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Sample records for chiral cationic diphosphine

  1. Remarkably diastereoselective synthesis of a chiral biphenyl diphosphine ligand and its application in asymmetric hydrogenation

    PubMed Central

    Qiu, Liqin; Wu, Jing; Chan, Shusun; Au-Yeung, Terry T.-L.; Ji, Jian-Xin; Guo, Rongwei; Pai, Cheng-Chao; Zhou, Zhongyuan; Li, Xingshu; Fan, Qing-Hua; Chan, Albert S. C.

    2004-01-01

    Essentially complete atropdiastereoselectivity was realized in the preparation of biaryl diphosphine dioxide by asymmetric intramolecular Ullmann coupling and oxidative coupling with central-to-axial chirality transfer. A bridged C2-symmetric biphenyl phosphine ligand possessing additional chiral centers on the linking unit of the biphenyl groups was synthesized. No resolution step was required for the preparation of the enantiomerically pure chiral ligand. These findings offer a general and practical tool for the development of previously uninvestigated atropdiastereomeric biaryl phosphine ligands. The diphosphine ligand was found to be highly effective in the asymmetric hydrogenation of α- and β-ketoesters, 2-(6′-methoxy-2′-naphthyl)propenoic acid, β-(acylamino)acrylates, and enol acetates. PMID:15067137

  2. Chloride-Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins.

    PubMed

    Kita, Yusuke; Hida, Shoji; Higashihara, Kenya; Jena, Himanshu Sekhar; Higashida, Kosuke; Mashima, Kazushi

    2016-07-11

    Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride-bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]2 , chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)-prop-1-ene-1,2-diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems. PMID:27088539

  3. Origins of enantioselectivity in the chiral diphosphine-ligated CuH-catalyzed asymmetric hydrosilylation of ketones.

    PubMed

    Zhang, Wei; Li, Weiyi; Qin, Song

    2012-01-21

    Computational investigations on the asymmetric hydrosilylation of acetophenone over ligated CuH catalysts were performed with the DFT method. The calculations predict that the catalytic reaction involves two steps: (1) CuH addition to the carbonyl group via a four-membered transition state (TS) with the formation of copper-alkoxide intermediates; (2) regeneration of the ligated CuH catalyst by an external SiH(4) through a metathesis process to yield the corresponding silyl ether. The calculations in the chiral diphosphine-ligated CuH systems suggest that the metathesis process is the rate-determining step (RDS). The CuH addition step is vital for the distribution of the racemic products and therefore represents the stereo-controlling step (SCT). In this step, the greater steric hindrance between the aromatic rings of the ligands and the substrate is identified as the major factor for enantioselectivity. The corresponding TS in the face-to-face mode, suffering less steric hindrance, is more stable than its analogue in the edge-to-face mode. The enantioselectivities are calculated to be related not only to the P-Cu-P bite angles in the stereo-controlling TSs, but also to the substituents at the P-aryl rings of the chiral ligands. In short, a larger P-Cu-P bite angle and suitably modified P-aryl rings together are necessary to achieve excellent ee values. PMID:22116075

  4. Niobium tetrahalide complexes with neutral diphosphine ligands.

    PubMed

    Benjamin, Sophie L; Chang, Yao-Pang; Hector, Andrew L; Jura, Marek; Levason, William; Reid, Gillian; Stenning, Gavin

    2016-05-10

    The reactions of NbCl4 with diphosphine ligands o-C6H4(PMe2)2, Me2PCH2CH2PMe2 or Et2PCH2CH2PEt2 in a 1 : 2 molar ratio in MeCN solution produced eight-coordinate [NbCl4(diphosphine)2]. [NbBr4(diphosphine)2] (diphosphine = o-C6H4(PMe2)2 or Me2PCH2CH2PMe2) were made similarly from NbBr4. X-ray crystal structures show that [NbCl4{o-C6H4(PMe2)2}2] has a dodecahedral geometry, but the complexes with dimethylene-backboned diphosphines are distorted square antiprisms. The Nb-P distances and diphosphine (diphosphine = Me2PCH2CH2PMe2, Et2PCH2CH2PEt2, Cy2PCH2CH2PCy2 and Ph2PCH2CH2CH2PPh2) afforded [NbCl4(diphosphine)], and [NbBr4(Me2PCH2CH2PMe2)] was obtained similarly. These 1 : 1 complexes are unstable in solution, preventing X-ray crystallographic study, but based upon their diamagnetism, IR, UV-visible and (31)P{(1)H} NMR spectra, they are formulated as halide-bridged dimers [(diphosphine)X2Nb(μ-X)4NbX2(diphosphine)], with single Nb-Nb bonds and chelating diphosphines. The Nb(iv) complexes are prone to hydrolysis and oxidation in solution and the structures of the Nb(v) complexes [NbBr4(Me2PCH2CH2PMe2)2][NbOBr4(MeCN)] with a dodecahedral cation, and [{NbOCl3{Et2P(CH2)2PEt2}}2{μ-Et2P(CH2)2PEt2}] which contains seven-coordinate Nb(v) centres with a symmetrical diphosphine bridge, are reported. The structure of niobium tetrabromide, conveniently made from NbCl4 and BBr3, is a chain polymer with edge-linked NbBr6 octahedra and alternating long and short Nb-Nb distances, the latter ascribed to Nb-Nb bonds. PMID:27094082

  5. Cationic Chiral Fluorinated Oxazaborolidines. More Potent, Second-Generation Catalysts for Highly Enantioselective Cycloaddition Reactions.

    PubMed

    Mahender Reddy, Karla; Bhimireddy, Eswar; Thirupathi, Barla; Breitler, Simon; Yu, Shunming; Corey, E J

    2016-02-24

    The coordination of chiral ligands to Lewis acid metal derivatives, a useful strategy for enantioselective, electrophilic catalysis, generally leads to a lower level of catalytic activity than that of the original uncomplexed compound. Activation by further attachment of a proton or strong Lewis acid to the complex provides a way to overcome the deactivating effect of a chiral ligand. The research described herein has demonstrated that further enhancement of catalytic activity is possible by the judicious placement of fluorine substituents in the chiral ligand. This approach has led to a new, second-generation family of chiral oxazaborolidinium cationic species which can be used to effect many Diels-Alder reactions in >95% yield and >95% ee using catalyst loadings at the 1-2 mol % level. The easy recovery of the chiral ligand makes the application of these new catalysts especially attractive for large-scale synthesis.

  6. Highly effective asymmetric hydrogenation of cyclic N-alkyl imines with chiral cationic Ru-MsDPEN catalysts.

    PubMed

    Chen, Fei; Ding, Ziyuan; Qin, Jie; Wang, Tianli; He, Yanmei; Fan, Qing-Hua

    2011-08-19

    A range of cyclic N-alkyl imines were efficiently hydrogenated by using a chiral cationic Ru(η(6)-cymene)(MsDPEN)(BArF) complex (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) in high yields and up to 98% ee. A one-pot synthesis of chiral 2-phenylpyrrolidine via reductive amination was also developed. PMID:21766831

  7. Cationic permethylated 6-monoamino-6-monodeoxy-β-cyclodextrin as chiral selector of dansylated amino acids in capillary electrophoresis.

    PubMed

    Németh, Krisztina; Domonkos, Celesztina; Sarnyai, Virág; Szemán, Julianna; Jicsinszky, László; Szente, Lajos; Visy, Júlia

    2014-10-01

    The resolution power of permethylated 6-monoamino-6-monodeoxy-βCD (PMMABCD) - a single isomer, cationic CD derivative - developed previously for chiral analyses in capillary electrophoresis was further studied here. Dansylated amino acids (Dns-AA) were chosen as amphoteric chiral model compounds. Changes in the resolutions of Dns-AAs by varying pH and selector concentrations were investigated and correlated with their structures and chemical properties (isoelectric point and lipophilicity). Maximal resolutions could be achieved at pH 6 or pH 4. The separations improved with increasing concentration of the selector. Baseline or substantially better resolution for 8 pairs of these Dns-AAs could be achieved. Low CD concentration was enough for the separation of the most apolar Dns-AAs. Chiral discrimination ability of PMMABCD was demonstrated by the separation of an artificial mixture of 8 Dns-AA pairs.

  8. Chiral Nanostructures from Helical Copolymer-Metal Complexes: Tunable Cation-π Interactions and Sergeants and Soldiers Effect.

    PubMed

    Arias, Sandra; Bergueiro, Julián; Freire, Félix; Quiñoá, Emilio; Riguera, Ricardo

    2016-01-13

    Poly(phenylacetylene) (PPA) copolymers containing (R)- or (S)-MPA as minor chiral pendant can be forced to selectively adopt the right- o left-handed helix, in the presence of small amounts of Na(+) or Ag(+) ("Sergeants and Soldiers Effect") by addition of a donor cosolvent. The helical sense depends exclusively on the chiral monomer/donor cosolvent ratio, and this allows a perfect on/off tuning of the helicity of the copolymer. When the amount of the donor cosolvent is low, the metal ion complex is stabilized by a cation-π interaction, which is selectively cleaved when the amount of cosolvent is higher. Macroscopically chiral nanospheres and nanotubes composed by helical copolymers with P or M helical sense are also described. Our results demonstrate that it is possible to obtain the two enantiomeric helical structures (P and M helicities) and the corresponding nanospheres and nanotubes from a single helical copolymer, by controlled activation/deactivation of the Sergeant and Soldiers Effect with a donor cosolvent. PMID:26578292

  9. Strong cation exchange chiral stationary phase--a comparative study in high-performance liquid chromatography and subcritical fluid chromatography.

    PubMed

    Wolrab, Denise; Macíková, Pavla; Boras, Mario; Kohout, Michal; Lindner, Wolfgang

    2013-11-22

    The performance of a strong cation exchange-type (SCX) chiral stationary phase (CSP) was evaluated with subcritical fluid chromatography (subFC) and high performance liquid chromatography (HPLC). The chromatographic conditions in subFC were optimized by changing the amount of polar organic modifier, concentration of a basic additive in the modifier, system pressure and temperature. In this way the concentration of in situ formed transient ionic species could be varied. The gradual change of the concentration of the transient buffer, i.e. gradient elution conditions in subFC, was found beneficial for separation of a mixture of racemic compounds. The strength and amount of the in situ formed buffer was estimated on the basis of comparative experiments in subSFC and HPLC.

  10. Asymmetric hydrogenation of 2- and 2,3-substituted quinoxalines with chiral cationic ruthenium diamine catalysts.

    PubMed

    Qin, Jie; Chen, Fei; Ding, Ziyuan; He, Yan-Mei; Xu, Lijin; Fan, Qing-Hua

    2011-12-16

    The enantioselective hydrogenation of 2-alkyl- and 2-aryl-subsituted quinoxalines and 2,3-disubstituted quinoxalines was developed by using the cationic Ru(η(6)-cymene)(monosulfonylated diamine)(BArF) system in high yields with up to 99% ee. The counteranion was found to be critically important for the high enantioselectivity and/or diastereoselectivity. PMID:22098608

  11. Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution.

    PubMed

    Lin, Yiji; Zou, Fang; Wan, Shigang; Ouyang, Jie; Lin, Lirong; Zhang, Hui

    2012-06-14

    Chiral tetrakis(β-diketonate) Ln(III) complexes Δ-[NaLa(d-hfc)(4)(CH(3)CN)] (1) and Λ-[NaLa(l-hfc)(4) (CH(3)CN)] (2) (d/l-hfc(-) = 3-heptafluo-robutylryl-(+)/(-)-camphorate) are a pair of enantiomers and crystallize in the same Sohncke space group (P2(1)2(1)2(1)) with dodecahedral (DD) geometry. Typically positive and negative exciton splitting patterns around 320 nm were observed in the solid-state circular dichroism (CD) spectra of complexes 1 and 2, which indicate that their shell configurational chiralities are Δ and Λ, respectively. The apparent bisignate couplets in the solid-state CD spectra of [CsLn(d-hfc)(4)(H(2)O)] [Ln = La (3), Yb (5)] and [CsLn(l-hfc)(4)(H(2)O)] [Ln = La (4), Yb (6)] show that they are a pair of enantiomers and their absolute configurations are denoted Δ and Λ, respectively. The crystallographic data of 5 reveals that its coordination polyhedron is the square antiprism (SAP) geometry and it undergoes a phase transition from triclinic (α phase, P1) to monoclinic (β phase, C2) upon cooling. The difference between the two phases is brought about by the temperature dependent behaviour of the coordination water molecules, but this did not affect the configurational chirality of the Δ-SAP-[Yb(d-hfc)(4)](-) moiety. Furthermore, time-dependent CD, UV-vis and (19)F NMR were applied to study the solution behavior of these complexes. It was found that the chiral-at-metal stability of the three pairs of complexes is different and affected by both the Ln(3+) and M(+) ion size. The results show that the Cs(+) cation can retain the metal center chirality and stablize the structures of [Ln(d/l-hfc)(4)](-) or the dissociated tris(d/l-hfc)Ln(III) species in solution for a longer time than that of the Na(+) cation, and it is important that the Cs(+) ion successfully lock the configurational chirality around the Yb(3+) center of the complex species in solution. This is reasoned by the short Cs(+)···FC, Cs(+)···O-Yb and Cs(+)···Yb(3

  12. Effects of substituent branching and chirality on the physical properties of ionic liquids based on cationic ruthenium sandwich complexes.

    PubMed

    Higashi, Tomomi; Ueda, Takahiro; Mochida, Tomoyuki

    2016-04-21

    An appropriate understanding of how substituents affect the physical properties of ionic liquids is important for the molecular design of ionic liquids. Toward this end, we investigated how the branching and chirality of substituents affect the physical properties of organometallic ionic liquids. We synthesized a series of ionic liquids bearing a branched or linear alkoxy group with the same number of carbons: [Ru(C5H5)(η(6)-C6H5OR)]X (rac-[1]X: R = -CH(C2H5)(C6H13), [2]X: R = -CH(C4H9)2, [3]X: R = -C9H19), where X = PF6(-), (SO2F)2N(-), and (SO2CF3)2N(-). rac-[1]X are racemic salts. Salts with less symmetrical substituents tend to maintain the liquid state due to suppression of crystallization; crystallization is completely suppressed in most of the rac-[1]X salts and in some of the [2]X salts, whereas not in [3]X salts. The glass-transition temperatures and viscosities of the salts with branched substituents are greater than those with linear substituents. Chiral resolution of rac-[1][PF6] was performed by chiral chromatography. The melting point of rac-[1][PF6] is much lower than that of the enantiopure salt (chiral-[1][PF6]), which we ascribe to the formation of a conglomerate in the solid state. X-ray structure analysis revealed that the solid salts form layered structures.

  13. Stationary phase-related investigations of quinine-based zwitterionic chiral stationary phases operated in anion-, cation-, and zwitterion-exchange modes.

    PubMed

    Hoffmann, Christian V; Reischl, Roland; Maier, Norbert M; Lämmerhofer, Michael; Lindner, Wolfgang

    2009-02-13

    The concept of recently introduced Cinchona alkaloid-type zwitterionic chiral stationary phases (CSPs) is based on fusing key cation- and anion-exchange (CX, AX) moieties in one single low-molecular mass chiral selector (SO) with the resulting CSPs allowing enantiomer separations of a wide range of chiral ionizable analytes comprising acids, bases, and zwitterionic compounds. Herein, we report principal, systematic investigations of the ion-exchange-type retention mechanisms available with the novel zwitterionic CSPs in nonaqueous polar organic mode. Typical CX and AX processes, corresponding to the parent single ion exchangers, are confirmed also for zwitterionic CSPs. Also the mechanism leading to recognition and retention of zwitterions was found to be ion exchange mediated in a zwitterion-exchange (ZX) mode. In both AX and CX modes the additional ionizable group within the SO besides the site responsible for the respective ion-exchange process could be characterized as an intramolecular counterion (IMCI) that effectively participates in the ion-exchange equilibria and thus, contributes to solute elution. In the ZX mode both oppositely charged groups of the zwitterionic SO were found not only to be the sites for simultaneous ion pairing with the analyte but also functioned as IMCIs at the same time. The main practical consequences of the IMCI feature were significant reduction of the amounts and even elimination of acidic and basic additives required in the eluent systems to afford analyte elution while still providing faster analysis than the parent single ion-exchanger-type CSPs. The set of ten structurally different zwitterionic CSPs employed in this study facilitated the establishment of correlations between chromatographic behavior of the CSPs with particular SO elements, thereby supporting the understanding of the working principles of these novel packing materials on a molecular level.

  14. Synthesis of planar chiral iridacycles by cationic metal π-coordination: facial selectivity, and conformational and stereochemical consequences.

    PubMed

    Djukic, Jean-Pierre; Iali, Wissam; Pfeffer, Michel; Le Goff, Xavier-Frédéric

    2012-05-01

    Facial selectivity during the π-coordination of pseudo-tetrahedral iridacycles by neutral (Cr(CO)(3)), monocationic (Cp*Ru(+)), and biscationic (Cp*Ir(2+)) metal centers was directly influenced by the coulombic imbalance in the coordination sphere of the chelated Ir center. We also showed by using theoretical calculations that the feasibility of the related metallacycles that displayed metallocenic planar chirality was dependent to the presence of an electron-donating group, such as NMe(2), which contributed to the overall stability of the complexes. When the π-bonded moiety was the strongly electron-withdrawing Cp*Ir(2+) group, the electron donation from NMe(2) resulted in major conformational changes, with a barrier to rotation of about 17 kcal  mol(-1) for this group that became spectroscopically diastereotopic (high-field (1)H NMR spectroscopy). This peculiar property is proposed as a means to introduce a new type of constitutional chirality at the nitrogen center: planar chirality at tertiary aromatic amines. PMID:22473841

  15. Separation of Cinchona alkaloids on a novel strong cation-exchange-type chiral stationary phase-comparison with commercially available strong cation exchanger and reversed-phase packing materials.

    PubMed

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

    2009-02-01

    A recently reported chiral strong cation exchanger (cSCX) type stationary phase was investigated for the LC separation of a series of Cinchona alkaloids and synthetic derivatives thereof to test its usefulness as alternative methodology for the separation of those important pharmaceuticals. The cSCX column-packing material was qualitatively compared on the one hand against a commercially available non-enantioselective SCX-material, PolySulfoethyl-A, and, on the other hand, against a modern C18 reversed-phase stationary phase which is commonly employed for Cinchona alkaloid analysis. Both SCX columns showed no pronounced peak-tailing phenomena which typically hamper Cinchona alkaloid RP analysis and require specific optimization. Thus, the cSCX-based assay provided new feasibilities for the separation of the Cinchona alkaloids in polar organic mode as opposed to conventional reversed-phase methodologies. In particular, a method for the simultaneous determination of eight Cinchona alkaloids (quinine, quinidine, cinchonine, cinchonidine, and their corresponding dihydro analogs) using the cSCX column in HPLC has been developed and exemplarily applied to impurity profiling of a commercial alkaloid sample. Furthermore, both SCX materials allowed successful separation of C9-epi and 10,11-didehydro derivatives from their respective educts in an application in synthetic Cinchona alkaloid chemistry. PMID:19107468

  16. Systematics of BX3 and BX2(+) Complexes (X = F, Cl, Br, I) with Neutral Diphosphine and Diarsine Ligands.

    PubMed

    Burt, Jennifer; Emsley, James W; Levason, William; Reid, Gillian; Tinkler, Iain S

    2016-09-01

    The coordination chemistry of the neutral diphosphines, R2P(CH2)2PR2 (R = Me or Et) and o-C6H4(PR'2)2 (R' = Me or Ph), and the diarsine, o-C6H4(AsMe2)2, toward the Lewis acidic BX3 (X = F, Cl, Br, and I) fragments is reported, including several rare complexes incorporating BF3 and BF2(+). The studies have revealed that the flexible dimethylene linked diphosphines form [(BX3)2{μ-R2P(CH2)2PR2}] exclusively, confirmed by multinuclear NMR ((1)H, (11)B, (19)F{(1)H}, and (31)P{(1)H}) and IR spectroscopy and microanalytical data. Crystallographic determinations of the four BX3 complexes with Et2P(CH2)2PEt2 confirm the 2:1 stoichiometry and, taken together with the spectroscopic data, reveal that the Lewis acid behavior of the BX3 fragment toward phosphine ligands increases in the order F ≪ Cl ∼ Br < I. The first diphosphine- and diarsine-coordinated dihaloboronium cations, [BX2{o-C6H4(EMe2)2}](+) (E = P, As), are obtained using the rigid, preorganized o-phenylene linkages. These complexes are characterized similarly, and the data indicate that the complexes with o-C6H4(AsMe2)2 are much more labile and readily decomposed than the phosphine analogues. X-ray crystallographic studies on [BX2{o-C6H4(PMe2)2}][BX4] (X = Cl, Br), [BI2{o-C6H4(PMe2)2}][I3], and [BCl2{o-C6H4(AsMe2)2}][BCl4] confirm the presence of distorted tetrahedral coordination at boron through a chelating diphosphine or diarsine and two X ligands, with d(B-P) revealing a similar increase in Lewis acidity down group 17. Comparison of d(B-P) and d(B-As) reveals an increase of ca. 0.08 Å from P to As. Reaction of BCl3 with the diphosphine dioxide Ph2P(O)CH2P(O)Ph2 gives the ligand-bridged dimer [(BCl3)2{Ph2P(O)CH2P(O)Ph2}], while using either BF3 gas or [BF3(SMe2)] gives a mixture containing both [(BF3)2{μ-Ph2P(O)CH2P(O)Ph2}] and the unexpected difluoroboronium salt, [BF2{Ph2P(O)CH2P(O)Ph2}][B2F7] containing a chelating phosphine oxide. The structure of the latter was confirmed crystallographically.

  17. Systematics of BX3 and BX2(+) Complexes (X = F, Cl, Br, I) with Neutral Diphosphine and Diarsine Ligands.

    PubMed

    Burt, Jennifer; Emsley, James W; Levason, William; Reid, Gillian; Tinkler, Iain S

    2016-09-01

    The coordination chemistry of the neutral diphosphines, R2P(CH2)2PR2 (R = Me or Et) and o-C6H4(PR'2)2 (R' = Me or Ph), and the diarsine, o-C6H4(AsMe2)2, toward the Lewis acidic BX3 (X = F, Cl, Br, and I) fragments is reported, including several rare complexes incorporating BF3 and BF2(+). The studies have revealed that the flexible dimethylene linked diphosphines form [(BX3)2{μ-R2P(CH2)2PR2}] exclusively, confirmed by multinuclear NMR ((1)H, (11)B, (19)F{(1)H}, and (31)P{(1)H}) and IR spectroscopy and microanalytical data. Crystallographic determinations of the four BX3 complexes with Et2P(CH2)2PEt2 confirm the 2:1 stoichiometry and, taken together with the spectroscopic data, reveal that the Lewis acid behavior of the BX3 fragment toward phosphine ligands increases in the order F ≪ Cl ∼ Br < I. The first diphosphine- and diarsine-coordinated dihaloboronium cations, [BX2{o-C6H4(EMe2)2}](+) (E = P, As), are obtained using the rigid, preorganized o-phenylene linkages. These complexes are characterized similarly, and the data indicate that the complexes with o-C6H4(AsMe2)2 are much more labile and readily decomposed than the phosphine analogues. X-ray crystallographic studies on [BX2{o-C6H4(PMe2)2}][BX4] (X = Cl, Br), [BI2{o-C6H4(PMe2)2}][I3], and [BCl2{o-C6H4(AsMe2)2}][BCl4] confirm the presence of distorted tetrahedral coordination at boron through a chelating diphosphine or diarsine and two X ligands, with d(B-P) revealing a similar increase in Lewis acidity down group 17. Comparison of d(B-P) and d(B-As) reveals an increase of ca. 0.08 Å from P to As. Reaction of BCl3 with the diphosphine dioxide Ph2P(O)CH2P(O)Ph2 gives the ligand-bridged dimer [(BCl3)2{Ph2P(O)CH2P(O)Ph2}], while using either BF3 gas or [BF3(SMe2)] gives a mixture containing both [(BF3)2{μ-Ph2P(O)CH2P(O)Ph2}] and the unexpected difluoroboronium salt, [BF2{Ph2P(O)CH2P(O)Ph2}][B2F7] containing a chelating phosphine oxide. The structure of the latter was confirmed crystallographically. PMID

  18. Synthesis, Structures, and Reactions of Manganese Complexes Containing Diphosphine Ligands With Pendant Amines

    SciTech Connect

    Welch, Kevin D.; Dougherty, William G.; Kassel, W. S.; DuBois, Daniel L.; Bullock, R. Morris

    2010-10-01

    Addition of the pendant amine ligand PNRP (PNRP = Et2PCH2NRCH2PEt2; R = Me, Ph, n-Bu) to Mn(CO)5Br gives fac-Mn(PNRP)(CO)3Br. Photolysis of fac-Mn(PNRP)(CO)3Br with dppm [dppm = 1,2-bis(diphenylphosphino)methane] provides mixed bis(diphosphine) complexes, trans-Mn(PNRP)(dppm)(CO)(Br). Reaction of trans-Mn(PNRP)(dppm)(CO)(Br) with LiAlH4 leads to trans-Mn(PNRP)(dppm)(CO)(H). The crystal structure of trans-Mn(PNMeP)(dppm)(CO)(H) determined by x-ray diffraction shows an unusual distortion of the Mn-H towards one C-H of the dppm ligand, resulting in an H Mn CO angle of 155(1)° and C H • • • H Mn distance of 2.10(3) Å. Mn(P2PhN2Bn)(dppm)(CO)(H) [P2PhN2Bn = 1, 5-diphenyl-3,7-dibenzyl-1,5-diaza-3,7-diphosphacyclooctane] can be prepared in a similar manner; its structure has one chelate ring in a chair conformation and the second in a boat conformation. The boat-conformer ring directs the nitrogen of the ring towards the carbonyl ligand, and the N • • • C distance between one N of the P2PhN2Bn ligand and CO is 3.171(4) Å, indicating a weak interaction between the N of the pendant amine and the CO ligand. Reaction of NaBArF4 (ArF = = 3,5-bis(trifluoromethyl)phenyl) with Mn(P P)(dppm)(CO)(Br) produces the cations [Mn(P P)(dppm)(CO)]+. The crystal structure of [Mn(PNMeP)(dppm)(CO)][BArF4] shows two very weak agostic interactions between C-H bonds on the phenyl ring and the Mn. The cationic complexes [Mn(P P)(dppm)(CO)]+ react with H2 to form dihydrogen complexes [Mn(H2)(P P)(dppm)(CO)]+ (Keq = 1 - 90 atm-1 in fluorobenzene, for a series of different P P ligands). Similar equilibria with N2 produce [Mn(N2)(P P)(dppm)(CO)]+ (Keq generally 1-3.5 atm-1 in fluorobenzene). This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  19. Chiral template induced homochiral MOFs built from achiral components: SHG enhancement and enantioselective sensing of chiral alkamines by ion-exchange.

    PubMed

    Han, Yun-Hu; Liu, Yue-Cheng; Xing, Xiu-Shuang; Tian, Chong-Bin; Lin, Ping; Du, Shao-Wu

    2015-10-01

    A pair of chiral template induced anionic homochiral frameworks constructed from achiral components has been synthesized. Ion-exchange of counter cations with polar or chiral organic cations enhances the SHG efficiency of the frameworks. The enantioselective sensing of chiral alkamines can be achieved by the SHG response.

  20. Facile P-C/C-H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes.

    PubMed

    Zhang, Shaoguang; Li, Haixia; Appel, Aaron M; Hall, Michael B; Bullock, R Morris

    2016-07-01

    Unusual cleavage of P-C and C-H bonds of the P2 N2 ligand, in heteroleptic [Ni(P2 N2 )(diphosphine)](2+) complexes under mild conditions, results in the formation of an iminium formyl nickelate featuring a C,P,P-tridentate coordination mode. The structures of both the heteroleptic [Ni(P2 N2 )(diphosphine)](2+) complexes and the resulting iminium formyl nickelate have been characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Density functional theory (DFT) calculations were employed to investigate the mechanism of the P-C/C-H bond cleavage, which involves C-H bond cleavage, hydride rotation, Ni-C/P-H bond formation, and P-C bond cleavage. PMID:27189413

  1. Stereoselective Binding of Chiral Ligands to Single Nucleotide Polymorphs (SNPs) of the Human Organic Cation Transporter-1 Determined Using Cellular Membrane Affinity Chromatography

    PubMed Central

    Moaddel, R.; Bighi, F.; Yamaguchi, R.; Patel, S.; Ravichandran, S.; Wainer, I.W.

    2010-01-01

    Membranes from stably transfected cell lines that expresses two point mutations of the human organic cation 1 transporter (hOCT1), R488M and G465R, have been immobilized on the immobilized artificial membrane (IAM) liquid chromatographic stationary phase to form the Cellular Membrane Affinity Chromatography (CMAC) (hOCT1G465R) and CMAC(hOCT1R488M). Columns were created using both stationary phases and frontal displacement chromatography experiments were conducted using [3H]-methyl phenyl pyridinium, [3H]-MPP+, as the marker ligand and various displacers, including the single enantiomers of verapamil, fenoterol and isoproterenol. The chromatographic data obtained was used to refine a previously developed pharmacophore for the hOCT1 transporter. PMID:20206116

  2. Pt-Catalyzed Enantioselective Cycloisomerization for the Synthesis of Planar-Chiral Ferrocene Derivatives.

    PubMed

    Shibata, Takanori; Uno, Ninna; Sasaki, Tomoya; Kanyiva, Kyalo Stephen

    2016-08-01

    Enantioselective cycloisomerization of 2-ethynyl-1-ferrocenylbenzene derivatives proceeded by using a chiral cationic platinum catalyst at room temperature. The intramolecular reaction gave planar-chiral naphthalene- and anthracene-fused ferrocene derivatives with high to excellent ee.

  3. Hydrogen oxidation catalysis by a nickel diphosphine complex with pendant tert-butyl amines

    SciTech Connect

    Yang, Jenny Y.; Chen, Shentan; Dougherty, William G.; Kassel, W. Scott; Bullock, R. Morris; DuBois, Daniel L.; Raugei, Simone; Rousseau, Roger; Dupuis, Michel; DuBois, M. Rakowski

    2010-01-01

    A bis-diphosphine nickel complex with tert-butyl functionalized pendant amines [Ni(PCy2Nt-Bu2)2]2+ has been synthesized. It is a highly active electrocatalyst for the oxidation of hydrogen in the presence of base. Finally, the turnover rate of 50 s-1 under 1.0 atm H2 at a potential of -0.77 V vs. the ferrocene couple is 5 times faster than the rate reported heretofore for any other synthetic molecular H2 oxidation catalyst.

  4. Chiral squaring

    NASA Astrophysics Data System (ADS)

    Nagy, S.

    2016-07-01

    We construct the states and symmetries of N = 4 super-Yang-Mills by tensoring two N = 1 chiral multiplets and introducing two extra SUSY generators. This allows us to write the maximal N = 8 supergravity as four copies of the chiral multiplet. We extend this to higher dimensions and discuss applications to scattering amplitudes.

  5. Stabilizing subnanometer Ag(0) nanoclusters by thiolate and diphosphine ligands and their crystal structures

    NASA Astrophysics Data System (ADS)

    Yang, Huayan; Wang, Yu; Zheng, Nanfeng

    2013-03-01

    The combined use of thiolate and diphosphine as surface ligands helps to stabilize subnanometer Ag(0) nanoclusters, resulting in the successful crystallization of two Ag(0)-containing nanoclusters (Ag16 and Ag32) for X-ray single crystal analysis. Both clusters have core-shell structures with Ag86+ and Ag2212+ as their cores, which are not simply either fragments of face-centered cubic metals or their five-fold twinned counterparts. The clusters display UV-Vis absorption spectra consisting of molecule-like optical transitions.The combined use of thiolate and diphosphine as surface ligands helps to stabilize subnanometer Ag(0) nanoclusters, resulting in the successful crystallization of two Ag(0)-containing nanoclusters (Ag16 and Ag32) for X-ray single crystal analysis. Both clusters have core-shell structures with Ag86+ and Ag2212+ as their cores, which are not simply either fragments of face-centered cubic metals or their five-fold twinned counterparts. The clusters display UV-Vis absorption spectra consisting of molecule-like optical transitions. Electronic supplementary information (ESI) available: Experimental details, more pictures of the structure and XPS spectra of the clusters. CCDC 916463 and 916464. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3nr34328f

  6. Soft diphosphine and diarsine complexes of niobium(V) and tantalum(V) fluorides: synthesis, properties, structures and comparisons with the corresponding chlorides.

    PubMed

    Levason, William; Light, Mark E; Reid, Gillian; Zhang, Wenjian

    2014-07-01

    The reactions of the soft diphosphines o-C6H4(PMe2)2, Me2P(CH2)2PMe2, Et2P(CH2)2PEt2 or o-C6H4(PPh2)2 with NbF5 or TaF5 in anhydrous MeCN solution produce [MF4(diphosphine)2][MF6] (M = Nb or Ta), which have been characterised by microanalysis, IR, (1)H, (19)F{(1)H}, (31)P{(1)H} and (93)Nb NMR spectroscopy. X-ray crystal structures are reported for the isomorphous [MF4{o-C6H4(PMe2)2}2][MF6], which confirm the presence of eight-coordinate (distorted dodecahedral) cations. The corresponding reactions using o-C6H4(AsMe2)2 produced [MF4{o-C6H4(AsMe2)2}2][MF6] which were similarly characterised, including by the X-ray structure of [NbF4{o-C6H4(AsMe2)2}2][NbF6]. These are very rare examples of arsine complexes of high valent metal fluorides. The chloro complexes [NbCl4{o-C6H4(PMe2)2}2]Cl, [TaCl4{o-C6H4(PMe2)2}2][TaCl6], [NbCl4{Me2P(CH2)2PMe2}2][NbCl6] and [MCl4{o-C6H4(AsMe2)2}2][MCl6] were prepared and their structural and spectroscopic properties compared with the fluoride analogues. Attempts to prepare diphosphine complexes of NbOF3 were unsuccessful, but the NbOCl3 complexes, [{{Me2P(CH2)2PMe2}NbOCl3}2{μ-Me2P(CH2)2PMe2}] and [{o-C6H4(PMe2)2}NbOCl3(μ-O)NbCl3(CH3CN){o-C6H4(PMe2)2}] were obtained. X-Ray structures are also reported for [NbCl4{o-C6H4(PMe2)2}2]Cl, [NbCl4{o-C6H4(AsMe2)2}2][NbCl5(OEt)], [NbCl4{o-C6H4(PMe2)2}2][NbOCl4(CH3CN)], [{{Me2P(CH2)2PMe2}NbOCl3}2{μ-Me2P(CH2)2PMe2}] and [{o-C6H4(PMe2)2}NbOCl3(μ-O)NbCl3(CH3CN){o-C6H4(PMe2)2}]. PMID:24827987

  7. Nuclear Chirality

    SciTech Connect

    Starosta, Krzysztof

    2005-04-05

    Nuclear chirality is a novel manifestation of spontaneous symmetry breaking resulting from an orthogonal coupling of angular momentum vectors in triaxial nuclei. Three perpendicular angular momenta can form two systems of opposite handedness; the time reversal operator, which reverses orientation of each of the angular momentum components, relates these two systems. The status of current experimental searches for chiral doubling of states, as well as recent progress on the theoretical side is reviewed.

  8. Isotopic chirality

    SciTech Connect

    Floss, H.G.

    1994-12-01

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

  9. Actinide cation-cation complexes

    SciTech Connect

    Stoyer, N.J.; Seaborg, G.T.

    1994-12-01

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO{sub 2}{sup +}) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO{sub 2}{sup +}; therefore, cation-cation complexes indicate something unique about AnO{sub 2}{sup +} cations compared to actinide cations in general. The first cation-cation complex, NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO{sub 2}{sup +} species, the cation-cation complexes of NpO{sub 2}{sup +} have been studied most extensively while the other actinides have not. The only PuO{sub 2}{sup +} cation-cation complexes that have been studied are with Fe{sup 3+} and Cr{sup 3+} and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, NpO{sub 2}{sup +}{center_dot}Th{sup 4+}, PuO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, and PuO{sub 2}{sup +}{center_dot}Th{sup 4+} at an ionic strength of 6 M using LIPAS are 2.4 {plus_minus} 0.2, 1.8 {plus_minus} 0.9, 2.2 {plus_minus} 1.5, and {approx}0.8 M{sup {minus}1}.

  10. Combined spectroscopic study on the growth mechanism of Diphosphine-stabilized Gold Nanoclusters

    NASA Astrophysics Data System (ADS)

    Bao, Jie; Yang, Lina; Liu, Wei; Huang, Yuanyuan; Huang, Ting; Cao, Yuanjie; Yao, Tao; Sun, Zhihu; Wei, Shiqiang

    2016-05-01

    The formation process of 1,5-Bis(diphenylphosphino) pentane (L5)-protected Au nanocluster through the reduction of precursor Au2L5Cl2 by borane-tert-butylamine (TBAB) is traced by a combination of time-dependent x-ray/UV-vis absorption spectroscopies and mass spectrometry. It is revealed that the initial generation of dual-core basic unit Au4L5 2Cl is a critical step, which allows for a subsequent size-growth process via incorporation of the existing Au monomer (Au(I)-Cl) or Au2L5 to form Au5L5 2, Au8L5 3Cl, Au10L5 4Cl and finally main Au11L5 4Cl2 This work advances one step further toward understanding the mechanism of formation and growth of diphosphine ligands-protected Au NCs.

  11. Hydrogen Oxidation Catalysis by a Nickel Diphosphine Complex with Pendant tert-Butyl Amines

    SciTech Connect

    Yang, Jenny Y.; Chen, Shentan; Dougherty, William G.; Kassel, W. S.; Bullock, R. Morris; DuBois, Daniel L.; Raugei, Simone; Rousseau, Roger J.; Dupuis, Michel; Rakowski DuBois, Mary

    2010-11-09

    A bis-diphosphine nickel complex with t-butyl functionalized pendant amines [Ni(PCy2Nt-Bu2)2]2+ has been synthesized. It is a highly active electrocatalyst for the oxidation of hydrogen in the presence of base. The turn-over rate of 50 s 1 under 1.0 atm H2 at a potential of –0.77 V vs the ferrocene couple is 5 times faster than the rate reported heretofore for any other molecular H2 oxidation catalyst. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. Computational resources were provided by the Environmental Molecular Science Laboratory (EMSL) and the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory.

  12. Biferrocene-Based Diphosphine Ligands: Synthesis and Application of Walphos Analogues in Asymmetric Hydrogenations

    PubMed Central

    2013-01-01

    A total of four biferrocene-based Walphos-type ligands have been synthesized, structurally characterized, and tested in the rhodium-, ruthenium- and iridium-catalyzed hydrogenation of alkenes and ketones. Negishi coupling conditions allowed the biferrocene backbone of these diphosphine ligands to be built up diastereoselectively from the two nonidentical and nonracemic ferrocene fragments (R)-1-(N,N-dimethylamino)ethylferrocene and (SFc)-2-bromoiodoferrocene. The molecular structures of (SFc)-2-bromoiodoferrocene, the coupling product, two ligands, and the two complexes ([PdCl2(L)] and [RuCl(p-cymene)(L)]PF6) were determined by X-ray diffraction. The structural features of complexes and the catalysis results obtained with the newly synthesized biferrocene-based ligands were compared with those of the corresponding Walphos ligands. PMID:23457421

  13. Diphosphine is an intermediate in the photolysis of phosphine to phosphorus and hydrogen. [Jupiter atmospheric chemistry

    NASA Technical Reports Server (NTRS)

    Ferris, J. P.; Benson, R.

    1980-01-01

    The photolysis of phosphine to red phosphorus (P4) and hydrogen is investigated in light of the potential significance of the reaction in the atmospheric chemistry of Jupiter. It is reported that the photolysis of PH3 at room temperature by a 206.2-nm light source gave rise to a product identified by its UV and IR spectra and gas chromatographic retention time as P2H4, the yield of which is found to increase to a maximum and then decrease to 20% of the maximum value with illumination time. A mechanism for phosphine photolysis including diphosphine formation as an intermediate step is proposed, and it is concluded that P2H4 is a likely constituent of the atmospheres of the Jovian planets.

  14. Prebiotic chirality

    NASA Astrophysics Data System (ADS)

    Mekki-Berrada, Ali

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

  15. Bioinspired Hydrogenase Models: The Mixed-Valence Triiron Complex [Fe3(CO)7(μ-edt)2] and Phosphine Derivatives [Fe3(CO)7–x(PPh3)x(μ-edt)2] (x = 1, 2) and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2] as Proton Reduction Catalysts

    PubMed Central

    2014-01-01

    The mixed-valence triiron complexes [Fe3(CO)7–x(PPh3)x(μ-edt)2] (x = 0–2; edt = SCH2CH2S) and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2] (diphosphine = dppv, dppe, dppb, dppn) have been prepared and structurally characterized. All adopt an anti arrangement of the dithiolate bridges, and PPh3 substitution occurs at the apical positions of the outer iron atoms, while the diphosphine complexes exist only in the dibasal form in both the solid state and solution. The carbonyl on the central iron atom is semibridging, and this leads to a rotated structure between the bridged diiron center. IR studies reveal that all complexes are inert to protonation by HBF4·Et2O, but addition of acid to the pentacarbonyl complexes results in one-electron oxidation to yield the moderately stable cations [Fe3(CO)5(PPh3)2(μ-edt)2]+ and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2]+, species which also result upon oxidation by [Cp2Fe][PF6]. The electrochemistry of the formally Fe(I)–Fe(II)–Fe(I) complexes has been investigated. Each undergoes a quasi-reversible oxidation, the potential of which is sensitive to phosphine substitution, generally occurring between 0.15 and 0.50 V, although [Fe3(CO)5(PPh3)2(μ-edt)2] is oxidized at −0.05 V. Reduction of all complexes is irreversible and is again sensitive to phosphine substitution, varying between −1.47 V for [Fe3(CO)7(μ-edt)2] and around −1.7 V for phosphine-substituted complexes. In their one-electron-reduced states, all complexes are catalysts for the reduction of protons to hydrogen, the catalytic overpotential being increased upon successive phosphine substitution. In comparison to the diiron complex [Fe2(CO)6(μ-edt)], [Fe3(CO)7(μ-edt)2] catalyzes proton reduction at 0.36 V less negative potentials. Electronic structure calculations have been carried out in order to fully elucidate the nature of the oxidation and reduction processes. In all complexes, the HOMO comprises an iron–iron bonding orbital localized between the two iron

  16. Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P C bond cleavage in the unsaturated cluster 1,1-Os3(CO)9(bmf): Synthesis and X-ray diffraction structures of the isomeric Os3(CO)10(bmf) clusters and HOs3(CO)8( -C6H4)[ -PhPCC(Ph2P)CH(OMe)OC(O)

    SciTech Connect

    Kandala, Srikanth; Yang, Li; Campana, Charles F.; Nesterov, Vladimir; Richmond, Michael G.

    2010-07-01

    The labile cluster 1,2-Os3(CO)10(MeCN)2 (1) reacts with the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) to furnish 1,2-Os3(CO)10(bmf) (2a) in high yield. Heating cluster 2a over the temperature range 358 383 K under CO leads to isomerization of the bmf ligand and formation of the diphosphine-chelated cluster 1,1-Os3(CO)10(bmf) (2b) and an equilibrium mixture consisting of 2a and 2b in a 15:85 ratio. Extended thermolysis of an equilibrium mixture of Os3(CO)10(bmf) is accompanied by CO loss and ortho-metalation of an aryl ring to afford an inseparable mixture of three diastereomeric hydride clusters HOs3(CO)9(C29H23O3P2) (3a c). Thermolysis of HOs3(CO)9(C29H23O3P2) (3a c) in refluxing toluene leads to P C bond cleavage and formation of the benzyne-substituted clusters HOs3(CO)8( -C6H4)( -C23H19O3P2) (4a,b) as a 4:1 mixture of diastereomers. The unequivocal identity of the major benzyne-substituted cluster has been determined by X-ray diffraction analysis, where the activation of one of the phenyl groups situated to the furanone carbonyl group in the bmf ligand has been established. The isomerization and activation of the bmf ligand are contrasted with other Os3(CO)10(diphosphine) derivatives prepared by our groups.

  17. Chiral streamers

    SciTech Connect

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

    2015-10-15

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

  18. Preparation of a diphosphine with persistent phosphinyl radical character in solution: characterization, reactivity with O2, S8, Se, Te, and P4, and electronic structure calculations.

    PubMed

    Giffin, Nick A; Hendsbee, Arthur D; Roemmele, Tracey L; Lumsden, Michael D; Pye, Cory C; Masuda, Jason D

    2012-11-01

    A new, easily synthesized diphosphine based on a heterocyclic 1,3,2-diazaphospholidine framework has been prepared. Due to the large, sterically encumbering Dipp groups (Dipp = 2,6-diisopropylphenyl) on the heterocyclic ring, the diphosphine undergoes homolytic cleavage of the P-P bond in solution to form two phosphinyl radicals. The diphosphine has been reacted with O(2), S(8), Se, Te, and P(4), giving products that involve insertion of elements between the P-P bond to yield the related phosphinic acid anhydride, sulfide/disulfide, selenide, telluride, and a butterfly-type perphospha-bicyclobutadiene structure with a trans,trans-geometry. All molecules have been characterized by multinuclear NMR spectroscopy, elemental analysis, and single-crystal X-ray crystallography. Variable-temperature EPR spectroscopy was utilized to study the nature of the phosphinyl radical in solution. Electronic structure calculations were performed on a number of systems from the parent diphosphine [H(2)P](2) to amino-substituted [(H(2)N)(2)P](2) and cyclic amino-substituted [(H(2)C)(2)(NH)(2)P](2); then, bulky substituents (Ph or Dipp) were attached to the cyclic amino systems. Calculations on the isolated diphosphine at the B3LYP/6-31+G* level show that the homolytic cleavage of the P-P bond to form two phosphinyl radicals is favored over the diphosphine by ~11 kJ/mol. Furthermore, there is a significant amount of relaxation energy stored in the ligands (52.3 kJ/mol), providing a major driving force behind the homolytic cleavage of the central P-P bond.

  19. Systematic Introduction of Aromatic Rings to Diphosphine Ligands for Emission Color Tuning of Dinuclear Copper(I) Iodide Complexes.

    PubMed

    Okano, Yuka; Ohara, Hiroki; Kobayashi, Atsushi; Yoshida, Masaki; Kato, Masako

    2016-06-01

    We have newly synthesized two solution-stable luminescent dinuclear copper(I) complexes, [Cu2(μ-I)2(dpppy)2] (Cu-py) and [Cu2(μ-I)2(dpppyz)2] (Cu-pyz), where dpppy = 2,3-bis(diphenylphosphino)pyridine and dpppyz = 2,3-bis(diphenylphosphino)pyrazine, using chelating diphosphine ligands composed of N-heteroaromatic rings. X-ray analysis clearly indicates that the molecular structures of Cu-py and Cu-pyz are almost identical with that of the parent complex, [Cu2(μ-I)2(dppb)2] [Cu-bz; dppb = 2,3-bis(diphenylphosphino)benzene]. Complexes Cu-py and Cu-pyz exhibit luminescence [emission quantum yield (Φem) = 0.48 and 0.02, respectively] in the solid state at 298 K. A wide emission color tuning, from 497 to 638 nm (energy = 0.55 eV, with an emission color ranging from green to reddish-orange), was achieved in the solid state by the introduction of pyridinic N atoms into the bridging phenyl group between the two diphenylphosphine groups. Density functional theory calculations suggest that the emission could originate from the effective combination of the metal-to-ligand charge-transfer excited state with the halide-to-ligand charge-transfer excited state. Thus, the emission color change is due to stabilization of the π* levels of the central aryl group in the diphosphine ligand. Furthermore, these copper(I) complexes exhibit thermally activated delayed fluorescence at 298 K because of the small singlet-triplet energy difference (ΔE = 523 and 564 cm(-1) for Cu-py and Cu-pyz, respectively). The stability of these complexes in chloroform, due to the rigid bonds between the diphosphine ligands and the Cu(I) ions, enables the preparation of emissive poly(methyl methacrylate) films by the solution-doping technique. PMID:27152774

  20. Ligand substitution behavior of Ru6(mu6-C)(CO)17 with unsaturated diphosphines: facile capping of a polyhedral face and photochemically promoted P C bond cleavage in the cluster Ru6(mu6-C)(CO)14(mu3-bpcd)

    SciTech Connect

    Kandala, Srikanth; Hammons, Casey; Watson, William H.; Wang, Xiaoping; Richmond, Michael G.

    2010-01-01

    The ligand substitution chemistry of the hexaruthenium cluster Ru-6(mu(6)-C)(CO)(17) (1) with several unsaturated diphosphine ligands has been investigated. Thermolysis of 1 with (Z)-Ph2PCH=CHPPh2 (dppen) furnishes the new cluster compounds Ru-5(mu(5)-C)(CO)(12)(mu(3)-dppen) (2), Ru-6(mu(6)-C)(CO)(14)(mu(3)-dppen) (3), and Ru-6(mu(6)-C)(CO)(12)(mu(3)-dppen)(mu-dppen) (4). Clusters 2 and 3 are also obtained when a mixture of 1 and dppen is treated with the oxidative-decarbonylation reagent Me3NO. Thermolysis or Me3NO activation of 1 in the presence of 4,5-bis(diphenylphosphino)-4-cyclopenten- 1,3-dione (bpcd) yields Ru-6(mu(6)-C)(CO)(14)(mu(3)-bpcd) (4) as the sole observable product. Near-UV irradiation of 4 leads to P-C bond cleavage and the formation of phosphido-bridged cluster Ru-6(mu(6)-C)(CO)(13)[mu(3)-C=C(PPh2)C(O)CH2C(O)](mu-PPh2) (6) in essentially quantitative yield. The reaction between 1 and the ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) leads to the formation of Ru-6(mu(6)-C)(CO)(14)(mu(3)-bmf) (7), which exists as a single diastereomer in solution as shown by H-1 and P-31 NMR spectroscopy. The molecular structures and the binding mode of the ancillary diphosphine ligand(s) in 2-7 have all been established by X-ray diffraction analyses. The solid-state structure of 7 reveals that the chiral bmf ligand caps one of the metallic faces stereospecifically with the 5-methoxy moiety oriented distal or trans relative to the Ru-6 polyhedral core. The new substitution products are discussed relative to the products obtained from 1 and the related diphosphine ligands dppm, dppe, dppf, and dppbz.

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

    PubMed

    Wernisch, Stefanie; Pell, Reinhard; Lindner, Wolfgang

    2012-07-01

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

  2. Chiral mirrors

    NASA Astrophysics Data System (ADS)

    Plum, Eric; Zheludev, Nikolay I.

    2015-06-01

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

  3. Chiral shielding

    SciTech Connect

    Babukhadia, L.; Berdnikov, Ya. A.; Ivanov, A. N.; Scadron, M. D.

    2000-08-01

    We demonstrate how a chiral soft pion theorem (SPT) shields the scalar meson ground-state isoscalar {sigma}(600-700) and isospinor {kappa}(800-900) from detection in a{sub 1}{yields}{pi}({pi}{pi}){sub swave}, {gamma}{gamma}{yields}2{pi}{sup 0}, {pi}{sup -}p{yields}{pi}{sup -}{pi}{sup +}n and K{sup -}p{yields}K{sup -}{pi}{sup +}n processes. While pseudoscalar meson PVV transitions are known to be determined by (only) quark loop diagrams, the above SPT also constrains scalar meson SVV transitions to be governed (only) by meson loop diagrams. We apply this latter SVV theorem to a{sub 0}{yields}{gamma}{gamma} and f{sub 0}{yields}{gamma}{gamma} decays. (c) 2000 The American Physical Society.

  4. Understanding complex chiral plasmonics.

    PubMed

    Duan, Xiaoyang; Yue, Song; Liu, Na

    2015-11-01

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

  5. Regioselective synthesis of chiral dimethyl-bis(ethylenedithio)tetrathiafulvalene sulfones

    PubMed Central

    Pop, Flavia

    2015-01-01

    Summary Enantiopure (R,R) and (S,S)-dimethyl-bis(ethylenedithio)tetrathiafulvalene monosulfones have been synthesized by the aerial oxidation of the chiral dithiolates generated from the propionitrile-protected precursors. Both enantiomers crystallize in the orthorhombic chiral space group P212121. They show a boat-type conformation of the TTF moiety, a rather rigid dithiin sulfone ring and the methyl groups in a bisequatorial conformation. Cyclic voltammetry measurements indicate fully reversible oxidation in radical cation and dication species. PMID:26199666

  6. Chiral separation of new designer drugs (Cathinones) on chiral ion-exchange type stationary phases.

    PubMed

    Wolrab, Denise; Frühauf, Peter; Moulisová, Alena; Kuchař, Martin; Gerner, Christopher; Lindner, Wolfgang; Kohout, Michal

    2016-02-20

    We present the enantioseparation of new designer drugs from the cathinone family on structurally different chiral ion-exchange type stationary phases. A novel strong cation-exchange type chiral stationary phase was synthesized and its performance compared with previously reported ion-exchange type chiral stationary phases. The influence of structural elements of the chiral selectors on their chromatographic performance was studied and the possibilities of tuning chromatographic parameters by varying the polarity of the employed mobile phases were determined. Evidence is provided that a change in mobile phase composition strongly influences the solvation shell of the polarized and polarizable units of the selectors and analytes, as well as ionizable mobile phase additives. Furthermore, the structural features of the selectors (e.g. the size of aromatic units and their substitution pattern) are shown to play a key role in the effective formation of diastereomeric complexes with analytes. Thus, we have achieved the enantioseparation of all test analytes with a mass spectrometry-compatible mobile phase with a chiral strong cation-exchange type stationary phase.

  7. Protonation of ferrous dinitrogen complexes containing a diphosphine ligand with a pendent amine.

    PubMed

    Heiden, Zachariah M; Chen, Shentan; Mock, Michael T; Dougherty, William G; Kassel, W Scott; Rousseau, Roger; Bullock, R Morris

    2013-04-01

    The addition of acids to ferrous dinitrogen complexes [FeX(N2)(P(Et)N(Me)P(Et))(dmpm)](+) (X = H, Cl, or Br; P(Et)N(Me)P(Et) = Et2PCH2N(Me)CH2PEt2; and dmpm = Me2PCH2PMe2) gives protonation at the pendent amine of the diphosphine ligand rather than at the dinitrogen ligand. This protonation increased the νN2 band of the complex by 25 cm(-1) and shifted the Fe(II/I) couple by 0.33 V to a more positive potential. A similar IR shift and a slightly smaller shift of the Fe(II/I) couple (0.23 V) was observed for the related carbonyl complex [FeH(CO)(P(Et)N(Me)P(Et))(dmpm)](+). [FeH(P(Et)N(Me)P(Et))(dmpm)](+) was found to bind N2 about three times more strongly than NH3. Computational analysis showed that coordination of N2 to Fe(II) centers increases the basicity of N2 (vs free N2) by 13 and 20 pKa units for the trans halides and hydrides, respectively. Although the iron center increases the basicity of the bound N2 ligand, the coordinated N2 is not sufficiently basic to be protonated. In the case of ferrous dinitrogen complexes containing a pendent methylamine, the amine site was determined to be the most basic site by 30 pKa units compared to the N2 ligand. The chemical reduction of these ferrous dinitrogen complexes was performed in an attempt to increase the basicity of the N2 ligand enough to promote proton transfer from the pendent amine to the N2 ligand. Instead of isolating a reduced Fe(0)-N2 complex, the reduction resulted in isolation and characterization of HFe(Et2PC(H)N(Me)CH2PEt2)(P(Et)N(Me)P(Et)), the product of oxidative addition of the methylene C-H bond of the P(Et)N(Me)P(Et) ligand to Fe.

  8. Introduction to chiral symmetry

    SciTech Connect

    Koch, V.

    1996-01-08

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

  9. Synthesis and reactivity of molybdenum and tungsten bis(dinitrogen) complexes supported by diphosphine chelates containing pendant amines

    SciTech Connect

    Weiss, Charles J.; Groves, Amy N.; Mock, Michael T.; Dougherty, William G.; Kassel, W. S.; Helm, Monte L.; DuBois, Daniel L.; Bullock, R. Morris

    2012-04-30

    In this study, we report the synthesis and characterization of molybdenum bis(dinitrogen) complexes supported by two PNP diphosphine ligands, Mo(N{sub 2}){sub 2}(PNP){sub 2}; PNP = [(R{sub 2}PCH{sub 2}){sub 2}N(R'), R = Et (ethyl), Ph (phenyl); R'= Me (methyl), Bn (benzyl)], and a series of tungsten bis(dinitrogen) complexes containing one or two PNP ligands, W(N{sub 2}){sub 2}(dppe)(PNP) and W(N{sub 2}){sub 2}(PNP){sub 2}, respectively, and the analogues complexes without pendant amines for comparison. These Mo- and W-N{sub 2} complexes were characterized by NMR, IR, spectroscopy, cyclic voltammetry and structurally characterized by X-ray crystallography. In addition, reactivity of the complexes with CO is described.

  10. Syntheses and Structural Characterizations of Iron(II) Complexes Containing Cyclic Diphosphine Ligands with Positioned Pendant Nitrogen Bases

    SciTech Connect

    Jacobsen, George M.; Shoemaker, R. K.; McNevin, Michael J.; Rakowski DuBois, Mary; DuBois, Daniel L.

    2007-09-24

    A series of new iron(II) complexes that contain cyclic diphosphine ligands with pendant amine bases, P2RN2R’, have been synthesized and characterized (where P2RN2R’ are substituted 1,5-diaza-3,7-diphosphacyclooctanes). These compounds include [Fe(P2PhN2Ph)(CH3CN)4](BF4)2 (1), cis-[Fe(CH3CN)2(P2PhN2Ph)2](BF4)2 (2a), cis-[Fe(CH3CN)2(P2CyN2Bz)2](BF4)2 (2b), cis-Fe(CH3CN)2(P2PhN2Bz)2](BF4)2 (2c), cis-Fe (P2PhN2Ph)2(Cl)2 (3), and trans-[HFe(CH3CN)(P2PhN2Ph)2](BF4), (4). The molecular structures of 1, 2b, and 4 have been confirmed by X-ray diffraction studies. For all complexes the cyclic diphosphine ligands contain one six-membered ring in a chair conformation and one six-membered ring in a boat conformation. For complex 4, the two rings that are in boat conformations result in N--H distances between the pendant amine nitrogens and the hydride ligand of 2.6 to 2.7 Å. Protonation of the pendant bases in complex 4 have been found to form several products. A structural assignment for a dominant protonated isomer has been assigned on the basis of 1H, 31P and 15N spectroscopic techniques. This work was supported by Grant CHE-0240106 from the National Science Foundation. D. L. D. acknowledges the support of the Office of Basic Energy Sciences of the Department of Energy, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  11. Chiral symmetry and chiral-symmetry breaking

    SciTech Connect

    Peskin, M.E.

    1982-12-01

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

  12. Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(II).

    PubMed

    Das, Atanu K; Engelhard, Mark H; Lense, Sheri; Roberts, John A S; Bullock, R Morris

    2015-07-21

    Covalent tethering of P(Ph)2N(C6H4C≡CH)2 ligands (P(Ph)2N(C6H4C≡CH)2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) coupling reaction, using a BH3←P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [Ni(II)(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents Ni(II) per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, P(Ph)2N(Ph)2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [Ni(II)(diphosphine)2](2+) complex. PMID:25811536

  13. Water tuned the helical nanostructures and supramolecular chirality in organogels.

    PubMed

    Liu, Changxia; Jin, Qingxian; Lv, Kai; Zhang, Li; Liu, Minghua

    2014-04-11

    Water was found to tune the self-assembled nanostructures of a cationic amphiphile in organic solvents from nanofibers to helical tapes, helical tubes and chiral nanotwists with various pitch lengths depending on water content. Inversion of CD spectra was observed in the water-triggered polar and non-polar solvent gels.

  14. Chiral rotational spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  15. Chiral atomically thin films

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  16. Characterizing optical chirality

    SciTech Connect

    Bliokh, Konstantin Y.; Nori, Franco

    2011-02-15

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

  17. Chiral atomically thin films

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  18. Asymmetric catalytic hydrogenation. Design of new Ru catalysts and chiral ligands: from laboratory to industrial applications.

    PubMed

    Genet, Jean-Pierre

    2003-12-01

    This Account covers the design of Ru catalysts and ligands. Two classes of chiral phosphine ligands are prepared: the electron-rich trans-2,4-substituted phosphetanes, readily available from optically pure 1,3-diol cyclic sulfates, and atropoisomeric ligands (SYNPHOS, MeO-NAPhePHOS, bearing heterotopic biaryl moieties, and a chiral water-soluble diguanidinium binaphthyl diphosphine, Digm-BINAP). Applications of these ligands to rhodium- and ruthenium-mediated hydrogenation of ketones and olefins have been reported with high enantioselectivities. The recognition abilities of Ru-SYNPHOS for a wide range of ketones is superior to those observed with BINAP, MeO-NAPhePHOS, and MeO-BIPHEP. Several biologically active compounds have been prepared through dynamic kinetic resolution. This work gives access to a number of highly active catalysts of the type [Ru(biphosphane)(H)(eta(6)-cot)]BF(4). These catalysts have demonstrated their utility in the enantioselective hydrogenation of the tetrasubstituted cyclopentenone "dehydrodione", which leads to the commercially important perfume component Paradisone (Firmenich).

  19. High Catalytic Rates for Hydrogen Production Using Nickel Electrocatalysts with Seven-Membered Diphosphine Ligands Containing One Pendent Amine

    SciTech Connect

    Stewart, Michael P.; Ho, Ming-Hsun; Wiese, Stefan; Lindstrom, Mary L.; Thogerson, Colleen E.; Raugei, Simone; Bullock, R. Morris; Helm, Monte L.

    2013-04-24

    A series of Ni-based electrocatalysts, [Ni(7PPh2NC6H4X)2](BF4)2, featuring seven-membered cyclic diphosphine ligands incorporating a single amine base, 1-para-X-phenyl-3,6-triphenyl-1-aza-3,6-diphosphacycloheptane (7PPh2NC6H4X where X = OMe, Me, Br, Cl or CF3), have been synthesized and characterized. X-ray diffraction studies have established that the [Ni(7PPh2NC6H4X)2]2+ complexes have a square planar geometry, with bonds to four phosphorus atoms of the two bidentate diphosphine ligands. Coordination of the bidentate phosphine ligands to Ni result in one six-membered ring containing a pendent amine, and one five membered ring. Each of the complexes is an efficient electrocatalyst for hydrogen production at the potential of the Ni(II/I) couple, with turnover frequencies ranging from 2,400 to 27,000 s-1 with [(DMF)H]+ in acetonitrile. Addition of water (up to 1.0 M) accelerates the catalysis, giving turnover frequencies ranging from 4,100 - 96,000 s-1. Computational studies carried out on the [Ni(7PPh2NC6H4X)2]2+ family indicate the catalytic rates reach a maximum when the electron-donating character of X results in the pKa of the pendent amine matching that of the acid used for proton delivery. Additionally, the fast catalytic rates for hydrogen production by the [Ni(7PPh2NC6H4X)2]2+ family relative to the analogous [Ni(PPh2NC6H4X2)2]2+ family are attributed to preferred formation of endo protonated isomers with respect to the metal center in the former, which is essential for the protons to attain suitable proximity to the reduced metal center to generate H2. The results of this work highlight the importance of the necessity for precise pKa matching with the acid for proton delivery to the metal center, and the mechanistic details described herein will be used to guide future catalyst design. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of

  20. Chiral geometry in multiple chiral doublet bands

    NASA Astrophysics Data System (ADS)

    Zhang, Hao; Chen, Qibo

    2016-02-01

    The chiral geometry of multiple chiral doublet bands with identical configuration is discussed for different triaxial deformation parameters γ in the particle rotor model with . The energy spectra, electromagnetic transition probabilities B(M1) and B(E2), angular momenta, and K-distributions are studied. It is demonstrated that the chirality still remains not only in the yrast and yrare bands, but also in the two higher excited bands when γ deviates from 30°. The chiral geometry relies significantly on γ, and the chiral geometry of the two higher excited partner bands is not as good as that of the yrast and yrare doublet bands. Supported by Plan Project of Beijing College Students’ Scientific Research and Entrepreneurial Action, Major State 973 Program of China (2013CB834400), National Natural Science Foundation of China (11175002, 11335002, 11375015, 11461141002), National Fund for Fostering Talents of Basic Science (NFFTBS) (J1103206), Research Fund for Doctoral Program of Higher Education (20110001110087) and China Postdoctoral Science Foundation (2015M580007)

  1. Chirality-Discriminated Conductivity of Metal-Amino Acid Biocoordination Polymer Nanowires.

    PubMed

    Zheng, Jianzhong; Wu, Yijin; Deng, Ke; He, Meng; He, Liangcan; Cao, Jing; Zhang, Xugang; Liu, Yaling; Li, Shunxing; Tang, Zhiyong

    2016-09-27

    Biocoordination polymer (BCP) nanowires are successfully constructed through self-assembly of chiral cysteine amino acids and Cd cations in solution. The varied chirality of cysteine is explored to demonstrate the difference of BCP nanowires in both morphology and structure. More interestingly and surprisingly, the electrical property measurement reveals that, although all Cd(II)/cysteine BCP nanowires behave as semiconductors, the conductivity of the Cd(II)/dl-cysteine nanowires is 4 times higher than that of the Cd(II)/l-cysteine or Cd(II)/d-cysteine ones. The origin of such chirality-discriminated characteristics registered in BCP nanowires is further elucidated by theoretical calculation. These findings demonstrate that the morphology, structure, and property of BCP nanostructures could be tuned by the chirality of the bridging ligands, which will shed light on the comprehension of chirality transcription as well as construction of chirality-regulated functional materials. PMID:27556354

  2. Chirality-Discriminated Conductivity of Metal-Amino Acid Biocoordination Polymer Nanowires.

    PubMed

    Zheng, Jianzhong; Wu, Yijin; Deng, Ke; He, Meng; He, Liangcan; Cao, Jing; Zhang, Xugang; Liu, Yaling; Li, Shunxing; Tang, Zhiyong

    2016-09-27

    Biocoordination polymer (BCP) nanowires are successfully constructed through self-assembly of chiral cysteine amino acids and Cd cations in solution. The varied chirality of cysteine is explored to demonstrate the difference of BCP nanowires in both morphology and structure. More interestingly and surprisingly, the electrical property measurement reveals that, although all Cd(II)/cysteine BCP nanowires behave as semiconductors, the conductivity of the Cd(II)/dl-cysteine nanowires is 4 times higher than that of the Cd(II)/l-cysteine or Cd(II)/d-cysteine ones. The origin of such chirality-discriminated characteristics registered in BCP nanowires is further elucidated by theoretical calculation. These findings demonstrate that the morphology, structure, and property of BCP nanostructures could be tuned by the chirality of the bridging ligands, which will shed light on the comprehension of chirality transcription as well as construction of chirality-regulated functional materials.

  3. High affinity of water-soluble cryptophanes for cesium cations.

    PubMed

    Brotin, Thierry; Montserret, Roland; Bouchet, Aude; Cavagnat, Dominique; Linares, Mathieu; Buffeteau, Thierry

    2012-01-20

    Exceptionally high affinity for cesium cations was achieved in aqueous solution using two enantiopure cryptophanes. Complexation of cesium was evidenced by (133)Cs NMR spectroscopy and by electronic circular dichroism (ECD). Binding constants as high as 6 × 10(9) M(-1) have been measured by isothermal titration calorimetry (ITC). Very strong complexation of rubidium cations (K ~10(6) M(-1)) has also been measured. Chiral hosts allowed the detection of the two cations at low concentrations (μM) using ECD.

  4. Chiral discrimination by ionic liquids: impact of ionic solutes.

    PubMed

    Brown, Christopher J; Hopkins, Todd A

    2015-04-01

    Chiral ionic liquids hold promise in many asymmetric applications. This study explores the impact of ionic solutes on the chiral discrimination of five amino acid methyl ester-based ionic liquids, including L- and D-alanine methyl ester, L-proline methyl ester, L-leucine methyl ester, and L-valine methyl ester cations combined with bis(trifluoromethanesulfonimide) anion. Circularly polarized luminescence spectroscopy was used to study the chiral discrimination by measuring the racemization equilibrium of a dissymmetric europium complex, Eu(dpa)3(3-) (where dpa = 2,6-pyridinedicarboxylate). The chiral discrimination measured was dependent on the concentration of Eu(dpa)3(3-) and this concentration-dependence was different in each of the ionic liquids. Ionic liquids with L-leucine methyl ester and L-valine methyl ester even switched enantiomeric preference based on the solute concentration. Changing the cation of the Eu(dpa)3(3-) salt from tetrabutylammonium to tetramethylammonium ion also affected the chiral discrimination demonstrated by the ionic liquids.

  5. Molecular model for chirality phenomena

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    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.

  6. The covariant chiral ring

    NASA Astrophysics Data System (ADS)

    Bourget, Antoine; Troost, Jan

    2016-03-01

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

  7. Synthesis of Chiral Cyclopentenones.

    PubMed

    Simeonov, Svilen P; Nunes, João P M; Guerra, Krassimira; Kurteva, Vanya B; Afonso, Carlos A M

    2016-05-25

    The cyclopentenone unit is a very powerful synthon for the synthesis of a variety of bioactive target molecules. This is due to the broad diversity of chemical modifications available for the enone structural motif. In particular, chiral cyclopentenones are important precursors in the asymmetric synthesis of target chiral molecules. This Review provides an overview of reported methods for enantioselective and asymmetric syntheses of cyclopentenones, including chemical and enzymatic resolution, asymmetric synthesis via Pauson-Khand reaction, Nazarov cyclization and organocatalyzed reactions, asymmetric functionalization of the existing cyclopentenone unit, and functionalization of chiral building blocks. PMID:27101336

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  9. Spintronics: Chiral damping

    PubMed Central

    Kim, Kyoung-Whan; Lee, Hyun-Woo

    2016-01-01

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

  10. Nonlinear chiral transport phenomena

    NASA Astrophysics Data System (ADS)

    Chen, Jiunn-Wei; Ishii, Takeaki; Pu, Shi; Yamamoto, Naoki

    2016-06-01

    We study the nonlinear responses of relativistic chiral matter to the external fields such as the electric field E , gradients of temperature and chemical potential, ∇T and ∇μ . Using the kinetic theory with Berry curvature corrections under the relaxation time approximation, we compute the transport coefficients of possible new electric currents that are forbidden in usual chirally symmetric matter but are allowed in chirally asymmetric matter by parity. In particular, we find a new type of electric current proportional to ∇μ ×E due to the interplay between the effects of the Berry curvature and collisions. We also derive an analog of the "Wiedemann-Franz" law specific for anomalous nonlinear transport in relativistic chiral matter.

  11. The quest for chirality

    SciTech Connect

    Bonner, W.A.

    1996-07-01

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

  12. Arene C-H amination at nickel in terphenyl-diphosphine complexes with labile metal-arene interactions.

    PubMed

    Herbert, David E; Lara, Nadia C; Agapie, Theodor

    2013-11-25

    The meta-terphenyl diphosphine, m-P2, 1, was utilized to support Ni centers in the oxidation states 0, I, and II. A series of complexes bearing different substituents or ligands at Ni was prepared to investigate the dependence of metal-arene interactions on oxidation state and substitution at the metal center. Complex (m-P2)Ni (2) shows strong Ni(0)-arene interactions involving the central arene ring of the terphenyl ligand both in solution and the solid state. These interactions are significantly less pronounced in Ni(0) complexes bearing L-type ligands (2-L: L=CH3CN, CO, Ph2CN2), Ni(I)X complexes (3-X: X=Cl, BF4, N3, N3B(C6F5)3), and [(m-P2)Ni(II)Cl2] (4). Complex 2 reacts with substrates, such as diphenyldiazoalkane, sulfur ylides (Ph2 S=CH2 ), organoazides (RN3: R=para-C6H4OMe, para-C6H4CF3, 1-adamantyl), and N2O with the locus of observed reactivity dependent on the nature of the substrate. These reactions led to isolation of an η(1)-diphenyldiazoalkane adduct (2-Ph2CN2), methylidene insertion into a Ni-P bond followed by rearrangement of a nickel-bound phosphorus ylide (5) to a benzylphosphine (6), Staudinger oxidation of the phosphine arms, and metal-mediated nitrene insertion into an arene C-H bond of 1, all derived from the same compound (2). Hydrogen-atom abstraction from a Ni(I)-amide (9) and the resulting nitrene transfer supports the viability of Ni-imide intermediates in the reaction of 1 with 1-azido-arenes.

  13. X-ray-Excited Optical Luminescence (XEOL) and X-ray Absorption Fine Structures (XAFS) Studies of Gold(I) Complexes with Diphosphine and Bipyridine Ligands

    SciTech Connect

    Kim, Pil-Sook G.; Hu, Yongfeng; Brandys, Marie-C.; Burchell, Tara J.; Puddephatt, Richard J.; Sham, Tsun K.

    2008-10-14

    Synchrotron techniques, X-ray-excited optical luminescence (XEOL) combined with X-ray absorption fine structures (XAFS), have been used to study the electronic structure and optical properties of a series of luminescent gold(I) complexes with diphosphine and bipyridine ligands using tunable X-rays (in the regions of the C and P K-edges and the Au L{sub 3}-edge) and UV from synchrotron light sources. The effects of gold-ligand and aurophilic interactions on the luminescence from these gold(I) complexes have been investigated. It is found that the luminescence from these complexes is phosphorescence, primarily due to the decay of the Au (5d) {yields} PR{sub 3} ({pi}*), metal to ligand charge transfer (MLCT) excitation as well as contributions from the conjugated {pi}-system in the bipyridine ligands via the gold-nitrogen bond. The large Au 5d spin-orbit coupling enhances the intersystem crossing. The elongation of the hydrocarbon chain of the diphosphine ligand does not greatly affect the spectral features of the luminescence from the gold(I) complexes. However, the intensity of the luminescence was reduced significantly when the bipyridine ligand was replaced with 1,2-bis(4-pyridylamido)benzene. The aurophilic interaction, as investigated by EXAFS at the Au L{sub 3}-edge, is shown to be only one of the factors that contribute to the luminescence of the complexes.

  14. Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase.

    PubMed

    Chen, Xiangyang; Jing, Yuanyuan; Yang, Xinzheng

    2016-06-20

    Inspired by the active-site structure of the [NiFe] hydrogenase, we have computationally designed the iron complex [P(tBu) 2 N(tBu) 2 )Fe(CN)2 CO] by using an experimentally ready-made diphosphine ligand with pendant amines for the hydrogenation of CO2 to methanol. Density functional theory calculations indicate that the rate-determining step in the whole catalytic reaction is the direct hydride transfer from the Fe center to the carbon atom in the formic acid with a total free energy barrier of 28.4 kcal mol(-1) in aqueous solution. Such a barrier indicates that the designed iron complex is a promising low-cost catalyst for the formation of methanol from CO2 and H2 under mild conditions. The key role of the diphosphine ligand with pendent amine groups in the reaction is the assistance of the cleavage of H2 by forming a Fe-H(δ-) ⋅⋅⋅H(δ+) -N dihydrogen bond in a fashion of frustrated Lewis pairs. PMID:27225505

  15. Synthesis, Reactivity Investigation, and X-ray Diffraction Structures of New Platinum(II) Compounds Containing Redox-Active Diphosphine Ligands

    SciTech Connect

    Wang, Xiaoping; Richmond, Michael G.; Hunt, Sean W

    2009-01-01

    Substitution of the 1,5-cyclooctadiene (cod) ligand in PtCl2(cod) (1) by the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) yields PtCl2(bpcd) (2). Knoevenagel condensation of 2 with 9-anthracenecarboxaldehyde leads to the functionalization of the bpcd ligand and formation of the corresponding 2-(9-anthracenylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (abpcd) substituted compound PtCl2(abpcd) (3), which is also obtained from the direct reaction of 1 with the abpcd ligand in near quantitative yield. The reaction of 3 with disodium maleonitriledithiolate (Na2mnt) affords the chelating dithiolate compound Pt(mnt)(abpcd) (4). Compounds 2 C4 have been fully characterized in solution by IR and NMR spectroscopies (1H and 31P), and their molecular structures established by X-ray crystallography. The electrochemical properties of 2 C4 have examined by cyclic voltammetry, and the nature of the HOMO and LUMO levels in these systems has been established by MO calculations at the extended H ckel level, the results of which are discussed with respect to electrochemical data and related diphosphine derivatives.

  16. Unexpected formation of a fused double cycle trinuclear gold(i) complex supported by ortho-phenyl metallated aryl-diphosphine ligands and strong aurophilic interactions.

    PubMed

    Jobbágy, Csaba; Baranyai, Péter; Szabó, Pál; Holczbauer, Tamás; Rácz, Barbara; Li, Liang; Naumov, Panče; Deák, Andrea

    2016-08-01

    The first homoleptic trinuclear arylgold(i) complex, [Au3(L')2](NO3) (3), based on an ortho-phenyl metallated aryl-diphosphine ligand (L' = o-C6H4PPh(C15H10O)PPh2), has been obtained through a new thermolytic reaction of the corresponding diauracycle, [Au2(L)2](NO3)2 (L = xantphos). The formation of 3 involves activation of the ortho-phenyl C-H bond of the xantphos ligands. The presence of Au-C bonds in this new gold-diphosphine cluster is not its only remarkable feature, since it also displays two 12-membered rings fused together and a linear {Au3} chain with aurophilic interactions. Complex 3 exhibits strong sky-blue luminescence that can be assigned to a triplet metal-metal ((3)MM) transition partially mixed with a ligand-to-metal-metal charge transfer ((3)LMMCT) transition related to the aurophilic bonding. This [Au3(L')2](+) triauracycle also shows AIEE-activity, and is a selective luminescent chemosensor for metal ions. PMID:27439467

  17. Double interpenetration in a chiral three-dimensional magnet with a (10,3)-a structure.

    PubMed

    Grancha, Thais; Mon, Marta; Lloret, Francesc; Ferrando-Soria, Jesús; Journaux, Yves; Pasán, Jorge; Pardo, Emilio

    2015-09-21

    A unique chiral three-dimensional magnet with an overall racemic double-interpenetrated (10,3)-a structure of the formula [(S)-(1-PhEt)Me3N]4[Mn4Cu6(Et2pma)12](DMSO)3]·3DMSO·5H2O (1; Et2pma = N-2,6-diethylphenyloxamate) has been synthesized by the self-assembly of a mononuclear copper(II) complex acting as a metalloligand toward Mn(II) ions in the presence of a chiral cationic auxiliary, constituting the first oxamato-based chiral coordination polymer exhibiting long-range magnetic ordering. PMID:26322529

  18. Double interpenetration in a chiral three-dimensional magnet with a (10,3)-a structure.

    PubMed

    Grancha, Thais; Mon, Marta; Lloret, Francesc; Ferrando-Soria, Jesús; Journaux, Yves; Pasán, Jorge; Pardo, Emilio

    2015-09-21

    A unique chiral three-dimensional magnet with an overall racemic double-interpenetrated (10,3)-a structure of the formula [(S)-(1-PhEt)Me3N]4[Mn4Cu6(Et2pma)12](DMSO)3]·3DMSO·5H2O (1; Et2pma = N-2,6-diethylphenyloxamate) has been synthesized by the self-assembly of a mononuclear copper(II) complex acting as a metalloligand toward Mn(II) ions in the presence of a chiral cationic auxiliary, constituting the first oxamato-based chiral coordination polymer exhibiting long-range magnetic ordering.

  19. Chiral anomalies and differential geometry

    SciTech Connect

    Zumino, B.

    1983-10-01

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

  20. Dual chiral recognition system involving cyclodextrin derivatives in capillary electrophoresis II. Enhancement of enantioselectivity.

    PubMed

    Jakubetz, H; Juza, M; Schurig, V

    1998-05-01

    The enantiomer separation of hexobarbital was investigated by open tubular electrochromatography (OTEC) using the chiral stationary phase (CSP) CHIRASIL-DEX (a permethylated beta-cyclodextrin covalently linked to a dimethylpolysiloxane) and by cyclodextrin-electrokinetic chromatogaphy (CD-EKC) using anionic beta-cyclodextrin-sulfo-n-propyl ether (SPE-beta-CD) and cationic beta-cyclodextrin-2-hydroxy-3-trimethylammoniumpropyl ether chloride (HTAP-beta-CD) added to the running buffer. By employing two chiral selectors, the enantiomer separation of hexobarbital was then studied simultaneously by OTEC with CHIRASIL-DEX and by CD-EKC with either SPE-beta-CD or HTAP-beta-CD in the dual chiral recognition mode. In conjunction with CHIRASIL-DEX, anionic SPE-beta-CD decreased the chiral separation factor alpha due to compensation of enantioselectivity whereas the cationic additive HTAP-beta-CD increased the chiral separation factor alpha due to enhancement of enantioselectivity. It is concluded that CHIRASIL-DEX imparts an opposite enantioselectivity to the enantiomers of hexobarbital as compared to the charged CDs SPE-beta-CD and HTAP-beta-CD. Unusual peak broadening phenomena are observed in the dual chiral recognition system comprised of CHIRASIL-DEX and HTAP-beta-CD. The possible consequences of accidental dual chiral recognition systems caused by wall stacking effects of the mobile phase additives onto the inner surface of the capillary column are discussed. PMID:9629908

  1. Nanospheres, nanotubes, toroids, and gels with controlled macroscopic chirality.

    PubMed

    Arias, Sandra; Freire, Félix; Quiñoá, Emilio; Riguera, Ricardo

    2014-12-01

    The interaction of a highly dynamic poly(aryl acetylene) (poly-1) with Li(+), Na(+), and Ag(+) leads to macroscopically chiral supramolecular nanospheres, nanotubes, toroids, and gels. With Ag(+), nanospheres with M helicity and tunable sizes are generated, which complement those obtained from the same polymer with divalent cations. With Li(+) or Na(+), poly-1 yields chiral nanotubes, gels, or toroids with encapsulating properties and M helicity. Right-handed supramolecular structures can be obtained by using the enantiomeric polymer. The interaction of poly-1 with Na(+) produces nanostructures whose helicity is highly dependent on the solvation state of the cation. Therefore, structures with either of the two helicities can be prepared from the same polymer by manipulation of the cosolvent. Such chiral nanotubes, toroids, and gels have previously not been obtained from helical polymer-metal complexes. Chiral nanospheres made of poly(aryl acetylene) that were previously assembled with metal(II) species can now be obtained with metal(I) species. PMID:25209219

  2. Active Chiral Plasmonics.

    PubMed

    Yin, Xinghui; Schäferling, Martin; Michel, Ann-Katrin U; Tittl, Andreas; Wuttig, Matthias; Taubner, Thomas; Giessen, Harald

    2015-07-01

    Active control over the handedness of a chiral metamaterial has the potential to serve as key element for highly integrated polarization engineering approaches, polarization sensitive imaging devices, and stereo display technologies. However, this is hard to achieve as it seemingly involves the reconfiguration of the metamolecule from a left-handed into a right-handed enantiomer and vice versa. This type of mechanical actuation is intricate and usually neither monolithically realizable nor viable for high-speed applications. Here, enabled by the phase change material Ge3Sb2Te6 (GST-326), we demonstrate a tunable and switchable mid-infrared plasmonic chiral metamaterial in a proof-of-concept experiment. A large tunability range of the circular dichroism response from λ = 4.15 to 4.90 μm is achieved, and we experimentally demonstrate that the combination of a passive bias-type chiral layer with the active chiral metamaterial allows for switchable chirality, that is, the reversal of the circular dichroism sign, in a fully planar, layered design without the need for geometrical reconfiguration. Because phase change materials can be electrically and optically switched, our designs may open up a path for highly integrated mid-IR polarization engineering devices that can be modulated on ultrafast time scales.

  3. Chirality and Life

    NASA Astrophysics Data System (ADS)

    Barron, Laurence D.

    Chirality, meaning handedness, pervades much of modern science, from the physics of elementary particles to the chemistry of life. The amino acids and sugars from which the central molecules of life—proteins and nucleic acids—are constructed exhibit homochirality, which is expected to be a key biosignature in astrobiology. This article provides a brief review of molecular chirality and its significance for the detection of extant or extinct life on other worlds. Fundamental symmetry aspects are emphasized since these bring intrinsic physical properties of the universe to bear on the problem of the origin and role of homochirality in the living world.

  4. Chirality and Life

    NASA Astrophysics Data System (ADS)

    Barron, Laurence D.

    2008-03-01

    Chirality, meaning handedness, pervades much of modern science, from the physics of elementary particles to the chemistry of life. The amino acids and sugars from which the central molecules of life—proteins and nucleic acids—are constructed exhibit homochirality, which is expected to be a key biosignature in astrobiology. This article provides a brief review of molecular chirality and its significance for the detection of extant or extinct life on other worlds. Fundamental symmetry aspects are emphasized since these bring intrinsic physical properties of the universe to bear on the problem of the origin and role of homochirality in the living world.

  5. Molecular Basis for Chiral Selection in RNA Aminoacylation

    PubMed Central

    Tamura, Koji

    2011-01-01

    The chiral-selective aminoacylation of an RNA minihelix is a potential progenitor to modern tRNA-based protein synthesis using l-amino acids. This article describes the molecular basis for this chiral selection. The extended double helical form of an RNA minihelix with a CCA triplet (acceptor of an amino acid), an aminoacyl phosphate donor nucleotide (mimic of aminoacyl-AMP), and a bridging nucleotide facilitates chiral-selective aminoacylation. Energetically, the reaction is characterized by a downhill reaction wherein an amino acid migrates from a high-energy acyl phosphate linkage to a lower-energy carboxyl ester linkage. The reaction occurs under the restriction that the nucleophilic attack of O, from 3′-OH in the terminal CCA, to C, from C=O in the acyl phosphate linkage, must occur at a Bürgi-Dunitz angle, which is defined as the O–C=O angle of approximately 105°. The extended double helical form results in a steric hindrance at the side chain of the amino acid leading to chiral preference combined with cation coordinations in the amino acid and the phosphate oxygen. Such a system could have developed into the protein biosynthetic system with an exclusively chiral component (l-amino acids) via (proto) ribosomes. PMID:21845109

  6. Asymmetric Hydrogenation of α-Purine Nucleobase-Substituted Acrylates with Rhodium Diphosphine Complexes: Access to Tenofovir Analogues.

    PubMed

    Sun, Huan-Li; Chen, Fei; Xie, Ming-Sheng; Guo, Hai-Ming; Qu, Gui-Rong; He, Yan-Mei; Fan, Qing-Hua

    2016-05-01

    The first asymmetric hydrogenation of α-purine nucleobase-substituted α,β-unsaturated esters, catalyzed by a chiral rhodium (R)-Synphos catalyst, has been developed. A wide range of mono- and disubstituted acrylates were successfully hydrogenated under very mild conditions in high yields with good to excellent enantioselectivities (up to 99% ee). This method provides a convenient approach to the synthesis of a new kind of optically pure acyclic nucleoside and Tenofovir analogues. PMID:27112983

  7. Immobilization of a rhodium catalyst using a diphosphine-functionalized ionic liquid in RTIL for the efficient and recyclable biphasic hydroformylation of 1-octene.

    PubMed

    Li, Yong-Qi; Liu, Huan; Wang, Peng; Yang, Da; Zhao, Xiao-Li; Liu, Ye

    2016-08-15

    A highly efficient and stable Rh-P catalytic system in the RTIL of [PEmim]BF4 was developed for the biphasic hydroformylation of 1-octene by using the diphosphine-functionalized ionic liquid (FIL) of 2. While 2-Rh(acac)(CO)2 was immobilized in [PEmim]BF4 (solvent), a typical biphasic catalysis was fulfilled with advantages of facile separation and recycling ability - 9 runs without any loss of activity. It was found that not only the acquired π-acceptor character of 2, but also the synergetic role of the piperidyl group in [PEmim]BF4 as an N-containing donor, cooperatively contributed to the efficient hydroformylation due to the facilitated formation and stability of the Rh-H active species (ν 2045 cm(-1)). This was supported by the in situ high-pressure FT-IR spectral analysis.

  8. Well-defined, persistent, chiral phthalocyanine nanoclusters via G-quadruplex assembly.

    PubMed

    García-Iglesias, Miguel; Torres, Tomas; González-Rodríguez, David

    2016-07-19

    Octameric near-IR dye nanoclusters are produced by complexation of potassium cations with a phthalocyanine-guanosine conjugate. The combination of hydrogen-bonding, K(+) coordination, π-π stacking and steric interactions between the chiral side groups is responsible for defining a specific helical chromophore arrangement in the clusters, which display high stability and maintain their supramolecular identity onto substrates. PMID:27377372

  9. Optical properties of chiral nanotubes

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

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

  10. ENANTIOMER-SPECIFIC EFFECTS OF CHIRAL POLLUTANTS

    EPA Science Inventory

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

  11. Chiral Dynamics 2006

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

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

  12. Chiral symmetry and pentaquarks

    SciTech Connect

    Dmitri Diakonov

    2004-07-01

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

  13. Chiral Biomarkers in Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2010-01-01

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

  14. Molybdenum Hydride and Dihydride Complexes Bearing Diphosphine Ligands with a Pendant Amine: Formation of Complexes With Bound Amines

    SciTech Connect

    Zhang, Shaoguang; Bullock, R. Morris

    2015-07-06

    CpMo(CO)(PNP)H complexes (PNP = (R2PCH2)2NMe, R = Et or Ph) were synthesized by displacement of two CO ligands of CpMo(CO)3H by the PNP ligand; these complexes were characterized by IR and variable temperature 1H and 31P NMR spectroscopy. CpMo(CO)(PNP)H complexes are formed as mixture of cis and trans-isomers. Both cis-CpMo(CO)(PEtNMePEt)H and trans-CpMo(CO)(PPhNMePPh)H were analyzed by single crystal X-ray diffraction. Electrochemical oxidation of CpMo(CO)(PEtNMePEt)H and CpMo(CO)(PPhNMePPh)H in CH3CN are both irreversible at slow scan rates and quasi-reversible at higher scan rates, with E1/2 = -0.36 V (vs. Cp2Fe+/0) for CpMo(CO)(PEtNMePEt)H and E1/2 = -0.18 V for CpMo(CO)(PPhNMePPh)H. Hydride abstraction from CpMo(CO)(PNP)H with [Ph3C]+[A]- (A = B(C6F5)4 or BArF4; [ArF = 3,5-bis(trifluoromethyl)phenyl]) afforded “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes that feature the amine bound to the metal. Displacement of the κ3 Mo-N bond by CD3CN gives [CpMo(CO)(PNP)(CD3CN)]+. The kinetics of this reaction were studied by NMR spectroscopy, providing the activation parameters ΔH‡ = 22.1 kcal/mol, ΔS‡ = 1.89 cal/(mol·K), Ea = 22.7 kcal/mol. Protonation of CpMo(CO)(PEtNMePEt)H affords [CpMo(CO)(κ2-PEtNMePEt)(H)2]+ as a Mo dihydride complex, which loses H2 to generate [CpMo(CO)(κ3-PEtNMePEt)]+ at room temperature. CpMo(CO)(dppp)H (dppp = 1,2-bis(diphenylphosphino)propane) was studied as a Mo diphosphine analogue without a pendant amine, and the product of protonation of this complex gives [CpMo(CO)(dppp)(H)2]+. Our results show that the pendant amine has a strong driving force to form stable “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes, and also promotes hydrogen elimination from [CpMo(CO)(PNP)(H)2]+ complexes by formation of Mo-N dative bond. We thank the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences for support. Pacific Northwest National Laboratory is operated by

  15. Generalized simplicial chiral models

    NASA Astrophysics Data System (ADS)

    Alimohammadi, Masoud

    2000-02-01

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

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

    SciTech Connect

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

    2006-07-10

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

  17. Chiral microemulsion electrokinetic chromatography with two chiral components: Improved separations via synergies between a chiral surfactant and a chiral cosurfactant.

    PubMed

    Kahle, Kimberly A; Foley, Joe P

    2006-02-01

    In this study, the combination of two chiral components in a microemulsion formulation for the separation of enantiomers via microemulsion EKC (MEEKC) was successfully accomplished. Previous publications of chiral microemulsions have utilized only one chiral entity; the surfactant, cosurfactant, or oil was chiral. This is the first study, to date, of the effects of using two chiral species in a single pseudostationary phase (PSP). The chiral surfactant dodecoxycarbonylvaline (DDCV) was used in conjunction with the chiral cosurfactant S-2-hexanol. Ethyl acetate was incorporated as the oil core of the microemulsion and the buffer was 50 mM phosphate at a pH of 7. Additionally, a microemulsion prepared with racemic 2-hexanol was used for comparison to a previous DDCV microemulsion and as a baseline for the newly formulated dual chiral microemulsion. The efficiencies, resolutions, and enantioselectivities for the S-2-hexanol, racemic 2-hexanol, and original 1-butanol DDCV microemulsions are compared. The hexanol-based PSPs provide improved efficiencies and resolutions. To evaluate the combination of each DDCV enantiomer (R and S) with S-2-hexanol, changes in Gibb's free energy were calculated. A synergistic effect was found when two chiral components were combined to form a microemulsion.

  18. Chiral drag force

    NASA Astrophysics Data System (ADS)

    Rajagopal, Krishna; Sadofyev, Andrey V.

    2015-10-01

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

  19. Isothermal Titration Calorimetry of Chiral Polymeric Nanoparticles.

    PubMed

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

    2015-09-01

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

  20. Counteranion Driven Homochiral Assembly of a Cationic C3-Symmetric Gelator through Ion-Pair Assisted Hydrogen Bond.

    PubMed

    Maity, Arunava; Gangopadhyay, Monalisa; Basu, Arghya; Aute, Sunil; Babu, Sukumaran Santhosh; Das, Amitava

    2016-09-01

    The helical handedness in achiral self-assemblies is mostly complex due to spontaneous symmetry breaking or kinetically controlled random assembly formation. Here an attempt has been made to address this issue through chiral anion exchange. A new class of cationic achiral C3-symmetric gelator devoid of any conventional gelation assisting functional units is found to form both right- and left-handed helical structures. A chiral counteranion exchange-assisted approach is successfully introduced to control the chirality sign and thereby to obtain preferred homochiral assemblies. Formation of anion-assisted chiral assembly was confirmed by circular dichroism (CD) spectroscopy, microscopic images, and crystal structure. The X-ray crystal structure reveals the construction of helical assemblies with opposite handedness for (+)- and (-)-chiral anion reformed gelators. The appropriate counteranion driven ion-pair-assisted hydrogen-bonding interactions are found responsible for the helical bias control in this C3-symmetric gelator. PMID:27517868

  1. Role of cations and confinement in asymmetric photochemistry: enantio- and diastereo-selective photocyclization of tropolone derivatives within zeolites.

    PubMed

    Joy, Abraham; Kaanumalle, Lakshmi S; Ramamurthy, V

    2005-08-21

    Asymmetric induction in photochemical reactions has been explored using the photochemistry of tropolones as a model. Three approaches have been examined: chiral inductor, chiral auxiliary and [chiral inductor + chiral auxiliary]. All three methods gave excellent asymmetric induction in zeolite and very little or zero induction in solution. Results presented on tropolones clearly illustrate the remarkable influence that a confined space studded with cations can have on asymmetric induction. Tropolone derivatives, upon irradiation undergo 4pi-electron electrocyclization to yield a bicyclic product and a rearranged product. Enantiomeric excess up to 68% has been achieved in the cyclized product. In systems where a chiral inductor has been covalently linked, diastereomeric excess as high as 88% has been achieved within a zeolite while the same system in solution gave 10%. PMID:16186938

  2. Chiral Crystallization of Ethylenediamine Sulfate

    ERIC Educational Resources Information Center

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

    2005-01-01

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

  3. CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

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

  4. Controlling Chirality of Entropic Crystals

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  5. Controlling Chirality of Entropic Crystals.

    PubMed

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

    2015-10-01

    Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams. PMID:26550757

  6. Chiral Shielding Revisited

    SciTech Connect

    Scadron, M. D.

    2008-08-31

    A model-independent chiral soft-pion theorem (SPT) shields the now observed scalar-meson ground-state isoscalar {sigma}(600) and isospinor {kappa}(800) resonances from detection in a{sub 1}{yields}{pi}({pi}{pi}){sub S-wave}, {gamma}{gamma}{yields}2{pi}{sup 0}, {pi}{sup -}P{yields}{pi}{sup -}{pi}{sup +}n, and K{sup -}P{yields}K{sup -}{pi}{sup +}n processes. Moreover, for pseudoscalar-to-vector-vector (PVV) decays, quark loops only are required.

  7. Targeting divalent metal cations with Re(I) tetrazolato complexes.

    PubMed

    Fiorini, Valentina; Ranieri, Anna Maria; Muzzioli, Sara; Magee, Karen D M; Zacchini, Stefano; Akabar, Nurshadrina; Stefan, Alessandra; Ogden, Mark I; Massi, Massimiliano; Stagni, Stefano

    2015-12-21

    In order to exploit their potential as versatile luminescent sensors, four new Re(I)-tetrazolato complexes with the general formula fac-[Re(CO)3(diim)(L)], where diim is 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen) and L(-) is either the anion 5-(2'-pyridyl)tetrazolato (2-PTZ(-)) or 5-(2'-quinolyl)tetrazolato (2-QTZ(-)), were prepared and fully characterized. In all cases, the regioselective coordination of the Re(I) center through the N2 atom of the tetrazolato ring was observed. This particular feature ensures the availability of the diiminic (N^N) site that was systematically incorporated into the structure of the 2-PTZ(-) and 2-QTZ(-) ligands for further coordination with metal cations. Such a diimine-type coordination mode was preliminarily tested by using the mononuclear Re(I) complexes as N^N ligands for the preparation of two [(N^N)Cu(POP)] cationic species, where POP is the chelating diphosphine bis[2-(diphenylphosphino)phenyl]ether. The X-ray structures of the resulting Re(I)-Cu(I) dyads revealed that the Re(I) mononuclear complexes effectively behaved as chelating N^N ligands with respect to the [Cu(POP)](+) fragment, the coordination of which also resulted in significant modification of the Re(I)-centered luminescence. With these data in hand, the luminescent sensing abilities of the four new Re(I) tetrazolato complexes were screened with respect to divalent metal ions of toxicological and biological importance such as Zn(II), Cd(II) and Cu(II). The interaction of the Re(I) complexes with Zn(II) and Cd(II) was witnessed by the evident blue shift (Δλmax = 22-36 nm) of the emission maxima, which was also accompanied by a significant elongation of the emission lifetimes. On the contrary, the addition of the cupric ion caused substantial quenching of the radiative processes originating from the Re(I) luminophores. PMID:26554352

  8. Chiral limit of QCD

    SciTech Connect

    Gupta, R.

    1994-12-31

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

  9. Gyroscope-like molecules consisting of PdX₂/PtX₂ rotators within three-spoke dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties.

    PubMed

    Nawara-Hultzsch, Agnieszka J; Stollenz, Michael; Barbasiewicz, Michał; Szafert, Sławomir; Lis, Tadeusz; Hampel, Frank; Bhuvanesh, Nattamai; Gladysz, John A

    2014-04-14

    Threefold intramolecular ring-closing metatheses of trans-[MCl2(P{(CH2)(m)CH=CH2}3)2] are effected with Grubbs' catalyst. Following hydrogenation catalyzed by [RhCl(PPh3)3], the title complexes trans-[MCl2(P((CH2)n)3P)] (n=2m+2; M/n=Pt/14, 4 c; Pt/16, 4 d; Pt/18, 4 e; Pd/14, 5 c; Pd/18, 5 e) and sometimes isomers partly derived from intraligand metathesis, trans-[MCl2{P(CH2)n(CH2)n}P(CH2)n)] (4'c-e, 5'e), are isolated. These react with LiBr, NaI, and KCN to give the corresponding MBr2, MI2, and M(CN)2 species (58-99%). (13)C NMR data show that the MX2 moieties rapidly rotate within the diphosphine cage on the NMR timescale, even at -120 °C. The reaction of 4 c and KSCN gives separable Pt(NCS)2 and Pt(NCS)(SCN) adducts (13 c, 28%; 14 c, 20%), and those of 4 c,e and Ph2Zn give PtPh2 species (15 c, 61%; 15 e, 90%). (13)C NMR spectra of 13 c-15 c show two sets of CH2 signals (ca. 2:1 intensity ratios), indicating that MX2 rotation is no longer rapid. Reactions of 4 c or 4'c and excess NaC≡CH afford the free diphosphines P{(CH2)14}3P (91%) and (CH2)14P(CH2)14P(CH2)14 (90%). The latter has been crystallographically characterized as a bis(BH3) adduct. The crystal structures of eight complexes with P(CH2)14P linkages (PtCl2, PtBr2, PtI2, Pt(NCS)2, PtPh2, PdCl2, PdBr2, PdI2) and 15 e have been determined, and intramolecular distances analyzed with respect to MX2 rotation. The conformations of the (CH2)14 moieties and features of the crystal lattices are also discussed.

  10. Chiral quantum dot based materials

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  11. Chiral perturbation theory with nucleons

    SciTech Connect

    Meissner, U.G.

    1991-09-01

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

  12. Diastereomeric resolution directed towards chirality determination focussing on gas-phase energetics of coordinated sodium dissociation

    PubMed Central

    Kanie, Osamu; Shioiri, Yuki; Ogata, Koji; Uchida, Waka; Daikoku, Shusaku; Suzuki, Katsuhiko; Nakamura, Shinichiro; Ito, Yukishige

    2016-01-01

    Defining chiral centres is addressed by introducing a pair of chiral auxiliary groups. Ions of diastereomeric pairs of molecules could be distinguished utilising energy-resolved mass spectrometry, and the applicability of the method to a series of compounds carrying amine, carboxylic acid, alcohol, and all the amino acids was verified. The method was further strengthened by distinguishing diastereomeric ions that did not undergo fragmentation. Mass spectrometric evaluation of the dissociation process of adducted sodium cations from the diastereomeric precursors agreed with the theoretical calculations, indicating the potential usefulness of the method for the determination of absolute configurations. PMID:27040078

  13. Chiral analysis by capillary electrophoresis using antibiotics as chiral selector.

    PubMed

    Desiderio, C; Fanali, S

    1998-05-20

    The separation of chiral compounds by capillary electrophoresis (CE) is a very interesting field of research in different areas such as pharmaceutical, environmental, agricultural analysis etc. The separation of two enantiomers can be achieved in CE using a chiral environment interacting with the two analytes on forming diastereoisomers with different stability constants and thus different mobilities. A wide number of chiral selectors have been employed in CE and among them glycopeptide antibiotics exhibited excellent enantioselective properties towards a wide number of racemic compounds. Vancomycin, ristocetin A, rifamycins, teicoplanin, kanamycin, streptomycin, fradiomycin, and two vancomycin analogues, added to the background electrolyte (BGE), are the antibiotics studied by CE running the separation in untreated and/or coated fused-silica capillary. Due to adsorption and absorption phenomena, some drawbacks can be expected when using bare fused-silica capillary, e.g., changes of electroosmotic flow (EOF), broaden peaks, reduced efficiency and low sensitivity. Coated capillary and counter current mode can be the solution to overcome the above mentioned problems. This review surveys the separation of enantiomers by CE when macrocyclic antibiotics are used as chiral selector. The enantioselectivity can be easily controlled modifying several parameters such as antibiotic type and concentration, pH, ionic strength and concentration of the background electrolyte, organic modifier etc. The paper also presents a list of the latest chiral separations achieved by CE where antibiotics were used as chiral selector.

  14. Chirality in photonic systems

    NASA Astrophysics Data System (ADS)

    Solnyshkov, Dmitry; Malpuech, Guillaume

    2016-10-01

    The optical modes of photonic structures are the so-called TE and TM modes that bring intrinsic spin-orbit coupling and chirality to these systems. This, combined with the unique flexibility of design of the photonic potential, and the possibility to mix photon states with excitonic resonances, sensitive to magnetic field and interactions, allows us to achieve many phenomena, often analogous to other solid-state systems. In this contribution, we review in a qualitative and comprehensive way several of these realizations, namely the optical spin Hall effect, the creation of spin currents protected by a non-trivial geometry, the Berry curvature for photons, and the photonic/polaritonic topological insulator.

  15. Amino Acids and Chirality

    NASA Technical Reports Server (NTRS)

    Cook, Jamie E.

    2012-01-01

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

  16. Chiral Bosonization of Superconformal Ghosts

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

  17. Life's chirality from prebiotic environments

    NASA Astrophysics Data System (ADS)

    Gleiser, Marcelo; Walker, Sara Imari

    2012-10-01

    A key open question in the study of life is the origin of biomolecular homochirality: almost every life-form on Earth has exclusively levorotary amino acids and dextrorotary sugars. Will the same handedness be preferred if life is found elsewhere? We review some of the pertinent literature and discuss recent results suggesting that life's homochirality resulted from sequential chiral symmetry breaking triggered by environmental events. In one scenario, autocatalytic prebiotic reactions undergo stochastic fluctuations due to environmental disturbances, in a mechanism reminiscent of evolutionary punctuated equilibrium: short-lived destructive events may lead to long-term enantiomeric excess. In another, chiral-selective polymerization reaction rates influenced by environmental effects lead to substantial chiral excess even in the absence of autocatalysis. Applying these arguments to other potentially life-bearing platforms has implications to the search for extraterrestrial life: we predict that a statistically representative sampling of extraterrestrial stereochemistry will be racemic (chirally neutral) on average.

  18. Rotation of the chiral bag

    NASA Astrophysics Data System (ADS)

    Kahana, David E.; Jackson, A. D.; Ripka, G.

    1986-11-01

    Cranking of the chiral bag model is carried out in order to generate the correct quantum numbers for SU(2) baryons. The moment of inertia of the system is found to be divided between the meson and quark sectors. A numerical evaluation of the contributions to the moment of inertia from valence quarks and from mesons is presented. Finally, a discussion is given of the nucleon-delta mass splitting predicted in the chiral bag model.

  19. Gluons in the chiral bag

    NASA Astrophysics Data System (ADS)

    Kahana, D. E.; Milana, J.

    1987-07-01

    A perturbative QCD calculation of gluon exchange corrections to the cranking moment of inertia of the chiral bag model is done using the full time-dependent cavity propagators. Cranking is used to construct the nucleon and delta states and a value of the effective strong coupling constant is extracted by fitting the empirical Δ N mass splitting. The MIT bag limit (large bag radius) of the chiral bag model is also examined.

  20. Bimolecular Coupling Reactions through Oxidatively Generated Aromatic Cations: Scope and Stereocontrol

    PubMed Central

    Cui, Yubo; Villafane, Louis A.; Clausen, Dane J.

    2013-01-01

    Chromenes, isochromenes, and benzoxathioles react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form stable aromatic cations that react with a range of nucleophiles. These oxidative fragment coupling reactions provide rapid access to structurally diverse heterocycles. Conducting the reactions in the presence of a chiral Brønsted acid results in the formation of an asymmetric ion pair that can provide enantiomerically enriched products in a rare example of a stereoselective process resulting from the generation of a chiral electrophile through oxidative carbon–hydrogen bond cleavage. PMID:23913987

  1. Optical properties of chiral nanostructures

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

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

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

    PubMed Central

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

    2016-01-01

    Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application. PMID:27401541

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    PubMed

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

    2016-07-12

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

  5. Correlation between structures of chiral polymers and their efficiency for chiral resolution by crystallization.

    PubMed

    Menahem, Tali; Pravda, Martin; Mastai, Yitzhak

    2009-10-01

    In this work, we describe the correlation between chiral polymer structures, particularly alpha-helical and random coil conformations, and their efficiency as chiral resolving agents in crystallization processes. A set of chiral block copolymers based on polyethylene oxide with chiral glutamic acid oligopeptide segments (PEG(113)-b-(+)-(S)-Glu(20)) were synthesized and employed as additives in the crystallization of rac-threonine. CD spectroscopy demonstrates that structures of chiral polymers could be switched between a helical and a disordered random coil by pH. The effect of these polymers at different conformations on the crystallization kinetics, crystal morphology, and chiral resolution of rac-threonine is reported. Our study demonstrates that only chiral polymers with alpha-helical conformations of the chiral segment are effective as additives for chiral resolution throughout crystallization. Overall, our results provide useful guidelines for the selection and design of chiral polymer additives that will act efficiently for chiral resolution by crystallization. PMID:19455618

  6. Chiral Heteroditopic Baskets Designed from Triazolated Calixarenes and Short Peptides.

    PubMed

    Gorbunov, Alexander; Sokolova, Nadezhda; Kudryashova, Elena; Nenajdenko, Valentine; Kovalev, Vladimir; Vatsouro, Ivan

    2016-08-22

    Cone calix[4]arenes and calix[6]arenes bearing two, three, and four short peptide units each having two chiral carbon atoms were prepared. The syntheses were performed by using an efficient modular approach that includes the Ugi preparation of the azido-peptide followed by its reactions with the propargylated calixarenes under CuAAC (Cu(I) -catalyzed azide-alkyne cycloaddition) conditions. The three novel multitopic hosts were probed for their ability to bind metal ions by UV titration, and showed the highest complexation efficiency towards copper(II) and lead(II). These two cations possessed quite different complexation modes with copper(II) bound predominantly by multiple-triazole sites, in contrast to lead(II), which is stabilized mainly by multiple interactions with amide groups of the peptide units. Circular dichroism data for the free chiral hosts, their equimolar mixtures with copper(II) perchlorate and lead(II) perchlorate, and for tertiary mixtures of all three compounds showed the formation of mono- and binuclear complexes, or a switching behavior, depending on the structure of the host and the addition order of the cations. PMID:27444143

  7. Enantioselective Catalysis of the Aza-Cope Rearrangement by a Chiral Supramolecular Assembly

    SciTech Connect

    Brown, Casey J.; Bergman, Robert G.; Raymond, Kenneth N.

    2009-07-29

    The chiral supramolecular catalyst Ga{sub 4}L{sub 6} [L = 1,5-bis(2,3-dihydroxybenzoylamino)naphthalene] is a molecular tetrahedron that catalyzes the 3-aza-Cope rearrangement of allyl enammonium cations. This catalysis is accomplished by preorganizing the substrate in a reactive conformation within the host. This work demonstrates that through the use of enantiopure assembly, its chiral cavity is capable of catalyzing the 3-aza-Cope rearrangement enantioselectively, with yields of 21-74% and enantiomeric excesses from 6 to 64% at 50 C. At lower temperatures, the enantioselectivity improved, reaching 78% ee at 5 C. This is the highest enantioselectivity to date induced by the chiral cavity of a supramolecular assembly.

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

    ERIC Educational Resources Information Center

    LeMarechal, Jean Francois

    2008-01-01

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

  9. Strange Disoriented Chiral Condensates

    NASA Astrophysics Data System (ADS)

    Abdel-Aziz, Mohamed; Gavin, Sean

    2002-10-01

    Enhancement of omega and anti-omega baryon production in Pb+Pb collisions at the CERN SPS can be explained by the formation of many small regions of disordered chiral condensate. This explanation implies that neutral and charged kaons as well as pions must exhibit novel isospin fluctuations. Fluctuations due to transient behavior of the Polyakov Loop condensate can produce similar phenomena. Kapusta and Gavin have computed the distribution of the fraction of neutral pions and kaons from such regions. We proposed robust statistical observables that can be used to extract the novel isospin fluctuations from background contributions in neutral/charged pion and K-short/K-charged correlation measurements at RHIC and LHC. The STAR experiment is currently examining K-short/K-charged correlations. Note that Pruneau, Voloshin and Gavin have proposed similar observables to study net-charge fluctuations. To obtain a baseline for comparison to RHIC and SPS experiments, Abdel-Aziz and Gavin compute these observables using numerical simulations using HIJING and URQMD event generators. We also obtain limits on the size and number of disordered regions by comparing to photon and charged-pion searches from WA98 and other SPS experiments. We will compare to the first results from STAR K-short/K-charged analysis.

  10. Phase diagram of chirally imbalanced QCD matter

    SciTech Connect

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

    2011-05-15

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

  11. Chiral Chlordane Components in Environmental Matrices

    EPA Science Inventory

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

  12. Separation of tryptophan enantiomers by ligand-exchange chromatography with novel chiral ionic liquids ligand.

    PubMed

    Qing, Haiqun; Jiang, Xinyu; Yu, Jingang

    2014-03-01

    Chiral ionic liquids (CILs) with amino acids as cations have been applied as novel chiral ligands coordinated with Cu(2+) to separate tryptophan enantiomers in ligand exchange chromatography. Four kinds of amino acid ionic liquids, including [L-Pro][CF3COO], [L-Pro][NO3], [L-Pro]2[SO4], and [L-Phe][CF3COO] were successfully synthesized and used for separation of tryptophan enantiomers. To optimize the separation conditions, [L-Pro][CF3COO] was selected as the model ligand. Some factors influencing the efficiency of chiral separation, such as copper ion concentration, CILs concentration, methanol ratio (methanol/H2O, v/v), and pH, were investigated. The obtained optimal separation conditions were as follows: 8.0 mmol/L Cu(OAc)2, 4.0 mmol/L [L-Pro][CF3COO], and 20% (v/v) methanol at pH 3.6. Under the optimum conditions, acceptable enantioseparation of tryptophan enantiomers could be observed with a resolution of 1.89. The results demonstrate the good applicability of CILs with amino acids as cations for chiral separation. Furthermore, a comparative study was also conducted for exploring the mechanism of the CILs as new ligands in ligand exchange chromatography.

  13. Dynamic high-resolution computer simulation of electrophoretic enantiomer separations with neutral cyclodextrins as chiral selectors.

    PubMed

    Breadmore, Michael C; Kwan, Hiu Ying; Caslavska, Jitka; Thormann, Wolfgang

    2012-03-01

    GENTRANS, a comprehensive one-dimensional dynamic simulator for electrophoretic separations and transport, was extended for handling electrokinetic chiral separations with a neutral ligand. The code can be employed to study the 1:1 interaction of monovalent weak and strong acids and bases with a single monovalent weak or strong acid or base additive, including a neutral cyclodextrin, under real experimental conditions. It is a tool to investigate the dynamics of chiral separations and to provide insight into the buffer systems used in chiral capillary zone electrophoresis (CZE) and chiral isotachophoresis. Analyte stacking across conductivity and buffer additive gradients, changes of additive concentration, buffer component concentration, pH, and conductivity across migrating sample zones and peaks, and the formation and migration of system peaks can thereby be investigated in a hitherto inaccessible way. For model systems with charged weak bases and neutral modified β-cyclodextrins at acidic pH, for which complexation constants, ionic mobilities, and mobilities of selector-analyte complexes have been determined by CZE, simulated and experimentally determined electropherograms and isotachopherograms are shown to be in good agreement. Simulation data reveal that CZE separations of cationic enantiomers performed in phosphate buffers at low pH occur behind a fast cationic migrating system peak that has a small impact on the buffer composition under which enantiomeric separation takes place. PMID:22528416

  14. Tactoids of chiral liquid crystals

    NASA Astrophysics Data System (ADS)

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

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

  15. Controlling Chirality of Entropic Crystals

    NASA Astrophysics Data System (ADS)

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

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

  16. Chiral Thirring–Wess model

    SciTech Connect

    Rahaman, Anisur

    2015-10-15

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

  17. Chirality: a relational geometric-physical property.

    PubMed

    Gerlach, Hans

    2013-11-01

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

  18. Chiral lattice fermions with correct vacuum polarization and chiral anomaly

    SciTech Connect

    Pryor, C. )

    1991-04-15

    An action for chiral lattice fermions is proposed, which avoids the Nielsen-Ninomiya theorem by virtue of its nonlocality and nonbilinearity. The action is constructed by eliminating the extra fermion modes with a gauge-violating Majorana-type Wilson mass, which is then rendered invariant by an integration over gauge transformations. The free propagator is calculated, and the one-loop vacuum polarization is shown to be identical to that for Wilson fermions, even at nonzero lattice spacing. Also the chiral anomaly is shown to be the same as for Wilson fermions in the continuum limit.

  19. Field induced spin chirality and chirality switching in magnetic multilayers

    NASA Astrophysics Data System (ADS)

    Tartakovskaya, Elena V.

    2015-05-01

    The physical origin of the field-induced spin chirality experimentally observed in rare earth multilayers is determined. It is shown that the effect is possible due to the interplay between solid-state exchange interactions (the Ruderman-Kittel-Kasuya-Yosida and the Dsyaloshinsky-Moriya interactions), the external magnetic field and a special confinement of magnetic constituents. The presented model describes a certain temperature dependence of the chirality factor in agreement with experimental data and opens a new way to design nanostructured objects with predicted handedness.

  20. Cesium cation affinities and basicities

    NASA Astrophysics Data System (ADS)

    Gal, Jean-François; Maria, Pierre-Charles; Massi, Lionel; Mayeux, Charly; Burk, Peeter; Tammiku-Taul, Jaana

    2007-11-01

    This review focuses on the quantitative data related to cesium cation interaction with neutral or negatively charged ligands. The techniques used for measuring the cesium cation affinity (enthalpies, CCA), and cesium cation basicities (Gibbs free energies, CCB) are briefly described. The quantum chemical calculations methods that were specifically designed for the determination of cesium cation adduct structures and the energetic aspects of the interaction are discussed. The experimental results, obtained essentially from mass spectrometry techniques, and complemented by thermochemical data, are tabulated and commented. In particular, the correlations between cesium cation affinities and lithium cation affinities for the various kinds of ligands (rare gases, polyatomic neutral molecules, among them aromatic compounds and negative ions) serve as a basis for the interpretation of the diverse electrostatic modes of interaction. A brief account of some recent analytical applications of ion/molecule reactions with Cs+, as well as other cationization approaches by Cs+, is given.

  1. Two Pathways for Electrocatalytic Oxidation of Hydrogen by a Nickel Bis(diphosphine) Complex with Pendant Amines in the Second Coordination Sphere

    SciTech Connect

    Yang, Jenny Y.; Smith, Stuart E.; Liu, Tianbiao L.; Dougherty, William G.; Hoffert, Wesley A.; Kassel, W. S.; Rakowski DuBois, Mary; DuBois, Daniel L.; Bullock, R. Morris

    2013-07-03

    A nickel bis(diphosphine) complex containing pendant amines in the second coordination sphere, [Ni(PCy2Nt-Bu2)2](BF4)2 (PCy2Nt-Bu2 = 1,5-di(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane), is an electrocatalyst for hydrogen oxidation. Under 1.0 atm H2 using NEt3 as a base and with added water, a turnover frequency of 45 s-1 is observed at 23 °C; this is the fastest observed for a molecular catalyst. The addition of hydrogen to the NiII complex gives thee isomers of the doubly protonated Ni0 complex [Ni(PCy2HNt-Bu2)2](BF4)2; these complexes have been studied by 1H and 31P NMR spectroscopy, and for one isomer, an X-ray diffraction study. Using the pKa values and NiII/I and NiI/0 redox potentials in a thermochemical cycle, the free energy of hydrogen addition to [Ni(PCy2Nt-Bu2)2]2+ was determined to be -7.9 kcal mol-1. The catalytic rate observed in dry acetonitrile for the oxidation of H2 at the NiII/I couple depends on base size, with larger bases (NEt3, tert-BuNH2) resulting in slower catalysis than n-BuNH2. Addition of water accelerates the rate of catalysis, especially for the larger bases. The results of these studies provide important insights into the design of catalysts for hydrogen oxidation that facilitate proton movement and operate at moderate potentials. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  2. Two pathways for electrocatalytic oxidation of hydrogen by a nickel bis(diphosphine) complex with pendant amines in the second coordination sphere.

    PubMed

    Yang, Jenny Y; Smith, Stuart E; Liu, Tianbiao; Dougherty, William G; Hoffert, Wesley A; Kassel, W Scott; Rakowski DuBois, M; DuBois, Daniel L; Bullock, R Morris

    2013-07-01

    A nickel bis(diphosphine) complex containing pendant amines in the second coordination sphere, [Ni(P(Cy)2N(t-Bu)2)2](BF4)2 (P(Cy)2N(t-Bu)2 = 1,5-di(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane), is an electrocatalyst for hydrogen oxidation. The addition of hydrogen to the Ni(II) complex gives three isomers of the doubly protonated Ni(0) complex [Ni(P(Cy)2N(t-Bu)2H)2](BF4)2. Using the pKa values and Ni(II/I) and Ni(I/0) redox potentials in a thermochemical cycle, the free energy of hydrogen addition to [Ni(P(Cy)2N(t-Bu)2)2](2+) was determined to be -7.9 kcal mol(-1). The catalytic rate observed in dry acetonitrile for the oxidation of H2 depends on base size, with larger bases (NEt3, t-BuNH2) resulting in much slower catalysis than n-BuNH2. The addition of water accelerates the rate of catalysis by facilitating deprotonation of the hydrogen addition product before oxidation, especially for the larger bases NEt3 and t-BuNH2. This catalytic pathway, where deprotonation occurs prior to oxidation, leads to an overpotential that is 0.38 V lower compared to the pathway where oxidation precedes proton movement. Under the optimal conditions of 1.0 atm H2 using n-BuNH2 as a base and with added water, a turnover frequency of 58 s(-1) is observed at 23 °C.

  3. Chiral cardiovascular drugs: an overview.

    PubMed

    Ranade, Vasant V; Somberg, John C

    2005-01-01

    Stereochemistry in drug molecules is rapidly becoming an important aspect in drug research, design, and development. Recently, individual stereoisomers of drug molecules with asymmetric centers such as fexofenadine, cetirizine, verapamil, fluoxetine, levalbutarol, and amphetamine, for example, have been separated and developed as individual drugs. These stereoisomers have different therapeutic activity, and each isomer has contributed differently with respect to its formulation's pharmacologic activity, side effects, and toxicity. The present overview discusses chirality among a select group of cardiovascular drugs, their stereochemical synthesis/preparation, isolation techniques using chiral chromatography, methods for confirmation of their enantiomeric purity, pharmacodynamics, and pharmacokinetics. Chirality has been visualized as an important factor in cardiovascular research. It is also becoming evident in other areas of therapeutics.

  4. Chirality and gravitational parity violation.

    PubMed

    Bargueño, Pedro

    2015-06-01

    In this review, parity-violating gravitational potentials are presented as possible sources of both true and false chirality. In particular, whereas phenomenological long-range spin-dependent gravitational potentials contain both truly and falsely chiral terms, it is shown that there are models that extend general relativity including also coupling of fermionic degrees of freedom to gravity in the presence of torsion, which give place to short-range truly chiral interactions similar to that usually considered in molecular physics. Physical mechanisms which give place to gravitational parity violation together with the expected size of the effects and their experimental constraints are discussed. Finally, the possible role of parity-violating gravity in the origin of homochirality and a road map for future research works in quantum chemistry is presented. PMID:25919812

  5. Chirality and gravitational parity violation.

    PubMed

    Bargueño, Pedro

    2015-06-01

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

  6. Collisions in Chiral Kinetic Theory.

    PubMed

    Chen, Jing-Yuan; Son, Dam T; Stephanov, Mikhail A

    2015-07-10

    Using a covariant formalism, we construct a chiral kinetic theory Lorentz invariant to order O(ℏ), which includes collisions. We find a new contribution to the particle number current due to the side jumps required by the conservation of angular momentum during collisions. We also find a conserved symmetric stress-energy tensor as well as the H function obeying Boltzmann's H theorem. We demonstrate their use by finding a general equilibrium solution and the values of the anomalous transport coefficients characterizing the chiral vortical effect.

  7. Chiral symmetry on the lattice

    SciTech Connect

    Creutz, M.

    1994-11-01

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

  8. Chiral xenobiotics bioaccumulations and environmental health prospectives.

    PubMed

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

    2015-08-01

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

  9. Chirality effect in disordered graphene ribbon junctions

    NASA Astrophysics Data System (ADS)

    Long, Wen

    2012-05-01

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

  10. Micropatterning of cells reveals chiral morphogenesis

    PubMed Central

    2013-01-01

    Invariant left-right (LR) patterning or chirality is critical for embryonic development. The loss or reversal of LR asymmetry is often associated with malformations and disease. Although several theories have been proposed, the exact mechanism of the initiation of the LR symmetry has not yet been fully elucidated. Recently, chirality has been detected within single cells as well as multicellular structures using several in vitro approaches. These studies demonstrated the universality of cell chirality, its dependence on cell phenotype, and the role of physical boundaries. In this review, we discuss the theories for developmental LR asymmetry, compare various in vitro cell chirality model systems, and highlight possible roles of cell chirality in stem cell differentiation. We emphasize that the in vitro cell chirality systems have great promise for helping unveil the nature of chiral morphogenesis in development. PMID:23672821

  11. Basics of Resonance Chiral Theory

    SciTech Connect

    Portoles, J.

    2010-12-28

    We review the main components that have to be considered, within Resonance Chiral Theory, in the study of processes whose dynamics is dominated by hadron resonances. We show its application in the study of the {tau}{yields}{pi}{pi}{pi}{nu}{sub {tau}} decay.

  12. Chiral asymmetry in spiral galaxies?

    PubMed

    Kondepudi, D K; Durand, D J

    2001-07-01

    Spiral galaxies are chiral entities when coupled with the direction of their recession velocity. As viewed from the Earth, the S-shaped and Z-shaped spiral galaxies are two chiral forms. What is the nature of chiral symmetry in spiral galaxies? In the Carnegie Atlas of Galaxies that lists photographs of a total of 1,168 galaxies, we found 540 galaxies, classified as normal or barred spirals, that are clearly identifiable as S- or Z- type. The recession velocities for 538 of these galaxies could be obtained from this atlas and other sources. A statistical analysis of this sample reveals no overall asymmetry but there is a significant asymmetry in certain subclasses: dominance of S-type galaxies in the Sb class of normal spiral galaxies and a dominance of Z-type in the SBb class of barred spiral galaxies. Both S- and Z-type galaxies seem to have similar velocity distribution, indicating no spatial segregation of the two chiral forms.

  13. Baryon and chiral symmetry breaking

    SciTech Connect

    Gorsky, A.; Krikun, A.

    2014-07-23

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

  14. Nuclear chiral dynamics and thermodynamics

    NASA Astrophysics Data System (ADS)

    Holt, Jeremy W.; Kaiser, Norbert; Weise, Wolfram

    2013-11-01

    This presentation reviews an approach to nuclear many-body systems based on the spontaneously broken chiral symmetry of low-energy QCD. In the low-energy limit, for energies and momenta small compared to a characteristic symmetry breaking scale of order 1 GeV, QCD is realized as an effective field theory of Goldstone bosons (pions) coupled to heavy fermionic sources (nucleons). Nuclear forces at long and intermediate distance scales result from a systematic hierarchy of one- and two-pion exchange processes in combination with Pauli blocking effects in the nuclear medium. Short distance dynamics, not resolved at the wavelengths corresponding to typical nuclear Fermi momenta, are introduced as contact interactions between nucleons. Apart from a set of low-energy constants associated with these contact terms, the parameters of this theory are entirely determined by pion properties and low-energy pion-nucleon scattering observables. This framework (in-medium chiral perturbation theory) can provide a realistic description of both isospin-symmetric nuclear matter and neutron matter, with emphasis on the isospin-dependence determined by the underlying chiral NN interaction. The importance of three-body forces is emphasized, and the role of explicit Δ(1232)-isobar degrees of freedom is investigated in detail. Nuclear chiral thermodynamics is developed and a calculation of the nuclear phase diagram is performed. This includes a successful description of the first-order phase transition from a nuclear Fermi liquid to an interacting Fermi gas and the coexistence of these phases below a critical temperature Tc. Density functional methods for finite nuclei based on this approach are also discussed. Effective interactions, their density dependence and connections to Landau Fermi liquid theory are outlined. Finally, the density and temperature dependences of the chiral (quark) condensate are investigated.

  15. Toxicity of cationic lipids and cationic polymers in gene delivery.

    PubMed

    Lv, Hongtao; Zhang, Shubiao; Wang, Bing; Cui, Shaohui; Yan, Jie

    2006-08-10

    Gene therapy, as a promising therapeutics to treat genetic or acquired diseases, has achieved exciting development in the past two decades. Appropriate gene vectors can be crucial for gene transfer. Cationic lipids and polymers, the most important non-viral vectors, have many advantages over viral ones as non-immunogenic, easy to produce and not oncogenic. They hold the promise to replace viral vectors to be used in clinic. However, the toxicity is still an obstacle to the application of non-viral vectors to gene therapy. For overcoming the problem, many new cationic compounds have been developed. This article provides a review with respect to toxicity of cationic lipids and polymers in gene delivery. We evaluate the structural features of cationic compounds and summarize the relationship of toxicity and structure and hope to provide available suggestions on the development of these cationic compounds.

  16. REVIEW ARTICLE: Chiral metamaterials: simulations and experiments

    NASA Astrophysics Data System (ADS)

    Wang, Bingnan; Zhou, Jiangfeng; Koschny, Thomas; Kafesaki, Maria; Soukoulis, Costas M.

    2009-11-01

    Electromagnetic metamaterials are composed of periodically arranged artificial structures. They show peculiar properties, such as negative refraction and super-lensing, which are not seen in natural materials. The conventional metamaterials require both negative epsilon and negative μ to achieve negative refraction. Chiral metamaterial is a new class of metamaterials offering a simpler route to negative refraction. In this paper, we briefly review the history of metamaterials and the developments on chiral metamaterials. We study the wave propagation properties in chiral metamaterials and show that negative refraction can be realized in chiral metamaterials with a strong chirality, with neither epsilon nor μ negative required. We have developed a retrieval procedure, adopting a uniaxial bi-isotropic model to calculate the effective parameters such as n ± , κ, epsilon and μ of the chiral metamaterials. Our work on the design, numerical calculations and experimental measurements of chiral metamaterials is introduced. Strong chiral behaviors such as optical activity and circular dichroism are observed and negative refraction is obtained for circularly polarized waves in these chiral metamaterials. We show that 3D isotropic chiral metamaterials can eventually be realized.

  17. Chiral sensing by nonchiral tetrapyrroles.

    PubMed

    Labuta, Jan; Hill, Jonathan P; Ishihara, Shinsuke; Hanyková, Lenka; Ariga, Katsuhiko

    2015-03-17

    Enantiomeric excess (ee) is a measure of the purity of an enantiomer of a chiral compound with respect to the presence of the complementary enantiomer. It is an important aspect of chemistry, especially in the fields of pharmaceuticals and asymmetric catalysis. Existing methods for determination of enantiomeric excesses using nuclear magnetic resonance (NMR) spectroscopy mostly rely on special chiral reagents (auxiliaries) that form two or more diastereomeric complexes with a chiral compound. As a result of this, the NMR spectrum of each enantiomer is different, allowing the determination of enantiomeric excess. In this Account, we describe a molecular design process that has allowed us to prepare prochiral solvating agents for NMR determination of ee of a wide variety of analyte types. At the outset of this work, we initially encountered the phenomenon of NMR peak splitting in the oxoporphyrinogen (OxP) host component of a supramolecular host-guest complex, where the extent of the splitting is apparently proportional to the guests' ee. Upon closer examination of the mechanism of action, it was found that several complicating factors, including prototropic tautomerism, macrocyclic inversion (ring-flipping), and 1:2 host-guest stoichiometry, obstruct potential applications of OxP as a chiral solvating agent. By considering the molecular conformation of the OxP host, a saddle-shaped calix[4]pyrrole, we moved to study the tetraphenylporphyrin (TPP) dication since it has a similar form, and it was found that it could also be used to probe ee. However, although TPP does not suffer from disadvantageous tautomeric processes, it is still subject to macrocyclic inversion and has the additional serious disadvantage of operating for ee sensing only at depressed temperatures. The intrinsic disadvantages of the OxP and TPP systems were finally overcome by covalently modifying the OxP chromophore by regioselective N-alkylation at one face of the molecule. This procedure yields a

  18. Stabilization of Nickel Complexes with Ni0•••H-N Bonding Interactions Using Sterically Demanding Cyclic Diphosphine Ligands

    SciTech Connect

    Wiedner, Eric S.; Yang, Jenny Y.; Chen, Shentan; Raugei, Simone; Dougherty, William G.; Kassel, W. S.; Helm, Monte L.; Bullock, R. Morris; Rakowski DuBois, Mary; DuBois, Daniel L.

    2012-01-09

    The series of complexes Ni(P{sub 2}{sup tBu}N{sub 2}{sup R}), [Ni(P{sub 2}{sup tBu}N{sub 2}{sup R}){sub 2}]BF{sub 4}, [HNi(P{sub 2}{sup tBu}N{sub 2}{sup Ph}){sub 2}]BF{sub 4}, and [Co(P{sub 2}{sup tBu}N{sub 2}{sup Ph}){sub 2}]BF{sub 4} (P{sub 2}{sup tBu}N{sub 2}{sup R} = 1,5-dialkyl-3,7-tert-butyl-1,5-diaza-3,7-diphosphacyclooctane; alkyl (R) = phenyl, benzyl) have been synthesized and characterized. Spectroscopic, electrochemical, and X-Ray diffraction studies indicate these complexes are stable as a result of the tetrahedral arrangement of the two diphosphine ligands. Electrochemical oxidation of [HNi(P{sub 2}{sup tBu}N{sub 2}{sup Ph}){sub 2}]BF{sub 4} results in rapid proton transfer from nickel at a rate faster that can be observed on the CV timescale. Double protonation of Ni(P{sub 2}{sup tBu}N{sub 2}{sup BN}){sub 2} forms the endo-endo, endo exo, and exo-exo isomers of [Ni(P{sub 2}{sup tBu}N{sup BN}HN{sup BN}){sub 2}](BF{sub 4}){sub 2}, which were found to be more stable towards loss of H{sub 2} than previously observed for similar complexes. The presence of Ni{sup 0} {hor_ellipsis} HN bonds at the endo-protonation sites of [Ni(P{sub 2}{sup tBu}N{sup Bn}HN{sup BN}){sub 2}](BF{sub 4}){sub 2} results in significant differences in the Ni(I/0) oxidation potentials of each of the isomers. The differences in E{sub 1/2}(I/0) values correspond to bond free energies of 7.4 and 3.7 kcal/mol for the first and second Ni{sup 0} {hor_ellipsis} HN bonds of the endo-exo and endo-endo isomers, respectively. Computational studies of related model complexes reproduce these Ni{sup 0} {hor_ellipsis} HN bonds within 1-2 kcal/mol.

  19. Stabilization of Nickel Complexes with Ni 0 ···H–N Bonding Interactions Using Sterically Demanding Cyclic Diphosphine Ligands

    SciTech Connect

    Wiedner, Eric S.; Yang, Jenny Y.; Chen, Shentan; Raugei, Simone; Dougherty, William G.; Kassel, W. Scott; Helm, Monte L.; Bullock, R. Morris; Rakowski DuBois, M.; DuBois, Daniel L.

    2012-01-09

    The series of complexes Ni(PtBu₂NR₂)₂, [Ni(PtBu₂NR₂)₂]BF₄, [HNi(PtBu₂NR₂)₂]BF₄, and [Co(PtBu₂NPh₂)₂]BF₄ (PtBu₂NR₂ = 1,5-dialkyl-3,7-tert-butyl-1,5-diaza-3,7-diphosphacyclooctane; alkyl = phenyl, benzyl) have been synthesized and characterized. Spectroscopic, electrochemical, and X-ray diffraction studies indicate these complexes are stable as a result of the tetrahedral arrangement of the two diphosphine ligands. Electrochemical oxidation of [HNi(PtBu₂NPh₂)₂]BF₄ results in rapid proton transfer from nickel at a rate faster than can be observed on the CV time scale. Double protonation of Ni(PtBu₂NBn₂)₂ forms the endo-endo, endo-exo, and exo-exo isomers of [Ni(PtBu₂NBnHNBn)₂](BF₄)₂, which were found to be more stable toward loss of H₂ than previously observed for similar complexes. The presence of Ni⁰···HN hydrogen bonds at the endo protonation sites of [Ni(PtBu₂NBnHNBn)₂](BF₄)₂ results in significant differences in the Ni(I/0) oxidation potentials of each of the isomers. The differences in E1/2(I/0) values correspond to bond free energies of 7.4 and 3.7 kcal/mol for the first and second Ni⁰···HN hydrogen bonds of the endo-exo and endo-endo isomers, respectively. Computational studies give bond dissociation energies of the Ni⁰···HN bonds that are within 1–2 kcal/mol of the experimentally determined values.

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

    PubMed

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

    2012-05-18

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

  1. Chiral logarithms in quenched QCD

    SciTech Connect

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

    2004-08-01

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

  2. Mild access to planar-chiral ortho-condensed aromatic ferrocenes via gold(i)-catalyzed cycloisomerization of ortho-alkynylaryl ferrocenes.

    PubMed

    Urbano, Antonio; Hernández-Torres, Gloria; Del Hoyo, Ana M; Martínez-Carrión, Alicia; Carmen Carreño, M

    2016-05-11

    An efficient approach to (Rp) planar-chiral tri- and tetracyclic ortho-condensed aromatic ferrocenes was developed through the enantioselective cationic Au(i)-catalyzed cycloisomerization, in the presence of bidentate phosphine ligand (R)-DTBM-Segphos, from readily available ortho-alkynylaryl ferrocenes under very mild conditions (11 examples, up to 92% yield and 93% ee).

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

    NASA Astrophysics Data System (ADS)

    Katsuno, Hiroyasu; Uwaha, Makio

    2016-01-01

    By grinding crystals in a solution, the chirality of crystal structure (and the molecular chirality for the case of chiral molecules as well) can be converted, and the cause of the phenomenon is attributed to crystal growth with chiral clusters. We show that the recently found chirality conversion with a periodic change of temperature can also be explained by crystal growth with chiral clusters. With the use of a generalized Becker-Döring model, which includes enantio-selective incorporation of small chiral clusters to large solid clusters, the change of cluster distribution and the mass flow between clusters are studied. The chiral clusters act as a reservoir to pump out the minority species to the majority, and the exponential amplification of the enantiomeric excess found in the experiment is reproduced in the numerical calculation.

  4. Stable Pentaquarks from Strange Chiral Multiplets

    SciTech Connect

    Silas Beane

    2004-12-01

    The assumption of strong diquark correlations in the QCD spectrum suggests flavor multiplets of hadrons that are degenerate in the chiral limit. Generally it would be unnatural for there to be degeneracy in the hadron spectrum that is not protected by a QCD symmetry. Here we show--for pentaquarks constructed from diquarks--that these degeneracies can be naturally protected by the full chiral symmetry of QCD. The resulting chiral multiplet structure recovers the ideally-mixed pentaquark mass spectrum of the diquark model, and interestingly, requires that the axial couplings of the pentaquarks to states outside the degenerate multiplets vanish in the chiral limit. This result suggests that if these hadrons exist, they are stable in the chiral limit and therefore have widths that scale as the fourth power of the kaon mass over the chiral symmetry breaking scale. Natural-size widths are of order a few MeV.

  5. Asymmetric synthesis using chiral-encoded metal.

    PubMed

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-08-26

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity.

  6. Asymmetric synthesis using chiral-encoded metal.

    PubMed

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-01-01

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity. PMID:27562028

  7. Anomalous Maxwell equations for inhomogeneous chiral plasma

    NASA Astrophysics Data System (ADS)

    Gorbar, E. V.; Shovkovy, I. A.; Vilchinskii, S.; Rudenok, I.; Boyarsky, A.; Ruchayskiy, O.

    2016-05-01

    Using the chiral kinetic theory we derive the electric and chiral current densities in inhomogeneous relativistic plasma. We also derive equations for the electric and chiral chemical potentials that close the Maxwell equations in such a plasma. The analysis is done in the regimes with and without a drift of the plasma as a whole. In addition to the currents present in the homogeneous plasma (Hall current, chiral magnetic, chiral separation, and chiral electric separation effects, as well as Ohm's current) we derive several new terms associated with inhomogeneities of the plasma. Apart from various diffusionlike terms, we find also new dissipationless terms that are independent of relaxation time. Their origin can be traced to the Berry curvature modifications of the kinetic theory.

  8. Asymmetric synthesis using chiral-encoded metal

    PubMed Central

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-01-01

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity. PMID:27562028

  9. Asymmetric synthesis using chiral-encoded metal

    NASA Astrophysics Data System (ADS)

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-08-01

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity.

  10. Enantioselective recognition at mesoporous chiral metal surfaces

    PubMed Central

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

    2014-01-01

    Chirality is widespread in natural systems, and artificial reproduction of chiral recognition is a major scientific challenge, especially owing to various potential applications ranging from catalysis to sensing and separation science. In this context, molecular imprinting is a well-known approach for generating materials with enantioselective properties, and it has been successfully employed using polymers. However, it is particularly difficult to synthesize chiral metal matrices by this method. Here we report the fabrication of a chirally imprinted mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and chiral template molecules. The porous platinum retains a chiral character after removal of the template molecules. A matrix obtained in this way exhibits a large active surface area due to its mesoporosity, and also shows a significant discrimination between two enantiomers, when they are probed using such materials as electrodes. PMID:24548992

  11. On chirality of slime mould.

    PubMed

    Dimonte, Alice; Adamatzky, Andrew; Erokhin, Victor; Levin, Michael

    2016-02-01

    Left-right patterning and lateralised behaviour is an ubiquitous aspect of plants and animals. The mechanisms linking cellular chirality to the large-scale asymmetry of multicellular structures are incompletely understood, and it has been suggested that the chirality of living cells is hardwired in their cytoskeleton. We examined the question of biased asymmetry in a unique organism: the slime mould Physarum polycephalum, which is unicellular yet possesses macroscopic, complex structure and behaviour. In laboratory experiment using a T-shape, we found that Physarum turns right in more than 74% of trials. The results are in agreement with previously published studies on asymmetric movement of muscle cells, neutrophils, liver cells and growing neural filaments, and for the first time reveal the presence of consistently-biased laterality in the fungi kingdom. Exact mechanisms of the slime mould's direction preference remain unknown.

  12. On chirality of slime mould.

    PubMed

    Dimonte, Alice; Adamatzky, Andrew; Erokhin, Victor; Levin, Michael

    2016-02-01

    Left-right patterning and lateralised behaviour is an ubiquitous aspect of plants and animals. The mechanisms linking cellular chirality to the large-scale asymmetry of multicellular structures are incompletely understood, and it has been suggested that the chirality of living cells is hardwired in their cytoskeleton. We examined the question of biased asymmetry in a unique organism: the slime mould Physarum polycephalum, which is unicellular yet possesses macroscopic, complex structure and behaviour. In laboratory experiment using a T-shape, we found that Physarum turns right in more than 74% of trials. The results are in agreement with previously published studies on asymmetric movement of muscle cells, neutrophils, liver cells and growing neural filaments, and for the first time reveal the presence of consistently-biased laterality in the fungi kingdom. Exact mechanisms of the slime mould's direction preference remain unknown. PMID:26747637

  13. On lattice chiral gauge theories

    NASA Technical Reports Server (NTRS)

    Maiani, L.; Rossi, G. C.; Testa, M.

    1991-01-01

    The Smit-Swift-Aoki formulation of a lattice chiral gauge theory is presented. In this formulation the Wilson and other non invariant terms in the action are made gauge invariant by the coupling with a nonlinear auxilary scalar field, omega. It is shown that omega decouples from the physical states only if appropriate parameters are tuned so as to satisfy a set of BRST identities. In addition, explicit ghost fields are necessary to ensure decoupling. These theories can give rise to the correct continuum limit. Similar considerations apply to schemes with mirror fermions. Simpler cases with a global chiral symmetry are discussed and it is shown that the theory becomes free at decoupling. Recent numerical simulations agree with those considerations.

  14. Optically controllable THz chiral metamaterials.

    PubMed

    Kenanakis, G; Zhao, R; Katsarakis, N; Kafesaki, M; Soukoulis, C M; Economou, E N

    2014-05-19

    Switchable and tunable chiral metamaterial response is numerically demonstrated here in different uniaxial chiral metamaterial structures operating in the THz regime. The structures are based on the bi-layer conductor design and the tunable/switchable response is achieved by replacing parts of the metallic components of the structures by photoconducting Si, which can be transformed from an insulating to an almost conducting state through photoexcitation, achievable under external optical pumping. All the structures proposed and discussed here exhibit frequency regions with giant tunable circular dichroism, as well as regions with giant tunable optical activity, showing unique potential in the achievement of active THz polarization components, like tunable polarizers and polarization filters. PMID:24921336

  15. Bootstrapping N=2 chiral correlators

    NASA Astrophysics Data System (ADS)

    Lemos, Madalena; Liendo, Pedro

    2016-01-01

    We apply the numerical bootstrap program to chiral operators in four-dimensional N=2 SCFTs. In the first part of this work we study four-point functions in which all fields have the same conformal dimension. We give special emphasis to bootstrapping a specific theory: the simplest Argyres-Douglas fixed point with no flavor symmetry. In the second part we generalize our setup and consider correlators of fields with unequal dimension. This is an example of a mixed correlator and allows us to probe new regions in the parameter space of N=2 SCFTs. In particular, our results put constraints on relations in the Coulomb branch chiral ring and on the curvature of the Zamolodchikov metric.

  16. Big, strong, neutral, twisted, and chiral π acids.

    PubMed

    Zhao, Yingjie; Huang, Guangxi; Besnard, Celine; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2015-04-13

    General synthetic access to expanded π-acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion-π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron-withdrawing substituents decreases and the high π acidity needed for strong anion-π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion-π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from -3.96 to -4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X-ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation-π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches -4.45 eV, whereas two sulfone moieties give a value of -4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion-π interactions, these conceptually innovative π-acidic surfaces are also of interest as electron transporters in conductive materials.

  17. Chiral anomaly, bosonization, and fractional charge

    SciTech Connect

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

    1985-06-15

    We present a method to evaluate the Jacobian of chiral rotations, regulating determinants through the proper-time method and using Seeley's asymptotic expansion. With this method we compute easily the chiral anomaly for ..nu.. = 4,6 dimensions, discuss bosonization of some massless two-dimensional models, and handle the problem of charge fractionization. In addition, we comment on the general validity of Fujikawa's approach to regulate the Jacobian of chiral rotations with non-Hermitian operators.

  18. Thin-wire scatterers in chiral media.

    PubMed

    Jaggard, D L; Liu, J C; Grot, A; Pelet, P

    1991-06-01

    The effect of the handedness of chiral materials on the differential scattering cross section of embedded conducting wires is examined. The bow-tie-shaped induced current distributions and the resulting forbidden zone of radiation are explained through fundamental physical principles. We find that thin-wire scatterers can be divided into subchiral, chiral, and superchiral classes according to the degree of chirality of the host material and the electromagnetic length of the wire.

  19. Chirality operators for Heisenberg spin systems

    SciTech Connect

    Subrahmanyam, V. )

    1994-09-01

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

  20. Flat-space chiral gravity.

    PubMed

    Bagchi, Arjun; Detournay, Stéphane; Grumiller, Daniel

    2012-10-12

    We provide the first evidence for a holographic correspondence between a gravitational theory in flat space and a specific unitary field theory in one dimension lower. The gravitational theory is a flat-space limit of topologically massive gravity in three dimensions at a Chern-Simons level of k=1. The field theory is a chiral two-dimensional conformal field theory with a central charge of c=24. PMID:23102291

  1. Anomalies and Discrete Chiral Symmetries

    SciTech Connect

    Creutz, M.

    2009-09-07

    The quantum anomaly that breaks the U(1) axial symmetry of massless multi-flavored QCD leaves behind a discrete flavor-singlet chiral invariance. With massive quarks, this residual symmetry has a close connection with the strong CP-violating parameter theta. One result is that if the lightest quarks are degenerate, then a first order transition will occur when theta passes through pi. The resulting framework helps clarify when the rooting prescription for extrapolating in the number of flavors is valid.

  2. Staggered chiral random matrix theory

    SciTech Connect

    Osborn, James C.

    2011-02-01

    We present a random matrix theory for the staggered lattice QCD Dirac operator. The staggered random matrix theory is equivalent to the zero-momentum limit of the staggered chiral Lagrangian and includes all taste breaking terms at their leading order. This is an extension of previous work which only included some of the taste breaking terms. We will also present some results for the taste breaking contributions to the partition function and the Dirac eigenvalues.

  3. Chiral symmetry and nucleon structure

    SciTech Connect

    Holstein, B.R. . Dept. of Physics and Astromony Washington Univ., Seattle, WA . Inst. for Nuclear Theory)

    1992-01-01

    Recently it has been realized that significant tests of the validity of QCD are available in low energy experiments (E < 500 MeV) by exploiting the property of (broken) chiral symmetry. This technique has been highly developed in The Goldstone boson sector by the work of Gasser and Leutwyler. Application to the nucleon system is much more difficult and is now being carefully developed.

  4. Chiral plasmons without magnetic field

    PubMed Central

    Song, Justin C. W.; Rudner, Mark S.

    2016-01-01

    Plasmons, the collective oscillations of interacting electrons, possess emergent properties that dramatically alter the optical response of metals. We predict the existence of a new class of plasmons—chiral Berry plasmons (CBPs)—for a wide range of 2D metallic systems including gapped Dirac materials. As we show, in these materials the interplay between Berry curvature and electron–electron interactions yields chiral plasmonic modes at zero magnetic field. The CBP modes are confined to system boundaries, even in the absence of topological edge states, with chirality manifested in split energy dispersions for oppositely directed plasmon waves. We unveil a rich CBP phenomenology and propose setups for realizing them, including in anomalous Hall metals and optically pumped 2D Dirac materials. Realization of CBPs will offer a powerful paradigm for magnetic field-free, subwavelength optical nonreciprocity, in the mid-IR to terahertz range, with tunable splittings as large as tens of THz, as well as sensitive all-optical diagnostics of topological bands. PMID:27071090

  5. Objects of Maximum Electromagnetic Chirality

    NASA Astrophysics Data System (ADS)

    Fernandez-Corbaton, Ivan; Fruhnert, Martin; Rockstuhl, Carsten

    2016-07-01

    We introduce a definition of the electromagnetic chirality of an object and show that it has an upper bound. Reciprocal objects attain the upper bound if and only if they are transparent for all the fields of one polarization handedness (helicity). Additionally, electromagnetic duality symmetry, i.e., helicity preservation upon interaction, turns out to be a necessary condition for reciprocal objects to attain the upper bound. We use these results to provide requirements for the design of such extremal objects. The requirements can be formulated as constraints on the polarizability tensors for dipolar objects or on the material constitutive relations for continuous media. We also outline two applications for objects of maximum electromagnetic chirality: a twofold resonantly enhanced and background-free circular dichroism measurement setup, and angle-independent helicity filtering glasses. Finally, we use the theoretically obtained requirements to guide the design of a specific structure, which we then analyze numerically and discuss its performance with respect to maximal electromagnetic chirality.

  6. Chiral plasmons without magnetic field.

    PubMed

    Song, Justin C W; Rudner, Mark S

    2016-04-26

    Plasmons, the collective oscillations of interacting electrons, possess emergent properties that dramatically alter the optical response of metals. We predict the existence of a new class of plasmons-chiral Berry plasmons (CBPs)-for a wide range of 2D metallic systems including gapped Dirac materials. As we show, in these materials the interplay between Berry curvature and electron-electron interactions yields chiral plasmonic modes at zero magnetic field. The CBP modes are confined to system boundaries, even in the absence of topological edge states, with chirality manifested in split energy dispersions for oppositely directed plasmon waves. We unveil a rich CBP phenomenology and propose setups for realizing them, including in anomalous Hall metals and optically pumped 2D Dirac materials. Realization of CBPs will offer a powerful paradigm for magnetic field-free, subwavelength optical nonreciprocity, in the mid-IR to terahertz range, with tunable splittings as large as tens of THz, as well as sensitive all-optical diagnostics of topological bands. PMID:27071090

  7. Chiral methyl-branched pheromones.

    PubMed

    Ando, Tetsu; Yamakawa, Rei

    2015-07-01

    Insect pheromones are some of the most interesting natural products because they are utilized for interspecific communication between various insects, such as beetles, moths, ants, and cockroaches. A large number of compounds of many kinds have been identified as pheromone components, reflecting the diversity of insect species. While this review deals only with chiral methyl-branched pheromones, the chemical structures of more than one hundred non-terpene compounds have been determined by applying excellent analytical techniques. Furthermore, their stereoselective syntheses have been achieved by employing trustworthy chiral sources and ingenious enantioselective reactions. The information has been reviewed here not only to make them available for new research but also to understand the characteristic chemical structures of the chiral pheromones. Since biosynthetic studies are still limited, it might be meaningful to examine whether the structures, particularly the positions and configurations of the branched methyl groups, are correlated with the taxonomy of the pheromone producers and also with the function of the pheromones in communication systems. PMID:25849023

  8. Lateral chirality-sorting optical forces.

    PubMed

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

    2015-10-27

    The transverse component of the spin angular momentum of evanescent waves gives rise to lateral optical forces on chiral particles, which have the unusual property of acting in a direction in which there is neither a field gradient nor wave propagation. Because their direction and strength depends on the chiral polarizability of the particle, they act as chirality-sorting and may offer a mechanism for passive chirality spectroscopy. The absolute strength of the forces also substantially exceeds that of other recently predicted sideways optical forces. PMID:26453555

  9. Generation of a Chiral Giant Micelle.

    PubMed

    Ito, Thiago H; Salles, Airton G; Priebe, Jacks P; Miranda, Paulo C M L; Morgon, Nelson H; Danino, Dganit; Mancini, Giovanna; Sabadini, Edvaldo

    2016-08-23

    Over the past few years, chiral supramolecular assemblies have been successfully used for recognition, sensing and enantioselective transformations. Several approaches are available to control chirality of discrete assemblies (e.g., cages and capsules), but few are efficient in assuring chirality for micellar aggregates. Optically active amino acid-derived surfactants are commonly used to generate chiral spherical micelles. To circumvent this limitation, we benefited from the uniaxial growth of spherical micelles into long cylindrical micelles usually called wormlike or giant micelles, upon the addition of cosolutes. This paper describes the unprecedented formation of chiral giant micelles in aqueous solutions of cetyltrimethylammonium bromide (CTAB) upon increasing addition of enantiopure sodium salt of 1,1'-bi-2-naphthol (Na-binaphtholate) as a cosolute. Depending on the concentrations of CTAB and Na-binaphtholate, chiral gel-like systems are obtained. The transition from spherical to giant micellar structures was probed using rheology, cryo-transmission electron microscopy, polarimetry, and electronic circular dichroism (CD). CD can be effectively used to monitor the incorporation of Na-binaphtholate into the micelle palisade as well as to determine its transition to giant micellar structures. Our approach expands the scope for chirality induction in micellar aggregates bringing the possibility to generate "smart" chiral systems and an alternative asymmetric chiral environment to perform enantioselective transformations. PMID:27499127

  10. Chiral selection on inorganic crystalline surfaces

    NASA Technical Reports Server (NTRS)

    Hazen, Robert M.; Sholl, David S.

    2003-01-01

    From synthetic drugs to biodegradable plastics to the origin of life, the chiral selection of molecules presents both daunting challenges and significant opportunities in materials science. Among the most promising, yet little explored, avenues for chiral molecular discrimination is adsorption on chiral crystalline surfaces - periodic environments that can select, concentrate and possibly even organize molecules into polymers and other macromolecular structures. Here we review experimental and theoretical approaches to chiral selection on inorganic crystalline surfaces - research that is poised to open this new frontier in understanding and exploiting surface-molecule interactions.

  11. Chiral Magnetic Effect in Hydrodynamic Approximation

    NASA Astrophysics Data System (ADS)

    Zakharov, Valentin I.

    We review derivations of the chiral magnetic effect (ChME) in hydrodynamic approximation. The reader is assumed to be familiar with the basics of the effect. The main challenge now is to account for the strong interactions between the constituents of the fluid. The main result is that the ChME is not renormalized: in the hydrodynamic approximation it remains the same as for non-interacting chiral fermions moving in an external magnetic field. The key ingredients in the proof are general laws of thermodynamics and the Adler-Bardeen theorem for the chiral anomaly in external electromagnetic fields. The chiral magnetic effect in hydrodynamics represents a macroscopic manifestation of a quantum phenomenon (chiral anomaly). Moreover, one can argue that the current induced by the magnetic field is dissipation free and talk about a kind of "chiral superconductivity". More precise description is a quantum ballistic transport along magnetic field taking place in equilibrium and in absence of a driving force. The basic limitation is the exact chiral limit while temperature—excitingly enough—does not seemingly matter. What is still lacking, is a detailed quantum microscopic picture for the ChME in hydrodynamics. Probably, the chiral currents propagate through lower-dimensional defects, like vortices in superfluid. In case of superfluid, the prediction for the chiral magnetic effect remains unmodified although the emerging dynamical picture differs from the standard one.

  12. Potential of chiral anion-exchangers operated in various subcritical fluid chromatography modes for resolution of chiral acids.

    PubMed

    Pell, Reinhard; Lindner, Wolfgang

    2012-07-01

    Anion-exchange-type chiral stationary phases (CSPs) derived from quinine or quinidine were applied in subcritical fluid chromatography (SFC) for the direct separation of chiral acidic compounds. Employing subcritical (sc) mobile phase modes (CO₂ + methanol as co-solvent and acids and bases as additives) first the influence of type and amount of acidic and basic additives on separation performance was investigated. Secondly, water was tested as a neutral additive and the influence of temperature variation on enantioselectivity was studied. Thirdly, we could chromatographically confirm that the often verbalized "inherent acidity" of sc CO₂ + methanol is manifested by the in situ formation of methylcarbonic acids in the sc mobile phase and thus functioning as acidic additive. Accordingly the dissociated methylcarbonic acid, acting as a counterion, enables an anion exchange mechanism between the cationic CSP and the corresponding acidic analyte. In the absence of a dissociable acid in the mobile phase such an ion exchange mode would not work following a stoichiometric displacement model. This finding is further corroborated by the use of ammonia in methanol as co-solvent thus generating in situ the ammonium salt of methylcarbonic acid. In summary, we report on ion-exchange mediated chromatographic separations in SFC modes by merely using (i) sc CO₂ and MeOH, (ii) sc CO₂ and ammonia in MeOH, and (iii) sc CO₂ and MeOH plus acids and bases as additives. Comparisons to HPLC mode have been undertaken to evaluate merits and limitations. This mode exhibits high potential for preparative chromatography of chiral acids combining pronounced enantioselectivity with high column loadability and avoiding possibly troublesome mobile phase additives, as the in situ formed methylcarbonic acid disintegrates to CO₂ and methanol upon pressure release.

  13. [Separation mechanism of chiral stationary phase based on quinine and crown ether for the direct stereoselective separation of amino acids].

    PubMed

    Wu, Haixia; Wang, Dongqiang; Zhao, Jianchao; Ke, Yanxiong; Liang, Xinmiao

    2016-01-01

    A novel chiral stationary phase combining quinine and crown ether (QN-CR CSP) was developed to separate amino acid enantiomers. This CSP showed good enantioselectivity for some amino acids. Since the synergistic effect of ion exchange and complexation in chiral recognition of amino acids, a new adsorption isotherm was built. Using the method of frontal analysis by characteristic point (FACP), the adsorption isotherms of tryptophan (Trp) under different mobile phase conditions were determined and fitted the proposed adsorption isotherm model well. With the increase of the competition between metal cationic and amino to crown ether, the equilibrium constant of complexing adsorption was found increased. The chiral separation ability was decreased. The adsorption isotherm improved the understanding of the retention behavior of amino acids on QN-CR CSP, which was also benefit to optimize the structure of the stationary phase.

  14. [Separation mechanism of chiral stationary phase based on quinine and crown ether for the direct stereoselective separation of amino acids].

    PubMed

    Wu, Haixia; Wang, Dongqiang; Zhao, Jianchao; Ke, Yanxiong; Liang, Xinmiao

    2016-01-01

    A novel chiral stationary phase combining quinine and crown ether (QN-CR CSP) was developed to separate amino acid enantiomers. This CSP showed good enantioselectivity for some amino acids. Since the synergistic effect of ion exchange and complexation in chiral recognition of amino acids, a new adsorption isotherm was built. Using the method of frontal analysis by characteristic point (FACP), the adsorption isotherms of tryptophan (Trp) under different mobile phase conditions were determined and fitted the proposed adsorption isotherm model well. With the increase of the competition between metal cationic and amino to crown ether, the equilibrium constant of complexing adsorption was found increased. The chiral separation ability was decreased. The adsorption isotherm improved the understanding of the retention behavior of amino acids on QN-CR CSP, which was also benefit to optimize the structure of the stationary phase. PMID:27319166

  15. The Cation-π Interaction

    PubMed Central

    DOUGHERTY, DENNIS A.

    2014-01-01

    CONSPECTUS The chemistry community now recognizes the cation-π interaction as a major force for molecular recognition, joining the hydrophobic effect, the hydrogen bond, and the ion pair in determining macromolecular structure and drug-receptor interactions. This Account provides the author’s perspective on the intellectual origins and fundamental nature of the cation-π interaction. Early studies on cyclophanes established that water-soluble, cationic molecules would forgo aqueous solvation to enter a hydrophobic cavity if that cavity was lined with π systems. Important gas phase studies established the fundamental nature of the cation-π interaction. The strength of the cation-π interaction – Li+ binds to benzene with 38 kcal/mol of binding energy; NH4+ with 19 kcal/mol– distinguishes it from the weaker polar-π interactions observed in the benzene dimer or water-benzene complexes. In addition to the substantial intrinsic strength of the cation-π interaction in gas phase studies, the cation-π interaction remains energetically significant in aqueous media and under biological conditions. Many studies have shown that cation-π interactions can enhance binding energies by 2 – 5 kcal/mol, making them competitive with hydrogen bonds and ion pairs in drug-receptor and protein-protein interactions. As with other noncovalent interactions involving aromatic systems, the cation-π interaction includes a substantial electrostatic component. The six (four) Cδ−–Hδ+ bond dipoles of a molecule like benzene (ethylene) combine to produce a region of negative electrostatic potential on the face of the π system. Simple electrostatics facilitate a natural attraction of cations to the surface. The trend for (gas phase) binding energies is Li+>Na+>K+>Rb+: as the ion gets larger the charge is dispersed over a larger sphere and binding interactions weaken, a classical electrostatic effect. On other hand, polarizability does not define these interactions. Cyclohexane

  16. Construction and probing of multisite chiral catalysts: dendrimer fixation of c2-symmetrical diphosphinerhodium complexes.

    PubMed

    Engel, Gerald D; Gade, Lutz H

    2002-09-16

    A series of chiral phosphine-functionalized poly(propyleneimine) (PPI) dendrimers was synthesized by the reaction of carboxyl-linked C(2)-chiral pyrphos ligand (pyrphos=3,4-bis(diphenylphosphino)pyrrolidine) with zeroth-fourth generation PPI using ethyl-N,N-dimethylaminopropylcarbodiimide (EDC)/1-hydroxybenzotriazol as a coupling reagent. The dendrimers obtained were characterized by NMR spectroscopy and elemental analysis as well as FAB and MALDI-TOF mass spectrometry, which established their molecular masses of up to 20 700 amu. Metalation of the multi-site phosphines with [Rh(COD)(2)]BF(4) cleanly yielded the cationic rhododendrimers containing up to 32 metal centers (for the fourth generation species), representing the largest chiral phosphine dendrimer catalyst studied to date. The complete metalation of the chiral phosphine sites was demonstrated by (31)P NMR spectroscopy and the observation of the coordination-shifted AB part of the ABX spin system (delta(A)=33.9, delta(B)=32.9; (1)J(Rh,P)=150, 153 Hz; (2)J(P,P)=28 Hz). The relationship between the size/generation of the dendrimer and its catalytic properties was established in the asymmetric hydrogenation of Z-methyl-alpha-acetamidocinammate and dimethyl itaconate. A decrease in both activity and selectivity of the dendrimer catalysts was observed on going to the higher generations. PMID:12298024

  17. Diarylferrocene tweezers for cation binding.

    PubMed

    Lima, Carlos F R A C; Fernandes, Ana M; Melo, André; Gonçalves, Luís M; Silva, Artur M S; Santos, Luís M N B F

    2015-10-01

    The host-guest chemistry of ferrocene derivatives was explored by a combined experimental and theoretical study. Several 1-arylferrocenes and 1,1'-diarylferrocenes were synthesized by the Suzuki-Miyaura cross-coupling reaction. The ability of these compounds to bind small cations in the gas phase was investigated experimentally by electrospray ionization mass spectrometry (ESI-MS). The results evidenced a noticeable ability of all 1,1'-diarylferrocenes studied to bind cations, while the same was not observed for the corresponding 1-arylferrocenes nor ferrocene. The 1,1'-diarylferrocenecation relative interaction energies were evaluated by ESI-MS and quantum chemical calculations and showed that cation binding in these systems follows electrostatic trends. It was found that, due to their unique molecular shape and smooth torsional potentials, 1,1'-diarylferrocenes can act as molecular tweezers of small-sized cations in the gas phase. PMID:26309143

  18. Evaluation of Dalbavancin as chiral selector for HPLC and comparison with Teicoplanin based chiral stationary phases

    PubMed Central

    ZHANG, XIAOTONG; BAO, YE; HUANG, KE; BARNETT-RUNDLETT, KIMBER L.; ARMSTRONG, DANIEL W.

    2015-01-01

    Dalbavancin is a new compound of the macrocyclic glycopeptide family. It was covalently linked to 5μm silica particles by using two different binding chemsitries. Approximately two hundred and fifty racemates including (A) heterocyclic compounds; (B) chiral acids; (C) chiral amines; (D) chiral alcohols; (E) chiral sulfoxides and sulfilimines; (F) amino acids and amino acid derivatives; and (G) other chiral compounds were tested on the two new chiral stationary phases (CSP) using three different mobile phases. As dalbavancin is structurally related to teicoplanin, the same set of chiral compounds was screened on two commercially available teicoplanin CSPs for comparison. The dalbavancin CSPs were able to separate some enantiomers that were not separated by the teicoplanin CSPs and also showed improved separations for many racemates. However, there were other compounds only separated or better separated on teicoplanin CSPS. Therefore, the dalbavancin CSPs are complementary to the teicoplanin CSPs. PMID:19676111

  19. Nonbonded interactions in membrane active cyclic biopolymers. IV - Cation dependence

    NASA Technical Reports Server (NTRS)

    Radhakrishnan, R.; Srinivasan, S.; Prasad, C. V.; Brinda, S. R.; Macelroy, R. D.; Sundaram, K.

    1980-01-01

    Interactions of valinomycin and form of its analogs in several conformations with the central ions Li(+), Na(+), K(+), Rb(+) and Cs(+) are investigated as part of a study of the specific preference of valinomycin for potassium and the mechanisms of carrier-mediated ion transport across membranes. Ion binding energies and conformational potential energies are calculated taking into account polarization energy formulas and repulsive energy between the central ion and the ligand atoms for conformations representing various stages in ion capture and release for each of the two ring chiralities of valinomycin and its analogs. Results allow the prediction of the chirality and conformation most likely to be observed for a given analog, and may be used to synthesize analogs with a desired rigidity or flexibility. The binding energies with the alkali metal cations are found to decrease with increasing ion size, and to be smaller than the corresponding ion hydration energies. It is pointed out that the observed potassium preference may be explainable in terms of differences between binding and hydration energies. Binding energies are also noted to depend on ligand conformation.

  20. Chiral hypervalent iodine reagents: synthesis and reactivity.

    PubMed

    Parra, Alejandro; Reboredo, Silvia

    2013-12-16

    Chiral hypervalent iodine chemistry has been steadily increasing in importance in recent years. This review catalogues enantioselective transformations triggered by chiral hypervalent iodine(III/V) reagents, in stoichiometric or catalytic quantities, highlighting the different reactivities in terms of yield and enantioselectivity. Moreover, the synthesis of the most remarkable and successful catalysts has been illustrated in detail.

  1. Three-dimensional Chiral Plasmonic Oligomers

    NASA Astrophysics Data System (ADS)

    Hentschel, Mario

    2013-03-01

    We demonstrate chiral optical response in stacked arrangements of plasmonic nanostructures. We show that three-dimensional arrangements of plasmonic ``meta-atoms'' only exhibit a chiral optical response if similar plasmonic ``atoms'' are arranged in a handed fashion as we require resonant plasmonic coupling. Moreover, we demonstrate that such particle groupings, similarly to molecular systems, possess the capability to encode their three-dimensional arrangement in unique and well-modulated spectra, making them ideal candidates for a three-dimensional chiral plasmon ruler. Furthermore, we discuss the onset of a broadband chiral optical response in the wavelength regime between 700 nm and 3500 nm upon charge transfer between the nanoparticles. We show in experiment and simulation that this response is due to the ohmic contact between adjacent particles which causes a strong red-shift of the fundamental mode. The geometrical shape of the resulting fused particles allows for efficient excitation of higher order modes. Calculated spectra and field distributions confirm our interpretation and show a number of interacting plasmonic modes. Finally, we will discuss plasmonic diastereomers which consist of multiple chiral centers. We find that the chiral optical response of the composite molecules can be traced back to the properties of the constituting building blocks. We demonstrate that the optical response of complex chiral plasmonic systems can be decomposed and understood in terms of fundamental building blocks, offering simple and straightforward design rules for future applications such as chiral optical elements and enantiomer sensors.

  2. A construction of lattice chiral gauge theories

    NASA Astrophysics Data System (ADS)

    Narayanan, Rajamani; Neuberger, Herbert

    1995-02-01

    Path integration over Euclidean chiral fermions is replaced by the quantum mechanics of an auxiliary system of non-interacting fermions. Our construction avoids the no-go theorem and faithfully maintains all the known important features of chiral fermions, including the violation of some perturbative conservation laws by gauge field configurations of non-trivial topology.

  3. Color Confinement and Dynamical Chiral Symmetry Breaking

    NASA Astrophysics Data System (ADS)

    Nakamura, Naoki; Suzuki, Tsuneo

    We study the relation between the quark confinement and the dynamical chiral symmetry breaking in SU(2) QCD by deriving an effective Lagrangian of a monopole field and the chiral fields from the dual Ginzburg-Landau type Lagrangian(DGL Lagrangian)…

  4. Quantization of the chiral soliton in medium

    NASA Astrophysics Data System (ADS)

    Nagai, S.; Sawado, N.; Shiiki, N.

    2006-01-01

    Chiral solitons coupled with quarks in medium are studied based on the Wigner-Seitz approximation. The chiral quark soliton model is used to obtain the classical soliton solutions. To investigate nucleon and Δ in matter, the semi-classical quantization is performed by the cranking method. The saturation for nucleon matter and Δ matter are observed.

  5. Generalized electromagnetic fields in a chiral medium

    NASA Astrophysics Data System (ADS)

    Bisht, P. S.; Singh, Jivan; Negi, O. P. S.

    2007-09-01

    The time-dependent Dirac-Maxwell's equations in the presence of electric and magnetic sources are reformulated in a chiral medium, and the solutions for the classical problem are obtained in a unique, simple and consistent manner. The quaternion reformulation of generalized electromagnetic fields in the chiral medium has also been discussed in a compact, simple and consistent manner.

  6. Chiral gravity, log gravity, and extremal CFT

    SciTech Connect

    Maloney, Alexander; Song Wei; Strominger, Andrew

    2010-03-15

    We show that the linearization of all exact solutions of classical chiral gravity around the AdS{sub 3} vacuum have positive energy. Nonchiral and negative-energy solutions of the linearized equations are infrared divergent at second order, and so are removed from the spectrum. In other words, chirality is confined and the equations of motion have linearization instabilities. We prove that the only stationary, axially symmetric solutions of chiral gravity are BTZ black holes, which have positive energy. It is further shown that classical log gravity--the theory with logarithmically relaxed boundary conditions--has finite asymptotic symmetry generators but is not chiral and hence may be dual at the quantum level to a logarithmic conformal field theories (CFT). Moreover we show that log gravity contains chiral gravity within it as a decoupled charge superselection sector. We formally evaluate the Euclidean sum over geometries of chiral gravity and show that it gives precisely the holomorphic extremal CFT partition function. The modular invariance and integrality of the expansion coefficients of this partition function are consistent with the existence of an exact quantum theory of chiral gravity. We argue that the problem of quantizing chiral gravity is the holographic dual of the problem of constructing an extremal CFT, while quantizing log gravity is dual to the problem of constructing a logarithmic extremal CFT.

  7. A lattice formulation of chiral gauge theories

    SciTech Connect

    Bodwin, G.T.

    1996-08-01

    We present a method for implementing gauge theories of chiral fermions on the lattice. Discussed topics include: the lattice as a UV regulator, a chiral QED model, modification of the fermion determinant, large gauge-field momenta, and a non-perturbative problem.

  8. Orientation-Dependent Handedness and Chiral Design

    NASA Astrophysics Data System (ADS)

    Efrati, Efi; Irvine, William T. M.

    2014-01-01

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

  9. Chiral THz metamaterial with tunable optical activity

    SciTech Connect

    Zhou, Jiangfeng; Taylor, Antoinette; O' Hara, John; Chowdhury, Roy; Zhao, Rongkuo; Soukoullis, Costas M

    2010-01-01

    Optical activity in chiral metamaterials is demonstrated in simulation and shows actively tunable giant polarization rotation at THz frequencies. Electric current distributions show that pure chirality is achieved by our bi-Iayer chiral metamaterial design. The chirality can be optically controlled by illumination with near-infrared light. Optical activity, occurring in chiral materials such as DNA, sugar and many other bio-molecules, is a phenomenon of great importance to many areas of science including molecular biology, analytical chemistry, optoelectronics and display applications. This phenomenon is well understood at an effective medium level as a magnetic/electric moment excited by the electric/magnetic field of the incident electromagnetic (EM) wave. Usually, natural chiral materials exhibit very weak optical activity e.g. a gyrotropic quartz crystal. The optical activity of chiral metamaterials, however, can be five orders of magnitude stronger. Chiral metamaterials are made of sub-wavelength resonators lacking symmetry planes. The asymmetry allows magnetic moments to be excited by the electric field of the incident EM wave and vice versa. Recently, chiral metamaterials have been demonstrated and lead to prospects in giant optical activity, circular dichroism, negative refraction and reversing the Casmir force. These fascinating optical properties require strong chirality, which may be designed through the microscopic structure of chiral metamaterials. However, these metamaterials have a fixed response function, defined by the geometric structuring, which limits their ability to manipulate EM waves. Active metamaterials realize dynamic control of response functions and have produced many influential applications such as ultra-fast switching devices, frequency and phase modulation and memory devices. Introducing active designs to chiral metamaterials will give additional freedom in controlling the optical activity, and therefore enable dynamic manipulation

  10. Tunable lithography masks using chiral nematic fluids

    NASA Astrophysics Data System (ADS)

    Jeong, Hyeon Su; Srinivasarao, Mohan; Jung, Hee-Tae

    2013-03-01

    We present a facile route for pattern formation using chiral nematic fluids as tunable masks in lithography process. The chiral nematic phase prepared by adding a chiral dopant (CB15) to 5CB acted as a set of parallel cylindrical lenses and as a polarization selective photomask for the preparation of periodic line patterns. The pitch of the helical twist was easily controlled by the concentration of chiral agent and the feature size of the resulting pattern was easily tuned. Because of the high mobility of the small liquid crystalline compound, the preparation of chiral nematic fluids based lithography masks requires only a few seconds. This approach has significant advantages including facility, range of surface ordering, and rate of forming periodic arrays. Current affiliation: SK Innovation, Daejeon, Korea

  11. Enantioselective environmental toxicology of chiral pesticides.

    PubMed

    Ye, Jing; Zhao, Meirong; Niu, Lili; Liu, Weiping

    2015-03-16

    The enantioselective environmental toxic effect of chiral pesticides is becoming more important. As the industry develops, increasing numbers of chiral insecticides and herbicides will be introduced into use, potentially posing toxic effects on nontarget living beings. Chiral pesticides, including herbicides such as acylanilides, phenoxypropanoic acids, and imidazolinones, and insecticides such as synthetic pyrethroids, organophosphates, and DDT often behave enantioselectively during agricultural use. These compounds also pose unpredictable enantioselective ecological threats to nontarget living beings and/or humans, affecting the food chain and entire ecosystems. Thus, to investigate the enantioselective toxic effects of chiral insecticides and herbicides is necessary during environmental protection. The environmental toxicology of chiral pesticides, especially the findings obtained from studies conducted in our laboratory during the past 10 years, is reviewed. PMID:25643169

  12. Chiral magnetic effect in condensed matter systems

    DOE PAGESBeta

    Li, Qiang; Kharzeev, Dmitri E.

    2016-12-01

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

  13. A liquid crystalline chirality balance for vapours

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  14. Axially chiral allenyl gold complexes.

    PubMed

    Johnson, Alice; Laguna, Antonio; Gimeno, M Concepción

    2014-09-17

    Unprecedented allenyl gold complexes have been achieved starting from triphenylpropargylphosphonium bromide. Two different coordination modes of the allene isomer of triphenylphosphoniumpropargylide to gold have been found depending on the gold oxidation state. Bromo-, pentafluorophenyl-, and triphenylphosphine-gold(I) allenyl complexes were prepared in which the α carbon coordinates to the gold(I) center. A chiral pentafluorophenyl-gold(III) allenyl complex with the gold atoms coordinated to the γ carbon was also prepared. All the complexes have been structurally characterized by X-ray diffraction showing the characteristic distances for a C═C═C unit.

  15. Nuclear forces and chiral theories

    SciTech Connect

    Friar, J.L. |

    1995-09-01

    Recent successes in ab initio calculations of light nuclei (A=2-6) will be reviewed and correlated with the dynamical consequences of chiral symmetry. The tractability of nuclear physics evinced by these results is evidence for that symmetry. The relative importance of three-nucleon forces, four-nucleon forces, multi-pion exchanges, and relativistic corrections will be discussed in the context of effective field theories and dimensional power counting. Isospin violation in the nuclear force will also be discussed in this context.

  16. Exploring Enantiospecific Ligand-Protein Interactions Using Cellular Membrane Affinity Chromatography: Chiral Recognition as a Dynamic Process

    PubMed Central

    Jozwiak, Krzysztof; Moaddel, Ruin; Ravichandran, Sarangan; Plazinska, Anita; Kozak, Joanna; Patel, Sharvil; Yamaguchi, Rika; Wainer, Irving

    2008-01-01

    The chiral recognition mechanisms responsible for the enantioselective binding on the α3β4 nicotinic acetyl choline receptor (α3β4 nAChR) and human organic cation transporter 1 (hOCT1) have been reviewed. The results indicate that chiral recognition on the α3β4 nAChR is a process involving initial tethering of dextromethorphan and levomethorphan at hydrophobic pockets within the central lumen followed by hydrogen bonding interactions favoring dextromethorphan. The second step is the defining enantioselective step. Studies with the hOCT1 indentified four binding sites within the transporter that participated in chiral recognition. Each of the enantiomers of the compounds used in the study interacted with three of these sites, while (R)-verapamil interacted with all four. Chiral recognition arose from the conformational adjustments required to produce optimum interactions. With respect to the prevailing interaction-based models, the data suggest that chiral recognition is a dynamic process and that the static point-based models should be amended to reflect this. PMID:18723411

  17. Reactivity of cationic agostic and carbene structures derived from platinum(II) metallacycles.

    PubMed

    Campos, Jesús; Ortega-Moreno, Laura; Conejero, Salvador; Peloso, Riccardo; López-Serrano, Joaquín; Maya, Celia; Carmona, Ernesto

    2015-06-01

    This paper describes the formation of new platinacyclic complexes derived from the phosphine ligands PiPr2 Xyl, PMeXyl2 , and PMe2 Ar Xyl 2 (Xyl=2,6-Me2 C6 H3 and Ar Xyl 2=2,6-(2,6-Me2 C6 H3 )2 -C6 H3 ) as well as reactivity studies of the trans-[Pt(C^P)2 ] bis-metallacyclic complex 1 a derived from PiPr2 Xyl. Protonation of compound 1 a with [H(OEt2 )2 ][BArF ] (BArF =B[3,5-(CF3 )2 C6 H3 ]4 ) forms a cationic δ-agostic structure 4 a, whereas α-hydride abstraction employing [Ph3 C][PF6 ] produces a cationic platinum carbene trans-[Pt{PiPr2 (2,6-CH(Me)C6 H3 }{PiPr2 (2,6-CH2 (Me)C6 H3 }][PF6 ] (8). Compounds 4 a and 8 react with H2 to yield the same 1:3 equilibrium mixture of 4 a and trans-[PtH(PiPr2 Xyl)2 ][BArF ] (6), in which one of the phosphine ligands participates in a δ-agostic interaction. DFT calculations reveal that H2 activation by 8 occurs at the highly electrophilic alkylidene terminus with no participation of the metal. The two compounds 4 a and 8 experience C-C coupling reactions of a different nature. Thus, 4 a gives rise to complex trans-[PtH{(E)-1,2-bis(2-(PiPr2 )-3-MeC6 H3 )CHCH}] (7) that contains a tridentate diphosphine-alkene ligand, through agostic CH oxidative cleavage and C-C reductive coupling steps, whereas the C-C coupling reaction in 8 involves classical migratory insertion of its [PtCH] and [PtCH2 ] bonds promoted by platinum coordination of CO or CNXyl. The mechanisms of the CC bond-forming reactions have also been investigated by computational methods. PMID:25959723

  18. Reactivity of cationic agostic and carbene structures derived from platinum(II) metallacycles.

    PubMed

    Campos, Jesús; Ortega-Moreno, Laura; Conejero, Salvador; Peloso, Riccardo; López-Serrano, Joaquín; Maya, Celia; Carmona, Ernesto

    2015-06-01

    This paper describes the formation of new platinacyclic complexes derived from the phosphine ligands PiPr2 Xyl, PMeXyl2 , and PMe2 Ar Xyl 2 (Xyl=2,6-Me2 C6 H3 and Ar Xyl 2=2,6-(2,6-Me2 C6 H3 )2 -C6 H3 ) as well as reactivity studies of the trans-[Pt(C^P)2 ] bis-metallacyclic complex 1 a derived from PiPr2 Xyl. Protonation of compound 1 a with [H(OEt2 )2 ][BArF ] (BArF =B[3,5-(CF3 )2 C6 H3 ]4 ) forms a cationic δ-agostic structure 4 a, whereas α-hydride abstraction employing [Ph3 C][PF6 ] produces a cationic platinum carbene trans-[Pt{PiPr2 (2,6-CH(Me)C6 H3 }{PiPr2 (2,6-CH2 (Me)C6 H3 }][PF6 ] (8). Compounds 4 a and 8 react with H2 to yield the same 1:3 equilibrium mixture of 4 a and trans-[PtH(PiPr2 Xyl)2 ][BArF ] (6), in which one of the phosphine ligands participates in a δ-agostic interaction. DFT calculations reveal that H2 activation by 8 occurs at the highly electrophilic alkylidene terminus with no participation of the metal. The two compounds 4 a and 8 experience C-C coupling reactions of a different nature. Thus, 4 a gives rise to complex trans-[PtH{(E)-1,2-bis(2-(PiPr2 )-3-MeC6 H3 )CHCH}] (7) that contains a tridentate diphosphine-alkene ligand, through agostic CH oxidative cleavage and C-C reductive coupling steps, whereas the C-C coupling reaction in 8 involves classical migratory insertion of its [PtCH] and [PtCH2 ] bonds promoted by platinum coordination of CO or CNXyl. The mechanisms of the CC bond-forming reactions have also been investigated by computational methods.

  19. Chiral Potts spin glass in d =2 and 3 dimensions

    NASA Astrophysics Data System (ADS)

    Ćaǧlar, Tolga; Berker, A. Nihat

    2016-09-01

    The chiral spin-glass Potts system with q =3 states is studied in d =2 and 3 spatial dimensions by renormalization-group theory and the global phase diagrams are calculated in temperature, chirality concentration p , and chirality-breaking concentration c , with determination of phase chaos and phase-boundary chaos. In d =3 , the system has ferromagnetic, left-chiral, right-chiral, chiral spin-glass, and disordered phases. The phase boundaries to the ferromagnetic, left- and right-chiral phases show, differently, an unusual, fibrous patchwork (microreentrances) of all four (ferromagnetic, left-chiral, right-chiral, chiral spin-glass) ordered phases, especially in the multicritical region. The chaotic behavior of the interactions, under scale change, are determined in the chiral spin-glass phase and on the boundary between the chiral spin-glass and disordered phases, showing Lyapunov exponents in magnitudes reversed from the usual ferromagnetic-antiferromagnetic spin-glass systems. At low temperatures, the boundaries of the left- and right-chiral phases become thresholded in p and c . In d =2 , the chiral spin-glass Potts system does not have a spin-glass phase, consistently with the lower-critical dimension of ferromagnetic-antiferromagnetic spin glasses. The left- and right-chirally ordered phases show reentrance in chirality concentration p .

  20. Static and dynamic effects of chirality in dielectric media

    NASA Astrophysics Data System (ADS)

    Lakes, R. S.

    2016-09-01

    Chiral dielectrics are considered from the perspective of continuum representations of spatial heterogeneity. Static effects in isotropic chiral dielectrics are predicted, provided the electric field has nonzero third spatial derivatives. The effects are compared with static chiral phenomena in Cosserat elastic materials which obey generalized continuum constitutive equations. Dynamic monopole-like magnetic induction is predicted in chiral dielectric media.

  1. Chiral magnetism at oxide interfaces

    NASA Astrophysics Data System (ADS)

    Randeria, Mohit

    2014-03-01

    There are tantalizing hints of magnetism at the n-type LaAlO3/SrTiO3 interface, but the experimental evidence remains controversial in view of some of the differences between different samples and probes. I will argue that if magnetism exists at interfaces, symmetry arguments imply chiral interactions that lead to a spiral ground state in zero external field and skyrmion crystals for H ≠ 0 . I will next present a microscopic model that provides a possible mechanism for the formation of local moments. I will show that the coupling of these moments to itinerant electrons leads to ferromagnetic double exchange together with Dzyaloshinskii-Moriya (DM) interactions and an easy-plane ``compass'' anisotropy, which arise from Rashba spin-orbit coupling (SOC) due to the lack of inversion symmetry at the interface. The compass term, often ignored in the literature on chiral magnetism, is shown to play a crucial role in determining the magnetic ground state. I will compare our results with existing torque magnetometry data on LAO/STO and try to reconcile it with scanning SQUID magnetometry. Finally, I will present the phase diagram in a field and show that easy-plane anisotropy stabilizes an unexpectedly large skyrmion crystal phase and describe its properties. (Work done in collaboration with Sumilan Banerjee, Onur Erten, Daniel Kestner and James Rowland). Supported by DOE-BES DE-SC0005035, NSF-DMR-1006532 and NSF MRSEC DMR-0820414.

  2. Nucleic acids, proteins, and chirality

    NASA Technical Reports Server (NTRS)

    Usher, D. A.; Profy, A. T.; Walstrum, S. A.; Needels, M. C.; Bulack, S. C.; Lo, K. M.

    1984-01-01

    The present investigation is concerned with experimental results related, in one case, to the chirality of nucleotides, and, in another case, to the possibility of a link between the chirality of nucleic acids, and that of peptides. It has been found that aminoacylation of the 'internal' hydroxyl group of a dinucleoside monophosphate can occur stereoselectively. However, this reaction has not yet been made a part of a working peptide synthesis scheme. The formation and cleavage of oligonucleotides is considered. In the event of the formation of a helical complex between the oligonucleotide and the polymer, 1-prime,5-prime-bonds in the oligomer are found to become more resistant towards cleavage. The conditions required for peptide bond formation are examined, taking into account the known structures of RNA and possible mechanisms for prebiotic peptide bond formation. The possibility is considered that the 2-prime,5-prime-internucleotide linkage could have played an important part in the early days of biological peptide synthesis.

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

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

    PubMed

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

    2013-01-01

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

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

    PubMed Central

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

    2013-01-01

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

  6. Spontaneous Planar Chiral Symmetry Breaking in Cells

    NASA Astrophysics Data System (ADS)

    Hadidjojo, Jeremy; Lubensky, David

    Recent progress in animal development has highlighted the central role played by planar cell polarity (PCP) in epithelial tissue morphogenesis. Through PCP, cells have the ability to collectively polarize in the plane of the epithelium by localizing morphogenetic proteins along a certain axis. This allows direction-dependent modulation of tissue mechanical properties that can translate into the formation of complex, non-rotationally invariant shapes. Recent experimental observations[1] show that cells, in addition to being planar-polarized, can also spontaneously develop planar chirality, perhaps in the effort of making yet more complex shapes that are reflection non-invariant. In this talk we will present our work in characterizing general mechanisms that can lead to spontaneous chiral symmetry breaking in cells. We decompose interfacial concentration of polarity proteins in a hexagonal cell packing into irreducible representations. We find that in the case of polar concentration distributions, a chiral state can only be reached from a secondary instability after the cells are polarized. However in the case of nematic distributions, we show that a finite-amplitude (subcritical, or ``first-order'') nematic transition can send the system from disorder directly to a chiral state. In addition, we find that perturbing the system by stretching the hexagonal packing enables direct (supercritical, or ``second-order'') chiral transition in the nematic case. Finally, we do a Landau expansion to study competition between stretch-induced chirality and the tendency towards a non-chiral state in packings that have retained the full 6-fold symmetry.

  7. Broken chiral symmetry on a null plane

    SciTech Connect

    Beane, Silas R.

    2013-10-15

    On a null-plane (light-front), all effects of spontaneous chiral symmetry breaking are contained in the three Hamiltonians (dynamical Poincaré generators), while the vacuum state is a chiral invariant. This property is used to give a general proof of Goldstone’s theorem on a null-plane. Focusing on null-plane QCD with N degenerate flavors of light quarks, the chiral-symmetry breaking Hamiltonians are obtained, and the role of vacuum condensates is clarified. In particular, the null-plane Gell-Mann–Oakes–Renner formula is derived, and a general prescription is given for mapping all chiral-symmetry breaking QCD condensates to chiral-symmetry conserving null-plane QCD condensates. The utility of the null-plane description lies in the operator algebra that mixes the null-plane Hamiltonians and the chiral symmetry charges. It is demonstrated that in a certain non-trivial limit, the null-plane operator algebra reduces to the symmetry group SU(2N) of the constituent quark model. -- Highlights: •A proof (the first) of Goldstone’s theorem on a null-plane is given. •The puzzle of chiral-symmetry breaking condensates on a null-plane is solved. •The emergence of spin-flavor symmetries in null-plane QCD is demonstrated.

  8. Chirally symmetric but confining dense, cold matter

    NASA Astrophysics Data System (ADS)

    Glozman, L. Ya.; Wagenbrunn, R. F.

    2008-03-01

    The folklore tradition about the QCD phase diagram is that at the chiral restoration phase transition at finite density hadrons are deconfined and there appears the quark matter. We address this question within the only known exactly solvable confining and chirally symmetric model. It is postulated within this model that there exists linear Coulomb-like confining interaction. The chiral symmetry breaking and the quark Green function are obtained from the Schwinger-Dyson (gap) equation while the color-singlet meson spectrum results from the Bethe-Salpeter equation. We solve this model at T=0 and finite chemical potential μ and obtain a clear chiral restoration phase transition at the critical value μcr. Below this value the spectrum is similar to the previously obtained one at μ=0. At μ>μcr the quarks are still confined and the physical spectrum consists of bound states which are arranged into a complete set of exact chiral multiplets. This explicitly demonstrates that a chirally symmetric matter consisting of confined but chirally symmetric hadrons at finite chemical potential is also possible in QCD. If so, there must be nontrivial implications for astrophysics.

  9. Chirally symmetric but confining dense, cold matter

    SciTech Connect

    Glozman, L. Ya.; Wagenbrunn, R. F.

    2008-03-01

    The folklore tradition about the QCD phase diagram is that at the chiral restoration phase transition at finite density hadrons are deconfined and there appears the quark matter. We address this question within the only known exactly solvable confining and chirally symmetric model. It is postulated within this model that there exists linear Coulomb-like confining interaction. The chiral symmetry breaking and the quark Green function are obtained from the Schwinger-Dyson (gap) equation while the color-singlet meson spectrum results from the Bethe-Salpeter equation. We solve this model at T=0 and finite chemical potential {mu} and obtain a clear chiral restoration phase transition at the critical value {mu}{sub cr}. Below this value the spectrum is similar to the previously obtained one at {mu}=0. At {mu}>{mu}{sub cr} the quarks are still confined and the physical spectrum consists of bound states which are arranged into a complete set of exact chiral multiplets. This explicitly demonstrates that a chirally symmetric matter consisting of confined but chirally symmetric hadrons at finite chemical potential is also possible in QCD. If so, there must be nontrivial implications for astrophysics.

  10. Chiral Alfvén Wave in Anomalous Hydrodynamics.

    PubMed

    Yamamoto, Naoki

    2015-10-01

    We study the hydrodynamic regime of chiral plasmas at high temperature. We find a new type of gapless collective excitation induced by chiral effects in an external magnetic field. This is a transverse wave, and it is present even in incompressible fluids, unlike the chiral magnetic and chiral vortical waves. The velocity is proportional to the coefficient of the gravitational anomaly. We briefly discuss the possible relevance of this "chiral Alfvén wave" in physical systems. PMID:26551804

  11. Elastic waves in structurally chiral composites

    SciTech Connect

    Yang, Shiuhkuang.

    1990-01-01

    Elastic wave propagation through structurally chiral (handed) media was studied. The primary objectives are to construct structurally chiral composites and to characterize their properties. Structurally chiral composites are constructed by stacking identical uniaxial plates, whose consecutive symmetric axes describe either a right- or a left-handed spiral. A matrix representation method is used to solve the elastic wave propagation in such layered composites. Numerical computation of the plane wave reflection and transmission characteristics for chiral arrangements are compared with those for the non-chiral one. It is concluded that the co-polarized characteristics are unaffected by the structural chirality, while the cross-polarized reflected and transmitted fields are greatly influenced by it. Numerical modeling is also applied for the real samples. The polarization ellipse of the transmitted field of each sample is calculated. To verify the form chirality, four glass-reinforced chiral and non-chiral composite samples are made from helix tape, molded, debulked, and cured individually under identical temperature and pressure histories. The spiral composites are characterized using shear and longitudinal wave transducers in ultrasonic experiments. Both the material properties and the polarization ellipse of the transmitted field of each sample are measured. It is proved conclusively that left and right handedness in the microstructures of a material rotates the plane of polarization of a propagating shear wave in the opposite directions. Thus it is now possible to say that by reducing the length scale of the handed microstructures tone more appropriate to its propagating wavelength, a medium is obtained that gives rise to effects similar to optical radar and optical dichroism.

  12. Extreme optical chirality of plasmonic nanohole arrays due to chiral Fano resonance

    NASA Astrophysics Data System (ADS)

    Kondratov, A. V.; Gorkunov, M. V.; Darinskii, A. N.; Gainutdinov, R. V.; Rogov, O. Y.; Ezhov, A. A.; Artemov, V. V.

    2016-05-01

    We study the physical origin of extreme optical chirality of subwavelength arrays of chiral holes in metal. We reconstruct the nanoscale relief of the hole arrays by the atomic-force microscopy and post-process the data to acquire an average unit-cell shape clear of noise and defects. For this shape, we perform the electromagnetic finite difference time domain simulations that reproduce all important features observed by the light-transmission experiments, including the notably strong circular dichroism and optical activity covering the whole range of possible values. To interpret the simulation results, we develop a chiral coupled-mode model which yields analytical expressions that fit accurately the numerical data in a broad wavelength range. Our conclusions undoubtedly link the extreme optical chirality to the plasmon resonances of chiral holes and the associated chiral Fano-type transmission resonance.

  13. Induced chirality through electromagnetic coupling between chiral molecular layers and plasmonic nanostructures.

    PubMed

    Abdulrahman, Nadia A; Fan, Z; Tonooka, Taishi; Kelly, Sharon M; Gadegaard, Nikolaj; Hendry, Euan; Govorov, Alexander O; Kadodwala, Malcolm

    2012-02-01

    We report a new approach for creating chiral plasmonic nanomaterials. A previously unconsidered, far-field mechanism is utilized which enables chirality to be conveyed from a surrounding chiral molecular material to a plasmonic resonance of an achiral metallic nanostructure. Our observations break a currently held preconception that optical properties of plasmonic particles can most effectively be manipulated by molecular materials through near-field effects. We show that far-field electromagnetic coupling between a localized plasmon of a nonchiral nanostructure and a surrounding chiral molecular layer can induce plasmonic chirality much more effectively (by a factor of 10(3)) than previously reported near-field phenomena. We gain insight into the mechanism by comparing our experimental results to a simple electromagnetic model which incorporates a plasmonic object coupled with a chiral molecular medium. Our work offers a new direction for the creation of hybrid molecular plasmonic nanomaterials that display significant chiroptical properties in the visible spectral region.

  14. Enhanced Chiral Recognition by Cyclodextrin Dimers

    PubMed Central

    Voskuhl, Jens; Schaepe, Kira; Ravoo, Bart Jan

    2011-01-01

    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. PMID:21845101

  15. Towards chirality-pure carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zhang, Yani; Zheng, Lianxi

    2010-10-01

    Current as-grown single-walled carbon nanotubes vary in diameter and chirality, which results in variations in their electronic and optical properties. Two approaches have been intensively studied to obtain chirality-pure nanotube structures and thus uniform properties for advanced applications. The first approach involves the post-synthesis separation according to the nanotubes' chiral vectors (n, m), and the second one involves direct synthes of carbon nanotubes with the same (n, m). This paper reviews the efforts along these two directions, with emphasis on the most recent progress of post-synthesis separation and the perspectives of controllable synthesis.

  16. Chiral Isotropic Liquids from Achiral Molecules

    SciTech Connect

    L Hough; M Spannuth; M Nakata; D Coleman; C Jones; G Dantlgraber; C Tschierske; J Watanabe; N Clark; et al.

    2011-12-31

    A variety of simple bent-core molecules exhibit smectic liquid crystal phases of planar fluid layers that are spontaneously both polar and chiral in the absence of crystalline order. We found that because of intralayer structural mismatch, such layers are also only marginally stable against spontaneous saddle splay deformation, which is incompatible with long-range order. This results in macroscopically isotropic fluids that possess only short-range orientational and positional order, in which the only macroscopically broken symmetry is chirality - even though the phases are formed from achiral molecules. Their conglomerate domains exhibit optical rotatory powers comparable to the highest ever found for isotropic fluids of chiral molecules.

  17. Synthesis of chiral dopants based on carbohydrates.

    PubMed

    Tsuruta, Toru; Koyama, Tetsuo; Yasutake, Mikio; Hatano, Ken; Matsuoka, Koji

    2014-07-01

    Chiral dopants based on carbohydrates for nematic liquid crystals were synthesized from D-glucose, and their helical twisting power (HTP) values were evaluated. The chiral dopants induced helices in the host nematic liquid crystals. An acetyl derivative having an ether-type glycosidic linkage between carbohydrate and a mesogenic moiety showed the highest HTP value of 10.4 μm(-1), while an acetyl derivative having an anomeric ester-type linkage did not show any HTP. It was surprising that this molecule had no HTP despite the presence of chirality in the molecule. A relationship between HTP and specific rotation was not observed in this study.

  18. A lattice chiral theory with multifermion couplings

    NASA Astrophysics Data System (ADS)

    Xue, She-Sheng

    1996-02-01

    Analyzing an SUL(2) ⊗ UR(1) chiral theory with multifermion couplings on a lattice, we find a possible region in the phase space of multifermion couplings, where no spontaneous symmetry breaking occurs, doublers are decoupled as massive Dirac fermions consistently with the SUL(2) ⊗ UR(1) chiral symmetry, the “spectator” fermion ψR( x) is free mode, whereas the normal mode of ψLi( x) is plausibly speculated to be chiral in the continuum limit. This is not in agreement with the general belief of the definite failure of theories so constructed.

  19. Undoubled Chiral Fermions on a Lattice

    NASA Astrophysics Data System (ADS)

    Xue, She-Sheng

    1997-02-01

    We analyze the dynamics of an SU L(2)⊗ U R(1) chiral theory on the lattice with a strong multifermion coupling. It is shown that no spontaneous symmetry breaking occurs; the "spectator" fermion ψR is a free mode; doublers are decoupled as massive Dirac fermions consistently with the chiral symmetries. In 1+1 dimension, we show that the right-handed three-fermion state disappears at the threshold and an undoubled left-handed chiral fermion remains in the continuum limit.

  20. The paradigm of Pseudodual Chiral Models

    SciTech Connect

    Zachos, C.K.; Curtright, T.L.

    1994-08-01

    This is a synopsis and extension of Phys. Rev. D49 5408 (1994). The Pseudodual Chiral Model illustrates 2-dimensional field theories which possess an infinite number of conservation laws but also allow particle production, at variance with naive expectations-a folk theorem of integrable models. We monitor the symmetries of the pseudodual model, both local and nonlocal, as transmutations of the symmetries of the (very different) usual Chiral Model. We refine the conventional algorithm to more efficiently produce the nonlocal symmetries of the model. We further find the canonical transformation which connects the usual chiral model to its fully equivalent dual model, thus contradistinguishing the pseudodual theory.

  1. The convoluted evolution of snail chirality

    NASA Astrophysics Data System (ADS)

    Schilthuizen, M.; Davison, A.

    2005-11-01

    The direction that a snail (Mollusca: Gastropoda) coils, whether dextral (right-handed) or sinistral (left-handed), originates in early development but is most easily observed in the shell form of the adult. Here, we review recent progress in understanding snail chirality from genetic, developmental and ecological perspectives. In the few species that have been characterized, chirality is determined by a single genetic locus with delayed inheritance, which means that the genotype is expressed in the mother's offspring. Although research lags behind the studies of asymmetry in the mouse and nematode, attempts to isolate the loci involved in snail chirality have begun, with the final aim of understanding how the axis of left-right asymmetry is established. In nature, most snail taxa (>90%) are dextral, but sinistrality is known from mutant individuals, populations within dextral species, entirely sinistral species, genera and even families. Ordinarily, it is expected that strong frequency-dependent selection should act against the establishment of new chiral types because the chiral minority have difficulty finding a suitable mating partner (their genitalia are on the ‘wrong’ side). Mixed populations should therefore not persist. Intriguingly, however, a very few land snail species, notably the subgenus Amphidromus sensu stricto, not only appear to mate randomly between different chiral types, but also have a stable, within-population chiral dimorphism, which suggests the involvement of a balancing factor. At the other end of the spectrum, in many species, different chiral types are unable to mate and so could be reproductively isolated from one another. However, while empirical data, models and simulations have indicated that chiral reversal must sometimes occur, it is rarely likely to lead to so-called ‘single-gene’ speciation. Nevertheless, chiral reversal could still be a contributing factor to speciation (or to divergence after speciation) when

  2. New chiral zinc complexes: synthesis, structure, and induction of axial chirality.

    PubMed

    Degenbeck, Helmut; Felten, Anne-Sophie; Escudero-Adán, Eduardo C; Benet-Buchholz, Jordi; Di Bari, Lorenzo; Pescitelli, Gennaro; Vidal-Ferran, Anton

    2012-08-20

    We describe an efficient methodology for the preparation of new chiral zinc complexes by assembling dynamically racemic biphenol derivatives and chiral 1,2-diamines with suitable zinc(II) precursors. Mononuclear and dinuclear zinc(II) complexes were formed from differently substituted biphenols. The solid-state and solution structural characterization of the resulting compounds allowed us to demonstrate a preferential sense of induced axial chirality for mononuclear complexes, a phenomenon that was not observed for the dinuclear ones. PMID:22862880

  3. Controlled chiral supramolecular assemblies of water soluble achiral porphyrins induced by chiral counterions.

    PubMed

    Rananaware, Anushri; La, Duong Duc; Al Kobaisi, Mohammad; Bhosale, Rajesh S; Bhosale, Sidhanath V; Bhosale, Sheshanath V

    2016-08-11

    We demonstrate a controlled chiral supramolecular assembly of achiral porphyrins induced by chiral d- and l-arginine (Arg) in water. Induction of chirality was confirmed by circular dichroism. TEM and SEM images confirm that these twisted ribbons are indeed formed by right- and left-handed helices with d- and l-Arg in water, respectively. The chiral assembly pathways described here are hierarchical, opening up the possibility that simple changes on microscopic (nm) length scales can be used to control structures on macroscopic (mm) length scales. PMID:27464524

  4. Chiral supramolecular polymers consisting of planar-chiral pillar[5]arene enantiomers.

    PubMed

    Ogoshi, Tomoki; Furuta, Takuya; Yamagishi, Tada-Aki

    2016-09-14

    Supramolecular polymers with diverse chiralities were constructed by supramolecular polymerization of planar-chiral host-guest conjugates in pS and pR forms. Hetero-chiral supramolecular polymerization using a racemic mixture of host-guest conjugates with pS and pR forms afforded a supramolecular polymer with a larger hydrodynamic radius than that obtained through homo-chiral supramolecular polymerization of host-guest conjugates with either pS or pR forms alone. PMID:27510359

  5. Scalar Mesons and Chiral States

    NASA Astrophysics Data System (ADS)

    Ishida, M.; Ishida, S.

    2004-08-01

    The essential points and physical backgrounds of the covariant level-classification scheme, based on Ū(12)SF⊗O(3, 1)L, are reviewed: This scheme is extended from the non-relativistic SU(6)SF⊗O(3)L scheme by introducing the new SU(2)-spin (ρ-spin) degree of freedom, which is necessary for covariant description of composite hadrons. Our scheme predicts the existence of new type of chiral mesons and baryons (Chiralons) out of the conventional SU(6)SF⊗O(3)L scheme. The σ nonet is a typical example of chiralons to be assigned to the (qq¯) relativistic S-wave state. The new narrow mesons Ds(2317)/Ds(2463) are naturally assigned as the ground-state scalar and axial-vector chiralons in the (cs¯) system.

  6. Chiral exceptional points in metasurfaces

    NASA Astrophysics Data System (ADS)

    Kang, Ming; Chen, Jing; Chong, Y. D.

    2016-09-01

    An exceptional point (EP) is a degeneracy occurring in a non-energy-conserving system, in which two eigenvectors of a non-Hermitian Hamiltonian coalesce. We explore how EPs can be realized in a metamaterial surface, or metasurface, consisting of a pair of lossy coupled linear antennas in each unit cell. EPs appear in the eigenvectors of the transmission matrix by tuning the frequency and the coupling and loss rates of the metasurface. Each EP is associated with the appearance of a circularly polarized transmission eigenstate; hence, within the parameter space of the system, the EPs lie along pairs of curves with distinct chirality. Our results are obtained using finite-difference time-domain simulations, as well as a fitted coupled-mode theory. The coupled-mode theory agrees well with the numerical results and is capable of accurately predicting the EP f curves.

  7. Cationic surfactants based on ferrocene

    SciTech Connect

    Pankratov, V.A.; Kucherova, N.L.; Abramzon, A.A.

    1988-07-20

    Quaternary ammonium salts based on ferrocene were synthesized and their surface active properties were studied as potential cationic surfactants and for uses including antiknock compounds. The salts were halide and nitrate derivatives of dimethylferrocenylmethylammonium and were prepared by aminomethylation of ferrocene. Chemical reaction yields, melting points, surface tension isotherms, and other characteristics were assessed.

  8. Instantons, chiral dynamics, and hadronic resonances

    SciTech Connect

    Cristoforetti, M.; Faccioli, P.; Traini, M.

    2007-03-01

    We use the interacting instanton liquid model (IILM) as a tool to study the role played by the chiral interactions in the lowest-lying vector and axial-vector meson resonances. We find that narrow a{sub 1} and {rho} meson resonances can be generated by instanton-induced chiral forces, even in the absence of confinement. In the IILM, these hadrons are found to have masses only about 30% larger than the experimental value and small width < or approx. 10-50 MeV. This result suggests that chiral interactions are very important in these systems and provide most of their mass. We explore the decaying patterns of the {rho} meson, in the absence of confinement. We argue that, in our model where only chiral forces are switched on, this meson decays dissociating into its quark-antiquark constituents.

  9. Personal recollections on chiral symmetry breaking

    NASA Astrophysics Data System (ADS)

    Kobayashi, Makoto

    2016-07-01

    The author's work on the mass of pseudoscalar mesons is briefly reviewed. The emergence of the study of CP violation in the renormalizable gauge theory from consideration of chiral symmetry in the quark model is discussed.

  10. Chiral Magnetic Effect in Heavy Ion Collisions

    DOE PAGESBeta

    Liao, Jinfeng

    2016-12-01

    The Chiral Magnetic Effect (CME) is a remarkable phenomenon that stems from highly nontrivial interplay of QCD chiral symmetry, axial anomaly, and gluonic topology. We show 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 |Β→|~m2π are present during the early stage of such collisions. Significant efforts have been made to look for CME signals in heavy ion collision experiments. Lastly, in this contribution we give a brief overview onmore » the status of such efforts.« less

  11. Application of cyclodextrins in chiral capillary electrophoresis.

    PubMed

    Rezanka, Pavel; Navrátilová, Klára; Rezanka, Michal; Král, Vladimír; Sýkora, David

    2014-10-01

    CE represents a very powerful separation tool in the area of chiral separations. CD-mediated chiral CE is a continuously flourishing technique within the frame of the electromigration methods. In this review, a brief overview of the synthetic procedures leading to modified CDs is provided first. Next, selected aspects related to the utilization of CDs in chiral CE are discussed specifically in the view of recently published data. Advantages of CDs and basic principles of chiral CE are remained. The topic of the determination of binding constants is touched. Particular attention is paid to the effort aiming at better understanding of the molecular level of the enantiorecognition between CDs and the analyte in the solution. Powerful approaches extensively utilized in this field are NMR, molecular modeling, and computer simulations. Then, a summary of applications of CDs in the CE enantioseparations is given, covering years 2008-2013. Finally, the general trend of modified CDs use in separation science is statistically evaluated.

  12. Chiral Pesticide Pharmacokinetics: A Range of Values

    EPA Science Inventory

    Approximately 30% of pesticides are chiral and used as mixtures of two or more stereoisomers. In biological systems, these stereoisomers can exhibit significantly different pharmacokinetics (absorption, distribution, metabolism, and elimination). In spite of these differences, th...

  13. Chirality in thiolate-protected gold clusters.

    PubMed

    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

  14. DH(*) in chiral smectics under electric field.

    PubMed

    Meyer, C; Rabette, C; Gisse, P; Antonova, K; Dozov, I

    2016-07-01

    The behavior of double helices (DH(*) formed in the temperature interval N(*) -SmA(*) in compounds of non-chiral liquid crystals doped with chiral molecules was investigated. Two different systems presenting left-handed and right-handed chirality were studied. A statistics of the handedness of the DH(*) revealed a correlation with the mixture chirality, as predicted theoretically in C. Meyer, Yu. A. Nastishin, M. Kleman, Phys. Rev. E 82, 031704 (2010). By applying a gradually increasing AC electric field, one can observe the shrinking of the cylinder circumscribing the DH(*) . This shrink is accompanied by a reduction of the DH(*) 's pitch. This effect was similar to the one produced by the decrease of temperature in the absence of the field. PMID:27465656

  15. Nondipole Photoemission from Chiral Enantiomers of Camphor

    NASA Astrophysics Data System (ADS)

    Bowen, K. P.; Stolte, W. C.; Young, J. A.; Demchenko, I. N.; Guillemin, R.; Hemmers, O.; Piancastelli, M. N.; Lindle, D. W.

    2010-03-01

    K-shell photoemission from the carbonyl carbon in the chiral molecule camphor has been studied in the region just above the core-shell ionization threshold. Differences between angular distributions of emitted photoelectrons from the two enantiomers are attributed to the influence of chirality combined with nondipole effects in the photoemission process, despite the fact the measurements were taken using linearly polarized x-rays. The results suggest the possibility of a new form of linear dichroism.

  16. Tests of Chiral Perturbation Theory with COMPASS

    SciTech Connect

    Friedrich, Jan

    2010-12-28

    The COMPASS experiment at CERN studies with high precision pion-photon induced reactions on nuclear targets via the Primakoff effect. This offers the possibility to test chiral perturbation theory (ChPT) in various channels: Pion Compton scattering allows to clarify the longstanding question of the pion polarisabilities, single neutral pion production is related to the chiral anomaly, and for the two-pion production cross sections exist as yet untested ChPT predictions.

  17. Chiral susceptibility in an effective interaction model

    SciTech Connect

    Min He; Yu Jiang; Sun Weimin; Zong Hongshi

    2008-04-01

    A closed integral expression for the chiral susceptibility at finite temperature is derived. The corresponding disconnected part, which proves to be of major physical relevance and free from the additive quadratic ultraviolet divergence, is identified. Then a calculation based on an effective model gluon propagator is conducted within the framework of the Dyson-Schwinger equations for two flavors in the chiral limit. A narrow, divergent peak is observed as temperature varies, and its implications are discussed.

  18. Chiral extrapolation of SU(3) amplitudes

    SciTech Connect

    Ecker, Gerhard

    2011-05-23

    Approximations of chiral SU(3) amplitudes at NNLO are proposed to facilitate the extrapolation of lattice data to the physical meson masses. Inclusion of NNLO terms is essential for investigating convergence properties of chiral SU(3) and for determining low-energy constants in a controllable fashion. The approximations are tested with recent lattice data for the ratio of decay constants F{sub K}/F{sub {pi}}.

  19. Control of normal chirality at hexagonal interfaces

    SciTech Connect

    Haraldsen, Jason T; Fishman, Randy Scott

    2010-01-01

    We study the net chirality created by the Dzyaloshinkii-Moriya interaction (DMI) at the boundary between hexagonal layers of magnetic and non-magnetic materials. It is shown that another mechanism besides elastic torsion is required to understand the change in chirality observed in Dy/Y multilayers during field-cooling. The paper shows that due to the overlap between magnetic and non-magnetic atoms, interfacial steps may produce a DMI normal to the interface in magnetic heterostructures.

  20. Analysis of rainbow scattering by a chiral sphere.

    PubMed

    Shang, Qing-Chao; Wu, Zhen-Sen; Qu, Tan; Li, Zheng-Jun; Bai, Lu; Gong, Lei

    2013-09-23

    Based on the scattering theory of a chiral sphere, rainbow phenomenon of a chiral sphere is numerically analyzed in this paper. For chiral spheres illuminated by a linearly polarized wave, there are three first-order rainbows, with whose rainbow angles varying with the chirality parameter. The spectrum of each rainbow structure is presented and the ripple frequencies are found associated with the size and refractive indices of the chiral sphere. Only two rainbow structures remain when the chiral sphere is illuminated by a circularly polarized plane wave. Finally, the rainbows of chiral spheres with slight chirality parameters are found appearing alternately in E-plane and H-plane with the variation of the chirality.

  1. Analysis of rainbow scattering by a chiral sphere.

    PubMed

    Shang, Qing-Chao; Wu, Zhen-Sen; Qu, Tan; Li, Zheng-Jun; Bai, Lu; Gong, Lei

    2013-09-23

    Based on the scattering theory of a chiral sphere, rainbow phenomenon of a chiral sphere is numerically analyzed in this paper. For chiral spheres illuminated by a linearly polarized wave, there are three first-order rainbows, with whose rainbow angles varying with the chirality parameter. The spectrum of each rainbow structure is presented and the ripple frequencies are found associated with the size and refractive indices of the chiral sphere. Only two rainbow structures remain when the chiral sphere is illuminated by a circularly polarized plane wave. Finally, the rainbows of chiral spheres with slight chirality parameters are found appearing alternately in E-plane and H-plane with the variation of the chirality. PMID:24104080

  2. A Molecular Model for Chiral Symmetry Breaking

    NASA Astrophysics Data System (ADS)

    Latinwo, Folarin; Stillinger, Frank; Debenedetti, Pablo

    In this work, we present a new class of molecular models for chiral phenomena in condensed matter systems. A key feature of these models is the ability of the four-site (tetramer) ``molecules'' to inter-convert between two distinct chiral forms (enantiomers). Given this feature, we use analytical theory and computer simulations to investigate the emergent chiral properties (including symmetry breaking) over a range of conditions. In particular, we consider the single-molecule level and condensed-phase behavior of our model system. Interestingly, we find that our liquid-phase predictions are in excellent agreement with recent experimental reports on chiral self-sorting in isotropic liquids. From this perspective, our model demonstrates accurate predictive capabilities, as well as a platform for understanding the microscopic origins of a variety of chiral phenomena. In a broader context, we anticipate that this class of models will be relevant to chirality-dominated areas such as the pharmaceutical industry and pre-biotic geochemistry.

  3. Staggered heavy baryon chiral perturbation theory

    SciTech Connect

    Bailey, Jon A.

    2008-03-01

    Although taste violations significantly affect the results of staggered calculations of pseudoscalar and heavy-light mesonic quantities, those entering staggered calculations of baryonic quantities have not been quantified. Here I develop staggered chiral perturbation theory in the light-quark baryon sector by mapping the Symanzik action into heavy baryon chiral perturbation theory. For 2+1 dynamical quark flavors, the masses of flavor-symmetric nucleons are calculated to third order in partially quenched and fully dynamical staggered chiral perturbation theory. To this order the expansion includes the leading chiral logarithms, which come from loops with virtual decuplet-like states, as well as terms of O(m{sub {pi}}{sup 3}), which come from loops with virtual octet-like states. Taste violations enter through the meson propagators in loops and tree-level terms of O(a{sup 2}). The pattern of taste symmetry breaking and the resulting degeneracies and mixings are discussed in detail. The resulting chiral forms are appropriate to lattice results obtained with operators already in use and could be used to study the restoration of taste symmetry in the continuum limit. I assume that the fourth root of the fermion determinant can be incorporated in staggered chiral perturbation theory using the replica method.

  4. Staggered heavy baryon chiral perturbation theory

    NASA Astrophysics Data System (ADS)

    Bailey, Jon A.

    2008-03-01

    Although taste violations significantly affect the results of staggered calculations of pseudoscalar and heavy-light mesonic quantities, those entering staggered calculations of baryonic quantities have not been quantified. Here I develop staggered chiral perturbation theory in the light-quark baryon sector by mapping the Symanzik action into heavy baryon chiral perturbation theory. For 2+1 dynamical quark flavors, the masses of flavor-symmetric nucleons are calculated to third order in partially quenched and fully dynamical staggered chiral perturbation theory. To this order the expansion includes the leading chiral logarithms, which come from loops with virtual decuplet-like states, as well as terms of O(mπ3), which come from loops with virtual octet-like states. Taste violations enter through the meson propagators in loops and tree-level terms of O(a2). The pattern of taste symmetry breaking and the resulting degeneracies and mixings are discussed in detail. The resulting chiral forms are appropriate to lattice results obtained with operators already in use and could be used to study the restoration of taste symmetry in the continuum limit. I assume that the fourth root of the fermion determinant can be incorporated in staggered chiral perturbation theory using the replica method.

  5. Chirality measures of α-amino acids.

    PubMed

    Jamróz, Michał H; Rode, Joanna E; Ostrowski, Sławomir; Lipiński, Piotr F J; Dobrowolski, Jan Cz

    2012-06-25

    To measure molecular chirality, the molecule is treated as a finite set of points in the Euclidean R(3) space supplemented by k properties, p(1)((i)), p(2)((i)), ..., p(k)((i)) assigned to the ith atom, which constitute a point in the Property P(k) space. Chirality measures are described as the distance between a molecule and its mirror image minimized over all its arbitrary orientation-preserving isometries in the R(3) × P(k) Cartesian product space. Following this formalism, different chirality measures can be estimated by taking into consideration different sets of atomic properties. Here, for α-amino acid zwitterionic structures taken from the Cambridge Structural Database and for all 1684 neutral conformers of 19 biogenic α-amino acid molecules, except glycine and cystine, found at the B3LYP/6-31G** level, chirality measures have been calculated by a CHIMEA program written in this project. It is demonstrated that there is a significant correlation between the measures determined for the α-amino acid zwitterions in crystals and the neutral forms in the gas phase. Performance of the studied chirality measures with changes of the basis set and computation method was also checked. An exemplary quantitative structure–activity relationship (QSAR) application of the chirality measures was presented by an introductory model for the benchmark Cramer data set of steroidal ligands of the sex-hormone binding globulin.

  6. Implications of Chirality of Drugs and Excipients in Physical Pharmacy.

    NASA Astrophysics Data System (ADS)

    Duddu, Sarma P.

    1993-01-01

    The interactions of enantiomers of a chiral drug with other chemical entities, which may lead to changes and stereoselective differences in the physicochemical properties of the drug, were investigated. The various interactions described below employed ephedrine, pseudoephedrine and some of their salts, and to a minor extent, propranolol hydrochloride. The interaction of ephedrinium or pseudoephedrinium with the achiral anion, salicylate, yielded crystalline salts with the notable exception of homochiral ephedrine. Racemic ephedrinium salicylate exists as a centrosymmetric crystal (P2_1/n) whereas racemic pseudoephedrinium salicylate is a mixture of homochiral crystals (P2 _1). The inability of ephedrinium to exist as a homochiral salicylate salt is attributed to a high energy conformation of the ephedrinium cation, following conformational analysis. Arising from conformationally favorable interactions, the crystallization of racemic ephedrinium salicylate from aqueous solutions was utilized to improve the enantiomeric purity of a partially resolved mixture of ephedrine from 60% to 82% in one crystallization step. Interaction of the opposite enantiomers of ephedrine and pseudoephedrine in the solid, liquid, solution and vapor state produced the respective racemic compounds. The formation of racemic ephedrine in the solid state as predominantly second order (k = 392 mol^{-1} hr^{-1}), probably mediated by the vapor phase. The formation of racemic pseudoephedrine was predominantly diffusion-controlled in the solid state via an intermediate non-crystalline phase. The interaction with traces of the opposite enantiomer during crystallization of (RS)-(-)-ephedrinium 2-naphthalenesulfonate and (SS)-(+)-pseudoephedrinium salicylate changed pharmaceutically important solid state properties, including dissolution rate. Uptake of the enantiomeric impurity was measured by a new, sensitive HPLC method. The enantiomeric impurity, at mole fractions <= 0.0027 greatly increased the

  7. Chiral recognition of zinc phthalocyanine on Cu(100) surface

    NASA Astrophysics Data System (ADS)

    Chen, Feng; Chen, Xiu; Liu, Lacheng; Song, Xin; Liu, Shuyi; Liu, Juan; Ouyang, Hongping; Cai, Yingxiang; Liu, Xiaoqing; Pan, Haibing; Zhu, Junfa; Wang, Li

    2012-02-01

    The windmill-like chiral nature of individual ZnPc molecules adsorbed on Cu(100) surface at room temperature has been revealed by scanning tunneling microscopy (STM) and the origin of such chirality is attributed to asymmetrical charge transfer between the molecules and the copper surface. Such chiral enantiomers do recognize each other in molecular level and spontaneously form second-level chiral supramolecular structures with the same chirality during thermally driven movements. The interactions between the ZnPc molecules during such chiral recognition process have been discussed based on the analysis of the sub-molecule-resolution STM images.

  8. Integration of inherent and induced chirality into subphthalocyanine analogue

    NASA Astrophysics Data System (ADS)

    Zhao, Luyang; Qi, Dongdong; Wang, Kang; Wang, Tianyu; Han, Bing; Tang, Zhiyong; Jiang, Jianzhuang

    2016-06-01

    Conventional conjugated systems are characteristic of only either inherent or induced chirality because of synthetic challenge in combination of chiral segment into the main chromophore. In this work, chiral binaphthyl segment is directly fused into the central chromophore of a subphthalocyanine skeleton, resulting in a novel type of chiral subphthalocyanine analogue (R/S)-1 of integrated inherent and induced chirality. Impressively, an obviously enhanced optical activity is discerned for (R/S)-1 molecules, and corresponding enhancement mechanism is elucidated in detail. The synthesis strategy based on rational molecular design will open the door towards fabrication of chiral materials with giant optical activity, which will have great potential in chiroptical devices.

  9. [Advances in polymer materials as chiral stationary phase].

    PubMed

    Dai, Rongji; Wang, Huiting; Sun, Weiwei; Deng, Yulin; Lü, Fang; Liu, Xiujie

    2016-01-01

    The applications of chiral drugs had a profound impact on human health. With the development of disciplines of chemistry, materials and life science, the research on the separation and analysis of chiral drugs became intensified. Chromatography and the selection of chiral stationary phase played important roles in resolving chiral drugs. The optimization of polymer materials and their derivatives as chiral stationary phase become the main issue in recent years. Recent studies as well as prospects in polymer materials used as chiral stationary phase are presented in this paper. PMID:27319162

  10. The asymmetric alkylation of dimethylhydrazones; intermolecular chirality transfer using sparteine as chiral ligand.

    PubMed

    McSweeney, Christina M; Foley, Vera M; McGlacken, Gerard P

    2014-12-01

    The asymmetric alkylation of ketones represents a fundamental transformation in organic chemistry. Chiral auxiliaries have been used almost exclusively for this transformation. Herein we describe a strategy for the generation of enantiomerically enriched α-alkylated ketones up to an er of 83 : 17, using a chiral ligand protocol.

  11. Salan ligands assembled around chiral bipyrrolidine: predetermination of chirality around octahedral Ti and Zr centres.

    PubMed

    Sergeeva, Ekaterina; Kopilov, Jacob; Goldberg, Israel; Kol, Moshe

    2009-06-01

    The first synthesis of Salan ligands assembled around the chiral 2,2'-bipyrrolidine backbone is described; as chelation to a metal can only occur via specific faces of the two pyrrolidine nitrogens, these ligands lead to predetermined chirality at metal centres of octahedral titanium and zirconium complexes. PMID:19462084

  12. Arene-thioether mixed complex radical cations

    SciTech Connect

    Werst, D.W.

    1994-03-01

    Studies of radiolytically generated radical cations in aromatic hydrocarbon solvents have led to the first direct characterization of monomeric thioether radical cations in liquid solution. Observation of these very reactive chemical intermediates is made possible by the great sensitivity of fluorescence-detected magnetic resonance (FDMR) and by solvent stabilization of the thioether radical cations via electron donation. Monomeric thioether radical cations in arene solvents such as toluene exist as arene-thioether mixed complex radical cations -- the first {pi}-lone pair mixed complex radical cations ever observed. Such orbital interactions are of fundamental importance for open-shell intermediates as they have consequences for both electronic structure and reactivity. Thioether radical cations provide a valuable test system to probe the chemical influence of orbital interactions that are generic to all {pi}-type and heteroatom-containing organic radical cations, and magnetic resonance provides unsurpassed structural resolution for condensed-phase paramagnetic intermediates.

  13. Halogenated silanes, radicals, and cations

    NASA Astrophysics Data System (ADS)

    Wang, Liming; He, Yi-Liang

    2008-09-01

    Quantum chemistry study has been carried out on the structure and energetics of halogenated silanes, radicals, and cations (SiHxXy0,+1, X = F, Cl, Br; x + y = 1-4). The geometries are optimized at B3LYP/6-31+G(2df,p) level. The adiabatic ionization energiess (IEas), relative energetics of cations, proton affinities (PAs) of silanes, and the enthalpies of formation are predicted using G3(CC) model chemistry. Non-classical ion complex structures are found for hydrogenated cations and transition states connecting classical and non-classical structures are also located. The most stable cations for silylene and silyl radicals have their classical divalent and trivalent structures, and those for silanes have non-classical structures except for SiH3Br+ and SiH2Br2+. The non-classical structures for halosilane cations imply difficulty in experimentally measurement of the adiabatic ionization energies using photoionization or photoelectron studies. For SiH3X, SiH2X2, and SiHX3, the G3(CC) adiabatic IEas to classical ionic structures closest to their neutrals agree better with the photoelectron spectroscopic measurements. The transition states between classical and non-classical structures also hamper the photoionization determination of the appearance energies for silylene cations from silanes. The G3(CC) results for SiHx0,+1 agree excellently with the photoionization mass spectrometric study, and the results for fluorinated and chlorinated species also agree with the previous theoretical predictions at correlation levels from BAC-MP4 to CCSD(T)/CBS. The predicted enthalpy differences between SiH2Cl+, SiHCl2+, and SiCl3+ are also in accordance with previous kinetics study. The G3(CC) results show large discrepancies to the collision-induced charge transfer and/or dissociation reactions involving SiFx+ and SiClx+ ions, for which the G3(CC) enthalpies of formation are also significantly differed from the previous theoretical predictions, especially on SiFx+ (x = 2-4). The G3

  14. Chiral Ruthenium(II) Polypyridyl Complexes: Stabilization of G-Quadruplex DNA, Inhibition of Telomerase Activity and Cellular Uptake

    PubMed Central

    Yu, Qianqian; Liu, Yanan; Wang, Chuan; Sun, Dongdong; Yang, Xingcheng; Liu, Yanyu; Liu, Jie

    2012-01-01

    Two ruthenium(II) complexes, Λ-[Ru(phen)2(p-HPIP)]2+ and Δ-[Ru(phen)2(p-HPIP)]2+, were synthesized and characterized via proton nuclear magnetic resonance spectroscopy, electrospray ionization-mass spectrometry, and circular dichroism spectroscopy. This study aims to clarify the anticancer effect of metal complexes as novel and potent telomerase inhibitors and cellular nucleus target drug. First, the chiral selectivity of the compounds and their ability to stabilize quadruplex DNA were studied via absorption and emission analyses, circular dichroism spectroscopy, fluorescence-resonance energy transfer melting assay, electrophoretic mobility shift assay, and polymerase chain reaction stop assay. The two chiral compounds selectively induced and stabilized the G-quadruplex of telomeric DNA with or without metal cations. These results provide new insights into the development of chiral anticancer agents for G-quadruplex DNA targeting. Telomerase repeat amplification protocol reveals the higher inhibitory activity of Λ-[Ru(phen)2(p-HPIP)]2+ against telomerase, suggesting that Λ-[Ru(phen)2(p-HPIP)]2+ may be a potential telomerase inhibitor for cancer chemotherapy. MTT assay results show that these chiral complexes have significant antitumor activities in HepG2 cells. More interestingly, cellular uptake and laser-scanning confocal microscopic studies reveal the efficient uptake of Λ-[Ru(phen)2(p-HPIP)]2+ by HepG2 cells. This complex then enters the cytoplasm and tends to accumulate in the nucleus. This nuclear penetration of the ruthenium complexes and their subsequent accumulation are associated with the chirality of the isomers as well as with the subtle environment of the ruthenium complexes. Therefore, the nucleus can be the cellular target of chiral ruthenium complexes for anticancer therapy. PMID:23236402

  15. Developing a Diastereoselective Intramolecular [4 + 3] Cycloaddition of Nitrogen-Stabilized Oxyallyl Cations Derived from N-Sulfonyl-Substituted Allenamides

    PubMed Central

    Lohse, Andrew G.; Hsung, Richard P.; Leider, Mitchell D.; Ghosh, Sunil K.

    2011-01-01

    Efforts toward achieving a practical and diastereoselective intramolecular [4 + 3] cycloaddition of nitrogen-stabilized oxyallyl cations with tethered dienes are described. Epoxidation of N-sulfonyl substituted allenamides with dimethyldioxirane (DMDO) generates nitrogen-stabilized oxyallyl cations that would readily undergo stereoselective [4 + 3] cycloaddition with dienes. Selectivity is found to depend on the tethering length as well as the stability of the oxyallyl cation intermediate, whether generated from N-carbamoyl- or N-sulfonyl-substituted allenamides. The use of chiral N-sulfonyl-substituted allenamide provided minimal diastereoselectivity in the cycloaddition, while high diastereoselectivity can be achieved with a stereocenter present on the tether. These studies provide further support for the synthetic utility of allenamides. PMID:21449577

  16. The chiral magnetic effect and chiral symmetry breaking in SU(3) quenched lattice gauge theory

    SciTech Connect

    Braguta, V. V.; Buividovich, P. V. Kalaydzhyan, T. Kuznetsov, S. V. Polikarpov, M. I.

    2012-04-15

    We study some properties of the non-Abelian vacuum induced by strong external magnetic field. We perform calculations in the quenched SU(3) lattice gauge theory with tadpole-improved Luescher-Weisz action and chirally invariant lattice Dirac operator. The following results are obtained: The chiral symmetry breaking is enhanced by the magnetic field. The chiral condensate depends on the strength of the applied field as a power function with exponent {nu} = 1.6 {+-} 0.2. There is a paramagnetic polarization of the vacuum. The corresponding susceptibility and other magnetic properties are calculated and compared with the theoretical estimations. There are nonzero local fluctuations of the chirality and electromagnetic current, which grow with the magnetic field strength. These fluctuations can be a manifestation of the Chiral Magnetic Effect.

  17. Cationic electrodepositable coating composition comprising lignin

    DOEpatents

    Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

    2013-07-30

    A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

  18. Diastereoselective aziridination of chiral electron-deficient olefins with N-chloro-N-sodiocarbamates catalyzed by chiral quaternary ammonium salts.

    PubMed

    Murakami, Yuta; Takeda, Youhei; Minakata, Satoshi

    2011-08-01

    Chiral quaternary ammonium salt-catalyzed diastereoselective aziridination of electron-deficient olefins that possess a chiral auxiliary with N-chloro-N-sodiocarbamates was developed. The key to high stereoselectivity was found to be the employment of the "matching" stereochemical combination of chiral auxiliary/ammonium salt. For example, when 3-phenyl-(4R,7S)-4-methyl-7-isopropyl-4,5,6,7-tetrahydroindazole (L-menthopyrazole) as a chiral auxiliary and a cinchonidine-derived chiral ammonium salt as a catalyst were applied to the reaction system, perfect diastereoselectivity was realized. Furthermore, the preparation of enantiomerically pure aziridines by removal of the chiral auxiliary was demonstrated.

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

    PubMed Central

    Tian, Xiaorui; Fang, Yurui; Sun, Mengtao

    2015-01-01

    Chiral fields with large optical chirality are very important in chiral molecules analysis, sensing and other measurements. Plasmonic nanostructures have been proposed to realize such super chiral fields for enhancing weak chiral signals. However, most of them cannot provide uniform chiral near-fields close to the structures, which makes these nanostructures not so efficient for applications. Plasmonic helical nanostructures and blocked squares have been proved to provide uniform chiral near-fields, but structure fabrication is a challenge. In this paper, we show that very simple plasmonic dimer structures can provide uniform chiral fields in the gaps with large enhancement of both near electric fields and chiral fields under linearly polarized light illumination with polarization off the dimer axis at dipole resonance. An analytical dipole model is utilized to explain this behavior theoretically. 30 times of volume averaged chiral field enhancement is gotten in the whole gap. Chiral fields with opposite handedness can be obtained simply by changing the polarization to the other side of the dimer axis. It is especially useful in Raman optical activity measurement and chiral sensing of small quantity of chiral molecule. PMID:26621558

  20. Symmetry, Structure, and Dynamics of Monoaxial Chiral Magnets

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    Nontrivial spin orders with magnetic chirality emerge in a particular class of magnetic materials with structural chirality, which are frequently referred to as chiral magnets. Various interesting physical properties are expected to be induced in chiral magnets through the coupling of chiral magnetic orders with conduction electrons and electromagnetic fields. One promising candidate for achieving these couplings is a chiral spin soliton lattice. Here, we review recent experimental observations mainly carried out on the monoaxial chiral magnetic crystal CrNb3S6 via magnetic imaging using electron, neutron, and X-ray beams and magnetoresistance measurements, together with the strategy for synthesizing chiral magnetic materials and underlying theoretical backgrounds. The chiral soliton lattice appears under a magnetic field perpendicular to the chiral helical axis and is very robust and stable with phase coherence on a macroscopic length scale. The tunable and topological nature of the chiral soliton lattice gives rise to nontrivial physical properties. Indeed, it is demonstrated that the interlayer magnetoresistance scales to the soliton density, which plays an essential role as an order parameter in chiral soliton lattice formation, and becomes quantized with the reduction of the system size. These interesting features arising from macroscopic phase coherence unique to the chiral soliton lattice will lead to the exploration of routes to a new paradigm for applications in spin electronics using spin phase coherence.

  1. Calorimetric study of cationic photopolymerization

    NASA Astrophysics Data System (ADS)

    Czajlik, I.; Hedvig, P.; Ille, A.; Dobó, J.

    1996-03-01

    The photopolymerization of penta-erythritol tetra-glycidyl ether (initiator Degacure KI-85) was studied by a du Pont 910 type DSC. From our experimental results the following conclusions can be drawn: (1) During the cationic polymerization reaction the lifetime of the initiating centers are long compared to the lifetime of free radicals in case of radical polymerization. (2) The rate of deactivation of the initiating centers increases with increasing temperature.

  2. Chiral dynamics and peripheral transverse densities

    SciTech Connect

    Granados, Carlos G.; Weiss, Christian

    2014-01-01

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

  3. Isospin breaking and chiral symmetry restoration

    SciTech Connect

    Gomez Nicola, A.; Torres Andres, R.

    2011-04-01

    We analyze quark condensates and chiral (scalar) susceptibilities including isospin-breaking effects at finite temperature T. These include m{sub u{ne}}m{sub d} contributions as well as electromagnetic (e{ne}0) corrections, both treated in a consistent chiral Lagrangian framework to leading order in SU(2) and SU(3) chiral perturbation theory, so that our predictions are model-independent. The chiral restoration temperature extracted from = is almost unaffected, while the isospin-breaking order parameter grows with T for the three-flavor case SU(3). We derive a sum rule relating the condensate ratio (e{ne}0)/(e=0) with the scalar susceptibility difference {chi}(T)-{chi}(0), directly measurable on the lattice. This sum rule is useful also for estimating condensate errors in staggered lattice analysis. Keeping m{sub u{ne}}m{sub d} allows one to obtain the connected and disconnected contributions to the susceptibility, even in the isospin limit, whose temperature, mass, and isospin-breaking dependence we analyze in detail. The disconnected part grows linearly, diverging in the chiral (infrared) limit as T/M{sub {pi}}, while the connected part shows a quadratic behavior, infrared regular as T{sup 2}/M{sub {eta}}{sup 2}, and coming from {pi}{sup 0{eta}} mixing terms. This smooth connected behavior suggests that isospin-breaking correlations are weaker than critical chiral ones near the transition temperature. We explore some consequences in connection with lattice data and their scaling properties, for which our present analysis for physical masses, i.e. beyond the chiral limit, provides a useful model-independent description for low and moderate temperatures.

  4. Comparison of Cobalt and Nickel Complexes with Sterically Demanding Cyclic Diphosphine Ligands: Electrocatalytic H2 Production by [Co(PtBu2NPh2)(CH3CN)3](BF4)2

    SciTech Connect

    Wiedner, Eric S.; Yang, Jenny Y.; Dougherty, William G.; Kassel, W. S.; Bullock, R. Morris; Rakowski DuBois, Mary; DuBois, Daniel L.

    2010-11-08

    The cyclic diphosphine ligands PtBu2NPh2 and PtBu2NBz2 have been synthesized and used to prepare new complexes of Co(II) and Ni(II) with the formula [M(PtBu2NR2)(CH3CN)n](BF4)2 (n = 2, 3). The products have been characterized by variable temperature NMR data, X-ray diffraction studies, and cyclic voltammetry, and properties of the new complexes have been compared with previously studied complexes containing PPh2NR2 ligands. The variation of either phosphorus or nitrogen substituents in these ligands can result in significant differences in the structure, electrochemistry and reactivity of the metal complexes. [Co(PtBu2NPh2)(CH3CN)3](BF4)2 is found to be an effective electrocatalyst for the formation of hydrogen using bromoanilinium tetrafluoroborate as the acid, with a turnover frequency of 62 s-1 and an overpotential of 160 mV, and these cobalt derivatives are a promising class of catalysts for further study and optimization. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.

  5. Improved Measure of Local Chirality

    SciTech Connect

    Terrence Draper; Andrei Alexandru; Ying Chen; Shao-Jing Dong; Ivan Horvath; Frank Lee; Nilmani Mathur; Harry B. Thacker; Sonali Tamhankar; Jianbo Zhang

    2004-06-01

    It is popular to probe the structure of the QCD vacuum indirectly by studying individual fermion eigenmodes, because this provides a natural way to filter out UV fluctuations. The double-peaking in the distribution of the local chiral orientation parameter (X) has been offered as evidence, by some, in support of a particular model of the vacuum. Here we caution that the X-distribution peaking varies significantly with various versions of the definition of X. Furthermore, each distribution varies little from that resulting from a random reshuffling of the left-handed (and independently the right-handed) fields, which destroys any QCD-induced left-right correlation; that is, the double-peaking is mostly a phase-space effect. We propose a new universal definition of the X parameter whose distribution is uniform for randomly reshuffled fields. Any deviations from uniformity for actual data can then be directly attributable to QCD-induced dynamics. We find that the familiar double peak disappears.

  6. Enantioconvergent Nucleophilic Substitution Reaction of Racemic Alkyne-Dicobalt Complex (Nicholas Reaction) Catalyzed by Chiral Brønsted Acid.

    PubMed

    Terada, Masahiro; Ota, Yusuke; Li, Feng; Toda, Yasunori; Kondoh, Azusa

    2016-08-31

    Catalytic enantioselective syntheses enable a practical approach to enantioenriched molecules. While most of these syntheses have been accomplished by reaction at the prochiral sp(2)-hybridized carbon atom, little attention has been paid to enantioselective nucleophilic substitution at the sp(3)-hybridized carbon atom. In particular, substitution at the chiral sp(3)-hybridized carbon atom of racemic electrophiles has been rarely exploited. To establish an unprecedented enantioselective substitution reaction of racemic electrophiles, enantioconvergent Nicholas reaction of an alkyne-dicobalt complex derived from racemic propargylic alcohol was developed using a chiral phosphoric acid catalyst. In the present enantioconvergent process, both enantiomers of the racemic alcohol were transformed efficiently to a variety of thioethers with high enantioselectivity. The key to achieving success is dynamic kinetic asymmetric transformation (DYKAT) of enantiomeric cationic intermediates generated via dehydroxylation of the starting racemic alcohol under the influence of the chiral phosphoric acid catalyst. The present fascinating DYKAT involves the efficient racemization of these enantiomeric intermediates and effective resolution of these enantiomers through utilization of the chiral conjugate base of the phosphoric acid. PMID:27490239

  7. Enantioconvergent Nucleophilic Substitution Reaction of Racemic Alkyne-Dicobalt Complex (Nicholas Reaction) Catalyzed by Chiral Brønsted Acid.

    PubMed

    Terada, Masahiro; Ota, Yusuke; Li, Feng; Toda, Yasunori; Kondoh, Azusa

    2016-08-31

    Catalytic enantioselective syntheses enable a practical approach to enantioenriched molecules. While most of these syntheses have been accomplished by reaction at the prochiral sp(2)-hybridized carbon atom, little attention has been paid to enantioselective nucleophilic substitution at the sp(3)-hybridized carbon atom. In particular, substitution at the chiral sp(3)-hybridized carbon atom of racemic electrophiles has been rarely exploited. To establish an unprecedented enantioselective substitution reaction of racemic electrophiles, enantioconvergent Nicholas reaction of an alkyne-dicobalt complex derived from racemic propargylic alcohol was developed using a chiral phosphoric acid catalyst. In the present enantioconvergent process, both enantiomers of the racemic alcohol were transformed efficiently to a variety of thioethers with high enantioselectivity. The key to achieving success is dynamic kinetic asymmetric transformation (DYKAT) of enantiomeric cationic intermediates generated via dehydroxylation of the starting racemic alcohol under the influence of the chiral phosphoric acid catalyst. The present fascinating DYKAT involves the efficient racemization of these enantiomeric intermediates and effective resolution of these enantiomers through utilization of the chiral conjugate base of the phosphoric acid.

  8. The synthesis and structure of chiral enamine N-oxides.

    PubMed

    O'Neil, I A; McConville, M; Zhou, K; Brooke, C; Robertson, C M; Berry, N G

    2014-07-14

    Chiral enamine N-oxides have been synthesised by a diastereoselective intermolecular reverse-Cope cycloaddition reaction between chiral hydroxylamines and activated acetylenes. Their structures have been investigated by NMR, X-ray crystallography and computational methods.

  9. Macroscopic chirality of a liquid crystal from nonchiral molecules

    SciTech Connect

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

    2001-06-01

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

  10. METHODS DEVELOPMENT FOR THE ANALYSIS OF CHIRAL PESTICIDES

    EPA Science Inventory

    Chiral compounds exist as a pair of nonsuperimposable mirror images called enantiomers. Enantiomers have identical physical-chemical properties, but their interactions with other chiral molecules, toxicity, biodegradation, and fate are often different. Many pharmaceutical com...

  11. Chiral heteropoly blues and controllable switching of achiral polyoxometalate clusters.

    PubMed

    Wang, Yizhan; Li, Haolong; Wu, Che; Yang, Yang; Shi, Lei; Wu, Lixin

    2013-04-22

    Managing the blues: Chiral heteropoly blues of achiral polyoxometalate clusters were created through an intermolecular interaction with a chiral organic compound. Controllable chiroptical switching of the cluster complexes was possible through reversible photochromism of the polyoxometalates (see picture).

  12. PESTICIDE EXPOSURE AND CHIRAL CHEMISTRY: THE PYRETHROID FAMILY

    EPA Science Inventory

    Advances in chiral chromatography significantly advanced the ability to analyze individual enantiomers of chiral compounds. These techniques are being employed at the U.S. EPA for human exposure and ecological research studies. Enantiomer fractions (EFs) were measured for cisp...

  13. On the chiral imbalance and Weibel instabilities

    NASA Astrophysics Data System (ADS)

    Kumar, Avdhesh; Bhatt, Jitesh R.; Kaw, P. K.

    2016-06-01

    We study the chiral-imbalance and the Weibel instabilities in presence of the quantum anomaly using the Berry-curvature modified kinetic equation. We argue that in many realistic situations, e.g. relativistic heavy-ion collisions, both the instabilities can occur simultaneously. The Weibel instability depends on the momentum anisotropy parameter ξ and the angle (θn) between the propagation vector and the anisotropy direction. It has maximum growth rate at θn = 0 while θn = π / 2 corresponds to a damping. On the other hand the pure chiral-imbalance instability occurs in an isotropic plasma and depends on difference between the chiral chemical potentials of right and left-handed particles. It is shown that when θn = 0, only for a very small values of the anisotropic parameter ξ ∼ξc, growth rates of the both instabilities are comparable. For the cases ξc < ξ ≪ 1 or ξ ≳ 1 at θn = 0, the Weibel modes dominate over the chiral-imbalance instability if μ5 / T ≤ 1. However, when μ5 / T ≥ 1, it is possible to have dominance of the chiral-imbalance modes at certain values of θn for an arbitrary ξ.

  14. Chirality dependent spin polarization of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Wang, Jia; Jiang, Wanrun; Wang, Bo; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin

    2016-02-01

    The spin polarization of carbon nanotubes (CNTs) offers a tunable building block for spintronic devices and is also crucial for realizing carbon-based electronics. However, the effect of chiral CNTs is still unclear. In this paper, we use the density functional theory (DFT) method to investigate the spin polarization of a series of typical finite-length chiral CNTs (9, m). The results show that the spin density of chiral CNTs (9, m) decreases gradually with the increase in m and vanishes altogether when m is larger than or equal to 6. The armchair edge units on both ends of the (9, m) CNTs exhibit a clear inhibition of spin polarization, allowing control of the spin density of (9, m) CNTs by adjusting the number of armchair edge units on the tube end. Furthermore, analysis of the orbitals shows that the spin of the ground state for (9, m) CNTs mainly comes from the contributions of the frontier molecular orbitals (MOs), and the energy gap decreases gradually with the spin density for chiral CNTs. Our work further develops the study of the spin polarization of CNTs and provides a strategy for controlling the spin polarization of functional molecular devices through chiral vector adjustment.

  15. Ratchet transport powered by chiral active particles

    PubMed Central

    Ai, Bao-quan

    2016-01-01

    We numerically investigate the ratchet transport of mixtures of active and passive particles in a transversal asymmetric channel. A big passive particle is immersed in a ‘sea’ of active particles. Due to the chirality of active particles, the longitudinal directed transport is induced by the transversal asymmetry. For the active particles, the chirality completely determines the direction of the ratchet transport, the counterclockwise and clockwise particles move to the opposite directions and can be separated. However, for the passive particle, the transport behavior becomes complicated, the direction is determined by competitions among the chirality, the self-propulsion speed, and the packing fraction. Interestingly, within certain parameters, the passive particle moves to the left, while active particles move to the right. In addition, there exist optimal parameters (the chirality, the height of the barrier, the self-propulsion speed and the packing fraction) at which the rectified efficiency takes its maximal value. Our findings could be used for the experimental pursuit of the ratchet transport powered by chiral active particles. PMID:26795952

  16. A liquid crystalline chirality balance for vapours

    PubMed Central

    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 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). PMID:24781531

  17. Ratchet transport powered by chiral active particles.

    PubMed

    Ai, Bao-quan

    2016-01-01

    We numerically investigate the ratchet transport of mixtures of active and passive particles in a transversal asymmetric channel. A big passive particle is immersed in a 'sea' of active particles. Due to the chirality of active particles, the longitudinal directed transport is induced by the transversal asymmetry. For the active particles, the chirality completely determines the direction of the ratchet transport, the counterclockwise and clockwise particles move to the opposite directions and can be separated. However, for the passive particle, the transport behavior becomes complicated, the direction is determined by competitions among the chirality, the self-propulsion speed, and the packing fraction. Interestingly, within certain parameters, the passive particle moves to the left, while active particles move to the right. In addition, there exist optimal parameters (the chirality, the height of the barrier, the self-propulsion speed and the packing fraction) at which the rectified efficiency takes its maximal value. Our findings could be used for the experimental pursuit of the ratchet transport powered by chiral active particles.

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

    PubMed Central

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

    2012-01-01

    The use of iodine as a catalyst and either acetic or trifluoroacetic acid as a derivatizing reagent for determining the enantiomeric composition of acyclic and cyclic aliphatic chiral alcohols was investigated. Optimal conditions were selected according to the molar ratio of alcohol to acid, the reaction time, and the reaction temperature. Afterwards, chiral stability of chiral carbons was studied. Although no isomerization was observed when acetic acid was used, partial isomerization was detected with the trifluoroacetic acid. A series of chiral alcohols of a widely varying structural type were then derivatized with acetic acid using the optimal conditions. The resolution of the enantiomeric esters and the free chiral alcohols was measured using a capillary gas chromatograph equipped with a CP Chirasil-DEX CB column. The best resolutions were obtained with 2-pentyl acetates (α = 3.00) and 2-hexyl acetates (α = 1.95). This method provides a very simple and efficient experimental workup procedure for analyzing chiral alcohols by chiral-phase GC. PMID:22649749

  19. Chiral electronic transitions in fluorescent silver clusters stabilized by DNA.

    PubMed

    Swasey, Steven M; Karimova, Natalia; Aikens, Christine M; Schultz, Danielle E; Simon, Anna J; Gwinn, Elisabeth G

    2014-07-22

    Fluorescent, DNA-stabilized silver clusters are receiving much attention for sequence-selected colors and high quantum yields. However, limited knowledge of cluster structure is constraining further development of these "AgN-DNA" nanomaterials. We report the structurally sensitive, chiroptical activity of four pure AgN-DNA with wide ranging colors. Ubiquitous features in circular dichroism (CD) spectra include a positive dichroic peak overlying the lowest energy absorbance peak and highly anisotropic, negative dichroic peaks at energies well below DNA transitions. Quantum chemical calculations for bare chains of silver atoms with nonplanar curvature also exhibit these striking features, indicating electron flow along a chiral, filamentary metallic path as the origin for low-energy AgN-DNA transitions. Relative to the bare DNA, marked UV changes in CD spectra of AgN-DNA and silver cation-DNA solutions indicate that ionic silver content constrains nucleobase conformation. Changes in solvent composition alone can reorganize cluster structure, reconfiguring chiroptical properties and fluorescence.

  20. Chirality Change by Grinding Crystals in Solution

    NASA Astrophysics Data System (ADS)

    Viedma, Cristobal

    2010-07-01

    One of the greatest unsolved problems in chemistry is the origin of homochirality in the biosphere, that is, the fact that l-amino acids and d-sugars dominate in biology, while laboratory experiments with stereoselective reactions only produce racemic mixtures. Several models have been proposed to address the question of how enantiomerically pure solutions or crystalline phases could have emerged from a presumably racemic prebiotic world. Here we show that two populations of amino acid crystals of "left" and "right" hand cannot coexist in solution: one of the chiral populations disappears in an irreversible autocatalytic process that nurtures the other one. Final and complete chiral purity seems to be an inexorable fate in our systems, under grinding, in the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking has become firmly established but the underlying mechanism is being debated and we have no definitive answer.

  1. Chirality Change by Grinding Crystals in Solution

    SciTech Connect

    Viedma, Cristobal

    2010-07-22

    One of the greatest unsolved problems in chemistry is the origin of homochirality in the biosphere, that is, the fact that l-amino acids and d-sugars dominate in biology, while laboratory experiments with stereoselective reactions only produce racemic mixtures. Several models have been proposed to address the question of how enantiomerically pure solutions or crystalline phases could have emerged from a presumably racemic prebiotic world. Here we show that two populations of amino acid crystals of 'left' and 'right' hand cannot coexist in solution: one of the chiral populations disappears in an irreversible autocatalytic process that nurtures the other one. Final and complete chiral purity seems to be an inexorable fate in our systems, under grinding, in the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking has become firmly established but the underlying mechanism is being debated and we have no definitive answer.

  2. A semiclassical formulation of the chiral magnetic effect and chiral anomaly in even d + 1 dimensions

    NASA Astrophysics Data System (ADS)

    Dayi, Ömer F.; Elbistan, Mahmut

    2016-05-01

    In terms of the matrix valued Berry gauge field strength for the Weyl Hamiltonian in any even space-time dimensions a symplectic form whose elements are matrices in spin indices is introduced. Definition of the volume form is modified appropriately. A simple method of finding the path integral measure and the chiral current in the presence of external electromagnetic fields is presented. It is shown that within this new approach the chiral magnetic effect as well as the chiral anomaly in even d + 1 dimensions are accomplished straightforwardly.

  3. Chiral Molecules Revisited by Broadband Microwave Spectroscopy

    NASA Astrophysics Data System (ADS)

    Schnell, Melanie

    2014-06-01

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

  4. Chirality: a blueprint for the future.

    PubMed

    Burke, D; Henderson, D J

    2002-04-01

    The chirality that is inherent in the enzyme systems of living organisms results in an abundance of enantiopure organic molecules in the living world. In addition to the optical properties first noticed by Pasteur, stereospecific interactions at recognition sites result in differences in both biological and toxicological effects. This fact underlies the continuing growth in chiral chemistry, rooted as it is in fundamental biochemistry. The pharmaceutical industry has undergone a strategic shift and embraced the wide spectrum of asymmetrical synthetic methods now available. The use of these processes in developmental synthesis and large-scale manufacturing has provided new challenges in drug discovery, motivated by a desire to improve industrial efficacy and decrease the time from the conception of a new drug to the market. The economic impact of the industrial production of chiral drugs is now huge--more than 50% of the 500 top-selling drugs were single-enantiomers in 1997. Sales have continued to increase by more than 20% for the past 6 yr and worldwide annual sales of enantiomeric drugs exceeded US$100 billion for the first time in the year 2000, chiral drugs representing close to one-third of all sales worldwide. While some 'chiral switches' may be of less apparent benefit, or indeed detrimental in some cases, encouragement by the regulatory agencies and the ability to extend the life cycle of a drug coming off patent promotes the trend. However, it may turn out to be the ability to provide chiral templates, and thereby attack the key targets of selectivity and specificity, that will lead to the greatest benefits. Research into new chemical entities that can interact specifically with enzyme families may potentially lead to new therapies for complex disease processes. As Richards has stated, the approach is designed to create a made to measure product, rather than one off the peg.

  5. Cation disorder in shocked orthopyroxene.

    NASA Technical Reports Server (NTRS)

    Dundon, R. W.; Hafner, S. S.

    1971-01-01

    The study of cation distributions over nonequivalent lattice sites in minerals may reveal information on the history of temperature and pressure in rocks. Chemically homogeneous orthopyroxene specimens were shocked under well-controlled conditions in the laboratory in order to provide a basis for the interpretation of more complex natural materials. As a result of the investigation it is concluded that the distribution of magnesium and iron over the M1 and M2 positions in Bamle enstatite shocked at 1 megabar is highly disordered. It corresponds to an equilibrium distribution of at least 1000 C.

  6. Probing Chiral Interactions in Light Nuclei

    SciTech Connect

    Nogga, A; Barrett, B R; Meissner, U; Witala, H; Epelbaum, E; Kamada, H; Navratil, P; Glockle, W; Vary, J P

    2004-01-08

    Chiral two- and three-nucleon interactions are studied in a few-nucleon systems. We investigate the cut-off dependence and convergence with respect to the chiral expansion. It is pointed out that the spectra of light nuclei are sensitive to the three-nucleon force structure. As an example, we present calculations of the 1{sup +} and 3{sup +} states of {sup 6}Li using the no-core shell model approach. The results show contributions of the next-to-next-to-leading order terms to the spectra, which are not correlated to the three-nucleon binding energy prediction.

  7. Chiral thermoelectrics with quantum Hall edge states.

    PubMed

    Sánchez, Rafael; Sothmann, Björn; Jordan, Andrew N

    2015-04-10

    The thermoelectric properties of a three-terminal quantum Hall conductor are investigated. We identify a contribution to the thermoelectric response that relies on the chirality of the carrier motion rather than on spatial asymmetries. The Onsager matrix becomes maximally asymmetric with configurations where either the Seebeck or the Peltier coefficients are zero while the other one remains finite. Reversing the magnetic field direction exchanges these effects, which originate from the chiral nature of the quantum Hall edge states. The possibility to generate spin-polarized currents in quantum spin Hall samples is discussed. PMID:25910147

  8. Chiral Thermoelectrics with Quantum Hall Edge States

    NASA Astrophysics Data System (ADS)

    Sánchez, Rafael; Sothmann, Björn; Jordan, Andrew N.

    2015-04-01

    The thermoelectric properties of a three-terminal quantum Hall conductor are investigated. We identify a contribution to the thermoelectric response that relies on the chirality of the carrier motion rather than on spatial asymmetries. The Onsager matrix becomes maximally asymmetric with configurations where either the Seebeck or the Peltier coefficients are zero while the other one remains finite. Reversing the magnetic field direction exchanges these effects, which originate from the chiral nature of the quantum Hall edge states. The possibility to generate spin-polarized currents in quantum spin Hall samples is discussed.

  9. Four-modulus ``Swiss Cheese'' chiral models

    NASA Astrophysics Data System (ADS)

    Collinucci, Andrés; Kreuzer, Maximilian; Mayrhofer, Christoph; Walliser, Nils-Ole

    2009-07-01

    We study the `Large Volume Scenario' on explicit, new, compact, four-modulus Calabi-Yau manifolds. We pay special attention to the chirality problem pointed out by Blumenhagen, Moster and Plauschinn. Namely, we thoroughly analyze the possibility of generating neutral, non-perturbative superpotentials from Euclidean D3-branes in the presence of chirally intersecting D7-branes. We find that taking proper account of the Freed-Witten anomaly on non-spin cycles and of the Kähler cone conditions imposes severe constraints on the models. Nevertheless, we are able to create setups where the constraints are solved, and up to three moduli are stabilized.

  10. Asymmetric petasis reactions catalyzed by chiral biphenols.

    PubMed

    Lou, Sha; Schaus, Scott E

    2008-06-01

    Chiral biphenols catalyze the enantioselective Petasis reaction of alkenyl boronates, secondary amines, and ethyl glyoxylate. The reaction requires the use of 15 mol % of (S)-VAPOL as the catalyst, alkenyl boronates as nucleophiles, ethyl glyoxylate as the aldehyde component, and 3 A molecular sieves as an additive. The chiral alpha-amino ester products are obtained in good yields (71-92%) and high enantiomeric ratios (89:11-98:2). Mechanistic investigations indicate single ligand exchange of acyclic boronate with VAPOL and tetracoordinate boronate intermediates. PMID:18459782

  11. Consistent Two-Dimensional Chiral Gravity

    NASA Astrophysics Data System (ADS)

    Smailagic, A.; Spallucci, E.

    We study chiral induced gravity in the light-cone gauge and show that the theory is consistent for a particular choice of chiralities. The corresponding Kac-Moody central charge has no forbidden region of complex values. Generalized analysis of the critical exponents is given and their relation to the SL(2,R) vacuum states is elucidated. All the parameters containing information about the theory can be traced back to the characteristics of the residual symmetry group in the light-cone gauge.

  12. Chirality, quantum mechanics, and biological determinism

    NASA Astrophysics Data System (ADS)

    Davies, P. C. W.

    2006-08-01

    The holy grail of astrobiology is the discovery of a second sample of life that has emerged de novo, independently of life on Earth (as opposed to extraterrestrial life that shares a common origin with terrestrial life via a panspermia process). It would then be possible to separate aspects of biology that are lawlike and expected from those that are accidental and contingent, and thus to address the question of whether the laws of nature are intrinsically bio-friendly. The popular assumption that life is an almost inevitable product of physics and chemistry, and therefore widespread in the universe, is known as biological determinism. It remains an open question whether biological determinism is correct, as there is little direct evidence in its favour from fundamental physics. Homochirality is a deep property of known life, and provides an important test case for the competing ideas of contingency versus lawfulness - or chance versus necessity. Conceivably, a chiral signature is imprinted on life by fundamental physics via parity-violating mixing of the weak and electromagnetic interactions. If so, homochirality would be universal and lawlike. On the other hand, it may be the result of chance: a random molecular accident during the pre-biotic phase. If the latter explanation is correct, one could expect that a second sample of life may have opposite chiral signature even if it resembled known life in its basic biochemistry. There is thus a curious obverse relationship between chirality and biogenesis in relation to biological determinism. If the chiral signature of life is the product of chance, we may hope to discover "mirror life" (i.e. organisms with opposite chiral signature) as evidence of a second genesis, and the latter would establish that life's emergence from non-life is quasi-deterministic. On the other hand, if the chiral signature is determined by fundamental physics, then it may be much harder to establish an independent origin for extraterrestrial

  13. Possible chiral bands in {sup 194}Tl

    SciTech Connect

    Masiteng, P. L.; Ramashidzha, T. M.; Maliage, S. M.; Sharpey-Schafer, J. F.; Vymers, P. A.; Lawrie, E. A.; Lawrie, J. J.; Bark, R. A.; Mullins, S. M.; Murray, S. H. T.; Kau, J.; Komati, F.; Lindsay, R.; Matamba, I.; Mutshena, P.; Zhang, Y.

    2011-10-28

    High spin states in {sup 194}Tl, excited through the {sup 181}Ta({sup 18}O,5n) fusion evaporation reaction, were studied using the AFRODITE array at iThemba LABS. Candidate chiral bands built on the {pi}h{sub 9/2} x {nu}i{sub 13/2}{sup 1} configuration were found. Furthermore these bands were observed through a band crossing caused by the excitation of a {nu}i{sub 13/2} pair. Above the band crossing the excitation energies remain close, suggesting that chirality may persist for the four quasiparticle configuration too.

  14. Supernovae, neutron stars and biomolecular chirality.

    PubMed

    Bonner, W A; Rubenstein, E

    1987-01-01

    Recent theoretical and experimental investigations of the origin of biomolecular chirality are reviewed briefly. Biotic and abiotic theories are evaluated critically with the conclusion that asymmetric photochemical processes with circulary polarized light (CPL), particularly asymmetric photolyses, constitute the most viable mechanisms. Solar CPL sources appear too weak and random to be effective. We suggest an alternative CPL source, namely, the synchrotron radiation from the neutron star remnants of supernova explosions. This could asymmetrically process racemic compounds in the organic mantles of the dust grains in interstellar clouds, and the resulting chiral molecules could be transferred to Earth by cold accretion as the solar system periodically traverses these interstellar clouds.

  15. Generalized Bloch theorem and chiral transport phenomena

    NASA Astrophysics Data System (ADS)

    Yamamoto, Naoki

    2015-10-01

    Bloch theorem states the impossibility of persistent electric currents in the ground state of nonrelativistic fermion systems. We extend this theorem to generic systems based on the gauged particle number symmetry and study its consequences on the example of chiral transport phenomena. We show that the chiral magnetic effect can be understood as a generalization of the Bloch theorem to a nonequilibrium steady state, similarly to the integer quantum Hall effect. On the other hand, persistent axial currents are not prohibited by the Bloch theorem and they can be regarded as Pauli paramagnetism of relativistic matter. An application of the generalized Bloch theorem to quantum time crystals is also discussed.

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

    USGS Publications Warehouse

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

    2012-01-01

    Anthropogenic chemicals, including pesticides, are a major source of contamination and pollution in the environment. Pesticides have many positive uses: increased food production, decreased damage to crops and structures, reduced disease vector populations, and more. Nevertheless, pesticide exposure can pose risks to humans and the environment, so various mitigation strategies are exercised to make them safer, minimize their use, and reduce their unintended environment effects. One strategy that may help achieve these goals relies on the unique properties of chirality or molecular asymmetry. Some common terms related to chirality are defined in Table 1.

  17. Sensitive chiral analysis by capillary electrophoresis.

    PubMed

    García-Ruiz, Carmen; Marina, María Luisa

    2006-01-01

    In this review, an updated view of the different strategies used up to now to enhance the sensitivity of detection in chiral analysis by CE will be provided to the readers. With this aim, it will include a brief description of the fundamentals and most of the recent applications performed in sensitive chiral analysis by CE using offline and online sample treatment techniques (SPE, liquid-liquid extraction, microdialysis, etc.), on-column preconcentration techniques based on electrophoretic principles (ITP, stacking, and sweeping), and alternative detection systems (spectroscopic, spectrometric, and electrochemical) to the widely used UV-Vis absorption detection.

  18. Band structure controlled by chiral imprinting

    NASA Astrophysics Data System (ADS)

    Castro-Garay, P.; Adrian Reyes, J.; Ramos-Garcia, R.

    2007-09-01

    Using the configuration of an imprinted cholesteric elastomer immersed in a racemic solvent, the authors find the solution of the boundary-value problem for the reflection and transmission of incident optical waves due to the elastomer. They show a significant width reduction of the reflection band for certain values of nematic penetration depth, which depends on the volume fraction of molecules from the solvent, whose handedness is preferably absorbed. The appearance of nested band gaps of both handednesses during the sorting mixed chiral process is also obtained. This suggests the design of chemically controlled optical filters and optically monitored chiral pumps.

  19. Band Structure Controlled by Chiral Imprinting

    NASA Astrophysics Data System (ADS)

    Reyes Cervantes, Adrian; Castro-Garay, P.; Ramos-Garcia, Ruben

    2008-03-01

    Using the configuration of an imprinted cholesteric elastomer immersed in a racemic solvent, we find the solution of the boundary--value problem for the reflection and transmission of incident optical waves due to the elastomer. We show a significant width reduction of the reflection band for certain values of nematic penetration depth, which depends on the volume fraction of molecules from the solvent, whose handedness is preferably absorbed. The appearance of nested bandgaps of both handednesses during the sorting mixed chiral process is also obtained. This suggests the design of chemically controlled optical filters and optically monitored chiral pumps.

  20. Chiral logarithms in the massless limit tamed.

    PubMed

    Kivel, Nikolai; Polyakov, Maxim V; Vladimirov, Alexei

    2008-12-31

    We derive nonlinear recursion relations for the leading chiral logarithms (LLs) in massless theories. These relations not only provide a very efficient method of computation of LLs (e.g., the 33-loop contribution is calculated in a dozen of seconds on a PC) but also equip us with a powerful tool for the summation of the LLs. Our method is not limited to chiral perturbation theory only; it is pertinent to any nonrenormalizable effective field theory such as, for instance, the theory of critical phenomena, low-energy quantum gravity, etc.

  1. Long-range interactions between chiral molecules

    SciTech Connect

    Salam, A.

    2015-01-22

    Results of molecular quantum electrodynamics calculations of discriminatory interactions between two chiral molecules undergoing resonance energy transfer, van der Waals dispersion, and optical binding are presented. A characteristic feature of the theory is that the radiation field is quantized with signals consequently propagating between centres at the speed of light. In order to correctly describe optically active chromophores, it is necessary to include magnetic as well as electric dipole coupling terms in the time-dependent perturbation theory computations. Recent work investigating the effect of an absorptive and dispersive chiral medium on the rate of migration of energy will also be discussed.

  2. Heavy-tailed chiral random matrix theory

    NASA Astrophysics Data System (ADS)

    Kanazawa, Takuya

    2016-05-01

    We study an unconventional chiral random matrix model with a heavy-tailed probabilistic weight. The model is shown to exhibit chiral symmetry breaking with no bilinear condensate, in analogy to the Stern phase of QCD. We solve the model analytically and obtain the microscopic spectral density and the smallest eigenvalue distribution for an arbitrary number of flavors and arbitrary quark masses. Exotic behaviors such as non-decoupling of heavy flavors and a power-law tail of the smallest eigenvalue distribution are illustrated.

  3. Steering Chiral Swimmers along Noisy Helical Paths

    NASA Astrophysics Data System (ADS)

    Friedrich, Benjamin M.; Jülicher, Frank

    2009-08-01

    Chemotaxis along helical paths towards a target releasing a chemoattractant is found in sperm cells and many microorganisms. We discuss the stochastic differential geometry of the noisy helical swimming path of a chiral swimmer. A chiral swimmer equipped with a simple feedback system can navigate in a concentration gradient of chemoattractant. We derive an effective equation for the alignment of helical paths with a concentration gradient which is related to the alignment of a dipole in an external field and discuss the chemotaxis index.

  4. Separation of enantiomers of ephedrine by capillary electrophoresis using cyclodextrins as chiral selectors: comparative CE, NMR and high resolution MS studies.

    PubMed

    Vega, Elena D; Lomsadze, Ketevan; Chankvetadze, Lali; Salgado, Antonio; Scriba, Gerhard K E; Calvo, Enrique; López, Juan A; Crego, Antonio L; Marina, Maria L; Chankvetadze, Bezhan

    2011-10-01

    The enantiomer migration order (EMO) of ephedrine was investigated in the presence of various CDs in CE. The molecular mechanisms of chiral recognition were followed for the ephedrine complexes with native α- and β-CD and heptakis(2,3-di-O-acetyl-6-O-sulfo)-β-CD (HDAS-β-CD) by CE, NMR spectroscopy and high-resolution MS. Minor structural differences were observed between the complexes of ephedrine with α- and β-CD although the migration order of enantiomers was opposite when these two CDs were applied as chiral selectors in CE. The EMO was also opposite between β-CD and HDAS-β-CD. Significant structural differences were observed between ephedrine complexes with the native CDs and HDAS-β-CD. The latter CD was advantageous as chiral CE selector not only due to its opposite electrophoretic mobility compared with that of the cationic chiral analyte, but also primarily due to its enhanced chiral recognition ability towards the enantiomers of ephedrine.

  5. Dispersion relations for electromagnetic wave propagation in chiral plasmas

    SciTech Connect

    Gao, M. X.; Guo, B. Peng, L.; Cai, X.

    2014-11-15

    The dispersion relations for electromagnetic wave propagation in chiral plasmas are derived using a simplified method and investigated in detail. With the help of the dispersion relations for each eignwave, we explore how the chiral plasmas exhibit negative refraction and investigate the frequency region for negative refraction. The results show that chirality can induce negative refraction in plasmas. Moreover, both the degree of chirality and the external magnetic field have a significant effect on the critical frequency and the bandwidth of the frequency for negative refraction in chiral plasmas. The parameter dependence of the effects is calculated and discussed.

  6. Disordered two-dimensional electron systems with chiral symmetry

    NASA Astrophysics Data System (ADS)

    Markoš, P.; Schweitzer, L.

    2012-10-01

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

  7. Chirally Symmetric but Confined Hadrons at Finite Density

    NASA Astrophysics Data System (ADS)

    Ya. Glozman, L.; Wagenbrunn, R. F.

    At a critical finite chemical potential and low temperature QCD undergoes the chiral restoration phase transition. The folklore tradition is that simultaneously hadrons are deconfined and there appears the quark matter. We demonstrate that it is possible to have confined but chirally symmetric hadrons at a finite chemical potential and hence beyond the chiral restoration point at a finite chemical potential and low temperature there could exist a chirally symmetric matter consisting of chirally symmetric but confined hadrons. If it does happen in QCD, then the QCD phase diagram should be reconsidered with obvious implications for heavy ion programs and astrophysics.

  8. When Chiral Photons Meet Chiral Fermions: Photoinduced Anomalous Hall Effects in Weyl Semimetals.

    PubMed

    Chan, Ching-Kit; Lee, Patrick A; Burch, Kenneth S; Han, Jung Hoon; Ran, Ying

    2016-01-15

    The Weyl semimetal is characterized by three-dimensional linear band touching points called Weyl nodes. These nodes come in pairs with opposite chiralities. We show that the coupling of circularly polarized photons with these chiral electrons generates a Hall conductivity without any applied magnetic field in the plane orthogonal to the light propagation. This phenomenon comes about because with all three Pauli matrices exhausted to form the three-dimensional linear dispersion, the Weyl nodes cannot be gapped. Rather, the net influence of chiral photons is to shift the positions of the Weyl nodes. Interestingly, the momentum shift is tightly correlated with the chirality of the node to produce a net anomalous Hall signal. Application of our proposal to the recently discovered TaAs family of Weyl semimetals leads to an order-of-magnitude estimate of the photoinduced Hall conductivity which is within the experimentally accessible range. PMID:26824561

  9. HPLC SEPARATION OF CHIRAL ORGANOPHOSPHORUS PESTICIDES ON POLYSACCHARIDE CHIRAL STATIONARY PHASES

    EPA Science Inventory

    High-performance liquid chromatographic separation of the individual enantiomers of 12 organophosphorus pesticides (OPs) were obtained on polysaccharide chiral HPLC columns using an alkane-alcohol mobile phase. The OP pesticides were crotoxyphos, dialifor, dyfonate, fenamiphos, ...

  10. When Chiral Photons Meet Chiral Fermions: Photoinduced Anomalous Hall Effects in Weyl Semimetals

    NASA Astrophysics Data System (ADS)

    Chan, Ching-Kit; Lee, Patrick A.; Burch, Kenneth S.; Han, Jung Hoon; Ran, Ying

    2016-01-01

    The Weyl semimetal is characterized by three-dimensional linear band touching points called Weyl nodes. These nodes come in pairs with opposite chiralities. We show that the coupling of circularly polarized photons with these chiral electrons generates a Hall conductivity without any applied magnetic field in the plane orthogonal to the light propagation. This phenomenon comes about because with all three Pauli matrices exhausted to form the three-dimensional linear dispersion, the Weyl nodes cannot be gapped. Rather, the net influence of chiral photons is to shift the positions of the Weyl nodes. Interestingly, the momentum shift is tightly correlated with the chirality of the node to produce a net anomalous Hall signal. Application of our proposal to the recently discovered TaAs family of Weyl semimetals leads to an order-of-magnitude estimate of the photoinduced Hall conductivity which is within the experimentally accessible range.

  11. Spintronics and chirality: spin selectivity in electron transport through chiral molecules.

    PubMed

    Naaman, Ron; Waldeck, David H

    2015-04-01

    Recent experiments have demonstrated that the electron transmission yield through chiral molecules depends on the electron spin orientation. This phenomenon has been termed the chiral-induced spin selectivity (CISS) effect, and it provides a challenge to theory and promise for organic molecule-based spintronic devices. This article reviews recent developments in our understanding of CISS. Different theoretical models have been used to describe the effect; however, they all presume an unusually large spin-orbit coupling in chiral molecules for the effect to display the magnitudes seen in experiments. A simplified model for an electron's transport through a chiral potential suggests that these large couplings can be manifested. Techniques for measuring spin-selective electron transport through molecules are overviewed, and some examples of recent experiments are described. Finally, we present results obtained by studying several systems, and we describe the possible application of the CISS effect for memory devices.

  12. Hg(2+) -induced in situ generated radical cation of (S)-BINOL-based polymer for highly enantioselective recognition of phenylalaninol.

    PubMed

    Jiao, Jiemin; Li, Fei; Zhang, Shuwei; Quan, Yiwu; Zheng, Wenhua; Cheng, Yixiang; Zhu, Chengjian

    2014-08-01

    Phenylalaninol enantiomers are one of the most important chiral compounds due to its presence in biologically active molecules and pharmaceutical products. In this paper, a novel chiral fluorescence polymer sensor incorporating (S)-BINOL and oligomeric aniline via a nucleophilic addition-elimination reaction is designed and synthesized. Polymer sensor exhibits "turn-off" fluorescence quenching response upon the addition of Hg(2+) , and "turn-on" moderate fluorescence enhancement behavior towards phenylalaninol enantiomers. Meanwhile, this kind of (S)-BINOL-based polymer sensor can exhibit highly selective enantioselective recognition response towards (L)-phenylalaninol upon the addition of Hg(2+) and the value of ef can reach as high as 5.4, which can be attributed to the formation of in situ generated radical cation arisen from oligomeric aniline moiety by Hg(2+) induction. PMID:25048009

  13. Bis(N-confused porphyrin) as a semirigid receptor with a chirality memory: a two-way host enantiomerization through point-to-axial chirality transfer.

    PubMed

    Chmielewski, Piotr J; Siczek, Marta; Stępień, Marcin

    2015-02-01

    The adduct formation of protonated bis(N-confused porphyrin) (BNCP, 3,3'-bis(meso-tetratolyl-2-aza-21-carbaporphyrin) with chiral anions, carboxylic acids, and alcohols was studied in solution by means of (1) H NMR and circular dichroism (CD) spectroscopic analysis and DFT methods. The addition of enantiopure guests to the acidified BNCP resulted in optical activity that vanished after neutralization. Pairs of the (1) H NMR-distinguishable diastereomers were formed when enantiopure guests were applied, although a single form was observed upon the addition of the racemic mixtures in each case. Unidirectional configuration change that led to diastereomeric excess was observed in several instances. Such an excess was memorized by metalation of the adducts with AgBF4 , thus resulting in optically active silver(III) complexes of BNCP with some enantiomeric excess. Absolute configurations of BNCP cations and bis(zinc) and bis(silver(III)) complexes were determined on the basis of time-dependent (TD)-DFT calculations of their CD spectra. It was shown that some of the chiral carboxylates induced opposite directions of enantiomerization of di- and tetracations or di-/tetracation and bis(zinc) complexes. The source of the optical activity of the equimolar diastereomeric mixture of adducts is discussed.

  14. Metal cation controls myosin and actomyosin kinetics

    PubMed Central

    Tkachev, Yaroslav V; Ge, Jinghua; Negrashov, Igor V; Nesmelov, Yuri E

    2013-01-01

    We have perturbed myosin nucleotide binding site with magnesium-, manganese-, or calcium-nucleotide complexes, using metal cation as a probe to examine the pathways of myosin ATPase in the presence of actin. We have used transient time-resolved FRET, myosin intrinsic fluorescence, fluorescence of pyrene labeled actin, combined with the steady state myosin ATPase activity measurements of previously characterized D.discoideum myosin construct A639C:K498C. We found that actin activation of myosin ATPase does not depend on metal cation, regardless of the cation-specific kinetics of nucleotide binding and dissociation. The rate limiting step of myosin ATPase depends on the metal cation. The rate of the recovery stroke and the reverse recovery stroke is directly proportional to the ionic radius of the cation. The rate of nucleotide release from myosin and actomyosin, and ATP binding to actomyosin depends on the cation coordination number. PMID:24115140

  15. Intelligent chiral sensing based on supramolecular and interfacial concepts.

    PubMed

    Ariga, Katsuhiko; Richards, Gary J; Ishihara, Shinsuke; Izawa, Hironori; Hill, Jonathan P

    2010-01-01

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

  16. Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

    PubMed Central

    Ariga, Katsuhiko; Richards, Gary J.; Ishihara, Shinsuke; Izawa, Hironori; Hill, Jonathan P.

    2010-01-01

    Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized. PMID:22163577

  17. The sonochemical synthesis and characterization of mesoporous chiral titania using a chiral inorganic precursor.

    PubMed

    Gabashvili, Alexandra; Major, Dan T; Perkas, Nina; Gedanken, Aharon

    2010-03-01

    The paper presents a successful sonochemical attempt to synthesize mesoporous chiral titania using a chiral inorganic precursor and dodecylamine, as the surfactant template. The resulting porous structure was characterized by nitrogen sorption experiments, transmission electron microscopy, and small-angle XRD. The enantioselectivity of this mesoporous titania after the extraction of the amine was examined by selective adsorption of enantiomers and racemic aqueous solution of camphor. The selective adsorption was measured by circular dichroism (CD) spectroscopy. PMID:19942471

  18. Chiral Light-Matter Interaction in Optical Resonators.

    PubMed

    Yoo, SeokJae; Park, Q-Han

    2015-05-22

    The Purcell effect explains the modification of the spontaneous decay rate of quantum emitters in a resonant cavity. For quantum emitters such as chiral molecules, however, the cavity modification of the spontaneous decay rate has been little known. Here we extend Purcell's work to the chiral light-matter interaction in optical resonators and find the differential spontaneous decay rate of chiral molecules coupled to left and right circularly polarized resonator modes. We determine the chiral Purcell factor, which characterizes the ability of optical resonators to enhance chiroptical signals, by the quality factor and the chiral mode volume of a resonator, representing, respectively, the temporal confinement of light and the spatial confinement of the helicity of light. We show that the chiral Purcell effect can be applied to chiroptical spectroscopy. Specifically, we propose a realistic scheme to achieve resonator enhanced chiroptical spectroscopy that uses the double fishnet structure as a nanoscale cuvette supporting the chiral Purcell effect.

  19. New chiral liquid crystal with unconventional dioxane terminal unit

    NASA Astrophysics Data System (ADS)

    Perkowski, Paweł; Bubnov, Alexej; Mrukiewicz, Mateusz; Pociecha, Damian; Piecek, Wiktor; Hamplová, Věra; Kašpar, Miroslav

    2014-11-01

    While designing new chiral self-assembling materials, i.e. those possessing the liquid crystalline behaviour, special attention should be paid to the specific architecture of different molecular parts, in particular: molecular core, linkage groups, type and place of the lateral substituents, structure of the chiral centre and the chiral and non-chiral chains. For the first time a new chiral photosensitive liquid crystalline compound possessing an unconventional 1,3-dioxanylmethyl terminal unit attached to the non-chiral chain has been designed and synthesized. On cooling from the isotropic phase, the material possesses only one tilted liquid crystalline phase, namely the smectic I* phase with hexagonal ordering. The crystal phase has been detected at lower temperatures. The self-assembling and structural behaviour have been studied by different techniques and compared to that of the materials with similar molecular structure but possessing structurally different terminal units in the non-chiral chain.

  20. Electronic spectra of astrophysically interesting cations

    SciTech Connect

    Maier, John P. Rice, Corey A. Mazzotti, Fabio J. Johnson, Anatoly

    2015-01-22

    The electronic spectra of polyacetylene cations were recorded at 20K in the laboratory in an ion trap instrument. These can then be compared with diffuse interstellar band (DIB) absorptions. Examination of recently published data shows that the attribution of a weak DIB at ∼506.9 nm to diacetylene cation is not justified. Study of the higher excited electronic states of polyacetylene cations shows that their widths can still be sufficiently narrow for consideration as DIB carriers.

  1. ADSORPTION METHOD FOR SEPARATING METAL CATIONS

    DOEpatents

    Khym, J.X.

    1959-03-10

    The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

  2. Chiral High-Speed Counter-Current Chromatography: Future Strategies for Chiral Selector Development.

    PubMed

    Ma, Ying; Ito, Yoichiro

    2014-01-01

    In conventional high-performance liquid chromatography, chiral separations are performed by chiral column with a chiral selector (CS) chemically boned to the solid support. In contrast, high-speed counter-current chromatography (HSCCC) performs chiral separations by dissolving CS in the liquid stationary phase. During the past two decades, several CSs were developed to successfully carry out chiral HSCCC which include N-dodecanoyl-L-proline-3,5-dimethylanilide, β-cyclodextrin derivatives, vancomycin, cinchona alkaloid derivatives, cellulose and amylose derivatives, tartaric acid derivatives, etc. Compared to HPLC which uses over hundred different kinds of CSs, the number of CSs effectively used in HSCCC is limited to several compounds. This may be due to the violent molecular movement of CS dissolved in the liquid stationary phase which reduces chiral selectivity based on steric affinity. Future development strategy of CS for HSCC proposed here is to suppress the molecular movement of the CS in the liquid stationary phase by the following three ways: 1) using viscous stationary phase such as aqueous-aqueous polymer phase system; 2) attaching a long hydrophobic chain to the asymmetric carbon, or 3) chemically bonding CS onto hydrophobic small particles such as carbon nanotubes, gold colloidal particles, and submicron silica particles.

  3. Chiral High-Speed Counter-Current Chromatography: Future Strategies for Chiral Selector Development

    PubMed Central

    Ma, Ying; Ito, Yoichiro

    2014-01-01

    In conventional high-performance liquid chromatography, chiral separations are performed by chiral column with a chiral selector (CS) chemically boned to the solid support. In contrast, high-speed counter-current chromatography (HSCCC) performs chiral separations by dissolving CS in the liquid stationary phase. During the past two decades, several CSs were developed to successfully carry out chiral HSCCC which include N-dodecanoyl-L-proline-3,5-dimethylanilide, β-cyclodextrin derivatives, vancomycin, cinchona alkaloid derivatives, cellulose and amylose derivatives, tartaric acid derivatives, etc. Compared to HPLC which uses over hundred different kinds of CSs, the number of CSs effectively used in HSCCC is limited to several compounds. This may be due to the violent molecular movement of CS dissolved in the liquid stationary phase which reduces chiral selectivity based on steric affinity. Future development strategy of CS for HSCC proposed here is to suppress the molecular movement of the CS in the liquid stationary phase by the following three ways: 1) using viscous stationary phase such as aqueous-aqueous polymer phase system; 2) attaching a long hydrophobic chain to the asymmetric carbon, or 3) chemically bonding CS onto hydrophobic small particles such as carbon nanotubes, gold colloidal particles, and submicron silica particles. PMID:24611132

  4. Separation of chiral nanotubes with an opposite handedness by chiral oligopeptide adsorption: A molecular dynamics study.

    PubMed

    Raffaini, Giuseppina; Ganazzoli, Fabio

    2015-12-18

    The separation of enantiomeric chiral nanotubes that can form non-covalent complexes with an unlike stability upon adsorption of chiral molecules is a process of potential interest in different fields and applications. Using fully atomistic molecular dynamics simulations, we report in this paper a theoretical study of the adsorption and denaturation of an oligopeptide formed by 16 chiral amino acids having a helical structure in the native state on both the inner and the outer surface of the chiral (10, 20) and (20, 10) single-walled carbon nanotubes having an opposite handedness, and of the armchair (16, 16) nanotube with a similar diameter for comparison. In the final adsorbed state, the oligopeptide loses in all cases its native helical conformation, assuming elongated geometries that maximize its contact with the surface through all the 16 amino acids. We find that the complexes formed by the two chiral nanotubes and the chosen oligopeptide have a strongly unlike stability both when adsorption takes place on the outer convex surface of the nanotube, and when it occurs on the inner concave surface. Thus, our molecular simulations indicate that separation of chiral, enantiomeric carbon nanotubes for instance by chromatographic methods can indeed be carried out using oligopeptides of a sufficient length.

  5. Chiral separation and twin-beam photonics

    NASA Astrophysics Data System (ADS)

    Bradshaw, David S.; Andrews, David L.

    2016-03-01

    It is well-known that, in a homogeneous fluid medium, most optical means that afford discrimination between molecules of opposite handedness are intrinsically weak effects. The reason is simple: the wide variety of origins for differential response commonly feature real or virtual electronic transitions that break a parity condition. Despite being electric dipole allowed, they manifest the chirality of the material in which they occur by breaking a selection rule that would otherwise preclude the simultaneous involvement of magnetic dipole or electric quadrupole forms of coupling. Although the latter are typically weaker than electric dipole effects by several orders of magnitude, it is the involvement of these weak forms of interaction that are responsible for chiral sensitivity. There have been a number of attempts to cleverly exploit novel optical configurations to enhance the relative magnitude - and hence potentially the efficiency - of chiral discrimination. The prospect of success in any such venture is enticing, because of the huge impact that such an advance might be expected to have in the health, food and medical sectors. Some of these proposals have utilized mirror reflection, and others surface plasmon coupling, or optical binding methods. Several recent works in the literature have drawn attention to a further possibility: the deployment of optical beam interference as a means to achieve chiral separations of sizeable extent. In this paper the underlying theory is fully developed to identify the true scope and limitations of such an approach.

  6. Efficient Biocatalytic Synthesis of Chiral Chemicals.

    PubMed

    Zhang, Zhi-Jun; Pan, Jiang; Ma, Bao-Di; Xu, Jian-He

    2016-01-01

    Chiral chemicals are a group of important chiral synthons for the synthesis of a series of pharmaceuticals, agrochemicals, and fine chemicals. In past decades, a number of biocatalytic approaches have been developed for the green and effective synthesis of various chiral chemicals. However, the practical application of these biocatalytic processes is still hindered by the lack of highly efficient and robust biocatalysts, which usually results in the low volumetric productivity and high cost of the bioprocesses. Further step forward of biocatalysis in industrial application strongly requires the development of versatile and highly efficient biocatalysts, aiming to increase the process efficiency and facilitate the downstream processing. Recently, the fast growth of genome sequences in the database in post-genomic era offers great opportunities for accessing numerous biocatalysts with practical application potential, and the so-called genome mining approach provides time-effective and highly specific strategy for the fast identification of target enzymes with desired properties and outperforms the traditional screening of soil samples for microbial enzyme producers of interest. A number of biocatalytic processes with industrial application potential were developed thereafter. Further development of protein engineering strategies, process optimization, and cooperative work between biologists, organic chemists, and engineers is expected to make biocatalysis technology the first choice approach for the eco-friendly, highly efficient, and cost-effective synthesis of chiral chemicals in the near future.

  7. Polar Superhelices in Ferroelectric Chiral Nanosprings

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  8. Chiral anomaly and transport in Weyl metals.

    PubMed

    Burkov, A A

    2015-03-25

    We present an overview of our recent work on transport phenomena in Weyl metals, which may be connected to their nontrivial topological properties, particularly to chiral anomaly. We argue that there are two basic phenomena, which are related to chiral anomaly in Weyl metals: anomalous Hall effect (AHE) and chiral magnetic effect (CME). While AHE is in principle present in any ferromagnetic metal, we demonstrate that a magnetic Weyl metal is distinguished from an ordinary ferromagnetic metal by the absence of the extrinsic and the Fermi surface part of the intrinsic contributions to the AHE, as long as the Fermi energy is sufficiently close to the Weyl nodes. The AHE in a Weyl metal is thus shown to be a purely intrinsic, universal property, fully determined by the location of the Weyl nodes in the first Brillouin zone. In other words, a ferromagnetic Weyl metal may be thought of as the only example of a ferromagnetic metal with a purely intrinsic AHE. We further develop a fully microscopic theory of diffusive magnetotransport in Weyl metals. We derive coupled diffusion equations for the total and axial (i.e. node-antisymmetric) charge densities and show that chiral anomaly manifests as a magnetic-field-induced coupling between them. We demonstrate that an experimentally-observable consequence of CME in magnetotransport in Weyl metals is a quadratic negative magnetoresistance, which will dominate all other contributions to magnetoresistance under certain conditions and may be regarded as a smoking-gun transport characteristic, unique to Weyl metals.

  9. Chiral damping in magnetic domain walls dynamics

    NASA Astrophysics Data System (ADS)

    Jué, Emilie

    Domain wall (DW) motion in materials with structural inversion asymmetry (SIA) and high spin-orbit coupling has attracted much interest in the recent years due to the discovery of unexpected physical mechanisms. Especially, it has been shown that the DW dynamics in such materials can be explained by chiral DWs with (partly or fully) Néel structure, whose stability derives from an interfacial Dzyaloshinskii-Moriya interaction (DMI). In this work, we show that DMI is not the only effect inducing chiral dynamics and demonstrate the existence of a chiral damping. This result is supported by the study of the asymmetry induced by an in-plane magnetic field on field induced domain wall motion in perpendicularly magnetized asymmetric Pt/Co/Pt trilayers. Using time reversal properties, we show that this asymmetry cannot be attributed to an effective field but originates from a purely dissipative mechanism. The observation of chiral damping, not only enriches the spectrum of physical phenomena engendered by the SIA, but since it can coexist with DMI it is essential for conceiving DW and skyrmion devices

  10. Chiral damping of magnetic domain walls

    NASA Astrophysics Data System (ADS)

    Jué, Emilie; Safeer, C. K.; Drouard, Marc; Lopez, Alexandre; Balint, Paul; Buda-Prejbeanu, Liliana; Boulle, Olivier; Auffret, Stephane; Schuhl, Alain; Manchon, Aurelien; Miron, Ioan Mihai; Gaudin, Gilles

    2016-03-01

    Structural symmetry breaking in magnetic materials is responsible for the existence of multiferroics, current-induced spin-orbit torques and some topological magnetic structures. In this Letter we report that the structural inversion asymmetry (SIA) gives rise to a chiral damping mechanism, which is evidenced by measuring the field-driven domain-wall (DW) motion in perpendicularly magnetized asymmetric Pt/Co/Pt trilayers. The DW dynamics associated with the chiral damping and those with Dzyaloshinskii-Moriya interaction (DMI) exhibit identical spatial symmetry. However, both scenarios are differentiated by their time reversal properties: whereas DMI is a conservative effect that can be modelled by an effective field, the chiral damping is purely dissipative and has no influence on the equilibrium magnetic texture. When the DW motion is modulated by an in-plane magnetic field, it reveals the structure of the internal fields experienced by the DWs, allowing one to distinguish the physical mechanism. The chiral damping enriches the spectrum of physical phenomena engendered by the SIA, and is essential for conceiving DW and skyrmion devices owing to its coexistence with DMI (ref. ).

  11. Polar Superhelices in Ferroelectric Chiral Nanosprings

    PubMed Central

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

    2016-01-01

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

  12. Chiral anomaly and transport in Weyl metals

    NASA Astrophysics Data System (ADS)

    Burkov, A. A.

    2015-03-01

    We present an overview of our recent work on transport phenomena in Weyl metals, which may be connected to their nontrivial topological properties, particularly to chiral anomaly. We argue that there are two basic phenomena, which are related to chiral anomaly in Weyl metals: anomalous Hall effect (AHE) and chiral magnetic effect (CME). While AHE is in principle present in any ferromagnetic metal, we demonstrate that a magnetic Weyl metal is distinguished from an ordinary ferromagnetic metal by the absence of the extrinsic and the Fermi surface part of the intrinsic contributions to the AHE, as long as the Fermi energy is sufficiently close to the Weyl nodes. The AHE in a Weyl metal is thus shown to be a purely intrinsic, universal property, fully determined by the location of the Weyl nodes in the first Brillouin zone. In other words, a ferromagnetic Weyl metal may be thought of as the only example of a ferromagnetic metal with a purely intrinsic AHE. We further develop a fully microscopic theory of diffusive magnetotransport in Weyl metals. We derive coupled diffusion equations for the total and axial (i.e. node-antisymmetric) charge densities and show that chiral anomaly manifests as a magnetic-field-induced coupling between them. We demonstrate that an experimentally-observable consequence of CME in magnetotransport in Weyl metals is a quadratic negative magnetoresistance, which will dominate all other contributions to magnetoresistance under certain conditions and may be regarded as a smoking-gun transport characteristic, unique to Weyl metals.

  13. Monopoles and fractional vortices in chiral superconductors

    PubMed Central

    Volovik, G. E.

    2000-01-01

    I discuss two exotic objects that must be experimentally identified in chiral superfluids and superconductors. These are (i) the vortex with a fractional quantum number (N = 1/2 in chiral superfluids, and N = 1/2 and N = 1/4 in chiral superconductors), which plays the part of the Alice string in relativistic theories and (ii) the hedgehog in the ^l field, which is the counterpart of the Dirac magnetic monopole. These objects of different dimensions are topologically connected. They form the combined object that is called a nexus in relativistic theories. In chiral superconductors, the nexus has magnetic charge emanating radially from the hedgehog, whereas the half-quantum vortices play the part of the Dirac string. Each half-quantum vortex supplies the fractional magnetic flux to the hedgehog, representing 1/4 of the “conventional” Dirac string. I discuss the topological interaction of the superconductor's nexus with the ‘t Hooft–Polyakov magnetic monopole, which can exist in Grand Unified Theories. The monopole and the hedgehog with the same magnetic charge are topologically confined by a piece of the Abrikosov vortex. Such confinement makes the nexus a natural trap for the magnetic monopole. Other properties of half-quantum vortices and monopoles are discussed as well, including fermion zero modes. PMID:10716980

  14. Skyrme-Einstein closed cosmic chiral strings

    SciTech Connect

    Rybakov, Yu. P. Ivanova, I. S.

    2007-07-15

    Within the theory of general relativity, the configuration of a closed string (vortex) characterized by a topological charge of the degree type is described for the Skyrme-Einstein SU (2) chiral model. In the approximation of a large vortex-closure radius (a), a solution to equations of motion is obtained, along with estimates for the vortex energy and radius.

  15. Chiral anomaly and transport in Weyl metals.

    PubMed

    Burkov, A A

    2015-03-25

    We present an overview of our recent work on transport phenomena in Weyl metals, which may be connected to their nontrivial topological properties, particularly to chiral anomaly. We argue that there are two basic phenomena, which are related to chiral anomaly in Weyl metals: anomalous Hall effect (AHE) and chiral magnetic effect (CME). While AHE is in principle present in any ferromagnetic metal, we demonstrate that a magnetic Weyl metal is distinguished from an ordinary ferromagnetic metal by the absence of the extrinsic and the Fermi surface part of the intrinsic contributions to the AHE, as long as the Fermi energy is sufficiently close to the Weyl nodes. The AHE in a Weyl metal is thus shown to be a purely intrinsic, universal property, fully determined by the location of the Weyl nodes in the first Brillouin zone. In other words, a ferromagnetic Weyl metal may be thought of as the only example of a ferromagnetic metal with a purely intrinsic AHE. We further develop a fully microscopic theory of diffusive magnetotransport in Weyl metals. We derive coupled diffusion equations for the total and axial (i.e. node-antisymmetric) charge densities and show that chiral anomaly manifests as a magnetic-field-induced coupling between them. We demonstrate that an experimentally-observable consequence of CME in magnetotransport in Weyl metals is a quadratic negative magnetoresistance, which will dominate all other contributions to magnetoresistance under certain conditions and may be regarded as a smoking-gun transport characteristic, unique to Weyl metals. PMID:25712419

  16. Laser spectroscopy and mass spectrometry of biologically relevant systems: chiral discrimination

    NASA Astrophysics Data System (ADS)

    Piccirillo, Susanna; Satta, Mauro; Coreno, Marcello; Catone, Daniele; Rondino, Flaminia; Scuderi, Debora; Paladini, Alessandra; Speranza, Maurizio; Giardini, Anna

    2005-06-01

    Radical ions are open-shell elusive species of paramount importance in many organic reactions and in biological processes. Oxidative bond breaking and forming involving radical ions are common process taking place in asymmetric enzyme cavities. Side-chain Cα-CΒ bond fragmentation in the radical cations of aromatic alcohols is a common process in solution [1-3], whose efficiency is enhanced in polar solvents such as water. Hydrogen-bonding between the ion and the solvent in the relevant transition structure is thought as responsible of the rate acceleration [4]. Effects of achiral and chiral microsolvation on the radical cation of R-(+)-l-phenyl-l-propanol, have been investigated. The energy thresholds of the homolytic Cα-Cβ bond breaking of R-(+)-1-phenyl-1-propanol radical cation, its mono-hydrated cluster, and its clusters with (2R,3R)-(-)-2,3-butanediol and (2S,3S)-(+)-2,3-butanediol have been studied through two color Resonant Two Photon Ionization, Photodissociation and Mass Spectrometry. The barrier of the Cα-Cβ fragmentation is appreciably higher for the unsolvated molecular ion than for its adducts with solvent molecules. Moreover, marked differences in the ethyl loss fragmentation energy are observed for the clusters with water and with the two diols. In particular the homochiral cluster with (2R, 3R)-(-)-2,3-butanediol exhibits a fragmentation barrier higher than that of the corresponding heterochiral adduct with (25, 35)-(+)-2,3-butanediol.

  17. Incorporation of Pendant Bases into Rh(diphosphine)2 Complexes: Synthesis, Thermodynamic Studies, And Catalytic CO2 Hydrogenation Activity of [Rh(P2N2)2](+) Complexes.

    PubMed

    Lilio, Alyssia M; Reineke, Mark H; Moore, Curtis E; Rheingold, Arnold L; Takase, Michael K; Kubiak, Clifford P

    2015-07-01

    A series of five [Rh(P2N2)2](+) complexes (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane) have been synthesized and characterized: [Rh(P(Ph)2N(Ph)2)2](+) (1), [Rh(P(Ph)2N(Bn)2)2](+) (2), [Rh(P(Ph)2N(PhOMe)2)2](+) (3), [Rh(P(Cy)2N(Ph)2)2](+) (4), and [Rh(P(Cy)2N(PhOMe)2)2](+) (5). Complexes 1-5 have been structurally characterized as square planar rhodium bis-diphosphine complexes with slight tetrahedral distortions. The corresponding hydride complexes 6-10 have also been synthesized and characterized, and X-ray diffraction studies of HRh(P(Ph)2N(Bn)2)2 (7), HRh(P(Ph)2N(PhOMe)2)2 (8) and HRh(P(Cy)2N(Ph)2)2 (9) show that the hydrides have distorted trigonal bipyramidal geometries. Equilibration of complexes 2-5 with H2 in the presence of 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane (Verkade's base) enabled the determination of the hydricities and estimated pKa's of the Rh(I) hydride complexes using the appropriate thermodynamic cycles. Complexes 1-5 were active for CO2 hydrogenation under mild conditions, and their relative rates were compared to that of [Rh(depe)2](+), a nonpendant-amine-containing complex with a similar hydricity to the [Rh(P2N2)2](+) complexes. It was determined that the added steric bulk of the amine groups on the P2N2 ligands hinders catalysis and that [Rh(depe)2](+) was the most active catalyst for hydrogenation of CO2 to formate. PMID:26042557

  18. Recent advances in SPE-chiral-HPLC methods for enantiomeric separation of chiral drugs in biological samples.

    PubMed

    Ali, Imran; Alam, Syed Dilshad; Al-Othman, Zeid A; Farooqi, Javed A

    2013-08-01

    In medical practices, the determination of enantiomeric ratio of the chiral drugs is very important for their activities, bioavailabilities and biodegradation. Only homochiral medication is safe for humans. The chiral analysis in biological samples is the first and most important step. The present article describes the technical strategies of the enantiomeric resolution of racemic drugs in biological samples. Attempts have been made to describe sample preparation by solid-phase extraction and enantiomeric resolution by chiral high-performance liquid chromatography. Various chiral stationary phases used in chiral separations of racemic drugs have been described. Efforts are also made to discuss the chiral recognition mechanism and future perspectives of chiral analyses in biological samples.

  19. A Cross-chiral RNA Polymerase Ribozyme

    PubMed Central

    Sczepanski, Jonathan T.; Joyce, Gerald F.

    2014-01-01

    Thirty years ago it was shown that the non-enzymatic, template-directed polymerization of activated mononucleotides proceeds readily in a homochiral system, but is severely inhibited by the presence of the opposing enantiomer.1 This finding poses a severe challenge for the spontaneous emergence of RNA-based life, and has led to the suggestion that either RNA was preceded by some other genetic polymer that is not subject to chiral inhibition2 or chiral symmetry was broken through chemical processes prior to the origin of RNA-based life.3,4 Once an RNA enzyme arose that could catalyze the polymerization of RNA, it would have been possible to distinguish among the two enantiomers, enabling RNA replication and RNA-based evolution to occur. It is commonly thought that the earliest RNA polymerase and its substrates would have been of the same handedness, but this is not necessarily the case. Replicating D-and L-RNA molecules may have emerged together, based on the ability of structured RNAs of one handedness to catalyze the templated polymerization of activated mononucleotides of the opposite handedness. Such a cross-chiral RNA polymerase has now been developed using in vitro evolution. The D-RNA enzyme, consisting of 83 nucleotides, catalyzes the joining of L-mono- or oligonucleotide substrates on a complementary L-RNA template, and similarly for the L-enzyme with D-substrates and a D-template. Chiral inhibition is avoided because the 106-fold rate acceleration of the enzyme only pertains to cross-chiral substrates. The enzyme's activity is sufficient to generate full-length copies of its enantiomer through the templated joining of 11 component oligonucleotides. PMID:25363769

  20. Chiral Sensitivity in Electron-Molecule Interactions

    NASA Astrophysics Data System (ADS)

    Dreiling, Joan

    2015-09-01

    All molecular forms of life possess a chiral asymmetry, with amino acids and sugars found respectively in L- and D-enantiomers only. The primordial origin of this enantiomeric excess is unknown. One possible explanation is given by the Vester- Ulbricht hypothesis, which suggests that left-handed electrons present in beta-radiation, produced by parity-violating weak decays, interacted with biological precursors and preferentially destroyed one of the two enantiomers. Experimental tests of this idea have thus far yielded inconclusive results. We show direct evidence for chirally-dependent bond breaking through a dissociative electron attachment (DEA) reaction when spin-polarized electrons are incident on gas-phase chiral molecules. This provides unambiguous evidence for a well-defined, chirally-sensitive destructive molecular process and, as such, circumstantial evidence for the Vester-Ulbricht hypothesis. I will also present the results of our systematic study of the DEA asymmetry for different chiral halocamphor molecules. Three halocamphor molecules were investigated: 3-bromocamphor (C10H15BrO), 3-iodocamphor(C10H15IO), and 10-iodocamphor. The DEA asymmetries collected for bromocamphor and iodocamphor are qualitatively different, suggesting that the atomic number of the heaviest atom in the molecule plays a crucial role in the asymmetric interactions. The DEA asymmetry data for 3- and 10-iodocamphor have the same qualitative behavior, but the 10-iodocamphor asymmetry is about twice as large at the lowest energies investigated, so the location of the heavy atom in the camphor molecule also affects the asymmetries. This work was performed at the University of Nebraska-Lincoln. This project is funded by NSF Grant PHY-1206067.

  1. Chemical synthesis of chiral conducting polymers

    SciTech Connect

    Wang, Hsing-Lin; Li, Wenguang

    2006-07-11

    An process of forming a chiral conducting polymer, e.g., polyaniline, is provided including reacting a monomer, e.g., an aniline monomer, in the presence of a chiral dopant acid to produce a first reaction mixture by addition of a solution including a first portion of an oxidizing agent, the first portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and further reacting the first reaction mixture in the presence of the chiral dopant acid by addition of a solution including a second portion of the oxidizing agent, the second portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and repeating the reaction by addition of further portions of the oxidizing agent until the monomer reaction is complete to produce a chiral conducting polymer, e.g., polyaniline. A preferred process includes addition of a catalyst during the reaction, the catalyst selected from among the group consisting of phenylene diamine, aniline oligomers and amino-capped aniline oligomers and metal salts. The processes of the present invention further provide a resultant polyaniline product having a chirality level defined by a molar ellipticity of from about 40.times.103 degree-cm2/decimole to about 700.times.103 degree-cm2/decimole. The processes of the present invention further provide a resultant polyaniline product having a nanofiber structure with a diameter of from about 30 nanometers to about 120 nanometers and from about 1 micron to about 5 microns in length.

  2. Chemical synthesis of chiral conducting polymers

    SciTech Connect

    Wang, Hsing-Lin; Li, Wenguang

    2009-01-13

    An process of forming a chiral conducting polymer, e.g., polyaniline, is provided including reacting a monomer, e.g., an aniline monomer, in the presence of a chiral dopant acid to produce a first reaction mixture by addition of a solution including a first portion of an oxidizing agent, the first portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and further reacting the first reaction mixture in the presence of the chiral dopant acid by addition of a solution including a second portion of the oxidizing agent, the second portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and repeating the reaction by addition of further portions of the oxidizing agent until the monomer reaction is complete to produce a chiral conducting polymer, e.g., polyaniline. A preferred process includes addition of a catalyst during the reaction, the catalyst selected from among the group consisting of phenylene diamine, aniline oligomers and amino-capped aniline oligomers and metal salts.The processes of the present invention further provide a resultant polyaniline product having a chirality level defined by a molar ellipticity of from about 40.times.10.sup.3 degree-cm.sup.2/decimole to about 700.times.10.sup.3 degree-cm.sup.2/decimole. The processes of the present invention further provide a resultant polyaniline product having a nanofiber structure with a diameter of from about 30 nanometers to about 120 nanometers and from about 1 micron to about 5 microns in length.

  3. Selective photochemistry at stereogenic metal and ligand centers of cis-[Ru(diphosphine)2(H)2]: preparative, NMR, solid state, and laser flash studies.

    PubMed

    Câmpian, Marius V; Perutz, Robin N; Procacci, Barbara; Thatcher, Robert J; Torres, Olga; Whitwood, Adrian C

    2012-02-22

    Three ruthenium complexes Λ-[cis-Ru((R,R)-Me-BPE)(2)(H)(2)] Λ-R,R-Ru1H(2), Δ-[cis-Ru((S,S)-Me-DuPHOS)(2)(H)(2)] Δ-S,S-Ru2H(2), and Λ-[cis-Ru((R,R)-Me-DuPHOS)(2)(H)(2)] Λ-R,R-Ru2H(2) (1 = (Me-BPE)(2), 2 = (Me-DuPHOS)(2)) were characterized by multinuclear NMR and CD spectroscopy in solution and by X-ray crystallography. The chiral ligands allow the full control of stereochemistry and enable mechanistic studies not otherwise available. Oxidative addition of E-H bonds (E = H, B, Si, C) was studied by steady state and laser flash photolysis in the presence of substrates. Steady state photolysis shows formation of single products with one stereoisomer. Solid state structures and circular dichroism spectra reveal a change in configuration at ruthenium for some Δ-S,S-Ru2H(2)/Λ-R,R-Ru2H(2) photoproducts from Λ to Δ (or vice versa) while the configuration for Λ-R,R-Ru1H(2) products remains unchanged as Λ. The X-ray structure of silyl hydride photoproducts suggests a residual H(1)···Si(1) interaction for Δ-[cis-Ru((R,R)-Me-DuPHOS)(2)(Et(2)SiH)(H)] and Δ-[cis-Ru((R,R)-Me-DuPHOS)(2)(PhSiH(2))(H)] but not for their Ru(R,R-BPE)(2) analogues. Molecular structures were also determined for Λ-[cis-Ru((R,R)-Me-BPE)(2)(Bpin)(H)], Λ-[Ru((S,S)-Me-DuPHOS)(2)(η(2)-C(2)H(4))], Δ-[Ru((R,R)-Me-DuPHOS)(2)(η(2)-C(2)H(4))], and trans-[Ru((R,R)-Me-DuPHOS)(2)(C(6)F(5))(H)]. In situ laser photolysis in the presence of p-H(2) generates hyperpolarized NMR spectra because of magnetically inequivalent hydrides; these experiments and low temperature photolysis with D(2) reveal that the loss of hydride ligands is concerted. The reaction intermediates [Ru(DuPHOS)(2)] and [Ru(BPE)(2)] were detected by laser flash photolysis and have spectra consistent with approximate square-planar Ru(0) structures. The rates of their reactions with H(2), D(2), HBpin, and PhSiH(3) were measured by transient kinetics. Rate constants are significantly faster for [Ru(BPE)(2)] than for [Ru(DuPHOS)(2

  4. Cation-Coupled Bicarbonate Transporters

    PubMed Central

    Aalkjaer, Christian; Boedtkjer, Ebbe; Choi, Inyeong; Lee, Soojung

    2016-01-01

    Cation-coupled HCO3− transport was initially identified in the mid-1970s when pioneering studies showed that acid extrusion from cells is stimulated by CO2/HCO3− and associated with Na+ and Cl− movement. The first Na+-coupled bicarbonate transporter (NCBT) was expression-cloned in the late 1990s. There are currently five mammalian NCBTs in the SLC4-family: the electrogenic Na,HCO3-cotransporters NBCe1 and NBCe2 (SLC4A4 and SLC4A5 gene products); the electroneutral Na,HCO3-cotransporter NBCn1 (SLC4A7 gene product); the Na+-driven Cl,HCO3-exchanger NDCBE (SLC4A8 gene product); and NBCn2/NCBE (SLC4A10 gene product), which has been characterized as an electroneutral Na,HCO3-cotransporter or a Na+-driven Cl,HCO3-exchanger. Despite the similarity in amino acid sequence and predicted structure among the NCBTs of the SLC4-family, they exhibit distinct differences in ion dependency, transport function, pharmacological properties, and interactions with other proteins. In epithelia, NCBTs are involved in transcellular movement of acid-base equivalents and intracellular pH control. In nonepithelial tissues, NCBTs contribute to intracellular pH regulation; and hence, they are crucial for diverse tissue functions including neuronal discharge, sensory neuron development, performance of the heart, and vascular tone regulation. The function and expression levels of the NCBTs are generally sensitive to intracellular and systemic pH. Animal models have revealed pathophysiological roles of the transporters in disease states including metabolic acidosis, hypertension, visual defects, and epileptic seizures. Studies are being conducted to understand the physiological consequences of genetic polymorphisms in the SLC4-members, which are associated with cancer, hypertension, and drug addiction. Here, we describe the current knowledge regarding the function, structure, and regulation of the mammalian cation-coupled HCO3− transporters of the SLC4-family. PMID:25428855

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

    PubMed

    Mori, Taizo; Sharma, Anshul; Hegmann, Torsten

    2016-01-26

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

  6. Memorized chiral arrangement of gemini surfactant assemblies in nanometric hybrid organic-silica helices.

    PubMed

    Ryu, Naoya; Okazaki, Yutaka; Hirai, Kana; Takafuji, Makoto; Nagaoka, Shoji; Pouget, Emilie; Ihara, Hirotaka; Oda, Reiko

    2016-04-30

    Hybrid nanohelices were obtained from silicification of self-assemblies of gemini surfactants with tartrate counterions. The chiral arrangement of these non-chiral gemini surfactants was preserved in the silica matrix even after the counterion exchange for a non-chiral bromide, and was capable of inducing the chiral organisation of a non-chiral dye, methyl orange. PMID:26961377

  7. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    DOEpatents

    Wasserman, Stephen R.; Anderson, Kenneth B.; Song, Kang; Yuchs, Steven E.; Marshall, Christopher L.

    1998-01-01

    A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate.

  8. Optical properties and circular dichroism of chiral metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Fan, Zhiyuan; Govorov, Alexander; OU Team

    2013-03-01

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

  9. Cation exchange capacity of pine bark substrates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cation exchange capacity (CEC) is an important soil and substrate chemical property. It describes a substrate's ability to retain cation nutrients. Higher CEC values for a substrate generally result in greater amounts of nutrients retained in the substrate and available for plant uptake, and great...

  10. Tripodal Receptors for Cation and Anion Sensors

    PubMed Central

    Kuswandi, Bambang; Nuriman; Verboom, Willem; Reinhoudt, David N.

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selective recognition and sensing of cations and anions. Examples on the relationship between structure and selectivity towards cations and anions are described. Furthermore, their applications as potentiometric ion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  11. Advancements in Anion Exchange Membrane Cations

    SciTech Connect

    Sturgeon, Matthew R.; Long, Hai; Park, Andrew M.; Pivovar, Bryan S.

    2015-10-15

    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  12. Analysis of Chiral Carboxylic Acids in Meteorites

    NASA Technical Reports Server (NTRS)

    Burton, A. S.; Elsila, J. E.; Hein, J. E.; Aponte, J. C.; Parker, E. T.; Glavin, D. P.; Dworkin, J. P.

    2015-01-01

    Homochirality of amino acids in proteins and sugars in DNA and RNA is a critical feature of life on Earth. In the absence of a chiral driving force, however, reactions leading to the synthesis of amino acids and sugars result in racemic mixtures. It is currently unknown whether homochirality was necessary for the origins of life or if it was a product of early life. The observation of enantiomeric excesses of certain amino acids of extraterrestrial origins in meteorites provides evidence to support the hypothesis that there was a mechanism for the preferential synthesis or destruction of a particular amino acid enantiomer [e.g., 1-3]. The cause of the observed chiral excesses is un-clear, although at least in the case of the amino acid isovaline, the degree of aqueous alteration that occurred on the meteorite parent body is correlated to the isovaline L-enantiomeric excess [3, 4]. This suggests that chiral symmetry is broken and/or amplified within the meteorite parent bodies. Besides amino acids, there have been only a few reports of other meteoritic compounds found in enantiomeric excess: sugars and sugar acids [5, 6] and the hydroxy acid lactic acid [7]. Determining whether or not additional types of molecules in meteorites are also present in enantiomeric excesses of extraterrestrial information will provide insights into mechanisms for breaking chiral symmetry. Though the previous measurements (e.g., enantiomeric composition of lactic acid [7], and chiral carboxylic acids [8]) were made by gas chromatography-mass spectrometry, the potential for increased sensitivity of liquid chromatography-mass spectrometry (LC-MS) analyses is important because for many meteorite samples, only small sample masses are available for study. Furthermore, at least in the case of amino acids, many of the largest amino acid enantiomeric excesses were observed in samples that contained lower abundances (tens of ppb) of a given amino acid enantiomer. In the present work, we describe

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

    PubMed

    Ogino, Yoshiyuki; Asahi, Toru

    2015-05-21

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

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

    PubMed

    Ogino, Yoshiyuki; Asahi, Toru

    2015-05-21

    In this study, systems of complicated pathways involved in chiral drug metabolism were investigated. The development of chiral drugs resulted in significant improvement in the remedies available for the treatment of various severe sicknesses. Enantiopure drugs undergo various biological transformations that involve chiral inversion and thus result in the generation of multiple enantiomeric metabolites. Identification of the specific active substances determining a given drug׳s efficacy among such a mixture of different metabolites remains a challenge. To comprehend this complexity, we constructed a mathematical model representing the complicated metabolic pathways simultaneously involving chiral inversion. Moreover, this model is applied to the metabolism of thalidomide, which has recently been revived as a potentially effective prescription drug for a number of intractable diseases. The numerical simulation results indicate that retained chirality in the metabolites reflects the original chirality of the unmetabolized drug, and a higher level of enantiomeric purity is preserved during spontaneous degradation. In addition, chirality remaining after equilibration is directly related to the rate constant not only for chiral inversion but also for generation and degradation. Furthermore, the retention of chirality is quantitatively predictable using this combination of kinetic parameters. Our simulation results well explain the behavior of thalidomide in the practical biological experimental data. Therefore, this model promises a comprehensive understanding of dynamic metabolic systems involving chiral drugs that express multiple enantiospecific drug efficacies. PMID:25791284

  15. Molecular-Level Design of Heterogeneous Chiral Catalysis

    SciTech Connect

    Francisco Zaera

    2012-03-21

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

  16. Advanced dress-up chiral columns: New removable chiral stationary phases for enantioseparation of chiral carboxylic acids.

    PubMed

    Todoroki, Kenichiro; Ishii, Yasuhiro; Ide, Takafumi; Min, Jun Zhe; Inoue, Koichi; Huang, Xin; Zhang, Wei; Hamashima, Yoshitaka; Toyo'oka, Toshimasa

    2015-07-01

    This paper describes the preparation of new dress-up columns featuring reproducibly removable and replaceable chiral stationary phases. After synthesizing perfluroalkylated quinine and quinidine derivatives as chiral stationary phase compounds (F-CSPs), we adsorbed them reversibly onto a fluorous LC column through pumping of their solutions. Using this dress-up chiral column and fluorophobic elution of aqueous ammonium formate/MeOH mixtures, we could enantioseparate four racemic N-acetyl amino acids, dichlorprop, and sixteen fluorescent 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC)-derivatized amino acids. Dressing and undressing of the coated F-CSPs could be controlled by varying the fluorophilicity and fluorophobicity of the eluent. The relative standard deviations of the retention times, the retention factors, the number of theoretical plates, the enantioseparation factors, and the resolutions of each of four preparations of such dress-up columns were all less than or equal to 5.26% (from 20 repeated analyses); the reproducibilities from four different preparations were all less than or equal to 10.6%. These columns also facilitated highly sensitive and selective analyses of AQC-amino acids when detected using LC-MS/MS.

  17. Simple chiral urea gelators, (R)- and (S)-2-heptylurea: their gelling ability enhanced by chirality.

    PubMed

    Kim, Jong-Uk; Schollmeyer, Dieter; Brehmer, Martin; Zentel, Rudolf

    2011-05-15

    We present the first report on the synthesis of chiral ureas, (R)- and (S)-2-heptylurea, and their gelling behaviors. The ureas were prepared by the reactions of chiral amines and phenyl carbamate in the presence of triethylamine. On cooling from homogeneous solutions, the chiral ureas form gels in water and various nonpolar organic solvents, such as cyclohexane, toluene, and tetrachloromethane, while the racemate gelatinize only toluene and tetrachloromethane among the solvents we examined. The gelling ability of the enantiomeric urea is higher than the racemate, as the critical gelling concentrations in toluene, for example, were 0.2% and 0.7% (wt/wt), respectively. The enhanced gelling ability of the enantiomeric ureas is due to the 1D supramolecular structure formed during gelation. In contrast, the racemate crystallizes into two-dimensional lamellae, where the (R)- and (S)-2-heptylurea exist alternatingly in a plane (P2(1)/c space group). Powder X-ray diffraction pattern of the enantiomeric urea showed that it has a different crystal lattice from that of the racemate, implying that the steric effect by the methyl group at the chiral center prevents the pure enantiomers from having 2D hydrogen bonding networks, which lead to sheet-like structures for the racemate and the achiral analog. Thus the pure enantiomers self-organize into one-dimensional fibrous structures. The simplicity and the ambidextrous gelling behaviors of the chiral ureas in forming both hydrogels and organogels present numerous possibilities for future applications. PMID:21396655

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

    SciTech Connect

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

    2015-10-14

    We theoretically investigate the pitch of lyotropic cholesteric phases composed of slender rods with steric chirality transmitted via a weak helical deformation of the backbone. In this limit, the model is amenable to analytical treatment within Onsager theory and a closed expression for the pitch versus concentration and helical shape can be derived. Within the same framework, we also briefly review the possibility of alternative types of chiral order, such as twist-bend or screw-like nematic phases, finding that cholesteric order dominates for weakly helical distortions. While long-ranged or “soft” chiral forces usually lead to a pitch decreasing linearly with concentration, steric chirality leads to a much steeper decrease of quadratic nature. This reveals a subtle link between the range of chiral intermolecular interaction and the pitch sensitivity with concentration. A much richer dependence on the thermodynamic state is revealed for polar helices where parallel and anti-parallel pair alignments along the local director are no longer equivalent. It is found that weak temperature variations may lead to dramatic changes in the pitch, despite the lyotropic nature of the assembly.

  19. Intracellular trafficking mechanism of cationic phospholipids including cationic liposomes in HeLa cells.

    PubMed

    Un, K; Sakai-Kato, K; Goda, Y

    2014-07-01

    The development of gene delivery methods is essential for the achievement of effective gene therapy. Elucidation of the intracellular transfer mechanism for cationic carriers is in progress, but there are few reports regarding the intracellular trafficking processes of the cationic phospholipids taken up into cells. In the present work, the trafficking processes of a cationic phospholipid (1,2-dioleoyl-3-trimethylammonium-propane, DOTAP) were investigated from intracellular uptake to extracellular efflux using cationic liposomes in vitro. Following intracellular transport of liposomes via endocytosis, DOTAP was localized in the endoplasmic reticulum, Golgi apparatus, and mitochondria. Moreover, the proteins involved in DOTAP intracellular trafficking and extracellular efflux were identified. In addition, helper lipids of cationic liposomes were found to partially affect this intracellulartrafficking. These findings might provide valuable information for designing cationic carriers and avoiding unexpected toxic side effects derived from cationic liposomal components.

  20. Integration of inherent and induced chirality into subphthalocyanine analogue

    PubMed Central

    Zhao, Luyang; Qi, Dongdong; Wang, Kang; Wang, Tianyu; Han, Bing; Tang, Zhiyong; Jiang, Jianzhuang

    2016-01-01

    Conventional conjugated systems are characteristic of only either inherent or induced chirality because of synthetic challenge in combination of chiral segment into the main chromophore. In this work, chiral binaphthyl segment is directly fused into the central chromophore of a subphthalocyanine skeleton, resulting in a novel type of chiral subphthalocyanine analogue (R/S)-1 of integrated inherent and induced chirality. Impressively, an obviously enhanced optical activity is discerned for (R/S)-1 molecules, and corresponding enhancement mechanism is elucidated in detail. The synthesis strategy based on rational molecular design will open the door towards fabrication of chiral materials with giant optical activity, which will have great potential in chiroptical devices. PMID:27294871

  1. Electrical magnetochiral anisotropy in a bulk chiral molecular conductor.

    PubMed

    Pop, Flavia; Auban-Senzier, Pascale; Canadell, Enric; Rikken, Geert L J A; Avarvari, Narcis

    2014-01-01

    So far, no effect of chirality on the electrical properties of bulk chiral conductors has been observed. Introduction of chiral information in tetrathiafulvalene precursors represents a powerful strategy towards the preparation of crystalline materials in which the combination of chirality and conducting properties might allow the observation of the electrical magnetochiral anisotropy effect. Here we report the synthesis by electrocrystallization of both enantiomers of a bulk chiral organic conductor based on an enantiopure tetrathiafulvalene derivative. The enantiomeric salts crystallize in enantiomorphic hexagonal space groups. Single crystal resistivity measurements show metallic behaviour for the enantiopure salts down to 40 K, in agreement with band structure calculations. We describe here the first experimental evidence of electrical magnetochiral anisotropy in these crystals, confirming the chiral character of charge transport in our molecular materials. PMID:24796572

  2. Detecting Chirality in Molecules by Linearly Polarized Laser Fields

    NASA Astrophysics Data System (ADS)

    Yachmenev, Andrey; Yurchenko, Sergei N.

    2016-07-01

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

  3. Progress of quartz crystal microbalance in chiral analysis.

    PubMed

    Guo, Huishi

    2014-02-01

    Chiral analysis is one of the most important/challenging analytical tasks due to the necessity for differentiation of very slight differences in the molecular configurations between chiral isomers. It consists of two processes, chiral recognition and signal transduction. Quartz crystal microbalance (QCM) holds a great promise for the next-generation sensors, due to its remarkable mass sensitivity, fast response, capable of online detection and low cost. It has been the focus of academic and practical research on chiral analysis during the last two decades. This review provides a detailed overview of recent advances made in chiral analysis based on QCM detection with regard to the recognition elements, which include synthetic macromolecules, molecular imprinting polymers (MIPs), proteins, amino acids and their derivatives, etc. The prospects of using QCM for chiral analysis are also put forward.

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

    PubMed

    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.

  5. Achiral flexible liquid crystal trimers exhibiting chiral conglomerates.

    PubMed

    Sasaki, Haruna; Takanishi, Yoichi; Yamamoto, Jun; Yoshizawa, Atsushi

    2016-04-14

    Chiral conglomerates of domains with opposite handedness have attracted much attention from researchers. We prepared a homologous series of achiral liquid crystal trimers in which two phenylpyrimidine units and one biphenyl unit were connected via flexible methylene spacers. We investigated their phase transition behaviour. Some trimers possessing odd-numbered spacers were found to exhibit a nematic phase and a dark chiral conglomerate phase possessing a layered structure. The chiral characteristics were confirmed by uncrossing the polarizers in opposite directions. The layer spacing detected using X-ray diffraction was about 80% of the molecular length. The structure-property relations indicate that intermolecular interactions cause a conformational change in the trimers possessing flexible odd-numbered methylene spacers to form helical conformers with axial chirality, which might induce chiral segregation and layer deformation to drive the chiral conglomerates.

  6. A molecular propeller effect for chiral separation and analysis

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  7. Development of chiral sulfoxide ligands for asymmetric catalysis.

    PubMed

    Trost, Barry M; Rao, Meera

    2015-04-20

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

  8. Detecting Chirality in Molecules by Linearly Polarized Laser Fields.

    PubMed

    Yachmenev, Andrey; Yurchenko, Sergei N

    2016-07-15

    A new scheme for enantiomer differentiation of chiral molecules using a pair of linearly polarized intense ultrashort laser pulses with skewed mutual polarization is presented. The technique relies on the fact that the off-diagonal anisotropic contributions to the electric polarizability tensor for two enantiomers have different signs. Exploiting this property, we are able to excite a coherent unidirectional rotation of two enantiomers with a π phase difference in the molecular electric dipole moment. The approach is robust and suitable for relatively high temperatures of molecular samples, making it applicable for selective chiral analysis of mixtures, and to chiral molecules with low barriers between enantiomers. As an illustration, we present nanosecond laser-driven dynamics of a tetratomic nonrigid chiral molecule with short-lived chirality. The ultrafast time scale of the proposed technique is well suited to study parity violation in molecular systems in short-lived chiral states. PMID:27472111

  9. A molecular propeller effect for chiral separation and analysis

    PubMed Central

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    Chirality is known to play a pivotal role in determining material properties and functionalities. However, it remains a great challenge to understand and control the emergence of chirality and the related enantioselective process particularly when the building components of the system are achiral. Here we explore the generic mechanisms driving the formation of two-dimensional chiral structures in systems characterized by isotropic interactions and three competing length scales. We demonstrate that starting from isotropic and rotationally invariant interactions, a variety of chiral ordered patterns and superlattices with anisotropic but achiral units can self-assemble. The mechanisms for selecting specific states are related to the length-scale coupling and the selection of resonant density wave vectors. Sample phase diagrams and chiral elastic properties are identified. These findings provide a viable route for predicting chiral phases and selecting the desired handedness.

  11. Supramolecular chirality in self-assembled peptide amphiphile nanostructures.

    PubMed

    Garifullin, Ruslan; Guler, Mustafa O

    2015-08-11

    Induced supramolecular chirality was investigated in the self-assembled peptide amphiphile (PA) nanosystems. Having shown that peptide chirality can be transferred to the covalently-attached achiral pyrene moiety upon PA self-assembly, the chiral information is transferred to molecular pyrene via weak noncovalent interactions. In the first design of a supramolecular chiral system, the chromophore was covalently attached to a peptide sequence (VVAGH) via an ε-aminohexanoic acid spacer. Covalent attachment yielded a PA molecule self-assembling into nanofibers. In the second design, the chromophore was encapsulated within the hydrophobic core of self-assembled nanofibers of another PA consisting of the same peptide sequence attached to lauric acid. We observed that supramolecular chirality was induced in the chromophore by PA assembly into chiral nanostructures, whether it was covalently attached, or noncovalently bound. PMID:26146021

  12. Generation of chiral spin state by quantum simulation

    NASA Astrophysics Data System (ADS)

    Tanamoto, Tetsufumi

    2016-06-01

    Chirality of materials in nature appears when there are asymmetries in their lattice structures or interactions in a certain environment. Recent development of quantum simulation technology has enabled the manipulation of qubits. Accordingly, chirality can be realized intentionally rather than passively observed. Here we theoretically provide simple methods to create a chiral spin state in a spin-1/2 qubit system on a square lattice. First, we show that switching on and off the Heisenberg and X Y interactions produces the chiral interaction directly in the effective Hamiltonian without controlling local fields. Moreover, when initial states of spin qubits are appropriately prepared, we prove that the chirality with desirable phase is dynamically obtained. Finally, even for the case where switching on and off the interactions is infeasible and the interactions are always on, we show that, by preparing an asymmetric initial qubit state, the chirality whose phase is π /2 is dynamically generated.

  13. Self-shaping of bioinspired chiral composites

    NASA Astrophysics Data System (ADS)

    Rong, Qing-Qing; Cui, Yu-Hong; Shimada, Takahiro; Wang, Jian-Shan; Kitamura, Takayuki

    2014-08-01

    Self-shaping materials such as shape memory polymers have recently drawn considerable attention owing to their high shape-changing ability in response to changes in ambient conditions, and thereby have promising applications in the biomedical, biosensing, soft robotics and aerospace fields. Their design is a crucial issue of both theoretical and technological interest. Motivated by the shape-changing ability of Towel Gourd tendril helices during swelling/deswelling, we present a strategy for realizing self-shaping function through the deformation of micro/nanohelices. To guide the design and fabrication of self-shaping materials, the shape equations of bent configurations, twisted belts, and helices of slender chiral composite are developed using the variation method. Furthermore, it is numerically shown that the shape changes of a chiral composite can be tuned by the deformation of micro/nanohelices and the fabricated fiber directions. This work paves a new way to create self-shaping composites.

  14. New approaches in sensitive chiral CE.

    PubMed

    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.

  15. Active control of chirality in nonlinear metamaterials

    SciTech Connect

    Zhu, Yu; Chai, Zhen; Yang, Hong; Hu, Xiaoyong Gong, Qihuang

    2015-03-02

    An all-optical tunabe chirality is realized in a photonic metamaterial, the metamolecule of which consists of a nonlinear nano-Au:polycrystalline indium-tin oxide layer sandwiched between two L-shaped gold nano-antennas twisted 90° with each other. The maximum circular dichroism reached 30%. Under excitation of a 40 kW/cm{sup 2} weak pump light, the peak in the circular dichroism shifts 45 nm in the short-wavelength direction. An ultrafast response time of 35 ps is maintained. This work not only opens up the possibility for the realization of ultralow-power and ultrafast all-optical tunable chirality but also offers a way to construct ultrahigh-speed on-chip biochemical sensors.

  16. Nonperturbative Regulator for Chiral Gauge Theories?

    PubMed

    Grabowska, Dorota M; Kaplan, David B

    2016-05-27

    We propose a nonperturbative gauge-invariant regulator for d-dimensional chiral gauge theories on the lattice. The method involves simulating domain wall fermions in d+1 dimensions with quantum gauge fields that reside on one d-dimensional surface and are extended into the bulk via gradient flow. The result is a theory of gauged fermions plus mirror fermions, where the mirror fermions couple to the gauge fields via a form factor that becomes exponentially soft with the separation between domain walls. The resultant theory has a local d-dimensional interpretation only if the chiral fermion representation is anomaly free. A physical realization of this construction would imply the existence of mirror fermions in the standard model that are invisible except for interactions induced by vacuum topology, and which could gravitate differently than conventional matter. PMID:27284646

  17. Imprintable membranes from incomplete chiral coalescence

    NASA Astrophysics Data System (ADS)

    Zakhary, Mark J.; Gibaud, Thomas; Nadir Kaplan, C.; Barry, Edward; Oldenbourg, Rudolf; Meyer, Robert B.; Dogic, Zvonimir

    2014-01-01

    Coalescence is an essential phenomenon that governs the equilibrium behaviour in a variety of systems from intercellular transport to planetary formation. In this report, we study coalescence pathways of circularly shaped two-dimensional colloidal membranes, which are one rod-length-thick liquid-like monolayers of aligned rods. The chirality of the constituent rods leads to three atypical coalescence pathways that are not found in other simple or complex fluids. In particular, we characterize two pathways that do not proceed to completion but instead produce partially joined membranes connected by line defects—π-wall defects or alternating arrays of twisted bridges and pores. We elucidate the structure and energetics of these defects and ascribe their stability to a geometrical frustration inherently present in chiral colloidal membranes. Furthermore, we induce the coalescence process with optical forces, leading to a robust on-demand method for imprinting networks of channels and pores into colloidal membranes.

  18. On Gauge Independent Dynamical Chiral Symmetry Breaking

    SciTech Connect

    Bashir, A.; Raya, A.

    2006-09-25

    Schwinger-Dyson equations (SDEs) are an ideal framework to study nonperturbative phenomena such as dynamical chiral symmetry breaking (DCSB). Loss of gauge invariance is an obstacle to achieve fully reliable predictions from these equations. In addition to Ward-Green-Takahashi identity (WGTI), Landau-Khalatnikov-Fradkin transformations (LKFT) also play an important role in restoring the said invariance at the level of physical observables. On one hand, they impose useful constraints on the transverse part of the fermion-boson vertex and on the other, they govern the change in dynamically generated fermion propagator with a variation of gauge. We consider the latter in this article and study the gauge (in)dependence of chiral condensate in quantum electrodynamics in (2+1) space-time dimensions (QED3)

  19. Chiral patterning in Paenibacillus colonies under stress

    NASA Astrophysics Data System (ADS)

    Levine, Herbert

    2012-02-01

    One of the most striking examples of bacterial colony patterning occurs in the C-morphotype of Paenibacillus strains. Here, macroscopic chirality results from the interaction of local liquid-crystal ordering of the long bacterial cells with the self-propelled motility driven by the non-reflection-symmetric flagella. This talk will review some of the original experimental data from the Ben-Jacob lab as well as recent insight obtained via genomics. I will then discuss attempts to model and simulate the chiral patterns via solving reaction-diffusion equations on random lattices. At the end, I will introduce the challenges still to be faced in understanding transitions between these patterns and more common branching structures

  20. Optical tractor beam with chiral light

    NASA Astrophysics Data System (ADS)

    Fernandes, David E.; Silveirinha, Mário G.

    2015-06-01

    We suggest a novel mechanism to induce the motion of a chiral material body towards an optical source with no optical traps. Our solution is based on the interference between a chiral light beam and its reflection on an opaque mirror. Surprisingly, it is theoretically shown that the electromagnetic response of the material may be tailored in such a way that independent of the specific body location with respect to the mirror, it is always pulled upstream against the photon flow associated with the incoming wave. Moreover, it is proven that by controlling the handedness of the incoming light it may be possible to harness the sign of the optical force, switching from a pulling force to a pushing force.

  1. Check for chirality in {sup 102}Rh

    SciTech Connect

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

    2012-10-20

    Excited states in {sup 102}Rh, populated by the fusion-evaporation reaction {sup 94}Zr({sup 11}B,3n){sup 102}Rh at a beam energy of 36 MeV, were studied using the INGA spectrometer at IUAC, New Delhi. The angular correlations and the electromagnetic character of some of the gamma-ray transitions observed were investigated in details. A new chiral candidate sister band was found in the level-scheme of {sup 102}Rh. Lifetimes of exited states in {sup 102}Rh were measured by means of the Doppler-shift attenuation technique. The experimental results do not support the presence of static chirality in {sup 102}Rh.

  2. Chiral meta-atoms rotated by light

    SciTech Connect

    Liu Mingkai; Powell, David A.; Shadrivov, Ilya V.

    2012-07-16

    We study the opto-mechanical properties of coupled chiral meta-atoms based on a pair of twisted split-ring resonators. By using a simple analytical model in conjunction with the Maxwell stress tensor, we capture insight into the mechanism and find that this structure can be used as a general prototype of subwavelength light-driven actuators over a wide range of frequencies. This coupled structure can provide a strong and tunable torque, and can support different opto-mechanical modes, including uniform rotation, periodically variable rotation and damped oscillations. Our results suggest that chiral meta-atoms are good candidates for creating sub-wavelength motors or wrenches controlled by light.

  3. Applications of partially quenched chiral perturbation theory

    SciTech Connect

    Golterman, M.F.; Leung, K.C.

    1998-05-01

    Partially quenched theories are theories in which the valence- and sea-quark masses are different. In this paper we calculate the nonanalytic one-loop corrections of some physical quantities: the chiral condensate, weak decay constants, Goldstone boson masses, B{sub K}, and the K{sup +}{r_arrow}{pi}{sup +}{pi}{sup 0} decay amplitude, using partially quenched chiral perturbation theory. Our results for weak decay constants and masses agree with, and generalize, results of previous work by Sharpe. We compare B{sub K} and the K{sup +} decay amplitude with their real-world values in some examples. For the latter quantity, two other systematic effects that plague lattice computations, namely, finite-volume effects and unphysical values of the quark masses and pion external momenta, are also considered. We find that typical one-loop corrections can be substantial. {copyright} {ital 1998} {ital The American Physical Society}

  4. Chiral fermions as classical massless spinning particles

    NASA Astrophysics Data System (ADS)

    Duval, C.; Horváthy, P. A.

    2015-02-01

    Semiclassical chiral fermion models with Berry term are studied in a symplectic framework. In the free case, the system can be obtained from Souriau's model for a relativistic massless spinning particle by "enslaving" the spin. The Berry term is identified with the classical spin two-form of the latter model. The Souriau model carries a natural Poincaré symmetry that we highlight, but spin enslavement breaks the boost symmetry. However the relation between the models allows us to derive a Poincaré symmetry of unconventional form for chiral fermions. Then we couple our system to an external electromagnetic field. For gyromagnetic ratio g =0 we get curious superluminal Hall-type motions; for g =2 and in a pure constant magnetic field in particular, we find instead spiraling motions.

  5. Chiral perturbation theory with tensor sources

    SciTech Connect

    Cata, Oscar; Cata, Oscar; Mateu, Vicent

    2007-05-21

    We construct the most general chirally-invariant Lagrangian for mesons in the presence of external sources coupled to the tensor current \\bar psi sigma_mu nu psi. In order to have only even terms in the chiral expansion, we consider the new source of O(p2). With this choice, we build the even-parity effective Lagrangian up to the p6-order (NLO). While there are only 4 new terms at the p4-order, at p6-order we find 78 terms for n_f=2 and 113 terms for n_f=3. We provide a detailed discussion on the different mechanisms that ensure that our final set of operators is complete and non-redundant. We also examine the odd-parity sector, to conclude that the first operators appear at the p8-order (NNLO).

  6. Absence of equilibrium chiral magnetic effect

    NASA Astrophysics Data System (ADS)

    Zubkov, M. A.

    2016-05-01

    We analyze the (3 +1 )D equilibrium chiral magnetic effect (CME). We apply derivative expansion to the Wigner transform of the two-point Green function. This technique allows us to express the response of electric current to the external electromagnetic field strength through the momentum space topological invariant. We consider the wide class of the lattice regularizations of quantum field theory (that includes, in particular, the regularization with Wilson fermions) and also certain lattice models of solid state physics (including those of Dirac semimetals). It appears that in these models the mentioned topological invariant vanishes identically at nonzero chiral chemical potential. That means that the bulk equilibrium CME is absent in those systems.

  7. Oscillating chiral tensor spectrum from axionic inflation

    NASA Astrophysics Data System (ADS)

    Obata, Ippei; Soda, Jiro

    2016-08-01

    We study axionic inflation with a modulated potential and examine if the primordial tensor power spectrum exhibits oscillatory feature, which is testable with future space-based gravitational-wave experiments such as DECIGO and BBO. In the case of single-field axion monodromy inflation, it turns out that it is difficult to detect an oscillation in the spectrum due to the suppression of the sub-Planckian decay constant of the axion. On the other hand, in the case of aligned chromo-natural inflation where the axion is coupled to a SU(2) gauge field, it turns out that a sizable oscillation in the tensor spectrum can occur due to the enhancement of chiral gravitational waves sourced by the gauge field. We expect that this feature will be a new probe for axion phenomenologies in the early Universe through chiral gravitational waves.

  8. Cationic Bolaamphiphiles for Gene Delivery

    NASA Astrophysics Data System (ADS)

    Tan, Amelia Li Min; Lim, Alisa Xue Ling; Zhu, Yiting; Yang, Yi Yan; Khan, Majad

    2014-05-01

    Advances in medical research have shed light on the genetic cause of many human diseases. Gene therapy is a promising approach which can be used to deliver therapeutic genes to treat genetic diseases at its most fundamental level. In general, nonviral vectors are preferred due to reduced risk of immune response, but they are also commonly associated with low transfection efficiency and high cytotoxicity. In contrast to viral vectors, nonviral vectors do not have a natural mechanism to overcome extra- and intracellular barriers when delivering the therapeutic gene into cell. Hence, its design has been increasingly complex to meet challenges faced in targeting of, penetration of and expression in a specific host cell in achieving more satisfactory transfection efficiency. Flexibility in design of the vector is desirable, to enable a careful and controlled manipulation of its properties and functions. This can be met by the use of bolaamphiphile, a special class of lipid. Unlike conventional lipids, bolaamphiphiles can form asymmetric complexes with the therapeutic gene. The advantage of having an asymmetric complex lies in the different purposes served by the interior and exterior of the complex. More effective gene encapsulation within the interior of the complex can be achieved without triggering greater aggregation of serum proteins with the exterior, potentially overcoming one of the great hurdles faced by conventional single-head cationic lipids. In this review, we will look into the physiochemical considerations as well as the biological aspects of a bolaamphiphile-based gene delivery system.

  9. Stereoselectivity of chiral drug transport: a focus on enantiomer-transporter interaction.

    PubMed

    Zhou, Quan; Yu, Lu-Shan; Zeng, Su

    2014-08-01

    Drug transporters and drug metabolism enzymes govern drug absorption, distribution, metabolism and elimination. Many literature works presenting important aspects related to stereochemistry of drug metabolism are available. However, there is very little literature on stereoselectivity of chiral drug transport and enantiomer-transporter interaction. In recent years, the experimental research within this field showed good momentum. Herein, an up-to-date review on this topic was presented. Breast Cancer Resistance Protein (BCRP), Multidrug Resistance Proteins (MRP), P-glycoprotein (P-gp), Organic Anion Transporters (OATs), Organic Anion Transporting Polypeptides (OATPs), Organic Cation Transporters (OCTs), Peptide Transport Proteins (PepTs), Human Proton-Coupled Folate Transporter (PCFT) and Multidrug and Toxic Extrusion Proteins (MATEs), have been reported to exhibit either positive or negative enantio-selective substrate recognition. The approaches utilized to study chirality in enantiomer-transporter interaction include inhibition experiments of specific transporters in cell models (e.g. Caco-2 cells), transport study using drug resistance cell lines or transgenic cell lines expressing transporters in wild type or variant, the use of transporter knockout mice, pharmacokinetics association of single nucleotide polymorphism in transporters, pharmacokinetic interaction study of racemate in the presence of specific transporter inhibitor or inducer, molecule cellular membrane affinity chromatography and pharmacophore modeling. Enantiomer-enantiomer interactions exist in chiral transport. The strength and/or enantiomeric preference of stereoselectivity may be species or tissue-specific, concentration-dependent and transporter family member-dependent. Modulation of specific drug transporter by pure enantiomers might exhibit opposite stereoselectivity. Further studies with integrated approaches will open up new horizons in stereochemistry of pharmacokinetics. PMID:24796860

  10. Terahertz chiral metamaterials with giant and dynamically tunable optical activity

    SciTech Connect

    Zhou, Jiangfeng; Chowdhury, Dibakar Roy; Zhao, Rongkuo; Azad, Abul K.; Chen, Hou-Tong; Soukoulis, Costas M.; Taylor, Antoinette J.; O'Hara, John F.

    2012-07-27

    We demonstrated giant optical activity using a chiral metamaterial composed of an array of conjugated bilayer metal structures. The chiral metamaterials were further integrated with photoactive inclusions to accomplish a wide tuning range of the optical activity through illumination with near-infrared light. The strong chirality observed in our metamaterials results in a negative refractive index, which can also be well controlled by the near-infrared optical excitation.

  11. Magnetotransport phenomena related to the chiral anomaly in Weyl semimetals

    NASA Astrophysics Data System (ADS)

    Spivak, B. Z.; Andreev, A. V.

    2016-02-01

    We present a theory of magnetotransport phenomena related to the chiral anomaly in Weyl semimetals. We show that conductivity, thermal conductivity, thermoelectric, and the sound absorption coefficients exhibit strong and anisotropic magnetic field dependencies. We also discuss properties of magnetoplasmons and magnetopolaritons, whose existences are entirely determined by the chiral anomaly. Finally, we discuss the conditions of applicability of the quasiclassical description of electron transport phenomena related to the chiral anomaly.

  12. Quenched QED in the chiral limit. [QED (quantum electrodynamics)

    SciTech Connect

    Vandermark, S.W.

    1993-01-01

    The main goal in this project has been to understand, through analytical methods, whether there could be a continuum limit for QED. This possibility is motivated by recent lattice simulations on quenched QED which apparently exhibit a chiral phase transition at strong coupling in the chiral limit. Another goal is to develop a novel perturbation expansion which may also be usefully applied to other theories. The author begins with the general expression for the chiral order parameter, ([bar [psi

  13. Chiral Biomarkers and Microfossils in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2010-01-01

    Homochirality of the biomolecules (D-sugars of DNA and RNA and L-amino acids of proteins) is a fundamental property of all life on Earth. Abiotic mechanisms yield racemic mixtures (D/L=1) of chiral molecules and after the death of an organism, the enantiopure chiral biomolecules slowly racemize. Several independent investigators have now established that the amino acids present in CI1 and CM2 carbonaceous meteorites have a moderate to strong excess of the L-enantiomer. Stable isotope data have established that these amino acids are both indigenous and extraterrestrial. Carbonaceous meteorites also contain many other strong chemical biomarkers including purines and pyrimidines (nitrogen heterocycles of nucleic acids); pristine and phytane (components of the chlorophyll pigment) and morphological biomarkers (microfossils of filamentous cyanobacteria). Energy dispersive X-ray Spectroscopy (EDS) analysis reveals that nitrogen is below the detectability level in most of the meteorite filaments as well as in Cambrian Trilobites and filaments of 2.7 Gya Archaean cyanobacteria from Karelia. The deficiency of nitrogen in the filaments and the total absence of sugars, of twelve of the life-critical protein amino acids, and two of the nucleobases of DNA and RNA provide clear and convincing evidence that these filaments are not modern biological contaminants. This paper reviews the chiral, chemical biomarkers morphological biomarkers and microfossils in carbonaceous meteorites. This paper reviews chiral and morphological biomarkers and discusses the missing nitrogen, sugars, protein amino acids, and nucleobases as ?bio-discriminators? that exclude modern biological contaminants as a possible explanation for the permineralized cyanobacterial filaments found in the meteorites.

  14. Hyperbolic Weyl Point in Reciprocal Chiral Metamaterials

    NASA Astrophysics Data System (ADS)

    Xiao, Meng; Lin, Qian; Fan, Shanhui

    2016-07-01

    We report the existence of Weyl points in a class of noncentral symmetric metamaterials, which has time reversal symmetry, but does not have inversion symmetry due to chiral coupling between electric and magnetic fields. This class of metamaterial exhibits either type-I or type-II Weyl points depending on its nonlocal response. We also provide a physical realization of such metamaterial consisting of an array of metal wires in the shape of elliptical helices which exhibits type-II Weyl points.

  15. Gauge cosmic chiral strings in general relativity

    SciTech Connect

    Rybakov, Yu. P.

    2009-05-15

    Cylindrically symmetric self-gravitating configurations of string (vortex) type are considered within the framework of the chiral SU(2) model with the inclusion of the Yang-Mills proper gauge field. In the approximation of the large topological charge n the solutions to the field equations are found, with the magnetic field of the vortex being longitudinal. The linear energy density of the vortex configuration is estimated.

  16. Chiral biomarkers and microfossils in carbonaceous meteorites

    NASA Astrophysics Data System (ADS)

    Hoover, Richard B.

    2010-09-01

    Homochirality of the biomolecules (D-sugars of DNA and RNA and L-amino acids of proteins) is a fundamental property of all life on Earth. Abiotic mechanisms yield racemic mixtures (D/L=1) of chiral molecules and after the death of an organism, the enantiopure chiral biomolecules slowly racemize. Several independent investigators have now established that the amino acids present in CI1 and CM2 carbonaceous meteorites have a moderate to strong excess of the L-enantiomer. Stable isotope data have established that these amino acids are both indigenous and extraterrestrial. Carbonaceous meteorites also contain many other strong chemical biomarkers including purines and pyrimidines (nitrogen heterocycles of nucleic acids); pristine and phytane (components of the chlorophyll pigment) and morphological biomarkers (microfossils of filamentous cyanobacteria). Energy dispersive X-ray Spectroscopy (EDS) analysis reveals that nitrogen is below the detectability level in most of the meteorite filaments as well as in Cambrian Trilobites and filaments of 2.7 Gya Archaean cyanobacteria from Karelia. The deficiency of nitrogen in the filaments and the total absence of sugars, of twelve of the life-critical protein amino acids, and two of the nucleobases of DNA and RNA provide clear and convincing evidence that these filaments are not modern biological contaminants. This paper reviews the chiral, chemical biomarkers morphological biomarkers and microfossils in carbonaceous meteorites. This paper reviews chiral and morphological biomarkers and discusses the missing nitrogen, sugars, protein amino acids, and nucleobases as "bio-discriminators" that exclude modern biological contaminants as a possible explanation for the permineralized cyanobacterial filaments found in the meteorites.

  17. Hyperbolic Weyl Point in Reciprocal Chiral Metamaterials.

    PubMed

    Xiao, Meng; Lin, Qian; Fan, Shanhui

    2016-07-29

    We report the existence of Weyl points in a class of noncentral symmetric metamaterials, which has time reversal symmetry, but does not have inversion symmetry due to chiral coupling between electric and magnetic fields. This class of metamaterial exhibits either type-I or type-II Weyl points depending on its nonlocal response. We also provide a physical realization of such metamaterial consisting of an array of metal wires in the shape of elliptical helices which exhibits type-II Weyl points.

  18. Circular Intensity Differential Scattering of chiral molecules

    SciTech Connect

    Bustamante, C.J.

    1980-12-01

    In this thesis a theory of the Circular Intensity Differential Scattering (CIDS) of chiral molecules as modelled by a helix oriented with respect to the direction of incidence of light is presented. It is shown that a necessary condition for the existence of CIDS is the presence of an asymmetric polarizability in the scatterer. The polarizability of the scatterer is assumed generally complex, so that both refractive and absorptive phenomena are taken into account.

  19. Cationic phospholipids: structure transfection activity relationships

    SciTech Connect

    Koynova, Rumiana; Tenchov, Boris

    2010-01-18

    Synthetic cationic lipids are presently the most widely used non-viral gene carriers. Examined here is a particularly attractive cationic lipid class, triester phosphatidylcholines (PCs) exhibiting low toxicities and good transfection efficiency. Similarly to other cationic lipids, they form stable complexes (lipoplexes) with the polyanionic nucleic acids. A summary of studies on a set of {approx}30 cationic PCs reveals the existence of a strong, systematic dependence of their transfection efficiency on the lipid hydrocarbon chain structure: transfection activity increases with increase of chain unsaturation from 0 to 2 double bonds per lipid and decreases with increase of chain length in the range {approx}30-50 total number of chain carbon atoms. Maximum transfection was observed for ethyl phosphate PCs (EPCs) with monounsaturated 14:1 chains (total of 2 double bonds and 30 chain carbon atoms). Lipid phase behavior is known to depend strongly on the chain molecular structure and the above relationships thus substantiate a view that cationic PC phase propensities are an important determinant of their activity. Indeed, X-ray structural studies show that the rate of DNA release from lipoplexes as well as transfection activity well correlate with non-lamellar phase progressions observed in cationic PC mixtures with membrane lipids. These findings appear to be of considerable interest because, according to current views, key processes in lipid-mediated transfection such as lipoplex disassembly and DNA release within the cells are believed to take place upon cationic lipid mixing with cellular lipids.

  20. Hybrid chiral metamaterials by dynamic shadowing growth

    NASA Astrophysics Data System (ADS)

    Gibbs, John; Fischer, Peer; Mark, Andrew; Eslami, Sahand; Lee, Tung-Chun

    2015-03-01

    Coupling optical and magnetic properties is possible in metamaterials and in higher-order magnetic field induced optical activities. Here, we show that these two mechanisms can be combined in nanostructures that are simultaneously ferromagnetic, chiral, and plasmonically resonant. In this talk, a short description of the fabrication of optically active helical metamaterials will first be given, followed by the highlighting of the materials' enhanced optical properties. Giant circular dichroism (CD) and optical rotatory dispersion (ORD) in the visible arise from helical plasmonic modes within the individual structures and can be tuned by altering the material composition, i.e. nanoalloys or nanocomposites, and/or by changing the structures' morphologies. By fabricating metamaterials which exhibit both strong CD and are ferromagnetic at room temperature, higher order terms in the generalized dielectric function in the presence of a B-field can be measured easily. In particular, magnetochiral dichroism (MChD) is a cross-term between chirality and an applied external B-field which has only been measured in crystals and molecules, but never in a metamaterial. We show that arrays of helical Ni nanostructures, due to the plasmonic nature of Ni, their chirality, as well as the fact they retain their ferromagnetism even at scales comparable to the average ferromagnetic domain size, exhibit an MChD signal that is much more pronounced in a metamaterial and can therefore be easily measured in the laboratory.

  1. Lagrangians for massive Dirac chiral superfields

    NASA Astrophysics Data System (ADS)

    Jiménez, Enrique; Vaquera-Araujo, C. A.

    2016-06-01

    A variant for the superspin one-half massive superparticle in 4D, N = 1, based on Dirac superfields, is offered. As opposed to the current known models that use spinor chiral superfields, the propagating fields of the supermultiplet are those of the lowest mass dimensions possible: scalar, Dirac and vector fields. Besides the supersymmetric chiral condition, the Dirac superfields are not further constrained, allowing a very straightforward implementation of the path-integral method. The corresponding superpropagators are presented. In addition, an interaction super Yukawa potential, formed by Dirac and scalar chiral superfields, is given in terms of their component fields. The model is first presented for the case of two superspin one-half superparticles related by the charged conjugation operator, but in order to treat the case of neutral superparticles, the Majorana condition on the Dirac superfields is also studied. We compare our proposal with the known models of spinor superfields for the one-half superparticle and show that it is equivalent to them.

  2. Energetic molding of chiral magnetic bubbles

    NASA Astrophysics Data System (ADS)

    Lau, Derek; Sundar, Vignesh; Zhu, Jian-Gang; Sokalski, Vincent

    2016-08-01

    Topologically protected magnetic structures such as skyrmions and domain walls (DWs) have drawn a great deal of attention recently due to their thermal stability and potential for manipulation by spin current, which is the result of chiral magnetic configurations induced by the interfacial Dzyaloshinskii-Moriya interaction (DMI). Designing devices that incorporate DMI necessitates a thorough understanding of how the interaction presents and can be measured. One approach is to measure growth asymmetry of chiral bubble domains in perpendicularly magnetized thin films, which has been described elsewhere by thermally activated DW motion. Here, we demonstrate that the anisotropic angular dependence of DW energy originating from the DMI is critical to understanding this behavior. Domains in Co/Ni multilayers are observed to preferentially grow into nonelliptical teardrop shapes, which vary with the magnitude of an applied in-plane field. We model the domain profile using energetic calculations of equilibrium shape via the Wulff construction, which serves as a new paradigm for describing chiral domains that explains both the teardrop shape and the reversal of growth symmetry at large fields.

  3. Pion scattering poles and chiral symmetry restoration

    SciTech Connect

    Fernandez-Fraile, D.; Nicola, A. Gomez; Herruzo, E. T.

    2007-10-15

    Using unitarized chiral perturbation theory methods, we perform a detailed analysis of the {pi}{pi} scattering poles f{sub 0}(600) and {rho}(770) behavior when medium effects such as temperature or density drive the system towards chiral symmetry restoration. In the analysis of real poles below threshold, we show that it is crucial to extend properly the unitarized amplitudes so that they match the perturbative Adler zeros. Our results do not show threshold enhancement effects at finite temperature in the f{sub 0}(600) channel, which remains as a pole of broad nature. We also implement T=0 finite-density effects related to chiral symmetry restoration, by varying the pole position with the pion decay constant. Although this approach takes into account only a limited class of contributions, we reproduce the expected finite-density restoration behavior, which drives the poles towards the real axis, producing threshold enhancement and {pi}{pi} bound states. We compare our results with several model approaches and discuss the experimental consequences, both in relativistic heavy ion collisions and in {pi}{yields}{pi}{pi} and {gamma}{yields}{pi}{pi} reactions in nuclei.

  4. Chiral discrimination in optical trapping and manipulation

    NASA Astrophysics Data System (ADS)

    Bradshaw, David S.; Andrews, David L.

    2014-10-01

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

  5. AkF ¯ chiral gauge theories

    NASA Astrophysics Data System (ADS)

    Shi, Yan-Liang; Shrock, Robert

    2015-11-01

    We study asymptotically free chiral gauge theories with an SU (N ) gauge group and chiral fermions transforming according to the antisymmetric rank-k tensor representation, Ak≡[k ]N , and the requisite number, nF ¯, of copies of fermions in the conjugate fundamental representation, F ¯ ≡[1] ¯ N , to render the theories anomaly-free. We denote these as AkF ¯ theories. We take N ≥2 k +1 so that nF ¯≥1 . The A2F ¯ theories form an infinite family with N ≥5 , but we show that the A3F ¯ and A4F ¯ theories are only asymptotically free for N in the respective ranges 7 ≤N ≤17 and 9 ≤N ≤11 , and that there are no asymptotically free AkF ¯ theories with k ≥5 . We investigate the types of ultraviolet to infrared evolution for these AkF ¯ theories and find that, depending on k and N , they may lead to a non-Abelian Coulomb phase, or may involve confinement with massless gauge-singlet composite fermions, bilinear fermion condensation with dynamical gauge and global symmetry breaking, or formation of multifermion condensates that preserve the gauge symmetry. We also show that there are no asymptotically free, anomaly-free SU (N ) SkF ¯ chiral gauge theories with k ≥3 , where Sk denotes the rank-k symmetric representation.

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

    PubMed

    Owerre, S A

    2016-11-30

    In this Letter, we study the magnetic transport in AA-stacked bilayer honeycomb chiral magnets coupled either ferromagnetically or antiferromagnetically. For both couplings, we observe chirality-induced gaps, chiral protected edge states, magnon Hall and magnon spin Nernst effects of magnetic spin excitations. For ferromagnetically coupled layers, thermal Hall and spin Nernst conductivities do not change sign as function of magnetic field or temperature similar to single-layer honeycomb ferromagnetic insulator. In contrast, for antiferromagnetically coupled layers, we observe a sign change in the thermal Hall and spin Nernst conductivities as the magnetic field is reversed. We discuss possible experimental accessible honeycomb bilayer quantum materials in which these effects can be observed. PMID:27636333

  7. Enantiomeric separations of chiral pharmaceuticals using chirally modified tetrahexahedral Au nanoparticles

    NASA Astrophysics Data System (ADS)

    Shukla, N.; Yang, D.; Gellman, A. J.

    2016-06-01

    Tetrahexahedral (THH, 24-sided) Au nanoparticles modified with D- or L-cysteine (Cys) have been used as enantioselective separators of the chiral pharmaceutical propranolol (PLL) in solution phase. Polarimetry has been used to measure the rotation of linearly polarized light by solutions containing mixtures of PLL and Cys/THH-Au NPs with varying enantiomeric excesses of each. Polarimetry yields clear evidence of enantiospecific adsorption of PLL onto the Cys/THH-Au NPs. This extends prior work using propylene oxide as a test chiral probe, by using the crystalline THH Au NPs with well-defined facets to separate a real pharmaceutical. This work suggests that chiral nanoparticles, coupled with a density separation method such as centrifugation, could be used for enantiomeric purification of real pharmaceuticals. A simple robust model developed earlier has also been used to extract the enantiospecific equilibrium constants for R- and S-PLL adsorption onto the D- and L-Cys/THH-Au NPs.

  8. Chiral light intrinsically couples to extrinsic/pseudo-chiral metasurfaces made of tilted gold nanowires

    NASA Astrophysics Data System (ADS)

    Belardini, Alessandro; Centini, Marco; Leahu, Grigore; Hooper, David C.; Li Voti, Roberto; Fazio, Eugenio; Haus, Joseph W.; Sarangan, Andrew; Valev, Ventsislav K.; Sibilia, Concita

    2016-08-01

    Extrinsic or pseudo-chiral (meta)surfaces have an achiral structure, yet they can give rise to circular dichroism when the experiment itself becomes chiral. Although these surfaces are known to yield differences in reflected and transmitted circularly polarized light, the exact mechanism of the interaction has never been directly demonstrated. Here we present a comprehensive linear and nonlinear optical investigation of a metasurface composed of tilted gold nanowires. In the linear regime, we directly demonstrate the selective absorption of circularly polarised light depending on the orientation of the metasurface. In the nonlinear regime, we demonstrate for the first time how second harmonic generation circular dichroism in such extrinsic/pseudo-chiral materials can be understood in terms of effective nonlinear susceptibility tensor elements that switch sign depending on the orientation of the metasurface. By providing fundamental understanding of the chiroptical interactions in achiral metasurfaces, our work opens up new perspectives for the optimisation of their properties.

  9. Chiral light intrinsically couples to extrinsic/pseudo-chiral metasurfaces made of tilted gold nanowires.

    PubMed

    Belardini, Alessandro; Centini, Marco; Leahu, Grigore; Hooper, David C; Li Voti, Roberto; Fazio, Eugenio; Haus, Joseph W; Sarangan, Andrew; Valev, Ventsislav K; Sibilia, Concita

    2016-01-01

    Extrinsic or pseudo-chiral (meta)surfaces have an achiral structure, yet they can give rise to circular dichroism when the experiment itself becomes chiral. Although these surfaces are known to yield differences in reflected and transmitted circularly polarized light, the exact mechanism of the interaction has never been directly demonstrated. Here we present a comprehensive linear and nonlinear optical investigation of a metasurface composed of tilted gold nanowires. In the linear regime, we directly demonstrate the selective absorption of circularly polarised light depending on the orientation of the metasurface. In the nonlinear regime, we demonstrate for the first time how second harmonic generation circular dichroism in such extrinsic/pseudo-chiral materials can be understood in terms of effective nonlinear susceptibility tensor elements that switch sign depending on the orientation of the metasurface. By providing fundamental understanding of the chiroptical interactions in achiral metasurfaces, our work opens up new perspectives for the optimisation of their properties. PMID:27553888

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

    PubMed

    Owerre, S A

    2016-11-30

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

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

    NASA Astrophysics Data System (ADS)

    Owerre, S. A.

    2016-11-01

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

  12. Chiral light intrinsically couples to extrinsic/pseudo-chiral metasurfaces made of tilted gold nanowires

    PubMed Central

    Belardini, Alessandro; Centini, Marco; Leahu, Grigore; Hooper, David C.; Li Voti, Roberto; Fazio, Eugenio; Haus, Joseph W.; Sarangan, Andrew; Valev, Ventsislav K.; Sibilia, Concita

    2016-01-01

    Extrinsic or pseudo-chiral (meta)surfaces have an achiral structure, yet they can give rise to circular dichroism when the experiment itself becomes chiral. Although these surfaces are known to yield differences in reflected and transmitted circularly polarized light, the exact mechanism of the interaction has never been directly demonstrated. Here we present a comprehensive linear and nonlinear optical investigation of a metasurface composed of tilted gold nanowires. In the linear regime, we directly demonstrate the selective absorption of circularly polarised light depending on the orientation of the metasurface. In the nonlinear regime, we demonstrate for the first time how second harmonic generation circular dichroism in such extrinsic/pseudo-chiral materials can be understood in terms of effective nonlinear susceptibility tensor elements that switch sign depending on the orientation of the metasurface. By providing fundamental understanding of the chiroptical interactions in achiral metasurfaces, our work opens up new perspectives for the optimisation of their properties. PMID:27553888

  13. On consistency of hydrodynamic approximation for chiral media

    NASA Astrophysics Data System (ADS)

    Avdoshkin, A.; Kirilin, V. P.; Sadofyev, A. V.; Zakharov, V. I.

    2016-04-01

    We consider chiral liquids, that is liquids consisting of massless fermions and right-left asymmetric. In such media, one expects existence of electromagnetic current flowing along an external magnetic field, associated with the chiral anomaly. The current is predicted to be dissipation-free. We consider dynamics of chiral liquids, concentrating on the issues of possible instabilities and infrared sensitivity. Instabilities arise, generally speaking, already in the limit of vanishing electromagnetic constant, αel → 0. In particular, liquids with non-vanishing chiral chemical potential might decay into right-left asymmetric states containing vortices.

  14. Identification of chiral drug isomers by capillary electrophoresis.

    PubMed

    Fanali, S

    1996-05-31

    Separation of optical isomers of compounds of pharmaceutical interest by capillary electrophoretic techniques is reviewed. The direct and indirect separation method, as well as the main resolution mechanisms and the parameters influencing the stereoselectivity are discussed considering capillary zone electrophoresis, micellar electrokinetic chromatography, isotachophoresis and electrochromatography. Several chiral selectors have been successfully used in CE for chiral separation, including cyclodextrins and their derivatives, modified crown-ethers, proteins, antibiotics, linear saccharides and chiral surfactants. Only applications in the pharmaceutical field with the most important experimental conditions are summarised in the Tables reported in this paper. The chiral analyses of drugs in real samples like biological fluids or pharmaceutical formulations are also reported.

  15. Magnetic fields and chiral asymmetry in the early hot universe

    NASA Astrophysics Data System (ADS)

    Sydorenko, Maksym; Tomalak, Oleksandr; Shtanov, Yuri

    2016-10-01

    In this paper, we study analytically the process of external generation and subsequent free evolution of the lepton chiral asymmetry and helical magnetic fields in the early hot universe. This process is known to be affected by the Abelian anomaly of the electroweak gauge interactions. As a consequence, chiral asymmetry in the fermion distribution generates magnetic fields of non-zero helicity, and vice versa. We take into account the presence of thermal bath, which serves as a seed for the development of instability in magnetic field in the presence of externally generated lepton chiral asymmetry. The developed helical magnetic field and lepton chiral asymmetry support each other, considerably prolonging their mutual existence, in the process of `inverse cascade' transferring magnetic-field power from small to large spatial scales. For cosmologically interesting initial conditions, the chiral asymmetry and the energy density of helical magnetic field are shown to evolve by scaling laws, effectively depending on a single combined variable. In this case, the late-time asymptotics of the conformal chiral chemical potential reproduces the universal scaling law previously found in the literature for the system under consideration. This regime is terminated at lower temperatures because of scattering of electrons with chirality change, which exponentially washes out chiral asymmetry. We derive an expression for the termination temperature as a function of the chiral asymmetry and energy density of helical magnetic field.

  16. Chiral nucleon-nucleon forces in nuclear structure calculations

    NASA Astrophysics Data System (ADS)

    Coraggio, L.; Gargano, A.; Holt, J. W.; Itaco, N.; Machleidt, R.; Marcucci, L. E.; Sammarruca, F.

    2016-05-01

    Realistic nuclear potentials, derived within chiral perturbation theory, are a major breakthrough in modern nuclear structure theory, since they provide a direct link between nuclear physics and its underlying theory, namely the QCD. As a matter of fact, chiral potentials are tailored on the low-energy regime of nuclear structure physics, and chiral perturbation theory provides on the same footing two-nucleon forces as well as many-body ones. This feature fits well with modern advances in ab-initio methods and realistic shell-model. Here, we will review recent nuclear structure calculations, based on realistic chiral potentials, for both finite nuclei and infinite nuclear matter.

  17. Micropolar modeling of planar orthotropic rectangular chiral lattices

    NASA Astrophysics Data System (ADS)

    Chen, Yi; Liu, Xiaoning; Hu, Gengkai

    2014-05-01

    Rectangular chiral lattices possess a two-fold symmetry; in order to characterize the overall behavior of such lattices, a two-dimensional orthotropic chiral micropolar theory is proposed. Eight additional material constants are necessary to represent the anisotropy in comparison with triangular ones, four of which are devoted to chirality. Homogenization procedures are also developed for the chiral lattice with rigid or deformable circles, all material constants in the developed micropolar theory are derived analytically for the case of the rigid circles and numerically for the case of the deformable circles. The dependences of these material constants and of wave propagation on the microstructural parameters are also examined.

  18. Single-Beam Optical Conveyor Belt for Chiral Particles

    NASA Astrophysics Data System (ADS)

    Fernandes, David E.; Silveirinha, Mário G.

    2016-07-01

    A different paradigm is proposed to selectively manipulate and transport small engineered chiral particles and discriminate different enantiomers using unstructured chiral light. It is theoretically shown that the response of a chiral metamaterial particle may be tailored to enable an optical conveyor-belt operation with no optical traps, such that for a fixed incident light helicity the nanoparticle is either steadily pushed towards the direction of the photon flow or steadily pulled against the photon flow, independent of its position. Our findings create distinct opportunities for unconventional optical manipulations of tailored nanoparticles and may have applications in sorting racemic mixtures of artificial chiral molecules and in particle delivery.

  19. Surface chirality induced by rotational electrodeposition in magnetic fields

    PubMed Central

    Mogi, Iwao; Morimoto, Ryoichi; Aogaki, Ryoichi; Watanabe, Kazuo

    2013-01-01

    The surfaces of minerals could serve important catalytic roles in the prebiotic syntheses of organic molecules, such as amino acids. Thus, the surface chirality is responsible for the asymmetric syntheses of biomolecules. Here, we show induction of the surface chirality of copper metal film by electrodeposition via electrochemical cell rotation in magnetic fields. Such copper film electrodes exhibit chiral behaviour in the electrochemical reaction of alanine enantiomers, and the rotating direction allows control of the chiral sign. These findings are discussed in connection with the asymmetric influence of the system rotation on the magnetohydrodynamic micro-vortices around the electrode surfaces. PMID:23999254

  20. Impact of immobilized polysaccharide chiral stationary phases on enantiomeric separations.

    PubMed

    Ali, Imran; Aboul-Enein, Hassan Y

    2006-04-01

    Immobilized polysaccharide-based chiral stationary phases (CSPs) are gaining importance in the resolution of racemic compounds due to their stable nature on working with normal solvents and those prohibited for use with coated phases (tetrahydrofuran, chloroform, dichloromethane, acetone, 1,4-dioxane, ethyl acetate, and certain other ethers). This review discusses the use of immobilized polysaccharide CSPs in the chiral resolution of various racemates by liquid chromatography. The discussion includes immobilization methodologies, enantioselectivities, efficiencies, and a comparison of chiral recognition capabilities of coated vs. immobilized CSPs. Some applications of immobilized CSPs to the chiral resolution of racemic compounds are also presented. PMID:16830488

  1. Topological state engineering by potential impurities on chiral superconductors

    NASA Astrophysics Data System (ADS)

    Kaladzhyan, Vardan; Röntynen, Joel; Simon, Pascal; Ojanen, Teemu

    2016-08-01

    In this work we consider the influence of potential impurities deposited on top of two-dimensional chiral superconductors. As discovered recently, magnetic impurity lattices on an s -wave superconductor may give rise to a rich topological phase diagram. We show that a similar mechanism takes place in chiral superconductors decorated by nonmagnetic impurities, thus avoiding the delicate issue of magnetic ordering of adatoms. We illustrate the method by presenting the theory of potential impurity lattices embedded on chiral p -wave superconductors. While a prerequisite for the topological state engineering is a chiral superconductor, the proposed procedure results in vistas of nontrivial descendant phases with different Chern numbers.

  2. Structure of liquid crystal droplets with chiral propeller texture.

    PubMed

    Yang, Deng-Ke; Jeong, Kwang-Un; Cheng, S Z D

    2008-02-01

    We experimentally studied a nematic liquid crystal whose molecules form twisted head-to-head H-bonded dimers. We observed that when the material transformed from the isotropic to nematic phase, it formed droplets with chiral propeller textures. We carried out a computer simulation to investigate the liquid crystal director configuration inside the droplets and to study the effects of elastic constants and chirality on the droplet texture. Results of our study show it is likely that the material in the droplets had nonzero chirality due to spontaneous chiral phase separation.

  3. Coupled achiral/chiral column techniques in subcritical fluid chromatography for the separation of chiral and nonchiral compounds.

    PubMed

    Phinney, K W; Sander, L C; Wise, S A

    1998-06-01

    A multicolumn approach was developed to address the limited achiral selectivity of chiral stationary phases. Groups of structurally related compounds, including beta-blockers and 1,4-benzodiazepines, were separated using coupled achiral/chiral stationary phases under subcritical fluid conditions. The achiral selectivity of amino and cyano stationary phases was used to modify the resolution of compounds on a Chiralcel OD chiral stationary phase by combining the achiral and chiral columns in series. In the case of the benzodiazepines, separation of achiral compounds was performed concurrently with the enantioseparation of chiral molecules. The separation of components of a multidrug cough and cold medication was also demonstrated on a cyano column coupled with a Chiralpak AD chiral stationary phase. The use of modified carbon dioxide eluents eliminated the mobile phase incompatibility problems associated with column coupling in liquid chromatography and incorporated the high efficiency of sub- and supercritical fluid chromatography.

  4. Enantiodivergent Atroposelective Synthesis of Chiral Biaryls by Asymmetric Transfer Hydrogenation: Chiral Phosphoric Acid Catalyzed Dynamic Kinetic Resolution.

    PubMed

    Mori, Keiji; Itakura, Tsubasa; Akiyama, Takahiko

    2016-09-12

    Reported herein is an enantiodivergent synthesis of chiral biaryls by a chiral phosphoric acid catalyzed asymmetric transfer hydrogenation reaction. Upon treatment of biaryl lactols with aromatic amines and a Hantzsch ester in the presence of chiral phosphoric acid, dynamic kinetic resolution (DKR) involving a reductive amination reaction proceeded smoothly to furnish both R and S isomers of chiral biaryls with excellent enantioselectivities by proper choice of hydroxyaniline derivative. This trend was observed in wide variety of substrates, and various chiral biphenyl and phenyl naphthyl adducts were synthesized with satisfactory enantioselectivities in enantiodivergent fashion. The enantiodivergent synthesis of synthetically challenging, chiral o-tetrasubstituted biaryls were also accomplished, and suggests high synthetic potential of the present method. PMID:27491630

  5. Cation distributions on rapidly solidified cobalt ferrite

    NASA Technical Reports Server (NTRS)

    De Guire, Mark R.; Kalonji, Gretchen; O'Handley, Robert C.

    1990-01-01

    The cation distributions in two rapidly solidified cobalt ferrites have been determined using Moessbauer spectroscopy at 4.2 K in an 8-T magnetic field. The samples were obtained by gas atomization of a Co0-Fe2O3-P2O5 melt. The degree of cation disorder in both cases was greater than is obtainable by cooling unmelted cobalt ferrite. The more rapidly cooled sample exhibited a smaller departure from the equilibrium cation distribution than did the more slowly cooled sample. This result is explained on the basis of two competing effects of rapid solidification: high cooling rate of the solid, and large undercooling.

  6. Antibacterial properties of cationic steroid antibiotics.

    PubMed

    Savage, Paul B; Li, Chunhong; Taotafa, Uale; Ding, Bangwei; Guan, Qunying

    2002-11-19

    Cationic steroid antibiotics have been developed that display broad-spectrum antibacterial activity. These compounds are comprised of steroids appended with amine groups arranged to yield facially amphiphilic morphology. Examples of these antibiotics are highly bactericidal, while related compounds effectively permeabilize the outer membranes of Gram-negative bacteria sensitizing these organisms to hydrophobic antibiotics. Cationic steroid antibiotics exhibit various levels of eukaryote vs. prokaryote cell selectivity, and cell selectivity can be increased via charge recognition of prokaryotic cells. Studies of the mechanism of action of these antibiotics suggest that they share mechanistic aspects with cationic peptide antibiotics. PMID:12445638

  7. Inherently chiral calix[4]arenes via oxazoline directed ortholithiation: synthesis and probe of chiral space.

    PubMed

    Herbert, Simon A; van Laeren, Laura J; Castell, Dominic C; Arnott, Gareth E

    2014-01-01

    The diastereoselective oxazoline-directed lithiation of calix[4]arenes is reported with diastereoselective ratios of greater than 100:1 in some instances. Notably, it has been found that the opposite diastereomer can be accessed via this approach merely through the choice of an alkyllithium reagent. The inherently chiral oxazoline calix[4]arenes have also been preliminarily examined as ligands in the palladium-catalyzed Tsuji-Trost allylation reaction, returning results comparable to their planar chiral ferrocene counterparts pointing towards future application of these types of compounds.

  8. Gyroscope like molecules consisting of trigonal or square planar osmium rotators within three-spoked dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties.

    PubMed

    Fiedler, Tobias; Bhuvanesh, Nattamai; Hampel, Frank; Reibenspies, Joseph H; Gladysz, John A

    2016-04-28

    Reactions of (NH4)2OsX6 (X = Cl, Br) with CO and the phosphines P((CH2)mCH[double bond, length as m-dash]CH2)3 (m = 6, a; 7, b; 8, c) give cis,cis,trans-Os(CO)2(X)2(P((CH2)mCH[double bond, length as m-dash]CH2)3)2 (46-73%). These are treated with Grubbs' catalyst (7 mol%, 0.0010 M, C6H5Cl). Subsequent hydrogenations (PtO2) yield the gyroscope like complexes cis,cis,trans-Os(CO)2(X)2(P((CH2)n)3P) (n = 2m + 2; X = Cl, 6a-c; Br, 7a-c ; 5-31%) and the isomers cis,cis,trans-Os(CO)2(X)2(P(CH2)n-1CH2)((CH2)n)(P(CH2)n-1CH2) (X = Cl, 6'ac; Br, 7'a-c;12-51%) derived from a combination of interligand and intraligand metatheses. Reductions of 6a,c, 6’b, and 7'b with C8K under CO atmospheres afford trans-Os(CO)3(P((CH2)n)3P) (9a,c, 79-82%) and trans-Os(CO)3(P(CH2)15CH2)((CH2)16)(P(CH2)15CH2) (9’b, 53-84%). Reaction of 9a and CF3SO3H yields the cationic hydride complex mer,trans-[Os(H)(CO)3(P((CH2)14)3P)](+) CF3SO3(-) (9a-H(+) CF3SO3(-); quantitative by NMR). Preparative reactions of 9a,c or 9'b and [H(OEt2)2](+) BArf(-) (BArf(-) = B(3,5-C6H3(CF3)2)4(-)) afford 9a,c-H(+) BArf(-) (80%) or 9'b-H(+) BArf(-) (68%). Reactions of 6a, 6’b, and 7a with MeLi or PhLi give cis,cis,trans-Os(CO)2(Me)2(P((CH2)14)3P) (11a, 98%), cis,cis,trans-Os(CO)2(Me)2(P(CH2)15CH2)((CH2)16)(P(CH2)15CH2) (98%), and cis,cis,trans-Os(CO)2(Ph)2(P((CH2)14)3P) (12a, 58%). NMR data for 6a–c, 7a–c, 9a,c, 9a,c-H(+) X(-), and 11a indicate that rotation of the OsLy moieties is fast on the NMR time scale at room temperature. In contrast, the phenyl groups in 12a act as "brakes" and two sets of (13)C NMR signals are observed for the methylene chains (2 : 1). The crystal structures of 6a–c, 7b,c, 7’a, 9a, 9a -H(+) BArf(-), 11a, and 12a are analyzed with respect to OsLy rotation in solution and the solid state.

  9. Gyroscope like molecules consisting of trigonal or square planar osmium rotators within three-spoked dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties.

    PubMed

    Fiedler, Tobias; Bhuvanesh, Nattamai; Hampel, Frank; Reibenspies, Joseph H; Gladysz, John A

    2016-04-28

    Reactions of (NH4)2OsX6 (X = Cl, Br) with CO and the phosphines P((CH2)mCH[double bond, length as m-dash]CH2)3 (m = 6, a; 7, b; 8, c) give cis,cis,trans-Os(CO)2(X)2(P((CH2)mCH[double bond, length as m-dash]CH2)3)2 (46-73%). These are treated with Grubbs' catalyst (7 mol%, 0.0010 M, C6H5Cl). Subsequent hydrogenations (PtO2) yield the gyroscope like complexes cis,cis,trans-Os(CO)2(X)2(P((CH2)n)3P) (n = 2m + 2; X = Cl, 6a-c; Br, 7a-c ; 5-31%) and the isomers cis,cis,trans-Os(CO)2(X)2(P(CH2)n-1CH2)((CH2)n)(P(CH2)n-1CH2) (X = Cl, 6'ac; Br, 7'a-c;12-51%) derived from a combination of interligand and intraligand metatheses. Reductions of 6a,c, 6’b, and 7'b with C8K under CO atmospheres afford trans-Os(CO)3(P((CH2)n)3P) (9a,c, 79-82%) and trans-Os(CO)3(P(CH2)15CH2)((CH2)16)(P(CH2)15CH2) (9’b, 53-84%). Reaction of 9a and CF3SO3H yields the cationic hydride complex mer,trans-[Os(H)(CO)3(P((CH2)14)3P)](+) CF3SO3(-) (9a-H(+) CF3SO3(-); quantitative by NMR). Preparative reactions of 9a,c or 9'b and [H(OEt2)2](+) BArf(-) (BArf(-) = B(3,5-C6H3(CF3)2)4(-)) afford 9a,c-H(+) BArf(-) (80%) or 9'b-H(+) BArf(-) (68%). Reactions of 6a, 6’b, and 7a with MeLi or PhLi give cis,cis,trans-Os(CO)2(Me)2(P((CH2)14)3P) (11a, 98%), cis,cis,trans-Os(CO)2(Me)2(P(CH2)15CH2)((CH2)16)(P(CH2)15CH2) (98%), and cis,cis,trans-Os(CO)2(Ph)2(P((CH2)14)3P) (12a, 58%). NMR data for 6a–c, 7a–c, 9a,c, 9a,c-H(+) X(-), and 11a indicate that rotation of the OsLy moieties is fast on the NMR time scale at room temperature. In contrast, the phenyl groups in 12a act as "brakes" and two sets of (13)C NMR signals are observed for the methylene chains (2 : 1). The crystal structures of 6a–c, 7b,c, 7’a, 9a, 9a -H(+) BArf(-), 11a, and 12a are analyzed with respect to OsLy rotation in solution and the solid state. PMID:27007878

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

    PubMed

    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.

  11. True and false chirality, {ital CP} violation, and the breakdown of microscopic reversibility in chiral molecular and elementary particle processes

    SciTech Connect

    Barron, L.D.

    1996-07-01

    The concept of chirality is extended to cover systems that exhibit enantiomorphism on account of motion. This is achieved by applying time reversal in addition to space inversion and leads to a more precise definition of a chiral system. Although spatial enantiomorphism is sufficient to guarantee chirality in a stationary system such as a finite helix, enantiomorphous systems are not necessarily chiral when motion is involved, which leads to the concept of true and false chirality associated with time-invariant and time-noninvariant enantiomorphism, respectively. Only a truly chiral influence can induce an enantiomeric excess in a reaction that has reached true thermodynamic equilibrium (i.e., when all possible interconversion pathways have equilibrated); however, false chirality can suffice in a reaction under kinetic control due to a breakdown of microscopic reversibility analogous to that observed in particle-antiparticle processes involving the neutral K-meason as a result of {ital CP} violation, with the apparently contradictory kinetic and thermodynamic aspects being reconciled by an appeal to unitarity. This reveals that {ital CP} violation is analogous to chemical catalysis since it affects the rates of certain particle-antiparticle interconversion pathways without affecting the initial and final particle energies and hence the equilibrium thermodynamics. Consideration of falsely chiral influences, including the {open_quote}ratchet effect{close_quote} arising from the associated breakdown in microscopic reversibility, greatly enlarges the range of possible chiral advantage factors in prebiotic chemical processes if far from equilibrium. {copyright} {ital 1996 American Institute of Physics.}

  12. Molecular-level Design of Heterogeneous Chiral Catalysts

    SciTech Connect

    Gellman, Andrew John; Sholl, David S.; Tysoe, Wilfred T.; Zaera, Francisco

    2013-04-28

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

  13. Cationic ruthenium alkylidene catalysts bearing phosphine ligands.

    PubMed

    Endo, Koji; Grubbs, Robert H

    2016-02-28

    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

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

    PubMed

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

    2011-01-01

    Proteins are often enantioselective towards their binding partners. When designing small molecules to interact with these targets, one should consider stereoselectivity. As considerations for exploring structure space evolve, chirality is increasingly important. Binding affinity for a chiral drug can differ for diastereomers and between enantiomers. For the virtual screening and computational design stage of drug development, this problem can be compounded by incomplete stereochemical information in structure libraries leading to a "coin toss" as to whether or not the "ideal" chiral structure is present. Creating every stereoisomer for each chiral compound in a structure library leads to an exponential increase in the number of structures resulting in potentially unmanageable file sizes and screening times. Therefore, only key chiral structures, enantiomeric pairs based on relative stereochemistry need be included, and lead to a compromise between exploration of chemical space and maintaining manageable libraries. In clinical environments, enantiomers of chiral drugs can have reduced, no, or even deleterious effects. This underscores the need to avoid mixtures of compounds and focus on chiral synthesis. Governmental regulations emphasizing the need to monitor chirality in drug development have increased. The United States Food and Drug Administration issued guidelines and policies in 1992 concerning the development of chiral compounds. These guidelines require that absolute stereochemistry be known for compounds with chiral centers and that this information should be established early in drug development in order that the analysis can be considered valid. From exploration of structure space to governmental regulations it is clear that the question of chirality in drug design is of vital importance. PMID:21291399

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

    PubMed

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

    2011-01-01

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

  16. Plasmonic enhancement of chiral light-matter interactions

    NASA Astrophysics Data System (ADS)

    Alizadeh, Mohammadhossein

    Plasmonic nanostructures provide unique opportunities to improve the detection limits of chiroptical spectroscopies by enhancing chiral light-matter interactions. The most significant of such interaction occur in ultraviolet (UV) range of the electromagnetic spectrum that remains challenging to access by conventional localized plasmon resonance based sensors. Although Surface Plasmon Polaritons (SPPs) on noble metal films can sustain resonances in the desired spectral range, their transverse magnetic nature has been an obstacle for enhancing chiroptical effects. We demonstrate, both analytically and numerically, that SPPs excited by near-field sources can exhibit rich and non-trivial chiral characteristics. In particular, we show that the excitation of SPPs by a chiral source not only results in a locally enhanced optical chirality but also achieves manifold enhancement of net optical chirality. Our finding that SPPs facilitate a plasmonic enhancement of optical chirality in the UV part of the spectrum is of great interest in chiral bio-sensing. Next we focus on the new concepts of transverse spin angular momentum and Belinfante spin momentum of evanescent waves, which have recently drawn considerable attention. We investigate these novel physical properties of electromagnetic fields in the context of chiral surface plasmon polaritons. We demonstrate, both analytically and numerically, that locally excited surface plasmon polaritons possess transverse Spin angular momentum and Belinfante momentum with rich and non-trivial characteristics. We also show that the transverse spin angular momentum of locally excited surface plasmon polaritons leads to the emergence of transverse chiral forces in opposite directions for chiral objects of different handedness. The magnitude of such a transverse force is comparable to the optical gradient force and scattering forces. This finding may pave the way for realization of optical separation of chiral biomolecules.

  17. Chiral charge erasure via thermal fluctuations of magnetic helicity

    NASA Astrophysics Data System (ADS)

    Long, Andrew J.; Sabancilar, Eray

    2016-05-01

    We consider a relativistic plasma of fermions coupled to an Abelian gauge field and carrying a chiral charge asymmetry, which might arise in the early Universe through baryogenesis. It is known that on large length scales, λ gtrsim 1/(αμ5), the chiral anomaly opens an instability toward the erasure of chiral charge and growth of magnetic helicity. Here the chemical potential μ5 parametrizes the chiral asymmetry and α is the fine-structure constant. We study the process of chiral charge erasure through the thermal fluctuations of magnetic helicity and contrast with the well-studied phenomenon of Chern-Simons number diffusion. Through the fluctuation-dissipation theorem we estimate the amplitude and time scale of helicity fluctuations on the length scale λ, finding δScript H ~ λT and τ ~ αλ3T2 for a relativistic plasma at temperature T. We argue that the presence of a chiral asymmetry allows the helicity to grow diffusively for a time t ~ T3/(α5μ54) until it reaches an equilibrium value Script H ~ μ5T2/α, and the chiral asymmetry is partially erased. If the chiral asymmetry is small, μ5 < T/α, this avenue for chiral charge erasure is found to be slower than the chiral magnetic effect for which t ~ T/(α3μ52). This mechanism for chiral charge erasure can be important for the hypercharge sector of the Standard Model as well as extensions including U(1) gauge interactions, such as asymmetric dark matter models.

  18. Test procedure for cation exchange chromatography

    SciTech Connect

    Cooper, T.D.

    1994-08-24

    The purpose of this test plan is to demonstrate the synthesis of inorganic antimonate ion exchangers and compare their performance against the standard organic cation exchangers. Of particular interest is the degradation rate of both inorganic and organic cation exchangers. This degradation rate will be tracked by determining the ion exchange capacity and thermal stability as a function of time, radiation dose, and chemical reaction.

  19. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    DOEpatents

    Wasserman, S.R.; Anderson, K.B.; Song, K.; Yuchs, S.E.; Marshall, C.L.

    1998-04-28

    A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate. 3 figs.

  20. Enantiopurity analysis of new types of acyclic nucleoside phosphonates by capillary electrophoresis with cyclodextrins as chiral selectors.

    PubMed

    Solínová, Veronika; Kaiser, Martin Maxmilián; Lukáč, Miloš; Janeba, Zlatko; Kašička, Václav

    2014-02-01

    CE methods have been developed for the chiral analysis of new types of six acyclic nucleoside phosphonates, nucleotide analogs bearing [(3-hydroxypropan-2-yl)-1H-1,2,3-triazol-4-yl]phosphonic acid, 2-[(diisopropoxyphosphonyl)methoxy]propanoic acid, or 2-(phosphonomethoxy)propanoic acid moieties attached to adenine, guanine, 2,6-diaminopurine, uracil, and 5-bromouracil nucleobases, using neutral and cationic cyclodextrins as chiral selectors. With the exception of the 5-bromouracil-derived acyclic nucleoside phosphonate with a 2-(phosphonomethoxy)propanoic acid side chain, the R and S enantiomers of the other five acyclic nucleoside phosphonates were successfully separated with sufficient resolutions, 1.51-2.94, within a reasonable time, 13-28 min, by CE in alkaline BGEs (50 mM sodium tetraborate adjusted with NaOH to pH 9.60, 9.85, and 10.30, respectively) containing 20 mg/mL β-cyclodextrin as the chiral selector. A baseline separation of the R and S enantiomers of the 5-bromouracil-derived acyclic nucleoside phosphonate with 2-(phosphonomethoxy)propanoic acid side chain was achieved within a short time of 7 min by CE in an acidic BGE (20:40 mM Tris/phosphate, pH 2.20) using 60 mg/mL quaternary ammonium β-cyclodextrin chiral selector. The developed methods were applied for the assessment of the enantiomeric purity of the above acyclic nucleoside phosphonates. The preparations of all these compounds were found to be synthesized in pure enantiomeric forms. Using UV absorption detection at 206 nm, their concentration detection limits were in the low micromolar range.

  1. Appearance and disappearance of dendritic and chiral patterns in domains of Langmuir monolayers observed with Brewster angle microscopy.

    PubMed

    Hoffmann, Frank; Stine, Keith J; Hühnerfuss, Heinrich

    2005-01-13

    Investigations on the aggregation behavior and morphology of Langmuir films of enantiomeric (L) and racemic (DL) N-acyl amino acids on pure aqueous as well as metal cation containing subphases were carried out at the mesoscale level with the help of Brewster angle microscopy (BAM). In the case of N-hexadecanoyl alanine on a pure aqueous subphase at 298 K the L-enantiomer forms crystal platelets, while the irregular fractal-like shape of the domains of the racemic mixture can be explained by a diffusion limited aggregation (DLA) growth mechanism. At 303 K the L-enantiomer shows a dendritic growth pattern, which leads to explicitly chiral domain shapes that correspond with the chirality of the film-forming molecules and for which hydrogen bridges as directed attractive forces are assumed to be responsible. The compression of the L-enantiomer on a zinc ion containing subphase is accompanied by a remarkable metamorphosis of the condensed structure. Starting from torus-like domains they were at first converted into strongly wound S-shaped domains, finally turning into a seahorse-like appearance. The origin of these chiral shapes can be explained on the basis of an electrostatic growth model. The enantiomer of N-hexadecanoyl alanine methyl ester shows three different asymmetric dendritic growth patterns. The domains of the racemic mixture are dendritic too, but in contrast they are symmetric and have a notably low branching density. On a pure aqueous subphase the L-enantiomer of N-octadecanoyl valine exhibits dendritic growth as well, but the overall outer shape of the domains is not explicitly chiral. PMID:16851010

  2. Characterization and performance of short cationic antimicrobial peptide isomers.

    PubMed

    Juba, Melanie; Porter, Devin; Dean, Scott; Gillmor, Susan; Bishop, Barney

    2013-07-01

    Cationic antimicrobial peptides (CAMPs) represent an ancient defense mechanism against invading bacteria, with peptides such as the cathelicidins being essential elements of vertebrate innate immunity. CAMPs are typically associated with broad-spectrum antimicrobial potency and limited bacterial resistance. The cathelicidin identified from the elapid snake Naja atra (NA-CATH) contains a semi-conserved repeated 11-residue motif (ATRA motif) with a sequence pattern consistent with formation of an amphipathic helical conformation. Short peptide amides (ATRA-1, -1A, -1P, and -2) generated based on the pair of ATRA motifs in NA-CATH exhibited varied antimicrobial potencies. The small size of the ATRA peptides, coupled with their varied antimicrobial performances, make them interesting models to study the impact various physico-chemical properties have on antimicrobial performance in helical CAMPs. Accordingly, the D- and L-enantiomers of the peptide ATRA-1A, which in earlier studies had shown both good antimicrobial performance and strong helical character, were investigated in order to assess the impact peptide stereochemistry has on antimicrobial performance and interaction with chiral membranes. The ATRA-1A isomers exhibit varied potencies against four bacterial strains, and their conformational properties in the presence of mixed zwitterionic/anionic liposomes are influenced by anionic lipid content. These studies reveal subtle differences in the properties of the peptide isomers. Differences are also seen in the abilities of the ATRA-1A isomers to induce liposome fusion/aggregation, bilayer rearrangement and lysing through turbidity studies and fluorescence microscopy. The similarities and differences in the properties of the ATRA-1A isomers could aid in efforts to develop D-peptide-based therapeutics using high-performing L-peptides as templates.

  3. Divalent cation shrinks DNA but inhibits its compaction with trivalent cation.

    PubMed

    Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

    2016-05-28

    Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions. PMID:27250329

  4. Divalent cation shrinks DNA but inhibits its compaction with trivalent cation

    NASA Astrophysics Data System (ADS)

    Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

    2016-05-01

    Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

  5. Chirally modified platinum generated by adsorption of cinchonidine ether derivatives: towards uncovering the chiral sites.

    PubMed

    Bonalumi, Norberto; Vargas, Angelo; Ferri, Davide; Baiker, Alfons

    2007-01-01

    The adsorption behavior of O-methyl and O-trimethylsilyl derivatives of cinchonidine (CD), employed as chiral modifiers for heterogeneous enantioselective hydrogenations on supported Pt catalysts, has been investigated by using attenuated total reflection infrared spectroscopy (ATR-IR) and density functional theory (DFT) electronic structure calculations. The ATR-IR spectroscopic investigation provided detailed insight of the adsorbed modifiers under conditions close to those employed during catalytic processes, and electronic structure calculations were used as a complement to the experiments to uncover the implications of conformational changes in generating the topology of the surface chiral site. The structural investigation of the adsorbed modifiers revealed a relationship between the spatial positions of the ether substituents and the enantiodifferentiation induced by the modified catalyst observed in the hydrogenation of alpha-activated ketones. Experiments and calculations corroborate a model, according to which the addition of a bulky ether group to CD reshapes the chiral sites, thus generating catalytic chiral surfaces with different and, in some cases (e.g. hydrogenation of ketopantolactone), even opposite enantioselective properties to those obtained with CD without altering the absolute configuration of the modifier. The study also confirms that active surface conformations of cinchona modifiers are markedly different from those existing in vacuum and in solution, thus underlying the necessity of investigating the surface-modifier interaction in order to understand enantioselectivity.

  6. [Preparation and chiral recognition ability of chiral stationary phase based on immobilized polyacrylamide derivative].

    PubMed

    Song, Jiafeng; Feng, Siwei; Xu, Xiaodong; Liu, Lijia; Song, Chaokun; Wen, Xiaokun; Chen, Jinyong; Li, Fangkun; Okamoto, Yoshio

    2016-01-01

    High performance liquid chromatography (HPLC) has been widely considered as the most effective way for the separation and preparation of optically pure enantiomers. In the resolution by HPLC, the separation ability of a column strongly depends on the properties of a chiral stationary phase (CSP). Among many CSPs, the immobilized CSPs, which are becoming one of the most important kinds of CSPs, have the advantages of good solvent durability and enormous method flexibility. In this work, a novel optically active acrylamide derivative (S)-APACP was synthesized by two-step reactions, and its chemical structure was characterized by 1H NMR. The polyacrylamide derivatives were immobilized on silica gel by three-step reactions to prepare immobilized CSPs, and the immobilization amount of the polymers was tested by thermogravimetric analysis. The chiral recognition ability of the immobilized CSPs was evaluated by HPLC, and the effects of Lewis acid and mobile phase on the chiral recognition ability were investigated. The results showed that APACP polymer was successfully immobilized on silica gel to prepare immobilized-type CSP with better solvent durability, and the amount of immobilized polymer was 10. 2% to 11. 8%. The immobilized-type CSP showed good chiral recognition ability for several enantiomers. PMID:27319168

  7. TRANSFORMATION OF CHIRAL POLLUTANTS IN SOIL AND SEDIMENT MICROCOSMS

    EPA Science Inventory

    The transformation rates and enantiomeric ratios of several chiral pollutants were determined in laboratory microcosms (25oC). Aerobic and anaerobic agricultural soil slurries were separately dosed with the following chiral pesticides: o,p'-DDT, o,p'-methoxychlor, cis-chlordane, ...

  8. The first catalytic asymmetric thioacetalization by chiral phosphoric acid catalysis.

    PubMed

    Yu, Jin-Sheng; Wu, Wen-Biao; Zhou, Feng

    2016-02-21

    We report here the first catalytic asymmetric thioacetalization of salicylaldehyde and dithiol. Chiral phosphoric acid STRIP C5 is identified as a powerful catalyst for this reaction to afford various chiral dithioacetals in high to excellent yields and enantioselectivities under mild conditions. PMID:26810819

  9. Chirality determination of quartz crystals using electron backscatter diffraction.

    PubMed

    Winkelmann, Aimo; Nolze, Gert

    2015-02-01

    We demonstrate the determination of crystal chirality using electron backscatter diffraction (EBSD) in the scanning electron microscope. The chirality of α-quartz as a space-group-dependent property is verified via direct comparison of experimental diffraction features to simulations using the dynamical theory of electron diffraction.

  10. Synthesis of Chiral Fluorinated Propargylamines via Chemoselective Biomimetic Hydrogenation.

    PubMed

    Chen, Mu-Wang; Wu, Bo; Chen, Zhang-Pei; Shi, Lei; Zhou, Yong-Gui

    2016-09-16

    A highly enantioselective synthesis of chiral fluorinated propargylamines was developed through phosphoric acid and ruthenium-catalyzed chemoselective biomimetic hydrogenation of the carbon-nitrogen double bond of fluorinated alkynyl ketimines in the presence of a carbon-carbon triple bond. This reaction features high chemoselectivity and slow background reaction. In addition, selective transformations of the chiral fluorinated propargylamines were also reported. PMID:27571222

  11. Chiral interface at the finite temperature transition point of QCD

    NASA Technical Reports Server (NTRS)

    Frei, Z.; Patkos, A.

    1990-01-01

    The domain wall between coexisting chirally symmetric and broken symmetry regions is studied in a saddle point approximation to the effective three-flavor sigma model. In the chiral limit the surface tension varies in the range ((40 to -50)MeV)(exp 3). The width of the domain wall is estimated to be approximately or equal to 4.5 fm.

  12. Cyclodextrin-Functionalized Monolithic Capillary Columns: Preparation and Chiral Applications.

    PubMed

    Adly, Frady G; Antwi, Nana Yaa; Ghanem, Ashraf

    2016-02-01

    In this review, the recently reported approaches for the preparation of cyclodextrin-functionalized capillary monolithic columns are highlighted, with few applications in chiral separations using capillary liquid chromatography (CLC) and capillary electrochromatography (CEC). Chirality 28:97-109, 2016. © 2015 Wiley Periodicals, Inc.

  13. Enantiospecific adsorption of cysteine on a chiral Au34 cluster

    NASA Astrophysics Data System (ADS)

    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.

  14. Chiral Boson Theory on the Light-Front

    SciTech Connect

    Srivastava, Prem P.

    1999-09-16

    The framework for describing the quantized theory of chiral boson is discussed. It avoids the conflict with the requirement of the principle of microcausality as is found in the conventional treatment. The discussion of the Floreanini-Jackiw model and its modified version for describing the chiral boson becomes very transparent on the light-front.

  15. Chiral symmetry aspects in the open charm sector

    NASA Astrophysics Data System (ADS)

    Buchheim, T.; Hilger, T.; Kämpfer, B.

    2016-01-01

    QCD sum rules serve as tools to investigate changing hadronic properties in a hot and/or dense nuclear medium. The role of chiral symmetry breaking and restoration effects in a medium can be addressed also in the heavy-light meson sector. Thus, we consider Weinberg sum rules which refer to chiral partner mesons composed of a light and a heavy quark.

  16. Chiral Polychlorinated Biphenyl Transport, Metabolism and Distribution - A Review

    PubMed Central

    Lehmler, Hans-Joachim; Harrad, Stuart J.; Hühnerfuss, Heinrich; Kania-Korwel, Izabela; Lee, Cindy M.; Lu, Zhe; Wong, Charles S.

    2009-01-01

    Chirality can be exploited to gain insight into enantioselective fate processes that may otherwise remain undetected because only biological, but not physical and chemical transport and transformation processes in an achiral environment will change enantiomer compositions. This review provides an in-depth overview of the application of chirality to the study of chiral polychlorinated biphenyls (PCBs), an important group of legacy pollutants. Like other chiral compounds, individual PCB enantiomers may interact enantioselectively (or enantiospecifically) with chiral macromolecules, such as cytochrome P-450 enzymes or ryanodine receptors, leading to differences in their toxicological effects and the enantioselective formation of chiral biotransformation products. Species and congener-specific enantiomer enrichment has been demonstrated in environmental compartments, wildlife and mammals, including humans, typically due to a complex combination of biotransformation processes and uptake via the diet by passive diffusion. Changes in the enantiomer composition of chiral PCBs in the environment have been used to understand complex aerobic and anaerobic microbial transformation pathways, to delineate and quantify PCB sources and transport in the environment, to gain insight into the biotransformation of PCBs in aquatic food webs, and to investigate the enantioselective disposition of PCBs and their methylsulfonyl PCBs metabolites in rodents. Overall, changes in chiral signatures are powerful, but currently underutilized tools for studies of environmental and biological processes of PCBs. PMID:20384371

  17. Renormalization of NN Interaction with Relativistic Chiral Two Pion Exchange

    SciTech Connect

    Higa, R; Valderrama, M Pavon; Arriola, E Ruiz

    2007-06-14

    The renormalization of the NN interaction with the Chiral Two Pion Exchange Potential computed using relativistic baryon chiral perturbation theory is considered. The short distance singularity reduces the number of counter-terms to about a half as those in the heavy-baryon expansion. Phase shifts and deuteron properties are evaluated and a general overall agreement is observed.

  18. Power counting for nuclear forces in chiral effective field theory

    NASA Astrophysics Data System (ADS)

    Long, Bingwei

    2016-02-01

    The present note summarizes the discourse on power counting issues of chiral nuclear forces, with an emphasis on renormalization-group invariance. Given its introductory nature, I will lean toward narrating a coherent point of view on the concepts, rather than covering comprehensively the development of chiral nuclear forces in different approaches.

  19. Multistep hierarchical self-assembly of chiral nanopore arrays

    PubMed Central

    Kim, Hanim; Lee, Sunhee; Shin, Tae Joo; Korblova, Eva; Walba, David M.; Clark, Noel A.; Lee, Sang Bok; Yoon, Dong Ki

    2014-01-01

    A series of simple hierarchical self-assembly steps achieve self-organization from the centimeter to the subnanometer-length scales in the form of square-centimeter arrays of linear nanopores, each one having a single chiral helical nanofilament of large internal surface area and interfacial interactions based on chiral crystalline molecular arrangements. PMID:25246585

  20. Pulsar Kicks via Chiral Asymmetry of Magnetized Stellar Matter

    NASA Astrophysics Data System (ADS)

    Shovkovy, I.

    2015-11-01

    Unusual chiral properties of the ground state of relativistic matter in a strong magnetic field are briefly reviewed. The main emphasis is placed on the dynamical generation of the chiral asymmetry in dense stellar matter. The corresponding asymmetry provides a natural mechanism for the strong pulsar kicks.

  1. Mapping chiral symmetry breaking in the excited baryon spectrum

    NASA Astrophysics Data System (ADS)

    Bicudo, Pedro; Cardoso, Marco; Llanes-Estrada, Felipe J.; Van Cauteren, Tim

    2016-09-01

    We study the conjectured "insensitivity to chiral symmetry breaking" in the highly excited light baryon spectrum. While the experimental spectrum is being measured at JLab and CBELSA/TAPS, this insensitivity remains to be computed theoretically in detail. As the only existing option to have both confinement, highly excited states, and chiral symmetry, we adopt the truncated Coulomb-gauge formulation of QCD, considering a linearly confining Coulomb term. Adopting a systematic and numerically intensive variational treatment up to 12 harmonic oscillator shells we are able to access several angular and radial excitations. We compute both the excited spectra of I =1 /2 and I =3 /2 baryons, up to large spin J =13 /2 , and study in detail the proposed chiral multiplets. While the static-light and light-light spectra clearly show chiral symmetry restoration high in the spectrum, the realization of chiral symmetry is more complicated in the baryon spectrum than earlier expected.

  2. VCD Studies on Chiral Characters of Metal Complex Oligomers

    PubMed Central

    Sato, Hisako; Yamagishi, Akihiko

    2013-01-01

    The present article reviews the results on the application of vibrational circular dichroism (VCD) spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy levels or low-lying electronic states. The investigation is further extended to the oligomers of β-diketonato complex units. The induction of chiral structures is confirmed by the VCD spectra when chiral inert moieties are connected with labile metal ions. These results have demonstrated how VCD spectroscopy is efficient in revealing the static and dynamic properties of mononuclear and multinuclear chiral metal complexes, which are difficult to clarify by means of other spectroscopes. PMID:23296273

  3. Spontaneous chiral symmetry breaking in collective active motion

    NASA Astrophysics Data System (ADS)

    Breier, Rebekka E.; Selinger, Robin L. B.; Ciccotti, Giovanni; Herminghaus, Stephan; Mazza, Marco G.

    2016-02-01

    Chiral symmetry breaking is ubiquitous in biological systems, from DNA to bacterial suspensions. A key unresolved problem is how chiral structures may spontaneously emerge from achiral interactions. We study a simple model of active swimmers in three dimensions that effectively incorporates hydrodynamic interactions. We perform large-scale molecular dynamics simulations (up to 106 particles) and find long-lived metastable collective states that exhibit chiral organization although the interactions are achiral. We elucidate under which conditions these chiral states will emerge and grow to large scales. To explore the complex phase space available to the system, we perform nonequilibrium quenches on a one-dimensional Lebwohl-Lasher model with periodic boundary conditions to study the likelihood of formation of chiral structures.

  4. Chiral and deconfinement transition from Dyson-Schwinger equations

    SciTech Connect

    Fischer, Christian S.; Mueller, Jens A.

    2009-10-01

    We determine the quark condensate and the dressed Polyakov loop from the finite temperature Landau gauge quark propagator evaluated with U(1)-valued boundary conditions in an approximation to quenched QCD. These gauge invariant quantities allow for an investigation of the chiral and deconfinement transitions. We compare results from Dyson-Schwinger equations on a lattice with infinite volume continuum results and study the temperature and quark mass dependence of both quantities. In particular we investigate the chiral condensate and the dressed Polyakov loop in the chiral limit. We also consider an alternative order parameter for the deconfinement transition, the dual scalar quark dressing, and compare it with the dressed Polyakov loop. As a result we find only slightly different transition temperatures for the chiral and the deconfinement transitions at finite quark masses; in the chiral limit both transitions coincide.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Chirality-induced negative refraction in magnetized plasma

    SciTech Connect

    Guo, B.

    2013-09-15

    Characteristic equations in magnetized plasma with chirality are derived in simple formulations and the dispersion relations for propagation parallel and perpendicular to the external magnetic field are studied in detail. With the help of the dispersion relations of each eigenwave, the author explores chirality-induced negative refraction in magnetized plasma and investigates the effects of parameters (i.e., chirality degree, external magnetic field, etc.) on the negative refraction. The results show that the chirality is the necessary and only one factor which leads to negative refraction without manipulating electrical permittivity and magnetic permeability. Both increasing the degree of chirality and reducing the external magnetic field can result in greater range negative refraction. Parameter dependence of the effects is calculated and discussed.

  7. Chiral Brønsted Acids for Asymmetric Organocatalysis

    NASA Astrophysics Data System (ADS)

    Kampen, Daniela; Reisinger, Corinna M.; List, Benjamin

    Chiral Brønsted acid catalysis is an emerging area of organocatalysis. Since the pioneering studies of the groups of Akiyama and Terada in 2004 on the use of chiral BINOL phosphates as powerful Brønsted acid catalysts in asymmetric Mannich-type reactions, numerous catalytic asymmetric transformations involving imine activation have been realized by means of this catalyst class, including among others Friedel-Crafts, Pictet-Spengler, Strecker, cycloaddition reactions, transfer hydrogenations, and reductive aminations. More recently, chiral BINOL phosphates found application in multicomponent and cascade reactions as for example in an asymmetric version of the Biginelli reaction. With the introduction of chiral BINOL-derived N-triflyl phosphoramides in 2006, asymmetric Brønsted acid catalysis is no longer restricted to reactive substrates. Also certain carbonyl compounds can be activated through these stronger Brønsted acid catalysts. In dealing with sensitive substrate classes, chiral dicarboxylic acids proved of particular value.

  8. Dynamic control of chirality in phosphine ligands for enantioselective catalysis

    PubMed Central

    Zhao, Depeng; Neubauer, Thomas M.; Feringa, Ben L.

    2015-01-01

    Chirality plays a fundamental role in biology and chemistry and the precise control of chirality in a catalytic conversion is a key to modern synthesis most prominently seen in the production of pharmaceuticals. In enantioselective metal-based catalysis, access to each product enantiomer is commonly achieved through ligand design with chiral bisphosphines being widely applied as privileged ligands. Switchable phosphine ligands, in which chirality is modulated through an external trigger signal, might offer attractive possibilities to change enantioselectivity in a catalytic process in a non-invasive manner avoiding renewed ligand synthesis. Here we demonstrate that a photoswitchable chiral bisphosphine based on a unidirectional light-driven molecular motor, can be used to invert the stereoselectivity of a palladium-catalysed asymmetric transformation. It is shown that light-induced changes in geometry and helicity of the switchable ligand enable excellent selectivity towards the racemic or individual enantiomers of the product in a Pd-catalysed desymmetrization reaction. PMID:25806856

  9. Lasing in chiral photonic structures [review article

    NASA Astrophysics Data System (ADS)

    Kopp, Victor I.; Zhang, Zhao-Qing; Genack, Azriel Z.

    This article presents a review of the lasing and photonic properties of periodic one-dimensional anisotropic structures with the symmetry of a double helix. Examples are self-organized cholesteric liquid crystals (CLCs) and sculptured thin films created by vapor deposition. A reflection band with sharp, closely spaced transmission peaks at its edges occurs for circularly polarized light with the same handedness as the helical structure. Within the reflection band, this wave is evanescent, corresponding to a vanishing density of states (DOS). Oppositely polarized light is uniformly transmitted. Since optical emission is proportional to the DOS, it is suppressed within the reflection band. However, it is enhanced at the band edge, where a series of narrow long-lived transmission modes are found. For this reason lasing in dye-doped CLCs occurs at the edge of the stop band rather than at its center, where reflection is highest. Introducing an additional rotation or an isotropic layer within a chiral structure creates a single circularly polarized localized mode with the same handedness as the structure. A resonance appears in the transmission of light of this polarization in thin samples. In thicker samples, the resonance appears instead in the reflection for oppositely polarized light. In contrast to strong modulation of the intensity within the sample on a wavelength scale, a characteristic of layered dielectric medium, the intensity within a chiral medium varies slowly when the sample is excited either at the band edge or at a localized mode. A transverse coherence is created in emission over a length scale proportional to the square root of the photon dwell time at resonance with long-lived modes. This makes possible spatially coherent lasing over a large area in thin films. The photonic properties of chiral thin films make them promising candidates for a variety of filter and laser applications.

  10. Surfaces and chirality in liquid crystals

    NASA Astrophysics Data System (ADS)

    Kang, Daeseung

    1999-10-01

    The effects of surfaces and chirality in liquid crystals were studied in this thesis. Four different experiments were presented to investigate the different aspects of their role in liquid crystal physics. A liquid crystal cell treated for homeotropic alignment with different surfactants at the two surfaces was subjected to an electric field E in the plane of the cell. The longitudinal polarization at the surface couples with the external field, and in consequence exerts a torque on molecules. The differential optical retardation deltaalpha due to a slight deformation was found to be linear in field over a frequency range 10 < o < 105 Hz, where d(deltaalpha)/dE is proportional to o -1. As a different aspect of the surface, the phenomenon of a chiral liquid crystal in highly restricted geometry was also investigated, where the random surface dominates the bulk. The optical rotatory power of the chiral liquid crystal in the porous medium was drastically altered from that of the bulk liquid crystal. The observed behavior may be attributed to a combination of surface interactions and finite size effects, which are discussed in terms of an infrared cutoff in the orientational pair correlation function. Chirality manifests itself not only as an optical activity in nematics, but more strikingly in forms of ferroelectric and antiferroelectric phases in smectics. The anticlinic interlayer coupling coefficient U between smectic layers was evaluated for a pitch-compensated antiferroelectric liquid crystal by optical observation of the optic mode response to an in-plane electric field. The result is in good agreement with Us estimated from the threshold field for the onset of solitary waves, and provides a strong support for the switching model based on the free energy. Finally, a new trimer liquid crystal based on a terminal-lateral-lateral-terminal connection was investigated. Magnetically induced Freedericksz measurements were performed to extract the elastic constants of

  11. Enantioselective cellular uptake of chiral semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Martynenko, I. V.; Kuznetsova, V. A.; Litvinov, I. K.; Orlova, A. O.; Maslov, V. G.; Fedorov, A. V.; Dubavik, A.; Purcell-Milton, F.; Gun'ko, Yu K.; Baranov, A. V.

    2016-02-01

    The influence of the chirality of semiconductor nanocrystals, CdSe/ZnS quantum dots (QDs) capped with L- and D-cysteine, on the efficiency of their uptake by living Ehrlich Ascite carcinoma cells is studied by spectral- and time-resolved fluorescence microspectroscopy. We report an evident enantioselective process where cellular uptake of the L-Cys QDs is almost twice as effective as that of the D-Cys QDs. This finding paves the way for the creation of novel approaches to control the biological properties and behavior of nanomaterials in living cells.

  12. Hyperbolic Weyl Point in Reciprocal Chiral Metamaterials.

    PubMed

    Xiao, Meng; Lin, Qian; Fan, Shanhui

    2016-07-29

    We report the existence of Weyl points in a class of noncentral symmetric metamaterials, which has time reversal symmetry, but does not have inversion symmetry due to chiral coupling between electric and magnetic fields. This class of metamaterial exhibits either type-I or type-II Weyl points depending on its nonlocal response. We also provide a physical realization of such metamaterial consisting of an array of metal wires in the shape of elliptical helices which exhibits type-II Weyl points. PMID:27517792

  13. Chiral partition functions of quantum Hall droplets

    SciTech Connect

    Cappelli, Andrea Viola, Giovanni; Zemba, Guillermo R.

    2010-02-15

    Chiral partition functions of conformal field theory describe the edge excitations of isolated Hall droplets. They are characterized by an index specifying the quasiparticle sector and transform among themselves by a finite-dimensional representation of the modular group. The partition functions are derived and used to describe electron transitions leading to Coulomb blockade conductance peaks. We find the peak patterns for Abelian hierarchical states and non-Abelian Read-Rezayi states, and compare them. Experimental observation of these features can check the qualitative properties of the conformal field theory description, such as the decomposition of the Hilbert space into sectors, involving charged and neutral parts, and the fusion rules.

  14. Chirality--a new era of therapeutics.

    PubMed

    Agrawal, Y K; Bhatt, H G; Raval, H G; Oza, P M; Gogoi, P J

    2007-05-01

    To develop the newer pharmaceuticals and to spur the strong growth, being a general property of 'handedness', chirality plays a major role. The Easson-Stedman principle shows the differences in the biological activity between enantiomers resulted from selective reactivity of one enantiomer with its receptor. It helps to improve the pharmacokinetic properties and to remove undesirable side effects by virtue of the unique activity of enantiomers. Racemic switching and marketing drug combinations are used as tools for drug life-cycle management and to redevelop racemic mixtures as single enantiomers. PMID:17504180

  15. Chiral phase transition from string theory.

    PubMed

    Parnachev, Andrei; Sahakyan, David A

    2006-09-15

    The low energy dynamics of a certain D-brane configuration in string theory is described at weak t'Hooft coupling by a nonlocal version of the Nambu-Jona-Lasinio model. We study this system at finite temperature and strong t'Hooft coupling, using the string theory dual. We show that for sufficiently low temperatures chiral symmetry is broken, while for temperatures larger then the critical value, it gets restored. We compute the latent heat and observe that the phase transition is of the first order.

  16. Chirality in the RNA world and beyond

    NASA Astrophysics Data System (ADS)

    Sandars, P. G. H.

    2005-01-01

    Homochirality is an essential feature of biology, but how it developed in early life remains unclear. Our aim in this paper is to add to the discussion by taking a somewhat arbitrary but definite sequence of events and examining carefully the chirality at each stage. Our scenario for the development of life starts with the prebiotic, continues through a pre-RNA stage to the RNA world. This leads to the development of proteins and then to the incorporation of DNA in RNA-DNA-protein biochemistry.

  17. Chiral polymerization and the RNA world

    NASA Astrophysics Data System (ADS)

    Wattis, Jonathan A. D.; Coveney, Peter V.

    2005-01-01

    The purpose of this paper is to review two mathematical models: one for the formation of homochiral polymers from an originally chirally symmetric system; and the other, to show how, in an RNA-world scenario, RNA can simultaneously act both as information storage and a catalyst for its own production. We note the similarities and differences in chemical mechanisms present in the systems. We review these two systems, analysing steady states, interesting kinetics and the stability of symmetric solutions. In both systems we show that there are ranges of parameter values where some chains increase their own concentrations faster than others.

  18. Passerini Reactions on Biocatalytically Derived Chiral Azetidines.

    PubMed

    Moni, Lisa; Banfi, Luca; Basso, Andrea; Bozzano, Andrea; Spallarossa, Martina; Wessjohann, Ludger; Riva, Renata

    2016-01-01

    The purpose of this study was to explore a series of Passerini reactions on a biocatalytically derived enantiopure azetidine-2-carboxyaldehyde in order to obtain, in a diastereoselective manner, polyfunctionalised derivatives having the potential to be cyclized to chiral bridged bicyclic nitrogen heterocycles. While diastereoselectivity was poor under classical Passerini conditions, a significant increase of diastereoselectivity (up to 76:24) was gained by the use of zinc bromide as promoter. The methodology has a broad scope and yields are always good. PMID:27589709

  19. Efficient chemoenzymatic synthesis of chiral pincer ligands.

    PubMed

    Felluga, Fulvia; Baratta, Walter; Fanfoni, Lidia; Pitacco, Giuliana; Rigo, Pierluigi; Benedetti, Fabio

    2009-05-01

    Chiral, nonracemic pincer ligands based on the 6-phenyl-2-aminomethylpyridine and 2-aminomethylbenzo[h]quinoline scaffolds were obtained by a chemoenzymatic approach starting from 2-pyridyl and 2-benzoquinolyl ethanone. In the enantiodifferentiating step, secondary alcohols of opposite absolute configuration were obtained by a baker's yeast reduction of the ketones and by lipase-mediated dynamic kinetic resolution of the racemic alcohols. Their transformation into homochiral 1-methyl-1-heteroarylethanamines occurred without loss of optical purity, giving access to pincer ligands used in enantioselective catalysis.

  20. Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

    SciTech Connect

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2012-11-29

    The ionic charge state of monodisperse cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine in the presence of 1,3-bis(diphenylphosphino)propane. The polydisperse gold clusters were introduced into the gas phase by electrospray ionization and mass selection was employed to select a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at coverages of 1011 and 1012 clusters/mm2. Employing the spatial profiling capabilities of in-situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano, 2012, 6, 573) the coverage of cationic gold clusters on the surface may be used to control the distribution of ionic charge states of the soft-landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol SAM (FSAM) almost complete retention of charge by the deposited Au11L53+ clusters was observed at a lower coverage of 1011 clusters/mm2. In contrast, at a higher coverage of 1012 clusters/mm2, pronounced reduction of charge to Au11L52+ and Au11L5+ was observed on the FSAM. When soft landed onto 16- and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au11L53+ clusters exhibited partial reduction of charge to Au11L52+ at lower coverage and additional reduction of charge to both Au11L52+ and Au11L5+ at higher coverage. The reduction of charge was found to be more pronounced on the surface of the shorter (thinner) C11 than the longer (thicker) C16-COOH-SAM. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge state