclear Information System (INIS)

    Lawrie, E A

    2017-01-01

    Nuclear chiral systems exhibit chiral symmetry bands, built on left-handed and right-handed angular momentum nucleon configurations. The experimental search for such chiral systems revealed a number of suitable candidates, however an unambiguous identification of nuclear chiral symmetry is still outstanding. In this work it is shown that the decay patterns of chiral bands built on multi-quasiparticle configurations are different from those involving different single-particle configurations. It is suggested to use the observed decay patterns of chiral candidates as a new model-independent test of chiral symmetry. (paper)

  20. Chiral symmetry on the lattice

    International Nuclear Information System (INIS)

    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

  1. Field-dependent spin chirality and frustration in V3 and Cu3 nanomagnets in transverse magnetic field. 2. Spin configurations, chirality and intermediate spin magnetization in distorted trimers

    International Nuclear Information System (INIS)

    Belinsky, Moisey I.

    2014-01-01

    Highlights: • Distorted spin configurations determine field behavior of the variable chiralities. • Distortions change spin chiralities, intermediate M 12 ± and staggered magnetization. • Magnetizations, distorted vector and scalar chiralities are strongly correlated. • Distorted V 3 , Cu 3 nanomagnets possess large vector chirality in the ground state in B ⊥ . • Chiralities and distortions in EPR, INS and NMR spectra were considered. - Abstract: Correlated spin configurations, magnetizations, frustration, vector κ ¯ z and scalar χ ¯ chiralities are considered for distorted V ‾ 3 , /Cu 3 / anisotropic DM nanomagnets in transverse B x ‖X and longitudinal B‖Z fields. Different planar configurations in the ground and excited states of distorted nanomagnets in B x determine different field behavior of the vector chiralities and the degenerate frustration in these states correlated with the M ~ 12 ± (B x ) intermediate spin (IS) magnetization which describes the S 12 characteristics, χ=0. Distortion results in the reduced κ ¯ z <1 chirality in the ground distorted configuration and in the maximum κ z =±1 in the excited states with the planar 120° configurations at avoided level crossing. In B‖Z, distorted longitudinal spin-collinear configurations are characterized by the reduced degenerate frustration, out-of-plane staggered and IS M ~ 12 ± (B z ) magnetizations, and in-plane toroidal moments, correlated with the κ ¯ z , χ ¯ chiralities, χ ¯ =±|κ ¯ z |. The chiralities and IS magnetization in EPR, INS and NMR spectra are considered. The quantitative correlations describe variable spin chirality, frustration and field manipulation of chiralities in nanomagnets

  2. Examination of the Potential for Adaptive Chirality of the Nitrogen Chiral Center in Aza-Aspartame

    Directory of Open Access Journals (Sweden)

    Samir H. Bouayad-Gervais

    2013-11-01

    Full Text Available 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.

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

    Science.gov (United States)

    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.

  4. Pro-aromatic and anti-aromatic π-conjugated molecules: an irresistible wish to be diradicals

    KAUST Repository

    Zeng, Zebing

    2015-01-01

    © 2015 The Royal Society of Chemistry. Aromaticity is an important concept to understand the stability and physical properties of π-conjugated molecules. Recent studies on pro-aromatic and anti-aromatic molecules revealed their irresistible tendency to become diradicals in the ground state. Diradical character thus becomes another very important concept and it is fundamentally correlated to the physical (optical, electronic and magnetic) properties and chemical reactivity of most of the organic optoelectronic materials. Molecules with distinctive diradical character show unique properties which are very different from those of traditional closed-shell π-conjugated systems, and thus they have many potential applications in organic electronics, spintronics, non-linear optics and energy storage. This critical review first introduces the fundamental electronic structure of Kekulé diradicals within the concepts of anti-aromaticity and pro-aromaticity in the context of Hückel aromaticity and diradical character. Then recent research studies on various stable/persistent diradicaloids based on pro-aromatic and anti-aromatic compounds are summarized and discussed with regard to their synthetic chemistry, physical properties, structure-property relationships and potential material applications. A summary and personal perspective is given at the end.

  5. Chiral Topological Orders in an Optical Raman Lattice (Open Source)

    Science.gov (United States)

    2016-03-01

    PAPER • OPEN ACCESS Chiral topological orders in an optical Raman lattice To cite this article: Xiong-Jun Liu et al 2016 New J. Phys. 18...... chiral spin liquid Abstract Wefind an optical Raman lattice without spin-orbit coupling showing chiral topological orders for cold atoms. Two

  6. Synthesis, Characterisation and DFT Calculations of Azo-Imine Dyes

    Directory of Open Access Journals (Sweden)

    Sevil Özkınalı

    2017-11-01

    Full Text Available In this study, azo dyes containing an imine group were synthesised by coupling p-hydroxybenzylidene aniline with the diazonium salts of p-toluidine, 4-aminophenol, aniline, p-chloroaniline, p-fluoroaniline, and p-nitroaniline. The compounds were characterised by melting point, elemental, UV-Vis and IR analyses as well as 1H-NMR and 13C-NMR spectroscopies. Moreover, the experimental data were supplemented with density functional theory (DFT calculations. The experimental data on FT-IR and UV–Vis spectra of the compounds were compared with theoretical results. The DFT calculations were performed to obtain the ground state geometries of the compounds using the B3LYP hybrid functional level with 6-311++g(2d,2p basis set. Frontier molecular orbital energies, band gap energies and some chemical reactivity parameters, such as chemical hardness and electronegativity, were calculated and compared with experimental values. A significant correlation was observed between the dipole moment and polarities of the solvents and the absorption wavelength of the compounds.

  7. Chiral symmetry and strangeness at SIS energies

    International Nuclear Information System (INIS)

    Lutz, M.F.M.

    2003-11-01

    In this talk we review the consequences of the chiral SU(3) symmetry for strangeness propagation in nuclear matter. Objects of crucial importance are the meson-baryon scattering amplitudes obtained within the chiral coupled-channel effective field theory. Results for antikaon and hyperon-resonance spectral functions in cold nuclear matter are presented and discussed. The importance of the Σ(1385) resonance for the subthreshold antikaon production in heavy-ion reaction at SIS is pointed out. The in-medium properties of the latter together with an antikaon spectral function based on chiral SU(3) dynamics suggest a significant enhancement of the π Λ → anti Κ N reaction in nuclear matter. (orig.)

  8. The Kinetics of Chirality Assignment in Catalytic Single Walled Carbon Nanotube Growth

    OpenAIRE

    Xu, Ziwei; Yan, Tianying; Ding, Feng

    2014-01-01

    Chirality-selected single-walled carbon nanotubes (SWCNTs) ensure a great potential of building ~1 nm sized electronics. However, the reliable method for chirality-selected SWCNT is still pending. Here we present a theoretical study on the SWCNT's chirality assignment and control during the catalytic growth. This study reveals that the chirality of a SWCNT is determined by the kinetic incorporation of the pentagon formation during SWCNT nucleation. Therefore, chirality is randomly assigned on...

  9. Bag model with broken chiral symmetry

    International Nuclear Information System (INIS)

    Efrosinin, V.P.; Zaikin, D.A.

    1986-01-01

    A variant of the bag model in which chiral symmetry is broken and which provides a description of all the experimental data on the light hadrons, including the pion, is discussed. The pion and kaon decay constants are calculated in this model. The problem of taking into account the center-of-mass motion in bag models and the boundary conditions in the bag model with broken chiral symmetry are also discussed

  10. Second-harmonic generation circular dichroism spectroscopy from tripod-like chiral molecular films

    International Nuclear Information System (INIS)

    Wang Xiao-Ou; Chen Li-An; Chen Li-Xue; Sun Xiu-Dong; Li Jun-Qing; Li Chun-Fei

    2010-01-01

    The second-harmonic generation (SHG) circular dichroism in the light of reflection from chiral films of tripod-like chiral molecules is investigated. The expressions of the second-harmonic generation circular dichroism are derived from our presented three-coupled-oscillator model for the tripod-like chiral molecules. Spectral dependence of the circular dichroism of SHG from film surface composed of tripod-like chiral molecules is simulated numerically and analysed. Influence of chiral parameters on the second-harmonic generation circular dichroism spectrum in chiral films is studied. The result shows that the second-harmonic generation circular dichroism is a sensitive method of detecting chirality compared with the ordinary circular dichroism in linear optics. All of our work indicates that the classical molecular models are very effective to explain the second-harmonic generation circular dichroism of chiral molecular system. The classical molecular model theory can give us a clear physical picture and brings us very instructive information about the link between the molecular configuration and the nonlinear processes

  11. Nuclear matter from chiral effective field theory

    International Nuclear Information System (INIS)

    Drischler, Christian

    2017-01-01

    Nuclear matter is an ideal theoretical system that provides key insights into the physics of different length scales. While recent ab initio calculations of medium-mass to heavy nuclei have demonstrated that realistic saturation properties in infinite matter are crucial for reproducing experimental binding energies and charge radii, the nuclear-matter equation of state allows tight constraints on key quantities of neutron stars. In the present thesis we take advantage of both aspects. Chiral effective field theory (EFT) with pion and nucleon degrees of freedom has become the modern low-energy approach to nuclear forces based on the symmetries of quantum chromodynamics, the fundamental theory of strong interactions. The systematic chiral expansion enables improvable calculations associated with theoretical uncertainty estimates. In recent years, chiral many-body forces were derived up to high orders, allowing consistent calculations including all many-body contributions at next-to-next-to-next-to-leading order (N 3 LO). Many further advances have driven the construction of novel chiral potentials with different regularization schemes. Here, we develop advanced methods for microscopic calculations of the equation of state of homogeneous nuclear matter with arbitrary proton-to-neutron ratio at zero temperature. Specifically, we push the limits of many-body perturbation theory (MBPT) considerations to high orders in the chiral and in the many-body expansion. To address the challenging inclusion of three-body forces, we introduce a new partial-wave method for normal ordering that generalizes the treatment of these contributions. We show improved predictions for the neutron-matter equation of state with consistent N 3 LO nucleon-nucleon (NN) plus three-nucleon (3N) potentials using MBPT up to third order and self-consistent Green's function theory. The latter also provides nonperturbative benchmarks for the many-body convergence. In addition, we extend the normal

  12. Nuclear matter from chiral effective field theory

    Energy Technology Data Exchange (ETDEWEB)

    Drischler, Christian

    2017-11-15

    Nuclear matter is an ideal theoretical system that provides key insights into the physics of different length scales. While recent ab initio calculations of medium-mass to heavy nuclei have demonstrated that realistic saturation properties in infinite matter are crucial for reproducing experimental binding energies and charge radii, the nuclear-matter equation of state allows tight constraints on key quantities of neutron stars. In the present thesis we take advantage of both aspects. Chiral effective field theory (EFT) with pion and nucleon degrees of freedom has become the modern low-energy approach to nuclear forces based on the symmetries of quantum chromodynamics, the fundamental theory of strong interactions. The systematic chiral expansion enables improvable calculations associated with theoretical uncertainty estimates. In recent years, chiral many-body forces were derived up to high orders, allowing consistent calculations including all many-body contributions at next-to-next-to-next-to-leading order (N{sup 3}LO). Many further advances have driven the construction of novel chiral potentials with different regularization schemes. Here, we develop advanced methods for microscopic calculations of the equation of state of homogeneous nuclear matter with arbitrary proton-to-neutron ratio at zero temperature. Specifically, we push the limits of many-body perturbation theory (MBPT) considerations to high orders in the chiral and in the many-body expansion. To address the challenging inclusion of three-body forces, we introduce a new partial-wave method for normal ordering that generalizes the treatment of these contributions. We show improved predictions for the neutron-matter equation of state with consistent N{sup 3}LO nucleon-nucleon (NN) plus three-nucleon (3N) potentials using MBPT up to third order and self-consistent Green's function theory. The latter also provides nonperturbative benchmarks for the many-body convergence. In addition, we extend the

  13. Baryon Chiral Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Becher,

    2002-08-08

    After contrasting the low energy effective theory for the baryon sector with one for the Goldstone sector, I use the example of pion nucleon scattering to discuss some of the progress and open issues in baryon chiral perturbation theory.

  14. Chiral cavity ring down polarimetry: Chirality and magnetometry measurements using signal reversals.

    Science.gov (United States)

    Bougas, Lykourgos; Sofikitis, Dimitris; Katsoprinakis, Georgios E; Spiliotis, Alexandros K; Tzallas, Paraskevas; Loppinet, Benoit; Rakitzis, T Peter

    2015-09-14

    We present the theory and experimental details for chiral-cavity-ring-down polarimetry and magnetometry, based on ring cavities supporting counterpropagating laser beams. The optical-rotation symmetry is broken by the presence of both chiral and Faraday birefringence, giving rise to signal reversals which allow rapid background subtractions. We present the measurement of the specific rotation at 800 nm of vapors of α-pinene, 2-butanol, and α-phellandrene, the measurement of optical rotation of sucrose solutions in a flow cell, the measurement of the Verdet constant of fused silica, and measurements and theoretical treatment of evanescent-wave optical rotation at a prism surface. Therefore, these signal-enhancing and signal-reversing methods open the way for ultrasensitive polarimetry measurements in gases, liquids and solids, and at surfaces.

  15. Chiral cavity ring down polarimetry: Chirality and magnetometry measurements using signal reversals

    International Nuclear Information System (INIS)

    Bougas, Lykourgos; Sofikitis, Dimitris; Katsoprinakis, Georgios E.; Spiliotis, Alexandros K.; Rakitzis, T. Peter; Tzallas, Paraskevas; Loppinet, Benoit

    2015-01-01

    We present the theory and experimental details for chiral-cavity-ring-down polarimetry and magnetometry, based on ring cavities supporting counterpropagating laser beams. The optical-rotation symmetry is broken by the presence of both chiral and Faraday birefringence, giving rise to signal reversals which allow rapid background subtractions. We present the measurement of the specific rotation at 800 nm of vapors of α-pinene, 2-butanol, and α-phellandrene, the measurement of optical rotation of sucrose solutions in a flow cell, the measurement of the Verdet constant of fused silica, and measurements and theoretical treatment of evanescent-wave optical rotation at a prism surface. Therefore, these signal-enhancing and signal-reversing methods open the way for ultrasensitive polarimetry measurements in gases, liquids and solids, and at surfaces

  16. Surface enhanced Raman spectroscopy and structural characterization of Ag/Cu chiral nano-flower sculptured thin films

    International Nuclear Information System (INIS)

    Savaloni, Hadi; Babaei, Reza

    2013-01-01

    Silver chiral nano-flower sculptured thin films with 3-, 4- and 5-fold symmetry were produced on copper substrates using oblique angle deposition method in conjunction with rotation of sample holder with different speeds at different sectors of each revolution corresponding to symmetry order of the acquired nano-flower. Atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM) were employed to obtain morphologies and nano-structure of the films. Raman spectroscopy was performed on all samples that were subject to impregnation by 4,4′-bipyridine (C 10 H 8 N 2 ) solution. A high degree of enhancement of the main bands at 1610, 1297, and 1009 cm −1 that can be assigned to the C=C stretching mode, aromatic ring stretching ring and in-plane ring mode of 4,4′-bipyridine, is achieved.

  17. Surface enhanced Raman spectroscopy and structural characterization of Ag/Cu chiral nano-flower sculptured thin films

    Energy Technology Data Exchange (ETDEWEB)

    Savaloni, Hadi, E-mail: savaloni@khayam.ut.ac.ir [Department of Physics, University of Tehran, North-Kargar Street, Tehran (Iran, Islamic Republic of); Babaei, Reza, E-mail: reza_babaee_62@yahoo.com [Department of Physics, Islamic Azad University, Science and Research Branch, Tehran (Iran, Islamic Republic of)

    2013-09-01

    Silver chiral nano-flower sculptured thin films with 3-, 4- and 5-fold symmetry were produced on copper substrates using oblique angle deposition method in conjunction with rotation of sample holder with different speeds at different sectors of each revolution corresponding to symmetry order of the acquired nano-flower. Atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM) were employed to obtain morphologies and nano-structure of the films. Raman spectroscopy was performed on all samples that were subject to impregnation by 4,4′-bipyridine (C{sub 10}H{sub 8}N{sub 2}) solution. A high degree of enhancement of the main bands at 1610, 1297, and 1009 cm{sup −1} that can be assigned to the C=C stretching mode, aromatic ring stretching ring and in-plane ring mode of 4,4′-bipyridine, is achieved.

  18. Chiral pyrrolidinium salts derived from menthol as precursor – synthesis and properties

    Directory of Open Access Journals (Sweden)

    Janus Ewa

    2017-09-01

    Full Text Available Six new chiral pyrolidinium salts with chiral substituent at quaternary nitrogen atom were synthesized with high overall yields from (--menthol as cheap chiral precursor and were identified by NMR and HRMS spectroscopy. It was shown that anion type had the effect on chemical shift of protons adjacent to quaternary nitrogen atom and physical properties of these salts. Salts with NTf2 or NPf2 were in a liquid state at room temperature and characterized with the highest thermal stability among others. Furthermore, chiral ionic liquid with NTf2 anion was used as solvent in Diels-Alder reaction and gave higher yield and stereoselectivity than in ionic liquids with achiral cations. Synthesized chiral salts have the potential as chiral solvents in synthesis and auxiliaries in analytical methods to improve chiral recognition.

  19. Enantioselective catalytic syntheses of alpha-branched chiral amines

    DEFF Research Database (Denmark)

    Brase, S.; Baumann, T.; Dahmen, S.

    2007-01-01

    Chiral amines play a pivotal role in fine chemical and natural product syntheses and the design of novel materials.......Chiral amines play a pivotal role in fine chemical and natural product syntheses and the design of novel materials....

  20. Chiral perturbation theory approach to hadronic weak amplitudes

    International Nuclear Information System (INIS)

    Rafael, E. de

    1989-01-01

    We are concerned with applications to the non-leptonic weak interactions in the sector of light quark flavors: u, d and s. Both strangeness changing ΔS=1 and ΔS=2 non-leptonic transitions can be described as weak perturbations to the strong effective chiral Lagrangian; the chiral structure of the weak effective Lagrangian being dictated by the transformation properties of the weak non-leptonic Hamiltonian of the Standard Model under global SU(3) Left xSU(3) Right rotations of the quark-fields. These lectures are organized as follows. Section 2 gives a review of the basic properties of chiral symmetry. Section 3 explains the effective chiral realization of the non-leptonic weak Hamiltonian of the Standard Model to lowest order in derivatives and masses. Section 4 deals with non-leptonic weak transitions in the presence of electromagnetism. Some recent applications to radiative kaon decays are reviewed and the effect of the so called electromagnetic penguin like diagrams is also discussed. Section 5 explains the basic ideas of the QCD-hadronic duality approach to the evaluation of coupling constants of the non-leptonic chiral weak Lagrangian. (orig./HSI)