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Sample records for high chiral recognition

  1. Retention and chiral recognition mechanism of organo-phosphorus compounds in high-performance liquid chroma-tography

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In normal phase condition, a series of chiral phosphorus organic compounds have been separated by high-performance liquid chromatography. In order to study the retention and chiral recognition mechanism, the method of quantitative structure-enantioselectivity retention relationships (QSERRs) has been investigated from the quantitative equations established between the chromatographic retention of enantiomers and their molecular descriptors of physicochemical properties. The results show that on the Pirkle-type chiral stationary phase (CSP) of Sumichiral OA4700, it is the parameter of LUMO that gives the most contribution to the chromatographic re-tention of O-ethyl O-(substituted) phenyl N-isopropyl phosphoroamidothioates resulting from the interaction of hydrogen bond and (or) p-p interaction. Meanwhile, the chiral recognition is formed from the contribution of logP and LUMO.

  2. Enhanced Chiral Recognition by Cyclodextrin Dimers

    Directory of Open Access Journals (Sweden)

    Bart Jan Ravoo

    2011-07-01

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

  3. Highly selective single nucleotide polymorphism recognition by a chiral (5S) PNA beacon.

    Science.gov (United States)

    Totsingan, Filbert; Tedeschi, Tullia; Sforza, Stefano; Corradini, Roberto; Marchelli, Rosangela

    2009-01-01

    A chiral peptide nucleic acid (PNA) beacon containing a C-5 modified monomer based on L-lysine was synthesized. The terminal amino group of the lysine side chain was linked to a spacer for future applications on surfaces. The PNA beacon bears a carboxyfluorescein fluorophore and a dabcyl quencher at opposite ends. The DNA binding properties were compared with those of a homologous PNA beacon containing only achiral monomers. Both beacons underwent a fluorescence increase in the presence of complementary DNA, with higher efficiency and higher selectivity (evaluated using single mismatched DNA sequences) observed for the chiral monomer containing PNA. Ion exchange (IE) HPLC with fluorimetric detection was used in combination with the beacon for the selective detection of complementary DNA. A fluorescent peak corresponding to the PNA beacon:DNA duplex was observed at a very low detection limit (1 nM). The discriminating capacity of the chiral PNA beacon for a single mismatch was found to be superior to those observed with the unmodified one, thus confirming the potency of chirality for increasing the affinity and specificity of DNA recognition.

  4. Highly Enantioselective Fluorescent Recognition of Both Unfunctionalized and Functionalized Chiral Amines by a Facile Amide Formation from a Perfluoroalkyl Ketone.

    Science.gov (United States)

    Wang, Chao; Anbaei, Parastoo; Pu, Lin

    2016-05-17

    The H8 BINOL-based perfluoroalkyl ketone (S)-2 is found to exhibit highly enantioselective fluorescent enhancements toward both unfunctionalized and functionalized chiral amines. It greatly expands the substrate scope of the corresponding BINOL-based sensor. A dramatic solvent effect was observed for the reaction of the amines with compound (S)-2. In DMF, cleavage of the perfluoroalkyl group of compound (S)-2 to form amides was observed but not in other solvents, such as methylene chloride, chloroform, THF, hexane, and perfluorohexane. Thus, the addition of another solvent, such as THF, can effectively quench the reaction of compound (S)-2 with amines in DMF to allow stable fluorescent measurement. This is the first example that the formation of strong amide bonds under very mild conditions is used for the enantioselective recognition of chiral amines. The mechanism of the reaction of compound (S)-2 with chiral amines is investigated by using various analytical methods including mass spectrometry as well as NMR and UV/Vis absorption spectroscopy.

  5. Development of Enantioselective Fluorescent Sensors for Chiral Recognition

    Institute of Scientific and Technical Information of China (English)

    Lin Pu

    2004-01-01

    Novel chiral compounds have been synthesized for the enantioselective fluorescent recognition of alpha-hydroxycarboxylic acids and amino acids. By introducing dendritic branches to the chiral receptor units, the fluorescence signals of the receptors are significantly amplified because of the light-harvesting effect of the dendritic structure. This has greatly increased the sensitivity of the sensors in the fluorescent recognition. Highly enantioselective fluorescent responses have also been achieved. These sensors are potentially useful for the high throughput screening of chiral catalysts for asymmetric synthesis.

  6. Enantioselective recognition at mesoporous chiral metal surfaces

    Science.gov (United States)

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

    2014-02-01

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

  7. Investigation of retention and chiral recognition mechanism using quantitative structure-enantioselectivity retention relationship in high performance liquid chromatography

    Institute of Scientific and Technical Information of China (English)

    CHEN, Hui; LU, Xian-Yu; GAO, Ru-Yu; HUANG, Jun-Min; YANG, Hua-Zheng; WANG, Qin-Sun

    2000-01-01

    The enantiomers of a series of fourteen O-ethyl O-(substituted) phenyl N-isopropyl-phosphoroamidothioates have been separated by high performance liquid chromatography (HPLC) on the Pirkde-type chiral stationary phase. Seven molecular descriptors were lculated and four .significant descriptors were chosen to correlate against the experimental Ink′ values in order to form thequantitative structure-enantioselectivity retention relationships (QSERRs). Through the QSERRs, the retention and enantioselectivity meehanism were examined.

  8. Synthesis and Chiral Recognition of a New Type of Chiral Calix[4]arene Derivatives

    Institute of Scientific and Technical Information of China (English)

    HE,Yong-Bing; LI,Jian-Feng; XIAO,Yuan-Jing; WEI,Lan-Hua; WU,Xiao-Jun; MENG,Ling-Zhi

    2003-01-01

    Two new chiral calix[4] arenes bearing chiral pendants, which were from by-product of the antibiotic industry, were synthesized and characterized by 1H NMR, MS-FAB and elemental analysis. Studies of 1H NMR of the two calix [4] arene derivatives indicate that they exist in cone conformation in solution. Results of chiral recognition of the two chiral ligands 2a and 2b towards the tartaric acid derivative 3 show that ligand 2a exhibited good chiral recognition abilities compared to ligand 2b.

  9. New Chiral Calixarene Derivatives: Syntheses and Their Chiral Recognition Toward Amino Acids by UV-Vis Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Three novel types of chiral calixarene derivatives 5, 8, and 10 were designed and synthesized by introducing chiral units to parent calixarenes. Their chiralities were confirmed by rotational analysis. Chiral recognition properties of these host compounds towards L- and D-threonine were studied by UV-Vis spectroscopy. The results indicated that calixarene derivatives 5 and 8 exhibited good chiral recognition capabilities toward L- or D-threonine. Although calixarene derivative 10 had no evident chiral recognition ability, the supramolecules of calixarene derivative 10 with L- or D-threonine showed a hypochromic effect or hyperchromic effect respectively. Therefore, calixarene derivative 10 might serve as a good chiral UV-indicator.

  10. Chiral recognition detected by fast atom bombardment mass spectrometry.

    Science.gov (United States)

    Sawada, M

    1997-01-01

    Detection of chiral recognition in various intermolecular interaction systems using mass spectrometry has become important for the modern fields of analytical chemistry, organic chemistry, and biochemistry due to the characteristic nature of the rapid method and the trace amount needed. This review presents the various methods for detecting and evaluating chiral recognition used primarily in fast atom bombardment mass spectrometry. Emphasis is put on fundamentals and applications of these methods for variously existing enantioselective intermolecular interaction systems.

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

    Science.gov (United States)

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

    2010-06-01

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

  12. Chiral Recognition and Enantioseparation Mechanisms in Capillary Electrokinetic Chromatography

    Science.gov (United States)

    Chankvetadze, Bezhan

    This chapter deals with the basic theory of enantiomeric separations in electrokinetic chromatography (EKC) in general and with the relationships between the recognition and the separation of enantiomers in EKC, in particular. It is important to note that the dependence between recognition and separation is not as straightforward in EKC as it is in chromatographic separation techniques. Therefore, a clear understanding of these dependences is very important for the explanation of experimentally observed results, as well as for a design of new powerful separation systems, technologies, and materials. Cyclodextrins (CDs) are mainly discussed as chiral selectors not only because the author has a long-term experience of working with these multifunctional macrocycles but also because CDs belong to the most widely used chiral selectors in EKC. In addition, these materials are quite well-characterized molecules of medium size. In addition, CDs are used for separation of enantiomers almost in all analytical separation techniques, as well as for determination of the enantiomeric excess in nonseparation techniques such as nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry. This chapter does not address applications of chiral EKC in chemistry, pharmaceutical and biomedical, environmental, and food analyses.

  13. Measurement of Chiral Recognition Properties of Crown Ethers Using Matrix Assisted Laser Desorption Ionization Mass Spectrometry

    OpenAIRE

    SAWADA, Masami; Harada, Manabu; TAKAI, Yoshio; NAKANO, Kazurou; Kuroda, Masao; ARAKAWA, Ryuichi; 荒川, 隆一

    2000-01-01

    Hydrogen bonding host-guest complex ions between chiral crown ethers and chiral amino acid ester salts, detected by matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS) with a DHBA or MSA matrix, were studied on the view point of chiral recognition properties of the chiral crown hosts. The chiral recognition property (IR/IS-dn value≅1.0) obtained by the present MALDI-MS is sharply different from the IR/IS-dn value obtained by FAB-MS or ESI-MS (≠1.0) in the same host-gues...

  14. Synthesis of novel glucose-based polymers and their applications as chiral stationary phases for high performance liquid chromatography

    Institute of Scientific and Technical Information of China (English)

    Tomoyuki IKAI; Takayuki YAMADA

    2016-01-01

    Two novel polymers containing glucose units as the main-chain that only differ in terms of their regioregularity were synthesized to evaluate their chiral recognition abilities as chiral stationary phases( CSPs) for high performance liquid chromatography( HPLC). The regioregular polymer( poly-5)shows clear resolution ability for the racemate of cobalt(Ⅲ)acetylacetonate( Co( acac)3 ),whereas the corresponding regioirregular polymer(poly-3)does not show any chiral recognition for Co(acac)3. The regioregular polymer main-chain seems to play an important role not only in providing an efficient interaction with the racemate but also in expressing the chiral recognition ability as a CSP for HPLC.

  15. 环境分析中的手性识别方法展望%Outlook of Chiral Recognition Method in Environmental Analysis

    Institute of Scientific and Technical Information of China (English)

    赵艳梅; 吴环; 杨季冬

    2015-01-01

    环境中广泛存在着众多的天然和人工合成的手性对映体,手性对映体主导着自然界的奇妙和生命的奥秘.在环境分析中需要探索手性对映体污染物的作用和变迁,自然环境中的手性环境能自然开启手性识别和激活手性,而人为介入的手性识别需要高灵敏度和高选择性相结合的分析手段.许多高灵敏度且简便易行的光谱分析方法,借助有机染料、纳米粒子或量子点等手性选择性试剂,或合成设计某些光散射探针试剂可形成高效的选择性手段.筛查手性选择性试剂或手性光散射探针试剂与荧光、散射相结合的手性识别则是一项创新工作.发展不经分离而同时测定手性污染物的新分析方法是一项有意义的探索.%Chiral enantiomers dominate the wonders of nature and the mysteries of life. Numerous natural and synthetic chiral enantiomers exist widely in the environment, which plays a magnificent variety of roles. Chiral recognition and analysis are used to measure, characterize and explore the functions and changes of the chiral enantiomers in environmental analysis. In Natural environment, chiral environment can naturally launch into chiral recognition and chiral activation, while chiral recognition in human intervention requires the analytical tools to combine high sensitivity with high selectivity. Many spectral analysis methods with high sensitivity and simplicity draw support from chiral selective reagents such as organic dyes, nanoparticles, quantum dots, or synthesize and design certain light scattering probe reagents to form high effective and selective means. Chiral recognition of screening combines chiral selective reagents or chiral light scattering probe reagents with fluorescence, and scattering is an innovative work. It is a valuable exploration to develop molecular spectroscopy analysis methods of chiral recognition as the leading of chiral selective reagents or chiral light scattering

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

    Science.gov (United States)

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

    2017-01-26

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

  17. The role of central ion in chiral recognition by taking phenylalanine as an example

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Chiral recognition of phenylalanine(Phe) was achieved in the gas phase by electrospray ionization Q-TOF tandem mass spectrometry.In this method,two central ions,i.e.proton and divalent copper,were used and chiral crown ether,(+)-2,3,11,12-tetracarboxylic acid-18-crown-6(18-C-6-TCA),was used as a chiral host.Dimeric complexes were readily formed by electrospray ionization of a methanol/water(50/50,V/V) solution containing central ions,Phe and 18-C-6-TCA.The dimeric complex included proton-bound(18-C-6-TCA)(Phe)H+ and copper-bound deprotonated [Cu2+(18-C-6-TCA)(Phe)-H]+ ions were mass selected and then collided with Ar in the CID experiments.The chiral recognition capability of these complexes was evaluated using the relative abundance of daughter ion to parent ion.A higher degree of chiral recognition ability was observed with Cu2+ compared to that of H+.Different central ions exhibited distinctive dissociation pathways and unique chiral recognition characteristics.The chiral recognition mechanism was also discussed in detail with the help of the structure of copper-bound complex predicted by theoretical calculation.

  18. The role of central ion in chiral recognition by taking phenylalanine as an example

    Institute of Scientific and Technical Information of China (English)

    YU Qing; CAO Jie; LU Gang; WANG ZhiXiang

    2009-01-01

    Chiral recognition of phenylalanine(Phe)was achieved in the gas phase by electrospray ionization Q-TDF tandem mass spectrometry.In this method,two central ions,i.e.proton and divalent copper,were used and chiral crown ether,(+)-2,3,11,12-tetracarboxylic acid-18-crown-6(18-C-6-TCA),was used as a chiral host.Dimeric complexes were readily formed by electrospray ionization of a methanol/water(50/50,VIV)solution containing central ions,Phe and 18-C-6-TCA.The dimeric complex included proton-bound(18-C-6-TCA)(Phe)H+ and copper-bound deprotonated[Cu2+(18-C-6-TCA)(Phe)-H]+ ions were mass selected and then collided with Ar in the CID experiments.The chiral recognition capability of these complexes was evaluated using the relative abundance of daughter ion to parent ion.A higher degree of chiral recognition ability was observed with Cu2+ compared to that of H+.Different central ions exhibited distinctive dissociation pathways and unique chiral recognition characteristics.The chiral recognition mechanism was also discussed in detail with the help of the structure of copper-bound complex predicted by theoretical calculation.

  19. 信息动态%Preparation of Polysaccharide Derivatives-based Composite Chiral Stationary Phases and Their Chiral Recognition

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Two coated-type composite chiral stationary phases (CSPs) were prepared based on cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC) and amylose tris (3,5-dimethylphenylcarbamate)(ADMPC) by coating the corresponding derivatives onto 3-aminopropyl silica gel separately and then mixing or by coating the mixed derivatives onto silica gel. The CSPs containing only CDMPC or ADMPC were also prepared for comparison. The mixing method does not significantly influence the enantioselectivities. The composite CSPs generally show chiral recognition abilities intermediate between those of the two individual phases, while some racemates were poorer and at the same time one was better resolved on the composite CSPs.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-11-01

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

  1. Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds

    Directory of Open Access Journals (Sweden)

    Márcio S. Silva

    2017-02-01

    Full Text Available Nuclear magnetic resonance (NMR is a powerful tool for the elucidation of chemical structure and chiral recognition. In the last decade, the number of probes, media, and experiments to analyze chiral environments has rapidly increased. The evaluation of chiral molecules and systems has become a routine task in almost all NMR laboratories, allowing for the determination of molecular connectivities and the construction of spatial relationships. Among the features that improve the chiral recognition abilities by NMR is the application of different nuclei. The simplicity of the multinuclear NMR spectra relative to 1H, the minimal influence of the experimental conditions, and the larger shift dispersion make these nuclei especially suitable for NMR analysis. Herein, the recent advances in multinuclear (19F, 31P, 13C, and 77Se NMR spectroscopy for chiral recognition of organic compounds are presented. The review describes new chiral derivatizing agents and chiral solvating agents used for stereodiscrimination and the assignment of the absolute configuration of small organic compounds.

  2. Metal-organic complex-functionalized protein nanopore sensor for aromatic amino acids chiral recognition.

    Science.gov (United States)

    Guo, Yanli; Niu, Aihua; Jian, Feifei; Wang, Ying; Yao, Fujun; Wei, Yongfeng; Tian, Lei; Kang, Xiaofeng

    2017-03-27

    Chiral recognition at single-molecule level for small active molecules is important, as exhibited by many nanostructures and molecular assemblies in biological systems, but it presents a significant challenge. We report a simple and rapid sensing strategy to discriminate all enantiomers of natural aromatic amino acids (AAA) using a metal-organic complex-functionalized protein nanopore, in which a chiral recognition element and a chiral recognition valve were equipped. A trifunctional molecule, heptakis-(6-deoxy-6-amino)-β-cyclodextrin (am7βCD), was non-covalently lodged within the nanopore of an α-hemolysin (αHL) mutant, (M113R)7-αHL. Copper(ii) ion reversibly bonds to the amino group of am7βCD to form an am7βCD-Cu(II) complex, which allowed chiral recognition for each enantiomer in the mixture of AAA by distinct current signals. The Cu(II) plugging valve plays a crucial rule that holds chiral molecules in the nanocavity for a sufficient registering time. Importantly, six enantiomers of all nature AAA could be simultaneously recognized at one time. Enantiomeric excess (ee) could also be accurately detected by this approach. It should be possible to generalize this approach for sensing of other chiral molecules.

  3. Chiral Recognition Mechanisms in Enantiomers Separations: A General View

    Science.gov (United States)

    Berthod, Alain

    In 1858, Louis Pasteur, the first to accomplish the separation of two enantiomers wrote: “Most natural organic products, the essential products of life, are asymmetric and possess such asymmetry that they are not superimposable on their image. This establishes perhaps the only well-marked line of demarcation that can at present be drawn between the chemistry of dead matter and the chemistry of living matter.” Enantiomers have exactly the same properties in isotropic conditions. They behave differently only in anisotropic conditions. Chiral-chiral interactions are needed for enantiomeric separations. The fundamental mechanisms for chiral separations are listed along with the commercially available chiral selectors. Two chemometric examples are commented: one on quantitative structure enantioselectivity relationship and the second one on linear solvation energy relationships. It is shown that the solvents used in the mobile phase may play the most critical role in the chiral mechanism.

  4. Preparation of Two New Diasteromeric Chiral Stationary Phases Based on (+-(18-Crown-6-2,3,11,12-tetracarboxylic Acid and (R- or (S-1-(1-Naphthylethylamine and Chiral Tethering Group Effect on the Chiral Recognition

    Directory of Open Access Journals (Sweden)

    Rajalingam Agneeswari

    2016-08-01

    Full Text Available Two new diastereomeric chiral stationary phases (CSPs based on (+-(18-crown-6-2,3,11,12-tetracarboxylic acid as a chiral tethering group and a Π-basic chiral unit such as (R-1-(1-naphthylethylamine (CSP 1 or (S-1-(1-naphthylethylamine (CSP 2 were prepared. The two CSPs were applied to the enantiomeric separation of N-(3,5-dinitrobenzoyl-1-phenylalkylamines and N-(3,5-dinitrobenzoyl-α-amino acid derivatives using 20% isopropyl alcohol in hexane as a normal mobile phase. To elucidate the effect of the two chiral units on the chiral recognition, the chiral recognition abilities of the two CSPs were compared with each other and with that of a CSP (CSP 3 based on (R-1-(1-naphthylethylamine. From the chromatographic chiral recognition results, (R-1-(1-naphthylethylamine and (+−(18-crown-6-2,3,11,12-tetracarboxylic acid constituting CSP 1 were concluded to show a cooperative (“matched” effect on the chiral recognition while (S-1-(1-naphthylethylamine and (+-(18-crown-6-2,3,11,12-tetracarboxylic acid constituting CSP 2 were concluded to show an uncooperative (“mismatched” effect on the chiral recognition. From these results, it was concluded that (+-(18-crown-6-2,3,11,12-tetracarboxylic acid can be successfully used as a chiral tethering group for the preparation of new CSPs.

  5. Preparation of Two New Diasteromeric Chiral Stationary Phases Based on (+)-(18-Crown-6)-2,3,11,12-tetracarboxylic Acid and (R)- or (S)-1-(1-Naphthyl)ethylamine and Chiral Tethering Group Effect on the Chiral Recognition.

    Science.gov (United States)

    Agneeswari, Rajalingam; Sung, Ji Yeong; Jo, Eun Sol; Jeon, Hee Young; Tamilavan, Vellaiappillai; Hyun, Myung Ho

    2016-08-12

    Two new diastereomeric chiral stationary phases (CSPs) based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid as a chiral tethering group and a Π-basic chiral unit such as (R)-1-(1-naphthyl)ethylamine (CSP 1) or (S)-1-(1-naphthyl)ethylamine (CSP 2) were prepared. The two CSPs were applied to the enantiomeric separation of N-(3,5-dinitrobenzoyl)-1-phenylalkylamines and N-(3,5-dinitrobenzoyl)-α-amino acid derivatives using 20% isopropyl alcohol in hexane as a normal mobile phase. To elucidate the effect of the two chiral units on the chiral recognition, the chiral recognition abilities of the two CSPs were compared with each other and with that of a CSP (CSP 3) based on (R)-1-(1-naphthyl)ethylamine. From the chromatographic chiral recognition results, (R)-1-(1-naphthyl)ethylamine and (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid constituting CSP 1 were concluded to show a cooperative ("matched") effect on the chiral recognition while (S)-1-(1-naphthyl)ethylamine and (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid constituting CSP 2 were concluded to show an uncooperative ("mismatched") effect on the chiral recognition. From these results, it was concluded that (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid can be successfully used as a chiral tethering group for the preparation of new CSPs.

  6. Chiral Recognition of Amino Acids by Magnetoelectrodeposited Cu Film Electrodes

    Directory of Open Access Journals (Sweden)

    Iwao Mogi

    2011-01-01

    Full Text Available Chiral behavior of magnetoelectrodeposited (MED Cu film electrodes was investigated for the electrochemical reactions of amino acids. The Cu films were electrodeposited under a magnetic field of 5 T perpendicular to the electrode surface. Such MED Cu films were employed as an electrode, and cyclic voltammograms were measured for the electrochemical reactions of several kinds of amino acids. Chiral behavior was clearly observed as oxidation current difference between the enantiomers of alanine, aspartic acid, and glutamic acid. The MED film electrodes with the thickness of 50~500 nm exhibited such chiral behavior, and their surface morphologies had network structures, which could be induced by the micro-MHD effect.

  7. Dissipative vibrational model for chiral recognition in olfaction

    Science.gov (United States)

    Tirandaz, Arash; Taher Ghahramani, Farhad; Shafiee, Afshin

    2015-09-01

    We examine the olfactory discrimination of left- and right-handed enantiomers of chiral odorants based on the odorant-mediated electron transport from a donor to an acceptor of the olfactory receptors embodied in a biological environment. The chiral odorant is effectively described by an asymmetric double-well potential whose minima are associated to the left- and right-handed enantiomers. The introduced asymmetry is considered an overall measure of chiral interactions. The biological environment is conveniently modeled as a bath of harmonic oscillators. The resulting spin-boson model is adapted by a polaron transformation to derive the corresponding Born-Markov master equation with which we obtain the elastic and inelastic electron tunneling rates. We show that the inelastic tunneling through left- and right-handed enantiomers occurs with different rates. The discrimination mechanism depends on the ratio of tunneling frequency to localization frequency.

  8. Molecular Recognition of Biomolecules by Chiral CdSe Quantum Dots

    Science.gov (United States)

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

    2016-04-01

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

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

    Institute of Scientific and Technical Information of China (English)

    刘涛; 阮文娟; 南晶; 朱志昂

    2003-01-01

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

  10. Metal complexes of chiral pentaazacrowns as conformational templates for β-turn recognition

    Science.gov (United States)

    Reaka, Andrea J. H.; Ho, Chris M. W.; Marshall, Garland R.

    2002-08-01

    Examples of reverse turns as recognition motifs in biological systems can be found in high-resolution crystal structures of antibody-peptide complexes. Development of peptidomimetics is often based on replacing the amide backbone of peptides by sugar rings, steroids, benzodiazepines, or other hetero- and carbocycles. In this approach, the chemical scaffold of the peptide backbone can be replaced while retaining activity as long as the pharmacophoric groups of the peptide side chains stay in relatively the same place; in other words, similar functional groups must overlap in space for interaction with critical receptor sites. This study evaluates the potential of metal complexes of chiral pentaazacrowns (PAC) derived by reduction of cyclic pentapeptides as β-turn mimetics. Due to the limited flexibility of the pendant chiral side groups in these metal complexes, one can potentially elicit information about the receptor-bound conformation from their binding affinities. 11 PAC crystal structures with different substitution patterns complexed with 3 different metals (Mn, Fe, Cd) as a prototypical database of potential side-chain orientations. Complexation with different metals induces subtle differences in the conformations of a particular azacrown scaffold. The lack of parameterization of transition metals for force field calculations precludes a thorough theoretical study. Thus, this study utilizes a simple geometrical comparison between the experimental data for crystalline PAC complexes and the side-chain orientations seen in classic β-turns. The FOUNDATION program was used to overlap the Cα-Cβ vectors of the corresponding ideal β-turn side-chains to all possible leaving groups of the PAC complexes. When comparing the relative orientations of the chiral side chains, a strong overlap of the bonds (between about 0.1 Å to about 0.5 Å RMS for 3 residues and up to about 1 Å RMS for 4 residues) was observed for many of the molecules. Such metal complexes may lack

  11. Metal complexes of chiral pentaazacrowns as conformational templates for beta-turn recognition.

    Science.gov (United States)

    Reaka, Andrea J H; Ho, Chris M W; Marshall, Garland R

    2002-01-01

    Examples of reverse turns as recognition motifs in biological systems can be found in high-resolution crystal structures of antibody-peptide complexes. Development of peptidomimetics is often based on replacing the amide backbone of peptides by sugar rings, steroids, benzodiazepines, or other hetero- and carbocycles. In this approach, the chemical scaffold of the peptide backbone can be replaced while retaining activity as long as the pharmacophoric groups of the peptide side chains stay in relatively the same place; in other words, similar functional groups must overlap in space for interaction with critical receptor sites. This study evaluates the potential of metal complexes of chiral pentaazacrowns (PAC) derived by reduction of cyclic pentapeptides as beta-turn mimetics. Due to the limited flexibility of the pendant chiral side groups in these metal complexes, one can potentially elicit information about the receptor-bound conformation from their binding affinities. 11 PAC crystal structures with different substitution patterns complexed with 3 different metals (Mn, Fe, Cd) as a prototypical database of potential side-chain orientations. Complexation with different metals induces subtle differences in the conformations of a particular azacrown scaffold. The lack of parameterization of transition metals for force field calculations precludes a thorough theoretical study. Thus, this study utilizes a simple geometrical comparison between the experimental data for crystalline PAC complexes and the side-chain orientations seen in classic beta-turns. The FOUNDATION program was used to overlap the Calpha-Cbeta vectors of the corresponding ideal beta-turn side-chains to all possible leaving groups of the PAC complexes. When comparing the relative orientations of the chiral side chains, a strong overlap of the bonds (between about 0.1 A to about 0.5 A RMS for 3 residues and up to about 1 A RMS for 4 residues) was observed for many of the molecules. Such metal complexes

  12. A universal strategy for visual chiral recognition of α-amino acids with L-tartaric acid-capped gold nanoparticles as colorimetric probes.

    Science.gov (United States)

    Song, Guoxin; Zhou, Fulin; Xu, Chunli; Li, Baoxin

    2016-02-21

    The ability to recognize and quantify the chirality of alpha-amino acids constitutes the basis of many critical areas for specific targeting in drug development and metabolite probing. It is still challenging to conveniently distinguish the enantiomer of amino acids largely due to the lack of a universal and simple strategy. In this work, we report a strategy for the visual recognition of α-amino acids. It is based on the chirality of L-tartaric acid-capped gold nanoparticles (L-TA-capped AuNPs, ca. 13 nm in diameter). All of 19 right-handed α-amino acids can induce a red-to-blue color change of L-TA-capped AuNP solution, whereas all of the left-handed amino acids (except cysteine) cannot. The chiral recognition can be achieved by the naked eye and a simple spectrophotometer. This method does not require complicated chiral modification, and excels through its low-cost, good availability of materials and its simplicity. Another notable feature of this method is its high generality, and this method can discriminate almost all native α-amino acid enantiomers. This versatile method could be potentially used for high-throughput chiral recognition of amino acids.

  13. Chiral Recognition for the Two Enantiomers of Phenylalanine and Four Amino Acid Derivatives with (S)-Phenylethylamine Derived Nickel(II) Macrocyclic Complex

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jeong Jae; Ryoo, Jae Jeong [Kyungpook National Univ., Daegu (Korea, Republic of)

    2013-11-15

    The potency of new chiral selector candidate was assessed by this simple chiral discrimination test. This experiment showed that the macrocyclic molecule can be a powerful candidate as a chiral selector to obtain optically pure amino acid or amino acid derivatives, particularly phenylalanine and N-benzoyl-phenylalanine enantiomers from racemic mixtures. This study attempted to use the chiral metal organic framework (MOF), 1, as a good chiral selector candidate for the chiral discrimination of racemic phenylalanine, N-benzoyl-alanine, N-benzoyl-phenylalanine, N-benzoyl-methionine, N-CBZ-alanine. The chiral recognition ability of the chiral macromolecule, was examined by varying the molar ratio of the macromolecule and racemates.

  14. Chirality as a tool in nucleic acid recognition: principles and relevance in biotechnology and in medicinal chemistry.

    Science.gov (United States)

    Corradini, Roberto; Sforza, Stefano; Tedeschi, Tullia; Marchelli, Rosangela

    2007-05-05

    The understanding of the interaction of chiral species with DNA or RNA is very important for the development of new tools in biology and of new drugs. Several cases in which chirality is a crucial point in determining the DNA binding mode are reviewed and discussed, with the aim of illustrating how chirality can be considered as a tool for improving the understanding of mechanisms and the effectiveness of nucleic acid recognition. The review is divided into two parts: the former describes examples of chiral species interacting with DNA: intercalators, metal complexes, and groove binders; the latter part is dedicated to chirality in DNA analogs, with discussion of phosphate stereochemistry and chirality of ribose substitutes, in particular of peptide nucleic acids (PNAs) for which a number of works have been published recently dealing with the effect of chirality in DNA recognition. The discussion is intended to show how enantiomeric recognition originates at the molecular level, by exploiting the enormous progresses recently achieved in the field of structural characterization of complexes formed by nucleic acid with their ligands by crystallographic and spectroscopic methods. Examples of application of the DNA binding molecules described and the role of chirality in DNA recognition relevant for biotechnology or medicinal chemistry are reported.

  15. Enantioselective Recognition of Chiral Carboxylic Acids by a β-Amino Acid and 1,10-Phenanthroline Based Chiral Fluorescent Sensor.

    Science.gov (United States)

    Zhang, Yonghong; Hu, Fangzhi; Wang, Bin; Zhang, Xiaomei; Liu, Chenjiang

    2015-05-06

    A novel chiral 1,10-phenanthroline-based fluorescent sensor was designed and synthesized from optical active β-amino acids. It used 1,10-phenanthroline moiety as a fluorescent signaling site and binding site, with optically active β-amino acids as a chiral barrier site. Notably, the optically active β-amino acids were obtained by a Lewis base catalyzed hydrosilylation of β-enamino esters according to our former work. The chiral sensor has been used to conduct the enantioselective recognition of chiral mono and dicarboxylic acids derivatives. Using this fluorescent sensor, a moderate "turn-off" fluorescence-diminishment response towards enantiomer of tartaric acids, and proline was observed. It found that l-enantiomers quench the chiral fluorescence sensor more efficiently than d-enantiomers due to the absolute configuration of the β-amino acid.

  16. Enantioselective Recognition of Chiral Carboxylic Acids by a β-Amino Acid and 1,10-Phenanthroline Based Chiral Fluorescent Sensor

    Directory of Open Access Journals (Sweden)

    Yonghong Zhang

    2015-05-01

    Full Text Available A novel chiral 1,10-phenanthroline-based fluorescent sensor was designed and synthesized from optical active β-amino acids. It used 1,10-phenanthroline moiety as a fluorescent signaling site and binding site, with optically active β-amino acids as a chiral barrier site. Notably, the optically active β-amino acids were obtained by a Lewis base catalyzed hydrosilylation of β-enamino esters according to our former work. The chiral sensor has been used to conduct the enantioselective recognition of chiral mono and dicarboxylic acids derivatives. Using this fluorescent sensor, a moderate “turn-off” fluorescence-diminishment response towards enantiomer of tartaric acids, and proline was observed. It found that l-enantiomers quench the chiral fluorescence sensor more efficiently than d-enantiomers due to the absolute configuration of the β-amino acid.

  17. Direct Measurement of the Thermodynamics of Chiral Recognition in Bile Salt Micelles.

    Science.gov (United States)

    Anderson, Shauna L; Rovnyak, David; Strein, Timothy G

    2016-04-01

    Isothermal titration calorimetry (ITC) is shown to be a sensitive reporter of bile salt micellization and chiral recognition. Detailed ITC characterization of bile micelle formation as well as the chiral recognition capabilities of sodium cholate (NaC), deoxycholate (NaDC), and taurodeoxycholate (NaTDC) micelle systems are reported. The ΔH(demic) of these bile salt micelle systems is directly observable and is strongly temperature-dependent, allowing also for the determination of ΔCp(demic). Using the pseudo-phase separation model, ΔG(demic) and TΔS(demic) were also calculated. Chirally selective guest-host binding of model racemic compounds 1,1'-bi-2-napthol (BN) and 1,1'-binaphthyl-2,2'-diylhydrogenphosphate (BNDHP) to bile salt micelles was then investigated. The S-isomer was shown to bind more tightly to the bile salt micelles in all cases. A model was developed that allows for the quantitative determination of the enthalpic difference in binding affinity that corresponds to chiral selectivity, which is on the order of 1 kJ mol(-1).

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

    Energy Technology Data Exchange (ETDEWEB)

    Lu Yan; Li Chenxi; Zhang Hesheng; Liu Xiaohang

    2003-08-11

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

  19. Recognition behavior of chiral nanocomposites toward biomolecules and its application in electrochemical immunoassay

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The novel nanocomposites were obtained by covalently linking arginine enantiomers with the sidewall of multi-walled carbon nanotubes,and utilized as sensing materials for biomolecular recognition in electrochemical immunoassay.They were characterized by X-ray photoelectron spectroscopy (XPS),transmission electron microscopy (TEM) and circular dichroism spectroscopy (CD).Nano-gold and Prussian Blue were employed to amplify the analytical signal responses.Prostate specific antibody/antigen and carcinoembryonic antibody/antigen were used as model systems.The results showed that the different configurations of nanocomposites could readily facilitate chiral recognition of antibodies,and D-nanocomposites displayed a larger signal.

  20. Chiral Fluorescent Receptors Based on (R)-1,1'-Binaphthylene-2,2'-bisthiourea: Synthesis and Chiral Recognition

    Institute of Scientific and Technical Information of China (English)

    隗兰华; 何永炳; 徐括喜; 刘顺英; 孟令芝

    2005-01-01

    Two chiral fluorescent receptors 1 and 2 based on (R)-1,1'-binaphthylene-2,2'-bisthiourea were synthesized, and their chiral recognition properties for enantiomeric mandelate anions were studied by fluorescence spectra and molecular modeling. Addition of the L- and D-mandelate anions caused considerable fluorescent increases in the fluorescent intensity of the host solution. The L-enantiomer can enhance the fluorescence intensity of 1 much more than the D-enantiomer can do, and 1 shows a better enantioselective recognition ability than 2.

  1. Resolution of α-cyclohexyl-mandelic acid enantiomers by two-phase (O/W) recognition chiral extraction

    Institute of Scientific and Technical Information of China (English)

    TANG; KeWen; ZHANG; GuoLi; HUANG; KeLong; LI; Yuanjian; YI; JianMin

    2007-01-01

    This paper presents a new chiral separation technology: two-phase (O/W) recognition chiral extraction. Distribution behavior of α-cyclohexyl-mandelic acid enantiomers was studied in the extraction system with D(L)-isobutyl tartrate in 1,2-dichloroethane organic phase and β-CD derivatives in aqueous phase, and the influence of the kind and concentration of extractant and pH on extraction performance was investigated. The experimental results indicate that two-phase (O/W) recognition chiral extraction is of strong chiral separation ability. HP-β-CD, HE-β-CD and Me-β-CD have higher recognition ability for S-CHMA than that for R-CHMA, among which HP-β-CD has the strongest ability; whereas, D-isobutyl tartrate has reversed recognition ability for them. In the extraction system containing HP-β-CD and D-isobutyl tartrate, e.e.% of S-CHMA in aqueous phase reached 27.6% by one stage extraction, and the distribution ratio for R-CHMA(kR) and for S-CHMA(kS) and separation factor (α) are 2.44, 0.89 and 2.49, respectively. Meanwhile, pH and concentration of extractant have great effects on chiral separation ability. Two-phase (O/W) recognition chiral extraction has great significance for preparative separation of racemic compounds.

  2. Synthesis and anion recognition properties of shape-persistent binaphthyl-containing chiral macrocyclic amides

    Directory of Open Access Journals (Sweden)

    Marco Caricato

    2012-06-01

    Full Text Available We report on the synthesis and characterization of novel shape-persistent, optically active arylamide macrocycles, which can be obtained using a one-pot methodology. Resolved, axially chiral binol scaffolds, which incorporate either methoxy or acetoxy functionalities in the 2,2' positions and carboxylic functionalities in the external 3,3' positions, were used as the source of chirality. Two of these binaphthyls are joined through amidation reactions using rigid diaryl amines of differing shapes, to give homochiral tetraamidic macrocycles. The recognition properties of these supramolecular receptors have been analyzed, and the results indicate a modulation of binding affinities towards dicarboxylate anions, with a drastic change of binding mode depending on the steric and electronic features of the functional groups in the 2,2' positions.

  3. Chiral stationary phases based on chitosan bis(methylphenylcarbamate)-(isobutyrylamide) for high-performance liquid chromatography.

    Science.gov (United States)

    Tang, Sheng; Bin, Qin; Chen, Wei; Bai, Zheng-Wu; Huang, Shao-Hua

    2016-04-01

    A series of chitosan bis(methylphenylcarbamate)-(isobutyrylamide) derivatives were synthesized by carbamylating chitosan isobutyrylamide with different methylphenyl isocyanates. Then the prepared chitosan derivatives were coated onto 3-aminopropyl silica particles, resulting in a series of new chiral stationary phases (CSPs) for high-performance liquid chromatography. It was observed that the chiral recognition abilities of these coated-type CSPs depended very much on the substituents on the phenyl moieties of the chitosan derivatives, the eluent composition, as well as the structure of racemates. As a typical example, the eluent tolerance of the prepared CSP with the best enantioseparation ability was investigated in detail, and the results revealed that the CSP exhibited extraordinary solvent tolerance and could still work without significant loss in enantioseparation capability after being flushed with chloroform (100%), ethyl acetate (100%) and even THF/n-hexane (70/30, v/v), while the traditional coated-type CSPs based on the cellulose and amylose derivatives, such as cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC) and amylose tris(3,5-dimethylphenylcarbamate) (ADMPC), might be dissolved or highly swollen in these eluents. Therefore, the application of the resultant CSPs could address the problem of the dissolution and high swelling of traditional coated-type CSPs in some unusual eluents, broadening the possibility of eluent choice. In addition, a comparison of the prepared CSPs with the well known CDMPC- and ADMPC- based CSPs concerning the chiral recognition ability was also made. Separation performances achieved on the as-prepared CSPs in different eluents were found to be even superior to CDMPC- and ADMPC-based CSPs for the tested chiral compounds. In summary, we could safely draw the conclusion that the CSPs derived from chitosan isobutyrylamide derivatives were capable of excellent chiral recognition ability, and meanwhile possessed satisfactory

  4. Separation of basic drug enantiomers by capillary electrophoresis using chicken alpha1-acid glycoprotein: insight into chiral recognition mechanism.

    Science.gov (United States)

    Matsunaga, Hisami; Sadakane, Yutaka; Haginaka, Jun

    2003-08-01

    Recombinant chicken alpha(1)-acid glycoprotein (alpha(1)-AGP) was prepared by the Escherichia coli expression system and completely deglycosylated alpha(1)-AGP (cd-alpha(1)-AGP) was obtained by treatments of native alpha(1)-AGP with a mixture of endoglycosidase and N-glycosidase. The average molecular masses of chicken alpha(1)-AGP, cd-alpha(1)-AGP and recombinant alpha(1)-AGP were estimated to be about 29 200, 21 700 and 20 700, respectively, by matrix-assisted laser desorption-time of flight-mass spectrometry. We compared the chiral recognition ability of chicken alpha(1)-AGP, cd-alpha(1)-AGP and recombinant alpha(1)-AGP using them as chiral selectors in capillary electrophoresis. The chicken alpha(1)-AGP showed higher resolution for eperisone, pindolol and tolperisone than cd-alpha(1)-AGP or recombinant alpha(1)-AGP. Recombinant alpha(1)-AGP still showed chiral recognition for three basic drugs tested. By addition of propranolol as a competitor in the separation solution in CE, no enantioseparations of three basic drugs were observed with chicken alpha(1)-AGP, cd-alpha(1)-AGP or recombinant alpha(1)-AGP. These results reveal that the protein domain of the chicken alpha(1)-AGP is responsible for the chiral recognition ability, and that the chiral recognition site(s) for basic drugs exists on the protein domain.

  5. Using chiral molecules as an approach to address low-druggability recognition sites.

    Science.gov (United States)

    Lucas, Xavier; Günther, Stefan

    2014-11-05

    The content of chiral carbon atoms or structural complexity, which is known to correlate well with relevant physicochemical properties of small molecules, represents a promising descriptor that could fill the gap in existing drug discovery between ligand library filtering rules and the corresponding properties of the target's recognition site. Herein, we present an in silico study on the yet unclear underlying correlations between molecular complexity and other more sophisticated physicochemical and biological properties. By analyzing thousands of protein-ligand complexes from DrugBank, we show that increasing molecular complexity of drugs is an approach to addressing particularly low-druggability and polar recognition sites. We also show that biologically relevant protein classes characteristically bind molecules with a certain degree of structural complexity. Three distinct behaviors toward drug recognition are described. The reported results set the basis for a better understanding of protein-drug recognition, and open the possibility of including target information in the filtering of large ligand libraries for screening.

  6. Self-Assembled Core-Satellite Gold Nanoparticle Networks for Ultrasensitive Detection of Chiral Molecules by Recognition Tunneling Current.

    Science.gov (United States)

    Zhang, Yuanchao; Liu, Jingquan; Li, Da; Dai, Xing; Yan, Fuhua; Conlan, Xavier A; Zhou, Ruhong; Barrow, Colin J; He, Jin; Wang, Xin; Yang, Wenrong

    2016-05-24

    Chirality sensing is a very challenging task. Here, we report a method for ultrasensitive detection of chiral molecule l/d-carnitine based on changes in the recognition tunneling current across self-assembled core-satellite gold nanoparticle (GNP) networks. The recognition tunneling technique has been demonstrated to work at the single molecule level where the binding between the reader molecules and the analytes in a nanojunction. This process was observed to generate a unique and sensitive change in tunneling current, which can be used to identify the analytes of interest. The molecular recognition mechanism between amino acid l-cysteine and l/d-carnitine has been studied with the aid of SERS. The different binding strength between homo- or heterochiral pairs can be effectively probed by the copper ion replacement fracture. The device resistance was measured before and after the sequential exposures to l/d-carnitine and copper ions. The normalized resistance change was found to be extremely sensitive to the chirality of carnitine molecule. The results suggested that a GNP networks device optimized for recognition tunneling was successfully built and that such a device can be used for ultrasensitive detection of chiral molecules.

  7. Temperature-Triggered Switchable Helix-Helix Inversion of Poly(phenylacetylene Bearing l-Valine Ethyl Ester Pendants and Its Chiral Recognition Ability

    Directory of Open Access Journals (Sweden)

    Yanli Zhou

    2016-11-01

    Full Text Available A phenylacetylene containing the l-valine ethyl ester pendant (PAA-Val was synthesized and polymerized by an organorhodium catalyst (Rh(nbdBPh4 to produce the corresponding one-handed helical cis-poly(phenylacetylene (PPAA-Val. PPAA-Val showed a unique temperature-triggered switchable helix-sense in chloroform, while it was not observed in highly polar solvents, such as N,N′-dimethylformamide (DMF. By heating the solution of PPAA-Val in chloroform, the sign of the CD absorption became reversed, but recovered after cooling the solution to room temperature. Even after six cycles of the heating-cooling treatment, the helix sense of the PPAA-Val’s backbone was still switchable without loss of the CD intensity. The PPAA-Val was then coated on silica gel particles to produce novel chiral stationary phases (CSPs for high-performance liquid chromatography (HPLC. These novel PPAA-Val based CSPs showed a high chiral recognition ability for racemic mandelonitrile (α = 2.18 and racemic trans-N,N′-diphenylcyclohexane-1,2-dicarboxamide (α = 2.60. Additionally, the one-handed helical cis-polyene backbone of PPAA-Val was irreversibly destroyed to afford PPAA-Val-H by heating in dimethyl sulfoxide (DMSO accompanied by the complete disappearance of the Cotton effect. Although PPAA-Val-H had the same l-valine ethyl ester pendants as its cis-isomer PPAA-Val, it showed no chiral recognition. It was concluded that the one-handed helical cis-polyene backbone of PPAA-Val plays an important role in the chiral recognition ability.

  8. Biomimetic Taste Receptors with Chiral Recognition by Photoluminescent Metal-Organic Frameworks Chelated with Polyaniline Helices.

    Science.gov (United States)

    Lee, Tu; Lin, Tsung Yan; Lee, Hung Lin; Chang, Yun Hsuan; Tsai, Yee Chen

    2016-01-22

    The adsorption of phenylaniline (Phe) enantiomers on (+)-polyaniline (PAN)-chelated [In(OH)(bdc)]n microcrystals was carefully designed and studied by using the Job titration, circular dichroism, X-ray photoelectron spectroscopy, and photoluminescence to mimic heterotrimeric guanine nucleotide-binding protein (G protein)-coupled receptors in selective, but not specific, ligand binding with chiral recognition and signal transduction. Six essential working principles across different length scales are unraveled: 1) a chiral (+)-PAN (host), 2) specific sites for Phe-(+)/PAN (guest-host) binding, 3) a conformational change of (+)-PAN after binding with Phe enantiomers, 4) different degrees of packing for (+)-PAN, 5) interactions between (+)-PAN and the underlying signal-generating framework (i.e., [In(OH)(bdc)]n microcrystals), and 6) a systematic photoluminescent signal combination by using principal-component analysis from the other three polymer-chelated metal-organic frameworkds (MOFs), such as poly(acrylic acid) (PAA), sodium alginate (SA), and polyvinylpyrrolidone (PVP) to enhance the selectivity and discrimination capabilities.

  9. Highly enantioselective asymmetric autocatalysis using chiral ruthenium complex-ion-exchanged synthetic hectorite as a chiral initiator.

    Science.gov (United States)

    Kawasaki, Tsuneomi; Omine, Toshiki; Suzuki, Kenta; Sato, Hisako; Yamagishi, Akihiko; Soai, Kenso

    2009-03-21

    The synthetic hectorite containing intercalated chiral Delta- and Lambda-tris(1,10-phenanthroline)ruthenium(II) ions acts as a heterogeneous chiral catalyst in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde to afford, in combination with asymmetric autocatalytic amplification of enantiomeric excess, 5-pyrimidyl alkanol with high enantiomeric excess.

  10. Highly selective separation of enantiomers using a chiral porous organic cage.

    Science.gov (United States)

    Zhang, Jun-Hui; Xie, Sheng-Ming; Wang, Bang-Jin; He, Pin-Gang; Yuan, Li-Ming

    2015-12-24

    Porous solids composed of shape-persistent organic cage molecules have attracted considerable attention due to their important applications such as molecular separation, heterogeneous catalysis, and gas storage. In this study, an imine-linked porous organic cage (POC) CC10 diluted with a polysiloxane OV-1701 was explored as a novel stationary phase for high-resolution gas chromatography (GC). A wide variety of enantiomers belonging to different classes of organic compounds have been resolved on the coated capillary column, including chiral alcohols, esters, ketones, ethers, halohydrocarbons, epoxides, and organic acids. The fabricated column complements to commercial β-DEX 120 column and our recently reported CC3-R column for separating enantiomers, which indicates that the excellent chiral recognition ability of CC10 is not only interesting academically, but also has potential for practical application. In addition, CC10 also exhibits good selectivity for the separation of n-alkanes, n-alcohols, Grob mixture, and positional isomers. This work also indicates that this type of chiral POCs will become a new class of chiral selector in the near future. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Disoriented Chiral Condensates in High-Energy Nuclear Collisions

    Energy Technology Data Exchange (ETDEWEB)

    Randrup, Jorgen

    2000-10-18

    This brief lecture series discusses how our current understanding of chiral symmetry may be tested more globally in high-energy nuclear collisions by suitable extraction of pionic observables. After briefly recalling the general features of chiral symmetry, we focus on the SU(2) linear sigma model and show how a semi-classical mean-field treatment makes it possible to calculate its statistical properties, including the chiral phase diagram. Subsequently, we consider scenarios of relevance to high-energy collisions and discuss the features of the ensuing non-equilibrium dynamics and the associated characteristic signals. Finally, we illustrate how the presence of vacuum fluctuations or the inclusion of strangeness may affect the results quantitatively.

  12. Influence of Mobile Phase Composition on the Enantioseparation of Methoxyl Flavanones with Self-prepared CDMPC Column and Chiral Recognition Mechanism

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The influence of different alcohol modifiers in mobile phase on the chiral separation of 4`-methoxyl flavanone, 5-methoxyl flavanone and 6-methoxyl flavanone on cellulose tris (3, 5-dimethylphenylcarbamate) (CDMPC) column was studied and the chiral recognition mechanism was discussed. Using hexane-tert-butanol (1.31 mol L-1) as the mobile phase, those three methoxyl flavanones were excellently separated on CDMPC chiral column.

  13. Quantitative chiral analysis of amino acids in solution using enantiomer-selective photodissociation of cold gas-phase tryptophan via chiral recognition.

    Science.gov (United States)

    Fujihara, Akimasa; Maeda, Naoto

    2017-08-01

    To explore the origin of biomolecule homochirality in interstellar molecular clouds, enantiomer-selective photodissociation via chiral recognition between amino acids in the gas phase was examined using a tandem mass spectrometer containing an electrospray ionization source and a cold ion trap. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of sodiated l-tryptophan ion, Na(+)(l-Trp), with an amino acid such as serine (Ser), threonine (Thr), or alanine (Ala) were obtained by the photo-excitation of l-Trp in the noncovalent complexes. Dissociation of l-Trp via CO2 loss occurred when it was noncovalently complexed with d-Ser or d-Thr in the presence of Na(+). For the l-enantiomers, the energy absorbed by l-Trp was released through evaporation of l-Ser or l-Thr, and dissociation of the amino acids was suppressed. In contrast, the enantiomer-selective phenomenon was not observed in the noncovalent complex with Ala, suggesting that a side-chain OH group plays an important role in chiral recognition and enantiomer-selective photodissociation. The enantiomer-selective photodissociation was applied to the quantitative chiral analysis of amino acids. The enantiomeric excess of Ser and Thr in solution could be determined by measuring the relative abundance ratio of the enantiomer-selective photodissociation of Trp to amino acid evaporation in a single photodissociation mass spectrum obtained by photo-excitation of l-Trp used as a chiral probe in cold gas-phase noncovalent complexes with the analyte amino acids, and by referring to the linear relationships established in this work. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Chiral recognition of alanine across modified carbon electrodes with 3,4-dihydroxyphenylalanine

    Energy Technology Data Exchange (ETDEWEB)

    Bustos, E. [Electrochemistry Department, Centro de Investigacion y Desarrollo Tecnologico en Electroquimica S.C., P.O. Box 064, C.P. 76700 Pedro Escobedo, Queretaro (Mexico); Chemistry Department, Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional, P.O. Box 14-740, C.P. 07360 Mexico, D.F. (Mexico)], E-mail: ebustos@cideteq.mx; Godinez, Luis A. [Electrochemistry Department, Centro de Investigacion y Desarrollo Tecnologico en Electroquimica S.C., P.O. Box 064, C.P. 76700 Pedro Escobedo, Queretaro (Mexico); Rangel-Reyes, G.; Juaristi, E. [Chemistry Department, Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional, P.O. Box 14-740, C.P. 07360 Mexico, D.F. (Mexico)

    2009-11-01

    3,4-Dihydroxyphenylalanine (DOPA) was covalently grafted onto a glassy carbon electrode (GCE) by the formation of an amine cation radical in the electro-oxidation of the amino-containing compound. Cyclic voltammetric experiments proved that the DOPA was formed on the GCE as a monolayer. Its electron transfer over the GCE surface at different pH values was studied by cyclic voltammetry. Changes in solution pH resulted in the variation of the charge state of the terminal group and the surface pK{sub a} was estimated on the basis of these results. Because of electrostatic interactions between the negatively charged groups on the electrode surface and the alanine (Ala) in solution, the modified electrode was used as an enantioselective sensor. The peak current for D(+) or L(-)DOPA over the modified electrode decreased as a result of the chiral recognition across the blocking interaction with the respective enantiomer of L(-) or D(+)Ala. The recognition was verified with the protection of L(-)DOPA with a Fmoc group.

  15. 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.

  16. CHIRALITY OF HIGH-LATITUDE FILAMENTS OVER SOLAR CYCLE 23

    Energy Technology Data Exchange (ETDEWEB)

    Yeates, A. R. [Department of Mathematical Sciences, Durham University, Durham, DH1 3LE (United Kingdom); Mackay, D. H., E-mail: anthony.yeates@durham.ac.uk, E-mail: duncan@mcs.st-and.ac.uk [School of Mathematics and Statistics, University of St Andrews, St Andrews, KY16 9SS (United Kingdom)

    2012-07-10

    A non-potential quasi-static evolution model coupling the Sun's photospheric and coronal magnetic fields is applied to the problem of filament chirality at high latitudes. For the first time, we run a continuous 15 year simulation, using bipolar active regions determined from US National Solar Observatory, Kitt Peak magnetograms between 1996 and 2011. Using this simulation, we are able to address the outstanding question of whether magnetic helicity transport from active latitudes can overcome the effect of differential rotation at higher latitudes. Acting alone, differential rotation would produce high-latitude filaments with opposite chirality to the majority type in each hemisphere. We find that differential rotation can indeed lead to opposite chirality at high latitudes, but only for around 5 years of the solar cycle following the polar field reversal. At other times, including the rising phase, transport of magnetic helicity from lower latitudes overcomes the effect of in situ differential rotation, producing the majority chirality even on the polar crowns at polar field reversal. These simulation predictions will allow for future testing of the non-potential coronal model. The results indicate the importance of long-term memory and helicity transport from active latitudes when modeling the structure and topology of the coronal magnetic field at higher latitudes.

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

    Directory of Open Access Journals (Sweden)

    Yifeng Chai

    2012-01-01

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

  18. Chiral Ionic Liquids in Chromatographic Separation and Spectroscopic Discrimination

    Science.gov (United States)

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

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

  19. Chirality recognition in the glycidol···propylene oxide complex: a rotational spectroscopic study.

    Science.gov (United States)

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

    2011-04-11

    Chirality recognition in the hydrogen-bonded glycidol···propylene oxide complex has been studied by using rotational spectroscopy and ab initio calculations. An extensive conformational search has been performed for this binary adduct at the MP2/6-311++G(d,p) level of theory and a total of 28 homo- and heterochiral conformers were identified. The eight binary conformers, built of the two dominant glycidol monomeric conformers, g-G+ and g+G-, were predicted to be the most stable ones. Jet-cooled rotational spectra of six out of the eight conformers were observed and unambiguously assigned for the first time. The experimental stability ordering has been obtained and compared with the ab initio predictions. The relative stability of the two dominant glycidol monomeric conformers is reversed in some cases when binding to propylene oxide. The contributions of monomeric energy, deformation energy, and binary intermolecular interaction energy to the relative stability of the binary conformers are discussed.

  20. Enantiopure cyclic O-substituted phenylphosphonothioic acid: synthesis and chirality-recognition ability.

    Science.gov (United States)

    Ribeiro, Nigel; Kobayashi, Yuka; Maeda, Jin; Saigo, Kazuhiko

    2011-07-01

    As a new acidic selector (resolving agent), we synthesized an enantiopure O-alkyl phenylphosphonothioic acid with a seven-membered ring ((R)-5), which was designed on the basis of the results for the enantioseparation of 1-arylethylamine derivatives with acyclic O-ethyl phenylphosphonothioic acid (I). The phosphonothioic acid (R)-5 showed unique chirality-recognition ability in the enantioseparation of 1-naphthylethylamine derivatives, aliphatic secondary amines, and amino alcohols; the ability was complementary to that of I. The X-ray crystallographic analyses of the less- and more-soluble diastereomeric salts showed that hydrogen-bonding networks in the salt crystals are 2(1) -column-type with a single exception which is cluster-type. In the cases of the 2(1) -column-type crystals, stability of the crystals is firstly governed by hydrogen bonds to form a 2(1) -column and secondly determined by intra-columnar T-shaped CH/π interaction(s), intra-columnar hydrogen bond(s), inter-columnar van der Waals interaction and/or inter-columnar T-shaped CH/π interaction(s). In contrast, the cluster-type salt crystal is stabilized by the assistance of inter-cluster T-shaped CH/π and van der Waals interactions. To realize still more numbers of intra- and inter-columnar and -cluster T-shaped CH/π interactions, the seven-membered ring of (R)-5 plays a considerable role.

  1. 识别手性六螺烯分子的计算机模拟%Computer Simulation on Recognition of Chiral Hexahelicenes

    Institute of Scientific and Technical Information of China (English)

    孙凯; 李霆; 梁太宁; 杨小震

    2001-01-01

    Molecular interactions are the key to understanding the structure and properties of materials. Also, it is critical of chiral recognition. Since the molecular interactions at play in chiral discrimination is difficult to investigate under traditional experiment conditions. We have undertaken a computer experiment of van der Waals interaction between chiral molecules and a polymer, which works for chiral separation. Building molecular models, choosing proper force field and Monte Carlo method, we have calculated the difference of interaction energy between isotactic poly-(triphenylmethyl methacrylate) and (+)-hexahelicene or (-)-hexahelicene. It is finally found about 1.379 4 kJ/mol between the polymer and the two chiral hexahelicenes. Reasonably, this difference is regardd as the main reason which induced chiral separation. Furthermore, we compared the results from computer smulation with that from experiment. It can be seen that some details during chiral separation process, such as trailing effect, can also be predicted, and be consistent with the experiment results. Finally, the effective structureal characteristics of the recognition site are pointed out.

  2. Why Do Deconfinement and Chiral Restoration Coincide at High Temperature?

    Institute of Scientific and Technical Information of China (English)

    杨树; 郭华; 赵恩广; 吕晓夫

    2004-01-01

    The global colour model in free space is extended to finite temperature to study the deconfinement and chiral phase transitions at high temperature T and zero chemical potential in the mean field approximation. Both possibilities of coincidence and non-coincidence of the two distinct phase transitions are found when the model parameters are varied in a certain range. The underlying mechanisms of the coincidence and noncoincidence are analysed and discussed. The validity of the T-dependent model propagator as the input is also discussed.

  3. Development of chiral metal amides as highly reactive catalysts for asymmetric [3 + 2] cycloadditions

    Science.gov (United States)

    Yamashita, Yasuhiro; Yoshimoto, Susumu; Dutton, Mark J

    2016-01-01

    Summary Highly efficient catalytic asymmetric [3 + 2] cycloadditions using a chiral copper amide are reported. Compared with the chiral CuOTf/Et3N system, the CuHMDS system showed higher reactivity, and the desired reactions proceeded in high yields and high selectivities with catalyst loadings as low as 0.01 mol %. PMID:27559396

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

    Science.gov (United States)

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

    2011-08-21

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

  5. Chiral-phase high-performance liquid chromatography of rotenoid racemates

    Science.gov (United States)

    Abidi, S.L.

    1987-01-01

    The high-performance liquid chromatograhic (HPLC) behavior of parent rotenoids (type I) and the hydroxyl-analogues (type II) on three different chiral stationary phases (CSPs) was studied. Separations of optical isomers were achieved in various degrees depending largely upon the rotenoidal structures and the CSP types employed. Enantiomers of all but elliptone compounds were separable on β-cyclodextrin-bonded silica (CDS). Without exception, the 12a-hydroxyrotenoid antipodes were resolved on Pirkle's phenylglycine-bonded silica (PGS) despite unsuccessful attenmpts to resolve the type I rotenoidal racemates. Conversely, optical resolution of the latter rotenoids was accomplished by using a helical polytriphenylmethylacrylate-coated silica (TPS) column and the observed separation factors (α values) ranged from 1.14 to 1.90. The results from HPLC of type II rotenoids on TPS (α = 1.00–1.63) suggested that variations in E-ring structures had profound influence on the resolution outcome. Conjugated double bonds on the E-ring and the desisopropylation of the five-membered E-ring ot type II rotenoids appeared to be important structural features for chiral recognition involving the TPS substrate. In both reversed-phase (CDS) and normal-pahse (PGS and TPS) HPLC modes, the less polar enantiomers were the 6aβ,12aβ-rotenoids as observed in most cases, though this relationship was reversed in the cases of deguelin and hydroxyelliptone probably due to conformational effects of rotenoidal ring systems.

  6. Comparison of chiral recognition capabilities of cyclodextrins for the separation of basic drugs in capillary zone electrophoresis.

    Science.gov (United States)

    Jin, L J; Li, S F

    1998-04-24

    The enantiomeric separation of some racemic anti-histamines and anti-malarials, namely (+/-)-pheniramine, (+/-)-brompheniramine, (+/-)-chlorpheniramine, (+/-)-doxylamine, and (+/-)-chloroquine, was investigated by capillary zone electrophoresis. The enantiomeric separation of five compounds was obtained by addition of approximately 7 mM (1%, w/v) sulfated-beta-cyclodextrin into the buffer as a chiral selector. The effects of sulfated-beta-cyclodextrin concentration and buffer pH on migration and resolution are discussed. Two other cyclodextrins, carboxyethylated-beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin were also investigated. Four of the racemic compounds were resolved using 14 mM (2%, w/v) carboxyethylated-beta-cyclodextrin while 28 mM (4%, w/v) hydroxypropyl-beta-cyclodextrin resolved only two of them. It was found that the type of substituent and the degree of substitution on the rim of the CD structure played an important role in enhancing the chiral recognition. Cyclodextrins with negatively charged substituents and higher degree of substitution on the rim of the structure proved to give better resolution to the cationic racemic compounds compared with cyclodextrin with neutral substituents. This is due to the countercurrent mobility of the negatively charged cyclodextrin relative to the cationic analytes thus allowing for a smaller difference in interaction constants to achieve a successful resolution of enantiomers. Furthermore, lower concentrations of negatively charged cyclodextrins were necessary to achieve the equivalent resolutions as compared with the neutral ones.

  7. A pair of chiral fluorescent sensors for enantioselective recognition of mandelate in water

    Science.gov (United States)

    Xu, Kuo-xi; Kong, Hua-jie; Zu, Fu-li; Yang, Li; Wang, Chen-juan

    2014-01-01

    A pair of chiral compounds S-1 and R-1 derived from (1S, 2S) or (1R, 2R)-1, 2-diphenylethane-1, 2-diamine were designed and synthesized, the interactions of S-1 and R-1 with mandelate were studied in H2O (0.01 M HEPES buffer, pH = 7.4) by fluorescence titration experiments. The sensors S-1 and R-1 were found to present enantioselective fluorescent sensing ability to mandelate. The results indicated that the sensors S-1 and R-1 were very promising to be used as fluorescent sensors in determining the enantiomeric composition of mandelate in H2O.

  8. Vintage High School Citizenship Recognition Program.

    Science.gov (United States)

    Napa Valley Unified School District, Napa, CA.

    THE FOLLOWING IS THE FULL TEXT OF THIS DOCUMENT: Recognition of good citizenship is one component of the Vintage High School Student Incentive Program which could be easily adapted for any school. The only direct cost is for postage to mail congratulatory letters home and a small initial cost for printing award certificates. On a rotating basis,…

  9. High-Throughput Genetic Analysis and Combinatorial Chiral Separations Based on Capillary Electrophoresis

    Energy Technology Data Exchange (ETDEWEB)

    Wenwan Zhong

    2003-08-05

    Capillary electrophoresis (CE) offers many advantages over conventional analytical methods, such as speed, simplicity, high resolution, low cost, and small sample consumption, especially for the separation of enantiomers. However, chiral method developments still can be time consuming and tedious. They designed a comprehensive enantioseparation protocol employing neutral and sulfated cyclodextrins as chiral selectors for common basic, neutral, and acidic compounds with a 96-capillary array system. By using only four judiciously chosen separation buffers, successful enantioseparations were achieved for 49 out of 54 test compounds spanning a large variety of pKs and structures. Therefore, unknown compounds can be screened in this manner to identify optimal enantioselective conditions in just one rn. In addition to superior separation efficiency for small molecules, CE is also the most powerful technique for DNA separations. Using the same multiplexed capillary system with UV absorption detection, the sequence of a short DNA template can be acquired without any dye-labels. Two internal standards were utilized to adjust the migration time variations among capillaries, so that the four electropherograms for the A, T, C, G Sanger reactions can be aligned and base calling can be completed with a high level of confidence. the CE separation of DNA can be applied to study differential gene expression as well. Combined with pattern recognition techniques, small variations among electropherograms obtained by the separation of cDNA fragments produced from the total RNA samples of different human tissues can be revealed. These variations reflect the differences in total RNA expression among tissues. Thus, this Ce-based approach can serve as an alternative to the DNA array techniques in gene expression analysis.

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

    Science.gov (United States)

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

    2016-09-19

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

  11. Chiral Recognition of Diketopiperazine Cyclo(Pro-Gly) and Propranolol Using (-)-Epigallocatechin-3-O-gallate.

    Science.gov (United States)

    Ishizu, Takashi; Tsutsumi, Hiroyuki; Yokoyama, Emi; Tanabe, Haruka; Yokoyama, Aoi

    2016-01-01

    In the (1)H-NMR spectrum of a solution containing an equimolecular amount of cyclo(L-Pro-Gly), cyclo(D-Pro-Gly) and (-)-epigallocatechin-3-O-gallate (EGCg) in a D2O, a difference in the chemical shift of (1)H-NMR signal for H7α, H7β,8α of the Pro residue was observed. Judging from the crystal structures of the 2 : 2 complexes of EGCg and cyclo(L-Pro-Gly), cyclo(D-Pro-Gly), the difference in the chemical shift resulted mainly from a magnetic anisotropic shielding effect by the ring current from the B ring of EGCg. Therefore, it was considered that chirality of cyclo(Pro-Gly) was recognized by EGCg in the D2O solution. Furthermore, in the (1)H-NMR spectrum of a solution containing an equimolecular amount of racemic propranolol ((R)- and (S)-propranolols) and EGCg in D2O, the (1)H-NMR signal for H2 of the naphthalene group was observed as two doublets, suggesting that the racemic propranolol formed diastereomers of complexes with EGCg; as a result, chirality of propranolol was recognized by EGCg in the D2O solution.

  12. The combination of high Q factor and chirality in twin cavities and microcavity chain.

    Science.gov (United States)

    Song, Qinghai; Zhang, Nan; Zhai, Huilin; Liu, Shuai; Gu, Zhiyuan; Wang, Kaiyang; Sun, Shang; Chen, Zhiwei; Li, Meng; Xiao, Shumin

    2014-09-29

    Chirality in microcavities has recently shown its bright future in optical sensing and microsized coherent light sources. The key parameters for such applications are the high quality (Q) factor and large chirality. However, the previous reported chiral resonances are either low Q modes or require very special cavity designs. Here we demonstrate a novel, robust, and general mechanism to obtain the chirality in circular cavity. By placing a circular cavity and a spiral cavity in proximity, we show that ultra-high Q factor, large chirality, and unidirectional output can be obtained simultaneously. The highest Q factors of the non-orthogonal mode pairs are almost the same as the ones in circular cavity. And the co-propagating directions of the non-orthogonal mode pairs can be reversed by tuning the mode coupling. This new mechanism for the combination of high Q factor and large chirality is found to be very robust to cavity size, refractive index, and the shape deformation, showing very nice fabrication tolerance. And it can be further extended to microcavity chain and microcavity plane. We believe that our research will shed light on the practical applications of chirality and microcavities.

  13. 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.

  14. Application of High Performance Liquid Chromatography to Separation of Novel Chiral Tetrahedral Heterometal Clusters

    Institute of Scientific and Technical Information of China (English)

    Xin Yi ZHU; Wei Qiang ZHANG; Yu Hua ZHANG; Li Ren CHEN; Yong Min LI

    2003-01-01

    A series of novel chiral tetrahedral heterometal clusters have firstly been separated oncellulose tris-(3,5-dimethylphenylcarbamate) stationary phase by high performance liquid chrom-atography, using hexane as the mobile phase with various alcohols as modifiers.

  15. Recognition and one-pot extraction of right- and left-handed semiconducting single-walled carbon nanotube enantiomers using fluorene-binaphthol chiral copolymers.

    Science.gov (United States)

    Akazaki, Kojiro; Toshimitsu, Fumiyuki; Ozawa, Hiroaki; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

    2012-08-01

    Synthesized single-walled carbon nanotubes (SWNTs) are mixtures of right- and left-handed helicity and their separation is an essential topic in nanocarbon science. In this paper, we describe the separation of right- and left-handed semiconducting SWNTs from as-produced SWNTs. Our strategy for this goal is simple: we designed copolymers composed of polyfluorene and chiral bulky moieties because polyfluorenes with long alkyl-chains are known to dissolve only semiconducting SWNTs and chiral binaphthol is a so-called BINAP family that possesses a powerful enantiomer sorting capability. In this study, we synthesized 12 copolymers, (9,9-dioctylfluorene-2,7-diyl)x((R)- or (S)-2,2'-dimethoxy-1,1'-binaphthalen-6,6-diyl)y, where x and y are copolymer composition ratios. It was found that, by a simple one-pot sonication method, the copolymers are able to extract either right- or left-handed semiconducting SWNT enantiomers with (6,5)- and (7,5)-enriched chirality. The separated materials were confirmed by circular dichroism, vis-near IR and photoluminescence spectroscopies. Interestingly, the copolymer showed inversion of SWNT enantiomer recognition at higher contents of the chiral binaphthol moiety. Molecular mechanics simulations reveal a cooperative effect between the degree of chirality and copolymer conformation to be responsible for these distinct characteristics of the extractions. This is the first example describing the rational design and synthesis of novel compounds for the recognition and simple sorting of right- and left-handed semiconducting SWNTs with a specific chirality.

  16. Opportunities for chiral discrimination using high harmonic generation in tailored laser fields

    CERN Document Server

    Smirnova, Olga; Patchkovskii, Serguei

    2015-01-01

    Chiral discrimination with high harmonic generation (cHHG method) has been introduced in the recent work by R. Cireasa et al ( Nat. Phys. 11, 654 - 658, 2015). In its original implementation, the cHHG method works by detecting high harmonic emission from randomly oriented ensemble of chiral molecules driven by elliptically polarized field, as a function of ellipticity. Here we discuss future perspectives in the development of this novel method, the ways of increasing chiral dichroism using tailored laser pulses, new detection schemes involving high harmonic phase measurements, and concentration-independent approaches. Using the example of the epoxypropane molecule C$_3$H$_6$O (also known as 1,2-propylene oxide), we show theoretically that application of two-color counter-rotating elliptically polarized laser fields yields an order of magnitude enhancement of chiral dichroism compared to single color elliptical fields. We also describe how one can introduce a new functionality to cHHG: concentration-independen...

  17. Chiral Recognition of Hydroxyproline by Water-Soluble Chiral Lanthanide Shift Reagent%水溶性镧系位移试剂对羟基脯氨酸的手性识别

    Institute of Scientific and Technical Information of China (English)

    刘洋来; 许美凤; 颜贤忠

    2012-01-01

    用1 H NMR和13C NMR研究了水溶性镧系位移试剂Sm-pdta对反式-4-羟基脯氨酸的手性识别.反式-4-羟基脯氨酸与Sm-pdta形成络合物后,其1 H NMR和13C NMR图谱的化学位移有所变化,手性碳附近的某些原子所对应的吸收峰裂分为2组信号,分别对应反式-4-羟基脯氨酸的两种对映异构体.结果显示,对于反式-4-羟基脯胺酸,Sm-pdta是一个既方便又有效的手性位移试剂.%1H and 13C NMR spectroscopy was carried out to investigate the chiral recognition of franx-4-hydroxyproline using water-soluble chiral lanthanide shift reagent Sm-pdta. When complexed with Sm-pdta, most signals in the 1H and 13C NMR spectra of iran.s-4-hydroxy-L-proline and iraws-4-hydroxy-D-prolme were shifted, leading to separation of the signals from the two enantiomers. The results showed that Sm-pdta is an effective reagent for chiral recognition of jrara.s-4-hydroxyproline.

  18. Industrial-scale separation of high-purity single-chirality single-wall carbon nanotubes for biological imaging.

    Science.gov (United States)

    Yomogida, Yohei; Tanaka, Takeshi; Zhang, Minfang; Yudasaka, Masako; Wei, Xiaojun; Kataura, Hiromichi

    2016-06-28

    Single-chirality, single-wall carbon nanotubes are desired due to their inherent physical properties and performance characteristics. Here, we demonstrate a chromatographic separation method based on a newly discovered chirality-selective affinity between carbon nanotubes and a gel containing a mixture of the surfactants. In this system, two different selectivities are found: chiral-angle selectivity and diameter selectivity. Since the chirality of nanotubes is determined by the chiral angle and diameter, combining these independent selectivities leads to high-resolution single-chirality separation with milligram-scale throughput and high purity. Furthermore, we present efficient vascular imaging of mice using separated single-chirality (9,4) nanotubes. Due to efficient absorption and emission, blood vessels can be recognized even with the use of ∼100-fold lower injected dose than the reported value for pristine nanotubes. Thus, 1 day of separation provides material for up to 15,000 imaging experiments, which is acceptable for industrial use.

  19. Composite chiral metamaterials with negative refractive index and high values of the figure of merit.

    Science.gov (United States)

    Li, Zhaofeng; Alici, Kamil Boratay; Caglayan, Humeyra; Kafesaki, Maria; Soukoulis, Costas M; Ozbay, Ekmel

    2012-03-12

    A composite chiral metamaterial (CCMM) is designed and studied both numerically and experimentally. The CCMM is constructed by the combination of a continuous metallic wires structure and a purely chiral metamaterial (CMM) that consists of conjugated Rosettes. For the CMM, only very small, useful bands of negative index can be obtained for circularly polarized waves. These bands are all above the chiral resonance frequencies because of the high value of the effective parameter of relative permittivity ε. After the addition of the continuous metallic wires, which provide negative permittivity, the high value of ε can be partially compensated. Thus, a negative index band for the left circularly polarized wave that is below the chiral resonance frequency is obtained for the CCMM. At the same time, a negative index band for the right circularly polarized wave that is above the chiral resonance frequency is also obtained. Furthermore, both negative index bands correspond to the transmission peaks and have high values of the figure of merit. Therefore, the CCMM design that is proposed here is more suitable than the CMM for the construction of chiral metamaterials with a negative index.

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

    Science.gov (United States)

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

    2016-10-31

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

  1. Use of chiral cell shape to ensure highly directional swimming in trypanosomes.

    Science.gov (United States)

    Wheeler, Richard John

    2017-01-01

    Swimming cells typically move along a helical path or undergo longitudinal rotation as they swim, arising from chiral asymmetry in hydrodynamic drag or propulsion bending the swimming path into a helix. Helical paths are beneficial for some forms of chemotaxis, but why asymmetric shape is so prevalent when a symmetric shape would also allow highly directional swimming is unclear. Here, I analyse the swimming of the insect life cycle stages of two human parasites; Trypanosoma brucei and Leishmania mexicana. This showed quantitatively how chirality in T. brucei cell shape confers highly directional swimming. High speed videomicrographs showed that T. brucei, L. mexicana and a T. brucei RNAi morphology mutant have a range of shape asymmetries, from wild-type T. brucei (highly chiral) to L. mexicana (near-axial symmetry). The chiral cells underwent longitudinal rotation while swimming, with more rapid longitudinal rotation correlating with swimming path directionality. Simulation indicated hydrodynamic drag on the chiral cell shape caused rotation, and the predicted geometry of the resulting swimming path matched the directionality of the observed swimming paths. This simulation of swimming path geometry showed that highly chiral cell shape is a robust mechanism through which microscale swimmers can achieve highly directional swimming at low Reynolds number. It is insensitive to random variation in shape or propulsion (biological noise). Highly symmetric cell shape can give highly directional swimming but is at risk of giving futile circular swimming paths in the presence of biological noise. This suggests the chiral T. brucei cell shape (associated with the lateral attachment of the flagellum) may be an adaptation associated with the bloodstream-inhabiting lifestyle of this parasite for robust highly directional swimming. It also provides a plausible general explanation for why swimming cells tend to have strong asymmetries in cell shape or propulsion.

  2. Molecular model for chirality phenomena.

    Science.gov (United States)

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

    2016-10-21

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

  3. Chiral separation of neonicotinoid insecticides by polysaccharide-type stationary phases using high-performance liquid chromatography and supercritical fluid chromatography.

    Science.gov (United States)

    Zhang, Cheng; Jin, Lixia; Zhou, Shanshan; Zhang, Yifan; Feng, Shuoli; Zhou, Qinyan

    2011-03-01

    The enantiomeric separations of three neonicotinoid insecticides (identified as compounds 1, 2, and 3) were performed on three polysaccharide-type chiral columns, that is, Chiralcel OD-H, Chiralpak AD-H, and Chiralpak IB, by high-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC). Effects of the modifier percentage and column temperature on chiral recognitions of chiral stationary phases were also studied. Both 1 and 2 could be resolved on all three columns selected, with the highest R(s) values obtained on Chiralpak AD-H and Chiralcel OD-H, respectively. However, satisfactory separation of the four stereoisomers of 3 was only achieved on Chiralcel OD-H. Considering the effects of ethanol on the values of k, α, and R(s), we concluded that hydrogen bonding, π-π, and/or dipole-dipole interactions might be all responsible for the chiral separation. In comparison to HPLC, a shorter run time was achieved for 1 and 2 by SFC. However, 3 could not be stereoselectively resolved using SFC. On the basis of the calculated thermodynamic parameters, we found that the separation processes of enantiomers of 1 and 2 were entropy controlled and enthalpy controlled, respectively.

  4. Separation of chiral primary amino compounds by forming a sandwiched complex in reversed-phase high performance liquid chromatography.

    Science.gov (United States)

    Zhang, Chen; Huang, Wei X; Chen, Zhi; Rustum, Abu M

    2010-07-23

    Separation of chiral primary amino compounds was efficiently achieved under reversed-phase high performance liquid chromatography (RP-HPLC) conditions using a mixture of non-chiral crown ether (18-crown-6) and dimethyl-beta-cyclodextrin (DM-beta-CD) in the mobile phase. Under these conditions, the amino group of the chiral compound was protonated in a low pH mobile phase, and then interacted with 18-crown-6 and DM-beta-CD to form a sandwiched complex [18-crown-6+amine+CD]. Enantiomers of the compound in the sandwiched complex were separated with good enantioselectivity. Formation of the sandwiched complex among the chiral compound and additives in the mobile phase is a key step of the chiral separation. Four different chiral amino compounds namely, 1-aminoindan (AI), 1,2,3,4-tetrahydro-1-naphthylamine (THNA), tyrosine (Tyr), and phenylalanine (Phe), were selected to demonstrate the separation using the sandwiched complex mechanism in RP-HPLC.

  5. Traffic Sign Recognition with High Accuracy Using Mixture of Experts

    Directory of Open Access Journals (Sweden)

    Reza Azad

    2014-06-01

    Full Text Available Traffic signs provide the driver various information for safe and efficient navigation. Automatic recognition of traffic signs is, therefore, important for automated driving or driver assistance systems.In this paper, a new and efficient traffic sign recognition system based on extracting diverse feature set, and applying mixture of experts'architecture on the extracted featuresis proposed.In the result part, the proposed approach is evaluated on the German traffic sign recognition and Grigorescu traffic signsbenchmark and high recognition rate is achieved.Comparison with some of the most related methods indicates that the proposed novel model yields excellent recognition rate in traffic sign recognition that is the recognition rate of 99.94% for the training set and 98.50% for the test set.In addition, experimental results have demonstrated our method robust in successful recognition of traffic signs even with variant lighting.

  6. Non-Abelian chiral instabilities at high temperature on the lattice

    Science.gov (United States)

    Akamatsu, Yukinao; Rothkopf, Alexander; Yamamoto, Naoki

    2016-03-01

    We report on an exploratory lattice study on the phenomenon of chiral instabilities in non-Abelian gauge theories at high temperature. It is based on a recently constructed anomalous Langevin-type effective theory of classical soft gauge fields in the presence of a chiral number density n 5 = n R - n L. Evaluated in thermal equilibrium using classical lattice techniques it reveals that the fluctuating soft fields indeed exhibit a rapid energy increase at early times and we observe a clear dependence of the diffusion rate of topological charge (sphaleron rate) on the the initial n 5, relevant in both early universe baryogenesis and relativistic heavy-ion collisions. The topological charge furthermore shows a drift among distinct vacuum sectors, roughly proportional to the initial n 5 and in turn the chiral imbalance is monotonously reduced as required by helicity conservation.

  7. Non-Abelian chiral instabilities at high temperature on the lattice

    CERN Document Server

    Akamatsu, Yukinao; Yamamoto, Naoki

    2015-01-01

    We report on an exploratory lattice study on the phenomenon of chiral instabilities in non-Abelian gauge theories at high temperature. It is based on a recently constructed anomalous Langevin-type effective theory of classical soft gauge fields in the presence of a chiral number density $n_5=n_{\\rm R}-n_{\\rm L}$. Evaluated in thermal equilibrium using classical lattice techniques it reveals that the fluctuating soft fields indeed exhibit a rapid energy increase at early times and we observe a clear dependence of the diffusion rate of topological charge (sphaleron rate) on the the initial $n_5$, relevant in both early universe baryogenesis and relativistic heavy-ion collisions. The topological charge furthermore shows a drift among distinct vacuum sectors, roughly proportional to the initial $n_5$ and in turn the chiral imbalance is monotonously reduced as required by helicity conservation.

  8. Novel chiral thioureas for highly enantioselective Michael reactions of malonates to nitroalkenes

    Institute of Scientific and Technical Information of China (English)

    Li Jun Yan; Quan Zhong Liu; Xue Lian Wang

    2009-01-01

    Highly efficient Michael addition reactions of malonates to nitroalkenes catalyzed by novel chiral thioureas derived from optically pure BINOL and amino acids are reported. Various trans-nitroalkenes reacted with malonates affording the desired products in up to 95% yield with excellent enantioselectivities (up to 97% ee).

  9. Bromoporphyrins as versatile synthons for modular construction of chiral porphyrins: cobalt-catalyzed highly enantioselective and diastereoselective cyclopropanation.

    Science.gov (United States)

    Chen, Ying; Fields, Kimberly B; Zhang, X Peter

    2004-11-17

    5,10-Bis(2',6'-dibromophenyl)porphyrins bearing various substituents at the 10 and 20 positions were demonstrated to be versatile synthons for modular construction of chiral porphyrins via palladium-catalyzed amidation reactions with chiral amides. The quadruple carbon-nitrogen bond formation reactions were accomplished in high yields with different chiral amide building blocks under mild conditions, forming a family of D2-symmetric chiral porphyrins. Cobalt(II) complexes of these chiral porphyrins were prepared in high yields and shown to be active catalysts for highly enantioselective and diastereoselective cyclopropanation under a practical one-pot protocol (alkenes as limiting reagents and no slow addition of diazo reagents).

  10. Highly Excited Mesons, Linear Regge Trajectories and the Pattern of the Chiral Symmetry Realization

    CERN Document Server

    Shifman, M

    2007-01-01

    The chiral symmetry of QCD shows up in the linear Weyl--Wigner mode at short Euclidean distances or at high temperatures. On the other hand, low-lying hadronic states exhibit the nonlinear Nambu--Goldstone mode. An interesting question was raised as to whether the linear realization of the chiral symmetry is asymptotically restored for highly excited states. We address it in a number of ways. On the phenomenological side we argue that to the extent the meson Regge trajectories are observed to be linear and equidistant, the Weyl--Wigner mode is not realized. This picture is supported by quasiclassical arguments implying that the quark spin interactions in high excitations are weak, the trajectories are linear, and there is no chiral symmetry restoration. Then we use the string/gauge duality. In the top-down Sakai--Sugimoto construction the nonlinear realization of the chiral symmetry is built in. In the bottom-up AdS/QCD construction by Erlich et al., and Karch et al. the situation is more ambiguous. However, ...

  11. Chiral Cyclobutane β-Amino Acid-Based Amphiphiles: Influence of Cis/Trans Stereochemistry on Solution Self-Aggregation and Recognition.

    Science.gov (United States)

    Sorrenti, Alessandro; Illa, Ona; Pons, Ramon; Ortuño, Rosa M

    2015-09-08

    Novel diastereomeric anionic amphiphiles based on the rigid cyclobutane β-amino acid scaffold have been synthesized and deeply investigated with the aim of generating new functional supramolecular architectures on the basis of the rational design of original amphiphilic molecules and the control of their self-assembly. The main interest has been focused on the effect that cis/trans stereochemistry exerts on their molecular organization and recognition. In diluted solutions, the relative stereochemistry mainly influences the headgroup solvation and anionic-charge stabilization, i.e., better stabilized in the cis diastereoisomer due to intramolecular hydrogen-bonding and/or charge-dipole interactions. This provokes differences in their physicochemical behavior (pKa, cmc, conductivity) as well as in the structural parameters of the spherical micelles formed. Although both diastereoisomers form fibers that evolve with time from the spherical micelles, they display markedly different morphology and kinetics of formation. In the lyotropic liquid crystal domain, the greatest differences are observed at the highest concentrations and can be ascribed to different hydrogen-bonding and molecular packing imposed by the stereochemical constraints. Remarkably, the spherical micelles of the two anionic surfactants show dramatically diverse enantioselection ability for bilirubin enantiomers. In addition, both the surfactants form heteroaggregates with bilirubin at submicellar concentrations but with a different expression of supramolecular chirality. This points out that the unlike relative configuration of the two surfactants influences their chiral recognition ability as well as the fashion in which chirality is expressed at the supramolecular level by controlling the molecular organization in both micellar aggregates and surfactant/bilirubin heteroaggregates. All these differential features can be appropriate and useful for the design and development of new soft materials with

  12. Fluorescence turn-on recognition of chiral amino acids using dye incorporated β-CD functionalized AuNPs assembly

    Energy Technology Data Exchange (ETDEWEB)

    Aswathy, B., E-mail: aswathybv@gmail.com; Sony, G., E-mail: emailtosony@gmail.com

    2014-10-15

    An assembly of dye incorporated β-cyclodextrin (βCD) functionalized AuNPs for the fluorescent probing of chiral amino acids is presented. Gold nanoparticles (AuNPs) possessing a high extinction coefficient function can be used as excellent fluorescent quenchers in AuNP–fluorophore system. Inclusion of fluorescein (FL) into β-cyclodextrin (βCD) makes energy transfer to occur through the donor and quencher nearby. This energy transfer switches off by virtue of the analyte induced release of FL from β-CD cavity, which results in the fluorescence recovery of the quenched dye. Analysis suggests that the assembly of AuNPs–βCDs–FL is effective as a turn-on fluorescent probe for the chiroselective optical discrimination between D,L-tryptophan, D,L-phenyl alanine and D,L-tyrosine. The detection limits for analyzing L-tryptophan, L-phenyl alanine and L-tyrosine were found to be 0.59, 1.2 and 1.5 μM respectively. - Highlights: • Fluorescence quenching AuNP–βCD–dye assembly via energy transfer. • Energy transfer from dye to AuNPs is a SET process. • Fluorescence turn-on detection of amino acids by the competitive binding method. • Chiroselective discrimination between enantiomeric amino acids.

  13. Catalytic Enantioselective Olefin Metathesis in Natural Product Synthesis. Chiral Metal-Based Complexes that Deliver High Enantioselectivity and More

    Science.gov (United States)

    Malcolmson, Steven J.; Meek, Simon J.; Zhugralin, Adil R.

    2012-01-01

    Chiral olefin metathesis catalysts enable chemists to access enantiomerically enriched small molecules with high efficiency; synthesis schemes involving such complexes can be substantially more concise than those that would involve enantiomerically pure substrates and achiral Mo alkylidenes or Ru-based carbenes. The scope of research towards design and development of chiral catalysts is not limited to discovery of complexes that are merely the chiral versions of the related achiral variants. A chiral olefin metathesis catalyst, in addition to furnishing products of high enantiomeric purity, can offer levels of efficiency, product selectivity and/or olefin stereoselectivity that are unavailable through the achiral variants. Such positive attributes of chiral catalysts (whether utilized in racemic or enantiomerically enriched form) should be considered as general, applicable to other classes of transformations. PMID:19967680

  14. Velocity gap mode of capillary electrophoresis developed for high-resolution chiral separations.

    Science.gov (United States)

    Li, Xue; Li, Youxin; Zhao, Lumeng; Shen, Jianguo; Zhang, Yong; Bao, James J

    2014-10-01

    A new CE method based on velocity gap (VG) theory has been developed for high-resolution chiral separations. In VG, two consecutive electric fields are adopted to drive analytes passing through two capillaries, which are linked together through a joint. The joint is immersed inside another buffer vial which has conductivity communication with the buffer inside the capillary. By adjusting the field strengths onto the two capillaries, it is possible to observe different velocities of an analyte when it passes through those two capillaries and there would be a net velocity change (NVC) for the same analyte. Different analytes may have different NVC which may be specifically meaningful for enantioseparations because enantiomers are usually hard to resolve. By taking advantage of this NVC, it is possible to enhance the resolution of a chiral separation if a proper voltage program is applied. The feasibility of using NVC to enhance chiral separation was demonstrated in the separations of three pairs of enantiomers: terbutaline, chlorpheniramine, and promethazine. All separations started with partial separation in a conventional CE and were significantly improved under the same experimental conditions. The results indicated that VG has the potential to be used to improve the resolving power of CE in chiral separations.

  15. Enantiomeric Separations of Pyriproxyfen and its Six Chiral Metabolites by High-Performance Liquid Chromatography.

    Science.gov (United States)

    Zhang, Chuntao; Liu, Hui; Liu, Donghui; Wang, Liying; Gao, Jing; Zhou, Zhiqiang; Wang, Peng

    2016-03-01

    Pyriproxyfen is a chiral insecticide, and over 10 metabolites have been identified in the environment. In this work the separations of the enantiomers of pyriproxyfen and its six chiral metabolites were studied by high-performance liquid chromatography (HPLC). Both normal phase and reverse phase were applied using the chiral columns Chiralpak IA, Chiralpak IB, Chiralpak IC, Chiralcel OD, Chiralcel OD-RH, Chiralpak AY-H, Chiralpak AD-H, Chiracel OJ-H, (R,R)-Whelk-O 1, and Lux Cellulose-3. The effects of the chromatographic parameters such as mobile phase composition and temperature on the separations were investigated and the enantiomers were identified with an optical rotation detector. The enantiomers of these targets could obtain complete separations (resolution factor Rs > 1.5) on Chiralpak IA, Chiralpak IB, Chiralcel OD, Chiralpak AY-H, or Chiracel OJ-H under normal conditions. Chiralcel OJ-H showed the best chiral separation results with n-hexane as mobile phase and isopropanol (IPA) as modifier. The simultaneous enantiomeric separation of pyriproxyfen and four chiral metabolites was achieved on Chiralcel OJ-H under optimized condition: n-hexane/isopropanol = 80/20, 15°C, flow rate of 0.8 ml/min, and UV detection at 230 nm. The enantiomers of pyriproxyfen and the metabolites , , and obtained complete separations on Chiralpak IA, Chiralpak IC, and Lux Cellulose-3 under reverse phase using acetonitrile/water as the mobile phase. The retention factors (k) and selectivity factors (α) decreased with increasing temperature, and the separations were better under low temperature in most cases. The work is of significance for the investigation of the environmental behaviors of pyriproxyfen on an enantiomeric level.

  16. An Inherent Chiral Calix[4]arene Bearing Chiral Groups without Forming Sub-ring

    Institute of Scientific and Technical Information of China (English)

    Xian Xian LIU; Yan Song ZHENG; Wan Ling MO

    2006-01-01

    The NMR spectra revealed that the calixarene frame of 1, 3-disubstituted calix[4]arenes bearing optically active groups is asymmetric, even without the formation of a sub-ring. This inherent chirality arises from the interaction of the two chiral groups, which hinder the substituents' free rotation. Thus, these chiral calix[4]arenes display good chiral recognition ability.

  17. Scientific Recognition and Communication Behavior in High Energy Physics.

    Science.gov (United States)

    Zeltman, Gerald

    The study is concerned with scientific (i.e., professional) recognition and communication behavior in theoretical high energy physics. The sample consists of 977 respondents working in thirty-eight countries. The conferral of two components of professional recognition, research leadership and advisorship, as they are affected by geopolitical and…

  18. Chiral recognition of N-phthaloyl, N-tetrachlorophthaloyl, and N-naphthaloyl α-amino acids and their esters on polysaccharide-derived chiral stationary phases.

    Science.gov (United States)

    Kim, Byoung-Hyoun; Lee, Sang Uck; Moon, Dong Cheul

    2012-12-01

    Enantiomeric separations of N-phthaloyl (N-PHT), N-tetrachlorophthaloyl (N-TCPHT), and N-naphthaloyl (N-NPHT) α-amino acids and their esters were examined on several kinds of polysaccharide-derived chiral stationary phases (CSPs). Resolution capability of CSPs was greater Chiralcel OF than the others for N-PHT and N-NPHT α-amino acids and their esters. In N-TCPHT α-amino acids and their esters, good enantioselectivities showed Chiralcel OG for N-TCPHT α-amino acids, Chiralpak AD for N-TCPHT α-amino acid methyl esters, and Chiralcel OD for N-TCPHT α-amino acid ethyl esters, respectively. From the results of liquid chromatography and computational chemistry, it is concluded that l-form is preferred and more retained with electrostatic interaction in case of interaction between N-PHT α-amino acid derivatives and Chiralcel OF, N-TCPHT α-amino acid derivatives and Chiralcel OD, and N-NPHT α-amino acid derivatives and Chiracel OF. On the other hand, d-form is preferred and more retained with van der Waals interaction in case of interaction between N-TCPHT α-amino acid ester derivatives and Chiralcel OG and Chiralpak AD.

  19. Evaluation of the chiral recognition properties as well as the column performance of four chiral stationary phases based on cellulose (3,5-dimethylphenylcarbamate) by parallel HPLC and SFC.

    Science.gov (United States)

    Nelander, Hanna; Andersson, Shalini; Ohlén, Kristina

    2011-12-30

    The performance of four commercially available cellulose tris(3,5-dimethylphenylcarbamate) based chiral stationary phases (CSPs) was evaluated with parallel high performance liquid chromatography (HPLC) and super critical fluid chromatography (SFC). Retention, enantioselectivity, resolution and efficiency were compared for a set of neutral, basic and acidic compounds having different physico-chemical properties by using different mobile phase conditions. Although the chiral selector is the same in all the four CSPs, a large difference in the ability to retain and resolve enantiomers was observed under the same chromatographic conditions. We believe that this is mainly due to differences in the silica matrix and immobilization techniques used by the different vendors. An extended study of metoprolol and structure analogues gave a deeper understanding of the accessibility of the chiral discriminating interactions and its impact on the resolution of the racemic compounds on the four CSPs studied. Also, a clear difference in enantioselectivity is observed between SFC and LC mode, hydrogen bonding was found to play an important role in the differential binding of the enantiomers to the CSPs.

  20. Isothermal Titration Calorimetry of Chiral Polymeric Nanoparticles.

    Science.gov (United States)

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

    2015-09-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-12-05

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

  2. Chiral counteranion synergistic organocatalysis under high temperature: efficient construction of optically pure spiro[cyclohexanone-oxindole] backbone.

    Science.gov (United States)

    Lan, Yu-Bao; Zhao, Hua; Liu, Zhao-Min; Liu, Guo-Gui; Tao, Jing-Chao; Wang, Xing-Wang

    2011-09-16

    The combination of a cinchona-based chiral primary amine and a BINOL-phosphoric acid has been demonstrated as a powerful and synergistic catalyst system for the double Michael addition of isatylidene malononitriles with α,β-unsaturated ketones, to provide the novel chiral spiro [cyclohexane-1,3'-indoline]-2',3-diones in high yields (88-99%) with excellent diastereo- and enantioselectivities (94:6-99:1 dr's, 95-99% ee's).

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

    Institute of Scientific and Technical Information of China (English)

    WU; Yanbo; ZHANG; Cuiping

    2006-01-01

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

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

    Science.gov (United States)

    Ghatee, Mohammad Hadi; Sedghamiz, Tahereh

    2014-12-01

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

  5. Pion Structure at High and Low Energies in Chiral Quark Models

    CERN Document Server

    Ruiz-Arriola, E

    2002-01-01

    Low and high energy properties of the pion are reviewed in the framework of chiral quark models. Particular emphasis is put on the simplest version of the SU(2) NJL model as prototype. The role of gauge invariance in this kind of calculations is stressed. The results are used as initial conditions for perturbative QCD evolution equations. At leading order the quark model scale is $\\mu_0 \\sim 320 {\\rm MeV} $ as determined from the pion distribution functions and the pion distribution amplitudes.

  6. Highly Active Chiral Ruthenium Catalysts for Asymmetric Ring-Closing Olefin Metathesis

    Science.gov (United States)

    Funk, Timothy W.; Berlin, Jacob M.

    2008-01-01

    The synthesis of olefin metathesis catalysts containing chiral, monodentate N-heterocyclic carbenes and their application to asymmetric ring-closing metathesis (ARCM) is reported. These catalysts retain the high levels of reactivity found in the related achiral variants (1a and 1b). Using the parent chiral catalysts 2a and 2b and derivatives that contain steric bulk in the meta positions of the N-bound aryl rings (catalysts 3-5), five- through seven-membered rings were formed in up to 92% ee. The addition of sodium iodide to catalysts 2a-4a (to form 2b-4bin situ) caused a dramatic increase in enantioselectivity for many substrates. Catalyst 5a, which gave high enantiomeric excesses for certain substrates without the addition of NaI, could be used in loadings of ≤1 mol %. Mechanistic explanations for the large sodium iodide effect as well as possible mechanistic pathways leading to the observed products are discussed. PMID:16464082

  7. Application of cyanuric chloride-based six new chiral derivatizing reagents having amino acids and amino acid amides as chiral auxiliaries for enantioresolution of proteinogenic amino acids by reversed-phase high-performance liquid chromatography.

    Science.gov (United States)

    Bhushan, Ravi; Dixit, Shuchi

    2012-04-01

    Six dichloro-s-triazine (DCT) reagents having L-Leu, D-Phg, L-Val, L-Met, L-Ala and L-Met-NH(2) as chiral auxiliaries in cyanuric chloride were introduced for enantioseparation of 13 proteinogenic amino acids. Four other DCTs and six monochloro-s-triazine (MCT) reagents having amino acid amides as chiral auxiliaries were also synthesized. These 16 chiral derivatizing reagents (CDRs) were used for synthesis of diastereomers of all the 13 analytes using microwave irradiation, which were resolved by reversed-phase high-performance liquid chromatography (RP-HPLC) using C18 column and gradient eluting mixture of aqueous TFA and acetonitrile with UV detection at 230 nm. It required only 60-90 s for derivatization using microwave irradiation. Better resolution and lower retention times were observed for the diastereomers prepared with CDRs having amino acids as chiral auxiliaries as compared to counterparts prepared with reagents having amino acid amides as chiral auxiliaries. As the best resolution of all the 13 analytes was observed for their diastereomers prepared using the DCT reagent having L-Leu as chiral auxiliary, this CDR was further employed for derivatization of Lys, Tyr, His and Arg followed by RP-HPLC analysis of resulting diastereomers. The results are discussed in light of acid and amide groups of chiral auxiliaries constituting CDRs, electronegativities of the atoms of achiral moieties constituting CDRs and hydrophobicities of side chains of amino acids constituting CDRs and analytes.

  8. Sensitive Method for Enantioseparation of Rivastigmine with Highly Sulfated Cyclodextrin as Chiral Selector by Capillary Electrophoresis

    Institute of Scientific and Technical Information of China (English)

    WANG Zhao-Yan; XU Xing-Xiang; HU Zhi-De; KANG Jing-Wu

    2006-01-01

    A sensitive method for enantioseparation of a basic drug rivastigmine and determination of its optical impurity by capillary electrophoresis with highly sulfatedβ-cyclodextrin (HS-β-CD) as the chiral selector is described. In general, enantioseparation of basic chiral compounds is carried out in acidic condition (pH 2.5) to prevent analytes from adsorption on the capillary wall. However, in the case of rivastigmine, the detection sensitivity was too limited to determine the optical impurity of S-rivastigmine lower than 1% when buffer pH was 2.5. It was found that the detection sensitivity was improved 1.6 times just by raising the buffer pH value from 2.5 to 5.8. The poor column efficiency due to the adsorption of the analytes on the capillary wall was resolved by using dynamical coating of the capillary wall with the linear polyacrylamide solution. The experimental parameters such as the concentration of HS-β-CD, buffer pH and buffer ionic strength were optimized, respectively. The method was validated in terms of repeatability, linearity, limit of detection (LOD) and limit of quantitation (LOQ). Using the present method, the optical purity of nonracemic rivastigmine with the enantiomeric excess (ee) value of 99.14% was determined.

  9. Broadband and high-efficiency circular polarizer based on planar-helix chiral metamaterials

    Science.gov (United States)

    Wang, Jiang; Shen, Zhongxiang; Wu, Wen

    2017-09-01

    We reveal a broadband and high-efficiency circular polarizer based on chiral metamaterials composed of an array of planar helices, which can effectively reject the incident left-hand circularly polarized (LCP) wave, while allowing the right-hand circularly polarized (RCP) wave to pass through it. The physical mechanism of the proposed circular polarizer is explained with the aid of the current distributions under the excitations of LCP and RCP waves. Microwave experiments are performed to verify this idea, and measured results are in good agreement with the numerical ones. Experimental results show that a fractional bandwidth of 75.6% for the transmittance of the LCP wave lower than 0.2 can be obtained. Moreover, the proposed circular polarizer exhibits a high transmittance of over 0.9 for the RCP incident wave and a high circular polarization selection efficiency of over 0.95. The proposed circular polarizer will be potentially very useful for satellite and optical communications.

  10. Synthesis of novel chiral stationary phases for high-performance liquid chromatography

    Institute of Scientific and Technical Information of China (English)

    Xu Lin Tan; Shi Cong Hou; Qing Hua Bian; Min Wang

    2007-01-01

    Three novel chiral selectors 4a-c were synthesized from (S)-amino acids and (R)- 1-phenyl-2-(4-methylphenyl)ethylamine. 4a-c were connected to 3-aminopropylsilanized silica gel to be used as the chiral stationary phase for HPLC. Five amino acid derivatives and two pyrethroid insecticides were fairly resolved on these three new chiral stationary phases under normal phase condition.

  11. 3-(1H-Indol-3-yl)-2-[3-(4-nitrophenyl)ureido]propanamide Enantiomers With Human Formyl-Peptide Receptor Agonist Activity: Molecular Modeling of Chiral Recognition by FPR2

    Science.gov (United States)

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

    2012-01-01

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

  12. A chiral rhenium complex with predicted high parity violation effects: synthesis, stereochemical characterization by VCD spectroscopy and quantum chemical calculations

    CERN Document Server

    Saleh, Nidal; Roisnel, Thierry; Guy, Laure; Bast, Radovan; Saue, Trond; Darquié, Benoît; Crassous, Jeanne

    2015-01-01

    With their rich electronic, vibrational, rotational and hyperfine structure, molecular systems have the potential to play a decisive role in precision tests of fundamental physics. For example, electroweak nuclear interactions should cause small energy differences between the two enantiomers of chiral molecules, a signature of parity symmetry breaking. Enantioenriched oxorhenium(VII) complexes S-(-)- and R-(+)-3 bearing a chiral 2-methyl-1-thio-propanol ligand have been prepared as potential candidates for probing molecular parity violation effects via high resolution laser spectroscopy of the Re=O stretching. Although the rhenium atom is not a stereogenic centre in itself, experimental vibrational circular dichroism (VCD) spectra revealed a surrounding chiral environment, evidenced by the Re=O bond stretching mode signal. The calculated VCD spectrum of the R enantiomer confirmed the position of the sulfur atom cis to the methyl, as observed in the solid-state X-ray crystallographic structure, and showed the ...

  13. Experimental comparison of chiral metal-organic framework used as stationary phase in chromatography.

    Science.gov (United States)

    Xie, Sheng-Ming; Zhang, Mei; Fei, Zhi-Xin; Yuan, Li-Ming

    2014-10-10

    Chiral metal-organic frameworks (MOFs) are a new class of multifunctional material, which possess diverse structures and unusual properties such as high surface area, uniform and permanent cavities, as well as good chemical and thermal stability. Their chiral functionality makes them attractive as novel enantioselective adsorbents and stationary phases in separation science. In this paper, the experimental comparison of a chiral MOF [In₃O(obb)₃(HCO₂)(H₂O)] solvent used as a stationary phase was investigated in gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The potential relationship between the structure and components of chiral MOFs with their chiral recognition ability and selectivity are presented. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Separation of piracetam derivatives on polysaccharide-based chiral stationary phases.

    Science.gov (United States)

    Kažoka, H; Koliškina, O; Veinberg, G; Vorona, M

    2013-03-15

    High-performance liquid chromatography was used for the enantiomeric separation of two chiral piracetam derivatives. The suitability of six commercially available polysaccharide-based chiral stationary phases (CSPs) under normal phase mode for direct enantioseparation has been investigated. The influence of the CSPs as well the nature and content of an alcoholic modifier in the mobile phase on separation and elution order was studied. It was established that CSP Lux Amylose-2 shows high chiral recognition ability towards 4-phenylsubstituted piracetam derivatives. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Development of Amylose- and β-Cyclodextrin-Based Chiral Fluorescent Sensors Bearing Terthienyl Pendants

    Directory of Open Access Journals (Sweden)

    Tomoyuki Ikai

    2016-11-01

    Full Text Available Phenylcarbamate derivatives of amylose and β-cyclodextrin show excellent chiral recognition when used as chiral stationary phases (CSPs for high-performance liquid chromatography. To open up new possibilities of carbohydrate-based materials, we developed chiral fluorescent sensors based on amylose and β-cyclodextrin (Am-1b and CyD-1b, respectively by attaching fluorescent π-conjugated units on their side chains. Their recognition abilities toward chiral analytes containing a nitrophenyl unit were evaluated by measuring the enantioselective fluorescence quenching behavior. Both sensors showed the same degree of enantioselective fluorescence response for various aromatic nitro compounds. However, in some cases, their enantioselectivities were different depending on the analytes. The difference in the chiral recognition abilities between Am-1b and CyD-1b seems to be based on the structural difference of their inherent backbones, that is, the one-handed helical structure and cyclic structure, respectively. The study on the resolution ability of the Am-1b-based CSP revealed that the terthienyl-based pendant of Am-1b provides not only a fluorescent functionality but also a different chiral recognition site from that of amylose tris(phenylcarbamate.

  16. Highly E-Selective and Enantioselective Michael Addition to Electron-Deficient Internal Alkynes Under Chiral Iminophosphorane Catalysis.

    Science.gov (United States)

    Uraguchi, Daisuke; Yamada, Kohei; Ooi, Takashi

    2015-08-17

    A highly E-selective and enantioselective conjugate addition of 2-benzyloxythiazol-5(4H)-ones to β-substituted alkynyl N-acyl pyrazoles is achieved under the catalysis of a P-spiro chiral iminophosphorane. Simultaneous control of the newly generated central chirality and olefin geometry is possible with a wide array of the alkynyl Michael acceptors possessing different aromatic and aliphatic β-substituents, as well as the various α-amino acid-derived thiazolone nucleophiles. This protocol provides access to structurally diverse, optically active α-amino acids bearing a geometrically defined trisubstituted olefinic component at the α-position.

  17. Highly Selective Molecular Recognition of Biologically Active Substances Using Liquid Phase Separation%液相分离法对生物活性材料的高选择性分子识别

    Institute of Scientific and Technical Information of China (English)

    MANO Nariyasu; ASAKAWA Naoki; GOTO Junichi

    2003-01-01

    The development of new chiral stationary phases has been very important in the accurate analysis of drug enantiomers and their metabolites in biological samples during drug discovery and development. New chiral stationary phases have been developed using conalbumin and flavoprotein from chicken egg whites, which have been applied to a broad range of drug enantiomers. The application and characterization of these two chiral columns for high-performance liquid chromatography have been documented. Both specific and non-specific interactions, based on the silica gel surface and linker moiety, influenced retention and chiral separation of solutes. Interactions between drug enantiomers and proteins, as a pseudo chiral stationary phase, were investigated with affinity capillary electrophoresis, in order to avoid the effects of non-specific interactions. The chiral discrimination region for ketoprofen on the flavoprotein surface was concluded to consist of an α-helix structure. Studies with chemically modified flavoprotein indicated that two types of interactions at the chiral discrimination region were required for chiral separation: a π-π interaction between a tryptophan residue and the aromatic ring of ketoprofen, and an ionic interaction between the carboxyl group of ketoprofen and an amino and carboxyl group of the protein. In the body, drugs and biologically active substances having a carboxyl group have been known to transform various metabolites such as acyl glucuronide. The acyl adenylate has also been noted as a chemically active intermediate of coenzyme A ligation. Both the acyl adenylate and the acyl glucuronide produced protein adducts by reacting with nucleophilic groups such as amino groups on protein molecules. To characterize both active intermediates and protein adducts, analytical techniques conferring highly selective molecular recognition, such as high-performance liquid chromatography and mass spectrometry, were required.

  18. High-density myoelectric pattern recognition toward improved stroke rehabilitation.

    Science.gov (United States)

    Zhang, Xu; Zhou, Ping

    2012-06-01

    Myoelectric pattern-recognition techniques have been developed to infer user's intention of performing different functional movements. Thus electromyogram (EMG) can be used as control signals of assisted devices for people with disabilities. Pattern-recognition-based myoelectric control systems have rarely been designed for stroke survivors. Aiming at developing such a system for improved stroke rehabilitation, this study assessed detection of the affected limb's movement intention using high-density surface EMG recording and pattern-recognition techniques. Surface EMG signals comprised of 89 channels were recorded from 12 hemiparetic stroke subjects while they tried to perform 20 different arm, hand, and finger/thumb movements involving the affected limb. A series of pattern-recognition algorithms were implemented to identify the intended tasks of each stroke subject. High classification accuracies (96.1% ± 4.3%) were achieved, indicating that substantial motor control information can be extracted from paretic muscles of stroke survivors. Such information may potentially facilitate improved stroke rehabilitation.

  19. Spin and chirality effects in antler-topology processes at high energy e{sup +}e{sup -} colliders

    Energy Technology Data Exchange (ETDEWEB)

    Choi, S. Y. [Department of Physics, Chonbuk National University, 561-756, Jeonbuk (Korea, Republic of); Department of Physics and Astronomy, Pittsburgh Particle physics, Astrophysics, and Cosmology Center, University of Pittsburgh, 15260, Pittsburgh, PA (United States); Christensen, N. D. [Department of Physics, Illinois State University, 61790, Normal, IL (United States); Salmon, D.; Wang, X., E-mail: xiw77@pitt.edu [Department of Physics and Astronomy, Pittsburgh Particle physics, Astrophysics, and Cosmology Center, University of Pittsburgh, 15260, Pittsburgh, PA (United States)

    2015-10-06

    We perform a model-independent investigation of spin and chirality correlation effects in the antler-topology processes e{sup +}e{sup -}→P{sup +}P{sup -}→(ℓ{sup +}D{sup 0})(ℓ{sup -}D{sup -bar0}) at high-energy e{sup +}e{sup -} colliders with polarized beams. Generally the production process e{sup +}e{sup -}→P{sup +}P{sup -} can occur not only through the s-channel exchange of vector bosons, V{sup 0}, including the neutral Standard Model (SM) gauge bosons, γ and Z, but also through the s- and t-channel exchanges of new neutral states, S{sup 0} and T{sup 0}, and the u-channel exchange of new doubly charged states, U{sup --}. The general set of (non-chiral) three-point couplings of the new particles and leptons allowed in a renormalizable quantum field theory is considered. The general spin and chirality analysis is based on the threshold behavior of the excitation curves for P{sup +}P{sup -} pair production in e{sup +}e{sup -} collisions with longitudinal- and transverse-polarized beams, the angular distributions in the production process and also the production-decay angular correlations. In the first step, we present the observables in the helicity formalism. Subsequently, we show how a set of observables can be designed for determining the spins and chiral structures of the new particles without any model assumptions. Finally, taking into account a typical set of approximately chiral invariant scenarios, we demonstrate how the spin and chirality effects can be probed experimentally at a high-energy e{sup +}e{sup -} collider.

  20. Online pattern recognition for the ALICE high level trigger

    CERN Document Server

    Bramm, R; Lien, J A; Lindenstruth, V; Loizides, C; Röhrich, D; Skaali, B; Steinbeck, T M; Stock, Reinhard; Ullaland, K; Vestbø, A S; Wiebalck, A

    2003-01-01

    The ALICE High Level Trigger system needs to reconstruct events online at high data rates. Focusing on the Time Projection Chamber we present two pattern recognition methods under investigation: the sequential approach (cluster finding, track follower) and the iterative approach (Hough Transform, cluster assignment, re-fitting). The implementation of the former in hardware indicates that we can reach the designed inspection rate for p-p collisions of 1 kHz with 98% efficiency.

  1. Online pattern recognition for the ALICE high level trigger

    Energy Technology Data Exchange (ETDEWEB)

    Bramm, R.; Helstrup, H.; Lien, J.; Lindenstruth, V.; Loizides, C. E-mail: loizides@ikf.uni-frankfurt.de; Rohrich, D.; Skaali, B.; Steinbeck, T.; Stock, R.; Ullaland, K.; Vestboe, A.; Wiebalck, A

    2003-04-21

    The ALICE High Level Trigger system needs to reconstruct events online at high data rates. Focusing on the Time Projection Chamber we present two pattern recognition methods under investigation: the sequential approach (cluster finding, track follower) and the iterative approach (Hough Transform, cluster assignment, re-fitting). The implementation of the former in hardware indicates that we can reach the designed inspection rate for p-p collisions of 1 kHz with 98% efficiency.

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

    DEFF Research Database (Denmark)

    Nazmutdinov, Renat R.; Bronshtein, Michael D.; Zinkicheva, Tamara T.;

    2016-01-01

    We have studied electron transfer between cytochrome c and the chiral transition-metal complex pair Λ- and Δ-[Co(Ox)3]3− (Ox2− = oxalate) via strong ion-pair formation. Chirality was found in both ion-pair formation and electron transfer, with the Λ enantiomer the more strongly bound and faster r...... reacting. Investigations of the chirality using electron-transfer theory combined with quantum-chemical and statistical-mechanical calculations showed that chirality is solely in inter-reactant interaction and electronic overlap....

  3. Synergistic chiral iminium and palladium catalysis: Highly regio- and enantioselective [3 + 2] annulation reaction of 2-vinylcyclopropanes with enals

    Science.gov (United States)

    Zhu, Haipan; Du, Peile; Li, Jianjun; Liao, Ziyang; Liu, Guohua

    2016-01-01

    Summary A cooperative catalytic strategy of chiral iminium catalysis by regioselective activation of the C=C bond in enals and a transition metal promoting to open the 2-vinylcyclopropanes for highly regio- and enantioselective [3 + 2] cycloaddition reaction of 2-vinylcyclopropanes with α,β-unsaturated aldehydes has been developed. PMID:27559383

  4. Highly enantioselective aza-Diels-Alder reaction of 1-azadienes with enecarbamates catalyzed by chiral phosphoric acids.

    Science.gov (United States)

    He, Long; Laurent, Gregory; Retailleau, Pascal; Folléas, Benoît; Brayer, Jean-Louis; Masson, Géraldine

    2013-10-11

    On demand: A highly enantio- and diastereoselective synthesis of 6-amino- trisubstituted tetrahydropyridine compounds has been developed through the inverse-electron-demand aza-Diels-Alder reaction of N-aryl α,β-unsaturated ketimines with enecarbamates (E)-1. Chiral phosphoric acid catalysts achieve simultaneous activation of both the 1-azadiene and dienophile partners.

  5. High proton conduction in a chiral ferromagnetic metal-organic quartz-like framework.

    Science.gov (United States)

    Pardo, Emilio; Train, Cyrille; Gontard, Geoffrey; Boubekeur, Kamal; Fabelo, Oscar; Liu, Hongbo; Dkhil, Brahim; Lloret, Francesc; Nakagawa, Kosuke; Tokoro, Hiroko; Ohkoshi, Shin-ichi; Verdaguer, Michel

    2011-10-05

    A complex-as-ligand strategy to get a multifunctional molecular material led to a metal-organic framework with the formula (NH(4))(4)[MnCr(2)(ox)(6)]·4H(2)O. Single-crystal X-ray diffraction revealed that the anionic bimetallic coordination network adopts a chiral three-dimensional quartz-like architecture. It hosts ammonium cations and water molecules in functionalized channels. In addition to ferromagnetic ordering below T(C) = 3.0 K related to the host network, the material exhibits a very high proton conductivity of 1.1 × 10(-3) S cm(-1) at room temperature due to the guest molecules.

  6. Enantioseparation of Timolol on a Novel β-Cyclodextrin Derivative Chiral Stationary Phase in HPLC.

    Science.gov (United States)

    Zhou, Jie; Sun, Fang; Du, Qiuzheng; Zhao, Suzhen; Pei, Wenjuan

    2016-01-01

    A novel chiral stationary phase was prepared by bonding a novel β-cyclodextrin derivative on silica gel, and it was used for the separation of timolol in high efficiency liquid phase. In the reverse mode, the factors such as the proportion of chiral additives, flow rate, column temperature, repeatability and stability were investigated. The optimum chromatographic conditions are as follows: column temperature was 25°C, flow rate was 0.6 mL min(-1) and mobile phase was methanol-25 mM KH2PO4 (80/20, v/v). The chiral column has good reproducibility (Rs = 4.49, 4.51 and 4.40, respectively) and a certain degree of stability (Rs = 4.49, 3.01 and 0.72, respectively). This chiral stationary phase presented good chiral recognition performance toward timolol with good resolution (Rs = 4.49).

  7. Chiral 1,3,4-oxadiazol-2-ones as highly selective FAAH inhibitors.

    Science.gov (United States)

    Patel, Jayendra Z; Parkkari, Teija; Laitinen, Tuomo; Kaczor, Agnieszka A; Saario, Susanna M; Savinainen, Juha R; Navia-Paldanius, Dina; Cipriano, Mariateresa; Leppänen, Jukka; Koshevoy, Igor O; Poso, Antti; Fowler, Christopher J; Laitinen, Jarmo T; Nevalainen, Tapio

    2013-11-14

    In the present study, identification of chiral 1,3,4-oxadiazol-2-ones as potent and selective FAAH inhibitors has been described. The separated enantiomers showed clear differences in the potency and selectivity toward both FAAH and MAGL. Additionally, the importance of the chirality on the inhibitory activity and selectivity was proven by the simplification approach by removing a methyl group at the 3-position of the 1,3,4-oxadiazol-2-one ring. The most potent compound of the series, the S-enantiomer of 3-(1-(4-isobutylphenyl)ethyl)-5-methoxy-1,3,4-oxadiazol-2(3H)-one (JZP-327A, 51), inhibited human recombinant FAAH (hrFAAH) in the low nanomolar range (IC50 = 11 nM), whereas its corresponding R-enantiomer 52 showed only moderate inhibition toward hrFAAH (IC50 = 0.24 μM). In contrast to hrFAAH, R-enantiomer 52 was more potent in inhibiting the activity of hrMAGL compared to S-enantiomer 51 (IC50 = 4.0 μM and 16% inhibition at 10 μM, respectively). The FAAH selectivity of the compound 51 over the supposed main off-targets, MAGL and COX, was found to be >900-fold. In addition, activity-based protein profiling (ABPP) indicated high selectivity over other serine hydrolases. Finally, the selected S-enantiomers 51, 53, and 55 were shown to be tight binding, slowly reversible inhibitors of the hrFAAH.

  8. Dynamic Behavior of Clobazam on High-Performance Liquid Chromatography Chiral Stationary Phases.

    Science.gov (United States)

    Sabia, Rocchina; De Martino, Michela; Cavazzini, Alberto; Villani, Claudio

    2016-01-01

    Clobazam, a 1,5-benzodiazepin-2,4-dione, is a chiral molecule because its ground state conformation features a nonplanar seven-membered ring lacking reflection symmetry elements. The two conformational enantiomers of clobazam interconvert at room temperature by a simple ring-flipping process. Variable temperature HPLC on the Pirkle type (R)-N-(3,5-dinitronenzoyl)phenylglycine and (R,R)-Whelk-O1 chiral stationary phases (CSPs) allowed us to separate for the first time the conformational enantiomers of clobazam and to observe peak coalescence-decoalescence phenomena due to concomitant separation and interconversion processes occurring on the same time scale. Clobazam showed temperature dependent dynamic high-performance liquid chromatography (HPLC) profiles with interconversion plateaus on the two CSPs indicative of on-column enantiomer interconversion. (enantiomerization) in the column temperature range between Tcol = 10°C and Tcol = 30°C, whereas on-column interconversion was absent at temperature close to or lower than Tcol = 5°C. Computer simulation of exchange-deformed HPLC profiles using a program based on the stochastic model yielded the apparent rate constants for the on-column enantiomerization and the corresponding free energy activation barriers. At Tcol = 20°C the averaged enantiomerization barriers, ΔG(‡), for clobazam were found in the range 21.08-21.53 kcal mol(-1) on the two CSPs. The experimental dynamic chromatograms and the corresponding interconversion barriers reported in this article are consistent with the literature data measured by DNMR at higher temperatures and in different solvents.

  9. High-Temperature Target Recognition Based on Spectral Radiation Information

    Institute of Scientific and Technical Information of China (English)

    Fan Xueliang; Cheng Xiaofang; Xu Jun

    2006-01-01

    Based on the principles of optics and radiometry, the imaging mathematical model is established and the factors of the contrast (signal-noise-ratio) of high-temperature target and the scenery are given. By analyzing not only the differences in spectral properties between objects in the scene, but also the CCD spectral response theoretically, a new method of enhancement of contrast is given. By optimizing the initial image capture stage, using liquid crystal light valve to make a simple modification of the imaging system, the goal of high-temperature object recognition is achieved. The experimental results agree with the theoretical predict.

  10. The U(1)A anomaly in high temperature QCD with chiral fermions on the lattice

    CERN Document Server

    Sharma, Sayantan; Karsch, Frithjof; Laermann, Edwin; Mukherjee, Swagato

    2015-01-01

    The magnitude of the $U_A(1)$ symmetry breaking is expected to affect the nature of $N_f=2$ QCD chiral phase transition. The explicit breaking of chiral symmetry due to realistic light quark mass is small, so it is important to use chiral fermions on the lattice to understand the effect of $U_A(1)$ near the chiral crossover temperature, $T_c$. We report our latest results for the eigenvalue spectrum of 2+1 flavour QCD with dynamical Mobius domain wall fermions at finite temperature probed using the overlap operator on $32^3\\times 8$ lattice. We check how sensitive the low-lying eigenvalues are to the sea-light quark mass. We also present a comparison with the earlier independent results with domain wall fermions.

  11. High resolution spectroscopy of methyltrioxorhenium: towards the observation of parity violation in chiral molecules

    CERN Document Server

    Stoeffler, Clara; Shelkovnikov, Alexander; Daussy, Christophe; Amy-Klein, Anne; Chardonnet, Christian; Guy, Laure; Crassous, Jeanne; Huet, Thérèse; Soulard, Pascale; Asselin, Pierre

    2010-01-01

    Originating from the weak interaction, parity violation in chiral molecules has been considered as a possible origin of the biohomochirality. It was predicted in 1974 but has never been observed so far. Parity violation should lead to a very tiny frequency difference in the rovibrational spectra of the enantiomers of a chiral molecule. We have proposed to observe this predicted frequency difference using the two photon Ramsey fringes technique on a supersonic beam. Promising candidates for this experiment are chiral oxorhenium complexes, which present a large effect, can be synthesized in large quantity and enantiopure form, and can be seeded in a molecular beam. As a first step towards our objective, a detailed spectroscopic study of methyltrioxorhenium (MTO) has been undertaken. It is an ideal test molecule as the achiral parent molecule of chiral candidates for the parity violation experiment. For the 187Re MTO isotopologue, a combined analysis of Fourier transform microwave and infrared spectra as well as...

  12. Spin and chirality effects in antler-topology processes at high energy e{sup +}e{sup -} colliders

    Energy Technology Data Exchange (ETDEWEB)

    Choi, S.Y. [Chonbuk National University, Department of Physics, Jeonbuk (Korea, Republic of); University of Pittsburgh, Department of Physics and Astronomy, Pittsburgh Particle physics, Astrophysics, and Cosmology Center, Pittsburgh, PA (United States); Christensen, N.D. [Illinois State University, Department of Physics, Normal, IL (United States); Salmon, D.; Wang, X. [University of Pittsburgh, Department of Physics and Astronomy, Pittsburgh Particle physics, Astrophysics, and Cosmology Center, Pittsburgh, PA (United States)

    2015-10-15

    We perform a model-independent investigation of spin and chirality correlation effects in the antler-topology processes e{sup +}e{sup -} → P{sup +}P{sup -} → (l{sup +}D{sup 0})(l{sup +} anti D{sup 0}) at highenergy e{sup +}e{sup -} colliders with polarized beams. Generally the production process e{sup +}e{sup -} → P{sup +}P{sup -} can occur not only through the s-channel exchange of vector bosons, V{sup 0}, including the neutral Standard Model (SM) gauge bosons, γ and Z, but also through the s- and t-channel exchanges of new neutral states, S{sup 0} and T{sup 0}, and the u-channel exchange of new doubly charged states, U{sup --}. The general set of (nonchiral) three-point couplings of the new particles and leptons allowed in a renormalizable quantum field theory is considered. The general spin and chirality analysis is based on the threshold behavior of the excitation curves for P{sup +}P{sup -} pair production in e{sup +}e{sup -} collisions with longitudinal- and transverse-polarized beams, the angular distributions in the production process and also the production-decay angular correlations. In the first step, we present the observables in the helicity formalism. Subsequently, we show how a set of observables can be designed for determining the spins and chiral structures of the new particles without any model assumptions. Finally, taking into account a typical set of approximately chiral invariant scenarios, we demonstrate how the spin and chirality effects can be probed experimentally at a high-energy e{sup +}e{sup -} collider. (orig.)

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

    Science.gov (United States)

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

    2016-07-12

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

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

    Science.gov (United States)

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

    2016-07-01

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

  15. Inherent predominance of high chiral angle metallic carbon nanotubes in continuous fibers grown from a molten catalyst

    Science.gov (United States)

    Alemán, B.; Bernal, M. Mar; Mas, B.; Pérez, Emilio M.; Reguero, V.; Xu, G.; Cui, Y.; Vilatela, Juan J.

    2016-02-01

    We present evidence that high temperature CVD growth of SWNTs under conditions of continuous spinning of macroscopic fibers leads to an inherent predominance of high chiral angle CNTs, peaking at the armchair end. Raman, UV-vis-NIR absorption, and photoluminescence spectroscopy measurements show the prevalence of metallic SWNTs. The complete chiral angle distribution is obtained by electron diffraction of over 390 CNTs. It is biased towards high chiral angles and peaks at the armchair end (30°), in good agreement with the established atomistic models for SWNT growth from a liquid catalyst. Based on the Fe-C-S constituent binary and ternary phase diagrams, thermodynamic calculations of phase compositions from fast cooling and experimental evidence of a post-synthesis catalyst, the proposed thermodynamic path of the catalyst is to form a solid FCC Fe core and a liquid Fe-S shell. S in the outer liquid shell first stabilizes the edge of the nascent CNT, but once a graphitic wall forms it is rejected due to the high interfacial energy of the Fe-C-S alloy.We present evidence that high temperature CVD growth of SWNTs under conditions of continuous spinning of macroscopic fibers leads to an inherent predominance of high chiral angle CNTs, peaking at the armchair end. Raman, UV-vis-NIR absorption, and photoluminescence spectroscopy measurements show the prevalence of metallic SWNTs. The complete chiral angle distribution is obtained by electron diffraction of over 390 CNTs. It is biased towards high chiral angles and peaks at the armchair end (30°), in good agreement with the established atomistic models for SWNT growth from a liquid catalyst. Based on the Fe-C-S constituent binary and ternary phase diagrams, thermodynamic calculations of phase compositions from fast cooling and experimental evidence of a post-synthesis catalyst, the proposed thermodynamic path of the catalyst is to form a solid FCC Fe core and a liquid Fe-S shell. S in the outer liquid shell first

  16. Prosody recognition in adults with high-functioning autism spectrum disorders: from psychoacoustics to cognition.

    Science.gov (United States)

    Globerson, Eitan; Amir, Noam; Kishon-Rabin, Liat; Golan, Ofer

    2015-04-01

    Prosody is an important tool of human communication, carrying both affective and pragmatic messages in speech. Prosody recognition relies on processing of acoustic cues, such as the fundamental frequency of the voice signal, and their interpretation according to acquired socioemotional scripts. Individuals with autism spectrum disorders (ASD) show deficiencies in affective prosody recognition. These deficiencies have been mostly associated with general difficulties in emotion recognition. The current study explored an additional association between affective prosody recognition in ASD and auditory perceptual abilities. Twenty high-functioning male adults with ASD and 32 typically developing male adults, matched on age and verbal abilities undertook a battery of auditory tasks. These included affective and pragmatic prosody recognition tasks, two psychoacoustic tasks (pitch direction recognition and pitch discrimination), and a facial emotion recognition task, representing nonvocal emotion recognition. Compared with controls, the ASD group demonstrated poorer performance on both vocal and facial emotion recognition, but not on pragmatic prosody recognition or on any of the psychoacoustic tasks. Both groups showed strong associations between psychoacoustic abilities and prosody recognition, both affective and pragmatic, although these were more pronounced in the ASD group. Facial emotion recognition predicted vocal emotion recognition in the ASD group only. These findings suggest that auditory perceptual abilities, alongside general emotion recognition abilities, play a significant role in affective prosody recognition in ASD.

  17. Bounding the Probability of Error for High Precision Recognition

    CERN Document Server

    Kae, Andrew; Learned-Miller, Erik

    2009-01-01

    We consider models for which it is important, early in processing, to estimate some variables with high precision, but perhaps at relatively low rates of recall. If some variables can be identified with near certainty, then they can be conditioned upon, allowing further inference to be done efficiently. Specifically, we consider optical character recognition (OCR) systems that can be bootstrapped by identifying a subset of correctly translated document words with very high precision. This "clean set" is subsequently used as document-specific training data. While many current OCR systems produce measures of confidence for the identity of each letter or word, thresholding these confidence values, even at very high values, still produces some errors. We introduce a novel technique for identifying a set of correct words with very high precision. Rather than estimating posterior probabilities, we bound the probability that any given word is incorrect under very general assumptions, using an approximate worst case ...

  18. 扁桃酸及其衍生物对映体的手性识别研究%Studies on Chiral Recognition of Mandelic Acid and Its Derivatives Enantiomers

    Institute of Scientific and Technical Information of China (English)

    周发; 刘佳佳; 肖清波; 刘言萍; 尹军; 刘丰良

    2012-01-01

    The chiral recognition ability of these two chiral amino alcohols were evaluated as chiral solvating agent (host) for 7 mandelic acid derivatives enantiomers (guest) in the presence of an equimolar amount, respectively. As a result, the biggest chemical shift non-equivalences (△△δ) of 4-tert-butyl mandelic acid enantiomers induced by the two polydentate ligands was 37.6 Hz.%以两种手性氨基醇作为主体,运用1H NMR分别考察其对客体7个扁桃酸衍生物对映异构体的手性识别能力。结果表明,主客体物质的量之比为1:1时,主体诱导客体对叔丁基扁桃酸消旋体最高产生37.6Hz的化学位移差值。

  19. Chiral photochemistry

    CERN Document Server

    Inoue, Yoshihisa

    2004-01-01

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

  20. Applications of chiral symmetry

    Energy Technology Data Exchange (ETDEWEB)

    Pisarski, R.D.

    1995-03-01

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

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

    Institute of Scientific and Technical Information of China (English)

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

    2006-01-01

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

  2. Chiral algebras

    CERN Document Server

    Beilinson, Alexander

    2004-01-01

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

  3. Racemic but tropos (chirally flexible) BIPHEP ligands for Rh(I)-complexes: highly enantioselective ene-type cyclization of 1,6-enynes.

    Science.gov (United States)

    Mikami, Koichi; Kataoka, Shohei; Yusa, Yukinori; Aikawa, Kohsuke

    2004-10-14

    [reaction: see text] The tropos (chirally flexible) or atropos (chirally rigid) nature of BIPHEP-Rh complexes at room temperature critically depends on the amines complexed. The aliphatic DPEN complex is atropos, whereas the aromatic DABN complex is tropos. BIPHEP-Rh chirality can thus be controlled by DABN at room temperature. The amine-free BIPHEP-Rh complex is tropos. At 5 degrees C, even amine-free BIPHEP-Rh complexes are atropos and hence can be used as enantiopure catalysts to give high enantioselectivity in ene-type cyclization of 1,6-enynes.

  4. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

    OpenAIRE

    2016-01-01

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to st...

  5. Chiral enantioresolution of cathinone derivatives present in "legal highs", and enantioselectivity evaluation on cytotoxicity of 3,4-methylenedioxypyrovalerone (MDPV).

    Science.gov (United States)

    Silva, Bárbara; Fernandes, Carla; Tiritan, Maria Elizabeth; Pinto, Madalena M M; Valente, Maria João; Carvalho, Márcia; de Pinho, Paula Guedes; Remião, Fernando

    Recently, great interest has been focused on synthetic cathinones since their consumption has increased exponentially. All synthetic cathinones exist as chiral molecules; the biological and/or toxicological properties of cathinones generally differ according to the enantiomers in human body. In this study, a chiral liquid chromatography method was developed to separate and determine the enantiomeric ratio of synthetic cathinones present in "legal highs" acquired in old smart shops or over the Internet. All the synthetic cathinones were efficiently enantio-separated with α and Rs ranging from 1.24 to 3.62 and from 1.24 to 10.52, respectively, using polysaccharide-based chiral stationary phases. All synthetic cathinones, with the exception of 4-methylethcathinone (4-MEC), were present in the commercialized "legal highs" in an enantiomeric proportion of 50:50. One of the studied chiral compounds was 3,4-methylenedioxypyrovalerone (MDPV), one of the most consumed cathinone derivative worldwide. Our research group has recently reported its hepatotoxicity in the racemic form. Thus, the analytical enantioresolution of the MDPV was scaled up to multi-milligram using a semi-preparative amylose tris-3,5-dimethylphenylcarbamate column (20 cm × 7.0 mm ID, 7 µm particle size). Both enantiomers were isolated with high enantiomeric purity (enantiomeric excess > 99 %). The toxicity of S-(-)-MDPV and R-(+)-MDPV was evaluated, for the first time, using primary cultures of rat hepatocytes. It was also possible to verify that MDPV enantiomers showed hepatotoxicity in a concentration-dependent manner, but displayed no enantioselective toxicity in this cell culture model.

  6. Enantioselective and diastereoselective separation of synthetic pyrethroid insecticides on a novel chiral stationary phase by high-performance liquid chromatography.

    Science.gov (United States)

    Tan, Xulin; Hou, Shicong; Wang, Min

    2007-07-01

    A novel chiral packing material for high-performance liquid chromatography (HPLC) was prepared by connecting (R)-1-phenyl-2-(4-methylphenyl) ethylamine (PTE) amide derivative of (S)-isoleucine to aminopropyl silica gel through 2-amino-3,5-dinitro-1-carboxamido-benzene unit. This chiral stationary phase was applied to the enantioselective and diastereoselective separation of five pyrethroid insecticides by HPLC under normal phase condition. To achieve satisfactory baseline separation an optimization of the variables of mobile phase composition was required. The two enantiomers of fenpropathrin and four stereoisomers of fenvalerate were baseline separated using hexane-1,2-dichloroethane-2-propanol as mobile phase. The results show that the enantioselectivity of CSP is better than Pirkle type 1-A column for these compounds. Only partial separations for the cypermethrin and cyfluthrin stereoisomers were observed. Seven peaks and eight peaks were observed for cypermethrin and cyfluthrin, respectively. The elution orders were assigned by using different stereoisomer-enriched products.

  7. 铂掺杂L-缬氨酸聚合膜对普萘洛尔的识别研究%Chiral recognition of propranolol based on Pt doped L-valine polymer

    Institute of Scientific and Technical Information of China (English)

    陈翠; 李洋; 傅英姿

    2015-01-01

    该文将氯铂酸与L-缬氨酸按一定比例混合,通过循环伏安法在玻碳电极表面电沉积形成铂掺杂L-缬氨酸聚合膜,“一步”构建一个简单的手性传感平台,以普萘洛尔自身为氧化还原探针,采用差分脉冲伏安法研究了该手性传感平台与普萘洛尔对映异构体之间的相互作用。结果表明:该传感平台与普萘洛尔产生相互作用,并与R-普萘洛尔作用更强,能成功用于普萘洛尔的电化学识别。%In this work, chloroplatinic acid and L-valine (L-val) were mixed by a certain percentage, and then the L-val platinum-doped polymeric films were synthesized on the glassy carbon electrode (GCE) surface with “one-step” strategy, building a simple chiral sensing nanoplatform, and used to electrochemical identify of propranolol enantiomers (R-or S-PRO) successfully. Differential pulse voltammetry (DPV) technique was used to study the effect between this chiral interface and propranolol enantiomers, which propranolol was treated as redox probes. In addition, the recognition was considerably affected by the interface. The results showed that this chiral interface has a stronger interact with R-PRO, and it was efficacious to achieve the selective recognition of propranolol enantiomers.

  8. Robust, Chiral, and Porous BINAP-Based Metal–Organic Frameworks for Highly Enantioselective Cyclization Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Thacker, Nathan C.; Lin, Zekai; McIsaac, Alexandra R.; Lin, Wenbin (UC)

    2016-05-06

    We report here the design of BINAP-based metal–organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active and enantioselective single-site solid catalysts for the asymmetric cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs of UiO topology, BINAP-MOF (I) or BINAP-dMOF (II), were prepared using purely BINAP-derived dicarboxylate linkers or by mixing BINAP-derived linkers with unfunctionalized dicarboxylate linkers, respectively. Upon metalation with Rh(nbd)2BF4 and [Rh(nbd)Cl]2/AgSbF6, the MOF precatalysts I·Rh(BF4) and I·Rh(SbF6) efficiently catalyzed highly enantioselective (up to 99% ee) reductive cyclization and Alder-ene cycloisomerization of 1,6-enynes, respectively. I·Rh catalysts afforded cyclization products at comparable enantiomeric excesses (ee’s) and 4–7 times higher catalytic activity than the homogeneous controls, likely a result of catalytic site isolation in the MOF which prevents bimolecular catalyst deactivation pathways. However, I·Rh is inactive in the more sterically encumbered Pauson–Khand reactions between 1,6-enynes and carbon monoxide. In contrast, with a more open structure, Rh-functionalized BINAP-dMOF, II·Rh, effectively catalyzed Pauson–Khand cyclization reactions between 1,6-enynes and carbon monoxide at 10 times higher activity than the homogeneous control. II·Rh was readily recovered and used three times in Pauson–Khand cyclization reactions without deterioration of yields or ee’s. Our work has expanded the scope of MOF-catalyzed asymmetric reactions and showed that the mixed linker strategy can effectively enlarge the open space around the catalytic active site to accommodate highly sterically demanding polycyclic metallocycle transition states/intermediates in asymmetric intramolecular cyclization reactions.

  9. Online Pattern Recognition for the ALICE High Level Trigger

    CERN Document Server

    Lindenstruth, V; Röhrich, D; Skaali, B; Steinbeck, T M; Stock, Reinhard; Tilsner, H; Ullaland, K; Vestbø, A S; Vik, T

    2004-01-01

    The ALICE High Level Trigger has to process data online, in order to select interesting (sub)events, or to compress data efficiently by modeling techniques.Focusing on the main data source, the Time Projection Chamber (TPC), we present two pattern recognition methods under investigation: a sequential approach "cluster finder" and "track follower") and an iterative approach ("track candidate finder" and "cluster deconvoluter"). We show, that the former is suited for pp and low multiplicity PbPb collisions, whereas the latter might be applicable for high multiplicity PbPb collisions, if it turns out, that more than 8000 charged particles would have to be reconstructed inside the TPC. Based on the developed tracking schemes we show, that using modeling techniques a compression factor of around 10 might be achievable

  10. Online Pattern Recognition for the ALICE High Level Trigger

    Science.gov (United States)

    Lindenstruth, V.; Loizides, C.; Rohrich, D.; Skaali, B.; Steinbeck, T.; Stock, R.; Tilsner, H.; Ullaland, K.; Vestbo, A.; Vik, T.

    2004-06-01

    The ALICE high level trigger has to process data online, in order to select interesting (sub)events, or to compress data efficiently by modeling techniques. Focusing on the main data source, the time projection chamber (TPC), we present two pattern recognition methods under investigation: a sequential approach (cluster finder and track follower) and an iterative approach (track candidate finder and cluster deconvoluter). We show, that the former is suited for pp and low multiplicity PbPb collisions, whereas the latter might be applicable for high multiplicity PbPb collisions of dN/dy>3000. Based on the developed tracking schemes we show that using modeling techniques, a compression factor of around 10 might be achievable.

  11. Modified High Frequency Radial Spin Wave Mode Spectrum in a Chirality-Controlled Nanopillar

    Science.gov (United States)

    Kolthammer, J. E.; Rudge, J.; Choi, B. C.; Hong, Y. K.

    2016-09-01

    Circular magnetic spin valve nanopillars in a dual vortex configuration have dynamic characteristics strongly dependent on the interlayer dipole coupling. We report here on frequency domain properties of such nanopillars obtained by micromagnetic simulations. After the free layer is chirality switched with spin transfer torque, a radial spin wave eigenmode spectrum forms in the free layer with unusually large edge amplitude. The structure of these modes indicate a departure from the magnetostatic processes typically observed experimentally and treated analytically in low aspect ratio isolated disks. Our findings give new details of dynamic chirality control and relxation in nanopillars and raise potential signatures for experiments.

  12. Chiral symmetry breaking, color superconductivity and equation of state at high density a variational approach

    CERN Document Server

    Mishra, H; Mishra, Hiranmaya; Parikh, Jitendra C.

    2001-01-01

    We discuss in this note simultaneous existence of chiral symmetry breakingand color superconductivity at finite temperature and density in aNambu-Jona-Lasinio type model. The methodology involves an explicitconstruction of a variational ground state and minimisation of thethermodynamic potential. There appears to be a phase at finite densities withboth quark antiquark as well as diquark condensates for the "ground" state.Chiral symmetry breaking phase appear to catalyse the threshold for the diquarkcondensates to appear. We also compute the equation of state in this model.

  13. Novel chiral derivatization reagents possessing a pyridylthiourea structure for enantiospecific determination of amines and carboxylic acids in high-throughput liquid chromatography and electrospray-ionization mass spectrometry for chiral metabolomics identification.

    Science.gov (United States)

    Nagao, Ryuji; Tsutsui, Haruhito; Mochizuki, Toshiki; Takayama, Takahiro; Kuwabara, Tomohiro; Min, Jun Zhe; Inoue, Koichi; Todoroki, Kenichiro; Toyo'oka, Toshimasa

    2013-06-28

    This paper reports the synthesis and the application of novel derivatization reagents possessing a pyridylthiourea structure for the enantiospecific determination of chiral amines and carboxylic acids in high-throughput LC-ESI-MS/MS. The novel reagents, i.e., (R)-N-(3-pyridylthiocarbamoyl)pyrrolidine-2-carboxylic acid (PyT-C) and (S)-3-amino-1-(3-pyridylthiocarbamoyl)pyrrolidine (PyT-N), were evaluated as chiral derivatization reagents for the enantiomeric determination of chiral amines and carboxylic acids, respectively, in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. The chiral amines and carboxylic acids were easily labeled with PyT-C and PyT-N, respectively, at 60°C in 60min in the presence of 2,2'-dipyridyl disulfide (DPDS) and triphenylphosphine (TPP) as the activation reagents. The resulting diastereomers were completely separated by reversed-phase chromatography using a small particle (1.7μm) ODS column (Rs=3.54-6.00 for carboxylic acids and Rs=3.07-4.75 for amines). A highly sensitive detection at the sub-fmol level was also obtained from the SRM chromatograms at a single monitoring ion, m/z 137.0 (0.72-1.46fmol for carboxylic acids and 0.55-1.89fmol for amines). The proposed procedure using PyT-C and PyT-N was applied to the determination of chiral amines and carboxylic acids spiked into human saliva, as a model study of chiral metabonomics identification. dl-Amino acid methyl esters and N-acetyl dl-amino acids, which are the representatives as the chiral amines and carboxylic acids, in the saliva were clearly identified by the present method. Because the same product ion at m/z 137.0 was obtained from collision-induced dissociation (CID) of protonated molecular ions of all the derivatives, the proposed procedure using both reagents (i.e., PyT-C and PyT-N) seems to be useful for chiral metabolomics identification having selected functional groups (i.e., amines and carboxylic acids).

  14. 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.

  15. Ionic Liquids Derived from the Chiral Pool: New Media for Fine Chemistry

    Institute of Scientific and Technical Information of China (English)

    A.C. Gaumont; D. Bregeon; J. Levillain; C. Baudequin; F. Guillen; J.C. Plaquevent

    2005-01-01

    @@ 1Introduction Ionic liquids (Ils) are low melting point salts, which are characterized by properties such as high ability to dissolve organic, organometallic and even inorganic compounds, absence of flammability, lack of measurable vapour pressure and high thermal stability. Due to these peculiar properties, they have recently attracted considerable attention as greener alternatives to volatile organic solvents[1]. A few chiral ionic liquids, which could provide a renewal in the field of chiral solvents, have also been reported recently[2]. Herein, we will present the synthesis of a new family of ionic liquids based on a thiazolinium skeleton. Preliminary results on the use of these chiral ionic liquids in the field of chiral recognition and organic synthesis will also be reported.

  16. High performance liquid chromatographic separation of eight drugs collected in Chinese Pharmacopoeia 2010 on amylose ramification chiral stationary phase

    Directory of Open Access Journals (Sweden)

    Yan Wang

    2012-10-01

    Full Text Available The enantiomers separation of eight pharmaceutical racemates collected in Chinese Pharmacopoeia 2010 (Ch.P2010, including nitrendipine, felodipine, omeprazole, praziquantel, sulpiride, clenbuterol hydrochloride, verapamil hydrochloride and chlorphenamine maleate, was performed on chiral stationary phase of amylose ramification by high performance liquid chromatography (HPLC on Chiralpak AD-H column and Chiralpak AS-H column with the mobile phase consisted of isopropanol and n-hexane. The detection wavelength and the flow rate were set at 254 nm and 0.7 mL/min, respectively. The effects of proportion of organic additives, alcohol displacer and temperature on the separation were investigated. The results indicated that eight chiral drugs were separated on chiral stationary phase of amylase ramification in normal phase chromatographic system. The chromatographic retention and resolution of enantiomers were adjusted by factors, including the changes of the concentration of alcohol displacer in mobile phase, organic alkaline modifier and column temperature. It was shown that the resolution was improved with reducing concentration of alcohol displacer. When the concentration of organic alkaline modifier was 0.2%, the resolution and the peak shape were fairly good. Most racemates mentioned above had the best resolution at column temperature of 25 °C. The best temperature should be kept unchanged in the process of separation so as to obtain stable separation results.

  17. COVALENTLY BONDING CHIRAL POLYURETHANE ON AMINATED SILICA GEL: A NEW STRATEGY TO PREPARE CHIRAL STATIONARY PHASE FOR HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

    Institute of Scientific and Technical Information of China (English)

    Shao-hua Huang; Zheng-wu Bai; Chuan-qi Yin; Shi-rong Li

    2006-01-01

    Two polyurethanes of different molecular weights were prepared by the copolymerization of phenyl diisocyanate and diisopropyl tartrate. The polyurethanes having terminal isocyanate groups were reacted with 3-aminopropyl silica gel to afford two chiral stationary phases. The (M-)n of the two polyurethanes were 4057 g/mol and 6442 g/mol. The polyurethanes and the corresponding chiral stationary phases were characterized by FT-IR, 1H NMR and elemental analysis. The loading capacities of the polyurethanes on silica gel were 0.68 mmol units/g and 0.61 mmol units/g, respectively. The separation performance and the influence of additives, triethylamine and trichloroacetic acid, on the separation of chiral compounds were investigated by HPLC. The chiral stationary phase prepared from polyurethane with (M-)n of 4057 g/mol demonstrated better enantioseparation capability than that with (M-)n of 6442 g/mol. Additionally, it was found that the addition of triethylamine and trichloroacetic acid in the mobile phases significantly improved the enantioseparation for these two chiral stationary phases.

  18. Engineering chiral porous metal-organic frameworks for enantioselective adsorption and separation

    Science.gov (United States)

    Peng, Yongwu; Gong, Tengfei; Zhang, Kang; Lin, Xiaochao; Liu, Yan; Jiang, Jianwen; Cui, Yong

    2014-07-01

    The separation of racemic molecules is of substantial significance not only for basic science but also for technical applications, such as fine chemicals and drug development. Here we report two isostructural chiral metal-organic frameworks decorated with chiral dihydroxy or -methoxy auxiliares from enantiopure tetracarboxylate-bridging ligands of 1,1‧-biphenol and a manganese carboxylate chain. The framework bearing dihydroxy groups functions as a solid-state host capable of adsorbing and separating mixtures of a range of chiral aromatic and aliphatic amines, with high enantioselectivity. The host material can be readily recycled and reused without any apparent loss of performance. The utility of the present adsorption separation is demonstrated in the large-scale resolution of racemic 1-phenylethylamine. Control experiments and molecular simulations suggest that the chiral recognition and separation are attributed to the different orientations and specific binding energies of the enantiomers in the microenvironment of the framework.

  19. Synthesis of a series of soluble main-chain chiral nonracemic poly(alkyl-aryl ketone

    Directory of Open Access Journals (Sweden)

    2008-06-01

    Full Text Available A series of main-chain chiral polyketones have been synthesized through condensation polymerization of a dihalide and a diketone with optically pure binaphthyl moiety as linkage in the polymer backbone. The solubility of the polymers can be easily enhanced by substituents at the alpha position next to the carbonyl groups. Reducing the steric hindrance of the substituents in the monomers increases the reactivity of the polymerization. The chiral polymers exhibit large optical rotations. Circular Dichroism (CD spectra of the polymers are similar to those of the corresponding monomers. The novel synthetic strategy may have great impact on future development of palladium catalyzed condensation polymerizations. The highly soluble chiral polymers synthesized allow for preparation of materials in the form of thin films and have potentials applications in various areas such as chiral separation and recognition.

  20. Structure recognition from high resolution images of ceramic composites

    Energy Technology Data Exchange (ETDEWEB)

    Ushizima, Daniela; Perciano, Talita; Krishnan, Harinarayan; Loring, Burlen; Bale, Hrishikesh; Parkinson, Dilworth; Sethian, James

    2015-01-05

    Fibers provide exceptional strength-to-weight ratio capabilities when woven into ceramic composites, transforming them into materials with exceptional resistance to high temperature, and high strength combined with improved fracture toughness. Microcracks are inevitable when the material is under strain, which can be imaged using synchrotron X-ray computed micro-tomography (mu-CT) for assessment of material mechanical toughness variation. An important part of this analysis is to recognize fibrillar features. This paper presents algorithms for detecting and quantifying composite cracks and fiber breaks from high-resolution image stacks. First, we propose recognition algorithms to identify the different structures of the composite, including matrix cracks and fibers breaks. Second, we introduce our package F3D for fast filtering of large 3D imagery, implemented in OpenCL to take advantage of graphic cards. Results show that our algorithms automatically identify micro-damage and that the GPU-based implementation introduced here takes minutes, being 17x faster than similar tools on a typical image file.

  1. The Optical Resolution of Chiral Tetrahedrone-type Clusters Contai- ning SCoFeM (M=Mo or W) Using High Performance Liquid Chromatography Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Amylose tris (phenylcarbamate) chiral stationary phase (ATPC-CSP) was prepared and used for optical resolution of clusters 1 and 2. n-Hexane/2-propanol ( 99/1; v/v) were found to be the most suitable mobile phase on ATPC-CSP.

  2. Highly nonlinear wave solutions in a dual to the chiral model

    CERN Document Server

    Rajeev, S G

    2016-01-01

    We consider a two-dimensional scalar field theory with a nilpotent current algebra, which is dual to the Principal Chiral Model. The quantum theory is renormalizable and not asymptotically free: the theory is strongly coupled at short distances (encountering a Landau pole). We suggest it can serve as a toy model for $\\lambda\\phi^{4}$ theory in four dimensions, just as the principal chiral model is a useful toy model for Yang-Mills theory. We find some classical wave solutions that survive the strong coupling limit and quantize them by the collective variable method. They describe excitations with an unusual dispersion relation $\\omega\\propto|k|^{\\frac{2}{3}}$ . Perhaps they are the "preons" at strong coupling, whose bound states form massless particles over long distances.

  3. Highly nonlinear wave solutions in a dual to the chiral model

    Science.gov (United States)

    Rajeev, S. G.; Ranken, Evan

    2016-05-01

    We consider a two-dimensional scalar field theory with a nilpotent current algebra, which is dual to the Principal Chiral Model. The quantum theory is renormalizable and not asymptotically free; the theory is strongly coupled at short distances (encountering a Landau pole). We suggest it can serve as a toy model for λ ϕ4 theory in four dimensions, just as the principal chiral model is a useful toy model for Yang-Mills theory. We find some classical wave solutions that survive the strong coupling limit and quantize them by the collective variable method. They describe excitations with an unusual dispersion relation ω ∝|k |2/3 . Perhaps they are the "preons" at strong coupling, the bound states of which form massless particles over long distances.

  4. 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.

  5. Learning high-level features for chord recognition using Autoencoder

    Science.gov (United States)

    Phongthongloa, Vilailukkana; Kamonsantiroj, Suwatchai; Pipanmaekaporn, Luepol

    2016-07-01

    Chord transcription is valuable to do by itself. It is known that the manual transcription of chords is very tiresome, time-consuming. It requires, moreover, musical knowledge. Automatic chord recognition has recently attracted a number of researches in the Music Information Retrieval field. It has known that a pitch class profile (PCP) is the commonly signal representation of musical harmonic analysis. However, the PCP may contain additional non-harmonic noise such as harmonic overtones and transient noise. The problem of non-harmonic might be generating the sound energy in term of frequency more than the actual notes of the respective chord. Autoencoder neural network may be trained to learn a mapping from low level feature to one or more higher-level representation. These high-level representations can explain dependencies of the inputs and reduce the effect of non-harmonic noise. Then these improve features are fed into neural network classifier. The proposed high-level musical features show 80.90% of accuracy. The experimental results have shown that the proposed approach can achieve better performance in comparison with other based method.

  6. Localised polymer networks in chiral nematic liquid crystals for high speed photonic switching

    Energy Technology Data Exchange (ETDEWEB)

    Tartan, Chloe C., E-mail: chloe.tartan@eng.ox.ac.uk, E-mail: steve.elston@eng.ox.ac.uk; Salter, Patrick S.; Booth, Martin J.; Morris, Stephen M.; Elston, Steve J., E-mail: chloe.tartan@eng.ox.ac.uk, E-mail: steve.elston@eng.ox.ac.uk [Department of Engineering Science, University of Oxford, Parks Road, Oxford OX1 3PJ (United Kingdom)

    2016-05-14

    Self-assembled periodic structures based upon chiral liquid crystalline materials have significant potential in the field of photonics ranging from fast-switching optoelectronic devices to low-threshold lasers. The flexoelectro-optic effect, which is observed in chiral nematic liquid crystals (LCs) when an electric field is applied perpendicular to the helical axis, has significant potential as it exhibits analogue switching in 10–100 μs. However, the major technological barrier that prohibits the commercial realisation of this electro-optic effect is the requirement of a uniform, in-plane alignment of the helix axis between glass substrates. Here, it is shown that periodic polymer structures engineered in the nematic phase of a chiral nematic LC device using direct laser writing can result in the spontaneous formation of the necessary uniform lying helix (ULH) state. Specifically, two-photon polymerization is used in conjunction with a spatial light modulator so as to correct for aberrations introduced by the bounding glass substrates enabling the polymer structures to be fabricated directly into the device. The ULH state appears to be stable in the absence of an externally applied electric field, and the optimum contrast between the bright and dark states is obtained using polymer structures that have periodicities of the order of the device thickness.

  7. Localised polymer networks in chiral nematic liquid crystals for high speed photonic switching

    Science.gov (United States)

    Tartan, Chloe C.; Salter, Patrick S.; Booth, Martin J.; Morris, Stephen M.; Elston, Steve J.

    2016-05-01

    Self-assembled periodic structures based upon chiral liquid crystalline materials have significant potential in the field of photonics ranging from fast-switching optoelectronic devices to low-threshold lasers. The flexoelectro-optic effect, which is observed in chiral nematic liquid crystals (LCs) when an electric field is applied perpendicular to the helical axis, has significant potential as it exhibits analogue switching in 10-100 μs. However, the major technological barrier that prohibits the commercial realisation of this electro-optic effect is the requirement of a uniform, in-plane alignment of the helix axis between glass substrates. Here, it is shown that periodic polymer structures engineered in the nematic phase of a chiral nematic LC device using direct laser writing can result in the spontaneous formation of the necessary uniform lying helix (ULH) state. Specifically, two-photon polymerization is used in conjunction with a spatial light modulator so as to correct for aberrations introduced by the bounding glass substrates enabling the polymer structures to be fabricated directly into the device. The ULH state appears to be stable in the absence of an externally applied electric field, and the optimum contrast between the bright and dark states is obtained using polymer structures that have periodicities of the order of the device thickness.

  8. Highly efficient chiral resolution of DL-arginine by cocrystal formation followed by recrystallization under preferential-enrichment conditions.

    Science.gov (United States)

    Iwama, Sekai; Kuyama, Kazunori; Mori, Yuko; Manoj, Kochunnoonny; Gonnade, Rajesh G; Suzuki, Katsuaki; Hughes, Colan E; Williams, P Andrew; Harris, Kenneth D M; Veesler, Stéphane; Takahashi, Hiroki; Tsue, Hirohito; Tamura, Rui

    2014-08-11

    An excellent chiral symmetry-breaking spontaneous enantiomeric resolution phenomenon, denoted preferential enrichment, was observed on recrystallization of the 1:1 cocrystal of dl-arginine and fumaric acid, which is classified as a racemic compound crystal with a high eutectic ee value (>95 %), under non-equilibrium crystallization conditions. On the basis of temperature-controlled video microscopy and in situ time-resolved solid-state (13) C NMR spectroscopic studies on the crystallization process, a new mechanism of phase transition that can induce preferential enrichment is proposed.

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

    Science.gov (United States)

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

    2016-08-01

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

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

    Institute of Scientific and Technical Information of China (English)

    张来新; 赵卫星

    2011-01-01

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

  11. High speed optical object recognition processor with massive holographic memory

    Science.gov (United States)

    Chao, T.; Zhou, H.; Reyes, G.

    2002-01-01

    Real-time object recognition using a compact grayscale optical correlator will be introduced. A holographic memory module for storing a large bank of optimum correlation filters, to accommodate the large data throughput rate needed for many real-world applications, has also been developed. System architecture of the optical processor and the holographic memory will be presented. Application examples of this object recognition technology will also be demonstrated.

  12. Ultra-broad band and dual-band highly efficient polarization conversion based on the three-layered chiral structure

    Science.gov (United States)

    Xu, Kai-kai; Xiao, Zhong-yin; Tang, Jing-yao; Liu, De-jun; Wang, Zi-hua

    2016-07-01

    In the paper, a novel three-layered chiral structure is proposed and investigated, which consists of a split-ring resonator sandwiched between two layers of sub-wavelength gratings. This designed structure can achieve simultaneously asymmetric transmission with an extremely broad bandwidth and high amplitude as well as multi-band 90° polarization rotator with very low dispersion. Numerical simulations adopted two kinds of softwares with different algorithms demonstrate that asymmetric parameter can reach a maximum of 0.99 and over than 0.8 from 4.6 to 16.8 GHz, which exhibit magnitude and bandwidth improvement over previous chiral metamaterials in microwave bands (S, C, X and Ku bands). Specifically, the reason of high amplitude is analyzed in detail based on the Fabry-perot like resonance. Subsequently, the highly efficient polarization conversion with very low dispersion between two orthogonal linearly polarized waves is also analyzed by the optical activity and ellipticity. Finally, the electric fields are also investigated and further demonstrate the correctness of the simulated and calculated results.

  13. Chiral Graphene Quantum Dots.

    Science.gov (United States)

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

    2016-02-23

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

  14. Metal Complexes:Novel Chiral Dopants with High Helical Twisting Power in Liquid Crystals

    Institute of Scientific and Technical Information of China (English)

    Manfred; Braun; R.Fleischer; A.Hahn; M.Engelmann; S.Schlecht

    2007-01-01

    1 Introduction A particularly efficient and elegant route to chiral mesophases is based on the addition of small amounts of an enantiomerically pure dopant to a nematic phase so that the latter is converted into a cholesteric phase(See Fig.1).Fig.1 A nematic phase is converted into a cholesteric phase Fig.2 Bis-chelated imine-alkoxy-titanium complexes2 ExperimetalBis-chelated imine-alkoxy-titanium complexes like 1 and 2 (Fig.2) have been synthesizedstarting from triphenyl-substituted aminoethanols, T...

  15. High efficiency, narrow particle size distribution, sub-2 μm based macrocyclic glycopeptide chiral stationary phases in HPLC and SFC.

    Science.gov (United States)

    Barhate, Chandan L; Wahab, M Farooq; Breitbach, Zachary S; Bell, David S; Armstrong, Daniel W

    2015-10-22

    State of the art chiral chromatography still employs 3-5 μm bonded or immobilized chiral selectors in 10-25 cm columns. With the availability of 1.9 μm narrow particle size distribution (NPSD) silica, it is now possible to make ever shorter, high efficiency columns practical for sub-minute chiral separations. Three macrocyclic glycopeptides (teicoplanin, teicoplanin aglycone, and vancomycin) were bonded onto 1.9 μm NPSD particles. Such packed columns had ∼80% lower backpressure as compared to polydisperse (PD) 1.7 μm silica materials when using the same mobile phase. The decreased backpressure allowed for diminution of frictional heating and allowed for the use of the 1.9 μm NPSD particle based columns at high flow rates. The 1.9 μm NPSD particle based columns showed up to 190,000 plates m(-1) for chiral molecules and 210,000 plates m(-1) for achiral probes. Representative enantiomeric separations are shown for wide classes of compounds, including different types of amino acids, β-blockers, and pharmaceutically important heterocyclic compounds such as oxazolidinones. Applications in three liquid chromatography modes, namely, reversed phase, polar organic mode and normal phase chiral separations were shown with resolution values ranging from 1.5 to 5.7. Additionally, the same columns were used with supercritical fluid chromatography (SFC) for ultrafast separations.

  16. 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.

  17. Majority-Rules-Type Helical Poly(quinoxaline-2,3-diyl)s as Highly Efficient Chirality-Amplification Systems for Asymmetric Catalysis.

    Science.gov (United States)

    Ke, Yuan-Zhen; Nagata, Yuuya; Yamada, Tetsuya; Suginome, Michinori

    2015-08-01

    A highly efficient majority-rules effect of poly(quinoxaline-2,3-diyl)s (PQXs) bearing 2-butoxymethyl chiral side chains at the 6- and 7-positions was established and attributed to large ΔG(h) values (0.22-0.41 kJ mol(-1)), which are defined as the energy difference between P- and M-helical conformations per chiral unit. A PQX copolymer prepared from a monomer derived from (R)-2-octanol (23% ee) and a monomer bearing a PPh2 group adopted a single-handed helical structure (>99%) and could be used as a highly enantioselective chiral ligand in palladium-catalyzed asymmetric reactions (products formed with up to 94% ee), in which the enantioselectivity could be switched by solvent-dependent inversion of the helical PQX backbone.

  18. Chiral liquids

    Directory of Open Access Journals (Sweden)

    Zakharov V.I.

    2015-01-01

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

  19. Social power and recognition of emotional prosody: High power is associated with lower recognition accuracy than low power.

    Science.gov (United States)

    Uskul, Ayse K; Paulmann, Silke; Weick, Mario

    2016-02-01

    Listeners have to pay close attention to a speaker's tone of voice (prosody) during daily conversations. This is particularly important when trying to infer the emotional state of the speaker. Although a growing body of research has explored how emotions are processed from speech in general, little is known about how psychosocial factors such as social power can shape the perception of vocal emotional attributes. Thus, the present studies explored how social power affects emotional prosody recognition. In a correlational study (Study 1) and an experimental study (Study 2), we show that high power is associated with lower accuracy in emotional prosody recognition than low power. These results, for the first time, suggest that individuals experiencing high or low power perceive emotional tone of voice differently.

  20. Direct enantioseparation of nitrogen-heterocyclic pesticides on cellulose-based chiral column by high-performance liquid chromatography.

    Science.gov (United States)

    Chai, Tingting; Yang, Wenwen; Qiu, Jing; Hou, Shicong

    2015-01-01

    The enantiomeric separation of eight pesticides including bitertanol (), diclobutrazol (), fenbuconazole (), triticonazole (), imazalil (), triapenthenol (), ancymidol (), and carfentrazone-ethyl () was achieved, using normal-phase high-performance liquid chromatography on two cellulosed-based chiral columns. The effects of isopropanol composition from 2% to 30% in the mobile phase and column temperature from 5 to 40 °C were investigated. Satisfactory resolutions were obtained for bitertanol (), triticonazole (), imazalil () with the (+)-enantiomer eluted first and fenbuconazole () with the (-)-enantiomer eluted first on Lux Cellulose-2 and Lux Cellulose-3. (+)-Enantiomers of diclobutrazol () and triapenthenol () were first eluted on Lux Cellulose-2. (-)-Carfentrazone-ethyl () were eluted first on Lux Cellulose-2 and Lux Cellulose-3 with incomplete separation. Reversed elution orders were obtained for ancymidol (7). (+)-Ancymidol was first eluted on Lux Cellulose-2 while on Lux Cellulose-3 (-)-ancymidol was first eluted. The results of the elution order at different column temperatures suggested that column temperature did not affect the optical signals of the enantiomers. These results will be helpful to prepare and analyze individual enantiomers of chiral pesticides.

  1. Chiral symmetry restoration versus deconfinement in heavy-ion collisions at high baryon density

    CERN Document Server

    Cassing, W; Moreau, P; Bratkovskaya, E L

    2015-01-01

    We study the production of strange hadrons in nucleus-nucleus collisions from 4 to 160 A GeV within the Parton-Hadron-String Dynamics (PHSD) transport approach that is extended to incorporate essentials aspects of chiral symmetry restoration (CSR) in the hadronic sector (via the Schwinger mechanism) on top of the deconfinement phase transition as implemented in PHSD. Especially the $K^+/\\pi^+$ and the $(\\Lambda+\\Sigma^0)/\\pi^-$ ratios in central Au+Au collisions are found to provide information on the relative importance of both transitions. The modelling of chiral symmetry restoration is driven by the pion-nucleon $\\Sigma$-term in the computation of the quark scalar condensate $$ that serves as an order parameter for CSR and also scales approximately with the effective quark masses $m_s$ and $m_q$. Furthermore, the nucleon scalar density $\\rho_s$, which also enters the computation of $$, is evaluated within the nonlinear $\\sigma-\\omega$ model which is constraint by Dirac-Brueckner calculations and low energy...

  2. The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Ji, Pengfei; McIsaac, Alexandra R.; Lin, Zekai; Abney, Carter W.; Lin, Wenbin [UC

    2016-02-01

    We have designed the first chiral diene-based metal–organic framework (MOF), E₂-MOF, and postsynthetically metalated E₂-MOF with Rh(I) complexes to afford highly active and enantioselective single-site solid catalysts for C–C bond formation reactions. Treatment of E₂-MOF with [RhCl(C₂H₄)₂]₂ led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E₂-MOF with Rh(acac)(C₂H₄)₂ afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E₂-MOF·Rh(acac) showed higher activity and enantioselectivity than the homogeneous control catalyst, likely due to the formation of a true single-site catalyst in the MOF. E₂-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.

  3. A novel chiral aliphatic-aromatic diamine promoted direct, highly enantio- and diastereoselective Michael addition of cyclohexanone to nitroolefins under solvent-free conditions.

    Science.gov (United States)

    Miao, Shifeng; Bai, Jinjin; Yang, Jin; Zhang, Yawen

    2010-10-01

    A series of new highly efficient chiral aliphatic-aromatic diamine catalysts have been designed and successfully applied to the asymmetric Michael addition of cyclohexanone with nitroolefins under solvent-free conditions without any acidic additives. The desired adducts were obtained in high yields with excellent enantio- and diastereoselectivities of syn products (up to >99% ee, >99:1 dr).

  4. Preparation of surface imprinted material of single enantiomer of mandelic acid with a new surface imprinting technique and study on its chiral recognition and resolution properties.

    Science.gov (United States)

    Gao, Baojiao; Chen, Lulu; Li, Yanbin

    2016-04-22

    A surface imprinted material of the single enantiomer of mandelic acid with high performance was successfully prepared with a new surface imprinting technique of synchronously graft-polymerizing and molecule imprinting, and its enantiomeric recognition and resolution properties were investigated. Micro-sized silica gel particles were first modified with coupling agent γ-mercaptopropyl trimethoxysilane (MPMS), obtaining the modified particles MPMS-SiO2 on which mercapto groups were introduced. A surface initiating system of -SH/BPO was constituted with the mercapto group (-SH) on MPMS-SiO2 particles and dibenzoyl peroxide (BPO) in N,N-dimethyl formamide (DMF) solution. In DMF solution, (R)-mandelic acid molecule was used as the template and the functional monomer hydroxyethyl methylacrylate (HEMA) were combined together by right of multi-site hydrogen bonds. The free radicals produced on MPMS-SiO2 particles initiate HEMA molecules around (R)-mandelic acid molecules and the crosslinking agent N,N'-Methylenebisacrylamide (MBA) to produce graft/crosslinking-polymerization. At the same time, the template (R)-mandelic acid molecules were enveloped within the thin grafted polymer layer on the surfaces of SiO2 particles, obtaining (R)-mandelic acid surface imprinted material MIP-PHEMA/SiO2. The experimental results show that MIP-PHEMA/SiO2 particles have excellent enantiomeric recognition and resolution ability. The binding capacity of MIP-PHEMA/SiO2 particles for (R)-mandelic acid reaches up to 278 mg/g. As the resolution experiment of a racemic mixture was carried out with MIP-PHEMA/SiO2 particles as solid adsorbent, relative another enantiomer, (S)-mandelic acid, the selectivity coefficient of the imprinted particles for (R)-mandelic acid is 5.02. As a consequence, the two enantiomers were well separated, and the optical purities (ee values) of the supernatant and eluant get up to 44% (corresponding to (S)-mandelic acid excess) and 85% (corresponding to (R

  5. Influences of High and Low Variability on Infant Word Recognition

    Science.gov (United States)

    Singh, Leher

    2008-01-01

    Although infants begin to encode and track novel words in fluent speech by 7.5 months, their ability to recognize words is somewhat limited at this stage. In particular, when the surface form of a word is altered, by changing the gender or affective prosody of the speaker, infants begin to falter at spoken word recognition. Given that natural…

  6. High-Level Event Recognition in Unconstrained Videos

    Science.gov (United States)

    2013-01-01

    for human detection. In: Proceedings of IEEE conference on com- puter vision and pattern recognition 28. Deng J,DongW,SocherR,LiLJ,LiK,Fei- FeiL (2009...Multimed Info Retr (2013) 2:73–101 99 84. Martin A, Doddington G, Kamm T, Ordowski M, Przybocki M (1997) The det curve in assessment of detection task

  7. Emotion Recognition in Fathers and Mothers at High-Risk for Child Physical Abuse

    Science.gov (United States)

    Asla, Nagore; de Paul, Joaquin; Perez-Albeniz, Alicia

    2011-01-01

    Objective: The present study was designed to determine whether parents at high risk for physical child abuse, in comparison with parents at low risk, show deficits in emotion recognition, as well as to examine the moderator effect of gender and stress on the relationship between risk for physical child abuse and emotion recognition. Methods: Based…

  8. Regional fusion for high-resolution palmprint recognition using spectral minutiae representation

    NARCIS (Netherlands)

    Wang, R.; Ramos, D.; Veldhuis, R.N.J.; Fierrez, J.; Spreeuwers, L.J.; Xu, Haiyun

    2014-01-01

    The spectral minutiae representation (SMC) has been recently proposed as a novel method to minutiae-based fingerprint recognition, which is invariant to minutiae translation and rotation and presents low computational complexity. As high-resolution palmprint recognition is also mainly based on minut

  9. Chiral Nanoscience and Nanotechnology

    OpenAIRE

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

    2008-01-01

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

  10. Preparation and application of methylcalix[4]resorcinarene-bonded silica particles as chiral stationary phase in high-performance liquid chromatography.

    Science.gov (United States)

    Tan, Huey Min; Soh, Shu Fang; Zhao, Jia; Yong, E L; Gong, Yinhan

    2011-01-01

    Two new types of methylcalix[4]resorcinarene-bonded stationary phases, (3-(C-methylcalix[4]resorcinarene)-2-hydroxypropoxy)-propylsilyl-appended silica particles (MCR-HPS) and bromoacetate-substituted MCR-HPS particles (BAMCR-HPS), have been synthesized and used as chiral stationary phases for high-performance liquid chromatography (HPLC) for the first time. The synthetic stationary phases are characterized by means of elemental analysis and Fourier-transform infrared spectroscopy. The chromatographic behavior of MCR-HPS and BAMCR-HPS was studied with several disubstituted benzenes and some chiral drug compounds under both normal phase and reversed-phase conditions. The results show that MCR-HPS has excellent selectivity for the separation of aromatic positional isomers and BAMCR-HPS exhibits excellent performance for separation of enantiomers of chiral compounds.

  11. Relationship between amygdala volume and emotion recognition in adolescents at ultra-high risk for psychosis.

    Science.gov (United States)

    Bartholomeusz, Cali F; Whittle, Sarah L; Pilioussis, Eleanor; Allott, Kelly; Rice, Simon; Schäfer, Miriam R; Pantelis, Christos; Amminger, G Paul

    2014-12-30

    Amygdala volume has been proposed as a neural risk biomarker for psychotic illness, but findings in the ultra-high risk for psychosis (UHR) population have been somewhat inconsistent, which may be related to underlying social cognitive abilities. The current study investigated whether amygdala volumes were related to emotion-recognition impairments in UHR individuals, and whether volumes differed by sex. Secondary aims were to assess whether (a) emotion-recognition performance was associated with interhemispheric amygdala volume asymmetry and (b) amgydala volume and volume asymmetry acted as a mediator between emotion-recognition and outcome measures. The amygdala was manually delineated from magnetic resonance images for 39 UHR individuals who had also completed facial and prosody emotion-recognition tasks. Partial correlations were conducted to examine associations between amydgala volume/asymmetry and recognition of negative emotions. Mediation analyses were conducted using regression and bootstrapping techniques. Amygdala volume was positively correlated with sadness emotion recognition, in particular prosody, for females only. Left amygdala volume mediated the effect of sadness recognition on depressive symptoms, negative symptoms, overall psychopathology, and global functioning in females. Findings suggest a complex relationship between emotion recognition, the structure of the amygdala and illness outcome, where recognition of sadness appears to be the precipitator of this relationship in UHR females. Further research is needed to determine illness specificity and to confirm our sex- and emotion-specific results.

  12. Biomimetic catalytic transformation of toxic α-oxoaldehydes to high-value chiral α-hydroxythioesters using artificial glyoxalase I

    Science.gov (United States)

    Park, Sang Yeon; Hwang, In-Soo; Lee, Hyun-Ju; Song, Choong Eui

    2017-04-01

    Glyoxalase I plays a critical role in the enzymatic defence against glycation by catalysing the isomerization of hemithioacetal, formed spontaneously from cytotoxic α-oxoaldehydes and glutathione, to (S)-α-hydroxyacylglutathione derivatives. Upon the hydrolysis of the thioesters catalysed by glyoxalase II, inert (S)-α-hydroxy acids, that is, lactic acid, are then produced. Herein, we demonstrate highly enantioselective glyoxalase I mimic catalytic isomerization of in-situ-generated hemithioacetals, providing facile access to both enantiomers of α-hydroxy thioesters. Owing to the flexibility of thioesters, a family of optically pure α-hydroxyamides, which are highly important drug candidates in the pharmaceutical industry, were prepared without any coupling reagents. Similar to real enzymes, the enforced proximity of the catalyst and substrates by the chiral cage in situ formed by the incorporation of potassium salt can enhance the reactivity and efficiently transfer the stereochemical information.

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

    Science.gov (United States)

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

    2016-10-28

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

  14. On Chiral Space Groups and Chiral Molecules

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

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

  15. On Chiral Space Groups and Chiral Molecules

    Institute of Scientific and Technical Information of China (English)

    NgSeikWng; HUSheng-Zhi

    2003-01-01

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

  16. Effect of Single-walled Carbon Nanotubes on Cellulose Phenylcarbamate Chiral Stationary Phases

    Institute of Scientific and Technical Information of China (English)

    CHANG Yin-xia; REN Chao-xing; RUAN Qiong; YUAN Li-ming

    2007-01-01

    Single-walled carbon nanotubes(SWNTs) have a high adsorption ability and nanoscale interactions. Cellulose trisphenylcarbamates possess high enantioseparation ability in high-performance liquid chromatography(HPLC). Single-walled carbon nanotubes mixed with cellulose trisphenylcarbamate are coated on the silica gel as chiral stationary phases and higher enantioseparation factors are obtained. After a single-walled carbon nanotube is linked to the 6-position of cellulose 2,3-bisphenylcarbamate, its enantioseparation resolution increases compared to that of the cellulose trisphenylcarbamate. It is the first time that SWNTs have been applied to enantioseparation. The results indicate that the single-walled carbon nanotubes are good promoters of chiral recognition. This method can be used to improve the enantioseparation efficiency of the polysaccharide chiral stationary phases.

  17. High-quality two-nucleon potentials up to fifth order of the chiral expansion

    Science.gov (United States)

    Entem, D. R.; Machleidt, R.; Nosyk, Y.

    2017-08-01

    We present NN potentials through five orders of chiral effective field theory ranging from leading order (LO) to next-to-next-to-next-to-next-to-leading order (N4LO ). The construction may be perceived as consistent in the sense that the same power counting scheme as well as the same cutoff procedures are applied in all orders. Moreover, the long-range parts of these potentials are fixed by the very accurate π N low-energy constants (LECs) as determined in the Roy-Steiner equations analysis by Hoferichter, Ruiz de Elvira, and coworkers. In fact, the uncertainties of these LECs are so small that a variation within the errors leads to effects that are essentially negligible, reducing the error budget of predictions considerably. The NN potentials are fit to the world NN data below the pion-production threshold of the year 2016. The potential of the highest order (N4LO ) reproduces the world NN data with the outstanding χ2/datum of 1.15, which is the highest precision ever accomplished for any chiral NN potential to date. The NN potentials presented may serve as a solid basis for systematic ab initio calculations of nuclear structure and reactions that allow for a comprehensive error analysis. In particular, the consistent order by order development of the potentials will make possible a reliable determination of the truncation error at each order. Our family of potentials is nonlocal and, generally, of soft character. This feature is reflected in the fact that the predictions for the triton binding energy (from two-body forces only) converges to about 8.1 MeV at the highest orders. This leaves room for three-nucleon-force contributions of moderate size.

  18. Chiral extraction of ketoprofen enantiomers with chiral selector tartaric esters

    Institute of Scientific and Technical Information of China (English)

    ZHOU Dan; LIU Jia-jia; TANG Ke-wen; HUANG Ke-long

    2007-01-01

    Distribution behavior of ketoprofen enantiomers was examined in methanol aqueous and organic solvent mixture containing tartaric esters. The influence of length of alkyl chain of tartaric esters, concentration of L-tartaric esters and methanol aqueous, kind of organic solvent on partition ratio and separation factors was investigated. The results show that L-tartaric and D-tartaric esters have different chiral recognition abilities. S-ketoprofen is easily extracted by L-tartaric esters, and R-ketoprofen is easily extracted by D-tartaric esters. L-tartaric esters form more stable diastereomeric complexes with S-enantiomer than that with R-enantiomer. This distribution behavior is consistent with chiral recognition mechanism. With the increase of the concentration of tartaric ester from 0 to 0.3 mol/L, partition coefficient K and separation factor α increase. Also, the kind of organic solvent and the concentration of the methanol aqueous have significant influence on K and α.

  19. Highly diastereoselective dioxetane formation in the photooxygenation of enecarbamates with an oxazolidinone chiral auxiliary: steric control in the [2 + 2] cycloaddition of singlet oxygen through conformational alignment.

    Science.gov (United States)

    Adam, Waldemar; Bosio, Sara G; Turro, Nicholas J

    2002-07-31

    The photooxygenation of oxazolidinone-substituted enecarbamates leads to diastereomerically pure dioxetanes. The high diastereoselectivity is rationalized in terms of effective pi-facial control achieved by shielding one side of the double bond with the chiral auxiliary. The absolute configuration of the dioxetanes is assigned by derivatization to diols.

  20. 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.

  1. 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.

  2. High Performance Human Face Recognition using Independent High Intensity Gabor Wavelet Responses: A Statistical Approach

    CERN Document Server

    Kar, Arindam; Basu, Dipak Kumar; Nasipuri, Mita; Kundu, Mahantapas

    2011-01-01

    In this paper, we present a technique by which high-intensity feature vectors extracted from the Gabor wavelet transformation of frontal face images, is combined together with Independent Component Analysis (ICA) for enhanced face recognition. Firstly, the high-intensity feature vectors are automatically extracted using the local characteristics of each individual face from the Gabor transformed images. Then ICA is applied on these locally extracted high-intensity feature vectors of the facial images to obtain the independent high intensity feature (IHIF) vectors. These IHIF forms the basis of the work. Finally, the image classification is done using these IHIF vectors, which are considered as representatives of the images. The importance behind implementing ICA along with the high-intensity features of Gabor wavelet transformation is twofold. On the one hand, selecting peaks of the Gabor transformed face images exhibit strong characteristics of spatial locality, scale, and orientation selectivity. Thus these...

  3. Enantioselective determination of chiral toxaphene congeners in laying hens and eggs using multidimensional high-resolution gas chromatography.

    Science.gov (United States)

    Hamed, Sobhy; Leupold, Guenter; Ismail, Ahmed; Parlar, Harun

    2005-09-07

    A total of 22 chiral toxaphene congeners were analyzed in organ tissues and eggs of laying hens after they had been fed with food spiked with technical toxaphene. For the analysis, multidimensional high-resolution gas chromatography using a chiral column coated with randomly silylated heptakis(O-tert-butyldimethylsilyl)-beta-cyclodextrin, electron capture detection, and valveless "live column switching" technique was applied. The analytical results were additionally confirmed with mass spectral data, recorded in electron-capture negative ionization mode with selected-ion monitoring mass spectrometry. During both the feeding period of the laying hens with toxaphene-contaminated food (38 weeks, accumulation phase) and the following subsiding period without toxaphenes (another 14 weeks, decontamination phase), organs (liver, kidney, skin/fat), blood, meat, and eggs of the hens served as model matrices for toxaphene uptake. The enantiomeric ratios (ERs) of congeners 26, 31, 32, 40, 41, 42(a+b), 44, 50, and 62--known as the most important components of technical toxaphene occurring in the environment--could be analytically determined. Significant differences were observed with respect to their initial racemic ratios. On the basis of their chemical structures, the metabolic pathways of some congeners could be explained. Astonishingly, some of the toxaphenes applied as racemates could merely be found as single enantiomers at the end of the feeding program, for example, congener 32 in blood and meat samples or congener 44, especially in organ tissues, which showed ERs of zero or infinity. The findings of this study impressively emphasize that it is essential to isolate and analyze individual toxaphene enantiomers in food and biota tissues to be capable of evaluating their toxicity and metabolization more specifically.

  4. The Optical Chirality Flux as a Useful Far-Field Probe of Chiral Near Fields

    CERN Document Server

    Poulikakos, Lisa V; McPeak, Kevin M; Burger, Sven; Niegemann, Jens; Hafner, Christian; Norris, David J

    2016-01-01

    To optimize the interaction between chiral matter and highly twisted light, quantities that can help characterize chiral electromagnetic fields near nanostructures are needed. Here, by analogy with Poynting's theorem, we formulate the time-averaged conservation law of optical chirality in lossy dispersive media and identify the optical chirality flux as an ideal far-field observable for characterizing chiral optical near fields. Bounded by the conservation law, we show that it provides precise information, unavailable from circular dichroism spectroscopy, on the magnitude and handedness of highly twisted fields near nanostructures.

  5. Stegosaurus chirality

    OpenAIRE

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

    2016-01-01

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

  6. The Author Recognition and Magazine Recognition Tests, and Free Voluntary Rereading as Predictors of Vocabulary Development in English as a Foreign Language for Korean High School Students.

    Science.gov (United States)

    Kim, Haeyoung; Krashen, Stephen

    1998-01-01

    In this study, performance on Author and Magazine Recognition Tests were found to predict second-language vocabulary among high school English-as-a-Foreign-Language students in Korea. Reported free reading in English was also related to vocabulary development, but the effect of the author and magazine recognition tests was independent of free…

  7. Enantioseparation of Racemic Naproxen Esters on Cellulose Tris (4-methylbenzoate) Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Several kinds of racemic naproxen ester were successfully separated on CTMB chiral stationary phase with hexane-ethanol (98:2, vol./vol.) as the mobile phase. The influence of mobile phase composition and structure of racemic naproxen ester on chiral separation was studied and the chiral recognition mechanism of CTMB was discussed.

  8. Enantioseparation of Racemic Naproxen Esters on Cellulose Tris(4—methylbenzoate) Chiral Stationary Phase

    Institute of Scientific and Technical Information of China (English)

    BaoHaiSHAO; XiuZhuXU; 等

    2002-01-01

    Several kinds of racemic naproxen ester were successfully separated on CTMB chiral stationary phase with hexane-ethanol(98:2,vol./vol.) as the mobile phase. The influence of mobile phase composition and structure of racemic naproxen ester on chiral separation was studied and the chiral recognition mechanism of CTMB was discussed.

  9. Identification of Enantioselective Extractants for Chiral Separation of Amines and Amino-Alcohols

    NARCIS (Netherlands)

    Steensma, M.; Kuipers, N.J.M.; de Haan, A.B.; Kwant, Gerard

    2006-01-01

    lack of versatile enantioselective extractants. Therefore, a rational approach is developed to transfer the extensive knowledge of chiral selectors reported in the literature on chiral recognition and other chiral separation techniques to extraction. Based on a similarity in separation mechanisms, i

  10. Highly photoresponsive and wavelength-selective circularly-polarized-light detector based on metal-oxides hetero-chiral thin film.

    Science.gov (United States)

    Lee, Seung Hee; Singh, Dhruv Pratap; Sung, Ji Ho; Jo, Moon-Ho; Kwon, Ki Chang; Kim, Soo Young; Jang, Ho Won; Kim, Jong Kyu

    2016-01-22

    A highly efficient circularly-polarized-light detector with excellent wavelength selectivity is demonstrated with an elegant and simple microelectronics-compatible way. The circularly-polarized-light detector based on a proper combination of the geometry-controlled TiO2-SnO2 hetero-chiral thin film as an effective chiroptical filter and the Si active layer shows excellent chiroptical response with external quantum efficiency as high as 30% and high helicity selectivity of ~15.8% in an intended wavelength range. Furthermore, we demonstrated the ability of manipulating both bandwidth and responsivity of the detector simultaneously in whole visible wavelength range by a precise control over the geometry and materials constituting hetero-chiral thin film. The high efficiency, wavelength selectivity and compatibility with conventional microelectronics processes enabled by the proposed device can result in remarkable developments in highly integrated photonic platforms utilizing chiroptical responses.

  11. Highly photoresponsive and wavelength-selective circularly-polarized-light detector based on metal-oxides hetero-chiral thin film

    Science.gov (United States)

    Lee, Seung Hee; Singh, Dhruv Pratap; Sung, Ji Ho; Jo, Moon-Ho; Kwon, Ki Chang; Kim, Soo Young; Jang, Ho Won; Kim, Jong Kyu

    2016-01-01

    A highly efficient circularly-polarized-light detector with excellent wavelength selectivity is demonstrated with an elegant and simple microelectronics-compatible way. The circularly-polarized-light detector based on a proper combination of the geometry-controlled TiO2-SnO2 hetero-chiral thin film as an effective chiroptical filter and the Si active layer shows excellent chiroptical response with external quantum efficiency as high as 30% and high helicity selectivity of ~15.8% in an intended wavelength range. Furthermore, we demonstrated the ability of manipulating both bandwidth and responsivity of the detector simultaneously in whole visible wavelength range by a precise control over the geometry and materials constituting hetero-chiral thin film. The high efficiency, wavelength selectivity and compatibility with conventional microelectronics processes enabled by the proposed device can result in remarkable developments in highly integrated photonic platforms utilizing chiroptical responses. PMID:26795601

  12. High resolution of racemic phenylalanine with dication imidazolium-based chiral ionic liquids in a solid-liquid two-phase system.

    Science.gov (United States)

    Huang, Xiaoxia; Wu, Haoran; Wang, Zhixia; Luo, Yingjie; Song, Hang

    2017-01-06

    A novel solid-liquid two-phase system was developed for the chiral separation of racemic phenylalanine with new dication imidazolium-based chiral ionic liquids. Preliminary experiments showed distinct enantioselectivity in amino acid extraction with the novel solid-liquid two-phase system, more L-enantiomer of amino acid cooperatively interacted with ionic liquids and copper ions to be the solid phase. Various factors, including the alkyl chain length of cations of ionic liquids, the amount of copper acetate, the ratio of n(ILs)/n(Cu(2+)), the amount of water and racemic phenylalanine, the resolution time together with the resolution temperature, were systematically investigated for their influence on resolution efficiency. The results showed that, under a certain condition, the enantiomeric excess value and the yield of phenylalanine in liquid phase (mainly containing D-enantiomer) were 67.8% and 96.5%, the enantiomeric excess value and the yield of phenylalanine in solid phase (mainly containing L-enantiomer) were 99.2% and 85.2%. Finally, 2D NMR technology, infrared spectroscopy and molecular simulation method were used to study the interaction mechanism. The results indicated that L-enantiomer of phenylalanine interacts more strongly with chiral ILs and Cu(2+). The novel system has characteristics of free-organic solvent, simple operation, fast separation process and very high resolution efficiency for racemic phenylalanine. This work could provide a new and alternative resolution approach for other chiral separations.

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

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

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

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

    Institute of Scientific and Technical Information of China (English)

    刘育; 康诗钊

    2001-01-01

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

  15. A NUFFT Based Step-frequency Chirp Signal High Resolution Imaging Algorithm and Target Recognition Algorithm

    Directory of Open Access Journals (Sweden)

    Xiang Yin

    2015-12-01

    Full Text Available Radar Automatic Target Recognition (RATR is the key technique to be breaked through in the fuure development of intelligent weapon system. Compared to the 2-D SAR image target recognition, High Resolution Range Profile (HRRP target recognition has the advantage of low data dimension, low requirement of radar system's calculation and storage ability, and the imaging algorithm is also not complicated. HRRP imaging is the first and the key process in target recognition, its speed and imaging quality can directly influence the real-time capability and accuracy of target recognition. In this paper a new HRRP imaging algorithm — NUFFT algorithm is proposed, the derivation of mathematical expression is given, both for the echo simulation process and the imaging process. In the meantime, by analyzing each step's calculation complexity, we compared the calculation complexity of four different imaging algorithms, we also simulate two target's imaging and target recognition processing. Theoretical analysis and simulation both prove that the proposed algorithm's calculation complexity is improved in various degree compared with the others, thus can be effectively used in target recognition.

  16. Study on the chiral recognition of the enantiomers of ephedrine derivatives with neutral and sulfated heptakis(2,3-O-diacetyl)-beta-cyclodextrins using capillary electrophoresis, UV, nuclear magnetic resonance spectroscopy and mass spectrometry.

    Science.gov (United States)

    Hellriegel, C; Händel, H; Wedig, M; Steinhauer, S; Sörgel, F; Albert, K; Holzgrabe, U

    2001-04-20

    The enantiomers of methylephedrine, pseudoephedrine and ephedrine showed a different migration behavior in capillary electrophoresis in the presence of beta-cyclodextrin (beta-CD), heptakis(2,3-O-diacetyl)-beta-cyclodextrin and heptakis(2,3-O-diacetyl-6-sulfato)-beta-cyclodextrin (HDAS). Utilizing UV, MS and NMR spectroscopy, in particular rotating frame Overhauser experiments, an attempt was made to elucidate the chiral recognition mechanism. In the case of the neutral CDs 1:1 complexes were formed with ephedrine and methylephedrine characterized by the inclusion of the phenyl ring in the cavity and the side chain pointing out of the wider rim. In contrast, manifold complexes were formed with HDAS, which on average are characterized by an upside down inclusion of the phenyl ring in the cavity and the side chain pointing out of the narrow rim. This complex geometry is likely be stabilized by an ion-ion interaction between the positively charged nitrogens of the ephedrine derivatives and the negative charges of HDAS. In addition, an attachment of the ligand to the outside of HDAS and other complex stoichiometries are also possible.

  17. High enantioselective Novozym 435-catalyzed esterification of (R,S)-flurbiprofen monitored with a chiral stationary phase.

    Science.gov (United States)

    Siódmiak, Tomasz; Mangelings, Debby; Vander Heyden, Yvan; Ziegler-Borowska, Marta; Marszałł, Michał Piotr

    2015-03-01

    Lipases form Candida rugosa and Candida antarctica were tested for their application in the enzymatic kinetic resolution of (R,S)-flurbiprofen by enantioselective esterification. Successful chromatographic separation with well-resolved peaks of (R)- and (S)-flurbiprofen and their esters was achieved in one run on chiral stationary phases by high-performance liquid chromatography (HPLC). In this study screening of enzymes was performed, and Novozym 435 was selected as an optimal catalyst for obtaining products with high enantiopurity. Additionally, the influence of organic solvents (dichloromethane, dichloroethane, dichloropropane, and methyl tert-butyl ether), primary alcohols (methanol, ethanol, n-propanol, and n-butanol), reaction time, and temperature on the enantiomeric ratio and conversion was tested. The high values of enantiomeric ratio (E in the range of 51.3-90.5) of the esterification of (R,S)-flurbiprofen were obtained for all tested alcohols using Novozym 435, which have a great significance in the field of biotechnological synthesis of drugs. The optimal temperature range for the performed reactions was from 37 to 45 °C. As a result of the optimization, (R)-flurbiprofen methyl ester was obtained with a high optical purity, eep = 96.3 %, after 96 h of incubation. The enantiomeric ratio of the reaction was E = 90.5 and conversion was C = 35.7 %.

  18. Intrinsic chirality and prochirality at Air/R-(+)- and S-(-)-limonene interfaces: spectral signatures with interference chiral sum-frequency generation vibrational spectroscopy.

    Science.gov (United States)

    Fu, Li; Zhang, Yun; Wei, Zhe-Hao; Wang, Hong-Fei

    2014-09-01

    We report in this work detailed measurements of the chiral and achiral sum-frequency vibrational spectra in the C-H stretching vibration region (2800-3050 cm(-1)) of the air/liquid interfaces of R-(+)-limonene and S-(-)-limonene, using the recently developed high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The achiral SFG spectra of R-limonene and S-limonene, as well as the RS racemic mixture (50/50 equal amount mixture), show that the corresponding molecular groups of the R and S enantiomers are with the same interfacial orientations. The interference chiral SFG spectra of the limonene enantiomers exhibit a spectral signature from the chiral response of the Cα-H stretching mode, and a spectral signature from the prochiral response of the CH(2) asymmetric stretching mode, respectively. The chiral spectral feature of the Cα-H stretching mode changes sign from R-(+)-limonene to S-(-)-limonene surfaces, and disappears for the RS racemic mixture surface. While the prochiral spectral feature of the CH(2) asymmetric stretching mode is the same for R-(+)-limonene and S-(-)-limonene surfaces, and also surprisingly remains the same for the RS racemic mixture surface. Therefore, the structures of the R-(+)-limonene and the S-(-)-limonene at the liquid interfaces are nevertheless not mirror images to each other, even though the corresponding groups have the same tilt angle from the interfacial normal, i.e., the R-(+)-limonene and the S-(-)-limonene at the surface are diastereomeric instead of enantiomeric. These results provide detailed information in understanding the structure and chirality of molecular interfaces and demonstrate the sensitivity and potential of SFG-VS as a unique spectroscopic tool for chirality characterization and chiral recognition at the molecular interface.

  19. Aromatic amino acids in high selectivity bismuth(III) recognition.

    Science.gov (United States)

    Ghatak, Sumanta Kumar; Dey, Debarati; Sen, Souvik; Sen, Kamalika

    2013-04-21

    The three aromatic amino acids, tyrosine, tryptophan and phenylalanine, play different physiological roles in life processes. Metal ions capable of binding these amino acids may aid in the reduction of effective concentration of these amino acids in any physiological system. Here we have studied the efficacy of some heavy metals for their complexation with these three amino acids. Bismuth has been found to bind selectively with these aromatic amino acids and this was confirmed using spectrofluorimetric, spectrophotometric and cyclic voltammetric studies. The series of heavy metals has been chosen because each of these metals remains associated with the others at very low concentration levels and Bi(III) is the least toxic amongst the other elements. So, selective recognition for Bi(III) would also mean no response for the other heavy elements if contaminants are present even at low concentration levels. The affinity towards these amino acids has been found to be in the order tryptophan phenylalanine amino acids have been calculated using Benesi-Hildebrand equations and the corresponding free energy change has also been calculated. The values of the association constants obtained from BH equations using absorbance values corroborate with the Stern-Volmer constants obtained from fluorimetric studies. The evidence for complexation is also supported by the results of cyclic voltammetry.

  20. 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.

  1. Helicity-selective phase-matching and quasi-phase matching of circularly polarized high-order harmonics: towards chiral attosecond pulses

    Science.gov (United States)

    Kfir, Ofer; Grychtol, Patrik; Turgut, Emrah; Knut, Ronny; Zusin, Dmitriy; Fleischer, Avner; Bordo, Eliyahu; Fan, Tingting; Popmintchev, Dimitar; Popmintchev, Tenio; Kapteyn, Henry; Murnane, Margaret; Cohen, Oren

    2016-06-01

    Phase matching of circularly polarized high-order harmonics driven by counter-rotating bi-chromatic lasers was recently predicted theoretically and demonstrated experimentally. In that work, phase matching was analyzed by assuming that the total energy, spin angular momentum and linear momentum of the photons participating in the process are conserved. Here we propose a new perspective on phase matching of circularly polarized high harmonics. We derive an extended phase matching condition by requiring a new propagation matching condition between the classical vectorial bi-chromatic laser pump and harmonics fields. This allows us to include the influence of the laser pulse envelopes on phase matching. We find that the helicity dependent phase matching facilitates generation of high harmonics beams with a high degree of chirality. Indeed, we present an experimentally measured chiral spectrum that can support a train of attosecond pulses with a high degree of circular polarization. Moreover, while the degree of circularity of the most intense pulse approaches unity, all other pulses exhibit reduced circularity. This feature suggests the possibility of using a train of attosecond pulses as an isolated attosecond probe for chiral-sensitive experiments.

  2. Chiral Nanoscience and Nanotechnology

    Directory of Open Access Journals (Sweden)

    Dibyendu S. Bag

    2008-09-01

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

  3. Chiral nanoparticles in singular light fields

    Science.gov (United States)

    Vovk, Ilia A.; Baimuratov, Anvar S.; Zhu, Weiren; Shalkovskiy, Alexey G.; Baranov, Alexander V.; Fedorov, Anatoly V.; Rukhlenko, Ivan D.

    2017-04-01

    The studying of how twisted light interacts with chiral matter on the nanoscale is paramount for tackling the challenging task of optomechanical separation of nanoparticle enantiomers, whose solution can revolutionize the entire pharmaceutical industry. Here we calculate optical forces and torques exerted on chiral nanoparticles by Laguerre-Gaussian beams carrying a topological charge. We show that regardless of the beam polarization, the nanoparticles are exposed to both chiral and achiral forces with nonzero reactive and dissipative components. Longitudinally polarized beams are found to produce chirality densities that can be 109 times higher than those of transversely polarized beams and that are comparable to the chirality densities of beams polarized circularly. Our results and analytical expressions prove useful in designing new strategies for mechanical separation of chiral nanoobjects with the help of highly focussed beams.

  4. Analysis of stereochemistry and biosynthesis of epicatechin in tea plants by chiral phase high performance liquid chromatography.

    Science.gov (United States)

    Qian, Yumei; Zhao, Xianqian; Zhao, Lei; Cui, Lilan; Liu, Li; Jiang, Xiaolan; Liu, Yajun; Gao, Liping; Xia, Tao

    2015-12-01

    Tea (Camellia sinensis) is rich in flavan-3-ols (catechins), especially epicatechin (EC), which is the predominant extension unit of polymeric proanthocyanidins (PAs). However, studies assessing EC's stereochemistry are scarce. Here, a high performance liquid chromatography column using amylose tris-(3, 5-dimethylphenylcarbamate) immobilized on silica-gel as chiral stationary phases (CSPs) was applied to explore its stereochemistry and biosynthetic pathway in tea plants. The results revealed (-)-epicatechin [(-)-EC] was the predominant di-hyroxy-non-galloylated-catechins, while (+)-epicatechin [(+)-EC] was not detected. Interestingly, (-)-EC was the only product obtained from cyanidin using the partially purified native C. sinensis anthocyanidin reductase (CsANR) in the presence of reduction nicotinamide adenine dinucleotide phosphate (NADPH); meanwhile, (+)-EC was the main product using recombinant CsANR in the same conditions. In addition, (-)-EC could be obtained from (+)-catechin [(+)-C] using recombinant CsANR, which displayed C3-epimerase activity in the presence of oxidation nicotinamide adenine dinucleotide phosphate (NADP(+)). But the partially purified native CsANR did not possess this function. Finally, (-)-EC could result from the de-gallate acid reaction of epicatechin gallate (ECG) catalyzed by a novel partially purified native galloylated catechins hydrolase (GCH) from tea leaves. In summary, (-)-EC is likely the product of native protein from the tea plants, and (+)-EC is only produced in a reaction catalyzed by recombinant CsANR in vitro.

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

    Science.gov (United States)

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

    2014-05-01

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

  6. Calixarene based chiral solvating agents for α-hydroxy carboxylic acids

    Science.gov (United States)

    Bozkurt, Selahattin

    2013-09-01

    Novel chiral calix[4]arene derivatives functionalized at the lower rim have been prepared from the reaction of p-tert-butylcalix[4]arene diamine derivative with N-Phthaloyl-L-phenylalanine or (2S)-2-((benzyloxy)carbonyl)amino)-3-hydroxypropanoic acid or (2S,3R)-2-((benzyloxy)carbonyl)amino-3-hydroxybutanoic acid in 63-81% yield. The structures of these receptors were characterized by FTIR, 1H, 13C and 2D COSY NMR spectroscopy. The enantioselective recognition of these receptors towards the enantiomers of racemic carboxylic acids was studied by 1H NMR spectroscopy. The molar ratios of the chiral compounds with each of the enantiomers of guests were determined by using Job plots. The Job plots indicate that the hosts form 1:2 instantaneous complexes with all guests. The receptors exhibited different chiral recognition abilities toward the enantiomers of racemic guests. NMR studies demonstrated that the receptors function as highly effective chiral shift reagents for determining the enantiomeric purity of a series of carboxylic acids.

  7. Chiral mirrors

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-06-01

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

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

    Directory of Open Access Journals (Sweden)

    Yuji Okada

    2016-11-01

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

  9. Chiral Separation of Calcium (-)-2(S)-2-Benzyl-4-oxo-4-(cis-hexahydro-2-isoindolinyl)butyrate Enantiomers by High-performance Liquid Chromatography

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhefeng; YANG Gengliang; GAO Wenhui; CHEN yia

    2009-01-01

    A chiral high-performance liquid chromatographic method was developed for the enantioseparation of a new insulinotropic drug of the glinide class with rapid onset. The chiral separation was performed on a Sumichiral OA-3300 column (250 mm×4.6 mm, 5μm) with methanol containing 0.05 mol/L ammonium acetate as the opti-mized mobile phase at detection wavelengh 210 nm. Baseline separation of the two enantiomers was obtained in 22 (r=0.9997) for S-enantiomer and y=1.15 ×103x-1.78 (γ=0.9998) for R-enantiomer, respectively. The limits of detection obtained by S/N=3 were 0.15 ng for S-and 0.10 ng for R-enantiomer, respectively. RSD of the method was below 1.0% (n=5).

  10. Direct Separation of Pregabalin Enantiomers Using a Zwitterionic Chiral Selector by High Performance Liquid Chromatography Coupled to Mass Spectrometry and Ultraviolet Detection

    Directory of Open Access Journals (Sweden)

    Lakshmi Narayana Chennuru

    2016-11-01

    Full Text Available The chromatographic resolution of pregabalin enantiomers has been often achieved by derivatization of the molecule, in order to reach enough sensitivity at low concentrations of the minor enantiomer present in the active principle. In the present article, the development and optimization of two liquid chromatographic methods are presented for the direct resolution of pregabalin enantiomers on a chiral stationary phase (CSP containing a zwitterionic selector derived from cinchona alkaloid and sulfonic acid (CHIRALPAK ZWIX. The key parameters for the separation as well as the compatibility of chromatographic conditions with different detection modes (ultraviolet and mass spectrometry were investigated. The resulting methods were found to be selective, of high performance and low limits of detection (2 µg/mL by UV and 1 ng/mL by MS, respectively and quantification (6 µg/mL by UV and 5 ng/mL by MS, respectively for the minor enantiomer which is considered as a chiral impurity.

  11. 用AFM研究DL-缬氨酸晶体的结构及其表面分子的排列%Surface Recognition of the Space Group and Chiral Array on DL-valine Crystalline Structure Observed by AFM

    Institute of Scientific and Technical Information of China (English)

    龚(龙天); 王文清; 刘虹雯; 杜世萱; 郭海明; 王业亮; 高鸿钧

    2005-01-01

    利用原子力显微镜(AFM)成像技术来观察DL-缬氨酸晶体表面分子的规则排列,研究表明对映体分子在DL-缬氨酸晶体中相互配对排列,每个晶胞单元中包含两个对映体分子,属于具有中心对称结构P1群,整个晶体是消旋的.通过原子力显微镜对DL-缬氨酸晶体表面重复单元的测量结果与X衍射数据对比,发现用AFM观察到的DL-缬氨酸晶体中分子表面形貌的规整排列的距离,同X衍射得出的三斜晶系晶胞参数数据基本一致,由此判定该晶体属于三斜晶系而不是单斜晶系.探讨了利用纳米技术的研究手段在分子水平研究生命起源中的手性问题,在确定的晶面上通过分子周期性结构排列规律,对DL-缬氨酸晶体表面分子进行手性识别.%Atomic force microscopy(AFM) has been used to image arrays of molecules at the surface of DL-valine crystals. AFM images of DL-valine show that D- and L- molecular pairs formed from a DL-racemic mixture are exclusively homochiral. There are two different conclusions about the crystal structure of DL-valine with the data of X-ray crystallography. First, the structure of DL-valine was solved in the monoclinic space group P21/c. Second, the crystal structure of DL-valine has been refined in the centrosymmetric space group P1 and indicated a triclinic rather than a monoclinic space group. The present work emphasizes to solve the contradicting observations of space group and to provide direct evidence for chiral recognition at molecular level. DL-valine molecules {001 } are all in zwitterionic form with the isopropyl groups close to the surface and methyl groups on the top site, showing an ordered molecular morphology of triclinic unit cells, which are in fair agreement with the X-ray diffraction data. The application of AFM to the investigation of protein' s origins and a molecular-level illustration of chiral recognition at a periodic 2D surface structure ofracemic crystals is discussed.

  12. Pirkle-type chiral stationary phase on core-shell and fully porous particles: Are superficially porous particles always the better choice toward ultrafast high-performance enantioseparations?

    Science.gov (United States)

    Ismail, Omar H; Pasti, Luisa; Ciogli, Alessia; Villani, Claudio; Kocergin, Jelena; Anderson, Scott; Gasparrini, Francesco; Cavazzini, Alberto; Catani, Martina

    2016-09-30

    Pirkle-type Whelk-O1 chiral stationary phase (CSP) was prepared on 2.6μm superficially porous particles (SPPs). The chromatographic behavior of columns packed with this new CSP was compared with that of columns packed respectively with 1.8 and 2.5μm Whelk-O1 fully porous particles (FPPs). In the comparison, both thermodynamic and kinetic aspects were considered. Contrary to initial expectations, chiral columns packed with 2.6μm SPPs were quasi-comparable to those packed with 2.5μm FPPs, apparently due to larger contributions to band broadening from both eddy dispersion and, especially for the second eluted enantiomer, adsorption-desorption kinetics. These findings raise the question if SPPs, in spite of the undeniable advantages of their morphology to speed up mass transfer, are always the best choice for high-efficient ultrafast chiral separations. The last part of the work focuses on the use of short columns (10mm long) and very high flow rates to realize the separation of the enantiomers of trans-stilbene oxide (TSO) in normal phase mode in less than 1s.

  13. Molecular chirality at surfaces

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-11-15

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

  14. The Stepwise Reaction of Rhodium and Iridium Complexes of Formula [MCl2 (κ(4) C,N,N',P-L)] with Silver Cations: A Case of trans-Influence and Chiral Self-Recognition.

    Science.gov (United States)

    Carmona, María; Tejedor, Leyre; Rodríguez, Ricardo; Passarelli, Vincenzo; Lahoz, Fernando J; García-Orduña, Pilar; Carmona, Daniel

    2017-07-27

    Acetonitrile suspensions of the dichlorido complexes [MCl2 (κ(4) C,N,N',P-L)] [M=Rh (1), Ir (2)] react with AgSbF6 in a 1:2 molar ratio affording the bis-acetonitrile complexes [M(κ(4) C,N,N',P-L)(NCMe)2 ][SbF6 ]2 (3 and 4). The reaction takes place in a sequential manner and the intermediates can be isolated varying the M:Ag molar ratio. In a 2:1 molar ratio, it affords the dimetallic monochlorido-bridged compounds [{MCl(κ(4) C,N,N',P-L)}2 (μ-Cl)][SbF6 ] (5 and 6). In a 1:1 molar ratio, the monosubstituted solvato-complexes [MCl(κ(4) C,N,N',P-L)(Solv)][SbF6 ] (Solv=H2 O, MeCN, 7-10) were obtained. Finally, in a 2:3 molar ratio, it gives complexes 11 and 12 of formula [{M(κ(4) C,N,N',P-L)(NCMe)(μ-Cl)}2 Ag][SbF6 ]3 in which a silver cation joints two cationic monosubstituted acetonitrile-complexes [MCl(κ(4) C,N,N',P-L)(NCMe)](+) through the remaining chlorido ligands and two Ag⋅⋅⋅C interactions with one of the phenyl rings of each PPh2 group. In all the complexes, the aminic nitrogen and the central metal atom are stereogenic centers. In the trimetallic complexes 11 and 12, the silver atom is also a stereogenic center. The formation of the cation of the dimetallic complexes 5 and 6, as well as that of the trimetallic complexes 11 and 12, takes place with chiral molecular self-recognition. Experimental data and DFT calculations provide plausible explanations for the observed molecular recognition. The new complexes have been characterized by analytical, spectroscopic means and by X-ray diffraction methods. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Highly Stereoselective Methylene Transfers onto Butanediacetal-Protected Chiral Non-Racemic Sulfinyl Imines Using S-Ylide Technology

    Science.gov (United States)

    Bettigeri, Sampada V.; Pischek, Susanna C.

    2009-01-01

    Reaction of sulfur ylide with chiral non-racemic imine afforded the desired aziridine in excellent yield. Diastereomeric ratios of >95:5 were obtained. Both enantiomeric lines of the butanediacetal-protected chiral non-racemic sulfinyl imines were examined. The sulfur ylides were generated in situ upon thermal decarboxylation of carboxylmethyl betaine functionality. The enantiomeric pairs of D-mannitol with (S)-(-)-2-methyl-2-propane sulfinamide and ascorbic acid with (R)-(-)-2-methyl-2-propane sulfinamide resulted in the highest levels of diastereocontrol when performing aziridination reactions. PMID:19319433

  16. Manifold Matching for High-Dimensional Pattern Recognition

    OpenAIRE

    HOTTA, Seiji

    2008-01-01

    In this chapter manifold matching for high-dimensional pattern classification was described. The topics described in this chapter were summarized as follows: The meaning and effectiveness of manifold matching The similarity between various classifiers from the point of view of manifold matching Accuracy improvement for manifold matching Learning rules for manifold matching Experimental results on handwritten digit datasets showed that manifold matching achieved lower error rates than other cl...

  17. Chiral conducting polymers.

    Science.gov (United States)

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

    2010-07-01

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

  18. Facial Emotion Recognition in Children with High Functioning Autism and Children with Social Phobia

    Science.gov (United States)

    Wong, Nina; Beidel, Deborah C.; Sarver, Dustin E.; Sims, Valerie

    2012-01-01

    Recognizing facial affect is essential for effective social functioning. This study examines emotion recognition abilities in children aged 7-13 years with High Functioning Autism (HFA = 19), Social Phobia (SP = 17), or typical development (TD = 21). Findings indicate that all children identified certain emotions more quickly (e.g., happy [less…

  19. Facial Emotion Recognition in Children with High Functioning Autism and Children with Social Phobia

    Science.gov (United States)

    Wong, Nina; Beidel, Deborah C.; Sarver, Dustin E.; Sims, Valerie

    2012-01-01

    Recognizing facial affect is essential for effective social functioning. This study examines emotion recognition abilities in children aged 7-13 years with High Functioning Autism (HFA = 19), Social Phobia (SP = 17), or typical development (TD = 21). Findings indicate that all children identified certain emotions more quickly (e.g., happy [less…

  20. Selective gas adsorption and unique structural topology of a highly stable guest-free zeolite-type MOF material with N-rich chiral open channels.

    Science.gov (United States)

    Li, Jian-Rong; Tao, Ying; Yu, Qun; Bu, Xian-He; Sakamoto, Hirotoshi; Kitagawa, Susumu

    2008-01-01

    A new multifunctional di-topic tetrazolate-based ligand, 2,3-di-1H-tetrazol-5-ylpyrazine (H(2)dtp) has been designed and synthesized. The solvothermal reaction of this ligand with ZnCl(2) gave a robust guest-free three-dimensional zeolite-like chiral metal-organic framework (MOF) complex, [Zn(dtp)], which crystallized in chiral space group P6(1) and possessed chiral open channels with nitrogen-rich walls and the diameter of approximately 4.1 A. This framework presents a unique uniform etd (8,3) topology, is the first example of its type in MOFs, and exhibits high thermal stability with the decomposition temperature above 380 degrees C and permanent porosity. It is interesting that this material is able to selectively adsorb O(2) and CO(2) over N(2) gas, being a rare example in MOFs. In addition, C(2)H(2) and MeOH adsorption results show that although the framework channel holds nitrogen-rich walls that may provide H-bonding sites, no NH H-bond effect between the guest molecules and microporous surface was observed.

  1. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

    Science.gov (United States)

    Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong

    2016-09-01

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface.

  2. Chiral ligand-exchange high-performance liquid chromatography with copper (II)-L-phenylalanine complexes for separation of 3,4-dimethoxy-α-methylphenylalanine racemes.

    Science.gov (United States)

    Jia, Dong-Xu; Ai, Zheng-Gui; Xue, Ya-Ping; Zheng, Yu-Guo

    2014-11-01

    L-3, 4-dimethoxy-α-methylphenylalanine (L-DMMD) is an important intermediate for the synthesis of 3-hydroxy-α-methyl-L-tyrosine (L-methyldopa). This paper describes an efficient, accurate, and low-priced method of high-performance liquid chromatography (HPLC) using chiral mobile phase and conventional C18 column to separate L-DMMD from its enantiomers. The effects of ligands, copper salts, organic modifiers, pHs of mobile phase, and temperatures on the retention factors (k') and selectivity (α) were evaluated to achieve optimal separation performance. Then, thermal analysis of the optimal separation conditions was investigated as well. It was confirmed that the optimal mobile phase was composed of 20 % (v/v) methanol, 8 mM L-phenylalanine (L-Phe), and 4 mM cupric sulfate in water of pH 3.2, and the column temperature was set at 20 °C. Baseline separation of two enantiomers could be obtained through the conventional C18 column with a resolution (R) of 3.18 in less than 18 min. Thermodynamic data (∆∆H and ∆∆S) obtained by Van't Hoff plots revealed the chiral separation was an enthalpy-controlled process. To the best of our knowledge, this is the first report regarding the enantioseparation of DMMD by chiral ligand-exchange HPLC.

  3. Facile Isolation of Adsorbent-Free Long and Highly-Pure Chirality-Selected Semiconducting Single-Walled Carbon Nanotubes Using A Hydrogen-bonding Supramolecular Polymer

    Science.gov (United States)

    Toshimitsu, Fumiyuki; Nakashima, Naotoshi

    2015-12-01

    The ideal form of semiconducting-single-walled carbon nanotubes (sem-SWNTs) for science and technology is long, defect-free, chirality pure and chemically pure isolated narrow diameter tubes. While various techniques to solubilize and purify sem-SWNTs have been developed, many of them targeted only the chiral- or chemically-purity while sacrificing the sem-SWNT intrinsic structural identities by applying strong ultra-sonication and/or chemical modifications. Toward the ultimate purification of the sem-SWNTs, here we report a mild-conditioned extraction of the sem-SWNTs using removable supramolecular hydrogen-bonding polymers (HBPs) that are composed of dicarboxylic- or diaminopyridyl-fluorenes with ~70%-(8,6)SWNT selective extraction. Replacing conventional strong sonication techniques by a simple shaking using HPBs was found to provide long sem-SWNTs (>2.0 μm) with a very high D/G ratio, which was determined by atomic force microscopy observations. The HBPs were readily removed from the nanotube surfaces by an outer stimulus, such as a change in the solvent polarities, to provide chemically pure (8,6)-enriched sem-SWNTs. We also describe molecular mechanics calculations to propose possible structures for the HBP-wrapped sem-SWNTs, furthermore, the mechanism of the chiral selectivity for the sorted sem-SWNTs is well explained by the relationship between the molecular surface area and mass of the HBP/SWNT composites.

  4. High-voltage cable insulation online monitoring in coal mine based on pattern recognition

    Science.gov (United States)

    Zhao, Yongmei; Li, Junfeng; Wu, Lingjie; Wang, Yanwen

    2017-03-01

    The single-phase grounding fault is the main electrical fault types of the mine power grid. A new cable insulation online monitoring based on pattern recognition is proposed, in case single-phase grounding fault in coal mine. Firstly, using the pattern recognition method, the insulation state of the cable is divided into three types: "good insulation" and "insulation decline symmetrically" and "insulation decline asymmetrically". Then the cables with "insulation decline asymmetrically" can be further analysed and calculated and its insulation parameter value can be determined. The algorithm is simulated and verified. Simulation result shows that: The zero-sequence voltage and each phase voltage and the zero-sequence current of each cable are taken in the coal mine high-voltage system, and the insulation parameter value of each cable can be calculated accurately by using the pattern recognition method.

  5. Antibody Recognition of a Highly Conserved Influenza Virus Epitope

    Energy Technology Data Exchange (ETDEWEB)

    Ekiert, Damian C.; Bhabha, Gira; Elsliger, Marc-André; Friesen, Robert H.E.; Jongeneelen, Mandy; Throsby, Mark; Goudsmit, Jaap; Wilson, Ian A.; Scripps; Crucell

    2009-05-21

    Influenza virus presents an important and persistent threat to public health worldwide, and current vaccines provide immunity to viral isolates similar to the vaccine strain. High-affinity antibodies against a conserved epitope could provide immunity to the diverse influenza subtypes and protection against future pandemic viruses. Cocrystal structures were determined at 2.2 and 2.7 angstrom resolutions for broadly neutralizing human antibody CR6261 Fab in complexes with the major surface antigen (hemagglutinin, HA) from viruses responsible for the 1918 H1N1 influenza pandemic and a recent lethal case of H5N1 avian influenza. In contrast to other structurally characterized influenza antibodies, CR6261 recognizes a highly conserved helical region in the membrane-proximal stem of HA1 and HA2. The antibody neutralizes the virus by blocking conformational rearrangements associated with membrane fusion. The CR6261 epitope identified here should accelerate the design and implementation of improved vaccines that can elicit CR6261-like antibodies, as well as antibody-based therapies for the treatment of influenza.

  6. Enhancing and reducing chirality by opposite circularly-polarized light irradiation on crystalline chiral domains consisting of nonchiral photoresponsive W-shaped liquid crystal molecules.

    Science.gov (United States)

    Choi, Suk-Won; Takezoe, Hideo

    2016-09-28

    We found possible chirality enhancement and reduction in chiral domains formed by photoresponsive W-shaped molecules by irradiation with circularly polarized light (CPL). The W-shaped molecules exhibit a unique smectic phase with spontaneously segregated chiral domains, although the molecules are nonchiral. The chirality control was generated in the crystalline phase, which shows chiral segregation as in the upper smectic phase, and the result appeared to be as follows: for a certain chiral domain, right-CPL stimuli enhanced the chirality, while left-CPL stimuli reduced the chirality, and vice versa for another chiral domain. Interestingly, no domain-size change could be observed after CPL irradiation, suggesting some changes in the causes of chirality. In this way, the present system can recognize the handedness of the applied chiral stimuli. In other words, the present material can be used as a sensitive chiral-stimuli-recognizing material and should find invaluable applications, including in chiroptical switches, sensors, and memories as well as in chiral recognition.

  7. Chiral Gravitational Waves from Chiral Fermions

    CERN Document Server

    Anber, Mohamed M

    2016-01-01

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

  8. Chiral gravitational waves from chiral fermions

    Science.gov (United States)

    Anber, Mohamed M.; Sabancilar, Eray

    2017-07-01

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

  9. Use of chiral amino acid ester-based ionic liquids as chiral selectors in CE.

    Science.gov (United States)

    Stavrou, Ioannis J; Kapnissi-Christodoulou, Constantina P

    2013-02-01

    In this study, the applicability of a chiral ionic liquid (CIL) as the sole chiral selector in CE was investigated for the first time. In particular, five amino acid ester-based CILs were synthesized and used as additives in the BGE in order to evaluate their chiral recognition ability. The performance of these CILs as the sole chiral selectors was evaluated by using 1,1'-binaphthyl-2,2-diylhydrogenphosphate (BNP) as the analyte and by comparing the resolution values. Different parameters were examined, such as the alkyl group bulkiness and the configuration of the cation, the anion type of the CIL and its concentration, and the pH of the BGE, in order to optimize the separation of the enantiomers and to demonstrate the effect that each parameter has on the chiral-recognition ability of the CIL. Baseline separation of BNP within 13 min was achieved by using a BGE of 100 mM Tris/10 mM sodium tetraboratedecahydrate (pH 8) and a chiral selector of 60 mM l-alanine tert butyl ester lactate. The run-to-run and batch-to-batch reproducibilities were also evaluated by computing the %RSD values of the EOF and the two enantiomer peaks. In both cases, very good reproducibilities were observed, since all %RSD values were below 1%. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Asymmetric hydrogenation of quinazolinium salts catalysed by halide-bridged dinuclear iridium complexes bearing chiral diphosphine ligands.

    Science.gov (United States)

    Kita, Yusuke; Higashida, Kosuke; Yamaji, Kenta; Iimuro, Atsuhiro; Mashima, Kazushi

    2015-03-14

    Asymmetric hydrogenation of quinazolinium salts was catalysed by halogen-bridged dinuclear iridium complexes bearing chiral diphosphine ligands, yielding tetrahydroquinazoline and 3,4-dihydroquinazoline with high enantioselectivity. A derivative of chiral dihydroquinazoline was used as a chiral NHC ligand.

  11. Highly efficient enantioselective epoxidation of α,β-enones catalyzed by cheap chiral lanthanum and gadolinium alkoxides

    NARCIS (Netherlands)

    Chen, Ruifang; Qian, Changtao; Vries, Johannes G. de

    2001-01-01

    (S)-6,6'-Dibromo-BINOL and (S)-6,6'-diphenyl-BINOL have been developed as efficient chiral ligands applicable to lanthanoid catalyzed asymmetric epoxidation of α,β-unsaturated ketones in the presence of cumene hydroperoxide. Excellent chemical yield and enantioselectivity have been achieved for seve

  12. Chiral Nuclear Dynamics II

    CERN Document Server

    Rho, Mannque

    2008-01-01

    This is the sequel to the first volume to treat in one effective field theory framework the physics of strongly interacting matter under extreme conditions. This is vital for understanding the high temperature phenomena taking place in relativistic heavy ion collisions and in the early Universe, as well as the high-density matter predicted to be present in compact stars. The underlying thesis is that what governs hadronic properties in a heat bath and/or a dense medium is hidden local symmetry which emerges from chiral dynamics of light quark systems and from the duality between QCD in 4D and

  13. Evidence for Separate Contributions of High and Low Spatial Frequencies during Visual Word Recognition

    Directory of Open Access Journals (Sweden)

    Kurt Winsler

    2017-06-01

    Full Text Available Previous studies have shown that different spatial frequency information processing streams interact during the recognition of visual stimuli. However, it is a matter of debate as to the contributions of high and low spatial frequency (HSF and LSF information for visual word recognition. This study examined the role of different spatial frequencies in visual word recognition using event-related potential (ERP masked priming. EEG was recorded from 32 scalp sites in 30 English-speaking adults in a go/no-go semantic categorization task. Stimuli were white characters on a neutral gray background. Targets were uppercase five letter words preceded by a forward-mask (####### and a 50 ms lowercase prime. Primes were either the same word (repeated or a different word (un-repeated than the subsequent target and either contained only high, only low, or full spatial frequency information. Additionally within each condition, half of the prime-target pairs were high lexical frequency, and half were low. In the full spatial frequency condition, typical ERP masked priming effects were found with an attenuated N250 (sub-lexical and N400 (lexical-semantic for repeated compared to un-repeated primes. For HSF primes there was a weaker N250 effect which interacted with lexical frequency, a significant reversal of the effect around 300 ms, and an N400-like effect for only high lexical frequency word pairs. LSF primes did not produce any of the classic ERP repetition priming effects, however they did elicit a distinct early effect around 200 ms in the opposite direction of typical repetition effects. HSF information accounted for many of the masked repetition priming ERP effects and therefore suggests that HSFs are more crucial for word recognition. However, LSFs did produce their own pattern of priming effects indicating that larger scale information may still play a role in word recognition.

  14. Evidence for Separate Contributions of High and Low Spatial Frequencies during Visual Word Recognition.

    Science.gov (United States)

    Winsler, Kurt; Holcomb, Phillip J; Midgley, Katherine J; Grainger, Jonathan

    2017-01-01

    Previous studies have shown that different spatial frequency information processing streams interact during the recognition of visual stimuli. However, it is a matter of debate as to the contributions of high and low spatial frequency (HSF and LSF) information for visual word recognition. This study examined the role of different spatial frequencies in visual word recognition using event-related potential (ERP) masked priming. EEG was recorded from 32 scalp sites in 30 English-speaking adults in a go/no-go semantic categorization task. Stimuli were white characters on a neutral gray background. Targets were uppercase five letter words preceded by a forward-mask (#######) and a 50 ms lowercase prime. Primes were either the same word (repeated) or a different word (un-repeated) than the subsequent target and either contained only high, only low, or full spatial frequency information. Additionally within each condition, half of the prime-target pairs were high lexical frequency, and half were low. In the full spatial frequency condition, typical ERP masked priming effects were found with an attenuated N250 (sub-lexical) and N400 (lexical-semantic) for repeated compared to un-repeated primes. For HSF primes there was a weaker N250 effect which interacted with lexical frequency, a significant reversal of the effect around 300 ms, and an N400-like effect for only high lexical frequency word pairs. LSF primes did not produce any of the classic ERP repetition priming effects, however they did elicit a distinct early effect around 200 ms in the opposite direction of typical repetition effects. HSF information accounted for many of the masked repetition priming ERP effects and therefore suggests that HSFs are more crucial for word recognition. However, LSFs did produce their own pattern of priming effects indicating that larger scale information may still play a role in word recognition.

  15. Fast Track Pattern Recognition in High Energy Physics Experiments with the Automata Processor

    CERN Document Server

    Wang, Michael H L S; Green, Christopher; Guo, Deyuan; Wang, Ke; Zmuda, Ted

    2016-01-01

    We explore the Micron Automata Processor (AP) as a suitable commodity technology that can address the growing computational needs of track pattern recognition in High Energy Physics experiments. A toy detector model is developed for which a track trigger based on the Micron AP is used to demonstrate a proof-of-principle. Although primarily meant for high speed text-based searches, we demonstrate that the Micron AP is ideally suited to track finding applications.

  16. New Chiral Metal Cluster Systems for Catalytic Asymmetric Syntheses of Chiral Alcohols

    Institute of Scientific and Technical Information of China (English)

    LI Yan-yun; CHEN Jian-shan; YANG Chuan-bo; DONG Zhen-rong; LI Bao-zhu; ZHANG Hui; GAO Jing-xing; TAKAO Ikariya

    2004-01-01

    The efficient chiral Ru3(CO)12 systems were prepared in situ from Ru3(CO)12 and various chiral diiminoor diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu3(CO)11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru3 framework.

  17. Observing Disoriented Chiral Condensates

    CERN Document Server

    Bjorken, James D; Taylor, C C

    1993-01-01

    We speculate that, in very high energy hadronic collisions, large fireballs may be produced with interiors which have anomalous chiral order parameters. Such a process would result in radiation of pions with distinctive momentum and isospin distributions, and may provide an explanation of Centauro and related phenomena in cosmic-ray events. The phenomenology of such events is reviewed, with emphasis on the possibility of observing such phenomena at Fermilab experiment T-864 (MiniMax), or at a Full Acceptance Detector (FAD) at the SSC.

  18. Chiral recognition of macromolecules with cyclodextrins: pH- and thermosensitive copolymers from N-isopropylacrylamide and N-acryloyl-D/L-phenylalanine and their inclusion complexes with cyclodextrins

    Directory of Open Access Journals (Sweden)

    Helmut Ritter

    2011-02-01

    Full Text Available In the present work we report the enantioselective recognition of water soluble stimuli-responsive polymers bearing phenylalanine moieties via host-guest interaction with β-cyclodextrin and randomly-methylated-β-cyclodextrin (RAMEB-CD. We synthesised N-acryloyl-D/L-phenylalanine monomers (2D, 2L which were then copolymerised under free radical conditions with N-isopropylacrylamide (NIPAAm. The resulting copolymers 3D and 3L exhibit a lower critical solution temperature (LCST of 25 °C. As a further benefit, the presence of a free carboxylic group in the copolymer system gives a high sensitivity to the pH value in respect to the LCST value. The enantioselective recognition of the side groups of copolymers 3D and 3L and their solubility behaviour were investigated by dynamic light scattering and 2D NMR spectroscopy, respectively.

  19. Chiral separation of agricultural fungicides.

    Science.gov (United States)

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

    2011-09-23

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

  20. High-Resolution Sonars: What Resolution Do We Need for Target Recognition?

    Directory of Open Access Journals (Sweden)

    Pailhas Yan

    2010-01-01

    Full Text Available Target recognition in sonar imagery has long been an active research area in the maritime domain, especially in the mine-counter measure context. Recently it has received even more attention as new sensors with increased resolution have been developed; new threats to critical maritime assets and a new paradigm for target recognition based on autonomous platforms have emerged. With the recent introduction of Synthetic Aperture Sonar systems and high-frequency sonars, sonar resolution has dramatically increased and noise levels decreased. Sonar images are distance images but at high resolution they tend to appear visually as optical images. Traditionally algorithms have been developed specifically for imaging sonars because of their limited resolution and high noise levels. With high-resolution sonars, algorithms developed in the image processing field for natural images become applicable. However, the lack of large datasets has hampered the development of such algorithms. Here we present a fast and realistic sonar simulator enabling development and evaluation of such algorithms.We develop a classifier and then analyse its performances using our simulated synthetic sonar images. Finally, we discuss sensor resolution requirements to achieve effective classification of various targets and demonstrate that with high resolution sonars target highlight analysis is the key for target recognition.

  1. A liquid crystalline chirality balance for vapours

    Science.gov (United States)

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

    2014-04-01

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

  2. Contributions of low and high spatial frequency processing to impaired object recognition circuitry in schizophrenia.

    Science.gov (United States)

    Calderone, Daniel J; Hoptman, Matthew J; Martínez, Antígona; Nair-Collins, Sangeeta; Mauro, Cristina J; Bar, Moshe; Javitt, Daniel C; Butler, Pamela D

    2013-08-01

    Patients with schizophrenia exhibit cognitive and sensory impairment, and object recognition deficits have been linked to sensory deficits. The "frame and fill" model of object recognition posits that low spatial frequency (LSF) information rapidly reaches the prefrontal cortex (PFC) and creates a general shape of an object that feeds back to the ventral temporal cortex to assist object recognition. Visual dysfunction findings in schizophrenia suggest a preferential loss of LSF information. This study used functional magnetic resonance imaging (fMRI) and resting state functional connectivity (RSFC) to investigate the contribution of visual deficits to impaired object "framing" circuitry in schizophrenia. Participants were shown object stimuli that were intact or contained only LSF or high spatial frequency (HSF) information. For controls, fMRI revealed preferential activation to LSF information in precuneus, superior temporal, and medial and dorsolateral PFC areas, whereas patients showed a preference for HSF information or no preference. RSFC revealed a lack of connectivity between early visual areas and PFC for patients. These results demonstrate impaired processing of LSF information during object recognition in schizophrenia, with patients instead displaying increased processing of HSF information. This is consistent with findings of a preference for local over global visual information in schizophrenia.

  3. Baryons and Chiral Symmetry

    CERN Document Server

    Liu, Keh-Fei

    2016-01-01

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

  4. Preparation and characterization of highly stable hybrid organosilica cellulose derivative-based chiral stationary phase%高稳定性硅基杂化纤维素衍生物手性固定相的制备及其色谱拆分性能

    Institute of Scientific and Technical Information of China (English)

    罗飞; 翁西伦; 鲍宗必; 杨亦文; 任其龙

    2015-01-01

    Chiral chromatography plays an important role in obtaining optically pure enantiomers. The key to preparative chiral chromatography is the availability of chiral stationary phases (CSPs) with broad chiral recognition, high sample loading as well as solvent tolerance. In order to overcome the shortcoming of traditional coating-type or bonding-type cellulose-based CSPs, a novel hybrid CSP based on cellulose derivative bearing a small amount of 3-(triethoxysilyl)propyl groups was proposed, which was used to crosslink with bis(triethoxysilyl)ethane (BTSE)via a sol-gel reaction. The prepared stationary phase was then evaluated by HPLC. The experimental results indicated that the CSP showed excellent chiral recognition ability and could run steadily at back column pressure more than 2000 psi (1 psi=6894.76 Pa) with flow-rate up to 3 ml·min−1 in the mobile phase containing 10% chloroform. It was worth mentioning that the selectivity of 2,2,2-trifluoro-1-(9-anthryl)ethanol and trans-stilbene oxide up to 2.99 and 2.48 was achieved, respectively, confirming its excellent chiral recognition performance. In addition, the reported CSP showed a promising packing for application in preparative chromatography such as simulated moving bed chromatography.%合成了含少量3-(三乙氧基硅)丙基氨基甲酸酯的纤维素3,5-二甲基苯基氨基甲酸酯衍生物(CDMPC),并采用1,2-二(三乙氧基硅基)乙烷(BTSE)为偶联剂,通过溶胶-凝胶法成功制备得到新型硅基杂化手性固定相。该固定相的CDMPC含量达60%,在含有10%氯仿的流动相中保持良好的手性识别性能和机械强度。使用其拆分了多种手性化合物,拆分效果优于商品柱Chiralpak IB,其中对2,2,2-三氟-1-(9-蒽基)乙醇和反式二苯乙烯氧化物对映体的分离选择性分别达到2.99和2.48,表明该类硅基杂化类手性固定相在制备色谱领域中有潜在应用前景。

  5. Chirally Pure Prodrugs and Their Converting Enzymes Lead to High Supersaturation and Rapid Transcellular Permeation of Benzodiazepines.

    Science.gov (United States)

    Kapoor, Mamta; Cheryala, Narsihmulu; Rautiola, Davin; Georg, Gunda I; Cloyd, James C; Siegel, Ronald A

    2016-08-01

    Water-soluble prodrugs can be rapidly converted by enzymes to hydrophobic drugs, whose aqueous thermodynamic solubilities are low, but are maintained in aqueous solution at supersaturated concentrations due to slow precipitation kinetics. Recently, we investigated avizafone (AVF) in combination with Aspergillus oryzae protease as a prodrug/enzyme system intended to produce supersaturated diazepam (DZP). Several fold enhancement of permeation of supersaturated DZP across Madin-Darby canine kidney II-wild type (MDCKII-wt) monolayers was observed, compared to saturated DZP solutions. However, prodrug conversion was incomplete, putatively due to partial racemization of AVF and stereoselectivity of A oryzae protease. Here we report synthesis of chirally pure AVF, and demonstrate complete conversion to supersaturated DZP followed by complete DZP permeation at enhanced rates across MDCKII-wt cell monolayers. We also synthesized, for the first time, a chirally pure prodrug of midazolam (MDZ-pro) and carried out the same sequence of studies. A oryzae protease was identified as a benign and efficient activating enzyme for MDZ-pro. The MDZ-pro/A oryzae protease system showed greater than 25-fold increase in absorption rate of MDZ across MDCKII-wt monolayers, compared to saturated MDZ. Such chirally pure prodrug/enzyme systems are promising candidates for efficient intranasal delivery of benzodiazepine drugs used in the treatment of seizure emergencies. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  6. Evaluation of sulfated maltodextrin as a novel anionic chiral selector for the enantioseparation of basic chiral drugs by capillary electrophoresis.

    Science.gov (United States)

    Tabani, Hadi; Mahyari, Mojtaba; Sahragard, Ali; Fakhari, Ali Reza; Shaabani, Ahmad

    2015-01-01

    Introducing a new class of chiral selectors is an interesting work and this issue is still one of the hot topics in separation science and chirality. In this study, for the first time, sulfated maltodextrin (MD) was synthesized as a new anionic chiral selector and then it was successfully applied for the enantioseparation of five basic drugs (amlodipine, hydroxyzine, fluoxetine, tolterodine, and tramadol) as model chiral compounds using CE. This chiral selector has two recognition sites: a helical structure and a sulfated group which contribute to three corresponding driving forces; inclusion complexation, electrostatic interaction, and hydrogen binding. Under the optimized condition (buffer solution: 50 mM phosphate (pH 3.0) and 2% w/v sulfated MD; applied voltage: 18 kV; temperature: 20°C), baseline enantioseparation was observed for all mentioned chiral drugs. When instead of sulfated MD neutral MD was used under the same condition, no enantioseparation was observed which means the resolution power of sulfated MD is higher than neutral MD due to the electrostatic interaction between sulfated groups and protonated chiral drugs. Also, the countercurrent mobility of negatively charged MD (sulfated MD) allows more interactions between the chiral selector and chiral drugs and this in turn results in a successful resolution for the enantiomers. Furthermore, a higher concentration of neutral MD (approximately five times) is necessary to achieve the equivalent resolution compared with the negatively charged MD.

  7. New Organocatalytic Asymmetric Synthesis of Highly Substituted Chiral 2-Oxospiro-[indole-3,4′- (1′,4′-dihydropyridine] Derivatives

    Directory of Open Access Journals (Sweden)

    Fernando Auria-Luna

    2015-08-01

    Full Text Available Herein, we report our preliminary results concerning the first promising asymmetric synthesis of highly functionalized 2-oxospiro-[indole-3,4′-(1′,4′-dihydropyridine] via the reaction of an enamine with isatylidene malononitrile derivatives in the presence of a chiral base organocatalyst. The moderate, but promising, enantioselectivity observed (30%–58% ee (enantiomeric excess opens the door to a new area of research for the asymmetric construction of these appealing spirooxindole skeletons, whose enantioselective syntheses are still very limited.

  8. Chiral Rotational Spectroscopy

    CERN Document Server

    Cameron, Robert P; Barnett, Stephen M

    2015-01-01

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

  9. Fabrication and characterization of three-dimensional biomimetic chiral composites.

    Science.gov (United States)

    Turner, Mark D; Schröder-Turk, Gerd E; Gu, Min

    2011-05-09

    Here we show the fabrication and characterization of a novel class of biomimetic photonic chiral composites inspired by a recent finding in butterfly wing-scales. These three-dimensional networks have cubic symmetry, are fully interconnected, have robust mechanical strength and possess chirality which can be controlled through the composition of multiple chiral networks, providing an excellent platform for developing novel chiral materials. Using direct laser writing we have fabricated different types of chiral composites that can be engineered to form novel photonic devices. We experimentally show strong circular dichroism and compare with numerical simulations to illustrate the high quality of these three-dimensional photonic structures.

  10. Exploration of portfolio characteristics for the recognition of prior learning : the identification, assessment and recognition of actual competencies of highly-skilled immigrants

    NARCIS (Netherlands)

    Scholten, Astrid Marianne

    2007-01-01

    This research study explores the characteristics of the portfolio as an instrument for highly-skilled immigrants to facilitate the identification, assessment and recognition of their actual competencies in order to define guidelines for portfolio design and implementation. The two research questions

  11. 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)

  12. Highly Selective Fluoride Recognition by a Simple Carbazole-based Hydrozone Derivative

    Institute of Scientific and Technical Information of China (English)

    TANG Li-jun; ZHAO Guo-you; HUANG Zhen-long; WANG Nan-nan; GUO Jiao-jiao

    2013-01-01

    A simple carbazole hydrozone derivative(1) was synthesized and used as an optical probe for fluoride recognition in CH3CN.Receptor 1 exhibited colorimetric and fluorescent dual-channel response to fluoride anions.Addition of fluoride to a receptor 1 solution in CH3CN induced a distinct color change from yellow to magenta,the solution also displayed significant fluorescence blue shift.Thus receptor 1 exhibited dual-channel responses to fluoride with a high selectivity and sensitivity.

  13. Face Memory and Object Recognition in Children with High-Functioning Autism or Asperger Syndrome and in Their Parents

    Science.gov (United States)

    Kuusikko-Gauffin, Sanna; Jansson-Verkasalo, Eira; Carter, Alice; Pollock-Wurman, Rachel; Jussila, Katja; Mattila, Marja-Leena; Rahko, Jukka; Ebeling, Hanna; Pauls, David; Moilanen, Irma

    2011-01-01

    Children with Autism Spectrum Disorders (ASDs) have reported to have impairments in face, recognition and face memory, but intact object recognition and object memory. Potential abnormalities, in these fields at the family level of high-functioning children with ASD remains understudied despite, the ever-mounting evidence that ASDs are genetic and…

  14. Emotion Recognition in Faces and the Use of Visual Context in Young People with High-Functioning Autism Spectrum Disorders

    Science.gov (United States)

    Wright, Barry; Clarke, Natalie; Jordan, Jo; Young, Andrew W.; Clarke, Paula; Miles, Jeremy; Nation, Kate; Clarke, Leesa; Williams, Christine

    2008-01-01

    We compared young people with high-functioning autism spectrum disorders (ASDs) with age, sex and IQ matched controls on emotion recognition of faces and pictorial context. Each participant completed two tests of emotion recognition. The first used Ekman series faces. The second used facial expressions in visual context. A control task involved…

  15. Examining the Relationship Between Information Acquisition, Entrepreneurial Opportunity Recognition, and Innovation Performance in the High Technology Sector in Taiwan

    Science.gov (United States)

    Wang, Yu-Lin; Ellinger, Andrea D.

    2007-01-01

    The purpose of this study was to investigate the relationships between information acquisition, entrepreneurial opportunity recognition, and innovation performance in the high technology sector in Taiwan. The results suggest that both information acquisition and entrepreneurial opportunity recognition positively contribute to individual-level and…

  16. Emotion Recognition in Faces and the Use of Visual Context in Young People with High-Functioning Autism Spectrum Disorders

    Science.gov (United States)

    Wright, Barry; Clarke, Natalie; Jordan, Jo; Young, Andrew W.; Clarke, Paula; Miles, Jeremy; Nation, Kate; Clarke, Leesa; Williams, Christine

    2008-01-01

    We compared young people with high-functioning autism spectrum disorders (ASDs) with age, sex and IQ matched controls on emotion recognition of faces and pictorial context. Each participant completed two tests of emotion recognition. The first used Ekman series faces. The second used facial expressions in visual context. A control task involved…

  17. Single chirality through crystal grinding

    NARCIS (Netherlands)

    Noorduin, W.L.

    2010-01-01

    The properties of chiral molecules in living organisms can be different for left- and right-handed molecules. Therefore, ways to produce molecules of single handedness are of paramount importance, especially for economical, high yielding processes to synthesize pharmaceutical compounds that must be

  18. Chiral symmetry and chiral-symmetry breaking

    Energy Technology Data Exchange (ETDEWEB)

    Peskin, M.E.

    1982-12-01

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

  19. Enantiomer separation of polychlorinated biphenyls on chiral chromatographic columns of cellulose and amylose by high-performance liquid chromatography%多氯联苯在纤维素和直链淀粉衍生物类手性色谱柱上的拆分

    Institute of Scientific and Technical Information of China (English)

    尹文华; 吴丞往; 方力; 张安平

    2012-01-01

    由于多氯联苯(Polychlorinated biphenyls)的纯对映体样品非常难得,国内外大多数的研究工作仅局限于外消旋体,而较少对其对映体的环境行为、生物毒性进行研究.采用三种不同的手性色谱柱对21种手性多氯联苯在不同流动相体系进行了拆分.最终有17种手性多氯联苯达到基线或部分分离,在纯正己烷流动相体系的拆分效果最佳.直链淀粉-三(5-氯-2-甲基苯基氨基甲酸酯)固定相具有很强的手性识别能力,Lux 3u Amylose-2柱可以作为Lux 3u Cellulose-1柱手性拆分的很好补充.当手性多氯联苯分子只含一个4号位氯代或同时含有5,5,号位氯代时,三种手性色谱柱较难对其分离完全.该方法分离速度快,可以作为纯对映体样品的制备方法.%Due to the enantiomer of polychlorinated biphenyls is rare, most of researches were focused on racemes, rather than environmental behavior or biotoxicity of enantiomer at home and abroad. The work investigated enantiomeric separation of 21 kinds of polychlorinated biphenyls with different chiral chromatographic columns by high-performance liquid chromatography. 17 kinds of PCBs achieved baseline or were at least partially separated. This was proved to be the most efficient for the chiral separation of 100% n-hexane mobile phase. As a kind of chiral stationary phases (CSPs), amylose tris (5-chlorine 2-methylphenylcarbamate) has a strong capacity of chiral recognition. Lux 3u Amylose-2 CSP is a great complementary for the chiral separation of Lux 3u Cellulose-1 CSP. The separations are difficult to be achieved for these three CSPs when polychlorinated biphenyls with chlorine substitution only in 4 position or in 5, 5' positions simultaneously. However, this approach could be used to obtain pure enantiomer of PCBs.

  20. Biocatalysis: synthesis of chiral intermediates for drugs.

    Science.gov (United States)

    Patel, Ramesh N

    2006-11-01

    Chirality is a key factor in the safety and efficacy of many drug products and thus the production of single enantiomers of drug intermediates has become increasingly important in the pharmaceutical industry. Chiral intermediates and fine chemicals are in high demand for the bulk preparation of drug substances and agricultural products. There has been an increasing awareness of the enormous potential of the use of microorganisms and microorganism-derived enzymes for the transformation of synthetic chemicals with high chemo-, regio- and enantioselectivities. In this article, biocatalytic processes are described for the synthesis of chiral intermediates for drugs.

  1. Synthesis of New Chiral Bis(BINOL) Substituted 2,2'-Bipyridine Ligands

    Institute of Scientific and Technical Information of China (English)

    BAI,Xiao-Li; GAO,Lian-Xun

    2004-01-01

    @@ Chiral 2,2'-bipyridines have been reported to be highly efficient catalysts and useful building blocks of supramolecular.[1,2] Chirality of bipyridines was introduced by chiral substituents. Because 1,1'-binaphthyl (BINOL) and its derivatives belong to the most important components of asymmetric catalysts, we would like to synthesize 5,5'-and 6,6'-positions substituted chiral bipyridine-type ligands, the chiral moieties of ligands originate from enationpure 1, 1'-binapthyl units.

  2. Extrinsic electromagnetic chirality in metamaterials

    OpenAIRE

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

    2009-01-01

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

  3. 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.

  4. Enantioselective Nanoporous Carbon Based on Chiral Ionic Liquids.

    Science.gov (United States)

    Fuchs, Ido; Fechler, Nina; Antonietti, Markus; Mastai, Yitzhak

    2016-01-04

    One of the greatest challenges in modern chemical processing is to achieve enantiospecific control in chemical reactions using chiral media such as chiral mesoporous materials. Herein, we describe a novel and effective synthetic pathway for the preparation of enantioselective nanoporous carbon, based on chiral ionic liquids (CILs). CILs of phenylalanine (CIL(Phe)) are used as precursors for the carbonization of chiral mesoporous carbon. We employ circular dichroism spectroscopy, isothermal titration calorimetry (ITC), and chronoamperometry in order to demonstrate the chiral nature of the mesoporous carbon. The approach presented in this paper is highly significant for the development of a new type of chiral porous materials for enantioselective chemistry. In addition, it contributes significantly to our understanding of the structure and nature of chiral nanoporous materials and surfaces. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Chiral rotational spectroscopy

    Science.gov (United States)

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

    2016-09-01

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

  6. Chiral Superfluidity for QCD

    CERN Document Server

    Kalaydzhyan, Tigran

    2014-01-01

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

  7. Emerging chirality in nanoscience.

    Science.gov (United States)

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

    2013-04-07

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

  8. Mechanical separation of chiral dipoles by chiral light

    CERN Document Server

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

    2013-01-01

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

  9. Hippocampal NMDA receptors are involved in rats' spontaneous object recognition only under high memory load condition.

    Science.gov (United States)

    Sugita, Manami; Yamada, Kazuo; Iguchi, Natsumi; Ichitani, Yukio

    2015-10-22

    The possible involvement of hippocampal N-methyl-D-aspartate (NMDA) receptors in spontaneous object recognition was investigated in rats under different memory load conditions. We first estimated rats' object memory span using 3-5 objects in "Different Objects Task (DOT)" in order to confirm the highest memory load condition in object recognition memory. Rats were allowed to explore a field in which 3 (3-DOT), 4 (4-DOT), or 5 (5-DOT) different objects were presented. After a delay period, they were placed again in the same field in which one of the sample objects was replaced by another object, and their object exploration behavior was analyzed. Rats could differentiate the novel object from the familiar ones in 3-DOT and 4-DOT but not in 5-DOT, suggesting that rats' object memory span was about 4. Then, we examined the effects of hippocampal AP5 infusion on performance in both 2-DOT (2 different objects were used) and 4-DOT. The drug treatment before the sample phase impaired performance only in 4-DOT. These results suggest that hippocampal NMDA receptors play a critical role in spontaneous object recognition only when the memory load is high.

  10. A simulation-based approach towards automatic target recognition of high resolution space borne radar signatures

    Science.gov (United States)

    Anglberger, H.; Kempf, T.

    2016-10-01

    Specific imaging effects that are caused mainly by the range measurement principle of a radar device, its much lower frequency range as compared to the optical spectrum, the slanted imaging geometry and certainly the limited spatial resolution complicates the interpretation of radar signatures decisively. Especially the coherent image formation which causes unwanted speckle noise aggravates the problem of visually recognizing target objects. Fully automatic approaches with acceptable false alarm rates are therefore an even harder challenge. At the Microwaves and Radar Institute of the German Aerospace Center (DLR) the development of methods to implement a robust overall processing workflow for automatic target recognition (ATR) out of high resolution synthetic aperture radar (SAR) image data is under progress. The heart of the general approach is to use time series exploitation for the former detection step and simulation-based signature matching for the subsequent recognition. This paper will show the overall ATR chain as a proof of concept for the special case of airplane recognition on image data from the space borne SAR sensor TerraSAR-X.

  11. Enantiospecific adsorption of cysteine on a chiral Au34 cluster

    Science.gov (United States)

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

    2015-12-01

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

  12. Detecting subtle facial emotion recognition deficits in high-functioning Autism using dynamic stimuli of varying intensities.

    Science.gov (United States)

    Law Smith, Miriam J; Montagne, Barbara; Perrett, David I; Gill, Michael; Gallagher, Louise

    2010-07-01

    Autism Spectrum Disorders (ASD) are characterised by social and communication impairment, yet evidence for deficits in the ability to recognise facial expressions of basic emotions is conflicting. Many studies reporting no deficits have used stimuli that may be too simple (with associated ceiling effects), for example, 100% 'full-blown' expressions. In order to investigate subtle deficits in facial emotion recognition, 21 adolescent males with high-functioning Austism Spectrum Disorders (ASD) and 16 age and IQ matched typically developing control males completed a new sensitive test of facial emotion recognition which uses dynamic stimuli of varying intensities of expressions of the six basic emotions (Emotion Recognition Test; Montagne et al., 2007). Participants with ASD were found to be less accurate at processing the basic emotional expressions of disgust, anger and surprise; disgust recognition was most impaired--at 100% intensity and lower levels, whereas recognition of surprise and anger were intact at 100% but impaired at lower levels of intensity.

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

    Institute of Scientific and Technical Information of China (English)

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

    2002-01-01

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

  14. High performance liquid chromatography with photo diode array for separation and analysis of naproxen and esomeprazole in presence of their chiral impurities: Enantiomeric purity determination in tablets.

    Science.gov (United States)

    Ragab, Marwa A A; El-Kimary, Eman I

    2017-05-12

    A stereoselective high performance liquid chromatographic method with diode array detection (HPLC-DAD) was introduced for S-naproxen and esomeprazole determination in tablets. The separation was achieved on a Kromasil Cellucoat chiral column using a mobile phase consisting of hexane: isopropanol: trifluoroacetic acid (TFA) (90:9.9:0.1 v/v/v). The proposed system was found to be suitable for the enantioseparation of naproxen and omeprazole biologically active isomers. After optimization of the chromatographic conditions, resolution values of 3.84 and 2.17 could be obtained for naproxen and omeprazole isomers, respectively. The method was fully validated for the determination of S-isomers of each drug in their dosage form. Also, the enentiomeric purity was determined in commercial tablet containing S-naproxen and esomeprazole. The enantiomeric purity was calculated for each drug and the chiral impurities (R-isomers) could be determined at 1% level. The method was validated and good results with respect to linearity, precision, accuracy, selectivity and robustness were obtained. The limits of detection (LOD) and quantification (LOQ) were 2.00, 6.50 and 0.10, 0.35μgmL(-1) for S-naproxen and esomeprazole, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Direct high-performance liquid chromatography enantioseparation of terazosin on an immobilised polysaccharide-based chiral stationary phase under polar organic and reversed-phase conditions.

    Science.gov (United States)

    Ferretti, Rosella; Gallinella, Bruno; La Torre, Francesco; Zanitti, Leo; Turchetto, Luciana; Mosca, Antonina; Cirilli, Roberto

    2009-07-10

    High-performance liquid chromatography (HPLC) enantioseparation of terazosin (TER) was accomplished on the immobilised-type Chiralpak IC chiral stationary phase (CSP) under both polar organic and reversed-phase modes. A simple analytical method was validated using a mixture of methanol-water-DEA 95:5:0.1 (v/v/v) as a mobile phase. Under reversed-phase conditions good linearities were obtained over the concentration range 8.76-26.28 microg mL(-1) for both enantiomers. The limits of detection and quantification were 10 and 30 ng mL(-1), respectively. The intra- and inter-day assay precision was less than 1.66% (RSD%). The optimised conditions also allowed to resolve chiral and achiral impurities from the enantiomers of TER. The proposed HPLC method supports pharmacological studies on the biological effects of the both forms of TER and analytical investigations of potential drug formulations based on a single enantiomer. At the semipreparative scale, 5.3 mg of racemic sample were resolved with elution times less than 12 min using a mobile phase consisting of methanol-DEA 100:0.1 (v/v) and both enantiomers were isolated with a purity of > or = 99% enantiomeric excess (ee). The absolute configuration of TER enantiomers was assigned by comparison of the measured specific rotations with those reported in the literature.

  16. Chiral atomically thin films

    Science.gov (United States)

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

    2016-06-01

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

  17. Chiral Shock Waves

    CERN Document Server

    Sen, Srimoyee

    2016-01-01

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

  18. Anomalous chiral superfluidity

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-02-08

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

  19. 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.

  20. Doped Chiral Polymer Metamaterials Project

    Data.gov (United States)

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

  1. Chiral HPLC analysis of milnacipran and its FMOC-derivative on cellulose-based stationary phases.

    Science.gov (United States)

    Patti, Angela; Pedotti, Sonia; Sanfilippo, Claudia

    2008-02-01

    The HPLC enantioseparation of the last generation antidepressive drug milnacipran (+/-)-1 was investigated on different cellulose-based chiral stationary phases (CSPs). On carbamate-type columns, Chiralcel OD and OD-H (+/-)-1 could be separated with alpha value about 1.20 but the resolution was quite low because of the tailing of the peaks. Direct determination of (+/-)-1 with high selectivity and resolution was obtained on Chiralcel OJ in normal phase mode elution. Precolumn derivatization of milnacipran with Fmoc-Cl gave compound (+/-)-2 which was enantioseparated on all the investigated CSPs and allowed enhanced UV or fluorimetric detection. The Chiralpak IB, that could be considered the immobilized version of Chiralcel OD-H, was found completely ineffective in the chiral recognition of (+/-)-1 and moderately efficient in the separation of (+/-)-2.

  2. Movement recognition technology as a method of assessing spontaneous general movements in high risk infants

    Directory of Open Access Journals (Sweden)

    Claire eMarcroft

    2015-01-01

    Full Text Available Preterm birth is associated with increased risks of neurological and motor impairments such as cerebral palsy. The risks are highest in those born at the lowest gestations. Early identification of those most at risk is challenging meaning that a critical window of opportunity to improve outcomes through therapy-based interventions may be missed. Clinically, the assessment of spontaneous general movements is an important tool which can be used for the prediction of movement impairments in high risk infants.Movement recognition aims to capture and analyze relevant limb movements through computerized approaches focusing on continuous, objective, and quantitative assessment. Different methods of recording and analyzing infant movements have recently been explored in high risk infants. These range from camera-based solutions to body-worn miniaturized movement sensors used to record continuous time-series data that represent the dynamics of limb movements. Various machine learning methods have been developed and applied to the analysis of the recorded movement data. This analysis has focused on the detection and classification of atypical spontaneous general movements. This paper aims to identify recent translational studies using movement recognition technology as a method of assessing movement in high risk infants. The application of this technology within pediatric practice represents a growing area of inter-disciplinary collaboration which may lead to a greater understanding of the development of the nervous system in infants at high risk of motor impairment.

  3. GNSS seismometer: Seismic phase recognition of real-time high-rate GNSS deformation waves

    Science.gov (United States)

    Nie, Zhaosheng; Zhang, Rui; Liu, Gang; Jia, Zhige; Wang, Dijin; Zhou, Yu; Lin, Mu

    2016-12-01

    High-rate global navigation satellite systems (GNSS) can potentially be used as seismometers to capture short-period instantaneous dynamic deformation waves from earthquakes. However, the performance and seismic phase recognition of the GNSS seismometer in the real-time mode, which plays an important role in GNSS seismology, are still uncertain. By comparing the results of accuracy and precision of the real-time solution using a shake table test, we found real-time solutions to be consistent with post-processing solutions and independent of sampling rate. In addition, we analyzed the time series of real-time solutions for shake table tests and recent large earthquakes. The results demonstrated that high-rate GNSS have the ability to retrieve most types of seismic waves, including P-, S-, Love, and Rayleigh waves. The main factor limiting its performance in recording seismic phases is the widely used 1-Hz sampling rate. The noise floor also makes recognition of some weak seismic phases difficult. We concluded that the propagation velocities and path of seismic waves, macro characteristics of the high-rate GNSS array, spatial traces of seismic phases, and incorporation of seismographs are all useful in helping to retrieve seismic phases from the high-rate GNSS time series.

  4. High Speed Railway Environment Safety Evaluation Based on Measurement Attribute Recognition Model

    Directory of Open Access Journals (Sweden)

    Qizhou Hu

    2014-01-01

    Full Text Available In order to rationally evaluate the high speed railway operation safety level, the environmental safety evaluation index system of high speed railway should be well established by means of analyzing the impact mechanism of severe weather such as raining, thundering, lightning, earthquake, winding, and snowing. In addition to that, the attribute recognition will be identified to determine the similarity between samples and their corresponding attribute classes on the multidimensional space, which is on the basis of the Mahalanobis distance measurement function in terms of Mahalanobis distance with the characteristics of noncorrelation and nondimensionless influence. On top of the assumption, the high speed railway of China environment safety situation will be well elaborated by the suggested methods. The results from the detailed analysis show that the evaluation is basically matched up with the actual situation and could lay a scientific foundation for the high speed railway operation safety.

  5. High Speed Railway Environment Safety Evaluation Based on Measurement Attribute Recognition Model

    Science.gov (United States)

    Hu, Qizhou; Zhang, Bing

    2014-01-01

    In order to rationally evaluate the high speed railway operation safety level, the environmental safety evaluation index system of high speed railway should be well established by means of analyzing the impact mechanism of severe weather such as raining, thundering, lightning, earthquake, winding, and snowing. In addition to that, the attribute recognition will be identified to determine the similarity between samples and their corresponding attribute classes on the multidimensional space, which is on the basis of the Mahalanobis distance measurement function in terms of Mahalanobis distance with the characteristics of noncorrelation and nondimensionless influence. On top of the assumption, the high speed railway of China environment safety situation will be well elaborated by the suggested methods. The results from the detailed analysis show that the evaluation is basically matched up with the actual situation and could lay a scientific foundation for the high speed railway operation safety. PMID:25435866

  6. High speed railway environment safety evaluation based on measurement attribute recognition model.

    Science.gov (United States)

    Hu, Qizhou; Gao, Ningbo; Zhang, Bing

    2014-01-01

    In order to rationally evaluate the high speed railway operation safety level, the environmental safety evaluation index system of high speed railway should be well established by means of analyzing the impact mechanism of severe weather such as raining, thundering, lightning, earthquake, winding, and snowing. In addition to that, the attribute recognition will be identified to determine the similarity between samples and their corresponding attribute classes on the multidimensional space, which is on the basis of the Mahalanobis distance measurement function in terms of Mahalanobis distance with the characteristics of noncorrelation and nondimensionless influence. On top of the assumption, the high speed railway of China environment safety situation will be well elaborated by the suggested methods. The results from the detailed analysis show that the evaluation is basically matched up with the actual situation and could lay a scientific foundation for the high speed railway operation safety.

  7. Normal and polar-organic-phase high-performance liquid chromatographic enantioresolution of omeprazole, rabeprazole, lansoprazole and pantoprazole using monochloro-methylated cellulose-based chiral stationary phase and determination of dexrabeprazole.

    Science.gov (United States)

    Dixit, Shuchi; Dubey, Rituraj; Bhushan, Ravi

    2014-01-01

    Enantioresolution of four anti-ulcer drugs (chiral sulfoxides), namely, omeprazole, rabeprazole, lansoprazole and pantoprazole, was carried out by high-performance liquid chromatography using a polysaccharide-based chiral stationary phase consisting of monochloromethylated cellulose (Lux cellulose-2) under normal and polar-organic-phase conditions with ultraviolet detection at 285 nm. The method was validated for linearity, accuracy, precision, robustness and limit of detection. The optimized enantioresolution method was compared for both the elution modes. The optimized method was further utilized to check the enantiomeric purity of dexrabeprazole.

  8. A liquid crystalline chirality balance for vapours

    OpenAIRE

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

    2014-01-01

    Chiral discrimination of vapours plays an important role in olfactory perception of biological systems and its realization by artificial sensors has been an intriguing challenge. Here, we report a simple method that tangibly visualizes the chirality of a diverse variety of molecules dissolved from vapours with high sensitivity, by making use of a structural change in a periodic microstructure of a nematic liquid crystal confined in open microchannels. This microstructure is accompanied by a t...

  9. Common and specific brain regions in high- versus low-confidence recognition memory

    Science.gov (United States)

    Kim, Hongkeun; Cabeza, Roberto

    2009-01-01

    The goal of the present functional magnetic resonance imaging (fMRI) study was to investigate whether and to what extent brain regions involved in high-confidence recognition (HCR) versus low-confidence recognition (LCR) overlap or separate from each other. To this end, we performed conjunction analyses involving activations elicited during high-confidence hit, low-confidence hit, and high-confidence correct-rejection responses. The analyses yielded 3 main findings. First, sensory/perceptual and associated posterior regions were common to HCR and LCR, indicating contribution of these regions to both HCR and LCR activity. This finding may help explain why these regions are among the most common in functional neuroimaging studies of episodic retrieval. Second, medial temporal lobe (MTL) and associated midline regions were associated with HCR, possibly reflecting recollection-related processes, whereas specific prefrontal cortex (PFC) regions were associated with LCR, possibly reflecting executive control processes. This finding is consistent with the notion that the MTL and PFC networks play complementary roles during episodic retrieval. Finally, within posterior parietal cortex, a dorsal region was associated with LCR, possibly reflecting top-down attentional processes, whereas a ventral region was associated with HCR, possibly reflecting bottom-up attentional processes. This finding may help explain why functional neuroimaging studies have found diverse parietal effects during episodic retrieval. Taken together, our findings provide strong evidence that HCR versus LCR, and by implication, recollection versus familiarity processes, are represented in common as well as specific brain regions. PMID:19501072

  10. Applications of chiral symmetry

    CERN Document Server

    Pisarski, R D

    1995-01-01

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

  11. Synthesis and Enantioselective Discrimination of Chiral Fluorescence Receptors Bearing Amino Acid Units

    Institute of Scientific and Technical Information of China (English)

    XU Kuo-Xi; HE Yong-Bing; QING Guang-Yan; QIN Hai-duan; LIU Shun-Ying; MENG Ling-Zhi

    2007-01-01

    Two chiral fluorescence receptors (1, 2) were synthesized, and their structures were characterized by IR, 1H NMR, 13C NMR, mass spectra and elemental analysis. The chiral recognition of receptors was studied by 1H NMR and fluorescence spectra. The results demonstrate that receptors and dibenzoyl tartrate anion formed a 1 : 1 complex. The receptor 1 exhibited a good enantioselective recognition ability toward the enantiomers of dibenzoyl tartrate anion.

  12. Crystal structure analysis and chiral recognition study of Delta-[Ru(bpy)2(py)2][(+)-O,O'-dibenzoylD-tartrate].12H2O and Lambda-[Ru(bpy)2(py)2][(-)-O,O'-dibenzoyl-L-tartrate].12H2O.

    Science.gov (United States)

    Kolp, B; Viebrock, H; von Zelewsky, A; Abeln, D

    2001-03-12

    The molecular structure and crystal-packing mode of the enantiopure chiral building blocks Delta-[Ru(bpy)(2)(py)(2)][(+)-O,O'-dibenzoyl-D-tartrate].12H(2)O (I) and Lambda-[Ru(bpy)(2)(py)(2)][(-)-O,O'-dibenzoyl-L-tartrate].12H(2)O (II) have been determined by single-crystal X-ray diffraction data. This study proposes a model of how the L- and D-dibenzoyltartrate anions recognize the chirality of the hydrophobic [Ru(bpy)(2)(py)(2)](2+) complex. The monoclinic unit cell contains four complex cations, four tartrate anions, and 48 water molecules. Since there are no possibilities to form hydrogen bonds between the cations and anions, chiral recognition is due to crystal packing. Two benzoyl rings of two different tartrate anions are gripping the two bpy-planes of the Ru-complex. Further a third benzoyl ring from a tartrate anion is packed between the two pyridine rings, favoring one enantiomeric form to crystallize from aqueous solution. Crystal structure data for I at 153 K: a = 15.342(3) A, b = 19.200(4) A, c = 18.872(4) A, beta = 104.841(3) degrees, monoclinic space group C(2), R(1)= 0.0239 (I > 2sigma(I)), R(2) = 0.0606, Flack parameter = 0.0115 (with esd 0.0166). For II at 293 K: a = 15.376(4) A, b = 19.388(11) A, c = 19.085(7) A, beta = 105.11(2) degrees, monoclinic space group C121, R(1)= 0.0686 (I > 2sigma(I)), R(2) = 0.1819, Flack parameter = -0.0100 (with esd 0.0521).

  13. Chiral Magnetic Effect in Heavy Ion Collisions

    CERN Document Server

    Liao, Jinfeng

    2016-01-01

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

  14. 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.

  15. Highly selective nanocomposite sorbents for the specific recognition of S-ibuprofen from structurally related compounds

    Science.gov (United States)

    Sooraj, M. P.; Mathew, Beena

    2016-06-01

    The aim of the present work was to synthesize highly homogeneous synthetic recognition units for the selective and specific separation of S-ibuprofen from its closely related structural analogues using molecular imprinting technology. The molecular imprinted polymer wrapped on functionalized multiwalled carbon nanotubes (MWCNT-MIP) was synthesized using S-ibuprofen as the template in the imprinting process. The characterization of the products and intermediates were done by FT-IR spectroscopy, PXRD, TGA, SEM and TEM techniques. The high regression coefficient value for Langmuir adsorption isotherm ( R 2 = 0.999) showed the homogeneous imprint sites and surface adsorption nature of the prepared polymer sorbent. The nano-MIP followed a second-order kinetics ( R 2 = 0.999) with a rapid adsorption rate which also suggested the formation of recognition sites on the surface of MWCNT-MIP. MWCNT-MIP showed 83.6 % higher rebinding capacity than its non-imprinted counterpart. The higher relative selectivity coefficient ( k') of the imprinted sorbent towards S-ibuprofen than that for its structural analogues evidenced the capability of the nano-MIP to selectively and specifically rebind the template rather than its analogues.

  16. 基于手性金纳米粒子圆二色光谱法识别与检测银离子%Recognition and Detection of Silver Ion by Circular Dichroism Spectrum Based on Chiral Gold Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    韦克毅; 王猛; 杜宇; 蔡波; 江云宝

    2016-01-01

    In this work,chiral gold particles with optical activity can be obtained by a facile liquid phase method.The textural proper-ties of the as-prepared samples were characterized by high resolution transmission electron microscopy,circular dichroism spectrum and absorption spectrum.The results show that the average particle size for the production is 3.6 nm and silver ion can be selectively recognized from 1 3 kinds of metal ions in 1 2 min with universal recurrence.We also established the standard curve for detecting silver ion.This study demonstrates that the linear range for this curve is 0.2-30μmol/L,the linearly dependent coefficient is 0.995(n=15),which supplies a simple new environmentally friendly method for quickly detecting and recognizing silver ion in environmental water samples with high precision.%采用液相制备方法获得具有光学活性的手性金纳米粒子,通过吸收光谱和圆二色光谱及高分辨透射电镜对手性金纳米粒子进行表征.利用圆二色光谱法建立手性金纳米粒子对 Ag+选择性识别方法,结果表明手性金纳米粒子对Ag+响应时间仅需12 min,手性金纳米粒子能够从13种常见金属离子中选择性识别 Ag+,并对多种常见金属离子具有较好的抗干扰能力,检测灵敏度高并且具有良好的重现性.所建立标准曲线线性范围为0.2~30μmol/L,线性相关系数R2=0.995(n=15),Ag+的检测限为0.2μmol/L;为环境水样中 Ag+的识别和检测提供了一种简单、精确、快速、环境友好的新方法.

  17. 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...

  18. Spectral study of a chiral limit without chiral condensate

    CERN Document Server

    Bietenholz, Wolfgang

    2009-01-01

    Random Matrix Theory (RMT) has elaborated successful predictions for Dirac spectra in field theoretical models. However, a generic assumption by RMT has been a non-vanishing chiral condensate $\\Sigma$ in the chiral limit. Here we consider the 2-flavour Schwinger model, where this assumption does not hold. We simulated this model with dynamical overlap hypercube fermions, and entered terra incognita by analysing this Dirac spectrum. The usual RMT prediction for the unfolded level spacing distribution in a unitary ensemble is precisely confirmed. The microscopic spectrum does not perform a Banks-Casher plateau. Instead the obvious expectation is a density of the lowest eigenvalue $\\lambda_{1}$ which increases $\\propto \\lambda_{1}^{1/3}$. That would correspond to a scale-invariant parameter $\\propto \\lambda V^{3/4}$, which is, however, incompatible with our data. Instead we observe to high precision a scale-invariant parameter $z \\propto \\lambda V^{5/8}$. This surprising result implies a microscopic spectral den...

  19. Online Pattern Recognition for the ALICE High Level Trigger (tracking and compression techniques)

    CERN Document Server

    INSPIRE-00171460; Loizides, C.; Rohrich, D.; Skaali, B.; Steinbeck, T.; Stock, R.; Tilsner, H.; Ullaland, K.; Vestbo, A.; Vik, T.

    2004-01-01

    The ALICE High Level Trigger has to process data online, in order to select interesting (sub)events, or to compress data efficiently by modeling techniques. Focusing on the main data source, the Time Projection Chamber (TPC), we present two pattern recognition methods under investigation: a sequential approach (cluster finder and track follower) and an iterative approach (track candidate finder and cluster deconvoluter). We show, that the former is suited for pp and low multiplicity PbPb collisions, whereas the latter might be applicable for high multiplicity PbPb collisions of dN/dy>3000. Based on the developed tracking schemes we show that using modeling techniques a compression factor of around 10 might be achievable.

  20. Pattern recognition in high-resolution electron microscopy of complex materials.

    Science.gov (United States)

    Niermann, Tore; Thiel, Karsten; Seibt, Michael

    2006-12-01

    Structural features like defects or heterointerfaces in crystals or amorphous phases give rise to different local patterns in high-resolution electron micrographs or object wave functions. Pattern recognition techniques can be used to identify these typical patterns that constitute the image itself, as was already demonstrated for compositional changes in isostructural heterostructures, where the patterns within unit cells of the lattice were analyzed. To extend such analyses to more complex materials, we examined patterns in small circular areas centered on intensity maxima of the image. Nonsupervised clustering, namely, Ward's clustering method, was applied to these patterns. In two examples, a highly defective ZnMnTe layer on GaAs and a tunnel magneto resistance device, we demonstrate how typical patterns are identified by this method and how these results can be used for a further investigation of the microstructural properties of the sample.

  1. Task Phase Recognition for Highly Mobile Workers in Large Building Complexes

    DEFF Research Database (Denmark)

    Stisen, Allan; Mathisen, Andreas; Krogh, Søren

    2016-01-01

    available for sensing and recognizing the activities and task phases the workers currently perform as such technologies have to be easily deployable and maintainable at a large scale. The methods presented in this paper consist of features that utilize data from sensing systems which are common in large......Being aware of activities of co-workers is a basic and vital mechanism for efficient work in highly distributed work settings. Thus, automatic recognition of the task phases the mobile workers are currently (or have been) in has many applications, e.g., efficient coordination of tasks...... by visualizing coworkers’ task progress, automatic notifications based on context awareness, and record filing of task statuses and completions. This paper presents methods to sense and detect highly mobile workers’ tasks phases in large building complexes. Large building complexes restrict the technologies...

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

    Institute of Scientific and Technical Information of China (English)

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

    2003-01-01

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

  3. 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

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

    Science.gov (United States)

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

    2009-12-07

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

  5. Detecting chirality in molecules by linearly polarized laser fields

    CERN Document Server

    Yachmenev, Andrey

    2016-01-01

    A new scheme for enantiomer differentiation of chiral molecules using a pair of linearly polarized intense ultrashort laser pulses with skewed mutual polarization is presented. The technique relies on the fact that the off-diagonal anisotropic contributions to the electric polarizability tensor for two enantiomers have different signs. Exploiting this property, we are able to excite a coherent unidirectional rotation of two enantiomers with a {\\pi} phase difference in the molecular electric dipole moment. The approach is robust and suitable for relatively high temperatures of molecular samples, making it applicable for selective chiral analysis of mixtures, and to chiral molecules with low barriers between enantiomers. As an illustration, we present nanosecond laser-driven dynamics of a tetratomic non-rigid chiral molecule with short-lived chirality. The ultrafast time scale of the proposed technique is well suited to study parity violation in molecular systems in short-lived chiral states.

  6. Study of surface plasmon chirality induced by Archimedes' spiral grooves.

    Science.gov (United States)

    Ohno, Tomoki; Miyanishi, Shintaro

    2006-06-26

    A chirality of surface plasmons excited on a silver film with Archimedes' spiral grooves during incidence of a circularly polarized light is analytically and numerically studied by using the finite-difference time-domain (FDTD) modeling method. We found that the surface of a plasmon has selective chirality, which is given by the sum of the chiralities of the incident light and the spiral structure. The surface plasmons with the chirality lead to zero-order, first-order, and high-order evanescent Bessel beams with electric charge distributions on the film. This selectivity could be widely applied for chiral detection of the incident light and chiral excitation of several optical modes in nanophotonics.

  7. Chirality in thiolate-protected gold clusters.

    Science.gov (United States)

    Knoppe, Stefan; Bürgi, Thomas

    2014-04-15

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

  8. Chiral supergravity and anomalies

    CERN Document Server

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

    1999-01-01

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

  9. 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...

  10. Robust metastable skyrmions and their triangular-square lattice structural transition in a high-temperature chiral magnet

    Science.gov (United States)

    Karube, K.; White, J. S.; Reynolds, N.; Gavilano, J. L.; Oike, H.; Kikkawa, A.; Kagawa, F.; Tokunaga, Y.; Rønnow, H. M.; Tokura, Y.; Taguchi, Y.

    2016-12-01

    Skyrmions, topologically protected nanometric spin vortices, are being investigated extensively in various magnets. Among them, many structurally chiral cubic magnets host the triangular-lattice skyrmion crystal (SkX) as the thermodynamic equilibrium state. However, this state exists only in a narrow temperature and magnetic-field region just below the magnetic transition temperature Tc, while a helical or conical magnetic state prevails at lower temperatures. Here we describe that for a room-temperature skyrmion material, β-Mn-type Co 8Zn 8Mn 4, a field-cooling via the equilibrium SkX state can suppress the transition to the helical or conical state, instead realizing robust metastable SkX states that survive over a very wide temperature and magnetic-field region. Furthermore, the lattice form of the metastable SkX is found to undergo reversible transitions between a conventional triangular lattice and a novel square lattice upon varying the temperature and magnetic field. These findings exemplify the topological robustness of the once-created skyrmions, and establish metastable skyrmion phases as a fertile ground for technological applications.

  11. Highly Catalytic Enantioselective Addition of Diethyl Zinc to Aldehydes and Chalcone in the Presence of Chiral Ligands

    Institute of Scientific and Technical Information of China (English)

    WANG; Rui

    2001-01-01

    Catalytic asymmetric carbon-carbon bond formation is one of the most important reactions and have attracted much attention to develop more efficient enantioselective C-C formation methods in organic synthesis. In this field, asymmetric addition of diethylzinc to aldehydes[1] and conjugate addition to enones[2] have drawn special interests and have been greatly developed. Regardless of it, much spaces in these areas still exist, so it needs more extensive and intensive researches for the purpose of as follows: (1) attaching ligands to a polymer for the easy separation of the catalysts so as to be able to allow very efficient recovery and reuse of the catalysts, and the possibility of carrying out the desired transfomation in continuous mode in a flow reactor, etc., (2) searching for novel chiral catalysts with such features as more suitable for more extensive substrates varieties, and more convenient and economical as well as possessing applicable prospect, and so on. Here we report some works in these areas done in our laboratory.  ……

  12. Highly Catalytic Enantioselective Addition of Diethyl Zinc to Aldehydes and Chalcone in the Presence of Chiral Ligands

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Catalytic asymmetric carbon-carbon bond formation is one of the most important reactions and have attracted much attention to develop more efficient enantioselective C-C formation methods in organic synthesis. In this field, asymmetric addition of diethylzinc to aldehydes[1] and conjugate addition to enones[2] have drawn special interests and have been greatly developed. Regardless of it, much spaces in these areas still exist, so it needs more extensive and intensive researches for the purpose of as follows: (1) attaching ligands to a polymer for the easy separation of the catalysts so as to be able to allow very efficient recovery and reuse of the catalysts, and the possibility of carrying out the desired transfomation in continuous mode in a flow reactor, etc., (2) searching for novel chiral catalysts with such features as more suitable for more extensive substrates varieties, and more convenient and economical as well as possessing applicable prospect, and so on. Here we report some works in these areas done in our laboratory.

  13. β-环糊精对α-环己基扁桃酸异构体手性识别作用的计算机模拟研究%The study of chiral recognition between β-cyclodextrin and α-cyclohexyl-mandelic acid stereisomers by computer simulation

    Institute of Scientific and Technical Information of China (English)

    李亮洪; 李芬芳

    2012-01-01

    Host-guest complexation of p-cyclodextrin (P-CD) with a-cyclohexyl-mandelic acid enantiomers was simulated by quantum mechanics PM3 method for understanding the chiral recognition mechanism. The modeling results can correctly predict the retention order and provide an atomistic account of how chiral discrimination takes place. Modeling results showed that the stabilization of complexes formed by (R/S)-CHMA enantiomers and P-CD were different. The hydrophobic block of benzene moiet of (R)-CHMA was located in the cavity of P-CD to form an inclusion molecule, while it is the cyclohexyl that be inserted in the cavity in the case of (S)-CHMA to form an inclusion molecule. What is more, as for (S)-CHMA/ P-CD complex, there is an intermolecular hydrogen bonds. The stabilization energy of the (S)-CHMA/ P-CD complex was lower than that of the (R)-CHMA/ P-CD complex. The main driving forces responsible for chiral recognition are hydrophobic forces and weak hydrogen bondings.%运用量子力学PM3方法模拟α-环己基扁桃酸((R/S)-CHMA)与β-环糊精(β-CD)的主客体相互作用,探讨(R/S)-CHMA在β-CD上的手性识别机理.模拟结果能够准确预测色谱出峰顺序从而能从原子层次上对手性识别机制给予理论解释.PM3方法的计算结果表明:(S)-CHMA与β-CD形成的结合物比(R)-CHMA与β-CD形成的结合物稳定.从模拟包结物的构型可以看出(R/S)-CHMA与β-CD结合方式完全不同:(R)-CHMA是将苯环插入β-CD空腔形成包结物,而(S)-CHMA是将环己基插入β-CD空腔形成包结物.此外,(S)-CHMA除了自身的分子内氢键外,与β-CD分子之间还存在分子间氢键作用;而(R)-CHMA与β-CD之间没有分子间氢键作用.从而说明疏水作用以及弱的分子间氢键作用是造成手性识别的主要驱动力.

  14. Enantiomer-Specific State Transfer of Chiral Molecules

    CERN Document Server

    Eibenberger, Sandra; Patterson, David

    2016-01-01

    State-selective enantiomeric excess is realized using microwave-driven coherent population transfer. The method selectively promotes either R- or S- molecules to a higher rotational state by phase-controlled microwave pulses that drive electric-dipole allowed rotational transitions. We demonstrate the method using a racemic mixture of 1,2-propanediol. This method of chiral enrichment can be applied to nearly any chiral molecule that can be vaporized and cooled to the point where rotationally resolved spectroscopy is possible, including molecules that rapidly racemize. The rapid chiral switching demonstrated here allows for new applications in high-precision spectroscopic searches for parity violation in chiral molecules.

  15. Experimental Overview of the Search for Chiral Effects at RHIC

    Science.gov (United States)

    Wang, Gang

    2017-01-01

    In high-energy heavy-ion collisions, various novel transport phenomena in local chiral domains result from the interplay of quantum anomalies with magnetic field and vorticity, and could survive the expansion of the fireball and be detected in experiments. Among these phenomena are the chiral magnetic effect, the chiral vortical effect and the chiral magnetic wave, the experimental searches for which have aroused extensive interest. This review will describe the current status of experimental studies at Relativistic Heavy Ion Collider at BNL, and outline the future work in experiment needed to eliminate the existing uncertainties in the interpretation of the data.

  16. Experimental results on chiral magnetic and vortical effects

    CERN Document Server

    Wang, Gang

    2016-01-01

    Various novel transport phenomena in chiral systems result from the interplay of quantum anomalies with magnetic field and vorticity in high-energy heavy-ion collisions, and could survive the expansion of the fireball and be detected in experiments. Among them are the chiral magnetic effect, the chiral vortical effect and the chiral magnetic wave, the experimental searches for which have aroused extensive interest. The goal of this review is to describe the current status of experimental studies at Relativistic Heavy Ion Collider at BNL and the Large Hadron Collider at CERN, and to outline the future work in experiment needed to eliminate the existing uncertainties in the interpretation of the data.

  17. Chiral Separation of Naproxen with Immobilized Liquid Phases

    NARCIS (Netherlands)

    Corderi Gandara, Sandra; Vitasari, C.R.; Gramblicka, M.; Giard, T.; Schuur, Boelo

    2016-01-01

    The use of solvent-impregnated resins (SIRs) as a hybrid technology between liquid extraction and adsorption was investigated for the enantioseparation of naproxen. A chiral recognition system from the enantioselective liquid–liquid extraction from the literature was taken as a starting point, compr

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

    CERN Document Server

    Braguta, V V

    2016-01-01

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

  19. Standard object recognition memory and "what" and "where" components: Improvement by post-training epinephrine in highly habituated rats.

    Science.gov (United States)

    Jurado-Berbel, Patricia; Costa-Miserachs, David; Torras-Garcia, Meritxell; Coll-Andreu, Margalida; Portell-Cortés, Isabel

    2010-02-11

    The present work examined whether post-training systemic epinephrine (EPI) is able to modulate short-term (3h) and long-term (24 h and 48 h) memory of standard object recognition, as well as long-term (24 h) memory of separate "what" (object identity) and "where" (object location) components of object recognition. Although object recognition training is associated to low arousal levels, all the animals received habituation to the training box in order to further reduce emotional arousal. Post-training EPI improved long-term (24 h and 48 h), but not short-term (3 h), memory in the standard object recognition task, as well as 24 h memory for both object identity and object location. These data indicate that post-training epinephrine: (1) facilitates long-term memory for standard object recognition; (2) exerts separate facilitatory effects on "what" (object identity) and "where" (object location) components of object recognition; and (3) is capable of improving memory for a low arousing task even in highly habituated rats.

  20. Pattern recognition of typical defects in high-voltage storage capacitors based on DC partial discharge

    Institute of Scientific and Technical Information of China (English)

    WU GuangNing; BIAN ShanShan; ZHOU LiRen; ZHANG XueQin; RAN HanZheng; YU ChengLong

    2009-01-01

    High-voltage storage capacitors(hereinafter call capacitors for short)have been widely used in pulsed power technology.In accordance with the actual work conditions of capacitors,direct current partial discharge(DCPD)detection was put forward.The whole test system was based on the impedance balance circuit characterized by good configuration and anti-interference ability.Through DCPD detection on capacitors which contained four typical defects respectively,test results revealed that DCPD signals could well reflect the state of capacitor insulation.DCPD distribution spectra of capacitors containing four typical defects were obviously different.Defects in capacitors could be exactly judged by computer-aided pattern recognition based on support vector machine(SVM).

  1. Pattern recognition of typical defects in high-voltage storage capacitors based on DC partial discharge

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    High-voltage storage capacitors(hereinafter call capacitors for short)have been widely used in pulsed power technology.In accordance with the actual work conditions of capacitors,direct current partial discharge(DCPD)detection was put forward.The whole test system was based on the impedance balance circuit characterized by good configuration and anti-interference ability.Through DCPD detection on capacitors which contained four typical defects respectively,test results revealed that DCPD signals could well reflect the state of capacitor insulation.DCPD distribution spectra of capacitors containing four typical defects were obviously different.Defects in capacitors could be exactly judged by computer–aided pattern recognition based on support vector machine(SVM).

  2. The research on high speed underwater target recognition based on fuzzy logic inference

    Institute of Scientific and Technical Information of China (English)

    JIANG Xiang-Dong; YANG De-Sen; SHI Sheng-guo; LI Si-Chun

    2006-01-01

    The underwater target recognition is a key technology in acoustic confrontation and underwater defence. In this article, a recognition system based on fuzzy logic inference (FLI) is set up. This system is mainly composed of three parts: the fuzzy input module, the fuzzy logic inference module with a set of inference rules and the de-fuzzy output module. The inference result shows the recognition system is effective in most conditions.

  3. The research on high speed underwater target recognition based on fuzzy logic inference

    Science.gov (United States)

    Jiang, Xiang-Dong; Yang, De-Sen; Shi, Sheng-Guo; Li, Si-Chun

    2006-06-01

    The underwater target recognition is a key technology in acoustic confrontation and underwater defence. In this article, a recognition system based of fuzzy logic inference (FLI) is set up. This system is mainly composed of three parts: the fuzzy input module, the fuzzy logic inference module with a set of inference rules and the de-fuzzy output module. The inference result shows the recognition system is effective in most conditions.

  4. Color chiral solitons

    CERN Document Server

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

    2002-01-01

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

  5. Chiral brownian heat pump.

    Science.gov (United States)

    van den Broek, M; Van den Broeck, C

    2008-04-04

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

  6. Chiral Brownian heat pump

    OpenAIRE

    Van Den Broek, Martijn; Van Den Broeck, Christian

    2007-01-01

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

  7. Chiral discrimination in biomimetic systems: Phenylalanine

    Indian Academy of Sciences (India)

    K Thirumoorthy; K Soni; T Arun; N Nandi

    2007-09-01

    Chiral discrimination and recognition is important in peptide biosynthesis, amino acid synthesis and drug designing. Detailed structural information is available about the peptide synthesis in ribosome. However, no detailed study is available about the discrimination in peptide synthesis. We study the conformational energy variation of neutral methoxy phenyl alanine molecule as a function of its different dihedral angle to locate the minimum energy conformation using quantum chemical theory. We compared the intermolecular energy surfaces of phenyl alanine molecule in its neutral and zwitterionic state using quantum chemical theory as a function of distance and mutual orientation. The energy surfaces are studied with rigid geometry by varying the distance and orientation. The potential energy surfaces of - and - pairs are found to be dissimilar and reflect the underlying chirality of the homochiral pair and racemic nature of the heterochiral pair. The intermolecular energy surface of homochiral pair is more favourable than the corresponding energy surface of heterochiral pair.

  8. Electrodynamics of chiral matter

    Science.gov (United States)

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

    2017-02-01

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

  9. Chiral Odd GPDs

    Directory of Open Access Journals (Sweden)

    Goldstein Gary R.

    2015-01-01

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

  10. Cation-mediated optical resolution and anticancer activity of chiral polyoxometalates built from entirely achiral building blocks

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhi-Ming; Duan, Xiaopin; Yao, Shuang; Wang, Zhishu; Lin, Zekai; Li, Yang-Guang; Long, La-Sheng; Wang, En-Bo; Lin, Wenbin

    2016-01-01

    We report the crystallization of homochiral polyoxometalate (POM) macroanions {CoSb6O4(H2O)3[Co(hmta)SbW8O31]3}15- (1, hmta = hexamethylenetetramine) via the counter cation-mediated chiral symmetry breaking and asymmetric autocatalytic processes. In the presence of low Co2+ concentrations both Δ- and Λ-enantiomers of 1 formed in the reaction, crystallizing into the racemic crystal rac-1. At a high Co2+ concentration, the polyoxoanion enantiomers showed a high level of chiral recognition via H-bonding interactions to crystallize into enantiopure crystals of Δ- or Λ-[Co(H2O)6{CoSb6O4(H2O)3[Co(hmta)SbW8O31]3}]13-. During crystallization, a microscale symmetry-breaking event and a nonlinear asymmetric autocatalysis process make the enantiomers crystallize in different batches, which provides an opportunity to isolate the homochiral bulk materials. The defined structures of the racemic and homochiral crystals thus provide a molecular-level illustration that H-bonding interactions are responsible for such high-level chiral recognition, in a process similar to the supramolecular chirality frequently observed in biology. These POM macroanions showed a high cytotoxicity against various cancer cells, particularly ovarian cancer cells. The antitumor activity of these compounds resulted at least in part from the activation of the apoptotic pathways, as shown by the flow cytometry, Annexin V staining, DNA ladder, and TUNEL assay, likely by blocking the cell cycle and complexing with proteins in cells. The POM macroanions reported herein provide promising and novel antitumor agents for the potential treatment of various cancers.

  11. Automated, high accuracy classification of Parkinsonian disorders: a pattern recognition approach.

    Directory of Open Access Journals (Sweden)

    Andre F Marquand

    Full Text Available Progressive supranuclear palsy (PSP, multiple system atrophy (MSA and idiopathic Parkinson's disease (IPD can be clinically indistinguishable, especially in the early stages, despite distinct patterns of molecular pathology. Structural neuroimaging holds promise for providing objective biomarkers for discriminating these diseases at the single subject level but all studies to date have reported incomplete separation of disease groups. In this study, we employed multi-class pattern recognition to assess the value of anatomical patterns derived from a widely available structural neuroimaging sequence for automated classification of these disorders. To achieve this, 17 patients with PSP, 14 with IPD and 19 with MSA were scanned using structural MRI along with 19 healthy controls (HCs. An advanced probabilistic pattern recognition approach was employed to evaluate the diagnostic value of several pre-defined anatomical patterns for discriminating the disorders, including: (i a subcortical motor network; (ii each of its component regions and (iii the whole brain. All disease groups could be discriminated simultaneously with high accuracy using the subcortical motor network. The region providing the most accurate predictions overall was the midbrain/brainstem, which discriminated all disease groups from one another and from HCs. The subcortical network also produced more accurate predictions than the whole brain and all of its constituent regions. PSP was accurately predicted from the midbrain/brainstem, cerebellum and all basal ganglia compartments; MSA from the midbrain/brainstem and cerebellum and IPD from the midbrain/brainstem only. This study demonstrates that automated analysis of structural MRI can accurately predict diagnosis in individual patients with Parkinsonian disorders, and identifies distinct patterns of regional atrophy particularly useful for this process.

  12. Micro-X-ray fluorescence as a general high-throughput screening method for catalyst discovery and small molecule recognition.

    Science.gov (United States)

    Miller, Thomasin C; Mann, Grace; Havrilla, George J; Wells, Cyndi A; Warner, Benjamin P; Baker, R Tom

    2003-01-01

    A powerful high-throughput screening technique is described for the rapid screening of bead-based libraries for catalyst discovery and molecular recognition. Micro-X-ray fluorescence (MXRF) screens materials for elemental composition with mesoscale analysis. This method is nondestructive and requires minimal sample preparation and no special tags for analysis, and the screening time is dependent on the desired sensitivity. The speed, sensitivity, and simplicity of MXRF as a high-throughput screening technique were applied to screen bead-based libraries of oligopeptides for phosphate hydrolysis catalysts and molecular recognition of selective receptors for the degradation products and analogues of chemical warfare agents. This paper demonstrates the analytical or HTS capability of MXRF for combinatorial screening. It is meant only to show the capabilities of MXRF and is not meant as an exhaustive study of the catalyst and molecular recognition systems presented.

  13. Modeling the retention mechanism for high-performance liquid chromatography with a chiral ligand mobile phase and enantioseparation of mandelic acid derivatives.

    Science.gov (United States)

    Tong, Shengqiang; Shen, Mangmang; Zhang, Hu; Cheng, Dongping; Yan, Jizhong

    2015-06-01

    The chromatographic retention mechanism describing relationship between retention factor and concentration of Cu(2+) (l-phenylalanine)2 using chiral ligand mobile phase was investigated and eight mandelic acid derivatives were enantioseparated by chiral ligand exchange chromatography. The relationship between retention factor and concentration of the Cu(2+) (l-phenylalanine)2 complex was proven to be in conformity with chromatographic retention mechanism in which chiral discrimination occurred both in mobile and stationary phase. Different copper(II) salts, chiral ligands, organic modifier, pH of aqueous phase, and conventional temperature on retention behavior were optimized. Eight racemates were successfully enantioseparated on a common reversed-phase column with an optimized mobile phase composed of 6 mmol/L of l-phenylalanine or N,N-dimethyl-l-phenylalanine and 3 mmol/Lof copper(II) acetate or copper(II) sulfate aqueous solution and methanol. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Controlling the amplification of chirality in hydrogen-bonded assemblies

    NARCIS (Netherlands)

    Mateos-Timoneda, Miguel A.; Crego-Calama, Mercedes; Reinhoudt, David N.

    2005-01-01

    The amplification of chirality (a high enantiomeric or diastereomeric excess induced by a small initial amount of chiral bias) on hydrogen-bonded assemblies has been studied using “sergeants-and-soldiers” experiments under thermodynamically controlled conditions. Here it is shown that different subs

  15. 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.

  16. Chirality imprinting and direct asymmetric reaction screening using a stereodynamic Brønsted/Lewis acid receptor

    Science.gov (United States)

    Bentley, Keith W.; Proano, Daysi; Wolf, Christian

    2016-08-01

    Molecular recognition, activation and dynamic self-assembly with Brønsted and Lewis acids play a central role across the chemical sciences including catalysis, crystal engineering, supramolecular architectures and drug design. Despite this general advance, the utilization of the corresponding binding motifs for fast and robust quantitative chemosensing of chiral compounds in a complicate matrix has remained challenging. Here we show that a stereodynamic probe carrying complementary boronic acid and urea units achieves this goal with hydroxy carboxylic acids. Synergistic dual-site binding and instantaneous chirality imprinting result in characteristic ultraviolet and CD readouts that allow instantaneous determination of the absolute configuration, enantiomeric excess and concentration of the target compound even in complex mixtures. The robustness and practicality of this strategy for high-throughput screening purposes is demonstrated. Comprehensive sensing of only 0.5 mg of a crude reaction mixture of an asymmetric reduction eliminates cumbersome work-up protocols and minimizes analysis time, labour and waste production.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-01-15

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

  18. 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.

  19. Chiral Random Matrix Theory and Chiral Perturbation Theory

    CERN Document Server

    Damgaard, P H

    2011-01-01

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

  20. Chiral Random Matrix Theory and Chiral Perturbation Theory

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-04-01

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

  1. Figures of merit in the quantification of ibuprofen enantiomers by chiral HPLC.

    Science.gov (United States)

    Valderrama, Patrícia; Romero, Adriano Lopes; Imamura, Paulo Mitsuo; Poppi, Ronei Jesus

    2009-10-01

    The determination of ibuprofen (IBU) enantiomers by chiral high-performance liquid chromatographic is described. The methodology is based on chiral recognition of ibuprofen by a chiral column based on cellulose tris(4-methylbenzoate) coated on silica gel (Chiralcel OJ-H). The mobile phase is n-hexane-2-propanol-trifluoroacetic acid (98:2:0.1, v/v/v). The flow rate was 1.0 mL/min, and UV detection was 254 nm. The samples of ibuprofen were prepared in n-hexane in the concentration range 50-100% of (S)-IBU 1 x 10(-3) mol/L. Calibration and validation method were performed with six and nine samples, respectively. Goodness-of-fit measures represented by correlation coefficient, y-intercept, and slope of the regression line were 0.9836, 21373, 2162, respectively. Average of the relative error of the proposed method was 3.0%, 0.9% (S)-IBU selectivity, and 2162% (S)-IBU-1 sensitivity. The minimum concentration difference between two samples that could be determined in the linear dynamic range was 0.4% (S)-IBU. Limits of detection and quantification were 8.1 and 27.0% (S)-IBU, respectively. These results indicate that the proposed method can be employed for determination of the enantiomeric composition of IBU.

  2. Effects of steep high-frequency hearing loss on speech recognition using temporal fine structure in low-frequency region.

    Science.gov (United States)

    Li, Bei; Hou, Limin; Xu, Li; Wang, Hui; Yang, Guang; Yin, Shankai; Feng, Yanmei

    2015-08-01

    The present study examined the effects of steep high-frequency sensorineural hearing loss (SHF-SNHL) on speech recognition using acoustic temporal fine structure (TFS) in the low-frequency region where the absolute thresholds appeared to be normal. In total, 28 participants with SHF-SNHL were assigned to 3 groups according to the cut-off frequency (1, 2, and 4 kHz, respectively) of their pure-tone absolute thresholds. Fourteen age-matched normal-hearing (NH) individuals were enrolled as controls. For each Mandarin sentence, the acoustic TFS in 10 frequency bands (each 3-ERB wide) was extracted using the Hilbert transform and was further lowpass filtered at 1, 2, and 4 kHz. Speech recognition scores were compared among the NH and 1-, 2-, and 4-kHz SHF-SNHL groups using stimuli with varying bandwidths. Results showed that speech recognition with the same TFS-speech stimulus bandwidth differed significantly in groups and filtering conditions. Sentence recognition in quiet conditions was better than that in noise. Compared with the NH participants, nearly all the SHF-SNHL participants showed significantly poorer sentence recognition within their frequency regions with "normal hearing" (defined clinically by normal absolute thresholds) in both quiet and noisy conditions. These may result from disrupted auditory nerve function in the "normal hearing" low-frequency regions. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Robust modulation formats recognition technique using wavelet transform for high speed optical networks

    Science.gov (United States)

    Guesmi, Latifa; Hraghi, Abir; Menif, Mourad

    2015-09-01

    There is a need, for high speed optical communication networks, in the monitoring process, to determine the modulation format type of a received signal. In this paper, we present a new achievement of modulation format recognition technique, where we proposed the use of wavelet transform of the detected signal in conjunction with the artificial neural network (ANN) algorithm. Besides, wavelet transform is one of the most popular candidates of the time-frequency transformations, where the wavelets are generated from a basic wavelet function by dilations and translations. We proved that this technique is capable of recognizing the multi-carriers modulation scheme with high accuracy under different transmission impairments such as chromatic dispersion (CD), differential group delay (DGD) and accumulated amplified spontaneous emission (ASE) noise with different ranges. Both the theoretical analysis and the simulation results showed that the wavelet transform not only can be used for modulation identification of optical communication signals, but also has a better classification accuracies under appropriate OSNR (optical signal-to-noise ratio) values.

  4. High and Low Trait Anger, Angry Thoughts, and the Recognition of Anger Problems.

    Science.gov (United States)

    Alcázar-Olán, Raúl J; Deffenbacher, Jerry L; Hernández Guzmán, Laura; Jurado Cárdenas, Samuel

    2015-01-01

    This research had two goals: (1) it tested hypotheses of the State-Trait Model of anger, and (2) it explored characteristics that may distinguish individuals with high trait anger who recognize problems with their anger from those who do not recognize anger problems. Regarding the first goal, findings supported three hypotheses tested. In particular, compared to those low in trait anger, individuals with high trait anger reported: (a) more intense anger (intensity hypothesis), p anger expression (anger-out), p anger suppression (anger-in), p anger control-in), p anger control-out), p anger: those who identified anger as a personal problem and wanted help, and those who did not identify anger as a personal issue. As a result, compared to those who did not report anger problems, those who reported anger problems demonstrated a higher overall propensity to experience anger (i.e., higher trait anger), p anger suppression and harboring grudges (anger-in), p anger-control-in), p anger-control-out), p anger or anger problem recognition. Findings were discussed in terms of State-Trait Theory and implications for anger interventions.

  5. The effect of high and low exercise intensity periods on a simple memory recognition test

    Institute of Scientific and Technical Information of China (English)

    Ben Rattray; Disa J. Smee

    2016-01-01

    Purpose: The purpose of this study was to investigate the effect of variable intensities on a simple memory recognition task during exercise. Methods: Twenty active participants took part in initial testing, a familiarization trial and then four 60 min cycling interventions in a randomized order. Interventions consisted of no exercise (control), constant exercise at 90%ventilatory threshold (constant) and 2 trials that initially mimicked the constant trial, but then included periods of high (∼90%VO2peak) and low intensities (∼50%VO2peak). Cardiorespiratory measures and capillary blood samples were taken throughout. A short tablet-based cognitive task was completed prior to and during (50 and 55 min into exercise) each intervention. Results: The exercise conditions facilitated response time (p=0.009), although the extent of this effect was not as strong in the variable exercise conditions (p = 0.011–0.089). High intensity exercise periods resulted in some cognitive regression back towards control trial performance. Elevations in cardiorespiratory measures and periods of hypocapnia could not explain changes in cognitive performance. Conclusion: Changes in cognitive performance with variations in exercise intensity are likely to have implications for sport and occupational settings. The timing of cognitive tests to exercise intensity changes as well as use of short cognitive assessments will be important for future work.

  6. Translation Recognition in Highly Proficient Hindi-English Bilinguals: The Influence of Different Scripts but Connectable Phonologies

    Science.gov (United States)

    Sunderman, Gretchen L.; Priya, Kanu

    2012-01-01

    This study investigates the phonological nature of the lexical links in the bilingual lexicon using different-script bilinguals. Highly proficient Hindi-English bilinguals performed a translation recognition task (i.e., decide whether two words presented sequentially are a correct translation pair). For the critical trials, the second word was a…

  7. Combining high-speed SVM learning with CNN feature encoding for real-time target recognition in high-definition video for ISR missions

    Science.gov (United States)

    Kroll, Christine; von der Werth, Monika; Leuck, Holger; Stahl, Christoph; Schertler, Klaus

    2017-05-01

    For Intelligence, Surveillance, Reconnaissance (ISR) missions of manned and unmanned air systems typical electrooptical payloads provide high-definition video data which has to be exploited with respect to relevant ground targets in real-time by automatic/assisted target recognition software. Airbus Defence and Space is developing required technologies for real-time sensor exploitation since years and has combined the latest advances of Deep Convolutional Neural Networks (CNN) with a proprietary high-speed Support Vector Machine (SVM) learning method into a powerful object recognition system with impressive results on relevant high-definition video scenes compared to conventional target recognition approaches. This paper describes the principal requirements for real-time target recognition in high-definition video for ISR missions and the Airbus approach of combining an invariant feature extraction using pre-trained CNNs and the high-speed training and classification ability of a novel frequency-domain SVM training method. The frequency-domain approach allows for a highly optimized implementation for General Purpose Computation on a Graphics Processing Unit (GPGPU) and also an efficient training of large training samples. The selected CNN which is pre-trained only once on domain-extrinsic data reveals a highly invariant feature extraction. This allows for a significantly reduced adaptation and training of the target recognition method for new target classes and mission scenarios. A comprehensive training and test dataset was defined and prepared using relevant high-definition airborne video sequences. The assessment concept is explained and performance results are given using the established precision-recall diagrams, average precision and runtime figures on representative test data. A comparison to legacy target recognition approaches shows the impressive performance increase by the proposed CNN+SVM machine-learning approach and the capability of real-time high

  8. Chirality sensing with stereodynamic biphenolate zinc complexes.

    Science.gov (United States)

    Bentley, Keith W; de Los Santos, Zeus A; Weiss, Mary J; Wolf, Christian

    2015-10-01

    Two bidentate ligands consisting of a fluxional polyarylacetylene framework with terminal phenol groups were synthesized. Reaction with diethylzinc gives stereodynamic complexes that undergo distinct asymmetric transformation of the first kind upon binding of chiral amines and amino alcohols. The substrate-to-ligand chirality imprinting at the zinc coordination sphere results in characteristic circular dichroism signals that can be used for direct enantiomeric excess (ee) analysis. This chemosensing approach bears potential for high-throughput ee screening with small sample amounts and reduced solvent waste compared to traditional high-performance liquid chromatography methods.

  9. Chiral anomalies and differential geometry

    Energy Technology Data Exchange (ETDEWEB)

    Zumino, B.

    1983-10-01

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

  10. Superconductivity in a chiral nanotube

    Science.gov (United States)

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

    2017-02-01

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

  11. High-accuracy and robust face recognition system based on optical parallel correlator using a temporal image sequence

    Science.gov (United States)

    Watanabe, Eriko; Ishikawa, Mami; Ohta, Maiko; Kodate, Kashiko

    2005-09-01

    Face recognition is used in a wide range of security systems, such as monitoring credit card use, searching for individuals with street cameras via Internet and maintaining immigration control. There are still many technical subjects under study. For instance, the number of images that can be stored is limited under the current system, and the rate of recognition must be improved to account for photo shots taken at different angles under various conditions. We implemented a fully automatic Fast Face Recognition Optical Correlator (FARCO) system by using a 1000 frame/s optical parallel correlator designed and assembled by us. Operational speed for the 1: N (i.e. matching a pair of images among N, where N refers to the number of images in the database) identification experiment (4000 face images) amounts to less than 1.5 seconds, including the pre/post processing. From trial 1: N identification experiments using FARCO, we acquired low error rates of 2.6% False Reject Rate and 1.3% False Accept Rate. By making the most of the high-speed data-processing capability of this system, much more robustness can be achieved for various recognition conditions when large-category data are registered for a single person. We propose a face recognition algorithm for the FARCO while employing a temporal image sequence of moving images. Applying this algorithm to a natural posture, a two times higher recognition rate scored compared with our conventional system. The system has high potential for future use in a variety of purposes such as search for criminal suspects by use of street and airport video cameras, registration of babies at hospitals or handling of an immeasurable number of images in a database.

  12. Quarkyonic Chiral Spirals

    CERN Document Server

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

    2009-01-01

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

  13. [Preparations and biological properties of chiral compounds].

    Science.gov (United States)

    Sinko, Goran

    2005-12-01

    Enantiomers of chiral compounds may express various biological activities and also different toxicities. Examples of different pharmacological effects of some chiral drugs such as fluoxetine, penicillamine, ibuprofen and albuterol are provided in this paper. Due to possible differences in activity, the chiral drugs are required to be pure enantiomeric compounds in order to be more effective and safer to use. In the laboratory, enantiomers are mainly synthesized as racemates (an equimolar mixture of enantiomers) while in biological pathways only one enantiomeric form is produced, such as amino acids, sugars and lipids. This paper presents the principles of chirality, general information about enantiomers and their biological aspects. It gives an outline of stereoselective methods for chromatographic resolution of enantiomers with stereoselective protein stationary phases, i.e. capillary electrochromatography (CEC) and high performance liquid chromatography (HPLC). The use of enzyme biotransformations (hydrolysis, oxidation and reduction) in chiral syntheses of carboxyl-, phosphoryl- or beta-hydroxy esters, alcohols, epoxides and cis-carboxyl sulphoxide is described. This article also includes an example of lipase stereoselectivity improvement by amino acid mutations within the enzyme active site.

  14. Chiral Synthons in Pesticide Syntheses

    NARCIS (Netherlands)

    Feringa, Bernard

    1988-01-01

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

  15. Chiral fermions on the lattice

    CERN Document Server

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

    2002-01-01

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

  16. Aptamer modified organic-inorganic hybrid silica monolithic capillary columns for highly selective recognition of thrombin.

    Science.gov (United States)

    Deng, Nan; Liang, Zhen; Liang, Yu; Sui, Zhigang; Zhang, Liyuan; Wu, Qi; Yang, Kaiguang; Zhang, Lihua; Zhang, Yukui

    2012-12-04

    A novel kind of aptamer modified organic-inorganic hybrid silica monolithic capillary column has been developed, via the covalent bonding of 5'-NH(2)-modified aptamer for human α-thrombin on hybrid silica monolith, prepared by sol-gel method, with tetraethoxysilane and 3-aminopropyltriethoxysilane as precursors. Due to the large specific surface area of the hybrid matrix, the average coverage density of aptamer reached 568 pmol/μL, and the thrombin binding capacity was 1.15 μg/μL, 14 times higher than that of aptamer modified open tubular capillaries. By such an affinity capillary column, the limit of detection of thrombin was decreased to 3.4 nM with a UV detector. Furthermore, even when thrombin was mixed with 1000 times more concentrated human serum, it could be selectively enriched and detected with the signal-to-noise ratio as ca.10. These results indicate that the developed preparation strategy for aptamer based hybrid silica monolithic capillary column might provide an effective method to achieve highly selective recognition of trace targets.

  17. Photogrammetry for Early Recognition of High Mountain Hazards: New Techniques and Applications

    Science.gov (United States)

    Kaab, A.

    2000-09-01

    Steady mass shift as well as catastrophic massmovement events are the natural expression of the dynamics of high-mountain mass-transport systems, causing a variety of natural hazards. Computer-aided aerial photogrammetry, especially a newly developed technique for determining surface velocity fields in 3D, offers a wide range of possibilities to map disasters and hazard potentials, to monitor medium- and long-term development of dangerous situations and to provide area-wide boundary conditions for 2D- and 3D-modelling of kinetic and dynamic processes. Three pilot studies in the Swiss Alps illustrate the potential of highprecision and multi-temporal image analysis for early recognition of glacial and periglacial hazards: (1) The increasing risk of lake-outbursts and related debris-flows (up to several 105m3) was detected by a 25-year monitoring series of glacier geometry, ice flow, permafrost creep and changes of glacier-lakes. (2) Analyzing permafrost creep above a potential starting zone of debris flows allowed for assessing mass transport and accumulation rates in this zone. (3) The kinetic processes and the extent of a rock slide (∼ 106-107m3), induced by a marked retreat of a glacier tongue and the related stress-relief at the valley flanks could be determined.

  18. THE INFLUENCE OF SPECKLE ON HIGH RESOLUTION RANGE PROFILE RECOGNITION BASED ON THE MATCHING SCORE

    Institute of Scientific and Technical Information of China (English)

    Zhang Rui; Wei Xizhang; Li Xiang

    2012-01-01

    Template database is the key to radar automation target recognition based on High Resolution Range Profile (HRRP).From the traditional perspective,average HRRP is a valid template for it can represent each HRRP without scatterer Moving Through Range Cell (MTRC).However,template database based on this assumption is always challenged by measured data.One reason is that speckle happens in the frame without scatterer MTRC.Speckle makes HRRP fluctuate sharply and not match well with the average HRRP.We precisely introduce the formation mechanism of speckle.Then,we make an insight into the principle of matching score.Based on the conclusion,we study the properties of matching score between speckled HRRP and the average HRRP.The theoretical analysis and Monte Carlo experimental results demonstrate that speckle makes HRRP not to match well with the average HRRP according to the energy ratio of speckled scatterers.On the assumption of ideal scattering centre model,speckled HRRP has a matching score less than 85% with the average HRRP if speckled scatterers occupy more than 50% energy of the target.

  19. High-performance liquid chromatographic enantioseparation of cyclic β-aminohydroxamic acids on zwitterionic chiral stationary phases based on Cinchona alkaloids

    Energy Technology Data Exchange (ETDEWEB)

    Lajkó, Gyula [Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7 (Hungary); Institute of Pharmaceutical Chemistry, University of Szeged, H-6720 Szeged, Eötvös u. 6 (Hungary); Orosz, Tímea [Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7 (Hungary); Grecsó, Nóra [Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7 (Hungary); Institute of Pharmaceutical Chemistry, University of Szeged, H-6720 Szeged, Eötvös u. 6 (Hungary); Fekete, Beáta; Palkó, Márta; Fülöp, Ferenc [Institute of Pharmaceutical Chemistry, University of Szeged, H-6720 Szeged, Eötvös u. 6 (Hungary); Lindner, Wolfgang [Department of Analytical Chemistry, University of Vienna, Währingerstrasse 38, A-1090 Vienna (Austria); Péter, Antal [Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7 (Hungary); Ilisz, István, E-mail: ilisz@chem.u-szeged.hu [Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7 (Hungary)

    2016-05-19

    Cyclic β-aminohydroxamic acid enantiomer pairs were stereoselectively separated by high-performance liquid chromatography on the recently developed Cinchona alkaloid-based zwitterionic chiral stationary phases Chiralpak ZWIX(+)™, ZWIX(−)™, ZWIX(+A) and ZWIX(−A). The results of variation of the applied chromatographic conditions, such as the bulk solvent composition, the concentrations and ratio of the acid and base additives, the presence of water as mobile phase additive and the counter-ion concentration furnished a better understanding of the retention mechanism. A thermodynamic study in the temperature range 5–50 °C revealed enthalpy-controlled enantiodiscrimination in all cases. The structure–selectivity relationships clearly indicated the importance of the strereochemistry of the functional groups. From an enantiorecognition aspect, the diexo position of the functional groups always proved more favorable than the diendo position. The elution sequence was determined in all cases and was found to reversed when ZWIX(+)™ was changed to ZWIX(−)™ or ZWIX(+A) to ZWIX(−A). - Highlights: • Zwitterionic columns were applied for the enantioseparation of cyclic β-aminohydroxamic acids. • Enthalpy controlled enantiodiscriminations were observed. • Enantiorecognition depended on the stereochemistry of the functional group.

  20. Enantioseparation of pyroglutamide derivatives on polysaccharide based chiral stationary phases by high-performance liquid chromatography and supercritical fluid chromatography: a comparative study.

    Science.gov (United States)

    Baudelet, Davy; Schifano-Faux, Nadège; Ghinet, Alina; Dezitter, Xavier; Barbotin, Florent; Gautret, Philippe; Rigo, Benoit; Chavatte, Philippe; Millet, Régis; Furman, Christophe; Vaccher, Claude; Lipka, Emmanuelle

    2014-10-10

    Analytical enantioseparation of three pyroglutamide derivatives with pharmacological activity against the purinergic receptor P2X7, was run in both high-performance liquid chromatography and supercritical fluid chromatography. Four polysaccharide based chiral stationary phases, namely amylose and cellulose tris (3,5-dimethylphenylcarbamate), amylose tris ((S)-α-methylbenzylcarbamate) and cellulose tris (4-methylbenzoate) with various mobile phases consisted of either heptane/alcohol (ethanol and 2-propanol) or carbon dioxide/alcohol (methanol or ethanol) mixtures, were investigated. After analytical screenings, the best conditions were transposed, for compound 1, to semi-preparative scale. Each approach was fully validated to meet the International Conference on Harmonisation requirements and compared. Whereas the limits of detection and quantification were near six-fold better in HPLC than in SFC (respectively 0.20 and 0.66 μM versus 1.11 and 3.53 μM for one of the enantiomers), in terms of low solvent consumption (7.2 mL of EtOH versus 3.2 mL of EtOH plus 28.8 mL of toxic and inflammable heptane per injection in SFC and HPLC, respectively), time effective cost (9 min versus 40 min per injection in SFC and HPLC, respectively) and yields (98% versus 71% in SFC and HPLC, respectively), the latter method proved its ecological superiority.

  1. Enantiospecific adsorption of cysteine on a chiral Au34 cluster

    Science.gov (United States)

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

    2015-12-01

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

  2. Chiral Quantum Optics

    CERN Document Server

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

    2016-01-01

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

  3. Doped Chiral Polymer Metamaterials

    Science.gov (United States)

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

    2017-01-01

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

  4. [Chirality and drugs].

    Science.gov (United States)

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

    2000-07-01

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

  5. Status of chiral meson physics

    Energy Technology Data Exchange (ETDEWEB)

    Bijnens, Johan [Department of Astronomy and Theoretical Physics, Lund University, Sölvegatan 14A, SE 22362 Lund (Sweden)

    2016-01-22

    This talk includes a short introduction to Chiral Perturbation Theory in the meson sector concentrating on a number of recent developments. I discuss the latest fit of the low-energy constants. Finite volume corrections are discussed for the case with twisted boundary conditions for form-factors and first results at two-loops for three flavours for masses. The last part discusses the extension to other symmetry breaking patterns relevant for technicolour and related theories as well as the calculation of leading logarithms to high loop orders.

  6. Chiral scars in chaotic Dirac fermion systems.

    Science.gov (United States)

    Xu, Hongya; Huang, Liang; Lai, Ying-Cheng; Grebogi, Celso

    2013-02-08

    Do relativistic quantum scars in classically chaotic systems possess unique features that are not shared by nonrelativistic quantum scars? We report a class of relativistic quantum scars in massless Dirac fermion systems whose phases return to the original values or acquire a 2π change only after circulating twice about some classical unstable periodic orbits. We name such scars chiral scars, the successful identification of which has been facilitated tremendously by our development of an analytic, conformal-mapping-based method to calculate an unprecedentedly large number of eigenstates with high accuracy. Our semiclassical theory indicates that the physical origin of chiral scars can be attributed to a combined effect of chirality intrinsic to massless Dirac fermions and the geometry of the underlying classical orbit.

  7. Chiral quark model

    Indian Academy of Sciences (India)

    H Weigel

    2003-11-01

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

  8. Using the automata processor for fast pattern recognition in high energy physics experiments-A proof of concept

    Science.gov (United States)

    Wang, Michael H. L. S.; Cancelo, Gustavo; Green, Christopher; Guo, Deyuan; Wang, Ke; Zmuda, Ted

    2016-10-01

    We explore the Micron Automata Processor (AP) as a suitable commodity technology that can address the growing computational needs of pattern recognition in High Energy Physics (HEP) experiments. A toy detector model is developed for which an electron track confirmation trigger based on the Micron AP serves as a test case. Although primarily meant for high speed text-based searches, we demonstrate a proof of concept for the use of the Micron AP in a HEP trigger application.

  9. Using the automata processor for fast pattern recognition in high energy physics experiments—A proof of concept

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Michael H.L.S., E-mail: mwang@fnal.gov [Fermi National Accelerator Laboratory, Batavia, IL 60510 (United States); Cancelo, Gustavo; Green, Christopher [Fermi National Accelerator Laboratory, Batavia, IL 60510 (United States); Guo, Deyuan; Wang, Ke [University of Virginia, Charlottesville, VA 22904 (United States); Zmuda, Ted [Fermi National Accelerator Laboratory, Batavia, IL 60510 (United States)

    2016-10-01

    We explore the Micron Automata Processor (AP) as a suitable commodity technology that can address the growing computational needs of pattern recognition in High Energy Physics (HEP) experiments. A toy detector model is developed for which an electron track confirmation trigger based on the Micron AP serves as a test case. Although primarily meant for high speed text-based searches, we demonstrate a proof of concept for the use of the Micron AP in a HEP trigger application.

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

    Science.gov (United States)

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

    2017-03-01

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

  11. 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.

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

    Science.gov (United States)

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

    2016-11-01

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

  13. Simultaneous analysis of D-alanine, D-aspartic acid, and D-serine using chiral high-performance liquid chromatography-tandem mass spectrometry and its application to the rat plasma and tissues.

    Science.gov (United States)

    Karakawa, Sachise; Shimbo, Kazutaka; Yamada, Naoyuki; Mizukoshi, Toshimi; Miyano, Hiroshi; Mita, Masashi; Lindner, Wolfgang; Hamase, Kenji

    2015-11-10

    A highly sensitive and selective chiral LC-MS/MS method for D-alanine, D-aspartic acid and D-serine has been developed using the precolumn derivatization reagents, 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AccQ-Tag) or p-N,N,N-trimethylammonioanilyl N'-hydroxysuccinimidyl carbamate iodide (TAHS). The thus N-tagged enantiomers of the derivatized amino acids were nicely separated within 20min using the cinchona alkaloid-based zwittterionic ion-exchange type enantioselective column, Chiralpak ZWIX(+). The selected reaction monitoring was applied for detecting the target d-amino acids in biological matrices. By using the present chiral LC-MS/MS method, the three d-amino acids and their l-forms could be simultaneously determined in the range of 0.1-500nmol/mL. Finally, the technique was successfully applied to rat plasma and tissue samples.

  14. Asymmetric allylation of α-ketoester-derived N-benzoylhydrazones promoted by chiral sulfoxides/N-oxides Lewis bases: highly enantioselective synthesis of quaternary α-substituted α-allyl-α-amino acids.

    Science.gov (United States)

    Reyes-Rangel, Gloria; Bandala, Yamir; García-Flores, Fred; Juaristi, Eusebio

    2013-09-01

    Chiral sulfoxides/N-oxides (R)-1 and (R,R)-2 are effective chiral promoters in the enantioselective allylation of α-keto ester N-benzoylhydrazone derivatives 3a-g to generate the corresponding N-benzoylhydrazine derivatives 4a-g, with enantiomeric excesses as high as 98%. Representative hydrazine derivatives 4a-b were subsequently treated with SmI2, and the resulting amino esters 5a-b with LiOH to obtain quaternary α-substituted α-allyl α-amino acids 6a-b, whose absolute configuration was assigned as (S), with fundament on chemical correlation and electronic circular dichroism (ECD) data. © 2013 Wiley Periodicals, Inc.

  15. Investigation on enantiomeric separations of fluorenylmethoxycarbonyl amino acids and peptides by high-performance liquid chromatography using native cyclodextrins as chiral stationary phases.

    Science.gov (United States)

    Tang, Y; Zukowski, J; Armstrong, D W

    1996-09-06

    A systematic study was carried out to investigate enantiomeric separations of fluorenylmethoxycarbonyl (FMOC) amino acids and their peptides. Twenty amino acids were derivatized by 9-fluorenylmethyl chloroformate (FMOC-Cl) and its analogues, FMOC-glycyl-Cl and FMOC-beta-alanyl-Cl. All derivatives were chromatographed on native beta- and gamma-cyclodextrin columns using acetonitrile as the main mobile phase component. The results indicated that glycyl and beta-alanyl groups between FMOC and amino acid moieties enhanced chiral selectivities of amino acid derivatives. The addition of modifiers, triethylamine, acetic acid and methanol, into the mobile phase caused alterations in retention, enantiorecognition and elution order. The structures of amino acids and the type of chiral stationary phase employed exhibited significant impacts on chiral resolutions. It is also found that the number and position of glycyl moieties affect the retentions and enantioselectivities of FMOC derivatized glycyl containing peptides.

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

    Science.gov (United States)

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

    2012-01-04

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

  17. Recognition memory for low- and high-frequency-filtered emotional faces: Low spatial frequencies drive emotional memory enhancement, whereas high spatial frequencies drive the emotion-induced recognition bias.

    Science.gov (United States)

    Rohr, Michaela; Tröger, Johannes; Michely, Nils; Uhde, Alarith; Wentura, Dirk

    2017-02-17

    This article deals with two well-documented phenomena regarding emotional stimuli: emotional memory enhancement-that is, better long-term memory for emotional than for neutral stimuli-and the emotion-induced recognition bias-that is, a more liberal response criterion for emotional than for neutral stimuli. Studies on visual emotion perception and attention suggest that emotion-related processes can be modulated by means of spatial-frequency filtering of the presented emotional stimuli. Specifically, low spatial frequencies are assumed to play a primary role for the influence of emotion on attention and judgment. Given this theoretical background, we investigated whether spatial-frequency filtering also impacts (1) the memory advantage for emotional faces and (2) the emotion-induced recognition bias, in a series of old/new recognition experiments. Participants completed incidental-learning tasks with high- (HSF) and low- (LSF) spatial-frequency-filtered emotional and neutral faces. The results of the surprise recognition tests showed a clear memory advantage for emotional stimuli. Most importantly, the emotional memory enhancement was significantly larger for face images containing only low-frequency information (LSF faces) than for HSF faces across all experiments, suggesting that LSF information plays a critical role in this effect, whereas the emotion-induced recognition bias was found only for HSF stimuli. We discuss our findings in terms of both the traditional account of different processing pathways for HSF and LSF information and a stimulus features account. The double dissociation in the results favors the latter account-that is, an explanation in terms of differences in the characteristics of HSF and LSF stimuli.

  18. [Synthesis and applications of chiral metal-organic framework in the selective separation of enantiomers].

    Science.gov (United States)

    Qi, Xiaoyue; Li, Xianjiang; Bai, Yu; Liu, Huwei

    2016-01-01

    Chirality is a universal phenomenon in nature. Chiral separation is vitally important in drug development, agricultural chemistry, pharmacology, environmental science, biology and many other fields. Chiral metal-organic frameworks (MOFs) are a new group of porous materials with special topology and designable pore structures, as well as their high specific surface area, porosity, excellent thermal stability, solvent resistance, etc. Thus, chiral MOFs are promising with various applications in the field of analytical chemistry. This review summarizes the synthesis strategies of chiral MOFs and their applications in the selective separation of enantiomers, as well as related mechanism.

  19. Non-Cooperative Target Recognition by Means of Singular Value Decomposition Applied to Radar High Resolution Range Profiles

    Directory of Open Access Journals (Sweden)

    Patricia López-Rodríguez

    2014-12-01

    Full Text Available Radar high resolution range profiles are widely used among the target recognition community for the detection and identification of flying targets. In this paper, singular value decomposition is applied to extract the relevant information and to model each aircraft as a subspace. The identification algorithm is based on angle between subspaces and takes place in a transformed domain. In order to have a wide database of radar signatures and evaluate the performance, simulated range profiles are used as the recognition database while the test samples comprise data of actual range profiles collected in a measurement campaign. Thanks to the modeling of aircraft as subspaces only the valuable information of each target is used in the recognition process. Thus, one of the main advantages of using singular value decomposition, is that it helps to overcome the notable dissimilarities found in the shape and signal-to-noise ratio between actual and simulated profiles due to their difference in nature. Despite these differences, the recognition rates obtained with the algorithm are quite promising.

  20. Fragile X mental retardation protein recognition of G quadruplex structure per se is sufficient for high affinity binding to RNA.

    Science.gov (United States)

    Bole, Medhavi; Menon, Lakshmi; Mihailescu, Mihaela-Rita

    2008-12-01

    Fragile X syndrome, the most common form of inherited mental retardation is caused by the expansion of a CGG trinucleotide repeat in the fragile X mental retardation 1 (fmr1) gene. The abnormal expansion of the CGG repeat causes hypermethylation and subsequent silencing of the fmr1 gene, resulting in the loss of the fragile X mental retardation protein (FMRP). FMRP has been shown to use its arginine-glycine-glycine rich region (RGG box) to bind to messenger RNAs that form G quadruplex structures. Several studies reported that the G quadruplex RNA recognition alone is not sufficient for FMRP RGG box binding and that an additional stem and/or a G quadruplex-stem junction region may also be important in recognition. In this study we have used biophysical methods such as fluorescence, UV, CD and NMR spectroscopy to demonstrate that the recognition of the RNA G quadruplex structure per se, in the absence of a stem region, is sufficient for the FMRP high affinity and specific binding. These findings indicate that the presence of a stem structure in some of the FMRP G quadruplex forming mRNAs is not a requirement for protein recognition as previously believed, but rather for the proper formation of the correct RNA G quadruplex structure recognized by FMRP.

  1. Interweaving Chiral Spirals

    CERN Document Server

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

    2011-01-01

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

  2. Simplicial chiral models

    CERN Document Server

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

    1995-01-01

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

  3. Electroweak Chiral Lagrangian for Neutral Higgs Boson

    Institute of Scientific and Technical Information of China (English)

    WANG Shun-Zhi; WANG Qing

    2008-01-01

    A neutral Higgs boson is added into the traditional electroweak chiral Lagrangian by writing down all possible high dimension operators. The matter part of the Lagrangian is investigated in detail. We find that if Higgs field dependence of Yukawa couplings can be factorized out, there will be no flavour changing neutral couplings; neutral Higgs can induce coupling between light and heavy neutrinos.

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

    CERN Document Server

    Kharzeev, Dmitri; Meyer, Rene

    2016-01-01

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

  5. Revealing atropisomer axial chirality in drug discovery.

    Science.gov (United States)

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

    2011-03-07

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

  6. Highly diastereoselective synthesis of quaternary α-trifluoromethyl α-amino acids from chiral imines of trifluoropyruvate.

    Science.gov (United States)

    Min, Qiao-Qiao; He, Chun-Yang; Zhou, Haibing; Zhang, Xingang

    2010-11-14

    An efficient method for highly diastereoselective synthesis of quaternary α-trifluoromethyl α-amino acids was developed via indium mediated allylation of (R)-phenylglycinol methyl ether based imines of trifluoropyruvate in good yields with high diastereoselectivities at room temperature; to illustrate the application of this method in organic synthesis, 2-allyl-2-(trifluoromethyl) aziridine was prepared in an efficient manner.

  7. Microbial/enzymatic synthesis of chiral pharmaceutical intermediates.

    Science.gov (United States)

    Patel, Ramesh N

    2003-11-01

    Chirality is a key factor in the efficacy of many drugs; thus, the production of single enantiomers of drug intermediates has become increasingly important in the pharmaceutical industry. Chiral intermediates and fine chemicals are in high demand from the pharmaceutical and agrochemical industries for the preparation of bulk drug substances and agricultural products. There has been an increasing awareness of the enormous potential of microorganisms and enzymes for the transformation of synthetic chemicals with high chemo-, regio- and enantioselectivity. In this article, biocatalytic processes for the synthesis of chiral pharmaceutical intermediates are described.

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

    CERN Document Server

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

    2016-01-01

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

  9. Chiral transition with magnetic fields

    CERN Document Server

    Ayala, Alejandro; Mizher, Ana Julia; Rojas, Juan Cristobal; Villavicencio, Cristian

    2014-01-01

    We study the nature of the chiral transition for an effective theory with spontaneous breaking of symmetry, where charged bosons and fermions are subject to the effects of a constant external magnetic field. The problem is studied in terms of the relative intensity of the magnetic field with respect to the mass and the temperature. When the former is the smallest of the scales, we present a suitable method to obtain magnetic and thermal corrections up to ring order at high temperature. By these means, we solve the problem of the instability in the boson sector for these theories, where the squared masses, taken as functions of the order parameter, can vanish and even become negative. The solution is found by considering the screening properties of the plasma, encoded in the resummation of the ring diagrams at high temperature. We also study the case where the magnetic field is the intermediate of the three scales and explore the nature of the chiral transition as we vary the field strength, the coupling const...

  10. Highly diastereoselective synthesis of enantiopure β-trifluoromethyl β-amino alcohols from chiral trifluoromethyl oxazolidines (Fox).

    Science.gov (United States)

    Simon, Julien; Chelain, Evelyne; Brigaud, Thierry

    2012-01-20

    The organolithium species addition to 2-hydroxymethyl fluorinated oxazolidines (Fox) provides a highly diastereoselective and straightforward route for the synthesis of enantiopure trifluoromethyl β-amino alcohols quaternarized at the β-position.

  11. Detecting the chirality for coupled quantum dots

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-04-21

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

  12. Homochiral metal-organic framework used as a stationary phase for high-performance liquid chromatography.

    Science.gov (United States)

    Kong, Jiao; Zhang, Mei; Duan, Ai-Hong; Zhang, Jun-Hui; Yang, Rui; Yuan, Li-Ming

    2015-02-01

    Metal-organic frameworks are promising porous materials. Chiral metal-organic frameworks have attracted considerable attention in controlling enantioselectivity. In this study, a homochiral metal-organic framework [Co(2) (D-cam)(2) (TMDPy)] (D-cam = D-camphorates, TMDPy = 4,4'-trimethylenedipyridine) with a non-interpenetrating primitive cubic net has been used as a chiral stationary phase in high-performance liquid chromatography. It has allowed the successful separation of six positional isomers and six chiral compounds. The good selectivity and baseline separation, or at least 60% valley separation, confirmed its excellent molecular recognition characteristics. The relative standard deviations for the retention time of run-to-run and column-to-column were less than 1.8 and 3.1%, respectively. These results demonstrate that [Co(2) (D-cam)(2) (TMDPy)] may represent a promising chiral stationary phase for use in high-performance liquid chromatography.

  13. Stepping towards highly flexible aptamers: enzymatic recognition studies of unlocked nucleic acid nucleotides

    DEFF Research Database (Denmark)

    Dubois, Camille; Campbell, Meghan A; Edwards, Stacey L

    2012-01-01

    Enzymatic recognition of unlocked nucleic acid (UNA) nucleotides was successfully accomplished. Therminator DNA polymerase was found to be an efficient enzyme in primer extension reactions. Polymerase chain reaction (PCR) amplification of a 81 mer UNA-modified DNA library was efficiently achieved...

  14. Molecule Recognition Imaging and Highly Ordered Gold Nanoparticle Templating of Functional Bacterial S-Layer Nanoarrays

    Institute of Scientific and Technical Information of China (English)

    Jilin TANG; Andreas Ebner; Helga Badelt-Lichtblau; Christian Rankl; Michael Leitner; Hermann J.Gruber; Uwe B.Sleytr; Nicola Ilk; Peter Hinterdorfer

    2009-01-01

    @@ Molecular recognition between receptors and their cognate ligands plays an important role in life sciences.Such specific interactions include those between complementary strands of DNA,enzyme and substrate,antigen and antibody,lectin and carbohydrate,ligands and cell surface receptors as well as between cell adhesion proteins.

  15. A microprocessor-based single board computer for high energy physics event pattern recognition

    CERN Document Server

    Bernstein, H; Imossi, R; Kopp, J K; Kramer, M A; Love, W A; Ozaki, S; Platner, E D

    1981-01-01

    A single board MC 68000 based computer has been assembled and benchmarked against the CDC 7600 running portions of the pattern recognition code used at the MPS. This computer has a floating coprocessor to achieve throughputs equivalent to several percent that of the 7600. A major part of this work was the construction of a FORTR

  16. Molecular recognition in homogeneous transition metal catalysis: a biomimetic strategy for high selectivity.

    Science.gov (United States)

    Das, Siddartha; Brudvig, Gary W; Crabtree, Robert H

    2008-01-28

    Traditional methods for selectivity control in homogeneous transition metal catalysis either employ steric effects in a binding pocket or chelate control. In a supramolecular strategy, encapsulation of the substrate can provide useful shape and size selectivity. A fully developed molecular recognition strategy involving hydrogen bonding or solvophobic forces has given almost completely regioselective functionalization of remote, unactivated C-H bonds.

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

    Science.gov (United States)

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

    2011-10-01

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

  18. Chiral resolution of basic drugs by capillary electrophoresis with new glycosaminoglycans.

    Science.gov (United States)

    Tsukamoto, T; Ushio, T; Haginaka, J

    1999-12-09

    New glycosaminoglycans, fucose-containing glycosaminoglycan (FGAG) and depolymerized holothurian glycosaminoglycan (DHG), were investigated as chiral additives for the separation of drug enantiomers by capillary electrophoresis. The average molecular masses of FGAG and DHG were estimated to be about 59,000 and 14,000, respectively. A variety of basic drug enantiomers were resolved using 10 mM phosphate buffer, pH 5.0, containing 3% FGAG or DHG. Since chiral recognition properties of FGAG and DHG are different, some drug enantiomers were only separated by using FGAG or DHG. With regard to comparison of chiral recognition abilities of FGAG and DHG with other chiral selectors, tolperisone and eperisone enantiomers were not separated with alpha- or beta-cyclodextrin, or heparin as the chiral additives, but were separated with FGAG and DHG. The results obtained reveal that FGAG and DHG are useful as the chiral selectors for separations of drug enantiomers by CE, and that they could be complementarily used with other chiral additives.

  19. Pattern recognition in pulmonary tuberculosis defined by high content peptide microarray chip analysis representing 61 proteins from M. tuberculosis.

    Directory of Open Access Journals (Sweden)

    Simani Gaseitsiwe

    Full Text Available BACKGROUND: Serum antibody-based target identification has been used to identify tumor-associated antigens (TAAs for development of anti-cancer vaccines. A similar approach can be helpful to identify biologically relevant and clinically meaningful targets in M. tuberculosis (MTB infection for diagnosis or TB vaccine development in clinically well defined populations. METHOD: We constructed a high-content peptide microarray with 61 M. tuberculosis proteins as linear 15 aa peptide stretches with 12 aa overlaps resulting in 7446 individual peptide epitopes. Antibody profiling was carried with serum from 34 individuals with active pulmonary TB and 35 healthy individuals in order to obtain an unbiased view of the MTB epitope pattern recognition pattern. Quality data extraction was performed, data sets were analyzed for significant differences and patterns predictive of TB+/-. FINDINGS: Three distinct patterns of IgG reactivity were identified: 89/7446 peptides were differentially recognized (in 34/34 TB+ patients and in 35/35 healthy individuals and are highly predictive of the division into TB+ and TB-, other targets were exclusively recognized in all patients with TB (e.g. sigmaF but not in any of the healthy individuals, and a third peptide set was recognized exclusively in healthy individuals (35/35 but no in TB+ patients. The segregation between TB+ and TB- does not cluster into specific recognition of distinct MTB proteins, but into specific peptide epitope 'hotspots' at different locations within the same protein. Antigen recognition pattern profiles in serum from TB+ patients from Armenia vs. patients recruited in Sweden showed that IgG-defined MTB epitopes are very similar in individuals with different genetic background. CONCLUSIONS: A uniform target MTB IgG-epitope recognition pattern exists in pulmonary tuberculosis. Unbiased, high-content peptide microarray chip-based testing of clinically well-defined populations allows to visualize

  20. Determination of enantiomeric composition by negative-ion electrospray ionization-mass spectrometry using deprotonated N-(3,5-dinitrobenzoyl)amino acids as chiral selectors.

    Science.gov (United States)

    Brewer, Bobby N; Zu, Chengli; Koscho, Michael E

    2005-10-01

    The ability to use mixtures of deprotonated N-(3,5-dinitrobenzoyl)amino acids as chiral selectors for the determination of enantiomeric composition by electrospray ionization-mass spectrometry is demonstrated. For each experiment, two N-(3,5-dinitrobenzoyl)amino acids were chosen such that each would have opposite selectivity for the enantiomers of the analyte. Electrospray ionization-mass spectrometry, monitored in the negative ion mode, of solutions containing the two N-(3,5-dinitrobenzoyl)amino acids, sodium hydroxide, and the analyte, in a one-to-one mixture of methanol and water, afford peaks in the mass spectrum that correspond to the deprotonated 1:1 analyte-selector complexes. The ratio of the intensities of the complexes in the mass spectrum can be related to the enantiomeric composition of the analyte. Additionally, the sense and extent of chiral recognition is consistent with chromatographic observations, using chiral stationary phases derived from N-(3,5-dinitrobenzoyl)amino acids. Each analysis of enantiomeric composition requires less than 10 s to complete, indicating that this method has great potential for the development of fast-/high-throughput chiral analyses.

  1. Highly enantioselective transfer hydrogenation of ketones with chiral (NH)2 P2 macrocyclic iron(II) complexes.

    Science.gov (United States)

    Bigler, Raphael; Huber, Raffael; Mezzetti, Antonio

    2015-04-20

    Bis(isonitrile) iron(II) complexes bearing a C2 -symmetric diamino (NH)2 P2 macrocyclic ligand efficiently catalyze the hydrogenation of polar bonds of a broad scope of substrates (ketones, enones, and imines) in high yield (up to 99.5 %), excellent enantioselectivity (up to 99 % ee), and with low catalyst loading (generally 0.1 mol %). The catalyst can be easily tuned by modifying the substituents of the isonitrile ligand.

  2. Chlorophylls, Symmetry, Chirality, and Photosynthesis

    Directory of Open Access Journals (Sweden)

    Mathias O. Senge

    2014-09-01

    Full Text Available Chlorophylls are a fundamental class of tetrapyrroles and function as the central reaction center, accessory and photoprotective pigments in photosynthesis. Their unique individual photochemical properties are a consequence of the tetrapyrrole macrocycle, the structural chemistry and coordination behavior of the phytochlorin system, and specific substituent pattern. They achieve their full potential in solar energy conversion by working in concert in highly complex, supramolecular structures such as the reaction centers and light-harvesting complexes of photobiology. The biochemical function of these structures depends on the controlled interplay of structural and functional principles of the apoprotein and pigment cofactors. Chlorophylls and bacteriochlorophylls are optically active molecules with several chiral centers, which are necessary for their natural biological function and the assembly of their supramolecular complexes. However, in many cases the exact role of chromophore stereochemistry in the biological context is unknown. This review gives an overview of chlorophyll research in terms of basic function, biosynthesis and their functional and structural role in photosynthesis. It highlights aspects of chirality and symmetry of chlorophylls to elicit further interest in their role in nature.

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

    Science.gov (United States)

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

    2011-01-01

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

  4. Electro-optical characteristics of a chiral hybrid in-plane switching liquid crystal mode for high brightness.

    Science.gov (United States)

    Gwag, Jin Seog; Sohn, Kyunghwa; Kim, Young-Ki; Kim, Jae-Hoon

    2008-08-04

    We propose a new in-plane switching (IPS) nematic liquid crystal (LC) mode which uses a twist effect with a hybrid LC alignment and interdigitated electrodes as an approach for a high brightness. This is optimized to a normally white mode to minimize loss of transmittance at the electrode compared to the conventional IPS mode. The proposed mode shows an excellent dark state because the bulk LCs are aligned in parallel to the optic axis of the polarizer under low electric fields. Consequently, this proposed mode exhibits a much higher contrast ratio (980:1) than that of the conventional IPS mode (550:1).

  5. Soldering Chiralities; 2, Non-Abelian Case

    CERN Document Server

    Wotzasek, C

    1996-01-01

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

  6. Chiral gold nanowires with boerdijk-coxeter-bernal structure

    KAUST Repository

    Zhu, Yihan

    2014-09-10

    A Boerdijk-Coxeter-Bernal (BCB) helix is made of linearly stacked regular tetrahedra (tetrahelix). As such, it is chiral without nontrivial translational or rotational symmetries. We demonstrate here an example of the chiral BCB structure made of totally symmetrical gold atoms, created in nanowires by direct chemical synthesis. Detailed study by high-resolution electron microscopy illustrates their elegant chiral structure and the unique one-dimensional "pseudo-periodicity". The BCB-type atomic packing mode is proposed to be a result of the competition and compromise between the lattice and surface energy.

  7. Two-dimensional chiral topological superconductivity in Shiba lattices

    Science.gov (United States)

    Li, Jian; Neupert, Titus; Wang, Zhijun; MacDonald, A. H.; Yazdani, A.; Bernevig, B. Andrei

    2016-07-01

    The chiral p-wave superconductor is the archetypal example of a state of matter that supports non-Abelian anyons, a highly desired type of exotic quasiparticle. With this, it is foundational for the distant goal of building a topological quantum computer. While some candidate materials for bulk chiral superconductors exist, they are subject of an ongoing debate about their actual paring state. Here we propose an alternative route to chiral superconductivity, consisting of the surface of an ordinary superconductor decorated with a two-dimensional lattice of magnetic impurities. We furthermore identify a promising experimental platform to realize this proposal.

  8. The no-drag frame for anomalous chiral fluid

    CERN Document Server

    Stephanov, Mikhail A

    2015-01-01

    We show that for an anomalous fluid carrying dissipationless chiral magnetic and/or vortical currents there is a frame in which a stationary obstacle experiences no drag, but energy and charge currents do not vanish, resembling superfluidity. However, unlike ordinary superfluid flow, the anomalous chiral currents do transport entropy in this frame. We show that the second law of thermodynamics completely determines the amounts of these anomalous non-dissipative currents in the "no-drag frame" as polynomials in temperature and chemical potential with known anomaly coefficients. These general results are illustrated and confirmed by a calculation in the chiral kinetic theory and quark-gluon plasma at high temperature.

  9. Collective Modes of Chiral Kinetic Theory in Magnetic Field

    CERN Document Server

    Stephanov, Mikhail; Yin, Yi

    2015-01-01

    We study collective excitations in systems described by chiral kinetic theory in external magnetic field. We consider high-temperature weak-coupling plasma, as well as high-density Landau Fermi liquid with interaction not restricted to be weak. We show that chiral magnetic wave (CMW) emerges in hydrodynamic regime (at frequencies smaller than collision relaxation rate) and the CMW velocity is determined by thermodynamic properties only. We find that in a plasma of opposite chiralities, at frequencies smaller than the chirality-flipping rate, the CMW excitation turns into a vector-like diffusion mode. In the interacting Fermi liquid, the CMW turns into the Landau zero sound mode in the high-frequency collisionless regime.

  10. A Combined Synchrotron-Based High Resolution FTIR and Diode Laser Jet Infrared Spectroscopy Study of the Chiral Molecule CDBrClF

    Science.gov (United States)

    Albert, S.; Albert, K. Keppler; Quack, M.; Lerch, Ph.; Boudon, V.

    2013-06-01

    The experimental detection of molecular parity violation Δ_{PV}E is of great interest because of its importance in the understanding of fundamental aspects of molecular dynamics and symmetries. One possible method for this is measuring rovibrational or rotational frequency shifts in the infrared or microwave spectra of enantiomers. For that reason we have measured and analysed the rotationally resolved infrared spectrum of CDBrClF as a prototype spectrum for a chiral molecule using three different techniques. The spectrum has been recorded at room temperature with the Zurich Bruker IFS spectrometer ZP 2001 and with the Bruker interferometer 2009 connected to the Swiss synchrotron using a resolution of 0.0007 cm^{-1}. In addition, the IR spectrum of CDBrClF has been measured at low temperature with our diode laser jet setup in the ν_5 region. The spectra of the two major isotopomers CD^{81}Br^{35}ClF and CD^{79}Br^{35}ClF have been analysed within the ν_5 (CCl-stretch), ν_4 (CF-stretch) and ν_3 (CDF-bend) regions. A detailed rovibrational analysis of these bands is presented. The role for possible experiments in the experimental detection of molecular parity violation shall be discussed. M. Quack, Fundamental symmetries and symmetry violations in Handbook of High Resolution Spectroscopy, Vol. 1(Eds. M. Quack and F. Merkt), Wiley, Chichester, New York 2011, 659-722, M. Quack, J. Stohner and M. Willeke, Annu. Rev. Phys. Chem. 2008, 59, 741, A. Bakasov, T.K. Ha, and M. Quack, J. Chem. Phys. 1998, 109, 7263, R. Berger and M. Quack, J. Chem. Phys, 2000, 112, 3148. M. Quack and J. Stohner, Phys. Rev. Lett. 2000, 84, 3807, M. Quack and J. Stohner. J. Chem. Phys., 2003, 119, 11228. S. Albert, K. Keppler Albert and M. Quack, High Resolution Fourier Transform Infrared Spectroscopy in Handbook of High Resolution Spectroscopy, Vol. 2 (Eds. M. Quack and F. Merkt), Wiley, Chichester, New York 2011, 965-1019, S. Albert and M. Quack, ChemPhysChem, 2007, 8, 1271-1281. S. Albert

  11. Spiral Galaxies as Chiral Objects?

    CERN Document Server

    Capozziello, S; Capozziello, Salvatore; Lattanzi, Alessandra

    2005-01-01

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

  12. Development, reliability, and validity of PRESTO: a new high-variability sentence recognition test.

    Science.gov (United States)

    Gilbert, Jaimie L; Tamati, Terrin N; Pisoni, David B

    2013-01-01

    There is a pressing need for new clinically feasible speech recognition tests that are theoretically motivated, sensitive to individual differences, and access the core perceptual and neurocognitive processes used in speech perception. PRESTO (Perceptually Robust English Sentence Test Open-set) is a new high-variability sentence test designed to reflect current theories of exemplar-based learning, attention, and perception, including lexical organization and automatic encoding of indexical attributes. Using sentences selected from the TIMIT (Texas Instruments/Massachusetts Institute of Technology) speech corpus, PRESTO was developed to include talker and dialect variability. The test consists of lists balanced for talker gender, keywords, frequency, and familiarity. To investigate the performance, reliability, and validity of PRESTO. In Phase I, PRESTO sentences were presented in multitalker babble at four signal-to-noise ratios (SNRs) to obtain a distribution of performance. In Phase II, participants returned and were tested on new PRESTO sentences and on HINT (Hearing In Noise Test) sentences presented in multitalker babble. Young, normal-hearing adults (N = 121) were recruited from the Indiana University community for Phase I. Participants who scored within the upper and lower quartiles of performance in Phase I were asked to return for Phase II (N = 40). In both Phase I and Phase II, participants listened to sentences presented diotically through headphones while seated in enclosed carrels at the Speech Research Laboratory at Indiana University. They were instructed to type in the sentence that they heard using keyboards interfaced to a computer. Scoring for keywords was completed offline following data collection. Phase I data were analyzed by determining the distribution of performance on PRESTO at each SNR and at the average performance across all SNRs. PRESTO reliability was analyzed by a correlational analysis of participant performance at test (Phase I

  13. 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

  14. Chiral Biomarkers in Meteorites

    Science.gov (United States)

    Hoover, Richard B.

    2010-01-01

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

  15. Enantioselective Diels-Alder reactions of carboxylic ester dienophiles catalysed by titanium-based chiral Lewis acid

    Directory of Open Access Journals (Sweden)

    Yogesh K. Choughule

    2016-05-01

    Full Text Available A new titanium-based chiral Lewis acid 1 has been developed using (1R,2R-1,2-bis-(2-methoxyphenyl-ethane-1,2-diol as a chiral vicinal diol ligand. This chiral catalyst was found to exhibit uniformly high enantioselectivity towards carboxylic ester dienophiles in Diels-Alder reactions. The chiral vicinal ligand (1R,2R-1,2-bis-(2-methoxyphenyl-ethane-1,2-diol is inexpensive and is easily accessible.

  16. Generalized simplicial chiral models

    CERN Document Server

    Alimohammadi, M

    2000-01-01

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

  17. Chiral nuclear thermodynamics

    CERN Document Server

    Fiorilla, Salvatore; Weise, Wolfram

    2011-01-01

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

  18. Ultra-fast high-efficiency enantioseparations by means of a teicoplanin-based chiral stationary phase made on sub-2 μm totally porous silica particles of narrow size distribution.

    Science.gov (United States)

    Ismail, Omar H; Ciogli, Alessia; Villani, Claudio; De Martino, Michela; Pierini, Marco; Cavazzini, Alberto; Bell, David S; Gasparrini, Francesco

    2016-01-01

    A new ultra-high performance teicoplanin-based stationary phase was prepared starting from sub-2 μm totally porous silica particles of narrow size distribution. Columns of different lengths were packed at high pressure and a deep and systematic evaluation of kinetic performance, in terms of van Deemter analysis, was performed under different elution conditions (HILIC, POM, RP and NP) by using both achiral and chiral probes. For the achiral probes, the efficiency of the columns at the minimum of the van Deemter curves were very high leading to some 278,000, 270,000, 262,000 and 232,000 plates/m in hydrophilic interaction liquid chromatography (HILIC), polar organic mode (POM), normal phase (NP) and reversed phase (RP) respectively. The lowest plate height, Hmin=3.59 μm (h(/)=1.89), was obtained under HILIC conditions at a flow rate of 1.4 mL/min. Efficiency as high as 200,000-250,000 plates/m (at the optimum flow rate) was obtained in the separation of the enantiomers of chiral probes under HILIC/POM conditions. N-protected amino acids, α-aryloxy acids, herbicides, anti-inflammatory agents were baseline separated on short (2-cm) and ultra-short (1-cm) columns, with analysis time in the order of 1 min. The enantiomers of N-BOC-d,l-methionine were successfully baseline separated in only 11s in HILIC mode. Several examples of fast and efficient resolutions in sub/supercritical fluid chromatography were also obtained for a range of chiral carboxylic acids.

  19. Free-standing chiral plasmonics

    Science.gov (United States)

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

    2014-11-01

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

  20. Architecture of Chiral Poly(phenylacetylene)s: From Compressed/Highly Dynamic to Stretched/Quasi-Static Helices.

    Science.gov (United States)

    Rodríguez, Rafael; Quiñoá, Emilio; Riguera, Ricardo; Freire, Félix

    2016-08-03

    The remarkable consequences in elongation, dynamic character, response to external stimuli (e.g., solvent effects, metal cations), and aggregation observed in helical poly(phenylacetylene)s (PPAs) when either the type of linkage with the pendant groups (i.e., anilide, benzamide) or the aromatic substitution pattern (i.e., ortho, meta, para) of the parent phenylacetylene monomer undergo modification are analyzed in depth. Two series of PPAs substituted at the phenyl ring in ortho, meta, and para with either (S)-α-methoxy-α-phenylacetic acid (MPA) or (S)-phenylglycine methyl ester (PGME) linked through anilide or benzamide bonds were prepared (i.e., o-, m-, p-poly-1 and poly-2 series) and characterized both in solution and in the solid state (CD, UV-vis, Raman, NMR, DSC, TGA, X-ray, AFM, SEM). Para-substituted polymers (p-poly-1 and p-poly-2) present the most compressed and dynamic helices, which respond easily to external stimuli. Meta-substituted PPAs (m-poly-1 and m-poly-2) exist as a mixture in equilibrium of two different helices (compressed and stretched), both less dynamic than the para counterparts and with a weak response to external stimuli. Moreover, in the solid state, m-poly-1 and m-poly-2 show separate fields for the compressed and for the stretched helices. For its part, the ortho-substituted PPA (o-poly-1) presents a highly stretched, almost planar and practically rigid helical structure, inert to external stimuli and prone to aggregate. These structural changes (elongation/dynamic behavior) are rationalized on the basis of the increasing difficulties imposed by the meta- and ortho-substitution on the accommodation of the pendants within the helical structure.

  1. The development of chiral nematic mesoporous materials.

    Science.gov (United States)

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

    2014-04-15

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

  2. Effects of related and unrelated context on recall and recognition by adults with high-functioning autism spectrum disorder.

    Science.gov (United States)

    Bowler, Dermot M; Gaigg, Sebastian B; Gardiner, John M

    2008-03-07

    Memory in autism spectrum disorder (ASD) is characterised by greater difficulties with recall rather than recognition and with a diminished use of semantic or associative relatedness in the aid of recall. Two experiments are reported that test the effects of item-context relatedness on recall and recognition in adults with high-functioning ASD (HFA) and matched typical comparison participants. In both experiments, participants studied words presented inside a red rectangle and were told to ignore context words presented outside the rectangle. Context words were either related or unrelated to the study words. The results showed that relatedness of context enhanced recall for the typical group only. However, recognition was enhanced by relatedness in both groups of participants. On a behavioural level, these findings confirm the Task Support Hypothesis [Bowler, D. M., Gardiner, J. M., & Berthollier, N. (2004). Source memory in Asperger's syndrome. Journal of Autism and Developmental Disorders, 34, 533-542], which states that individuals with ASD will show greater difficulty on memory tests that provide little support for retrieval. The findings extend this hypothesis by showing that it operates at the level of relatedness between studied items and incidentally encoded context. By showing difficulties in memory for associated items, the findings are also consistent with conjectures that implicate medial temporal lobe and frontal lobe dysfunction in the memory difficulties of individuals with ASD.

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

    Directory of Open Access Journals (Sweden)

    Anderson Rouge dos Santos

    2007-02-01

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

  4. Highly stable atropisomers by electrophilic amination of a chiral γ-lactam within the synthesis of an elusive conformationally restricted analogue of α-methylhomoserine.

    Science.gov (United States)

    Amabili, Paolo; Amici, Adolfo; Civitavecchia, Annafelicia; Maggiore, Beatrice; Orena, Mario; Rinaldi, Samuele; Tolomelli, Alessandra

    2016-02-01

    Starting from chiral-protected 4-hydroxymethyl pyrrolidin-2-ones, the otherwise elusive 3,4-trans-3,3,4-trisubstituted isosteres of α-methyl homoserine, tethered on a γ-lactam ring, were prepared exploiting stereoselective electrophilic aminations. These reactions led to the isolation and characterization of a novel type of atropisomers, exceedingly stable at room temperature, that were directly converted to the desired products by a novel non-reductive N-N bond cleavage reaction.

  5. Annelated, Chiral [pi]-Conjugated Systems: Tetraphenylenes and Helical [beta]-Oligothiophenes

    Energy Technology Data Exchange (ETDEWEB)

    Rajca, Andrzej; Rajca, Suchada; Pink, Maren; Miyasaka, Makoto (UNL); (Indiana)

    2008-10-03

    Compounds with highly annelated, chiral {pi}-systems, such as tetraphenylenes and [n]helicenes, are known to possess strong chiral properties and high configurational stability, which are prerequisites for many chiral materials. This account describes the unfolding story about our research on the synthesis and X-ray crystallographic characterization of functionalized nonracemic tetraphenylenes and helical {beta}-oligothiophenes, as well as related [n]helicene derivatives.

  6. 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. .

  7. Antikaon induced Ξ production from a chiral model at NLO

    Directory of Open Access Journals (Sweden)

    Feijoo A.

    2014-01-01

    Full Text Available We study the meson-baryon interaction in the strangeness S = −1 sector using a chiral unitary approach, paying particular attention to the K̄N → KΞ reaction, especially important for constraining the next-to-leading order chiral terms, and considering also the effect of high spin hyperonic resonances. We also present results for the production of Ξ hyperons in nuclei

  8. Cardinality as a highly descriptive feature in myoelectric pattern recognition for decoding motor volition.

    Science.gov (United States)

    Ortiz-Catalan, Max

    2015-01-01

    Accurate descriptors of muscular activity play an important role in clinical practice and rehabilitation research. Such descriptors are features of myoelectric signals extracted from sliding time windows. A wide variety of myoelectric features have been used as inputs to pattern recognition algorithms that aim to decode motor volition. The output of these algorithms can then be used to control limb prostheses, exoskeletons, and rehabilitation therapies. In the present study, cardinality is introduced and compared with traditional time-domain (Hudgins' set) and other recently proposed myoelectric features (for example, rough entropy). Cardinality was found to consistently outperform other features, including those that are more sophisticated and computationally expensive, despite variations in sampling frequency, time window length, contraction dynamics, type, and number of movements (single or simultaneous), and classification algorithms. Provided that the signal resolution is kept between 12 and 14 bits, cardinality improves myoelectric pattern recognition for the prediction of motion volition. This technology is instrumental for the rehabilitation of amputees and patients with motor impairments where myoelectric signals are viable. All code and data used in this work is available online within BioPatRec.

  9. Cardinality as a Highly Descriptive Feature in Myoelectric Pattern Recognition for Decoding Motor Volition

    Directory of Open Access Journals (Sweden)

    Max eOrtiz-Catalan

    2015-10-01

    Full Text Available Accurate descriptors of muscular activity play an important role in clinical practice and rehabilitation research. Such descriptors are features of myoelectric signals extracted from sliding time windows. A wide variety of myoelectric features have been used as inputs to pattern recognition algorithms that aim to decode motor volition. The output of these algorithms can then be used to control limb prostheses, exoskeletons, and rehabilitation therapies. In the present study, cardinality is introduced and compared with traditional time-domain (Hudgins’ set and other recently proposed myoelectric features (for example, rough entropy. Cardinality was found to consistently outperform other features, including those that are more sophisticated and computationally expensive, despite variations in sampling frequency, time window length, contraction dynamics, type and number of movements (single or simultaneous, and classification algorithms. Provided that the signal resolution is kept between 12 and 14 bits, cardinality improves myoelectric pattern recognition for the prediction of motion volition. This technology is instrumental for the rehabilitation of amputees and patients with motor impairments where myoelectric signals are viable. All code and data used in this work is available online within BioPatRec.

  10. High and low performers differ in the use of shape information for face recognition.

    Science.gov (United States)

    Kaufmann, Jürgen M; Schulz, Claudia; Schweinberger, Stefan R

    2013-06-01

    Previous findings demonstrated that increasing facial distinctiveness by means of spatial caricaturing improves face learning and results in modulations of event-related-potential (ERP) components associated with the processing of typical shape information (P200) and with face learning and recognition (N250). The current study investigated performance-based differences in the effects of spatial caricaturing: a modified version of the Bielefelder famous faces test (BFFT) was applied to subdivide a non-clinical group of 28 participants into better and worse face recognizers. Overall, a learning benefit was seen for caricatured compared to veridical faces. In addition, for learned faces we found larger caricaturing effects in response times, inverse efficiency scores as well as in P200 and N250 amplitudes in worse face recognizers, indicating that these individuals profited disproportionately from exaggerated idiosyncratic face shape. During learning and for novel faces at test, better and worse recognizers showed similar caricaturing effects. We suggest that spatial caricaturing helps better and worse face recognizers accessing critical idiosyncratic shape information that supports identity processing and learning of unfamiliar faces. For familiarized faces, better face recognizers might depend less on exaggerated shape and make better use of texture information than worse recognizers. These results shed light on the transition from unfamiliar to familiar face processing and may also be relevant for developing training-programmes for people with difficulties in face recognition.

  11. Cross-recognition of a pit viper (Crotalinae) polyspecific antivenom explored through high-density peptide microarray epitope mapping

    DEFF Research Database (Denmark)

    Engmark, Mikael; Lomonte, Bruno; Gutiérrez, José María

    2017-01-01

    -throughput methodology based on custom designed high-density peptide microarrays. By combining data on antibody-peptide interactions with multiple sequence alignments of homologous toxin sequences and protein modelling, we have determined linear elements of antibody binding sites for snake venom metalloproteases (SVMPs...... at the catalytic active site responsible for toxicity, but instead at other sites, of which some are known for allosteric inhibition or for interaction with the tissue target. Antibody recognition was found to be preserved for several minor variations in the protein sequences, although the antibody...

  12. Pattern recognition

    CERN Document Server

    Theodoridis, Sergios

    2003-01-01

    Pattern recognition is a scientific discipline that is becoming increasingly important in the age of automation and information handling and retrieval. Patter Recognition, 2e covers the entire spectrum of pattern recognition applications, from image analysis to speech recognition and communications. This book presents cutting-edge material on neural networks, - a set of linked microprocessors that can form associations and uses pattern recognition to ""learn"" -and enhances student motivation by approaching pattern recognition from the designer's point of view. A direct result of more than 10

  13. Quark structure of chiral solitons

    CERN Document Server

    Diakonov, D

    2004-01-01

    There is a prejudice that the chiral soliton model of baryons is something orthogonal to the good old constituent quark models. In fact, it is the opposite: the spontaneous chiral symmetry breaking in strong interactions explains the appearance of massive constituent quarks of small size thus justifying the constituent quark models, in the first place. Chiral symmetry ensures that constituent quarks interact very strongly with the pseudoscalar fields. The ``chiral soliton'' is another word for the chiral field binding constituent quarks. We show how the old SU(6) quark wave functions follow from the ``soliton'', however, with computable relativistic corrections and additional quark-antiquark pairs. We also find the 5-quark wave function of the exotic baryon Theta+.

  14. Applications Of Chiral Perturbation Theory

    CERN Document Server

    Mohta, V

    2005-01-01

    Effective field theory techniques are used to describe the spectrum and interactions of hadrons. The mathematics of classical field theory and perturbative quantum field theory are reviewed. The physics of effective field theory and, in particular, of chiral perturbation theory and heavy baryon chiral perturbation theory are also reviewed. The geometry underlying heavy baryon chiral perturbation theory is described in detail. Results by Coleman et. al. in the physics literature are stated precisely and proven. A chiral perturbation theory is developed for a multiplet containing the recently- observed exotic baryons. A small coupling expansion is identified that allows the calculation of self-energy corrections to the exotic baryon masses. Opportunities in lattice calculations are discussed. Chiral perturbation theory is used to study the possibility of two multiplets of exotic baryons mixed by quark masses. A new symmetry constraint on reduced partial widths is identified. Predictions in the literature based ...

  15. Dileptons and Chiral Symmetry Restoration

    CERN Document Server

    Hohler, P M

    2015-01-01

    We report on recent work relating the medium effects observed in dilepton spectra in heavy-ion collisions to potential signals of chiral symmetry restoration. The key connection remains the approach to spectral function degeneracy between the vector-isovector channel with its chiral partner, the axialvector-isovector channel. Several approaches are discussed to elaborate this connection, namely QCD and Weinberg sum rules with input for chiral order parameters from lattice QCD, and chiral hadronic theory to directly evaluate the medium effects of the axialvector channel and the pertinent pion decay constant as function of temperature. A pattern emerges where the chiral mass splitting between rho and a_1 burns off and is accompanied by a strong broadening of the spectral distributions.

  16. Chiral Swiss rolls show a negative refractive index.

    Science.gov (United States)

    Wiltshire, M C K; Pendry, J B; Hajnal, J V

    2009-07-22

    Chiral Swiss rolls, consisting of a metal/dielectric laminate tape helically wound on an insulating mandrel, have been developed to form the basis of a highly chiral metamaterial. We have fabricated these elements using a custom-built machine, and have characterized them. We find that the permeability, permittivity, and chirality are all resonant in the region of 80 MHz. The chirality is so strong that it can be directly measured by observing the magnetic response to an applied electric field, and is larger than either the permeability or the permittivity. We have estimated the refractive indices from these data, and find both strong circular dichroism and a wide frequency range where the refractive index is negative.

  17. Polarization Control by Using Anisotropic 3D Chiral Structures

    CERN Document Server

    Chen, Menglin L N; Sha, Wei E I; Choy, Wallace C H; Itoh, Tatsuo

    2016-01-01

    Due to the mirror symmetry breaking, chiral structures show fantastic electromagnetic (EM) properties involving negative refraction, giant optical activity, and asymmetric transmission. Aligned electric and magnetic dipoles excited in chiral structures contribute to extraordinary properties. However, the chiral structures that exhibit n-fold rotational symmetry show limited tuning capability. In this paper, we proposed a compact, light, and highly tunable anisotropic chiral structure to overcome this limitation and realize a linear-to-circular polarization conversion. The anisotropy is due to simultaneous excitations of two different pairs of aligned electric and magnetic dipoles. The 3D omega-like structure, etched on two sides of one PCB board and connected by metallic vias, achieves 60% of linearto- circular conversion (transmission) efficiency at the operating frequency of 9.2 GHz. The desired 90-degree phase shift between the two orthogonal linear polarization components is not only from the finite-thick...

  18. Experimental Results on Chiral Magnetic and Vortical Effects

    Directory of Open Access Journals (Sweden)

    Gang Wang

    2017-01-01

    Full Text Available Various novel transport phenomena in chiral systems result from the interplay of quantum anomalies with magnetic field and vorticity in high-energy heavy-ion collisions and could survive the expansion of the fireball and be detected in experiments. Among them are the chiral magnetic effect, the chiral vortical effect, and the chiral magnetic wave, the experimental searches for which have aroused extensive interest. The goal of this review is to describe the current status of experimental studies at Relativistic Heavy-Ion Collider at BNL and the Large Hadron Collider at CERN and to outline the future work in experiment needed to eliminate the existing uncertainties in the interpretation of the data.

  19. Chirality-dependent vapor-phase epitaxial growth and termination of single-wall carbon nanotubes.

    Science.gov (United States)

    Liu, Bilu; Liu, Jia; Tu, Xiaomin; Zhang, Jialu; Zheng, Ming; Zhou, Chongwu

    2013-09-11

    Structurally uniform and chirality-pure single-wall carbon nanotubes are highly desired for both fundamental study and many of their technological applications, such as electronics, optoelectronics, and biomedical imaging. Considerable efforts have been invested in the synthesis of nanotubes with defined chiralities by tuning the growth recipes but the approach has only limited success. Recently, we have shown that chirality-pure short nanotubes can be used as seeds for vapor-phase epitaxial cloning growth, opening up a new route toward chirality-controlled carbon nanotube synthesis. Nevertheless, the yield of vapor-phase epitaxial growth is rather limited at the present stage, due in large part to the lack of mechanistic understanding of the process. Here we report chirality-dependent growth kinetics and termination mechanism for the vapor-phase epitaxial growth of seven single-chirality nanotubes of (9, 1), (6, 5), (8, 3), (7, 6), (10, 2), (6, 6), and (7, 7), covering near zigzag, medium chiral angle, and near armchair semiconductors, as well as armchair metallic nanotubes. Our results reveal that the growth rates of nanotubes increase with their chiral angles while the active lifetimes of the growth hold opposite trend. Consequently, the chirality distribution of a nanotube ensemble is jointly determined by both growth rates and lifetimes. These results correlate nanotube structures and properties with their growth behaviors and deepen our understanding of chirality-controlled growth of nanotubes.

  20. Plasmonic hole arrays with extreme optical chirality in linear and nonlinear regimes

    Science.gov (United States)

    Gorkunov, Maxim V.; Kondratov, Alexei V.; Darinskii, Alexander N.; Artemov, Vladimir V.; Rogov, Oleg Y.; Gainutdinov, Radmir V.

    2016-04-01

    Metamaterials with high optical activity (OA) and circular dichroism (CD) are desired for various prospective applications ranging from circular light polarizing to enhanced chiral sensing and biosensing. Modern techniques allow fabricating subwavelength arrays of holes of complex chiral shapes that exhibit extreme optical chirality: their OA and CD take the whole range of possible values in the visible. In order to understand the nature of extreme chirality, we performed the electromagnetic finite difference time domain simulations for the hole shapes resolved by atomic force microscopy. The analysis of the simulation data allowed us to develop an analytical chiral coupled-mode model that nicely fits the results and explains the extreme chirality as determined by the Fano-type transmission resonance due to the interference of a weak background channel and a resonant plasmon channel. The model shows critical importance of the dissipation losses, the hole shape symmetry and chirality. In a planar 2D-chiral hole array, the mirror asymmetry can be induced by the difference of dielectric materials adjacent to the array sides and even their weak deviation results in remarkably strong OA and CD. We note that such deviations can arise due to the dielectric nonlinearity and discuss how 2D-chiral metamaterials in symmetric environment can acquire optical chirality due to the nonlinear symmetry breaking.

  1. High affinity antigen recognition of the dual specific variants of herceptin is entropy-driven in spite of structural plasticity.

    Directory of Open Access Journals (Sweden)

    Jenny Bostrom

    Full Text Available The antigen-binding site of Herceptin, an anti-human Epidermal Growth Factor Receptor 2 (HER2 antibody, was engineered to add a second specificity toward Vascular Endothelial Growth Factor (VEGF to create a high affinity two-in-one antibody bH1. Crystal structures of bH1 in complex with either antigen showed that, in comparison to Herceptin, this antibody exhibited greater conformational variability, also called "structural plasticity". Here, we analyzed the biophysical and thermodynamic properties of the dual specific variants of Herceptin to understand how a single antibody binds two unrelated protein antigens. We showed that while bH1 and the affinity-improved bH1-44, in particular, maintained many properties of Herceptin including binding affinity, kinetics and the use of residues for antigen recognition, they differed in the binding thermodynamics. The interactions of bH1 and its variants with both antigens were characterized by large favorable entropy changes whereas the Herceptin/HER2 interaction involved a large favorable enthalpy change. By dissecting the total entropy change and the energy barrier for dual interaction, we determined that the significant structural plasticity of the bH1 antibodies demanded by the dual specificity did not translate into the expected increase of entropic penalty relative to Herceptin. Clearly, dual antigen recognition of the Herceptin variants involves divergent antibody conformations of nearly equivalent energetic states. Hence, increasing the structural plasticity of an antigen-binding site without increasing the entropic cost may play a role for antibodies to evolve multi-specificity. Our report represents the first comprehensive biophysical analysis of a high affinity dual specific antibody binding two unrelated protein antigens, furthering our understanding of the thermodynamics that drive the vast antigen recognition capacity of the antibody repertoire.

  2. New approaches in sensitive chiral CE.

    Science.gov (United States)

    Sánchez-Hernández, Laura; Guijarro-Diez, Miguel; Marina, María Luisa; Crego, Antonio L

    2014-01-01

    CE has shown to have a big potential for chiral separations, with advantages such as high efficiency, high resolution, and low sample and reagents consumption. Nevertheless, when UV detection is employed, CE has some drawbacks, especially the low sensitivity obtained due to the short optical path length. Notwithstanding, sensitivity improvements can be achieved when different approaches are employed, such as sample treatment strategies (off-line or on-line), in-capillary sample preconcentration techniques, and/or alternative detection systems to UV-Vis (such as fluorescence, conductimetry, electrochemiluminiscence, MS, etc.). This article reviews the most recent methodological and instrumental advances reported from June 2011 to May 2013 for enhancing the sensitivity in chiral analysis by CE. The sensitivity achieved for the enantioseparated analytes and the applications carried out using the developed methodologies are also summarized.

  3. Spontaneous Chiral Symmetry Breaking as Condensation of Dynamical Chirality

    CERN Document Server

    Alexandru, Andrei

    2012-01-01

    The occurrence of spontaneous chiral symmetry breaking (SChSB) is equivalent to sufficient abundance of Dirac near-zeromodes. However, dynamical mechanism leading to breakdown of chiral symmetry should be naturally reflected in chiral properties of the modes. Here we offer such connection, presenting evidence that SChSB in QCD proceeds via the appearance of modes exhibiting dynamical tendency for local chiral polarization. These modes form a band of finite width Lambda_ch (chiral polarization scale) around the surface of otherwise anti--polarized Dirac sea, and condense. Lambda_ch characterizes the dynamics of the breaking phenomenon and can be converted to a quark mass scale, thus offering conceptual means to determine which quarks of nature are governed by broken chiral dynamics. It is proposed that, within the context of SU(3) gauge theories with fundamental Dirac quarks, mode condensation is equivalent to chiral polarization, making Lambda_ch an "order parameter" of SChSB. Several uses of these features, ...

  4. Preferential Rotation of Chiral Dipoles in Isotropic Turbulence

    Science.gov (United States)

    Kramel, Stefan; Voth, Greg A.; Tympel, Saskia; Toschi, Federico

    2016-10-01

    We introduce a new particle shape which shows preferential rotation in three dimensional homogeneous isotropic turbulence. We call these particles chiral dipoles because they consist of a rod with two helices of opposite handedness, one at each end. 3D printing is used to fabricate these particles with a length in the inertial range and their rotations are tracked in a turbulent flow between oscillating grids. High aspect ratio chiral dipoles preferentially align with their long axis along the extensional eigenvectors of the strain rate tensor, and the helical ends respond to the extensional strain rate with a mean spinning rate that is nonzero. We use Stokesian dynamics simulations of chiral dipoles in pure strain flow to quantify the dependence of spinning on particle shape. Based on the known response to pure strain, we build a model that gives the spinning rate of small chiral dipoles using velocity gradients along Lagrangian trajectories from high resolution direct numerical simulations. The statistics of chiral dipole spinning determined with this model show surprisingly good agreement with the measured spinning of much larger chiral dipoles in the experiments.

  5. A high-speed readout scheme for fast optical correlation-based pattern recognition

    Science.gov (United States)

    McDonald, Gregor J.; Lewis, Meirion F.; Wilson, Rebecca

    2004-12-01

    We describe recent developments to a novel form of hybrid electronic/photonic correlator, which exploits component innovations in both electronics and photonics to provide fast, compact and rugged target recognition, applicable to a wide range of security applications. The system benefits from a low power, low volume, optical processing core which has the potential to realise man portable pattern recognition for a wide range of security based imagery and target databases. In the seminal Vander Lugt correlator the input image is Fourier transformed optically and multiplied optically with the conjugate Fourier transform of a reference pattern; the required correlation function is completed by taking the inverse Fourier transform of the product optically. The correlator described here is similar in principle, but performs the initial Fourier transforms and multiplication electronically, with only the final most computationally demanding output Fourier transform being performed optically. In this scheme the Fourier transforms of both the input scene and reference pattern are reduced to a binary phase-only format, where the multiplication process simplifies to a simple Boolean logic XOR function. The output of this XOR gate is displayed on a state-of-the-art Fast Bit Plane Spatial Light Modulator (FBPSLM). A novel readout scheme has been developed which overcomes the previous system output bottleneck and for the first time allows correlation frame readout rates capable of matching the inherently fast nature of the SLM. Readout rates of up to ~1 MHz are now possible, exceeding current SLM capabilities and meeting potential medium term SLM developments promised by SLMs based on novel materials and architectures.

  6. Repulsive Casimir Force in Chiral Metamaterials

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-09-04

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

  7. Repulsive Casimir Force in Chiral Metamaterials

    OpenAIRE

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

    2009-01-01

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

  8. Repulsive Casimir Force in Chiral Metamaterials

    Science.gov (United States)

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

    2009-09-01

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

  9. Glucose, cellobiose, lactose and raffinose used as chiral stationary phases in HPLC

    Institute of Scientific and Technical Information of China (English)

    Jian Yu Wang; Feng Zhao; Mei Zhang; Ya Peng; Li Ming Yuan

    2008-01-01

    This paper presents the enantioseparation using glucose,cellobiose,lactose and raffinose as chiral selector bonded to silica gel via an arm in HPLC.Surprisingly,they also possess high enantioseparation selectivity,may be used in normal-phase and reversedphase mode.and there is a big chiral discriminating complementary.This work indicates that oligosacchafides could soon become very attractive as a new class of chiral stationary phase for HPLC.

  10. Reprint of: Enantiomeric separation of functionalized ethano-bridged Tröger bases using macrocyclic cyclofructan and cyclodextrin chiral selectors in high-performance liquid chromatography and capillary electrophoresis with application of principal component analysis.

    Science.gov (United States)

    Weatherly, Choyce A; Na, Yun-Cheol; Nanayakkara, Yasith S; Woods, Ross M; Sharma, Ankit; Lacour, Jérôme; Armstrong, Daniel W

    2014-10-01

    The enantiomeric separation of a series of racemic functionalized ethano-bridged Tröger base compounds was examined by high performance liquid chromatography (HPLC) and capillary electrophoresis (CE). Using HPLC and CE the entire set of 14 derivatives was separated by chiral stationary phases (CSPs) and chiral additives composed of cyclodextrin (native and derivatized) and cyclofructan (derivatized). Baseline separations (Rs ≥ 1.5) in HPLC were achieved for 13 of the 14 compounds with resolution values as high as 5.0. CE produced 2 baseline separations. The separations on the cyclodextrin CSPs showed optimum results in the reversed phase mode, and the LARIHC cyclofructan CSPs separations showed optimum results in the normal phase mode. HPLC separation data of the compounds was analyzed using principal component analysis (PCA). The PCA biplot analysis showed that retention is governed by the size of the R1 substituent in the case of derivatized cyclofructan and cyclodextrin CSPs, and enantiomeric resolution closely correlated with the size of the R2 group in the case of non-derivatized γ-cyclodextrin CSP. It is clearly shown that chromatographic retention is necessary but not sufficient for the enantiomeric separations of these compounds.

  11. Enantiomeric separation of functionalized ethano-bridged Tröger bases using macrocyclic cyclofructan and cyclodextrin chiral selectors in high-performance liquid chromatography and capillary electrophoresis with application of principal component analysis.

    Science.gov (United States)

    Weatherly, Choyce A; Na, Yun-Cheol; Nanayakkara, Yasith S; Woods, Ross M; Sharma, Ankit; Lacour, Jérôme; Armstrong, Daniel W

    2014-04-01

    The enantiomeric separation of a series of racemic functionalized ethano-bridged Tröger base compounds was examined by high performance liquid chromatography (HPLC) and capillary electrophoresis (CE). Using HPLC and CE the entire set of 14 derivatives was separated by chiral stationary phases (CSPs) and chiral additives composed of cyclodextrin (native and derivatized) and cyclofructan (derivatized). Baseline separations (Rs≥1.5) in HPLC were achieved for 13 of the 14 compounds with resolution values as high as 5.0. CE produced 2 baseline separations. The separations on the cyclodextrin CSPs showed optimum results in the reversed phase mode, and the LARIHC™ cyclofructan CSPs separations showed optimum results in the normal phase mode. HPLC separation data of the compounds was analyzed using principal component analysis (PCA). The PCA biplot analysis showed that retention is governed by the size of the R1 substituent in the case of derivatized cyclofructan and cyclodextrin CSPs, and enantiomeric resolution closely correlated with the size of the R2 group in the case of non-derivatized γ-cyclodextrin CSP. It is clearly shown that chromatographic retention is necessary but not sufficient for the enantiomeric separations of these compounds.

  12. An Efficient Decoder for the Recognition of Event-Related Potentials in High-Density MEG Recordings

    Directory of Open Access Journals (Sweden)

    Christoph Reichert

    2016-04-01

    Full Text Available Brain–computer interfacing (BCI is a promising technique for regaining communication and control in severely paralyzed people. Many BCI implementations are based on the recognition of task-specific event-related potentials (ERP such as P300 responses. However, because of the high signal-to-noise ratio in noninvasive brain recordings, reliable detection of single trial ERPs is challenging. Furthermore, the relevant signal is often heterogeneously distributed over several channels. In this paper, we introduce a new approach for recognizing a sequence of attended events from multi-channel brain recordings. The framework utilizes spatial filtering to reduce both noise and signal space considerably. We introduce different models that can be used to construct the spatial filter and evaluate the approach using magnetoencephalography (MEG data involving P300 responses, recorded during a BCI experiment. Compared to the accuracy achieved in the BCI experiment performed without spatial filtering, the recognition rate increased significantly to up to 95.3% on average (SD: 5.3%. In combination with the data-driven spatial filter construction we introduce here, our framework represents a powerful method to reliably recognize a sequence of brain potentials from high-density electrophysiological data, which could greatly improve the control of BCIs.

  13. Artificial Neural Network for Probabilistic Feature Recognition in Liquid Chromatography Coupled to High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Woldegebriel, Michael; Derks, Eduard

    2017-01-17

    In this work, a novel probabilistic untargeted feature detection algorithm for liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) using artificial neural network (ANN) is presented. The feature detection process is approached as a pattern recognition problem, and thus, ANN was utilized as an efficient feature recognition tool. Unlike most existing feature detection algorithms, with this approach, any suspected chromatographic profile (i.e., shape of a peak) can easily be incorporated by training the network, avoiding the need to perform computationally expensive regression methods with specific mathematical models. In addition, with this method, we have shown that the high-resolution raw data can be fully utilized without applying any arbitrary thresholds or data reduction, therefore improving the sensitivity of the method for compound identification purposes. Furthermore, opposed to existing deterministic (binary) approaches, this method rather estimates the probability of a feature being present/absent at a given point of interest, thus giving chance for all data points to be propagated down the data analysis pipeline, weighed with their probability. The algorithm was tested with data sets generated from spiked samples in forensic and food safety context and has shown promising results by detecting features for all compounds in a computationally reasonable time.

  14. 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.

  15. Nonequilibrium chiral perturbation theory and disoriented chiral condensates

    CERN Document Server

    Nicola, A G

    1999-01-01

    We analyse the extension of Chiral Perturbation Theory to describe a meson gas out of thermal equilibrium. For that purpose, we let the pion decay constant be a time-dependent function and work within the Schwinger-Keldysh contour technique. A useful connection with curved space-time QFT allows to consistently renormalise the model, introducing two new low-energy constants in the chiral limit. We discuss the applicability of our approach within a Relativistic Heavy-Ion Collision environment. In particular, we investigate the formation of Disoriented Chiral Condensate domains in this model, via the parametric resonance mechanism.

  16. Chiral quantum optics.

    Science.gov (United States)

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

    2017-01-25

    Advanced photonic nanostructures are currently revolutionizing the optics and photonics that underpin applications ranging from light technology to quantum-information processing. The strong light confinement in these structures can lock the local polarization of the light to its propagation direction, leading to propagation-direction-dependent emission, scattering and absorption of photons by quantum emitters. The possibility of such a propagation-direction-dependent, or chiral, light-matter interaction is not accounted for in standard quantum optics and its recent discovery brought about the research field of chiral quantum optics. The latter offers fundamentally new functionalities and applications: it enables the assembly of non-reciprocal single-photon devices that can be operated in a quantum superposition of two or more of their operational states and the realization of deterministic spin-photon interfaces. Moreover, engineered directional photonic reservoirs could lead to the development of complex quantum networks that, for example, could simulate novel classes of quantum many-body systems.

  17. Chiral imbalance in QCD

    Directory of Open Access Journals (Sweden)

    Andrianov Alexander

    2017-01-01

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

  18. Chirally extended quantum chromodynamics

    CERN Document Server

    Brower, R C; Tan, C I; Richard C Brower; Yue Shen; Chung-I Tan

    1994-01-01

    We propose an extended Quantum Chromodynamics (XQCD) Lagrangian in which the fermions are coupled to elementary scalar %\\sigma and \\pi fields through a Yukawa coupling which preserves chiral invariance. Our principle motivation is to find a new lattice formulation for QCD which avoids the source of critical slowing down usually encountered as the bare quark mass is tuned to the chiral limit. The phase diagram and the weak coupling limit for XQCD are studied. They suggest a conjecture that the continuum limit of XQCD is the same as the continuum limit of conventional lattice formulation of QCD. As examples of such universality, we present the large N solutions of two prototype models for XQCD, in which the mass of the spurious pion and sigma resonance go to infinity with the cut-off. Even if the universality conjecture turns out to be false, we believe that XQCD will still be useful as a low energy effective action for QCD phenomenology on the lattice. Numerical simulations are recommended to further investiga...

  19. Chiral quantum dot based materials

    Science.gov (United States)

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

    2014-05-01

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

  20. One-Dimensional Chirality: Strong Optical Activity in Epsilon-Near-Zero Metamaterials.

    Science.gov (United States)

    Rizza, Carlo; Di Falco, Andrea; Scalora, Michael; Ciattoni, Alessandro

    2015-07-31

    We suggest that electromagnetic chirality, generally displayed by 3D or 2D complex chiral structures, can occur in 1D patterned composites whose components are achiral. This feature is highly unexpected in a 1D system which is geometrically achiral since its mirror image can always be superposed onto it by a 180 deg rotation. We analytically evaluate from first principles the bianisotropic response of multilayered metamaterials and we show that the chiral tensor is not vanishing if the system is geometrically one-dimensional chiral; i.e., its mirror image cannot be superposed onto it by using translations without resorting to rotations. As a signature of 1D chirality, we show that 1D chiral metamaterials support optical activity and we prove that this phenomenon undergoes a dramatic nonresonant enhancement in the epsilon-near-zero regime where the magnetoelectric coupling can become dominant in the constitutive relations.

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

    Science.gov (United States)

    Chen, Xuexian; Yuan, Liming

    2016-01-01

    In recent eight years, authors' group has repeated a lot of experiments of chiral thin layer chromatography coming from literature. From the practical opinion, we summarized that there are nine characteristics for chiral thin layer chromatography. Some progresses of chiral thin layer chromatography are reviewed, and the enantioselectivity of a commercial chiral thin layer plate is introduced. The study of vancomycin as the chiral selector in thin layer chromatography is also reported.

  2. On SU(3 Effective Models and Chiral Phase Transition

    Directory of Open Access Journals (Sweden)

    Abdel Nasser Tawfik

    2015-01-01

    Full Text Available Sensitivity of Polyakov Nambu-Jona-Lasinio (PNJL model and Polyakov linear sigma-model (PLSM has been utilized in studying QCD phase-diagram. From quasi-particle model (QPM a gluonic sector is integrated into LSM. The hadron resonance gas (HRG model is used in calculating the thermal and dense dependence of quark-antiquark condensate. We review these four models with respect to their descriptions for the chiral phase transition. We analyze the chiral order parameter, normalized net-strange condensate, and chiral phase-diagram and compare the results with recent lattice calculations. We find that PLSM chiral boundary is located in upper band of the lattice QCD calculations and agree well with the freeze-out results deduced from various high-energy experiments and thermal models. Also, we find that the chiral temperature calculated from HRG is larger than that from PLSM. This is also larger than the freeze-out temperatures calculated in lattice QCD and deduced from experiments and thermal models. The corresponding temperature and chemical potential are very similar to that of PLSM. Although the results from PNJL and QLSM keep the same behavior, their chiral temperature is higher than that of PLSM and HRG. This might be interpreted due the very heavy quark masses implemented in both models.

  3. Separation of Ofloxacin and Its Six Related Substances Enantiomers by Chiral Ligand-Exchange Chromatography.

    Science.gov (United States)

    Liang, Xinlei; Zhao, Longshan; Deng, Miaoduo; Liu, Lijie; Ma, Yongfu; Guo, Xingjie

    2015-11-01

    A chiral ligand-exchange high-performance liquid chromatography method was developed for the enantioseparation of ofloxacin and its six related substances termed impurities A, B, C, D, E, and F. The separation was performed on a conventional C18 column. Different organic modifiers, copper salts, amino acids, the ratio of Cu(2+) to amino acid, pH of aqueous phase, and column temperature were optimized. The optimal mobile phase conditions were methanol-water systems consisting of 5 mmol/L copper sulfate and 10 mmol/L L-isoleucine (L-Ile). Under such conditions, good enantioseparation of ofloxacin and impurities A, C, E, and F could be observed with resolutions (RS ) of 3.54, 1.97, 3.21, 3.50, and 2.12, respectively. On the relationship between the thermodynamic parameters and structures of analytes, the mechanism of chiral recognition was investigated. It was concluded that ofloxacin and impurities A, C, E, and F were all enthalpically driven enantioseparation and that low column temperature was beneficial to enantioseparation. Furthermore, the structure-separation relationship of these analytes is also discussed.

  4. Analysis of Chiral Carboxylic Acids in Meteorites

    Science.gov (United States)

    Burton, A. S.; Elsila, J. E.; Hein, J. E.; Aponte, J. C.; Parker, E. T.; Glavin, D. P.; Dworkin, J. P.

    2015-01-01

    our efforts to develop highly sensitive LC-MS methods for the analysis of chiral carboxylic acids including hydroxy acids.

  5. Kinetic resolution of racemic carboxylic acids through asymmetric protolactonization promoted by chiral phosphonous acid diester.

    Science.gov (United States)

    Sakuma, Masayuki; Sakakura, Akira; Ishihara, Kazuaki

    2013-06-07

    Chiral phosphonium salts induce the kinetic resolution of racemic α-substituted unsaturated carboxylic acids through asymmetric protolactonization. Both the lactones and the recovered carboxylic acids are obtained with high enantioselectivities and high S (= kfast/kslow) values. Asymmetric protolactonization also leads to the desymmetrization of achiral carboxylic acids. Notably, chiral phosphonous acid diester not only induced the enantioselectivity but also promoted protolactonization.

  6. Nickel-catalyzed enantioselective hydrovinylation of silyl-protected allylic alcohols:An efficient access to homoallylic alcohols with a chiral quaternary center

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Asymmetric hydrovinylation of silyl-protected allylic alcohols catalyzed by nickel complexes of chiral spiro phosphoramidite ligands was developed.A series of homoallylic alcohols with a chiral quaternary center were produced in high yields(up to 97%) and high enantioselectivities(up to 95% ee).The reaction provides an efficient method for preparing bifunctional compounds with a chiral quaternary carbon center.

  7. [[Chiral separation of five arylpropionic acid drugs and determination of their enantiomers in pharmaceutical preparations by reversed-phase high performance liquid chromatography with cellulose-tris-(4-methylbenzoate) stationary phase

    Science.gov (United States)

    Luo, An; Wan, Qiang; Fan, Huajun; Chen, Zhi; Wu, Xuehao; Huang, Xiaowen; Zang, Linquan

    2014-09-01

    Chromatographic behaviors for enantiomeric separation of arylpropionic acid drugs were systematically developed by reversed phase-high performance liquid chromatography (RP-HPLC) using cellulose-tris-(4-methylbenzoate) (CTMB) as chiral stationary phase (CSP). The effects of the composition of the mobile phase, additives and temperature on chiral separation of flurbiprofen, pranoprofen, naproxen, ibuprofen and loxoprofen were further investigated. The enantiomers had been successfully separated on CSP of CTMB by the mobile phase of methanol-0.1% (v/v) formic acid except naproxen by acetonitrile-0.1% (v/v) formic acid at 25 °C. The mechanisms of the racemic resolution for the above mentioned five drugs are discussed thermodynamically and structurally. The resolutions between respective enantiomers for arylpropionic acid drugs on CTMB had significant differences due to their chromatographic behaviors. The order of resolutions ranked pranoprofen, loxoprofen, flurbiprofen, ibuprofen and naproxen. The method established has been successfully applied to the determination of the enantiomers of the five drugs in commercial preparations under the optimized conditions. It proved that the method is simple, reliable and accurate.

  8. Chiral fermions in asymptotically safe quantum gravity

    Energy Technology Data Exchange (ETDEWEB)

    Meibohm, J. [Gothenburg University, Department of Physics, Goeteborg (Sweden); Universitaet Heidelberg, Institut fuer Theoretische Physik, Heidelberg (Germany); Pawlowski, J.M. [Universitaet Heidelberg, Institut fuer Theoretische Physik, Heidelberg (Germany); GSI Helmholtzzentrum fuer Schwerionenforschung mbH, ExtreMe Matter Institute EMMI, Darmstadt (Germany)

    2016-05-15

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

  9. Chiral fermions in asymptotically safe quantum gravity

    CERN Document Server

    Meibohm, Jan

    2016-01-01

    We study the consistency of dynamical fermionic matter with the asymptotic safety scenario of quantum gravity using the functional renormalisation group. Since this scenario suggests strongly coupled quantum gravity in the UV, one expects gravity-induced fermion self-interactions at energies of the Planck-scale. These could lead to chiral symmetry breaking at very high energies and thus to large fermion masses in the IR. The present analysis which is based on the previous works \\cite{Christiansen:2015rva, Meibohm:2015twa}, concludes that gravity-induced chiral symmetry breaking at the Planck scale is avoided for a general class of NJL-type models, regardless of the number of fermion flavours. This suggests that the phase diagram for these models is topologically stable under the influence of gravitational interactions.

  10. Chiral Magnetic Effect Task Force Report

    CERN Document Server

    Skokov, Vladimir; Koch, Volker; Schlichting, Soeren; Thomas, Jim; Voloshin, Sergei; Wang, Gang; Yee, Ho-Ung

    2016-01-01

    In this report, we briefly examine the current status of the study of the chiral magnetic effect including theory and experimental progress. We recommend future strategies for resolving uncertainties in interpretation including recommendations for theoretical work, recommendations for measurements based on data collected in the past five years, and recommendations for beam use in the coming years of RHIC. We have specifically investigated the case for colliding nuclear isobars (nuclei with the same mass but different charge) and find the case compelling. We recommend that a program of nuclear isobar collisions to isolate the chiral magnetic effect from background sources be placed as a high priority item in the strategy for completing the RHIC mission.

  11. Highly stretchable strain sensor based on SWCNTs/CB synergistic conductive network for wearable human-activity monitoring and recognition

    Science.gov (United States)

    Guo, Xiaohui; Huang, Ying; Zhao, Yunong; Mao, Leidong; Gao, Le; Pan, Weidong; Zhang, Yugang; Liu, Ping

    2017-09-01

    Flexible, stretchable, and wearable strain sensors have attracted significant attention for their potential applications in human movement detection and recognition. Here, we report a highly stretchable and flexible strain sensor based on a single-walled carbon nanotube (SWCNTs)/carbon black (CB) synergistic conductive network. The fabrication, synergistic conductive mechanism, and characterization of the sandwich-structured strain sensor were investigated. The experimental results show that the device exhibits high stretchability (120%), excellent flexibility, fast response (∼60 ms), temperature independence, and superior stability and reproducibility during ∼1100 stretching/releasing cycles. Furthermore, human activities such as the bending of a finger or elbow and gestures were monitored and recognized based on the strain sensor, indicating that the stretchable strain sensor based on the SWCNTs/CB synergistic conductive network could have promising applications in flexible and wearable devices for human motion monitoring.

  12. Chiral Fermions on the Lattice

    CERN Document Server

    Bietenholz, Wolfgang

    2010-01-01

    In the last century the non-perturbative regularization of chiral fermions was a long-standing problem. We review how this problem was finally overcome by the formulation of a modified but exact form of chiral symmetry on the lattice. This also provides a sound definition of the topological charge of lattice gauge configurations. We illustrate a variety of applications to QCD in the p-, the epsilon- and the delta-regime, where simulation results can now be related to Random Matrix Theory and Chiral Perturbation Theory. The latter contains Low Energy Constants as free parameters, and we comment on their evaluation from first principles of QCD.

  13. Coupling chiral bosons to gravity

    CERN Document Server

    Braga, N R F; Braga, N R F; Wotzasek, C

    1995-01-01

    chiral boson actions of Floreanini and Jackiw (FJ), and of McClain,Wu and Yu (MWY) have been recently shown to be different representations of the same chiral boson theory. MWY displays manifest covariance and also a (gauge) symmetry that is hidden in the FJ side, which, on the other hand, displays the physical spectrum in a simple manner. We make use of the covariance of the MWY representation for the chiral boson to couple it to background gravity showing explicitly the equivalence with the previous results for the FJ representation

  14. Chiral gravity in higher dimensions

    CERN Document Server

    Ootsuka, T; Ura, K; Ootsuka, Takayoshi; Tanaka, Erico; Ura, Kousuke

    2003-01-01

    We construct a chiral theory of gravity in 7 and 8 dimensions, which are equivalent to Einstein-Cartan theory using less variables. In these dimensions, we can construct such higher dimensional chiral gravity because of the existence of gravitational instanton. The octonionic-valued variables in the theory represent the deviation from the gravitational instanton, and from their non-associativity, prevents the theory to be SO(n) gauge invariant. Still the chiral gravity holds G_2 (7-D), and Spin(7) (8-D) gauge symmetry.

  15. Chiral Relaxation Time at the Chiral Crossover of Quantum Chromodynamics

    CERN Document Server

    Ruggieri, M; Chernodub, M

    2016-01-01

    We study microscopic processes responsible for chirality flips in the thermal bath of Quantum Chromodynamics at finite temperature and zero baryon chemical potential. We focus on the temperature range where the crossover from chirally broken phase to quark-gluon plasma takes place, namely $T \\simeq (150, 200)$ MeV. The processes we consider are quark-quark scatterings mediated by collective excitations with the quantum number of pions and $\\sigma$-meson, hence we refer to these processes simply as \\sugg{to} one-pion (one-$\\sigma$) exchange\\sugg{s}. We use a Nambu-Jona-Lasinio model to compute equilibrium properties of the thermal bath, as well as the relevant scattering kernel to be used in the collision integral to estimate the chiral relaxation time $\\tau$. We find $\\tau\\simeq 0.1 \\div 1$ fm/c around the chiral crossover.

  16. Consistent chiral kinetic theory in Weyl materials: chiral magnetic plasmons

    CERN Document Server

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

    2016-01-01

    We argue that the correct definition of the electric current in the chiral kinetic theory for Weyl materials should include the Chern--Simons contribution that makes the theory consistent with the local conservation of the electric charge in electromagnetic and strain-induced pseudoelectromagnetic fields. By making use of such a kinetic theory, we study the plasma frequencies of collective modes in Weyl materials in constant magnetic and pseudomagnetic fields taking into account the effects of dynamical electromagnetism. We show that the collective modes are chiral plasmons. While the plasma frequency of the longitudinal collective mode coincides with the Langmuir one, this mode is unusual because it is characterized not only by oscillations of the electric current density, but also oscillations of the chiral current density. The latter are triggered by a dynamical version of the chiral electric separation effect. We also find that the plasma frequencies of the transverse modes split up in a magnetic field. T...

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

    Energy Technology Data Exchange (ETDEWEB)

    Tartakovskaya, Elena V., E-mail: elena_tartakovskaya@yahoo.com [Institute of Magnetism NAS of Ukraine, Vernadsky blvd 36b, 03142 Kiev (Ukraine); Institute of High Technologies, Taras Shevchenko National University of Kiev, 03022 Kiev (Ukraine)

    2015-05-01

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

  18. Recognition of anesthetic barbiturates by a protein binding site: a high resolution structural analysis.

    Directory of Open Access Journals (Sweden)

    Simon Oakley

    Full Text Available Barbiturates potentiate GABA actions at the GABA(A receptor and act as central nervous system depressants that can induce effects ranging from sedation to general anesthesia. No structural information has been available about how barbiturates are recognized by their protein targets. For this reason, we tested whether these drugs were able to bind specifically to horse spleen apoferritin, a model protein that has previously been shown to bind many anesthetic agents with affinities that are closely correlated with anesthetic potency. Thiopental, pentobarbital, and phenobarbital were all found to bind to apoferritin with affinities ranging from 10-500 µM, approximately matching the concentrations required to produce anesthetic and GABAergic responses. X-ray crystal structures were determined for the complexes of apoferritin with thiopental and pentobarbital at resolutions of 1.9 and 2.0 Å, respectively. These structures reveal that the barbiturates bind to a cavity in the apoferritin shell that also binds haloalkanes, halogenated ethers, and propofol. Unlike these other general anesthetics, however, which rely entirely upon van der Waals interactions and the hydrophobic effect for recognition, the barbiturates are recognized in the apoferritin site using a mixture of both polar and nonpolar interactions. These results suggest that any protein binding site that is able to recognize and respond to the chemically and structurally diverse set of compounds used as general anesthetics is likely to include a versatile mixture of both polar and hydrophobic elements.

  19. High affinity recognition of a Phytophthora protein by Arabidopsis via an RGD motif.

    Science.gov (United States)

    Senchou, V; Weide, R; Carrasco, A; Bouyssou, H; Pont-Lezica, R; Govers, F; Canut, H

    2004-02-01

    The RGD tripeptide sequence, a cell adhesion motif present in several extracellular matrix proteins of mammalians, is involved in numerous plant processes. In plant-pathogen interactions, the RGD motif is believed to reduce plant defence responses by disrupting adhesions between the cell wall and plasma membrane. Photoaffinity cross-linking of [125I]-azido-RGD heptapeptide in the presence of purified plasma membrane vesicles of Arabidopsis thaliana led to label incorporation into a single protein with an apparent molecular mass of 80 kDa. Incorporation could be prevented by excess RGD peptides, but also by the IPI-O protein, an RGD-containing protein secreted by the oomycete plant pathogen Phytophthora infestans. Hydrophobic cluster analysis revealed that the RGD motif of IPI-O (positions 53-56) is readily accessible for interactions. Single amino acid mutations in the RGD motif in IPI-O (of Asp56 into Glu or Ala) resulted in the loss of protection of the 80-kDa protein from labelling. Thus, the interaction between the two proteins is mediated through RGD recognition and the 80-kDa RGD-binding protein has the characteristics of a receptor for IPI-O. The IPI-O protein also disrupted cell wall-plasma membrane adhesions in plasmolysed A. thaliana cells, whereas IPI-O proteins mutated in the RGD motif (D56A and D56E) did not.

  20. Highly effective recognition of carbohydrates by phenanthroline-based receptors: alpha- versus beta-anomer binding preference.

    Science.gov (United States)

    Mazik, Monika; Hartmann, Andrè; Jones, Peter G

    2009-09-14

    (1)H NMR spectroscopic titrations in competitive and non-competitive media, as well as binding studies in two-phase systems, such as phase transfer of sugars from aqueous into organic solvents and dissolution of solid carbohydrates in apolar media revealed both highly effective recognition of neutral carbohydrates and interesting binding preferences of an acyclic phenanthroline-based receptor 1. Compared to the previously described acyclic receptors, compound 1 displays significantly higher binding affinities, the rare capability to extract sugars from water into non-polar organic solutions and alpha- versus beta-anomer binding preference in the recognition of glycosides, which differs from those observed for other receptor systems. X-ray crystallographic investigations revealed the presence of water molecules in the binding pocket of 1 that are engaged in the formation of hydrogen-bonding motifs similar to those suggested by molecular modelling for the sugar OH groups in the receptor-sugar complexes. The molecular modelling calculations, synthesis, crystal structure and binding properties of 1 are described and compared with those of the previously described receptors.